CN113396189A

CN113396189A - Resin composition

Info

Publication number: CN113396189A
Application number: CN202080011267.4A
Authority: CN
Inventors: 菊地悠太; 爱敬雄介
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2019-02-05
Filing date: 2020-02-05
Publication date: 2021-09-14
Also published as: KR20210123302A; JP7438711B2; JP2020125449A; TW202039670A

Abstract

A resin composition comprising: a thermoplastic resin and/or a thermosetting resin; and a glass component dispersed in the thermoplastic resin and/or the thermosetting resin, wherein, when the ICP analysis is performed on a residue component obtained by ashing the resin composition, the calcium content in the resin composition is 0 to 27% by mass relative to 100% by mass of the metal component contained in the resin composition, and the calcium content in the glass component is 0 to 27% by mass relative to 100% by mass of the metal component contained in the glass component.

Description

Resin composition

Technical Field

The present invention relates to a resin composition.

The present application claims priority based on Japanese patent application No. 2019-.

Background

In the field of dielectric devices such as resonators, filters, antennas, circuit boards, and laminated circuit element boards, the use of high frequency bands (centimeter to millimeter waves) has been in progress with the recent increase in the amount of information, the advancement in communication technology, and the depletion of the use frequency band.

In general, inorganic materials tend to have low dielectric loss, but have a problem that it is difficult to reduce the relative dielectric constant. In contrast, there are many organic materials having a low relative dielectric constant.

Therefore, a dielectric material has been proposed which is formed by dispersing magnesium oxide fine particles as inorganic material particles in a resinous organic material (patent document 1).

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open No. 2014-24916.

Disclosure of Invention

Problems to be solved by the invention

However, if the relative dielectric constant and the dielectric characteristics of the dielectric loss tangent (dispersion factor) are to be reduced, the mechanical strength is impaired, and a material satisfying both the dielectric characteristics and the mechanical strength has not been found.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a resin composition having excellent mechanical strength, a small relative dielectric constant, and a small dielectric loss tangent.

Means for solving the problems

In order to solve the above problem, the present invention adopts the following configuration.

[1] A resin composition comprising: a thermoplastic resin and/or a thermosetting resin; and a glass component dispersed in the thermoplastic resin and/or the thermosetting resin, wherein in the resin composition,

and a calcium content of 0 to 27% by mass in the resin composition based on 100% by mass of the metal component contained in the resin composition when the ICP analysis is performed on the residue component after ashing the resin composition.

[2] The resin composition according to [1], wherein the content of silicon in the resin composition is 51% by mass or more based on 100% by mass of the metal component contained in the resin composition when the ICP analysis is performed on the residue component obtained by ashing the resin composition.

[3] A resin composition comprising: a thermoplastic resin and/or a thermosetting resin; and a glass component dispersed in the thermoplastic resin and/or the thermosetting resin, wherein in the resin composition,

the content of calcium contained in the glass component is 0-27% by mass relative to 100% by mass of the metal component contained in the glass component.

[4] The resin composition according to [3], wherein the silicon content in the glass component is 51% by mass or more with respect to 100% by mass of the metal component contained in the glass component.

[5]As described in [1]]～[4]The resin composition as described in any one of the above, wherein the resin composition has a relative dielectric constant ε at a frequency of 1GHz and a temperature of 25 ℃_rIs 3.4 or less.

[6]As described in [ 5]]The resin composition, wherein the resin composition has a dielectric loss tangent tan delta of 5.5 x 10 under a frequency of 1GHz and a temperature of 25 DEG C^-3The following.

[7]As described in [ 5]]Or [ 6]]The resin composition, wherein the resin composition has a thermal diffusivity of 0.14mm²More than s.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a resin composition having excellent mechanical strength, a small relative dielectric constant and a small dielectric loss tangent can be provided.

Detailed Description

< resin composition >

The resin composition of the present embodiment contains: a thermoplastic resin and/or a thermosetting resin; and a glass component dispersed in the thermoplastic resin and/or the thermosetting resin.

The resin composition of the present embodiment can be obtained by mixing a thermoplastic resin and/or a thermosetting resin with a glass component and dispersing the glass component in the thermoplastic resin and/or the thermosetting resin.

In the resin composition of the present embodiment, when the ICP analysis is performed on the residue component after ashing the resin composition, the calcium content in the resin composition is 0 to 27 mass% relative to 100 mass% of the metal component contained in the resin composition. The calcium content in the resin composition is preferably 0 to 20 mass%, more preferably 0 to 15 mass%, and particularly preferably 0 to 10 mass% with respect to 100 mass% of the metal component contained in the resin composition. The calcium content in the resin composition may be 0.2 mass% or more, 0.4 mass% or more, or 1.0 mass% or more with respect to 100 mass% of the metal component contained in the resin composition. That is, the calcium content in the resin composition may be 0.2 to 20 mass%, 0.4 to 15 mass%, or 1.0 to 10 mass% with respect to 100 mass% of the metal component contained in the resin composition. By setting the calcium content in the resin composition to the above range, the resin composition of the present embodiment can have a small relative permittivity and a small dielectric loss tangent, and can maintain the same mechanical strength as a resin composition containing a glass component in the same form.

In the present specification, the metal component refers to a component of a metal element, and here, semimetals of boron, silicon, germanium, arsenic, antimony, tellurium, selenium, polonium, and astatine are included in the metal element. As the metal component of the glass component, Al, Ba, Ca, Si, Ti, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Ni, P, Pb, Sb, V and Zn may be analyzed.

In the resin composition of the present embodiment, when ICP analysis is performed on a residue component after ashing the resin composition, the content of calcium in the resin composition is preferably 0 to 27 mass%, more preferably 0 to 20 mass%, even more preferably 0 to 15 mass%, and particularly preferably 0 to 10 mass%, relative to 100 mass% of the total content of Al, Ca, Si, K, Li, Mg, Na, and Zn in the resin composition. The calcium content in the resin composition may be 0.2 mass% or more, 0.4 mass% or more, or 1.0 mass% or more, based on 100 mass% of the total content of Al, Ca, Si, K, Li, Mg, Na, and Zn in the resin composition. That is, the calcium content in the resin composition may be 0.2 to 20 mass%, 0.4 to 15 mass%, or 1.0 to 10 mass% with respect to 100 mass% of the total content of Al, Ca, Si, K, Li, Mg, Na, and Zn in the resin composition.

In the resin composition of the present embodiment, the content of calcium contained in the glass component is 0 to 27 mass%, preferably 0 to 20 mass%, more preferably 0 to 15 mass%, and particularly preferably 0 to 10 mass% with respect to 100 mass% of the metal component contained in the glass component. The content of calcium contained in the glass component may be 0.2 mass% or more, 0.4 mass% or more, or 1.0 mass% or more with respect to 100 mass% of the metal component contained in the glass component. That is, the content of calcium contained in the glass component may be 0.2 to 20 mass%, 0.4 to 15 mass%, or 1.0 to 10 mass% with respect to 100 mass% of the metal component contained in the glass component. By setting the content of calcium in the glass component to the above range, the resin composition of the present embodiment can have a small relative permittivity and a small dielectric loss tangent, and can maintain the same level of mechanical strength as compared with a resin composition containing a glass component of the same form.

In the resin composition of the present embodiment, the content of calcium in the glass component is preferably 0 to 27 mass%, more preferably 0 to 20 mass%, even more preferably 0 to 15 mass%, and particularly preferably 0 to 10 mass%, relative to 100 mass% of the total content of Al, Ca, Si, K, Li, Mg, Na, and Zn in the glass component. The content of calcium contained in the glass component may be 0.2 mass% or more, 0.4 mass% or more, or 1.0 mass% or more with respect to 100 mass% of the metal component contained in the glass component. That is, the content of calcium contained in the glass component may be 0.2 to 20 mass%, 0.4 to 15 mass%, or 1.0 to 10 mass% with respect to 100 mass% of the metal component contained in the glass component. By setting the content of calcium in the glass component to the above range, the resin composition of the present embodiment can have a small relative permittivity and a small dielectric loss tangent, and can maintain the same level of mechanical strength as compared with a resin composition containing a glass component of the same form.

In the resin composition of the present embodiment, when the ICP analysis is performed on the residue component after ashing the resin composition, the silicon content in the resin composition is preferably 51 mass% or more, more preferably 55 mass% or more, and particularly preferably 60 mass% or more, relative to 100 mass% of the metal component contained in the resin composition. By setting the silicon content in the resin composition to the above range, the resin composition of the present embodiment can have a small relative permittivity and a small dielectric loss tangent, and can maintain the same mechanical strength as a resin composition containing a glass component in the same form.

Further, in the resin composition of the present embodiment, when ICP analysis is performed on a residue component obtained after ashing the resin composition, the silicon content in the resin composition is preferably 62 mass% or more, more preferably 65 mass% or more, and particularly preferably 70 mass% or more, with respect to 100 mass% of the metal component contained in the resin composition. By setting the silicon content in the resin composition to the above range, the resin composition of the present embodiment can have a small relative permittivity, a small dielectric loss tangent, and a small thermal diffusivity, and can maintain the same mechanical strength as a resin composition containing a glass component in the same form.

In the resin composition of the present embodiment, when the ICP analysis is performed on the residue component after ashing the resin composition, the silicon content in the resin composition may be 100 mass% or less, 99.8 mass% or less, or 99.5 mass% or less with respect to 100 mass% of the metal component contained in the resin composition.

In the resin composition of the present embodiment, when the ICP analysis is performed on the residue component after ashing the resin composition, the silicon content in the resin composition may be 51 mass% or more and 100 mass% or less, 55 mass% or more and 99.8 mass% or less, 60 mass% or more and 99.5 mass% or less, 62 mass% or more and 100 mass% or less, 65 mass% or more and 99.8 mass% or less, or 70 mass% or more and 99.5 mass% or less with respect to 100 mass% of the metal component contained in the resin composition.

In the resin composition of the present embodiment, when ICP analysis is performed on a residue component after ashing the resin composition, the content of silicon in the resin composition is preferably 51 mass% or more, more preferably 55 mass% or more, and particularly preferably 60 mass% or more, with respect to 100 mass% of the total content of Al, Ca, Si, K, Li, Mg, Na, and Zn in the resin composition.

Further, in the resin composition of the present embodiment, when ICP analysis is performed on a residue component obtained by ashing the resin composition, the content of silicon in the resin composition is preferably 62 mass% or more, more preferably 65 mass% or more, and particularly preferably 70 mass% or more, with respect to 100 mass% of the total content of Al, Ca, Si, K, Li, Mg, Na, and Zn in the resin composition.

In the resin composition of the present embodiment, when ICP analysis is performed on a residue component after ashing the resin composition, the silicon content in the resin composition may be 100 mass% or less, 99.8 mass% or less, or 99.5 mass% or less with respect to 100 mass% of the total content of Al, Ca, Si, K, Li, Mg, Na, and Zn in the resin composition.

In the resin composition of the present embodiment, when ICP analysis is performed on the residue component after ashing the resin composition, the silicon content in the resin composition may be 51 mass% or more and 100 mass% or less, 55 mass% or more and 99.8 mass% or less, 60 mass% or more and 99.5 mass% or less, 62 mass% or more and 100 mass% or less, 65 mass% or more and 99.8 mass% or less, or 70 mass% or more and 99.5 mass% or less, with respect to 100 mass% of the total content of Al, Ca, Si, K, Li, Mg, Na, and Zn in the resin composition.

In the resin composition of the present embodiment, the content of silicon contained in the glass component is preferably 51 mass% or more, more preferably 55 mass% or more, and particularly preferably 60 mass% or more, with respect to 100 mass% of the metal component contained in the glass component. By setting the content of silicon in the glass component to the above range, the resin composition of the present embodiment can have a small relative permittivity and a small dielectric loss tangent, and can maintain the same mechanical strength as a resin composition containing a glass component of the same form.

Further, in the resin composition of the present embodiment, the content of silicon contained in the glass component is preferably 62 mass% or more, more preferably 65 mass% or more, and particularly preferably 70 mass% or more, with respect to 100 mass% of the metal component contained in the glass component.

By setting the content of silicon in the glass component to the above range, the resin composition of the present embodiment can have a small relative permittivity, a small dielectric loss tangent, and a large thermal diffusivity, and can maintain the same mechanical strength as a resin composition containing a glass component in the same form.

In the resin composition of the present embodiment, the content of silicon contained in the glass component may be 100 mass% or less, 99.8 mass% or less, or 99.5 mass% or less with respect to 100 mass% of the metal component contained in the glass component.

In the resin composition of the present embodiment, the content of silicon contained in the glass component may be 51 mass% or more and 100 mass% or less, 55 mass% or more and 99.8 mass% or less, 60 mass% or more and 99.5 mass% or less, 62 mass% or more and 100 mass% or less, 65 mass% or more and 99.8 mass% or less, or 70 mass% or more and 99.5 mass% or less with respect to 100 mass% of the metal component contained in the glass component.

In the resin composition of the present embodiment, the content of silicon in the glass component is preferably 51 mass% or more, more preferably 55 mass% or more, and particularly preferably 60 mass% or more, with respect to 100 mass% of the total content of Al, Ca, Si, K, Li, Mg, Na, and Zn in the glass component.

Further, in the resin composition of the present embodiment, the content of silicon contained in the glass component is preferably 62 mass% or more, more preferably 65 mass% or more, and particularly preferably 70 mass% or more, with respect to 100 mass% of the total content of Al, Ca, Si, K, Li, Mg, Na, and Zn contained in the glass component.

In the resin composition of the present embodiment, the content of silicon in the glass component may be 99.8 mass% or less, 55 mass% or less, or 99.5 mass% or less with respect to 100 mass% of the total content of Al, Ca, Si, K, Li, Mg, Na, and Zn in the glass component.

In the resin composition of the present embodiment, the content of silicon in the glass component may be 51 mass% or more and 100 mass% or less, 55 mass% or more and 99.8 mass% or less, 60 mass% or more and 99.5 mass% or less, 62 mass% or more and 100 mass% or less, 65 mass% or more and 99.8 mass% or less, or 70 mass% or more and 99.5 mass% or less with respect to 100 mass% of the total content of Al, Ca, Si, K, Li, Mg, Na, and Zn in the glass component.

With respect to the resin composition of the present embodiment, the relative dielectric constant ε of the resin composition is obtained under the conditions of a frequency of 1GHz and a temperature of 25 DEG C_rPreferably 3.4 or less, more preferably 3.35 or less, and particularly preferably 3.3 or less. By making the relative dielectric constant ε of the resin composition_rThe dielectric material having the above upper limit or less can be used as a dielectric material that can be used also in high-frequency band applications in the field of dielectric devices such as resonators, filters, antennas, circuit boards, and laminated circuit element boards.

As a relative dielectric constant ε of the resin composition_rThe lower limit of (b) is not particularly limited, and may be 2.0 or more, 2.5 or more, or 3.0 or more.

Namely, the relative dielectric constant ε of the resin composition_rPreferably 2.0 to 3.4, more preferably 2.5 to 3.35, and particularly preferably 3.0 to 3.3.

Relative dielectric constant ε of resin composition under frequency of 1GHz and temperature condition of 25 DEG C_rA flat plate-shaped test piece was prepared from the target resin composition, and the measurement was performed by the method described in the examples using a commercially available impedance analyzer.

For the resin composition of the present embodiment, the dielectric loss tangent tan δ of the resin composition is preferably 5.5 × 10 under the frequency of 1GHz and the temperature condition of 25 ℃^-3Hereinafter, more preferably 5.0 × 10^-3Hereinafter, particularly preferably 4.8 × 10^-3The following.

When the resin composition has a dielectric loss tangent tan δ of not more than the above upper limit, the dielectric loss and the transmission loss can be suppressed to be low when the resin composition is used as a dielectric material for various dielectric devices.

The lower limit of the dielectric loss tangent tan δ of the resin composition is not particularly limited, and may beIs 4.0X 10^-3Above, it may be 4.3 × 10^-3Above, the value may be 4.5 × 10^-3The above.

That is, the dielectric loss tangent tan delta of the resin composition is preferably 4.0 × 10^-3Above and 5.5X 10^-3Hereinafter, more preferably 4.3 × 10^-3Above and 5.0X 10^-3Hereinafter, particularly preferably 4.5X 10^-3Above and 4.8 × 10^-3The following.

The dielectric loss tangent tan δ of the resin composition under the frequency of 1GHz and temperature condition of 25 ℃ can be measured by preparing a flat plate-like test piece from the subject resin composition and measuring by the method described in the examples using a commercially available impedance analyzer.

The thermal diffusivity of the resin composition of the present embodiment is preferably 0.14mm²Is more than or equal to s, and is more preferably 0.15mm²A thickness of 0.16mm or more, particularly preferably²More than s. When the thermal diffusivity of the resin composition is not less than the lower limit, heat can be easily released and the temperature rise can be suppressed to a low level when the resin composition is used as a dielectric material for various dielectric devices.

The upper limit of the thermal diffusivity of the resin composition is not particularly limited, and may be 0.25mm²Less than s, and may be 0.20mm²A thickness of 0.18mm or less²The ratio of the water to the water is less than s.

That is, the thermal diffusivity of the resin composition is preferably 0.14mm²0.25mm of more than s²Less than s, more preferably 0.15mm²0.20mm of more than s²A thickness of 0.16mm or less, particularly preferably²0.18mm and more than s²The ratio of the water to the water is less than s.

The thermal diffusivity of the resin composition can be measured by a method described in examples using a commercially available thermal diffusivity meter by preparing a sheet-like test piece from the target resin composition.

(thermoplastic resin and/or thermosetting resin)

The matrix resin of the resin composition of the present embodiment may be a thermoplastic resin, a thermosetting resin, or a mixture of a thermoplastic resin and a thermosetting resin.

Thermoplastic resin

The thermoplastic resin may be a general-purpose plastic, an engineering plastic, or a super engineering plastic.

Specifically, it is possible to preferably use: general-purpose plastics such AS Polyethylene (PE), High Density Polyethylene (HDPE), Medium Density Polyethylene (MDPE), Low Density Polyethylene (LDPE), polypropylene (PP), polyvinyl chloride (PVC), polyvinylidene chloride (pvdf), Polystyrene (PS), polyvinyl acetate (PVAc), Polyurethane (PUR), Polytetrafluoroethylene (PTFE), ABS resin (acrylonitrile-butadiene-styrene resin), AS resin, acrylic resin (PMMA), and the like;

engineering plastics such as Polyamide (PA), Polyacetal (POM), Polycarbonate (PC), modified polyphenylene ether (m-PPE, modified PPE, PPO), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and cyclic polyolefin (COP);

super engineering plastics such as polyphenylene sulfide (PPS), Polytetrafluoroethylene (PTFE), Polysulfone (PSF), Polyethersulfone (PES), amorphous Polyarylate (PAR), Liquid Crystal Polymer (LCP), Polyetheretherketone (PEEK), thermoplastic Polyimide (PI), and Polyamideimide (PAI);

among them, Liquid Crystal Polymers (LCP) are particularly preferable. The Liquid Crystal Polymer (LCP) exhibits liquid crystallinity in a molten state, and the resin composition containing the Liquid Crystal Polymer (LCP) also preferably exhibits liquid crystallinity in a molten state, and is preferably a liquid crystal polymer that melts at a temperature of 450 ℃.

The Liquid Crystal Polymer (LCP) used in the present embodiment may be a liquid crystal polyester, a liquid crystal polyester amide, a liquid crystal polyester ether, a liquid crystal polyester carbonate, or a liquid crystal polyester imide. The Liquid Crystal Polymer (LCP) used in the present embodiment is preferably a liquid crystal polyester, and particularly preferably a wholly aromatic liquid crystal polyester using only an aromatic compound as a raw material monomer.

Typical examples of the liquid crystal polyester used in the present embodiment include a liquid crystal polyester obtained by polymerizing (polycondensing) an aromatic hydroxycarboxylic acid, an aromatic dicarboxylic acid, and at least 1 compound selected from the group consisting of an aromatic diol, an aromatic hydroxylamine, and an aromatic diamine, a liquid crystal polyester obtained by polymerizing a plurality of aromatic hydroxycarboxylic acids, a liquid crystal polyester obtained by polymerizing an aromatic dicarboxylic acid and at least 1 compound selected from the group consisting of an aromatic diol, an aromatic hydroxylamine, and an aromatic diamine, and a liquid crystal polyester obtained by polymerizing a polyester such as polyethylene terephthalate and an aromatic hydroxycarboxylic acid. Here, the aromatic hydroxycarboxylic acid, the aromatic dicarboxylic acid, the aromatic diol, the aromatic hydroxylamine, and the aromatic diamine may be partially or entirely replaced with their polymerizable derivatives, respectively and independently.

Examples of polymerizable derivatives of compounds having a carboxyl group such as aromatic hydroxycarboxylic acids and aromatic dicarboxylic acids include derivatives (esters) in which a carboxyl group is converted into an alkoxycarbonyl group or an aryloxycarbonyl group, derivatives (acid halides) in which a carboxyl group is converted into a haloformyl group, and derivatives (acid anhydrides) in which a carboxyl group is converted into an acyloxycarbonyl group. Examples of polymerizable derivatives of compounds having a hydroxyl group such as aromatic hydroxycarboxylic acids, aromatic diols, and aromatic hydroxylamines include derivatives (acylates) obtained by acylating a hydroxyl group to convert it into an acyloxy group. Examples of polymerizable derivatives of compounds having an amino group such as aromatic hydroxylamine and aromatic diamine include derivatives (acylates) obtained by acylating an amino group and converting the amino group into an acylamino group.

The liquid crystal polyester used in the present embodiment preferably has a repeating unit represented by the following formula (1) (hereinafter, may be referred to as "repeating unit (1)"), more preferably has a repeating unit (1), a repeating unit represented by the following formula (2) (hereinafter, may be referred to as "repeating unit (2)"), and a repeating unit represented by the following formula (3) (hereinafter, may be referred to as "repeating unit (3)").

(1)-O-Ar¹-CO-

(2)-CO-Ar²-CO-

(3)-X-Ar³-Y-

(in formulae (1) to (3), Ar¹Represents phenylene, naphthylene or biphenylene, Ar²And Ar³Each independently represents a phenylene group, a naphthylene group, a biphenylene group or a group represented by the following formula (4). X and Y each independently represent an oxygen atom or an imino group. From Ar¹、Ar²And Ar³The hydrogen atoms in the groups represented by (a) may each be independently substituted with a halogen atom, an alkyl group or an aryl group. )

(4)-Ar⁴-Z-Ar⁵-

(in formula (4), Ar⁴And Ar⁵Each independently represents a phenylene group or a naphthylene group. Z represents an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group or an alkylene group. )

The liquid crystal polyester used in the present embodiment includes a repeating unit represented by a repeating unit (1), a repeating unit (2) or a repeating unit (3),

the content of the repeating unit (1) is 30 mol% or more and 100 mol% or less with respect to the total amount of the repeating unit (1), the repeating unit (2) or the repeating unit (3),

the content of the repeating unit (2) is 0 mol% or more and 35 mol% or less with respect to the total amount of the repeating unit (1), the repeating unit (2) or the repeating unit (3),

the content of the repeating unit (3) is preferably 0 mol% or more and 35 mol% or less with respect to the total amount of the repeating unit (1), the repeating unit (2), or the repeating unit (3).

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a n-hexyl group, a 2-ethylhexyl group, a n-octyl group and a n-decyl group, and the number of carbon atoms is preferably 1 to 10. Examples of the aryl group include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 1-naphthyl group and a 2-naphthyl group, and the carbon number thereof is preferably 6 to 20. When the hydrogen atom is substituted by these groups, the number thereof is each represented by Ar¹、Ar²Or Ar³Each of the groups represented is independently preferably 2 or moreThe number of the cells is more preferably 1 or less.

Examples of the alkylene group include a methylene group, an ethylene group, an isopropylene group, an n-butylene group and a 2-ethylhexyl group, and the carbon number thereof is preferably 1 to 10.

The repeating unit (1) is a repeating unit derived from a predetermined aromatic hydroxycarboxylic acid. As the repeating unit (1), Ar is preferred¹Is a repeating unit of p-phenylene (repeating unit derived from p-hydroxybenzoic acid), and Ar¹Is a repeating unit of 2, 6-naphthylene group (repeating unit derived from 6-hydroxy-2-naphthoic acid).

In the present specification, "derived" means that the chemical structure of a functional group contributing to polymerization is changed for polymerization of a raw material monomer and no other structural change is caused.

The repeating unit (2) is a repeating unit derived from a predetermined aromatic dicarboxylic acid. As the repeating unit (2), Ar is preferred²Is a repeating unit of p-phenylene (repeating unit derived from terephthalic acid), Ar²Repeating units of m-phenylene (repeating units derived from isophthalic acid), Ar²Is a repeating unit of 2, 6-naphthylene group (repeating unit derived from 2, 6-naphthalenedicarboxylic acid), and Ar²A repeating unit of diphenyl ether-4, 4 '-diyl (a repeating unit derived from diphenyl ether-4, 4' -dicarboxylic acid).

The repeating unit (3) is a repeating unit derived from a predetermined aromatic diol, aromatic hydroxylamine or aromatic diamine. As the repeating unit (3), Ar is preferred³Repeating units which are p-phenylene (repeating units derived from hydroquinone, p-aminophenol or p-phenylenediamine), and Ar³Is a repeating unit of 4, 4 '-biphenylene (a repeating unit derived from 4, 4' -dihydroxybiphenyl, 4-amino-4 '-hydroxybiphenyl, or 4, 4' -diaminobiphenyl).

The content of the repeating unit (1) is preferably 30 mol% or more, more preferably 30 mol% or more and 80 mol% or less, further preferably 40 mol% or more and 70 mol% or less, and particularly preferably 45 mol% or more and 65 mol% or less, relative to the total amount of all repeating units (a value obtained by adding the amount of the substance of each repeating unit obtained by dividing the mass of each repeating unit constituting the liquid crystal polyester resin by the chemical formula weight of each repeating unit).

The content of the repeating unit (2) is preferably 35 mol% or less, more preferably 10 mol% or more and 35 mol% or less, further preferably 15 mol% or more and 30 mol% or less, and particularly preferably 17.5 mol% or more and 27.5 mol% or less, based on the total amount of all repeating units.

The content of the repeating unit (3) is preferably 35 mol% or less, more preferably 10 mol% or more and 35 mol% or less, further preferably 15 mol% or more and 30 mol% or less, and particularly preferably 17.5 mol% or more and 27.5 mol% or less, based on the total amount of all repeating units.

The more the content of the repeating unit (1), the more easily the melt flowability, heat resistance, strength and rigidity are improved, but the more the content is, the higher the melt temperature and melt viscosity are easily, and the higher the temperature required for molding is easily.

The ratio of the content of the repeating unit (2) to the content of the repeating unit (3) is preferably 0.9/1 to 1/0.9, more preferably 0.95/1 to 1/0.95, and further preferably 0.98/1 to 1/0.98, in terms of [ the content of the repeating unit (2) ]/[ the content of the repeating unit (3) ] (mol/mol).

The liquid crystal polyester used in the present embodiment may have 2 or more kinds of repeating units (1) to (3) independently. The liquid-crystalline polyester may have a repeating unit other than the repeating units (1) to (3), and the content thereof is preferably 10 mol% or less, more preferably 5 mol% or less, relative to the total amount of all the repeating units.

The liquid crystal polyester used in the present embodiment preferably has only a repeating unit in which X and Y are each an oxygen atom as the repeating unit (3), that is, a repeating unit derived from a predetermined aromatic diol, because the melt viscosity is easily lowered, and therefore, it is more preferable to have only a repeating unit in which X and Y are each an oxygen atom as the repeating unit (3).

Preferably, the liquid crystal polyester used in the present embodiment is produced by melt-polymerizing raw material monomers corresponding to the repeating units constituting the liquid crystal polyester and solid-phase polymerizing the obtained polymer (hereinafter, may be referred to as "prepolymer"). Thus, a high molecular weight liquid crystalline polyester having high heat resistance, strength and rigidity can be produced with good workability. The melt polymerization may be carried out in the presence of a catalyst, and examples of the catalyst include metal compounds such as magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, and antimony trioxide, nitrogen-containing heterocyclic compounds such as 4- (dimethylamino) pyridine and 1-methylimidazole, and nitrogen-containing heterocyclic compounds are preferably used.

The flow initiation temperature of the liquid crystal polyester used in the present embodiment is preferably 280 ℃ or higher, more preferably 280 ℃ or higher and 400 ℃ or lower, and further preferably 280 ℃ or higher and 380 ℃ or lower.

The higher the flow initiation temperature of the liquid crystal polyester used in the present embodiment is, the higher the heat resistance, strength and rigidity of the liquid crystal polyester tend to be. On the other hand, when the flow initiation temperature of the liquid crystal polyester is more than 400 ℃, the melt temperature and melt viscosity of the liquid crystal polyester tend to be high. Therefore, the temperature required for molding the liquid crystal polyester tends to be high.

In the present specification, the flow initiation temperature of the liquid-crystalline polyester is also referred to as a flow temperature (flow temperature) or a flow temperature, and is a temperature which is a standard for the molecular weight of the liquid-crystalline polyester (see "liquid-crystalline polymer synthesis, molding, and application"), abbreviated as "kokai", CMC (co. シーエムシー), 6/5/1987, p.95). The flow initiation temperature was measured using a capillary rheometer at 9.8MPa (100 kg/cm)²) Under the load of (3), a temperature at which the liquid crystal polyester was melted while heating at a rate of 4 ℃/min and the melt exhibited a viscosity of 4800 pas (48000 poises) when extruded from a nozzle having an inner diameter of 1mm and a length of 10 mm.

The content ratio of the liquid crystal polyester in 100% by mass of the thermoplastic resin is preferably 80% by mass or more and 100% by mass or less. Examples of the resin other than the liquid crystal polyester contained in the thermoplastic resin include polypropylene, polyamide, and polyester other than liquid crystal polyester; and thermoplastic resins other than liquid crystal polyesters, such as polysulfone, polyphenylene sulfide, polyether ketone, polycarbonate, polyphenylene oxide, and polyether imide.

Thermosetting resin

Examples of the thermoplastic resin include phenol resin, urea resin, melamine resin, unsaturated polyester resin, epoxy resin, and silicone resin.

The matrix resin of the resin composition of the present embodiment may be a thermosetting resin alone or a mixture with a thermoplastic resin.

(glass component)

In the resin composition of the present embodiment, the glass component can be dispersed in the matrix resin of the thermoplastic resin and/or the thermosetting resin, and the dielectric characteristics, the thermal diffusivity, and the mechanical strength of the resin composition can be adjusted.

As the glass component used in the resin composition of the present embodiment, a glass component known as a filler containing a glass component, such as a fibrous glass filler, a flake (flake) glass filler, a glass bead, or a glass balloon, can be used, and a fibrous glass filler or a flake glass filler is preferable.

The weight-average fiber length of the fibrous glass filler is preferably 30 μm or more, more preferably 50 μm or more, and particularly preferably 80 μm or more. When the weight average fiber length of the fibrous glass filler is equal to or greater than the lower limit value, the mechanical strength can be made appropriate. The number average fiber length of the fibrous glass filler is preferably 30 μm or more, more preferably 50 μm or more, and particularly preferably 60 μm or more. When the number average fiber length of the fibrous glass filler is equal to or greater than the lower limit value, the mechanical strength can be made appropriate.

The weight-average fiber length of the fibrous glass filler is preferably 300 μm or less, more preferably 150 μm or less, and particularly preferably 100 μm or less. When the weight-average fiber length of the fibrous glass filler is not more than the above upper limit, molding becomes easy.

The number average fiber length of the fibrous glass filler is preferably 300 μm or less, more preferably 150 μm or less, and particularly preferably 90 μm or less. When the number-average fiber length of the fibrous glass filler is not more than the above upper limit, molding becomes easy.

The weight-average fiber length of the fibrous glass filler is preferably 30 μm or more and 300 μm or less, more preferably 50 μm or more and 150 μm or less, and particularly preferably 80 μm or more and 100 μm or less.

The number average fiber length of the fibrous glass filler is preferably 30 μm or more and 300 μm or less, more preferably 50 μm or more and 150 μm or less, and particularly preferably 60 μm or more and 90 μm or less.

The number average fiber diameter of the fibrous glass filler is not particularly limited, but is preferably 1 to 40 μm, more preferably 3 to 30 μm, further preferably 5 to 20 μm, and particularly preferably 8 to 15 μm.

The number average fiber diameter of the fibrous glass filler was calculated as an arithmetic mean of values obtained by observing the fibrous glass filler with a scanning electron microscope (1000 times) and measuring the fiber diameter of 50 fibrous glass fillers.

When the number average fiber diameter of the fibrous glass filler is equal to or more than the lower limit of the above-mentioned preferable range, the fibrous glass filler is easily dispersed in the resin composition. In addition, the fibrous glass filler is easy to handle when producing the resin composition. On the other hand, when the number average fiber diameter is not more than the upper limit of the above preferable range, the mechanical reinforcement of the resin composition is efficiently performed using the fibrous glass filler.

As the fibrous glass filler, chopped glass fiber or milled glass fiber is preferable. The chopped Glass fiber is obtained by cutting a Glass strand, and is, for example, a Glass filler having a cutting length of 3 to 6mm and a fiber diameter of 9 to 13 μm, and is commercially available from nippon Glass co.ltd (セントラル nit co., Central Glass co., Ltd.). The milled glass fiber is obtained by pulverizing glass fiber, and has an intermediate property between chopped glass fiber and powdered glass. For example, a glass filler having an average fiber length of 30 to 150 μm and a fiber diameter of 6 to 13 μm is commercially available from Nippon Mitsui Kabushiki Kaisha.

The average particle diameter of the glass flake filler is preferably 30 μm or more, more preferably 50 μm or more, and particularly preferably 80 μm or more. When the average particle diameter of the glass flake filler is not less than the lower limit, the mechanical strength can be made appropriate.

The average particle diameter of the flake glass filler is preferably 300 μm or less, more preferably 200 μm or less, and particularly preferably 150 μm or less. When the average particle diameter of the glass flake filler is not more than the above upper limit, molding becomes easy.

The average particle diameter of the glass flake filler is preferably 30 μm or more and 300 μm or less, more preferably 50 μm or more and 200 μm or less, and particularly preferably 80 μm or more and 150 μm or less.

The average thickness of the glass flake filler is preferably 0.2 μm or more, more preferably 0.5 μm or more, and particularly preferably 1.0 μm or more. When the average thickness of the glass flake filler is equal to or greater than the lower limit value, the mechanical strength can be made appropriate.

The average thickness of the flake glass filler is preferably 30 μm or less, more preferably 20 μm or less, and particularly preferably 10 μm or less. When the average thickness of the glass flake filler is not more than the upper limit, molding becomes easy.

The average thickness of the glass flake filler is preferably 0.2 μm or more and 30 μm or less, more preferably 0.5 μm or more and 20 μm or less, and particularly preferably 1.0 μm or more and 10 μm or less.

As the flake Glass filler, for example, Glass flakes (Glass flakes) having an average thickness of 2 to 5 μm and a particle size of 10 to 4000 μm and fine flakes having an average thickness of 0.4 to 2.0 μm and a particle size of 10 to 4000 μm are commercially available from Nippon Sheet Glass Company, Limited. As the glass used for the glass flakes, there are glass compositions such as C glass and E glass.

The C glass contains an alkali component and has high acid resistance. Since E glass contains almost no alkali, stability in the resin is high.

Examples of the glass component include E glass (i.e., alkali-free glass), S glass, and T glass (i.e., high glass content)Strength, high elasticity glass), C glass (i.e., glass oriented for acid resistant applications), D glass (i.e., low dielectric constant glass), ECR glass (i.e., glass without B)₂O₃、F₂Glass fibers for FRP reinforcing materials such as E glass of (2), AR glass (i.e., glass for alkali-resistant use), and the like.

Relative dielectric constant ε as a glass component_rIt is preferable to use a glass component having a low dielectric constant and a relative dielectric constant ε of the glass component at a frequency of 1GHz and a temperature of 25 DEG C_rPreferably 4.80 or less, more preferably 4.30 or less, and particularly preferably 4.00 or less. Relative dielectric constant epsilon for glass composition_rA glass component of 3.00 or more, a glass component of 3.10 or more, and a glass component of 3.15 or more can be used.

In the resin composition of the present embodiment, the content of the glass component is preferably 1 to 60% by mass, more preferably 10 to 50% by mass, and particularly preferably 20 to 40% by mass, based on 100% by mass of the resin composition.

When the content of the glass component is not less than the lower limit of the preferable range, the adhesion between the thermoplastic resin and/or the thermosetting resin and the glass component is easily improved. On the other hand, if the content of the glass component is not more than the upper limit of the preferable range, the glass component is easily dispersed.

< other ingredients >

The resin composition of the present embodiment may contain, as a raw material, 1 or more kinds of other components such as a filler and an additive, as necessary, in addition to the thermoplastic resin and/or the thermosetting resin and the glass component. When the resin composition contains a thermosetting resin, the resin composition may contain a solvent.

The filler may be other particulate fillers such as plate-like fillers and spherical fillers. The filler may be an inorganic filler or an organic filler.

Examples of the plate-like inorganic filler include talc, mica, graphite, wollastonite, barium sulfate, and calcium carbonate. The mica can be muscovite, phlogopite, fluorophlogopite or tetrasilicic mica.

Examples of the particulate inorganic filler include silica, alumina, titanium oxide, boron nitride, silicon carbide, and calcium carbonate.

Examples of the additives include antioxidants, heat stabilizers, ultraviolet absorbers, antistatic agents, surfactants, flame retardants, and colorants.

(method for producing resin composition)

The resin composition containing the thermoplastic resin of the present embodiment can be prepared, for example, by mixing the thermoplastic resin, the glass component, and other components as needed, melt-kneading the mixture while degassing the mixture with a twin-screw extruder, ejecting the obtained mixture of the thermoplastic resin melt and the glass component in a strand shape through a circular nozzle (ejection port), and then pelletizing the mixture with a strand cutter.

Further, for example, a resin composition containing the thermosetting resin of the present embodiment can be obtained by mixing the thermosetting resin, the glass component, and other components as necessary.

(molded body)

The resin composition of the present embodiment can be molded into a molded article by a known molding method. As a method for molding a molded article from a resin composition containing a thermoplastic resin, a melt molding method is preferable, and examples thereof include an extrusion molding method such as an injection molding method, a T-die method, an inflation method, a compression molding method, a blow molding method, a vacuum molding method, and a press molding method. Among them, injection molding is preferable. Examples of the method for molding a molded article from a resin composition containing a thermosetting resin include injection molding and press molding. Among them, injection molding is preferable.

For example, when a resin composition containing a thermoplastic resin is used as a molding material and molded by an injection molding method, the resin composition is melted by a known injection molding machine, and the melted resin composition containing the thermoplastic resin is injected into a mold to be molded.

Examples of known injection molding machines include TR450EH3 manufactured by sandek corporation of japan (ソディック, Sodick co., Ltd.), and a hydraulic horizontal molding machine PS40E5ASE manufactured by seika resin industry.

The cylinder temperature of the injection molding machine is suitably determined depending on the type of the thermoplastic resin, and is preferably set to a temperature 10 to 80 ℃ higher than the flow initiation temperature of the thermoplastic resin to be used, for example, 300 to 400 ℃.

From the viewpoint of the cooling rate and productivity of the resin composition containing the thermoplastic resin, the temperature of the mold is preferably set to a range of room temperature (for example, 23 ℃) to 180 ℃.

For example, when a resin composition containing a thermosetting resin is used as a molding material and molded by injection molding, the molding material is put into a mold by a known injection molding machine, and then the temperature of the mold is raised to about 150 ℃. After the molding material is cured, the molded body can be taken out of the mold.

The molded article of the present embodiment can be used for dielectric devices such as resonators, filters, antennas, circuit boards, and laminated circuit element boards.

Examples

The present invention will be described in further detail below with reference to specific examples. However, the present invention is not limited to the following examples.

< glass Filler >

Glass fillers (a) to (F) shown in table 1 below were prepared.

TABLE 1

< number average fiber length of fibrous glass filler of raw material >

The glass fillers (a) and (B) as raw materials were fibrous glass fillers (milled glass fibers) having the compositions shown in table 1.

The number-average fiber length of the fibrous glass filler was determined by collecting 1.0g of the fibrous glass filler as a raw material, dispersing the collected material in methanol, taking a photomicrograph of the dispersion while it was spread on a glass slide, directly reading the shape of the fibrous glass filler from the photomicrograph, and calculating the average value. In calculating the average value, the number of parents (parent number) is set to 400 or more. The results are shown in Table 1.

< average thickness and average particle diameter of flaky glass filler as raw Material >

The glass fillers (C) to (F) as raw materials were flake glass fillers having the compositions shown in table 1.

The flaky glass filler as a raw material was observed at a magnification of 1000 times by SEM, and the thickness and number average particle diameter of 100 flaky glass fillers randomly selected from SEM images were measured, and the average of 100 measured values was calculated, thereby obtaining the average thickness and number average particle diameter of the flaky glass filler as a raw material. The results are shown in Table 1.

Glass filler (G) shown in table 2 below was prepared by mixing 20 parts by mass of glass filler (D) and 10 parts by mass of glass filler (F).

Glass filler (H) shown in table 2 below was prepared by mixing 15 parts by mass of glass filler (D) and 15 parts by mass of glass filler (F).

7.5 parts by mass of the glass filler (D) and 22.5 parts by mass of the glass filler (F) were mixed to prepare a glass filler (I) shown in Table 2 below.

TABLE 2

< production of Polymer >

(1) Melt polymerization

A reactor equipped with a stirrer, a torquemeter, a nitrogen inlet, a thermometer, and a reflux condenser was charged with p-hydroxybenzoic acid (994.5g, 7.20 moles), terephthalic acid (272.1g, 1.64 moles), isophthalic acid (126.6g, 0.76 moles), 4' -dihydroxybiphenyl (446.9g, 2.40 moles), and acetic anhydride 1347.6g (13.20 moles). After the gas in the reactor was replaced with nitrogen, 0.18g of 1-methylimidazole was added thereto, and the mixture was refluxed at 150 ℃ for 30 minutes while being stirred under a nitrogen stream at room temperature to 150 ℃ for 30 minutes.

Subsequently, 2.40g of 1-methylimidazole was added thereto, and while by-produced acetic acid and unreacted acetic anhydride were distilled off, the temperature was raised from 150 ℃ to 320 ℃ over 2 hours and 50 minutes, and the reaction was terminated when an increase in torque was observed, and the prepolymer as a content was taken out from the reactor and cooled to room temperature.

(2) Solid phase polymerization

Then, the prepolymer was pulverized by a pulverizer, and the resultant pulverized product was heated from room temperature to 250 ℃ over 1 hour, from 250 ℃ to 280 ℃ over 5 hours, and held at 280 ℃ for 3 hours under a nitrogen atmosphere, thereby carrying out solid-phase polymerization. The obtained solid phase polymer was cooled to room temperature, thereby obtaining a liquid crystal polyester (1).

The liquid-crystalline polyester (1) has 60 mol% of Ar in the molecule thereof relative to the total proportion of all repeating units¹Is a repeating unit of 1, 4-phenylene (u12), 13.65 mol% Ar²Is a repeating unit of 1, 4-phenylene (u22), 6.35 mol% Ar²Is a repeating unit of 1, 3-phenylene (u23) and 20 mol% Ar³Is a repeating unit of 4, 4' -biphenylene (u32), and its flow initiation temperature is 312 ℃.

Comparative example 1

< production of particles >

After drying the liquid crystal polyester (1) at 120 ℃ for 5 hours, 70 parts by mass of the liquid crystal polyester (1) and 30 parts by mass of a glass filler (A) were fed to a vacuum vent twin-screw extruder ("PCM-30" manufactured by Kupffer corporation), melt-kneaded at a cylinder temperature of 340 ℃ and a screw rotation speed of 150rpm while degassing was performed at the vacuum vent by a water-sealed vacuum pump ("SW-25S" manufactured by Shengang Seiko Co., Ltd.), and discharged in a strand form through a circular nozzle (discharge port) having a diameter of 3 mm. Subsequently, the discharged kneaded material was immersed in a water bath with a water temperature of 30 ℃ for 1.5 seconds, and then pelletized by a strand cutter (manufactured by tankfield plastic machinery corporation), thereby obtaining resin composition pellets (1) (a pelletized liquid crystal polyester resin composition (1)) of comparative example 1.

[ example 1]

< production of particles >

In comparative example 1, resin composition pellets (2) of example 1 (granular liquid crystal polyester resin composition (2)) were obtained in the same manner as in comparative example 1 except that 30 parts by mass of the glass filler (a) was changed to 30 parts by mass of the glass filler (B).

Comparative example 2

< production of particles >

Resin composition pellets (3) (liquid crystal polyester resin composition (3) in pellet form) of comparative example 2 were obtained in the same manner as in comparative example 1 except that 30 parts by mass of the glass filler (a) was changed to 30 parts by mass of the glass filler (C) in comparative example 1.

Comparative example 3

< production of particles >

In the same manner as in comparative example 1 except that 30 parts by mass of the glass filler (a) was changed to 30 parts by mass of the glass filler (D) in comparative example 1, resin composition pellets (4) (granular liquid crystal polyester resin composition (4)) of comparative example 3 were obtained.

[ example 2]

< production of particles >

Resin composition pellets (5) (a granular liquid crystal polyester resin composition (5)) of example 2 were obtained in the same manner as in comparative example 1 except that 30 parts by mass of the glass filler (a) was changed to 30 parts by mass of the glass filler (E) in comparative example 1.

[ example 3]

< production of particles >

In the same manner as in comparative example 1 except that 30 parts by mass of the glass filler (a) was changed to 30 parts by mass of the glass filler (F) in comparative example 1, resin composition pellets (6) of example 3 (granular liquid crystal polyester resin composition (6)) were obtained.

[ example 4]

< production of particles >

In the same manner as in comparative example 1 except that 30 parts by mass of the glass filler (a) was changed to 30 parts by mass of the glass filler (G) in comparative example 1, resin composition pellets (7) of example 4 (granular liquid crystal polyester resin composition (7)) were obtained.

[ example 5]

< production of particles >

In the same manner as in comparative example 1 except that 30 parts by mass of the glass filler (a) was changed to 30 parts by mass of the glass filler (H) in comparative example 1, resin composition pellets (8) (granular liquid crystal polyester resin composition (8)) of example 5 were obtained.

[ example 6]

< production of particles >

In the same manner as in comparative example 1 except that 30 parts by mass of the glass filler (a) was changed to 30 parts by mass of the glass filler (I) in comparative example 1, resin composition pellets (9) of example 6 (granular liquid crystal polyester resin composition (9)) were obtained.

< ICP analysis/test item >

A total of 22 elements of Al, Ba, Ca, Si, Ti, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Ni, P, Pb, Sb, V, and Zn were used as test items.

< ICP analysis/test method >

(sample Heat treatment)

The samples of the resin composition pellets obtained in the examples and comparative examples were heat-treated at 600 ℃ for 6 hours to obtain analysis samples.

(Al、Ba、Ca、Si、Ti)

An analysis sample is heated and dissolved with an acid such as hydrofluoric acid or nitric acid, and then alkali-melted with sodium carbonate, and the solution adjusted to a predetermined concentration with hydrochloric acid is used as a sample solution to be measured by inductively coupled plasma emission spectrometry (ICP-AES). The analysis/test results are shown in tables 3 and 4. Ba was less than the detection limit (0.2 mass%).

(17 other items (Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Ni, P, Pb, Sb, V, Zn))

An analysis sample is heated and dissolved with an acid such as hydrofluoric acid or nitric acid, and the solution adjusted to a predetermined concentration is measured by inductively coupled plasma emission spectrometry (ICP-AES) as a sample solution. The analysis/test results are shown in tables 3 and 4. Cd. Co, Cr, Cu, Mn, Mo, Ni, P, Pb, Sb and V were all less than detection limits (0.2 mass%).

(measurement of relative dielectric constant and dielectric loss tangent)

Pellets of the resin compositions obtained in examples and comparative examples were dried under vacuum at 120 ℃ for 5 hours, supplied to PNX-40-5A (manufactured by Hitachi resin industries, Ltd.), and molded at a cylinder temperature of 350 ℃ to form a 64mm square plate having a thickness of 1.0 mm. The relative dielectric constant and the dielectric loss tangent at 1GHz were measured on the obtained plate under the following conditions.

The determination method comprises the following steps: volumetric method (apparatus: impedance analyzer (model: E4991A, made by Agilent corporation))

The electrode model is as follows: 16453A

And (3) measuring environment: 23 ℃ and 50% RH

Voltage application: 1V

(measurement of thermal diffusivity)

Pellets of the resin compositions obtained in examples and comparative examples were dried under vacuum at 120 ℃ for 5 hours, supplied to PNX-40-5A (manufactured by Hitachi resin industries, Ltd.), and molded into a 64mm square piece having a thickness of 1.0mm under molding conditions in which the cylinder temperature was 350 ℃, and cut out to have a thickness of 10 mm. times.10 mm. times.1.0 mm as a test piece. The thermal diffusivity of the test piece was measured by a laser pulse method using a thermal diffusivity meter "NanoFlash LFA 457" (manufactured by Bruker AXS).

(tensile test)

Pellets of the resin compositions obtained in examples and comparative examples were dried under vacuum at 120 ℃ for 5 hours, supplied to PNX-40-5A (manufactured by Hitachi resins industries, Ltd.), and injection-molded under molding conditions at a cylinder temperature of 350 ℃ to ASTM4 dumbbell test pieces. For each of 5 samples of the test piece, a tensile test was carried out according to ASTM D638 using a tensile tester TENSILON RTG-1250 (manufactured by AINDER, A & D Company, Limited) at a crosshead speed of 10 mm/min, and the tensile strength and the elongation at that time were measured to determine the average value of the tensile strength and elongation. The results are shown in tables 3 and 4.

< weight average fiber length and number average fiber length of fibrous glass filler in resin composition >

From the resin composition pellets obtained in comparative example 1 and example 1, 1.0g of each pellet was collected and placed in a crucible, and treated in an electric furnace at 600 ℃ for 4 hours to be ashed. The residue was dispersed in methanol and developed on a glass slide, and the shape of the fibrous glass filler was directly read from the micrograph, and the average value was calculated to determine the weight average fiber length and the number average fiber length of the fibrous glass filler in the resin composition. In the calculation of the average value, the number of parents is 400 or more. The weight of the fibrous glass filler relative to the length of each fiber was calculated from the specific gravity of the fibrous glass filler, and the weight-average fiber length was calculated by using the total weight of the sample of 400 or more matrix numbers as a denominator. The results are shown in Table 3.

< average thickness and average particle diameter of flaky glass filler in resin composition >

From the resin composition pellets obtained in comparative examples 2 and 3 and examples 2 to 6, 1.0g of each pellet was collected and placed in a crucible, treated at 600 ℃ for 4 hours in an electric furnace and ashed, and the residue was dispersed in methanol and developed on a glass slide, and observed with SEM at 1000 × magnification, the shape of 100 flaky glass fillers randomly selected from the SEM image was directly read, and the arithmetic mean value of the maximum oriented wire Diameter (Feret Diameter) was calculated to determine the number average particle Diameter of the flaky glass filler in the resin composition. Further, the arithmetic mean of the thicknesses was calculated to determine the average thickness of the glass flake filler in the resin composition. In the calculation of the average value, the number of parents is 400 or more. The results are shown in tables 3 and 4.

TABLE 3

TABLE 4

From the results shown in tables 3 and 4, the liquid crystal polyester resin composition of example 1 to which the present invention was applied was a liquid crystal polyester resin composition having a small relative permittivity, a small dielectric loss tangent and a large thermal diffusivity as compared with the liquid crystal polyester resin composition of comparative example 1. The mechanical strength was also comparable.

The liquid crystal polyester resin composition of example 2 to which the present invention was applied was also able to be a liquid crystal polyester resin composition having a small relative permittivity and a small dielectric loss tangent as compared with the liquid crystal polyester resin compositions of comparative examples 2 to 3. The mechanical strength was also comparable.

The liquid crystal polyester resin compositions of examples 3 and 4 to 6 of the present invention were able to be obtained as liquid crystal polyester resin compositions having a smaller relative dielectric constant, a smaller dielectric loss tangent and a larger thermal diffusivity than the liquid crystal polyester resin compositions of comparative examples 2 to 3. The mechanical strength was also comparable.

Claims

1. A resin composition, wherein,

comprises the following components: a thermoplastic resin and/or a thermosetting resin; and a glass component dispersed in the thermoplastic resin and/or the thermosetting resin,

2. The resin composition according to claim 1, wherein the content of silicon in the resin composition is 51% by mass or more based on 100% by mass of the metal component contained in the resin composition when the ICP analysis is performed on the residue component obtained after ashing the resin composition.

3. A resin composition, wherein,

4. The resin composition according to claim 3, wherein the silicon content in the glass component is 51 mass% or more with respect to 100 mass% of the metal component contained in the glass component.

5. The resin composition according to any one of claims 1 to 4, wherein the resin composition has a relative dielectric constant ε at a frequency of 1GHz and a temperature of 25 ℃_rIs 3.4 or less.

6. The resin composition according to claim 5, wherein the resin composition has a dielectric loss tangent tan δ of 5.5 x 10 at a frequency of 1GHz and a temperature of 25 ℃^-3The following.

7. The resin composition according to claim 5 or 6, wherein the resin composition has a thermal diffusivity of 0.14mm²More than s.