KR20210123302A - resin composition - Google Patents

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 the resin composition contains the residue after incineration of the resin composition when subjected to ICP analysis The calcium content contained in the resin composition is 0 to 27 mass % with respect to 100 mass % of the metal content to be used, and the calcium content contained in the glass component with respect to 100 mass % of the metal content contained in the glass component is The resin composition which is 0-27 mass %.

Description

resin composition

The present invention relates to a resin composition.

This application claims priority based on Japanese Patent Application No. 2019-019007 filed in Japan on February 5, 2019, and based on Japanese Patent Application No. 2019-191071 filed on October 18, 2019 in Japan Claiming priority and referencing their contents here.

In the field of dielectric devices such as resonators, filters, antennas, circuit boards, and laminated circuit element boards, with the recent increase in the amount of information, the advancement of communication technology, and the depletion of the used frequency band, the high-frequency band (centimeter wave to milliwave) is being used.

In general, inorganic materials tend to have relatively low dielectric loss, but there is a problem in that it is difficult to reduce the relative dielectric constant. Conversely, many organic materials with low dielectric constant exist.

For this reason, a dielectric material constituted by dispersing magnesium oxide fine particles as inorganic material particles in a resin-based organic material has been proposed (Patent Document 1).

Japanese Patent Laid-Open No. 2014-24916

However, when the dielectric constant and the dielectric properties of the dielectric loss tangent are made small, the mechanical strength is inhibited, and no material has been found that satisfies both the dielectric properties and the mechanical strength.

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

In order to solve the said subject, this invention employ|adopts the following structures.

[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,

The resin composition whose calcium content contained in the said resin composition is 0-27 mass % with respect to 100 mass % of the metal content contained in the said resin composition, when ICP analysis of the residue fraction after incineration of the said resin composition is carried out.

[2] When the residual fraction after incineration of the resin composition is subjected to ICP analysis, the silicon content in the resin composition is 51 mass% or more with respect to 100 mass% of the metal content contained in the resin composition as described in [1] above. 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,

The resin composition whose calcium content contained in the said glass component is 0-27 mass % with respect to 100 mass % of the metal content contained in the said glass component.

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

[5] The resin composition according to any one of [1] to [4], wherein the _{relative dielectric constant (ε r} ) of the resin composition is 3.4 or less at a frequency of 1 GHz and a temperature of 25°C.

[6] The resin composition according to [5], wherein the dielectric loss tangent (tanδ) of the resin composition is 5.5 × 10 ^{-3 or less at a frequency of 1 GHz and a temperature of 25°C.}

[7] The resin composition according to [5] or [6], wherein the resin composition has a thermal diffusivity of 0.14 mm 2 /s or more.

ADVANTAGE OF THE INVENTION According to this invention, it is excellent in mechanical strength, a dielectric constant is small, and the resin composition with a small dielectric loss tangent can be provided.

<Resin composition>

The resin composition of this embodiment contains a thermoplastic resin and/or a thermosetting resin, and the glass component disperse|distributed in the said thermoplastic resin and/or the said thermosetting resin.

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

When the resin composition of this embodiment performs ICP analysis of the residual fraction after incineration of the said resin composition, the calcium content contained in the said resin composition is 0-27 mass % with respect to 100 mass % of the metal content contained in the said resin composition. am. With respect to 100 mass % of the metal content contained in the said resin composition, it is preferable that the calcium content contained in the said resin composition is 0-20 mass %, It is more preferable that it is 0-15 mass %, It is 0-10 mass % It is particularly preferred. With respect to 100 mass % of the metal content contained in the said resin composition, 0.2 mass % or more may be sufficient as the calcium content contained in the said resin composition, 0.4 mass % or more may be sufficient, and 1.0 mass % or more may be sufficient as it. That is, 0.2-20 mass % may be sufficient as the calcium content contained in the said resin composition with respect to 100 mass % of the metal content contained in the said resin composition, 0.4-15 mass % may be sufficient, and 1.0-10 mass % may be sufficient as it. When calcium content contained in the said resin composition exists in the said range, the resin composition of this embodiment can be made into a thing with a small dielectric constant and a small dielectric loss tangent, Comparing with what the glass component of the same form is contained. Therefore, the mechanical strength can also be maintained at the same level.

In this specification, the metal powder means a component of a metal element, and here, the semimetal of boron, silicon, germanium, arsenic, antimony, tellurium, selenium, polonium, and astatine shall be contained in the metal element. As the metal powder 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 You can analyze

100 mass % of total content of Al, Ca, Si, K, Li, Mg, Na, and Zn contained in the said resin composition, when the resin composition of this embodiment performs ICP analysis of the residue after incineration of the said resin composition , the calcium content contained in the resin composition is preferably 0 to 27 mass%, more preferably 0 to 20 mass%, still more preferably 0 to 15 mass%, and 0 to 10 mass% It is particularly preferred. With respect to 100 mass % of total content of Al, Ca, Si, K, Li, Mg, Na and Zn contained in the said resin composition, 0.2 mass % or more may be sufficient as the calcium content contained in the said resin composition, and 0.4 mass % or more may be sufficient, and 1.0 mass % or more may be sufficient as it. That is, with respect to 100 mass % of total content of Al, Ca, Si, K, Li, Mg, Na and Zn contained in the said resin composition, 0.2-20 mass % of calcium content contained in the said resin composition may be sufficient, and 0.4 -15 mass % may be sufficient, and 1.0-10 mass % may be sufficient.

In the resin composition of this embodiment, the calcium content contained in the glass component is 0 to 27 mass%, preferably 0 to 20 mass%, and 0 to 15 mass% with respect to 100 mass% of the metal content contained in the glass component. It is more preferable that it is mass %, and it is especially preferable that it is 0-10 mass %. With respect to 100 mass % of the metal content contained in the said glass component, 0.2 mass % or more may be sufficient, 0.4 mass % or more, and 1.0 mass % or more of calcium content contained in the said glass component may be sufficient. That is, with respect to 100 mass % of the metal content contained in the said glass component, 0.2-20 mass % may be sufficient as calcium content contained in the said glass component, 0.4-15 mass % may be sufficient, and 1.0-10 mass % may be sufficient as it. When calcium content contained in the said glass component exists in the said range, the resin composition of this embodiment can be made into a thing with a small dielectric constant and a small dielectric loss tangent, Comparing with that containing the glass component of the same form. Therefore, the mechanical strength can also be maintained at the same level.

In the resin composition of this embodiment, the calcium content contained in the glass component is 0 to 27 with respect to 100% by mass of the total content of Al, Ca, Si, K, Li, Mg, Na, and Zn contained in the glass component. It is preferable that it is mass %, It is more preferable that it is 0-20 mass %, It is still more preferable that it is 0-15 mass %, It is especially preferable that it is 0-10 mass %. With respect to 100 mass % of the metal content contained in the said glass component, 0.2 mass % or more may be sufficient, 0.4 mass % or more, and 1.0 mass % or more of calcium content contained in the said glass component may be sufficient. That is, with respect to 100 mass % of the metal content contained in the said glass component, 0.2-20 mass % may be sufficient as calcium content contained in the said glass component, 0.4-15 mass % may be sufficient, and 1.0-10 mass % may be sufficient as it. When calcium content contained in the said glass component exists in the said range, the resin composition of this embodiment can be made into a thing with a small dielectric constant and a small dielectric loss tangent, Comparing with that containing the glass component of the same form. Therefore, the mechanical strength can also be maintained at the same level.

As for the resin composition of this embodiment, when ICP analysis of the residual fraction after incineration of the said resin composition is carried out, it is that silicon content contained in the said resin composition is 51 mass % or more with respect to 100 mass % of the metal content contained in the said resin composition. It is preferable, it is more preferable that it is 55 mass % or more, and it is especially preferable that it is 60 mass % or more. When silicon content contained in the said resin composition exists in the said range, the resin composition of this embodiment can be made into a thing with a small dielectric constant and a small dielectric loss tangent, Comparing with what the glass component of the same form is contained. Therefore, the mechanical strength can also be maintained at the same level.

In addition, when the resin composition of this embodiment performs ICP analysis of the residual fraction after incineration of the said resin composition, silicon content contained in the said resin composition is 62 mass % with respect to 100 mass % of the metal content contained in the said resin composition. It is preferable that it is more than it, It is more preferable that it is 65 mass % or more, It is especially preferable that it is 70 mass % or more. When silicon content contained in the said resin composition exists in the said range, the resin composition of this embodiment can be made into a thing with a small dielectric constant, a small dielectric loss tangent, and a large thermal diffusivity, The glass component of the same form Compared with the inclusion of this, the mechanical strength can also be maintained to the same degree.

When the resin composition of this embodiment performs ICP analysis of the residual fraction after incineration of the resin composition, the silicon content contained in the resin composition is 100 mass% or less with respect to 100 mass% of the metal content contained in the resin composition. and 99.8 mass % or less may be sufficient, and 99.5 mass % or less may be sufficient as it.

As for the resin composition of this embodiment, when ICP analysis of the residual fraction after incineration of the said resin composition is carried out, silicon content contained in the said resin composition with respect to 100 mass % of the metal content contained in the said resin composition is 51 mass % or more 100 Mass % or less may be sufficient, 55 mass % or more and 99.8 mass % or less may be sufficient, 60 mass % or more and 99.5 mass % or less may be sufficient, 62 mass % or more and 100 mass % or less may be sufficient, 65 mass % or more and 99.8 mass % or less may be sufficient, 70 mass % or more and 99.5 mass % or less may be sufficient.

100 mass % of total content of Al, Ca, Si, K, Li, Mg, Na, and Zn contained in the said resin composition, when the resin composition of this embodiment performs ICP analysis of the residue after incineration of the said resin composition It is preferable that the silicon content contained in the said resin composition is 51 mass % or more with respect to it, It is more preferable that it is 55 mass % or more, It is especially preferable that it is 60 mass % or more.

Moreover, when the resin composition of this embodiment performs ICP analysis of the residue after incineration of the said resin composition, the total content of Al, Ca, Si, K, Li, Mg, Na, and Zn contained in the said resin composition 100 With respect to mass %, it is preferable that the silicon content contained in the said resin composition is 62 mass % or more, It is more preferable that it is 65 mass % or more, It is especially preferable that it is 70 mass % or more.

100 mass % of total content of Al, Ca, Si, K, Li, Mg, Na, and Zn contained in the said resin composition, when the resin composition of this embodiment performs ICP analysis of the residue after incineration of the said resin composition With respect to this, 100 mass % or less may be sufficient as silicon content contained in the said resin composition, and 99.8 mass % or less may be sufficient, and 99.5 mass % or less may be sufficient as it.

100 mass % of total content of Al, Ca, Si, K, Li, Mg, Na, and Zn contained in the said resin composition, when the resin composition of this embodiment performs ICP analysis of the residue after incineration of the said resin composition The silicon content contained 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 100 mass% Mass % or less may be sufficient, 65 mass % or more and 99.8 mass % or less may be sufficient, and 70 mass % or more and 99.5 mass % or less may be sufficient.

In the resin composition of this embodiment, it is preferable that the silicon content contained in the said glass component is 51 mass % or more with respect to 100 mass % of the metal content contained in the said glass component, It is more preferable that it is 55 mass % or more, It is 60 mass % The above is particularly preferable. When the silicon content contained in the glass component is within the above range, the resin composition of the present embodiment has a small relative permittivity and a small dielectric loss tangent, compared with that containing a glass component of the same form. Therefore, the mechanical strength can also be maintained at the same level.

Moreover, in the resin composition of this embodiment, it is preferable that the silicon content contained in the said glass component with respect to 100 mass % of the metal content contained in the said glass component is 62 mass % or more, It is more preferable that it is 65 mass % or more, 70 It is especially preferable that it is mass % or more.

When silicon content contained in the said glass component exists in the said range, the resin composition of this embodiment can be made into a thing with a small dielectric constant, a small dielectric loss tangent, and a large thermal diffusivity, The glass component of the same form Compared with the inclusion of this, the mechanical strength can also be maintained to the same degree.

In the resin composition of this embodiment, with respect to 100 mass % of the metal content contained in the said glass component, the silicon content contained in the said glass component may be 100 mass % or less, 99.8 mass % or less may be sufficient, and 99.5 mass % or less may be sufficient as it. .

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

As for the resin composition of this embodiment, the silicon content contained in the said glass component is 51 mass % with respect to 100 mass % of total content of Al, Ca, Si, K, Li, Mg, Na, and Zn contained in the said glass component. It is preferable that it is more than it, It is more preferable that it is 55 mass % or more, It is especially preferable that it is 60 mass % or more.

Moreover, in the resin composition of this embodiment, the silicon content contained in the said glass component is 62 with respect to 100 mass % of total content of Al, Ca, Si, K, Li, Mg, Na, and Zn contained in the said glass component. It is preferable that it is mass % or more, It is more preferable that it is 65 mass % or more, It is especially preferable that it is 70 mass % or more.

As for the resin composition of this embodiment, the silicon content contained in the said glass component is 99.8 mass % with respect to 100 mass % of total content of Al, Ca, Si, K, Li, Mg, Na, and Zn contained in the said glass component. It may be less than or 99.5 mass % or less.

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

In the resin composition of this embodiment, at a frequency of 1 GHz and a temperature of 25°C, the dielectric constant (ε _r ) of the resin composition is preferably 3.4 or less, more preferably 3.35 or less, and particularly preferably 3.3 or less. . When the dielectric constant (ε _r ) of the resin composition is less than or equal to the upper limit, in the field of dielectric devices such as resonators, filters, antennas, circuit boards, and laminated circuit element boards, it is a dielectric material that can be used even for use of high frequency bands. can do.

Although it does not specifically limit as a lower limit of the dielectric constant (epsilon _{) r} of the said resin composition, 2.0 or more may be sufficient, 2.5 or more may be sufficient, and 3.0 or more may be sufficient as it.

That is, it is preferable that the dielectric constants (epsilon _{) r} of the said resin composition are 2.0 or more and 3.4 or less, It is more preferable that they are 2.5 or more and 3.35 or less, It is especially preferable that they are 3.0 or more and 3.3 or less.

_{The relative dielectric constant (ε r} ) of the resin composition at a frequency of 1 GHz and a temperature of 25° C. is measured by the method described in the Examples using a commercially available impedance analyzer by preparing a flat test piece from the target resin composition. can do.

In the resin composition of the present embodiment, at a frequency of 1 GHz and a temperature of 25°C, the dielectric loss tangent (tanδ) of the resin composition ^{is preferably 5.5 × 10 -3} or less, more preferably 5.0 × 10 ^-3 or less, , 4.8 × 10 ^-3 or less is particularly preferred.

When the dielectric loss tangent (tan?) of the resin composition is equal to or less than the upper limit, when used as a dielectric material for various dielectric devices, dielectric loss and transmission loss can be kept low.

As the lower limit of the dielectric loss tangent (tanδ) of the resin composition is not particularly limited, 4.0 × 10 may be either more than ^-3, 4.3 × 10 ^-3 or more, and may be, or may be more than 4.5 × 10 ^-3.

That is, the dielectric loss tangent (tanδ) of the resin composition ^{is preferably 4.0×10 −3} or more and 5.5×10 ⁻³ or less, more preferably 4.3×10 ⁻³ or more and 5.0×10 ⁻³ or less, and 4.5×10 ^{− 3} is especially preferred less than 4.8 × 10 ^-3.

The dielectric loss tangent (tanδ) of the resin composition at a frequency of 1 GHz and a temperature of 25 ° C. is measured by the method described in the Examples using a commercially available impedance analyzer by preparing a flat test piece from the target resin composition. can

It is preferable that the thermal diffusivity of the resin composition of this embodiment is 0.14 mm<2>/s or more, It is more preferable that it is 0.15 mm<2>/s or more, It is especially preferable that it is 0.16 mm<2>/s or more. When the thermal diffusivity of the resin composition is equal to or greater than the lower limit, when used as a dielectric material for various dielectric devices, heat is easily emitted and the temperature rise can be suppressed low.

Although it does not specifically limit as an upper limit of the thermal diffusivity of the said resin composition, 0.25 mm<2>/s may be sufficient, 0.20 mm<2>/s or less may be sufficient, and 0.18 mm<2>/s or less may be sufficient.

That is, the heat diffusivity of the resin composition is preferably 0.14 mm2/s or more and 0.25 mm2/s or less, more preferably 0.15 mm2/s or more and 0.20 mm2/s or less, and 0.16 mm2/s or more and 0.18 mm2/s or less. Especially preferred.

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

(thermoplastic and/or thermosetting resin)

As matrix resin of the resin composition of this embodiment, a thermoplastic resin may be sufficient, a thermosetting resin may be sufficient, and the mixture of a thermoplastic resin and a thermosetting resin may be sufficient.

・Thermoplastic resin

As a thermoplastic resin, general-purpose plastics may be sufficient, engineering plastics may be sufficient, and super engineering plastics may be sufficient.

Specifically, polyethylene (PE), high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), polypropylene (PP), polyvinyl chloride (PVC), polyvinylidene chloride, polystyrene (PS) , polyvinyl acetate (PVAc), polyurethane (PUR), polytetrafluoroethylene (PTFE), ABS resin (acrylonitrile-butadiene styrene resin), AS resin, acrylic resin (PMMA), and other general-purpose plastics;

Polyamide (PA), polyacetal (POM), polycarbonate (PC), modified polyphenylene ether (m-PPE, modified PPE, PPO), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), Engineering plastics, such as cyclic polyolefin (COP);

Polyphenylene sulfide (PPS), polytetrafluoroethylene (PTFE), polysulfone (PSF), polyethersulfone (PES), amorphous polyarylate (PAR), liquid crystal polymer (LCP), polyetheretherketone (PEEK) ), thermoplastic polyimide (PI), and super engineering plastics such as polyamideimide (PAI);

can be preferably used.

Among these, a liquid crystal polymer (LCP) is especially 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 melts at a temperature of 450° C. or less. do.

As the liquid crystal polymer (LCP) used in the present embodiment, liquid crystal polyester may be sufficient, liquid crystal polyester amide may be sufficient, liquid crystal polyester ether may be sufficient, liquid crystal polyester carbonate may be sufficient, and liquid crystal polyester imide may be sufficient. As the liquid crystal polymer (LCP) used in the present embodiment, a liquid crystal polyester is preferable, and a wholly aromatic liquid crystal polyester formed using only an aromatic compound as a raw material monomer is particularly preferable.

A typical example of the liquid crystal polyester used in this embodiment is polymerization (polycondensation) of at least one compound selected from the group consisting of aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, aromatic diol, aromatic hydroxyamine, and aromatic diamine. sum), a compound formed by polymerizing a plurality of aromatic hydroxycarboxylic acids, an aromatic dicarboxylic acid and at least one compound selected from the group consisting of an aromatic diol, an aromatic hydroxyamine, and an aromatic diamine, What is formed by polymerizing polyester, such as polyethylene terephthalate, and aromatic hydroxycarboxylic acid, is mentioned. Here, as for aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, aromatic diol, aromatic hydroxyamine, and aromatic diamine, the derivative(s) which can be superposed|polymerized may be used instead of some or all of them independently, respectively.

Examples of polymerizable derivatives of compounds having a carboxyl group, such as aromatic hydroxycarboxylic acids and aromatic dicarboxylic acids, include those formed by converting a carboxyl group into an alkoxycarbonyl group or an aryloxycarbonyl group (ester), a carboxyl group by converting a haloformyl group What is formed by (acid halide), and what is formed by converting a carboxyl group into an acyloxycarbonyl group (acid anhydride) is mentioned. Examples of polymerizable derivatives of compounds having a hydroxyl group such as aromatic hydroxycarboxylic acids, aromatic diols and aromatic hydroxylamines include those formed by acylating a hydroxyl group and converting it to an acyloxyl group (acylate). can be heard Examples of the polymerizable derivative of a compound having an amino group, such as aromatic hydroxyamine and aromatic diamine, include those formed by acylating an amino group to convert it to an acylamino group (acylate).

The liquid crystalline polyester used in the present embodiment preferably has a repeating unit represented by the following formula (1) (hereinafter sometimes referred to as “repeating unit (1)”), and a repeating unit (1); A repeating unit represented by the following formula (2) (hereinafter sometimes referred to as “repeating unit (2)”) and a repeating unit represented by the following formula (3) (hereinafter referred to as “repeating unit (3)”) It is more preferable to have ).

(1) -O-Ar ¹ -CO-

(2) -CO-Ar ² -CO-

(3) -X-Ar ³ -Y-

(In formulas (1) to (3), Ar ¹ represents a phenylene group, a naphthylene group or a biphenylrylene group, Ar ² and Ar ³ are each independently a phenylene group, a naphthylene group, a biphenylene group, or a Represents the group represented by formula (4).X and Y each independently represents an oxygen atom or an imino group.The hydrogen atom in the group represented by ^{Ar 1} , Ar ² and Ar ^{3 is each independently a halogen atom,} It may be substituted with an alkyl group or an aryl group.)

(4) -Ar ⁴ -Z-Ar ⁵ -

(In formula (4), Ar ⁴ and Ar ⁵ each independently represent a phenylene group or a naphthylene group. Z represents an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or an alkylidene group.)

The liquid crystal polyester used in the present embodiment contains 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) with respect to the total amount of the repeating unit (1), the repeating unit (2) or the repeating unit (3) is 30 mol% or more and 100 mol% or less,

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

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

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 methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-hexyl group, 2-ethylhexyl group, n -octyl group and n-decyl group are mentioned, As for the carbon number, 1-10 are preferable. Examples of the aryl group include a phenyl group, an o-tolyl group, a 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 said hydrogen atom is substituted by these groups, the number is ^{each independently for each said group represented by Ar 1} , Ar ² or Ar ³ , preferably 2 or less, more preferably 1 or less.

Examples of the alkylidene group include a methylene group, an ethylidene group, an isopropylidene group, an n-butylidene group and a 2-ethylhexylidene group, and the number of carbon atoms 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 ¹ is a p-phenylene group (a repeating unit derived from p-hydroxybenzoic acid), and Ar ¹ is a 2,6-naphthylene group (6-hydroxy-2-naph) repeating units derived from local acids) are preferred.

In addition, in this specification, since the raw material monomer superposes|polymerizes, the chemical structure of the functional group which contributes to superposition|polymerization changes, and does not generate|occur|produce other structural change.

The repeating unit (2) is a repeating unit derived from a predetermined aromatic dicarboxylic acid. As the repeating unit (2), Ar ² is a p-phenylene group (a repeating unit derived from terephthalic acid), Ar ² is an m-phenylene group (a repeating unit derived from isophthalic acid), and Ar ² is 2,6 - a naphthylene group (a repeating unit derived from 2,6-naphthalenedicarboxylic acid), and Ar ² is a diphenylether-4,4'-diyl group (diphenylether-4,4'-dica) A repeating unit derived from carboxylic acid) is preferred.

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 ³ is a p-phenylene group (a repeating unit derived from hydroquinone, p-aminophenol, or p-phenylenediamine), and Ar ³ is 4,4′-biphenylrylene group (a repeating unit derived from 4,4'-dihydroxybiphenyl, 4-amino-4'-hydroxybiphenyl or 4,4'-diaminobiphenyl) is preferable.

The content of the repeating unit (1) is the total amount of all repeating units (by dividing the mass of each repeating unit constituting the liquid crystalline polyester resin by the food amount of each repeating unit, the amount of substance equivalent (mol) of each repeating unit is obtained, , the sum of them), preferably 30 mol% or more, more preferably 30 mol% or more and 80 mol% or less, still more preferably 40 mol% or more and 70 mol% or less, and 45 mol% or more and 65 mol% or more. % or less is particularly preferred.

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, with respect to the total amount of all repeating units, , 17.5 mol% or more and 27.5 mol% or less are particularly preferable.

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, with respect to the total amount of all repeating units, , 17.5 mol% or more and 27.5 mol% or less are particularly preferable.

As the content of the repeating unit (1) increases, the melt fluidity, heat resistance, strength, and rigidity tend to improve, but when the content is too large, the melting temperature or melt viscosity tends to become high, and the temperature required for molding tends to increase.

The ratio of the content of the repeating unit (2) to the content of the repeating unit (3) is expressed by [content of repeating unit (2)]/[content of repeating unit (3)] (mol/mol), 0.9/1 to 1/0.9 is preferable, 0.95/1 - 1/0.95 are more preferable, and 0.98/1 - 1/0.98 are still more preferable.

In addition, the liquid crystal polyester used by this embodiment may have 2 or more types each independently of repeating units (1)-(3). Moreover, although the liquid crystalline polyester may have repeating units other than repeating units (1) - (3), the content is preferably 10 mol% or less, and 5 mol% or less with respect to the total amount of all repeating units. more preferably.

Liquid crystalline polyester used in the present embodiment has a repeating unit (3) in which X and Y are oxygen atoms, that is, a repeating unit derived from a predetermined aromatic diol tends to have a lower melt viscosity. Therefore, it is preferable and, as the repeating unit (3), it is more preferable to have only X and Y each being an oxygen atom.

Liquid crystalline polyester used in the present embodiment is produced by solid-state polymerization of a polymer obtained by melt polymerization of a raw material monomer corresponding to the repeating unit constituting it (hereinafter, sometimes referred to as "prepolymer"). desirable. Thereby, high molecular weight liquid crystal polyester with high heat resistance, strength, and rigidity can be manufactured with favorable operability. 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, 4- and nitrogen-containing heterocyclic compounds such as (dimethylamino)pyridine and 1-methylimidazole, and nitrogen-containing heterocyclic compounds are preferably used.

280 degreeC or more is preferable, as for the flow initiation temperature of the liquid crystalline polyester used by this embodiment, 280 degreeC or more and 400 degrees C or less are more preferable, 280 degreeC or more and 380 degrees C or less are still more preferable.

The higher the flow initiation temperature of the liquid crystal polyester used in the present embodiment, the higher the heat resistance and the strength and rigidity of the liquid crystal polyester tend to be improved. On the other hand, when the flow start temperature of liquid crystal polyester exceeds 400 degreeC, there exists a tendency for the melting temperature and melt viscosity of liquid crystal polyester to become high. Therefore, there exists a tendency for the temperature required for shaping|molding of liquid crystalline polyester to become high.

In the present specification, the flow start temperature of the liquid crystal polyester is also called a flow temperature or a flow temperature, and is a temperature that serves as a reference for the molecular weight of the liquid crystal polyester. See CMC, Inc., 5 June 1987, p.95). The flow initiation temperature is, using a capillary rheometer, the liquid crystal polyester is melted while the temperature is rising at a rate of 4° C./min under a load of 9.8 MPa (100 kg/cm 2 ), and extruded from a nozzle having an inner diameter of 1 mm and a length of 10 mm It is a temperature showing a viscosity of 4800 Pa·s (48000 poise).

It is preferable that the content rate of the said liquid crystal polyester with respect to 100 mass % of the said thermoplastic resin is 80 mass % or more and 100 mass % or less. Examples of the resin other than the liquid crystal polyester contained in the thermoplastic resin include polypropylene, polyamide, polyester other than liquid crystal polyester, polysulfone, polyphenylene sulfide, polyether ketone, polycarbonate, polyphenylene ether, Thermoplastic resins other than liquid crystal polyester, such as polyetherimide, are mentioned.

· Thermosetting resin

Examples of the thermosetting resin include a phenol resin, a urea resin, a melamine resin, an unsaturated polyester resin, an epoxy resin, and a silicon resin.

As matrix resin of the resin composition of this embodiment, a thermosetting resin may be used independently and may be used as a mixture with a thermoplastic resin.

(glass component)

The resin composition of this embodiment WHEREIN: A glass component is disperse|distributed in the matrix resin of a thermoplastic resin and/or a thermosetting resin, and can adjust the dielectric characteristic, heat diffusivity, and mechanical strength of the said resin composition.

As a glass component used for the resin composition of this embodiment, a well-known thing can be used as a filler containing glass powder, such as a fibrous glass filler, a flaky glass filler, a glass bead, and a glass balloon, A fibrous glass filler or flake shape can be used. It is preferable that it is a glass filler.

It is preferable that the weight average fiber length of a fibrous glass filler is 30 micrometers or more, It is more preferable that it is 50 micrometers or more, It is especially preferable that it is 80 micrometers or more. When the weight average fiber length of a fibrous glass filler is more than the said lower limit, mechanical strength can be made into a preferable thing. It is preferable that it is 30 micrometers or more, and, as for the number average fiber length of a fibrous glass filler, it is more preferable that it is 50 micrometers or more, It is especially preferable that it is 60 micrometers or more. When the number average fiber length of a fibrous glass filler is more than the said lower limit, mechanical strength can be made into a preferable thing.

It is preferable that the weight average fiber length of a fibrous glass filler is 300 micrometers or less, It is more preferable that it is 150 micrometers or less, It is especially preferable that it is 100 micrometers or less. When the weight average fiber length of a fibrous glass filler is below the said upper limit, it becomes easy to shape|mold.

It is preferable that it is 300 micrometers or less, and, as for the number average fiber length of a fibrous glass filler, it is more preferable that it is 150 micrometers or less, It is especially preferable that it is 90 micrometers or less. When the number average fiber length of a fibrous glass filler is below the said upper limit, it becomes easy to shape|mold.

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.

Although the number average fiber diameter of a fibrous glass filler is not specifically limited, It is preferable that it is 1-40 micrometers, It is more preferable that it is 3-30 micrometers, It is more preferable that it is 5-20 micrometers, It is 8-15 micrometers Especially preferred.

As for the number average fiber diameter of a fibrous glass filler, the number average value of the value which observed the fibrous glass filler with a scanning electron microscope (1000 times) and measured the fiber diameter about 50 fibrous glass fillers is employ|adopted.

If the number average fiber diameter of a fibrous glass filler is more than the lower limit of the said preferable range, it is easy to disperse|distribute a fibrous glass filler in a resin composition. Moreover, it is easy to handle a fibrous glass filler at the time of manufacture of a resin composition. On the other hand, mechanical strengthening of the resin composition by a fibrous glass filler is performed efficiently as it is below the upper limit of said preferable range.

As a fibrous glass filler, chopped glass fiber or milled glass fiber is preferable. Chopped glass fiber is what cut|disconnected the glass strand, for example, the thing with a cut length of 3-6 mm and a fiber diameter of 9-13 micrometers is marketed from Central Glass Corporation. Milled glass fibers are obtained by pulverizing glass fibers, and have intermediate properties between chopped glass fibers and powdered glass. For example, those having an average fiber length of 30 to 150 µm and a fiber diameter of 6 to 13 µm are marketed from Central Glass Corporation.

As an average particle diameter of a flaky glass filler, it is preferable that it is 30 micrometers or more, It is more preferable that it is 50 micrometers or more, It is especially preferable that it is 80 micrometers or more. When the average particle diameter of a flaky glass filler is more than the said lower limit, mechanical strength can be made into a preferable thing.

It is preferable that it is 300 micrometers or less, and, as for the average particle diameter of a flaky glass filler, it is more preferable that it is 200 micrometers or less, It is especially preferable that it is 150 micrometers or less. When the average particle diameter of a flaky glass filler is below the said upper limit, it becomes easy to shape|mold.

The average particle diameter of the flaky glass 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.

As an average thickness of a flaky glass filler, it is preferable that it is 0.2 micrometer or more, It is more preferable that it is 0.5 micrometer or more, It is especially preferable that it is 1.0 micrometer or more. When the average thickness of a flaky glass filler is more than the said lower limit, mechanical strength can be made preferable.

It is preferable that it is 30 micrometers or less, and, as for the average thickness of a flaky glass filler, it is more preferable that it is 20 micrometers or less, It is especially preferable that it is 10 micrometers or less. When the average thickness of a flaky glass filler is below the said upper limit, it becomes easy to shape|mold.

The average thickness of the flaky glass 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.

Examples of the flaky glass filler include 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. It is marketed from Nippon Plate Glass Co., Ltd. Glasses used for glass flakes have glass compositions such as C glass and E glass.

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

Examples of the glass component include E glass (ie, alkali-free glass), S glass or T glass (ie, high strength, high modulus glass), C glass (ie, acid-resistant glass), D glass (ie low dielectric constant glass), and glass fibers for FRP reinforcing materials, such as ECR glass (ie, _{E glass replacement glass that does not contain B 2} O ₃ , F ₂ ) and AR glass (ie, glass for alkali-resistant applications).

As the dielectric constant (ε _r ) of the glass component, it is preferable to use a low dielectric constant, and at a frequency of 1 GHz and a temperature of 25°C, the relative dielectric constant (ε _r ) of the glass component is preferably 4.80 or less, and 4.30 or less. The following are more preferable, and 4.00 or less are especially preferable. The relative dielectric constant (ε _r ) of the glass component may be 3.00 or more, 3.10 or more, and 3.15 or more.

In the resin composition of this embodiment, it is preferable that content of a glass component is 1-60 mass % with respect to 100 mass % of the said resin composition, It is more preferable that it is 10-50 mass %, It is 20-40 mass % Especially preferred.

When content of a glass component is more than the lower limit of the said preferable range, it will become easy to improve the adhesiveness of the said thermoplastic resin and/or the said thermosetting resin, and a glass component. On the other hand, dispersion|distribution of a glass component becomes easy as it is below the upper limit of said preferable range.

<Other ingredients>

As a raw material, the resin composition of this embodiment may contain 1 or more types of other components, such as a filler and an additive, as needed other than the said thermoplastic resin and/or the said thermosetting resin, and the said glass component. When the resin composition contains a thermosetting resin, the resin composition may contain a solvent.

As a filler, a plate-shaped filler, a spherical filler, and other granular fillers may be sufficient. Moreover, an inorganic filler may be sufficient as a filler, and an organic filler may be sufficient as it.

Examples of the plate-shaped inorganic filler include talc, mica, graphite, wollastonite, barium sulfate, and calcium carbonate. Mica may be muscovite, phlogopite mica, fluorine phlogopite mica, or tetrasilicon mica.

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

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

(Method for producing a resin composition)

The resin composition containing the thermoplastic resin of this embodiment mixes a thermoplastic resin, a glass component, and other components as needed, melt-kneading, for example, degassing with a twin screw extruder, The melt of the thermoplastic resin obtained And the mixture of the glass component can be discharged in the form of a strand via a circular nozzle (discharge port), and then, it can pelletize with a strand cutter, and it can be set as resin composition pellet.

Moreover, for example, the resin composition containing the thermosetting resin of this embodiment can be obtained by mixing a thermosetting resin, a glass component, and another component as needed.

(formed body)

The resin composition of this embodiment can obtain a molded object by a well-known shaping|molding method. As a method of molding a molded article from a resin composition containing a thermoplastic resin, a melt molding method is preferable, and examples thereof include an injection molding method, an extrusion molding method such as a T-die method or an inflation method, a compression molding method, a blow molding method, a vacuum molding method, and a press molding is included. Among them, the injection molding method is preferable. An injection molding method and press molding are mentioned as a method of shape|molding a molded object from the resin composition containing a thermosetting resin. Among them, the injection molding method 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 using a known injection molding machine to obtain a resin composition containing the molten thermoplastic resin, It is molded by injection into a mold.

As a well-known injection molding machine, the TR450EH3 by Sodick Co., Ltd.|KK, hydraulic type horizontal molding machine PS40E5ASE type|mold by the Nissei resin industry, etc. are mentioned, for example.

The cylinder temperature of the injection molding machine is appropriately determined according to the type of the thermoplastic resin, and is preferably set at a temperature higher than the flow start temperature of the thermoplastic resin to be used by 10 to 80°C, for example, from 300 to 400°C.

The temperature of the mold is preferably set in a range from room temperature (eg, 23°C) to 180°C from the viewpoint of the cooling rate and productivity of the resin composition containing the thermoplastic resin.

For example, when a resin composition containing a thermosetting resin is used as a molding material and molded by an injection molding method, using a known injection molding machine, the molding material is put into the mold, and then the mold temperature is heated to about 150 ° C. After the molding material is cured, the molded body can be taken out from the mold.

Moreover, the molded object of this embodiment is applicable to uses, such as a dielectric device, such as a resonator, a filter, an antenna, a circuit board, and a laminated circuit element board|substrate.

Example

Hereinafter, the present invention will be described in more detail by way of specific examples. However, this invention is not limited at all to the Example shown below.

<Glass filler>

Glass fillers (A) to (F) shown in Table 1 below were prepared.

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

The raw material glass fillers (A) and (B) are fibrous glass fillers (milled glass fibers) having the compositions shown in Table 1.

1.0 g of the fibrous glass filler of the raw material is taken, dispersed in methanol, and a photomicrograph is taken in the state of being developed on a slide glass, the shape of the fibrous glass filler is directly read from the photo, the average value is calculated, and the fibrous The number average fiber length of the glass filler was obtained. In addition, in calculation of an average value, the parameter was made into 400 or more. The results are shown in Table 1.

<Average thickness and average particle diameter of flaky glass filler of raw material>

Glass fillers (C) to (F) of the raw material are flaky glass fillers having the composition shown in Table 1.

The flaky glass filler of the raw material is observed by SEM at a magnification of 1000 times, the thickness and number average particle diameter of 100 flaky glass fillers randomly selected from the SEM image are measured, respectively, and the average value of 100 measured values is calculated to calculate the flake shape of the raw material. The average thickness and number average particle diameter of the glass filler were calculated|required. The results are shown in Table 1.

20 mass parts of glass filler (D) and 10 mass parts of glass fillers (F) were mixed, and the glass filler (G) shown in following Table 2 was prepared.

15 mass parts of glass fillers (D) and 15 mass parts of glass fillers (F) were mixed, and the glass filler (H) shown in following Table 2 was prepared.

7.5 mass parts of glass filler (D) and 22.5 mass parts of glass fillers (F) were mixed, and the glass filler (I) shown in following Table 2 was prepared.

<Production of polymer>

(1) melt polymerization

In a reactor equipped with a stirring device, a torque meter, a nitrogen gas inlet tube, a thermometer and a reflux condenser, p-hydroxybenzoic acid (994.5 g, 7.20 mol), terephthalic acid (272.1 g, 1.64 mol), and isophthalic acid (126.6 g) , 0.76 mol), 4,4'-dihydroxybiphenyl (446.9 g, 2.40 mol), and 1347.6 g (13.20 mol) of acetic anhydride were injected. After replacing the gas in the reactor with nitrogen gas, 0.18 g of 1-methylimidazole was added, and the temperature was raised from room temperature to 150°C over 30 minutes while stirring under a nitrogen gas stream, and refluxed at 150°C for 30 minutes.

Subsequently, after adding 2.40 g of 1-methylimidazole, the temperature was raised from 150° C. to 320° C. over 2 hours and 50 minutes while distilling off by-produced acetic acid and unreacted acetic anhydride, and an increase in torque was confirmed. It was set as the completion|finish of reaction at this time, and the prepolymer of the content was taken out from the reactor, and it cooled to room temperature.

(2) solid-state polymerization

Next, the prepolymer was pulverized using a pulverizer, and the obtained pulverized product was heated from room temperature to 250° C. over 1 hour in a nitrogen gas atmosphere, and heated from 250° C. to 280° C. over 5 hours, and at 280° C. By holding for 3 hours, solid-state polymerization was performed. The obtained solid-state polymer was cooled to room temperature, and liquid crystal polyester (1) was obtained.

Liquid crystal polyester (1) has, for the ratio of the total amount of all repeating units, 60 mol% of Ar ¹ a 1,4-phenylene group, repeat unit (u12) in the molecule, Ar ² is 1,4-phenylene group 13.65 mol% of the repeating unit (u22), 6.35 mol% of the repeating unit (u23) in which ^{Ar 2} is a 1,3-phenylene group, and 20 in the repeating unit (u32) in which ^{Ar 3 is a 4,4'-biphenylylene group} mol%, and the flow initiation temperature was 312°C.

[Comparative Example 1]

<Production of pellets>

After drying liquid crystal polyester (1) at 120 degreeC for 5 hours, 70 mass parts of liquid crystal polyester (1) and 30 mass parts of glass filler (A) were mixed with a vacuum vent twin screw extruder (Ikegai Iron Co., Ltd.) "PCM-30" manufactured by the company), and using a water ring vacuum pump ("SW-25S" manufactured by Shinko Seiki Co., Ltd.) and degassed with a vacuum vent, a cylinder temperature of 340°C, and a screw rotation speed of 150 rpm Melt-kneading was carried out under the conditions of Next, the discharged kneaded material was immersed in a water bath having a water temperature of 30°C for 1.5 seconds, and then pelletized with a strand cutter (manufactured by Tanabe Plastics Machinery Co., Ltd.), and resin composition pellets (1) of Comparative Example 1 ( A pellet-form liquid crystal polyester resin composition (1)) was obtained.

[Example 1]

<Production of pellets>

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), in the same manner as in Comparative Example 1, the resin composition pellets (2) of Example 1 (pellet-like liquid crystal poly An ester resin composition (2)) was obtained.

[Comparative Example 2]

<Production of pellets>

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 the same manner as in Comparative Example 1, the resin composition pellets (3) of Comparative Example 2 (pellet-like liquid crystal poly An ester resin composition (3)) was obtained.

[Comparative Example 3]

<Production of pellets>

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 the same manner as in Comparative Example 1, the resin composition pellets (4) of Comparative Example 3 (pellet-like liquid crystal poly An ester resin composition (4)) was obtained.

[Example 2]

<Production of pellets>

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 the same manner as in Comparative Example 1, the resin composition pellets (5) of Example 2 (pellet-shaped liquid crystal poly An ester resin composition (5)) was obtained.

[Example 3]

<Production of pellets>

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 the same manner as in Comparative Example 1, the resin composition pellets (6) of Example 3 (pellet-like liquid crystal poly An ester resin composition (6)) was obtained.

[Example 4]

<Production of pellets>

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 the same manner as in Comparative Example 1, the resin composition pellets (7) of Example 4 (pellet-like liquid crystal poly An ester resin composition (7)) was obtained.

[Example 5]

<Production of pellets>

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 the same manner as in Comparative Example 1, the resin composition pellets (8) of Example 5 (pellet-like liquid crystal poly An ester resin composition (8)) was obtained.

[Example 6]

<Production of pellets>

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 the same manner as in Comparative Example 1, the resin composition pellets (9) of Example 6 (pellet-like liquid crystal poly An ester resin composition (9)) was obtained.

<ICP analysis, test item>

A total of 22 elements including Al, Ba, Ca, Si, Ti, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Ni, P, Pb, Sb, V, and Zn were tested. was done with

<ICP analysis/test method>

(sample heat treatment)

The target sample of the resin composition pellet obtained by each Example and the comparative example was heat-processed at 600 degreeC for 6 hours, and it was set as the analysis blank sample.

(Al, Ba, Ca, Si, Ti)

After heating and dissolving the analysis sample with an acid such as hydrofluoric acid or nitric acid, alkali melting with sodium carbonate, and adjusting the concentration to a predetermined concentration with hydrochloric acid as a test solution, inductively coupled plasma emission spectrometry (ICP-AES) was performed. The analysis and test results are shown in Tables 3 and 4. Ba was less than the detection limit (0.2 mass %).

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

A sample for analysis was heated and dissolved with an acid such as hydrofluoric acid or nitric acid, adjusted to a predetermined concentration, as a test solution, and measured by inductively coupled plasma emission spectrometry (ICP-AES). The analysis and 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 the detection limit (0.2 mass%).

(Measurement of dielectric constant and dielectric loss tangent)

The resin composition pellets obtained by each Example and the comparative example were vacuum-dried at 120 degreeC for 5 hours, and it used for PNX-40-5A (made by Nissei Resin Industry Co., Ltd.), and cylinder temperature: 64 in all directions under the molding conditions of 350 degreeC. mm and a flat plate having a thickness of 1.0 mm was produced. About the obtained flat plate, the dielectric constant and dielectric loss tangent in 1 GHz were measured under the following conditions.

Measurement method: capacitive method (device: impedance analyzer (Agilent manufactured model: E4991A))

Electrode type: 16453A

Measurement environment: 23℃, 50%RH

Applied voltage: 1 V

(Measurement of heat diffusivity)

The resin composition pellets obtained by each Example and Comparative Example were vacuum-dried at 120°C for 5 hours, provided to PNX-40-5A (manufactured by Nissei Resin Industry Co., Ltd.), cylinder temperature: under the molding conditions of 350°C, horizontally and vertically A sheet of 64 mm and a thickness of 1.0 mm was molded and cut out to a size of 10 mm × 10 mm × 1.0 mm to obtain a test piece. About this test piece, the thermal diffusivity was measured by the laser flash method using the thermal diffusivity meter "nano flash LFA457" (made by Bruker AXS).

(tensile test)

The resin composition pellets obtained by each Example and Comparative Example were vacuum-dried at 120°C for 5 hours, provided to PNX-40-5A (manufactured by Nissei Resin Industry Co., Ltd.), cylinder temperature: ASTM No. 4 under molding conditions of 350°C Dumbbell specimens were injection molded. For each of 5 samples of this test piece, a tensile test was performed at a crosshead speed of 10 mm/min using a tensile tester Tensilon RTG-1250 (manufactured by A&Day Co., Ltd.) according to ASTM D638, and the tensile strength and The growth at that time was measured, and the average value of them was calculated|required. The results are shown in Tables 3 and 4.

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

Among the resin composition pellets obtained in Comparative Example 1 and Example 1, 1.0 g was each collected in a crucible, and it was incinerated by processing at 600°C in an electric furnace for 4 hours. The residue was dispersed in methanol and developed on a slide glass, a photomicrograph was taken, the shape of the fibrous glass filler was directly read from the photo, the average value was calculated, and the weight average fiber of the fibrous glass filler in the resin composition The length and number average fiber length were obtained. In addition, in calculation of an average value, the parameter was made into 400 or more. The weight for each fiber length was calculated from the specific gravity of the fibrous glass filler, and the total weight of the sample having a parameter of 400 or more was used as the denominator to calculate the weight average fiber length. The results are shown in Table 3.

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

Of the resin composition pellets obtained in Comparative Examples 2 and 3 and Examples 2 to 6, 1.0 g each was collected in a crucible, treated in an electric furnace at 600° C. for 4 hours to incinerate, and the residue was dispersed in methanol. In the state of being spread on a glass slide, it was observed with SEM at a magnification of 1000 times, the shapes of 100 flaky glass fillers randomly selected from the SEM image were directly read, and the number average value of the maximum ferret diameter was calculated in the resin composition. The number average particle diameter of the flaky glass filler was calculated|required. Moreover, the number average value of thickness was computed and the average thickness of the flaky glass filler in a resin composition was calculated|required. In addition, in calculation of an average value, the parameter was made into 400 or more. The results are shown in Tables 3 and 4.

From the results shown in Tables 3 and 4, the liquid crystal polyester resin composition of Example 1 to which the present invention is applied has a small relative dielectric constant, a small dielectric loss tangent, and heat resistance compared to the liquid crystal polyester resin composition of Comparative Example 1 It could be said that the diffusion rate was large. The mechanical strength was also about the same.

The liquid-crystal polyester resin composition of Example 2 to which this invention was applied was also small compared with the liquid-crystal polyester resin composition of Comparative Examples 2-3, and was able to be made into a thing with a small dielectric loss tangent. The mechanical strength was also about the same.

The liquid crystal polyester resin compositions of Examples 3 and 4 to 6 to which the present invention is applied also have a small relative dielectric constant, a small dielectric loss tangent, and a large thermal diffusivity compared with the liquid crystal polyester resin compositions of Comparative Examples 2 to 3 Could. The mechanical strength was also about the same.

Claims (7)

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,
The resin composition whose calcium content contained in the said resin composition is 0-27 mass % with respect to 100 mass % of the metal content contained in the said resin composition, when ICP analysis of the residue fraction after incineration of the said resin composition is carried out. The method of claim 1,
When ICP analysis of the residue fraction after incineration of the said resin composition is carried out, the silicon content contained in the said resin composition with respect to 100 mass % of the metal content contained in the said resin composition is 51 mass % or more resin composition. 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,
The resin composition whose calcium content contained in the said glass component is 0-27 mass % with respect to 100 mass % of the metal content contained in the said glass component. 4. The method of claim 3,
The resin composition in which silicon content contained in the said glass component is 51 mass % or more with respect to 100 mass % of the metal content contained in the said glass component. 5. The method according to any one of claims 1 to 4,
A frequency of 1 GHz and a temperature of 25°C WHEREIN: The resin composition whose dielectric constant (ε _r ) of the said resin composition is 3.4 or less. 6. The method of claim 5,
At a frequency of 1 GHz and a temperature of 25°C, the dielectric loss tangent (tanδ) of the resin composition is 5.5×10 ⁻³ or less. 7. The method according to claim 5 or 6,
The resin composition whose thermal diffusivity of the said resin composition is 0.14 mm<2>/s or more.