JP2018177931A - Resin composition and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition excellent in impact resistance and electric characteristics, and a molded article.SOLUTION: A resin composition contains a melt-moldable fluorine resin having a melting point of 100°C or higher and 325°C or lower and having at least one reactive functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group and an isocyanate group, and a liquid crystal polymer.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition containing a liquid crystal polymer excellent in electrical properties and mechanical properties.

With the development of information communication technology, the demand for high-performance high-frequency electronic components that can be adapted in the high frequency region of microwaves and millimeter waves is increasing. With respect to materials used for enhancing the performance of high-frequency electronic components that constitute information communication devices, characteristics of appropriate dielectric constant and low dielectric loss are required according to their respective designs.
The relative dielectric constant (ε) is a parameter indicating the degree of polarization in the dielectric, and the higher the relative dielectric constant, the larger the propagation delay of the electric signal (Td = 3.3√ε, Td; electric signal propagation delay time). Therefore, in order to increase the propagation speed of the signal and enable high-speed operation, it is preferable that the dielectric constant be low. The dielectric loss tangent (tan δ) is a parameter that indicates the amount of loss of a signal propagating in the dielectric body that is converted to heat and lost. The lower the dielectric loss tangent, the smaller the signal loss and the better the signal transmission rate.

Liquid crystal polymers are excellent in mechanical properties such as low relative dielectric constant, low dielectric loss tangent, heat resistance, rigidity, etc., chemical resistance, dimensional accuracy, etc., and their use is expanding as molded products, but in recent years The requirements for high-frequency electronic components have come to be required to have a lower dielectric constant and a lower dielectric loss tangent than liquid crystal polymers.
In order to lower the dielectric constant of a liquid crystal polymer material, attempts have been made to lower the dielectric constant by kneading polytetrafluoroethylene (PTFE) powder in a resin (see Patent Document 1).

Unexamined-Japanese-Patent No. 2003-171538

  However, since PTFE has no melt flowability and low affinity with liquid crystal polymers, PTFE particles aggregate during melt-kneading or injection molding, resulting in a decrease in the moldability of the resin composition, and resistance to moldings. It has been a problem to cause a decrease in impact resistance, a decrease in mechanical strength, and a deterioration in the appearance of a molded article.

As a result of investigations by the present inventors, in the molded article made of a resin composition containing a specific fluorocarbon resin in the liquid crystal polymer, the above problems are solved, and a molded article excellent in electrical characteristics, impact resistance and mechanical strength can be obtained. I understood it.
The present invention provides resin compositions and molded articles excellent in impact resistance and electrical properties.

The present invention has the following aspects.
[1] Melt-moldable fluororesin having a melting point of 100 ° C. or more and 325 ° C. or less and having at least one functional group selected from the group consisting of a carbonyl group-containing group, a hydroxyl group, an epoxy group and an isocyanate group Resin composition containing a polymer.
[2] The resin composition according to [1], wherein the functional group is an acid anhydride group.
[3] The resin composition according to [1] or [2], wherein the content of the fluororesin with respect to the total of the fluororesin and the liquid crystal polymer is 1 to 45% by volume.
[4] The resin composition according to any one of [1] to [3], further containing at least one selected from the group consisting of an inorganic filler and an organic filler.
The molded article formed by shape | molding the resin composition in any one of [5] [1]-[4].
[6] The molded article according to [5], wherein the molded article is a connector.
[7] A molded article characterized in that the resin composition according to any one of [1] to [4] is molded by extrusion molding, injection molding, cutting, thermoforming, or laminate molding. Production method.

  According to the present invention, a resin composition and a molded article excellent in impact resistance and electrical properties can be obtained.

The following definitions of terms apply throughout the specification and claims.
The "melting point" is the temperature corresponding to the maximum value of the melting peak measured by differential scanning calorimetry (DSC).
By "melt-moldable" is meant exhibiting melt flowability.
“Show melt flowability” means that there is a temperature at which the melt flow rate is 0.1 to 1000 g / 10 min at a load of 49 N and at a temperature 20 ° C. or more higher than the melting point of the resin. .
The "melt flow rate" is a melt mass flow rate (MFR) defined in JIS K 7210: 1999 (ISO 1133: 1997).
The “carbonyl group-containing group” means a group having a carbonyl group (—C (= O) —) in the structure.
The “acid anhydride group” means a group represented by —C (= O) —O—C (= O) —.
The “unit based on a monomer” is a generic name of an atomic group directly formed by polymerizing a monomer, and an atomic group obtained by chemically converting a part of the atomic group.

The resin composition of the present invention contains a fluorine resin and a liquid crystal polymer.
Moreover, the resin composition of this invention may contain other components other than a fluororesin and a liquid crystal polymer in the range which does not impair the effect of this invention.

  The fluorine resin is a fluorine resin having at least one functional group (hereinafter referred to as a functional group (f)) selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group and an isocyanate group (hereinafter referred to as , Also referred to as fluorine resin A). By having the adhesive functional group (f), the miscibility with the liquid crystal polymer is excellent, and the mechanical properties, moldability and impact resistance of the molded product are not impaired.

The functional group (f) is preferably present as one or both of an end group of the main chain of the fluororesin A and a pendant group of the main chain from the viewpoint of excellent miscibility with the liquid crystal polymer.
The functional group (f) may be of one type, or of two or more types.

The fluorine resin A preferably has at least a carbonyl group-containing group as the functional group (f) from the viewpoint of the compatibility with the liquid crystal polymer.
Examples of the carbonyl group-containing group include a group having a carbonyl group between carbon atoms of a hydrocarbon group, a carbonate group, a carboxy group, a haloformyl group, an alkoxycarbonyl group, an acid anhydride group and the like.

As a hydrocarbon group in the group which has a carbonyl group between carbon atoms of a hydrocarbon group, a C2-C8 alkylene group etc. are mentioned, for example. In addition, carbon number of this alkylene group is carbon number in the state which does not contain carbon which comprises a carbonyl group. The alkylene group may be linear or branched.
A haloformyl group is represented by -C (= O) -X (however, X is a halogen atom). A fluorine atom, a chlorine atom, etc. are mentioned as a halogen atom in a haloformyl group, A fluorine atom is preferable. That is, as the haloformyl group, a fluoroformyl group (also referred to as a carbonyl fluoride group) is preferable.
The alkoxy group in the alkoxycarbonyl group may be linear or branched, and is preferably an alkoxy group having 1 to 8 carbon atoms, and particularly preferably a methoxy group or an ethoxy group.

The content of the functional group (f) in the fluororesin A is preferably 10 to 60000, more preferably 100 to 50000, with respect to 1 × 10 ⁶ carbon atoms in the main chain of the fluororesin A, and 100 to 10000 More preferably, 300 to 5000 are particularly preferable. When the content of the functional group (f) is at least the lower limit value of the above range, the miscibility with the liquid crystal polymer is extremely excellent. If content of a functional group (f) is below the upper limit of the said range, it is excellent in the compatibility at the time of melt-kneading.

  The content of the functional group (f) can be measured by nuclear magnetic resonance (NMR) analysis, infrared absorption spectrum analysis or the like. For example, the proportion (mol%) of the unit having a functional group (f) in all the units constituting the fluororesin A using a method such as infrared absorption spectrum analysis as described in JP-A-2007-314720. The content of the functional group (f) can be calculated from the ratio.

  The melting point of the fluororesin A is 100 ° C. or more and 325 ° C. or less, preferably 100 ° C. or more and less than 260 ° C., and more preferably 120 ° C. or more and 220 ° C. or less. If the melting point of the fluorine resin A is at least the lower limit value of the above range, the heat resistance of the molded article is excellent. If the melting point of the fluororesin A is equal to or less than the upper limit value of the above range, a general-purpose device can be used when producing the resin composition and the molded article.

When the fluororesin A having a relatively low melting point is used, the composition can be obtained without causing decomposition of the resin during the production process, even when using a resin having a low thermal decomposition temperature among liquid crystal polymers. Therefore, in this case, the melting point of the fluororesin A is preferably 120 ° C. or more and 220 ° C. or less, and more preferably 120 ° C. or more and 200 ° C. or less.
The melting point of the fluorine resin A can be adjusted by the type and ratio of the units constituting the fluorine resin A, the molecular weight of the fluorine resin A, and the like. For example, the melting point tends to rise as the proportion of units (u1) described later increases.

  When the liquid crystal polymer to be used has a high melting point, it is preferable that the melting point of the fluororesin A be also high. In this case, the melting point is preferably 250 to 320 ° C, more preferably 280 to 315 ° C, and still more preferably 290 to 310 ° C. The melting point can be adjusted by the kind and ratio of units constituting the fluororesin A, the molecular weight of the fluororesin A, and the like. For example, the melting point tends to rise as the proportion of units (u1) described later increases.

As the fluorine resin A, those which can be melt-molded are used from the viewpoint of the productivity of the resin composition and the molded article.
As the fluorine resin A which can be melt molded, a known melt resin which can be melt molded (tetrafluoroethylene / fluoroalkyl vinyl ether copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, ethylene / tetrafluoroethylene copolymer) And fluorine resins in which a functional group (f) is introduced into polyvinylidene fluoride, polychlorotrifluoroethylene, an ethylene / chlorotrifluoroethylene copolymer, etc.).

  As the fluororesin A, used is one having a temperature at which the melt flow rate becomes 0.1 to 1000 g / 10 min at a temperature of 20 ° C. or more higher than the melting point of the fluororesin A under the condition of a load of 49N. The melt flow rate is preferably 0.5 to 100 g / 10 minutes, more preferably 1 to 30 g / 10 minutes, still more preferably 5 to 20 g / 10 minutes. If the melt flow rate is at least the lower limit value of the above range, the moldability of the fluororesin A is excellent. If the melt flow rate is not more than the upper limit value of the above range, the mechanical properties of the molded article are excellent.

As the fluororesin A, for example, the following may be mentioned depending on the difference in the production method.
A fluorine-containing polymer having a functional group (f) derived from at least one selected from the group consisting of a monomer, a chain transfer agent and a polymerization initiator used in the production of the fluorine-containing polymer. Hereinafter, it is also referred to as fluoropolymer A1.
A fluorine resin in which a functional group (f) is introduced to a fluorine resin having no functional group (f) by surface treatment such as corona discharge treatment or plasma treatment.
The fluorine resin obtained by graft-polymerizing the monomer which has a functional group (f) to the fluorine resin which does not have a functional group (f).

As the fluorine resin A, the fluorine-containing polymer A1 is preferable from the following reason.
In the fluoropolymer A1, since the functional group (f) is present in either or both of the terminal group of the main chain and the pendant group of the main chain of the fluoropolymer A1, the compatibility with the liquid crystal polymer is Outstandingly outstanding.

When the functional group (f) in the fluoropolymer A1 is derived from the monomer used for the production of the fluoropolymer A1, the fluoropolymer A1 can be produced by the following method (i). In this case, the functional group (f) is present in a unit derived from the monomer formed by polymerizing the monomer at the time of production.
Method 1: In producing the fluoropolymer A1 by polymerizing monomers, a monomer having a functional group (f) is used.

When the functional group (f) in the fluoropolymer A1 is derived from the chain transfer agent used for the production of the fluoropolymer A1, the fluoropolymer A1 can be produced by the following method 2. In this case, the functional group (f) is present as an end group of the main chain of the fluoropolymer A1.
Method 2: In the presence of a chain transfer agent having a functional group (f), a fluoropolymer A1 is produced by polymerization of monomers.
Examples of chain transfer agents having a functional group (f) include acetic acid, acetic anhydride, methyl acetate, ethylene glycol and propylene glycol.

When the functional group (f) in the fluoropolymer A1 is derived from the polymerization initiator used for the production of the fluoropolymer A1, the fluoropolymer A1 can be produced by the following method 3. In this case, the functional group (f) is present as an end group of the main chain of the fluoropolymer A1.
Method 3: In the presence of a polymerization initiator such as a radical polymerization initiator having a functional group (f), a fluoropolymer A1 is produced by polymerization of monomers.
As a radical polymerization initiator having a functional group (f), di-n-propylperoxydicarbonate, diisopropylperoxycarbonate, tert-butylperoxyisopropylcarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, di-2 -Ethylhexyl peroxydicarbonate etc. are mentioned.

  When the functional group (f) in the fluoropolymer A1 is derived from two or more of the monomer used for producing the fluoropolymer A1, a chain transfer agent, and a polymerization initiator, the fluoropolymer A1 can be produced by using two or more of the above methods 1 to 3 in combination.

As the fluorine-containing polymer A1, the content of the functional group (f) can be easily controlled, and therefore, from the viewpoint of easily adjusting the miscibility with the liquid crystal polymer, it is possible to use a monomer produced by method (i) The fluorine-containing polymer A11 which has a functional group (f) derived from is preferable.
As a monomer having a functional group (f), a monomer having a carboxy group (maleic acid, itaconic acid, citraconic acid, undecylenic acid, etc.); a monomer having an acid anhydride group (itaconic anhydride (hereinafter referred to as , "IAH"), citraconic anhydride (hereinafter also referred to as "CAH"), 5-norbornene-2,3-dicarboxylic acid anhydride (hereinafter referred to as "NAH"), maleic anhydride etc. And monomers having a hydroxyl group and an epoxy group (hydroxybutyl vinyl ether, glycidyl vinyl ether, etc.) and the like.

As the fluorine-containing polymer A11 having a functional group (f) derived from a monomer, the following fluorine-containing polymer A11 is particularly preferable because the miscibility with the liquid crystal polymer is remarkably excellent.
A unit (u1) based on tetrafluoroethylene (hereinafter also referred to as “TFE”) or chlorotrifluoroethylene (hereinafter also referred to as “CTFE”) (hereinafter simply referred to as “unit (u1)”. Other units And the unit (u2) based on a cyclic hydrocarbon monomer having an acid anhydride group (hereinafter also referred to as "acid anhydride group-containing cyclic hydrocarbon monomer"), and a fluorine-containing group The fluorine-containing polymer (A11) which has a unit (u3) based on a monomer (however, except TFE and CTFE).
Here, the acid anhydride group of the unit (u2) corresponds to the functional group (f).

  As an acid anhydride group containing cyclic hydrocarbon monomer which constitutes a unit (u2), IAH, CAH, NAH, maleic anhydride, etc. are mentioned. The acid anhydride group-containing cyclic hydrocarbon monomer may be used alone or in combination of two or more.

The acid anhydride group-containing cyclic hydrocarbon monomer is preferably one or more selected from the group consisting of IAH, CAH and NAH. When one or more members selected from the group consisting of IAH, CAH and NAH are used, acid anhydride can be obtained without using a special polymerization method (see JP-A-11-193312) which is required when using maleic anhydride. The fluorine-containing polymer (A11) having an organic group can be easily produced.
As the acid anhydride group-containing cyclic hydrocarbon monomer, IAH or NAH is preferable from the viewpoint that the miscibility with the liquid crystal polymer is remarkably excellent.

As the fluorine-containing monomer constituting unit (u3), a fluorine-containing compound having one polymerizable carbon-carbon double bond is preferable, and, for example, fluoroolefins (vinyl fluoride, vinylidene fluoride, trifluoroethylene, Hexafluoropropylene (hereinafter also referred to as “HFP”), hexafluoroisobutylene etc. However, TFE is excluded, CF ₂ CCFOR ^f1 (where R ^f1 is a carbon number of 1 to 10 and an oxygen atom between carbon atoms) (Hereinafter, also referred to as “PAVE”), CF ₂ CCFOR ^f ₂ SO ₂ X ¹ (wherein R ^f2 is a carbon number of 1 to 10 and an oxygen atom is interposed between carbon atoms) A perfluoroalkylene group which may be contained, and X ¹ is a halogen atom or a hydroxyl group), CF ₂ CCFOR ^{f 3} CO 2 ₂ X ² (wherein R ^f3 is a perfluoroalkylene group having 1 to 10 carbon atoms and optionally containing an oxygen atom between carbon atoms, and X ² is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), CF ₂ CFCF (CF ₂ ) _p OCF = CF ₂ (where p is 1 or 2), CH ₂ CXCX ³ (CF ₂ ) _q X ⁴ (where X ³ is a hydrogen atom or a fluorine atom) And q is an integer of 2 to 10, and X ⁴ is a hydrogen atom or a fluorine atom) (hereinafter also referred to as “FAE”), a fluorine-containing monomer having a ring structure (perfluoro (2, 2 -Dimethyl-1,3-dioxole), 2,2,4-trifluoro-5-trifluoromethoxy-1,3-dioxole, perfluoro (2-methylene-4-methyl-1,3-dioxolane), etc. Are listed That.

The fluorine-containing monomer is preferably at least one selected from the group consisting of HFP, PAVE and FAE from the viewpoint of the excellent formability of the fluorine-containing polymer (A11), and one or both of FAE and HFP Is more preferred.
Examples of PAVE include CF ₂ CCFOCF ₂ CF ₃ , CF ₂ CCFOCF ₂ CF ₂ CF ₃ , CF ₂ CCFOCF ₂ CF ₂ CF ₂ CF ₃ , CF ₂ CCFO (CF ₂ ) ₆ F, etc. ₂ = CFOCF ₂ CF ₂ CF ₃ (hereinafter also referred to as “PPVE”) is preferable.

As the FAE, CH ₂ CFCF (CF ₂ ) ₂ F, CH ₂ CFCF (CF ₂ ) ₃ F, CH ₂ CFCF (CF ₂ ) ₄ F, CH ₂ CFCF (CF ₂ ) ₅ F, CH _{2 = CF (CF 2) 6 F} , CH 2 = CF (CF 2) 2 H, CH 2 = CF (CF 2) 3 H, CH 2 = CF (CF 2) 4 H, CH 2 = CF (CF 2) ₅ H, CH ₂ CFCF (CF ₂ ) ₆ H, CH ₂ CHCH (CF ₂ ) ₂ F, CH ₂ CHCH (CF ₂ ) ₃ F, CH ₂ CHCH (CF ₂ ) ₄ F, CH ₂ = _{CH (CF 2) 5 F,} CH 2 = CH (CF 2) 6 F, CH 2 = CH (CF 2) 2 H, CH 2 = CH (CF 2) 3 H, CH 2 = CH (CF 2) 4 _{H, CH 2 = CH (CF} 2) 5 H, CH 2 = CH (CF 2) 6 H , and the like .
As FAE, CH ₂ CHCH (CF ₂ ) _{q 1} X ⁴ (wherein q 1 is 2 to 6, preferably 2 to 4) is preferable, and CH ₂ CHCH (CF ₂ ) ₂ F, CH ₂ = CH (CF ₂ ) ₃ F, CH ₂ CHCH (CF ₂ ) ₄ F, CH ₂ CFCF (CF ₂ ) ₃ H, CH ₂ CFCF (CF ₂ ) ₄ H, more preferably CH ₂ 2CH ( CF ₂ ) ₄ F or CH ₂ CHCH (CF ₂ ) ₂ F is particularly preferred.

When the fluoropolymer A consists of the unit (u1), the unit (u2) and the unit (u3), the unit relative to a total of 100 mol% of the unit (u1), the unit (u2) and the unit (u3) 50-99.89 mol% is preferable, as for content of (u1), 50-99.4 mol% is more preferable, and 50-98.9 mol% is further more preferable. 0.01-5 mol% is preferable, as for content of a unit (u2), 0.1-3 mol% is more preferable, and 0.1-2 mol% is more preferable. The content of the unit (u3) is preferably 0.1 to 49.99 mol%, more preferably 0.5 to 49.9 mol%, and still more preferably 1 to 49.9 mol%.
If the ratio of each unit is in the above-mentioned range, it is excellent in heat resistance, chemical resistance, and elastic modulus at high temperature.
When the proportion of the unit (u2) is within the above range, the amount of the acid anhydride group in the fluoropolymer A becomes appropriate, and the miscibility with the liquid crystal polymer is extremely excellent.
When the proportion of the unit (u3) is within the above range, the moldability of the fluoropolymer A is excellent, and when the composition of the present invention is formed into a molded article, the flexibility is excellent.
The proportion of each unit can be calculated by melt NMR analysis, fluorine content analysis, infrared absorption spectrum analysis or the like of the fluoropolymer.

When the fluoropolymer A is composed of the unit (u1), the unit (u2) and the unit (u3), the proportion of the unit (u2) is 0.01 mol%, the acid in the fluoropolymer A The content of the anhydride group corresponds to 100 per 1 × 10 ⁶ carbon atoms of the main chain of the fluoropolymer A. The content of the acid anhydride group in the fluoropolymer A is 50000 for the main chain carbon number 1 × 10 ^{6 of the} fluoropolymer A that the proportion of the unit (u2) is 5 mol% It corresponds to being
In the fluoropolymer A, a part of the acid anhydride group in the unit (u2) is hydrolyzed, and as a result, a dicarboxylic acid corresponding to the acid anhydride group-containing cyclic hydrocarbon monomer (itaconic acid, citraconic acid) , 5-norbornene-2,3-dicarboxylic acid, maleic acid, etc.) may be included. When the unit based on the dicarboxylic acid is included, the ratio of the unit is included in the ratio of the monomer unit (u2).

The fluoropolymer A11 is, in addition to the units (u1) to (u3), a unit (u4) based on a monomer having no fluorine (but excluding the acid anhydride group-containing cyclic hydrocarbon monomer). May be included.
As the monomer having no fluorine, a compound having no fluorine having one polymerizable carbon-carbon double bond is preferable, and, for example, olefins (ethylene, propylene, 1-butene etc.), vinyl esters (vinyl acetate etc.) Etc.). The monomer which does not have a fluorine may be used individually by 1 type, and may use 2 or more types together.
As a monomer which does not have a fluorine, ethylene, propylene and 1-butene are preferable from the point which is excellent in the mechanical characteristic etc. of a molded article, and ethylene is especially preferable.

The preferable ratio of each unit when unit (u4) is ethylene is as follows.
The proportion of the unit (u1) is preferably 25 to 80 mol%, and 40 to 65 mol% of the total 100 mol% of the unit (u1), the unit (u2), the unit (u3) and the unit (u4) More preferably, 45 to 63 mol% is more preferable.
The proportion of the unit (u2) is preferably 0.01 to 5 mol% of the total 100 mol% of the unit (u1), the unit (u2), the unit (u3) and the unit (u4), and 0.03 to 3 mol% is more preferable, and 0.05 to 1 mol% is more preferable.
The proportion of the unit (u3) is preferably 0.2 to 20% by mol, out of the total 100 mol% of the unit (u1), the unit (u2), the unit (u3) and the unit (u4), and 0.5 to 0.5 15 mol% is more preferable, and 1 to 12 mol% is more preferable.
The proportion of the unit (u4) is preferably 20 to 75 mol%, more preferably 35 to 50 mol%, based on the total 100 mol% of the units (u1), (u2), (u3) and (u4) Is more preferable, and 37 to 55 mol% is more preferable.

If the ratio of each unit is within the above range, the flame retardancy, chemical resistance and the like of the molded article are remarkably excellent.
When the proportion of the unit (u2) is within the above range, the amount of the acid anhydride group in the fluoropolymer A11 becomes appropriate, and the miscibility with the liquid crystal polymer is extremely excellent.
If the proportion of the unit (u3) is within the above range, the formability of the fluoropolymer A11 is remarkably excellent.
The proportion of each unit can be calculated by melt NMR analysis, fluorine content analysis, infrared absorption spectrum analysis, etc. of the fluoropolymer A11.

Preferred specific examples of the fluoropolymer A11 include TFE / NAH / PPVE copolymer, TFE / IAH / PPVE copolymer, TFE / CAH / PPVE copolymer, TFE / IAH / HFP copolymer, TFE / CAH / HFP copolymer, TFE / IAH / CH ₂ CHCH (CF ₂ ) ₄ F / E copolymer, TFE / CAH / CH ₂ CHCH (CF ₂ ) ₄ F / E copolymer, TFE / IAH / CH ₂ CHCH (CF ₂ ) ₂ F / E copolymer, TFE / CAH / CH ₂ CHCH (CF ₂ ) ₂ F / E copolymer, TFE / IAH / HFP / CH ₂ CHCH (CF _{2) 4} ) ₄ F / E copolymer etc. are mentioned.

The fluorine resin A can be manufactured by a conventional method. When the fluororesin A is produced by polymerization of monomers, a polymerization method using a radical polymerization initiator is preferable as the polymerization method.
As a polymerization method, a bulk polymerization method, a solution polymerization method using an organic solvent (fluorohydrocarbon, chlorohydrocarbon, fluorochlorohydrocarbon, alcohol, hydrocarbon, etc.), an aqueous medium and, if necessary, an appropriate organic solvent And an emulsion polymerization method using an aqueous medium and an emulsifier, and a solution polymerization method is preferable.

The liquid crystal polymer of the present invention (hereinafter also referred to as liquid crystal polymer B) is a thermoplastic polymer that forms an anisotropic melt phase. Specifically, there is no particular limitation as long as it is a thermoplastic liquid crystalline polyester or polyesteramide, and is generally called a thermotropic liquid crystalline polyester or a thermotropic liquid crystalline polyester amide. In addition, it may be a polymer in which an imide bond, a carbonate bond, an isocyanate-derived bond such as a carbodiimide bond or a carbodiimide bond, or the like is further introduced into the aromatic polyester or the aromatic polyester amide. In particular, thermoplastic liquid crystalline polyester is preferred.
The anisotropic molten phase can be confirmed, for example, by placing the sample on a hot stage, heating by heating in a nitrogen atmosphere, and observing the transmitted light of the sample. 280-360 degreeC is preferable and, as for melting | fusing point of a thermoplastic liquid crystal polymer, 290-350 degreeC is more preferable.
Examples of liquid crystal polymers available on the market include “Laperos” made by Polyplastics, “Vektra” made by Celanese, “UENOLCP” made by Ueno Pharmaceutical, “Sumika Super LCP” made by Sumitomo Chemical, “XYDAR made by SOLVAY SPECIALTY POLYMERS” And “Xyder” manufactured by JX Nippon Mining & Energy Co., Ltd., “Cyberasu” manufactured by Toray Industries, Inc., and the like.

  The content of the fluororesin A in the resin composition of the present invention is not particularly limited, and is appropriately selected according to the required performance of the intended application. If the amount of the fluorine resin A added is too small, the effect of improving the low relative dielectric constant and impact strength will be small, so preferably 10% by volume of the fluorine resin A with respect to the total of the fluorine resin A and the liquid crystal polymer B The above amount is more preferably 20% by volume or more.

  50 mass% or more is preferable with respect to the resin composition of this invention, and, as for the total amount of fluororesin A and liquid crystal polymer B in the resin composition of this invention, 70 mass% or more is more preferable.

  Examples of other components contained in the resin composition of the present invention include inorganic fillers, organic fillers, organic pigments, metal soaps, surfactants, UV absorbers, lubricants, silane coupling agents, organic compounds (for example, organic monomers, Organic oligomers having a degree of polymerization of 50 or less, etc.) and the like are mentioned, and inorganic fillers are preferred.

  As the inorganic filler, silica, clay, talc, calcium carbonate, mica, diatomaceous earth, alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, calcium oxide, calcium hydroxide, magnesium hydroxide, water Aluminum oxide, basic magnesium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawsonite, hydrotalcite, calcium sulfate, barium sulfate, calcium silicate, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, glass Beads, silica-based balloons, carbon black, carbon nanotubes, carbon nanohorns, graphite, carbon fibers, glass balloons, carbon burns, wood flour, zinc borate and the like can be mentioned. An inorganic filler may be used individually by 1 type, and may use 2 or more types together.

The inorganic filler may be subjected to surface treatment with a surface treatment agent such as a silane coupling agent or a titanate coupling agent from the viewpoint of improving the dispersibility in the resin.
When the inorganic filler is contained, the content of the inorganic filler is preferably 0.1 to 100 parts by mass, and more preferably 0.1 to 60 parts by mass with respect to a total of 100 parts by mass of the fluororesin A and the liquid crystal polymer B.

Examples of the organic filler include aromatic polyamide fiber, polyaramid fiber, polyparaphenylene benzoxazole (PBO) fiber, polyphenylene sulfide fiber, polyester fiber, acrylic fiber, nylon fiber, polyethylene fiber and the like.
With respect to the other additives, any ratio can be added as long as the properties of the molded article of the present invention are not impaired.

  The method for producing the resin composition of the present invention is not particularly limited, and a wide variety of known methods for producing a thermoplastic resin composition can be adopted. Specifically, each component is mixed in advance using various mixers such as tumblers and Henschel mixers, and then melt-kneaded using a Banbury mixer, rolls, Brabender, single-screw kneading extruder, twin-screw kneading extruder, kneader, etc. The resin composition can be manufactured by carrying out.

Also, for example, a resin used for the three-dimensional circuit component of the present invention, without mixing each component in advance, or mixing only a part of components in advance, supplying it to an extruder using a feeder, and melt kneading it. Compositions can also be made.
Furthermore, for example, a resin composition obtained by mixing some components in advance and supplying them to an extruder for melt-kneading is used as a masterbatch, and this masterbatch is mixed with the remaining components again and melt-kneaded. Can also be manufactured.

The molded article of the present invention is obtained by molding the resin composition of the present invention. As a molding method, an injection molding method, an extrusion molding method, a cutting process, a thermoforming method, a lamination molding, etc. can be used.
As the injection molding method, general injection molding method, high speed injection, multicolor molding, coinjection, injection compression molding, gas assisted injection molding, foam injection molding (MUCELL), heat and cool molding using a rapid heating mold , Insert molding, in-mold decoration, etc. can be selected.
As the extrusion molding, film sheet molding using a T-die, tube molding using a circular die, profile extrusion molding, melt spinning, and blow molding for hollow part molding can be used.
It can also be formed as a multi-layer molding of two or more layers as a form, or a multi-layer fiber of core-sheath structure.
It can also be shaped by thermoforming a single layer or multilayer sheet obtained by the T-die method.
The molded article of the present invention can also be produced by the additive manufacturing method. The additive manufacturing method is not particularly limited, and methods widely used in molding methods generally called 3D printing and additive manufacturing can be applied.

  There is no limitation in particular as a use of the molded article of this invention. For example, electrical and electronic parts such as connectors, sockets, relay parts, coil bobbins, optical pickups, oscillators, printed wiring boards, computer related parts, etc .; semiconductor manufacturing process related parts such as IC trays and wafer carriers, VTR, television, iron, Household electric appliance parts such as air conditioners, stereos, vacuum cleaners, refrigerators, rice cookers, lighting fixtures, lighting fixtures parts such as lamp reflectors and lamp holders, acoustic products parts such as compact discs and speakers, ferrules for optical cables, telephone parts, facsimiles Parts, communication equipment parts such as modems, separation claws, copying machine related parts such as heater holder, impellers, fans, gears, gears, bearings, mechanical parts such as motor parts and cases, mechanical parts for automobiles, engine parts, engine room Internal parts, electrical parts, interior parts Automotive parts, microwave cooking pots, cooking utensils such as heat resistant dishes, floor materials, heat insulation such as wall materials, soundproofing materials, supporting materials such as beams and columns, building materials such as roofing materials or civil engineering Materials, aircraft, spacecraft, parts for space equipment, radiation facility members such as nuclear reactors, marine facilities members, cleaning jigs, optical equipment parts, valves, pipes, nozzles, filters, membranes, for medical use It can be used in a wide range of applications such as equipment parts and medical materials, sensor parts, and sanitary accessories.

Furthermore, applications such as sliding members, seals, gears, actuators, pistons, bearings, housings, tubes for fuel, bushes, tubes, hoses, tanks, seals, wires, cables, films, sheets, bottles, fibers, etc. can be mentioned. .
As a tube, a hose, a tank, a seal, and a wire, those described in paragraphs [0041] to [0043] of WO 2015/182702 can be mentioned. Moreover, as a tube and a hose, the tube for energy resource excavations, such as oil, natural gas, and shale oil, is mentioned. A wire coating material such as a wire or cable is preferably used as an insulation coating of a wire for motor coil or a flat copper wire, particularly a flat conductor used for a motor for driving a hybrid vehicle (HEV) or an electric vehicle (EV) In that case, it is preferable to carry out insulation coating with a film. Other applications include downhole cables for drilling energy resources such as oil, natural gas and shale oil.

  Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto.

(Evaluation of surface condition (strand appearance))
The surface of the strand-like resin material obtained after melt-kneading of the following Example 1 etc. was visually observed, and the presence or absence of the surface roughening by aggregation of the additive was confirmed. Those with no surface roughening due to the aggregation of additives on the surface were "A", those with slight roughening were "B", and those with overall roughening were "C".
(Izod impact strength)
The press sheet was cut using a contour machine (manufactured by Amada Co., Ltd., V-400) to obtain a sample having a height of 63 mm, a width of 13 mm, and a thickness of 2.8 mm. A notch was inserted at a height of 32 mm of the sample to obtain a test piece.
About the test piece, hammer capacity: 2.75 J, hammer weight: 13.97 N, distance from axis to center of gravity: 10.54 cm, distance from axis to striking point using Izod tester (made by Toyo Seiki Co., Ltd.) : Izod impact strength was measured under the condition of 33.5 cm.

Fluorinated polymer A-1: Type of functional group (f): content of carbonyl group-containing group, functional group (f): 1000 to main chain carbon number 1 × 10 ^{6 of the} fluorine-containing polymer A-1 Pieces, specific gravity: 2.15, melting point: 300 ° C., melt flow rate (372 ° C., load 49 N): 22 g / 10 min). The resin was prepared as in Example 5 of WO 2015/182702, and the TFE / NAH / PPVE molar ratio was 97.9 / 0.1 / 2.
Fluorinated polymer A-2: Type of functional group (f): content of carbonyl group-containing group, functional group (f): 3000 to main chain carbon number 1 × 10 ^{6 of} fluoropolymer A-2 Melting point: 240 ° C., melt flow rate (297 ° C., load 49 N): 18.5 g / 10 min). The resin, [0080] [0081] and prepared in the same manner, the molar ratio of _{TFE / IAH / CH 2 = CH} (CF 2) 2 F / E of JP is 58.5 / 2.0 / 0. It was 3 / 39.1.
Liquid crystal polymer B-1: Vectra S135 (melting point 355 ° C.) manufactured by Celanese
Liquid crystal polymer B-2: Vectra A130 manufactured by Celanese (melting point 280 ° C.)
PTFE powder: FLUON L169J manufactured by Asahi Glass Co., Ltd.

Examples 1-4:
Dry blend the fluoropolymer A-1 and the liquid crystal polymer B-1 in the proportions shown in Table 1 and place them in a twin screw extruder (manufactured by Technobel, KZW15TW-45MG), resin discharge amount: 2.0 kg / hour The resin material was obtained by melt-kneading under the conditions of screw rotation speed: 200 rpm and setting resin temperature: 370 ° C. The obtained resin material was press-molded with a melt heat press manufactured by Tester Sangyo Co., Ltd. to obtain a 2.8 mm thick sheet. The pressing conditions were a processing temperature of 370 ° C., a preheating of 10 minutes, a pressure of 10 MPa, and a pressing time of 3 minutes. The Izod impact strength was measured using the obtained sheet. The results are shown in Table 1. In Table 1, the proportions of the fluoropolymer A-1 and the liquid crystal polymer B-1 are respectively% by volume with respect to the total of the fluoropolymer A-1 and the liquid crystal polymer B-1.

Examples 5-8:
Preparation Method of Composition The fluoropolymer A-2 and the liquid crystal polymer B-2 were dry-blended at a ratio shown in Table 2 and charged into a twin-screw extruder (manufactured by Technobel, KZW15TW-45MG), and the resin discharge amount: It melt-kneaded on the conditions of 2.0 kg / hour, screw rotation speed: 200 rpm, and setting resin temperature: 300 degreeC, and obtained the resin material. The obtained resin material was press-molded with a melt heat press manufactured by Tester Sangyo Co., Ltd. to obtain a 2.8 mm thick sheet. The pressing conditions were a processing temperature of 300 ° C., preheating of 10 minutes, a pressure of 10 MPa, and a pressing time of 3 minutes. The Izod impact strength was measured using the obtained sheet. The results are shown in Table 2. In Table 2, the proportions of the fluoropolymer A-2 and the liquid crystal polymer B-2 are respectively% by volume with respect to the total of the fluoropolymer A-2 and the liquid crystal polymer B-2.

Comparative Examples 1-2:
A sheet was produced in the same manner as in Example 1 except that PTFE was used instead of the fluoropolymer A-1, and the Izod impact strength was measured. The results are shown in Table 1.

Claims (7)

  Melt-moldable fluororesin having a melting point of 100 ° C. or more and 325 ° C. or less and having at least one functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group and an isocyanate group Resin composition.   The resin composition according to claim 1, wherein the functional group is an acid anhydride group.   The resin composition of Claim 1 or 2 whose content of the said fluororesin with respect to the sum total of the said fluororesin and the said liquid crystal polymer is 1 to 45 volume%.   The resin composition according to any one of claims 1 to 3, further comprising at least one selected from the group consisting of an inorganic filler and an organic filler.   The molded article formed by shape | molding the resin composition as described in any one of Claims 1-4.   The molded article according to claim 5, wherein the molded article is a connector.   The manufacturing method of the molded article characterized by shape | molding the resin composition as described in any one of Claims 1-4 by either extrusion molding, injection molding, cutting, thermoforming, or lamination molding.