WO2017110646A1 - Composition de résine cristalline - liquide et article moulé par insertion - Google Patents

Composition de résine cristalline - liquide et article moulé par insertion Download PDF

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WO2017110646A1
WO2017110646A1 PCT/JP2016/087373 JP2016087373W WO2017110646A1 WO 2017110646 A1 WO2017110646 A1 WO 2017110646A1 JP 2016087373 W JP2016087373 W JP 2016087373W WO 2017110646 A1 WO2017110646 A1 WO 2017110646A1
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resin composition
resin
liquid crystalline
mass
crystalline resin
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PCT/JP2016/087373
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English (en)
Japanese (ja)
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大輔 依藤
愛 石附
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ポリプラスチックス株式会社
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Priority to JP2017531640A priority Critical patent/JP6225297B1/ja
Priority to KR1020187018627A priority patent/KR101915731B1/ko
Priority to CN201680075983.2A priority patent/CN108431138B/zh
Publication of WO2017110646A1 publication Critical patent/WO2017110646A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

  • the present invention relates to a liquid crystalline resin composition and an insert molded product.
  • Liquid crystalline resins represented by liquid crystalline polyester resins are widely used in the field of small connectors because they are excellent in high fluidity, low burr properties, reflow resistance, and the like.
  • the liquid crystalline resin is excellent in water vapor permeability, it is expected to be applied to the semiconductor package field.
  • liquid crystalline resin does not provide sufficient adhesion to metal, in the case of insert molded products molded integrally with metal by injection molding, the airtightness at the interface between the resin and metal is low. There is. Therefore, the liquid crystalline resin is in a situation where it is difficult to apply it to an insert molded product that requires waterproofness. Also, if the air tightness at the interface between the resin and the metal is low, the flux in the solder tends to rise to the terminal part when the insert molded product is reflowed. It is also difficult to apply it to insert molded products that require climbability.
  • Patent Document 1 contains 0.5 to 30 parts by mass of a non-liquid crystalline resin with respect to 100 parts by mass of the liquid crystalline resin.
  • a liquid crystalline resin composition for molded articles has been proposed.
  • Patent Document 2 proposes a waterproof connector formed of an electrically insulating synthetic resin in which a liquid crystal polyester resin and a polyphenylene sulfide resin are mixed.
  • Patent Document 3 proposes a thermoplastic resin composition comprising 40 to 90% by weight of polyphenylene sulfide, 5 to 50% by weight of liquid crystalline polyester, and 1 to 20% by weight of elastomer. JP 2003-268241 A JP 2013-118174 A JP 2013-227366 A
  • An object of the present invention is to provide a liquid crystalline resin composition capable of obtaining an insert molded article having excellent airtightness, and an insert molded article having a resin member made of the liquid crystalline resin composition.
  • the inventor In the course of researching a resin composition that can improve the adhesion with an insert member formed of metal or the like and obtain an insert molded product having excellent airtightness, the inventor Increase the affinity of the interface, reduce the difference between the linear thermal expansion coefficient of the resin composition and the linear thermal expansion coefficient of the insert member, and enter the fine irregularities on the surface of the insert member during injection molding. It has been found that the three elements of improving the uneven transferability (hereinafter also simply referred to as “uneven transfer”), which is the performance of reproducing the above, are important. However, when the main component of the resin composition is a liquid crystalline resin, it has been difficult to improve the uneven transferability.
  • the liquid crystalline resin composition has anisotropy, the difference between the shrinkage rate in the direction perpendicular to the flow direction of the resin and the shrinkage rate in the flow direction of the resin (hereinafter simply referred to as “shrinkage”) when injection molded. Also called “rate anisotropy”), and as a result, the hermeticity of the insert molded product tended to be low.
  • the present inventor has further advanced research, and the thermoplastic resin having a specific glass transition temperature and a plate having a specific particle size and aspect ratio are included in the liquid crystalline resin. As a result of adding the filler, it is possible to improve the uneven transferability of the resin composition and reduce the anisotropy of the shrinkage rate, thereby completing the present invention. It was.
  • the liquid crystalline resin composition according to the present invention is a plate having a liquid crystalline resin, a thermoplastic resin having a glass transition temperature Tg of less than 230 ° C., an average particle size of 15 ⁇ m to 100 ⁇ m, and an aspect ratio of 10 or more.
  • a filler, and the content of the liquid crystalline resin is 40% by mass or more and 65% by mass or less in the total resin composition, and the content of the thermoplastic resin is 12% by mass or more and 35% by mass in the total resin composition.
  • the content of the plate-like filler is 10% by mass or more and 35% by mass or less in the total resin composition.
  • thermoplastic resin is preferably one or more selected from polyarylene sulfide resins, polyphenylene ether resins, and cyclic olefin resins.
  • the difference between the shrinkage rate in the direction perpendicular to the flow direction and the shrinkage rate in the flow direction of the resin may be 0.51% or less.
  • an epoxy group-containing copolymer is further contained in an amount of 6% by mass or less in the entire resin composition. Furthermore, it is preferable to contain 12% by mass or less of a fibrous filler in the total resin composition.
  • the insert molded product according to the present invention is characterized by having a resin member made of the liquid crystalline resin composition described above and an insert member made of a metal, an alloy, or an inorganic solid material.
  • liquid crystalline resin composition capable of obtaining an insert molded article having excellent airtightness, and an insert molded article having a resin member made of the liquid crystalline resin composition.
  • a liquid crystalline resin composition (hereinafter simply referred to as “resin composition”) includes a liquid crystalline resin, a thermoplastic resin having a glass transition temperature Tg of less than 230 ° C., an average particle size of 15 ⁇ m to 100 ⁇ m, and an aspect ratio. And a plate-like filler having a ratio of 10 or more. Since the resin composition contains a liquid crystalline resin, a resin composition excellent in fluidity, low burr property, reflow resistance and water vapor permeability can be obtained.
  • the resin composition contains the thermoplastic resin and the plate-like filler that satisfy the above-mentioned predetermined conditions, the uneven transferability of the resin composition can be improved and the anisotropy of the shrinkage rate is reduced. be able to. As a result, it can be set as the resin composition which can obtain the insert molding goods which are equipped with the outstanding performance of liquid crystalline resin, and have high airtightness. Moreover, as shown in the Example mentioned later, the insert molded product using this resin composition can prevent that airtightness falls after a reflow process.
  • the liquid crystalline resin refers to a melt processable polymer having a property capable of forming an optically anisotropic molten phase.
  • the property of the anisotropic molten phase can be confirmed by a conventional polarization inspection method using an orthogonal polarizer. More specifically, the anisotropic molten phase can be confirmed by using a Leitz polarizing microscope and observing a molten sample placed on a Leitz hot stage under a nitrogen atmosphere at a magnification of 40 times.
  • the liquid crystalline resin is inspected between crossed polarizers, the polarized light is normally transmitted even in a molten stationary state, and optically anisotropic.
  • the liquid crystalline resin is not particularly limited, but is preferably an aromatic polyester or an aromatic polyester amide. Further, it is also possible to use a polyester partially containing an aromatic polyester or an aromatic polyester amide in the same molecular chain.
  • the aromatic polyester or aromatic polyester amide is particularly preferably an aromatic polyester having at least one compound selected from the group of aromatic hydroxycarboxylic acids, aromatic hydroxyamines, and aromatic diamines as a constituent component, or Aromatic polyester amide.
  • the liquid crystalline resin may be a mixture of two or more liquid crystalline resins selected from the above.
  • specific compounds (monomers) constituting the liquid crystalline resin include aromatic hydroxycarboxylic acids such as p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, 2,6-dihydroxynaphthalene, 1, Aromatic diols such as 4-dihydroxynaphthalene, 4,4′-dihydroxybiphenyl, hydroquinone, resorcin, a compound represented by the following general formula (I), and a compound represented by the following general formula (II); terephthalic acid, Aromatic dicarboxylic acids such as isophthalic acid, 4,4′-diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and compounds represented by the following general formula (III); p-aminophenol, p-phenylenediamine, etc.
  • aromatic hydroxycarboxylic acids such as p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, 2,6-dihydroxyna
  • Aromatic amines can be mentioned.
  • X is a group selected from alkylene (C 1 -C 4 ), alkylidene, —O—, —SO—, —SO 2 —, —S—, and —CO—.
  • the method for preparing the liquid crystalline resin is not particularly limited, and can be adjusted by a known method using a direct polymerization method or a transesterification method using the above-described monomer compound (or a mixture of monomers). For example, a melt polymerization method or a slurry polymerization method is used. In the case of a compound having an ester forming ability, it may be used for polymerization as it is, or a compound modified from a precursor to a derivative having an ester forming ability may be used in the previous stage of polymerization. In the polymerization, various catalysts can be used.
  • catalysts that can be used include dialkyl tin oxides, diaryl tin oxides, titanium dioxide, alkoxy titanium silicates, titanium alcoholates, alkali and alkaline earth metal salts of carboxylic acids, Lewis such as BF 3 .
  • An acid salt etc. can be mentioned.
  • the amount of the catalyst used is generally about 0.001 to 1% by mass, particularly about 0.01 to 0.2% by mass, based on the total weight of the monomers. If necessary, the polymer produced by these polymerization methods can be increased in molecular weight by solid-phase polymerization by heating in reduced pressure or in an inert gas.
  • the content of the liquid crystalline resin is 40% by mass or more and 65% by mass or less in the total resin composition.
  • the content of the liquid crystalline resin is more preferably 42% by mass or more and 62% by mass or less.
  • the lower limit value of the content of the liquid crystalline resin can be 45% by mass or more, and the upper limit value can be 60% by mass or less.
  • the melt viscosity of the liquid crystalline resin is not particularly limited, and the melt viscosity measured at a cylinder temperature 10 to 30 ° C. higher than the melting point of the liquid crystalline resin and a shear rate of 1000 sec ⁇ 1 is 5 Pa ⁇ s to 100 Pa ⁇ s. More preferably, it is 10 Pa ⁇ s or more and 50 Pa ⁇ s or less.
  • “Cylinder temperature 10-30 ° C. higher than the melting point of the liquid crystalline resin” means the cylinder temperature at which the liquid crystalline resin can be melted to such an extent that the melt viscosity can be measured. Whether the cylinder temperature is high depends on the type of liquid crystalline resin in the range of 10 to 30 ° C.
  • Japanese Patent Application Laid-Open No. 2010-3661 discloses as liquid crystal polymer 1 2 mol% of a structural unit introduced from 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid.
  • a liquid crystalline resin having 48 mol% of structural units introduced from an acid, 25 mol% of structural units introduced from terephthalic acid, and 25 mol% of a structural unit introduced from 4,4′-dihydroxybiphenyl is disclosed.
  • the melting point is 352 ° C., and the melt viscosity is measured at a cylinder temperature of 380 ° C.
  • liquid crystalline polymer 2 a constitutional unit introduced from 4-hydroxybenzoic acid, 50 mol%, a constitutional unit introduced from 6-hydroxy-2-naphthoic acid, 2.5 mol%, a constitution introduced from terephthalic acid.
  • a liquid crystalline resin having 23.9 mol% of units, 18.6 mol% of structural units introduced from 4,4′-dihydroxybiphenyl, and 5 mol% of structural units introduced from 4-acetamidophenol is disclosed.
  • the melting point is 367 ° C., and the melt viscosity is measured at a cylinder temperature of 380 ° C.
  • liquid crystalline polymer 3 a structural unit introduced from 4-hydroxybenzoic acid is 60 mol%, a structural unit introduced from 6-hydroxy-2-naphthoic acid is 5 mol%, and a structural unit 17 introduced from terephthalic acid.
  • a liquid crystalline resin having 0.7 mol%, 112.3 mol% of structural units introduced from 4,4′-dihydroxybiphenyl, and 5 mol% of structural units introduced from 4-acetamidophenol.
  • the melting point is 335 ° C., and the melt viscosity is measured at a cylinder temperature of 350 ° C.
  • thermoplastic resin The resin composition contains a thermoplastic resin having a glass transition temperature Tg of less than 230 ° C. (hereinafter also simply referred to as “thermoplastic resin”). According to the research of the present inventors, it has been found that the uneven transferability of the resin composition can be improved when a thermoplastic resin having a glass transition temperature Tg of less than 230 ° C. is added to the liquid crystalline resin. As a result, as shown in the examples described later, the hermeticity of the insert-molded product can be increased, and it is possible to prevent the hermeticity from being lowered after the reflow treatment of the molded product.
  • the glass transition temperature Tg refers to a value measured under a temperature rising rate of 10 ° C./min by the DSC method (method described in JIS K7121).
  • the lower limit value of the glass transition temperature Tg is not particularly limited, and can be 60 ° C. or higher or 80 ° C. or higher.
  • the upper limit value of the glass transition temperature Tg may be 220 ° C. or lower.
  • thermoplastic resin having a glass transition temperature Tg of less than 230 ° C. examples include polyarylene sulfide resin (PAS); polyphenylene ether resin (PPE); cyclic olefin resin; polycarbonate resin (PC); polyethylene resin (PE); (PP); Polyacetal resin (POM); Polyamide resin such as polyamide 6, polyamide 66 or polyamide 46 (PA); Polyester resin such as polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), modified polyethylene terephthalate (PET) Polyether ether ketone resin (PEEK); polystyrene resin (PS); polyvinyl chloride resin (PVC); acrylonitrile-styrene copolymer resin (AS); polymethyl methacrylate resin (P) MA); acrylonitrile - butadiene - styrene copolymer resin (ABS); polyarylate resin (PAR); can be exemplified and polyether sulf
  • the polyarylene sulfide resin is composed mainly of — (Ar—S) — (where “Ar” represents an arylene group) as a repeating unit, and is a generally known molecule.
  • a PAS resin of structure can be used.
  • the arylene group is not particularly limited.
  • arylene sulfide groups composed of such arylene groups in addition to a homopolymer using the same repeating unit, depending on the application, a copolymer containing a repetition of different arylene sulfide groups may be used.
  • the homopolymer is preferably a homopolymer having a p-phenylene sulfide group as a repeating unit as the arylene group, depending on the application.
  • a homopolymer having a p-phenylene sulfide group as a repeating unit has extremely high heat resistance, and exhibits high strength, high rigidity, and high dimensional stability in a wide temperature range. By using such a homopolymer, a molded product having very excellent physical properties can be obtained.
  • a combination of two or more types of arylene sulfide groups that are different from the above-mentioned arylene sulfide groups containing an arylene group can be used.
  • a combination containing a p-phenylene sulfide group and an m-phenylene sulfide group is preferable in that a molded product having high physical properties such as heat resistance, moldability, and mechanical properties can be obtained.
  • a polymer containing a p-phenylene sulfide group in a proportion of 70 mol% or more is more preferable, and a polymer containing a proportion of 80 mol% or more is more preferable.
  • the polyarylene sulfide resin having a phenylene sulfide group is a polyphenylene sulfide resin.
  • a polyarylene sulfide resin produced by a general polymerization method is usually washed several times with water or acetone and then washed with acetic acid, ammonium chloride or the like in order to remove by-product impurities and the like.
  • the end of the polyarylene sulfide resin contains a carboxyl end group in a predetermined amount.
  • polyphenylene ether resin examples include modified polyphenylene ether in addition to polyphenylene ether.
  • cyclic olefin resin examples include a cyclic olefin polymer (COP) and a cyclic olefin copolymer (COC).
  • the content of the thermoplastic resin is 12% by mass or more and 35% by mass or less in the total resin composition. In a state where the content of the thermoplastic resin is 12% by mass or more and 35% by mass or less in the total resin composition, while maintaining properties such as high fluidity and keeping the anisotropy of the shrinkage ratio small, The unevenness transferability can be improved.
  • the content of the thermoplastic resin is preferably 15% by mass or more and 30% by mass or less.
  • the weight average molecular weight (Mw) of the thermoplastic resin is not particularly limited, and is preferably 15000 or more and 40000 or less. By setting the thermoplastic weight average molecular weight within this range, a resin composition having a more excellent balance between mechanical properties and fluidity can be obtained.
  • the weight average molecular weight of the thermoplastic resin is more preferably 20000 or more and 38000 or less.
  • the resin composition contains a plate-like filler.
  • the plate-like filler has an average particle size of 15 ⁇ m or more and 100 ⁇ m or less and an aspect ratio of 10 or more.
  • the anisotropy of the shrinkage rate at the time of injection molding can be reduced.
  • the hermeticity of the insert-molded product can be increased, and it is possible to prevent the hermeticity from being lowered after the reflow treatment of the molded product.
  • the average particle diameter is preferably 20 ⁇ m or more and 50 ⁇ m or less.
  • the aspect ratio is preferably 35 or more, and more preferably 35 or more and 55 or less. This definition relates to the shape of the plate-like filler before the plate-like filler is blended into the resin composition.
  • the average particle diameter is a value measured by a laser diffraction / scattering particle size distribution measuring method, and is an integrated particle diameter of 50% in a volume-based particle size distribution.
  • the average aspect ratio is a value obtained by measuring the length and thickness of several tens of fillers by electron microscope (SEM) observation, calculating the aspect ratio, and calculating the average value.
  • the plate-like filler examples include mica, talc, glass flake, graphite, various metal foils (for example, aluminum foil, iron foil, copper foil) and the like. Two or more kinds can be used. Among these, mica is preferable from the viewpoint of easily reducing the difference between the shrinkage rate in the flow direction of the resin and the shrinkage rate in the direction perpendicular to the flow direction of the resin.
  • the content of the plate-like filler is 10% by mass or more and 35% by mass or less in the total resin composition.
  • the resin composition preferably further contains an epoxy group-containing copolymer.
  • an epoxy group-containing copolymer By containing the epoxy group-containing copolymer, the affinity of the interface with the insert member can be increased.
  • the epoxy group-containing copolymer is not particularly limited, and examples thereof include at least one selected from the group consisting of an epoxy group-containing olefin copolymer and an epoxy group-containing styrene copolymer.
  • the epoxy group-containing copolymer can be used alone or in combination of two or more selected from the above.
  • Examples of the epoxy group-containing olefin copolymer include a copolymer composed of a repeating unit derived from an ⁇ -olefin and a repeating unit derived from a glycidyl ester of an ⁇ , ⁇ -unsaturated acid.
  • the ⁇ -olefin is not particularly limited and includes, for example, ethylene, propylene, butene, etc. Among them, ethylene is preferably used.
  • the glycidyl ester of ⁇ , ⁇ -unsaturated acid is represented by the following general formula (IV).
  • R ′ represents hydrogen or an alkyl group having 1 to 10 carbon atoms.
  • the glycidyl ester of ⁇ , ⁇ -unsaturated acid is, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, etc., and glycidyl methacrylate is particularly preferable.
  • the content of the repeating unit derived from ⁇ -olefin is 87 to 98% by mass, and the content of the repeating unit derived from the glycidyl ester of ⁇ , ⁇ -unsaturated acid is 13 to 2% by mass is preferable.
  • the epoxy group-containing olefin-based copolymer is an olefin-based copolymer such as acrylonitrile, acrylic acid ester, methacrylic acid ester, ⁇ -methylstyrene, maleic anhydride, etc. as a third component in addition to the above two components within the scope of the present invention.
  • You may contain 0-48 mass parts of repeating units derived from 1 type, or 2 or more types chosen from unsaturated ester with respect to 100 mass parts of said 2 components.
  • the epoxy group-containing olefin copolymer can be easily prepared by a normal radical polymerization method using a monomer corresponding to each component and a radical polymerization catalyst. More specifically, the presence of a suitable solvent or chain transfer agent is usually obtained by mixing ⁇ -olefin and glycidyl ester of ⁇ , ⁇ -unsaturated acid in the presence of a radical generator at 500 to 4000 atm and 100 to 300 ° C. It can be produced by a method of copolymerization under or in the absence.
  • It can also be produced by a method in which an ⁇ -olefin, a glycidyl ester of ⁇ , ⁇ -unsaturated acid and a radical generator are mixed and melt graft copolymerized in an extruder.
  • Examples of the epoxy group-containing styrene-based copolymer include a copolymer composed of a repeating unit derived from styrene and a repeating unit derived from a glycidyl ester of an ⁇ , ⁇ -unsaturated acid. Since the glycidyl ester of ⁇ , ⁇ -unsaturated acid is the same as that described for the epoxy group-containing olefin copolymer, description thereof is omitted.
  • Examples of styrenes include styrene, ⁇ -methylstyrene, brominated styrene, divinylbenzene and the like, and styrene is preferably used.
  • the epoxy group-containing styrenic copolymer may be a multi-component copolymer containing a repeating unit derived from one or more of the other vinyl monomers as the third component in addition to the two components.
  • Suitable as the third component is a repeating unit derived from one or more olefinic unsaturated esters such as acrylonitrile, acrylic acid ester, methacrylic acid ester, and maleic anhydride.
  • An epoxy group-containing styrene copolymer containing 40% by mass or less of these repeating units in the copolymer is preferred.
  • the content of the repeating unit derived from the glycidyl ester of ⁇ , ⁇ -unsaturated acid is 2 to 20% by mass, and the content of the repeating unit derived from styrene is from 80 to It is preferable that it is 98 mass%.
  • the epoxy group-containing styrenic copolymer can be prepared by a normal radical polymerization method using a monomer corresponding to each component and a radical polymerization catalyst. More specifically, styrenes and glycidyl esters of ⁇ , ⁇ -unsaturated acids are usually present in the presence of a radical generator at 500 to 4000 atm and 100 to 300 ° C. in the presence of a suitable solvent or chain transfer agent. Or it can manufacture by the method of copolymerizing in absence.
  • It can also be produced by a method in which styrenes, an ⁇ , ⁇ -unsaturated glycidyl ester and a radical generator are mixed and subjected to melt graft copolymerization in an extruder.
  • the epoxy group-containing copolymer is preferably an epoxy group-containing olefin copolymer from the viewpoint of heat resistance.
  • the epoxy group-containing olefin copolymer and the epoxy group-containing styrene copolymer are used in combination, the ratio of these components can be appropriately selected according to the required characteristics.
  • the content of the epoxy group-containing copolymer is 6% by mass or less in the total resin composition because the combustibility is deteriorated.
  • the lower limit of the content of the epoxy group-containing copolymer is not particularly limited, and can be, for example, 0.01% by mass, 0.1% by mass or more, or 1% by mass or more in the total resin composition.
  • the resin composition further contains a fibrous filler.
  • a fibrous filler By containing a fibrous filler, mechanical strength can be improved.
  • the fibrous filler means one having an average ratio of different diameter ratios of 1 or more and 4 or less and an aspect ratio of 2 or more and 1500 or less. This definition relates to the shape of the fibrous filler before the fibrous filler is incorporated into the resin composition.
  • the fibrous filler those conventionally used as fillers or reinforcing agents in various resin compositions can be used without particular limitation.
  • Specific examples of the fibrous filler include glass fiber, milled glass fiber, asbestos fiber, carbon fiber, silica fiber, silica / alumina fiber, alumina fiber, zirconia fiber, boron nitride fiber, boron fiber, potassium titanate fiber, wall
  • examples thereof include inorganic fiber materials such as silicate fibers such as lastite, magnesium sulfate fibers, aluminum borate fibers, and metal fibers such as stainless steel, aluminum, titanium, copper, and brass.
  • These fibrous fillers can be used in combination of two or more.
  • glass fiber is preferable.
  • the glass fiber one having a circular or substantially circular cross section is usually used, but a glass fiber having a so-called irregular cross section can also be used.
  • the shape of the irregular cross section is not limited to these, but includes polygons such as rectangles and rhombuses, ellipses, eyebrows, and the like.
  • the resin composition can contain other additives for imparting desired physical properties as long as the effects of the present invention are not impaired.
  • other additives include nucleating agents, carbon black, pigments, antioxidants, stabilizers, plasticizers, lubricants, mold release agents, and flame retardants.
  • the content of other additives can be appropriately adjusted according to desired physical properties.
  • the resin composition is obtained by injection molding of a molded product of 80 mm ⁇ 80 mm ⁇ 2 mm under the conditions of a cylinder temperature 10 to 30 ° C. higher than the melting point of the liquid crystalline resin, a mold temperature 150 ° C. and a holding pressure 50 MPa.
  • the difference between the shrinkage rate in the direction perpendicular to the flow direction of the resin and the shrinkage rate in the flow direction of the resin is preferably 0.51% or less.
  • Resin portion when insert molded product is manufactured by injection molding by reducing the difference between shrinkage in the direction perpendicular to the resin flow direction and shrinkage in the resin flow direction to 0.51% or less It is possible to reduce the solidification shrinkage.
  • the “cylinder temperature higher by 10 to 30 ° C. than the melting point of the liquid crystalline resin” here is as described above, and is not described here.
  • the actual molding is used.
  • the shrinkage that occurs between the insert member and the resin member varies depending on the shape, but is less affected by either the shrinkage rate in the resin flow direction or the shrinkage rate in the direction perpendicular to the flow, both This is because it is estimated that it is necessary to consider both of them because they are affected by the shrinkage rate.
  • the melt viscosity of the resin composition is preferably 5 Pa ⁇ s or more and 100 Pa ⁇ s or less at a shear rate of 1000 sec ⁇ 1 measured at a cylinder temperature 10 to 30 ° C. higher than the melting point of the liquid crystalline resin. More preferably, it is 10 Pa ⁇ s or more and 50 Pa ⁇ s or less.
  • the melt viscosity is 5 Pa ⁇ s or more and 100 Pa ⁇ s or less, the insert member and the resin member can obtain better adhesion.
  • the method for producing the resin composition is not particularly limited as long as the components in the resin composition can be uniformly mixed, and can be appropriately selected from conventionally known methods for producing resin compositions. For example, after melt-kneading and extruding each component using a melt-kneading apparatus such as a single-screw or twin-screw extruder, the resulting resin composition is processed into a desired form such as powder, flakes, pellets, etc. Is mentioned.
  • the insert molded article has a resin member made of the liquid crystalline resin composition described above and an insert member.
  • the insert molded product is obtained by integrally molding a resin member made of the liquid crystalline resin composition described above and an insert member by insert molding.
  • the insert member is not particularly limited, but is preferably used for the purpose of taking advantage of its characteristics and compensating for the defects of the resin, so that it does not change shape or melt when it comes into contact with the resin during molding.
  • metals such as aluminum, magnesium, copper, iron, brass, and alloys thereof, and those previously molded into rods, pins, screws, etc., using inorganic solids such as glass and ceramics.
  • the effects of the present invention are remarkably exhibited.
  • the shape or the like of the insert member is not limited.
  • the surface of the insert member may be roughened or untreated.
  • the roughening treatment may be performed by a physical method such as sandblasting or laser irradiation, or may be chemically processed.
  • a chemical bond effect such as a covalent bond, hydrogen bond, or intermolecular force is imparted between the insert member and the resin member, so that airtightness at the interface between the insert member and the resin member is provided. It becomes easy to improve.
  • the chemical treatment include dry treatment such as corona discharge, triazine treatment (see JP-A-2000-218935), chemical etching (JP-A-2001-225352), and the like.
  • a hot water treatment Japanese Patent Laid-Open No. 142142/1990
  • Examples of the hot water treatment include immersion in water at 100 ° C. for 3 to 5 minutes.
  • a plurality of chemical treatments may be combined.
  • the insert molding method can be a general method.
  • an insert member made of metal or the like is mounted in advance on a molding die, and a resin composition is filled on the outside thereof to perform composite molding.
  • a molding method for filling the resin composition into the mold there are an injection molding method, an extrusion compression molding method and the like, and an injection molding method is general.
  • excellent fluidity like the resin composition according to the present invention is required.
  • the insert molded article manufactured using the resin composition according to the present invention can be used for various applications.
  • the resin composition according to the present invention provides an insert-molded product having excellent airtightness, it is suitably used for applications requiring high airtightness.
  • an insert-molded product manufactured using the resin composition according to the present invention is suitable as an insert-molded product including an electrical / electronic component such as a connector or a semiconductor package that is easily affected by humidity and moisture. .
  • an electrical / electronic component such as a connector or a semiconductor package that is easily affected by humidity and moisture.
  • the insert-molded product is also useful as a sensor such as a tilt sensor or a fuel sensor. As an inclination sensor, what is used for vehicle-mounted uses, such as attitude control, and what is used for a game controller are illustrated.
  • the fuel sensor examples include those used for in-vehicle applications such as fuel amount measurement.
  • the insert-molded product is useful, for example, as a housing for an electric / electronic device including a resin boss, a holding member, and the like inside.
  • cases for electric / electronic devices in addition to mobile phones, cases for portable video electronic devices such as cameras, video integrated cameras, digital cameras, notebook computers, pocket computers, calculators, electronic notebooks , Portable information such as PDC, PHS, mobile phone, etc., housing of communication terminals, MD, cassette headphone stereo, housing of portable acoustic electronic equipment such as radio, LCD TV / monitor, telephone, facsimile, hand scanner, etc.
  • a housing of household appliances and the like can be given.
  • Examples 1 to 12 Comparative Examples 1 to 11
  • the compositions and content ratios shown in Tables 1 and 2 were melt-kneaded with a twin screw extruder having a cylinder temperature of 350 ° C. to produce pellets of resin compositions of Examples and Comparative Examples.
  • the plate-like filler and the fibrous filler were introduced into the extruder using a side feeder.
  • the content unit is “mass%”.
  • Examples 13 to 16 Except having used the material shown below by the composition and content rate which are shown in Table 3, it carried out similarly to Example 1, and produced the pellet of the resin composition. In Table 3, the unit of content is “mass%”.
  • Examples 17 and 18, Comparative Example 12 Resin composition pellets were prepared in the same manner as in Example 1 except that the materials shown below were used in the compositions and content ratios shown in Table 3 and melt-kneaded with a twin-screw extruder having a cylinder temperature of 380 ° C. .
  • Liquid crystal resin LCP
  • LCP liquid crystalline polyesteramide resin
  • the stirring torque reached a predetermined value, nitrogen was introduced and the pressure was changed from the reduced pressure state to the normal pressure state, the polymer was discharged from the lower part of the polymerization vessel, and the strands were pelletized to obtain pellets.
  • the obtained pellets were heat-treated at 300 ° C. for 2 hours under a nitrogen stream to obtain the target polymer.
  • the obtained polymer had a melting point of 335 ° C. and a melt viscosity of 14.0 Pa ⁇ s.
  • the melt viscosity of the polymer was measured in the same manner as the melt viscosity measurement method described later.
  • LCP2 Liquid crystal resin
  • LCP2 Liquid crystal resin
  • the stirring torque reached a predetermined value
  • nitrogen was introduced and the pressure was changed from the reduced pressure state to the normal pressure state
  • the polymer was discharged from the lower part of the polymerization vessel, and the strands were pelletized to obtain pellets.
  • the obtained pellets were heat-treated at 300 ° C. for 8 hours under a nitrogen stream to obtain the target polymer.
  • the melting point of the obtained polymer was 352 ° C. and the melt viscosity at 380 ° C. was 27.0 Pa ⁇ s.
  • the melt viscosity of the polymer was measured in the same manner as the melt viscosity measurement method described later.
  • Polyphenylene sulfide resin PPS: “K203A” manufactured by Kureha Co., Ltd., glass transition temperature Tg 85 ° C.
  • Polyphenylene ether resin PPE: manufactured by Mitsubishi Engineering Plastics Co., Ltd., “PX100F”, glass transition temperature Tg 213 ° C.
  • Cyclic olefin copolymer COC: “TOPAS 6017S-04” manufactured by TOPAS Advanced Polymers, glass transition temperature Tg 178 ° C.
  • Polyetheretherketone resin (PEEK): manufactured by Daicel-Evonik Co., Ltd., “VESTAKEEP2000P”, glass transition temperature Tg 143 ° C.
  • Ethylene-glycidyl methacrylate-methyl acrylate copolymer (Epoxy group-containing olefin copolymer): manufactured by Sumitomo Chemical Co., Ltd., “Bond First 2C” (glycidyl methacrylate unit content 6 mass%)
  • FIG. 1 is a plan view of the test specimen 100 obtained.
  • the size of the test specimen 100 is 80 mm ⁇ 80 mm ⁇ thickness 2 mm.
  • the dimensions of the test piece that had been allowed to stand for one day were measured at a flow direction measurement point a and a perpendicular direction measurement point b shown in FIG.
  • c of FIG. 1 shows a gate. From the measured dimensions of the test piece and the dimensions of the mold at the location on the mold corresponding to the measurement location, the mold shrinkage was determined according to the equation (1). The mold dimensions were 80.021 mm in the flow direction and 79.991 mm in the right-angle direction. (Die size-Test piece size) / Die size x 100 (1)
  • the average value of the shrinkage rate in the flow direction and the shrinkage rate in the perpendicular direction obtained as described above is defined as “shrinkage rate (average)”, and the difference between the shrinkage rate in the flow direction and the shrinkage rate in the perpendicular direction is expressed as “shrinkage rate ( Anisotropy) ”.
  • the results of Examples 1 to 12 and Comparative Examples 1 to 11 are shown in Tables 1 and 2.
  • the results of Examples 13 to 18 and Comparative Example 12 are shown in Table 3. In Tables 1 to 3, the unit of shrinkage is “%”.
  • FIG. 2A is a plan view of the insert-molded article 10
  • FIG. 2B is a cross-sectional view taken along line MM of FIG. 2A
  • FIG. 2C is a bottom view.
  • the resin member 1 and the insert member 2 are integrally molded by using the resin member 1 and the insert member 2 made of the resin compositions of the examples and comparative examples in order to evaluate the unevenness transferability and the airtightness.
  • the insert molded article 10 of the Example and the comparative example was manufactured. Note that there are six recesses 3 as shown in FIG. 2 on the upper surface of the insert-molded product 10 for use in the evaluation described later.
  • FIGS. 3A and 3B are views showing the insert member 2, wherein FIG. 3A is a plan view, FIG. 3B is a front view, and the insert member 2 is a copper member.
  • the member 2 has a length in the long direction of 19 mm, a width in the short direction of 8.5 mm, and a thickness of 0.2 mm.
  • the insert member 2 used the thing by which the surface was not processed and the thing which performed the chemical process previously by the method shown below.
  • the surface of the copper insert member is immersed in an etching solution A (aqueous solution) having the following composition for 1 minute to remove the anticorrosive film, and then immersed in an etching solution B (aqueous solution) having the following composition for 5 minutes.
  • Etching solution A (temperature 20 ° C.): hydrogen peroxide 26 g / L, sulfuric acid 90 g / L
  • Etching solution B (temperature 25 ° C.): hydrogen peroxide 80 g / L, sulfuric acid 90 g / L, benzotriazole 5 g / L, sodium chloride 0.2 g / L
  • Insert molding was performed as follows. Insert member 2 is placed in a mold for injection molding, and pellets of resin compositions of Examples and Comparative Examples are used under the following conditions using a solid injection molding machine (TR-40VR, manufactured by Sodick Co., Ltd.). It was melted and injected into a mold to form a resin member 1 to produce an insert molded product 10. Cylinder temperature: 350 ° C. (Examples 1 to 12, Comparative Examples 1 to 11) 350 ° C. (Examples 13 to 16) 380 ° C. (Examples 17 and 18, Comparative Example 12) Mold temperature: 160 ° C Injection speed: 70mm / s Holding pressure: 50 MPa
  • FIG. 4 is an explanatory diagram for producing the airtightness test sample 20
  • FIG. 5 is a block diagram of the airtightness test evaluation apparatus 101.
  • an insert molded product 10 was arranged in a space inside the fixing jigs 4, 4 ′ divided into two upper and lower parts, thereby obtaining a sample 20.
  • this sample 20 was connected to an evaluation apparatus 101 whose schematic diagram is shown in FIG.
  • Sample 20 blank 30 and differential pressure gauge 40 were connected using a tube in the arrangement shown in FIG.
  • a tube is connected to the upper fixing jig 4. Air is fed into the fixing jig from the tube, and pressure is applied to the six recesses 3 formed on the upper surface of the insert molded product 10. And if the junction part of the resin member 1 and the insert member 2 peels from the boundary of the resin member 1 and the insert member 2 of the bottom of the recessed part 3, air will leak to the lower side of a fixing jig.
  • the blank 30 is for confirming the pressure concerning the said recessed part in the state with which joining with the resin member 1 and the insert member 2 is maintained. Since a pressure difference ⁇ P is generated between the pressure applied to the blank 30 and the pressure applied to the sample when a gap is generated at the joint between the resin member 1 and the insert member 2, the airtightness of the insert molded product should be evaluated in this evaluation. Can do.
  • the amount Q of air leakage was obtained from the following formula (2) and used as an index of airtightness.
  • the results of Examples 1 to 12 and Comparative Examples 1 to 11 are shown in Tables 1 and 2.
  • the results of Examples 13 to 18 and Comparative Example 12 are shown in Table 3.
  • Q Ve ⁇ ⁇ P / T (2)
  • Ve: Volume (m 3 ) ( 0.000005 m 3 )
  • ⁇ P differential pressure (Pa)
  • the leakage amount Q is 2.8 ⁇ 10 ⁇ 4 Pa ⁇ m 3 / s or less, it can be said that this is an insert-molded product with high airtightness.
  • the liquid crystalline resin compositions of the examples all have high unevenness transferability to the metal surface and low shrinkage anisotropy. Moreover, the insert molded article using this resin composition is excellent in the initial airtightness, and can prevent the airtightness from being lowered after the reflow treatment.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)

Abstract

Le problème posé est de produire une composition de résine cristalline-liquide qui permet de donner des articles moulés par insertion ayant une excellente étanchéité à l'air; et un article moulé par insertion qui comprend un élément de résine comprenant la composition de résine cristalline-liquide. [Solution] Le problème précité est résolu au moyen d'une composition de résine cristalline-liquide qui comprend une résine cristalline-liquide, une résine thermoplastique ayant une température de transition vitreuse Tg inférieure à 230 °C, et une charge lamellaire ayant un diamètre de particule moyen de 15 à 100 µm et un rapport de forme égal ou supérieur à 10, la teneur de la résine cristalline-liquide étant comprise entre 40 et 65 % en masse de la totalité de la composition de résine, la teneur en résine thermoplastique étant comprise entre 12 et 35 % en masse de la totalité de la composition de résine, et la teneur de la charge lamellaire étant comprise entre 10 et 35 % en masse de la totalité de la composition de résine.
PCT/JP2016/087373 2015-12-22 2016-12-15 Composition de résine cristalline - liquide et article moulé par insertion WO2017110646A1 (fr)

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JP2017125176A (ja) * 2016-08-31 2017-07-20 三井化学株式会社 低誘電性樹脂組成物、硬化物、ドライフィルム、フィルム、プリプレグ、金属張積層板、プリント配線基板および電子機器
KR101901662B1 (ko) 2018-04-27 2018-09-27 주식회사 더원테크 휴대용 통신 단말기의 방수용 유심 트레이 및, 그 제조 방법
WO2019087961A1 (fr) * 2017-10-30 2019-05-09 株式会社クラレ Composant étanche à l'eau et équipement électronique pourvu de ce dernier, procédé d'imperméabilisation d'un corps moulé par insertion et procédé d'imperméabilisation d'un équipement électronique
CN110997820A (zh) * 2017-09-12 2020-04-10 宝理塑料株式会社 耐滑动摩耗构件用液晶性树脂组合物和使用了其的耐滑动摩耗构件
WO2020175389A1 (fr) * 2019-02-25 2020-09-03 株式会社クラレ Composant imperméable, équipement électronique le comprenant, procédé d'imperméabilisation utilisant un corps moulé par insertion et procédé d'imperméabilisation pour équipement électronique
JPWO2020175390A1 (fr) * 2019-02-25 2020-09-03
JP2020151980A (ja) * 2019-03-20 2020-09-24 三井化学株式会社 金属樹脂複合体の製造方法および金属樹脂複合体
US10829634B2 (en) 2017-12-05 2020-11-10 Ticona Llc Aromatic polymer composition for use in a camera module
CN114616286A (zh) * 2019-10-31 2022-06-10 韩华思路信株式会社 结晶速率得到提高的高分子组合物及其制备方法

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KR20200060585A (ko) 2018-11-21 2020-06-01 삼성전자주식회사 액정 고분자, 복합체 조성물, 성형품, 전지 케이스, 및 전지
US11086200B2 (en) 2019-03-20 2021-08-10 Ticona Llc Polymer composition for use in a camera module
JP7461959B2 (ja) 2019-03-20 2024-04-04 ティコナ・エルエルシー カメラモジュールのためのアクチュエータアセンブリ
JP7355523B2 (ja) * 2019-05-16 2023-10-03 上野製薬株式会社 液晶ポリマー組成物

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JP2017125176A (ja) * 2016-08-31 2017-07-20 三井化学株式会社 低誘電性樹脂組成物、硬化物、ドライフィルム、フィルム、プリプレグ、金属張積層板、プリント配線基板および電子機器
CN110997820A (zh) * 2017-09-12 2020-04-10 宝理塑料株式会社 耐滑动摩耗构件用液晶性树脂组合物和使用了其的耐滑动摩耗构件
TWI762713B (zh) * 2017-09-12 2022-05-01 日商寶理塑料股份有限公司 耐滑動磨耗構件用液晶性樹脂組合物及使用該組合物的耐滑動磨耗構件
CN110997820B (zh) * 2017-09-12 2021-05-11 宝理塑料株式会社 耐滑动摩耗构件用液晶性树脂组合物和使用了其的耐滑动摩耗构件
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WO2019087961A1 (fr) * 2017-10-30 2019-05-09 株式会社クラレ Composant étanche à l'eau et équipement électronique pourvu de ce dernier, procédé d'imperméabilisation d'un corps moulé par insertion et procédé d'imperméabilisation d'un équipement électronique
EP3705257A4 (fr) * 2017-10-30 2021-03-03 Kuraray Co., Ltd. Composant étanche à l'eau et équipement électronique pourvu de ce dernier, procédé d'imperméabilisation d'un corps moulé par insertion et procédé d'imperméabilisation d'un équipement électronique
US10829634B2 (en) 2017-12-05 2020-11-10 Ticona Llc Aromatic polymer composition for use in a camera module
US11725106B2 (en) 2017-12-05 2023-08-15 Ticona Llc Aromatic polymer composition for use in a camera module
KR101901662B1 (ko) 2018-04-27 2018-09-27 주식회사 더원테크 휴대용 통신 단말기의 방수용 유심 트레이 및, 그 제조 방법
WO2020175390A1 (fr) * 2019-02-25 2020-09-03 株式会社クラレ Élément étanche à l'eau, équipement électronique comprenant un tel élément étanche à l'eau, procédé d'étanchéification au moyen d'un corps moulé par insertion, et procédé d'étanchéification destiné à un équipement électronique
JPWO2020175390A1 (fr) * 2019-02-25 2020-09-03
JPWO2020175389A1 (ja) * 2019-02-25 2021-12-23 株式会社クラレ 防水部品およびそれを備えた電子機器、インサート成形体を用いる防水方法ならびに電子機器の防水方法
WO2020175389A1 (fr) * 2019-02-25 2020-09-03 株式会社クラレ Composant imperméable, équipement électronique le comprenant, procédé d'imperméabilisation utilisant un corps moulé par insertion et procédé d'imperméabilisation pour équipement électronique
JP7413344B2 (ja) 2019-02-25 2024-01-15 株式会社クラレ 防水部品およびそれを備えた電子機器、インサート成形体を用いる防水方法ならびに電子機器の防水方法
JP2020151980A (ja) * 2019-03-20 2020-09-24 三井化学株式会社 金属樹脂複合体の製造方法および金属樹脂複合体
CN114616286A (zh) * 2019-10-31 2022-06-10 韩华思路信株式会社 结晶速率得到提高的高分子组合物及其制备方法

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