KR20180081151A - Liquid crystalline resin composition and insert molding product - Google Patents

Abstract

[PROBLEMS] 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.
A thermoplastic resin having a glass transition temperature (Tg) of less than 230 占 폚, a plate-like filler having an average particle diameter of 15 占 퐉 or more and 100 占 퐉 or less and an aspect ratio of 10 or more, And the content of the thermoplastic resin in the total resin composition is 12 mass% or more and 35 mass% or less, and the content of the plate filler in the total resin composition is 10 mass% or more and 65 mass% By mass or more and 35% by mass or less.

Description

Liquid crystalline resin composition and insert molding product

The present invention relates to a liquid crystalline resin composition and an insert molded article.

The liquid crystalline resin typified by the liquid crystalline polyester resin has excellent properties such as high flowability, low burr-forming property and reflow resistance, It is widely used. Further, the liquid crystalline resin is expected to be applied to the semiconductor package field in view of its excellent water vapor permeability. However, since the liquid crystalline resin can not sufficiently obtain adhesion with metals, the airtightness of the interface between the resin and the metal may be lowered in an insert molded product integrally molded with metal by injection molding. Therefore, it is difficult to apply the liquid crystalline resin to an insert molded article which requires waterproofness. Further, when the airtightness of the interface between the resin and the metal is low, a so-called flux penetration phenomenon, in which the flux in the solder rises to the terminal portion, is likely to occur when the insert molded article is reflowed, And it is also difficult to apply it to a molded article.

As a technique for improving the adhesion of a resin composition containing a liquid crystalline resin to a metal, Patent Document 1 discloses a liquid crystalline resin composition for a molded article comprising 0.5 to 30 parts by mass of a non-liquid crystalline resin per 100 parts by mass of the liquid crystalline resin Has been proposed. Patent Document 2 proposes a waterproof connector formed of an electrically insulating synthetic resin mixed with a liquid crystal polyester resin and a polyphenylene sulfide resin. Patent Document 3 proposes a thermoplastic resin composition comprising 40 to 90% by weight of polyphenylene sulfide, 5 to 50% by weight of a liquid crystalline polyester, and 1 to 20% by weight of an elastomer.

Patent Document 1: JP-A-2003-268241 Patent Document 2: JP-A-2013-118174 Patent Document 3: JP-A-2013-227366

It is an object of the present invention 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 present inventors have found that it is possible to improve the affinity between the resin composition and the insert member at the interface in the process of studying the resin composition which can obtain the insert molded article having excellent airtightness by increasing the adhesion with the insert member formed of metal, (Hereinafter simply referred to as " abrasion-transfer property ", hereinafter referred to simply as " abrasive transfer property ", hereinafter referred to as " abrasion- (Which is also called "irregular transference") is important. However, when the main component of the resin composition is a liquid crystalline resin, it is difficult to increase the irregularity transfer property. In addition, since the liquid crystalline resin composition has anisotropy, the difference between the shrinkage ratio in the direction perpendicular to the flow direction of the resin and the shrinkage rate in the resin flow direction (hereinafter, simply referred to as " shrinkage anisotropy " And as a result, the airtightness of the insert-molded article tends to be lowered. The inventor of the present invention has conducted further studies to solve the problems peculiar to the liquid crystalline resin, and has found that by adding a thermoplastic resin having a specific glass transition temperature and a plate-like filler having a specific particle diameter and aspect ratio to the liquid crystalline resin , It was found that the irregularity transferability of the resin composition can be improved and the anisotropy of the shrinkage ratio can be reduced, and the present invention has been accomplished.

The liquid crystalline resin composition according to the present invention comprises a liquid crystalline resin, a thermoplastic resin having a glass transition temperature (Tg) of less than 230 占 폚, and a plate filler having an average particle diameter of 15 占 퐉 or more and 100 占 퐉 or less and an aspect ratio of 10 or more, Wherein the content of the liquid crystalline resin in the total resin composition is 40% by mass or more and 65% by mass or less, the content of the thermoplastic resin in the total resin composition is 12% by mass or more and 35% by mass or less, And 10% by mass or more and 35% by mass or less of the composition.

In the present invention, the thermoplastic resin is preferably one or more selected from a polyarylene sulfide resin, a polyphenylene ether resin, and a cyclic olefin resin.

In the present invention, when a molded article of 80 mm x 80 mm x 2 mm is injection molded under conditions of a cylinder temperature higher by 10 to 30 DEG C than the melting point of the liquid crystalline resin, a mold temperature of 150 DEG C and a compression pressure of 50 MPa, The difference between the shrinkage ratio in the direction perpendicular to the first direction and the shrinkage rate in the flow direction of the resin is 0.51% or less.

In the present invention, it is preferable to further contain an epoxy group-containing copolymer in an amount of not more than 6% by mass of the total resin composition. It is preferable that the fibrous filler is further contained in an amount of 12 mass% or less in the total resin composition.

The insert molded article according to the present invention is characterized by having a resin member made of the liquid crystalline resin composition described in any one of the above-mentioned items, and an insert member made of a metal, an alloy, or an inorganic solid material.

According to the present invention, it is possible 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.

1 is a plan view of a test piece for shrinkage test.
2 (a) is a plan view, (b) is a cross-sectional view of the MM line in (a), and FIG. 2 (c) is a bottom view.
3 is a view showing an example of an insert member, wherein (a) is a plan view and (b) is a front view.
Fig. 4 is an explanatory diagram when a sample for airtightness test is produced.
5 is a block diagram of the airtightness testing evaluation device.

Hereinafter, one embodiment of the present invention will be described in detail. The present invention is not limited to the following embodiments, but can be carried out by appropriately changing the range without hindering the effect of the present invention.

[Liquid crystalline resin composition]

The liquid crystalline resin composition (hereinafter simply referred to as " resin composition ") comprises a liquid crystalline resin, a thermoplastic resin having a glass transition temperature (Tg) of less than 230 占 폚, and an average particle diameter of 15 占 퐉 or more and 100 占 퐉 or less And an aspect ratio of 10 or more. Since the resin composition contains a liquid crystalline resin, it can be made into a resin composition having excellent flowability, low burr formation, bottom flowability and water vapor permeability. Further, since the resin composition contains the thermoplastic resin and the plate filler satisfying the above-mentioned predetermined conditions, the irregularity transfer property of the resin composition can be improved and the anisotropy of the shrinkage ratio can be reduced. As a result, it is possible to obtain a resin composition capable of providing an insert molded article having high airtightness while having excellent performance of a liquid crystalline resin. Further, as shown in Examples described later, the insert molded product using such a resin composition can prevent the airtightness from being lowered even after the reflow treatment.

(Liquid crystalline resin)

The liquid crystalline resin refers to a melt processible polymer having properties capable of forming an optically anisotropic melt phase. The properties of the anisotropic molten phase can be confirmed by an ordinary polarization test using an orthogonal polarizer. More specifically, confirmation of the anisotropic molten phase can be carried out by observing a molten sample put on a Leitz hot stage at a magnification of 40 times under a nitrogen atmosphere using a Leitz polarization microscope. When the liquid crystalline resin is examined between orthogonal polarizers, the polarized light is usually transmitted even in the state of the molten state, and the optically anisotropic property is exhibited.

The liquid crystalline resin is not particularly limited, but is preferably an aromatic polyester or an aromatic polyester amide. Further, a polyester partially containing an aromatic polyester or an aromatic polyester amide in the same molecular chain may be used.

The aromatic polyester or aromatic polyester amide is particularly preferably an aromatic polyester or aromatic polyester amide having at least one compound selected from the group of aromatic hydroxycarboxylic acid, aromatic hydroxyamine and aromatic diamine as constituent components to be. The liquid crystalline resin may be a mixture of two or more liquid crystalline resins selected from the above.

More specifically,

(1) a polyester mainly composed of one or more kinds of aromatic hydroxycarboxylic acids and derivatives thereof;

(2) at least one of (a) one or more aromatic hydroxycarboxylic acids and derivatives thereof, (b) one or more of aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and derivatives thereof, (c) a polyester comprising at least one or more kinds of aromatic diols, alicyclic diols, aliphatic diols, and derivatives thereof;

(3) at least one of (a) one or more aromatic hydroxycarboxylic acids and derivatives thereof, (b) one or more of aromatic hydroxamines, aromatic diamines, and derivatives thereof, and (c) A polyester amide comprising one or more of aromatic dicarboxylic acid, alicyclic dicarboxylic acid, and derivatives thereof;

(C) one or more of (a) one or more aromatic hydroxycarboxylic acids and derivatives thereof, (b) one or more of aromatic hydroxamines, aromatic diamines and derivatives thereof, (c) (D) at least one kind or two or more kinds of aromatic diols, alicyclic diols, aliphatic diols and derivatives thereof, and (d) at least one kind of aromatic dicarboxylic acid, alicyclic dicarboxylic acid, Polyester amide, and the like. Further, a molecular weight regulator may be used in combination with the above-mentioned components as required.

Specific examples of 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, Aromatic diols such as 4-dihydroxynaphthalene, 4,4'-dihydroxybiphenyl, hydroquinone, resorcin, compounds represented by the following formula (I) and compounds represented by the following formula ; Aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 4,4'-diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and compounds represented by the following general formula (III); p-aminophenol, p-phenylenediamine, and other aromatic amines.

(X is a group selected from alkylene (C ₁ -C ₄ ), alkylidene, -O-, -SO-, -SO ₂ -, -S-, and -CO-.

(Y is a group selected from - (CH ₂ ) _n - (n = 1 to 4) and -O (CH ₂ ) _n O- (n = 1 to 4)

The method of preparing the liquid crystalline resin is not particularly limited and can be adjusted by a known method using a direct polymerization method or an ester exchange method using the monomer compound (or a mixture of monomers) described above. Usually, Or a slurry polymerization method or the like is used. In the case of a compound having an ester-forming ability, it is also possible to use a compound which can be used for polymerization in the form as it is and which has been modified from a precursor to a derivative having the ester-forming ability in the former stage of polymerization. When the polymerization is carried out, various catalysts can be used. Typical examples of usable catalysts include dialkyltin oxide, diaryl tin oxide, titanium dioxide, alkoxytitanium silicates, titanium alcoholates, alkali and alkaline earth metal salts of carboxylic acid, and Lewis acid salts such as BF ₃ . . The amount of the catalyst to be used is generally about 0.001 to 1 mass%, particularly about 0.01 to 0.2 mass%, based on the total weight of the monomer. If necessary, the polymer produced by these polymerization methods can be increased in molecular weight by solid state polymerization, which is carried out under reduced pressure or in an inert gas.

The content of the liquid crystalline resin in the total resin composition is 40 mass% or more and 65 mass% or less. By setting the content of the liquid crystalline resin to 40% by mass or more and 65% by mass or less, it is possible to improve the irregularity transfer property of the liquid crystalline resin while maintaining the fluidity property, the excellent low burr formation property, the down flow property and the water vapor permeability At the same time, the anisotropy of the shrinkage ratio can be reduced. As a result, it is possible to produce a resin composition capable of obtaining a molded article having high airtightness while having excellent performance of a liquid crystalline resin. The content of the liquid crystalline resin is more preferably 42 mass% or more and 62 mass% or less. The lower limit of the content of the liquid crystalline resin may be 45% by mass or more, and the upper limit may be 60% by mass or less.

The melt viscosity of the liquid crystalline resin is not particularly limited and is preferably not more than 5 Pa · s and not more than 100 Pa · s as measured at a cylinder temperature of 10 to 30 ° C. higher than the melting point of the liquid crystalline resin and a shear rate of 1,000 sec ^-1 , It is preferably 10 Pa · s or more and 50 Pa · s or less. Cylinder temperature higher than the melting point of the liquid crystalline resin "means a cylinder temperature at which the liquid crystalline resin can be melted to a measurable degree of melt viscosity, and whether the cylinder temperature is higher than the melting point by several degrees Celsius is 10 To 30 占 폚 depending on the kind of the liquid crystalline resin. For example, Japanese Patent Application Laid-Open No. 2010-3661 (particularly paragraphs 0048 and 0051) discloses that 2 mol% of constituent units to be introduced from 4-hydroxybenzoic acid as liquid crystalline polymer 1, 48 mol% of constituent units to be introduced from the acid, 25 mol% of constituent units to be introduced from terephthalic acid, and 25 mol% of constituent units to be introduced from 4,4'-dihydroxybiphenyl. Its melting point is 352 ° C, and its melt viscosity is measured at a cylinder temperature of 380 ° C. Further, as the liquid crystalline polymer 2, 50 mol% of constituent units to be introduced from 4-hydroxybenzoic acid, 2.5 mol% of constituent units to be introduced from 6-hydroxy-2-naphthoic acid, 23.9 mol% , 18.6 mol% of the constituent unit introduced from 4'-dihydroxybiphenyl, and 5 mol% of the constituent unit introduced from 4-acetamidephenol. Its melting point is 367 캜, and its melt viscosity is measured at a cylinder temperature of 380 캜. And a structural unit introduced from 4-hydroxybenzoic acid as liquid crystalline polymer 3, 5 mol% of constituent units introduced from 6-hydroxy-2-naphthoic acid, 17.7 mol% of constituent units introduced from terephthalic acid, 112.3 mol% of the constituent unit introduced from 4'-dihydroxybiphenyl and 5 mol% of the constituent unit introduced from 4-acetamidephenol are disclosed. Its melting point is 335 ° C, and its 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 占 폚 (hereinafter, simply referred to as "thermoplastic resin"). According to the study by the present inventors, it has been found that when a thermoplastic resin having a glass transition temperature (Tg) of less than 230 占 폚 is added to a liquid crystalline resin, the irregularity transferability of the resin composition can be improved. As a result, as shown in Examples to be described later, the airtightness of the insert molded article can be enhanced, and the airtightness can be prevented from being lowered even after the reflow processing of the molded article.

Here, the glass transition temperature (Tg) refers to a value measured at a temperature raising rate of 10 ° C / minute by the DSC method (method described in JIS K7121). The lower limit of the glass transition temperature (Tg) is not particularly limited and may be 60 占 폚 or higher, or 80 占 폚 or higher. The upper limit of the glass transition temperature (Tg) may be 220 캜 or lower.

As the thermoplastic resin having a glass transition temperature (Tg) of less than 230 占 폚, polyarylene sulfide resin (PAS); Polyphenylene ether resin (PPE); Cyclic olefin based resins; Polycarbonate resin (PC); Polyethylene resin (PE); Polypropylene resin (PP); Polyacetal resin (POM); Polyamide resin (PA) such as polyamide 6, polyamide 66 or polyamide 46; Polyester resins such as polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and modified polyethylene terephthalate (PET); Polyetheretherketone resin (PEEK); Polystyrene resin (PS); Polyvinyl chloride resin (PVC); Acrylonitrile-styrene copolymer resin (AS); Polymethyl methacrylate resin (PMMA); Acrylonitrile-butadiene-styrene copolymer resin (ABS); Polyarylate resins (PAR); Polyetherimide resin (PEI); And polyethersulfone resin (PES).

Among them, one or more selected from a polyarylene sulfide resin, a polyphenylene ether resin, and a cyclic olefin resin is preferable.

The polyarylene sulfide resin (PAS resin) is constituted mainly of - (Ar-S) - ("Ar" represents an arylene group) as a repeating unit, and a PAS resin having a generally known molecular structure can be used have.

Examples of the arylene group include, but are not limited to, p-phenylene, m-phenylene, o-phenylene, substituted phenylene, p, p'- P, p'-diphenylene ether group, p, p'-diphenylene carbonyl group, naphthalene group and the like. Of the arylene sulfide groups constituted by such arylene groups, besides the homopolymers using the same repeating units, copolymers containing repeating heterogeneous arylene sulfide groups may be used depending on the use.

As the homopolymer, it is preferable that the repeating unit is a p-phenylene sulfide group as the arylene group, depending on the use. Homopolymers having a p-phenylene sulfide group as a repeating unit have extremely high heat resistance and exhibit high strength, high rigidity and high dimensional stability in a wide temperature range. By using such a homopolymer, a molded article having excellent physical properties can be obtained.

As the copolymer, a combination of two or more different arylene sulfide groups in the above-mentioned arylene sulfide group-containing arylene group can be used. Among these, a combination comprising a p-phenylene sulfide group and an m-phenylene sulfide group is preferable in that a molded article having high physical properties such as heat resistance, moldability, and mechanical properties can be obtained. Further, a polymer containing a p-phenylene sulfide group in an amount of 70 mol% or more is more preferable, and a polymer containing 80 mol% or more is more preferable. The polyarylene sulfide resin having a phenylene sulfide group is a polyphenylene sulfide resin.

As a method of adjusting the polyarylene sulfide resin, conventionally known polymerization methods can be used. The polyarylene sulfide resin produced by the general polymerization method is usually washed several times with water or acetone to remove by-product impurities, and then washed with acetic acid, ammonium chloride, or the like. As a result, the terminal of the polyarylene sulfide resin contains a carboxyl end group in a predetermined amount.

Examples of the polyphenylene ether resin include polyphenylene ether and modified polyphenylene ether. Examples of the cyclic olefin resin include cyclic olefin polymer (COP) and cyclic olefin copolymer (COC).

The content of the thermoplastic resin is 12 mass% or more and 35 mass% or less in the total resin composition. By setting the content of the thermoplastic resin to 12 mass% or more and 35 mass% or less in the total resin composition, it is possible to improve the irregularity transfer property while maintaining the properties such as high fluidity and keeping the anisotropy of the shrinkage ratio small. The content of the thermoplastic resin is preferably 15 mass% or more and 30 mass% or less.

The weight average molecular weight (Mw) of the thermoplastic resin is not particularly limited and is preferably 15,000 or more and 40000 or less. By setting the weight average molecular weight of the thermoplastic resin within the above range, it is possible to make a resin composition having better balance of mechanical properties and fluidity. The weight average molecular weight of the thermoplastic resin is more preferably 20000 or more and 38000 or less.

(Plate filler)

The resin composition contains a plate filler. The plate filler has an average particle diameter of 15 占 퐉 or more and 100 占 퐉 or less and an aspect ratio of 10 or more. By containing such a plate filler, the anisotropy of the shrinkage ratio at the time of injection molding can be reduced. As a result, as shown in Examples to be described later, the airtightness of the insert molded article can be enhanced, and the airtightness can be prevented from being lowered even after the reflow processing of the molded article.

The average particle diameter is preferably 20 占 퐉 or more and 50 占 퐉 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 filler before the plate filler is incorporated into the resin composition. The average particle diameter is a value measured by a laser diffraction / scattering type particle size distribution measurement method, and is a particle diameter of an integrated value of 50% in a particle size based particle size distribution. Average aspect ratio is a value obtained by calculating the aspect ratio by measuring the length and thickness of dozens of fillers by observation under an electron microscope (SEM), and calculating an average value thereof.

Examples of the plate-like filler include mica, talc, glass flake, graphite, various metal foils (for example, aluminum foil, steel foil and copper foil), and one or more selected from these may be used . Of these, mica is preferable from the viewpoint that the difference between the shrinkage ratio in the flow direction of the resin and the shrinkage ratio in the direction perpendicular to the flow direction of the resin can be further reduced.

The content of the plate filler in the total resin composition is 10% by mass or more and 35% by mass or less. When the content of the plate filler in the total resin composition is 10% by mass or more and 35% by mass or less, an effect of reducing the anisotropy of shrinkage during injection molding in a state having high concave-convex transfer property can be sufficiently obtained.

(Epoxy group-containing copolymer)

The resin composition preferably further contains an epoxy group-containing copolymer. By containing the epoxy group-containing copolymer, the affinity of the interface with the insert member can be enhanced.

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 may be used alone or in combination of two or more selected from the above.

As the epoxy group-containing olefin-based copolymer, for example, α - a copolymer consisting of a repeating unit derived from a glycidyl ester of an unsaturated acid-repeating units and α, β derived from olefins.

The? -olefin is not particularly limited and includes, for example, ethylene, propylene, and butene, among which ethylene is preferably used. The glycidyl ester of the ?,? - unsaturated acid is represented by the following general formula (IV). In the general formula (IV), R 'represents hydrogen or an alkyl group having 1 to 10 carbon atoms. Examples of glycidyl esters of ?,? - unsaturated acids include glycidyl acrylate esters, glycidyl methacrylate esters, glycidyl esters of ethacrylic acid, glycidyl esters of itaconic acid, The glycidyl acrylate esters are preferred.

In the epoxy group-containing olefin-based copolymer, the content of the repeating unit derived from the? -Olefin is 87 to 98% by mass and the content of the repeating unit derived from the glycidyl ester of the ?,? - unsaturated acid is 13 to 2 % By mass.

The epoxy group-containing olefin-based copolymer may contain an olefinic unsaturated group such as acrylonitrile, acrylic acid ester, methacrylic acid ester ,? -Methylstyrene and maleic anhydride as the third component in addition to the above- And 0 to 48 parts by mass of the repeating unit derived from two or more kinds selected from 100 parts by mass of the two components can be contained.

The epoxy group-containing olefin-based copolymer can be easily prepared by a conventional radical polymerization method using a monomer corresponding to each component and a radical polymerization catalyst. More specifically, the normal, α - olefin and α, β - a glycidyl ester of an unsaturated acid in the presence of a radical generator, and 500 ~ 4000 atm, in the presence of a suitable solvent or chain transfer agent at 100 ~ 300 ℃ or absence In the presence of a catalyst. It is also possible to prepare by melt-graft copolymerizing an α -olefin with a glycidyl ester of an α, β -unsaturated acid and a radical generator in an extruder.

Examples of the epoxy group-containing styrenic copolymer include a copolymer composed of a repeating unit derived from styrene and a repeating unit derived from glycidyl ester of ?,? - unsaturated acid. The glycidyl esters of the ?,? - unsaturated acids are the same as those described in the epoxy group-containing olefin-based copolymer, and therefore the description thereof is omitted. As the styrenes, styrene, α - methylstyrene and the like, brominated styrene, divinylbenzene, it is used as styrene is preferred.

The epoxy group-containing styrenic copolymer may be a multi-component copolymer containing, as the third component, the repeating units derived from one kind or two or more kinds of other vinyl monomers in addition to the above two components. Preferred 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 styrenic copolymer containing 40% by mass or less of these repeating units in the copolymer is preferable.

In the epoxy group-containing styrenic copolymer, the content of the repeating unit derived from the glycidyl ester of the ?,? - unsaturated acid is 2 to 20 mass%, the content of the repeating unit derived from the styrene is 80 to 98 mass% .

The epoxy group-containing styrenic copolymer can be prepared by a conventional radical polymerization method using a monomer and a radical polymerization catalyst corresponding to each component. More specifically, usually, styrenes and glycidyl esters of?,? - unsaturated acids are reacted in the presence of a radical generator at 500 to 4000 atm and 100 to 300 ° C in the presence or absence of a suitable solvent or chain transfer agent Followed by copolymerization. It is also possible to prepare by a method in which styrene is mixed with a glycidyl ester of an ?,? - unsaturated acid and a radical generator and melt graft copolymerized in an extruder.

As the epoxy group-containing copolymer, an epoxy group-containing olefin-based copolymer is preferable from the viewpoint of heat resistance. When the epoxy group-containing olefin-based copolymer and the epoxy group-containing styrene-based copolymer are used in combination, the ratio of these components can be appropriately selected depending on the required characteristics.

The content of the epoxy group-containing copolymer is 6% by mass or less in the total resin composition from the viewpoint of deteriorating the combustibility. The lower limit of the content of the epoxy group-containing copolymer is not particularly limited and may be, for example, 0.01 mass%, 0.1 mass% or more, or 1 mass% or more in the total resin composition.

(Fibrous filler)

The resin composition further contains a fibrous filler. By containing the fibrous filler, the mechanical strength can be improved. The fibrous filler means that the average value of the specific diameter ratio is 1 or more and 4 or less and the aspect ratio is 2 or more and 1,500 or less. This definition relates to the shape of the fibrous filler before the fibrous filler is incorporated into the resin composition.

As the fibrous filler, those conventionally used as fillers or reinforcing agents in various resin compositions can be used without any particular limitation. Specific examples of the fibrous filler include silicate fibers such as glass fibers, mud glass fibers, asbestos fibers, carbon fibers, silica fibers, silica-alumina fibers, alumina fibers, zirconia fibers, boron nitride fibers, boron fibers, potassium titanate fibers, Fibers, magnesium sulfate fibers, aluminum borate fibers, and inorganic fibrous materials such as fibers of metals such as stainless steel, aluminum, titanium, copper and brass. These fibrous fillers may be used in combination of two or more kinds.

Among these, from the viewpoint that it is easy to obtain inexpensively and that the difference between the contraction ratio in the flow direction of the resin and the difference in the direction perpendicular to the flow direction of the resin of the molded article obtained by molding under predetermined conditions can be easily adjusted, Fiber is preferred. As the glass fiber, a generally circular or nearly circular cross-sectional shape is used, but glass fibers having a so-called deformed cross-section may also be used. Examples of the shape of the modified cross section include, but are not limited to, a polygon such as a rectangle or a diamond, an ellipse, a cocoon shape, and the like.

(Other additives)

The resin composition may contain other additives for imparting desired physical properties to the resin composition within a range that does not impair the effects of the present invention. Examples of other additives include a nucleating agent, carbon black, a pigment, an antioxidant, a stabilizer, a plasticizer, a lubricant, a release agent or a flame retardant. The content of the other additives can be appropriately adjusted depending on the desired physical properties.

(Resin composition)

The resin composition is preferably such that when a molded product of 80 mm x 80 mm x 2 mm is injection molded under conditions of a cylinder temperature higher than the melting point of the liquid crystalline resin by 10 to 30 DEG C, a mold temperature of 150 DEG C and a compression pressure of 50 MPa, The difference between the shrinkage ratio in the perpendicular direction and the shrinkage ratio in the flow direction of the resin is preferably 0.51% or less. The difference between the shrinkage ratio in the direction perpendicular to the flow direction of the resin and the shrinkage rate in the flow direction of the resin is reduced to 0.51% or less, whereby the solidification shrinkage of the resin portion can be reduced when the insert molding is produced by injection molding. When the solidification shrinkage of the resin member is small, minute voids are not easily generated between the insert member and the resin member, and an insert molded article having high airtightness is easily obtained. Here, the " cylinder temperature 10 to 30 DEG C higher than the melting point of the liquid crystalline resin " is the same as described above, and thus description thereof is omitted here.

The reason for using the difference between the shrinkage ratio in the flow direction of the resin and the shrinkage ratio in the direction perpendicular to the flow direction of the resin (hereinafter also referred to as the direction perpendicular to the flow) with respect to the shrinkage ratio is that in the actual molded article, The shrinkage generated between the resin members varies depending on the shape but is not influenced only by either one of the shrinkage ratio in the flow direction of the resin and the shrinkage ratio in the direction perpendicular to the flow and is influenced by both shrinkage factors, It is presumed that it is necessary to think.

The melt viscosity of the resin composition preferably has a melt viscosity of 5 Pa · s or more and 100 Pa · s or less at a shear rate of 1000 sec ^-1 measured at a cylinder temperature which is 10 to 30 ° C. higher than the melting point of the liquid crystalline resin, More preferably 50 Pa · s or less. When the melt viscosity is not less than 5 Pa · s and not more than 100 Pa · s, better adhesion between the insert member and the resin member can be obtained.

(Production method of resin composition)

The method for producing the resin composition is not particularly limited as long as it can uniformly mix the components in the resin composition, and can be appropriately selected in a known method for producing a resin composition. For example, a melt kneading apparatus such as a single-screw extruder or a twin screw extruder may be used to melt-knead and extrude each component, and then the obtained resin composition may be processed into a desired form such as powder, flake, pellet .

[Molded insert]

The insert molded article has a resin member made of the liquid crystalline resin composition and an insert member. An insert molded article is obtained by integrally molding a resin member made of the liquid crystalline resin composition and an insert member by insert molding.

Although the insert member is not particularly limited, it is preferably used so as to compensate for the defects of the resin while making good use of the properties thereof, so that the shape of the insert member is not changed or melted when brought into contact with the resin at the time of molding. For example, a material which is previously molded with a rod, a pin, a screw or the like by an inorganic solid such as aluminum, magnesium, copper, iron, brass or an alloy thereof or an inorganic solid such as glass or ceramic is used. In the present invention, the effect of the present invention is remarkable when metal is used as the insert member. The shape of the insert member and the like are not limited.

The surface of the insert member may be roughened or untreated. The roughening treatment may be carried out by a physical method such as sandblasting or laser irradiation, or may be chemically treated. When chemically treated, a chemical bonding effect such as covalent bonding, hydrogen bonding, or intermolecular force is given between the insert member and the resin member, so that the airtightness at the interface between the insert member and the resin member is easily improved. Examples of the chemical treatment include a dry treatment of a corona discharge lamp, a triazine treatment (see Japanese Patent Application Laid-Open No. 2000-218935), and a chemical etching (Japanese Patent Application Laid-Open No. 2001-225352). Further, when the material constituting the insert member is aluminum, hot water treatment (Japanese Patent Laid-Open No. 142110/1990) is also available. The hot water treatment may include immersion in water at 100 ° C for 3 to 5 minutes. Or a combination of a plurality of chemical treatments.

The insert molding method can be performed by a general method. For example, an insert member formed of metal or the like is previously mounted on a molding die, and a resin composition is filled on the outside of the insert member to perform a complex molding. As a molding method for filling the resin composition into a mold, there are an injection molding method, an extrusion compression molding method and the like, and an injection molding method is generally used. Particularly, in the case of the injection molding method, excellent fluidity like the resin composition according to the present invention is required.

(Usage)

The insert molded articles produced using the resin composition according to the present invention can be used for various purposes. Particularly, since the resin composition according to the present invention gives an insert molded article having excellent airtightness, it is suitably used for applications requiring high airtightness.

For example, insert molded articles manufactured using the resin composition according to the present invention are suitable as insert molded articles having electrical and electronic parts, such as connectors and semiconductor packages, which are liable to be adversely affected by humidity and moisture. Particularly, it is preferable to use it as a component for an electric or electronic device in which penetration of moisture or moisture is connected to a fault, which is expected to be used in a field requiring waterproofing at a high level, for example, in a river, a swimming pool, . The insert molded article is also useful as, for example, a sensor such as a tilt sensor or a fuel sensor. The inclination sensor may be used for on-vehicle use such as attitude control, or may be used for a game controller. As the fuel sensor, there is exemplified a fuel sensor which is used for a vehicle use such as a fuel amount measurement. The insert-molded article is also useful as a case for an electric or electronic device, for example, which is provided with a resin boss or a holding member inside. Examples of the case for the electric / electronic device include portable electronic devices such as cameras, video-integrated cameras and digital cameras, portable computers such as a notebook computer, a pocket computer, a calculator, an electronic notebook, a PDC, a PHS, A casing of information or communication terminal, a case of portable acoustic electronic device such as MD, cassette headphone stereo, and radio, and a case of a household telephone appliance such as a liquid crystal TV monitor, a telephone, a facsimile, and a hand scanner.

[ Example ]

Hereinafter, the present invention will be described in more detail with reference to examples, but the interpretation of the present invention is not limited by these examples.

[Examples 1 to 12, Comparative Examples 1 to 11]

The following materials were used for melt kneading in a twin screw extruder having a cylinder temperature of 350 DEG C at the composition and content shown in Tables 1 and 2 to prepare pellets of the resin compositions of Examples and Comparative Examples. The plate filler and the fibrous filler were introduced into an extruder using a side feeder. In Table 1 and 2, the unit of the content is "% by mass".

[Examples 13 to 16]

Pellets of the resin composition were prepared in the same manner as in Example 1 except that the materials shown below were used in the composition and content ratios shown in Table 3. [ In Table 3, the unit of the content is " mass% ".

[Examples 17, 18, Comparative Example 12]

The pellets of the resin composition were prepared in the same manner as in Example 1 except that the materials shown below were used in the composition and content ratios shown in Table 3 and melt kneaded in a twin screw extruder at a cylinder temperature of 380 캜.

(Liquid crystalline resin: LCP)

The liquid crystalline polyester amide resin (LCP) was adjusted as follows. After the following materials were charged into the polymerization vessel, the temperature of the reaction system was raised to 140 占 폚 and the reaction was carried out at 140 占 폚 for 1 hour. Thereafter, the temperature was further raised to 340 캜 for 4.5 hours, and the pressure was reduced to 10 Torr (i.e., 1330 Pa) for 15 minutes, and melt polymerization was carried out while distilling acetic acid, excess acetic anhydride and other low boiling components Respectively. After the stirring torque reached a predetermined value, nitrogen was introduced to bring the pressure from the reduced pressure state to the atmospheric 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 subjected to heat treatment at 300 DEG C for 2 hours in a nitrogen stream to obtain a desired polymer. The obtained polymer had a melting point of 335 占 폚 and a melt viscosity of 14.0 Pa 占 퐏. The melt viscosity of the polymer was measured in the same manner as the melt viscosity measurement method described later.

[Raw material]

(I) 4-hydroxybenzoic acid; 188.4 g (60 mol%)

(II) 2-hydroxy-6-naphthoic acid; 21.4 g (5 mol%)

(III) terephthalic acid; 66.8 g (17.7 mol%)

(IV) 4,4'-dihydroxybiphenyl; 52.2 g (12.3 mol%)

(V) 4-acetoxyaminophenol; 17.2 g (5 mol%)

 Metal catalyst (potassium acetate catalyst); 15 mg

 Acylating agent (acetic anhydride); 226.2 g

(Liquid crystalline resin: LCP2)

The liquid crystalline polyester resin (LCP2) was adjusted as follows. After the following materials were charged into the polymerization vessel, the temperature of the reaction system was raised to 140 占 폚 and the reaction was carried out at 140 占 폚 for 1 hour. Thereafter, the temperature was further raised to 360 deg. C over 5.5 hours, and the pressure was reduced to 5 Torr (i.e., 667 Pa) over 30 minutes, and melt polymerization was carried out while distilling acetic acid, excess acetic anhydride and other low- After the stirring torque reached a predetermined value, nitrogen was introduced to bring the pressure from the reduced pressure state to the atmospheric pressure state. The polymer was discharged from the lower part of the polymerization vessel and the strands were pelletized to obtain pellets. The resulting pellets were subjected to heat treatment at 300 DEG C for 8 hours in a nitrogen stream to obtain the desired 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.

[Raw material]

(I) 2-hydroxy-6-naphthoic acid (HNA); 166 g (48 mol%)

(II) terephthalic acid (TA); 76 g (25 mol%)

(III) 4,4'-dihydroxybiphenyl (BP); 86g (25 mol%)

(IV) 4-hydroxybenzoic acid (HBA); 5 g (2 mol%)

Metal catalyst (potassium acetate catalyst); 22.5 mg

Acylating agent (acetic anhydride); 191 g

(Thermoplastic resin)

Polyphenylene sulfide resin (PPS): "W203A" manufactured by Krehase Co., Ltd., glass transition temperature (Tg) of 85 ° C

Polyphenylene ether resin (PPE): "PX100F" manufactured by Mitsubishi Engineering Plastic Co., Ltd., glass transition temperature (Tg) 213 ° C.

Cycloaliphatic olefin copolymer (COC): TOPAS 6017S-04 manufactured by TOPAS Advanced Polymers, glass transition temperature (Tg) 178 DEG C

Polyetheretherketone resin (PEEK): "VESTAKEEP 2000P" manufactured by Daicel Eicon Co., Ltd., glass transition temperature (Tg) 143 ° C

Polyimide resin (PI): "PL450C" manufactured by Mitsui Chemicals, Inc., glass transition temperature (Tg) 250 ° C.

(Plate filler)

Mica: "AB-25S" manufactured by YAMAGUCHI MICASE CORPORATION, average particle diameter 23.4 μm, aspect ratio 40 to 50

Mica: "A-41S" manufactured by YAMAGUCHI MICASE CORPORATION, average particle diameter 48.5 μm, aspect ratio 40 to 50

Glass flake: " REF160 ", manufactured by Nihon Itagaras Co., Ltd., average particle diameter 160 탆, aspect ratio 32

Talc: "Crown talc PP" manufactured by Matsumura Industry Co., Ltd., average particle diameter 12.8 탆, aspect ratio 8

(Epoxy group-containing olefin-based copolymer)

Ethylene-glycidyl methacrylate-methyl acrylate copolymer (EGMA): "Bond Fast 2C" (glycidyl methacrylate unit content: 6 mass%) manufactured by Sumitomo Chemical Co.,

(Fibrous filler)

Glass fiber: "ECS03T-786H" made by Nippon Denshikagarasu Co., Ltd., fiber strand 10 μm, length 3 mm Strand

Milled glass fiber: "PF70E-001" manufactured by Nitto Boseki Co., Ltd., fiber diameter 10 μm, average fiber length 70 μm

[evaluation]

(Melt viscosity)

The resin composition pellets of the examples and comparative examples were measured for an apparent melt viscosity according to ISO 11443 under the following conditions using a capillary rheometer (Capilograph 1D manufactured by Toyo Seiki Seisaku-sho, Ltd., piston diameter 10 mm) Respectively. For the measurement, an orifice having an inner diameter of 1 mm and a length of 20 mm was used. 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.

Cylinder temperature: 350 占 폚 (Examples 1 to 12, Comparative Examples 1 to 11)

             350 占 폚 (Examples 13 to 16)

             380 占 폚 (Examples 17 and 18, Comparative Example 12)

Shear rate: 1000sec ^-1

(Shrinkage ratio)

The shrinkage ratio of the resin composition was measured by the following method. The resin composition pellets of Examples and Comparative Examples were molded under the following molding conditions in a molding machine ("SE-100DU" manufactured by Sumitomo Heavy Industries, Ltd.).

Cylinder temperature: 350 占 폚 (Examples 1 to 12, Comparative Examples 1 to 11)

             350 占 폚 (Examples 13 to 16)

             380 占 폚 (Examples 17 and 18, Comparative Example 12)

Mold temperature: 150 ℃

Injection speed: 33mm / sec

Boom pressure: 50MPa

1 is a plan view of the test piece 100 for test. The size of the test piece 100 for test is 80 mm 80 mm 2 mm thickness. The dimensions of this test piece, which was allowed to stand for one day, were measured in the flow direction measuring portion (a) and the perpendicular direction measuring portion (b) shown in Fig. 1 (c) shows a gate. The molding shrinkage ratio was obtained from the dimensions of the measured test piece and the dimensions of the mold at the positions on the mold surface corresponding to the measurement points according to the formula (1). The dimensions of the mold were 80.021 mm in the flow direction and 79.991 mm in the perpendicular direction.

(Mold dimension - specimen dimension) / mold dimension Х100 (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 referred to as a "shrinkage ratio (average)", and the difference between the shrinkage rate in the flow direction and the shrinkage rate in the perpendicular direction is referred to as "shrinkage ratio (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 "%".

(Production of insert molded article)

Fig. 2 (a) is a plan view of the insert molded article 10, Fig. 2 (b) is a cross-sectional view taken along line M-M of Fig. 2 (a), and Fig. 2 (c) is a bottom view. The resin member 1 and the insert member 2 were integrally formed by using the resin member 1 and the insert member 2 made of the resin compositions of Examples and Comparative Examples for use in evaluating the unevenness transfer property and the airtightness Molded inserts 10 and comparative examples were produced. There are six concave portions 3 shown in Fig. 2 on the upper surface of the insert molded article 10 for use in the evaluation to be described later.

3 is a plan view of the insert member 2, FIG. 3 (b) is a front view thereof, and the insert member 2 is a member made of copper (copper). This member 2 has a length of 19 mm in the long direction, a width of 8.5 mm in the short direction, and a thickness of 0.2 mm. The insert member 2 was prepared by subjecting the surface of the insert member 2 to an untreated surface and a surface treated by chemical treatment in the following manner. In the chemical treatment, the surface of the insert member made of copper (copper) was immersed in the etching solution A (aqueous solution) having the following composition for 1 minute to remove the rust-inhibitive coating, and then the etching solution B (aqueous solution) And the surface was etched by immersion.

Etching solution A (temperature 20 캜): hydrogen peroxide 26 g / L, sulfuric acid 90 g / L

Etching solution B (temperature 25 캜): hydrogen peroxide 80 g / L, sulfuric acid 90 g / L, benzotriazole 5 g /    Sodium chloride 0.2 g / L

The insert molding was carried out as follows. The pellets of the resin compositions of Examples and Comparative Examples were melted under the following conditions by using the injection molder (TR-40VR, manufactured by SODICK Co., Ltd.), and the insert member 2 was placed in a mold for injection molding And injected into a mold to obtain a resin member (1), thereby producing an insert molded article (10).

Cylinder temperature: 350 占 폚 (Examples 1 to 12, Comparative Examples 1 to 11)

             350 占 폚 (Examples 13 to 16)

             380 占 폚 (Examples 17 and 18, Comparative Example 12)

Mold temperature: 160 ℃

Injection speed: 70mm / s

Boom pressure: 50MPa

(Uneven transfer property)

The insert member 2 was immersed in a mixed solution of hydrochloric acid (10 wt% aqueous solution) and nitric acid (60 wt% aqueous solution) at room temperature and the surface of the remaining resin member 1 was observed with a scanning electron microscope Quot; S-3000H " manufactured by Hitachi High Technologies, Ltd., magnification: 1000 times). The degree of concavity and convexity of the surface of the resin member 1 was evaluated in five steps with 1 having large unevenness and 5 having small unevenness. 3 or less, it can be said that the irregularity transfer property is high. 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.

(Initial confidentiality)

The airtightness of the insert molded article 10 was evaluated as follows. For the airtightness evaluation, a differential pressure gauge MODEL DP-330BA manufactured by Cosmo Instruments Co., Ltd. was used (precision: ± 0.03 kPa, differential pressure range: 100 kPa). A specific evaluation method will be described with reference to Figs. Fig. 4 is an explanatory view of the sample 20 for airtightness test, and Fig. 5 is a block diagram of the airtightness test evaluating apparatus 101. Fig. First, as shown in Fig. 4, the insert molded article 10 is placed in the inner space of the fixing jigs 4, 4 'divided into upper and lower parts to form a sample 20. As shown in Fig. Subsequently, the sample 20 was connected to the evaluation apparatus 101 schematically shown in Fig. The sample 20, the blank 30, and the differential pressure gauge 40 were connected using a tube in the arrangement shown in Fig. In the sample 20, a tube is connected to the upper fixture 4. Air is fed from the tube into the fixture so that pressure is applied to the six concave portions 3 formed on the upper surface of the insert molded article 10. When the joint between the resin member 1 and the insert member 2 is peeled off from the boundary between the resin member 1 and the insert member 2 on the bottom of the concave portion 3 so that the air leaks to the lower side of the fixture . The blank 30 is for checking the pressure applied to the concave portion in a state in which the bonding between the resin member 1 and the insert member 2 is maintained. When a gap is formed between the resin member 1 and the insert member 2, a pressure difference? P between the pressure applied to the blank 30 and the pressure applied to the sample is generated. Therefore, in this evaluation, the airtightness of the insert- have.

The amount of air leakage (Q) 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)

Q: Leakage amount (Pa · m ³ / s)

Ve: volume (m ³ ) (= 0.000005 m ³ )

? P: differential pressure (Pa)

T: detection time (s) (= 60s)

When the leakage amount Q is 2.8 × 10 ^-4 Pa · m ³ / s or less, it can be said that it is an insert molded article having high airtightness.

(Airtightness after reflow)

The airtightness of the insert molded product 10 after the reflow treatment was evaluated. The reflow treatment was carried out using Asahi Enzianering agent Co., Ltd., TPF-20L under the following conditions.

Sample transfer rate: 0.4m / min

Reflow Uno Transit Time: 5min

Temperature conditions: preheating 200 ° C, reflow zone 395 ° C, peak temperature 258 ° C

The airtightness measurement was carried out in the same manner as described above. 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.

As is clear from Tables 1 and 3, all of the liquid crystalline resin compositions of the Examples have a high irregularity transfer property with respect to the metal surface and a small anisotropy of the shrinkage ratio. Further, the insert molded product using such a resin composition has excellent initial airtightness and can prevent the airtightness from being lowered after the reflow process.

1 resin member
2 insert member
3 concave portion
4,4 'fixing jig
10 insert molding products
20 Sample for airtightness test
100 Test piece for shrinkage test
101 Evaluation device for airtightness test
a Flow direction measurement point
b Angle measurement point
c gate

Claims (6)

A liquid crystalline resin, a thermoplastic resin having a glass transition temperature (Tg) of less than 230 占 폚, and a plate filler having an average particle diameter of 15 占 퐉 or more and 100 占 퐉 or less and an aspect ratio of 10 or more,
The content of the liquid crystalline resin in the total resin composition is 40% by mass or more and 65% by mass or less,
Wherein the content of the thermoplastic resin is 12 mass% or more and 35 mass% or less in the total resin composition,
Wherein the content of the plate filler in the total resin composition is 10% by mass or more and 35% by mass or less. The method according to claim 1,
Wherein the thermoplastic resin is at least one selected from a polyarylene sulfide resin, a polyphenylene ether resin, a cyclic olefin resin, and a polyetheretherketone resin. 3. The method according to claim 1 or 2,
When a molded article of 80 mm x 80 mm x 2 mm is injection molded under conditions of a cylinder temperature higher by 10 to 30 DEG C than the melting point of the liquid crystalline resin, a mold temperature of 150 DEG C and a compression pressure of 50 MPa, a shrinkage ratio in a direction perpendicular to the flowing direction of the resin And the shrinkage ratio in the flow direction of the resin is 0.51% or less. 4. The method according to any one of claims 1 to 3,
And the epoxy group-containing copolymer is contained in an amount of not more than 6% by mass of the total resin composition. 5. The method according to any one of claims 1 to 4,
Wherein the fibrous filler contains 12 mass% or less of the total resin composition.  An insert molded article comprising a resin member made of the liquid crystalline resin composition according to any one of claims 1 to 5 and an insert member made of a metal, an alloy or an inorganic solid material.

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