JP3376735B2 - Liquid crystalline resin molded products - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is excellent in mold releasability from a mold at the time of molding, is thermally and chemically stable, does not generate decomposition gas, etc. TECHNICAL FIELD The present invention relates to a liquid crystalline resin molded product having excellent weldability and excellent dimensional accuracy in which the mechanical properties and moldability are well balanced.

[0002]

2. Description of the Related Art In recent years, demands for higher performance of plastics have been increasing, and many polymers having various new properties have been developed and put on the market. Among them, optics characterized by parallel arrangement of molecular chains Anisotropic liquid crystalline polymers are drawing attention because they have excellent fluidity, heat resistance, mechanical properties, and dimensional stability.

Polymers that form an anisotropic molten phase include
For example, a liquid crystalline polymer obtained by copolymerizing polyethylene terephthalate with p-hydroxybenzoic acid (Japanese Patent Laid-Open No. 49-723).
93), a liquid crystalline polymer obtained by copolymerizing p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid (JP-A-54-77691), and p-hydroxybenzoic acid containing 4,4′- Liquid crystalline polymer obtained by copolymerizing dihydroxybiphenyl with terephthalic acid and isophthalic acid
7-24407), 6-hydroxy-2-naphthoic acid, a liquid crystalline polymer formed from p-aminophenol and terephthalic acid (JP-A-57-172921),
A liquid crystalline polymer formed from p-hydroxybenzoic acid, 4,4'-dihydroxybiphenyl and terephthalic acid, p-aminobenzoic acid and polyethylene terephthalate (JP-A-64-33123) is disclosed.

These liquid crystalline polymers have a drawback that they have large mechanical anisotropy and dimensional anisotropy, but for example, a method of adding glass fiber to the liquid crystalline polymer (rubber digest, Vol. 27, No. 8, 7-14). Page (1975)), a method of blending a liquid crystalline polymer with a plate-like powder typified by mica, talc and graphite (JP-A-63-146959).
The anisotropy is alleviated and the mechanical strength, heat resistance, moldability and dimensional stability are further improved by the
It is used in a wide range of applications such as electric / electronic parts, precision machine parts, and office machine parts.

The liquid crystalline resin is generally excellent in fluidity and thus can be easily molded and used as a thin-walled molded product or a molded product having a complicated shape. However, in such a thin-walled molded product or a molded product having a complicated shape, molding is possible. Various problems have come to be pointed out, such as deformation due to mold release during processing, resulting in poor dimensional accuracy of the molded product, work requiring removal of the molded product due to deformation, and reduced productivity. ing.

Generally, as a method for improving the releasing property, a method of adding various releasing agents, for example, fatty acid esters, fatty acid metal salts, fatty acid amides, low molecular weight polyolefin polymers, etc. to a resin, Kaihei 2-20803
JP-A-4-120162 discloses a method of blending a liquid crystalline polyester with a fatty acid ester, and JP-A-4-120162 discloses a thermoplastic polyester resin comprising a polyhydric alcohol (glycerin and pentaerythritol) and a fatty acid having 12 or more carbon atoms. A method of adding a fatty acid ester is disclosed.

However, even if these methods are applied to the liquid crystalline resin, since the processing temperature of the liquid crystalline resin is high, these releasing agents are thermally decomposed to generate volatile gas, which adversely affects the appearance of the molded product. In addition, since the effect of the release agent is impaired, there is a problem that the molded product is not well separated from the mold and the molded product is deformed. Further, in particular, in the case of a molded product having a welded portion, there is a problem that the strength of the welded portion is greatly reduced, the strength of the molded product is insufficient, and it cannot be practically used as a molded product.

[0008]

SUMMARY OF THE INVENTION Therefore, the present invention solves the above-mentioned problems, is excellent in mold releasability from a mold during molding, and is thermally and chemically stable and decomposes without deformation of the molded product. The objective is to obtain a liquid crystalline resin molded product with excellent dimensional accuracy that does not generate gas or the like, has little weakness in the strength of the weld part, has an excellent weld part with balanced heat resistance, mechanical properties, and moldability. .

[0009]

The present inventors have arrived at the present invention as a result of extensive studies to solve the above problems.

That is, the present invention relates to (A) 100 parts by weight of a liquid crystalline resin selected from a liquid crystalline polyester and a liquid crystalline polyester amide forming an anisotropic molten phase, and (B) polyethylene, Polypropylene, copolymer of ethylene and α-olefin having 3 or more carbon atoms, copolymer of propylene and α-olefin having 4 or more carbon atoms, ethylene, α-olefin having 3 or more carbon atoms and non-conjugated diene An olefin polymer having at least one selected from a copolymer and a copolymer consisting of propylene, an α-olefin having 4 or more carbon atoms and a non-conjugated diene, and having a weight average molecular weight of 10,000 to 600,000. It is a composition containing from 1 to 2 parts by weight, and the composition is injection molded under the following set conditions. Weld strength obtained by the equation (1) from the bending strengths of the welded product (X) having a welded part in the welded part and the non-welded product not having a welded part (Y), respectively. Liquid crystalline resin molded product having a weld portion formed by melt molding a composition having a retention ratio of 15% or more, weld strength retention ratio (%) = (bending strength of weld molded product (X) having weld portion / weld Bending strength of non-welded molded product (Y) without parts) × 100 ---- (1) (Setting condition Cylinder temperature: [melting point of liquid crystalline resin (A) +10] ℃ Mold temperature: 90 ℃ Molding Product: Width 6.0 mm x Length 127 mm x Thickness 1 mm) The above liquid crystalline resin molded product having a weld portion having a weld strength retention rate of 25% or more, and a liquid crystalline resin (A) is a wholly aromatic liquid crystalline polyester. , Wholly aromatic The above-mentioned liquid crystalline resin molded article, which is one or more liquid crystalline resins selected from liquid crystalline polyesteramides, liquid crystalline polyesters having ethylenedioxy units, and liquid crystalline polyesteramides having ethylenedioxy units, liquid crystalline resins (A ) Is a liquid crystalline polyester comprising the following structural units (I), (III) and (IV), (I), (II) and (IV)
A liquid crystalline polyester comprising the structural unit of (I),
The above-mentioned liquid crystalline resin molded article, which is one or more selected from liquid crystalline polyesters composed of structural units (II), (III) and (IV),

[Chemical 5] (However, R1 in the formula is

[Chemical 6] Represents one or more groups selected from

[Chemical 7] Represents one or more groups selected from Further, in the formula, X represents a hydrogen atom or a chlorine atom, and the structural unit [(II) + (III)
] And the structural unit (IV) are substantially equimolar. The above liquid crystalline resin composition, wherein the composition further comprises 400 parts by weight or less of a filler with respect to 100 parts by weight of the liquid crystalline resin (A), and the composition is the liquid crystalline resin 100.
The liquid crystalline resin composition described above, which further comprises 0.5 to 60 parts by weight of an organic bromide with respect to parts by weight, one of the following structural units in which the organic bromide is produced from brominated styrene monomer: The above liquid crystalline resin composition and composition which are polybrominated styrene having the above-mentioned main constituents and a weight average molecular weight of 1 × 10 ^{3 to} 120 × 10 ⁴ are carbon black 0. 01-
The present invention provides the above liquid crystalline resin molded article containing 10 parts by weight.

[0011]

[Chemical 8]

The liquid crystalline polyester referred to in the present invention forms an anisotropic melt phase composed of structural units selected from aromatic oxycarbonyl units, aromatic dioxy units, aromatic dicarbonyl units, ethylenedioxy units and the like. For example, polyester. Further, the liquid crystalline polyesteramide is a liquid crystalline polyesteramide that forms an anisotropic molten phase composed of structural units selected from the structural units and aromatic iminocarbonyl units, aromatic diimino units, aromatic iminooxy units, and the like. is there.

The liquid crystalline polyester and / or the liquid crystalline polyesteramide used in the present invention is a polyester and / or a polyesteramide capable of forming an anisotropic molten phase when melted. For example, a liquid crystal having a wholly aromatic ring, preferably a naphthalene ring. It may be a liquid crystalline polyester, a wholly aromatic, preferably a liquid crystalline polyesteramide having a naphthalene ring, a liquid crystalline polyester having an ethylenedioxy unit, or a liquid crystalline polyesteramide having an ethylenedioxy unit.

Preferred examples of the liquid crystalline polyester include a liquid crystalline polyester composed of the structural units (I), (III) and (IV), and a liquid crystal composed of the structural units (I), (II) and (IV). Examples of the liquid crystalline polyester include liquid crystalline polyesters composed of structural units of (I), (II), (III) and (IV), and among them, structural units of (I), (II) and (IV). Or a liquid crystalline polyester comprising (I) or (I
A liquid crystalline polyester comprising the structural units I), (III) and (IV) is preferred.

The structural unit (I) is a polyester structural unit produced from p-hydroxybenzoic acid, and the structural unit (II) is 4,4'-dihydroxybiphenyl.
3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, phenylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene,
A structural unit produced from an aromatic dihydroxy compound selected from 2,2-bis (4-hydroxyphenyl) propane and 4,4′-dihydroxydiphenyl ether, a structural unit (III) is a structural unit produced from ethylene glycol, Structural unit (IV) is terephthalic acid, isophthalic acid, 4,4′-diphenyldicarboxylic acid, 2,
6-naphthalenedicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4'-dicarboxylic acid, 1,2-bis (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid and 4,4'diphenyl ether Each of the structural units formed from an aromatic dicarboxylic acid selected from dicarboxylic acids is shown.

Of these, R ₁ is

[Chemical 9] And R ₂ is

[Chemical 10] Are particularly preferred.

The liquid crystalline polyester which can be preferably used in the present invention includes the above structural units (I), (II) and (I).
V) or a copolymer comprising (I), (II), (III) and (IV), wherein the amount of the above structural units (I), (II), (III) and (IV) is copolymerized Is optional. However, from the viewpoint of fluidity, the following copolymerization amount is preferable.

That is, when the structural unit (III) is contained, [(I) + for structural unit [(I) + (II) + (III)] from the viewpoint of heat resistance, flame retardancy and mechanical properties. The molar fraction of (II)] is preferably 60 to 95 mol%, more preferably 75 to 93 mol%. Further, for the structural unit [(I) + (II) + (III)], (I
The molar fraction of II) is preferably 40 to 5 mol%, 25 to 25
7 mol% is more preferable. Further, the structural unit (I) / (I
The molar ratio of I) is preferably 75/25 to 95/5, more preferably 7 from the viewpoint of the balance between heat resistance and fluidity.
It is 8/22 to 93/7. Further, the number of moles of the structural unit (IV) is substantially equal to the total number of moles of the structural unit [(II) + (III)]. Here, "substantially" means that the number of the terminal groups of the polyester can be either carboxyl group terminals or hydroxyl group terminals in many cases, and in such a case, the number of moles of the structural unit (IV) is This is because it is not completely equal to the total number of moles of the structural unit [(II) + (III)].

On the other hand, when the structural unit (III) is not contained, the structural unit [(I) + (I
The molar fraction of (I) with respect to (I)] is preferably 40 to 90 mol%, more preferably 60 to 88 mol%. Further, the number of moles of the structural unit (IV) is substantially equal to the number of moles of the structural unit (II). Here, "substantially" means the same as in the case of containing the structural unit (III), and the same also in the case of the liquid crystal polyester composed of the structural units (I), (III) and (IV). .

When the above-mentioned liquid crystalline polyester which can be preferably used in the present invention is polycondensed, 3,3'-diphenyldicarboxylic acid, 2,2 are added in addition to the components constituting the structural units (I) to (IV). '-Diphenyldicarboxylic acid and other aromatic dicarboxylic acids, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and other aliphatic dicarboxylic acids, hexahydroterephthalic acid and other alicyclic dicarboxylic acids, chlorohydroquinone, methylhydroquinone, 4 , 4'-dihydroxydiphenyl sulfone, 4,
4'-dihydroxydiphenyl sulfide, 4,4'-
Aromatic diols such as dihydroxybenzophenone, 1,
Aliphatic such as 4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol,
Alicyclic diol and m-hydroxybenzoic acid, 2,6
-Aromatic hydroxycarboxylic acids such as hydroxynaphthoic acid, p-aminophenol, p-aminobenzoic acid and the like can be further copolymerized in a small proportion within a range not impairing the object of the present invention.

As the liquid crystalline polyesteramide, a polyesteramide which forms an anisotropic melt phase containing a p-iminofexoxy unit formed from p-aminophenol in addition to the above structural units (I) to (IV) is preferable.

The method for producing the liquid crystalline resin (A) in the present invention is not particularly limited and can be produced according to the known polycondensation method of polyester or polyesteramide.

For example, in the production of the above-mentioned preferably used liquid crystalline polyester, the above structural unit (III) is used.
When it does not contain the following (1) and (2), when it contains the structural unit (III), the production method of the following (3) is preferably mentioned.

(1) p-acetoxybenzoic acid and 4,
A method for producing a diacylated aromatic dihydroxy compound such as 4′-diacetoxybiphenyl or 4,4′-diacetoxybenzene and an aromatic dicarboxylic acid such as terephthalic acid by a deacetic acid polycondensation reaction. (2) p-Hydroxybenzoic acid, aromatic dihydroxy compounds such as 4,4′-dihydroxybiphenyl and hydroquinone, and aromatic dicarboxylic acids such as terephthalic acid are reacted with acetic anhydride to acylate the phenolic hydroxyl group, A method for producing by deacetic acid polycondensation reaction. (3) Polyester polymers such as polyethylene terephthalate, oligomers or bis (β of aromatic dicarboxylic acids such as bis (β-hydroxyethyl) terephthalate
-A method for producing by the method (1) or (2) in the presence of hydroxyethyl) ester.

Although these polycondensation reactions proceed without a catalyst, it is sometimes preferable to add a metal compound such as stannous acetate, tetrabutyl titanate, potassium acetate and sodium acetate, antimony trioxide, or magnesium metal. .

Some of the liquid crystalline resins (A) in the present invention are capable of measuring the logarithmic viscosity in pentafluorophenol, and in this case, the concentration is 6 at a concentration of 0.1 g / dl.
The value measured at 0 ° C. is preferably 0.5 dl / g or more, particularly 1.0 to 3.0 dl when the above structural unit (III) is contained.
/ G is preferable, and when the structural unit (III) is not contained, 2.0 to 10.0 dl / g is preferable.

The melt viscosity of the liquid crystalline resin (A) in the present invention is preferably 10 to 20,000 poise, and more preferably 20 to 10,000 poise.

The above melt viscosity is the melting point (Tm) +1.
It is a value measured by a Koka flow tester under conditions of 0 ° C. and a shear rate of 1,000 (1 / sec).

Here, the melting point (Tm) is Tm1 after the endothermic peak temperature Tm1 observed when the polymer is measured from the room temperature under a temperature rising condition of 20 ° C./min by differential calorimetry.
After the temperature was raised to + 20 ° C. and kept at the same temperature for 5 minutes, the temperature was once cooled to room temperature under the temperature lowering condition of 20 ° C./min.
The endothermic peak temperature observed when measured again under the temperature rising condition of 20 ° C./min is shown.

The olefin polymer used in the present invention is polyethylene, polypropylene, a copolymer of ethylene and an α-olefin having 3 or more carbon atoms, a copolymer of propylene and an α-olefin having 4 or more carbon atoms, It is one or more selected from a copolymer consisting of ethylene and an α-olefin having 3 or more carbon atoms and a non-conjugated diene, and a copolymer consisting of propylene and an α-olefin having 4 or more carbon atoms and a non-conjugated diene.

The α-olefin having 3 or more carbon atoms is preferably propylene, butene-1, pentene-.
1,3-methylpentene-1, octacene-1, etc. are more preferable, and propylene and butene-1 are more preferable, and these can be used in combination of two or more kinds.

Examples of the α-olefin having 4 or more carbon atoms include those excluding propylene among the α-olefins having 3 or more carbon atoms, and these can be used in combination of two or more kinds.

The non-conjugated diene is preferably 5-ethylidene-2-norbornene, dicyclopentadiene,
1,4-hexadiene or the like can be used.

The copolymerization ratio of ethylene and the α-olefin having 3 or more carbon atoms is usually 40/60 to 99 / in the copolymer comprising ethylene and the α-olefin having 3 or more carbon atoms.
1 (molar ratio), preferably 70/30 to 95/5 (molar ratio). Further, the copolymerization ratio of propylene and α-olefin having 4 or more carbon atoms is usually 40/6 in the copolymer consisting of propylene and α-olefin having 4 or more carbon atoms.
0-99 / 1 (molar ratio), preferably 70 / 30-95
/ 5 (molar ratio).

The copolymerization amount of ethylene in the copolymer consisting of ethylene, an α-olefin having 3 or more carbon atoms and a non-conjugated diene is usually 5 to 96.9 mol%, preferably 30 to 84.5 mol%. And the copolymerization amount of the α-olefin having 3 or more carbon atoms is usually 3 to 80 mol%, preferably 15 to 60 mol%, and the copolymerization amount of the non-conjugated diene is usually 0.1 to 15 mol%. Mol%, preferably 0.5-1
It is 0 mol%. The copolymerization amount of propylene in the copolymer of propylene and an α-olefin having 4 or more carbon atoms and a non-conjugated diene is usually 5 to 96.9 mol%, preferably 30 to 84.5 mol%. The copolymerization amount of the α-olefin having 3 or more carbon atoms is usually 3 to 80.
The amount of the non-conjugated diene copolymerized is usually 0.1 to 15 mol%, preferably 0.5 to 10 mol%.

Specific examples of these copolymers include ethylene / propylene copolymer, ethylene / butene-1 copolymer, ethylene / pentene-1 copolymer, ethylene / propylene / butene-1 copolymer, propylene. / Penten-
1 copolymer, propylene / butene-1 copolymer, ethylene / propylene / 5-ethylidene-2-norbornene copolymer, ethylene / propylene / 1,4-hexadiene copolymer, propylene / butene-1 / 1 It is a 4-hexadiene copolymer, an ethylene / propylene / dicyclopentadiene copolymer, and the like. Among them, an ethylene / propylene copolymer and an ethylene / butene-1 copolymer are more preferable because of excellent heat resistance.

Two or more of the above olefin polymers may be used in combination.

From the viewpoint of fluidity of the resulting composition, it is preferable that these olefin polymers are not copolymerized with a monomer containing an epoxy group, a carboxylic acid group or the like.

The weight average molecular weight of the above olefin polymer is 10,000 to 600,000, preferably 30,000.
500,000, more preferably 100,000 to 450
A low molecular weight polyolefin polymer having a weight-average molecular weight of less than 10,000, which is well known as a mold release agent, which is desirable to be in the range of 000, not only has a poor mold release effect, but also has a weak weld strength and a gas burn on a molded product. It is not preferred.

When the weight average molecular weight exceeds 600,000, fluidity and physical properties are deteriorated, which is not preferable.

The addition amount of the olefin polymer is 0.0
1 to 2 parts by weight, preferably 0.05 to 1.90 parts by weight,
Particularly preferred is 0.1 to 1.80 parts by weight. Addition amount is 0.
If the amount is less than 01 parts by weight, the releasability improving effect is not exhibited at all and 2
If it exceeds the weight part, the weld strength is lowered, which is not preferable.

In the present invention, a filler can be further added, and specific examples thereof include glass fiber, carbon fiber,
Aromatic polyamide fiber, potassium titanate fiber, gypsum fiber, brass fiber, stainless fiber, steel fiber, ceramic fiber, boron whisker fiber, asbestos fiber, mica, talc, silica, calcium carbonate, glass beads, glass flakes, glass microballoons , Clay, molybdenum disulfide, wollastonite, titanium oxide,
Examples thereof include fibrous, powdery, granular or plate-like fillers such as calcium polyphosphate and graphite. Among the above fillers, glass fiber is preferably used.

The type of glass fiber is not particularly limited as long as it is generally used for reinforcing a resin, and for example, long fiber type or short fiber type chopped strand, milled fiber or the like can be selected and used.

When the above-mentioned filler is added, the addition amount is usually 400 parts by weight or less, preferably 50 to 250 parts by weight, more preferably 70 to 200 parts by weight, based on 100 parts by weight of the liquid crystalline resin. .

The surface of the above-mentioned filler used in the present invention is treated with a known coupling agent (for example, a silane coupling agent, a titanate coupling agent, etc.) or another surface treatment agent before use. You can also

Further, the glass fiber may be coated or bundled with a thermoplastic resin such as ethylene / vinyl acetate copolymer or the like, or a thermosetting resin such as an epoxy resin or the like.

In the present invention, an organic bromine compound may be further blended, and the organic bromine compound which can be used includes a known organic bromine compound which is usually used as a flame retardant, and particularly, the bromine content is 20% by weight. The above is preferable. Specifically, hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, hexabromocyclodecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis (pentabromophenoxy) ethane, ethylene-bis (tetra Bromophthalimide), low molecular weight organic bromine compounds such as tetrabromobisphenol A, brominated polycarbonate (for example, a polycarbonate oligomer produced from brominated bisphenol A as a raw material or a copolymer thereof with bisphenol A, brominated epoxy compound (for example, brominated) By the reaction of a diepoxy compound produced by the reaction of bisphenol A with epichlorohydrin or the reaction of brominated phenols with epichlorohydrin Monoepoxy compounds obtained), poly (brominated benzyl acrylate), a condensation product of brominated polyphenylene ether, brominated bisphenol A cyanuric chloride and brominated phenols, brominated polystyrene, crosslinked brominated polystyrene, crosslinked brominated poly α-
Examples thereof include halogenated polymers and oligomers such as methylstyrene, and mixtures thereof. Among them, ethylene bis (tetrabromophthalimide), brominated epoxy oligomer or polymer, brominated polystyrene, crosslinked brominated polystyrene, brominated polyphenylene ether. And brominated polycarbonate are preferred, and brominated polystyrene is most preferred.

The above-mentioned preferable organic bromide will be described in more detail. As the brominated epoxy polymer, those represented by the following general formula (i) are preferable.

[0049]

[Chemical 11]

The polymerization degree n in the general formula (i) is preferably 15 or more, more preferably 50 to 80.

As the brominated polystyrene used in the present invention, brominated polystyrene and crosslinked brominated polystyrene produced by brominating polystyrene obtained by radical polymerization or anionic polymerization, or brominated styrene monomer by radical polymerization or anion Examples thereof include polybrominated styrene having a brominated styrene unit represented by the formula (ii) and / or (iii) produced by polymerization, preferably radical polymerization. )and/
Alternatively, polybrominated styrene having a structural unit represented by the formula (iii) as a main constituent and a weight average molecular weight of 1 × 10 ^{3 to} 120 × 10 ⁴ is preferable.

[0052]

[Chemical 12]

The term "brominated styrene monomer" as used herein is preferably one having two to three bromine atoms introduced into its aromatic ring by a substitution reaction per one styrene monomer, such as dibrominated styrene and / or tribrominated. In addition to styrene, monobrominated styrene and the like may be contained.

The polybrominated styrene preferably contains 60% by weight or more of dibrominated styrene and / or tribrominated styrene units, more preferably 70% by weight or more. In addition to dibrominated styrene and / or tribrominated styrene, polybrominated styrene obtained by copolymerizing 40% by weight or less, preferably 30% by weight or less of monobrominated styrene may be used. The weight average molecular weight of this polybrominated styrene is more preferably 1 × 10 ⁴ to 15 × 10 ⁴ . The weight average molecular weight is a value measured using a gel permeation chromatograph and is a relative value based on polystyrene molecular weight.

The crosslinked brominated polystyrene is preferably polystyrene obtained by brominated porous polystyrene crosslinked with divinylbenzene.

As the brominated polycarbonate, those represented by the following general formula (iv) are preferable.

[0057]

[Chemical 13] (R3 and R4 each represent a substituted or unsubstituted aryl group, and a pt-butylphenyl group is most preferable.)

The degree of polymerization n in the general formula (iv) is 4
The above is preferable, 8 or more, especially 8 to 2
5 can be used more preferably.

The amount of the organic bromide compounded is 0.5 to 60 parts by weight, especially 1 to 100 parts by weight of the liquid crystalline resin.
30 parts by weight is preferred.

In the liquid crystalline resin molded article of the present invention, the organic bromide has an average diameter of 25 μm in the resin composition before molding.
It is preferably dispersed below, and more preferably 2.0 μm or less.

In the present invention, carbon black can be further blended, and the carbon black that can be used is not particularly limited, but from the viewpoint of mechanical properties of the composition obtained, PH of 3 to 10 is preferable. Preferably PH
Those having 5 to 9 are particularly preferably used.

The liquid crystalline resin molded article of the present invention comprises an antioxidant and a heat stabilizer (eg hindered phenol, hydroquinone, phosphites and their substitution products), an ultraviolet absorber (eg resorcinol, salicylate, benzo). Triazole, benzophenone, etc.),
Lubricants, dyes (eg nigrosine etc.) and pigments (eg cadmium sulfide, phthalocyanine etc.), colorants including plasticizers, flame retardant aids, antistatic agents etc. and other thermoplastic resins (fluorine resin etc.) ) Can be added.

The method for producing the liquid crystalline resin molded article of the present invention is not particularly limited, but a desired molded article can be obtained by producing a liquid crystalline resin composition by melt-kneading and then performing melt molding.

The production method of melt-kneading the liquid crystalline resin composition is not particularly limited, but for example, a Banbury mixer, a rubber roll machine, a kneader, a single-screw or twin-screw extruder, etc. are used and the temperature is 200 to 400 ° C. Can be melt-kneaded to obtain a composition. Among them, a twin-screw extruder is used, and other additives such as (A) liquid crystalline resin, (B) olefin polymer and glass fiber as raw materials are sequentially and continuously supplied to the extruder. It is recommended to apply a method such as melt kneading.

In the present invention, the liquid crystal resin composition obtained as described above has a weld strength retention measured by the following method of 15% or more, more preferably 20% or more, and particularly preferably 25% or more. . When the weld strength retention rate is less than 15%, the strength of the weld portion of the liquid crystalline resin molded product is low and it cannot be practically used.

The weld strength retention rate in the present invention can be determined by the following method.

(1) A test piece (molded product) is produced under the following conditions.

A: Test piece The setting conditions for injection molding the test piece are as follows.

Cylinder temperature: [melting point of liquid crystalline resin (A) +10] ° C. Mold temperature: 90 ° C. Molded product: width 6.0 mm × length 127 mm × thickness 1 mm More specifically, 3 mm from both ends in the length direction. Cylinder temperature of injection molding machine [melting point of liquid crystalline resin (A) +10] using molds with gates each having a width of 3 mm
Injection molding under conditions of ℃, mold temperature 90 ℃, width 6.00m
A weld molded product (X) having a weld portion at approximately the center of m × length 127 mm × thickness 1 mm is prepared. Also,
In the above, the non-weld molded article (Y) having no welded portion, which was injection molded from one of the gates, was subjected to the same conditions as above.
That is, injection molding is performed under the conditions that the cylinder temperature of the injection molding machine is [melting point of liquid crystal resin (A) +10] ° C. and the mold temperature is 90 ° C.

In the actual injection molding, as an error of the above setting conditions, the following range is usually allowable: Cylinder temperature: [melting point of liquid crystalline resin (A) +10] ± 8
℃ Mold temperature: 90 ℃ ± 10 ℃ Molded product: Width 6.0 ± 0.30mm × Length 127 ± 3mm
× Thickness 1 ± 0.2 mm When the melting point of the liquid crystalline resin used is difficult to measure, the cylinder temperature is [liquid crystal starting temperature +40].
The liquid crystal starting temperature + 40 ° C. ± 8 ° C. can be used as a substitute.

FIG. 1 is a conceptual perspective view of a weld-molded product (X), which is injection-molded with gate positions 2 provided at positions 3 mm from both ends in the length direction, and has a length (L1) 127.
1 shows a weld molded product (X) 1 having dimensions of mm × width (w1) 6.0 mm × thickness (t1) 1 mm.

(2) Method for measuring weld strength retention rate The test piece was tested at room temperature of 23 ± 2 ° C. and relative humidity of 50 ± 5.
% Down for more than 15 hours.

Next, the bending strength of the weld molded product (X) and the non-weld molded product (Y) having no weld portion are measured under the conditions of a span distance of 20 mm and a strain rate of 0.7 mm / min.

The weld strength retention rate is obtained by substituting the bending strength of each test piece into the equation (1).

As a method for measuring the weld strength retention rate,
The bending strength of each of a weld-molded product (X) having a weld part in the substantially central part and a non-weld molded product (Y) having no weld part, which were obtained by injection-molding the above-mentioned composition under the following setting conditions, was measured. It is calculated from the bending strength of the product by the formula (1).

Weld strength retention rate (%) = (bending strength of weld molded product (X) having weld part / bending strength of non-weld molded product (Y) having no weld part) × 100 ---- ( 1) The liquid crystalline resin molded product of the present invention can be produced by melt-molding the above liquid crystalline resin composition. The melt molding method is not limited to injection molding, extrusion molding, blow molding, etc., but injection molding is preferable.
As a preferable injection molding method, for example, a range of the melting point of the liquid crystalline resin composition from −30 ° C. to + 50 ° C. (in the case of a liquid crystalline resin whose melting point is difficult to measure, the liquid crystal starting temperature + 10 ° C. to the liquid crystal starting temperature The above liquid crystalline resin composition is supplied to an in-line type injection molding machine set at + 90 ° C), the mold temperature is set to a temperature condition of about 70 ° C to 150 ° C, and injection molding is performed on the mold of the desired molded product. Then, a method such as obtaining a liquid crystalline resin molded product having a weld portion is recommended.
The number of gates for injection-molding the molded product is not particularly limited, and one or more gates can be used for molding.

The molded product of the present invention can be molded as described above, for example, but it is necessary that the molded product has at least one weld portion.

The term "weld portion" as used in the present invention means a portion formed by contacting at least one resin with the other resin in a molten state during the molding process. The resins may be the same or different.

The liquid crystalline resin molded product of the present invention thus obtained is used as a three-dimensional molded product, a molded product such as a sheet, a container or a pipe, for example, various gears, various cases, sensors,
LEP lamp, connector, socket, resistor, relay case, switch, coil bobbin, capacitor, variable capacitor case, optical pickup, oscillator, various terminal boards, transformer, plug, printed wiring board, tuner, speaker, microphone, headphones, small size Electric / electronic parts such as motors, magnetic head bases, power modules, housings, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, computer related parts; VTRs
Parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, audio parts, audio equipment parts such as audio / laser disks / compact disks, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, etc. , Household electric appliances, office computer related parts, telephone related parts, facsimile related parts, copier related parts, cleaning jigs, oilless bearings, stern bearings, underwater bearings, and other bearings, motors Mechanical parts such as parts, lighters and typewriters, optical devices such as microscopes, binoculars, cameras and watches, precision mechanical parts; alternator terminals, alternator connectors, IC regulators, light deer potentiometers , Various valves such as exhaust gas, exhaust gas valve, various pipes related to fuel, exhaust system, intake system, air intake nozzle snorkel, intake manifold, fuel pump, engine cooling water joint, carburetor main body, carburetor spacer, exhaust gas sensor, cooling water Sensor, Oil temperature sensor, Brake pad wear sensor, Throttle position sensor, Crankshaft position sensor, Air flow meter, Brake butt wear sensor, Air conditioner thermostat base, Heating hot air flow control valve, Radiator motor brush holder, Water pump impeller , Turbine vanes, wiper motor related parts, Dust tributors, starter switches, starter relays, transformers Wiring harness, window washer nozzle, air conditioner panel switch board, fuel related electromagnetic valve coil, fuse connector, horn terminal, electrical component insulating plate, step motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, solenoid. It is useful for automobile / vehicle related parts such as bobbins, engine oil filters, ignition device cases, and other various applications.

[0080]

EXAMPLES The present invention will be described in more detail below with reference to examples.

Reference Example 1 p-Hydroxybenzoic acid 994 parts by weight, 4,4'-dihydroxybiphenyl 126 parts by weight, terephthalic acid 112
Parts by weight, 216 parts by weight of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g and 960 parts by weight of acetic anhydride are charged into a reaction vessel equipped with a stirring blade and a distilling tube to carry out polycondensation to complete polycondensation. (A) was obtained. The melting point (Tm) of this resin is 314 ° C., 324 ° C., shear rate 10
The melt viscosity at 00 / sec was 400 poise.

Reference Example 2 994 parts by weight of p-hydroxybenzoic acid, 222 parts by weight of 4,4'-dihydroxybiphenyl, 147 parts by weight of 2,6-diacetoxynaphthalene, 1078 parts by weight of acetic anhydride and 299 parts by weight of terephthalic acid were stirred. It was charged in a reaction vessel equipped with blades and a distillation tube, polycondensation was performed, and the polycondensation was completed to obtain a resin (B). The melting point (Tm) of this resin is 336 ° C.
And the melt viscosity at 346 ° C. and a shear rate of 1000 / sec was 520 poise.

Reference Example 3 According to JP-A-49-72393, 1296 parts by weight of p-acetoxybenzoic acid and an intrinsic viscosity of about 0.6 dl /
346 parts by weight of polyethylene terephthalate (g) was charged into a reaction vessel equipped with a stirring blade and a distilling tube to carry out polycondensation,
The melting point (Tm) of the resin (C) obtained was 283 ° C., and the melt viscosity at a shear rate of 293 ° C. of 1000 / sec was 1,200 poises.

Reference Example 4 According to JP-A-54-77691, 921 parts by weight of p-acetoxybenzoic acid and 435 parts by weight of 6-acetoxynaphthoic acid were placed in a reaction vessel equipped with a stirring blade and a distillation tube, and the weight was increased. Condensation was performed to obtain a resin (D). The melting point (Tm) of this resin is 283 ° C., 293 ° C., shear rate 100
The melt viscosity at 0 / sec was 2,000 poise.

Examples 1 to 4, Comparative Examples 1 to 5 The liquid crystalline resins obtained in Reference Examples 1 to 4 were dry blended with the olefin polymers shown in Table 1 at the ratio shown in Table 1, and then the cylinder temperature was changed. Were melt-kneaded using a 30 mmφ twin-screw extruder set to the melting point of each liquid crystalline resin to give pellets. Next, the obtained pellets were subjected to a Sumitomo Nestal injection molding machine Promat (manufactured by Sumitomo Heavy Industries, Ltd.), and the cylinder temperature was set to the melting point of the liquid crystalline resin + 10 ° C and the mold temperature of 9
Weld molded article (X) having a weld portion at a substantially central portion of width 6 mm x length 127 mm x thickness 1 mm under the condition of 0 ° C.
And a non-weld molded product (Y) having no welded portion is injection-molded. The molded product was adjusted to room temperature of 23 ± 2 ° C. and relative humidity of 50 ± 5% for 15 hours or more, and then the weld molded product was spun at room temperature (X) and a non-weld molded product (Y) having no weld part. The bending strength was measured under the conditions of a distance of 20 mm and a strain rate of 0.7 mm, and the bending strength of the molded product was substituted into the formula (1) to obtain the weld strength retention rate.

Weld strength retention rate (%) = bending strength of weld molded product (X) having weld part / bending strength of non-weld molded product (Y) having no weld part × 100 ---- (1) Further, the pellets were subjected to a Toshiba IS55EPN injection molding machine (manufactured by Toshiba Machine Plastics Engineering Co., Ltd.), the cylinder temperature was the melting point of the liquid crystalline resin + 10 ° C, and the mold temperature was 90 ° C. 10m
It is a box-shaped product of m × 100 mm in length and 1 mm in thickness, and has two 0.8 mm thick partition walls at equal intervals.
Injection molding was performed at the point gate, and the ejection force (release force) when the molded product was ejected from the mold was measured, and the releasability was evaluated. FIG. 2 is a conceptual perspective view of the box-shaped molded product. The molded product 3 is injection-molded from two gate positions 2 and has a size of width (w2) 8 mm × height (t2) 10 mm.
X Length (L2) is 100 mm, and it has a box shape.

In the measurement of the ejection force (release force), the smaller the ejection force (release force), the better the releasability. Further, the shape of the partition wall portion of the molded product was visually observed for the presence or absence of deformation due to the protruding pin at the time of release, and used as a measure of dimensional stability.

[0088]

[Table 1]

Examples 5 to 17 and Comparative Examples 6 to 12 Table 2 shows the liquid crystalline resins obtained in Reference Examples 1 to 4 with the olefin polymers shown in Table 2 and other additives shown in Table 2. After dry blending at different ratios, the mixture was melt-kneaded into pellets using a 30 mmφ twin-screw extruder in which the cylinder temperature was set to the melting point of each liquid crystalline resin. Next, the pellets obtained were subjected to Sumitomo Nestal injection molding machine Promat (Sumitomo Heavy Industries, Ltd.), and the cylinder temperature was the melting point of the liquid crystalline resin + 10 ° C, and the mold temperature was 90 ° C, and the width was 6.00 mm.
A weld-molded product (X) having a weld portion at approximately the center of 127 mm length × 1 mm thickness and a non-weld molded product (Y) having no weld portion are injection-molded.

The molded product was kept at room temperature of 23 ± 2 ° C. and relative humidity of 50.
After adjusting to ± 5% for 15 hours or more, then bend strength of weld molded product (X) and non-weld molded product (Y) having no weld part under span distance of 20 mm and strain rate of 0.7 mm. Measure and calculate the bending strength of the molded product using formula (1)
To obtain the weld strength retention rate.

Weld strength retention rate (%) = bending strength of weld molded product (X) having weld part / bending strength of non-weld molded product (Y) having no weld part × 100 ---- (1) Further, the pellets were subjected to a Toshiba IS55EPN injection molding machine (manufactured by Toshiba Machine Plastic Engineering Co., Ltd.) and prepared in Example 1 under the conditions that the cylinder temperature was the melting point of the liquid crystalline resin + 10 ° C and the mold temperature was 90 ° C. A box-shaped molded product similar to that in Example 1 was produced, and the protruding force (mold releasing force) when the molded product was ejected from the mold and the presence or absence of deformation by the ejecting pin at the time of mold release were visually observed as in Example 1. . In addition, the molded product has a span distance of 50 mm and a strain rate of 3 mm.
The bending test was performed under the conditions of and the strength at which a crack was generated in the weld was measured. The results are shown in Table 2.

[0092]

[Table 2]

Examples 18 to 23 Compositions were prepared in the same manner as in Example 5 except that the organic bromide shown in Table 4 was added in the proportion shown in Table 4 to 100 parts by weight of the liquid crystalline resin. Pellets were produced. The pellets were subjected to Sumitomo Nestal injection molding machine Promat 40/25 (Sumitomo Heavy Industries, Ltd.), the cylinder temperature was the melting point of the liquid crystalline resin + 10 ° C, and the mold temperature was 9
0.5 mm (thickness) x 12.7 mm x 1 at 0 ° C
The same procedure as in Example 5 was carried out except that a 27 mm combustion test piece was molded, and a vertical combustion test was performed according to UL94 standard to evaluate the flame retardancy using the combustion test piece. The results are shown in Table 3.

[0094]

[Table 3]

[0095]

[Table 4]

Examples 24 to 28 The same procedure as in Example 5 was carried out except that the carbon black shown in Table 5 was blended in the proportion shown in Table 5 with respect to 100 parts by weight of the liquid crystalline resin.

The results are shown in Table 5.

[0098]

[Table 5]

[0099]

The liquid crystalline resin molded product of the present invention has excellent heat resistance, mechanical properties, dimensional accuracy and mold releasability of the liquid crystalline resin, and has excellent weld strength. It is suitable for various other applications such as equipment, office equipment, automobile / vehicle related parts, etc.

[Brief description of drawings]

FIG. 1 is a conceptual perspective view of a weld molded product (X).

FIG. 2 is a conceptual perspective view of a box-shaped molded product molded in Example 1.

[Explanation of symbols]

1. Weld molding (X) 2. Gate position 3. Box-shaped molded product

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ identification code FI C08L 23:02) (C08L 77/12 23:02) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 67 / 00 C08L 77/12

Claims (9)

(57) [Claims] (1) Polyethylene, polypropylene, ethylene (B) based on 100 parts by weight of one or more liquid crystalline resins selected from liquid crystalline polyesters and liquid crystalline polyesteramides that form an anisotropic molten phase. And a copolymer of α-olefins having 3 or more carbon atoms, a copolymer of propylene and α-olefins of 4 or more carbon atoms, a copolymer of ethylene and α-olefins of 3 or more carbon atoms, and a non-conjugated diene And at least one selected from copolymers consisting of propylene, an α-olefin having 4 or more carbon atoms and a non-conjugated diene, and having a weight average molecular weight of 10
A composition comprising 0.01 to 2 parts by weight of an olefinic polymer in the range of 000 to 600,000, and having a welded portion at approximately the center formed by injection molding the composition under the following set conditions. The bending strengths of the weld-molded product (X) and the non-weld-molded product (Y) having no weld portion were measured, and the weld-strength retention rate calculated by the formula (1) from the bending strength of these molded products was 15% or more. A liquid crystalline resin molded article having a welded part obtained by melt-molding the composition of Weld strength retention rate (%) = (bending strength of weld molded product (X) having weld part / bending strength of non-weld molded product (Y) having no weld part) × 100 ---- (1) ( Setting conditions Cylinder temperature: [melting point of liquid crystalline resin (A) +10] ° C Mold temperature: 90 ° C Molded product: width 6.0 mm x length 127 mm x thickness 1 mm) 2. The liquid crystalline resin molded article according to claim 1, which has a welded portion having a weld strength retention rate of 20% or more. 3. The liquid crystalline resin (A) comprises a wholly aromatic liquid crystalline polyester, a wholly aromatic liquid crystalline polyesteramide, a liquid crystalline polyester having an ethylenedioxy unit and a liquid crystalline polyesteramide having an ethylenedioxy unit. The liquid crystalline resin molded article according to claim 1, which is one or more selected liquid crystalline resins. 4. The liquid crystalline resin (A) is one or more liquid crystalline resin selected from a liquid crystalline polyester having an ethylenedioxy unit and a liquid crystalline polyesteramide having an ethylenedioxy unit. Liquid crystalline resin molded product. 5. A liquid crystal resin (A) is the following (I) or (II)
Liquid crystalline polyester comprising structural units of I) and (IV), liquid crystalline polyester comprising structural units of (I), (II) and (IV) and (I), (II), (I
The liquid crystalline resin molded article according to claim 4, which is one or more selected from liquid crystalline polyesters comprising the structural units of II) and (IV). [Chemical 1] (However, R1 in the formula is R2 represents one or more groups selected from Represents one or more groups selected from Further, in the formula, X represents a hydrogen atom or a chlorine atom, and the structural unit [(II) + (III)
] And the structural unit (IV) are substantially equimolar. ) 6. The liquid crystalline resin molded article according to claim 1, wherein the composition further comprises 400 parts by weight or less of a filler with respect to 100 parts by weight of the liquid crystalline resin (A). 7. A liquid crystalline resin molded article according to claim 1, wherein the composition further comprises 0.5 to 60 parts by weight of an organic bromide per 100 parts by weight of the liquid crystalline resin (A). . 8. An organic bromide is polybrominated styrene having a weight average molecular weight of 1 × 10 ^{3 to} 120 × 10 ⁴ and having at least one of the following structural units produced from a brominated styrene monomer as a main constituent. Item 7. A liquid crystalline resin molded article according to item 7. [Chemical 4] 9. The liquid crystalline resin molded article according to claim 1, wherein the composition further comprises 0.01 to 10 parts by weight of carbon black based on 100 parts by weight of the liquid crystalline resin (A).