WO2005116141A1

WO2005116141A1 - Thermoplastic resin composition

Info

Publication number: WO2005116141A1
Application number: PCT/JP2005/000987
Authority: WO
Inventors: Yoshiaki Taguchi; Toshio Nakane; Toshiaki Yokota
Original assignee: Polyplastics Co., Ltd.
Priority date: 2004-05-26
Filing date: 2005-01-26
Publication date: 2005-12-08

Abstract

A thermoplastic resin composition which comprises 100 parts by weight of an amorphous liquid crystalline resin (A) having the following characteristics (1) to (4): (1) it exhibits no melting point in the DSC measurement using a temperature elevation speed of 20°C/min, (2) it has a glass transition temperature of 100 to 180°C, (3) it exhibits a melt viscosity at 230°C and a shear rate of 1000 sec-1 of 50 to 2000 Pa·s, and (4) it exhibits optical anisotropy when it is softened and flows, and 100 to 900 parts by weight of a molding resin (B) which exhibits no optical anisotropy during melting. The thermoplastic resin composition has excellent heat distortion temperature and rigidity and further is reduced in the exfoliation of the surface of a formed article therefrom and is excellent in its appearance, and thus can be suitably used for an outer panel of an automobile and a housing for electric and electronic products.

Description

Specification

Thermoplastic resin composition

Technical field

The present invention relates to a thermoplastic resin composition suitably used for injection molded articles and the like, comprising a non-crystalline liquid crystal resin and a molding resin that does not show optical anisotropy when melted. More specifically, it significantly improves the fluidity of a molding resin that does not exhibit optical anisotropy when melted into a matrix, has excellent heat deformation temperature and rigidity, and has less peeling of the surface of the molded body. The present invention also relates to a thermoplastic resin composition having excellent heat resistance.

Background art

[0002] Liquid crystal resins are well-suited and widely used as high-performance engineering plastics because they have excellent balance of fluidity, mechanical strength, heat resistance, chemical resistance, and electrical properties.

[0003] With the remarkable industrial development in recent years, the applications of such liquid crystal resins have been diversified, and there has been a tendency to become more sophisticated and specialized. By taking advantage of the high fluidity of liquid crystal resins, injection molding and the like make it more efficient and economical. It has been expected to obtain an injection molded product or the like which retains its excellent physical properties by molding. For example, high mechanical properties and high heat resistance are required for outer panels of automobiles, housings for electric and electronic products, etc. in order to reduce the weight and thickness of the molded body, and the molded body is large and has a high appearance. Is required. However, liquid crystal resin is not suitable for the exterior of automobiles and housings for electric and electronic products because of the appearance of the molded product, and it is difficult to use it versatile for large products from the viewpoint of cost. there were.

[0004] On the other hand, conventional amorphous resins have excellent appearance, but it has been difficult to satisfy these requirements, especially both fluidity and heat resistance.

[0005] Therefore, in recent years, a resin composition of an amorphous resin and a liquid crystal resin has been studied. For example, Patent Documents 13 and 13 all attempt to improve fluidity, heat resistance, and mechanical properties by using a resin composition of an amorphous resin and a liquid crystal resin. However, when it is used for a housing of an outer panel material of an automobile or an electric or electronic product, there is a further problem that the appearance of the molded body, particularly the surface of the molded body is peeled off by a small impact, and the technology disclosed in these patent documents is disclosed. Now, solve this problem It is hard to say that there is.

Patent Document 1: JP 2002-80724 A

Patent Document 2: JP 2001-192518 A

Patent Document 3: JP 2000-159957 A

Disclosure of the invention

Problems to be solved by the invention

[0006] The present invention solves the above-mentioned problems of the prior art, and has excellent heat deformation temperature and rigidity.

It is another object of the present invention to provide a thermoplastic resin composition which is less likely to peel off the surface of a molded product and has excellent appearance, and which is suitably used for an outer panel for automobiles and a housing for electric and electronic products.

Means for solving the problem

[0007] The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, by mixing a specific liquid crystal resin with a molding resin that does not exhibit optical anisotropy when molten as a matrix. The present inventors have found that a thermoplastic resin composition having excellent mechanical properties and appearance can be obtained while significantly improving the fluidity of a molding resin serving as a matrix and maintaining good heat resistance. Reached.

[0008] That is, the present invention relates to a molding resin (A) having no optical anisotropy when melted with respect to 100 parts by weight of an amorphous liquid crystal resin (A) having the following features (1) and (4). B) A thermoplastic resin composition containing 100 to 900 parts by weight.

(1) Melting point was not observed by DSC measurement at a heating rate of 20 ° C / min.

(2) the glass transition temperature is in the range of 100-180 ° C,

(3) The melt viscosity at 230 ° C and a shear rate of lOOOOsec- ¹ is 50 2000 Pa's,

(4) exhibits optical anisotropy during softening flow.

The invention's effect

The thermoplastic resin composition comprising the specific amorphous liquid crystal resin (A) of the present invention and a molding resin which does not exhibit optical anisotropy when melted) has high fluidity and moldability. Further, the surface of the obtained molded article has little peeling and is excellent in appearance. In addition, since it has excellent rigidity and heat deformation temperature, it is suitable for outer panels for automobiles and housings for electric and electronic products. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the resin composition constituting the present invention will be described in detail step by step. The amorphous liquid crystal resin (A) used in the present invention has no melting point observed by DSC measurement at a heating rate of 20 ° C / min, softens near the glass transition temperature, and becomes substantially amorphous. It is necessary that This is because the amorphous liquid crystal resin shows excellent fluidity by cooling from the molten state and maintaining the molten state up to the glass transition temperature without being crystallized in the process and being flowable. For polymers that can be observed, the fluidity improving effect is not desirable due to the higher temperature processing process, which is not desirable.

[0011] The glass transition temperature and liquid crystallinity can be considered as indices of the processability of the present invention. Whether or not it exhibits liquid crystallinity is closely related to the fluidity during melting, and it is essential that the amorphous liquid crystal resin of the present application exhibit liquid crystallinity in a molten state.

[0012] In general, a nematic liquid crystal resin exhibits liquid crystallinity at a temperature equal to or higher than the melting point, and is subjected to various molding processes and then cooled to a temperature lower than a crystallization temperature, thereby solidifying the shape of the molded product. Is done. However, since the amorphous liquid crystal resin of the present invention does not crystallize, the fluidity is not impaired until the resin temperature reaches the vicinity of the glass transition temperature. It can be said. Therefore, the glass transition temperature is preferably 100 ° C. or more from the viewpoints of heat resistance of the molded article and efficiency of the drying step of the resin pellets. On the other hand, if the glass transition temperature is higher than 180 ° C, it is necessary to raise the process temperature significantly, which is not preferable.

[0013] Further, the melt viscosity at a shear rate of 100 sec- ¹ at a temperature 70 to 120 ° C higher than the glass transition temperature, preferably 230 ° C, is preferably 502000 Pa's. More preferably, it is 800 Pa's or less. These melt viscosities are generally realized by having liquid crystallinity.

[0014] The property of melt anisotropy can be confirmed by a conventional polarization inspection method using a crossed polarizer. More specifically, the melting anisotropy can be confirmed by using a Olympus polarizing microscope, melting a sample placed on a Lincom hot stage, and observing the sample under a nitrogen atmosphere at a magnification of 150 times. The amorphous liquid crystal resin used in the present invention is optically anisotropic and transmits light when inserted between orthogonal polarizers. When the sample is optically anisotropic, polarized light is transmitted, for example, even in the state of a molten still liquid. [0015] In order to obtain the amorphous liquid crystal resin (A) having the above characteristics, as monomers constituting the amorphous liquid crystal resin (A), the following (i) 4-hydroxybenzoic acid and (ii) 6- It must contain hydroxy-2-naphthoic acid and the ratio (i) / (ii) must be in the range of 0.15-4.0. (i) 4-hydroxybenzoic acid and (ii) 6-hydroxy-2-naphthoic acid may be derivatives thereof. Further, it is necessary to contain 735 mol% of a monomer derived from a 1,3-phenylene group as a component of the amorphous liquid crystal resin (A).

Here, the monomer derived from the 1,3-phenylene group is, for example, isophthalic acid, resorcinol, 3-hydroxybenzoic acid, 3-aminophenol, 1,3-phenylenediamine, Examples thereof include 3-aminobenzoic acid and derivatives thereof, and it is preferable that one or more of these are selected.

Further, the skeleton component of the amorphous liquid crystal resin (A) is a wholly aromatic polyesteramide, and the amide component is preferably contained in the total bond in a ratio of 7 to 35 mol%. , 4-aminophenol, 3-aminophenol, 4-aminobenzoic acid, 3-aminobenzoic acid, 1,3-phenylenediamine, 1,4-phenylenediamine and their derivatives in the polymer as monomers Is preferably introduced. Preferably it is 5 to 25 mol%, more preferably 10 to 20 mol%. If the amide component is less than 7 mol% in the total bond, surface peeling of the target molded article cannot be suppressed, and if it exceeds 35 mol%, the toughness of the liquid crystalline polyesteramide is lost, and the mechanical properties are greatly reduced.

More preferably, an amorphous liquid crystal resin (A) 1S a wholly aromatic polyesteramide obtained by copolymerizing the following (i) one (iv) monomer in the range described below,

(i) 4-hydroxy benzoic acid; 20- 60 mole ^_0/0

(ii) 6- hydroxy _2_ Nafute acid; 20 60 mole ^_0/0

(iii) 4_ Aminofuwenoru; 7 35 mole ^_0/0

(iv) isophthalic acid; 10- 25 mole ^_0/0

Alternatively, it is a wholly aromatic polyesteramide obtained by copolymerizing the following monomers (i), (ii) and (V) within the range described below.

(0 4-hydroxybenzoic acid; 10- 85 mole ^_0/0

(ii) 6- hydroxy - 2_ Nafute acid; 10 85 mole ^_0/0 (v) 3- Amino acid; 7- 35 mole ^_0/0

In the above wholly aromatic polyester amide, the copolymerization ratio of each component is remarkable even in alloys with heterogeneous amorphous polymers having excellent mechanical properties while maintaining good fluidity, which is the object of the present invention. This is important for suppressing surface peeling of molded products without reducing heat resistance. When the ratio is out of this range, the melting point is observed by DSC measurement at a heating rate of 20 ° C / min, and the effect of improving fluidity and surface peeling of the molded product is small.

[0019] Further, other monomers such as 4,4'-biphenol may be further supplementarily added to the amorphous liquid crystal resin of the present invention as long as the object of the present invention is not impaired.

[0020] The amorphous liquid crystal resin of the present invention is polymerized using a direct polymerization method or a transesterification method, and a polymerization method such as a melt polymerization method, a solution polymerization method, or a slurry polymerization method is used.

In the present invention, in the polymerization, an acylating agent for the polymerized monomer or a monomer having an activated terminal as an acid chloride derivative can be used. Examples of the acylating agent include acid anhydrides such as acetic anhydride. From the viewpoint of controlling the polymerization, the amount used is preferably 1.01 to 1.10 times the total equivalent of amino groups and hydroxyl groups, more preferably 1.02 to 1.0 times. 1.05 times.

[0022] Various catalysts can be used in these polymerizations, and typical ones are dialkyl tin oxide, diaryl tin oxide, titanium dioxide, alkoxytitanium silicates, titanium alcoholates, carboxylic acids Alkali and alkaline earth metal salts, such as BF

3 Isocyanate and the like. The amount of catalyst used is generally about 1% based on the total weight of the monomers.

0.001 to 1% by weight, especially about 0.003 to 0.2% by weight, is preferred.

When performing solution polymerization or slurry polymerization, liquid paraffin, high heat-resistant synthetic oil, inert mineral oil, or the like is used as a solvent.

[0024] The reaction conditions include a reaction temperature of 200-380 ° C and a final ultimate pressure of 0.1 760 Torr (ie,

13—101,080 Pa). Particularly in the case of a melting reaction, the reaction temperature is 260-380 ° C, preferably 300-360 ° C, and the final ultimate pressure is 1-1100 Torr (ie, 133-13,300 Pa), preferably 1-150.

Torr (ie, 133--1,670 Pa).

[0025] In the melt polymerization, after the inside of the reaction system reaches a predetermined temperature, the pressure is reduced to a predetermined degree. After the torque of the stirrer reaches a predetermined value, an inert gas is introduced, and the polymer is discharged from the reaction system under a normal pressure from a reduced pressure to a predetermined pressurized state. [0026] Next, the molding resin (B) which does not show optical anisotropy when melted used in the present invention includes polycarbonate, polyethenoleimide, polysanolefon, polyarylate, polyamide, polyphenylene ether, and olefin-based resin. Resins and the like are exemplified. Preferred is polyphenylene ether, and particularly preferred is modified polyphenylene ether from the viewpoint of handling during the processing process. Further, as the modified polyphenylene ether, those having a melt flow rate based on IS01133 of 320 g / l0 min are preferable in order to improve fluidity and appearance.

[0027] A polyamide resin is also a preferable component (B). The polyamide resin used in the present invention is a polyamide containing amino acid, ratatam, or diamine and dicarboxylic acid as main components. Typical examples of the main components are 6_aminocaproic acid, 11-aminoundecanoic acid, Amino acids such as 12-aminodecanoic acid and paraaminomethylbenzoic acid; ε-force product; _ω— ratatum such as lauguchi ratatam; tetramethylenediamine; hexamethylenediamine; 2-methylpentamethylenediamine; Nonamethylene diamine, pendecamethylene diamine, dodecamethylene diamine, 2,2,4- / 2,4,4-trimethylhexamethylene diamine, 5-methylnonamethylene diamine , Meta-xylylenediamine, para-xylylenemethylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl L) cyclohexane, 1-amino-1-3-aminomethyl-1,3,5,5-trimethylcyclohexane, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane Aliphatic, alicyclic, aromatic diamines such as 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine, and adipic acid, suberic acid, azelaic acid , Sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylterephthalic acid, 5_sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthal Examples thereof include aliphatic, alicyclic, and aromatic dicarboxylic acids such as acids. In the present invention, a polyamide homopolymer or copolymer derived from these components may be used alone, or a plurality thereof may be used as a mixture.

[0028] In the present invention, a polyamide resin having a melting point of 200 ° C or more is particularly useful from the viewpoint of excellent heat resistance and strength. Specific examples include polycaprolamide (Naiguchi 6), polyhexamethylene adipamide (nylon 66), polycaprolamide / polyhexamethylene adipamide copolymer (nylon 6/66), polytetramethylene adipamide (nylon 46), polyhexamethylene Sebacamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polyhexamethylene terephthalamide (nylon 6T), polyhexamethylene terephthalamide / polyamide copolymer (nylon 6TZ6), poly Hexamethylene adipamide / polyhexamethylene terephthalamide copolymer (nylon 66 / 6T), polyhexamethylene adipamide / polyhexamethylene isophthalamide copolymer (nylon 66/61), polyhexamethylene adipamide / poly Xamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (Nylon 66Z6TZ6I), polyhexamethylene terephthalamide Z polyhexamethylene isophthalamide copolymer (nylon 6T / 6I), polyhexamethylene terephthalamide / polydodecaneamide copolymer (nylon 6T / 12), polyhexamethylene terephthalate Amide / poly (2-methylpentamethylene) terephthalamide copolymer (Nylon 6T / M5T), polyxylylene adipamide (Nylon XD6), polynonamethylene terephthalamide (Nylon 9T), and mixtures or copolymers thereof Etc.

Further, an olefin resin is also a preferable component (B). The olefin resin used in the present invention is a polymer or copolymer containing ethylene, propylene or other olefin monomer as a main component, and specifically, high-density polyethylene, polypropylene, polybutene-11, poly-3-ethylene. Ethylene and α-olefin such as methylbutene-11, poly-4-methylbutene-11, and vinyl esters such as biel acetate, acrylic acid and methacrylic acid derivatives (eg, methyl acrylate, methyl methacrylate, dimethylaminoethyl acrylate) Amides), glycidyl esters of α, β-unsaturated acids (eg, glycidyl acrylate, daricidinole methacrylate, etc.), and copolymers with gens such as butadiene and isoprene. Further, a polyolefin modified with a polar compound can also be used. Examples of the polar compound include acrylates such as methyl acrylate and ethyl acrylate, vinyl acetate, acrylic acid, methacrylic acid, and maleic anhydride. These polar compounds are modified with 0.1 to 50% by weight. Polyethylene or the like is preferably used.

[0030] In addition, in order to improve fluidity and appearance, the melt flow rate based on IS01133 is 290 gZ olefin resin, which is lOmin, is preferred.

[0031] Such a molding resin (B) can be obtained by a known method, and a commercially available product can be used in the present invention.

In the present invention, the mixing ratio of the amorphous liquid crystal resin (A) and the molding resin (B) is (B) 100 to 900 parts by weight with respect to (A) 100 parts by weight. If the molding resin (B) force is less than S100 parts by weight, and if the molding resin (B) is more than 900 parts by weight to form a matrix, the effect of improving the fluidity, which is the object of the present invention, is unfavorably small. Particularly preferably, the molding resin (B) power is 00 to 700 parts by weight based on 100 parts by weight of the amorphous liquid crystal resin (A).

[0033] The resin composition of the present invention may contain various fibrous, powdery or plate-like inorganic fillers depending on the purpose of use.

[0034] Examples of the fibrous filler include glass fiber, asbestos fiber, silica fiber, silica'alumina fiber, alumina fiber, dinoreconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, wollastonite. And inorganic fibrous materials such as silicate fibers, magnesium sulfate fibers, aluminum borate fibers, and metal fibrous materials such as stainless steel, aluminum, titanium, copper, and brass. A particularly typical fibrous filler is glass fiber. In addition, a high melting point organic fibrous substance such as polyamide, fluorine resin, polyester resin, and acrylic resin can also be used.

[0035] On the other hand, examples of the particulate filler include carbon black, graphite, silica, quartz powder, glass beads, milled glass fiber, glass balloon, glass powder, calcium silicate, aluminum silicate aluminum, kaolin, clay, and silicon. Alkaline earth, silicate such as wollastonite, iron oxide, titanium oxide, zinc oxide, antimony trioxide, metal oxide such as alumina, metal carbonate such as calcium carbonate, magnesium carbonate, calcium sulfate, sulfuric acid Examples thereof include sulfates of metals such as barium, ferrite, silicon carbide, silicon nitride, boron nitride, and various metal powders.

[0036] Examples of the plate-like filler include My power, glass flake, talc, various metal foils, and the like.

[0037] These inorganic fillers can be used alone or in combination of two or more. However, when a large amount of inorganic filler is contained, the toughness is significantly reduced. %. From the viewpoint of improving rigidity, it is preferable that at least one type contains glass fiber.

[0038] When using these fillers, a sizing agent or a surface treatment agent can be used if necessary.

[0039] Further, other thermoplastic resins other than those described above may be further supplementarily added to the thermoplastic resin composition of the present invention as long as the object intended by the present invention is not impaired.

[0040] Examples of the thermoplastic resin used in this case include polyolefins such as polyethylene and polypropylene, aromatic dicarboxylic acids such as polyethylene terephthalate and polybutylene terephthalate, and aromatic polyesters composed of diols and the like, and polyacetals (homoplastics). Or copolymers), polystyrene, polyvinyl chloride, polycarbonate, ABS, polyphenylene oxide, polyphenylene sulfide, fluororesin, and the like. These thermoplastic resins can be used as a mixture of two or more kinds.

[0041] In the production of the resin composition of the present invention, each component such as an amorphous liquid crystal resin, a molding resin that does not show optical anisotropy when melted, and an inorganic filler that is used if necessary, is used. A method in which melt kneading is performed simultaneously using an extruder is exemplified. The melting temperature at the time of melt-kneading is preferably from 220 to 350 ° C from the viewpoint of suppressing resin decomposition. It is extremely useful to be able to knead at a melting temperature of 220-350 ° C, especially when blending a thermoplastic resin whose melt stability at high temperatures is slightly inferior, since thermal decomposition of the resin can be avoided.

[0042] Further, kneading may be performed by using a master batch in which any one is melt-kneaded in advance. The resin composition obtained by melt-kneading with an extruder is preferably cut into pellets by a pelletizer, and then a molded product is obtained by injection molding.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. The methods for measuring physical properties in the examples are as follows.

[Melting point, glass transition temperature]

The measurement was performed with a differential scanning calorimeter (DSC7, manufactured by PerkinElmer) at a heating condition of 20 ° C / min.

[Melt viscosity] The amorphous liquid crystal resin was measured at a temperature of 230 ° C. and a shear rate of 100 sec- ¹ using an orifice having an inner diameter of lmm and a length of 20 mm using a Capillograph IB manufactured by Toyo Seiki.

[0044] For the resin composition, the molding temperature described below (270 ° C or 300 when the thermoplastic resin is modified polyphenylene ether; 220C for nylon 12, 220C for nylon 66, 270.C for nylon 66, polyolefin) At a shear rate of 100 sec- ¹ using an orifice having an inner diameter of lmm and a length of 20 mm, using a Capillograph IB manufactured by Toyo Seiki Co., Ltd.

[Flexural modulus]

Using an injection molded piece of 125 mm X 12.7 mm X 0.8 mm, the flexural modulus was measured in accordance with ASTM D790.

[Load deflection temperature]

The measurement was performed at a measurement pressure of 1.8 MPa according to IS075 / A.

[Tape peel test]

A Scotch transparent adhesive tape manufactured by Sumitomo 3M Co., Ltd. was pressure-bonded to the surface of the above-mentioned injection molded piece, and the presence or absence of peeling at the time of peeling force S was evaluated according to the following three grades.

〇; good to peel off on the molded product surface

△: Slight peeling can be observed on the molded product surface

X: The tape contact surface of the molded product surface is completely peeled off

Production Example 1 (Production of liquid crystalline polyesteramide <1>-<3>)

The following raw material monomer, catalyst, and acylate were charged into a polymerization vessel equipped with a stirrer, a reflux column, a monomer inlet, a nitrogen inlet, and a vacuum / outflow line, and nitrogen replacement was started.

[0045] (A) 4- hydroxybenzoic acid 122.8 g (40 mole ^_0/0)

(B) 6- hydroxy - 2_ Nafute acid 125.5 g (30 mole ^_0/0)

(C) isophthalic acid ^55. ⁴ g (l ⁵ mole ^_0/0)

(D) 4-Asetokishi - Aminofuwenoru 50.4 g (15 mole ^_0/0)

Potassium acetate 22.5mg

Acetic anhydride 196.7g

After charging the raw materials, the temperature of the reaction system was raised to 140 ° C, and the reaction was performed at 140 ° C for 1 hour. After that, the temperature was further increased to 330 ° C over 3.3 hours, and then lOTorr (ie, The pressure was reduced to 1330 Pa), and melt polymerization was carried out while distilling acetic acid, excess acetic anhydride and other low-boiling components. After the stirring torque reached a predetermined value, nitrogen was introduced to change the pressure from a reduced pressure to a normal pressure, and the polyesteramide <1> was discharged from the lower part of the polymerization vessel.

[0046] Polyesteranolamide <2>-<3> having the same monomer formulation was produced in the same manner, except for changing only the target value of the stirring torque.

Production Example 2 (Production of liquid crystalline polyesteramide <4>)

The following raw material monomer, catalyst, and acylating agent were charged into the same polymerization vessel as in Production Example 1, and nitrogen substitution was started.

[0047] (A) 4_ hydroxybenzoic acid 132.6 g (55 mole ^_0/0)

(B) 6- hydroxy - 2_ Nafute acid 114.9 g (35 mole ^_0/0)

(C) 3_ amino acid ^23. ⁹ g (10 mole ^_0/0)

Potassium acetate 18.0mg

Acetic anhydride 181.7g

After charging the raw materials, the temperature of the reaction system was raised to 140 ° C, and the reaction was performed at 140 ° C for 1 hour. Thereafter, the temperature was further increased to 330 ° C over 3.5 hours, and から (that is, かけて

The pressure was reduced to 1330 Pa), and melt polymerization was carried out while distilling acetic acid, excess acetic anhydride and other low-boiling components. After the stirring torque reached a predetermined value, nitrogen was introduced to change the pressure from a reduced pressure to a pressurized state through normal pressure, and the polyesteramide <4> was discharged from the lower part of the polymerization vessel.

Production Example 3 (Production of liquid crystalline polyester <5>)

[0048] (A) 4-hydroxy benzoic acid ^⁴ l. ⁴ g (30 mole ^_0/0)

(B) 6- hydroxy - 2_ Nafute acid 56.5 g (30 mole ^_0/0)

(C) terephthalic acid ^33. ^² g ⁽² 0 mole ^_0/0)

(D) ^4, 4, _ Bifuwenoru l ^8. ⁶ g (10 mole ^_0/0)

(E) resorcinol 11.0g (10 mole ^_0/0) Potassium acetate 20.0mg

Acetic anhydride 105.5g

After charging the raw materials, the temperature of the reaction system was raised to 140 ° C, and the reaction was performed at 140 ° C for 1 hour. Thereafter, the temperature was further increased to 320 ° C over 3.3 hours, and then reduced to lOTorr (that is, 1330 Pa) over 20 minutes while distilling off acetic acid, excess acetic anhydride, and other low-boiling components. Melt polymerization was performed. After the stirring torque reached a predetermined value, nitrogen was introduced to change the pressure from a reduced pressure to a pressurized state through normal pressure, and the polyester <5> was discharged from the lower part of the polymerization vessel. Production Example 4 (Production of liquid crystalline polyester <6>)

[0049] (A) 4- hydroxybenzoic acid charged in succession with 226.4 g (73 mole ^_0/0)

(B) 6- hydroxy one 2- Nafute acid 114. lg (27 mole ^_0/0)

Potassium acetate 22.5mg

Acetic anhydride 233.8g

After charging the raw materials, the temperature of the reaction system was raised to 140 ° C, and the reaction was performed at 140 ° C for 1 hour. Thereafter, the temperature was further increased to 330 ° C over 3.5 hours, and then reduced to lOTorr (that is, 1330 Pa) over 20 minutes while distilling off acetic acid, excess acetic anhydride, and other low-boiling components. Melt polymerization was performed. After the stirring torque reached a predetermined value, nitrogen was introduced to change the pressure from a reduced pressure to a normal pressure and then to a pressurized state, and the polyester <6> was discharged from the lower part of the polymerization vessel.

[0050] The resulting polyester amide 1> one 4> and the polyester 5> 6> were observed under a crossed Nicols with a polarizing microscope in a molten state at 300 ° C. Clear optical differences

It showed anisotropy and was confirmed to be a thermotope pick liquid crystal resin. Table 1 shows the characteristics of each liquid crystal resin. From the observation results of the glass transition temperature and the melting point by DSC, it was confirmed that polyesteramide <1>-<4> and polyester <5> are amorphous liquid crystal resins, and polyester <6> is a crystalline liquid crystal resin. Was.

[Table 1] o

o Popopopopolipopopolyteriris remariteritete tester sul esolesul sul sue

Dodododoku> <> Ami <> 1 <> <> Mi <> Amir 32654

Moth transition temperature. Las measurement c measurement is DC in S

Not observed

Melting point ° measurement z constant fixed constant measurement c measurement is measurement is DSC with DS and S with DSC with CS with DC DC

Observed Observed Observed Observed Observed Observed Not observed

Melt viscosity ° () P230C a's of solid state

Measurement impossible

m

o

Example 11-7, Comparative Example 11-5

As shown in Table 2, liquid crystalline polyester amide 1>-<4>, liquid crystalline polyester 5> — <6>, modified polyphenylene ether (AH90, manufactured by Mitsubishi Engineering-Plastics Corporation), polystyrene (Toyo Styrol Co., Ltd., G19), glass fiber (Asahi Fiber Glass Co., Ltd., CS03JA416), and stabilizer (Asahi Denka Kogyo Co., Ltd., PEP36) after dry blending in the proportions shown in Table 2. Using a twin-screw extruder (PCM-30, manufactured by Ikegai Iron Works Co., Ltd.), the mixture was melt-kneaded at a cylinder temperature of 300 ° C. and pelletized. Injection molding machine from this pellet The test piece was prepared under the following conditions and evaluated. Table 2 shows the results.

(Injection molding conditions)

Molding machine; JSW J75SSII-A

Cylinder temperature; 270_270_260_250 ° C

Mold temperature; 115 ° C

Injection speed; 2m / min

Holding pressure: 58.8MPa

Cycle; injection holding pressure 7sec + cooling molding 7sec

Screw rotation speed: 100m

Screw back pressure; 3.5MPa

[Table 2]

SU M room¾s05481611 ~~

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example F Comparative Example "! Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Modified polyphenylene ether (parts by weight) 400 400 400 400 400 400 400 400 400 400 65 100 Polyester amide <1> (parts by weight) 100 100

Polyesteramide <2> (parts by weight) 100

Polyester amide <3> (parts by weight) 100

Polyester amide <4> (parts by weight) 100 100

Polyester <5> (parts by weight) 100

Polyester <6> (parts by weight) 100 100

Glass fiber (parts by weight) 200 200 200

Polystyrene (parts by weight) 100 100

Stabilizer (parts by weight) 2 2 2 2 2 2.7 2.7 2 2.7 2 0.7

Melt viscosity / Pa's (300 ° C) 186 160 136 250 186 203 307 191 319 348 145 564 Melt viscosity / Pa's (270 ° C) 477 480 378 678 452 480 734 943 Measurement impossible Measurement impossible 512 Measurement impossible Bending Modulus / MPa 4200 3900 4100 4300 3800 10000 11000 4600 11000 3200 3400 2800 Deflection temperature under load / ¾ 137 137 136 136 135 133 153 153 149 149 161 128 102 147 Tape peeling 〇〇〇〇 Δ 〇 XX XX 〇〇〇

Amide (nylon 12, Daicel Degussa Co., Ltd., X4442), polyamide (nylon 66, Ube Industries, Ltd., 2020U10), glass fiber (Asahi Fiberglass Co., Ltd., CS03JA416), stabilizer (Asahi After dry blending of Denka Kogyo Co., Ltd., PEP36) at the ratio shown in Table 3, it was melted at a cylinder temperature of 300 ° C using a twin-screw extruder (PCM-30, manufactured by Ikegai Iron Works Co., Ltd.). It was kneaded and pelletized. Test pieces were prepared from the pellets in the same manner as described above (however, the cylinder temperature of the injection molding machine was as described below) and evaluated. Table 3 shows the results. (Examples 8-9, Comparative Examples 6-8)

Cylinder temperature; 220-220-210_200 ° C (nylon 12)

(Examples 10-11, Comparative Examples 9-11)

Cylinder temperature; 270_270_260_250 ° C (nylon 66)

[Table 3]

ο o o o o

o o o

ο 1 o <o o O o

o o o

ο 1 o 〇

«

o o m O m

o o ο 1 o o Ο X

Comparative Comparative Example Comparative Example Comparative Example Comparative Example Example Ratio Ratio Ratio Ratio 11610107989

Nine 12 o o o

o o ο 1 〇

Nine 6b 6

o Podritesulami> D 3 o o

o ο 1 o 〇

Police> Sur 6

Moth fiber weight part () lath

o O ο

o ο 1

Agent stability <

Viscosity melting Z (°) P220Ca's

o o o o

o o

o o ο Viscosity melting (°) P270Ca's 1 〇

oo ε 00127

Flexural modulus MPa

ο o o o

o o Packing degree ° C Warm zc

ο 1 o X

Peeling tape

00

o σ m

o o ο m 1 O 〇

m

σ o o

ο in

ο I 〇瞓 iim ιΐϋ M

ilimj 瞷

Examples 12-15, Comparative Examples 12 17

As shown in Table 4, liquid crystalline polyester amide <3>, liquid crystalline polyester 6>, high-density polyethylene (HD548B, manufactured by Idemitsu Petrochemical Industries, Ltd.), maleic anhydride-modified poly After dry-blending ethylene (FT61AR3, manufactured by Adtex Co., Ltd.) at the ratios shown in Table 4, the cylinder temperature was raised to 300 ° C using a twin-screw extruder (PCM-30, manufactured by Ikegai Iron Works Co., Ltd.). The mixture was melted and kneaded, and the pellets were made. Test pieces were prepared from the pellets in the same manner as described above (however, the cylinder temperature of the injection molding machine was as described below) and evaluated. Table 4 shows the results.

[0057] Cylinder temperature; 240—240—230—220 ° C

[Table 4]

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Comparative Example 12 Example 12 Comparative Example 13 Example 13 Comparative Example 14 Comparative Example 15 Example 14 Comparative Example 16 Example 15 Comparative Example 17 High density polyethylene (parts by weight) 100 400 400 100 100

Maleic anhydride-modified polyethylene (parts by weight) 100 400 400 100 100 Polyester amide <3> (parts by weight) 100 100 100 100

Polyester <6> (parts by weight) 100 100 100 100 Melt viscosity ZPa's (240 ° C) 285 165 300 130 380 415 190 430 170 530 Flexural modulus MPa 1000 2200 1300 5100 Molding impossible 400 1600 1200 4500 Molding impossible Load Deflection temperature Z ° C 60 90 65 1 15 Unmoldable <50 70 85 112 Unmoldable

After amide (Nylon 6T, C2000, manufactured by Mitsui Chemicals, Inc.) was dry-blended at the ratio shown in Table 5, the cylinder temperature was adjusted using a twin-screw extruder (PCM-30, manufactured by Ikegai Iron Works, Ltd.). The mixture was melted and kneaded at 320 ° C, and pelletized. Test pieces were prepared from the pellets in the same manner as described above (however, the cylinder temperature of the injection molding machine was as described below) and evaluated. Table 5 shows the results.

[0060] Cylinder temperature; 320—320—310—300 ° C

[Table 5] Comparative Example 18 Example 16 Comparative Example 19

Nylon 6T (C2000) (parts by weight) 100 570 570

Polyesteramide <1> (parts by weight) 100

Polyester <6> (parts by weight) 100

Melt viscosity ZPa's (320 ° C) 204 47 66

Flexural modulus / ^ MPa 3300 3600 3400 Deflection temperature under load / ° C 104 125 1 18

Tape peeling 0 〇〇

Claims

Claims [1] An amorphous liquid crystal resin having the following features (1) and (4): (A) 100 parts by weight of an amorphous liquid crystal resin that does not show optical anisotropy when melted; B) A thermoplastic resin composition containing 900 parts by weight of 100.

(2) the glass transition temperature is within the range of 100 to 180 ° C,

(3) The melt viscosity at 230 ° C and a shear rate of 100sec- ¹ is 50-2000Pa's,

(4) exhibits optical anisotropy during softening flow.

[2] The amorphous liquid crystal resin (A) has the following monomers (i) and (ii) in the ratio (i) / (ii)

2. The thermoplastic resin composition according to claim 1, which is contained in the range of 0.15 to 4.0, and contains 7 to ₃₅ mol% of a monomer derived from a 1,3-phenylene group as a component of (A).

(D 4-hydroxybenzoic acid

(ii) 6-hydroxy-2-naphthoic acid

[3] Amorphous liquid crystal resin (A), a component that also induces 1,3-phenylene group power, isophthalic acid, resorcinol, 3-hydroxybenzoic acid, 3-aminophenol, 1, Three

-One or more selected from phenylenediamine and 3-aminobenzoic acid.

2. The thermoplastic resin composition according to 2.

[4] The amorphous liquid crystal resin (A) according to claim 13, wherein the skeleton structure is a wholly aromatic polyester amide, and the amide component is contained at a ratio of 735 mol% in all bonds. 12. The thermoplastic resin composition according to claim 1.

[5] The amorphous liquid crystal resin (A) is a wholly aromatic polyester amide obtained by copolymerizing the following monomers G) to (iv) within the range described below, and the ratio of (i) ZGi) The thermoplastic resin composition according to claim 1, wherein is in the range of 0.15 to 4.0.

(0 4-hydroxybenzoic acid; 20- 60 mole ^_0/0

(ii) 6- hydroxy-2_ Nafute acid; 20- 60 mole ^_0/0

(iii) 4 over § Minofu enol; 7- 35 mole ^_0/0

(iv) isophthalic acid; 10- 25 mole ^_0/0

[6] Amorphous liquid crystal resin (A) The following monomers (i), (ii) and (V) are copolymerized within the range described below. 2. The thermoplastic resin composition according to claim 1, which is a wholly aromatic polyesteramide obtained by the above, wherein the ratio of (i) / (ii) is in the range of 0.15 to 4.0.

(i) 4-hydroxy benzoic acid; 10- 85 mole ^_0/0

(ii) 6- hydroxy - 2_ Nafute acid; 10 85 mole ^_0/0

(V) 3_aminobenzoic acid; 7 35 mol%

[7] The thermoplastic resin composition according to any one of claims 16 to 17, wherein the molding resin (B) that does not exhibit optical anisotropy when melted is a polyphenylene ether.

[8] The molding resin (B) having no optical anisotropy when melted is a modified polyphenylene ether, and the melt flow rate based on 13-1133 is 3-2 (^ / 100 1). Item 7. The thermoplastic resin composition according to any one of Items 1 to 6.

[9] The thermoplastic resin composition according to any one of claims 16 to 16, wherein the molding resin (B) that does not show optical anisotropy when melted is a polyamide resin.

[10] The thermoplastic resin composition according to any one of [16] to [16], wherein the molding resin (B) that does not show optical anisotropy when melted is an olefin resin.

[11] The molding resin (B), which does not show optical anisotropy when melted, is an olefin resin, and

The melt flow rate based on IS01133 is 2 to 90 g / 10 min, any one of claims 1 to 6.

2. The thermoplastic resin composition according to item 1.

12. The thermoplastic resin composition according to claim 11, further comprising 5-40% by weight (in the resin composition) of an inorganic filler (C).

13. The thermoplastic resin composition according to claim 12, wherein at least one of the inorganic fillers (C) is a glass fiber.

[14] An injection-molded article comprising the thermoplastic resin composition according to any one of claims 113.

15. The injection-molded article according to claim 14, wherein the molded article is a car outer panel or a housing for electric / electronic products.