JP3048457B2 - Resin composition containing liquid crystal polyester - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition containing a thermotropic liquid crystal polyester, and more particularly, to a polyphenylene ether (hereinafter sometimes referred to as PPE) resin, a polyester resin, a polycarbonate resin, and a thermotropic liquid crystal. The present invention relates to a resin composition containing a polyester.

[0002]

2. Description of the Related Art PPE resins have heat resistance, mechanical strength,
Although excellent in dimensional stability, electrical properties, etc., this resin was not used alone because of poor solvent resistance and moldability. On the other hand, polyester resins are excellent in mechanical strength, electrical properties, solvent resistance, and the like, and are used in various fields. However, since heat resistance and impact resistance are inferior, they may be restricted in applications. Was.

[0003] Many attempts have been made to melt and mix both PPE resins and polyester resins in order to produce a resin composition that takes advantage of the advantages of the resins (Japanese Patent Application Laid-Open Nos. 49-75662 and 59-75662). -159847).

[0004] However, the moldability of the resin obtained by melting and mixing the two resins is greatly improved as compared with the PPE resin alone, but the dispersibility of the two resins is poor, so that the mechanical strength and heat resistance and the like are different. Only those that were worse than the values predicted from the mixing ratio of the resin were obtained.

In order to improve the dispersibility of both resins, it has been disclosed in JP-A-1-2426 that a polycarbonate resin is blended.
No. 63, JP-A-2-218737 and JP-A-2-18739
No. 6,009,045.

However, when sufficient rigidity, strength, and low coefficient of linear expansion are required, various fillers such as glass fiber, carbon fiber, glass flake, mica, and talc must be mixed. This leads to deterioration of the appearance of the molded product, decrease in fluidity and increase in specific gravity.

[0007] On the other hand, thermotropic liquid crystal polyesters are known. It has a rigid molecular skeleton and exhibits anisotropy in a molten state, and when it is molded, the rigid molecules are easily oriented by shear stress. Then, this orientation remains in the molded article after cooling. The molded article has a self-reinforcing structure, exhibits high strength and high elastic modulus, and has excellent heat resistance, dimensional stability, and chemical resistance. As an attempt to combine the characteristics of the thermotropic liquid crystal polyester with other resins, blends with various resins such as polyesters such as polycarbonate and PET have been proposed (JP-A-56-115357 and JP-A-63-115357). -215769, JP-A-1-301749, JP-A-2-263849, JP-A-2-27555 and the like.

However, since the thermotropic liquid crystal polyester has poor compatibility with other resins, the mechanical properties of the obtained resin composition are lower than those predicted from the mixing ratio. In addition, delamination tends to occur in an injection-molded product, which is not satisfactory in practical use.

[0009]

Accordingly, the present invention relates to a PP
The excellent properties of E-based resins, polyester resins, polycarbonate-based resins, etc., namely, without impairing the heat resistance, solvent resistance, moldability, etc., and without increasing the specific gravity, the reinforcing effect of the thermotropic liquid crystal polyester and low wire An object is to provide a resin composition having an expansion coefficient.

[0010]

The present invention provides (A) a polyphenylene ether-based resin, (B) a polyester resin,
A resin composition comprising (C) a polycarbonate-based resin and (D) a thermotropic liquid crystal polyester, wherein component (A) is 5 parts by weight based on 100 parts by weight of the entire resin composition.
The present invention provides a resin composition containing about 40 parts by weight, 25 to 92 parts by weight of the component (B), 2 to 35 parts by weight of the component (C), and 1 to 50 parts by weight of the component (D).

In the present invention, known PPE resins can be used. The PPE resin is, for example, a compound represented by the general formula (Chemical Formula 1):

[0012]

Embedded image (Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group and at least 2
Represents a monovalent substituent selected from haloalkyl groups and haloalkoxy groups having no carbon atoms and having no tertiary α-carbon, and n is an integer representing the degree of polymerization. It is a generic term and may be a single polymer of the general formula or a copolymer of two or more. In a preferred embodiment, R ₁ and R ₂ are an alkyl group having 1 to 4 carbon atoms, and R ₃ and R ₄ are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. For example, poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4) -
Phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-ethyl-
6-propyl-1,4-phenylene) ether and the like. Examples of the PPE copolymer include copolymers in which the above-mentioned polyphenylene ether repeating unit partially contains an alkyl trisubstituted phenol, for example, 2,3,6-trimethylphenol. Further, a copolymer in which a styrene-based compound is grafted on these PPEs may be used. The styrene-based compound-grafted polyphenylene ether is a copolymer obtained by graft-polymerizing, for example, styrene, α-methylstyrene, vinyltoluene, chlorostyrene or the like as the styrene-based compound on the above-mentioned PPE.

The polyester resin of the component (B) in the present invention is a polyester that does not exhibit a liquid crystal behavior, and generally, a known aromatic polyester resin can be used. Here, the aromatic polyester-based resin is a polyester having an aromatic ring in a chain unit of a polymer, and is obtained by a polycondensation reaction mainly containing an aromatic dicarboxylic acid and a diol (or an ester-forming derivative thereof). It is a polymer or a copolymer.

The aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, naphthalene-2,5-dicarboxylic acid,
Naphthalene-2,6-dicarboxylic acid, biphenyl-2,2'-dicarboxylic acid, biphenyl-3,3'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, diphenyl ether-4,
4'-dicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid,
Diphenylisopropylidene-4,4'-dicarboxylic acid, 1,
2-bis (phenoxy) ethane-4,4'-dicarboxylic acid, anthracene-2,5-dicarboxylic acid, anthracene-2,6-
Examples thereof include dicarboxylic acid, p-terphenylene-4,4'-dicarboxylic acid, and pyridine-2,5-dicarboxylic acid. Terephthalic acid is preferably used.

These aromatic dicarboxylic acids may be used as a mixture of two or more kinds. In addition, a small amount of these aromatic dicarboxylic acids along with adipic acid, azelaic acid,
One or more kinds of aliphatic dicarboxylic acids such as dodecandioic acid and sebacic acid and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid can be used.

The diol component includes ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol,
Aliphatic diols such as 2-methylpropane-1,3-diol, diethylene glycol, triethylene glycol,
Alicyclic diols such as cyclohexane-1,4-dimethanol and the like, and mixtures thereof; In addition,
If the amount is small, one or more long-chain diols having a molecular weight of 400 to 6,000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol or the like may be copolymerized.

Specific examples of the aromatic polyester resin include polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate (PBT), polyethylene naphthalate, polybutylene naphthalate, and polyethylene-1,2-bis (phenoxy).
Examples thereof include ethane-4,4'-dicarboxylate and polycyclohexanedimethanol terephthalate. Further, copolymerized polyesters such as polyethylene isophthalate / terephthalate, polybutylene terephthalate / isophthalate, and polybutylene terephthalate / decanedicarboxylate can also be used. Of these, polybutylene terephthalate is preferred.

The polycarbonate resin (C) used in the present invention is an aromatic polycarbonate prepared by a known phosgene method or a melt method (for example, Japanese Patent Application Laid-Open No. Sho 63-2).
15763 and JP-A-2-124934). The polycarbonate resin is composed of a carbonate component and a diphenol component. Examples of the precursor for introducing the carbonate component include phosgene and diphenyl carbonate. Suitable diphenols include, for example, 2,2-bis (4-hydroxyphenyl) propane (so-called bisphenol A); 2,2-bis (3,5-
Dibromo-4-hydroxyphenyl) propane; 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane;
1-bis (4-hydroxyphenyl) cyclohexane; 1,1-
Bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane; 1,1-bis (4-hydroxyphenyl) decane; 1,
4-bis (4-hydroxyphenyl) propane; 1,1-bis (4-hydroxyphenyl) cyclododecane; 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclododecane; 4,4-dihydroxy Diphenyl ether; 4,4-thiodiphenol; 4,4-dihydroxy-3,3-dichlorodiphenyl ether; and 4,4-dihydroxy-2,5-dihydroxydiphenyl ether. These can be used alone or in combination. In addition,
It is also possible to use compounds having three or more phenolic hydroxyl groups.

The polycarbonate resin also includes a polycarbonate having another characteristic group such as copolyestercarbonate and a copolymer.

The (D) thermotropic liquid crystal polyester used in the present invention can be selected from the group of polyesters containing a segment having the following structure.

--OR--O--CO--R--CO-- --OR--CO-- Here, R can be selected from the following group.

[0022]

Embedded image Further, the aromatic ring, aliphatic group, alicyclic group and the like in R may be substituted by a substituent selected from the following group.

[0023]

Embedded image In the present invention, component (A) is 5 to 40 parts by weight, preferably 10 to 4 parts by weight, based on 100 parts by weight of the entire resin composition.
0 parts by weight, component (B) is contained in an amount of 25 to 92 parts by weight, preferably 30 to 80 parts by weight, and component (C) is contained in an amount of 2 to 92 parts by weight.
35 parts by weight, preferably 5 to 30 parts by weight, and component (D) are compounded in 1 to 50 parts by weight, preferably 3 to 40 parts by weight. When the component (A) is less than 5 parts by weight, mechanical strength,
Heat resistance and dimensional stability are not sufficient, and if it is more than 40 parts by weight, moldability deteriorates. If the amount of the component (B) is less than 25 parts by weight, the solvent resistance decreases, and if it exceeds 92 parts by weight, the mechanical strength and the dimensional stability decrease. When the amount of the component (C) is less than 2 parts by weight, delamination tends to occur. When the amount is more than 35 parts by weight, the heat resistance is lowered. When the amount of (D) is less than 1 part by weight, the properties of the liquid crystal polyester are not sufficiently exhibited.
If it exceeds 0 parts by weight, delamination tends to occur.

The method for producing the resin composition of the present invention is not particularly limited, and ordinary methods can be used satisfactorily. However, the melt-kneading method is generally preferred. The use of small amounts of solvents is possible but generally not necessary. Examples of the apparatus include an extruder, a Banbury mixer, a roller, a kneader, etc., which are operated batchwise or continuously.

In order to make the effect of the present invention more remarkable, at the time of melt-kneading, at least a part of the components (B) and / or (C) and at least a part of the component (D) are previously melted. It is preferable to knead (preliminary kneading).

The resin composition of the present invention may contain a small amount of filler such as glass fiber, carbon fiber, potassium titanate fiber, mica, talc, clay, glass flake, glass to supplement the reinforcing effect of thermotropic liquid crystal polyester. Beads and the like can be used in combination.

The resin composition of the present invention may be mixed with other resins, various rubbers, conventional additives, or the like at the time of mixing or molding the resin according to the purpose, as long as the physical properties are not impaired.
For example, pigments, dyes, stabilizers, antioxidants, weathering agents,
Lubricants, release agents, nucleating agents, plasticizers, antistatic agents and the like can be added.

[0028]

The resin composition of the present invention is expected to exhibit the effects of the present invention as follows. That is, since the polyester forms a continuous phase and the PPE is well dispersed therein, it is excellent in solvent resistance and molding workability, and is given heat resistance, high rigidity and low warpage.
Further, by dispersing the liquid crystal polyester in the form of fibrils, a reinforcing effect and a low coefficient of linear expansion can be obtained without deterioration in appearance and increase in specific gravity when a reinforcing material such as a filler is used.

The reinforcing effect of the liquid crystal polyester is higher as the liquid crystal polyester is more strongly oriented (with respect to the flow direction) in the matrix, and the continuity of the liquid crystal with the flow in the vertical direction is lost, so that the phase is hardly separated. Therefore, when the method of dispersing the liquid crystal polyester more finely in the pellets after the melt-kneading and orienting the polyester at the time of molding is adopted,
That is, when the (D) liquid crystal polyester is preliminarily kneaded with the component (B) or (C), the effect of the present invention is more exerted.

[0030]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

The following compounds were used in the examples. Component (A) PPE: intrinsic viscosity (chloroform, 25 ° C.) 0.48 dl /
g of poly (2,6-dimethyl-1,4-phenylene) ether Component (B) Polyester: Polybutylene terephthalate, trademark Barox 310 (manufactured by General Electric), hereinafter referred to as PBT Component (C) PC: Bisphenol A polycarbonate, trademark LE
XAN 141 (manufactured by General Electric) Component (D) Thermotropic liquid crystal polyester (LCP): liquid crystal polyester composed of p-hydroxybenzoic acid, terephthalic acid and ethylene glycol, rod run LC-5000
(Trademark, manufactured by Unitika Ltd.) Optional component SEBS: Kraton KG1651 (trademark, manufactured by Shell Chemical Co., Ltd.) Example 1 The amounts (parts by weight) of PPE and SEBS shown in Table 1 were 32.
The mixture was melt-kneaded in advance with a twin-screw extruder set at 0 ° C. This P
The PE / SEBS pre-kneaded product and the remaining components shown in Table 1 were extruded with a twin-screw extruder set at 260 ° C. to produce pellets. Test pieces for various tests were injection molded from the pellets and subjected to the following tests. Table 1 shows the results.

Izod impact strength: ASTM D256
Flexural modulus: Measured according to ASTM D790 Flexural modulus: Measured according to ASTM D790 Heat deformation temperature (HDT): 4.6 kg / cm ² according to ASTM D648 Coefficient of linear expansion: The same part of an injection-molded article of the same shape was cut out and measured in the flow direction from room temperature to 120 ° C. Appearance of molded article: visually evaluated Example 2 PBT and LCP are shown in Table 1. In proportion (weight ratio), 2
The mixture was melt-kneaded in advance with a twin-screw extruder set at 60 ° C. In addition, the PPE / SEBS pre-kneaded product and the remaining components produced in Example 1 were extruded again in the same manner as in Example 1 to form pellets, and then injection-molded. The test was performed. Table 1 shows the results. Example 3 PC and LCP were mixed at the ratio (weight ratio) shown in Table 1 to 27
The mixture was melt-kneaded in advance with a twin-screw extruder set at 0 ° C. In addition, the PPE / SEBS pre-kneaded product and the remaining components produced in Example 1 were extruded again in the same manner as in Example 1 to form pellets, and then injection-molded. The test was performed. Table 1 shows the results. Example 4 The amounts (parts by weight) of PPE and SEBS shown in Table 1 were 32
The mixture was melt-kneaded in advance with a twin-screw extruder set at 0 ° C. next,
PBT and LCP were preliminarily kneaded in the ratio (weight ratio) shown in Table 1 in the same manner as in Example 2. This PBT / LCP
The pre-kneaded material, the PPE / SEBS pre-kneaded material, and the remaining components were extruded again in the same manner as in Example 1 to produce pellets, and then subjected to injection molding, and various tests were performed under the same conditions as in Example 1. . Table 1 shows the results. COMPARATIVE EXAMPLE 1 The amounts (parts by weight) of PPE and SEBS shown in Table 1 were 32
The mixture was melt-kneaded in advance with a twin-screw extruder set at 0 ° C. This P
After the PE / SEBS pre-kneaded material and the remaining components shown in Table 1 were treated in the same manner as in Example 1, various tests were conducted under the same conditions. Table 1 shows the results. Comparative Example 2 After treating in the same manner as in Example 1 except that glass fiber was used instead of LCP, various tests were performed under the same conditions.
Table 1 shows the results. Comparative Example 3 The PPE / SEBS pre-kneaded product, PBT, and LCP produced in Example 1 were treated in the same manner as in Example 1, and then various tests were performed under the same conditions. Table 1 shows the results.

[0033]

[Table 1]

The resin composition of the present invention has a small coefficient of linear expansion, a good appearance without delamination, etc., and has a mechanical strength equivalent to that of a conventional reinforcing agent. Also, the specific gravity is small. As described above, various characteristics are excellent in a well-balanced manner, so that it can be used for a wide range of applications and is industrially useful.

Claims (1)

(57) [Claims] (A) a polyphenylene ether-based resin,
A resin composition comprising (B) a polyester resin, (C) a polycarbonate resin, and (D) a thermotropic liquid crystal polyester, wherein the resin composition is 100 parts by weight, and the component (A) is 5 to 40 parts by weight. And a resin composition containing 25 to 92 parts by weight of the component (B), 2 to 35 parts by weight of the component (C), and 1 to 50 parts by weight of the component (D).