JP2001026701A - Liquid crystal polyester resin composition and molded article thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject liquid crystal polyester resin composition that has excellent mechanical properties, heat resistance, particularly welding heat resistance and is useful as a heat-resistant material for electronic and electric parts by using specific glass fiber with an ignition loss in a specific range and a liquid crystal polyester resin. SOLUTION: The objective composition comprises (A) glass fibers surface- treated with a thermosetting resin and (B) a liquid crystal polyester resin where the ignition loss of the component A is adjusted to 0.05-0.4 wt.% In a preferred embodiment, the amount of the component A is 10-200 pts.wt. per 100 pts.wt. of the component B. The thermosetting resin as a component A is at least one selected from the group consisting of epoxy resin, urethane resin, and epoxy urethane resin. The component B preferably includes >=30 mol.% of the recurring structural units of the formula. The component B can include one or more kinds of additives, for example, a colorant in the range where the additives may not damage the purposes of this invention.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a liquid crystal polyester resin composition. More specifically, the present invention relates to a liquid crystal polyester resin composition comprising a glass fiber surface-treated with a thermosetting resin.

[0002]

2. Description of the Related Art A molten liquid crystalline polyester resin which exhibits liquid crystallinity when melted (hereinafter referred to as a liquid crystal polyester resin).
Because of its excellent heat resistance and excellent fluidity, that is, processability at the time of melting, it is being used as a molding material capable of precision molding in various fields including the electric and electronic field. In particular, a resin composition in which a liquid crystal polyester resin is filled with a fibrous reinforcing material such as glass fiber surface-treated with a thermosetting resin is a material suitable for an electric / electronic component having a thin portion or a complicated shape. However, since the resin composition has a high processing temperature, for example, in a step of obtaining a pellet-shaped resin composition for injection molding by melt extrusion, in a resin composition injection molding step, and the like, a resin composition by heat is used. Degradation, decomposition, and generation of decomposition gas may occur. Some of the degraded products such as gas during processing are embedded in the molded product, and thus may cause various problems when used as parts. For example, foaming due to gas generation in a soldering step and the like can be mentioned.

[0003]

DISCLOSURE OF THE INVENTION The present invention solves the above problems and provides a liquid crystal polyester resin composition containing glass fibers, which has excellent mechanical properties and heat resistance, especially solder heat resistance. It is an object of the present invention to provide a molded article.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, the above-mentioned object is achieved by containing or blending a specific glass fiber with a liquid crystal polyester resin. That is, the present invention has been achieved. That is, the present invention is as follows. (1) It contains glass fiber surface-treated with a thermosetting resin and a liquid crystal polyester resin, and the glass fiber surface-treated with a thermosetting resin has a loss on ignition of 0.05 to 0.4% by weight.
The liquid crystal polyester resin composition which is in the range of. (2) Glass fiber surface-treated with a thermosetting resin is mixed with a liquid crystal polyester resin, and the glass fiber surface-treated with a thermosetting resin has a loss on ignition of 0.05 to 0.
A liquid crystal polyester resin composition in the range of 4% by weight. (3) The amount of the glass fiber surface-treated with the thermosetting resin is 10 to 10 parts by weight of the liquid crystal polyester resin.
The liquid crystal polyester resin composition according to the above (1) or (2), wherein the content is 200 parts by weight. (4) The thermosetting resin is an epoxy resin, a urethane resin,
And the liquid crystal polyester resin composition according to any one of the above (1) to (3), which is at least one resin selected from the group consisting of epoxy urethane resins. (5) a liquid crystal polyester resin, the containing repeating structural unit represented by the formula A ₁ below 30 mol% (1) -
The liquid crystal polyester resin composition according to any one of (4). (6) A molded article using the liquid crystal polyester resin composition according to any one of the above (1) to (5).

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[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The liquid crystal polyester resin used in the present invention includes (1) a resin comprising a combination of an aromatic dicarboxylic acid, an aromatic diol and an aromatic hydroxycarboxylic acid, and (2) a different aromatic hydroxycarboxylic acid. A carboxylic acid; (3) a combination of an aromatic dicarboxylic acid and an aromatic diol; (4) a polyester such as polyethylene terephthalate reacted with an aromatic hydroxycarboxylic acid; ° C
Those which form an anisotropic melt at the following temperatures are preferred from the viewpoint of molding and the like. Note that, instead of these aromatic dicarboxylic acids, aromatic diols, and aromatic hydroxycarboxylic acids, ester-forming derivatives thereof may be used. Examples of the repeating structural unit of the liquid crystal polyester resin include the following. Repeating structural unit derived from aromatic hydroxycarboxylic acid:

[0006]

Embedded image Repeating structural unit derived from aromatic dicarboxylic acid:

[0007]

Embedded image Repeating structural unit derived from aromatic diol:

[0008]

Embedded image

[0009]

Embedded image Of the substituents X _{1 to} X ₃ in the formula of the above repeating structural unit, the alkyl (group) is preferably an alkyl group having 1 to 6 carbon atoms, and the aryl (group) is preferably an alkyl group having 6 carbon atoms.
To 20 aryl groups.

A liquid crystal polyester which is particularly preferred in view of the balance among heat resistance, mechanical properties and workability contains at least 30 mol% of the repeating structural unit represented by the formula (A ₁ ). Specifically, those having the following combinations of repeating structural units (a) to (f) are exemplified. (A): (A ₁ ), (B ₁ ) or a mixture of (B ₁ ) and (B ₂ ), (C ₁ ). (B): (A ₁ ), (A ₂ ). (C) in those combinations of the structural units of :( a), that replaces the part of A ₁ in A _2. (D) In those combinations of the structural units of :( a), that replaces the part of B ₁ in B _3. (E) in what combination of structural units of :( a), that replaces the part of the C ₁ at C _3. (F): A combination of the structural units of (b), B ₁
Plus the structural unit of the C ₂ and. As a method for preparing the liquid crystal polyester resin used in the present invention, a known method can be adopted. For example, the liquid crystal polyester resins (a) and (b) are described in JP-B-47-47870 and JP-B-63-3888.

The glass fiber used in the present invention is generally a glass obtained by processing glass containing silicate as a main component into a fibrous form. Examples of the type of glass include alkali glass for general use (A glass), acid-resistant glass for chemical use (C glass), low-density glass (D glass), and borosilicate glass (E glass). E glass is preferred from the viewpoint of the strength and the like of a molded product formed using E. For producing glass fibers, a method of spinning glass in a molten state (1300 ° C. or higher) is generally used. The glass fiber may be treated with a silane coupling agent, a titanium coupling agent, or the like, if necessary.

The surface treatment of glass fiber with a thermosetting resin is to coat a part or all of the glass fiber surface with an uncured or cured thermosetting resin.
It also serves as a glass fiber convergence process. The surface treatment contributes to the handleability of the glass fiber, the affinity with the liquid crystal polyester resin, and the like. As a procedure for surface treatment of glass fibers with a thermosetting resin, usually, the thermosetting resin is emulsified with an anionic, cationic, or nonionic surfactant, and the glass fiber melt-spun is immersed in the emulsion, Through a process of removing and removing moisture.
The thermosetting resin may be cured by heating if necessary.
It is also a useful method to introduce the above-mentioned coupling agent into the thermosetting resin in advance.

As the kind of the thermosetting resin, an epoxy resin, a urethane resin and an epoxy urethane resin are preferable from the viewpoints of heat resistance and handleability, and a urethane resin or an epoxy urethane resin is particularly preferable. Also, for example,
Two or more thermosetting resins may be used in combination, such as a combination of an epoxy resin and a urethane resin. Known thermosetting resins are generally used. For example, when a urethane resin is used, an isocyanate alone or a mixture of isocyanate and a polyol can be used as the uncured urethane resin. A catalyst such as an amine may be included as necessary, or a part of the uncured urethane resin may be cured. Examples of isocyanates include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthalene diisocyanate (N
DI) and the like, and examples of the polyol include various polyether polyols and polyester polyols. The epoxy urethane resin used in the present invention may be a combination of an epoxy resin having a hydroxyl group and an isocyanate compound, or an epoxy resin having a hydroxyl group by opening a part of the epoxy group of the epoxy resin with an amine or alcohol. It is a term such as resin, which is combined with an isocyanate compound, and is not particularly limited.

In the present invention, the ignition loss of the glass fiber surface-treated with the thermosetting resin is 0.05 to 0.4% by weight (per glass fiber surface-treated with the thermosetting resin).
, Preferably 0.1 to
It is in the range of 0.3% by weight. The loss on ignition is a value obtained by dividing the weight loss when a glass fiber surface-treated with a thermosetting resin is subjected to heat treatment at 625 ° C. for 10 minutes or more until a constant weight is obtained, divided by the total amount before the treatment, and conforms to JISR3420. Can be measured. If the ignition loss is less than 0.05% by weight, the surface treatment of the glass fiber becomes insufficient, the handleability becomes poor, and the incorporation into the liquid crystal polyester resin becomes difficult. Further, when the ignition loss is more than 0.4% by weight, degradation of the resin composition due to heat, generation of decomposition gas due to decomposition, and the like may occur, which may affect the stability of the resin composition when heated. There is not preferred. In the present invention, the ignition loss of the glass fiber surface-treated with the thermosetting resin is determined by the amount of the thermosetting resin adhered to the glass fiber surface (when the above-described coupling agent or the like is used, (The sum of the amounts).

The number average fiber diameter of the glass fibers used in the present invention is preferably 1 to 20 μm, and more preferably 5 to 15 μm.
Is more preferable. When the number average fiber diameter is smaller than 1 μm, the surface treatment of the glass fiber becomes insufficient, the handleability becomes poor, and the compounding of the glass fiber into the liquid crystal polyester resin becomes difficult. The number average fiber diameter is 20 μ
If it is larger than m, the take-up of the strand during melt granulation of the resin composition becomes unstable, which is not preferable. The number average fiber length of the glass fibers is 25 to 6000 μm.
m, more preferably 30 to 3000 μm. If the number average fiber length is shorter than 25 μm, the reinforcing effect of the glass fibers is undesirably reduced. Further, if the number average fiber length is longer than 6000 μm, the take-off of strands during melt granulation of the resin composition becomes unstable, and the surface condition of a product molded from the obtained resin composition is further deteriorated, which is not preferable. .

In the resin composition of the present invention, the amount of the glass fiber surface-treated with the thermosetting resin is preferably in the range of 10 to 200 parts by weight, more preferably 100 parts by weight of the liquid crystal polyester resin. Is 15 to 100 parts by weight. When the amount is more than 200 parts by weight, the biting property to the screw during pelletization becomes poor, and plasticization at the time of molding becomes unstable, and furthermore, the mechanical strength of the molded body is reduced, and the appearance is reduced. Not preferred. On the other hand, if the amount is less than 10 parts by weight, the mechanical strength of the molded product becomes insufficient, which is not preferable.

Means for blending the raw materials for obtaining the resin composition of the present invention include a liquid crystal polyester resin, glass fibers surface-treated with a thermosetting resin, an inorganic filler if necessary, a release improver, It is common to mix the ingredients using a Henschel mixer, tumbler or the like, and then melt-knead using an extruder. As the melt-kneading method at that time, all the raw materials may be mixed at once and fed to an extruder, or if necessary, raw materials such as reinforcing materials such as glass fibers and inorganic fillers may be mixed with resin. It may be fed separately from raw materials mainly composed of.
In the present invention, a small amount of other fillers can be added to the liquid crystal polyester resin, if necessary, in addition to the glass fibers. As the filler, silica alumina fiber,
Fibrous or needle-like reinforcing materials such as wollastonite, carbon fiber, potassium titanate whiskers, aluminum borate whiskers, and titanium oxide whiskers; inorganic fillers such as calcium carbonate, dolomite, talc, mica, clay, and glass beads And one or two or more thereof can be used.

The liquid crystal polyester resin used in the present invention may be added to a colorant such as a dye or a pigment without impairing the object of the present invention; an antioxidant; a heat stabilizer; an ultraviolet absorber; One or more conventional additives such as surfactants can be added.

In the present invention, in addition to the liquid crystal polyester resin, a small amount of other thermoplastic resins such as polyamide, polyester, polyphenylene sulfide, polyether ketone, polycarbonate, polyphenylene ether and modified products thereof, polysulfone, polyether It is also possible to add one or more of sulfone, polyetherimide and the like, and a small amount of a thermosetting resin such as a phenol resin, an epoxy resin and a polyimide resin.

Next, the molded article of the present invention is formed using the liquid crystal polyester resin composition of the present invention, and can be obtained by molding the liquid crystal polyester resin composition by a known method. Examples of the molding method include an injection molding method, a compression molding method, an extrusion molding method, and a hollow molding method, and the injection molding method is preferable. Examples of applications of parts and members molded from the resin composition of the present invention include electric and electronic parts such as connectors, sockets, relay parts, coil bobbins, optical pickups, oscillators, printed wiring boards, computer-related parts, and the like; Parts related to semiconductor manufacturing process such as IC tray, wafer carrier, etc .; VTR, TV, iron, air conditioner, stereo, vacuum cleaner, refrigerator,
Home appliance parts such as rice cookers and lighting equipment; lighting equipment parts such as lamp reflectors and lamp holders; sound product parts such as compact discs, laser discs (registered trademark), speakers, etc .; ferrules for optical cables, telephone parts, Communication equipment parts such as facsimile parts, modems, etc .; Copier-related parts such as separation claws, heater holders, etc .; Mechanical parts such as impellers, fans, gears, gears, bearings, motor parts and cases; Automobile mechanical parts, engines Parts, engine room parts, electrical parts, interior parts,
Automobile parts such as; microwave cooking pots, heat-resistant dishes, etc .; cooking utensils; flooring, wall materials, etc., heat insulation materials, soundproofing materials, beams, etc.
Supporting materials such as pillars, building materials such as roofing materials or civil engineering building materials; radiation facility members such as aircraft parts, spacecraft parts, nuclear reactors, marine facilities members, cleaning jigs, optical equipment parts, valves, Pipes, nozzles, filters,
Membranes, medical equipment parts and medical materials, sensor parts,
Sanitary equipment, sporting goods, leisure goods.

[0021]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited to these examples. In addition, the superiority or inferiority of the performance of the injection molded article in the examples was determined by the following method. (1) Flexural modulus: 127 mm in length, 12.7 mm in width,
It measured using the test piece of 6.4 mm in thickness according to ASTM D790. (2) Tensile strength: ASTM No. 4 dumbbell, AS
It was measured according to TM D638. (3) Izod impact strength (without notch): length 127
ASTM D256 using a bending test piece having a width of 12.7 mm, a width of 12.7 mm and a thickness of 6.4 mm divided in the injection direction into two equal parts.
It measured according to. (4) Deflection temperature under load: length 127 mm, width 12.7 m
ASTM D648 using a test piece having a thickness of 6.4 mm and a thickness of 6.4 mm.
It was measured at a load of 18.6 kg / cm ² in accordance with (5) Solder heat resistance: Using a dumbbell test piece (thickness: 1.2 mm) according to JIS K7113 (1/2), the test piece was immersed in a solder bath heated to a predetermined temperature for 60 seconds, and then the test piece after removal. The appearance was visually inspected for any swelling or deformation. Solder bath temperature from 200 ℃ to 5 ℃
The test was performed while raising the temperature step by step.

Example 1 A repeating structural unit is composed of A ₁ , B ₁ , B ₂ , and C ₁ , and the molar ratio of A ₁ : B ₁ : B ₂ : C ₁ is 60: 15: 5: 2.
Glass short fibers (CS03JAPX-1, manufactured by Asahi Fiberglass Co., Ltd., number average fiber length: 100 parts by weight of a liquid crystal polyester resin having a weight of 0, and a urethane resin having a loss on ignition of 0.20% by weight; 36.7 mm, number average fiber diameter: 10 μm) After mixing 66.7 parts by weight with a tumbler,
Granulation was performed at a cylinder temperature of 340 ° C. using a twin-screw extruder [Ikegai Iron Works Co., Ltd. PCM-30 type] to obtain liquid crystal polyester resin composition pellets. 600 ° C pelletized granules
When the optical microscope image of the residual glass fiber was photographed and the image analysis was performed, the number average fiber diameter was 10
μm, and the number average fiber length was 250 μm. The obtained pellets were subjected to injection molding at a cylinder temperature of 350 ° C. and a mold temperature of 130 ° C. using a PS40E5ASE type injection molding machine manufactured by Nissei Resin Industry Co., Ltd. to form test pieces for the above evaluation. Table 1 shows the evaluation results.

Example 2 In Example 1, instead of the glass fiber surface-treated with a urethane resin having a loss on ignition of 0.20% by weight, the surface was replaced with a urethane resin having a loss on ignition of 0.25% by weight. Treated glass fiber (RES03TP78, manufactured by Nippon Sheet Glass Co., Ltd., number average fiber length: 3 mm, number average fiber diameter: 10
μm) was used in the same manner as in Example 1.
Table 1 shows the evaluation results.

Example 3 In Example 1, an epoxy urethane resin having a loss on ignition of 0.20% by weight was replaced by an epoxy urethane resin having a loss on ignition of 0.20% by weight instead of the glass fiber surface-treated with a urethane resin having a loss on ignition of 0.20% by weight. Surface-treated glass fiber (CS03-256S, manufactured by Nitto Boseki Co., Ltd., number average fiber length: 3 mm, number average fiber diameter: 10)
μm) was used in the same manner as in Example 1.
Table 1 shows the evaluation results.

Comparative Example 1 In Example 1, glass fibers not surface-treated (CS03JAPX-1, Asahi Fiberglass) were used in place of the glass fibers surface-treated with a urethane resin having a loss on ignition of 0.20% by weight. (Manufactured by Co., Ltd., treated at 600 ° C. for 2 hours to remove the urethane resin), but the production of resin composition pellets was attempted in the same manner as in Example 1; Could not be continuously and quantitatively supplied to the granulator.

Comparative Example 2 In Example 1, the glass fiber treated with a urethane resin having a loss on ignition of 0.20% by weight was replaced with a urethane resin having a loss on ignition of 0.5% by weight. Treated glass fiber (CS03-494, Asahi Fiberglass
Co., Ltd., number average fiber length: 3 mm, number average fiber diameter: 10 μ
m) was performed in the same manner as in Example 1 except that m) was used. Table 1 shows the evaluation results.

Comparative Example 3 In Example 1, the surface was treated with an epoxy resin having a loss on ignition of 0.9% by weight instead of the glass fiber surface-treated with a urethane resin having a loss on ignition of 0.20% by weight. The procedure was performed in the same manner as in Example 1 except that the treated glass fiber (EX-9, manufactured by Nippon Sheet Glass Co., Ltd., number average fiber length: 3 mm, number average fiber diameter: 10 μm) was used. Table 1 shows the evaluation results.

Comparative Example 4 In Example 1, a surface treatment was carried out with an epoxy resin having a loss on ignition of 1.2% by weight instead of a glass fiber bundled with a urethane resin having a loss on ignition of 0.20% by weight. Except for using the obtained glass fiber (EX-12, manufactured by Nippon Sheet Glass Co., Ltd., number average fiber length: 3 mm, number average fiber diameter: 10 μm), the same procedure as in Example 1 was performed. Table 1 shows the evaluation results.

[0029]

[Table 1]

[0030]

Industrial Applicability The liquid crystal polyester resin composition of the present invention and a molded article using the same have excellent mechanical properties and heat resistance, especially solder heat resistance, and are used for heat resistance mainly for electronic and electric parts. It is extremely useful as a material for use.

Claims (6)

[Claims] A glass fiber surface-treated with a thermosetting resin and a liquid crystal polyester resin, wherein the glass fiber surface-treated with a thermosetting resin has a loss on ignition of 0.05 to 0.4.
A liquid crystal polyester resin composition characterized by being in the range of% by weight. 2. A glass fiber surface-treated with a thermosetting resin is mixed with a liquid crystal polyester resin, and the glass fiber surface-treated with the thermosetting resin has a loss on ignition of 0.05.
A liquid crystal polyester resin composition in an amount of from 0.4 to 0.4% by weight. 3. The amount of glass fiber surface-treated with a thermosetting resin is 1 to 100 parts by weight of a liquid crystal polyester resin.
3. The liquid crystal polyester resin composition according to claim 1, wherein the amount is in the range of 0 to 200 parts by weight. 4. The thermosetting resin according to claim 1, wherein the thermosetting resin is at least one resin selected from the group consisting of an epoxy resin, a urethane resin, and an epoxy urethane resin. Liquid crystal polyester resin composition. 5. A liquid crystal polyester resin, liquid crystal polyester resin composition according to any one of claims 1 to 4, characterized in that it comprises the formula repeating structural unit represented by A ₁ or 30 mole% of the below. Embedded image 6. A molded article comprising the liquid crystal polyester resin composition according to claim 1.