JPH08302024A - Production of pulplike material - Google Patents

Abstract

PURPOSE: To produce a destaticized readily handleable pulplike material useful as an asbestos substitute material, etc., by applying an antistatic agent to the surface of a thermoplastic liquid crystal resin molding capable of forming an anisotropic melting phase and then dry pulverizing the resultant molding. CONSTITUTION: An antistatic agent in an amount of >=1×10<-5> g based on 1cm<2> surface area of a thermoplastic liquid crystal resin molding capable of forming an anisotropic melting phase is initially applied to the surface of the thermoplastic liquid crystal resin molding and the resultant molding is then preferably dry pulverized with a high-speed rotating impact type pulverizer. A resin, etc., comprising units of the formulas A-X-CO, OC-Y-CO and B-Z-O (A and B are each O or NH; X is formula II, III, etc.; Y is formula II, III, etc.; Z is formula I, CH2 -CH2 , etc.) are preferred as the liquid crystal resin. For example, a quaternary ammonium chloride or an alkylsulfonate is cited as the antistatic agent; however, a water-soluble one is preferably used.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an antistatic pulp-like material composed of a thermoplastic liquid crystal resin capable of forming an anisotropic melt phase. Since it is difficult to take on, it can overcome various handling problems caused by static electricity such as scattering or adhesion to containers, and as a reinforcing material for heat resistant composite materials combined with other thermoplastic resins or thermosetting resins It is also useful as a substitute material for asbestos, as a friction material for automobile brake pads or clutch fading, a sliding material, a heat resistant filter, a chemical resistant filter, and the like.

[0002]

2. Description of the Related Art As a method for antistatically treating a molded product or fiber made of a thermoplastic resin, generally known is a method of immersing and adhering it in an antistatic agent solution, or a method of spraying an antistatic agent solution. Has been. As a method for subjecting a molded article made of a thermoplastic liquid crystal resin to an antistatic treatment, for example, in JP-A-61-285282, a thermoplastic liquid crystal resin is charged in a composition comprising a thermoplastic liquid crystal resin and an antistatic agent. A method of kneading the inhibitor is exemplified. Regarding the antistatic method of the pulp-like material made of the thermoplastic liquid crystal resin, by using these methods, the antistatic effect can be imparted, but since the pulp-like material made of the thermoplastic liquid crystal resin is generally bulky, There is a problem that it is not easy to handle the pulp-like material when it is immersed in the antistatic agent solution or when the antistatic agent solution is sprayed, and a large-volume device is required for the weight-equivalent production amount. .

The method of kneading an antistatic agent into a thermoplastic liquid crystal resin has problems that the manufacturing process is complicated and that a thermally stable antistatic agent must be used. In the present invention, an antistatic agent is attached to the surface of a thermoplastic liquid crystal resin molding capable of forming an anisotropic molten phase before being made into a pulp, and the molding is dry pulverized to form an antistatic pulp. Method, which is clearly different from the above method.

If a pulp-like material made of a thermoplastic liquid crystal resin which has not been subjected to antistatic treatment is used as it is, static electricity is easily generated. For example, if the pulp-like material is agitated by a high speed rotating mixer, the pulp-like material adheres to the wall surface of the mixer. Or
Various problems occur in handling such as scattering of pulp. There is also a method of preventing electrification by increasing water absorption, such as adhering water to a pulp-like material made of a thermoplastic liquid crystal resin, but it is difficult to say that it is a preferable method because a drying step is required depending on the application.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above problems of the prior art and to provide a method for easily obtaining a pulp-like material comprising an antistatic thermoplastic liquid crystal resin.

[0006]

Means for Solving the Problems As a result of intensive studies on the method for preventing static electricity of pulp-like materials, the present inventors have found that a thermoplastic liquid crystal resin molded article is impregnated with a certain amount or more of an antistatic agent, or is sprayed. It was found that an antistatic pulp-like material can be easily produced by adhering it by means of dry-grinding, and completed the present invention.

That is, according to the present invention, an antistatic agent is adhered to the surface of a thermoplastic liquid crystal resin molding capable of forming an anisotropic melt phase, and the molding is dry-ground to obtain an antistatic pulp-like material. The present invention relates to a method for producing a pulp-like material comprising an antistatic thermoplastic liquid crystal resin. The present invention will be described in more detail below.

Any of the thermoplastic liquid crystal resins used in the present invention can be used in the present invention as long as they form an anisotropic molten phase in the molten state. What is formed is desirable. The thermoplastic liquid crystal resin that forms an anisotropic molten phase at a temperature higher than 280 ° C. is unlikely to cause fusion during pulverization. Also, above 450 ℃
A thermoplastic liquid crystal resin that forms an anisotropic molten phase at the following temperatures is preferable because it facilitates melt molding. Whether or not the anisotropic molten phase is formed can be easily determined by observing the sample in a polarized state using an optical microscope equipped with an apparatus that allows observation while heating the sample.

As the thermoplastic liquid crystal resin used in the present invention, the following (formula 1) or (formula 2) and (formula 3),
Alternatively, examples include those composed of structural units represented by (Formula 1), (Formula 2), and (Formula 3), but the present invention is not limited to these structural units. -AX-CO- (Formula 1) In (Formula 1), A is one or more kinds of bonding groups selected from -O- and -NH-. X is at least one selected from the structural formulas shown in Chemical Formula 1 below, and at least one hydrogen atom on the aromatic ring is a halogen atom, an alkyl group having 1 to 10 carbon atoms, or 6 to 10 carbon atoms.
It may be substituted with one or more groups selected from 18 aryl groups.

[0010]

Embedded image

—OC—Y—CO— (Formula 2) In (Formula 2), Y is at least one selected from the structural formulas shown in Chemical Formula 2 below, and at least one hydrogen atom on the aromatic ring is halogen. It may be substituted with at least one group selected from an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 18 carbon atoms.

[0012]

Embedded image

Ar in Chemical Formula 2 is at least one selected from the following Chemical Formula 3.

Embedded image

—B—Z—O— (Formula 3) In (Formula 3), B is one or more kinds of bonding groups selected from —O— and —NH—, and Z is shown in Chemical Formula 4 below. It is one or more selected from structural units, and one or more hydrogen atoms on the aromatic ring is a halogen, an alkyl group having 1 to 10 carbon atoms, or 6 to 10 carbon atoms.
It may be substituted with one or more groups selected from 18 aryl groups.

[0015]

[Chemical 4]

(Equation 1) or (Equation 2) and (Equation 3)
The present invention provides a thermoplastic liquid crystal resin which forms an anisotropic melt phase at 280 to 450 ° C., which is obtained by appropriately combining structural units consisting of or structural units consisting of (Formula 1), (Formula 2) and (Formula 3). Is preferably used in.

Specifically, the above combinations are specifically described in US Pat. Nos. 3,637,595, 4,067,852, 4,161,470 and 3,80.
4,805, and 4,118,372, and JP-A-63-27.
5628, JP-A-62-207327, JP-A-61-2
36819, JP-A-62-232432, JP-A-63-
39622, JP-A-63-39918, JP-A-3-12
630, JP-A-3-91534, and JP-A-3-9153.
3, those disclosed in JP-A-236231 and JP-A-2-208317 can be exemplified.

The method for producing the thermoplastic liquid crystal resin capable of forming the anisotropic molten phase used in the present invention is not particularly limited, and it can be produced according to a conventionally known method. As a typical preparation method, the structural unit (Equation 3) -CH ₂ CH
If it is other than _2- , for example, the following (a) ~
In the method of (C), the structural unit (formula 3) is —CH ₂ CH ₂ —
In this case, the following method (d) may be mentioned, but the method is not limited to these.

(A) A method of producing from an aromatic dicarboxylic acid compound, a diacetic acid ester of an aromatic dihydroxy compound and an acetic acid ester of an aromatic hydroxycarboxylic acid compound by a deacetic acid polycondensation reaction. (B) A method of producing by acetic acid polycondensation reaction after acetylating a phenolic hydroxyl group by allowing acetic anhydride to coexist with aromatic dicarboxylic acid compounds, aromatic dihydroxy compounds and aromatic hydroxycarboxylic acid compounds.

(C) A method for producing from a diphenyl ester of an aromatic dicarboxylic acid compound, an aromatic dihydroxy compound and a phenyl ester of an aromatic hydroxycarboxylic acid compound by a dephenol polycondensation reaction. (D) A method of producing by the method (a) or (b) while coexisting an aromatic aromatic dicarboxylic acid compound such as polyethylene terephthalate and a polyester composed of ethylene glycol.

As long as the object of the present invention is not impaired, the thermoplastic liquid crystal resin may be blended with an inorganic filler such as talc, mica, clay or barium sulfate, or carbon pitch. Also,
Additives such as pigments, lubricants and antioxidants can also be added.

The thermoplastic liquid crystal resin molded product in the present invention can be used in the present invention as long as it is a molded product having a shape that can be supplied to a crusher, but it is continuously extruded to form a strand or a film. Those obtained are preferably used. It is also possible to use a method in which a molded product is roughly crushed in advance with a hammer mill or the like and then this is supplied to a crusher.

The antistatic agent used in the present invention can be used in the present invention as long as it can be used as a liquid or a solution. In cation type, quaternary ammonium chloride, quaternary ammonium sulfate, quaternary ammonium nitrate, etc., in amphoteric type, alkyl betaine type, alkyl imidazoline type, alkyl alanine type, etc.
In the anionic system, it has an alkyl sulfonate, an alkyl benzene sulfonate, an alkyl sulfate, an alkyl phosphate, etc., and in the non-ionic system, it has a polyoxyethylene alkylamine, a polyoxyethylene alkylamide, a polyoxyethylene alkyl ether, etc., and further has a polyvinylbenzyl cation etc. Examples of the conductive resin include, but are not limited to. Of these, water-soluble antistatic agents are particularly preferably used in the invention.

The method of attaching the antistatic agent to the thermoplastic liquid crystal resin molded article according to the present invention varies depending on the manufacturing method and shape of the molded article. For example, the thermoplastic liquid crystal resin molded article is immersed in a solution containing the antistatic agent. There is a method of stacking and adhering, or a method of spraying a solution containing an antistatic agent onto a thermoplastic liquid crystal resin molding to adhere it. However, the method for attaching the antistatic agent to the thermoplastic liquid crystal resin molded article in the present invention is not limited to these methods.

The concentration of the antistatic agent solution varies depending on the shape of the thermoplastic liquid crystal resin molded product and the method of adhering it, but for adhering 1 × 10 ⁻⁵ g or more of the antistatic agent to 1 cm ² of the surface area of the molded product. Is preferably at least a concentration of 1% or more.

As the antistatic agent, it is necessary to attach 1 × 10 ⁻⁵ g or more of the antistatic agent per 1 cm ² of the surface area of the thermoplastic liquid crystal resin molded product. If the amount of adhesion is smaller than this, the antistatic agent does not adhere to the entire pulp-like material even if the molded product is dry-ground, and a sufficient antistatic effect cannot be obtained.

The pulverizer used in the dry pulverization for producing the pulp-like material may be of any type, and among them, the high-speed rotary impact pulverizer provides a good-shaped pulp-like material. Therefore, it is preferable. The high-speed rotary impact crusher is a crusher in which a pin rotating in a crushing chamber or a rotor having a special structure gives a shock or shear to the resin to crush the resin.

As a crusher having this type, a free crusher, New Cosmomizer (manufactured by Nara Machinery Co., Ltd.), Victory Mill, Far In Victory Mill (manufactured by Hosokawa Micron Co., Ltd.), Turbo Mill (Turbo Industry Co., Ltd.) Manufactured), Ultra Rotor (WIR Co., Ltd.)
), Makino crusher, Ultraplex (Makino Sangyo Co., Ltd.), Fine mill (Nippon Pneumatic Mfg. Co., Ltd.), Impeller mill (Seishin Enterprise Co., Ltd.)
Etc.

One of the advantages of the method of dry pulverizing after attaching the antistatic agent to the thermoplastic liquid crystal resin molded product of the present invention is that the pulverized and bulky pulp-like material is discharged smoothly, It is also easy to handle. When crushing a molded product that does not have an antistatic agent attached, it is difficult to smoothly collect the pulp-like substance after the crushing, because electrostatically charged pulp-like substances aggregate or attach to the discharge route. Is.

The pulp-like material produced by the above-mentioned method is easy to handle, and serves as a reinforcing agent for a heat-resistant composite material combined with another thermoplastic resin or a thermosetting resin, and as a substitute material for asbestos. It is useful as a friction material for automobile brake pads or clutch fading, a sliding material, a heat resistant filter, a chemical resistant filter, and the like.

[0031]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples. “Parts” described in the following examples and the like means “parts by weight”. still,
Various measurements in Reference Example 1 were performed by the following methods.

(1) Melting point Differential scanning calorimeter (DSC) (manufactured by Seiko Denshi KK, S
SC-560S type), about 10 mg of a sample was placed in an aluminum non-sealed container, and the nitrogen gas stream (30 ml / 30 ml /
Min) and the temperature was raised from 30 ° C. at a heating rate of 20 ° C./min for measurement, and the temperature showing an endothermic peak was taken as the melting point.

(2) Flow initiation temperature and presence / absence of anisotropic molten phase formation Using an optical microscope (Nikon Corporation, trade name: Optiphot-pol) equipped with a hot stage (Colette Industry Co., Ltd.) The sample was observed in a polarized state while the temperature was raised at a heating rate of 10 ° C / min. The temperature at which a part of the sample started to flow was defined as the flow start temperature.

(3) Logarithmic viscosity of the thermoplastic liquid crystal resin The logarithmic viscosity [(lnηrel) / c] is 0.16 g / dl.
A pentafluorophenol solution having a concentration was measured at 60 ° C.

(4) Moisture Content of Thermoplastic Liquid Crystal Resin Micro moisture measuring device (CA-05 manufactured by Mitsubishi Kasei Kogyo Co., Ltd.)
Type) in a nitrogen gas stream (300 ml / min), 2
It was measured at 80 ° C.

(5) Surface resistivity of thermoplastic liquid crystal resin, half-life It was measured using an electric resistance measuring instrument (trade name: Hiresta IP, manufactured by Mitsubishi Petrochemical Co., Ltd.).

Reference Example 1 Production of LCP-A A reactor equipped with a stirrer, a thermometer, a pressure gauge, a nitrogen gas introducing pipe, a distillation head connected to a condenser, etc., was charged with 1081 parts of p-acetoxybenzoic acid, 1,4. -388 parts of diacetoxybenzene, N, N '-(4,4'-diphenylether) -bis-3,4'-dicarboximide benzoic acid 11
After charging 0 part and 389 parts of 2,6-naphthalenedicarboxylic acid and purging with nitrogen three times, the temperature was raised to 200 ° C. while slowly flowing a small amount of nitrogen into the reaction vessel while stirring.

After the temperature was raised to 200 ° C., the stirring speed was increased, the temperature of this mixture was raised stepwise, and the mixture was heated at 240 ° C. for 1 hour, 260.
The reaction was performed at 1 ° C for 1 hour, at 280 ° C for 1 hour, and at 300 ° C for 1 hour. Then, the pressure inside the reaction vessel was gradually reduced to 0.
While maintaining a vacuum of 5 Torr, at 300 ° C for 1 hour, 32
Polymerization was completed by stirring at 0 ° C for 1 hour and at 340 ° C for 1 hour. After the polymerization is completed, the pressure inside the reaction vessel is 2.5 kg.
/ Cm ^2, and the strand was taken out from the bottom valve through the die and cut into a pellet by a cutter. The melting point of this polymer (hereinafter referred to as LCP-A) is 317.
C., the flow starting temperature was 312.degree. C., and showed an anisotropic melt phase. Logarithmic viscosity was 4.2 dl / g and specific gravity was 1.40.

Example 1 The polymer of LCP-A obtained in Reference Example 1 was discharged from a 4 mmφ nozzle attached to the tip of a 45 mm twin-screw extruder at 330 ° C. at a single hole discharge rate of 37 / min, and Eretat M- 65
A strand with an antistatic agent obtained by passing it through a cooling water tank containing a 5% aqueous solution of (an antistatic agent manufactured by Yushisha Yushi Kogyo Co., Ltd.) has a length of 4 by a pelletizer.
mm, 2 mm diameter pellets were cut. After drying for 6 hours / 120 ° C. using a hot air dryer, 100 g of pellets were precisely weighed. This was washed with water to completely remove the antistatic agent adhering to the pellets, and then dried again using a hot air drier for 6 hours / 120 ° C. The pellets were precisely weighed and the amount of the antistatic agent attached was determined. As a result, 6.5 × 10 ⁻⁵ g of the antistatic agent was attached per 1 cm ² of the surface area of the pellet.

The pellets are made into a small crusher A- manufactured by Aika.
Pulverized product obtained by crushing with a 10 type (dry type / rotary blade type), and 23 R, 50R. H. After controlling the humidity for 2 days in the atmosphere described above, the water content was measured. In addition, 8 g of this pulp-like material was put into a mold for producing a 50 mmφ columnar tablet, and an effective pressure of 1940 kg was obtained using a molding press manufactured by Otake Machinery Co., Ltd.
Compression molding was carried out under the conditions of f / cm ² , pressure holding time of 1 minute and room temperature to produce a 50 mmφ cylindrical tablet. Using this tablet, surface resistivity and half-life were measured. The results are shown in Table 1.

Example 2 Pellets were prepared under the same conditions as in Example 1 except that the concentration of the Eretat M-65 aqueous solution in the cooling water tank was set to 1%. As a result of calculating the adhesion amount of the antistatic agent, the surface area of the pellet is 1
1.1 × 10 ⁻⁵ g of antistatic agent was attached per cm ² . After that, the same measurement as in Example 1 was performed. The results are shown in Table 1.

Example 3 The strand discharged under the same conditions as in Example 1 was passed through a water tank,
It was cut into pellets having a length of 4 mm and a diameter of 2 mm by a pelletizer. Use these pellets for Eretat M-65 5
% Aqueous solution, followed by filtration and drying with a hot air drier for 6 hours / 120 ° C. to obtain pellets to which an antistatic agent was attached. As a result of calculating the adhesion amount of the antistatic agent, 8.5 × 10 ⁻⁵ g of the antistatic agent was adhered to 1 cm ² of the surface area of the pellet. After that, the same measurement as in Example 1 was performed. The results are shown in Table 1.

Comparative Example 1 A strand discharged under the same conditions as in Example 1 was passed through a water tank,
It was cut into pellets having a length of 4 mm and a diameter of 2 mm by a pelletizer. After that, the same measurement as in Example 1 was performed.
The results are shown in Table 1.

Comparative Example 2 The concentration of the Eretat M-65 aqueous solution in the cooling water tank was 0.5%.
Pellets were produced under the same conditions as in Example 1 except for the above. As a result of calculating the adhesion amount of the antistatic agent, 0.5 × 10 ⁻⁵ g of the antistatic agent was adhered to 1 cm ² of the surface area of the pellet. After that, the same measurement as in Example 1 was performed.
The results are shown in Table 1.

Table 1 Example 1 Example 2 Example 3 Adhesion amount of antistatic agent (g / cm ² ) 6.5 × 10 ⁻⁵ 1.1 × 10 ⁻⁵ 8.5 × 10 ⁻⁵ Moisture content (%) 0.05 0.03 0.06 Surface resistance Rate (Ω) 2.1 × 10 ¹² 5.2 × 10 ¹² 1.0 × 10 ¹² Half-life (sec) 0.3 0.5 0.2

Table 2 Comparative Example 1 Comparative Example 2 Adhesion amount of antistatic agent (g / cm ² ) 0 0.5 × 10 ⁻⁵ Moisture content (%) 0.01 0.02 Surface resistivity (Ω)> 1.0 × 10 ¹³ > 1.0 × 10 ¹³ Half-life (sec) 15520 (4.3 hours) 357

[0047]

As is apparent from the above detailed description of the invention and Examples, the present invention makes it possible to prevent the formation of static electricity due to the antistatic effect, and as a result, a pulp-like resin comprising a thermoplastic liquid crystal resin having improved handleability. The product can be easily manufactured, and its industrial significance is extremely high.

Claims (4)

[Claims] 1. A thermoplastic liquid crystal resin molded product capable of forming an anisotropic molten phase is coated with an antistatic agent, and the molded product is dry-ground to obtain an antistatic pulp-like product. And a method for producing a pulp-like material comprising an antistatic thermoplastic liquid crystal resin. 2. A pulp-like material comprising an antistatic thermoplastic liquid crystal resin according to claim 1, wherein the active ingredient of the antistatic agent is attached in an amount of 1 × 10 ⁻⁵ g or more per 1 cm ² of surface area of the thermoplastic liquid crystal resin molding. Manufacturing method. 3. A method for producing a pulp-like material, wherein the thermoplastic liquid crystal resin molding capable of forming an anisotropic melt phase is a strand-shaped molding or a film-shaped molding. 4. The method for producing a pulp-like material according to claim 1, wherein the antistatic agent is a water-soluble antistatic agent.