JPH03172340A - Phenolic resin molding material for extrusion molding - Google Patents

Abstract

PURPOSE:To obtain a molding material capable of subjecting to continuous extrusion molding having excellent dimensional accuracy by mixing phenolic resin with filler and additive, as necessary, blending and heat-treating at a specific range of temperature to adjust to a specific monohole flowing value. CONSTITUTION:(A) 100 pts.wt. phenolic resin (novolak resin or resol resin) is mixed with 100-400 pts.wt., preferably 150-250 pts.wt. filler (e.g., glass fiber or carbon black) and hardener, lubricant, coloring matter, plasticizer or fire retardant additive, etc. The, resultant mixture is kneaded and (B) subjected to heat treatment at a constant temperature in a range of 70-100 deg.C, preferably 80-90 deg.C within a temperature range of + or -2 deg.C and adjusted to 0.1-15g, preferably 1-5g monohole flow indicating flow properties to afford a phenolic resin molding material capable of continuously performing extrusion molding giving molded articles having excellent dimensional accuracy and appearance.

Description

Detailed Description of the Invention [Industrial Application Field 3] The present invention is an extrusion molding device which is suitably used for continuous extrusion molding of phenolic resin molded products such as rollers, pipes, and cylinders having excellent shape accuracy. Regarding phenolic resin molding materials.

[Conventional technology]

Phenolic resin molded products have mechanical properties, electrical properties,
It has excellent heat resistance, flame retardance, physical properties, and chemical properties, and is relatively inexpensive, so it is manufactured by compression molding, transfer molding, injection molding, extrusion molding, etc. A phenolic resin molding material that has been passed through the process is used.

Among these molding methods for phenolic resin molding materials, plunger extrusion and screw extrusion have been developed as extrusion molding methods.

Products that require shape accuracy have traditionally been manufactured using metal materials. However, metal materials have problems with chemical stability such as corrosion and chemical resistance.

There is a desire for inexpensive plastic pipes, round bars, etc. that solve these drawbacks and have various excellent properties.For example, in the continuous extrusion method of phenolic resin molding materials,
Attempts have been made to manufacture phenol pipes, round bars, etc.

Plunger extrusion is used to produce long extruded products with monotonous shapes, such as pipes and round bars. However, in plunger extrusion molding equipment, the extrusion pressure in the mold part is high and intermittent extrusion is used, so there is no extrudable phenolic resin molding material suitable for obtaining uniform molded products with excellent shape accuracy. Not discovered.

The screw extrusion molding method is an apparatus in which a phenolic resin composition kneaded and melted in an extruder is introduced into a mold through an adapter and shaped into a final shape.

However, in the case of phenolic resin molding materials, the extrusion pressure in the mold section is high, and moreover, the extrusion is performed intermittently. In such molding equipment, the flow path of the composition changes in a complicated manner, and the curing reaction of the phenolic resin molding material may proceed rapidly due to a slight difference in temperature or pressure, or the curing reaction may occur locally due to stagnation. No phenolic resin molding material has been found that can be used to mold a vibrator-like object, round bar, etc., which is stable over a long period of time and has excellent shape accuracy.

[Problem to be solved by the invention]

The object of the present invention was invented in view of the above circumstances, and it is an object of the present invention to provide a phenolic resin molding material for extrusion molding that has excellent shape accuracy and can be continuously extruded.

[Means to solve the problem]

As a result of various studies to solve the above-mentioned problems, the inventors of the present invention have found that after kneading a mixture of phenolic resin, filler, and various additives as necessary, the mixture is heated to a specific temperature. It was discovered that a phenolic resin molding material heat-treated at a constant temperature within a range and adjusted to a specific monohole flow value has a uniform monohole flow, and allows for excellent shape accuracy and continuous stable extrusion molding. It has arrived.

That is, the present invention provides a phenolic resin molding material for extrusion molding, which is made by blending a filler and various additives in desired amounts with a phenolic resin, after kneading the compounding agent mixture. This is a phenolic resin molding material for extrusion molding, characterized in that it is heat treated at a constant temperature within the range of C and the monohole flow is adjusted to 0.1 to 15 g.

The phenolic resin used in the present invention is a novolak resin obtained by reacting phenols with a formaldehyde such as an aqueous formaldehyde solution, paraformaldehyde, or trioxane using an acidic catalyst, or a resol obtained by reacting using an alkaline catalyst. Any resin can be used.

Moreover, both can also be used together.

Examples of phenols include n-butylphenol,
ρ-tert-butylphenol, rhopropylphenol, 1so-propylphenol, p-amylphenol, nonylphenol, octylphenol, 0-chlorophenol, --chlorophenol, p-chlorophenol, 2I4-dichlorophenol, p-isopropenylphenol, 0-iodophenol, m-iodophenol, p-iodophenol, 0-methoxyphenol, tomethoxyphenol, 2,2-his(4-hydroxyphenyl)propane, phenol, hydroquinone, catechol, resorcin, 0-cresol, tomethoxyphenol, Cresol, p-cresol, 2.3-xylenol, 2,
Examples include 4-xylenol, 2.5-xylenol, 2,6-xylenol, 3,4-xylenol, and 3.5-xylenol.

Fillers used in the present invention include, but are not limited to, carbon black, colloidal silica, glass powder magnesia, basic magnesium silicate, magnesium carbonate, magnesium hydroxide, various silicates, aluminum hydroxide, Inorganic materials such as alumina powder, calcium carbonate, diatomaceous earth powder, kaolin, celite, acid clay, ceramic fiber, asbestos, rock wool, glass fiber,
It can be used in the form of inorganic fibers such as carbon fibers, organic fibers such as pulp, cotton, linters, polyimide fibers, vinylon fibers, aromatic polyamide fibers, and aromatic polyester fibers, or in the form of woven or non-woven fabrics.

The amount of filler used is usually 100 to 400 parts by weight, preferably 150 to 25 parts by weight, per 100 parts by weight of the phenolic resin.
It is 0 parts by weight.

Additives that may be used as necessary include curing agents, lubricants, colorants, plasticizers, flame retardants, and the like.

Hexamethylenetetramine is usually used as a curing agent added to the novolak resin. In this case, hexamethylenetetramine is generally used in an amount of 5 parts by weight or more and less than 25 parts by weight, preferably in a range of 5 to 20 parts by weight, based on 100 parts by weight of the novolak resin. If this value is less than 5 parts by weight, it will be difficult to obtain a satisfactory molded product, and if it is 25 parts by weight or more, the surface roughness and shape accuracy of the molded product will deteriorate.

It is not necessary to add a curing agent when a resol resin is used alone or in combination with a novolac resin.

Examples of lubricants include, but are not limited to, higher fatty acids such as stearic acid and palmitic acid, alkaline earth metal salts of higher fatty acids (calcium salts and magnesium salts), waxes such as montanic acid wax, and amides of higher fatty acids. Can be used. The amount of lubricant used is usually 0.5 to 2.0 parts by weight per 100 parts by weight of the phenolic resin.

As the coloring agent, carbon blank, subirito black, molybdenum red, phthalocyan blue, phthalocyan green, Hansa yellow, etc. can be used.

As plasticizers, furfural, alkylphenol,
tricresyl phosphate, polyethylene glycol,
Commonly used substances such as dibutyl phthalate are effective. The amount of plasticizer used is usually 0.2 to 2.0 parts by weight per 100 parts by weight of the phenolic resin.

Flame retardants include, but are not limited to, antimony oxide, chlorinated paraffin, perchloropentacyclodecane, tris (β-chloroethyl) phosphate,
Tris(dichloropropyl)phosphate, Tris(2
, 3-dibromopropyl) phosphate, tris(bromo, chloropropyl) phosphate, triphenyl phosphate, decabromodiphenyl ether, hexamodiphenyl ether, red phosphorus, tin oxide, tin hydroxide, molybdenum oxide, ammonium molybdate, zirconium oxide, water Examples include zirconium oxide, barium metaborate, zinc borate, and the like. The amount of flame retardant used is usually in the range of 10 to 20 parts by weight per 100 parts by weight of the phenolic resin.

In the present invention, in order to obtain the desired phenolic resin molding material for extrusion molding, after kneading a mixture of phenolic resin, filler, and, if necessary, various additives in desired amounts, The product is pulverized by heat treatment at a constant temperature within the range of ~100°C and within a temperature range of ±2°C, and the monohole flow, which indicates the flow characteristics of thermosetting resin, is adjusted to a range of 0.1 to 15 g. I can do it.

There are two methods for kneading: (1) a dry method using a roll or co-kneader, and (2) a wet method using a Henschel mixer, omni mixer, ribbon blender, etc.

For example, in the case of a dry method, a mixture of a phenolic resin, a filler, and, if necessary, various additives in desired amounts is kneaded, and the monohole flow is adjusted to 20 to 40 g, preferably 25 to 35 g. .

(However, the test method for monohole flow is JIS K 691.
According to 1, mold temperature 150°C 1 pressure 150kg/cd
, material input 1i55. og. ) In the case of a wet method, a desired amount of filler and various additives as necessary are blended into a 10 to 60% phenolic resin face and mixed with a Henschel mixer. Alternatively, one or more solvents such as methanol, acetone, toluene, methyl ethyl ketone, etc. are added to a mixture of a phenolic resin, a filler, and, if necessary, various additives, and kneaded.

The kneaded material is treated in the following manner to prepare a phenolic resin molding material for extrusion molding, and then pulverized.

In the dry method, the kneaded product is pulverized (using a known method such as a power mill, speed mill, sheet cutter, etc.) or in the form of a kneaded product, and in the wet method, the kneaded product is heated at 70 to 100°C. Maintain a constant temperature within the range and temperature range of ±2 ° C, and use a known dryer, such as a fluidized bed dryer,
A method of uniformly heating the molding material in a dynamic state for a certain period of time using a conical dryer or a vibration dryer, or a method of heating the molding material in a stationary state for a certain period of time such as in an oven is used.

If the heating temperature of the kneaded material is less than 70° C., the curing of the phenolic resin is slow, and it takes time to adjust the monohole flow. On the other hand, if the temperature exceeds 100°C, the phenolic resin will harden quickly, which will hinder the adjustment of the monohole flow. Therefore, the heating temperature is practically in the range of 70 to 100°C, preferably 80 to 90°C. Furthermore, if the constant temperature range is wide, it is difficult to obtain a uniform monohole flow.

The monohole flow of the heat-treated kneaded product is 0.1 to 15 g.
, preferably 1 to 5 g. If the amount of O is less than 1 g, the motor load of the extruder will be high and stable extrusion moldability will be lacking, the precision of the molded product will be poor, and the surface roughness of the molded product will also be poor. If it exceeds 15 g, the melt viscosity of the material changes greatly in the extruder, resulting in a lack of continuous stable extrusion moldability, making it impossible to obtain a molded product with excellent shape accuracy.

[Effect]

The feature of the present invention is that in continuous extrusion molding, after kneading a mixture of phenolic resin, filler, and various additives in desired amounts as required,
Shape accuracy can be improved by using a phenolic resin molding material for extrusion molding that has been heat-treated at a constant temperature within the range of ±2°C and the monohole flow has been adjusted within the range of 0.1 to 15 g. The advantages are that the molded product has a good appearance and can be continuously and stably molded.

〔Example〕

The present invention will be explained below with reference to Examples and Test Examples.

Examples 1 to 5 The fillers and other additives shown in Table 1 were mixed with the phenolic resin shown in Table 1 at the blending ratios shown in Table 1.

The resulting mixture was kneaded for 5 minutes at a temperature of 95 to 100°C with the front roll and 55 to 60°C with the back roll, and adjusted to the monohole flow after kneading shown in Table 1. This kneaded material was pulverized and sized using a power mill (screen 3 mm), charged into a conical dryer, and treated at 80°C for 6 hours.
The monohole flow after heat treatment was adjusted as shown in the table.

Examples 6-7 The phenolic resin shown in Table 1 was mixed with the fillers and other additives shown in Table 1 in the proportions shown in Table 1 using a Henschel mixer at room temperature to obtain granules. . The obtained granules were treated in an oven at 80° C. for 7 hours to adjust the monohole flow after heating shown in Table 1.

Comparative Examples 1 to 2 The fillers and other additives shown in Table 1 were mixed with the phenolic resin shown in Table 1 at the blending ratios shown in Table 1.

The resulting mixture was kneaded for 5 minutes at a temperature of 95-100°C for the front roll and 55-60°C for the back roll to adjust the monohole flow after kneading shown in Table 1. 3 mm) and sized the particles.

Extrusion molding test example Using an extruder with a diameter of 40 m and a Llo.24
Using a screw with a compression ratio of 2.0, which has a D1 compression part 16D, a bottom diameter of 34 gm, and a measuring part with a length of 5D, the cross section of the resin inlet has an outer diameter of 40 m, an inner diameter of 34 m, and a resin flow path on the outlet side. The cross section of the channel has an outer diameter of 46 m +, an inner diameter of 40 m, a flow path length of 120 m, which has the same cross section as the outlet side, and a total length of 180 t.
A die was installed at a position 0.5 m from the tip of the screw, and a pipe was extruded using the molding material shown in Table 1.

The conditions of the extruder are: 2D from the bottom of the hopper is water-cooled, 3-IO
D is 70”C, 11~16D is 85°C117~20D
is set at 95°C, 121-24D is set at 105°C, the die part is set at 160°C, and the screw rotation speed is 3Qr, p, m.
, and pressed it'a form.

The test results are shown in Table 2.

Vibration in the physical property measurement method for extruded products> After leaving the extruded products (length 500 nn) at 23°C ± 2°C1 relative temperature 50 ± 5% for more than 8 hours, a laser scanning micrometer (LSM- manufactured by Mitutoyo Aji) was used. 161
0M) at the center of the extrusion.

<Roundness> Extrusion molded product at 23°C ± 2°C, relative temperature 50 ± 5% 8
After standing for more than an hour, the roundness of the pipe was measured using a laser scan micrometer (LSM-1610, manufactured by Mitutoyo Aji).

〔Effect of the invention〕

The phenolic resin molding material for extrusion molding obtained by the present invention is rich in continuous stable extrusion moldability and has excellent shape accuracy, and can be continuously and stably molded into extruded pipes, extruded plates, extruded rods, etc. can.

Claims (1)

[Claims] 1. Add filler to phenolic resin and if necessary,
In the phenolic resin molding material for extrusion molding which is made by blending desired amounts of various additives, after kneading the additive mixture, 7
A phenolic resin molding material for extrusion molding, characterized in that it is heat treated at a constant temperature within the range of 0 to 100°C and the monohole flow is adjusted to 0.1 to 15 g.