JPS6149821A - Extrusion molding method of thermosetting resin - Google Patents

Abstract

PURPOSE:To manufacture continuously a molded article whose appearance is favorable, by performing screw extrusion of a thermosetting resin composite material whose maximum torque at the time of curing in a Bradender Plastograph is less than 600kg.cm. CONSTITUTION:Extrusion molding of thermosetting resin composite material which has been controlled so that the maximum torque value at the time of curing in a Brabender Plastograph (the temperature of a mixer, the number of revolutions per minute and a loading quantity of a material are made respectively into 100 deg.C, 30 turns/min and 34g by making use of a roller type mixer whose capacity is 30ml) becomes less than 600kg.cm is performed continuously by a screw type extruder. The control is performed by either performing control of a combination of resin, a curing agent and a filling agent or controlling heating and mixing processes of a roll and kneader. An extrusion-molded article whose thermal rigidity and mechanical strength are high and surface smoothness is excellent can be manufactured continuously.

Description

[Detailed Description of the Invention] [Industrial Field of Application] The present invention is applicable to the field of architecture, electricity, electronics, etc. [Prior Art] Methods for molding thermosetting resins include compression molding, transfer molding, Injection molding methods and extrusion molding methods are known, and molding materials suitable for each molding method are used.

Among these methods for molding thermosetting resins, two extrusion methods have been developed: a plunger extrusion method and a scree extrusion method.

[Problem that the invention seeks to solve]

The Pushinger extrusion method is used to produce long extruded products with simple shapes such as round bars and pipes. However, in the plunger extrusion molding apparatus, the pressing pressure in the mold section is high and intermittent extrusion is used, so it is difficult to obtain uniform molded products and the productivity is low.

Under these circumstances, a molding method using a so-called scree type extrusion molding apparatus has been developed. This is a molding device that guides thermosetting resin molding material kneaded and melted in an extruder into a mold through an adapter and shapes it into a final shape. However, with conventional thermosetting resin molding materials, the molding material gradually hardens inside the extruder, requiring a high extrusion pressure, and eventually extrusion becomes impossible, making it extremely difficult to operate for a long time.

[Means for solving problems]

The present inventors have conducted various studies to solve the above-mentioned problems of thermosetting resin molding materials with excellent flame retardancy and heat resistance, which are in strong market demand in the fields of architecture, electricity, electronics, etc. In the extrusion molding of thermosetting resins, we found that controlling the overall fluidity is especially important because the amount of other additives to the thermosetting resin material is large, and furthermore, we have The inventors have discovered that a thermosetting resin composite material with a maximum torque value of 600 kg/cm or less can solve these problems, and have thus arrived at the present invention.

That is, in the present invention, the maximum torque value at the time of curing in the Brabender plastograph of the thermosetting resin composite material is set to 600.
A thermosetting resin extrusion molding method characterized by continuous extrusion molding after adjusting the temperature to 1 kg/cm or less (however, the measurement conditions for the Brabender Plastograph are as follows: A roller type mixer with a capacity of 30 m1 is used, and the mixer temperature is 100°C. , the rotor rotation speed is 6° rpm, and the material input amount is 34 g).

The maximum torque value during curing of the thermosetting resin composite material of the present invention in the Prabender Plastograph was increased to 600 by 7.c.
This can be adjusted to below m by considering the combination of types and amounts of the constituent components of the molding material, such as resins, curing agents, fillers, lubricants, flame retardants, colorants, plasticizers, and other additives. becomes. Furthermore, in the case of the same composition, it is also effective to adjust the heating and mixing process of the ronopenider, co-kneader, etc. when manufacturing the molding material.
By advancing the so-called B stage (partial curing) in the mixing process, the maximum torque value during curing can be reduced. The maximum torque value during curing can also be reduced by adding a lubricant to the molding material granulated by crushing after the trenching, heating, and mixing steps and uniformly dispersing it using a ribbon blender or the like.

Thermosetting resins used in the present invention include thermosetting resins such as phenol resins, melamine resins, urea resins, epoxy resins, unsaturated polyester resins, allyl resins, silicone resins, xylene resins, aniline resins, and crosslinking agents. polyethylene, polypropylene, polystyrene,
Examples include thermoplastic resins such as polyvinyl chloride. Particularly, phenolic resins are suitable for extrusion molding using an extrusion molding machine incorporating the fabric I) x- of the present invention.

The phenolic resin used in this case is a novolac resin obtained by reacting phenols such as phenol, cresol, and xylenol with an aqueous solution of formaldehyde, paraformaldehyde, and formaldehyde such as trioxane using an acidic catalyst, or an alkaline resin. Any resol resin obtained using a catalyst can be used.

In addition to the above phenol resin, hexamine and paraformaldehyde may be used as a curing agent. Roughenol resin 100%
Usually 8 to 20 parts by weight are added. If the amount of the curing agent is less than 8 parts by weight, the resulting molded product will have poor thermal rigidity, while if it exceeds 20 parts by weight, a large amount of ammonia will be generated during molding and blisters will occur on the surface of the molded product. They tend not to be good-natured.

Further, commonly known fillers, lubricants, mold release agents, flame retardants and colorants are added, kneaded and pulverized to obtain a phenolic resin molding material for extrusion molding. All kneading and pulverization can be carried out by known methods. That is, a hot roll, kneader, co-kneader, etc. can be used for kneading, and a speed mill, power mill, etc. can be used for grinding.

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

As the lubricant, there are no particular limitations, but higher fatty acids such as stearic acid and palmitic acid, alkaline earth metal salts of higher fatty acids (calcium salts, magnesium salts), montanic acid wax, and amides of higher fatty acids can be used. . The lubricant may be added by being mixed with the phenol resin and others, or may be added after the molding material is prepared, if necessary.

As the coloring agent, carbon black, Spi IJ Sotobra Sok, molybdenum red, phthalocyanine blue, phthalocyanine green, and Hansa Yellow can be used.

As plasticizers, furfural, alkylphenol,
Tricresyl phosphate, polyethylene glycol,
Commonly used compounds such as dibutyl phthalate and p-toluenesulfonamide are effective.

Flame retardants are not particularly limited, but include antimony oxide, chlorinated paraffin, perchloropentacyclodecane, tris (β-chloroethyl) phosphate, tris (dichloropropyl) phosphate, tris (2,
3-dibromoglovir) phosphate, tris(bromo, chloropropyl) phosphate, triphenyl phosphate, thecabromodiphenyl ether, hexabromodiphenyl ether, red phosphorus, tin oxide, tin hydroxide,
Molybdenum oxide, ammonium molybdate, zirconium oxide, zirconium hydroxide, barium metaborate,
Examples include zinc borate.

The amount of filler used is novolak type phenolic resin material 10
The amount is usually 100 to 400 parts by weight, preferably 151 to 250 parts by weight. The lubricant is usually used in an amount of 05 to 20 parts by weight per 100 parts by weight of the novolac type phenolic resin. The amount of plasticizer used is usually 0.2 to 20 parts by weight per 100 parts by weight of novolac type phenolic resin.
Parts by weight. Further, 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 novolac type phenolic resin.

In the extrusion molding method with a built-in screw in the present invention, the compression ratio of the tube IJ x-, the gap between the tube IJ There are various restrictions depending on the characteristics. The larger or smaller the compression ratio of Suff+)x-, the larger or smaller the back pressure imparting function. If the back pressure is too large, excessive crosstalk will occur, resulting in excessive heat generation and hardening of the material, which is undesirable. On the other hand, if the back pressure is too small, compression and filling of the material and crosstalk will be insufficient, so it is also preferable, and appropriate back pressure and appropriate crosstalk are required. That is, in order to obtain stable extrusion and a good product, the extrusion molding machine used for the molding material and the compression ratio of 4-i, 0 to 5. 0,
It is preferably in the range of 12-401, more preferably 15-30.

[Effect]

The present invention is characterized by the use of a thermosetting resin composite material that has a maximum torque value of 600 to 9 r, m or less during continuous extrusion molding in shi lavender plast glass. The product has a good appearance and continuous stable molding is achieved by a plastograph with a maximum torque value of 600 kg/cm or less, preferably 550 kg/cm or less,
Further, it is preferable that the maximum torque value is 200 kg·cm or more.

If the maximum torque value during curing in Prabender Plastograph exceeds 600 kg/crn, the molded product will swell and deform, making stable continuous molding impossible over a long period of time, and in some cases curing within the extrusion barrel. It advances too far and becomes impossible to mold. In addition, if the maximum torque value is less than 200 cm, the molding in the extrusion barrel will be insufficient, so the molded product obtained will have excellent moldability and excellent surface smoothness. It has high thermal rigidity and excellent mechanical strength, and can be continuously and stably formed into extruded tubes, extruded plates, extruded rods, etc.

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

〔Example〕

Example 1 Novolac resin (manufactured by Mitsui Toatsu Chemical Co., Ltd.≠9000.

Hexamine, glass fiber (chopped strand), clay, asbestos, spirit black, stearic acid, and magnesium stearate were mixed at a softening point of 95° C. in the proportions shown in Table 1.

The obtained mixture was passed through the front roll at 95 to 100°C and the back roll at 5
Roll kneading was carried out for 6 minutes at a temperature of 5 to 60°C. The mixed material is pulverized and sized using a power mill (screen 4m/Im), and a lubricant (product name Daiwanoxue MN, Inuichi Kagaku (Trana)) is added after 0.5%, and it is uniformly dispersed using a ribbon blender to form a molding material. The Brabender plastograph of this molding material was measured under the following measurement conditions.

Equipment: Toyo Seiki Seisakusho "Labo Blast Mill" roller mixer R-60 Mixer capacity used: 30CC Rotor rotation speed: 30 rpm Mixer temperature = 100℃ Sample loading amount: 340f? When the molding material was measured under the above conditions, the chart was as shown in FIG. 1, and the maximum torque value during curing was 480 kg·cm.

Example 2 A molding material was produced in exactly the same manner as in Example 1, except that the amount of lubricant added afterwards was 10%. The Brabender chart of this product was as shown in Figure 1, and the maximum torque value during curing was 440 cm.

Comparative Example 1 A molding material was produced in exactly the same manner as in Example 1, except that no post-added lubricant was added. The Brabender chart of this product is shown in Figure 1, and the maximum torque value during curing was 660 cm.

Example 6 Novolac resin (Mitsui Toatsu Chemical (to) +2000.

Hexamine, glass fiber (chopped strand), clay, spirit plano resin, stearic acid, and magnesium stearate were mixed in the proportions shown in Table 1.

The obtained mixture was heated on the front roll at 95-100°C and on the back roll at 5°C.
Roll kneading was carried out for 20 minutes at a temperature of 6 to 60°C. The mixed material was crushed and sized using a power mill (screen 4r11/m2), and then a lubricant (Daiwasokuko 1φN) was added to the
% and then uniformly dispersed using a ribbon blender to obtain a molding material. The Brabender chart for this is No.
As shown in Figure 1, the maximum torque value during curing is 450K (
It was 7 cm.

Comparative Example 2 A molding material was obtained in the same manner as in Example 3, except that the roll crosstalk time was 15 minutes. The Brabender chart of this product was as shown in Figure 1, and the maximum torque value during curing was 750 kg·crn.

Example 4 Rubber-modified novolac resin (manufactured by Mitsui Toatsu Chemical Co., Ltd., Miresox RN-941f), softening point 96°C, hexamine,
Glass fiber (chopped strand), clay, asbestos, spirit black, stearic acid, and magnesium stearate were mixed in the proportions shown in Table 1.

The obtained mixture was passed through the front roll at 95 to 100°C and the back roll at 5
Roll kneading was carried out for 9 minutes at a temperature of 5 to 60°C. The kneaded material was pulverized and sized using a power mill, and a lubricant (Gui Wax IMN) was added after 50 minutes, and the mixture was uniformly dispersed using a ribbon blender to obtain a molding material.

The Brabender chart for this product is as shown in Figure 1, and the chestnut torque value at the time of hardening is 410 kg cm.
Met.

Comparative Example 6 A molding material was produced in exactly the same manner as in Example 4, except that the phenol resin was changed to +-2000. The Brabender chart for this product is shown in Figure 1, and the maximum torque value during curing is 800 Xfec.

Met.

Example 5 Bisphenol A type epoxy resin (Tobu Kasei ■, YD-
011, epoxy equivalent 475), ortho-cresol novolac type epoxy resin (Tobu Kasei YDCN-2
2OL) Epoxy equivalent: 225), 4.4'-diaminodiphenylmethane, silica powder, Montan Fuchs, and carbon blank were thoroughly mixed in a kneader at the mixing ratio shown in Table 1.

The obtained mixture was pulverized and sized using a power mill to obtain a molded powder.

The Brabender chart of this product is shown in FIG. 8, and the maximum torque value during curing was 280 kg·cm.

Example 6 Melamine formaldehyde resin liquid (formaldehyde/
Melamine ratio 2:1, solid content 90φ) and cut dissolving pulp (α-cellulose) were placed in a laminator and heated at 50°C.
The mixture was mixed for 3D minutes. After drying, zinc stearate and xamine were added and ground in a ball mill to obtain a shaped powder. The blending ratios are shown in Table 1.

The Brabender chart of this product was as shown in Figure 9, and the maximum torque value during curing was 470 cm.

Table 1 summarizes the blending ratios and Brabender maximum torque values of the above Examples and Comparative Examples.

Extrusion molding test example A land length of 3[]0 was placed at the tip of a conventional scree extruder with a diameter of 4oIT)/mXV'-D=18 and a compression ratio of 16.
The Unana die was attached to form a cylindrical pipe with an outer diameter of 40 rrVm and an inner diameter of 66 rings.

The conditions of the extruder are 0~4D from below the hopper, room temperature 5~12D,
...60℃ 13~18D...100℃ Head part ...110℃ Adapter part ...110℃ Land part
0~100m ・120℃100~200m =
・150℃ 200-300 ml...-1 (Set at 50℃,
It was extruded under the conditions of Suff+)z-rotation speed I B rpm.

The test results are shown in Table 2.

Table 2

[Brief explanation of the drawing]

1 to 9 show Brabender charts of examples and comparative examples of the present invention, where the horizontal axis represents crosstalk time and the vertical axis represents crosstalk resistance (torque). Point A in each figure indicates the maximum torque value during curing.

Claims (1)

[Claims] (1) Maximum torque value during curing of Brabender Plastograph, a thermosetting resin composite material, of 600 kg・cm
A thermosetting resin extrusion molding method characterized by continuous extrusion molding after the following adjustments (however, the measurement conditions for the Brabender Plastograph are that a roller mixer with a capacity of 30 ml is used, the mixer temperature is 100°C, and the rotor is rotated. several 30 rpm and a material charge of 34 g).