JPS6023006B2 - Method of transferring waxes to thermosetting formaldehyde base resin - Google Patents

Description

[Detailed description of the invention] This invention transfers waxes that are solid at room temperature onto the surface of a thermosetting formaldehyde base resin that is solid at room temperature,
This relates to maintaining the properties of the base resin after it has been cooled and solidified.

With the development of related industries, the properties of synthetic resin compositions are becoming more and more subdivided. In the case of thermosetting formaldehyde-based resin compositions, the resin itself or a basic compound or basic resin component (hereinafter referred to as base resin), which is obtained by adding a slight curing component to this resin, is prepared in advance, and the desired characteristics are caused to be exhibited. For this reason, a method has been adopted in which a base material, filler, solvent, colorant, boar powder, etc. are blended to form a resin composition, and this is subjected to resin processing. This method is an industrially meaningful method that is expected to continue to be developed in the future as a compromise between providing small quantities of a wide variety of resin compositions for specific purposes and reducing costs through mass production. Under these circumstances, thermosetting formaldehyde base resins are generally required to meet the following requirements.

In other words, ■It is solid at room temperature, making it easy to package and transport. ■The curing component must be added to the base resin itself at the time of manufacture, so that it works effectively and is contained as uniformly as possible in the base resin itself. (2) The resin should have a certain amount of leeway to remain uncured under the heat and pressure applied during resin processing, and then be cured quickly and completely using the desired heat and pressure. From the perspective of manufacturers of thermosetting formaldehyde-based base resins, these requirements often conflict with each other, and the reality is that they are struggling to find a solution. On the other hand, in order to use thermosetting formaldehyde-based base resins industrially advantageously, it is necessary to adopt a method of transporting them in bags (containers) containing hundreds of kilograms as bulk handling. I'm under pressure. In addition, Japan has a high humidity climate, and when the molten base resin solidifies, water adheres to it from the humidity in the base resin manufacturing atmosphere and cannot be completely removed. Eventually, adverse effects and defects such as voids and blisters will be caused to the properties of the material. The inventors have made many years of research to solve the above-mentioned requirements and current problems, and they have developed a thermosetting formaldehyde-based base resin that is solid at room temperature, and has a method of softening or melting at a temperature above its softening temperature. He discovered that by transferring a solid wax at room temperature onto the surface of an object, the resulting base resin would satisfy each requirement and easily solve the problems, and successfully developed a method for making such a base resin. It is well completed.

Possible methods for attaching waxes to thermosetting formaldehyde base resin include spraying the wax onto a pre-shaped base resin, or passing the pre-shaped base resin through a bath containing wax. It will be done.

However, with this method, when the wax adheres to the base resin, the thickness of the wax tends to be uneven, and in order to melt and adhere the wax, heat is applied to the thermosetting formaldehyde base resin. It is something that needs to be given. As a result, the thermosetting formaldehyde base resin, which is sensitive to heat, undergoes thermal history, and as the reaction progresses, its properties change, making it no longer passable to subsequent resin processing, so manufacturing conditions must be adjusted accordingly. Difficult to set up. According to the method of the present invention, the reacted thermosetting formaldehyde base resin, which is solid at room temperature, is not subjected to thermal history until it is processed into resin, so the fatal flaws of the above-mentioned method can be eliminated. . Furthermore, the method of the present invention is superior in that by using this method, it is easy to control the thickness of the wax transferred onto the base resin surface using the transfer roll, and the variation in the thickness can be reduced. It is in. To describe the characteristics of this method, first, a thermosetting formaldehyde base resin that is solid at room temperature and has at least a curing component is poured under conditions above its softening temperature, preferably in the form of a thin plate or a wide slab (i.e., a flower lining). urge

Next, the base resin, which is at a temperature higher than its softening temperature, is cooled and solidified between the guide rolls that it passes through, and waxes that are solid at room temperature and are melted and solidified on the guide rolls are added to the surface of the base resin. This is a method of metastasis. The thickness of the transferred wax layer is usually 0.01~
The thickness is 0.7 ribs, preferably 0.03 square to 0.3 column. Thermosetting formaldehyde base as used in the present invention
Thresin is a base resin consisting of a compound that forms a condensation product with formaldehyde.

Another example of this compound is Hido. Phenol, m-cresol, xylenol, which is collectively known as aromatic hydrocarbon, or para-
These include tertbutylphenol, aromatic hydrocarbons such as toluene and xylene, and polyfunctional amino compounds such as melamine, aniline, benzoguanamine, and acetobuanamine. Furthermore, at least one or two or more of these compounds must be involved in the production of the base resin. The base resin also includes a condensation product of formaldehyde or a compound that is a source thereof and one or more of these compounds, and a mixture of these condensation products, both of which are in a solid state at room temperature. This base resin contains, as a curing component, a compound having a methylol group or an amine/group, or a compound that substantially generates these functional groups, unless it is cured by itself by the desired heat or pressure. Note that this base resin may of course contain in advance a wax selected from the same type of wax that is to be transferred by the method of the present invention or from other types. One embodiment of this invention will be explained with reference to the drawings.

FIG. 1 is a sectional view showing the main points of an apparatus for industrially utilizing the method of the present invention. FIG. 2 shows the structure of a crushed piece of base resin prepared using this device. 1 in Figure 1
2 is a molten base resin, 2 is a resin reservoir, 3 is a receiver having this resin reservoir 2, 4 is a gap (lip) that allows the base resin to flow down in the form of a thin plate or wide slab, 5 is a layer of sprayed wax, 6 1 is a wax jetting port, 7 is a wax transfer roll (hereinafter referred to as a transfer roll) which also serves as a guide roll, 8 is a wiping roll, 9 is a saucer, 10' is a cold air device, and 11 is a crushing device. The molten base resin 1 is supplied from the lip 4 to the nip between the transfer rolls 7 in the form of a thin plate or a wide slab while a portion of the resin 1 remains in the resin reservoir 2. On the surface of the transfer roll 7, melted wax is injected from the wax injection port 6 in advance and then solidified. The jetting angle of the molten wax by the wax jetting port 6 is preferably such that the wax jetting port 6 is provided in a horizontal position as shown in FIG. The position is variable until the injection port 6 becomes vertical. If the wax jetting port 6 is lower than the horizontal position, the jetted wax will simply fall onto the saucer 9, reducing the jetting effect. Furthermore, if the wax injection port 6 is installed beyond the vertical position, the injected wax will not only fly up in a whirlpool, but also accumulate between the transfer rolls 7 above the nip. The smooth transfer effect is diminished. The surface of the transfer roll 7 is cooled to below room temperature. The wax used is a high melting point wax that is solid at room temperature. Although its melting point is from 100 qo to 200°C, it must be melted before being used for injection. This is because when unmelted wax is sprayed, it becomes fine dust and flies up, making it difficult to form a uniform layer on the transfer roll 7. Examples of such waxes include fatty acid salts that are solid at room temperature, such as calcium stearate, magnesium stearate, and pishamite stearate, and substances that are solid at room temperature, such as higher olefins and paraffin waxes. The jetted wax forehead layer 5 is transferred along the surface of the transfer roll 7 as it rotates, and is attached and transferred to the surface of the molten base resin 1. Although the surface of the transfer roll 7 may be smooth, it is preferably an engraved roll. This is because if the roll surface is smooth, the wax layer 5 formed by solidifying the jetted wax will easily slide off the roll surface. Furthermore, the surface area of the engraving roll 7 is increased as much as possible to facilitate heat exchange with the molten base resin 1, and the shape of the base resin with waxes transferred to the surface is adjusted to make it easier to crush into a size suitable for resin processing. This is because it has a particularly remarkable effect. By cooling the surface of the transfer roll 7, enlarging its surface area by engraving, and exchanging heat as the solid wax melts, the base resin passing through this roll is rapidly deprived of heat and becomes at least below its softening temperature. solidify. It goes without saying that Lip 4
The aperture width is set to be equal to or larger than the gap between the transfer rolls 7. The base resin with the waxes transferred onto its surface is introduced into the crushing device 11 through a cold air cooling device 10 connected thereto, and is prepared into a size and shape suitable for resin processing, ie, as shown in FIG. 2. be done. In FIG. 2, a shows a base resin on which waxes have been transferred and has been crushed into an irregular shape, and b shows a base resin which has been crushed into a regular shape. The base resin onto which the waxes prepared in this way are transferred has a smooth surface due to the action of the waxes, which are solid at room temperature, so even if the base resins are packaged in units of hundreds of kilograms, direct contact between the base resins will not occur. less,
When packaged in this way, it will not clump under the weight of the base resin. In addition, moisture adhesion can be kept to a minimum in the atmosphere during base resin preparation or in subsequent storage and standing. This makes packaging, transportation, and storage much more convenient. Furthermore, since the high melting point waxes that are solid at room temperature are transferred to the surface of the base resin, the high melting point waxes transferred to the surface are first transferred to the surface during resin processing, even though the base resin is a near-thermal support type. In order to remove the heat necessary for melting, the heat curing of the base resin is temporarily suppressed, and after that, the flow of waxes is promoted, and the apparent flow of the base resin continues to increase and the rapid heat curing reaction continues. As a result, thermal stability is maintained during resin processing. Therefore, it has good workability,
Uniform processed products can be produced. The wax transfer base resin thus prepared can be used as it is or in combination with various binders for various purposes such as hot melt adhesives, molding materials, laminates, organic and inorganic binders, and joint fillers. As a supplementary note to Fig. 1, the roll 8 for wiping off excess wax and base resin has an elastic or soft spongy surface.
It is used to wipe off the surface of the wax transfer roll 7 without damaging it, and good results are obtained when rubber or flannel cloth is used as the surface material.

FIG. 3 is a diagram showing one embodiment of one of the transfer rolls, the engraved roll having an engraved surface. w is the frontage dimension of the roll convex part, x is the frontage dimension of the roll concave part, w
and x can be determined as appropriate. FIG. 4 is an explanatory diagram of the cross section of the roll shown in FIG. 3, with the uneven portions particularly enlarged.
is the same as above, y is the bottom dimension of the deepest part of the roll recessed part, z is the depth dimension of the roll recessed part, and R is the chamfered curvature radius of the roll green part. To explain the method of this invention more specifically,
Examples are shown below. However, the present invention is not limited to these Examples. Furthermore, in the examples, unless otherwise specified, "parts" means parts by weight, and "%" means % by weight. In addition, Table 1 was created so that the contents of each example and comparative example could be clearly understood. The following descriptions of each example and the example are based on this table. Table 1 Example 1 A steel internal chromium-plated burr receiver (with a lip as shown in Table 1 at the bottom of the lower outlet of a reaction vessel with a cooler)
(hereinafter referred to as receiver) was attached.

A transfer roll was installed directly below this lip. A wax injection port was heated in advance to 25 mm, and calcium stearate melted by the heat was prepared to be injected onto a transfer roll to form a layer. Phenol 2 in a reaction pot with a cooler
00 Ikarito, 2590 parts of 37% formalin were charged, and then 16 parts of 28% aqueous ammonia was added, the temperature was gradually raised, and when the temperature reached 100q0, reflux reaction was carried out for 30 minutes.
After 15 parts of ethylene bisstearamide was added and mixed and dispersed, a dehydration reaction was carried out under vacuum. When the temperature of the resin reached 85 qC, the outlet at the bottom of the reaction vessel was opened and the molten resin was allowed to flow down through the receiver to the nib of two transfer rolls on which a calcium stearate layer had been previously formed. The transfer roll continued to rotate, and as the resin passed through this nip, the surface of the resin cooled and solidified, forming the engravings of the transfer roll on which the layer of calcium stearate was completely transferred. When this solidified resin was further cooled to room temperature under cold air and pressure was applied with a compression crusher, a base resin piece having a substantially regular shape as shown in FIG. 2b was obtained. When this base resin was subjected to a caking resistance test and a moisture absorption test, good results as shown in Table 2 were obtained. Example 2 The same procedure as in Example 1 was carried out, except that calcium stearate was replaced with ethylene bisstearamide.

In this case as well, the engraved shape of the transfer roll was formed on the resin surface, and the ethylene bisstearamide layer was completely transferred to it. This solidified resin was further cooled to room temperature under cold air, and pressure was applied using a compression crusher to obtain irregularly shaped base resin pieces as shown in FIG. 2a.
When this base resin was subjected to a caking resistance test and a moisture absorption test, good results as shown in Table 2 were obtained. Comparative Example In Example 1, the ethylene bisstearamide that should have been charged into the reaction vessel with a cooler was omitted, and the molten resin was passed through the transfer roll according to the contents of Table 1 for the purpose of diaphragm only, without transferring waxes. .

The solidified resin was cooled down to room temperature under cold air, and then pressure was applied using a compression crusher to obtain base resin pieces that maintained almost a fixed shape. When this base resin was subjected to a caking resistance test and a moisture absorption test, the results shown in Table 2 revealed that it was unsuitable for practical use. Table 2 Characteristics of base resin 1 Caking resistance 1.1 Measurement method Place the finished base resin piece in a bottomed cylindrical container with a diameter of 20 mm, apply a load of 6k9, and leave it in a temperature atmosphere of 35 qo to solidify. I watched to see if it would.

1.2 Judgment ○1 Not solidified △ - Partially solidified × - Completely solidified 2 Spread the hygroscopic resin 500 polygon plate uniformly and leave it at a temperature of 25 oos and humidity of 90% for 4 hours, then measure the weight. did.

The weight after standing relative to the initial weight was expressed as an increase rate.

[Brief explanation of the drawing]

FIG. 1 shows one embodiment of carrying out the method of the invention. FIG. 2 shows an example of a base resin piece prepared using the method of this invention. FIG. 3 is an external view showing one aspect of the engraved surface of the transfer roll. FIG. 4 is an enlarged view showing a part of the cross section of FIG. 3. 1...Melted base resin, 2...
・Resin reservoir, 3... Receiver, 5... Sprayed wax layer, 6... Wax injection port, 7... Transfer roll , 8... Roll for wiping off excess waxes and base resin, 9...
...Wax saucer, 10...Cold air device, 11
......Crushing device, a...Crushing device into an irregular shape,
b...The crushing device is shaped like a regular shape, a, the opening shows the transferred wax layer, w... Width dimension of the roll convex part, x...Front dimension of the roll concave part, y...Bottom dimension of the deepest part of the roll concave part, z...Depth of the roll concave part size,
R... Chamfering curvature radius of each green part of the roll. group l
Figure group 2 Figure detail 3 Figure 4

Claims (1)

[Claims] 1. A thermosetting formaldehyde base resin that is solid at room temperature and has at least a curing component is allowed to flow down under conditions above the softening temperature of the base resin, and is cooled and solidified between the guide rolls through which it passes. 1. A method for transferring waxes to a thermosetting formaldehyde base resin, which comprises transferring waxes solidified at room temperature to the surface of the base resin.