JPS5845215A - Powdery phenolic resin composition - Google Patents

Abstract

PURPOSE:To provide a powdery phenolic resin composition for wet forming, having improved dispersibility in water, keeping the original strength of the base resin, by modifying powder of phenol aldehyde resin with ligninsulfonic acid metal salt and powdery silica. CONSTITUTION:The objective powdery phenolic resin composition for wet forming use can be prepared by adding (A) 0.2-2.0(wt)% ligninsulfonic acid metal salt (e.g. sodium ligninsulfonate) and (B) 0.1-1.0% silica powder to a phenol formaldehyde resin, and mixing and pulverizing the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention mainly relates to a phenolic resin powder composition with improved water dispersibility, which is used after being previously dispersed in water when forming a wet-process mat-like product.

The method of dispersing phenolic resin powder in water has the following advantages.

(1) Since phenol formaldehyde resin (hereinafter simply referred to as phenol resin) does not dissolve into water, the COD load of wastewater can be reduced; (2) Migre! This is because the phenolic resin binder does not migrate to the surface layer of the mat due to the John phenomenon, and products actually manufactured using this method include wood boards, inorganic boards, and heat insulation materials. .

However, this method has the disadvantage that unless the temperature of the dispersion water is thoroughly controlled, the dispersed phenol resin becomes lumpy or gum-like.

Although the water temperature is normally controlled below 50℃, especially in the summer, the water temperature can reach as high as 40℃.
In the case of No. 7, the actual situation is that the dispersion water or circulating water must be used while being cooled.

However, as a result of extensive research aimed at improving the water dispersibility of powdered phenolic resin, the inventors of the present invention have found that strength performance can be improved by modifying this phenolic resin powder using a combination of lignin sulfonate and silicic acid powder. The present invention was completed by discovering a scale that significantly improves water dispersibility without causing any deterioration.

That is, the present invention provides a phenol resin for wet molding using a phenol formaldehyde resin powder dispersed in water prior to molding. A phenolic resin for wet process molding with improved water dispersibility, which is modified with a 0.2-10% geninsulfonic acid metal salt and a 0.1-10% silicic acid powder based on A powder composition is provided.

Next, the present invention will be explained in detail.

The above-mentioned phenolic resin used in obtaining the composition of the present invention is a resin prepared mainly from known and commonly used 7 enols and a formaldehyde supplying substance and using a known and commonly used alkali or acid as a reaction catalyst. Representative examples include resol type phenol formaldehyde resin and novolak type phenol formaldehyde resin.

Any of those commonly applied for this purpose may be used, and therefore small amounts of other 7 enols, such as cresol or t-butylphenol, or small amounts of other formaldehyde-supplying substances, such as acetaldehyde or glyogyzal, may be used. Of course, the modified resol type or novolac type phenol formaldehyde described above can also be used in the present invention.

In addition, typical examples of the ligninsulfonic acid metal salts used in the present invention include calcium salts and sodium salts, all of which have the effect of improving water dispersibility, but among these, ligninsulfonate Sodium chloride is much more effective. The amount of these added is 0.2 to 2.0 weight 1 liter to phenolic resin.
- is appropriate. The greater the amount of sodium lignin sulfonate added, the better the water dispersibility will be, but on the contrary, the strength II will be lowered, and because it will cause extreme black discoloration, the finished color of the product will change to black. The amount should be within the upper ml range, as this will reduce the commercial value. In addition, as for the method of adding it, it is advantageous to pre-melt-proof the phenol resin before taking it out after production, since it does not turn the circulating water black, but even if it is mixed during pulverization, it will not disperse in the water. Since there is almost no barley that has a sexual effect, there are no particular restrictions on the mixing method.

Incidentally, this sodium ligninsulfonate is commercially available under the trade name "Vanirex", so such a product may be used.

Furthermore, the above-mentioned genin sulfonic acid metal salt is added.

In addition, the above-mentioned silicic acid powder is added at the same time, and this silicic acid powder is allowed to coexist with the phenolic resin in an amount of 11-tots (vs. phenolic resin) during the pulverization of the phenolic resin, and these resins and metal salts are mixed together. By mixing and pulverizing the resin powder and the powder, the water dispersibility of the resin powder is further improved.

The reason for this is that the heat generated by crushing prevents the silicic acid powder, which is a solid lubricant, from fusing between microparticles, forming lumps or blocks, and the existence of microscopic lumps that act as cores. It is thought that this is because they do not.

The amount of this silicic acid powder is t relative to the phenol resin.
If it exceeds 0, the resultant composition will have chicken properties and its strength will be reduced, while if it is less than 114, almost no effect will be obtained, so both are not preferred.

Incidentally, this silicic acid powder is also commercially available under the brand name "Carplex" and the like, so such a powder may be used.

Next, the present invention will be explained with reference to Examples and Comparative Examples. In the following, all references to ``chi'' are based on weight unless otherwise specified.

Diameter Example (Preparation Example of Phenol Resin) Phenol 4,95511,4 was placed in a four-loaf flask equipped with a stirrer, reflux condenser, and temperature needle.
0% formalin 3.100 g and 55 tsp Shioshun 1
4.81. li' was charged, the temperature was raised to the reflux temperature for about 2 hours, maintained at the same temperature for 2 hours, and then heated to the reflux temperature for about 2 hours.
The reaction was continued while slowly adding hydrochloric acid 59.24 and SJ dropwise until the refractive index (n) reached t600, and then immediately dehydrated under reduced pressure and reacted to 180° C. under reduced pressure at 68 omB. Immediately after the reaction was completed, it was panned out and taken out. The phenol formaldehyde obtained here is used as a resin. Also, just before taking this out,
Resin-B is obtained by adding tons of sodium lignin sulfonate (manufactured by Chongyang Kokusaku Pulp ■) and melting and mixing.The melting points of these resins and resin-B are 107°C and 108°C, respectively. (ball and ring method).

Examples 1 to 5 40 g of hexamine for 50011 of resin-A [
8- for resin (hereinafter the same)], "Carplex" (silicic acid powder manufactured by Shionogi & Co., Ltd.) zsy<a, ss>, and "Vanirex NJ2.5.@(α5chi) were added and mixed and pulverized at the same time. A composition of the present invention was prepared by diluting (Example 1).

For 5ooy of Tsukudano-A, 40g of hexamine, [
Carplex J2.5.9 and Vanillex NJ
A composition of the present invention was prepared by adding 5.0it01) and mixing and pulverizing the mixture (Example 2).

Resin-B soo! For i, hexamine 40. !
A composition of the present invention was prepared by adding i' and 1-Carplex J2.5.9 and mixing and grinding (Example 6).

Comparative Examples 1 to 3 40g of hexamine to 500g of tree BFI-A
A comparative composition was obtained by adding and mixing and pulverizing the mixture (Comparative VAU1).

A comparative composition was obtained by adding Hexamine 4011 and Carplex J2.5.9 to 500 g of Resin-A and mixing and pulverizing the mixture (Comparative Example 2).
).

A comparative composition was obtained by adding Hexamine 409 to Resin-B 5001 and mixing and pulverizing it (Comparative Example 6).

Various performance tests were conducted on each of the compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 6.
Each test was conducted according to the following procedures.

Water dispersibility test Industrial water t,ooo9 is adjusted to a predetermined temperature in advance, and resin 100. ! Insert 9, 100 r from beginning to end
pm for a predetermined period of time. After that, take it out on a 52-mesh sieve, collect the resin lumps that remain there, and
It was dried at 5° C. x 50-RH for 7 days and expressed in terms of weight. The results are shown in Table 1.

Strength test disinch grater [Tarapy-Standard (T
appi 5 standard)], Lockwoo)
500. p1 asbeth) 21, resin 50y and industrial water 61 were added and stirred for 1 minute, then 20%
Approximately 50 μl of an aqueous solution of sulfate was added, and the mixture was further stirred for 2 minutes. After that, stop stirring, dehydrate by suction,
It was molded by cold press into a size of 25 cm x 25 inches. After molding, it was pre-dried at 120°C for 1 hour, and after another hour, the temperature was raised to 180°C and fired at the same temperature for 1 hour to produce a rock wool board.

Next, this board was cut out to a width of 30 mm and a span of 80 mm.
The bending strength (normal) was measured under the following conditions: angle and speed: 581111Z. Further, the water resistance bending strength was measured by immersing the previously cut test piece in industrial water at 25° C. for 3 hours and leaving it leaking. These results are shown in Table 2.

As is clear from the results shown in Table 2, by modifying with lignin sulfone #salt and silicic acid powder, the strength improves when the modified cap of lignin sulfonate is small, and conversely decreases when it is large. It can be seen that there is not much difference between the two.

On the other hand, the water dispersibility has been greatly improved, and although the effect of lignin sulfonate is large, using it alone tends to worsen the water dispersibility, and compared to silicic acid powder, It is known that the improvement can be further improved by the combined use of ligninsulfonic acid metal salt, and if the amount of ligninsulfonic acid metal salt added is within 2.0 cm, the finished color of the product will hardly change to black.

Claims (1)

[Claims] In the 7-enol resin powder for wet molding, which is used for molding in the form of a water-dispersed phenol formaldehyde resin powder, this phenol resin is preliminarily added to the water-dispersed form prior to water-dispersion.
Each resin is modified with CQ, 2 to 2.0-glygenin sulfonic acid metal salt, and 0.1 to 0.05 silicic acid powder, and has improved water dispersibility. Phenolic resin powder composition for wet molding.