JPS5939384B2 - Inorganic fiber surface treatment method and device - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula Zr(OR)4(R■C3H7,C4H
9) The vapor of the zircon compound 11 represented by the general formula T
i(0R)nC14-n(R=C3H7, C4H9, n
After mixing the vapors of the titanium compounds represented by = 0 to 4), water vapor is supplied and mixed, and the resulting treatment agent mixed vapor is flowed into contact with the inorganic fibers A immediately after cotton production to produce hydrolyzed products. The specified invention is an inorganic fiber surface treatment method characterized by contacting and adhering a material to the inorganic fibers, and the inorganic fibers A are passed through a perforated plate IT to the processing box 1 into which the inorganic fibers A are fed immediately after cotton production into the steam mixing zone 19. The general formula Zr (
0R)4 (R=C3H7, C4H9), the liquid level of the zircon compound 11 is opened, and the general formula Ti(OR)nC
The titanium compound vapor introduction pipe 6 represented by l4-n (R C3H7, C4H9, n-0 to 4) is connected to the vapor mixing chamber 20.
This is a combined invention of an inorganic fiber surface treatment device characterized in that it is connected to An object of the present invention is to provide a method and apparatus for surface treatment of inorganic fibers, which can be applied to the surface of inorganic fibers, prevent mechanical and chemical deterioration of the inorganic fibers with this protective film, and produce fibers with a large protective effect on initial strength.

Since glass fibers are extremely brittle, their strength deteriorates significantly due to surface scratches after melt spinning.

Therefore, if mechanical and chemical surface damage can be prevented, extremely high tensile strength (200 to 300 kg/md) can be achieved.
) can be obtained. Therefore, conventionally, various resin films called sizing agents have been uniformly applied to the fiber surface of long glass fibers. However, since short fibers such as glass wool and rock wool are produced in large quantities by the disc method or spraying method, the surface treatment after production is limited to a binder spray, and a uniform film is not formed on the fiber surface, leaving only a few spots. It is in a state where droplets are attached to the cotton, and the strength is significantly reduced due to mechanical contact after cotton making. Due to the above-mentioned circumstances, in order to form a uniform protective film on the surface of wool-like glass fibers and maintain their initial strength, a surface treatment agent is sprayed in vapor form immediately after cotton making, and thermal decomposition etc. Although methods of causing a chemical reaction are being considered, the current situation is that satisfactory results cannot be obtained because the uniformity and thickness of the film attached to the fiber surface is still insufficient. In general, inorganic fibers are produced by introducing mineral raw materials melted at a high temperature of 1,300 to 1,500 degrees Celsius onto a disk rotating at high speed, and forming fibers from around the disk due to centrifugal force, or by high-speed airflow or flame ejected from a nozzle. It can be blown away and turned into fibers.

These fibers are sent into a collection box by the transport air current, collected and conveyed on a conveyor net, and then processed into a board by spraying with resin, etc., or by removing particles, opening the fibers,
After going through the granulation process, it is used as a raw material for other secondary products.

When examining the fiber strength in the above process, it was as high as 200 to 300 k9/MT/l immediately after cotton milling, and 1
It becomes 70-230k9/MTll, and 40-100k9/w after shedding and opening! It was found that it had deteriorated significantly. This strength deterioration is mostly caused by mechanical contact between the fibers, and therefore, this strength deterioration can be prevented by forming a protective film on the fiber surface. In the present invention, the cotton is loosely placed (
The deposited inorganic fiber A (loosely) is left as it is (
(without applying a large external force) into the processing box 1 in batches.

The attached drawings schematically illustrate one embodiment of the processing apparatus used in the processing power method according to the present invention, and 1 is a processing box, 2 is an input/output port for the inorganic fiber A, and 3 is this input/output port 2. 4 is a heating heater or a heating steam pipe, and 5 is a heat insulating protection wall. At the bottom of the processing box 1 is a perforated plate 17.
A water vapor mixing zone 19 is formed below the perforated plate 17, and water vapor introducing pipes 8 and 9 are introduced on both sides of this water vapor mixing zone 19. Further, a perforated plate 18 is provided at the bottom of the water vapor mixing zone 19, and a liquid storage tank 10 containing the zircon compound 11 is provided below the perforated plate 18. 18 is a steam mixing chamber 20.

Titanium compound vapor introduction pipes 6 and 7 are communicated with this vapor mixing chamber 20 from both sides. In this case, the introduction pipes 6, 7
The tip is bent slightly downward toward the liquid level of the zircon compound 11. In the figure, 12 and 13 are zircon compounds 11
14 and 15 are valves attached to each of the introduction pipe 12 and the extraction pipe 13, and 16 is the processing box 1.
This is an exhaust pipe installed in the In addition, the above-mentioned perforated plates 17 and 18
A plurality of slit plates or a net may be used to obtain the same effect. First, organic titanium or organic halogenated titanium compound [Ti(0R)NCl4-NlR=C4H9,C3H
7,n=0~4] and tetrabutoxy or tetrapropoxyzircon [Zr(0R)-R-C4H9,C
3H7] and water vapor to form a mixed coating of a hydrolyzed and condensed amorphous titanium compound and an amorphous zircon compound on the entire surface of the inorganic fiber A.

However, the vapors of organic titanium, organic halogenated titanium compounds, and zircon compounds such as tetrabutoxy or tetrapropoxyzircone are all extremely unstable in the presence of moisture, and are susceptible to hydrolysis reactions. Therefore, the vapor of organic titanium or organic titanium halide compound is blown into the upper part of the liquid storage tank 10 from the introduction pipes 6 and 7, while the water vapor is introduced into the water vapor mixing zone 19 from the water vapor guide pipes 8 and 9, and is then treated. Excessive contact of chemical vapors with water vapor should be avoided. In particular, zircon compounds such as tetrabutoxy or tetrapropoxy zircone are extremely unstable to moisture, so it is difficult to transport them through piping in a vapor state. It has been found that it is possible to vaporize organic titanium or organic titanium halide by utilizing the heat retained in the vapor. That is, in the method of the present invention, an initial concentration of 50 ml of tetrabutoxy or tetrapropoxy zircon, which has been heated to 100 to 3500° C.
0 to 4000 ppm of organic titanium or organic halogenated titanium compound vapor was introduced by blowing, and the titanium compound vapor and zirconium compound vapor were mixed in the water vapor mixing zone 19 to have a water vapor concentration of 500 to 8000 ppm. Air or nitrogen gas is introduced and mixed. Here, the role of the steam mixing zone 19 is to appropriately mix the mixed processing agent vapor and water vapor and supply the mixed vapor into the processing box 1. This is to obtain a uniform coating. That is, if the mixing zone 19 is not provided, the inorganic fiber coating within the processing box 1 will be non-uniform;
Conversely, excessive mixing in the mixing zone leads to material loss. Now, to explain according to the attached drawings, the inside of the processing apparatus is set in advance to a processing temperature (100 to 350 C) using a heating heater or a heating steam pipe 4.

A zircon compound 11 such as tetrabutoxy or tetrapropoxy zircon is already stored in the liquid storage tank 10 . Next, after putting the inorganic fiber A into the processing box 1,
00~35' Initial concentration heated to 500~4000p
pm titanium compound vapor is introduced through guide tubes 6 and 7, and similarly, humidified air heated to a treatment temperature of 100 to 35°C and has a water vapor concentration of 500 to 8000 ppm is introduced through introduction tubes 8 and 9. In this case, if the water vapor concentration is too low, the processing speed will be slow and the efficiency will be low, whereas if the water vapor concentration is too high, the stability of the processing agent will be poor and the efficiency will be reduced. The mixed vapor introduced into the processing box 1 diffuses into the narrow gaps between the inorganic fibers A and forms a mixed coating of titanium compounds and zircon compounds on all the fiber surfaces. Therefore, the features of the method and apparatus of the present invention are listed as follows.

1) Tetrabutoxy or tetrapropoxyzircon, which is particularly unstable to moisture, is stored as a liquid, and heated organic titanium or organic titanium halide compound vapor is introduced to the liquid surface and brought into contact with it to create a mixed vapor of a treatment agent. thing.

2) A steam mixing zone is provided in front of the processing box, and the processing agent vapor and water vapor are appropriately mixed before being supplied to the processing box.

In the method of the present invention, as mentioned above, the inorganic fiber immediately after cotton-making is coated with the general formula Zr(0R)4 (R=C3H7, C4H,
) and the general formula Ti(0R)N
A treatment agent vapor of a titanium compound represented by Cl4-n (R=C3H7, C4H9, nO~4) is brought into contact with water vapor to hydrolyze the treatment agent, and a mixed film of the hydrolyzate is formed on the surface of the inorganic fiber. The hard mixed film of both protects the inorganic fibers from mechanical deterioration, and the amorphous zircon compound produced by hydrolysis in the mixed film protects the inorganic fibers from chemical deterioration such as alkali deterioration. It has the advantage of being protected from deterioration.

In addition, in order to generate such a mixed film, the steam of the titanium compound is mixed with the steam of the zircon compound in advance, and then water vapor is supplied to this mixture, so both treatment agents, especially moisture, are extremely unstable. It is possible to properly mix the three components while preventing excessive contact of the zircon compound with water vapor, and to bring it into contact with the inorganic fibers without losing activity, to efficiently generate a mixed film without loss, and to prevent the reaction from occurring. Because it is a gas phase reaction, the hydrolysis product has an extremely short lifetime, but within that short lifetime, the treatment agent mixed vapor smoothly diffuses into the narrow pores of the inorganic fibers and completely absorbs the product. Most of the processing agents are discarded undecomposed because they form a uniform mixed film on the fiber surface, and when they pass through the narrow pores of the inorganic fibers, the three components are even better mixed and consumed effectively. It's not worth it. In addition, in the device of the present invention, the liquid level of the zircon compound in the liquid storage tank is opened in the steam mixing chamber, and the titanium compound vapor introduction pipe is communicated with this vapor mixing chamber, so that the titanium compound that can be injected from the introduction pipe is The steam can contact and mix with the zircon compound vapor on the liquid surface of the zircon compound, and the zircon compound, which is extremely unstable in water, can be stored as a liquid without having to be transported in the vapor state. It has the advantage that it can be mixed into titanium compounds in a stable state. In addition, since the steam introduction pipe is connected to the steam mixing zone connected to the processing box and the steam mixing chamber is connected to this steam mixing zone, the titanium compound and zircon compound mixed in the steam mixing chamber can be mixed. Hydrolysis starts when the steam is mixed with steam in the steam mixing zone, and since the steam comes into contact with the inorganic fibers in the processing box immediately after the steam is mixed, there is less material loss due to excessive progress of hydrolysis. It is. Furthermore, since the processing box, steam mixing zone, and steam mixing chamber are each partitioned by perforated plates,
Both the mixing of the vapors of the titanium compound and the zirconium compound and the mixing of this mixed vapor with water vapor are promoted when they pass through the perforated plate, which has the advantage of producing a mixed film with a uniform composition. The present invention will be specifically described below based on examples.

〔Example〕

SlO24OWt%, CaO4OWtO as mineral materials
t), A. e2O3l5wtCf/), MgO5wt(
:! ), this material was melted in an electric furnace at 1500° C., and the molten material was made into cotton by the disk method.

The cotton milling disk used had a diameter of 200 paulownia and a rotation speed of 300.
0rpm1 throughput is 0.5t/hour. Cotton was produced under the above conditions, and the fibers loosely deposited on the conveyor net at the bottom of the cotton collection box were loosely thrown into a 300L x 400W x 300H processing box for treatment. The processing conditions were as follows. 1) Processing agent...Tl(
0Bu) 4 and Zr (0Bu) 42) Temperature inside the processing equipment
...250℃3) Initial concentration of Ti(0Bu)4 vapor... Temperature4.

= Nisaki.゛J. 100 answers: }-Ppm (carrier gas N2)
℃5) Processing time......The fibers obtained after 2 minutes have a fiber diameter of 2.
The average thickness of the produced film was about 190.

The tensile strength of the samples treated as described above and those not treated were measured, and the results were as shown in the table below.

However, the tensile strength measurement conditions were as follows.

[Brief explanation of the drawing]

The attached figure is a schematic sectional view of one embodiment of the apparatus of the present invention, in which 1 is a processing box, 6 is an introduction pipe, 8 is a steam introduction pipe,
10 is a liquid storage tank, 11 is a zircon compound, 17 and 18 are perforated plates, 19 is a steam mixing zone, 20 is a steam mixing chamber, A
indicates inorganic fiber.

Claims (1)

[Claims] 1 General formula Zr(OR)_4 (R=C_3H_7, C_
4H_9), the general formula Ti(OR)_nCl_4_-_n(R=C_3H_9
, C_4H_9, n=0 to 4), and then supplying water vapor thereto and mixing,
A method for surface treatment of inorganic fibers, characterized in that the obtained treatment agent mixed vapor is brought into contact with the inorganic fibers immediately after cotton making, so that a hydrolyzed product is brought into contact with and adhered to the inorganic fibers. 2. A water vapor mixing zone is connected to the processing box into which the inorganic fibers immediately after cotton production are introduced via a perforated plate, and the water vapor introduction pipe is connected to the water vapor mixing zone through the perforated plate. The general formula of the liquid storage tank is Zr(OR)_4 (R=C_3H_7
, C_4H_9), and the general formula Ti(OR)_nCl_4_-_n(R=
An inorganic fiber surface treatment device characterized in that an inlet pipe for introducing steam of a titanium compound represented by C_3H_7, C_4H_9, n=0 to 4) is connected to a steam mixing chamber.