JPS59116474A - Surface treatment of fiber or fabric - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for surface treatment of fibers or woven fabrics for fillers used in industrial composite resin materials for spacecraft, electrical equipment, automobiles, and the like.

Structures of conventional examples and their problems Traditionally, industrial composite resin materials have either used fibers as fillers or their woven fabrics mixed with resin materials as they are, or
In order to improve the physical properties of composite materials, such as tensile strength (+1) and bending strength (2) and flexural modulus (flexural modulus), the filler was surface-treated to improve the affinity between the resin and the filler. . Moreover, in order to improve the physical properties of the adhesive material, it must have good affinity with the resin and filler, so it is necessary to change various surface treatment agents and add various grafting agents. , we have to fight hard to improve that affinity.)/ζ
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At this time, there are various types of fillers and surface treatment agents, and although some of them are known, the optimal combination has not been systematically established, and it is difficult to find the best combination by actually molding. There was no way. Therefore, it is necessary to systematize and think about these combinations in one's own way, then mix and mold each combination one by one, and examine each physical property value, which requires a lot of time and effort. In addition, conventional surface treatment methods generally involve simply immersing the filler in a liquid surface treatment agent and then drying it, meaning that the chemical reaction between the surface treatment agent and the filler does not occur completely. However, the bond between the surface treatment agent filler and the resin was clearly incomplete.

On the other hand, Japanese Patent Publication No. 51-10265 describes a manufacturing method in which maleic anhydride is added to glass fiber as a filler and polypropylene as a resin to improve the affinity between the filler and the resin. Proposed.

In this method 1, the compatibility with polypropylene is improved by grafting the introduced maleic anhydride onto the silane-treated glass fibers, but in the case of other resins, grafting with maleic anhydride compatibility cannot be improved by

As described above, there is a problem in that the surface treatment technique for improving affinity is not very versatile, and it is not satisfactory.

OBJECT OF THE INVENTION The purpose of the present invention is to solve the above-mentioned problems and to provide an effective and versatile method for improving the affinity of fibers or woven fabrics used as fillers with resins for improving the properties of composite resin materials. The present invention provides a method for surface treatment.

Structure of the Invention The present inventors have conducted extensive research in view of the above-mentioned conventional problems, and as a result, have arrived at the present invention.

The present invention provides fibers or woven fabrics thereof with fluorinated+1',
A process of halogenation such as 71M hydrogenation, a process of conducting a Grignard reaction using a Grignard reagent, and a process of generating carboxyl groups in fibers or woven fabrics using carbon dioxide or hydrochloric acid, or hydrolysis after oxidation. The process consists of the steps of generating hydroxyl groups and then generating various functional groups using a coupling agent.

However, this surface treatment method can be applied to the surface of the filling! 1. ,7
carboxyl group, hydroxyl group, vinyl group, amino group.

It is easy to generate functional groups such as epochine groups,
Moreover, it is possible to efficiently form large quantities. As described above, the present inventors have discovered that this is a completely new and excellent manufacturing method that has not been found in conventional manufacturing methods, in which the affinity between the filler and the resin is dramatically improved. Ta.

For example, in order to generate carfoquinol groups on fibers or woven fabrics, it is preferable to fluorinate or chlorinate the fibers or woven fabrics, then carry out the Grignard reaction and react with carbon dioxide and hydrochloric acid. ′! In order to generate hydroxyl groups on the fiber or woven fabric, the material may be subjected to 7) oxidation, chlorination and Grignard reaction steps using a Grignard reagent, followed by oxidation treatment and hydrolysis. Furthermore, in order to generate vinyl groups, amine groups, epoxy groups, etc. on fibers or woven fabrics, it is preferable to generate hydroxyl groups by the method described above, and then apply respective silane coupling agents such as vinyl silane, amino silane, and epoxy silane. It is good to let it work.

In this way, as shown schematically in FIG. 1 as an example, the present invention provides a method for carrying out the following steps: 1. , vinyl group introduction step, amino group introduction step.

It consists of an epoxy group introduction step. Therefore, it is possible to apply this method to a wide range of applications as a surface treatment method for fibers or woven fabrics.

Description of examples The details of the present invention will be shown below in Examples.

Example (1): Aramid fibers are substituted with N2 gas in a reaction vessel at 600°C (0F), and oxalic acid F2 gas is introduced for 2 hours to convert the fibers into 7 atoms. This woven IJ and 2-bromopropane are immersed in a Grignard compound produced by applying metal magnesilanol and heated at 30° C. for about 5 minutes.

After washing this fiber with pure water, it is further immersed in water and carbon dioxide is blown into it at room temperature for 10 minutes. This is 0.
After immersing in 5N HCl, it was dried under reduced pressure. In order to confirm whether carboxyl groups were formed on the fiber surface, a part of the sample was immersed in water, 2 drops of thionyl chloride was added, evaporated to dryness, 2 drops of a saturated solution of hydrogizolamine hydrochloride and alcoholic water were added. After adding a few drops of sodium oxide to make the reaction alkaline, it was heated again and after K
．． A few drops of 6N hydrochloric acid were added to make it acidic, and 1% ferric chloride was added. As a result, a hydroxamic acid iron complex was formed, and the color was mostly purple or red, and it was confirmed that carboxyl groups were certainly formed on the surface of the aramid fiber.

The treated fibers and untreated fibers were each mixed with epoxy resin (Araldal) GY2 so that the volume was 3 parts °A.
60; 100q, Jeffamine D-230; 25q,
Jeffamine AC-398; 10q) was mixed and a plate was formed using Honto Breath.

Furthermore, a predetermined test piece according to ASTM standards was cut out from this plate, and the bending strength was measured using an Instron testing machine.
The llI & Z elastic modulus was measured. Table 1 shows a comparison between the invented product filled with treated fibers and the conventional product filled with untreated fibers. Compared to the conventional products A66-10, invented products 161-6 showed improvements in physical properties of 34.2% on average in bending strength and 2162% on average in flexural modulus.

Furthermore, when a part of this plate was cut out and its fractured surface was observed with a scanning electron microscope, it was confirmed that the treated fibers were smaller than the untreated fibers (1), which were more compatible with the resin.

Table 1 Examples In the same manner as in Example 1, aramid fibers were
After that, a Grignard reaction was carried out, the fibers were thoroughly washed, immersed in water, oxygen blown in for 10 minutes at room temperature, and dried under reduced pressure.To confirm whether hydroxyl groups were formed on the fiber surface, , a part of the sample was immersed in 1 ml of water and cerium ammonium nitrate (NH)Ce(NO3)
6 Add two drops of reagent 2 and the coordination compound [Ce(NO3)5(OR)]
was produced and exhibited a red color, confirming that hydroxyl groups were certainly formed on the aramid fiber.

Next, a predetermined test piece was prepared in the same manner as in μ Example 1, and its bending strength and bending elastic modulus were measured in accordance with ASTM standards. The results of the average values of the 20 test pieces are shown in Table 2, comparing the invented product and the conventional product. The invented product has a bending strength of 42.9% compared to the conventional product, and a bending modulus of elasticity of 25.
．． An improvement of 2% in physical property values was observed.

Furthermore, when the compatibility with the epoxy resin was observed using a scanning microscope in the same manner as in Example 1, it was found that the treated one was more compatible with the epoxy resin than the untreated one. 1 M2 was done.

Example (3) In the same manner as in Example 2, hydroxyl groups are formed on the surface of carbon fibers. 100q of this fiber, 100m of water
1, add 1 drop of hydrochloric acid and vinyl silane coupling agent vinyltriethoxysilane (Nippon Unicar).

NUC Nlankanop IJyf agent, A-161) 1
Add i1r'J to the mixture containing gW for 6 minutes at room temperature.
and dry it under reduced pressure.

In order to confirm whether unsaturated ethylenic double bonds were formed on the surface of this fiber, a portion of the sample was immersed in water, and 1 drop of 2N Na2CO3 and 0.5% KM
When 1 drop of No. 4 was added, the purple color immediately disappeared and the mixture turned brown, confirming that vinyl groups were formed. Third
Similarly, unsaturated vinyl groups could be formed on the fiber surface using the vinyl silane coupling agent shown in the table.

Next, a predetermined test piece was prepared in the same manner as in Example 1, and its bending strength and bending elastic modulus were measured in accordance with ASTM standards. The results of the average value of 20 test pieces are shown in Table 4, comparing the invented product and the conventional product. The invented product has a bending strength of 47.2%2 and a bending modulus of elasticity of 2% compared to the conventional product.
An improvement in physical property values of 8.7% was observed. The compatibility with the epoxy resin was observed using a scanning microscope in the same manner as in Example 1.

It was confirmed that the treated materials were more compatible than the untreated materials.

Table 3 Table 4 □ Example (4) Hydroxyl groups are formed on the carbon fiber surface in the same manner as in Example 2. These 100 (i = water 100 m/'
1 drop of hydrochloric acid and aminosilane coupling agent γ-aminopropyltriethoxy 7 run (Shin-Etsu Chemical KBE903)
The sample was immersed in a mixture containing 1 g of the sample at room temperature for 5 minutes, and then dried under reduced pressure.

In order to confirm whether amine groups were formed on this fiber, a portion of the sample was immersed in water and 5'101,2
-Naphthoquinone-4 ~ 2 drops of sulfonate solution, 2
When one drop of N-sodium was added, the solution turned reddish-orange, confirming that amine groups had indeed been formed. Similarly, with the aminosilane coupling agents shown in Table 5, amino-coating could be formed on the fibers.

Next, a predetermined test piece was prepared in the same manner as in Example 1, and its bending strength and bending elastic modulus were measured in accordance with ASTM standards. The results of the -V-uniform one-shift test of 20 test pieces are shown in No. 6k, comparing the conventional product and the invention product. The invented product has a bending strength of 35.0% and a bending modulus of elasticity of 3 compared to the conventional product.
An improvement in physical property values of 7.4% was observed. When the compatibility with the epoxy resin was observed using a scanning electron microscope in the same manner as in Example 1, it was confirmed that the treated resin had better compatibility than the untreated resin.

Table 6 Table 6 Example (6) Hydroxyl groups are formed on aramid fibers in the same manner as in Example 2. 100 g of this fiber was mixed with 1 drop of hydrochloric acid in 100 ml of water and an epoxy silane canobling agent γ-glycidquinopropyltrimethoxysilane (Shin-Etsu Chemical K B M 40).
3) Immerse it in a mixture of 1q for 6 minutes at room temperature,
This is dried under reduced pressure.

In order to confirm whether epoxy groups have formed on the surface of this fiber, a portion of the sample is immersed in water, 600 mq of methylamine is added thereto, and the sample is heated at 30° C. for 10 minutes.

After allowing it to cool, two drops of cerium ammonium nitrate reagent were added, and a red color was observed, which could be confirmed. Regarding the epoxy silane canopring agents shown in Table 7, epoxy groups were similarly formed on the surface of the fibers.

Next, a predetermined test piece was prepared in the same manner as in Example 1, and its bending strength and bending elastic modulus were measured in accordance with ASTM standards. The results of the average value of 20 test pieces are shown in Table 8 in comparison with the conventional product and the invention product. Compared to the conventional product, the invented product has a bending strength of 24.4% and a bending modulus of elasticity of 61.
A 5% improvement in physical property values was observed. When the compatibility with epoxy/resin was observed using a scanning electron microscope in the same manner as in Example 1, it was confirmed that the treated resin had better compatibility than the untreated resin.

Table 7 Effects of the Invention The present invention can be applied to carbon fibers, aramid fibers, glass fibers, etc. Regardless of the type of woven fabric, fibers undergo a halogenation process and a Grignard reaction process to efficiently create carboxyl groups on the surface of the fibers in large quantities.

Various functional groups such as a hydroxyl group, an epoxy group, an amine group, and a vinyl group can be formed as desired. This makes it possible to surface-treat fibers in a much more efficient and short process than the conventional technique in which two surface-treating agents are fixed individually depending on the type of fiber. This improves the compatibility of the composite resin material with the base polymer, which in turn becomes a factor that improves the dimensional stability and mechanical strength of the composite resin material. In particular, the performance can be improved by 25 to 60% compared to composite resin materials using untreated fibers in terms of flexural strength and flexural modulus.

[Brief explanation of drawings]

The figure is a schematic diagram showing one embodiment of the present invention.

Claims (3)

[Claims] (1) A method for surface treatment of fibers or cow woven fabric in which various functional groups are generated through a rogenization step and a Grignard reaction step. (2) The method for surface treatment of fibers or woven fabrics according to claim 1, wherein the fibers or woven fabrics are carbon fibers, aramid fibers, or glass fibers. (3) The method for surface treatment of woven fibers or woven fabrics according to claim 1, wherein the various functional groups are carboxyl groups, water groups, vinyl groups, amine groups, and epoxy groups.