WO1989010208A1

WO1989010208A1 - Process for improving surface properties of material and surface-treating apparatus therefor

Info

Publication number: WO1989010208A1
Application number: PCT/JP1989/000432
Authority: WO
Inventors: Atsushi Takeda; Kenji Yamazaki
Original assignee: Isi Ltd. Co.; Tomio Keisha Co., Ltd.
Priority date: 1988-04-27
Filing date: 1989-04-25
Publication date: 1989-11-02

Abstract

A process for improving surface properties of a material comprises irradiating the material with ultraviolet rays in vacuo or in an inert gas atmosphere to destroy atom-to-atom bonds of predetermined surface groups and remove specific atoms, and reacting the activated surface with radicals of a reactive gas or coating agent activated by irradiation with ultraviolet rays or laser beams to thereby produce new surface groups and modify the surface properties according to a particular purpose. An apparatus for conducting this process comprises a closed vessel (1) having an ultraviolet ray discharge tube (2) provided therein and an inert gas feed pipe (6), a reactive gas feed pipe (7) and a degassing apparatus (F) connected thereto to make the inside selectively vacuum or an atmosphere of inert gas or reactive gas.

Description

Specification

Technology for improving surface properties of materials and surface treatment equipment.

The present invention refers to a method for improving the surface properties of a material and a surface treatment apparatus for the method.

冃 Technology

In recent years, in addition to man-made fibers such as nylon, polyester, aramid, polyarene pyrene (PP), vinylon, polyethylene, and fluororesin, carbon fiber has been in the spotlight and various composite materials Is being developed.

In recent years, powders composed of fine ceramics materials, metal materials, carbon materials, magnetic materials, electronic materials, and other natural materials have been spotlighted, and development into various composite materials has been promoted. .

However, these fibers and powders have the disadvantage that they are not necessarily dispersed, and that they have poor hydrophilicity, poor wettability and adhesion to various materials.

For example, in the field of FRP, carbon fiber and aramide fiber are mainly applied only to ebox resin, and it is difficult to compound them with other resins.

In addition, since the dyeing method for polyester fibers and the like is different from that of ordinary wool (wool) materials, it is necessary to perform pressure dyeing, so even in the case of blending, wool does not require a pressure dyeing step. Nevertheless, it has the disadvantage that it can only be dyed by expensive means, and the dyes that can be used are also limited. And many.

Furthermore, when the fiber is compounded in another matrix material, if the coupling agent for the other resin is not properly adhered to the fiber surface, the resin elastomer may be removed. However, even when mixed with rubber or the like, the desired strength is often not exhibited by the phenomenon of fiber penetration, so that the fiber filling ratio must be increased, and conversely the cost increases. However, good results have not been obtained due to poor soldering characteristics.

Furthermore, in the development of a heat-resistant FRP composite, even if the fibrous surface has wettability suitable for a force-removing agent, if the coupling agent itself does not have heat resistance. It is important to use a coupling bar that is stable at as high a temperature as possible because it decomposes during the manufacturing process.

In addition, in the case of mixing with an inorganic adhesive, for example, when reinforcing fiber in cement, when the fiber is not wet or hard to wet, it takes a long time to knead. Inevitably, an organic dispersant or setting retarder must be added.Moreover, a large amount of air bubbles are trapped in the mortar during agitation, and a predetermined strength cannot be obtained. Due to poor adhesion, good results have not been obtained even if the mixing ratio is increased.

In particular, C-H, C-, C-O, C-F and many other surface groups are partially present on the surface of carbon fiber in addition to the original C-C group. When present, these surface groups may not always have a good affinity for other materials, or may rebound significantly.

The disadvantages of powders are that, for example, in the case of finceramics, the precursory molding process of sintered metals or sintered cores such as flat cores, complete uniformity during the wet molding process dispersion

-It is known that it is difficult to configure the system, and cracking and warpage occur due to uneven dispersibility in the drying process of the molded product etc., resulting in poor product yield. . Also, in the sintering process, if there is a large amount of partially aggregated aggregates, sintering causes kinks (cracks) and the like, which may cause poor performance and may also cause warpage. The same is true for the injection molding sintered body.

The biggest theme for powder sintering this time is how to improve the product yield, in other words, how to uniformly mix the powder with binder, water and dispersant. It is well known that this is an issue.

Furthermore, in the case where the powder is compounded in another matrix material, trace moisture and 0H groups adhering to the powder surface during the ripening or polymerization process of the compounding may be a destructive factor in the process. It is well known that the powder mixed and dispersed in the polymer re-agglomerates due to thermal shock, or blocks fluidity during blocking and bleeding. Defective, film in film forming process '' / It causes various phenomena such as generation of cracks, separation of the coating agent, and uneven coloring.

It is generally thought that this can be prevented by preventing the coating of the coupling agent and the activator against the powder, but the heat resistance of the coupling agent and the activator can be reduced. Problems, such as poor compatibility, compatibility with 0H groups, or homogeneous coupling to aggregates is not always good or, depending on the material, often lacks affinity at all. Often

Further, when the powder itself is used as a dispersion system in a medium, the surface has various heat resistance, chemical resistance, deterioration resistance, abrasion resistance, pressure resistance, insulation, conductivity, magnetic properties, etc. In some cases, the coating may be applied to a suitable film. In particular, in the case of high-temperature heat-resistant dispersion systems such as silicone oil systems and various types of paraffin dispersion systems in which precise temperature control can be performed, the first material, the powder material, has a surface as described above. In the case where such a second material is coated with a thin film, it is preferable that a surface most suitable for coating the second material is not formed on the powder of the first material. Coating film cannot be obtained. However, commercially available powders have hardly any such surface treatments.

In the production of a composite material of a powder and an inorganic adhesive, a powder made of a carbon material, a metal material, glass, or any other material exhibiting a special function is used, especially in a cement or stone powder. Mixed with plaster, plaster, water glass and other inorganic adhesives In the case of dispersing, if the wettability is poor, air is entrapped in the kneading system and the viscosity often increases, so various auxiliaries are used as a countermeasure. Auxiliaries have many physical and chemical adverse effects on molding systems

Especially in the case of secondary cement products and gypsum moldings, this causes a reduction in strength and cracks, and at present the surface coating of water glass-based materials cannot be performed uniformly. .

In particular, the above-mentioned problems have not been solved in the industry that deals with ultrafine particles.

In order to remedy these drawbacks, physicochemical means include plasma oxidation of the surface, surface oxidation by ultraviolet irradiation in an oxidizing atmosphere such as oxygen or ozone, and activation of the surface coating solution. Examples of the treatment, heat treatment, and chemical means include oxidation and reduction using chemicals such as calcium dichromate. These are generally carbon fibers, substrates, molded articles, and the like. The surface oxidation treatment method for electronic materials is known. For example, publicly known documents that disclose the above-mentioned conventional technologies include Japanese Patent Publication No. 47-33022, Japanese Patent Publication No. 47-24976, and Japanese Patent Application Laid-Open No. 49-91. 8 7 8 9 1, Japanese Patent Application Laid-Open No. 52-144 864, Japanese Patent Application Laid-Open No. 59-85 4 66, Japanese Patent Application Laid-Open No. 61-119 688 And Japanese Unexamined Patent Application Publication No. Sho 62-79253.

However, each of these processing methods has the following disadvantages. Do That is, the plasma method may deteriorate productivity and degrade various properties of the carbon fiber, and the chemical oxidation method may involve complicated post-processing steps of the material, making it difficult to treat waste liquid and the like.

The surface treatment method by the above-mentioned ultraviolet irradiation has been improved, but the improvement is insufficient, and there is room for improvement, and there are problems such as generation of harmful substances in the treatment process. Many experimental studies have shown that

That is, as described above, the surface of various materials, for example, carbon fiber or powder, is impure surface such as C—H, C—N, C—O, and C—F in addition to C—C groups. Although these groups were present, it was found that these surface groups hindered improvements in surface affinity, hydrophilicity, etc., and had to be removed. Therefore, as in the conventional case, the material is directly placed in the processing vessel, and the surface is purified and irradiated with ultraviolet rays in a reactive gas atmosphere such as air, oxygen, oxygen, or C. It was recognized that even after the oxidation treatment, sufficient improvement in affinity, hydrophilicity, etc. was not observed because the above surface groups were not removed.

In addition to using fibers, powders, and other materials alone, the coating is coated directly with a coating agent such as paint, adhesive, hot melt resin for molding, cement, etc. Molded resin, cement metal foil, film, sheet, board, etc., through a product, a coupling agent, or an adhesive to form a reinforced molded product or laminate fiber. When manufacturing composite products such as lumps and laminated boards, the surface of the material must be compatible However, conventional surface treatment methods have surface groups that inhibit the affinity and wettability of the material surface, so composite products with reduced peel strength and delamination strength It has the drawback of bringing about.

The surface properties inherent to the material are, for example, to make hydrophilic ones more water-soluble, or to coat conductive materials with a coating agent to coat insulating films and various synthetic resins that absorb microorganisms. It is sometimes desirable to bind firmly. It may also be desirable to modify the surface properties of the material to make it suitable for a particular coating agent coating. More specifically, in recent years, when oxidizing or gas reacting like ultra-fine metal particles or intermetallic compounds, they often cause explosions due to the heat generated, resulting in death or injury. Has been reached. Therefore, simply cleaning or oxidizing the surface of the powder may not only be totally counterproductive, but may be the most dangerous operation. In addition, fibers and powders are sometimes used alone, but in many cases, they are used as composite materials or molded products. Silane coupling agents, and monoalkoxy / titanate / coupling agents or aluminate-based coupling agents have been used in some cases.

However, many of the powders do not get wet with these coupling agents at all until the untreated first material. For example, many carbon fibers and carbon powders do not get wet with the silane coupling agent in the untreated state, or even if they do get wet, the coupling effect is weak. Similarly, the effects of monoalkoxy ■ titanate / coupling agents are not remarkable. Furthermore, conversely, when the final product must be an insulating material, neoalkoxy titanate ■ cupping agents cannot be used. Water and 0H are extremely harmful to boron nitride powder.However, since no physical surface treatment method has been developed for boron nitride, silane-based bonding agents such as It is difficult to respond. Therefore, _a method for improving the surface properties that solves these problems is desired.

Furthermore, when the surface of the object is directly oxidized with CF ₄ , F or CI gas, water, 0 H, H, etc. adhering or adsorbing to the material react with CI to form HF, HCI causes the inconvenience that occurs on the surface of the material or in the atmosphere. .

Disclosure of the invention

The present invention has been made in view of such circumstances, and solves the disadvantages of the conventional method, improves the surface properties such as excellent hydrophilicity and wettability, and further improves the novel surface properties. The purpose of the present invention is to provide a method for improving the surface properties of a material which can bring about a new product or which can modify the surface properties so as to be suitable for various products and uses such as raw materials for producing various composite products. UV light is applied to the material surface in a vacuum or inert gas atmosphere. A first step of irradiating for a predetermined time in an atmosphere to destroy or remove a predetermined surface group present on the surface, and then irradiating with at least one of ultraviolet rays and a laser beam while irradiating at least one of them. And the second step of photo-radicalizing a reactive gas to increase the ion potential and chemically bonding a specific gas ion to the surface of the material to form it on the surface of the material having a new chemical bond. This is the feature.

Furthermore, the present invention provides a coating agent on the surface of the material which has a greater delamination strength than the conventional method, and a coating agent of a type which was impossible with the conventional method. It provides a method for improving the surface properties of a material that is processed so as to have a new surface property so that it can be applied, after the treatment in the first step or in the first and second steps. It is characterized in that after the treatment, a coating agent is adhered to the surface of the material.

Further, the present invention provides a method for improving the surface properties of each material in a group of fine materials such as powders, so that the method can improve the surface characteristics of each material. In the second step, the method is characterized in that ultraviolet light is irradiated in a state where a large material such as a powder to be processed is rotated or floated.

Furthermore, the present invention provides an apparatus for treating the surface of a material for carrying out the above method, in which an inert gas supply pipe and a reaction gas supply pipe are provided on one side of a reaction-closed vessel, respectively. It is connected via a controller and connected to an exhaust device on the other side, an ultraviolet discharger is provided therein, and a material support device is provided for supporting the material to be processed facing the ultraviolet discharger.

Further, the present invention provides an apparatus capable of uniformly irradiating the material with ultraviolet rays. The apparatus is provided with an ultraviolet reflector in opposition to an ultraviolet discharger in a closed container of the apparatus.

Further, the present invention provides a device which is convenient for processing a long material. A partition is provided in a closed container of the device, and one side thereof is exposed to ultraviolet light in a vacuum or in an inert gas atmosphere. A first process chamber for irradiating the container, and a second process chamber for treating the other room with a reaction gas or a coating agent, and a long material is introduced from outside the one end wall of the closed vessel. It is provided with a guide device for airtightly inserting the partition wall and leading it out of the other end wall. '

Further, the present invention provides an apparatus suitable for uniformly surface-treating fine materials such as powders and short fibers, such as an ultrasonic generator for rotating or floating the fine materials in a closed container. A power source device is provided.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a diagram of a lav surface of one example of a surface treatment apparatus for implementing the method of the present invention, FIG. 2 is a diagram of a lav surface of another embodiment, and FIG. 3 is a cross-sectional view of FIG. FIG. 4 is a diagram showing still another embodiment. FIG. 5 shows a side view of still another embodiment.

BEST MODE FOR CARRYING OUT THE INVENTION

Next, the present invention will be described in detail.

The starting material of the present invention may be of any type and shape. Inorganic materials and organic materials can be used; ceramic materials such as fine ceramics, glass, metals, magnetic materials, carbon materials, synthetic resin materials, natural minerals, etc. , Powder, pellet, film, sheet, plate, various molded products, etc., and single-piece processing raw materials such as metal sintering and ceramic molding Coating products, molded products, laminates, and adsorbents for adsorbing specific bacteria, on the surface of which are firmly bound paint, synthetic resins for various applications, adhesives, coupling agents, etc. All raw materials or processed products that require surface modification, such as synthetic resins via a coupling agent, building materials such as cement, processing raw materials for various composite products such as construction materials, etc. .

Hereinafter, examples in which the present invention is applied to the improvement of the surface characteristics of carbon fibers will be described in detail.

As the first step, vacuum ultraviolet rays satisfying each required resonance line of 1,000 A to 30 Q 0 A and satisfying the required energy conditions are mainly used in a vacuum or an inert gas atmosphere in a closed container. The material surface is irradiated with ultraviolet rays at a normal temperature to destroy or remove specific surface groups, and then, as a second step, the ultraviolet rays or The surface modification according to the purpose can be obtained by causing the laser beam to act on the reactive gas to excite it, and reacting the activated ion with the material surface. Further, if necessary, after the treatment in the first step or after the treatment in the first and second steps, the surface properties of the material can be modified for the purpose by using a coating bar. Can be

In this case, a low-pressure mercury discharger made of, for example, high-purity quartz glass is used as a discharger for irradiating ultraviolet rays. The discharge device is a tubular low-pressure mercury discharge tube with a length of 1000 bunks and a diameter of 18.5 mm, and a spiral low-pressure mercury discharge tube with an inner diameter of 10αη and a length of 30 cm. The power supply is 100 V AC, 50/60 Hz. And two types of high frequency power supply (50-1000 KHz) and 200V. The main ultraviolet characteristic wavelength of this discharge tube is 2537, 1849 A or vacuum ultraviolet light of 1670 A or less by argon is also generated as a continuous vector.

In the second step, reactive gases such as oxygen, ammonia, fluorocarbon, and ethylene were photo-excited using a pulsed excimer laser beam containing a gas such as argon fluoride and the like to act on the carbon fiber surface.

The third step, which is performed as required, is to coat the carbon fiber or the organic fiber obtained in the second step with a coating agent such as silane force, a '/ printing agent solution, or neoplastic. After spraying or pouring the alkoxy-based printing agent into the solvent solution, the mixture was allowed to settle naturally or forcedly stirred.

However, the polarity of the medium for diluting the coupling agent Since the wettability to water may not depend on the characteristics of the fiber surface, the silane coupling agent was diluted with water as much as possible to act on the fiber.

Example 1

A 10,000-filament long fiber carbon fiber bundle is passed through the spiral low-pressure mercury discharge tube from the tube by the above-mentioned processing method.

While passing through at a speed of 1 mZ with 10 concessions away, C-H and C-N mainly exist partially on the surface mainly composed of C-C groups at room temperature in an argon atmosphere. After the removal of atoms mainly composed of H and N by forced destruction of the mixed surface groups, the atmosphere is replaced in the treatment vessel, and the ultraviolet radiation intensity at room temperature under atmospheric pressure is 0. It is set to be 5 mW / cm ² or more, for example, 5 mWZ cm ^2, and after removing these atoms,

In the process of moving at a speed of 1 mZ while radicalizing 0 z, 0 was bonded to the traces of removal of these atoms to form them. The result is as follows.

Untreated products The mixed surface groups are mainly C-H, C-N.

Treated product The mixed surface group is mainly composed of C1O or COOH.

These two types were mixed in a neoalkoxycitane-based coupling agent, a neoalkoxyzirconate-based coupling agent, and a zirconate-based silane coupling agent solution and stirred. The following results were obtained. The wettability of the coupling agent and carbon fiber floats on the liquid surface of the untreated product and does not wet at all, but the treated product has polyimide, phenol, PVC, polyester, ABS, urethane. It instantaneously settled in a silane coupling agent solution suitable for resins such as PPS, Nylon-16, etc., and was completely wetted, making it extremely easy to perform power ringing. The materials used are as follows.

Force printing agent

Ken Ritsuichi ■ Petrochemical Co., Ltd.

Neoalkoxy titanate Coupling agent (LICA) Neoalkoxy zirconate. Printing agent (LZ) Carbon fiber

Mitsubishi Rayon P AN-based carbon fiber

Example 2

While passing a bundle of 10 000 filament long fiber carbon fibers through a spiral low-pressure mercury discharge tube at a speed of 1 m / min in the above-described treatment method, the bundle was heated at room temperature in an argon atmosphere. After the forced destruction of the surface groups and the removal of atoms in the same manner as above, the air was replaced with a processing vessel and the light was carbon-woven using a box-shaped excimer laser generator in which fluorine fluoride was sealed at room temperature under atmospheric pressure. irradiating the維表plane, a 0 ₂ while Ri preparative plated at a rate of 1 m Z min while radicalized and tighten not generate C 10 bonds. The results are as follows.

Untreated product The mixed surface groups are mainly C-H and C-N To

Treated product Mixed surface group is mainly composed of C-OH or COOH

These two types were stirred in an aqueous solution or an alcohol solution of a silane coupling agent, and the following results were obtained.

The silane force and / or the wettability of the printing agent and the carbon fiber are not completely wet because they float on the liquid surface in the case of the untreated product, or they do not get wet without forcible agitation. Suitable silane coupling agent solution for polyimide, phenol, polyester, ABS, urethane, PPS, Nylon-16, Nylon-12, etc. It settled instantaneously and became completely wet, making it extremely easy to power-up. The materials used are as follows.

Force printing agent

Made of Toshiba silicon corn

T S L-8031, 8802, 8303, 8331, 8340, 8350, 8380, 8845 Carbon fiber

Osaka Gas pitch-type long fiber carbon fiber

Example 3

A short fiber carbon fiber having a length of 100 to 3 imn was carbonized at room temperature in an argon atmosphere for 10 minutes using a low-pressure mercury discharge tube with a length of 1 m and an outer diameter of 18.5 mm by the above-mentioned processing method. After the surface groups were forcibly destroyed and removed while irradiating the fibers with ultraviolet light, Using a box type excimer laser generator encapsulating off "/ of Al Gon at room temperature under atmospheric pressure to replace the atmosphere during the processing container, a light beam is irradiated on the carbon fiber surface, while the 0 ₂ is La radical of 1 While winding at a speed of mZ, a C-10 bond was generated, and the result is as follows.

Untreated product Mixed surface groups are mainly C-H, C-N

Treated product The mixed surface group is mainly composed of C-10 or COOH.

The following two results were obtained when these two types were placed in an alcoholic solution of a titanate-based neoalkoxy force printing agent and stirred. The wettability of the titanate-based neoalkoxy coupling agent and carbon fiber sediments while gradually getting wet in the untreated product, but in the treated product, polyimide, PVC, polyester, ABS, urethane It instantaneously sedimented in a neoalkoxy-titanate-based coupling agent solution suitable for carbon dioxide, PPS, Nylon-1-6, Nylon-1-12, etc., and was completely wetted, making it extremely easy to apply force. The materials used are as follows.

Force printing agent

Ken Rich-Petrochemical

Neoalkoxy, titanate, coupling agent (LICA) Carbon fiber

Mitsubishi Rayon's PAN type carbon fiber carbon fiber Example 4

The short-fiber carbon fiber with a length of 100 to 3 mm was treated at room temperature in an argon atmosphere for 10 minutes using a low-pressure mercury discharge tube with a length of 1 m and an outer diameter of 18.5 in the above treatment method. setting forced destruction of surface groups while irradiating with ultraviolet rays, after removal, at room temperature after replacing the atmosphere during the processing container, the earthenware pots by the ultraviolet radiation intensity is 5 mW / cm ² on the surface of the carbon fibers in the Then, the mixture was irradiated for 10 minutes while radicalizing 0 to form C-10 bonds on the surface of the chopped carbon fiber. The result is as follows. '

Untreated products The mixed surface groups are mainly C-H and C-N.

Treated product The mixed surface group is mainly composed of COH.

When these two types were put into an aqueous solution of a silane coupling agent or an alcohol solution and stirred, the following results were obtained.

The wettability of the silane coupling agent and the carbon fiber is such that the untreated product floats on the liquid surface and does not get wet without forced agitation, but the treated product is epoxy or poly. Instantaneous silane coupling agent solution suitable for mid, phenol, polyester, ABS, urethane, PPS, Nylon-16, Nylon-12, etc. It settled down completely and got completely wet, and cutting was extremely easy. The materials used are as follows. Force-upping agent

Made of Toshiba silicon corn

T S L-8031, 8802, 8303, 8331, 8340, 8350, 8380, 8845 Carbon fiber

Osaka Gas Pi, 7-inch short fiber carbon fiber

Example 5

Mill-like carbon fiber of length 3 awake to 0.1 mm was treated with the above-mentioned processing method using a low-pressure mercury discharge tube with a length of 1 m and an outer diameter of 18.5 mm for 10 minutes in an argon atmosphere at room temperature. After the surface groups were forcibly destroyed and removed while irradiating ultraviolet rays to the atmosphere, the atmosphere was replaced with a processing vessel, and at room temperature, the UV radiation intensity was 5 mW / og on the carbon fiber surface. set, 0 ₂ yielding C 10 bonded to the surface of the irradiated Ji Yo class tap carbon identify Wei 10 minutes while radicalized. The result is as follows.

Untreated products The mixed surface groups are mainly C-H, C-N.

Processing Π

cm Mixed surface group is mainly composed of C-10 or COOH

The wettability of the silane coupling agent and the carbon fiber is very low if the untreated product floats on the liquid surface and is hardly wet. It does not get wet unless it is agitated, but the processed products are epoxy, polyimide, phenol, polyester, ABS, urethane, PPS, Nylon-6, Nylon-12, etc. The sedimentation instantaneously settled in the silane coupling agent solution which was suitable for the coating, and was completely wetted, and the coupling was extremely easy. The materials used are as follows.

Force printing agent

Made by Toshiba Silicon

T S L-8031, 8802, 8303, 8331, 8340, 8350, 8380, 8845 Carbon fiber

Osaka Gas Co., Ltd.

Example 6

According to the above-mentioned processing method, the carbon fiber of length 3 to 0.1 is irradiated with ultraviolet rays on the carbon fiber at room temperature in an argon atmosphere for 10 minutes using a low-pressure mercury discharge tube having a length of 1 m and an outer diameter of 18.5. After forced destruction and removal of the surface groups, the atmosphere was replaced with a processing vessel, and a beam was applied to the surface of the carbon fiber using a box-shaped excimer laser generator filled with argon fluoride at room temperature under atmospheric pressure. Irradiation was performed for 10 minutes while radicalizing O ₂ to form C 1 O bonds on the surface of the chip-like carbon fiber. The result is as follows.

Untreated product The mixed surface group is mainly C-H, C-N.

Treated product Mixed surface group is mainly C-O or C-OH And.

The following two results were obtained when these two types were stirred in an aqueous solution or an alcohol solution of the silane coupling agent. The wettability of the silane coupling agent and carbon starvation shows that the untreated product floats on the liquid surface and does not get wet at all, or does not get wet without forced agitation, but the treated product does not get wet. Suitable for phenol, polyester, ABS, urethane, PPS, Nylon-16, Nylon-12, etc. The ring was extremely easy. The materials used are as follows.

Force coupling thorn

Made of Toshiba silicon corn

T S L-8031, 8802, 8303, 8331, 8351, 8350, 8380, 8845 Carbon fiber

Osaka Gas Milled Carbon Fiber

Example 7

While passing a bundle of 10,000 filament long fiber carbon fibers through the spiral type low pressure mercury discharge tube at a speed of 1 mZ in the above-described processing method, the surface-based forced breaking, after removal, ammonia led to § Noregon during processing vessel while balance, set to ultraviolet radiation intensity at room temperature under atmospheric pressure cormorants by ing to 5f ^ / cm ² on the surface of the carbon fibers And radicalize 0 ₂ for 1 mZ While winding at a speed of, a C-10 bond was generated. The result is as follows.

Untreated products The mixed surface groups are mainly C-H, C-N.

Treated product The mixed surface group is mainly C100H for CO.

When these two types were stirred in an aqueous solution or an alcohol solution of a silane coupling agent suitable for the NH group, the following results were obtained. The wettability of the silane coupling agent and carbon fiber floated on the liquid surface and did not get wet at all with the untreated product, but settled well with the treated product and could be cut well. . Example 8

While passing a bundle of 100,000 filament long fiber carbon fibers at a speed of 1 mZ through a spiral low-pressure mercury discharge tube in the above-described processing method, the mixture was heated at room temperature in an argon atmosphere. forced destruction of surface groups, after removal, lead to Furuorokabo emissions during processing chamber while balance argon, ultraviolet radiation intensity on the surface of the carbon fibers at room temperature under atmospheric pressure becomes 5 m W / cm ² set cormorants, but such is La radical of the CF ₄ while Ri preparative plated at a rate of al lm Z min were accounted not generate C one F bond. The result is as follows.

Untreated products The mixed surface groups are mainly C-H, C-N.

Treated product The mixed surface group is mainly C-F. Example 9

While passing a bundle of 100,000 filament filament fibers through the spiral low-pressure mercury discharge tube at the speed of 1 mZ in the above-mentioned processing method, the surface was heated at room temperature in an argon atmosphere. after the forced destruction of groups, the ethylene gas ultraviolet radiation intensity on carbon緻維surface under atmospheric pressure at room temperature leads in the processing vessel while balance to Arugo emissions and hydrogen gas, to 5 m W / ciu ² The carbon fiber was modified while winding at a speed of 1 m while radicalizing ethylene.

The results of the surface analysis by FTIR are as follows.

Untreated product The mixed surface group is mainly C-HC-N.

Treated product The mixed surface groups are mainly CH2 and CH3.

Example 10

The carbon fiber sheet was exposed to ultraviolet light at room temperature for 10 minutes using a low-pressure mercury discharge tube in a vacuum for 10 minutes without introducing inert gas. After forced destruction and removal, an acrylic water-based paint was applied evenly over the entire sheet surface to obtain a composite product dried at room temperature.

Untreated products The mixed surface groups are mainly C-H and C-N.

Treated product Mixed surface groups generate radicals (R) of C-paint Subject.

Improvement of the delamination strength was observed by the treatment of this method. The effects of the invention when the present invention is applied to carbon fibers are as follows.

The present invention is characterized in that the surface state of carbon fiber is modified by using high-energy short-wavelength ultraviolet light or laser light. Unlike conventional processing methods, various types of coatings can be formed that can modify the surface itself and increase peel strength, and all the processes of the present invention can be carried out at room temperature. It is suitable for upsizing and online processing equipment.

This effect has not been confirmed to date in published or published patent gazettes, nor has it been observed in recent research reports on plasma chemistry.

According to the present invention, application products of carbon fiber composite materials, which had been conventionally developed only with epoxy resins, have been developed using a silane coupling agent and a neo-alkoxy resin. Because it can be used directly, it can be used for Nylon, Polyimide, Polyacetal, PPS, other engineering plastics and SBR, NBR, ABS and other rubbers. High-performance composite materials can be developed at very low cost. '

Furthermore, conventionally, to improve the physical properties of the composite material, Although carbon fibers were added more than necessary by using a force such as a tantalum or a printing agent, the present invention can be expected to have an effect of reducing the unitary unit of carbon fiber. In addition to the effect of greatly reducing the total cost, it is also possible to ionize other gas species to act on carbon starvation, thereby providing inexpensive surface and water-based surface groups at low cost. Can be obtained.

In addition, when carbon fiber is mixed and used in an inorganic adhesive such as cement cement, the mixing and kneading conditions are complicated up to now. Although other organic admixtures and water reducing agents are used, the rice filling method has the disadvantage of deteriorating the strength of the mortar and concrete, and it has not been possible to obtain a sufficiently dense molded product.

The present invention solves these drawbacks and is extremely significant for the development of dry mix cement and the development of hardened cement containing CF containing no admixture. It is an invention.

As described above, various embodiments in which the present invention is suitable for improving the surface characteristics of carbon fiber (inorganic fiber) have been disclosed. However, the present invention is not limited to carbon fiber but also inorganic fiber such as glass fiber and metal fiber. It is extremely effective in improving the surface properties of fibers, and is also effective in various types of textiles (organic textiles). Next, an example in which the present invention is applied to various types of organic fibers will be described.

Example 1 1 In this embodiment, the fibers to be treated are nylon, polyester, aramide, PP (polypropylene), vinylon, polyethylene, and fluororesin. After selecting and performing the following treatments, wetting, ink staining, and cupping properties were tested.

Processing method

1st process, (under argon atmosphere)

A type

UV ray of 2537 A generated by a UV ray (ultraviolet ray) generator (output: 80 W, power frequency: 60 Hz, 100 V) for 5 minutes continuously (average UV energy intensity: 3 to 4 mW // d)

B type

Continuous irradiation of UV rays of 2537A and 1849A generated by a UV ray generator (output 80W, power frequency 60Hz, 100V) for 10 minutes (average UV energy intensity 6mW / cm)

2nd process, (Cf ₄ balance under argon base atmosphere)

Continuous irradiation of UV rays of 2537 A and 1849 A generated by a UV ray generator (output 150 W, 200 KHZ, 200 V) for 5 minutes (average UV energy intensity 6 W / ^) Test method

i) wettability

Polymer or silica with added fiber and solvent The oil was placed in a magnetic stirrer (stirrer), and the condition of the stirrer was checked. When the fiber was floating, it was judged as bad, and when it was sinking, it was judged as good.

ii) Ink stainability

After immersion in the container containing the ink, 6 (dried with TC for 30 minutes), the coloration was observed, and it was determined that the partial coloration was poor and the uniform coloration was good.

iii) Coupling properties

Put the textile in a magnetic stirrer containing a coupling agent and a neat liquid (water, alcohol), and observe the condition after stirring. It was considered good when it was out of order. '' Test Yuna

Table 1 shows the test results of each organic fiber.

l Table

◎ Good 良 Good Good Δ Better in some cases ：: Not suitable

The effect of the present invention when the present invention is applied to an organic fiber is that the one treated according to the present invention has a remarkably improved wettability, and is mixed with a composite material or in a concrete or the like. In this case, the dispersion and kneading can be performed easily and in a single time.

In addition, the dyeability is improved, and a colorful product can be obtained, which contributes to the improvement of the commercial value.

Example 1 2

Each of the plastics and plates shown in Table 2 below was placed in a first sealed container, which was divided into two sections with a partition and the inside of the sealed container was placed in a first sealed container, which was exposed to ultraviolet light at 2537 A in an argon atmosphere. The surface was irradiated for 10 minutes (average UV energy intensity: 4 mW / d). After treatment in the first step, it was led to the second closed chamber, and irradiated with ultraviolet rays of 2537 A and 1849 A for 10 minutes in an oxygen argon-based atmosphere ( The second step processing with an average UV energy intensity of 6 mW / ou ² ) was completed. As a pretreatment, _¾ The results are shown in Table 2 were measured contact angle with water of each of the processed enough and the second E after the first step process.

Table 2

In the above table, the control example shows the contact angle measured when the untreated synthetic resin plate was directly irradiated with ultraviolet rays in an oxygen atmosphere under the same conditions as in the second step.

For comparison, discoloration and devitrification were observed when synthetic resin plates such as PET, PPA, PEI, ALAMID, PEEK, and PI were directly subjected to the second step treatment as in the control example. .

On the other hand, according to the present invention, devitrification and discoloration occur when the oxygen atoms are bonded after the H atoms in the constituent molecules are removed and the surface groups are previously destroyed and removed. However, it was hardly recognized at all.

Example 13

In order to improve the wettability of the various metal plates shown in Table 3 below, they are housed in a sealed container, and their surfaces are irradiated with ultraviolet rays of 2537 A for 10 minutes in an atmosphere of argon at atmospheric pressure (average UV energy). After the first step treatment with an intensity of 4 mW / cii), the argon atmosphere was removed, the vessel was changed to an oxygen atmosphere, and ultraviolet rays were irradiated for 10 minutes (average UV energy intensity 6 mW / cm ² ). A second step treatment was performed. Before the treatment, the contact angles with water after the first-step treatment and after the second-step treatment were measured. Table 3 shows the results. 0 Table 3

The above various metal plates are directly irradiated with ultraviolet light of the same intensity in oxygen.

After irradiation for 10 minutes, the contact angle with water remained at about 10 to 20.

Next, a surface treatment apparatus for performing the method of the present invention will be exemplified.

Fig. 1 shows a fiber surface treatment device using a spiral-type low-pressure mercury discharge tube, 1 shows a reaction sealed container, and inside it is a high-purity quartz glass as an ultraviolet discharger. A spiral discharge tube 2 is provided, and the discharge tube 2 is connected to a variable frequency high frequency power supply 3. 4 and 5 indicate insulation sockets. The vessel 1 is connected to an external inert gas cylinder and a reactive gas cylinder B such as oxygen via its supply pipes 6 and 7 on its 1 lavatory wall, respectively, to supply the inert gas and the reactive gas, respectively. Make sure that it is supplied in the closed container 1. C is a mass flow controller interposed between supply pipes 6 and 7. D is a quench dryer for quenching and drying the gas passing through the supply pipes 6 and 7, and E is a pressure gauge. An exhaust system F is connected to the other side wall of the container 1. The device shows an on-off control valve interposed in a conduit G, which comprises, for example, an evacuation device such as a vacuum pump connected to an outer end thereof and an on-off control valve interposed in the conduit. Further, inside the vessel 1, on both sides of the discharge tube 2, there are disposed right-way rotating drums 8 and 9 in which a bundle of 10 000 filament long fiber carbon fibers a is stretched. At the same time, a pair of guide rolls 10 and 11 for supporting the carbon fiber bundle so as to pass through the center of the spiral discharge tube 2 are provided.

In order to carry out the present method using the device, first, the exhaust system device F is operated to evacuate the inside of the sealed container 1, and then, argon is flowed into the container 1 from the inert gas cylinder A. The inside of the container 1 is set to an argon gas atmosphere at atmospheric pressure. In this state, the power supply 5 is started, the ultraviolet discharge tube 2 is made to emit light, and the center of the discharge tube 2 is moved at a constant speed in one direction, and a carbon fiber monofilament bundle is required. Irradiate with the energy of 髙. Thus, while the long fiber bundle is wound on one of the drums 8 or 9, the first process for destroying and removing the surface group is completed. Next, after the argon is removed by the exhaust device F, oxygen is allowed to flow into the closed container 1 from the anti-gas cylinder B, for example. Activate in the opposite direction The drums 8 and 9 are rotated to transfer the carbon fiber bundle a, and a second process is performed to combine the active oxygen with the traces of the atoms on the surface where the atoms have been removed. Complete

FIGS. 2 and 3 show a surface treatment apparatus in which the surface treatment of the material is carried out as uniformly as possible over the entire surface of the material. In this method, a surface treatment of a linear long material a is performed, and a long ultraviolet straight tube lamp 4 parallel to this is provided below the material a stretched over the drums 8 and 9 before and after it. In the opposite direction, a strip-shaped ultraviolet reflector 12 having a width sufficiently larger than the width of the longitudinal material a and being parallel to the running direction of the material a was provided above the longitudinal material a. The reflecting plate 12 has a surface facing the lamp 4 as an aluminum vapor-deposited surface, and is suspended and supported by a hanging rod 13 from the ceiling of the closed casing 1. It is preferable that the reflector has an arc-shaped surface so as to surround the linear material a.

Thus, in the operation of this device, the running long material a, for example, a long fiber filament of carbon fiber, is irradiated by the lamp 2 from its lower surface, while its irradiation is performed. Since the ultraviolet rays are reflected on the facing reflector 12 and are reflected to irradiate the upper surface from the opposite side of the linear element, the element is uniformly irradiated with the ultraviolet ray and the first element is uniformly irradiated. Step processing and second step processing can be performed. FIG. 4 shows an apparatus according to still another embodiment. This apparatus performs the first step and the second step processing in the process of moving the material in one direction, and, if necessary, performs the processing. After the first step treatment or after the first or second step treatment, the coating treatment is performed in a closed container. That is, in the drawing, reference numeral 14 denotes a partition that divides the inside of the closed container 1 into at least two first containers 1a and second containers 1b, and 15 denotes the second partition. Shows the coating equipment installed in the downstream lavatory of Vessel 1b.

A pair of drums 8 and 9 are disposed outside both ends of the closed container 1, and the supply drum 8 is wound with a sheet material a such as synthetic resin film or woven fabric or non-woven fabric such as carbon fiber. The one-side wall of the container 1, the partition wall 14 and the other end wall are unwrapped with their nuclear penetration holes, and the sheet material a. One end of the drum 9 is wound around the take-up drum 9 so that it runs horizontally. Reference numeral 16 denotes a sealing member for sealing the gap between the poor hole and the material a passing therethrough in an airtight manner. In the nuclear enclosures 1a, 1b, a plurality of long tube lamps 2, 2,... Are arranged above and below each other at regular intervals and at an equal distance from the traveling horizontal material a. The lower discharge tube row 2, 2... Has a sufficient length in the width direction of the material a and is longer than its width, and the lower discharge tube row 2, 2,. Either or both could be used. Although not shown, each of the UV discharge tubes 2 has its own high frequency. Connected to generator power supply 3. In the downstream lavatory in the latter half of the internal space of the second container, a spraying device 15 for the coating agent, which is connected via a pump to an external coating agent adjustment tank, was introduced into the container 1b. Nozzles 16a, 16a ... arranged at the end in the width direction of the material a surface were provided at a predetermined interval above and facing the material a surface.

According to the device, the drums 8 and 9 are rotated and unwound from the supply drum 8, and the sheet material a travels horizontally in the closed container 1 at a constant speed. During the winding process, the surface a of the material is first destroyed by using a combination of an inert gas at a predetermined pressure and irradiation with high-energy ultraviolet light in the first container 1a. Then, after the removal treatment, the reactive gas ion such as oxygen is combined with the reactive gas and the ultraviolet ray in the second container 1b to combine with the lack of the surface group, and a new binding group is formed. A coating agent is formed and then, downstream thereof, is sprayed with a coating agent more uniformly on the modified surface than the coating device 15, and active atoms of the nascent surface group, for example, active oxygen Then, the active groups of the coating agent combine to form a strong coating layer, After that, the coating layer is dried by low-temperature drying or the like, wound around the winding drum 9, and a desired surface treatment is performed by a flow operation.

In accordance with the purpose of the surface treatment, the second step treatment was disabled, and after the surface group was destroyed and removed in the first step, Needless to say, it is permissible to perform the switching process. The coating process is suitable outside the container if the material is exposed to the air and can be safely used! The coating process may be performed using the means and materials described in (1).

The present invention is applicable to a case where a surface of a mass of carbon powder, mineral powder, fine ceramics, ceramic powder, sintered metal powder, ferrite, or coarse material is used. The surface treatment can be performed uniformly over the entire material in a state where the aggregate is kept stationary, and the first and second process treatments are performed while rotating or floating the group of fine materials. It is characterized by performing.

Hereinafter, examples in which the present invention is applied to the improvement of powder surface characteristics will be described in detail.

FIG. 5 shows an example of a surface treatment apparatus according to an embodiment of the present invention, in which a tubular discharge tube made of synthetic quartz that transmits at least 40% or more of ultraviolet light having a wavelength of 1800 A or more is used. A glass or aluminum tray 17 is adhered to the bottom of a sealed reaction vessel 1 containing a low-pressure ultraviolet discharge tube 2 inside, and the powder to be treated is supplied from a powder supply device 18 connected to the vessel 1. a. is configured to be supplied intermittently.

In addition, an inert gas (for example, argon) is quantitatively injected from a cylinder A through a mass flow controller C to stabilize the gas at almost atmospheric pressure.

The closed reaction vessel 1 has a power of 200 W or more. Placed on a large water ellipse 20 equipped with a powerful ultrasonic generator 19 to transmit ultrasonic vibrations to the powder a via the water 21 to give the powder a rotational or floating motion. It is configured.

The low-pressure ultraviolet discharge tube 2 is controlled by using a variable-frequency high-frequency power supply 3 capable of changing the frequency between 50 KHZ and 1 MHz, and can be adjusted by using a matching device 22 as necessary. ing .

The discharge tube 2 is about 1000 x 18.5 cm in size, and its electrodes are made of tungsten, iron, copper, fii, zinc, lead, selenium, and other metals in the form of a ribbon or coil. It was used in a shape that allows sufficient light emission, such as a round shape.

As shown in the figure, the gas used for the discharge tube 2 can be freely filled with hydrogen, nitrogen, oxygen, or the like via a connection tube 23, as shown in FIG. And a control device 24 having a low-pressure pump and the like. In the case of the embodiment, mercury was sealed for stabilization of discharge and used as a mercury lamp.

In this case, in the light emission spectrum of the discharge tube, in addition to 1849A and 2537A due to mercury, a characteristic spectrum for each electrode is generated.

In the first step, the powder on the tray 17 is tumbled by the ultrasonic generator 19 in the above apparatus, and the surface is irradiated with ultraviolet rays while an inert gas is applied at about atmospheric pressure.

As the second step, in the same processing system as the first step, — 3.7 In the reaction vessel 1, gaseous hydrocarbons such as CH ₄ and ethylene, as well as inorganic gases such as oxygen, hydrogen, nitrogen, ammonia, CF ₄ and argon The powder a is injected into the tray 17 at a constant ratio through the above-mentioned tray 25, and is irradiated with ultraviolet light while the scraper 26 is actuated. Acted on.

The third step, if necessary, is to add the powder obtained in the second step into a silane coupling agent solution or a neo-alkoxy-based coupling agent solution and then heat and stir. I did power-ups.

Silane couplings are diluted with water or alcohol, and neoalkoxy coupling agents are diluted with IPA (isopropyl alcohol), toluene, xylene, etc., or powdered by pretreatment. Acted on the body.

Next, various embodiments of the method of the present invention comprising the above-mentioned first step and second step using the above-mentioned apparatus will be described in detail.

Example 14 A

Various powders shown in Table 4 below were subjected to surface treatment under the conditions shown in the table to improve dispersibility in water. The ultraviolet irradiation time is 30 minutes for each of the first step and the second step, and the generated ultraviolet wavelength is, for example, 2537 A.

Table 4 shows the results. Table 4

Example — B

Various powders shown in the following Table 5 were treated under the conditions shown in the table, and dehydrated groups were adhered to the surfaces thereof. At this time, the gas used should be completely dry, and in the first step, the removal of water adhering to the material surface and the destruction of 0H groups and H removal, which are mixed surface groups, in particular, were also performed. went. The results are shown in Table 5.

Table 5

The UV intensity in the above test was β ~ 10ιιιΗ / '«3 on the powder surface,

4 Example 1 41 C

Table 6 shows the results of treating various powders shown in Table 6 below under the conditions shown in the table and substituting and generating organic functional groups on the surface.

Table 6

Next, an example of the present invention to which the third step is added will be described in detail.

Example 15

After treating the various powders shown in Table 7 below in the first step and the second step under the same conditions as in Example 14A, the surface was treated with various capping agents. I cut it. The powder treated according to the present invention thus obtained was mixed with various kinds of appropriate organic binders, heated and molded, and the appearance was observed.

This example requires a thorough understanding of its purpose, treatment method, and expected surface improvement requirements, and outlines the themes that the inventors are currently working on. The explanation is as follows.

For example, carbon powder has various chemical bonds on its surface, such as C-N, C-H, C-10, C-F, in addition to C = C, C-C.

However, these surface groups do not necessarily have different affinity for other materials. In particular, in the case of a C-H or C-F bond, the terminal has zero charge and does not tend to wet other materials. Therefore, when converting the surface of the powder to a desired surface group, the energy of the ultraviolet rays is directly applied to the powder ίΦ: to break the bonds of C—Η, C—F, etc., and remove H, F. There must be. When the powder was treated in the first step of the present invention, cutting and removal of, and F atoms could be performed quickly and favorably.

Furthermore, when the carbon powder obtained by the above treatment is treated as a second step, for example, in a mixed gas of argon and oxygen, oxygen is radicalized by short-wavelength ultraviolet rays and tends to strongly bind to carbon. An action occurred, and thus, the atom entered the trace where the atom was removed, and bonded to C to form a C-bond, and finally the surface of the carbon powder was modified to an excellent oxidation state. .

Also, the carbon powder obtained in this way has a strong affinity for water, so that when it is put into water, all of it instantaneously settles. On the other hand, the powder not subjected to the treatment is only floating on the water surface. Further, when a silane coupling agent is allowed to act on the surface-treated carbon powder as the third step, the type of silane coupling agent is not limited. Therefore, all surface-treated products have affinity. As described above, the first step, the second step, and the third step of the present invention have a remarkable coupling effect even on a material which has conventionally been difficult to force-couple to a surface. .

Next, the case where the present method is applied to heavy calcium carbonate (tancar) will be described in detail.

It is generally known that a tan powder has no surface group, and in the case of a fine powder, there is only a small amount of water adhering thereto. However, in the case where the fine powder of tancar is combined with a resin such as polyester or nylon which can mix water, even if the water on the surface is removed, further coupling is required. Become . In this case, it has been conventionally known that the silane coupling agent is ineffective.

Therefore, in the present invention, in the first step, adhering water and 0H groups were removed. As a result, a very fluid tanker powder was obtained, and in the second step, isopropyl alcohol gas was balanced with dry nitrogen to act while irradiating the powder with ultraviolet light. In a short time, the surface could be modified to be water-repellent. Since this powder has no affinity for water, when it is combined with a resin that must not be mixed with water as described above, neo-Al It has been found that a coxi titanate rubbing agent can be applied to the powder obtained by the above-mentioned method to impart fluidity, thermal shock resistance, etc., and to impart excellent surface properties. did.

Table 7 summarizes the results of this method for other powders.

Table 7 Item Purpose and treatment method Powering effect Other requirements with organic binder (type of cow powder, 'adhesion

(1) Single crystal alumina spacer

In the first step, water and OH groups attached to the surface are removed.

After that, in the second step, the classification of the run coupling agent from the 0H group was improved.

(2) Ketching Brass The static electricity jumping effect of Ketching Black Good dispersibility Acryl emulsion Electrical conductivity improvement In order to transfer the fruit more effectively into the matrix, it is effective for John etc. Neoalkoxy bonding after destruction and oxidation of

The surface was treated with a titanate coupling agent.

(3) Spherulite pitch Exist in the surface: ¾ 蒱 ^ ¹某某某某----------ヽ- Coupling can be used to form the film. The surface was treated with a silane coupling agent to increase the slip characteristics. Improved.

(4) Si, the surface of Si'-frite, a raw material for flexible magnets, has a remarkable dispersibility. A polyamide resin has strong magnetic properties. After removing water attached to it, it improves adhesion to isopropyl alcohol. Good mechanical strength is added, water-based groups are formed on the surface using gas, and the amount of resin can be further reduced (in molded products) Surface treatment ability using alkoxy-based coupling agent

did.

(Γ.) Production of reinforced resin moldings of tancar nay polyester and polyester i & W --------- '' MiVz iWUx '' To improve impact resistance etc., remove water adhering to tancar and have viscosity coefficient

Sopropyl alcohol forms water radicals and decreases

In addition, neoalkoxy titanate system power ringing

The surface was treated with the agent.

(6) Metallic aluminum- の Good for manufacturing conductive resin molded products, but good for metallurgy PVC, EVA Neoalkoxy

After removing the oil and fat adhering to the membrane, the surface is mixed with a net-based material mixed by oxidation, etc., and the silane coupling agent (Neoalkoxy) has good bonding properties. Surface-treated using

Next, an embodiment of the invention in which the first step is followed by direct treatment with a coating agent will be described.

Example 16—A

Here, an example in which the neodymium boron-based magnetic powder is applied will be described.

As the first step, the magnetic powder is known to grow at a remarkable rate when wet with water, or to react with oxygen in the atmosphere and burn. The powder was irradiated with ultraviolet light-The powder was flake-shaped and had a high specific gravity and was difficult to rotate.The main rolling operation was performed with a scrubber, but the particle diameter was coarse, 200 am, and was 30 minutes. Dehydration was sufficiently achieved in the processing time of the above. In addition, since the powder was rapidly cooled at the time of production, the magnetism was reduced when heated. However, it was found that the first step was a good treatment method because no heat was generated.

Next, Table 8 shows the results of the surface being coated with various neoalkoxy-based coupling agents immediately after the present powder was treated in the first step.

Table 8

Here LICA 09: Neopentyl (diary) ox

■ Tri (dodecyl) benzene sulfonole retinitanet

LICA 44: Neopentyl. '(Diallyl) Oxy • Tri (Ethylene. D. Amino) Ethyl' Titanate

LZ44: Neopentyl.

'Tri (Ν-Ethylene' D 'Amino) Etil ■ Zirconet

11 97: Neopentyl.

'Tri (πι-amino) pentyl. Zirconet

It is.

Of the above results, LICA 09 is low and low And easily react with the powder, but this is present in the structure

0

11

- Z r (0 one S I)> A ₂ H _{2 5)} ₃

! 1

It is thought that a reactive group such as 0 has an effect.

In addition, other neoalkoxy force-removing agents are good, and even if pellets obtained by kneading with a polyamide resin using a powder obtained by coupling these are simply stearic acid-treated. A remarkable and stronger protection effect was obtained compared to a product coated with this powder.

Example 16- B

The first step of the present invention and an example of a force-splitting process on high-purity silica submicron particles will be described.

In general, submicron particles or ultrafine particles having a strong force have extremely high hygroscopicity, and even if they are completely dry at the time of generation, they will have a weight ratio of about 0.5 to 0.3% in the presence of air. Has been found to absorb moisture.

However, the attached moisture, or the 0H groups originally present on the surface from the beginning, and the water of crystallization exert a remarkable obstructive effect when the silica powder is mixed with other organic binders. But is there . In addition to being peculiar to water-borne resins, the inventors' research has demonstrated that the same can be said for ultra-thin films that have been developed recently and are active. For this reason, in this embodiment, an example in which the present invention is applied particularly during a process of forming a heat-resistant film of a polyimide film type will be described.

First, in the first step, several types of particle size distribution adhere to the surface using silica contained in the sub-micron region (HI group, crystallization water, and attached water were removed. This is as shown in Table 9.

Table 9

The structural formulas of LICA38 and LICA97 are as follows (LICA38)

CH ₂ = CH-CH ₂ 0- CH ₂ 0 0

I Ιί II

CH ₃ CH ₂ -C-CH2 -0-T i (0-POP (0C ₈ H ₁₇ ),),

II CH ₂ = CH-CH ₂ 0- CH ₂ OH

(LICA97)

CH ₃ CH ₂ -C-CH2 -O-Ti (0-C ₆ H ₄ -H _Z ) ₃

In this experiment, the treatment time was fixed, and it was found that some of the materials were not sufficiently treated, but the tendency was uniform except for exceptions. In a good situation.

Next, a silane coupling agent that is compatible with the polyimide is applied to each of the sily powders obtained in the first step treatment to sufficiently cap the powder. After ringing, the powder was dried to obtain 3% of N-methylpyrrolidone. At this time, the sample in which the coupling agent is not sufficiently bonded to the powder or the sample in which water remains is N-methyl. The dispersion was allowed to stand for 5 days for gelation in pyrrolidone, and the state of the solution was observed.

Furthermore, the N-methylpyrrolidone-dispersed silica that had undergone the desired treatment was thoroughly mixed with a wholly aromatic polyamide varnish in a ratio of 1: 2 to obtain a polyamide aliquot. Of these, the polyimide solid content was 92.3% and the silica powder was 7.1%.

Next, this precursor was stretched extremely smoothly into a stainless steel plate shape using a bar coder, and the initial baking was performed at 100 to 150 for about 1 hour. Next, the specimens whose organic materials were sufficiently degreased by baking were polymerized by heating at 250 to 30 (KC. The results of these film forming processes are shown in Table 9 above.

As described above, in the production of polyimide films, it has been found that when powder is mixed, water adhering to the powder surface is a significant inhibitory factor for film formation. ing . In addition, when a cutting agent is not used, even if a powder treated only in the first step of the present invention is used, blocking or cracking may occur due to ripening during baking. It can be seen that no film was obtained due to the occurrence of.

Next, for reference, various powders were treated by applying only the treatment method of the first step to remove trace water and 0H groups on the surface. The results are shown in Table 10. Table 10

The UV intensity of the above test was 8 10niW 'd? On the powder surface,

In this way, as described above, a group of fine materials such as powders is given a vibration or the like in the processing in the first step and the second step to forcibly apply rolling and floating. Thereby, the contact of the inert gas, the irradiation of the ultraviolet ray, and the chemical bonding reaction with the reactive gas are carried out satisfactorily and uniformly, so that the surface characteristics can be modified with high efficiency.

Further, the method and apparatus of the present invention will be described.

If the inside of the closed vessel in the first step is evacuated or made into an inert gas atmosphere, and the ultraviolet ray is irradiated in this state, energy loss that occurs when the ultraviolet ray is irradiated in an oxygen or air atmosphere is avoided. In addition, the material surface can be irradiated with a predetermined high energy, and the bond of the surface group can be destroyed and removed with high efficiency. Further, the pressure inside the closed vessel is reduced to about 10 to 0.01 torr to remove air (oxygen). If moisture is attached to the material, it is particularly preferable to remove it with a dry inert gas. "

Adjust appropriately between about 0.1 Torr and atmospheric pressure. In this case, inert gas refers to rare gases such as argon, crypton, xenon, and other materials to be treated. On the other hand, it contains inert gas, and nitrogen can be used.

Usually, the distance between the UV discharge tube and the material surface is preferably as short as 20αα or less, but the distance between the discharge tube and the material tube can be adjusted by appropriate means according to the type of material to be treated. It may be configured in such a way. In addition, since the discharge tube absorbs the generated ultraviolet spectrum, even in the case where synthetic quartz sprozil, which has extremely low energy absorption even in the vacuum ultraviolet region, is used as a standard, even in the atmosphere. Also, at a distance of 5 to 1 5αη from the tube, the 185 nm mercury resonance line showed an extremely strong value of 0.5 to 0.2 mVcm ² (at 100 V, AC).

It goes without saying that the resonance line and intensity of ultraviolet rays are arbitrarily selected depending on the type of material and the purpose of modifying the surface properties.

It is preferable that a low frequency oscillator of 5 to 5 KHZ is used as the ultraviolet ray generator so that the applied power can be controlled.

In the present invention, the term “surface group” refers to a chemical bond atom or atomic group that constitutes the material itself, which is present on the surface of the material, is bonded to an atom on the surface of the material or exists between the atoms. In addition, the term refers to the bonding state of atoms or atomic groups that are adsorbed or chemically bonded by van der Waals bonds, ion bonds, or the like. For example, in the above-mentioned carbon and silica materials, surface groups in a bonded state, such as C-H, C-F, Si-0H, which are bonded instead of the original atoms, organic materials, such as synthetic resin materials In the case of, the surface group such as C-CI, C00H or the like, which is bonded at the terminal or side chain of the main chain, or the functional group itself, is destruction or removal of the surface group. Destroying a specific atom or group of atoms. Therefore, the surface group is destroyed and the specific atoms or atomic groups are removed according to the purpose whose surface characteristics are to be modified. At this time, the intensity of the ultraviolet rays, the distance between the discharge tube and the material surface, etc. are appropriately determined accordingly.

Accordingly, in the second step, various specific reactive gas species are selected in accordance with the desired modification of the surface characteristics in the trace of the removal of the atoms or atomic groups of the surface groups removed in the first step. It activates and introduces it to generate new surface groups. Is a reactive gas, air, 0 _2, ozone, Yo I Do full Tsu reduction based gas CF _4, hydrogen, nitrogen, chlorine, hydrochloric acid, NH _3, C 0 inorganic gas such as _2, Po Li Lee At least one, or a mixture of two or more of mid, propylene, xylene, toluene, benzene, ethylene, isopropyl alcohol, and any other organic gas can be used.

As described above, according to the present invention, in the first step, the surface of the material is irradiated with high-energy ultraviolet rays in a closed vessel under vacuum or at least one kind of inert gas atmosphere. After irradiating, destroying specific surface groups and removing specific atoms or atomic groups, in a second step, at least one specific reactive gas contained in a closed container is irradiated with ultraviolet light or laser. The material was activated with one light beam and brought into contact with the active surface group of the material, so that a material having various surface characteristics according to the purpose can be obtained. Thus, depending on the intended use of the material, the desired surface group can be destroyed, removed and the intensity of the reactive gas set or Combination with selection of types can improve the surface properties of materials and manufacture processed products of new materials with new surface characteristics, and can be carried out at room temperature, and the size of processing equipment can be increased. It has effects such as being suitable for conversion and online conversion.

Further, according to the present invention, when a desired coating agent for the purpose is attached to the surface of the material treated in the first step, the active surface of the material is used. The base is obtained from a coated material in which the coating agent is firmly coated on the material surface.

Further, according to the present invention, after performing the treatment in the first step and the second step, when applying the coating agent corresponding to the above-mentioned various purposes, the same as above is applied. Thus, a novel coating material coated with various coating agents, which has been difficult or impossible to bind to the material surface, can be obtained.

Furthermore, according to the present invention, the material is rotated or floated, particularly in the surface treatment of a group of fine materials such as powder, so that a uniform surface treatment can be achieved throughout. It has an effect that can be achieved.

Further, according to the present invention, as a processing device for carrying out the above method, a reaction sealed container is provided with an inert gas supply pipe and an inert gas supply pipe on one side thereof, and a flow control device. The first process was completed in the same container because the exhaust system was connected to the other room and the ultraviolet discharge tube was installed in that container. Thereafter, the second step can be performed, and a device with a small occupied space can be provided. Further, according to the present invention, when the first process chamber and the second process chamber are partitioned by the partition in the container, the long material is transferred in one direction and continuously. As a result, the first step and the second step can be performed, and the work efficiency can be improved.

Further, when a coating space or a separating wall is provided in the closed container, the coating process can be performed in the closed container.

Further, according to the present invention, when the reflector is provided on the facing surface of the ultraviolet lamp provided in the closed container with a passage for the material therebetween, the surface of the material facing the reflector is provided. In addition, it has an effect such that a good surface treatment can be performed by irradiating ultraviolet rays.

Industrial availability

As described above, the method for improving the surface properties of a material according to the present invention and the surface treatment apparatus for the method include various methods such as a reinforced plastic molded body, a reinforced cement molded body, a laminate, and a laminate processing. Manufacture of composite products, manufacture of sintered products such as ultrafine metal powders, metal powders, magnetic metal powders, fine ceramics, ceramics, etc., and various industries such as semiconductors, biotechnology, and paints. Suitable for coating process and other various industrial powders.

Claims

The scope of the claims

Irradiation of ultraviolet light on the surface of the material, in a vacuum or in at least one kind of inert gas atmosphere, for a predetermined period of time, in order to destroy or remove predetermined surface groups present on the surface. In the first and subsequent steps, while irradiating at least one of ultraviolet light and laser light, at least one kind of reactive gas is converted into a photo-radical to enhance ion potential, and A method for improving the surface properties of a material, comprising a second step of chemically bonding a specific gas ion to the surface to form the material surface having a new chemical bond. 2. The method for improving the surface characteristics of a material according to claim 1, wherein a coating agent is attached to the surface of the material after the treatment in the first step.

2. The method for improving surface properties of a material according to claim 1, wherein a coating agent is attached to a surface of the material after the treatment in the first step and the second step. The method for improving the surface properties of a material according to claim 1, wherein the material is a film, a plate, or a solid having a desired shape in addition to a fine material such as fiber or powder.

Claims 1, 2, and 3, wherein in each of the first step and the second step, a group of fine materials is processed while being rotated or suspended.

The method for improving surface properties of a material according to any one of the items 3. In a closed space, the ultraviolet intensity of each resonance line is 0.5 ffl W / a first step of irradiating the textile surface with vacuum ultraviolet rays and short wavelength ultraviolet rays of a cig or more from a short distance in a vacuum or in an inert gas atmosphere for a predetermined time to destroy and remove surface groups existing on the fiber surface; Next, at least one of the ultraviolet light and the laser beam is irradiated on the surface in the space to generate at least one reactive gas, and the gas species is photo-radicalized to form an ion. 2. The method for improving the surface properties of a material according to claim 1, comprising a second step of increasing a potential, causing a chemical reaction with a fiber surface, and generating a desired new chemical bond on a textile surface. .

7. After the treatment in the first step, silane coupling agent, neoalkoxy ■ titanate ■ coupling agent, neoalkoxy 'zirconate cutting agent, is applied to the surface of the fiber. 7. The method for improving surface properties of a material according to claim 6, wherein at least one kind of the coupling IJ is coated.

8. After the treatment in the first step and the second step, a silane coupling agent, a neoalkoxy.titanate ■ coupling agent, a neoalkoxy ■ a zirconate-coupling agent is applied to the surface of the fiber. 7. The method for improving the surface properties of a material according to claim 6, wherein at least one kind of a cutting agent is coated.

9. In an enclosed space, the UV intensity of each resonance line is 0.5 m / Irradiate vacuum or short-wavelength ultraviolet light of cm ² or more to the rotating or floating powder surface from a short distance in a vacuum or in an inert gas atmosphere for a predetermined time to destroy the surface groups present on the powder surface, A first step of removing, and then, irradiating the surface with the ultraviolet rays in the space to cause at least one reactive gas to act thereon, and the gas is photoradicalized by the ultraviolet rays. The second step of increasing the ion potential and causing a chemical reaction with the powder surface to form a desired new chemical bond on the powder surface. Claims 1 or 5 characterized by the above-mentioned. How to improve the surface properties of the described material.

After the treatment in the first step, the surface of the powder is coated with a silane coupling agent and a neoalkoxy titanate cutoff. 10. A coating agent according to claim 9, wherein one or more of the coupling agents in the coupling agent, neoalkoxy, zirconate, and coupling agent are subjected to a coating treatment. A method for improving the surface properties of materials.

After the treatment in the first step and the second step, a silane coupling agent, a neoalkoxy 'titanate coupling agent, and a neoalkoxy zirconate are coated on the surface of the powder. 10. The method for improving surface properties of a material according to claim 9, wherein at least one of the coupling agents is subjected to a coating treatment. .

An inert gas supply pipe (6) is provided on one side of the closed reaction vessel (1). And the reactive gas supply pipe (7) are connected via the flow control device (C), respectively, and the other side is connected to the exhaust device (F). A material surface treatment device comprising a discharge tube (2) and a material support device (10) (11) or (17) for supporting the material (a) to be treated facing the ultraviolet discharge tube (2).

13. The apparatus for treating a surface of a material according to claim 12, comprising a forward-reverse rotatable drum (8) (9) having both ends of a longitudinal material (a) wound thereon.

14. Provide a partition (14) inside the closed vessel (1), and use one side as the first process chamber (1a) for irradiating ultraviolet rays in a vacuum or in an inert gas atmosphere. The gas is activated by ultraviolet irradiation, and this is used as a second process chamber for acting on the surface of the material. A long material (a) is introduced from outside the one end wall of the closed vessel (1), A surface treatment device for a raw material comprising a guide roll (10) (11) and a drum (8) (9) for hermetically inserting a partition wall (14) through the other end wall.

15. The material surface treatment device according to claim 14, wherein a coating device (16) is provided in a downstream lavatory space of the second process chamber (1b).

16. In the closed container (1), an ultraviolet reflector (12) is provided so as to face the ultraviolet discharger (2), and a long linear line is provided between the discharger (2) and the reflector (12). A material according to claim 12 or 14, wherein the material (a) is passed through. Surface treatment equipment.

17. In the closed container (1), a fine material (a) An ultrasonic generator (19) that rolls and floats a group, and a water tank (20) and a tray (17) are placed in this order on the upper surface. 15. The material surface treatment apparatus according to claim 12 or claim 14, comprising:

18. The apparatus according to claim 12, wherein the ultraviolet discharger (2) is a spiral discharge tube made of high-purity quartz glass and a straight discharge tube.

19. An apparatus for treating a surface of a material, wherein the ultraviolet discharger (2) is connected to a variable frequency high frequency power supply (3).

20. The apparatus according to claim 12, wherein the distance between the discharger (2) and the surface of the material (a) is about 20 cm or less.