JP2000136483A - Bundled fiber material for improving polymer material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a bundled fiber material useful for modifying a polymer material having a high softening point. SOLUTION: This bundled fiber material for improvement is obtained through a manufacturing process comprising a step for preparing fiber groups of bundles of a large number of inorganic fiber threads, a step for impregnating the fiber groups with a solution containing a carbon precursor whose carbonizing yield is 1-80 wt.% after heating at 600 deg.C in an inert gas and a step for heat treating the fiber groups impregnated with the solution at a temperature higher than the softening point of the polymer material in an inert gas.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a fibrous material, in particular,
The present invention relates to a bundled fiber material for modifying a polymer material.

[0002]

2. Description of the Related Art Polymer materials such as thermoplastic resins are widely used in various technical fields because they can be easily formed into various shapes, and have high strength, elastic modulus, antistatic property and slidability. In order to improve the properties such as the above, they are often combined with an inorganic fiber material such as carbon fiber or glass fiber.

Incidentally, an inorganic fiber material used for the purpose of modifying a polymer material needs to have a property that it can be easily supplied (feeded) to the polymer material and that it is easily dispersed in the polymer material. is there. Therefore, such an inorganic fiber material is obtained by cutting a bundle obtained by loosely binding a large number of inorganic fibers using a sizing agent (sizing agent) into several millimeters (for example, about 6 mm). Bundled fiber materials are used. The sizing agent used here is usually a thermosetting resin such as a urethane resin or an epoxy resin. After the sizing fiber material is added to the polymer material, the binding between the inorganic fibers is loosened, and the inorganic fibers are increased. It can be dispersed in a molecular material.

[0004]

The polymer material mixed with the above-mentioned bundled fiber material is usually heated to a temperature higher than its softening point and formed into a desired shape. However, when the softening point of the polymer material is higher than the decomposition temperature of the sizing agent used in the sizing fiber material, for example, the polymer material has a softening point of 200 to 200, such as an engineering plastic such as polyetheretherketone resin. 500 ℃
In the case of a high degree, the sizing agent is thermally decomposed in the step of molding the polymer material. Such thermal decomposition of the sizing agent causes foaming of the molded body or causes voids to be formed in the molded body, and may impair properties such as strength and elastic modulus of the molded body.

An object of the present invention is to realize a bundled fiber material which can impart a required modifying effect to a molded article without impairing the properties of the molded article made of a polymer material. Another object of the present invention is to realize a bundled fiber material that is effective for modifying a polymer material having a high softening point.

[0006]

The bundled fiber material for modifying a polymer material according to the present invention is for modifying a polymer material having a softening point, and is a bundle of a large number of inorganic fibers. Preparing a fiber group; and 600 minutes in an inert gas.
A step of impregnating the fiber group with a solution containing a carbon precursor having a carbonization yield of 1 to 80% by weight after heating at ℃, and the step of impregnating the fiber group impregnated with the solution with an inert gas in an inert gas. A heat treatment at a temperature equal to or higher than the softening point.

Here, the inorganic fiber is, for example, at least one of carbon fiber and glass fiber. In this case, the carbon fibers are, for example, polyacrylonitrile-based carbon fibers. Further, the fiber group includes, for example, 12 inorganic fibers.
× 10 ^{3 to} 100 × 10 ³ are included.

The modified bundled fiber material is used, for example, for modifying a polymer material having a softening point of 200 ° C. or higher.

A bundled fiber material for modifying a polymer material according to another aspect of the present invention is for modifying a polymer material, and comprises a step of preparing a fiber group in which a large number of inorganic fibers are bundled. And a step of impregnating the fiber group with a solution containing a carbon precursor having a carbonization yield of 1 to 80% by weight after heating at 600 ° C. in an inert gas, and inactivating the fiber group impregnated with the solution. Heat treating at a temperature of 200 ° C. or higher in a gas.

A bundled fiber material for modifying a polymer material according to still another aspect of the present invention is for modifying a polymer material, and a fiber group obtained by bundling a large number of inorganic fibers, And a carbon material contained in the fiber group.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The modified bundle fiber material of the present invention comprises:
It can be obtained through the following manufacturing process. First,
A fiber group obtained by bundling a large number of inorganic fibers is prepared. The inorganic fibers used here are those usually used for the purpose of modifying the strength, elastic modulus, antistatic property or slidability of the polymer material, and the type is not particularly limited. For example, carbon fiber or glass fiber. Further, a mixture of carbon fiber and glass fiber may be used.

Here, as the carbon fiber, various known ones, for example, pitch-based carbon fiber, polyacrylonitrile-based carbon fiber, rayon-based carbon fiber, kainol-resin-based carbon fiber, lignin-based carbon fiber and the like can be used. . Incidentally, when the modified bundled fiber material of the present invention is used for reinforcing a polymer material, it is preferable to use a polyacrylonitrile-based carbon fiber since the reinforcing effect can be more effectively enhanced. On the other hand, as the glass fibers, various known ones, for example, glass fibers made of aluminoborosilicate-based alkali-free glass and glass fibers made of soda-quartz-based glass can be used.

[0013] The above-mentioned group of fibers made of inorganic fibers is, for example,
The inorganic fibers are bundled in a columnar shape with the length directions of many inorganic fibers aligned. The number of inorganic fibers included in this fiber group varies depending on the average fiber diameter of the inorganic fibers, and is not particularly limited, but is usually from 12 × 10 ^{3 to} 100 × 10 ^3.
Set in the book. When the number of inorganic fibers is less than 12 × 10 ³ , the bulk density is low. Conversely, if the number exceeds 100 × 10 ³ , cutting may be difficult.

Next, the fiber group is impregnated with a solution containing a carbon precursor. Thereby, the above-mentioned many inorganic fibers constituting the fiber group are loosely bonded to form an integrated bundle.

The carbon precursor used here has a carbonization yield of 1 to 8 after heating at 600 ° C. in an inert gas.
0% by weight, preferably 5 to 60% by weight, more preferably 10 to 50% by weight. When the carbonization yield is less than 1% by weight, it is difficult to stably bond the inorganic fibers to each other. As a result, when the fiber group is mixed with the polymer material, particularly when the fiber group is mixed with the polymer material using a feeder, the fiber group is easily unraveled, and the fiber group is mixed with the polymer material. And it is difficult to supply them stably.

The above-mentioned carbon precursor is not particularly limited as long as it has the above-mentioned carbonization yield.
Various known materials can be used. In particular,
Polyvinyl alcohol, lignin, phenol resin, furan resin, urethane resin, carboxymethyl cellulose, polyphenylene oxide, polyether sulfone, coal tar, pitch, polysulfone and the like can be used. In addition, these carbon precursors may be used as a mixture of two or more kinds as necessary.

The solution of the above carbon precursor used in the present invention is usually a solution of the above carbon precursor in an organic solvent (organic solvent solution) or an emulsion of the above carbon precursor. When using an organic solvent, the type thereof is not particularly limited as long as it can dissolve the carbon precursor to be used, but generally, alcohols,
Ketones, halogenated hydrocarbons and the like can be used.

Various methods for impregnating the fiber group with the solution of the carbon precursor include, for example, a method of immersing the fiber group in a solution of the carbon precursor and a method of impregnating the fiber group with the carbon precursor. A method of spraying a body solution can be adopted.

In the case of the organic solvent solution and the emulsion, the amount of the carbon precursor applied to the fiber group is 0.01 to 10% by weight in terms of solid content.
It is preferable to impregnate the fiber group so that When the amount of the carbon precursor given to the fiber group is less than 0.01% by weight, it becomes difficult to bond the inorganic fibers constituting the fiber group to each other, and the fiber group is stably supplied to the polymer material. In some cases. On the other hand, when the content exceeds 10% by weight, the bonding between the inorganic fibers constituting the fiber group is too strong, and when the fiber group is supplied into the polymer material, the inorganic fibers are hardly dispersed in the polymer material. There are cases. The more preferable range of the amount of the carbon precursor applied to the fiber group is 0.1 to 5% by weight, and the more preferable range is 1 to 3% by weight.

Next, the fiber group impregnated with the above solution is heat-treated in an inert gas. At this time, it is preferable to remove the solvent and the like of the solution impregnated in the fiber group in advance.
Here, the heat treatment temperature is set to a temperature equal to or higher than the softening point when the polymer material mixed (composited) with the modified bundled fiber material of the present invention has a softening point. For example, when the softening point of the polymer material is 200 ° C., the heat treatment is performed at a temperature of 200 ° C. or more, and when the softening point of the polymer material is 300 ° C., the heat treatment is performed at a temperature of 300 ° C. or more. When the heat treatment temperature is lower than the softening point of the polymer material, when the modified bundled fiber material, that is, the polymer material in which the fiber group is mixed is heated and formed, the carbon of the carbon precursor contained in the fiber group is There is a possibility that troubles such as foaming and generation of voids may occur in the molded body. As a result, a molded body made of a polymer material is originally expected by being composited with a fiber group,
Modification effects such as strength, elastic modulus, antistatic property and slidability may be impaired.

The heat treatment temperature in this step is preferably set to a temperature higher than the softening point of the polymer material as described above. However, when a polymer material having a softening point of 200 ° C. or more is used, When a polymer material having no spot (for example, a thermosetting resin) is used, if the inorganic fibers constituting the fiber group are carbon fibers, the temperature is usually 200 ° C. or higher and
C. or lower, preferably 300 to 800.degree. C., more preferably 450 to 700.degree. In particular, when the heat treatment temperature is set to 500 ° C. or higher, the carbonization of the above-described carbon precursor contained in the fiber group is substantially completed. The carbonized carbon precursor does not occur, and a molded article free from the above-mentioned problems can be obtained more reliably. On the other hand, in the same case, if the inorganic fibers constituting the fiber group are glass fibers, the heat treatment temperature is set to 200 ° C.
It is preferable to set the temperature to 500 ° C. or lower.

Incidentally, if the heat treatment temperature in this step is set to a temperature at which the carbonization of the carbon precursor contained in the fiber group can be completed, the obtained modified bundled fiber material will have a carbon content derived from the carbon precursor. Obtained as a fiber group containing the material. The carbon material included in the fiber group loosely bonds the inorganic fibers.

The modified bundled fiber material of the present invention obtained through the above-described production process usually has a length of 0.5 to 30.
mm, preferably 1 to 10 mm, more preferably 2 to 8 mm
After being cut to about mm, it is used for modifying the strength, elastic modulus, antistatic property, slidability and the like of a molded article made of a polymer material. In addition, cutting the modified bundled fiber material of the present invention so that the length after cutting is less than 0.5 mm,
Usually difficult. In contrast, the length after cutting is 30m
If m is exceeded, it may be difficult to supply a fixed amount of the polymer material when mixing with the polymer material.

The polymer material to which the modified bundled fiber material can be applied is various polymer materials such as thermoplastic resins and thermosetting resins, and is preferably a thermoplastic resin having a softening point. is there. In particular, this modified bundled fiber material has been subjected to the above-described heat treatment in advance, and since all or a part of the carbon precursor has been carbonized, a decomposition product is generated during heat molding of the polymer material. It is difficult to cause problems such as foaming and voids in the molded article. For this reason, the modified bundled fiber material is particularly effective when used for modifying a polymer material having a high softening point, for example, an engineering plastic. Incidentally, engineering plastics to which this modified bundled fiber material can be applied include, for example, polyether ether ketone resin, liquid crystal polymer, polyether sulfone resin, polyphenylene sulfide resin, polyvinylidene fluoride resin, polyphenylene sulfide resin, polyamide Resin, epoxy resin, polyimide resin,
Bismaleimide, polysulfone, polyethersulfone, polyetherimide, polyallylether nitrile, polybenzimidazole, ethylene tetrafluoride-perfluoroalkyl vinyl ether copolymer resin, ethylene tetrafluoride-ethylene copolymer resin, Fluorinated ethylene-propylene hexafluoride copolymer resin.

When the polymer material and the modified bundled fiber material of the present invention are mixed, the modified bundled fiber material is supplied to the polymer material using various known feeders. At this time, the modified bundled fiber material is difficult to be unraveled because the inorganic fibers constituting the fiber group are loosely bonded to each other by the carbon precursor or the carbon material derived therefrom. Can be supplied. In addition, the modified bundle fiber material supplied to the polymer material is easily dispersed uniformly in the polymer material because the inorganic fibers are loosely bonded as described above, and the polymer material is A uniform reforming effect can be imparted to the whole.

[0026]

EXAMPLE 1 A 6 mm long urethane resin-containing fiber group (Mitsubishi) obtained by impregnating a urethane resin as a carbon precursor into a group of 12 × 10 ³ polyacrylonitrile-based carbon fibers bundled together Rayon Co., Ltd. product name "Pyrofil": urethane resin content = 5.0% by weight) was heated at a rate of 10 ° C./min in a nitrogen atmosphere at 600 ° C., heat-treated at 600 ° C. for 10 minutes, and then cooled. . Thus, a modified bundled fiber material was obtained. The weight reduction rate of the urethane resin-containing fiber group after the heat treatment was 3%.

Example 2 A group of urethane resin-containing fibers having a length of 3 mm (Osaka Gas) obtained by impregnating 40 × 10 ³ pitch-based carbon fibers in a bundle with a urethane resin emulsion as a carbon precursor. Company name "Xylus GC03J"
431 ″: urethane resin content = 1.5% by weight)
The temperature was raised at a rate of 10 ° C./min in a nitrogen atmosphere at 0 ° C., and after a heat treatment at 600 ° C. for 10 minutes, it was cooled. Thus, a modified bundled fiber material was obtained. The weight reduction rate of the urethane resin-containing fiber group after the heat treatment was 1.2%.

Example 3 Pitch-based carbon fiber (trade name "Xyl" of Osaka Gas Co., Ltd.)
us GC03J4DK ") in a bundle of 40 × 10 ³ fibers was prepared, and a carbon precursor having a softening point of 30 was prepared.
3% by weight of pyridine solubles in coal tar pitch at 0 ° C
Containing pyridine solution. As a result, a 3 mm long coal tar pitch-containing fiber group containing 1.0% by weight of coal tar pitch was obtained. Next, this coal tar pitch-containing fiber group was placed in a nitrogen atmosphere at 600 ° C. for 10 minutes.
The temperature was raised at a rate of ° C./min, heat-treated at 600 ° C. for 10 minutes, and then cooled. Thus, a modified bundled fiber material was obtained. The weight reduction rate of the coal tar pitch-containing fiber group after the heat treatment was 0.5%.

Example 4 A fiber group obtained by impregnating a urethane resin as a carbon precursor into a fiber group obtained by bundling 5 × 10 ³ glass fibers, and having a length of 3
mm of urethane resin-containing fibers (trade name “RES-03-TP40” of Nippon Sheet Glass Co., Ltd .: urethane resin content = 0.6% by weight) at a rate of 10 ° C./min in a nitrogen atmosphere at 450 ° C. After heating and heat treatment at 450 ° C. for 10 minutes, it was cooled. Thus, a modified bundled fiber material was obtained. The weight reduction rate of the urethane resin-containing fiber group after the heat treatment was 0.3%.

Comparative Example 1 The urethane resin-containing fiber group used in Example 1 was immersed in acetone for 1 hour in a glass filter with a cock. Thereafter, the cock was opened to allow acetone to flow out, and the urethane resin-containing fiber group was dried as it was. Thereby, a fiber group from which the urethane resin was removed was obtained. The weight loss rate due to the transfer from the urethane resin-containing fiber group to the fiber group from which the urethane resin was removed was 4.5%.

Comparative Example 2 The urethane resin-containing fiber group used in Example 1 was directly used as a modified bundled fiber material.

Comparative Example 3 The urethane resin-containing fiber group used in Example 2 was directly used as a modified bundled fiber material.

Comparative Example 4 The urethane resin-containing glass fiber group used in Example 4 was directly used as a modified bundled fiber material.

Evaluation 1 The modified bundled fiber materials obtained in Examples 1 to 4 and Comparative Examples 1 and 3 were tested with a screw feeder (manufactured by Plastic Engineering Laboratory) and a vibration feeder (trade name of Kubota Corporation) having a diameter of 25 mm. "CM-P-ISA01")
Was used to evaluate the feed characteristics. The content of the evaluation is based on the presence or absence of fluff and the presence or absence of clogging,
The judgment was made according to the following criteria. Table 1 shows the results.

：: Very good quantitative supply. Δ: Quantitative supply is generally good. ×: Feeding is not possible.

[0036]

[Table 1]

Evaluation 2 A molded article obtained by combining the polymer material with the modified bundle fiber material of Examples 1 to 4 or Comparative Examples 2 to 4 was examined for the occurrence of voids. Here, first, a polyether ether ketone resin (trade name “Victrex 450G” of ICI) and a polyvinylidene fluoride resin (trade name “Kyner 720” of Atochem Corporation)
And polyphenylene sulfide resin (trade name “Ryton M2100” of Toray Industries, Inc.) respectively.
0 ″), the modified bundled fiber materials of Examples 1 to 4 and Comparative Examples 2 to 4 were individually mixed at a ratio of 20% by weight to prepare pellets, and manufactured by Sumitomo Heavy Industries, Ltd. Using a PROMAT injection molding machine, a disk having a diameter of 50 mm and a thickness of 3 mm was formed from each pellet under the conditions shown in Table 2.

[0038]

[Table 2]

The skin layer on the surface of the obtained disk was removed using sandpaper, and the occurrence of voids was observed with an optical microscope. The evaluation criteria are as follows. Table 3 shows the results. ：: No void was generated. Δ: Slight voids occurred. X: Many voids were generated.

[0040]

[Table 3]

Evaluation 3 The modified bundled fiber materials obtained in Examples 1, 2 and Comparative Example 2 were individually added to the polyvinylidene fluoride resin obtained in Evaluation 2, respectively. The molded product (disc) was examined for tensile strength. At this time, a 1157 testing machine manufactured by INSTRON was used, and a 13 mm × 3 mmt dumbbell was used for the measurement unit. As a result, the molded article containing the modified bundled fiber material of Example 1 had a tensile strength of 1,450 kgf / cm ² , and the molded article containing the modified bundled fiber material of Example 2 had a tensile strength of 780 kgf / cm ^2. The molded article containing the modified bundled fiber material of Comparative Example 2 had a tensile strength of 680 kgf / cm ² .

[0042]

The bundled fiber material for modifying a polymer material according to the present invention is produced by using the above-mentioned carbon precursor, and thus does not impair the characteristics of a molded article made of the polymer material. A required modifying effect can be imparted to the molded body. In particular, since the modified bundled fiber material of the present invention is previously heat-treated at a temperature equal to or higher than the softening point of the polymer material, it is particularly effective when used for modifying a polymer material having a high softening point. is there.

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Claims (7)

[Claims] 1. A bundled fiber material for modifying a polymer material having a softening point, comprising the steps of preparing a fiber group in which a number of inorganic fibers are bundled, and heating at 600 ° C. in an inert gas. Impregnating the fiber group with a solution containing a carbon precursor that results in a carbonization yield of 1 to 80% by weight after the above, and the fiber group impregnated with the solution is mixed with the polymer material in an inert gas. And b. Heat treating at a temperature equal to or higher than the softening point. 2. The bundled fiber material for modifying a polymer material according to claim 1, wherein the inorganic fiber is at least one of a carbon fiber and a glass fiber. 3. The bundled fiber material for modifying a polymer material according to claim 2, wherein the carbon fiber is a polyacrylonitrile-based carbon fiber. 4. The fiber group according to claim 1, wherein the inorganic fibers are 12 × 10
4. The method according to claim 1, wherein ^{3 to} 100 × 10 ³ are contained.
2. A bundled fiber material for modifying a polymer material according to item 1. 5. The bundled fiber material for modifying a polymer material according to claim 1, wherein the softening point of the polymer material is 200 ° C. or higher. 6. A bundled fiber material for modifying a polymer material, the method comprising: preparing a fiber group in which a number of inorganic fibers are bundled; and heating the carbon fiber at 600 ° C. in an inert gas. A step of impregnating the fiber group with a solution containing a carbon precursor having a yield of 1 to 80% by weight; and heat treating the fiber group impregnated with the solution at a temperature of 200 ° C. or more in an inert gas. And a bundled fiber material for modifying a polymer material obtained by the step comprising: 7. A bundled fiber material for modifying a polymer material, comprising: a fiber group obtained by bundling a large number of inorganic fibers; and a carbon material contained in the fiber group. Quality bundled fiber material.