JP5304085B2 - Manufacturing method of papermaking substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a papermaking base material that has excellent dispersed state of reinforcing fibers (no reaggregation) and excellent mechanical characteristics of a molded article in producing a molded article mixed with a thermoplastic resin in a short time. <P>SOLUTION: The method for producing a papermaking base material containing a reinforcing fiber base material includes: at least a step (I) for feeding a reinforcing fiber bundle to a dispersion medium; a step (II) for preparing a slurry in which the reinforcing fiber constituting the reinforcing fiber bundle is dispersed in the dispersion medium; a step (III) for transporting the slurry; and a step (IV) for removing the dispersion medium from the slurry to give a reinforcing fiber-containing papermaking base material. The steps (I)-(IV) are carried out on-line. The height H1 of the liquid level of the slurry in the step (II) is higher than the height H2 of the liquid level of the slurry in the step (IV). <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a method for producing a papermaking substrate.

  Fiber reinforced molded base materials made of reinforced fibers such as carbon fiber and glass fiber and thermoplastic resins are excellent in specific strength and specific rigidity, so they can be used in electrical / electronic applications, civil engineering / architecture applications, automotive applications, aircraft applications, etc. Widely used. In particular, a molded article using a base material in which reinforcing fibers are uniformly dispersed has isotropic mechanical properties, and if it exhibits high strength, the applicable applications are very many. Therefore, various studies have been made so far regarding the production conditions of the fiber-reinforced molded base material in which the reinforcing fibers are uniformly dispersed.

  In Patent Document 1 (International Publication No. 2007/97436 pamphlet), as a reinforcing fiber in a fiber-reinforced thermoplastic resin molded body, it is a monofilament carbon fiber and has a mass average fiber length of 0.5 to 10 mm. In addition, it is described that by setting the orientation parameter to −0.25 to 0.25, a molded body having excellent mechanical properties and isotropic mechanical properties can be obtained. This fiber-reinforced thermoplastic resin molded article is obtained by (I) a step of heating and melting a thermoplastic resin contained in a molding material, (II) a step of placing the molding material in a mold, and (III) adding a molding material in the mold. It is said that it can be manufactured by a step of pressing, (IV) a step of solidifying the molding material in the mold, and (V) a step of opening the mold and demolding the fiber-reinforced thermoplastic resin molded body.

  In Patent Document 2 (Japanese Patent Laid-Open No. 9-136969) and Patent Document 3 (Japanese Patent Laid-Open No. 8-232187), in a wet manufacturing method of a fiber-reinforced thermoplastic resin sheet, a structure in a head box through which a dispersion passes is disclosed. It also describes controlling the conditions for supplying the dispersion liquid from the head box onto the mesh belt. Thereby, there is no unevenness of local basis weight or abnormal orientation of the reinforcing fiber (Patent Document 2), or there is no variation in the distribution of the fabric weight in the width direction (Patent Document 3), whereby a fiber reinforced thermoplastic resin sheet can be obtained. Have been described.

International Publication No. 2007/97436 Pamphlet JP-A-9-136969 JP-A-8-232187

  In any of the production methods of Patent Documents 1 to 3, it is necessary to control the orientation of the carbon fibers, and for that purpose, it is necessary to set detailed conditions for each process. For this reason, time and labor are required for production, and there is a problem in applying the fiber-reinforced molded base material to efficient production. Moreover, in these manufacturing methods, since the thermoplastic resin is mix | blended with a fiber from the beginning of manufacture, the thermoplastic resin which can be used was limited.

  In the method of Patent Document 1, each process needs to be performed off-line, and more time and labor are required. In addition, in order to improve the dispersion state in the papermaking process, only general condition control such as lowering the carbon fiber concentration and increasing the stirring force is described, and this actually improves the dispersion state. It was not enough to make it happen.

  In the methods of Patent Document 2 and Patent Document 3, it is necessary to use a pump as power for transporting the slurry. Therefore, shearing occurs easily, and it is difficult to maintain the dispersed state for a long time.

  The present invention provides a method capable of obtaining in a short time a papermaking substrate that is excellent in the dispersion state of reinforcing fibers (no reagglomeration) and has excellent mechanical properties of a molded product when a thermoplastic resin is blended into a molded product. provide.

  As a result of repeated studies by the present inventors, it has been found that the above object can be achieved by adjusting the height of the liquid level of the slurry in a predetermined step during the production process, and the present invention has been achieved.

The present invention provides the following [1] to [19].
[1] A step (I) of feeding a reinforcing fiber bundle into a dispersion medium, a step (II) of preparing a slurry in which reinforcing fibers constituting the reinforcing fiber bundle are dispersed in the dispersion medium, and a step of transporting the slurry ( III) and at least step (IV) of obtaining a papermaking substrate containing reinforcing fibers by removing the dispersion medium from the slurry, wherein the steps (I) to (IV) are carried out online, The manufacturing method of the papermaking base material containing the reinforced fiber base material in which the height H1 of the liquid level of the slurry in II) exists in a position higher than the height H2 of the liquid level of the slurry in the said process (IV).
[2] The difference H1-H2 between the height H1 of the slurry level in the step (II) and the height H2 of the slurry level in the step (IV) is 0.1 to 5 m. ] The manufacturing method of the papermaking base material of description.
[3] In the step (I), the dispersion medium and the reinforcing fiber bundle are continuously added, and the steps (I) to (IV) are continuously performed. [1] or [2] A method for producing a papermaking substrate as described in 1.
[4] The paper surface height according to any one of [1] to [3], wherein the height H1 of the liquid level of the slurry in the step (II) is maintained at substantially the same height throughout the step (II). A method of manufacturing the material.
[5] The method for producing a papermaking substrate according to any one of [1] to [4], wherein the step (III) is performed by an overflow method.
[6] The step (I) and the step (II) are performed in a dispersion tank, the step (IV) is performed in a papermaking tank, and the step (III) is a transport unit that connects the dispersion tank and the papermaking tank. The method for producing a papermaking substrate according to any one of [1] to [5], wherein
[7] The method for producing a papermaking substrate according to [6], wherein the transport portion is linear.
[8] The method for producing a papermaking substrate according to [6] or [7], wherein the transport section has an inclination angle of 30 to 60 °.
[9] The papermaking according to any one of [6] to [8], wherein a ratio W1 / W2 between the width W1 of the transporting portion and the width W2 of the papermaking substrate is 0.5 to 1.0. A method for producing a substrate.
[10] The method for producing a papermaking substrate according to any one of [6] to [9], wherein the transport section has a height of 20 mm or more.
[11] The method for producing a papermaking substrate according to any one of [1] to [10], wherein a time required from the start of the step (I) to the start of the step (IV) is within 10 minutes.
[12] The method for producing a papermaking substrate according to any one of [1] to [11], wherein in the step (IV), the resulting papermaking substrate is taken up at a take-up speed of 10 m / min or more.
[13] The method for producing a papermaking substrate according to any one of [1] to [12], wherein the length of the reinforcing fiber bundle is 1 to 50 mm.
[14] The method for producing a papermaking substrate according to any one of [1] to [13], wherein the reinforcing fibers are carbon fibers.
[15] The method for producing a papermaking substrate according to [14], wherein the surface oxygen concentration ratio O / C measured by X-ray photoelectron spectroscopy of the carbon fiber is 0.05 to 0.50.
[16] Manufacture of a papermaking substrate according to any one of [1] to [15], wherein the mass content of the reinforcing fibers in the slurry prepared in the step (II) is 0.01 to 1% by mass. Method.
[17] The method for producing a papermaking substrate according to any one of [1] to [16], wherein the slurry is aqueous.
[18] The method for producing a papermaking substrate according to any one of [1] to [17], wherein the basis weight of the papermaking substrate is 10 to 500 g / m ² .
[19] Electrical / electronic equipment parts, civil engineering / architectural parts, structural parts for automobiles / motorcycles, or aircraft, using the papermaking substrate produced by the production method according to any one of [1] to [18] parts.

  According to the method for producing a fiber-reinforced web of the present invention, it is possible to obtain a paper base material that suppresses fiber aggregation and has excellent mechanical properties of a molded product in a short time when a thermoplastic resin is blended into a molded product.

  The method for producing a papermaking substrate of the present invention includes a step (I) of feeding a reinforcing fiber bundle into a dispersion medium, and a step (II) of preparing a slurry in which reinforcing fibers constituting the reinforcing fiber bundle are dispersed in the dispersion medium. And a step (III) of transporting the slurry and a step (IV) of removing a dispersion medium from the slurry to obtain a papermaking substrate containing reinforcing fibers.

  In step (I), a reinforcing fiber bundle is introduced into the dispersion medium.

  The dispersion medium (dispersion liquid) means a medium in which the reinforcing fiber bundle can be dispersed. Examples of the dispersion medium include so-called solvents such as water and alcohol, with water being preferred. As water, in addition to normal tap water, water such as distilled water and purified water can be used. A surfactant may be mixed in the water as necessary. Surfactants are classified into a cation type, an anion type, a nonionic type, and an amphoteric type. Of these, nonionic surfactants are preferably used, and polyoxyethylene lauryl ether is more preferably used. . The concentration of the surfactant when mixing the surfactant with water is usually 0.0001% by mass or more and 0.1% by mass or less, preferably 0.0005% by mass or more and 0.05% by mass or less.

The reinforcing fiber bundle means a fiber bundle composed of reinforcing fibers.
Examples of reinforcing fibers used in the present invention include carbon fibers, metal fibers, organic fibers, and inorganic fibers. Of these, carbon fibers are preferred.

  Examples of carbon fibers include PAN-based carbon fibers, pitch-based carbon fibers, cellulose-based carbon fibers, vapor-grown carbon fibers, and graphitized fibers thereof. PAN-based carbon fibers are carbon fibers made from polyacrylonitrile fibers. Pitch-based carbon fiber is carbon fiber made from petroleum tar or petroleum pitch. Cellulosic carbon fibers are carbon fibers made from viscose rayon, cellulose acetate, or the like. Vapor-grown carbon fibers are carbon fibers made from hydrocarbons or the like. Of these, PAN-based carbon fibers are preferable because they are excellent in balance between strength and elastic modulus.

  Examples of metal fibers include fibers made of metals such as aluminum, brass, and stainless steel. Examples of the organic fiber include fibers made of an organic material such as aramid, PBO, polyphenylene sulfide, polyester, acrylic, nylon, and polyethylene. Examples of inorganic fibers include fibers made of inorganic materials such as glass, basalt, silicon carbide, silicon nitride, and the like.

  The reinforcing fiber constituting the reinforcing fiber bundle may be one type or two or more types.

  The carbon fiber preferably has a surface oxygen concentration ratio O / C measured by X-ray photoelectron spectroscopy of 0.05 to 0.50, more preferably 0.06 to 0.3. Even more preferable is a value of 0.07 to 0.2. When the surface oxygen concentration ratio is 0.05 or more, the amount of polar functional groups on the surface of the carbon fiber is ensured and the affinity with the thermoplastic resin composition is increased, so that stronger adhesion can be obtained. Moreover, when the surface oxygen concentration ratio is 0.5 or less, it is possible to reduce a decrease in strength of the carbon fiber itself due to surface oxidation.

The surface oxygen concentration ratio means the ratio of the number of oxygen (O) and carbon (C) atoms on the fiber surface. The procedure for obtaining the surface oxygen concentration ratio by X-ray photoelectron spectroscopy will be described below with an example. First, the carbon fiber from which the sizing agent and the like adhering to the carbon fiber surface was removed with a solvent was cut to 20 mm, spread and arranged on a copper sample support, and then used as an X-ray source using A1Kα1,2. The chamber is maintained at 1 × 10 ⁸ Torr. The kinetic energy value (KE) of the main peak of C _1s is set to 1202 cV as a peak correction value associated with charging during measurement. C _1s peak area E. Is obtained by drawing a straight base line in the range of 1191 to 1205 eV. O _1s peak area E. Is obtained by drawing a straight base line in the range of 947 to 959 eV.

The surface oxygen concentration is calculated as an atomic ratio by using a sensitivity correction value unique to the apparatus from the ratio between the O _1s peak area and the C _1s peak area. As an X-ray photoelectron spectroscopy apparatus, a model ES-200 manufactured by Kokusai Electric Inc. can be used, and the sensitivity correction value can be calculated as 1.74.

  The means for controlling the surface oxygen concentration O / C of the carbon fiber to 0.05 to 0.5 is not particularly limited, and examples include techniques such as electric field oxidation treatment, chemical solution oxidation treatment, and gas phase oxidation treatment. Is done. Of these, electric field oxidation treatment is preferred because it is easy to handle.

  As the electrolytic solution used for the electric field oxidation treatment, aqueous solutions of the following compounds are preferably used. Inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid, inorganic hydroxides such as sodium hydroxide, potassium hydroxide and barium hydroxide, inorganic metal salts such as ammonia, sodium carbonate, sodium hydrogen carbonate, sodium acetate, sodium benzoate, etc. Organic salts, and in addition to these sodium salts, potassium salts, barium salts and other metal salts, ammonium salts, and other organic compounds such as hydrazine. Among these, an inorganic acid is preferable as the electrolytic solution, and sulfuric acid and nitric acid are particularly preferably used. The degree of the electric field treatment can control O / C on the surface of the carbon fiber by setting the amount of electricity flowing in the electric field treatment.

  The reinforcing fiber bundle may be composed of continuous reinforcing fibers or discontinuous reinforcing fibers, but in order to achieve a better dispersion state, the discontinuous reinforcing fiber bundles Preferably, chopped fiber is more preferable.

The reinforcing fiber bundle is preferably a fiber bundle composed of carbon fibers (carbon fiber bundle), and more preferably chopped carbon fibers.
The number of single fibers constituting the reinforcing fiber bundle is not particularly limited, but is preferably 24,000 or more, more preferably 48,000 or more from the viewpoint of productivity. The upper limit of the number of single fibers is not particularly limited, but considering the balance between dispersibility and handleability, productivity, dispersibility, and handleability can be kept good if there are about 300,000. .

  The length of the reinforcing fiber bundle is preferably 1 to 50 mm, and more preferably 3 to 30 mm. If it is less than 1 mm, it may be difficult to efficiently exhibit the reinforcing effect of the reinforcing fiber, and if it exceeds 50 mm, it may be difficult to maintain good dispersion. The length of the reinforcing fiber bundle means the length of the single fiber constituting the reinforcing fiber bundle. The length of the reinforcing fiber bundle in the fiber axis direction is measured with a caliper, or the single fiber is taken out from the reinforcing fiber bundle and observed with a microscope. Can be measured.

  The input amount of the reinforcing fiber bundle can be adjusted in the range of usually 0.1 g or more and 10 g or less, preferably 0.3 g or more and 5 g or less as the amount of water (dispersion) 1 l. By setting it as the said range, the reinforcing fiber bundle is efficiently dispersed in the dispersion medium, and a uniformly dispersed slurry can be obtained in a short time. When the reinforcing fiber bundle is dispersed in water (dispersion), stirring is performed as necessary.

  In step (II), a slurry is prepared in which reinforcing fibers constituting the reinforcing fiber bundle are dispersed in a dispersion medium.

  The slurry refers to a suspension in which solid particles are dispersed. In the present invention, an aqueous slurry is preferable.

  The mass content (solid content concentration in the slurry) of the reinforcing fiber in the slurry prepared in the step (II) is preferably 0.01% by mass or more and 1% by mass or less, and 0.03% by mass or more and 0.0. More preferably, it is 5 mass% or less. Papermaking can be performed efficiently by being in the above range.

  Step (II) is usually carried out in a dispersion tank. The dispersion tank is a tank (container) that can contain slurry. When using a dispersion tank, it is preferable that the dispersion medium and the reinforcing fiber bundle in step (I) are directly performed on the dispersion tank. Of course, it goes without saying that the dispersion medium and the reinforcing fiber bundle may be first introduced into a tank other than the dispersion tank, and the contents of the tank may be transferred to the dispersion tank to perform the step (II). A dispersion tank may be equipped with a stirring apparatus as needed.

  In step (III), the slurry obtained in step (III) is transported.

Step (III) is preferably performed by an overflow method. Thereby, it is possible to prevent the reinforcing fibers in the transported slurry from being sheared and to settle and aggregate, and to maintain dispersibility in the slurry. Moreover, economical transportation is possible without using power such as a pump.
The overflow method means a method of feeding liquid overflowing from a container (tank) to the next container (tank) using gravity. In other words, this is a system for feeding liquid without substantially using power such as a liquid feed pump.

  Step (III) is usually performed in a transport section that connects a dispersion tank in which step (II) is performed and a papermaking tank in which step (IV) is performed.

  The shape of the transport part is not particularly limited as long as it can transport the slurry, and is usually tubular. It is preferable that the transport portion is linear, that is, a shape having no direction change point such as a curved portion or a bent portion.

  It is preferable that the transport portion is inclined (so-called slider method). That is, when the transport section is viewed from the horizontal direction, it is preferable that the connection point between the dispersion tank and the transport section is higher than the connection point between the papermaking tank and the transport section. The inclination angle is preferably 30 to 60 °, and more preferably 40 to 55 °. If the inclination angle is less than 30 °, it may take a long time for transportation in the step (III). If the inclination angle exceeds 60 °, the flow rate during the transportation of the slurry increases, so that excessive shear is applied to the slurry when reaching the step (IV), and the dispersion state of the slurry in the step (IV) is insufficient. There is a risk.

  Here, the inclination angle means the angle on the vertically lower side of the portion where the center line of the pipe of the transport section and the line parallel to the direction of gravity intersect.

  In addition, when performing process (III) by an overflow system, it is preferable that the connection part with the dispersion tank of a transport part is located in the wall surface of a dispersion tank, especially upper direction.

  The shape of the transport section will be described with reference to FIGS. 1-7, the process (I) and the process (II) are performed in a dispersion tank, the process (IV) is performed in a papermaking tank, and the process (III) is connected to the dispersion tank and the papermaking tank. It is a figure which shows typically the positioning seen from the horizontal direction of a dispersion | distribution tank, a papermaking tank, and a transport part in the case of performing in a transport part. The transport part 13 in FIGS. 1 to 6 has a linear shape.

  The inclination angle of the transport portion means an angle r formed by the center line q of the transport portion 13 and the line P extending in the direction of gravity in the vertical direction in each figure. The transport section 13 in FIGS. 1, 5, and 6 is inclined from the dispersion tank 11 toward the papermaking tank 12, and the inclination angle is 30 to 60 °. The transport unit 13 in FIG. 2 connects the dispersion tank 11 and the papermaking tank 12 horizontally, and the inclination angle is approximately 90 °. The transport section 13 in FIG. 3 is inclined from the dispersion tank 11 toward the papermaking tank 12, and the inclination angle is 30 to 60 °. The transport section 13 in FIG. 4 connects the dispersion tank 11 and the papermaking tank 12 in the direction of gravity, and the inclination angle is approximately 0 °.

  In FIG. 1, FIG. 5 and FIG. 6, the connection portion 14 of the transport portion 13 with the dispersion tank 11 is located above the wall surface of the dispersion tank 11. Therefore, if the dispersion tank, papermaking tank, and transport section are positioned as shown in FIG. 1, step (III) can be performed by the overflow method.

  The width of the transport portion is not particularly defined, but the ratio W1 / W2 between the width W1 of the transport portion and the width W2 of the papermaking substrate is preferably 0.5 to 1.0, preferably 0.7 to 1.0. It is more preferable that If W1 / W2 is less than 0.5, it may take a long time for transportation in the step (III), and the slurry flowing portion increases in width when the slurry flows from the transportation portion to the step (IV). There is a possibility that the distributed state becomes insufficient due to a load on the. If W1 / W2 exceeds 1.0, the dispersion state of the slurry in step (IV) may be insufficient. Here, the “width of the transport part” means the major axis of the cross section of the transport part. For example, when the cross section of the transport part is rectangular, it means the longer diameter. “Width of the papermaking substrate” means the width (one shorter than the length) of the length, width, and thickness of the papermaking substrate obtained in step (IV). In addition, when each width changes with parts, it shall mean the average value.

  The width of the transport section is usually in the range of 0.1 to 2 m. The width of the papermaking substrate is usually 0.2 to 2 m.

  The height of the transport part is 60 mm or more, preferably 100 mm or more. By being 60 mm or more, the contact area between the wall surface of the transport section and the slurry can be made relatively small with respect to the amount of slurry to be transported, and re-aggregation of the dispersed fibers due to the generation of shearing force on the slurry when contacting the wall surface. Can be reduced. Here, the height of the transport section means the diameter of the transport section when the transport section is viewed from the horizontal direction. When the transport portion is rectangular (the long side is the base material width direction and the short side is the base material thickness direction), the length of the short side corresponds to the “height of the transport portion”. Although the upper limit of the height of a transport part is not specifically limited, Usually, it is 500 mm or less. If there is a difference in the height of the transport section depending on the part, the average value is meant.

  In step (IV), the dispersion medium is removed from the slurry to obtain a papermaking substrate containing reinforcing fibers.

  Step (IV) is usually carried out in a papermaking tank. The papermaking tank is a tank (container) that can contain slurry and has a papermaking surface capable of sucking moisture. The papermaking surface is generally provided near the bottom surface, and the material is exemplified by a mesh sheet.

  In the present invention, the papermaking substrate obtained in step (IV) can be taken up. The papermaking substrate can be taken up by being wound on a roll. The take-up speed is preferably 10 m / min or more. The upper limit of the take-up speed is usually 100 m / min or less.

  The time required from step (I) to the start of step (IV) is preferably within 10 minutes. If it exceeds 10 minutes, depending on the type of reinforcing fiber, the reinforcing fiber dispersed in the slurry may reaggregate. The lower limit of the time required from the step (I) to the start of the step (IV) is not particularly limited, but is usually 1 minute or more.

  The level H1 of the slurry liquid level in the step (II) is preferably higher than the height H2 of the slurry liquid level in the step (IV). “The height of the liquid level of the slurry” means the position of the liquid level when the slurry is viewed from the horizontal direction. “At a high position” means that when the height of two liquid levels is expressed as a measured value as a distance from a reference located vertically below the height, one height is higher than the other. That is, it means that one of the two liquid surface heights is located vertically below the other.

  Among them, the difference H1-H2 between the height H1 of the slurry level in the step (II) and the height H2 of the slurry level in the step (IV) is preferably 0.1 to 5 m. More preferably, it is 0.5-2m. If it is less than 0.1 m, it may take a long time for transportation in the step (III). On the other hand, if it exceeds 5 m, the dispersion state of the slurry in step (IV) may be insufficient.

  The height H1 of the liquid level of the slurry in the step (II) and the height H2 of the liquid level of the slurry in the step (IV) will be described with reference to FIGS. The liquid surface height H1 of the slurry (shaded portion) in the dispersion tank 11 is represented by a distance H1 of the liquid surface position B with respect to the reference A positioned vertically below H1 and H2. The liquid surface height H2 of the slurry (shaded portion) in the papermaking tank 12 is represented by a distance H2 of the liquid surface position C with respect to the liquid surface reference A. In order to maintain the difference between the heights H1 and H2 of the liquid level of the slurry, as shown in FIGS. 1, 3, 4 and 7, the dispersion tank 11 and the papermaking tank 12 are shifted with respect to the direction of gravity. 2, 5 and 6, as shown in FIG. 2, FIG. 5 and FIG. 6, if the height of the liquid level of the slurry in each tank is adjusted according to the amount of slurry and the size of the tank, the dispersion The positions in the gravity direction of the tank 11 and the papermaking tank 12 may be horizontal.

  In order to maintain the height H1 of the liquid level of the slurry in the step (II) at a position higher than the height H2 of the liquid level of the slurry in the step (IV), for example, the step (II) is a dispersion tank and the step (IV ) In a papermaking tank, it is preferable to install these two tanks so that the position of the bottom surface of the dispersion tank is located vertically above the position of the top surface of the papermaking tank.

  Step (I) to step (IV) are preferably performed online. Online is a system in which each process is continuously performed, and is an antonym of offline. That is, online means a process in which each process is performed as a series of flows, and is different from a process in which each process is independent. By carrying out step (I) to step (IV) online, a papermaking substrate can be obtained in a short time.

In the step (I), it is preferable that the dispersion medium and the reinforcing fiber bundle are continuously added and the steps (I) to (IV) are continuously performed. Thereby, a papermaking base material can be obtained in a shorter time. In addition, if a large amount of slurry is added at once, a part of the slurry may take a long time to be paper-made, and the dispersion state may be deteriorated. Can be made in small amounts efficiently while maintaining the dispersed state. “Continuously input” and “Continuously execute” means that the material is continuously input, and the raw materials to be administered in step (I) are sequentially or continuously performed (II) to (IV). It means to do. In other words, in a series of steps, it means a state in which the supply of the raw material of the dispersed slurry and the supply of the slurry are continued, and it means a process that considers mass production rather than the process of producing a certain amount of slurry first. Examples of the method of continuously charging and executing include a method other than the batch method, a method of charging at a constant speed, and a method of charging a substantially constant amount at a predetermined interval. Examples of the conditions for feeding at a constant rate include conditions for feeding the dispersion medium at 1 × 10 ³ to 1 × 10 ⁷ g / min and the reinforcing fiber bundle at 0.1 to 1 × 10 ⁵ g / min. As conditions for introducing a substantially constant amount at a predetermined interval, 1 × 10 ³ to 1 × 10 ⁷ g each of dispersion medium and 0.1 to 1 × 10 ⁵ g of reinforcing fiber bundle are added every 1 to 5 minutes. The conditions to do are illustrated.

  It is preferable that the height H1 of the liquid level of the slurry in the step (II) is maintained at substantially the same height throughout the step (II). Particularly when the steps (I) to (IV) are continuously performed, the level H1 of the liquid level of the slurry in the step (II) is kept substantially the same throughout the step (II). It is preferable.

  “Maintains substantially the same height throughout the step (II)” means that the height variation is within 100 mm, preferably within 50 mm, more preferably the variation during the step (II). It means not (0 mm). In order to keep the height H1 of the liquid level of the slurry in the step (II) substantially the same throughout the step (II), it is preferable to continuously perform the step (I). For example, when the step (II) is performed in a dispersion tank, it is preferable that the dispersion medium and the reinforcing fiber are continuously supplied to the dispersion tank and the steps (I) to (IV) are continuously performed. .

Basis weight of the paper substrate is preferably 10 to 500 g / m ^2, and more preferably 50 to 300 g / m ^2. If it is less than 10 g / m ^2, it may cause problems in handling properties such as tearing of the paper-making base, and if it exceeds 500 g / m ² , it will take a long time to dry the paper-making base, resulting in problems in subsequent processes. There is a fear.

  The papermaking substrate obtained in the present invention can be used as a fiber-reinforced molded substrate containing a thermoplastic resin or a thermosetting resin. The fiber reinforced molding base material can be used for various applications such as electrical / electronic equipment parts, civil engineering / architectural parts, automobile / motorcycle parts, aircraft parts, etc., and is preferably used for electronic equipment parts, automotive structural parts. It is done.

Production Example 1 (A1: PAN-based carbon fiber)
Using a copolymer composed of 99.4 mol% of acrylonitrile (AN) and 0.6 mol% of methacrylic acid, an acrylic fiber bundle having a single fiber denier 1d and a filament number of 12,000 was obtained by a dry and wet spinning method. The obtained acrylic fiber bundle is heated at a draw ratio of 1.05 in air at a temperature of 240 to 280 ° C., converted to flame-resistant fiber, and then heated in a temperature range of 300 to 900 ° C. in a nitrogen atmosphere. After 10% stretching at a rate of 200 ° C./min, the temperature was raised to a temperature of 1,300 ° C. and fired. This carbon fiber bundle is an aqueous solution containing sulfuric acid as an electrolyte, and is subjected to an electrolytic surface treatment of 3 coulombs per gram of carbon fiber, further provided with a sizing agent by an immersion method, and dried in heated air at a temperature of 120 ° C. Fiber A1 was obtained.
Total number of filaments 12,000 Single fiber diameter 7μm
Mass per unit length 0.8g / m
Specific gravity 1.8g / cm ³
Tensile strength (Note 1) 4.2 GPa
Tensile modulus (Note 2) 230 GPa
O / C (Note 3) 0.10
Sizing type Amount of polyoxyethylene oleyl ether sizing (Note 4) 1.5% by mass

Production Example 2 (A2: PAN-based carbon fiber)
Using a copolymer composed of 99.4 mol% of acrylonitrile (AN) and 0.6 mol% of methacrylic acid, an acrylic fiber bundle having a single fiber denier 1d and a filament number of 12,000 was obtained by a dry and wet spinning method. The obtained acrylic fiber bundle is heated at a draw ratio of 1.05 in air at a temperature of 240 to 280 ° C., converted to flame-resistant fiber, and then heated in a temperature range of 300 to 900 ° C. in a nitrogen atmosphere. After 10% stretching at a rate of 200 ° C./min, the temperature was raised to a temperature of 1,300 ° C. and fired. Further, a sizing agent was applied by an immersion method and dried in heated air at a temperature of 120 ° C. to obtain a PAN-based carbon fiber A2.
Total number of filaments 12,000 Single fiber diameter 7μm
Mass per unit length 0.8g / m
Specific gravity 1.8g / cm ³
Tensile strength (Note 1) 4.2 GPa
Tensile modulus (Note 2) 230 GPa
O / C (Note 3) 0.05
Sizing type Amount of polyoxyethylene oleyl ether sizing (Note 4) 1.5% by mass

Production Example 3 (F: acid-modified polypropylene resin film)
“Admer” (registered trademark) QE510 (specific gravity 0.91, melting point 160 ° C.) manufactured by Mitsui Chemicals, Inc. is press-molded at a temperature of 200 ° C. and a pressure of 20 Mpa for 1 minute to produce an acid-modified polypropylene resin film F having a thickness of 50 μm. did.

(Note 1) Tensile strength, (Note 2) Tensile modulus measurement conditions It was determined by the technique described in Japanese Industrial Standard (JIS) -R-7601 “Resin Impregnated Strand Test Method”. However, the resin-impregnated strand of carbon fiber to be measured is impregnated with “BAKELITE” (registered trademark) ERL 4221 (100 parts by mass) / 3 boron fluoride monoethylamine (3 parts by mass) / acetone (4 parts by mass). And cured at 130 ° C. for 30 minutes. The number of strands measured was 6, and the average value of each measurement result was the tensile strength and tensile modulus of the carbon fiber.

(Note 3) Measurement conditions for O / C measurement: Obtained by X-ray photoelectron spectroscopy according to the following procedure. First, carbon fibers from which deposits and the like were removed from the carbon fiber surface with a solvent were cut into 20 mm and spread on a copper sample support table. A1Kα1 and 2 were used as the X-ray source, and the inside of the sample chamber was kept at 1 × 10 ⁸ Torr. The kinetic energy value (KE) of the main peak of C _1s was adjusted to 1202 cV as a peak correction value associated with charging during measurement. C _1s peak area E. As a linear base line in the range of 1191 to 1205 eV. O _1s peak area, E. As a linear base line in the range of 947 to 959 eV.

The surface oxygen concentration was calculated as an atomic number ratio from the ratio of the O _1s peak area to the C _1s peak area using a sensitivity correction value unique to the apparatus. As an X-ray photoelectron spectroscopy apparatus, Kokusai Denki Co., Ltd. model ES-200 was used, and the sensitivity correction value was set to 1.74.

(Note 4) Measurement conditions for the amount of sizing agent attached As a sample, about 5 g of carbon fiber to which the sizing agent was attached was collected and placed in a heat-resistant container. The container was then dried at 120 ° C. for 3 hours. After cooling to room temperature while taking care in a desiccator so as not to absorb moisture, the weighed mass was defined as W ₁ (g). Subsequently, the whole container was heated in a nitrogen atmosphere at 450 ° C. for 15 minutes, and then cooled to room temperature while taking care not to absorb moisture in a desiccator, and the weighed mass was defined as W ₂ (g). Through the above treatment, the amount of the sizing agent attached to the carbon fiber was determined by the following equation.
(Formula) Adhering amount (% by mass) = 100 × {(W ₁ −W ₂ ) / W ₂ }

  In addition, the measurement was performed 3 times and the average value was employ | adopted as adhesion amount.

  The evaluation criteria of the carbon fiber web obtained in each example are as follows.

-(I)-(IV) Process time The time required from process (I) to process (IV) was measured.

-Evaluation of dispersed state of reinforcing fiber The web was cut into a square shape of 50 mm x 50 mm from an arbitrary part of the carbon fiber web obtained by papermaking and observed with a microscope. A state where 10 or more carbon fibers were bundled, that is, the number of carbon fiber bundles with insufficient dispersion was measured. This procedure is performed 20 times, and with the average value, less than 1 carbon fiber bundle with insufficient dispersion is double-round, and 1 to less than 5 carbon fiber bundles with insufficient dispersion. ◯, 5 to less than 10 carbon fiber bundles with insufficient dispersion were evaluated as Δ, and 10 or more carbon fiber bundles with insufficient dispersion were evaluated as x.

-Evaluation of molded product mechanical properties A carbon fiber web obtained by papermaking was cut into 200 mm x 200 mm and dried at 120 ° C for 1 hour. Three layers of the carbon fiber web after drying and the acid-modified polypropylene resin film F were laminated so as to be resin film F / carbon fiber web / resin film F. This laminate was press-molded at a temperature of 200 ° C. and a pressure of 30 MPa for 5 minutes, and cooled to 50 ° C. while maintaining the pressure to produce a carbon fiber reinforced resin sheet having a thickness of 0.12 mm. Eight of these resin sheets were laminated, press-molded at a temperature of 200 ° C. and a pressure of 30 MPa for 5 minutes, and cooled to 50 ° C. while maintaining the pressure to obtain a carbon fiber reinforced resin molded product having a thickness of 1.0 mm. Using the obtained molded product, the bending strength was evaluated by n = 10 according to ISO 178 method (1993). In addition, the evaluation result of bending strength was described as a relative value with Example 1 as 100. Moreover, the dispersion | variation in the evaluation result was described by the coefficient of variation (CV value).

Example 1
A papermaking substrate was produced using the papermaking substrate production apparatus 01 of FIG. The manufacturing apparatus 01 includes a cylindrical container having a diameter of 300 mm having an opening cock 15 at the bottom of the container as the dispersion tank 11, and a large square sheet machine (No. 2553-I, manufactured by Kumagai Riki Kogyo Co., Ltd.) as the papermaking tank 12. (Trade name)), a linear transport section (inclination angle 45 °) 13 connecting the dispersion tank 11 and the papermaking tank 12 is provided. A stirrer 16 is attached to the opening on the upper surface of the dispersion tank 11, and a carbon fiber bundle 17 and a dispersion liquid (dispersion medium) 18 can be introduced from the opening. The bottom of the papermaking tank 12 has a papermaking surface (made of mesh sheet) 19 having a length of 400 mm and a width of 400 mm, and a carbon fiber web 20 is obtained on the papermaking surface 19.

  A1 (carbon fiber) was cut to 6.4 mm with a cartridge cutter to obtain chopped carbon fiber (A1-1).

20 liters of a dispersion having a concentration of 0.1% by mass composed of water and a surfactant (manufactured by Nacalai Tex Co., Ltd., polyoxyethylene lauryl ether (trade name)) was prepared and transferred to a dispersion tank. To this dispersion, 9.6 g of A1-1 (chopped carbon fiber) was added (step (I)). A slurry was prepared by stirring for 10 minutes (step (II)). Thereafter, the opening cock at the bottom of the container was opened, and pouring into the papermaking tank was started via the transport section (step (III)). At this time, the height H1 of the slurry liquid level in the dispersion tank was 50 cm higher than the slurry liquid level H2 in the papermaking tank. Next, water was sucked from the papermaking surface of the papermaking tank to obtain a carbon fiber web having a length of 400 mm and a width of 400 mm (step (IV)). The basis weight of the carbon fiber web was 60 g / m ² . The execution conditions in each step and the evaluation results of the obtained carbon fiber web are shown in Table 1.

(Example 2)
A papermaking substrate was produced using the papermaking substrate production apparatus 02 of FIG. In the manufacturing apparatus 02, the papermaking tank 12 is a tank provided with a mesh conveyor 21 having a papermaking surface 19 having a width of 200 mm at the bottom, and a conveyor 22 capable of transporting a carbon fiber web (papermaking substrate) 20 is used as a mesh conveyor 21. The manufacturing apparatus 01 is the same as the manufacturing apparatus 01 except that it is further connected.

  A1 (carbon fiber) was cut to 6.4 mm with a cartridge cutter to obtain chopped carbon fiber (A1-1).

A dispersion liquid having a concentration of 0.1% by mass composed of water and a surfactant (manufactured by Nacalai Tex Co., Ltd., polyoxyethylene lauryl ether (trade name)) was prepared. The dispersion liquid and chopped carbon fiber (A1-1) were charged into the dispersion tank. While manufacturing, continuously adjusting the input amount so that the carbon fiber concentration in the slurry in the dispersion tank becomes a constant concentration and the height H1 of the liquid level of the slurry in the dispersion tank becomes constant. The above dispersion and chopped carbon fiber were continuously charged (step (I)). Stirring was started simultaneously with the start of charging of the raw material into the container to prepare a slurry (step (II)). When 40 liters of slurry was collected, the opening cock at the bottom of the container was adjusted to open and poured into the papermaking tank via the transport section (step (III)). At this time, the height H1 of the slurry liquid level in the dispersion tank was 50 cm higher than the slurry liquid level H2 in the papermaking tank. Water was sucked from the slurry and taken up at a speed of 10 m / min, and a carbon fiber web having a width of 200 mm was continuously obtained (Step IV). The basis weight of the carbon fiber web was 20 g / m ² . The execution conditions in each step and the evaluation results of the obtained carbon fiber web are shown in Table 1.

(Example 3)
A papermaking substrate was produced using the papermaking substrate production apparatus 03 of FIG. In the manufacturing apparatus 03 of FIG. 3, the dispersion tank 11 has a concave shape with two openings (a wide-mouth opening 23 and a narrow-mouth opening 24) on the upper surface, and the stirrer 16 is on the wide-mouth opening 23 side. The installed point, the connecting part 14 is located in the upper part (near the opening part), the liquid feeding from the dispersing tank 11 to the papermaking tank 12 is possible by the overflow method, and the connecting cock 14 has an opening cock. Except for the point not provided, it was the same as the manufacturing apparatus 02 of FIG.

Dispersion with a concentration of 0.1% by mass comprising chopped carbon fiber (A1-1), water and a surfactant (manufactured by Nacalai Tex Co., Ltd., polyoxyethylene lauryl ether (trade name)) using the production apparatus 03. The liquid was introduced from the narrow opening. Thereafter, the same treatment as in Example 2 was performed to obtain a carbon fiber web. The basis weight of the obtained carbon fiber web was 20 g / m ² . The execution conditions in each step and the evaluation results of the obtained carbon fiber web are shown in Table 1.

Example 4
In the papermaking substrate manufacturing apparatus 03, the same manufacturing apparatus 04 (FIG. 11) is used as in Example 3 except that the transport portion has a four-folded right angle structure and has an angle of 45 ° as a whole. A carbon fiber web was obtained. The basis weight of the obtained carbon fiber web was 20 g / m ² . The execution conditions in each step and the evaluation results of the obtained carbon fiber web are shown in Table 1.

(Example 5)
In the papermaking substrate manufacturing apparatus 03, the same processing apparatus (not shown) is used as in Example 3 except that the transport section has a structure of 90 ° (vertically downward). A carbon fiber web was obtained. The basis weight of the obtained carbon fiber web was 20 g / m ² . The execution conditions in each step and the evaluation results of the obtained carbon fiber web are shown in Table 1.

(Example 6)
In Example 5, the ratio W1 / W2 between the width W1 of the transport section and the carbon fiber web W2 is set using the same manufacturing apparatus (not shown) except that the transport section has a 45 ° angle. Except for changing from 0.6 to 0.2, the same treatment as in Example 5 was performed to obtain a carbon fiber web. The basis weight of the obtained carbon fiber web was 20 g / m ² . The execution conditions in each step and the evaluation results of the obtained carbon fiber web are shown in Table 1.

(Example 7)
In Example 1, except having changed the kind of carbon fiber from A1 to A2, it processed similarly to Example 1 and obtained the carbon fiber web. The basis weight of the obtained carbon fiber web was 60 g / m ² . The execution conditions in each step and the evaluation results of the obtained carbon fiber web are shown in Table 1.

(Comparative Example 1)
In Example 1, the same manufacturing apparatus (not shown) is used except that the transport part is linear (angle 45 °) in manufacturing apparatus 01, and only steps (I) to (II) are online. Steps (III) to (IV) were performed in the same manner as in Example 1 except that the steps were performed offline. The basis weight of the obtained carbon fiber web was 60 g / m ² . The execution conditions in each step and the evaluation results of the obtained carbon fiber web are shown in Table 1.

(Comparative Example 2)
In Example 1, the manufacturing apparatus (not shown) is the same as that in the manufacturing apparatus 01 of FIG. 11 except that the transport unit is a horizontal straight line (angle 0 °) and that a liquid feeding pump is used. The same procedure as in Example 1 was performed except that the point was used. The basis weight of the obtained carbon fiber web was 60 g / m ² . The execution conditions in each step and the evaluation results of the obtained carbon fiber web are shown in Table 1.

  As can be seen from Table 1, in Examples 1 to 7, carbon fiber webs excellent in dispersion state without reaggregation could be obtained in a short time. It has been clarified that the steps (I) to (IV) are performed on-line and the liquid is fed without using a liquid feeding pump, so that the settling and aggregation of reinforcing fibers during transportation can be prevented (Examples 1 to 1). 7 and Comparative Examples 1-2). Furthermore, the carbon fiber webs obtained in Examples 1 to 7 were also found to be excellent in the mechanical properties of the molded product when formed into molded products.

  By adjusting the height H1 of the liquid surface of the slurry to be constant while continuously supplying the dispersion liquid and chopped carbon fiber to the dispersion tank, or by making the transport part an overflow method, Processing in a shorter time was possible (see Examples 2 to 6).

  By making the transport part linear and further setting the inclination angle to 30 to 60 °, or by setting the W1 / W2 ratio to 0.5 to 1.0, the dispersion state of the carbon fiber web can be further enhanced. (See Examples 1-4 and Example 7).

  It was revealed that the mechanical properties of the molded article of the carbon fiber web can be further improved by using fibers having a high O / C (see Examples 1 and 7).

It is a figure which shows typically an example of the positioning seen from the horizontal direction of a dispersion tank, a papermaking tank, and a transport part. It is a figure which shows typically an example of the positioning seen from the horizontal direction of a dispersion tank, a papermaking tank, and a transport part. It is a figure which shows typically an example of the positioning seen from the horizontal direction of a dispersion tank, a papermaking tank, and a transport part. It is a figure which shows typically an example of the positioning seen from the horizontal direction of a dispersion tank, a papermaking tank, and a transport part. It is a figure which shows typically an example of the positioning seen from the horizontal direction of a dispersion tank, a papermaking tank, and a transport part. It is a figure which shows typically an example of the positioning seen from the horizontal direction of a dispersion tank, a papermaking tank, and a transport part. It is a figure which shows typically an example of the positioning seen from the horizontal direction of a dispersion tank, a papermaking tank, and a transport part. It is a horizontal sectional view which shows an example of the manufacturing apparatus of a papermaking base material. It is a horizontal sectional view which shows an example of the manufacturing apparatus of a papermaking base material. It is a horizontal sectional view which shows an example of the manufacturing apparatus of a papermaking base material. It is a horizontal sectional view which shows an example of the manufacturing apparatus of a papermaking base material.

Explanation of symbols

01, 02, 03, 04 Papermaking substrate production apparatus 11 Dispersion tank 12 Papermaking tank 13 Transport section 14 Connection section 15 between transport section and dispersion tank Opening cock 16 Stirrer 17 Chopped carbon fiber (carbon fiber bundle)
18 Dispersion (dispersion medium)
19 Papermaking surface 20 Carbon fiber web (papermaking substrate)
21 Mesh conveyor 22 Conveyor 23 Wide opening 24 Narrow opening H1 Slurry level in process (II) H2 Slurry level in process (IV) A Standard B Slurry in process (II) Liquid level C Liquid level P of the slurry in step (IV) Line q parallel to the direction of gravity Angle formed by the center line rp and q of the transport section on the vertically lower side

Claims (19)

  A step (I) of feeding a reinforcing fiber bundle into a dispersion medium, a step (II) of preparing a slurry in which the reinforcing fibers constituting the reinforcing fiber bundle are dispersed in the dispersion medium, a step (III) of transporting the slurry, and At least the step (IV) of obtaining a papermaking substrate containing reinforcing fibers by removing the dispersion medium from the slurry, wherein the steps (I) to (IV) are performed online, in the step (II) The manufacturing method of the papermaking base material containing the reinforced fiber base material in which the height H1 of the liquid level of a slurry exists in the position higher than the height H2 of the liquid level of the slurry in the said process (IV).   The difference H1-H2 between the height H1 of the liquid level of the slurry in the step (II) and the height H2 of the liquid level of the slurry in the step (IV) is 0.1 to 5 m. A method for producing a papermaking substrate.   The papermaking base according to claim 1 or 2, wherein in the step (I), a dispersion medium and a reinforcing fiber bundle are continuously added, and the steps (I) to (IV) are continuously performed. A method of manufacturing the material.   The manufacturing method of the papermaking base material in any one of Claims 1-3 with which the height H1 of the liquid level of the slurry in the said process (II) is kept substantially the same height through process (II).   The manufacturing method of the papermaking base material in any one of Claims 1-4 which performs the said process (III) by an overflow system.   The step (I) and the step (II) are performed in a dispersion tank, the step (IV) is performed in a papermaking tank, and the step (III) is performed in a transport unit that connects the dispersion tank and the papermaking tank. The manufacturing method of the papermaking base material in any one of Claims 1-5.   The manufacturing method of the papermaking base material of Claim 6 whose said transport part is linear.   The manufacturing method of the papermaking base material of Claim 6 or 7 whose inclination | tilt angle of the said transport part is 30-60 degrees.   The manufacturing method of the papermaking base material in any one of Claims 6-8 whose ratio W1 / W2 of the width W1 of the said transport part and the width W2 of the said papermaking base material is 0.5-1.0. .   The manufacturing method of the papermaking base material in any one of Claims 6-9 whose height of the said transport part is 20 mm or more.   The manufacturing method of the papermaking base material in any one of Claims 1-10 which makes the required time from the start of the said process (I) to the start of the said process (IV) within 10 minutes.   The manufacturing method of the papermaking base material of Claims 1-11 which pulls up the papermaking base material obtained by the taking-up speed | rate of 10 m / min or more in the said process (IV).   The manufacturing method of the papermaking base material in any one of Claims 1-12 whose length of the said reinforcing fiber bundle is 1-50 mm.   The manufacturing method of the papermaking base material in any one of Claims 1-13 whose said reinforced fiber is carbon fiber.   The manufacturing method of the papermaking base material of Claim 14 whose surface oxygen concentration ratio O / C measured by the X ray photoelectron spectroscopy of the said carbon fiber is 0.05-0.50.   The manufacturing method of the papermaking base material in any one of Claims 1-15 whose mass content of the reinforced fiber in the slurry prepared by the said process (II) is 0.01-1 mass%.   The method for producing a papermaking substrate according to any one of claims 1 to 16, wherein the slurry is aqueous. The manufacturing method of the papermaking base material in any one of Claims 1-17 whose fabric weights of the said papermaking base material are 10-500 g / m < ² >.   An electrical / electronic device part, a civil / architectural part, a structural part for an automobile / motorcycle, or an aircraft part using the papermaking substrate produced by the production method according to claim 1.

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