JP2011157637A - Papermaking substrate and method for producing fiber-reinforced forming substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for obtaining a papermaking substrate in a short time at a low cost, by which the papermaking substrate excellent in the dispersion state of reinforcing fibers can be obtained. <P>SOLUTION: The method for producing a papermaking substrate comprises at least (i): a process for continuously charging reinforcing fiber bundles into a papermaking tank having a dispersion medium, (ii): a process for dispersing the reinforcing fibers in the dispersion medium to prepare a slurry (a), (iii): a process for removing the dispersion medium from the slurry (a) to obtain the papermaking substrate containing the reinforcing fibers, and (iv): a process for pulling out the papermaking substrate obtained in the process (iii), wherein the processes (i) to (iv) are performed in an identical papermaking tank. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing a papermaking substrate. More specifically, the present invention relates to a method for producing a papermaking base material suitably used for a fiber reinforced molded base material composed of a reinforcing fiber such as carbon fiber or glass fiber and a matrix resin.

  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, as a reinforcing fiber in a fiber-reinforced thermoplastic resin molded body, it is a single fiber-like carbon fiber having a mass average fiber length of 0.5 to 10 mm, and an orientation parameter of −0.25. It is described that a molded body having excellent mechanical properties and isotropic mechanical properties can be obtained by setting the value to ˜0.25. 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 and Patent Document 4, in the wet manufacturing method of a fiber-reinforced thermoplastic resin sheet, the structure in the head box through which the dispersion passes and the conditions for supplying the dispersion from the head box onto the mesh belt are described. It is described to control. As a result, there is no variation in the fabric weight distribution in the width direction (Patent Document 2), or there is no uneven local weight or abnormal orientation of the reinforcing fibers (Patent Document 4), and a fiber-reinforced thermoplastic resin sheet can be obtained. Is described.

  Patent Document 3 describes that in a wet manufacturing method of a fiber-reinforced thermoplastic resin sheet, a fiber-reinforced resin sheet with random fiber orientation can be obtained by forming the flow of the dispersion in the alternating direction of the papermaking surface. Has been.

  In any of the production methods of Patent Documents 1 to 4, it is assumed that in obtaining a papermaking base material, a dispersion liquid in which reinforcing fibers and a thermoplastic resin are mixed in advance is prepared, and the dispersion liquid is transferred to a papermaking facility through a transport mechanism. It is said. Therefore, it is necessary to design and install necessary equipment for each process, and it is necessary to set detailed conditions for each process. Along with this, equipment costs and manufacturing man-hours increased, leading to an increase in product costs.

  Furthermore, the method of Patent Document 1 uses a batch-type manufacturing method, and it takes time and labor to prepare many molding materials. 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.

  Moreover, in addition to the above, the methods of Patent Documents 2 to 4 control the basis weight and fiber orientation of the papermaking base material, so the facilities and the control system must be complicated, and the increase in equipment costs and manufacturing steps is inevitable. . Further, since the process becomes complicated, it is necessary to maintain the dispersion state of the dispersion for a long time, and shear may be applied during the transport process, which may cause reaggregation of the fibers.

International Publication No. 2007/97436 Pamphlet JP-A-8-232187 Japanese Patent Laid-Open No. 9-94826 JP-A-9-136969

  An object of the present invention is to provide a method for obtaining a papermaking substrate at a low cost in a short time, and further to provide a method capable of obtaining a papermaking substrate excellent in the dispersion state of reinforcing fibers.

As a result of repeated studies by the present inventors, it has been found that the above-mentioned object can be achieved by condensing and reproducing the processes performed through a plurality of facilities into a single facility. Reached. That is, this invention is a manufacturing method of the papermaking base material which includes following process (i)-(iv) at least and implements at least process (i)-(iii) with the same papermaking tank.
(I): Step of continuously feeding a reinforcing fiber bundle into a papermaking tank having a dispersion medium (ii): Step of adjusting slurry (a) in which reinforcing fibers are dispersed in the dispersion medium (iii): Slurry (a) Step (iv) of removing the dispersion medium from the substrate to obtain a papermaking substrate containing reinforcing fibers: A step of taking the papermaking substrate obtained in step (iii).

  According to the method for producing a papermaking substrate of the present invention, a papermaking substrate can be produced in a short time and at a low cost with simple equipment and processes. It can be manufactured.

It is a model figure which shows an example of a papermaking tank. It is a model figure which shows an example of a papermaking tank. It is a model figure which shows an example of a papermaking tank. It is a model figure which shows an example of a papermaking tank. It is a model figure which shows an example of a papermaking tank. It is a model figure which shows an example of a papermaking tank. It is a model figure which shows an example of the division of an injection range. It is a model figure which shows an example of the division of an injection range. It is a model figure which shows an example of the division of an injection range. It is a model figure which shows an example of the division of an injection range. It is a model figure which shows an example of the division of an injection range. It is a model figure which shows an example of the apparatus used for the manufacturing method of a papermaking base material. It is a model figure which shows an example of the apparatus used for the manufacturing method of a papermaking base material. It is a model figure which shows an example of the apparatus used for the manufacturing method of a papermaking base material. It is a model figure which shows an example of the apparatus used for the manufacturing method of a papermaking base material. It is a model figure which shows an example of the apparatus used for the manufacturing method of a papermaking base material. It is a model figure which shows an example of the apparatus used for the manufacturing method of a papermaking base material. It is a model figure which shows an example of the apparatus used for the manufacturing method of a papermaking base material.

The method for producing a papermaking substrate of the present invention includes at least the following steps (i) to (iv), and at least steps (i) to (iii) are performed in the same papermaking tank.
(I): Step of continuously feeding a reinforcing fiber bundle into a papermaking tank having a dispersion medium (ii): Step of adjusting slurry (a) in which reinforcing fibers are dispersed in the dispersion medium (iii): Slurry (a) Step (iv) of removing the dispersion medium from the substrate to obtain a papermaking substrate containing reinforcing fibers: A step of taking the papermaking substrate obtained in step (iii).

  Step (i) is performed in a papermaking tank capable of storing the dispersion medium. That is, step (i) is carried out with the dispersion medium in the papermaking tank, that is, with the dispersion medium being supplied or circulated in the papermaking tank. In such a state, the reinforcing fiber bundle is continuously charged into the papermaking tank.

  Here, “continuously input” is a state in which some of the reinforcing fiber bundles are always input. For example, when producing the same amount of papermaking base material, when adjusting the slurry from a large amount of reinforcing fiber bundles (batch type), it is necessary to adjust a considerable amount of slurry at one time, and the slurry is dispersed in the slurry. Since places with different times occur, there is a high possibility that poor dispersion and uneven dispersion will occur in the product. On the other hand, when a small amount of reinforcing fiber bundle is continuously added to adjust the slurry (continuous type), a small amount of slurry is continuously adjusted and sequentially supplied to the next process. Therefore, it is possible to make paper efficiently and with the dispersion state maintained.

  That is, the method for producing a papermaking substrate of the present invention continuously performs raw material supply and slurry adjustment and supply into a dispersion medium in a series of steps including the steps described later, This is a manufacturing method that takes mass productivity and stability into consideration compared to the process of first producing a certain amount of slurry.

  In step (i), the reinforcing fiber bundle is input transversely with respect to the take-up direction of the papermaking base material, and the reinforcing fiber bundle is input in a range of 80 to 100% with respect to the width of the papermaking tank. It is preferable.

  By setting it as this aspect, since raw material supply is made | formed in the wide range in the width direction of a papermaking base material, there exists an effect in suppression of the fabric weight variation in the width direction of the papermaking base material obtained.

  The said aspect is demonstrated in detail using FIG.

  Transversely with respect to the take-up direction 2 of the papermaking substrate is not particularly limited as long as it crosses the take-up direction 2, but is preferably within a range of 45 to 135 ° with respect to the take-up direction (FIG. 1a). It is more preferable that it is orthogonal (90 °) (FIG. 1b).

  The input range 3 is preferably in the range of 80 to 100% with respect to the width 4 of the papermaking tank 1, and more preferably 100% with respect to the width of the papermaking tank. The width of the papermaking tank means the shortest distance among the distances connecting the side wall surfaces 5 and 5 'in the width direction of the papermaking tank on the slurry liquid surface 6 in the papermaking tank. The papermaking tank is usually rectangular and has a certain width in the take-up direction, but when the width is different in the take-up direction, the width of the papermaking tank at the position where the reinforcing fiber bundle is introduced is used as a reference. .

  Also, the shape of the input range is not particularly limited, and may be rectangular, parallelogram or rhombus (FIGS. 1a and 1b), circular (FIG. 1c), or independent. The ranges may be parallel or interspersed (FIG. 1d).

  In the step (i), it is preferable that the distance L between the draining position P1 for scooping up the reinforcing fiber from the slurry (a) in the step (iii) and the feeding position P2 of the reinforcing fiber bundle in the step (i) is 10 mm or more.

  By setting it as this aspect, time arises from injection | throwing-in of a reinforcement fiber bundle, and raising, and since the dispersion | distribution time of the reinforcement fiber in a slurry is ensured, the dispersion state of a slurry can be made favorable.

  The relationship between the draining position P1, the charging position P2, and the distance L is shown in FIGS. 2a and 2b.

  Here, the charging position P2 means a position closest to the draining position at a position where the charged reinforcing fiber bundle falls on the slurry liquid surface 6. The draining position P1 refers to the input position P2 among the boundary 7 between the slurry liquid surface and the papermaking substrate, which is generated when the dispersion medium is removed from the slurry in step (iii) to obtain a papermaking substrate containing reinforcing fibers. It means the closest position. Further, a distance between the draining position P1 and the charging position P2 is set as a distance L.

  The distance L can also be a space for carrying out the means (FIG. 2b) when a means for dispersing reinforcing fibers (stirrer 8 in the figure) is provided in the step (ii) described later.

  The distance L may be arbitrarily adjusted depending on, for example, the basis weight of the papermaking substrate to be manufactured. If the basis weight is small (the amount of the reinforcing fiber bundle is small), it may be 10 mm or more, and the basis weight is large (reinforced fiber). 100 mm or more is preferable, and 1000 mm or more is more preferable. The upper limit value of the distance L is not particularly limited, but is usually 10,000 mm or less from the viewpoint of expansion of equipment scale, increase of manufacturing time, and deterioration of dispersion state (reaggregation).

  In step (i), it is preferable that the feeding speed of the reinforcing fiber bundle is substantially constant. Here, the input speed is the input amount of the reinforcing fiber bundle per unit time and is expressed in units of kg / min. By making the input speed substantially constant, it is possible to suppress uneven dispersion of the reinforcing fibers in the slurry, uneven dispersion in the longitudinal direction of the papermaking substrate, and unevenness in the basis weight, thereby stabilizing the process and stabilizing the quality. Connected.

  The input rate is “substantially constant” means that the coefficient of variation (CV value) of the input rate per unit time is within 10% during the manufacturing time of the papermaking substrate. As a method for measuring the input speed, for example, the input speed can be calculated from the initial weight of the container in which the reinforcing fiber bundle to be input is stored and the reduced amount of the weight of the container after a unit time (for example, 1 minute) has elapsed. Furthermore, by monitoring the charging speed through the manufacturing time, the average charging speed during the manufacturing time can be calculated, and the coefficient of variation is calculated from each data.

  Furthermore, it is preferable that the reinforcing fiber bundle is input with a time difference within the input range.

  By adopting such an embodiment, it is possible to prevent the subsequent reinforcing fiber bundles from being input in a state where the input of the reinforcing fiber bundles does not concentrate locally and the unopened reinforcing fiber bundle remains on the liquid surface. it can. In particular, it is effective when the basis weight of the papermaking substrate to be produced is large (the amount of the reinforcing fiber bundle is large).

  An example of charging the reinforcing fiber bundle will be described in detail with reference to FIGS. Hereinafter, an example in which the reinforcing fiber bundle 9 is charged into the charging range 3 at a charging speed of 16 kg / min.

  In the case of charging without a time difference, the reinforcing fiber bundle is continuously charged at the charging speed of 1 kg / min in each of the sections 3-1 to 3-16 of the charging range 3 (FIG. 3a). On the other hand, as an example of the case where the charging is performed with a time difference, a case where the charging range 3 is divided into four sections 3-17 to 3-20 is illustrated. Each compartment is intermittently charged at a charging speed of 4 kg / min (FIG. 3b), and the charging time per one time for that section is 1 second. One or more sections are not thrown in, and one or more sections are always thrown in, while keeping one or more sections unfilled. In this case, the total charging time per section is 15 seconds per minute, and the charging speed in the charging range is 16 kg / min.

  Here, “intermittently input” means that when seeing the moment when the reinforcing fiber bundle is input, the reinforcing fiber bundle is input only in at most three of the respective sections. Because. In other words, when viewed in the entire input range, the reinforcing fiber bundle is continuously input. However, when viewed in each section, at least one section where the reinforcing fiber bundle is not input is at least one section. It means that it exists. That is, when viewed in each section, there is a time difference in feeding the reinforcing fiber bundle.

  As an input example, in addition to the above, the sections may be divided and input in a direction perpendicular to the paper-making substrate take-up direction (FIG. 3c), or the input range may be input obliquely across the input range. It may be good (FIG. 3d), or may be randomly entered in units of straw (FIG. 3e). The input range may be input to the entire input range (FIGS. 3b and c), or may be input locally to the input range (FIG. 3d and e), preferably the former, By making it wide, the input amount per unit area can be reduced, which leads to an improvement in the dispersibility of the reinforcing fibers. Further, the charging speed may be constant or different for each ridge and / or section, but it is preferably constant, and the dispersion state of the slurry and the resulting papermaking substrate Dispersion unevenness and basis weight variation can be suppressed.

  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. Among these, carbon fibers are preferable because they are excellent in specific strength and specific elastic modulus and are effective in reducing the weight of the FRP molded body.

  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 reinforcing fiber bundle may be either a continuous reinforcing fiber or a discontinuous reinforcing fiber. In order to achieve a better dispersion state, a discontinuous reinforcing fiber is used. A bundle is preferred, and chopped fibers are more preferred. Especially, it is preferable that a reinforcing fiber bundle is a fiber bundle (carbon fiber bundle) comprised by carbon fiber, and it is more preferable that it is a chopped carbon fiber.

  In the present invention, the surface oxygen concentration O / C of the carbon fiber is preferably 0.1 to 0.3. By setting the surface oxygen concentration O / C of the carbon fiber in such a range, the interaction with the matrix resin can be enhanced, and when viewed as a carbon fiber bundle, there is an effect of improving convergence. In the manufacture of a papermaking base material, carbon fibers are cut in advance into chopped carbon fibers, and then dispersed in a dispersion medium to make paper. That is, focusing is important from the viewpoint of cutting into chopped carbon fibers and handling of chopped carbon fibers. The fiber length may be longer than a predetermined length.

  Here, the surface oxygen concentration can be adjusted mainly by the electrolytic treatment amount of the surface oxidation treatment. As a method of surface participation treatment, it may be performed in either a liquid phase or a gas phase, but the method of oxidation treatment using carbon fiber as an anode in an aqueous electrolyte solution is said to be simple and reduce the strength of carbon fiber. Preferred from the advantages. Although it does not specifically limit as an electrolytic treatment liquid, For example, a sulfuric acid, ammonium carbonate, etc. are mentioned. Here, as the amount of electrolytic treatment, in order to minimize damage to the carbon fiber, the range of 0 (no treatment) to 100 coulomb per gram of carbon fiber can be exemplified as an appropriate amount of electrolytic treatment.

  The surface oxygen concentration of the carbon fiber can be obtained by X-ray photoelectron spectroscopy, and a specific method is exemplified in the examples.

Further, the carbon fiber preferably has a surface free energy γ ₀ measured by the Wilhelmi method of 40 to 60 mJ / m ² , and by setting the carbon fiber in such a range, the carbon fiber in the dispersion medium, particularly in the aqueous medium. The spreadability can be increased. The surface free energy γ ₀ is more preferably 45 to 60 mJ / m ² , and further preferably 50 to 60 mJ / m ² .

  Here, the surface free energy measured by the Wilhelmi method can be obtained using an approximate expression of Owens-Wendt based on each contact angle measured by the Wilhelmi method. An approximate expression of Owens-wentt is shown below.

Assign the contact angle θ for at least two types of liquids, the surface tension γ _l (eigenvalue) of each liquid, the polar component γ _lp (eigenvalue) of the surface tension, and the nonpolar component γ _ld (eigenvalue) of the surface tension to the following formula: The binary linear equation of the polar component γ _sd and the nonpolar component γ _sp of the surface free energy of the specimen is established.

γ _l (1 + cos θ) = 2 (γ _sd · γ _ld ) ^0.5 +2 (γ _sp · γ _lp ) ^0.5
From γ _sd and γ _sp , the surface free energy γ ₀ = γ _sd + γ _sp used in the present invention can be obtained.

That is, by maintaining the surface oxygen concentration (O / C) of the carbon fiber and the surface free energy γ ₀ measured by the Wilhelmi method within the above ranges, the shape of the carbon fiber is maintained during handling prior to the manufacture of the papermaking substrate. This is preferable because it is possible to achieve both a convergence property for the purpose of carrying out and a paper-making process and excellent fiber opening properties for promptly dispersing into a single fiber and suppressing reaggregation.

  In addition, the number of single fibers constituting the reinforcing fiber bundle is preferably 12,000 or more, more preferably 48,000 or more, from the viewpoint of productivity. If the upper limit of the number of single fibers is 100,000 or less in consideration of the balance between dispersibility and handleability, the dispersibility and handleability can be kept good.

  The length of the reinforcing fiber bundle is preferably 1 to 50 mm, more preferably 3 to 30 mm, from the viewpoint of efficiently exerting the reinforcing effect by the reinforcing fibers and from the viewpoint of maintaining good dispersion in the slurry. preferable. 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. And measure.

  The amount of the reinforcing fiber bundle added to 1 liter of water (dispersion medium) is usually 0.01 g to 10 g, preferably 0.1 g to 5 g. 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.

  In the step (i), the second reinforcing fiber may be dispersed in advance in the dispersion medium. The second reinforcing fiber may be the same fiber as the reinforcing fiber (hereinafter referred to as the first reinforcing fiber. In the case where only the reinforcing fiber is described, the first reinforcing fiber is referred to). Well, different fibers may be used. The type and form of the second reinforcing fiber are also selected from the same range as the first reinforcing fiber listed above.

  When the second reinforcing fiber dispersed in advance in the dispersion medium is the same as the first reinforcing fiber, the input amount of the reinforcing fiber bundle to be input in the step (i) can be reduced. Since dispersion becomes easy, it is particularly effective in producing a papermaking substrate having a large basis weight. When the second reinforcing fiber is different from the first reinforcing fiber, in the fiber reinforced resin molded body molded from the obtained paper making base material or paper making base material, by selecting the characteristics of the reinforcing fiber to be used as necessary Desirable characteristics such as handleability, moldability, conductivity, thermal characteristics, mechanical characteristics, and the like can be imparted.

  In step (i), organic fibers and / or organic particles may be dispersed in advance in the dispersion medium.

  The organic fibers and / or organic particles are preferably a thermoplastic resin.

Examples of the thermoplastic resin include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PENp), polyester resins such as liquid crystal polyester, polyethylene (PE), polypropylene ( PP), polyolefins such as polybutylene, acid-modified products thereof, styrene resins, urethane resins, polyoxymethylene (POM), polyamide (PA), polycarbonate (PC), polymethyl methacrylate (PMMA), polyvinyl chloride (PVC), polyphenylene sulfide (PPS), polyphenylene ether (PPE), modified PPE, polyimide (PI), polyamideimide (PAI), polyetherimide (PEI), polysulfone (PS) ), Modified PSU, polyethersulfone (PES), polyketone (PK), polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), polyarylate (PAR), polyethernitrile ( PEN), phenolic resins and phenoxy resins.
Among these, when organic fibers and / or organic particles are used as a matrix resin, a polyamide resin is preferable from the viewpoint of mechanical properties, a polypropylene resin is preferable from the viewpoint of lightness, and a PPS resin is more preferable from the viewpoint of heat resistance.

  In step (ii), the slurry is adjusted to a slurry (a) in which reinforcing fibers are dispersed in a dispersion medium. Step (ii) is performed in the same papermaking tank as in step (i) described above.

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

  Adjusting to a slurry is to disperse the reinforcing fiber bundle charged into the dispersion medium in the step (i) in the dispersion medium to a single fiber level of the reinforcing fiber, and a desired dispersion state, containing the mass of the reinforcing fiber. Means to form a quantity.

Examples of the means for dispersing the reinforcing fiber bundle include opening property of the reinforcing fiber bundle itself, liquid flow of the dispersion medium, and stirring by an external force, and are performed by at least one of them. In particular, when the mass content of the target reinforcing fiber is rich, the reinforcing fiber bundle may be dispersed by combining a plurality of means.
The spreadability of the reinforcing fiber bundle itself means a property for quickly dispersing into a single fiber when the fiber bundle is put into a dispersion medium and suppressing reaggregation. Dispersion capacity. By using a method for modifying the surface state of the reinforcing fiber or a method for imparting a treatment agent for improving dispersion to the reinforcing fiber, the opening property of the reinforcing fiber bundle itself can be improved. The liquid flow of the dispersion medium is to disperse the reinforcing fiber bundle using the flow of the dispersion medium supplied or circulated to the papermaking tank. Laminar flow, turbulent flow, vortex, and the like are arbitrarily adjusted by a dispersion medium feeding means, and the reinforcing fiber bundle is dispersed by applying a shearing force.
Stirring by external force is a stirrer equipped with power, a fixed obstacle such as a rod-like body or plate-like body, injection of fluid (gas, liquid), ultrasonic irradiation, etc. Good.

  As for the dispersion state of the reinforcing fiber, it is ideal that all of the reinforcing fibers contained in the dispersion medium are dispersed in a single fiber shape, but the state intended for dispersion here is limited to this. It is not something. The specific evaluation method and index of the dispersion state will be exemplified in the examples.

  The mass content (solid content concentration in the slurry) of the reinforcing fibers in the slurry (a) prepared in the step (ii) is preferably 0.001 to 1 mass%, and 0.01 mass% to 0.00. More preferably, it is 5 mass%. By being in the above range, the dispersion state of the reinforcing fibers can be kept good, and papermaking can be performed efficiently.

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

  Step (iii) is performed in the same papermaking tank as the above-described steps (i) and (ii). The papermaking tank has a papermaking surface capable of sucking the dispersion medium, and is generally arranged near the bottom surface of the papermaking tank. Examples of the papermaking material include woven fabric, non-woven fabric, and mesh sheet.

  The resulting papermaking substrate is in a state where the reinforcing fibers are entangled with each other and can be handled as a substrate. However, when the basis weight of the papermaking substrate is small, there is little entanglement between the reinforcing fibers, so that it is difficult to maintain the form as the substrate. In this case, the form can be maintained by aligning and handling the support as the lower surface of the papermaking substrate. The support is not particularly limited as long as it can be handled as a sheet, and can be selected from various forms such as a nonwoven fabric, a film, a mat, a mesh, a woven fabric, and a knitted fabric.

In consideration of the above, the basis weight of the resulting papermaking base material is to prevent tearing when taking up or handling the papermaking base material. from the viewpoint of good, it is preferably 10 to 500 g / ^{m 2,} and more preferably 50 to 300 g / ^{m 2.}

  In the present invention, the time required from the step (i) to the step (iii) is within 5 minutes from the viewpoint of enhancing the productivity of the papermaking substrate and suppressing the reaggregation of the reinforcing fibers dispersed in the slurry. It is preferable. Strictly speaking, the time required from the start of step (i) to the completion of step (iii) is within 5 minutes. More preferably, it is within 3 minutes, More preferably, it is within 1 minute. The lower limit of the time required from step (i) to completion of step (iii) is not particularly limited, but is usually 30 seconds or longer.

  In step (iv), the papermaking substrate obtained in step (iii) is taken up.

  The step (iv) is performed in various facilities capable of taking up the papermaking surface provided in the same papermaking tank as in the above steps (i) to (iii) and the papermaking substrate following the papermaking surface.

  The papermaking tank has a continuously moving papermaking surface, and the resulting papermaking substrate can be taken up on the papermaking surface by continuing from the step (iii). That is, as the positional relationship between reference numerals 1 and 12 in FIGS. 4, 7, and 8 indicates, some of the steps that contribute to taking the papermaking substrate obtained in step (iii) are the above-described steps (i) to (iii). ) In the same papermaking tank. Furthermore, by providing a conveyor belt, a winder, etc., exemplified by reference numerals 13, 15, and 16 in FIGS. The papermaking substrate can be taken up.

  The taken papermaking substrate can be wound into a roll, folded for each unit length, cut for each unit length, and adjusted to various forms according to the use of the papermaking substrate, basis weight, etc. .

  The take-up speed is preferably 1 to 30 m / min, and more preferably 15 to 30 m / min. By taking it within such a range, it is possible to obtain a process having an excellent balance of productivity, process stability and quality stability.

  In the manufacturing method of the papermaking base material of this invention, in addition to process (i)-(iv) mentioned above, the following processes may be included.

  When the second reinforcing fiber or the organic fiber and / or the organic particle is dispersed in advance in the dispersion medium, it is preferable to include the following steps before the step (i).

(Pre-i): a step of adjusting the slurry (b) in which the second reinforcing fibers or organic fibers and / or organic particles are dispersed in advance in the dispersion medium (pre-ii): the step (pre-i) A step of transporting the slurry (b) obtained in step 1 to a papermaking tank.

  The step (pre-i) is adjusted to a slurry (b) in which the second reinforcing fibers or organic fibers and / or organic particles are dispersed in advance in the dispersion medium.

  The adjustment of the slurry (b) is carried out in a dispersion tank provided separately from the papermaking tank. The dispersion tank is a tank (container) that can contain the slurry (b). The dispersion tank may include a means for dispersing the above-described reinforcing fibers as necessary.

  In the step (pre-i), the slurry (b) in an amount necessary for production may be prepared in advance, but preferably the slurry (b ) To adjust. That is, like the above-described slurry (a), it is not necessary to adjust a considerable amount of slurry at a time, and it is difficult to generate a portion having a different dispersion time in the slurry, which is preferable from the viewpoint of suppressing poor dispersion and uneven dispersion. . Therefore, it is preferable to continuously carry out the supply of the raw material into the dispersion medium and the adjustment of the slurry (b) so that the steps (pre-i) are linked to the steps (i) to (iv). By doing so, it is possible to make the process excellent in productivity and process stability.

  In the step (pre-ii), the slurry (b) obtained in the step (pre-i) is transported to a papermaking tank.

  The step (pre-ii) is usually performed in a transport unit that connects the dispersion tank in which the step (pre-i) is performed and the papermaking tank in which the step (i) is performed.

  As a means for transporting the slurry (b), a method of transporting using the power of the liquid feed pump can be mentioned, and a method of transporting from the dispersion tank in which the step (pre-i) is carried out is preferable. Thereby, an extreme shearing force is applied to the second reinforcing fibers in the slurry to be transported to prevent sedimentation and re-aggregation, and the second reinforcing fibers in the slurry can be transported while maintaining a dispersed state. 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.

  The shape of the transport portion is not particularly limited as long as it is a shape capable of transporting the slurry, and is usually tubular. It is preferable that the transport portion has a shape that does not have a direction change point such as a curved portion or a bent portion, that is, a linear shape.

  The transport section is preferably inclined (slider method), and when the transport section is viewed from the horizontal direction, 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. There should be. The inclination is preferably 30 to 60 °, more preferably 40 to 55 °. If the inclination angle is less than 30 °, the transportation in the step (pre-ii) may take a long time. If the inclination angle exceeds 60 °, the flow rate during transportation of the slurry (b) increases, so that excessive shear is applied to the slurry when reaching the step (i), and the slurry (b) is dispersed in the step (iv). The condition may be insufficient. 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 a process (pre-ii) 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 upwards.

  In addition, a plurality of series of papermaking substrate manufacturing processes are provided, and a process (v) in which the papermaking substrates obtained from each of the above series are aligned and laminated at a speed of 1 to 30 m / min is provided, and all processes are continuously performed online. It is preferable to carry out the process from the viewpoint of efficiently producing a substrate having a large basis weight and from the viewpoint of efficiently producing a laminated paper-making substrate comprising a plurality of types of reinforcing fibers.

  Such production steps are the above-described steps (i) to (iv), or steps (pre-i) (pre-ii) and steps (i) to (iv).

  In the step (v), the paper-making bases obtained from each of a plurality of production processes are aligned and laminated at a speed of 1 to 30 m / min.

The papermaking bases obtained from each series may be the same or different, and can be configured as desired depending on the application and purpose. Examples include carbon fiber / glass fiber / carbon fiber, fiber length 5 mm / fiber length 2 mm / fiber length 5 mm, basis weight 250 g / m ² / weight basis 250 g / m ² , etc. Various properties such as the basis weight of the papermaking substrate can be selected.

  The speed at which the papermaking base materials are aligned and laminated is preferably 1 to 30 m / min, and the resulting papermaking base material is prevented from being loosened or excessively tensioned, and the base material is wrinkled or torn. From the standpoint of suppressing, it is preferable that the speed is the same as the take-up speed of the papermaking substrate in the step (iv), and it is preferable that the speed is constant in all the series used.

  Note that the paper making base materials are aligned and laminated is an aspect in which the paper making base materials are taken up so as to overlap each other. Usually, when viewed perpendicular to the surface direction of the papermaking substrate, it is preferable that the centers of the substrate widths to be laminated are on the same axis. However, depending on the intended use, the layers may be intentionally shifted.

  The taken base material may be wound in a roll shape, cut into a predetermined length, folded, or handled in any final form.

  Such step (v) is preferably carried out continuously online with steps (i) to (iv), or steps (pre-i) (pre-ii) and steps (i) to (iv).

  On-line is a system in which each process is continuously performed, and means a process in which each process is performed as a series of flows. A product can be obtained in a short time by performing a series of steps online.

  Furthermore, the following steps can be provided after the step (iv) or (v), and all the steps can be continuously performed online.

(Vi): a step of applying a binder to the obtained paper base material online (vii): a step of drawing the paper base material provided with the binder at a speed of 1 to 30 m / min.

  Step (vi) is a step of applying a binder online to the obtained papermaking substrate.

  The binder has two roles: a role of interposing between the reinforcing fiber and the matrix resin and connecting the two, and a role of improving the handleability as a sheet by binding the reinforcing fibers in the papermaking substrate. . The binder is usually a thermoplastic resin. Examples of the thermoplastic resin include acrylic polymers, vinyl polymers, polyurethanes, polyamides, and polyesters. In the present invention, one or two or more selected from these examples are preferably used. In addition, from the viewpoint of increasing the affinity between the thermoplastic resin and the matrix resin, and from the viewpoint of enhancing the handling property when imparted to the papermaking substrate by increasing the affinity between the thermoplastic resins constituting the binder, It preferably has at least one functional group selected from a hydroxyl group, an amino group, an epoxy group, a carboxyl group, an oxazoline group, a carboxylate group and an acid anhydride group, and may have two or more types. Among these, a thermoplastic resin having a hydroxyl group, a carboxyl group, or an amino group is more preferable.

  The application of the binder to the papermaking substrate is preferably performed in the form of an aqueous solution, emulsion or suspension of a binder (for example, the above thermoplastic resin). An aqueous solution means a solution that is almost completely dissolved in water, and an emulsion means a solution (emulsion) in which two liquids that are not completely dissolved form fine particles in the liquid. Suspension means a solution (suspension) in a state of being suspended in water. The component particle sizes in the liquid are in the order of aqueous solution <emulsion <suspension. The application method is not particularly limited. For example, the method can be carried out by a method of immersing the papermaking substrate in an aqueous solution, emulsion or suspension of a thermoplastic resin, a shower method, or the like. After the application, before the drying step, it is preferable to remove excess binder, for example, by suction or absorption into an absorbent material such as absorbent paper.

  In the step (vi), the papermaking substrate is preferably heated after the binder is applied. Heating is preferable for drying the moisture at the time of applying the binder and for forming a film so that the binder spreads over the entire papermaking substrate. Thereby, the take-up speed in the step (vii) can be increased, and a fiber-reinforced molded substrate can be obtained in a short time. The heating temperature can set suitably the temperature which the papermaking base material after binder provision drys, Preferably it is 100-300 degreeC, More preferably, it is 120-250 degreeC.

  Step (vii) is a step of drawing the papermaking substrate to which the binder has been applied at a speed of 1 to 30 m / min.

  As a speed | rate which takes up the papermaking base material which provided the binder, 1-30 m / min is preferable.

  For the same reason as in step (v), the take-up speed in step (vii) is preferably equal to the take-up speed of the papermaking substrate in step (iv), and is used in the case where step (v) is provided. It is preferable that the speed of all the series is constant, and the speed at which the papermaking substrates in step (v) are aligned and laminated is also constant.

  Such steps (vi) and (vii) are carried out as steps (i) to (iv), or steps (i) to (v), or steps (pre-i) (pre-ii) and steps (i) to (iv). ) Or on-line continuously with steps (pre-i) (pre-ii) and steps (i) to (v).

  Furthermore, the following steps can be provided after the step (iv) or (v) or (vii), and all the steps can be continuously performed online.

(Viii): a step of obtaining a fiber reinforced molded base material by compounding a matrix resin on-line with the obtained paper base material (ix): a step of drawing the fiber reinforced molded base material at a speed of 1 to 30 m / min.

  Step (viii) is a step of obtaining a fiber-reinforced molded base material by combining a matrix resin online with the resulting papermaking base material.

  The matrix resin is preferably a thermosetting resin or a thermoplastic resin. Examples of the thermosetting resin include epoxy resins, unsaturated polyester resins, vinyl ester resins, diallyl phthalate resins, phenol resins, maleimide resins, and cyanate ester resins. Examples of the thermoplastic resin include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PENp), polyester resins such as liquid crystal polyester, polyethylene (PE), polypropylene ( PP), polyolefins such as polybutylene, acid-modified products thereof, styrene resins, urethane resins, polyoxymethylene (POM), polyamide (PA), polycarbonate (PC), polymethyl methacrylate (PMMA), polyvinyl chloride (PVC), polyphenylene sulfide (PPS), polyphenylene ether (PPE), modified PPE, polyimide (PI), polyamideimide (PAI), polyetherimide (PEI), polysulfone (PS) ), Modified PSU, polyethersulfone (PES), polyketone (PK), polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), polyarylate (PAR), polyethernitrile ( PEN), phenolic resins and phenoxy resins. Among these, a thermoplastic resin is preferable from the viewpoint of recyclability and repairability, and among them, a polyamide resin is preferable from the viewpoint of mechanical characteristics, a polypropylene resin is preferable from the viewpoint of light weight, and a PPS resin is more preferable from the viewpoint of heat resistance.

  The matrix resin can be combined with the papermaking substrate by bringing the matrix resin into contact with the papermaking substrate. The form of the matrix resin in this case is not particularly limited. For example, when the matrix resin is a thermoplastic resin, it is preferably at least one selected from a fabric, a nonwoven fabric, and a film, and more preferably a nonwoven fabric. preferable.

  The complexing is preferably performed by pressurization and / or heating, and more preferably both pressurization and heating are performed simultaneously. The pressure condition is preferably 0.01 to 10 MPa, more preferably 0.05 to 5 MPa. The heating condition is preferably a temperature at which the matrix resin to be used can be melted or flowed, and is preferably 50 to 400 ° C., more preferably 80 to 350 ° C. in the temperature range. Pressurization and / or heating can be performed in a state where the matrix resin is in contact with the papermaking substrate. For example, a matrix resin fabric, non-woven fabric or film may be disposed on the upper and lower surfaces of the papermaking substrate, and heated and / or heated from both sides (a method of sandwiching with a double belt press device, etc.).

  In addition, when the organic fiber and / or organic particle used as the matrix resin is already included in the papermaking substrate in the steps (iv) to (v), it is not necessary to separately prepare the matrix resin to be combined. The material may be directly combined.

  The papermaking base material to be combined is not particularly limited as long as it is a papermaking base material obtained in the step (iv), (v) or (vii). From the viewpoint of the mechanical properties of a molded product obtained by molding a material or a fiber-reinforced molded substrate, a papermaking substrate to which a binder obtained in the step (vii) is applied is preferable.

  Step (ix) is a step of pulling the fiber reinforced molded substrate at a speed of 1 to 30 m / min.

  The speed at which the fiber-reinforced molded substrate is taken up is 1 to 30 m / min.

  For the same reason as in step (vii), the take-up speed in step (iv) is preferably equal to the take-up speed of the paper-making substrate in step (iv), and further, the paper-making base material in step (vii) It is preferable that the take-up speed is constant, and in the case where the step (v) is provided, the speed is constant in all the series used, and the speed at which the paper-making base materials in the step (v) are aligned and laminated is equal. It is preferable that the speed is high.

  The taken-up fiber reinforced molded substrate may be wound into a roll, cut into a predetermined length, folded, or handled in any final form.

  Such steps (viii) and (ix) may be carried out in steps (i) to (iv), or steps (i) to (v), or steps (i) to (vii), or steps (pre-i) (pre- ii) and steps (i) to (iv), or steps (pre-i) (pre-ii) and steps (i) to (v), or steps (pre-i) (pre-ii) and steps (i ) To (vii) are preferably carried out continuously online.

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

  Hereinafter, the present invention will be described in more detail with reference to examples. In addition, the raw material used for the Example is as follows.

Reinforcing fiber A1 (PAN-based carbon fiber)
Reinforcing fiber A1 was manufactured as follows.

  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 was obtained.

Total number of filaments: 12,000 Single fiber diameter: 7 μm
Mass per unit length: 0.8 g / m
Specific gravity: 1.8 g / cm ³
Tensile strength (Note 1): 4.2 GPa
Tensile modulus (Note 2): 230 GPa
O / C (Note 3): 0.10
γ ₀ (Note 4): 43 mJ / m ²
Sizing type: Polyoxyethylene oleyl ether Sizing adhesion amount (Note 5): 1.5% by mass.

Reinforcing fiber A2 (PAN-based carbon fiber)
Reinforcing fiber A2 was manufactured as follows.

  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. In addition, the sizing agent was not provided.

Total number of filaments: 12,000 Single fiber diameter: 7 μm
Mass per unit length: 0.8 g / m
Specific gravity: 1.8 g / cm ³
Tensile strength (Note 1): 4.2 GPa
Tensile modulus (Note 2): 230 GPa
O / C (Note 3): 0.05
γ ₀ (Note 4): 35 mJ / m ² .

Organic fiber B1 (acid-modified polypropylene resin)
The organic fiber B1 was manufactured by extruding “Admer (registered trademark)” QE510 manufactured by Mitsui Chemicals, Inc. at 230 ° C. and processing it into a fiber shape. The physical properties are as follows.

Specific gravity: 0.91
Fiber diameter: 50 μm
Melting point: 160 ° C.

Matrix resin C1 (nylon 6 resin)
As the matrix resin C1, “Amilan (registered trademark)” CM1001 manufactured by Toray Industries, Inc. was used. The physical properties are as follows.

Specific gravity: 1.13
Melting point: 225 ° C.

Binder D1
The binder component constituting the binder D1 was prepared by the following procedure.

  A 1 L four-necked flask equipped with a stirrer, temperature sensor, reflux condenser, and monomer dropping port was charged with 137.4 g of Table 1 ion-exchanged water, degassed, and nitrogen gas bubbling was repeated several times to obtain a dissolved oxygen concentration of 2 mg / After deoxygenating to L or less, temperature increase was started. In the subsequent emulsion polymerization process, nitrogen gas blowing was continued.

  100 g of acrylic monomer mixture of 35.0 g of methyl methacrylate (MMA), 54.0 g of n-butyl methacrylate (BMA), 1.0 g of methacrylic acid (MA), 10.0 g of 2-hydroxyethyl methacrylate (HEMA) , "Adeka Resorb SR-1025" (Adeka Co., Ltd., reactive emulsifier, 25% aqueous solution) 8.0 g and ion-exchanged water 39.7 g for pre-emulsion production were mixed and emulsified for 10 minutes at 10,000 revolutions on an emulsifier. And a pre-emulsion was produced.

  When the temperature in the flask reached 75 ° C. of the polymerization temperature, 10 wt% (14.8 g) of the pre-emulsion was added. When the temperature in the flask recovered to 75 ° C., the polymerization temperature, 0.2 g of ammonium persulfate as a polymerization initiator was added, and then emulsion polymerization was performed at 75 ° C. for 1 hour.

  The remaining 90 wt% (132.9 g) of the pre-emulsion was dropped into the flask in 3 hours. After completion of the dropwise addition, polymerization was carried out at 75 ° C. for another 30 minutes, and then the temperature was raised to 80 ° C. in 30 minutes to conduct an aging reaction. It was. After 30 minutes of temperature increase, 0.020 g of ammonium persulfate and 0.400 g of ion-exchanged water were added. Then, 30 minutes later, 0.010 g of ammonium persulfate and 0.200 g of ion-exchanged water were further added. An aging reaction was performed and cooled.

  Cool to 40 ° C. or lower, add 0.05 g of “Adecanate B-1016” (Adeka Co., Ltd. antifoam), stir and mix for another 30 minutes, dilute 0.47 g of 25% aqueous ammonia An emulsion containing 15.0% by mass of an acrylic polymer was prepared by adding 393.5 g of ion exchange water for use.

(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 carbon fiber resin-impregnated strand 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 C1s was adjusted to 1202 cV as a peak correction value accompanying 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) Surface free energy of carbon fiber Measured by the Wilhelmi method according to the following procedure. In the present example, DCAT11 manufactured by Data Physics was used as a contact angle measuring device, and FH12 (a flat plate whose surface was coated with an adhesive substance) was used as a sample holder. After cutting eight carbon fiber single fibers as a sample into a length of 12 mm, the carbon fibers were attached to a dedicated holder FH12 in parallel so that the distance between the single fibers was 2 to 3 mm. Next, the tips of the single fibers were cut and the holder was set on DCAT11. The measurement was performed by bringing a cell containing purified water and each liquid medium into close proximity to the lower ends of the eight single fibers at a speed of 0.2 mm / s and immersing them from the tip of the single fibers to 5 mm, and then 0.2 mm / s. The single fiber was pulled up at a speed of. This operation is repeated four times or more, and when immersed in an aqueous solution, that is, when the single fiber is moving forward, the force F received by the single fiber is measured with an electronic balance, and this value is used to make a contact from The angle θ was calculated.
COSθ = (force F (mN) applied to eight single fibers) / ((8 (number of single fibers) × circumference of single fibers (m) × surface tension of liquid (mJ / m ² ))
Here, in the calculation of the contact angle θ, an average value of 1 to 4 times is usually used, but in the present example, the contact angle obtained in the first measurement was calculated as the first contact angle. . This is because when the component having high solubility in the liquid medium such as purified water adheres, the surplus adhering component is eluted in the liquid, so that it is more accurate to calculate the first contact angle.

  The measurement was carried out on single fibers extracted from three places with different carbon fiber bundles. That is, the average value of the contact angles for a total of 24 single fibers per one carbon fiber bundle was determined.

According to the above procedure, each contact angle measured by the Wilhelmi method for each liquid medium of water, ethylene glycol, and tricresol phosphate was calculated. Based on such numerical values, the surface free energy γ ₀ and the polar component γ _0P of the surface free energy were calculated using the following Owens approximate expression. The approximate expression of Owens (the polar component and the nonpolar component of the surface tension specific to each liquid, and the formula constituted by the contact angle θ) is the component of the surface tension of each liquid medium (a value specific to each medium), After substituting the contact angle and plotting it in X and Y, it was obtained by the square of the slope a and the intercept b when linearly approximating by the least square method.

Y = a · X + b
X = (polar component of liquid surface tension (mJ / m ² )) ^0.5 / (nonpolar component of liquid surface tension (mJ / m ² )) ^0.5
Y = ((1 + cos θ) · (liquid surface tension (mJ / m ² )) / 2 (nonpolar component of liquid surface tension (mJ / m ² )) ^0.5
γ _0P (mJ / m ² ) = a ²
γ ₀ (mJ / m ² ) = a ² + b ² .

The polar component and nonpolar component of the surface tension of each liquid medium are as follows using the following eigenvalues.
Purified water (PW): surface tension 72.8 mJ / m ² , polar component 51.0 mJ / m ² , nonpolar component 21.8 mJ / m ²
Ethylene glycol (EG): surface tension 48.0 mJ / m ² , polar component 19.0 mJ / m ² , nonpolar component 29.0 mJ / m ²
Tricresol phosphate (TP): surface tension 40.9 mJ / m ² , polar component 1.7 mJ / m ² , nonpolar component 39.2 mJ / m ² .

(Note 5) Measuring 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 being cooled 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.

Adhesion amount (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 papermaking substrate obtained in each example are as follows.

-Steps (i) to (iii) Time required Step (i) is the time from when the reinforcing fiber is introduced into the dispersion medium in step (i) until the papermaking substrate comes out of the slurry liquid surface in step (iii). It was measured as the required time of ~ (iii).

・ Real manufacturing time (T1)
The time from when the papermaking base material or the fiber reinforced molding base material arrived at the winder until the manufacturing of a predetermined amount of the base material was completed was measured as a substantial manufacturing time (T1).

・ Non-manufacturing time (T2)
The time required for manufacturing preparation and product switching, excluding the T1, was measured as non-manufacturing time (T2). In addition, when including processes other than process (i)-(iv), the time required for this process was excluded and counted.

-Man-hour required It calculated with the product of the number of operators required for process (i)-(iv), real manufacturing time (T1), and non-manufacturing time (T2). The number of operators was one for each facility, one for each of the dispersing tank, papermaking tank, and winder.

-Dispersion state of reinforcing fiber The base material was cut out in a square shape of 50 mm x 50 mm from an arbitrary part of the paper-making base material obtained in the step (iv) 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. The measurement was performed 20 times by such a procedure, and classification was performed from the average value by the following indices A to C. In particular, when the dispersion state was excellent (less than one carbon fiber bundle with insufficient dispersion), it was positioned as A +.
A +: Less than 1 carbon fiber bundle with insufficient dispersion A: 1 to less than 5 carbon fiber bundles with insufficient dispersion B: 5 to 10 carbon fiber bundles with insufficient dispersion Less than C: 10 or more carbon fiber bundles with insufficient dispersion.

-Fabrication stability in the width direction Three strip-shaped base materials having a length of 50 mm in the longitudinal direction are cut out from an arbitrary position in the longitudinal direction (production direction) of the papermaking substrate (effective width: 500 mm) obtained in the step (iv). . Cut out the base material in a square shape of 50 mm x 50 mm centering on a point of 100 mm, 250 mm, or 400 mm in the width direction (long side direction) of the cut base material in the width direction (long side direction), totaling 9 sheets Was measured with a precision balance with one decimal place as the effective digit. The CV value (%) was calculated from the average value and the individual value of the obtained weight, and the basis weight stability in the width direction was classified from the range of the CV value as follows.
A: CV value is less than 5% B: CV value is 5% or more and less than 8% C: CV value is 8% or more.

-Longitudinal basis weight stability Center point in the width direction (manufacturing direction) of the papermaking substrate (effective width: 500 mm) obtained in step (iv) (position 250 mm from one end in the widthwise direction of the papermaking substrate) Above, 9 base materials are cut out in a 50 mm × 50 mm square shape. About the cut-out base material, the weight measured with the precision balance to one decimal place as an effective digit was measured. The CV value (%) was calculated from the average value and the individual value of the obtained weight, and the basis weight stability in the longitudinal direction was classified from the range of the CV value as follows.
A: CV value is less than 5% B: CV value is 5% or more and less than 8% C: CV value is 8% or more.

Example 1
A papermaking substrate was produced using the apparatus shown in FIG. 4 includes a large square sheet machine (No. 2553-I (trade name), manufactured by Kumagai Riki Kogyo Co., Ltd.) as the papermaking tank 1, and a papermaking surface 10 having a width of 500 mm is provided at the bottom of the papermaking tank 1. A mesh conveyor 11 is provided. At the end of the papermaking tank 1, a conveyor 13 provided with a polypropylene guide cloth 18 capable of transporting the papermaking base material 12 is provided in connection with the mesh conveyor 11, followed by a mesh provided with a dryer 14. Connected to the conveyor 15. Furthermore, a winder 16 capable of winding the dried papermaking substrate 12 is provided at the end point of the apparatus.

First, the reinforcing fiber A2 was cut to 6.4 mm with a cartridge cutter while applying water to obtain chopped reinforcing fiber (A2-1) containing water. The mass content of water was adjusted to be 25% of the total weight of the chopped reinforcing fiber containing water. A dispersion medium 17 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)) is continuously supplied to the papermaking tank at a supply rate of 375 kg / min. In this state, A2-1 (chopped reinforcing fiber) was continuously charged at a charging speed of 0.015 kg / min. At this time, the distance L between the draining position P1 and the feeding position P2 in the papermaking tank was 100 mm, and the feeding range of the reinforcing fiber bundle was 50% in the width direction of the papermaking tank. In addition, A2-1 was manually charged, speed control was not performed, and there was no time difference within the charging range. (Process (i))
Next, a slurry having a solid component concentration of 0.004% by weight was adjusted in a papermaking tank. (Step (ii))
Next, the dispersion medium was sucked and removed from the paper making surface provided in the paper making tank, and the dispersion medium was rolled up by a mesh conveyor to obtain a paper making base material 12. (Process (iii))
The obtained papermaking substrate was placed on the guide cloth 18 by the conveyor 13, and further passed through a dryer at 130 ° C. by the conveyor 15, and wound in a roll together with the guide cloth by a winder. . The take-up speed at this time was 3 m / min. (Process (iv))
In this example, steps (i) to (iv) were online, and a papermaking substrate was continuously produced.

The obtained paper base material had a basis weight of 10 g / m ² and an effective width of 500 mm. About this papermaking base material, 250 m ² was manufactured, wound into a roll shape every 100 m, and the raw material was switched.

  About the above, the implementation conditions in each process and the evaluation result of the obtained papermaking base material were shown in Table 1.

(Example 2)
A papermaking substrate was obtained in the same manner as in Example 1 except that the feeding rate of the reinforcing fiber bundle was 0.075 kg / min and the solid content concentration of the slurry was 0.02 wt%.

The resulting papermaking substrate had a basis weight of 50 g / m ² and an effective width of 500 mm. About this papermaking base material, 250 m ² was manufactured, wound into a roll shape every 100 m, and the raw material was switched.

  About the above, the implementation conditions in each process and the evaluation result of the obtained papermaking base material were shown in Table 1.

(Example 3)
A papermaking substrate was obtained in the same manner as in Example 2 except that the input range of the reinforcing fiber bundle was 90% in the width direction of the papermaking tank.

The resulting papermaking substrate had a basis weight of 50 g / m ² and an effective width of 500 mm. About this papermaking base material, 250 m ² was manufactured, wound into a roll shape every 100 m, and the raw material was switched.

  About the above, the implementation conditions in each process and the evaluation result of the obtained papermaking base material were shown in Table 1.

Example 4
A papermaking substrate was obtained in the same manner as in Example 3 except that an electronically controlled feeder was used so that the feeding speed of the reinforcing fiber bundle was constant.

The resulting papermaking substrate had a basis weight of 50 g / m ² and an effective width of 500 mm. About this papermaking base material, 250 m ² was manufactured, wound into a roll shape every 100 m, and the raw material was switched.

  About the above, the implementation conditions in each process and the evaluation result of the obtained papermaking base material were shown in Table 1.

(Example 5)
A papermaking substrate was obtained in the same manner as in Example 4 except that a spirally grooved roll was provided at the supply port so that the reinforcing fiber bundle had a time difference within the input range.

The resulting papermaking substrate had a basis weight of 50 g / m ² and an effective width of 500 mm. About this papermaking base material, 250 m ² was manufactured, wound into a roll shape every 100 m, and the raw material was switched. About the above, the implementation conditions in each process and the evaluation result of the obtained papermaking base material were shown in Table 1.

(Example 6)
A papermaking substrate was obtained in the same manner as in Example 5 except that the reinforcing fiber used was the reinforcing fiber A1.

The resulting papermaking substrate had a basis weight of 50 g / m ² and an effective width of 500 mm. About this papermaking base material, 250 m ² was manufactured, wound into a roll shape every 100 m, and the raw material was switched.
About the above, the implementation conditions in each process and the evaluation result of the obtained papermaking base material were shown in Table 1.

(Example 7)
A papermaking substrate was obtained in the same manner as in Example 6 except that the distance L between the draining position P1 and the charging position P2 in the papermaking tank was 500 mm, and the stirrer 8 was installed between P1 and P2 (FIG. 5).

The resulting papermaking substrate had a basis weight of 50 g / m ² and an effective width of 500 mm. About this papermaking base material, 250 m ² was manufactured, wound into a roll shape every 100 m, and the raw material was switched. About the above, the implementation conditions in each process and the evaluation result of the obtained papermaking base material were shown in Table 1.

(Example 8)
A papermaking substrate was obtained in the same manner as in Example 7 except that the feeding rate of the reinforcing fiber bundle was 0.15 kg / min and the solid content concentration of the slurry was 0.04 wt%.

The obtained papermaking substrate had a basis weight of 100 g / m ² and an effective width of 500 mm. About this papermaking base material, 250 m ² was manufactured, wound into a roll shape every 100 m, and the raw material was switched.

  About the above, the implementation conditions in each process and the evaluation result of the obtained papermaking base material were shown in Table 1.

Example 9
A papermaking substrate was produced using the apparatus shown in FIG. FIG. 6 includes a cylindrical dispersion tank 19 having a diameter of 700 mm, and includes a linear transport section (inclination angle 45 °) 20 that connects the dispersion tank 19 and the papermaking tank 1. A stirrer 8 is attached to the upper surface opening of the dispersion tank 19, and the raw material can be charged from the opening. The equipment after the papermaking tank 1 was the same as in FIG.

First, the organic fiber B1 was cut into 3.0 mm with a cartridge cutter to obtain a chopped organic fiber (B1-1). Continuously supply a dispersion medium 17 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)) at a supply rate of 566 kg / min. In this state, B1-1 (chopped organic fiber) was continuously charged at a charging rate of 0.303 kg / min. These were stirred with a stirrer to prepare a slurry (b) having a solid component concentration of 0.05% by weight. (Process (pre-i))
The obtained slurry (b) was continuously supplied to the papermaking tank via the transport section. (Process (pre-ii)
Then, it continued to process (i)-(iv). For steps (i) to (iv), A1-1 (chopped reinforcing fiber) is continuously added to the slurry (b) supplied to the papermaking tank at a charging rate of 0.15 kg / min, and the solid content in the slurry A papermaking substrate was obtained in the same manner as in Example 8 except that the concentration was 0.08% by weight.

  In this example, steps (pre-i) (pre-ii) and steps (i) to (iv) were online, and a papermaking substrate was continuously produced.

The obtained papermaking substrate had a basis weight of 302 g / m ² (reinforced fiber basis weight: 100 g / m ² ) and an effective width of 500 mm. About this papermaking base material, 250 m ² was manufactured, wound into a roll shape every 100 m, and the raw material was switched.

  About the above, the implementation conditions in each process and the evaluation result of the obtained papermaking base material were shown in Table 1.

(Example 10)
A papermaking substrate was produced using the apparatus shown in FIG. 7 has two systems from the papermaking tank 1 to the conveyor 13 in FIG. 6, with the first system on the mezzanine floor and the second system on the ground.
The papermaking substrate (a) obtained in the first series (weight per unit: 100 g / m ² ) is the same as the papermaking base (b) obtained in the second series (weight per unit: 100 g / m ² ) in two series. They were layered together on the eye conveyor 13 ', passed through a dryer, and wound into a roll with a winder. The take-up speed at this time was 3 m / min. (Process (v))
In this example, steps (i) to (iv) were the same as those in Example 8 for both the first and second series.

  In this example, steps (i) to (v) were online, and a papermaking substrate was continuously produced.

The obtained papermaking substrate had a basis weight of 200 g / m ² (weight per layer: 100 g / m ² ) and an effective width of 500 mm. About this papermaking base material, 250 m ² was manufactured, wound into a roll shape every 100 m, and the raw material was switched.

  About the above, the implementation conditions in each process and the evaluation result of the obtained papermaking base material were shown in Table 1.

(Example 11)
A papermaking substrate was produced using the apparatus shown in FIG. FIG. 8 is the same as FIG. 4 except that a curtain coat type binder applicator 21 is provided above the conveyor 13 and the guide cloth 18 is not used.

A 0.4% by mass aqueous dispersion (emulsion) of binder D1 was applied to the papermaking substrate obtained in step (iii) at a rate of 1.13 kg / min with a binder applicator. (Process (vi))
Next, the papermaking substrate provided with the binder was passed through the dryer 14 at 200 ° C. by the conveyor 15 and wound into a roll by the winder 16. At this time, the take-up speed was 3 m / min, and no guiding cloth was used for taking-up. (Process (vii))
In this example, steps (i) to (iv) were the same as in Example 8.

  In this example, steps (i) to (iv) and steps (vi) (vii) were online, and a papermaking substrate was continuously produced.

The obtained papermaking substrate had a basis weight of 105 g / m ² (reinforcing fiber basis weight: 100 g / m ² ) and an effective width of 500 mm. About this papermaking base material, 250 m ² was manufactured, wound into a roll shape every 100 m, and the raw material was switched.

  About the above, the implementation conditions in each process and the evaluation result of the obtained papermaking base material were shown in Table 1.

(Example 12)
A papermaking substrate was produced using the apparatus shown in FIG. FIG. 9 shows a double belt press device 22 that is connected to the conveyor 15 and can be pressurized, heated, and cooled. A matrix resin (roll shape) is placed at two places above and below the introduction portion of the double belt press device. It is the same as that of the apparatus of FIG. 5 except providing the creel 23 for accommodating and not using the guiding cloth 18.

The papermaking substrate that passed through the dryer in step (iv) was sandwiched from above and below with a nonwoven fabric (weight per unit: 100 g / m2) made of matrix resin C1 supplied from a creel and introduced into a double belt press apparatus. . In the double belt press apparatus, the first half is heated and pressurized at 250 ° C. and 3.5 MPa, the second half is cooled and pressurized at 60 ° C. and 3.5 MPa, and the fiber reinforced molding base material in which the matrix resin is compounded is obtained. Obtained. (Process (viii))
The obtained fiber reinforced molding substrate was wound into a roll shape by a winder 16. At this time, the take-up speed was 3 m / min, and no guiding cloth was used for taking-up. (Process (ix))
In this example, steps (i) to (iv) were the same as in Example 8.

  In this example, steps (i) to (iv) and steps (viii) (ix) were online, and a fiber-reinforced molded substrate was continuously produced.

The obtained fiber reinforced molded base material had a basis weight of 300 g / m ² (reinforced fiber basis weight: 100 g / m ² ), a reinforcing fiber content of 20%, and an effective width of 500 mm. About this papermaking base material, 250 m ² was manufactured, wound into a roll shape every 100 m, and the raw material was switched.

  About the above, the implementation conditions in each process and the evaluation result of the obtained papermaking base material were shown in Table 1.

(Comparative Example 1)
A papermaking substrate was produced using the apparatus shown in FIG. FIG. 10 has a cylindrical dispersion tank 24 having a diameter of 700 mm, and is provided with a cock 25 that can be opened and closed at the bottom of the tank. Raw materials can be input. The cock 25 of the dispersion tank 24 is connected to a straight transport section 20 (inclination angle of 45 °), and is a large square sheet machine (No. 2553- manufactured by Kumagai Riki Kogyo Co., Ltd.) which is the papermaking tank 1. I (trade name)) and the dispersion tank 24 are connected. The bottom of the papermaking tank 1 is provided with a papermaking surface (made of mesh sheet) 10 having a length of 1000 mm × width of 1000 mm, and a papermaking substrate 12 is obtained on the papermaking surface.

First, the reinforcing fiber A1 was cut to 6.4 mm with a cartridge cutter while applying water to obtain chopped reinforcing fiber (A1-1) containing water. The mass content of water was adjusted to be 25% of the total weight of the chopped reinforcing fiber containing water. 250 kg of a dispersion medium 17 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 put into a dispersion tank 24. Further, 0.05 kg of A1-1 (chopped reinforcing fiber) was put into the dispersion tank 24. (Process (x))
Subsequently, it stirred with the stirrer 8 attached to the papermaking tank 1, and prepared the slurry whose solid component density | concentration is 0.02 mass%. (Process (xi))
Next, the cock 25 provided in the dispersion tank 24 was released, and the slurry was poured into the papermaking tank 1 via the transport unit 20. (Process (xii))
Subsequently, the dispersion medium was removed by suction on the papermaking surface 10 provided in the papermaking tank 1 to obtain a papermaking substrate 12 on the mesh sheet. (Process (xiii))
The obtained papermaking substrate 12 was dried in a dryer (not shown) at 130 ° C. to obtain a sheet-like papermaking substrate. (Process (xiv))
In this comparative example, the process (x) (xi) was performed online, and the process (xii) (xiii) (xiv) was performed offline to intermittently manufacture the papermaking substrate.

The obtained paper base material had a basis weight of 50 g / m ² and was 1000 mm long × 1000 mm wide. About this papermaking base material, 250 m < ² > was manufactured and the raw material was switched for every batch. In addition, process (x)-(xiv) in this comparative example is handled as equivalent to process (i)-(iv) in an Example.

  About the above, the implementation conditions in each process and the evaluation result of the obtained papermaking base material were shown in Table 1.

(Comparative Example 2)
A papermaking substrate was produced using the apparatus shown in FIG.

First, the reinforcing fiber A1 was cut to 6.4 mm with a cartridge cutter to obtain a chopped reinforcing fiber (A1-1). A dispersion medium 17 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)) is continuously supplied to the dispersion tank 19 at a feed rate of 375 kg / min. While supplying, A1-1 (chopped reinforcing fiber) was continuously charged at a charging speed of 0.075 kg / min. (Process (xv))
Subsequently, it stirred with the stirrer 8 attached to the papermaking tank 1, and the slurry whose solid component concentration is 0.02 mass% was continuously adjusted. (Process (xvi))
Next, the obtained slurry was continuously supplied to the papermaking tank 1 through the transport unit 20. (Process (xvii))
Next, the dispersion medium was sucked and removed by the papermaking surface 10 provided in the papermaking tank 1, and was rolled up by a mesh conveyor to obtain a papermaking substrate 12. (Process (xviii))
The obtained papermaking substrate 12 is placed on the guide cloth 18 by the conveyor 13, further passes through the dryer 14 at 130 ° C. by the conveyor 15, and rolls together with the guide cloth 18 by the winder 16. Wound around. The take-up speed at this time was 3 m / min. (Process (xix))
In this comparative example, the steps (xv) to (xix) were online, and the papermaking substrate was continuously produced.

The resulting papermaking substrate had a basis weight of 50 g / m ² and an effective width of 500 mm. About this papermaking base material, 250 m ² was manufactured, wound into a roll shape every 100 m, and the raw material was switched. In addition, process (xv)-(xix) in this comparative example is handled as equivalent to process (i)-(iv) in an Example.

  About the above, the implementation conditions in each process and the evaluation result of the obtained papermaking base material were shown in Table 1.

  As apparent from Table 1, in Examples 1 to 12, it was possible to obtain a papermaking substrate with reduced man-hours. By implementing steps (i) to (iv) in the same papermaking tank, it can be simplified compared to conventional equipment, leading to space savings and product cost reductions, as well as the manpower and time required for manufacturing. Can lead to further cost reduction (Examples 1 to 12 and Comparative Examples 1 and 2).

  Furthermore, by taking into account the method of charging the reinforcing fiber bundles (Examples 3 to 5, 7) and the formulation (Example 6), the papermaking base material is effective in the basis weight stability and dispersibility, and is particularly excellent in paper quality. A substrate can be produced.

  Moreover, it can be implemented on-line with various processes, and it is possible to produce hybrid materials, multilayer materials, and fiber-reinforced molded substrates (Examples 9 to 12).

  From the viewpoint of productivity and quality stability, Examples 7 and 8 are particularly preferred embodiments.

DESCRIPTION OF SYMBOLS 1 Papermaking tank 2 Taking-off direction 3 Input range 3-1-20 Division of input range 4 Papermaking tank width 5 Side wall surface of papermaking tank width direction 5 'Side wall surface of width direction of papermaking tank 6 Slurry liquid level 7 Slurry liquid level 8 Stirrer 9 Reinforcing fiber bundle 10 Paper making surface 11 Mesh conveyor 12 Paper making substrate 13 Conveyor 13 'Conveyor 14 of the second series 14 Dryer 15 Conveyor 16 equipped with dryer 16 Winder 17 Dispersion medium 18 Cloth 19 Cylindrical dispersion tank 20 Transport part 21 Binder application device 22 Double belt press device 23 Creel 24 Cylindrical dispersion tank with cock 25 Cock

Claims (19)

A method for producing a papermaking substrate, comprising at least the following steps (i) to (iv), wherein at least steps (i) to (iii) are carried out in the same papermaking tank.
(I): Step of continuously feeding a reinforcing fiber bundle into a papermaking tank having a dispersion medium (ii): Step of adjusting slurry (a) in which reinforcing fibers are dispersed in the dispersion medium (iii): Slurry (a) Step (iv) for obtaining a papermaking substrate containing reinforcing fibers by removing the dispersion medium from the step: Taking the papermaking substrate obtained in step (iii) In the step (i), the reinforcing fiber bundle is input transversely with respect to the take-up direction of the papermaking base material, and the reinforcing fiber bundle is input in a range of 80 to 100% with respect to the width of the papermaking tank. The method for producing a papermaking substrate according to claim 1. In the step (iii), the distance L between the draining position P1 for scooping up the reinforcing fibers from the slurry (a) and the input position P2 of the reinforcing fiber bundle in the step (i) is 10 mm or more. The manufacturing method of the papermaking base material of description. The manufacturing method of the papermaking base material in any one of Claims 1-3 whose mass content of the reinforced fiber in the slurry (a) adjusted by the said process (ii) is 0.001-1 mass%. . The manufacturing method of the papermaking base material in any one of Claims 1-4 whose take-up speed in the said process (iv) is 1-30 m / min. The manufacturing method of the papermaking base material in any one of Claims 1-5 which makes the required time to the said process (i)-(iii) within 5 minutes. The manufacturing method of the papermaking base material in any one of Claims 1-6 whose input speed of the reinforcing fiber bundle in the said process (i) is substantially constant. The method for producing a papermaking substrate according to any one of claims 1 to 7, wherein in the step (i), the reinforcing fiber bundle is charged with a time difference within a charging range. The manufacturing method of the papermaking base material in any one of Claims 1-8 in which the 2nd reinforcement fiber is previously disperse | distributed in the dispersion medium in the said process (i). The method for producing a papermaking substrate according to any one of claims 1 to 8, wherein in the step (i), organic fibers and / or organic particles are dispersed in advance in a dispersion medium. The step (pre-i) of preparing the slurry (b) in which the second reinforcing fibers or the organic fibers and / or the organic particles are dispersed in the dispersion medium in advance (pre-i) and the slurry obtained in the step (pre-i) ( The manufacturing method of the papermaking base material of Claim 9 or 10 provided with the process (pre-ii) which conveys b) to a papermaking tank. The manufacturing method of the papermaking base material in any one of Claims 1-11 whose length of the said reinforcing fiber bundle is 1-50 mm. The method for producing a papermaking substrate according to any one of claims 1 to 12, wherein the number of filaments of the reinforcing fiber bundle is 12,000 to 100,000. The manufacturing method of the papermaking base material in any one of Claims 1-13 whose said reinforced fiber is carbon fiber. The papermaking base according to claim 14, wherein the surface oxygen concentration O / C of the carbon fiber is 0.1 to 0.3, and the surface free energy γ0 measured by the Wilhelmi method is 40 to 60 mJ / m ^2. A method of manufacturing the material. The manufacturing method of the papermaking base material in any one of Claims 1-15 whose fabric weights of the said papermaking base material are 10-500 g / m < ² >. A process (v) comprising a plurality of series of methods for producing a papermaking base material according to claim 1-16, wherein the papermaking base materials obtained from each of the series are aligned and laminated at a speed of 1 to 30 m / min, and A method for producing a papermaking substrate in which all processes are continuously carried out online. A step (vi) of applying a binder online to the papermaking substrate obtained in claims 1 to 17 and a step (vii) of taking up the papermaking substrate provided with the binder at a speed of 1 to 30 m / min. A method for producing a papermaking substrate, wherein the process is continuously carried out online. A step of obtaining a fiber reinforced molded base material by compounding a matrix resin on-line with the papermaking base material obtained in claim 1 to 18 (viii) and a step of drawing the fiber reinforced molded base material at a speed of 1 to 30 m / min (ix) ), And a process for producing a fiber-reinforced molded base material in which all steps are continuously carried out online.

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