JP2011157638A - Papermaking substrate and method for producing fiber-reinforced forming substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a papermaking substrate, by which the paper-making substrate excellent in a dispersion state, even the papermaking substrate containing a plurality of solid components, further the papermaking substrate having a complicated substrate structure, can be produced in good productivity. <P>SOLUTION: The method for producing the papermaking substrate comprises at least: a process (i) for dispersing the first solid component in a dispersion medium to prepare a slurry (a); a process (ii) for dispersing the second solid component in the dispersion medium to prepare a slurry (b); a process (iii) for transporting the slurries (a) and (b) to an identical papermaking tank; and a process (iv) for removing the dispersion medium from the slurries transported in the process (iii) to obtain the papermaking substrate. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing a papermaking substrate. More specifically, it is a method for producing a papermaking substrate, which produces a papermaking substrate containing a plurality of solid components in a good dispersion state.

  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.

  Patent Document 2 describes that in a stampable sheet manufacturing method, a papermaking base material having no entanglement in the three-dimensional direction of fibers can be manufactured by adjusting the suction speed when sucking the dispersion into papermaking. ing.

  Patent Document 3 discloses a fiber-reinforced thermoplastic resin that is highly fiber-oriented in a specific direction by controlling the supply speed of the dispersion and the take-up speed of the papermaking substrate in the method for producing a fiber-reinforced thermoplastic resin sheet. It is described that a sheet can be obtained.

  Patent Document 4 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 a dispersion liquid containing two components of a reinforcing fiber and a thermoplastic resin is adjusted in the production of a papermaking substrate. Therefore, the solid component concentration in the dispersion is inevitably high, and in order to ensure a good dispersion state, the capacity of the dispersion medium, the basis weight of the papermaking substrate to be produced, or the production time is greatly limited. Become.

  In Patent Documents 2 to 4, techniques for controlling some of the fiber orientation of the fiber-reinforced resin sheet by controlling the flow state of the dispersion are disclosed in common. However, none of these techniques controls the fiber orientation, and does not reach the control of the base material configuration.

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

  In the methods of Patent Document 2, Patent Document 3 and Patent Document 4, since it is necessary to adjust the dispersion liquid containing the reinforcing fiber and the thermoplastic resin, interference between the reinforcing fiber and the thermoplastic resin occurs and uniform dispersion occurs. In addition, since the process time in a state where the two components are dispersed is long, the reinforcing fibers and / or the thermoplastic resin may reaggregate during the process. Further, since the two components are mixed at the initial stage of production, the obtained material is limited to a material in which the two components exist uniformly.

International Publication No. 2007/97436 Pamphlet Japanese Patent Laid-Open No. 8-155556 Japanese Patent Laid-Open No. 9-41280 Japanese Patent Laid-Open No. 9-94826

  In the production of a papermaking substrate containing a plurality of solid components, the present invention can provide a papermaking substrate that is excellent in the dispersion state of solid components, and moreover, a complicated substrate configuration (in which regions containing different solid components are parallel) It is an object of the present invention to provide a method capable of producing a papermaking substrate with high productivity even in the case of a configuration in which regions containing different solid components are laminated.

As a result of repeated studies by the present inventors, it has been found that the above object can be achieved by mixing each of the slurry obtained by independently adjusting each of the solid components at the end of the process, The present invention has been reached. That is, the present invention is a method for producing a papermaking substrate including at least the following steps (i) to (iv).
(I): a step of adjusting the slurry (a) in which the first solid component is dispersed in the dispersion medium (ii): a step of adjusting the slurry (b) in which the second solid component is dispersed in the dispersion medium (Iii): a step of transporting the slurry (a), (b) to the same papermaking tank (iv): a step of removing the dispersion medium from the slurry transported in the step (iii) to obtain a papermaking substrate.

  According to the method for producing a papermaking substrate of the present invention, even a papermaking substrate containing a plurality of solid components, a papermaking substrate excellent in the dispersion state of the solid components can be obtained. Even a papermaking substrate having a configuration can be manufactured with high productivity.

It is a model figure which shows one embodiment of a process (iii). It is a model figure which shows one embodiment of a process (iii). It is a model figure which shows an example of the papermaking base material obtained by this invention. It is a model figure which shows an example of the papermaking base material obtained by this invention. It is a model figure which shows an example of the papermaking base material obtained by this invention. It is a model figure which shows an example of the papermaking base material obtained by this invention. It is a model figure which shows one embodiment of a process (iii). It is a model figure which shows an example of a transport part. It is a model figure which shows an example of a transport part. 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. 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 manufacturing method of the papermaking base material of this invention is characterized by including the following process (i)-(iv) at least.
(I): a step of adjusting the slurry (a) in which the first solid component is dispersed in the dispersion medium (ii): a step of adjusting the slurry (b) in which the second solid component is dispersed in the dispersion medium (Iii): a step of transporting the slurry (a), (b) to the same papermaking tank (iv): a step of removing the dispersion medium from the slurry transported in the step (iii) to obtain a papermaking substrate.

  Steps (i) and (ii) are performed in a dispersion tank capable of storing a dispersion medium, and an individual dispersion tank is used for each step. Steps (i) and (ii) are performed with the dispersion medium in the dispersion tank, that is, with the dispersion medium stored, supplied, or circulated in the dispersion tank. In this state, the solid component is charged into the dispersion tank.

  The solid component may be charged continuously or intermittently. Here, “continuous” is a state in which some of the solid components are constantly charged, and is effective when a large amount of paper-making substrate is continuously produced. On the other hand, “intermittent” refers to a state in which some of the solid components are temporarily added, and a necessary amount of the solid components may be added whenever necessary. This is effective when manufacturing batch by batch.

  In the present invention, the dispersion medium means a medium capable of dispersing a solid component. 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 slurry refers to a suspension in which solid particles are dispersed, and in the present invention, an aqueous slurry is preferable. Here, “adjusting to a slurry” means that the solid components charged into the dispersion medium in steps (i) and (ii) are constructed in a desired form in the dispersion medium, that is, as desired. It is meant to form a dispersed state and a mass content of solid components.

  Examples of the means for dispersing the solid component include dispersibility of the solid component itself, liquid flow of the dispersion medium, and stirring by an external force, and at least one of these is performed. In particular, when the mass content of the target solid component is rich, the solid component may be dispersed by combining a plurality of means.

  The dispersibility of the solid component itself means a property for quickly dispersing the solid components constituting the solid component individually and suppressing reaggregation when the solid component is charged into the dispersion medium. Potential dispersion capacity. In particular, when the solid component is a reinforcing fiber bundle, it refers to the ability of the reinforcing fiber bundle to disperse in the form of single fibers constituting the reinforcing fiber bundle, and is also referred to as spreadability. The dispersibility of the reinforcing fiber bundle itself can be improved by using a method of modifying the surface state of the reinforcing fiber or a method of imparting a treatment agent for improving the dispersion to the reinforcing fiber.

  The liquid flow of the dispersion medium is to disperse the solid component using the flow of the dispersion medium supplied to or circulated into the papermaking tank. Laminar flow, turbulent flow, vortex, and the like are arbitrarily adjusted by a dispersion medium feeding means, and the solid component is dispersed by applying a shearing force.

  Stirring by external force is a stirrer with power, a fixed obstacle such as a rod-like body or a plate-like body, jetting of fluid (gas, liquid), ultrasonic irradiation, etc. Good.

  As for the dispersion state of the solid component, it is ideal that all of the solid components contained in the dispersion medium are individually dispersed. However, the state intended for the dispersion here refers to this. It is not limited. 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 solid components in the slurry (a) and (b) prepared in the steps (i) and (ii) are both 0.001 to 1% by mass. Preferably, it is 0.01 mass%-0.5 mass%. By being in the above-mentioned range, it is possible to keep the dispersed state of the solid component in good condition and efficiently perform papermaking.

  Each of the first solid component and the second solid component of the present invention may be the same or different. It can be selected from various combinations depending on the desired performance and application of the resulting papermaking substrate. Hereinafter, preferable modes of the first solid component and the second solid component are listed in the order of modes (1) to (3).

  The first solid component is a reinforcing fiber (A), the second solid component is a reinforcing fiber (B), the specific gravity of the reinforcing fiber (A) and the reinforcing fiber (B), number average fiber length, tensile strength, tensile It is preferable that at least one of the elastic moduli is different from each other (Aspect (1)).

  By setting it as this aspect, the desired characteristic can be provided in the papermaking base material obtained. For example, when the first solid component is carbon fiber (fiber length 6.4 mm) and the second solid component is carbon fiber (3 mm), the first solid component carbon fiber ( Compared with the case where the fiber length is only 6.4 mm), the dispersibility is improved, and the fiber reinforced molded base material produced from the resulting papermaking base material has excellent moldability (fluidity). Can be. By appropriately adjusting the proportion of the second solid component carbon fiber (3 mm), even if the carbon fiber used is 3 mm, the molded product using the resulting fiber reinforced molding substrate The mechanical properties are not degraded so much.

  In addition, when the first solid component is carbon fiber and the second solid component is glass fiber, in a fiber reinforced molded base material produced from the resulting papermaking base material, after satisfying predetermined mechanical properties, While reducing the cost of the raw material to be used, secondary characteristics such as conductivity and thermal conductivity can be imparted.

  Examples of reinforcing fibers used for the solid component of the present invention include carbon fibers, metal fibers, inorganic fibers, and plant fibers. Among these, carbon fiber or glass fiber is preferable, and excellent strength and elastic modulus can be exhibited when a fiber reinforced resin is used.

  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 inorganic fibers include fibers made of inorganic materials such as glass, basalt, silicon carbide, silicon nitride, and the like. Examples of plant fibers include plant-derived fibers such as cellulose fibers, kenaf fibers, and linen fibers.

  In addition, the reinforcing fiber is preferably a reinforcing fiber bundle. A reinforcing fiber bundle is a bundle of fibers in which a plurality of single fibers are aligned. 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 reinforcing fiber bundle may be composed of continuous reinforcing fibers or discontinuous reinforcing fibers. However, in order to achieve a better dispersion state, the reinforcing fiber bundle is discontinuous. Reinforcing fiber bundles are preferred, and chopped fibers are more preferred.

  The number average fiber length of the reinforcing fibers constituting the reinforcing fiber bundle is preferably 1 to 50 mm from the viewpoint of efficiently exerting the reinforcing effect by the reinforcing fibers and maintaining good dispersion in the slurry. More preferably, it is ˜30 mm. The number average fiber 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. Measure with a microscope. About the evaluation method of the number average fiber length of a reinforced fiber, a specific example is demonstrated in an Example.

  It is also preferred that the first solid component is a reinforcing fiber (A) and the second solid component is an organic fiber (C) (aspect (2)).

  By setting it as this aspect, the effect of the improvement of the productivity of a fiber reinforced molding base material or a fiber reinforced resin molding, and provision of the higher-order characteristic in fiber reinforced resin is acquired. For example, when the first solid component is carbon fiber and the second solid component is polypropylene fiber, the obtained paper-making substrate is heated and pressed directly to omit the step of laminating and compounding the resin directly. A reinforced molded substrate or a fiber reinforced resin molded product can be produced. In addition, when the first solid component is carbon fiber and the second solid component is nylon fiber, a fiber reinforced resin molded body obtained by impregnating an epoxy resin as a matrix resin to the obtained paper base material is included in the molded body. It can be expected that the contained nylon fiber has the effect of increasing the toughness of the molded body.

  In addition to the above-described organic fibers used in the present invention, fibers made of organic materials such as aramid, PBO, polyphenylene sulfide, polyester, acrylic, nylon, and polyethylene can be used.

  Among these, when the organic fiber is used as a matrix resin, it is preferably a thermoplastic resin from the viewpoint of recyclability and repairability. Polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene Polyester resins such as naphthalate (PENp) and liquid crystal polyester, polyolefins such as polyethylene (PE), polypropylene (PP) and polybutylene and their acid-modified products, styrene resins and urethane resins, and polyoxymethylene (POM) ), Polyamide (PA), polycarbonate (PC), polymethyl methacrylate (PMMA), polyvinyl chloride (PVC), polyphenylene sulfide (PPS), polyphenylene ether (PPE), modified PPE, polyi (PI), polyamideimide (PAI), polyetherimide (PEI), polysulfone (PSU), modified PSU, polyethersulfone (PES), polyketone (PK), polyetherketone (PEK), polyetheretherketone ( Examples include PEEK), polyether ketone ketone (PEKK), polyarylate (PAR), polyether nitrile (PEN), phenolic resin and phenoxy resin. Among these, a polyamide resin is more 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.

  The form of the organic fiber is not particularly limited, and examples include multifilaments, monofilaments, spun yarns, twisted yarns, felts, etc., which may be either continuous fibers or discontinuous fibers, but from the viewpoint of dispersibility To discontinuous fibers. The fiber length of the organic fiber is preferably 1 to 50 mm, more preferably 3 to 30 mm, like the reinforcing fiber.

  It is also preferred that the first solid component is a reinforcing fiber (A) and the second solid component is an organic particle (D) (aspect (3)).

  By setting it as this aspect, the effect of the improvement of the productivity of a fiber reinforced shaping | molding base material or a fiber reinforced resin molded object, and provision of the high-order characteristic in fiber reinforced resin is acquired similarly to aspect (2).

  For example, when the first solid component is carbon fiber and the second solid component is nylon 12 particles, the resulting paper-making substrate is heated to develop the binding property between the carbon fibers, and the handling property as a sheet Nylon 12 particles can also function as a tackifier when the papermaking base material is laminated and used. In addition, when the first solid component is carbon fiber and the second solid component is phosphinic acid metal salt particles, the fiber reinforced molded substrate or fiber reinforced resin molded body produced from the resulting papermaking substrate is excellent. Provides flame retardant effect.

  In addition to the above, the organic particles used in the present invention include elastomers, rubber components, fillers, conductivity imparting agents, flame retardants, flame retardant aids, pigments, dyes, lubricants, mold release agents, and compatibilizers. , Dispersant, crystal nucleating agent, plasticizer, heat stabilizer, antioxidant, anti-coloring agent, UV absorber, fluidity modifier, low shrinkage agent, foaming agent, antibacterial agent, vibration control agent, deodorant, Examples thereof include slidability modifiers and antistatic agents.

  When organic particles are used as a matrix resin, it is preferably a thermoplastic resin like the organic fiber described above, and can be selected from the same range as the organic fiber.

  The shape of the organic particles is not particularly limited, but the aspect ratio is preferably 10 or less from the viewpoint of facilitating uniform dispersion. More preferably, it is 8 or less, More preferably, it is 5 or less. Moreover, it is preferable that the length of a long side is 5-1000 micrometers from a viewpoint of the handleability of organic particles. More preferably, it is 10-700 micrometers, More preferably, it is 20-500 micrometers.

  Step (iii) is carried out in a transport section that connects the dispersion tank in which the slurry (a) is adjusted, the dispersion tank in which the slurry (b) is adjusted, and the papermaking tank.

  As a means for transporting the slurry, a method using the power of a liquid feed pump can be mentioned, and a method of transporting from a dispersion tank by an overflow method is preferable. Thereby, sedimentation and re-aggregation, which are generated when an extreme shearing force is applied to the solid component in the slurry to be transported, can be transported while maintaining the dispersed state of the solid component. 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.

  It is preferable that the transport section is inclined (slider method). When the transport section is viewed from the horizontal direction, the connecting section between the dispersion tank and the transport section is located higher than the connecting section between the papermaking tank and the transport section. There should be. As such an inclination, the step of shortening the transportation in the step (iii) and the flow rate at the time of slurry transportation are reduced so that excessive shear is not applied to the slurry when reaching the step (iv). From the viewpoint of improving the dispersion state of the slurry in (iv), the inclination angle is preferably 30 to 60 °, and more preferably 40 to 55 °.

  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 (iii) by an overflow system, it is preferable that the connection part of a transport part and a dispersion tank is located above the wall surface of a dispersion tank.

  In the step (iii) of the present invention, it is preferable to transport the slurries (a) and (b) through mutually independent routes. That is, in the step (iii), the slurry (a) and the slurry (b) are transported to the papermaking tank without any contact.

  Means satisfying the above aspect will be described with reference to FIGS.

  FIG. 1 includes a dispersion tank 1 for adjusting slurry (a) and a dispersion tank 2 for adjusting slurry (b), and transport sections 4 and 5 connecting dispersion tanks 1 and 2 and papermaking tank 3 are dispersed tanks. The connection parts 6 and 7 are connected to connection parts (supply ports) 8 and 9 with the papermaking tank. Each of the supply ports 8 and 9 is provided side by side at the same position in the vertical direction. The positional relationship between the dispersing tanks 1 and 2 and the papermaking tank 3 is such that the connecting part 6 of the dispersing tank 1 and the connecting part 7 of the dispersing tank 2 are in the same position in the vertical direction, and the connecting parts 8 and 9 of the papermaking tank 3. Is installed at a position lower than the connecting portions 6 and 7 of the dispersion tanks 1 and 2.

  On the other hand, FIG. 2 is the same as FIG. 1 except that the connection portions 8 and 9 of the papermaking tank 3 are provided vertically in the vertical direction.

  1 and 2, the dispersion medium 33, the first solid component 31, and the second solid component 32 introduced from the narrow opening 34 are stirred by the stirrer 10 to adjust the slurries (a) and (b). The The adjusted slurries (a) and (b) flow into the transport sections 4 and 5 by the overflow method, respectively, and are supplied to the papermaking tank 3 from the supply ports 8 and 9 without contacting each other. Slurries (a) and (b) contact and merge with each other only after reaching the papermaking tank 3.

  By setting it as the aspect of FIG.1, 2 mentioned above, the papermaking base material obtained at the process (iv) mentioned later can be made into the structure illustrated to FIG. 3a, 3b, 4a, 4b.

  From FIG. 1, the flow rates of the slurries (a) and (b) flowing through the transport sections 4 and 5, the slurries (a) and (b), and the first solid component 31 and the second solid component 32 in the papermaking tank 3. Of the dispersion medium 33 to be retained in the papermaking tank 3, the arrangement of the connecting portions 8 and 9, the opening shape of the connecting portions 8 and 9, and the slurry discharged from the connecting portions 8 and 9 (a) By appropriately adjusting the liquid flow state of (b), the width of the papermaking tank 3, the subsequent take-up speed of the papermaking base, and the like, the papermaking base having the structure of FIGS. 3a and 3b can be obtained.

  FIG. 3a shows that the three regions of the papermaking substrate are the region 11 containing the first solid component, the region 12 containing both the first solid component and the second solid component, and the region 13 containing the second solid component. It is a structure arranged in parallel along the take-up direction. FIG. 3b shows a region 17 where the first solid component is higher than the second solid component, a region 18 where the first solid component and the second solid component are included to the same extent, and the first solid component is the second solid component. Three regions 19 that are less than the solid component have a structure parallel to the take-up direction of the papermaking substrate. FIG. 3a is obtained by making a paper after a short distance from the merging of the slurry (a) and (b), and FIG. 3b is obtained by making a paper after a long distance from the merging of the slurry (a) and (b). The specific distance is such that the former is a distance equal to or smaller than the width W of the papermaking tank, and the latter is a distance longer than the width W of the papermaking tank. The lower limit and the upper limit of the distance are not particularly limited, but usually the lower limit is 30 mm or more from the merging of the slurry (a) and (b), and the upper limit is twice or less the width W of the papermaking tank. 3a and 3b are schematic diagrams, and the boundaries between the regions are not so clear as illustrated.

  The papermaking substrate having the configuration illustrated in FIGS. 3a and 3b is suitable for the following applications. That is, in producing a fiber reinforced resin molded article from the obtained papermaking substrate, for example, when having a simple shape part and a complex shape part in the in-plane direction of the fiber reinforced resin molded article, There is no particular need for the properties, areas where mechanical properties are required (for example, areas containing reinforcing fibers with a long fiber length), areas with excellent shapeability (for example, areas containing reinforcing fibers with a short fiber length) in complex shapes By arranging the shape, it is possible to impart formability to a necessary site. When the properties required in the fiber reinforced resin molded product are different, locally rigid (for example, a region containing highly elastic fibers), conductivity (for example, conductivity imparting agent, metal fiber), impact resistance (for example, Performance such as rubber component and elastomer) can also be imparted.

  From FIG. 2, the flow rates of the slurry (a) and (b) flowing through the transport sections 4 and 5, the slurry (a) and (b), and the first solid component 31 and the second solid component 32 in the papermaking tank 3. Of the dispersion medium 33 to be retained in the papermaking tank 3, the arrangement of the connecting portions 8 and 9, the opening shape of the connecting portions 8 and 9, and the slurry discharged from the connecting portions 8 and 9 (a) By appropriately adjusting the liquid flow state of (b), the width of the papermaking tank 3 and the subsequent take-up speed of the papermaking substrate, a papermaking substrate having the structure of FIGS. 4a and 4b can be obtained.

  FIG. 4a shows that three regions, ie, a region 20 containing the first solid component, a region 21 containing both the first solid component and the second solid component, and a region 22 containing the second solid component are stacked in the vertical direction. It is a structured. FIG. 4b shows a region 24 in which the first solid component is larger than the second solid component, a region 25 in which the first solid component and the second solid component are included to the same extent, and the first solid component is the second solid component. The three regions 26, which are less than the solid component, are stacked in the vertical direction. The configuration of FIG. 4b has a region in which the first solid component and the second solid component are mixed with a gradient of the solid component between the respective regions, in other words, the first solid component than the configuration of FIG. 4a. It is the structure by which the component and the 2nd solid component were mixed more. FIG. 4a is obtained by making a paper after a short distance from the merging of the slurry (a) and (b), and FIG. 4b is obtained by making a paper after a long distance from the merging of the slurry (a) and (b). The specific distance is such that the former is a distance equal to or smaller than the width W of the papermaking tank, and the latter is a distance longer than the width W of the papermaking tank. The lower limit and the upper limit of the distance are not particularly limited, but usually the lower limit is 30 mm or more from the merging of the slurry (a) and (b), and the upper limit is twice or less the width W of the papermaking tank. 4a and 4b are schematic diagrams, and the boundaries between the regions are not so clear as illustrated.

  The papermaking substrate having the configuration illustrated in FIGS. 4a and 4b is suitable for the following applications. That is, in producing a fiber reinforced resin molded body from the obtained papermaking substrate, for example, when surface quality is required on one surface of the fiber reinforced resin molded body, a region containing a low shrinkable solid component on one surface May be arranged, or a region having a small reinforcing fiber content may be arranged on one surface. When mechanical properties are required on one surface of a plate-like fiber reinforced resin molded article and adhesiveness is required on the other surface, a region containing reinforcing fibers having a long fiber length on one surface, or reinforcing fibers and elastomer or rubber A region containing the components may be arranged, and a region containing organic fibers and organic particles capable of heat welding as an adhesive layer may be arranged on the other surface.

  3a, 3b, 4a, and 4b are typically manufactured by individually manufacturing paper composites corresponding to the respective regions and combining them. According to the method for producing a paper-making substrate of the present invention exemplified in the above, since the same paper-making substrate can be produced in a single process, it can be said that the production method is particularly excellent in productivity.

  Moreover, in the manufacturing method illustrated by FIG.1, 2, the mass content rate of the solid component of the slurry (a) and (b) to be used may differ from each other.

  By adopting such an aspect, it is easy to form the configuration of the papermaking substrate exemplified in FIGS. 3a, 3b, 4a, and 4b, and when it is desired to form regions with different basis weights, the supply amount and flow rate of each slurry used. , Etc. can be manufactured in the same manner.

  Taking the configuration of FIG. 4a as an example, when the mass content of the slurry (a)> the mass content of the slurry (b), the slurry (a) is removed from the supply port vertically in the slurry (b). Is allowed to flow in from the upper supply port in the vertical direction, whereby a configuration in which the respective regions are stacked in the vertical direction can be easily formed.

  Furthermore, as another aspect, when the specific gravity of the first solid component> the specific gravity of the second solid component, the slurry (a) is vertically directed from the lower supply port, and the slurry (b) is vertically upward. As described above, a configuration in which the respective regions are stacked in the vertical direction can be easily formed.

  Moreover, as another aspect of the process (iii) of this invention, it is also preferable to make slurry (a) and (b) merge immediately before a papermaking tank, and to convey to a papermaking tank.

  Means satisfying the above-described embodiment will be described with reference to FIG.

  FIG. 5 shows that the transport parts 4 and 5 for feeding the slurry (a) and (b) are connected at the junction 27 and that there is only one connection part (supply port) 8 provided in the papermaking tank 3. 1 except that there is no point and the distance of the transport section 46 from the junction 27 to the supply port 8 is L.

  In FIG. 5, the slurry (a) and (b) adjusted in the dispersion tanks 1 and 2 flow into the transport parts 4 and 5 respectively by the overflow method, and are in contact with each other at the junction 27 and mixed. Is supplied from the supply port 8 to the papermaking layer 3. Slurries (a) and (b) reach the papermaking tank in a mixed solution state.

  By setting it as the aspect of FIG. 5 mentioned above, the paper-making base material obtained at the process (iv) mentioned later can be made excellent in the dispersibility. Usually, when producing a papermaking substrate in which a plurality of solid components are uniformly dispersed, a slurry is obtained by simply dispersing a plurality of solid components in a single dispersion tank, but in this case, the slurry in the dispersion tank Since it becomes a high concentration, there is a possibility that poor dispersion due to interference between solid components may occur, and since it passes through the subsequent process in the state of a high concentration slurry, the dispersion state must be maintained for a long time, During this time, problems such as reaggregation and sedimentation may occur. On the other hand, in the case of the present invention, each of the solid components is adjusted to a slurry in an individual dispersion tank and merged immediately before the papermaking tank, so that the above-described problems can be solved.

  Here, “merge just before the papermaking tank” means that at least the junction 27 is arranged before the supply port 8. From the viewpoint of efficiently mixing the slurries (a) and (b) and suppressing the reaggregation of solid components and shortening the process time, the diameter φa (mm) of the transport section 46 from the junction to the supply port 8 ) And the distance L (mm), the ratio L / φ is preferably 2-15, more preferably 5-10.

  As a preferred embodiment, the ratio va / vb between the flow rate va of the slurry (a) and the flow rate vb of the slurry (b) is preferably 1 to 10, and more preferably 1.5 to 5. Within this range, the position of the boundary between the slurry (a) and the slurry (b) moves, and if the slurry (a) is the main stream and the slurry (b) is the tributary, the slurry (a) ) Or a flow form in which the slurry (b) collides with the wall surface facing the confluence, so that the slurry can be mixed in a short time.

  Moreover, there is no restriction | limiting in particular as diameter ratio of the transport parts 4 and 5, Usually, it is 0.1-1.0. The diameter ratio here is calculated using the larger diameter as a parameter, and does not limit the diameter of one of the transport parts as a parameter.

  In the step (iii) of the present invention, it is preferable that the slurry (a) and (b) are transported with the same width as the width of the papermaking tank when reaching the papermaking tank.

  Means satisfying the above embodiment will be described with reference to FIGS. 6a and 6b.

  In FIG. 6a, the connection part (supply port) 8 between the transport part 4 and the papermaking tank 3 is provided on the bottom surface of the papermaking tank with the same width as the width W of the papermaking tank. FIG. 6b shows that the connecting sections (supply ports) 8 and 9 between the transport sections 4 and 5 and the papermaking tank 3 are provided vertically in the vertical direction with the same width as the width W of the papermaking layer on the process rear wall surface of the papermaking tank. It has been.

  By adopting the embodiment illustrated in FIGS. 6a and 6b, the raw material is supplied in a range corresponding to the manufacturing width of the papermaking substrate, and therefore, there is an effect of suppressing the variation in the basis weight in the width direction of the resulting papermaking substrate. Therefore, it is possible to ensure a wide effective width that can be used for the product part.

  Here, the width that is the same as the width of the papermaking tank is preferably that the width of the transport sections 4 and 5 in the connection parts (supply ports) 8 and 9 is 0.8 W to W with respect to the width W of the papermaking tank. Is 0.9 W to W, more preferably W.

  In most cases, the papermaking tank is rectangular and has a certain interval in the direction of take-up of the papermaking substrate. However, if the interval is different in the direction of take-up of the papermaking substrate, it is the position where the supply port is provided. Based on width.

  Step (iv) is performed in a papermaking tank having a papermaking surface capable of sucking the dispersion medium. The papermaking surface is generally disposed near the bottom surface of the papermaking tank, and examples of the material for the papermaking surface include woven fabric, non-woven fabric, and mesh sheet.

  The papermaking substrate obtained in the step (iv) is a state in which solid components, for example, fibrous bodies (reinforced fibers and / or organic 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 solid components, and it may be 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. Moreover, in the process (v) mentioned later, since a binder of solid components expresses and it can handle as a sheet | seat by providing a binder, it is preferable. If it can handle as a sheet | seat as said support body, there will be no restriction | limiting in particular in the form, It can select from various forms, such as a nonwoven fabric, a film, a mat | matte, 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.}

  It is preferable that the manufacturing method of the papermaking base material of this invention is equipped with the process (v) which provides a binder to the obtained papermaking base material following a process (iv).

  The binder intervenes between the solid component (for example, reinforcing fiber) and the matrix resin and connects the two, and the solid components in the papermaking substrate (for example, the fibrous body, or the fibrous body and the granular body). By binding, it plays two roles: a role of improving the handleability as a sheet, and a role of preventing solid components (for example, granular materials) from falling off. 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, the thermoplastic resin has a hydroxyl group and an amino group from the viewpoint of increasing the affinity with the solid component 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 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.

  It is preferable to apply the binder to the papermaking substrate in the form of an aqueous solution, emulsion or suspension of the binder. 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, and examples thereof include a method of immersing the papermaking substrate in an aqueous solution, emulsion or suspension, a shower method, and the like. After applying the binder, it is preferable to remove the excess binder by suction or absorption into an absorbent material such as absorbent paper before the drying step. In the step (v), the papermaking substrate is preferably heated after the application of the binder. Thereby, the time which manufactures the fiber reinforced shaping | molding base material mentioned later can be shortened, and a fiber reinforced shaping | molding base material 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.

  In the method for producing a papermaking substrate of the present invention, the dispersion medium and the first solid component are continuously added in step (i), and the dispersion medium and the second solid component are continuously added in step (ii). It is preferable that the method further includes a step (vi) of taking in the papermaking substrate at a speed of 1 to 30 m / min and continuously performing all the steps online.

  In order to satisfy such an embodiment, in steps (i) and (ii), it is necessary to continuously add a solid component into the dispersion medium. Here, “continuously charged” means a state in which some of the solid components are constantly charged. By continuously adding solid components, the slurry can be continuously adjusted and can be sequentially supplied to the previous process, thus eliminating time and labor loss between processes. In addition, since disturbances such as contamination of foreign substances in switching between processes or batches can be eliminated, it is possible to produce a papermaking substrate with stable quality.

  The step (vi) is performed by a mobile conveyor provided by connecting from the paper making surface. A dryer, a binder applicator, and a winder can be attached to the conveyor.

  The taken paper-making substrate may be wound in a roll shape, cut into a predetermined length, or folded, and handled in any final form according to the use, basis weight, etc. of the paper-making substrate. be able to.

  The take-up speed is preferably 1 to 30 m / min, and more preferably 5 to 30 m / min. By taking it within such a range, it is possible to obtain a process with an excellent balance between productivity and quality stability.

  In the present invention, it is preferable that all the steps described above are continuously performed online. By making all the processes online, the process can be made more productive.

  Further, the time required from the step (i) to the step (iv) is within 10 minutes from the viewpoint of increasing the productivity of the papermaking substrate and suppressing the reaggregation of the reinforcing fibers dispersed in the slurry. preferable. Strictly speaking, the time required from the start of the step (i) to the completion of the step (iv) is within 10 minutes. The lower limit of the time required from step (i) to completion of step (iv) is not particularly limited, but is usually 30 seconds or longer.

  The method for producing a papermaking substrate of the present invention can further include a step (vii) of combining a matrix resin with the papermaking substrate.

  There is no particular limitation on the means for compositing the matrix resin to the papermaking substrate, but when the matrix resin is a thermosetting resin, a method in which the matrix resin component is immersed in a solution diluted with a solvent (wet method), matrix resin Examples include a method of directly impregnating a component with a papermaking substrate (dry method), and the like. When the matrix resin is a thermoplastic resin, a method of bringing the matrix resin into contact with the papermaking substrate is preferable. The form of the thermoplastic resin in this case is preferably at least one form selected from woven fabrics, knitted fabrics, meshes, mats, nonwoven fabrics, films, and the like, more preferably films and nonwoven fabrics.

  The complexing is preferably performed by pressurization and / or heating, and more preferably both pressurization and heating are performed simultaneously. Below, conditions when the matrix resin is a thermoplastic resin will be described. 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, matrix resin woven fabrics, knitted fabrics, meshes, mats, non-woven fabrics, and films are arranged on the upper and lower surfaces of the papermaking substrate, and heating and / or heating is performed from both sides (intermittent press, double belt press, etc.). .

  If the second solid component is an organic fiber or organic particle serving as a matrix resin, there is no need to separately prepare a matrix resin to be combined, and this can be dealt with by directly combining the papermaking substrate. The papermaking base material to be combined is not particularly limited as long as it is a papermaking base material obtained in step (iv) or (v), but the resulting fiber reinforced molding base material or fiber reinforced molding base material is molded. From the viewpoint of enhancing the mechanical properties of the fiber-reinforced resin molded article obtained in this manner, a papermaking substrate provided with the binder obtained in step (v) is preferred.

  The matrix resin used in the present invention 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.

Further, following the step (vii), it is preferable to include a step (viii) of drawing the fiber reinforced molded base material at a speed of 1 to 30 m / min, and that all the steps are continuously performed online.
The speed at which the fiber-reinforced molded substrate is taken up is preferably 1 to 30 m / min.

  Similarly to step (vii), it is preferably the same speed as the paper-making substrate take-up speed in step (iv), and it is preferable that the paper-making base take-up speed in step (vii) is also equal. In the case where the step (v) is provided, it is preferable that all the series to be used have the same speed, and the speed at which the papermaking base materials are aligned and laminated in the step (v) is also constant.

  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 make the process excellent in the balance between productivity and quality stability as in the step (vi). Further, from the viewpoint of preventing slack and excessive tension from being applied to the obtained fiber reinforced molded base material, and suppressing wrinkles and tearing of the base material, the paper making base material take-up speed in the step (vi), etc. 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.

  In addition, it is preferable that all the processes including a process (viii) are continuously implemented on-line, and it can be set as the process excellent in productivity by setting it as this aspect.

  The papermaking substrate and fiber reinforced molding substrate obtained by the above-described manufacturing method can be used for various applications such as electrical / electronic equipment parts, civil engineering / architectural parts, automobile / motorcycle parts, aircraft parts, etc. It is preferably used for equipment parts and automobile parts.

  The raw materials used in the examples are as follows.

[Reinforcing fiber (A)]
・ Reinforcing fiber (PAN-based chopped carbon fiber) A1
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. A fiber bundle was obtained. The obtained PAN-based carbon fiber bundle was cut to 6.4 mm with a cartridge cutter to obtain reinforcing fiber A1.

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
Sizing type: Polyoxyethylene oleyl ether Sizing adhesion (Note 1): 1.5% by mass
Number average fiber length (Note 2): 6.4 mm.

[Reinforcing fiber (B)]
・ Reinforcing fiber (chopped glass fiber) B1
As the reinforcing fiber B1, chopped strand (product code: CS3J-451) manufactured by Nittobo Co., Ltd. was used.
Total number of filaments: 12,000 Single fiber diameter: 11 μm
Specific gravity: 2.5 g / cm ³
Sizing type: Silane coupling agent Number average fiber length: 3.0 mm (catalog value).

[Organic fiber (C)]
・ Organic fiber (acid-modified polypropylene resin) C1
The organic fiber C1 was manufactured by extruding “Admer (registered trademark)” QE510 manufactured by Mitsui Chemicals Co., Ltd. at 230 ° C. into a fiber shape. The physical properties are as follows.

Specific gravity: 0.91
Melting point: 160 ° C.

[Organic particles (D)]
・ Organic particles (flame retardant) D1
As the organic particles D1, melamine polyphosphate (product name: PHOSMEL-200) manufactured by Nissan Chemical Industries, Ltd. was used.

[Matrix resin (E)]
・ Matrix resin (nylon 6 resin) E1
As the matrix resin E2, “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 component (F)]
・ Binder component (acrylic polymer) F1
The binder component constituting the binder F1 was prepared by the following procedure.

  Charge 137.4 g of ion-exchanged water into a 1 L four-necked flask equipped with a stirrer, temperature sensor, reflux condenser, and monomer dropping port, repeat degassing and bubbling of nitrogen gas several times, and the dissolved oxygen concentration is 2 mg / L or less. After deoxygenating until, the temperature was started to rise. 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) Measurement conditions for the amount of sizing agent attached About 5 g of carbon fiber with the sizing agent attached thereto was sampled 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.
Adhering amount (% by mass) = 100 × {(W ₁ −W ₂ ) / W ₂ }
In addition, the measurement was performed 3 times and the average value was employ | adopted as adhesion amount.

(Note 2) Conditions for measuring the number average fiber length of reinforcing fibers The reinforcing fibers cut into a predetermined length were put into an aqueous dispersion and dispersed into a single fiber, followed by filtration to separate the reinforcing fibers. 400 single fibers were randomly extracted from the separated reinforcing fibers, their lengths were measured to the 10 μm unit with an optical microscope, and the average value was adopted as the number average fiber length.

[Time required for steps (i) to (iv)]
The time from when the solid component was added to the dispersion medium in step (i) until it was removed from the slurry liquid surface as a papermaking substrate in step (iv) was measured as the time required for steps (i) to (iv).

[Real manufacturing time (T)]
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 T.

[Method for evaluating dispersion state of reinforcing fiber]
From the arbitrary part of the papermaking base material obtained in the step (iv), the base material was cut into a 50 mm × 50 mm square shape 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.
A: Less than 5 bundles of carbon fibers with insufficient dispersion B: 5 or more and less than 10 bundles of carbon fibers with insufficient dispersion C: 10 or more bundles of carbon fibers with insufficient dispersion

[Evaluation method of basis weight stability]
Three strip-shaped substrates 50 mm long in the longitudinal direction are cut out from an arbitrary position in the longitudinal direction (manufacturing 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.

Example 1
A papermaking substrate was produced using the apparatus shown in FIG.

  FIG. 7 includes cylindrical dispersion tanks 1 and 2 having a diameter of 700 mm, and cocks 28 and 29 that can be opened and closed at the bottom of the tank. A stirrer 10 is attached to the openings on the upper surfaces of the dispersion tanks 1 and 2, from which raw materials can be charged. From the connection parts 6 and 7 of the dispersion tanks 1 and 2, linear transport parts 4 and 5 extend, and are integrated into one at the junction 27, and are large-sized corners that are papermaking tanks (width W = 1000 mm). It connects with the connection part (supply port) 8 of a type | mold sheet machine (Kumagaya Riki Kogyo Co., Ltd. make, No.2553-I (brand name)). The bottom of the papermaking tank 3 is provided with a papermaking surface (made of mesh sheet) 30 having a length of 1000 mm × width of 1000 mm, and a papermaking substrate is obtained on the papermaking surface. In FIG. 7, the dispersion tanks 1 and 2 are installed at a higher position than the papermaking tank 3, and the dispersion tanks 1 and 2 are installed at the same height. Each of the transport parts 4 and 5 has the same diameter (φ150 mm), and the ratio L / φ between the distance L (1500 mm) between the junction 27 and the connection part 8 and the diameter φ of the transport part is 10.

  Regarding the production method, first, 250 kg of a dispersion medium 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 prepared. 2 Next, 0.05 kg of the first solid component (reinforced fiber A1) 31 was charged into the dispersion tank 1, and 0.05 kg of the second solid component (reinforced fiber B1) 32 was charged into the dispersion tank 2. The charged raw materials were stirred using a stirrer 10 to adjust the slurries (a) and (b) so that the solid component concentration was 0.02% by mass [steps (i) and (ii)].

  Next, the cocks 28 and 29 provided in the dispersion tank are simultaneously released, and the slurries (a) and (b) flow into the transport section, are mixed at the junction 27 and fed to the papermaking tank 3 [Step ( iii)].

  Next, the dispersion medium was removed by suction on the papermaking surface 30 provided in the papermaking tank, and a papermaking substrate was made on the mesh sheet. The obtained papermaking substrate was dried in a dryer (not shown) at 130 ° C. to obtain a sheet-like papermaking substrate [step (iv)].

  In this example, steps (i) (ii) and (iii) (iv) were carried out online, and steps (ii) and (iii) were carried out offline to produce a papermaking substrate intermittently. .

The obtained paper base material had a basis weight of 100 g / m ² and was 1000 mm long × 1000 mm wide. The paper base material 100 m ² was continuously produced.

  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 produced using the apparatus shown in FIG.

  FIG. 8 shows that the dispersing tanks 1 and 2 have a concave shape with two openings (a wide-mouth opening 34 and a narrow-mouth opening 35) on the upper surface, and the stirrer 10 is installed in the wide-mouth opening 34. The connection parts 6 and 7 are located in the upper part (near opening part) of a dispersion tank, and the liquid feeding from a dispersion tank to the papermaking tank (width W = 500mm) 3 is possible by the overflow system, transportation Points that are not provided with cocks in the sections 4 and 5, points that are connected to the paper making surface 30 and are provided with a conveyor 36, points that are connected to the conveyor 36 and are provided with a conveyor 38 having a dryer 37, and are connected to the conveyor 38 and wound. The apparatus is the same as the apparatus of FIG.

  Regarding the production method, first, a dispersion medium 33 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 placed in the dispersion tanks 1 and 2. In a state of continuously supplying at a supply rate of 375 kg / min, the first solid component (reinforcing fiber A1) 31 is continuously supplied to the dispersion tank 1 at an input speed of 0.015 kg / min, and the second to the dispersion tank 2 The solid component (reinforced fiber B1) 32 was continuously charged at a charging rate of 0.015 kg / min. The charged raw material was stirred using stirring 10 and the slurry (a), (b) was continuously adjusted so that the solid component concentration was 0.02% by mass [steps (i), (ii) ]].

  Next, the slurry (a), (b) was flowed into the transport section from the connection sections 6 and 7 of the dispersion tank, and was fed into the papermaking tank 3 at the junction 27 [step (iii) ]].

  Next, the dispersion medium was sucked and removed on the papermaking surface 30 provided in the papermaking tank, and a papermaking substrate was made on the mesh sheet [step (iv)].

  The obtained papermaking substrate was placed on the guide cloth 40 by the conveyor 36, further passed through a dryer 37 at 130 ° C. by the conveyor 38, and wound in a roll together with the guide cloth by a winder 39. . The take-up speed at this time was 3 m / min [step (vi)].

  In this example, steps (i) to (iv) and (vi) were performed on-line to continuously produce a papermaking substrate.

The obtained papermaking substrate had a basis weight of 100 g / m ² and an effective width of 500 mm. The paper base material 100 m ² was continuously produced.

  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)
About the manufacturing method, the papermaking base material was obtained like Example 2 except having made the transportation of slurry (a), (b) the same as the width W of the papermaking tank 3 when reaching a papermaking tank.

The obtained papermaking substrate had a basis weight of 100 g / m ² and an effective width of 500 mm. The paper base material 100 m ² was continuously produced.

  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
About the manufacturing method, the papermaking base material was obtained similarly to Example 3 except having set the 2nd solid component to the organic fiber C1.

The obtained papermaking substrate had a basis weight of 100 g / m ² and an effective width of 500 mm. The paper base material 100 m ² was continuously produced.

  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)
About the manufacturing method, the papermaking base material was obtained similarly to Example 3 except having made the 2nd solid component into the organic particle D1.

The obtained papermaking substrate had a basis weight of 100 g / m ² and an effective width of 500 mm. The paper base material 100 m ² was continuously produced.

  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 produced using the apparatus shown in FIG.

  FIG. 9 shows that the transporting parts 4 and 5 are connected to the papermaking tank 3 in an independent state (separate), and the connecting parts (supply ports) 8 and 9 of the papermaking layer 3 have the same height in the vertical direction. The apparatus is the same as the apparatus shown in FIG. 8 except that it is provided side by side and the width of the transport section when reaching the papermaking tank 3 is W / 2.

  The manufacturing method was the same as in Example 2 except that the apparatus of FIG. 9 was used.

The obtained papermaking substrate had a basis weight of 100 g / m ² and an effective width of 500 mm. The paper base material 100 m ² was continuously produced.

  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 produced using the apparatus shown in FIG.

  FIG. 10 shows that the connection parts (supply ports) 8 and 9 of the papermaking tank 3 are provided vertically in the vertical direction, and the width of the transport part when reaching the papermaking tank 3 is the same as the width W of the papermaking tank. Except for a certain point, it is the same as the apparatus of FIG.

  The manufacturing method was the same as in Example 2 except that the apparatus shown in FIG. 10 was used.

The obtained papermaking substrate had a basis weight of 100 g / m ² and an effective width of 500 mm. The paper base material 100 m ² was continuously produced.

  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)
About the manufacturing method, it was the same as that of Example 8 except the point which made the input speed of reinforcement fiber A1 0.0375 kg / min, and the point which made the solid component density | concentration of slurry (a) 0.01 mass%.

The resulting papermaking substrate had a basis weight of 75 g / m ² and an effective width of 500 mm. The paper base material 100 m ² was continuously produced.

  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 manufactured using the apparatus shown in FIG.

  FIG. 11 is the same as the apparatus of FIG. 10 except that a shower-type binder applicator 41 is provided immediately above the conveyor 36 (equipment before the papermaking tank 3 is not shown).

  Regarding the production method, a 0.4 mass% aqueous dispersion (emulsion) of binder F1 was applied to the papermaking substrate obtained in step (iv) at a spraying rate of 1.13 kg / min. [Step (v)] provided.

  Subsequently, the papermaking base material to which the binder was applied passed through a dryer 37 at 200 ° C. on the conveyor 38 and was wound into a roll by the winder 39. At this time, the take-up speed was 3 m / min, and no guiding cloth was used for taking-up [Step (vi)].

  In this example, steps (i) to (iv) are the same as those in Example 2, and steps (i) to (iv) and steps (v) (vi) are online, and the papermaking substrate Was produced continuously.

The obtained papermaking substrate had a basis weight of 105 g / m ² (A1 basis weight: 100 g / m ² ) and an effective width of 500 mm. The paper base material 100 m ² was continuously produced.

  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 paper-making substrate was produced using the apparatus shown in FIG.

  FIG. 12 shows a double belt press device 42 that can be connected to the conveyor 38 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. The apparatus is the same as that of the apparatus shown in FIG. 11 except that a creel 43 for housing is provided (equipment before the papermaking tank 3 is not shown).

About a manufacturing method, the papermaking base material which passed the dryer 37 at the process (iv) is pinched from the up-down direction with the nonwoven fabric (weight per unit: 100g / m < ² >) which consists of matrix resin E2 supplied from the creel 43, Introduced in a double belt press machine. 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 [step (vii)].

  The obtained fiber reinforced molded base material was wound into a roll shape by a winder 39. At this time, the take-up speed was 3 m / min, and no guide cloth was used for taking-up [Step (viii)].

  In this example, steps (i) to (iv) are the same as those in Example 10, and steps (i) to (vi) and steps (vii) (viii) are online, and fiber reinforced molding The substrate was produced continuously.

The obtained fiber-reinforced molded base material had a basis weight of 300 g / m ² (A1 basis weight: 100 g / m ² ), a reinforcing fiber content of 20%, and an effective width of 500 mm. The paper base material 100 m ² was continuously produced.

  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 manufactured using the apparatus shown in FIG.

  FIG. 13 is the same as the apparatus of FIG. 8 except that the dispersion tank 1 and the transport unit 4 have only one series.

  About a manufacturing method, process (i)-(iv) is the point which supplied the 1st solid component (reinforced fiber A1) 31 and the 2nd solid component (reinforced fiber B1) 32 to the dispersion tank 1, ie, process ( The points where i) and (ii) were carried out in the same dispersion tank 1, the solid component concentration of the adjusted slurry was 0.04% by mass, and the adjusted slurry was made into a papermaking tank in one transport section 4. Example 2 was the same as Example 2 except that the solution was fed to No. 3.

  In this comparative example, steps (i) to (vi) and (iv) were online, and a fiber-reinforced molded base material was continuously produced.

The obtained papermaking substrate had a basis weight of 100 g / m ² and an effective width of 500 mm. The paper base material 100 m ² was continuously produced.

  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)
Process (1) for producing a papermaking machine containing the first solid component (reinforcing fiber A1) through steps (i) to (iv) (vi), second through steps (i) to (iv) and (vi) Process (2) for producing a papermaking substrate containing a solid component (reinforcing fiber B1), the papermaking substrates obtained in the processes (1) and (2) are aligned in parallel at a speed of 3 m / min, and rolled. The papermaking substrate was manufactured through three processes, the winding process (3).

  Processes (1) and (2) produced a papermaking substrate using the apparatus shown in FIG.

  Process (3) manufactured the papermaking base material using the apparatus of FIG.

  FIG. 14 includes a winder 39 on which a creel capable of accommodating two rolls 44 and 45 made of a papermaking base material is installed and a roll drawn from the creel can be wound.

  Regarding the production method, processes (1) and (2) were the same as in Comparative Example 1 except that a papermaking substrate was produced for each solid component. In the process (3), each of the rolls 44 and 45 made of the papermaking base material obtained in the processes (1) and (2) is arranged in parallel and set in a creel. It wound around one roll at a speed of 3 m / min.

The obtained paper base material had a basis weight of 100 g / m ² and an effective width of 1000 mm. The paper base material 100 m ² was continuously produced.

  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 3)
In the process (3), each of the rolls made of the papermaking substrate obtained in the processes (1) and (2) is set to be vertically aligned, and each of the papermaking substrates drawn from the creel is It was the same as Comparative Example 2 except that it was wound around a single roll at a speed of 3 m / min while being aligned and laminated (FIG. 15).

The obtained papermaking substrate had a basis weight of 100 g / m ² and an effective width of 500 mm. The paper base material 100 m ² was continuously produced.

  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 4)
The process was the same as that of Comparative Example 3, except that the roll obtained in Comparative Example 3 includes the process (4) of combining the matrix resin.

  In the process (3), a fiber reinforced molded base material was manufactured using the double belt press device 42 or later of the apparatus of FIG.

  Process (4) was the same as steps (vii) and (viii) of Example 11.

The obtained fiber-reinforced molded base material had a basis weight of 300 g / m ² (A1 basis weight: 100 g / m ² ), a reinforcing fiber content of 20%, and an effective width of 500 mm. The paper base material 100 m ² was continuously produced.

  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 5)
A papermaking substrate was manufactured using the apparatus shown in FIG.

  FIG. 16 is the same as the apparatus of FIG. 7 except that there is only one series of the dispersion tank 1 and the transport unit 4.

  About a manufacturing method, process (i)-(iv) is the point which supplied the 1st solid component (reinforced fiber A1) 31 and the 2nd solid component (reinforced fiber B1) 32 to the dispersion tank 1, ie, process ( The points where i) and (ii) were carried out in the same dispersion tank 1, the solid component concentration of the adjusted slurry was 0.04% by mass, and the adjusted slurry was made into a papermaking tank in one transport section 4. Example 3 was the same as Example 1 except that the solution was fed to No. 3.

The obtained paper base material had a basis weight of 100 g / m ² and was 1000 mm long × 1000 mm wide. The paper base material 100 m ² was continuously produced.

  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 is clear from Table 1, in Examples 1 to 5, it was possible to obtain a papermaking substrate having excellent dispersibility in a system containing two solid components. In step (i) (ii), by adjusting the slurry for each solid component, the solid component concentration in the slurry can be diluted, and the process time in the slurry containing two components of the solid component can be shortened. Further, reaggregation and sedimentation of solid components are suppressed, and a process having excellent dispersibility can be obtained (Examples 1 to 5, Comparative Examples 1 and 5).

  Moreover, in Examples 6-10, it is a process excellent in the dispersibility from the effect similar to the above-mentioned, and also the papermaking base material in which different solid components are arrange | positioned in parallel, and the papermaking by which a different solid component is laminated | stacked Since the substrate can be produced in a single process, it is usually produced through a plurality of processes, whereas it can be produced with particularly high productivity (Examples 6 to 10, Comparative Examples 2 to 4). ).

  Moreover, the solid component can be selected from various materials, and materials that can be applied to a wide range of uses can be manufactured (Examples 3 to 5).

  Furthermore, it is possible to carry out various processes and on-line, and it is possible to produce a paper-making base material to which a binder has been applied and a fiber-reinforced molding base material in which a matrix resin is combined (Examples 9 and 10).

1, 2 Dispersion tank 3 Papermaking tank 4, 5 Transport section 6, 7 Connection section 8, 9 Connection section (supply port)
DESCRIPTION OF SYMBOLS 10 Agitator 11, 20 Area | region containing 1st solid component 12, 21 Area | region containing both 1st solid component and 2nd solid component 13, 22 Area | region containing 2nd solid component 14 Papermaking base material 15 Papermaking base Material take-up direction 16 Width direction of papermaking substrate 17, 24 Region where the first solid component is larger than the second solid component 18, 25 Region containing the same amount of the first solid component and the second solid component 19, 26 Region in which the first solid component is less than the second solid component 23 Thickness direction (vertical direction) of the papermaking substrate
27 Confluence 28, 29 Cock 30 Papermaking surface 31 First solid component 32 Second solid component 33 Dispersion medium 34 Narrow opening 35 Wide opening 36, 38 Conveyor belt 37 Dryer 39 Winder 40 Cloth 41 Binder application device 42 Double belt press device 43 Creel 44, 45 Roll made of paper-making substrate

Claims (17)

A method for producing a papermaking substrate, comprising at least the following steps (i) to (iv).
(I): a step of adjusting the slurry (a) in which the first solid component is dispersed in the dispersion medium (ii): a step of adjusting the slurry (b) in which the second solid component is dispersed in the dispersion medium (Iii): Step of transporting slurry (a), (b) to the same papermaking tank (iv): Step of removing the dispersion medium from the slurry transported in step (iii) to obtain a papermaking substrate The method for producing a papermaking substrate according to claim 1, wherein in the step (iii), the transport of the slurry (a) and (b) is carried out by mutually independent routes. The method for producing a papermaking substrate according to claim 1, wherein in the step (iii), the slurries (a) and (b) are merged immediately before the papermaking tank and then transported to the papermaking tank. The papermaking according to any one of claims 1 to 3, wherein in the step (iii), the slurry (a), (b) is transported at the same width as the width of the papermaking tank when reaching the papermaking tank. A method for producing a substrate. Any one of Claims 1-4 whose mass content rate of the solid component in the slurry (a) and (b) prepared by the said process (i) and (ii) is 0.001-1 mass%. A method for producing a papermaking substrate according to claim 1. The manufacturing method of the papermaking base material of Claim 2 from which the mass content rate of the solid component of the said slurry (a) and (b) differs mutually. The first solid component is a reinforcing fiber (A), the second solid component is a reinforcing fiber (B), the specific gravity of the reinforcing fiber (A) and the reinforcing fiber (B), number average fiber length, tensile strength, tensile The method for producing a papermaking substrate according to any one of claims 1 to 6, wherein at least one of the elastic moduli is different from each other. The method for producing a papermaking substrate according to any one of claims 1 to 6, wherein the first solid component is a reinforcing fiber (A) and the second solid component is an organic fiber (C) or an organic particle (D). . The manufacturing method of the papermaking base material of Claim 8 whose said organic fiber (C) or organic particle (D) is a thermoplastic resin. The manufacturing method of the papermaking base material in any one of Claims 6-8 whose number average fiber length of the said reinforced fiber is 1-50 mm. The manufacturing method of the papermaking base material in any one of Claims 7-10 whose said reinforced fiber is carbon fiber or glass fiber. The basis weight of the paper substrate is 10 to 500 g / ^{m 2,} the production method of the paper substrate according to any one of claims 1 to 11. The manufacturing method of the papermaking base material in any one of Claims 1-12 provided with the process (v) which provides a binder to the papermaking base material obtained at the said process (iv). In the step (i), the dispersion medium and the first solid component are continuously charged. In the step (ii), the dispersion medium and the second solid component are continuously charged. The method for producing a papermaking substrate according to any one of claims 1 to 13, further comprising a step (vi) of drawing at 1 to 30 m / min, and all steps are continuously carried out online. The method for producing a papermaking substrate according to claim 14, wherein the time required for the steps (i) to (iv) is 10 minutes or less. A method for producing a fiber-reinforced molded substrate, wherein a matrix resin is combined with the papermaking substrate obtained in claims 1 to 15 (vii). The method for producing a fiber-reinforced molded substrate according to claim 16, further comprising a step (viii) of drawing the fiber-reinforced molded substrate at a speed of 1 to 30 m / min, and all the steps are continuously performed online. .

Images