JP2020059929A - Vegetable fiber bundle - Google Patents

Abstract

To provide a vegetable fiber bundle containing hemicellulose, lignin and a resin component around a cellulose fiber and having excellent functionality such as dispersibility and strength, which is obtained from various reproducible natural plant resources.SOLUTION: Plant resources are subjected to heat-treatment such as sulfite (sulfite salt) digestion, craft (sulfate salt) digestion, alkali digestion, hot water steam-cooking and the like to thereby obtain a vegetable fiber bundle containing 5 to 80 wt.% of lignin, 1 to 50 wt.% of a resin component and 15 wt.% or less of pentosan based on a cellulose weight.SELECTED DRAWING: None

Description

  TECHNICAL FIELD The present invention relates to plant-derived plant fiber bundles and molded products used for composite materials such as paving materials, structural materials, building materials, and furniture.

  Currently, in the energy field and the material field, the industrial structure is largely dependent on fossil resources such as petroleum. Plastic fiber or inorganic glass derived from petroleum resources such as organic carbon fiber and aramid fiber, which have high strength, for the purpose of providing reinforcement and functionality to cement products such as plastic products, asphalt pavement or reinforced concrete. Fiber-reinforced materials such as fibers have been used.

  Due to environmental problems such as exhaustion of petroleum resources, non-petroleum-based materials are being actively developed. As a natural resource that can be replaced, cellulose-based materials have a large amount of resources and are renewable and have excellent mechanical strength. In the field of engineered plastics, a method of extracting and blending monofilaments of cell units of a plant as a fiber reinforcing material has been put into practical use (Non-patent Documents 1 and 1).

  Cellulose fibers are also used in the fields of road paving materials and concrete materials, but they mainly appeal to thickening action, and how to use various functions such as mechanical strength of natural fibers. It was not (Patent Document 2).

  Further, attempts have been made to add an antistatic agent for the purpose of improving the dispersibility between fibers in a medium and expressing the mechanical strength of natural fibers. However, it is necessary to use an expensive drug, and not only the effective concentration range of the drug is limited, but also complication of the manufacturing process is inevitable (Patent Document 3).

  On the other hand, as an attempt to take out a fiber bundle of high strength and excellent toughness and a biodegradable fiber length of significant length from the plant body and impart strength to it, steam heating bamboo material in a high-pressure container at a constant temperature After holding for a period of time, opening the release valve to release the pressure and performing blasting, a method of crushing by crushing with a roller was examined, and the obtained fiber bundle had higher strength than the bamboo fiber bundle cut from raw bamboo. It has been reported (Non-patent document 2, Patent document 4).

  Further, in Patent Document 5, using a bamboo fiber bundle obtained by subjecting a bamboo material to a weak alkali treatment, a method for manufacturing a bamboo fiber bundle having strength by twisting a plurality of bamboo fiber bundles into a rope shape and further impregnating with a resin is provided. Proposed. However, the raw material was limited to bamboo, and it could not be applied to wood resources such as wood residue.

  Further, in Patent Document 6, it is not possible to completely remove lignin from the wood raw material, pulp without lignin being removed or a part of lignin being removed is steamed if necessary, and mechanically thawed. A method for producing a cellulose microfibril bundle having heat resistance of a structure in which hemicellulose and lignin are coated in this order by a fiber treatment has been proposed. It takes a complicated process and consumes a lot of energy to process up to the unit of fine fibers.

  On the other hand, in Non-Patent Document 3, after partially removing lignin and hemicellulose from natural wood by a boiling step in an aqueous mixture of caustic soda and sodium sulfite, the cell walls were crushed by hot compression to completely densify the natural wood. And highly align the cellulose nanofibers in the wood. A simple method for directly converting bulk natural wood into a high-performance structural material with 10 times or more strength, toughness, and ballistic resistance and excellent dimensional stability has been reported. However, it could not be processed into a fibrous form or a fiber bundle form.

JP 2009-516032 JP JP 2003-147709 A JP 2018-104263 JP 2009-166397 JP Japanese Patent Laid-Open No. 2009-154387 JP 2009-019200 JP

"Materials" Vol.60, No.1, pp.79-85, (2011) "Materials" Vol.52, No.4, pp.353-356, (2003) Nature volume 554, pages 224-228 (08 February 2018)

  As a fiber reinforced material composed of natural materials that resists the strength of synthetic fibers derived from petroleum resources, traditionally, the material is limited to bamboo, and further the manufacturing process is inevitable and energy consumption is large. Met.

  Further, in paper-making pulp mainly composed of cellulose, fibers are easily aggregated with each other regardless of whether they are water-based or non-water-based and they are difficult to be entangled and dispersed, and the strength as a fiber reinforcing material is insufficient.

  INDUSTRIAL APPLICABILITY The present invention organizes monofilaments of cell units containing hemicellulose, lignin, and resin components, which are efficiently extracted from various renewable natural plant resources typified by woodland residues, around cellulose fibers. The present invention relates to a fiber bundle having a significant length and excellent functionality such as dispersibility and strength.

  Traditionally, in the field of traditional crafts, bamboo is a technique called "oil removal". It is steamed in slightly alkaline hot water, and then dried and heat treated to give strength and durability to bamboo products such as fishing rods. It has been known that the physical properties can be enhanced by chemically modifying the material.

  Plant materials such as bamboo are high-strength cellulose and hemicellulose / lignin aggregates composed of a stack of fiber bundles of pipe-shaped cell units that form conduits, tracheids and phloems, and have a pipe-shaped structure. Imparts water conduction and plant rigidity and toughness. Furthermore, in monocotyledonous plants such as bamboo, the soft tissue exists in the same direction as the fiber bundle, and in wood, the radiation soft tissue exists in the direction perpendicular to the fiber bundle, which serves as a cushion for the transport and storage of biological components related to growth and the structure. Plays.

  INDUSTRIAL APPLICABILITY According to the present invention, a plant body is digested or cooked to soften the thin soft tissues of cell walls to form crevices, part of the hemicellulose / lignin is dropped from the laminate of fiber bundles, and then the crevices are mechanically widened. By defibrating the fibers in the direction, a fiber bundle having a significant length (length in the fiber direction of the raw material) formed by assembling single fibers of cell units is obtained.

  In addition, the resin component contained in the original raw material is coated on the surface of the fiber bundle by being solid-solubilized in the remaining lignin, and further, in the subsequent drying process, a pipe-shaped fiber bundle that forms a temporary tube or a master tube. By crushing the cavities, the bonds in the fiber bundle are strengthened and the density is increased, and high strength and various functions are exhibited.

  Furthermore, when dried at about 170 ° C to 200 ° C using superheated steam, the lignin component is thermally plasticized and then thermoset by the applied heat, whereby the binding of the single fibers is further strengthened, and the rigidity of the fiber bundle is increased. It is possible to obtain a dried product having a further increased temperature.

That is, the present invention provides the following inventions.
(1) A vegetable fiber bundle containing 5 to 80% by mass of lignin, 1 to 50% by mass of a resin component, and 15% by mass or less of pentosan relative to the weight of cellulose.
(2) The plant fiber bundle according to (1), wherein the plant raw material is heat-treated in an aqueous system and then mechanically defibrated.
(3) The plant fiber bundle according to (1) or (2), which has a higher-order structure in which monofilaments of cell units containing hemicellulose and / or lignin are organized around cellulose fibers.
(4) The vegetable fiber bundle is a fiber bundle obtained by at least one heat treatment selected from sulfite (sulfite) cooking, kraft (sulfate) cooking, alkaline cooking and hot water cooking (1) ~ The vegetable fiber bundle according to any one of (3).
(5) The plant fiber bundle according to any one of (1) to (4), which has an average fiber length of 5 to 50 mm and an aspect ratio of 20 to 200.
(6) A plant fiber bundle obtained by treating the plant fiber bundle according to any one of (1) to (5) with superheated steam.
(7) A fiber reinforcing material using the vegetable fiber bundle according to any one of (1) to (6).
(8) A fiber-reinforced material obtained by subjecting the vegetable fiber bundle according to any one of (1) to (6) to a hydrophobic treatment.
(9) A fiber-reinforced material obtained by compounding the plant fiber bundle according to any one of (1) to (6) with an inorganic component.
(10) A molded product containing the plant fiber bundle according to any one of (1) to (9).

  The fiber bundle of the present invention contains a hydrophobic lignin and a resin component, and the surface of the fiber bundle exhibits appropriate charge and hydrophobicity, and thus has excellent dispersibility in various media and high rigidity, and the fiber bundle It becomes a material that is hard to get entangled with each other. Further, when blended in various composite materials, the fiber bundles are fused during molding due to the thermoplasticity / thermosetting property of lignin, and a stronger molded body is obtained. Further, various functions such as antiseptic effect of the resin component can be imparted to the molded body.

  Conventionally, in the pulp and paper industry, in order to maintain the quality of the paper of the product, it is necessary to use monofilaments of uniform cell size, and there are limited tree species that can be adapted. On the other hand, in the present invention, a tissue portion in which monofilaments of cell units are overlaid is efficiently extracted while maintaining strength, and processed into a fiber bundle having an average length of about 5 to 50 mm and an aspect ratio of about 20 to 200. is there. Since this fiber bundle does not depend on the shape of the cell unit, it can be applied to various tree species and parts having different single fiber shapes.

  As the plant raw material for supplying the fiber bundle used in the present invention, plant raw materials that have been used in conventional pulp and building materials can be widely used, and examples thereof include wood, bamboo / bamboo grass, hemp, jute, kenaf, and crop residue. Waste, etc. are mentioned. Preferably, a wood material is preferable, and by binding flavonoids such as tannin contained in most wood, the binding between the single fibers is strengthened and the rigidity is increased. More preferably, a softwood material containing abundant resin components is preferable, and for example, if pine wood is used, the resin acids contained therein can impart a surface-active effect to the surface of the fiber bundle, and further cedar wood or cypress wood is used. By doing so, various functions such as anticidal activity, termite feeding inhibitory activity and antibacterial activity derived from terpenes such as ferguinol contained can be imparted to the molded body.

  As a method for taking out the fiber bundle from the plant raw material, any method may be used as long as the lignin and the resin component in the plant raw material remain, but preferably, the lignin-containing weight is 5 to 80% by mass with respect to the cellulose-containing weight in the fiber bundle. It is possible to use a fiber bundling method in which the resin content is 1 to 50 mass% and the pentosan is 15 mass% or less.

The following processing steps can be given as specific examples.
A. [raw material] ⇒ <cutting / crushing> ⇒ <digestion or steaming / selection> ⇒ <pressing / defibration / classification> ⇒ <drying>
B. [raw materials] ⇒ <cutting / crushing> ⇒ <digestion or steaming / selection> ⇒ <pressing> ⇒ <drying / defibration / classification>
In the present invention, the chemical heat treatment for taking out the fiber bundle is called "steaming", and "digestion" is a subordinate concept and solution including "steaming" and "defibration" for pulping. can do.

  In the case of the wood-based raw material of the raw materials of the present invention, it is preferable that the side / core material and the bark are divided and coarsely crushed to a size of 50 mm or less in advance so that the fiber bundle can be easily taken out. For the peeling and coarse pulverization, a crusher such as a barker, a crusher, and a chipper that is commonly used for ordinary coarse crushing can be used.

  Bamboo, bamboo grass and herbaceous materials do not need to be crushed because they have good steaming efficiency, and can be cut into a size that fits in a reaction vessel and used in a bundled state. You can even cut it.

  The cooking or the steaming / defibration treatment is, for example, commonly used in the pulp and paper industry, for raw materials such as sulfite (sulfite) cooking, kraft (sulfate) cooking, alkaline cooking, hot water cooking, alkaline treatment, oxygen oxidation treatment, Fiber bundles can be formed chemically or chemically and mechanically by sodium hypochlorite treatment, sulfite treatment and the like. Examples include chemical pulping processes (CP, (kraft pulping process (KP), sulfite pulping process (SP), etc.), semi-chemical pulping process (SCP), chemigrand pulping process (CGP), chemi-mechanical pulp. Examples include cooked / un-cooked pulp produced in the manufacturing process such as chemical conversion method (CMP), etc. If the lignin and the resin content remain and are contained in a predetermined amount, they can be used as the crude fiber bundle in the present invention. .

  In addition, for the steaming / defibration treatment, a crude fiber bundle obtained by a wet heat treatment such as hot water steaming, sulfite steaming, and alkali steaming, which are commonly used in the wood board industry, can be used. Further, it is effective to carry out the step of steaming and the step of defibration by using a device such as a defibrillator.

  Kraft (sulfate) cooking will be described below as one method for obtaining the plant fiber bundle of the present invention.

  It is preferable that the fiber bundle of the present invention is made of a so-called digested meal, which is a material that remains without being made into fibers after the wood chips are kraft cooked. The wood chips used as the raw material can be efficiently converted to cooked meal by blending wood pulp, which is traditionally difficult to make into chemical pulp, such as rosewood, ebony, and cedar heartwood. it can. In addition, if coarse chips or knot portions that are difficult to be cooked are mixed in the raw material wood chips, the cooking will be non-uniform, so that pulp containing cooked meal can be efficiently produced. For example, when the chips are sieved, it is preferable to mix 10% or more of coarse chips having a major axis of 22.4 mm or more, and more preferably 15% or more. Further, it becomes possible to separate the pulp content and the digested meal in the knotter or the refining process after the digestion.

  The wood chips are put into a digester together with the cooking liquor and used for craft cooking. Moreover, you may use for the cooking of the modified Kraft method, such as MCC, EMCC, ITC, and Lo-solid. In addition, there is no particular limitation on the cooking type such as 1-vessel liquid phase type, 1-vessel gas phase / liquid phase type, 2 vessel liquid phase / gas phase type, 2 vessel liquid phase type. That is, the step of impregnating the alkaline aqueous solution of the present application and holding the alkaline aqueous solution may be installed separately from the conventional apparatus or site for the purpose of permeating the cooking liquor. The liquid ratio of the wood chips and the chemical liquid can be, for example, 1.0 to 5.0 L / kg, preferably 1.5 to 4.5 L / kg, more preferably 2.0 to 4.0 L / kg. .

  Further, in the present invention, an alkaline cooking liquor containing a quinone compound may be added to the digester. When an alkaline cooking liquor containing a quinone compound is added, it is preferably 0.01 to 1.5% by mass per absolutely dried chips.

  The quinone compound used is a so-called known quinone compound as a cooking aid, a hydroquinone compound or a precursor thereof, and at least one compound selected from these can be used. Examples of these compounds include anthraquinone, dihydroanthraquinone (eg, 1,4-dihydroanthraquinone), tetrahydroanthraquinone (eg, 1,4,4a, 9a-tetrahydroanthraquinone, 1,2,3,4-tetrahydroanthraquinone). , Methylanthraquinone (eg 1-methylanthraquinone, 2-methylanthraquinone), methyldihydroanthraquinone (eg 2-methyl-1,4-dihydroanthraquinone), methyltetrahydroanthraquinone (eg 1-methyl-1,4,4a) , 9a-tetrahydroanthraquinone, 2-methyl-1,4,4a, 9a-tetrahydroanthraquinone), anthrahydroquinone (generally 9,10-dihydroxyanthracene), Cylanthrahydroquinone (for example, 2-methylanthrahydroquinone), dihydroanthrahydroanthraquinone (for example, 1,4-dihydro-9,10-dihydroxyanthracene) or an alkali metal salt thereof (for example, a disodium salt of anthrahydroquinone, 1 , 4-dihydro-9,10-dihydroxyanthracene disodium salt) and other precursors such as anthrone, anthranol, methylanthrone and methylanthranol. These precursors have the potential to be converted to quinone or hydroquinone compounds under cooking conditions.

The cooking liquor preferably has an active alkali addition rate (AA) per weight of absolutely dry wood chips of 5 to 35% by mass. If the addition rate of the active alkali is less than 5% by mass, the cooking will not proceed and the yield of the fiber bundle will decrease. If it exceeds 35% by mass, the cooking will be excessive and the yield of the fiber bundle will decrease. Here, the active alkali addition rate is calculated by converting the total addition rate of NaOH and Na ₂ S as the addition rate of Na ₂ O, and NaOH is multiplied by 0.775 and Na ₂ S is multiplied by 0.795. Therefore, it can be converted into the addition rate of Na ₂ O. Further, the sulfidity is preferably in the range of 20 to 35%.

  Kraft cooking is preferably performed in a temperature range of 100 to 180 ° C, more preferably 110 to 160 ° C. If the temperature is too low, the digestion will not proceed and the yield of fiber bundles will decrease. If the temperature is too high, the fiber bundles will be made into fibers and the yield will decrease. Further, the cooking time in the present invention is the time from when the cooking temperature reaches the maximum temperature to when the temperature starts to drop, but the cooking time is preferably 30 minutes or more and 360 minutes or less, and 50 minutes or more and 220 minutes or less. Is more preferable. If the cooking time is less than 30 minutes, the progress of cooking will not proceed, and the yield of the fiber bundle will decrease. If it exceeds 360 minutes, the fiber bundle will be fiberized and the yield will decrease.

In the kraft cooking according to the present invention, the treatment temperature and the treatment time can be set using the H factor (Hf) as an index. The H factor is a standard that represents the total amount of heat given to the reaction system during the cooking process, and is represented by the following formula. The H factor is calculated by time integration from the time when the chips and water are mixed to the time when the cooking is completed. The H factor is preferably 300 to 2000.
Hf = ∫exp (43.20-16113 / T) dt
[In the formula, T represents an absolute temperature at a certain time point]

  Further, in the kraft cooking, when the kraft cooking is carried out so that the Kappa number of the unbleached kraft pulp obtained at the same time becomes 30 or more, the cooked meal which is a raw material of the fiber bundle of the present invention without excessively cooking the wood chips. Is relatively preferable, so that it is preferable.

  The fiber bundle of the present invention preferably has an average fiber length of 5 to 50 mm and an aspect ratio (major axis ratio) of 20 to 200, and a corresponding fiber bundle can be obtained by applying the treatment process of the case of the present invention. it can. Further, if necessary, classification treatment may be carried out, and such a fiber bundle has an average fiber length of 5 to 50 mm by subjecting the plant raw material to the above-mentioned digestion or cooking / defibration treatment and then classification treatment. , The aspect ratio (major axis ratio) can be adjusted specifically for a specific fraction within the range of 20 to 200.

  The classification treatment of the fiber bundle may be either wet or dry.

  As a method for classifying fiber bundles by a wet method, for example, a slit screen method, a cyclone method, a specific gravity separation method, a floating sorting method and the like can be used. Among them, a method using a liquid cyclone using a water stream is preferable. The use of this method has the convenience of being able to directly add the fiber bundle mixture, and enables continuous classification and recovery at low cost. Further, as the liquid cyclone, conventionally known ones, for example, a single cyclone (trade name, Centric cleaner), a multi cyclone, etc. can be used.

  Further, as a method for classifying the fiber bundle by a dry method, a conventionally known method such as a sieving method or a cyclone method can be used. It is preferable to use the cyclone method, which enables continuous classification and low-cost recovery. It is also possible to use equipment known in the industry in which a cyclone is incorporated in a dryer or the like, and the process can be shortened.

  In the present invention, the crude fiber bundle containing the lignin and the resin component can be defibrated by a wet or dry method. As the machine used for defibration, refiners such as single disc refiner, double disc refiner, conical refiner, kneader, edge runner, beater, PFI mill and other beaters, blenders, agitators such as deflakers, hammer mills, etc. Crushers such as a pin mill and a roll mill, a crusher such as a fluffer, and an opening machine such as a fluffing machine.

  Furthermore, by pressing with a press such as a roll press, a screw press, or a reciprocating press, and applying pressure to the coarse fiber bundle to dehydrate it, the cavities in the pipe-shaped fiber bundle are deformed and crushed to bond within the fibers. Will be strengthened. The pressure dehydration can reduce the water content, reduce the drying energy, and contribute to energy saving.

  Further, superheated steam may be used in the drying step. The treatment can be performed at about 170 ° C. to 200 ° C., and the heat applied by drying heats the lignin component after it is plasticized and then thermoset, thereby strengthening the binding between the single fibers and increasing the rigidity of the fiber bundle. Further, by promoting the defibration by a dry method, it is possible to obtain a fiber bundle having an arbitrary size and excellent rigidity.

  As a dry method for defibrating the fiber bundle, a crusher such as a hammer mill and a roll mill, a crusher such as a fluffer, and an opening machine such as a fluffing machine can be used.

  As a device for obtaining such a fiber bundle, by using a known device in the industry such as a device that defibrates in a semi-dried state and a machine that combines flash drying by introducing superheated steam, a dried body of the fiber bundle can be efficiently obtained. Obtainable.

  Further, the crude fiber bundle obtained by the steaming and defibrating treatment can be subjected to pressing and crushing treatment at the same time by beating with a wet machine such as a kneader or an edge runner, and then steam drying.

  The fiber bundle thus obtained exhibits high dispersibility in an aqueous medium such as cement due to the appropriate charge, hydrophobicity and rigidity of the surface. Further, the moderately hydrophobic surface has excellent dispersibility in non-aqueous asphalt and plastic even though the support has hydrophilic fibers, and is suitable as a reinforcing fiber in various media.

  In addition, the lignins and resin components contained in the fiber bundle obtained in the present invention are highly reactive and can be easily chemically modified. Using a known method, the fiber bundle is impregnated with a hydrophobic component, or lignin having a phenolic hydroxyl group contained and aldehydes are condensed to be resinified for hydrophobic treatment, or the ion of the fiber bundle surface It can also be combined with an inorganic substance by utilizing the property.

Examples of the fiber reinforcing material and the molded product using the fiber bundle of the present invention are illustrated below, but the invention is not limited thereto.
1) Construction materials such as reinforced concrete
2) Road pavement materials such as asphalt pavement and cement concrete pavement
3) Materials used for large-scale 3D printers that contain reinforcing fibers, etc.
4) Cement board (wood cement board) added with wood chips, wood pulp, wood fibers, etc., cement extrusion board, pulp cement board, gypsum board, calcium silicate board, magnesium carbonate board, hard board, medium density fiber board, Construction materials such as firing boards, components such as daily necessities and musical instruments
5) Molded products such as reinforced plastics and WPC (wood plastic composites) blended fibers for home appliances that are processed into complicated shapes, aerospace materials, automobile parts, sports equipment, furniture, daily necessities, etc.
6) Multi-pack paper, non-woven fabric, Japanese paper, base paper for printed circuit boards, etc. By adding a surface-active effect and appropriate hydrophobicity to the raw materials, workability at the time of molding can be improved, and molding Not only does the body have the same reinforcing effect as petrochemical synthetic fibers, but it also has various functions of the raw materials such as water repellency, anticidal activity, termite feeding inhibition activity, antibacterial activity, and durability. Will also be excellent.

  The fiber bundle of the present invention can also be manufactured by utilizing existing equipment such as paper pulp or wood board manufacturing equipment. As a result, the amount of waste can be minimized, which can contribute to the energy saving of the business as a whole.

  The size of pulp produced from ordinary woody materials depends on the cell size peculiar to the plant species. Therefore, a pulp having a long fiber length cannot be obtained from the core material. On the other hand, by applying the present invention, it is possible to take out a fiber bundle of an arbitrary length having a relatively long fiber length regardless of the material type. Further, the physical strength is improved by further heat-treating the fiber bundle.

  The fiber bundle according to the present invention has a content of pentosan, which is inferior in heat stability, reduced to half that of the raw wood, and it is known from the literature that there is little deterioration even at a high temperature of about 100 to 200 ° C at which the durability of wood decreases. Can be expected (Patent Document 6). Therefore, it is possible to supply products with stable quality even if there is a high-temperature process in manufacturing and construction such as construction of asphalt pavement.

  Furthermore, regarding the resins contained in the raw material, various components can be contained in the fiber bundle by selecting the material type. For example, a fiber bundle obtained by kraft cooking hardwood contains polyphenols such as tannin, which is expected to have an antioxidant effect. In addition, the fiber bundle obtained by craft cooking using cedar wood as a raw material contains ferguinol, which is a terpene that has functions such as anticidal activity, termite feeding inhibitory activity, and antibacterial activity. Added value can be added.

  Furthermore, the fiber bundles made from cedar wood contain a large amount of terpenes and lignin having phenolic hydroxyl groups. Phenols are highly reactive, and by reacting with a polymerizing agent while being contained in a fiber bundle, a resin-impregnated fiber bundle with high strength can be obtained.

  On the other hand, the fiber bundle obtained by sulfite cooking contains a large amount of lignin sulfonic acid obtained by modifying lignin. A strong anionic sulfo group is formed in the molecule, and the fiber bundle is useful not only as a material having an anionic surface-active action but also as a support for forming a complex with a polyvalent cation.

  Further, the fiber bundle obtained by sulfite cooking using pine wood as a raw material contains a large amount of ligninsulfonic acid and resin acids. Resin acid forms a complex salt similar to metal soap with polyvalent metal cation, and is used as a concrete admixture with ligninsulfonic acid. Therefore, the dispersibility of the fiber bundle in the cement-based medium becomes good. As described above, the fiber bundle obtained in the present invention is useful not only as a fiber reinforcing material but also as a base material having various functions.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to the following examples. Unless otherwise stated, in the present invention,% and the like are based on weight, and the numerical range includes the end points thereof.

Experimental method <Analysis / Terminology>
In principle, the analysis and terminology of the present invention follow the Japan TAPPI paper pulp test method.
(1) Cellulose
Japan TAPPI paper pulp test method No. 65 "pulp material-holocellulose content test method", the holocellulose was measured α-cellulose according to JIS P8101: 1994 "dissolved pulp test method", and the amount of cellulose .
(2) Lignin (Klason Lignin)
The amount of lignin was measured according to Japan TAPPI paper pulp test method No. 61 “Pulp material-test method for lignin content”.
(3) Resin content (soluble in organic solvent)
According to Japan TAPPI Paper Pulp Test Method No. 63 “Pulp Material-Alcohol / Benzene Soluble Content Test Method”, the organic solvent soluble content was measured and used as the resin content.
(4) Pentosan
The amount of pentosan was measured according to Japan TAPPI paper pulp test method No. 64 "Pulp material-Pentosan content test method".
(5) Fiber length
According to JIS P8226-2: 2011 (ISO 16065-2: 2007) "Pulp-Method for measuring fiber length by optical automatic analysis method-Part 2: Non-polarizing method", the length is represented by a weight-average fiber length.

[Example 1]
The pine wood cutting chips for papermaking were sieved using a sieving machine (gyro shifter) and then mixed to obtain chips having a size of 9.5 to 31.5 mm.
The obtained pine wood chips were impregnated with a kraft cooking chemical solution at 120 ° C. for 60 minutes using a rotary autoclave and then cooked at a cooking temperature of 140 ° C. for 60 minutes to leave the original chip shape. Uncooked pulp was obtained. Chemical liquid, active alkali 105g / L (Na ₂ O equivalent _{value), NaOH75.6g / L (Na 2} O equivalent _{value), Na 2 S29.4g / L (} Na 2 O conversion value), the composition of the sulfide of 28% The liquid ratio of wood chips and cooking chemicals was 3.2 (L / kg).
After the completion of the cooking, the undigested material in which the shape of the chips was left was washed by hand with 15 times the amount of 60 ° C. hot water for 30 seconds. Furthermore, using a PFI mill, beating treatment was performed at a rotation speed of 1000 and a clearance width of 1 mm.

After that, the fiber bundle was lightly squeezed by a hand to loosen it, then treated with superheated steam in a steam microwave oven at 180 ° C. for 30 minutes and air dried.
The amount of cellulose, the amount of hemicellulose, the amount of lignin, the amount of resin, and the amount of pentosan of the obtained fiber bundle were measured and the ratio was calculated. The results are shown in Table 1.

[Comparative Example 1]
The fibrous digested pulp obtained by boiling the chips used in Example 1 at 160 ° C. for 240 minutes was subjected to the same drying treatment as in Example 1 for comparison.

[Example 2]
Screen knot dregs (wood knots and heartwood have poor reactivity and tend to remain in an undigested state) generated during the process of cooking kraft pulp mainly made of white birch wood at Nippon Paper Industries Co., Ltd. After refining with a refiner (Kumagaya Riki Kogyo BR-300CB) at a plate spacing of 0.7 mm and a concentration of 20%, it was squeezed with a screw press and a superheated steam device (Daiichi High Frequency Industry Co., Ltd. Super-Hi10) In a steam box connected to the above, it was treated with superheated steam at 200 ° C. for about 30 minutes and dried to obtain a fiber bundle section, and component analysis was performed.

[Comparative Example 2]
The digested pulp produced in the same lot as in Example 2 was subjected to the same analysis as in Example 2 after being dried with superheated steam without being subjected to crushing treatment and used as a comparison target.

[Example 3]
Screen knot meal produced in the pulp-based pulpite pulp cooking process at the Nippon Paper Mill is used as a raw material, suspended in 10 times the amount of water, then collected on an inclined screen and pressed with a screw press. Then, it is treated with superheated steam at 200 ° C for about 30 minutes in a steam box connected to a superheated steam device (Super High Hi10 Co., Ltd.) and dried, and a hammer mill (Nara Machinery Co., Ltd. hammer mill) (HM)) and then sieving with a 10-mesh screen to obtain a fiber bundle section as a non-passage section, and a component analysis was performed.

[Comparative Example 3]
The digested pulp produced in the same lot as in Example 3 was subjected to the same analysis as in Example 3 after being dried with superheated steam without being subjected to crushing treatment and used as a comparison target.

[Example 4]
The crushed wood chips made from the residual cedar wood of the forest material were sieved using a sieving machine (gyro shifter) to obtain wood chips having a size of 9.5 to 53 mm.
Using a vertical autoclave (volume: about 2.5 L), an alkali cooking liquid was added to this wood chip so that the liquid ratio was 3.2 L / kg, and cooking treatment was performed at 130 ° C. for about 50 minutes. Chemical liquid, active alkali 105g / L (Na ₂ O conversion value), the composition of NaOH75.6g / L (Na ₂ O conversion value), liquor ratio of wood chips and cooking liquid chemical is 3.2 (L / kg) And
Then, a pressured single disc refiner (BRP-45-300SS, Kumagai Riki Kogyo Co., Ltd.) was used to beat the digested chips under the conditions of 133 ° C., a plate interval of 0.7 mm, and a concentration of 40%.
Then, the non-passage was collected on a flat screen (5-cut plate plate, slit width 0.13 mm), and the obtained fraction was treated with superheated steam in a steam microwave oven at 180 ° C for 30 minutes and then air-dried. The obtained fiber bundle was analyzed.

[Comparative Example 4]
The chips used in Example 4 were steam-treated at 130 ° C. for about 50 minutes in a vertical autoclave using water as a chemical solution and putting the chips in an inner basket without direct contact between water and the chips. Was treated in the same manner as in Example 4 for comparison.

[Example 5]
The fiber bundle obtained was analyzed by performing the same operation as in Example 4 except that the raw material was changed to pine pine and the chemical solution used for steaming was changed to water.

[Comparative Example 5]
The chips used in Example 5 were steam-treated at 130 ° C. for about 50 minutes in a vertical autoclave using water as a chemical solution and putting the chips in an inner basket without direct contact between the chips and water. Was treated in the same manner as in Example 4 for comparison.

  As shown in Table 1, by adjusting the conditions of Kraft cooking (Examples 1 and 2), sulfite cooking (Example 3), alkaline cooking (Example 4), and hot water cooking (Example 5). It was possible to produce a plant fiber bundle containing 5 to 80% by mass of lignin, 1 to 50% by mass of a resin component, and 15% by mass or less of pentosan, based on the weight of cellulose of the present invention.

[Example 6]
Screen knot meal produced in the pulp-based sulfite pulp digestion process at the Nippon Paper Mill is used as a raw material, neutralized with an alkaline cleaning solution generated in the pulp production process, and then collected with an inclined screen and screwed. Compressed with a press, treated with superheated steam at 200 ° C for about 30 minutes in a steam box connected to a superheated steam device (Super High Hi10 Co., Ltd.) and dried, then hammer mill (Nara Machine Co., Ltd.) After crushing with a hammer mill (HM), it was sieved with a 10-mesh screen to obtain a fiber bundle section rich in hydrophobic components in the non-passage section. It can be used as a fiber reinforcing material to be added to concrete.

[Example 7]
Using screen knot meal produced in the pulp pulp cooking process of cedar wood at the Nippon Paper Mill as a raw material, using an atmospheric pressure refiner (Kumagaya Riki Kogyo BR-300CB) with a plate spacing of 0.7 mm and a concentration of 20% After defibrating under the conditions described above, add 10% of formaldehyde to the solid content and stir at room temperature for 1 hour, then squeeze the solid content with a screw press to produce a superheated steam device (Dai-ichi Kogyo Co., Ltd. Super-Hi10 In a steam box connected to the above), it was treated with superheated steam at 200 ° C. for about 30 minutes and dried to obtain a hydrophobic fiber bundle section in which a hydrophobic component was chemically modified. It has enhanced rigidity and can be used as various fiber reinforcements as a substitute for glass fiber.

[Example 8]
Screen knot meal produced in the cedar wood-based kraft pulp cooking process at the Nippon Paper Mill is used as a raw material, and an atmospheric pressure refiner (Kumagaya Riki Kogyo BR-300CB) has a plate spacing of 0.7 mm and a concentration of 20. % Of the fiber bundle, the slurry of fiber bundles was stirred at room temperature to add sulfuric acid pitch to adjust the pH to 6 to 8, and then the solid content was collected by a tilted screen and further squeezed by a screw press. , A hydrophobized fiber bundle section impregnated with a hydrophobic component by being treated with superheated steam at 200 ° C. for about 30 minutes in a steam box connected with a superheated steam device (Super-Hi10 Co., Ltd.) and dried. Got It can be used as a fiber reinforcement for blending in asphalt mix for pavement.

[Example 9]
Add 50% of the amount of waste cooking oil to solids to the slurry of screen knot meal generated in the cedar wood-based kraft pulp cooking process at the Nippon Paper Mill, and heat to about 70 degrees After stirring for a period of time, after defibrating with a normal pressure refiner (Kumagaya Riki Kogyo BR-300CB) under the conditions of a plate interval of 0.7 mm and a concentration of 20%, the solid content was collected with an inclined screen and further squeezed with a screw press. , Treated with superheated steam at 200 ° C for about 30 minutes in a steam box connected to a superheated steam device (Super-Hi10, Dai-ichi Kogyo Kogyo Co., Ltd.) and dried to obtain a hydrophobic fiber bundle section impregnated with fatty acids. Obtained. It can be used as a fiber reinforcing material to be added to the room temperature mixture of asphalt mixture for pavement.

[Example 10]
Screen knot meal produced in the pine wood-based sulfite pulp cooking process at Nippon Paper Mill is squeezed with a screw press, and the resulting crude fiber bundles (solid content about 30%) are put into a concrete mixer. The mixture was added, and an equal amount of slaked lime powder was added to the solid content of the fiber bundle while kneading to obtain a flake-shaped wet body. Curing was carried out for 1 week in a factory exhaust gas atmosphere in a wet state to obtain a composite of a fiber bundle and calcium carbonate. It can be used as a fiber reinforcement for compounding concrete and wood cement boards.

[Example 11]
Screen knot meal produced in the pine wood-based sulfite pulp cooking process at Nippon Paper Mill is squeezed with a screw press, and the resulting crude fiber bundles (solid content about 30%) are put into a concrete mixer. After being charged, slaked lime (40%), calcium nitrite (12%), and aluminum sulfate (30%) were sequentially added to the solid content of the fiber bundle while kneading to obtain a flake-like wet body. . The wet body is dried in the sun, and gypsum (CaSO ₄ · 2H ₂ O) as an inorganic component and nitrite type hydrocalumite (Ca ₂ Al (OH) ₆ · (NO ₂ ) · nH ₂ O with rust preventive action. ) Containing a fiber bundle. It can be used as a fiber reinforced material that has a rust preventive effect when mixed with reinforced concrete.

Claims (10)

  A vegetable fiber bundle containing 5 to 80% by mass of lignin, 1 to 50% by mass of a resin component, and 15% by mass or less of pentosan relative to the weight of cellulose.   The plant fiber bundle according to claim 1, wherein the plant raw material is mechanically defibrated after heat treatment of the plant raw material in an aqueous system.   The plant fiber bundle according to claim 1 or 2, which has a higher-order structure in which monofilaments of cell units containing hemicellulose and / or lignin are organized around cellulose fibers.   The plant fiber bundle is a fiber bundle obtained by subjecting a plant material to at least one heat treatment selected from sulfite (sulfite) cooking, kraft (sulfate) cooking, alkaline cooking and hot water cooking. Item 4. The vegetable fiber bundle according to any one of Items 1 to 3.   The plant fiber bundle according to any one of claims 1 to 4, having an average fiber length of 5 to 50 mm and an aspect ratio of 20 to 200.   A plant fiber bundle obtained by treating the plant fiber bundle according to any one of claims 1 to 5 with superheated steam.   A fiber reinforcing material using the plant fiber bundle according to claim 1.   A fiber reinforcing material obtained by subjecting the vegetable fiber bundle according to any one of claims 1 to 6 to a hydrophobic treatment.   A fiber reinforcing material comprising the plant fiber bundle according to any one of claims 1 to 6 combined with an inorganic component.   A molded product containing the plant fiber bundle according to any one of claims 1 to 9.