KR20200120369A - Manufacturing method of material for compounding comprising nano cellulose and composite material using the same - Google Patents

Abstract

The present invention is a technology with respect to a novel concept material using cellulose that can be used for the production of a composite material for compound use. A method for manufacturing an agglomerated compound containing cellulose according to an aspect of the present invention comprises the following steps: preparing a dispersion containing cellulose powder; adding a hydrophobic surface modifier to the cellulose dispersion to modify the surface of the cellulose; and forming an aggregate by using the surface-modified cellulose.

Description

Manufacturing method of agglomerated compound containing cellulose and composite material using the same {MANUFACTURING METHOD OF MATERIAL FOR COMPOUNDING COMPRISING NANO CELLULOSE AND COMPOSITE MATERIAL USING THE SAME}

The present invention is a technology for a new concept material using cellulose that can be used for the production of composite materials for compound use.

Cellulose is the most common natural polymer found on the planet, not only in most plants such as wood, cotton, and hemp, but also in animals with dry skins such as larvae and snails, and is a combination of carbon 1 and carbon 4 of β-D-glucose. It is a polymer polysaccharide having a linear structure through 1-4 glucoside bonds, and has a molecular weight of 4.6×10 ⁵ to 1.7×10 ⁶ . Cellulose, as a structural unit that forms the skeleton of plants, is a major component of cell membranes of all higher plant cells, and plays a key role in maintaining high strength of plants, especially wood.

Cellulose molecules having an effective diameter of about 6 Å to 7 Å are regularly and strongly bonded through hydrogen bonding to form microfibrillated or nanofibrillated celluloses having a diameter of 2 nm to 5 nm, and such fibrous cellulose Gather to form fibers, and these fibers make up the cell membrane of plants.

Recently, cellulose is a new functional material and is used in various applications due to its chemical, physical, and optical advantages. Since the past, it has been commercialized in biopolymer composite additives for application to automobile bodies, barrier films for food and electronic devices, additives for cosmetics, and additives for cement, and recently, pressure sensors, fine filters for water or air. , Flexible display substrate materials, flexible solar cell materials, electronic device encapsulation materials, optical devices, drug delivery, and other high value-added fields are expanding their application range.

The manufacturing method of such cellulose includes an acid-hydrolysis method, an electrospinning method, a bacterial culture method, a mechanical-physical method, and the like.In particular, the method of manufacturing through a mechanical-physical method is evaluated as the most promising technology in terms of physical properties and mass production.

However, the mechanical or physical method has a problem that reaggregation occurs even after separating from cellulose into fibrous cellulose when used as a compound material due to hydrogen bonding due to hydroxyl groups remaining on the surface of cellulose.

In particular, this agglomeration phenomenon acts as a major factor inhibiting the dispersion of fibrous cellulose in the process of manufacturing a compound material through complexing with different materials.

In order to solve this problem, an additional surface modification process is required to prevent re-aggregation and easy dispersion of the prepared fibrous cellulose. In this process, additional energy costs such as pulverization force, shear force, cavitation, etc., corresponding to the energy required in the fibrous cellulose manufacturing process, are incurred, as well as materials using such additional high energy. The dispersion treatment has a problem in that the crystallization and aspect ratio of the fibrous cellulose are lowered, resulting in a decrease in the mechanical and chemical performance of the fibrous cellulose.

In addition, since such microfibrous cellulose is a compound material and is mixed in the form of fine powder in the process of conjugating with heterogeneous materials, a scattering problem occurs in the process, thereby hindering the process environment, and in the continuous compounding process, the filler Due to the difficulty in quantitative mixing, there is a problem in that it is difficult to manufacture a compound having uniform physical properties.

An object of the present invention is to solve the above-described problems and to provide a technology for manufacturing a composite material for a compound using cellulose having excellent physical properties, while effectively mixing in the process of performing a composite process with heterogeneous materials It is to provide an easy cellulose modification technology.

Another object of the present invention is to provide a cellulose material of excellent quality, which is easy to disperse as it has both hydrophilicity and hydrophobicity, and minimizes re-aggregation by hydrogen bonding, a composite material using the same, and a method of manufacturing the same.

A method for producing an aggregated compound material comprising cellulose according to an aspect of the present invention includes: preparing a dispersion containing cellulose powder; Modifying the surface of the cellulose by adding a hydrophobic surface modifier to the cellulose dispersion; And forming an aggregate by using the surface-modified cellulose.

According to an embodiment of the present invention, in the step of modifying the surface of the cellulose, a chemical bond may be formed between the functional group of the cellulose and the functional group of the surface modifier.

According to an embodiment of the present invention, the surface modifier has a weight average molecular weight of 200 to 1,000, and a saturated fatty acid represented by the formula C _n H _2n+1 COOH (n is a natural number of 12 to 60) or the formula CnH _{2n- 1} COOH (n is a natural number of 12 to 60) is to include an unsaturated fatty acid; the content of the fatty acid in the surface-modified cellulose may be 30% by weight to 65% by weight.

According to an embodiment of the present invention, the surface modifier includes a quaternary ammonium salt compound,

The quaternary ammonium salt compound may include one or two linear alkyl groups having 5 or more carbon atoms, and the remaining alkyl groups may include alkyl ammonium having 5 or less carbon atoms or hydrogen.

According to an embodiment of the present invention, the surface modifier includes alkyl ammonium, and the weight ratio of the cellulose: the alkyl ammonium may be 1:0.15 to 1:5.

According to an embodiment of the present invention, the surface modifier includes an aromatic ammonium salt compound according to Formula 1 below, and the weight ratio of the cellulose: the aromatic ammonium salt compound may be 1:0.8 to 1:30.

[Formula 1]

(However, Ar is an alkyl group containing one or more aromatic rings, X is a halogenated element, R is C _n H _2n+1 (n is an even number from 8 to 18))

According to an embodiment of the present invention, the surface modifier includes a wax having a weight average molecular weight of 200 to 5000, and the wax includes a nonionic or cationic head; And a tail including a hydrophobic chain; it may have a structure consisting of.

According to an embodiment of the present invention, the surface modifier may include a PEG (PEG, poly(ethylene glycol))-based polymer, and the PEG-based polymer may have a weight average molecular weight of 350 or less.

According to an embodiment of the present invention, the step of forming an aggregate using the surface-modified cellulose; Before, the step of fibrillating the surface-modified cellulose; may be to include more.

According to an embodiment of the present invention, in the forming of the aggregate, the step of cyclizing the surface-modified cellulose may be forming a ring with spherical particles having a diameter of 0.1 mm to 100 mm.

The agglomerated compound material including cellulose provided by the other side of the present invention is an agglomerated compound material formed using the manufacturing method according to an embodiment of the present invention, and the agglomerated compound material is, It includes a surface-modified cellulose having a diameter of 5 nm to 100 nm and a length of 100 nm to 500 μm.

A composite material for a compound provided in another aspect of the present invention includes an aggregated compound material according to an embodiment of the present invention; And a hydrophobic or non-polar polymer; is mixed and dispersed.

According to an embodiment of the present invention, the hydrophobic or non-polar polymer is, high density polyethylene (HDPE), linear low density polyethylene (LLDPE), low density polyethylene (LDPE), ethylene- Ethylene-octene copolymer, ultra low density polyethylene, medium density polyethylene, ethylene-propylene copolymer, ethylene-butene copolymer copolymer), polypropylene, and rubber polymers.

According to an embodiment of the present invention, the cellulose in the composite material may be 0.1% to 50% by weight.

The compound material according to the present invention has the advantage of being easy to disperse in a material having hydrophobic properties by modifying the surface of cellulose, and it is formed as an agglomerate, so that there is no scattering problem in the form of powder, It is easy to mix by weighing a quantity, and in the compounding process of a continuous process, uniform physical properties are easily expressed.

In addition, the cellulose according to the present invention is a steric hindrance effect imparted by the surface modifier components bound to the surface, so that re-aggregation due to hydrogen bonds is minimized even after fibril, so that the intended effect as a high-quality cellulose can be realized.

According to the manufacturing method proposed in the present invention, the step of fibrillating cellulose and the step of surface-modifying cellulose are performed simultaneously or separately, thereby preventing aggregation due to hydrogen bonding of cellulose, as well as requiring additional high energy. Since a separate dispersing process is not required, fibrous cellulose having high crystallinity and high aspect ratio can be prepared.

According to the conventional process, due to the characteristics of the material of cellulose, the cumbersome process of two or more stages of mixing with different materials by passing through an extruder after compounding is integrated into a single process, thereby forming a composite material for a compound. It can be expected to be concise and reduce manufacturing costs.

1 is a view showing a process sequence of a method of manufacturing an aggregated compound material comprising cellulose according to an embodiment of the present invention.
2 is a schematic diagram showing a process of manufacturing an aggregated composite material by using the aggregated compound material including cellulose according to an embodiment of the present invention.
3 is a photograph showing a result of performing a surface modification experiment on cellulose according to an embodiment of the present invention using a variety of commercially available alkyl ammonium and modifying the cellulose surface to have hydrophobicity.
4(a) to 4(d) show whether cellulose according to an embodiment of the present invention and various amounts of alkyl ammonium are mixed to perform a surface modification experiment, and whether the surface properties of cellulose are modified according to the alkyl ammonium content. This is a picture showing the result of analysis on whether or not.
5(a) to 5(d) show a surface modification experiment by mixing cellulose according to an embodiment of the present invention and alkyl ammonium containing various alkyl groups, and according to the length of the alkyl group of the alkyl ammonium, This is a photograph showing the results of analysis on whether or not the surface properties are modified.
6(a) to 6(d) illustrate a surface modification experiment by mixing cellulose according to an embodiment of the present invention and benzalkonium halide in various amounts, and the surface properties of cellulose are determined according to the content of benzalkonium. This is a photograph showing the result of analysis on whether or not it is modified.
7(a) to 7(d) show a surface modification experiment by mixing cellulose and various contents of PEG (polyethylene glycol, poly(ethleneglycol)) according to an embodiment of the present invention, and the content of benzalkonium This is a photograph showing the results of analysis on whether the surface properties of cellulose are modified according to the following.

Hereinafter, exemplary embodiments will be described in detail with reference to the accompanying drawings. Unless otherwise stated, the same reference numerals in each drawing indicate the same member.

Various changes may be made to the embodiments described below. The embodiments described below are not intended to limit the scope of the invention to the described embodiments, and the scope to be claimed as a right through the present application should be understood to include all changes, equivalents, and substitutes for them.

The terms used in the examples are used only to describe specific embodiments, and are not intended to limit the embodiments. Singular expressions include plural expressions unless the context clearly indicates otherwise. In the present specification, terms such as "comprise" or "have" are intended to designate the presence of features, numbers, steps, actions, components, parts, or combinations thereof described in the specification, but one or more other features. It is to be understood that it does not exclude the possibility of the presence or addition of elements or numbers, steps, actions, components, parts, or combinations thereof.

Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which the embodiment belongs. Terms as defined in a commonly used dictionary should be interpreted as having a meaning consistent with the meaning in the context of the related technology, and should not be interpreted as an ideal or excessively formal meaning unless explicitly defined in this application. Does not.

In addition, in the description with reference to the accompanying drawings, the same reference numerals are assigned to the same components regardless of the reference numerals, and redundant descriptions thereof will be omitted. In describing the embodiments, when it is determined that a detailed description of related known technologies may unnecessarily obscure the subject matter of the embodiments, the detailed description thereof will be omitted.

In the present invention, the present invention proposes a technology for manufacturing a compound material using cellulose, and the inventors of the present invention have studied to improve the problems arising when manufacturing a compound material including the fibrillation process of the conventional cellulose. We propose the derived technology.

According to the technology proposed in the present invention, the hydrophilic component on the surface of cellulose is modified with a hydrophobic component, agglomeration between cellulose is prevented, quantitative mixing with other materials is facilitated, and the manufacturing process of the composite material for compound is simplified and the process Cost reduction can be expected.

A method for producing an aggregated compound material comprising cellulose according to an aspect of the present invention includes: preparing a dispersion containing cellulose powder; Modifying the surface of the cellulose by adding a hydrophobic surface modifier to the cellulose dispersion; And forming an aggregate by using the surface-modified cellulose.

The cellulose powder may be prepared in a dispersion state dissolved in a polar solvent. The polar solvent may preferably be a polar protic solvent or a polar aprotic solvent.

Specifically, the polar solvent is water, dimethyl sulfoxide (DMSO), hexamethylphosphoramide (HAPA), dimethylacetamide (DMAc), formamide, dimethyl formamide (Dimethylformamide, DMF), formic acid, N-methylmorpholine-N-oxide (NMMO), ethylene glycol, pyridine, sodium hydroxide/urea aqueous solution , Potassium hydroxide/urea aqueous solution, ammonium hydroxide/urea aqueous solution, and ionic liquid may be at least one selected from the group consisting of, but is not limited thereto.

The pH of the polar solvent may be selected from 5 to 14 range. When the cellulose is immersed in the polar solvent, the temperature of the polar solvent may be selected from 0 to 80°C.

The cellulose contained in the cellulose powder is not particularly limited, and one derived from a cellulose-containing material may be used. For example, pulp, chemical pulp, mechanical pulp, recycled pulp, cellulose powder, or mixtures thereof may be used. Examples of the cellulose-containing material include cellulose fibers produced by natural fibers such as plants or bacteria, cellulose derivatives such as cellulose acetate, sea urchins, chitin derivatives such as chitin and chitosan contained in crustaceans such as shrimp and crab, silk, spider web Protein fibers or natural rubber fibers such as, but are not limited thereto. In addition, the cellulose fiber-containing material using plants as a raw material may include wood such as coniferous or hardwood, cotton, hemp, or sheep horse. Cellulose fibers obtained from wood, such as conifers and hardwoods, are very finely composed, have high strength, and are the most widely distributed biological resources on the planet, and are highly practical in terms of productivity, so they can be useful for use.

The cellulose used at this time may have a crystal diameter of 10 to 1,000 μm and a length of 0.1 to 100 mm. Specifically, the cellulose used may have a crystal diameter of 10 to 500 μm and a length of 0.1 to 50 mm. However, the cellulose used in the present invention is not limited thereto.

In the present invention, a process of modifying the cellulose surface to be hydrophobic by adding a hydrophobic surface modifier to the cellulose dispersion may be included. In this case, the hydrophobic surface modifier is not particularly limited as long as it hydrophobicly modifies the hydrophilic surface of cellulose.

In the present invention, the surface modifier may include one or more of alkyl ammonium, fatty acid, wax, benzalkonium, and PEG, and has a hydrophobic characteristic capable of producing an effect similar to the above components and capable of being bonded to the surface of cellulose Can include.

In the present invention, it may include forming an aggregate using the surface-modified cellulose. In this case, the present invention does not specifically limit the apparatus used in the step of forming the aggregate. As the surface-modified cellulose is aggregated, storage becomes easy, and quantitative mixing is possible in the process of mixing with different materials later. In addition, conventionally, by using cellulose as a powder material, the process of making a separate master batch, which is a batch-type work process through a banbury mixer and a kneader mixer, was unnecessary, whereas the compound Compared to the case of using a powder material when producing the material for use, there is an advantage in that it is easy to mix and unnecessary processes can be omitted. As an example, the aggregate may be in the form of a spherical bead, as another example, may be in the form of a sheet, and as another example, may be in the form of a rod (rod).

According to an embodiment of the present invention, in the step of modifying the surface of the cellulose, a chemical bond may be formed between the functional group of the cellulose and the functional group of the surface modifier.

As an example, in the step of modifying the cellulose surface, an intermolecular bond may be formed through a chemical reaction between an OH group included in the cellulose and a specific functional group included in the surface modifier.

According to an embodiment of the present invention, the surface modifier has a weight average molecular weight of 200 to 1,000 and a formula C _n H _2n+1 COOH (n is a natural number of 12 to 60) or a formula C _n H _2n-1 COOH (n Is a natural number of 12 to 60) fatty acids; and the content of the fatty acid in the surface-modified cellulose may be 30 to 65% by weight.

As an example, the fatty acid may be a saturated fatty acid of the formula C _n H _2n+1 COOH (n is a natural number of 12 to 60) or an unsaturated fatty acid of the formula C _n H _2n-1 COOH (n is a natural number of 12 to 60). have. The unsaturated fatty acid may include two or more double bonds between carbons and/or one or more triple bonds.

As an example, the fatty acid may include a C12-C60 alkyl group, a C12-C60 alkenyl group, a C12-C60 alkynyl group, a C12-C60 cycloalkyl group, a C12-C60 cycloalkenyl group, or a C12-C60 aryl group.

At least one alkyl group of the fatty acid is a C12-C60 alkyl group, a C12-C60 alkenyl group, a C12-C60 alkynyl group, a C12-C60 cycloalkyl group, a C12-C60 cycloalkenyl group or a C12-C60 aryl group, a C1-C60 alkyl group, C2-C60 alkenyl group, C2-C60 alkynyl group, C3-C60 cycloalkyl group, C3-C60 cycloalkenyl group or C6-C60 aryl group substituted or unsubstituted with one or more substituents selected from the group consisting of, and substituted with a plurality of substituents If so, they may be the same or different from each other.

The "alkyl group" may mean a monovalent substituent derived from a linear or branched saturated hydrocarbon having 1 to 60 carbon atoms. Examples thereof include a methyl group, an ethyl group, a propyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group, but are not limited thereto. In addition, the C12-C60 alkyl group may mean a monovalent substituent derived from a linear or branched saturated hydrocarbon having 12 to 60 carbon atoms.

The "alkenyl group" refers to a monovalent substituent derived from a straight or branched unsaturated hydrocarbon having 2 to 60 carbon atoms having at least one carbon-carbon double bond. Examples thereof include vinyl (vinyl), allyl (allyl), isopropenyl (isopropenyl), 2-butenyl (2-butenyl), and the like, but is not limited thereto. Further, the C12-C60 alkenyl group may mean a monovalent substituent derived from a straight or branched unsaturated hydrocarbon having 12 to 60 carbon atoms having at least one carbon-carbon double bond.

The "alkynyl (alkynyl) group" refers to a monovalent substituent derived from a straight-chain or branched unsaturated hydrocarbon having 2 to 60 carbon atoms having at least one carbon-carbon triple bond. Examples thereof include, but are not limited to, ethynyl and 2-propynyl. In addition, the C12-C60 alkynyl group may mean a monovalent substituent derived from a straight or branched unsaturated hydrocarbon having 12 to 60 carbon atoms having at least one carbon-carbon triple bond.

The "cycloalkyl group" refers to a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 60 carbon atoms. Examples of such cycloalkyl include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, adamantine, and the like. Further, the C12-C60 cycloalkyl group may mean a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 12 to 60 carbon atoms.

The "cycloalkenyl group" refers to a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 60 carbon atoms having at least one carbon-carbon double bond. In addition, the C12-C60 cycloalkenyl group may mean a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 12 to 60 carbon atoms having one or more carbon-carbon double bonds.

The "aryl group" may mean a monovalent substituent derived from a single ring or an aromatic hydrocarbon having 6 to 60 carbon atoms in which two or more rings are combined. In addition, a form in which two or more rings are simply attached to each other or condensed may be included. Examples of such aryl include phenyl, naphthyl, phenanthryl, and anthryl, but are not limited thereto. Further, the C12-C60 aryl group may mean a monovalent substituent derived from a single ring or an aromatic hydrocarbon having 12 to 60 carbon atoms in which two or more rings are combined.

The carboxyl group of the fatty acid may be an esterification reaction with a hydroxyl group of the cellulose to form a chemical bond.

According to an embodiment of the present invention, the surface modifier includes a quaternary ammonium salt compound,

The quaternary ammonium salt compound may include one or two linear alkyl groups having 5 or more carbon atoms, and the remaining alkyl groups may include an alkyl group having 5 or less carbon atoms or an alkyl ammonium hydrogen. The surface modifier is one or two alkylammoniums. It may contain a relatively long, linear alkyl group having 5 or more carbon atoms.

When three or more linear alkyl groups having a relatively long length are included in the alkyl ammonium, the alkyl ammonium may not be able to enter between the cellulose stacked with strands due to steric hindrance due to its molecular structure. For this reason, even if a sufficient amount of the alkyl ammonium is added, there may be a problem in that the surface of the cellulose mixed together is not homogeneously hydrophobicly modified.

When only one or two of the long linear alkyl groups are included in the alkylammonium, the alkylammonium has few steric hindrances and thus can smoothly penetrate into the cellulose aggregated in layers, thus entering the cellulose aggregated in the form of bundles or particles to homogeneously cellulose The surface can be modified to be hydrophobic.

As an example, the alkyl ammonium may be one that does not contain a branched alkyl group. In the case of including a branched alkyl group, it may be difficult to homogeneously modify the surface of cellulose to hydrophobicity due to steric hindrance.

As an example, the alkyl ammonium may have a weight average molecular weight of 200 to 1000.

According to an embodiment of the present invention, the surface modifier includes alkyl ammonium, and the weight ratio of the cellulose: the alkyl ammonium may be 1:0.15 to 1:5.

When the weight ratio of the alkyl ammonium is less than 0.15 to the cellulose, the surface of the cellulose may not be modified to exhibit sufficient hydrophobicity, and when the amount of alkyl ammonium is more than 2, the amount of alkyl ammonium is too excessive and the expected physical properties are not realized by including cellulose. Problems can arise.

According to an embodiment of the present invention, the surface modifier includes an aromatic ammonium salt compound according to Formula 1 below, and the weight ratio of the cellulose: the aromatic ammonium salt compound may be 1:0.8 to 1:30.

As an example, the halogenated aromatic ammonium may be according to Formula 1 below.

[Formula 1]

(However, Ar is an alkyl group containing one or more aromatic rings, X is a halogenated element, R is C _n H _2n+1 (n is an even number from 8 to 18))

Formula 1 may be an ammonium halogenated aromateam salt. In this case, the aromatic ring Ar may include one or more phenyl groups or a phenyl group including one or more substituents.

As an example, the aromatic ammonium halide may be benzalkonium halide. As a more preferred example, the halogenated aromatic ammonium may be benzalkonium chloride.

In an example of the present invention, a halogenated aromatic ammonium may be used as a surface modifier. When using halogenated aromatic ammonium, the surface of the cellulose may be modified to be hydrophobic.

If the weight ratio of the halogenated aromatic ammonium is less than 0.8 relative to the cellulose, the surface of the cellulose may not be modified to exhibit sufficient hydrophobicity, and if it exceeds 15, the amount of aromatic ammonium halide is excessively excessive and thus the expected physical properties by including cellulose This can lead to problems that are not implemented.

As an example, the halogenated aromatic ammonium may be Benzalkonium Chloride, but the present invention is not limited thereto.

When aromatic ammonium is added, the surface may be modified by bonding to each other through an interaction reaction between the negative charge of the hydroxyl group (OH) on the surface of the cellulose and the positive charge formed on the nitrogen of the aromatic ammonium.

According to an embodiment of the present invention, the surface modifier includes a wax having a weight average molecular weight of 200 to 5000, and the wax includes a nonionic or cationic head; And a tail including a hydrophobic chain; it may have a structure consisting of.

As an example, the wax may have a head including ammonium ions (NH ₄ ⁺ ) and a tail of C _n H _2n+1 (n is a natural number of 50 to 100).

As an example, the wax may include one or more selected from the group consisting of natural or synthetic petroleum wax and ethylene wax.

As an example, the wax may be included in 50% by weight or more based on the weight of the cellulose.

According to an embodiment of the present invention, the surface modifier may include a PEG (PEG, poly(ethylene glycol))-based polymer, and the PEG-based polymer may have a weight average molecular weight of 350 or less.

As an example, the cellulose surface may be modified by using the PEG-based polymer. However, when using a PEG-based polymer, it is preferable that the weight average molecular weight is 350 or less.If the molecular weight exceeds 350 and exceeds 400, 500, it is difficult to penetrate into the cellulose where the PEG-based polymer is agglomerated. There may be a problem that cannot be modified.

According to an embodiment of the present invention, the step of forming an aggregate using the surface-modified cellulose; Before, the step of fibrillating the surface-modified cellulose; may be to include more.

When the surface-modified cellulose is fibrillated, the occurrence of hydrogen bonds between each other can be controlled due to the modification of the cellulose surface, thereby preventing agglomeration of the cellulose. This has the advantage of being able to induce homogeneous mixing in the process of forming agglomerates afterwards and forming a composite material with a heterogeneous material.

As an example, the step of forming the aggregate may be forming bead-shaped particles into spherical particles having a diameter of 0.1 mm to 100 mm.

The step of forming the agglomerates may be, for example, formed from spherical particles, and as an example, may be performed using a pulsing device used in a pulping process in the pharmaceutical field. However, the equipment used in the step of forming the aggregate in the present invention is not particularly limited to equipment conventionally used in the pharmaceutical field. The diameter of the aggregated particles may be 0.1 mm to 100 mm. This may correspond to an appropriate size in consideration of a subsequent compounding process. However, in the present invention, the form of the aggregate is not limited to spherical particles, and may be one of a sheet form or a rod form. The step of forming the aggregate may include a process of forming an aggregate after appropriately kneading the surface-modified cellulose and rolling in a state in which the moisture content is adjusted.

The rolling step may be a process included in order to facilitate formation of agglomeration, and may be to continuously discharge from an opening of an appropriate size after introducing the surface-modified cellulose into the rolling mill.

After that, the surface-modified cellulose, which has become a rolled dough, is pressed into a corrugated roll, cut to correspond to a certain volume, and then mechanically performed as in the principle of rounding in a palm to form an aggregate into spherical particles. The process can be carried out. In this case, if necessary, the amount of modified cellulose that becomes an aggregate can be controlled, and this can be controlled through control of the diameter of the particles. The diameter of the aggregated particles may be 0.1 mm to 100 mm.

Through the agglomeration process, since the agglomerated material contains cellulose whose surface is hydrophobically modified, it may have a characteristic of maintaining an appropriate shape after being aggregated while having less agglomeration and agglomeration phenomenon.

In the case of performing the step of forming the aggregate, it is possible to solve a problem in which quantitative feeding into the extruder is difficult due to a low specific gravity in the case of powder or powder form. When introduced into the extruder in the form of powder, excessive fluidity may be imparted to the particles themselves, resulting in a scattering problem. In addition, when crosslinking occurs, problems such as continuous injection may occur, and problems may also occur in transport and storage.

The agglomerated compound material comprising cellulose provided by the other side of the present invention is an agglomerated compound material formed using the manufacturing method according to an embodiment of the present invention, and the agglomerated compound material has a diameter It is to include a surface-modified cellulose having a length of 5 nm to 100 nm and a length of 100 nm to 500 μm.

The cellulose included in the present invention may be a microfibrous nanocellulose.

A composite material for a compound provided in another aspect of the present invention includes an aggregated compound material according to an embodiment of the present invention; And a hydrophobic or hydrophobic or non-polar polymer; is mixed and dispersed.

According to an embodiment of the present invention, the hydrophobic or hydrophobic or non-polar polymer is, high density polyethylene (HDPE), linear low density polyethylene (LLDPE), low density polyethylene (LDPE), Ethylene-octene copolymer, ultra low density polyethylene, medium density polyethylene, ethylene-propylene copolymer, ethylene-butene copolymer It may include one or more selected from the group consisting of -butene copolymer), polypropylene, and rubber polymer.

When the agglomerated compound material is used, it may be easily mixed with the above-described hydrophobic or hydrophobic or non-polar polymer material.

According to the conventional method, since nanocellulose has a process of mixing with a polymer material in a powder state, quantitative mixing is not easy, and there is a problem that the powder is scattered and contaminates the working environment. In the past, a separate process has been added to supplement this. However, when using the aggregated and surface-modified cellulose as in the present invention, it is easy to prepare a composite material for a compound, so that a polymer material and a cellulose material are mixed at a good mixing ratio without adding unnecessary processes, so that a compound can be easily prepared. There is an advantage.

According to an embodiment of the present invention, the cellulose in the composite material may be 0.1% to 15% by weight.

If the cellulose is contained in an amount of less than 0.1% by weight of the total weight of the composite material, it is difficult to expect the intended effect by administering cellulose because a very small amount of cellulose is included, and there may be a problem that only the process cost is increased.If the amount exceeds 50% by weight, the filler It is difficult to disperse and agglomerate, resulting in a problem that the physical properties of the material decrease.

<Example>

In relation to the cellulose modification proposed in the present invention, an experiment was conducted on the appropriate content and degree of modification using various surface modifiers.

The degree of hydrophobic surface modification of cellulose proposed in the present invention was confirmed on the basis of the migration of cellulose dissolved in water toward toluene, a hydrophobic solvent, using toluene, a hydrophobic solvent.

Examples 1-1 to 1-5: Experiments of application of various alkyl ammoniums

In a state in which cellulose was dissolved in 100 ml of DI water so as to be 3 wt% in a separate funnel, 1.5 g of five commercially available alkyl ammoniums (Examples 1 to 5) were added each and 750 watt, 20 kHz conditions Sonification was performed for 30 minutes at. Then, 150 ml of toluene was added, and it was observed whether the surface-modified cellulose migrates toward the toluene.

In this example, the degree of hydrophobic modification of cellulose was judged on the basis of sufficiently dissolving cellulose in the toluene solvent side.

Comparative Example 1

In Examples 1-1 to 1-5, the modification of cellulose was tested in the same manner except that alkyl ammonium was not administered.

3 is a photograph showing a result of performing a surface modification experiment on cellulose according to an embodiment of the present invention using a variety of commercially available alkyl ammonium and modifying the cellulose surface to have hydrophobicity.

From the results shown in FIG. 3, in Comparative Example 1, it was confirmed that the cellulose dissolved in the water layer moved toward toluene in Examples 1 to 5. Through this, it was confirmed that various kinds of alkylammoniums can hydrophobically modify the surface of cellulose.

Example 2: Surface modification experiment according to the content of alkyl ammonium

4(a) to 4(d) show whether cellulose according to an embodiment of the present invention and various amounts of alkyl ammonium are mixed to perform a surface modification experiment, and whether the surface properties of cellulose are modified according to the alkyl ammonium content. This is a picture showing the result of analysis on whether or not.

The remainder of Examples 1-1 to 1 except that the experiment was designed so that the weight ratio of cellulose and alkyl ammonium was 1: 1 and 1: 0.5 using the alkyl ammonium used in Examples 1-4. It was observed whether the cellulose moves toward toluene under the same conditions as -5 (Fig. 4(a)).

In addition, except that the experiment was designed so that the weight ratio of cellulose and alkyl ammonium was 1: 1 and 1: 0.5 using the alkyl ammonium used in Example 1-3, the rest were carried out in Example 1-1. It was observed whether cellulose migrates toward toluene under the same conditions as in Example 1-5 (Fig. 4(b)).

In addition, except that the experiment was designed so that the weight ratio of cellulose and alkyl ammonium was 1:0.1 and 1:0.2 using the alkyl ammonium used in Examples 1-4, the rest of Examples 1-1 to were carried out. It was observed whether cellulose migrates toward toluene under the same conditions as in Example 1-5 (Fig. 4(c)).

In addition, except that the experiment was designed so that the weight ratio of cellulose and alkyl ammonium was 1: 0.2 and 1: 0.3 using the alkyl ammonium used in Example 1-3, the rest of the examples 1-1 to were carried out. It was observed whether cellulose migrates toward toluene under the same conditions as in Example 1-5 (Fig. 4(d)).

Although the degree of modification was somewhat different depending on the type of alkyl ammonium through the experiment shown in FIGS. 4(a) to 4(d), it was found that the surface was modified to be hydrophobic when the surface modifier was contained in 20 wt% or more based on the weight of cellulose. It was confirmed, and it was confirmed that the surface was completely modified to be hydrophobic when it contained preferably 30 wt% or more.

Surface modification experiment according to the kind of alkyl ammonium chain

In order to confirm the availability of alkyl ammonium as a surface modifier according to the type of alkyl chain, the same conditions were applied except that alkyl ammonium containing various alkyl groups was added instead of the alkyl ammonium used in Examples 1-1 to 1-5. The experiment was conducted at.

5(a) to 5(d) show a surface modification experiment by mixing cellulose according to an embodiment of the present invention and alkyl ammonium containing various alkyl groups, and according to the length of the alkyl group of the alkyl ammonium, This is a photograph showing the results of analysis on whether or not the surface properties are modified.

5(a) is a photograph showing the case of Comparative Example 1.

5(b) to 5(d) are photographs showing the degree of surface modification of cellulose when alkyl ammonium having different lengths of alkyl chains is used as a surface modifier.

In the case of Figure 5(b), alkyl ammonium containing 4 methyl groups was used, and in the case of FIG. 5(c), alkyl ammonium containing 1 linear butyl group and 3 methyl groups was used. In the case, an alkyl group having a linear chain of C ₁₆ and an alkyl ammonium containing 3 methyl groups were used.

5(a) to 5(d), it was confirmed that the cellulose moves toward toluene when an alkyl ammonium having at least 5 alkyl chains is used.

On the other hand, In the case of using an alkyl ammonium, which through another experiment comprises three dogs and alkyl 1 group has a linear chain of C _10, with alkyl ammonium comprising two and one group 2 has a linear chain of the C ₁₀ methyl group In the case, the case of using an alkyl ammonium containing 3 alkyl groups and 1 methyl group having a C ₁₀ linear chain was tested to determine whether the surface of cellulose along the alkyl ammonium chain was hydrophobically modified.

On the other hand, through another experiment, it was confirmed whether the surface of cellulose was hydrophobically modified by using two types of alkyl ammonium containing one alkyl group and three methyl groups having different C ₁₀ branched chains.

Through this, it was confirmed that the alkylammonium containing one or two linear chains modified the cellulose surface, but in other cases, it was confirmed that the cellulose is not hydrophobicly modified. If it is not modified, it was analyzed that it is due to steric hindrance of alkyl ammonium.

Experiment using benzalkonium halide (alkyl ammonium halide) as a surface modifier

In order to use benzalkonium halide as a surface modifier, the experiment was conducted under the same conditions, except that Benzalkonium Chloride was added with varying amounts of the alkyl ammonium used in Examples 1-1 to 1-5. I did. After adding chlorinated benzalkonium at 0.5, 0.7, 0.9, 1, 5, 10 weights relative to 1 weight of cellulose, it was observed whether the cellulose surface was modified.

6(a) to 6(d) illustrate a surface modification experiment by mixing cellulose according to an embodiment of the present invention and benzalkonium halide in various amounts, and the surface properties of cellulose are determined according to the content of benzalkonium. This is a photograph showing the result of analysis on whether or not it is modified. 6(a) to 6(d) show that chlorinated benzalkonium is 0.5 (Fig. 6(a)), 1 (Fig. 6(b)), 5 (Fig. 6(c)), 10 (Fig. 6(d) )) It represents a mixed case.

It was confirmed through the experimental results shown in FIGS. 6(a) to 6(d) that the cellulose surface was sufficiently modified to be hydrophobic when 80% or more of the benzalkonium halide was added to the cellulose weight. When 15 times or more of the weight of cellulose is added, the surface is modified to be hydrophobic, but the cellulose content is too small, and there may be a problem of lowering process productivity.

Experiment using PEG as a surface modifier

In order to use PEG as a surface modifier, the experiment was conducted under the same conditions, except that PEGs having different weight average molecular weights were added instead of the alkyl ammonium used in Examples 1-1 to 1-5.

7(a) to 7(d) show a surface modification experiment by mixing cellulose according to an embodiment of the present invention with PEG (polyethylene glycol, poly(ethleneglycol)) of various molecular weights, and the content of benzalkonium This is a photograph showing the results of analysis on whether the surface properties of cellulose are modified according to the following.

In the case of FIG. 7(a), PEG 200, in FIG. 7(b), PEG 400, in FIG. 7(c), PEG 1000, and in FIG. 7(d), PEG 2000 were used.

In the case of PEG 400 or more, it was confirmed that the molecular weight of the polymer was too high, and the cellulose surface was not sufficiently hydrophobic due to the steric hindrance.

Using the surface-modified cellulose prepared in the above examples, each material was aggregated into a spherical shape by using an apparatus of the type shown in FIG. 6. At this time, the weight of each aggregate was quantified to be 30 g to form a ring.

Then, using the agglomerated compound material, a required amount of rings was added and compounding was performed to test the possibility of commercialization of the compound material of the present invention. Even if the compound material proposed in the present invention is used, it was confirmed that a compound having physical properties equivalent to that of the conventional fibrillated cellulose material for powder was secured.

That is, in the case of using the agglomerated compound material proposed in the present invention, while having the physical properties modified by using cellulose, the problem of non-oxidation is solved, and the convenience of quantitative measurement, storage and compounding process is improved, and the advantages of the process It was confirmed that this was secured.

Although the embodiments have been described by the limited embodiments and drawings as described above, various modifications and variations can be made from the above description to those of ordinary skill in the art. For example, even if the described techniques are performed in a different order from the described method, and/or the described components are combined or combined in a form different from the described method, or are replaced or substituted by other components or equivalents. Appropriate results can be achieved.

Therefore, other implementations, other embodiments, and claims and equivalents fall within the scope of the claims to be described later.

Claims (14)

Preparing a dispersion containing cellulose powder;
Modifying the surface of the cellulose by adding a hydrophobic surface modifier to the cellulose dispersion; And
Including; forming an aggregate by using the surface-modified cellulose
A method for producing a material for agglomerated compound containing cellulose.
The method of claim 1,
In the step of modifying the cellulose surface,
Chemical bond is formed between the functional group of the cellulose and the functional group of the surface modifier,
A method for producing a material for agglomerated compound containing cellulose.
The method of claim 1,
The surface modifier,
The weight average molecular weight is 200 to 1,000, and the saturated fatty acid represented by the formula C _n H _{2n + 1} COOH (n is a natural number of 12 to 60) or the formula CnH _2n-1 COOH (n is a natural number of 12 to 60) Unsaturated fatty acids; and
The content of the fatty acid in the surface-modified cellulose is 30% to 65% by weight,
A method for producing a material for agglomerated compound containing cellulose.
The method of claim 1,
The surface modifier,
It contains a quaternary ammonium salt compound,
The quaternary ammonium salt compound,
One or two linear alkyl groups having 5 or more carbon atoms, and the remaining alkyl groups are alkyl ammonium having 5 or less carbon atoms or hydrogen,
A method for producing a material for agglomerated compound containing cellulose.
The method of claim 1,
The surface modifier includes alkyl ammonium,
The cellulose: the weight ratio of the alkyl ammonium is 1: 0.15 to 1: 5,
A method for producing a material for agglomerated compound containing cellulose.
The method of claim 1,
The surface modifier includes an aromatic ammonium salt compound according to Formula 1 below,
The cellulose: the weight ratio of the aromatic ammonium salt compound is 1: 0.8 to 1: 30,
A method for producing a material for agglomerated compound containing cellulose.
[Formula 1]

(However, Ar is an alkyl group containing one or more aromatic rings, X is a halogenated element, R is C _n H _2n+1 (n is an even number from 8 to 18))
The method of claim 1,
The surface modifier includes a wax (wax) having a weight average molecular weight of 200 to 5000,
The wax may be a nonionic or cationic head; And a tail comprising a hydrophobic chain; which is a structure consisting of,
A method for producing a material for agglomerated compound containing cellulose.
The method of claim 1,
The surface modifier includes a PEG (PEG, poly(ethylene glycol))-based polymer,
The PEG-based polymer has a weight average molecular weight of 350 or less,
A method for producing a material for agglomerated compound containing cellulose.
The method of claim 1,
Forming an aggregate using the surface-modified cellulose; before,
Fibrillating the surface-modified cellulose; which further comprises
A method for producing a material for agglomerated compound containing cellulose.
The method of claim 1,
The step of forming the agglomerates is to form an agglomerate from spherical particles having a diameter of 0.1 mm to 100 mm,
A method for producing a material for agglomerated compound containing cellulose.
It is an agglomerated compound material formed using the manufacturing method of any one of claims 1 to 10,
The agglomerated compound material comprises a surface-modified cellulose having a diameter of 5 nm to 100 nm and a length of 100 nm to 500 μm,
Material for agglomerated compounds containing cellulose.
The material for agglomerated compound of claim 11; And
Hydrophobic or non-polar polymers; dispersed and formed by mixing,
Composite material for compounds.
The method of claim 12,
The hydrophobic or non-polar polymer is, high density polyethylene (HDPE), linear low density polyethylene (LLDPE), low density polyethylene (LDPE), ethylene-octene copolymer (ethylene-octene copolymer) , Ultra low density polyethylene, medium density polyethylene, ethylene-propylene copolymer, ethylene-butene copolymer, polypropylene, and Including one or more selected from the group consisting of rubber polymers,
Composite material for compounds.
The method of claim 12,
In the composite material, the cellulose is 0.1% to 50% by weight,
Composite material for compounds.

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