KR102124323B1 - Polypropylene resin composition for luggage board in car and luggage board in car comprising the same - Google Patents

Abstract

Resin composition for a luggage board according to various embodiments of the present invention, based on the total weight of the resin composition for a luggage board, polypropylene resin 85 to 94% by weight; And 4 to 15% by weight of a filler; wherein the filler comprises a plate-shaped inorganic filler and a fibrous organic filler, each of the plate-shaped inorganic filler and the fibrous organic filler, respectively. It is modified with ammonium ions, and may include the inorganic filler and the organic filler in a weight ratio of 1:1 to 1:5.

Description

POLYPROPYLENE RESIN COMPOSITION FOR LUGGAGE BOARD IN CAR AND LUGGAGE BOARD IN CAR COMPRISING THE SAME}

The present invention relates to a composition of a polypropylene composite material for a luggage board using blow or injection molding, and more particularly, a polypropylene composite material comprising an organic and inorganic filler with a high aspect ratio capable of manufacturing a lightweight luggage board. It relates to a composition.

Behind the rear seats of a wagon-type vehicle, a sport utility vehicle (SUV) and a multi-utility vehicle (MUV) is a luggage compartment with luggage or spare tires.

The luggage board is a part that is installed to store and load various passenger luggage while demarcating the spare tire loading space in the trunk room.

Recently, as the number and amount of luggage increased due to active family travel and leisure activities, the demand strength of luggage boards has increased.

In order to manufacture a high-strength luggage board according to the increase in the required strength, a multi-layered composite material using a thermosetting resin has been used.

However, luggage boards using composite materials for multi-layer structures combine various types of materials in a multi-layer structure compared to blow molding methods using thermoplastic resins, resulting in high manufacturing costs due to a large number of processes, high prices due to high material costs, high weight, and thermosetting properties. There are problems such as the limitation of resource recycling due to the use of resin.

Therefore, it is necessary to develop a new luggage board material and manufacturing technology for light weight, resource recycling and cost reduction compared to the multi-layer structural composite material while having mechanical rigidity comparable to that of the multi-layer structural composite material.

In various embodiments of the present invention, it is possible to provide a composition of a thermoplastic resin composite material for improving mechanical rigidity of a luggage board, reducing weight, recycling resources, and reducing costs.

Resin composition for a luggage board according to various embodiments of the present invention, based on the total weight of the resin composition for a luggage board, polypropylene resin 85 to 94% by weight; And 4 to 15% by weight of a filler; wherein the filler comprises a plate-shaped inorganic filler and a fibrous organic filler, each of the plate-shaped inorganic filler and the fibrous organic filler, respectively. It is modified with ammonium ions, and may include the inorganic filler and the organic filler in a weight ratio of 1:1 to 1:5.

The present invention can provide a resin composition excellent in dispersibility of the filler by preventing agglomeration between fillers. The resin composition according to the present invention may have improved mechanical strength, such as tensile strength, tensile modulus, flexural strength, flexural modulus, impact strength, and creep properties, than conventional polypropylene. The luggage board for a vehicle manufactured by using the resin composition according to the present invention has advantages of weight reduction, high mechanical properties, and cost savings compared to luggage boards using a multilayer structural composite material using a thermosetting resin.

Hereinafter, the examples and terms used therein are not intended to limit the technology described in this document to specific embodiments, and it should be understood that the examples include various modifications, equivalents, and/or substitutes.

Hereinafter, various embodiments of the present invention will be described in detail.

The present invention relates to a polypropylene composite material composition for a vehicle luggage board and a luggage board made of the composition.

Resin composition for luggage boards according to various embodiments of the present invention includes a polypropylene resin and a filler, based on the total weight of the resin composition for luggage boards, 85 to 94% by weight of polypropylene resin and 4 to 15 fillers % By weight. If the polypropylene resin is out of the above range, it may be difficult to secure the desired mechanical properties of the luggage board. If the filler is contained in less than 4% by weight, it may be difficult to secure the desired mechanical properties of the luggage board, and if the filler exceeds 15% by weight, mechanical properties may be deteriorated due to difficulty in dispersing the filler.

The melt index of the polypropylene resin (ASTM D-1238, 230°C) may be 0.1 to 2.0 g/10 min (230°C, 2.16 kg). If the melt index is outside the above range, it may cause a problem of unmolding.

At this time, the polypropylene resin is a polypropylene homopolymer, propylene-ethylene copolymer, propylene 1 butene copoly, propylene 1 pentene copoly, propylene 1 hexene copolymer, propylene 4 methyl 1 pentene copolymer, and random copolymer It may include one or more selected from the group consisting of. The weight average molecular weight of the polypropylene resin is in the range of 10,000 to 1,000,000, preferably in the range of 50,000 to 900,000, and even more preferably in the range of 100,000 to 800,000.

The filler may include a plate-shaped inorganic filler and a fibrous organic filler. In this case, the filler has a particle size of 0.1 to 5 μm, and an aspect ratio may be 10 to 100. The particle size means an average thickness in the case of a plate-shaped inorganic filler and an average diameter in the case of a fibrous organic filler. When the particle size of the filler exceeds 5 µm, the specific surface area cannot be sufficiently increased, and the hardness and impact resistance of the composition may deteriorate. In addition, through the filler having a specific particle size and a specific aspect ratio, it is possible to improve mechanical strengths such as tensile strength, tensile modulus, flexural strength, flexural modulus, impact strength, and creep property, compared to conventional polypropylene.

. The resin composition of the present invention may include an inorganic filler and an organic filler in a weight ratio of 1:1 to 5. When the weight ratio of the inorganic filler and the organic filler is out of the above range, it may be difficult to secure desired mechanical properties of the luggage board due to aggregation between the inorganic filler and the inorganic filler or between the organic filler and the organic filler.

The plate-shaped inorganic filler may be at least one selected from the group consisting of clay, talc, and calcium carbonate. Preferably, the plate-shaped inorganic filler may be a nanoclay surface-modified with ammonium ions having a weight average molecular weight of 300 to 10,000.

The fibrous organic filler is one selected from the group consisting of micronized cellulose, flax, hemp, jute, kenaf, abaca, and bamboo. It may be abnormal. Preferably, the micronized cellulose is selected from non-oxidized microfibrous cellulose surface-modified with ammonium ions having a weight average molecular weight of 300 to 10,000 and microfibrous cellulose surface-modified with fatty acids having a weight average molecular weight of 200 to 1,000 1 It may be more than a species.

Specifically, nanoclays surface-modified with ammonium ions or non-oxidized microfibrous celluloses surface-modified with ammonium ions are swelled by immersing clay or cellulose in a polar solvent, and the swelling clay or cellulose and the weight average molecular weight are 300 to 10,000. After the phosphorus ammonium ion is mixed in a polar solvent, the mixture can be fibrillated by using a shearing device, and the clay can be exfoliated. The -OH group and the ammonium ion on the surface of the peeled nanoclay or fibrillated microfibrous cellulose may be combined to modify the surface.

The ammonium ion is represented by Formula 1 below.

<Formula 1>

In Formula 1,

R1 to R4 are each independently hydrogen, deuterium, 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.

When R1 to R4 are independently of each other, 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, C1 independently of each other -C60 alkyl group, C2-C60 alkenyl group, C2-C60 alkynyl group, C3-C60 cycloalkyl group, C3-C60 cycloalkenyl group or C6-C60 aryl group is substituted or unsubstituted with one or more substituents selected from the group consisting of, plural When substituted with 4 substituents, they may be the same or different from each other.

The "alkyl group" means a monovalent substituent derived from a linear or branched saturated hydrocarbon having 1 to 60 carbon atoms. Examples include, but are not limited to, methyl group, ethyl group, propyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, and the like.

The "alkenyl (alkenyl) group" means a monovalent substituent derived from a linear or branched unsaturated hydrocarbon having 2 to 60 carbon atoms having at least one carbon-carbon double bond. Examples of this include, but are not limited to, vinyl, allyl, isopropenyl, 2-butenyl, and the like.

The "alkynyl (alkynyl) group" means a monovalent substituent derived from a linear or branched unsaturated hydrocarbon having 2 to 60 carbon atoms having at least one carbon-carbon triple bond. Examples of this include, but are not limited to, ethynyl, 2-propynyl, and the like.

The "cycloalkyl group" means 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.

The "cycloalkenyl group" means a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 60 carbon atoms having one or more carbon-carbon double bonds.

The "aryl group" means a monovalent substituent derived from an aromatic hydrocarbon having 6 to 60 carbon atoms in which a single ring or two or more rings are combined. Also, two or more rings may be simply attached to each other or condensed. Examples of such aryl include, but are not limited to, phenyl, naphthyl, phenanthryl, and anthryl.

The weight average molecular weight of the ammonium ion is 300 to 10,000. Specifically, the weight average molecular weight of the ammonium ion is 450 to 7,500. More specifically, the weight average molecular weight of the ammonium ion may be 500 to 5,000, but is not limited thereto.

When the weight average molecular weight of the ammonium ion is within the above range, the nanoclay and microfibrous cellulose are easily dispersed in a material having hydrophobic properties.

The ammonium ion is at least one selected from the group consisting of secondary ammonium ions, tertiary ammonium ions and quaternary ammonium ions.

For example, the ammonium ion may be a secondary ammonium ion in which two C18-C60 alkyl groups are substituted. Alternatively, the ammonium ion may be a secondary ammonium ion in which one C18-C60 alkyl group and one C18-C60 aryl group are substituted. As another example, the ammonium ion may be a tertiary ammonium ion in which two C18-C60 alkyl groups and one C6-C60 aryl group are substituted. Alternatively, the ammonium ion may be a quaternary ammonium ion with four C6-C60 alkyl groups substituted.

When the ammonium ion is at least one selected from the group consisting of secondary ammonium ions, tertiary ammonium ions, and quaternary ammonium ions, and when the ammonium ion is bound to the surface of nanoclay or microfibrous cellulose, it is bound to the ammonium ion Due to the steric hindrance effect by the chemical functional group, it is possible to prevent the problem of reaggregation between nanoclays or celluloses due to hydrogen bonding due to hydroxyl groups remaining on the surface of nanoclays or microfibrous celluloses. , It can be easily dispersed even in materials having hydrophobic properties.

The ammonium ion is bonded by electrostatic attraction to the -OH group of nanoclay or microfibrous cellulose.

The nanoclay or microfibrous cellulose has a -OH group (hydroxyl group, hydroxyl group) and a strong hydrogen bond between -OH group and H. However, the ammonium ion is bonded to the -OH group of the nanoclay or microfibrous cellulose by electrostatic attraction, thereby weakening the hydrogen bond.

Specifically, since the electronegativity of oxygen is large in the -OH group, oxygen partially exhibits a negative charge, and N in the ammonium ion has a positive charge, so that an electrostatic attraction is generated between N of the ammonium ion and O of the -OH group. Works.

It is possible to prevent the problem of reaggregation of the fibrillated nanoclay or microfibrous cellulose by bonding the ammonium ion to the -OH group of the nanoclay or microfibrous cellulose by electrostatic attraction.

The microfibrous cellulose is microfibrillated cellulose or nanofibrillated cellulose.

The microfibrous cellulose has a diameter of 0.1 to 5 μm.

The length of the microfibrous cellulose is 100 nm to 500 μm. Specifically, the length of the microfibrous cellulose may be 100 nm to 100 μm, more specifically 100 nm to 10 μm, but is not limited thereto.

The diameter and length of the microfiber cellulose refers to an average value of a plurality of fiber lengths and diameters measured by casting a microfiber cellulose dispersion thinly on a substrate and drying it, followed by observation using an atomic force microscope (AFM). do.

When the diameter and length of the microfibrous cellulose are within the above range, high-quality microfibrous cellulose can be produced, reaggregation can be prevented, and it is particularly advantageous to disperse when used as an additive of a polymer composite material.

On the other hand, the content of ammonium ions in the nanoclay or microfibrous cellulose is 0.1 to 5% by weight based on the total weight of the nanoclay or microfibrous cellulose. Specifically, the content of ammonium ions in the nanoclay or microfibrous cellulose is 0.1 to 3% by weight. More specifically, the content of the ammonium ion in the nanoclay or microfibrous cellulose may be 0.1 to 1% by weight, but is not limited thereto.

When the content of ammonium ions in the nanoclay or microfibrous cellulose is within the above range, reaggregation can be prevented and easy to disperse in a polymer composite material having hydrophobic properties, and it is also economical in terms of cost.

The microfibrous cellulose has a crystallinity of 50 to 100%. Specifically, the crystallinity of the microfibrous cellulose may be 70 to 100%, more specifically 80 to 100%, but is not limited thereto.

The crystallinity is the proportion of the weight of the crystalline portion of the total weight of the fibrous cellulose.

When the crystallinity of the fibrous cellulose is within the above range, it is advantageous to increase the mechanical strength of the fibrous cellulose.

The nanoclay or microfibrous cellulose surface-modified with the ammonium ion is combined with nanoclay or microfibrous cellulose having hydrophilic properties and the ammonium ion having hydrophobic properties, so that the surface-modified nanoclay or microfibrous cellulose has a heterogeneous material. It is easy to disperse with hydrophilic as well as hydrophobic materials in the complexation process of.

The method of manufacturing the above-described nanoclay or microfibrous cellulose is as follows.

(a) swelling the clay or cellulose by immersing it in a polar solvent;

(b) mixing the swollen clay or cellulose with an ammonium ion represented by Formula 1 below and having a weight average molecular weight of 300 to 10,000 in the polar solvent; And

(c) fibrillating the mixture of the swollen clay or cellulose with the ammonium ion using a shearing device to obtain nanoclay or microfibrous cellulose surface-modified with the ammonium ion.

<Formula 1>

First, clay or cellulose is swelled by dipping in a polar solvent.

The cellulose is not particularly limited, and one derived from a cellulose-containing material can be used. For example, pulp, chemical pulp, mechanical pulp, recycled pulp, cellulose powder or mixtures thereof can be used. Examples of the cellulose-containing material, cellulose fibers such as cellulose fibers produced by plants or bacteria, which are natural fibers, cellulose derivatives such as cellulose acetate, chitin derivatives such as chitin and chitosan contained in crustaceans such as shellfish, shrimp and crab, silk, spider web Protein fibers such as natural rubber fibers or the like, but is not limited thereto. In addition, the cellulosic fiber-containing material as a plant material may include wood, cotton, hemp, or hemp, such as coniferous or broad-leaved trees. Cellulose fibers obtained from wood, such as conifers and broad-leaved trees, are very finely structured and have high strength, and are the most widely distributed biological resources on the planet.

The polar solvent is a polar protic solvent or a polar aprotic solvent.

Specifically, the polar solvent includes water, dimethyl sulfoxide (DMSO), hexamethylphosphoramide (HAPA), dimethylacetamide (DMAc), formamide, dimethylformamide (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 may be one or more selected from the group consisting of an ionic liquid (Ionic liquid), but is not limited thereto.

The pH of the polar solvent may be selected from 5 to 14.

When the clay or cellulose is immersed in the polar solvent, the temperature of the polar solvent may be selected in the range of 0 to 80°C.

In addition, the clay or cellulose may be immersed in a polar solvent for 0.5 to 5 hours.

Next, the swollen clay or cellulose and ammonium ions represented by Chemical Formula 1 and having a weight average molecular weight of 300 to 10,000 are mixed in the polar solvent.

Mix sufficiently so that the ammonium ion can be bound to the swollen cellulose.

The mixing can be performed using a device selected from the group consisting of a homogenizer, a Quett Taylor reactor, a high pressure homogenizer, and combinations thereof.

Subsequently, the swelled clay or a mixture of cellulose and the ammonium ion may be fibrillated in cellulose using a shearing device, and the clay may be exfoliated. Through this, the nanoclay surface-modified with the ammonium ion or the microfibrous cellulose surface-modified with the ammonium ion is obtained.

The shearing device may use equipment having high shearing force. Specifically, the shearing device may be a device selected from the group consisting of high-pressure homogenizers, grinders, cryocrushings, ultrasonic waves, and combinations thereof.

The high pressure homogenizer is a device using the principle that the swollen cellulose is subjected to a large shear force and impact force while passing through a thin slit at a high pressure and fibrillated with microfibrous cellulose.

In addition, the grinder is a device using the principle of fibrillation into nanoclay or microfibrous cellulose using shear and friction forces generated by a grinding stone.

In addition, washing and separation steps of the surface-modified nanoclay or microfibrous cellulose selectively obtained may be performed.

The washing and separation may be performed using a device selected from the group consisting of filter presses, centrifuges, decants, and combinations thereof.

Through the above-described manufacturing method of nanoclay or microfibrous cellulose, dispersion is easy, reaggregation is minimized, and the high mechanical properties, low coefficient of thermal expansion, high specific surface area properties, high aspect ratio, transparency and high nature of nanoclay or cellulose are minimized. Nanoclay or microfibrous cellulose having dimensional stability may be prepared.

On the other hand, the microfibrous cellulose surface-modified with fatty acids is represented by the following formula (2) and has a weight average molecular weight of 200 to 1,000:

<Formula 2>

In Formula 2,

R is a C12-C60 alkyl group, C12-C60 alkenyl group, C12-C60 alkynyl group, C12-C60 cycloalkyl group, C12-C60 cycloalkenyl group or C12-C60 aryl group.

The modified microfibrous cellulose contains esters derived from the fatty acids.

In the microfibrous cellulose, an -OH group (hydroxyl group, hydroxyl group) exists, and a strong hydrogen bond exists between the -OH group and H. However, while forming an ester by an esterification reaction between the -OH group of the microfibrous cellulose and the fatty acid under a base catalyst, hydrogen bonds may be weakened as the fatty acid is covalently bonded to the microfibrous cellulose.

In addition, it is possible to prevent the problem of reaggregation of the fibrillated microfibrous cellulose by the fatty acid is bonded to the -OH group of cellulose by an esterification reaction.

The microfibrous cellulose is microfibrillated cellulose or nanofibrillated cellulose.

The modified microfibrous cellulose has a diameter of 5 nm to 100 nm. Specifically, the diameter of the modified microfibrous cellulose may be 5 nm to 50 nm, more specifically 5 nm to 10 nm, but is not limited thereto.

The modified microfibrous cellulose has a length of 100 nm to 500 μm. Specifically, the length of the modified microfibrous cellulose may be 100 nm to 100 μm, more specifically 100 nm to 10 μm, but is not limited thereto.

The diameter and length of the modified microfibrous cellulose are thinly cast on a substrate and dried, and then observed using an atomic force microscope (AFM) to measure the average length of the plurality of fiber lengths and diameters. Means

When the diameter and length of the modified microfibrous cellulose are within the above range, high-quality microfibrous cellulose can be produced, reaggregation can be prevented, and it is particularly advantageous to disperse when used as an additive of a polymer composite material.

The content of the ester-linked fatty acid in the modified microfibrous cellulose is 10 to 90% by weight based on the total weight of the modified microfibrous cellulose. Specifically, the content of the ester-linked fatty acid in the modified microfibrous cellulose is 20 to 85% by weight. More specifically, the content of the ester-linked fatty acid in the modified microfibrous cellulose may be 30 to 65% by weight, but is not limited thereto.

When the content of the ester-linked fatty acid in the modified microfibrous cellulose is within the above range, it is possible to prevent reaggregation and to be easily dispersed in a polymer composite material having hydrophobic properties, and is economical in terms of cost.

The crystallinity of the modified microfibrous cellulose is 50 to 100%. Specifically, the crystallinity of the modified microfibrous cellulose may be 70 to 100%, more specifically 80 to 100%, but is not limited thereto.

The crystallinity is the proportion of the weight of the crystalline portion of the total weight of the modified microfibrous cellulose.

When the crystallinity of the modified microfibrous cellulose is within the above range, it is advantageous to increase the mechanical strength of the modified microfibrous cellulose.

The method for producing the surface-modified microfibrous cellulose with fatty acids,

(A) swelling by immersing the cellulose in a dispersion containing water and a base catalyst;

(b) mixing the swollen cellulose, a fatty acid represented by Formula 1 below, and a weight average molecular weight of 200 to 1,000, and a surfactant in the dispersion; And

(c) fibrillating the mixture obtained in the step (b) using a shearing device to obtain microfibrous cellulose surface-modified with the fatty acid.

<Formula 2>

In Formula 2,

R is a C12-C60 alkyl group, C12-C60 alkenyl group, C12-C60 alkynyl group, C12-C60 cycloalkyl group, C12-C60 cycloalkenyl group or C12-C60 aryl group.

When R is a C12-C60 alkyl group, C12-C60 alkenyl group, C12-C60 alkynyl group, C12-C60 cycloalkyl group, C12-C60 cycloalkenyl group or C12-C60 aryl group, 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 is substituted or unsubstituted with one or more substituents selected from the group, and when substituted with a plurality of substituents, they are the same as each other Or it may be different.

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

The "alkenyl (alkenyl) group" means a monovalent substituent derived from a linear or branched unsaturated hydrocarbon having 2 to 60 carbon atoms having at least one carbon-carbon double bond. Examples of this include, but are not limited to, vinyl, allyl, isopropenyl, 2-butenyl, and the like. In addition, the C12-C60 alkenyl group means a monovalent substituent derived from a linear or branched unsaturated hydrocarbon having 12 to 60 carbon atoms having one or more carbon-carbon double bonds.

The "alkynyl (alkynyl) group" means a monovalent substituent derived from a linear or branched unsaturated hydrocarbon having 2 to 60 carbon atoms having at least one carbon-carbon triple bond. Examples of this include, but are not limited to, ethynyl, 2-propynyl, and the like. Further, the C12-C60 alkynyl group means a monovalent substituent derived from a linear or branched unsaturated hydrocarbon having 12 to 60 carbon atoms having at least one carbon-carbon triple bond.

The "cycloalkyl group" means 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. In addition, C12-C60 cycloalkyl group means a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 12 to 60 carbon atoms.

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

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

In order to prepare the modified fibrous cellulose, first, the cellulose is swelled by immersing it in a dispersion containing water and a base catalyst (step (a)).

The cellulose is not particularly limited, and one derived from a cellulose-containing material can be used. For example, pulp, chemical pulp, mechanical pulp, recycled pulp, cellulose powder or mixtures thereof can be used. As an example of the cellulose-containing material, cellulose derivatives such as cellulose fibers or cellulose acetate produced by plants or bacteria that are natural fibers, chitin derivatives such as chitin and chitosan contained in crustaceans such as shellfish, shrimp and crab, silk, spider web Protein fibers such as natural rubber fibers or the like, but is not limited thereto. In addition, the cellulosic fiber-containing material using a plant as a raw material may include wood, cotton, hemp, or hemp, such as coniferous or broad-leaved trees. Cellulose fibers obtained from wood, such as conifers and broad-leaved trees, are very finely structured, have high strength, and are the most widely distributed biological resources on the planet, and may be useful for utilization due to their high practicality in terms of productivity.

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 has a crystal diameter of 10 to 500 μm and a length of 0.1 to 50 mm, but is not limited thereto.

The dispersion contains water and a base catalyst.

The base catalyst may be at least one selected from the group consisting of sodium hydroxide (NaOH), potassium hydroxide (KOH), calcium hydroxide (Ca(OH)2), ammonium hydroxide (NH4OH) and magnesium hydroxide (Mg(OH)2). , But is not limited thereto. Specifically, the base catalyst may be sodium hydroxide, but is not limited thereto.

The dispersion may be an aqueous sodium hydroxide solution. Specifically, the dispersion may be an aqueous sodium hydroxide solution of 1 to 5% by weight.

In addition, the dispersion may further include a polar solvent.

The polar solvent is a polar protic solvent or a polar aprotic solvent.

Specifically, the polar solvent includes water, dimethyl sulfoxide (DMSO), hexamethylphosphoramide (HAPA), dimethylacetamide (DMAc), formamide, dimethylformamide (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 may be one or more selected from the group consisting of an ionic liquid (Ionic liquid), but is not limited thereto.

The pH of the dispersion may be selected from 5 to 14.

When the cellulose is immersed in the dispersion, the temperature of the dispersion may be selected in the range of 0 to 80°C.

In addition, the cellulose may be immersed in the dispersion for 0.5 to 5 hours.

Next, the swollen cellulose, a fatty acid represented by Formula 1 and a weight average molecular weight of 200 to 1,000 and a surfactant are mixed in the dispersion (step (b)).

The fatty acid may be represented by the formula (2), for a description of the formula 2, refer to the description described above.

In addition, the weight average molecular weight of the fatty acid is 200 to 1,000. Specifically, the weight average molecular weight of the fatty acid is 200 to 800. More specifically, the weight average molecular weight of the fatty acid may be 300 to 500, but is not limited thereto.

When the weight average molecular weight of the fatty acid is within the above range, the modification of the microfibrous cellulose is easy, and the modified microfibrous cellulose is easy to be dispersed in a composite material having hydrophobic properties.

Since R is a substituent having 12 or more carbon atoms among the fatty acids, hydrophobic properties may be increased. When the fatty acid is bound to the surface of the fibrous cellulose, it prevents the problem of reaggregation even after separation from the cellulose into the fibrous cellulose by hydrogen bonding due to the hydroxyl group remaining on the surface of the fibrous cellulose Not only can it be made, it can be easily dispersed even in materials having hydrophobic properties.

The fatty acid is bound to cellulose by an esterification reaction.

Specifically, a condensation reaction occurs between the carboxyl group of the fatty acid and the hydroxyl group of cellulose, and an ester group is generated.

In order to efficiently proceed the esterification reaction, a surfactant and a base catalyst are used.

In the esterification reaction, a reaction may be promoted by a base catalyst contained in the dispersion.

At this time, the base catalyst is preferably contained by 0.01 to 1.0% by weight relative to the total weight of the reaction raw material.

The swollen cellulose, the fatty acid and the surfactant are sufficiently mixed in the dispersion so that the esterification reaction can occur.

The mixing can be performed using a device selected from the group consisting of a homogenizer, a Quett Taylor reactor, a high pressure homogenizer, and combinations thereof.

Specifically, the swollen cellulose, the fatty acid and the surfactant are mixed in the dispersion at 25 to 100° C. for 30 to 120 minutes. More specifically, it may be mixed at 50 to 60° C. for 50 to 120 minutes.

The surfactant is at least one selected from the group consisting of monomethanolamine, monoethanolamine, N-methylethylamine, 1-aminoisopropanol, dimethylamine, diethylene triamine and triethylene tetraamine. Specifically, the surfactant may be diethylene triamine, but is not limited thereto.

By using the surfactant, a hydrophobic fatty acid can be easily dissolved in water, and an esterification reaction between the fatty acid and swollen cellulose is facilitated.

Subsequently, the mixture obtained in step (b) is fibrillated using a shearing device to obtain microfibrous cellulose surface-modified with the fatty acid (step (c)).

The shearing device may use equipment having high shearing force. Specifically, the shearing device may be a device selected from the group consisting of high-pressure homogenizers, grinders, cryocrushings, ultrasonic waves, and combinations thereof.

The high pressure homogenizer is a device using the principle that the swollen cellulose is subjected to a large shear force and impact force while passing through a thin slit at a high pressure and fibrillated with microfibrous cellulose.

In addition, the grinder is a device using the principle of fibrillation into microfibrous cellulose using shear and frictional forces generated by a grinding stone.

In addition, washing and separation steps of the surface-modified microfibrous cellulose selectively obtained may be performed.

The washing and separation may be performed using a device selected from the group consisting of filter presses, centrifuges, decants, and combinations thereof.

For the description of the surface-modified microfibrous cellulose, see the description in [Modified Microfibrous Cellulose] below.

Through the above-described manufacturing method of the microfibrous modified microfibrous cellulose, dispersion is easy, re-aggregation is minimized, the natural mechanical properties of cellulose, low coefficient of thermal expansion, high specific surface area properties, high aspect ratio, transparency and high dimensional stability Microfibrous cellulose having a can be produced.

Cellulose is swelled by immersing it in a dispersion containing water, a polar solvent, and a base catalyst, and after mixing the swollen cellulose, a fatty acid having a weight average molecular weight of 200 to 1,000, and a surfactant in the dispersion, the mixture is used using a shearing device. The fibrillated, fibrilated cellulose surface may be a surface-modified microfibrous cellulose by combining the -OH group with the fatty acid. The fibrous cellulose surface-modified with a fatty acid may have a content of 30 to 65% by weight of an ester-linked fatty acid by an esterification reaction.

According to various embodiments of the present invention, the plate-shaped inorganic filler and the fibrous organic filler can be easily dispersed in the polypropylene resin, and re-agglomeration can be minimized.

A luggage board may be manufactured by blow molding or injection molding a resin composition for a luggage board according to various embodiments of the present disclosure.

The luggage board using the resin composition according to various embodiments may be manufactured through the following specific examples.

Manufacturing example 1: Ammonium ion Modified Microfiber Preparation of nanoclay composite powder modified with cellulose and ammonium ion

Preparation of swollen cellulose and swollen clay

A 5 wt% NaOH aqueous solution was added to a pH of 10 in a 500 L jacketed reactor with a homogenizer, thermometer, and thermostat connected, and 5 kg of pulp powder and 5 kg of clay were added and stirred at 3,000 rpm for 1 hour at room temperature. Thereafter, the mixture was allowed to stand at room temperature for 24 hours or more to prepare cellulose swollen by water molecules and swollen clay.

Preparation of composite powder

Homogenizer, a thermometer and a thermostat connected to a jacketed reactor of 500 L capacity, 5 kg of swelled cellulose prepared above, 1 kg of swelled clay prepared above, and Dimethyldioctadecylammonium chloride (Dimethyldioctadecylammonium chloride) 1.0kg and 300 L of distilled water was added and stirred at room temperature for 1 hour at 3,000 rpm. Subsequently, the cellulose was fibrillated and the clay was exfoliated by applying a shearing force at a high pressure using a high pressure homogenizer. Fibroylated microfibrous cellulose modified with dimethyldioctadecylammonium by reacting with -OH group of the fibrillated microfibrous cellulose surface and -OH group of the peeled nanoclay surface with ammonium ion of dimethyldioctadecylammonium chloride, A nanoclay mixed dispersion modified with dimethyldioctadecylammonium was prepared.

The dispersion was filtered using a filter and then dried in a dryer at 80° C. for 24 hours to prepare microfibrous cellulose modified with powdered ammonium ion and nanoclay composite material modified with ammonium ion.

Examples 1 to 4 and Comparative Examples 1 to 2

The microfibrous cellulose modified with ammonium ion prepared in Preparation Example 1 and nanoclay composite material modified with ammonium ion and polypropylene resin were injected into a twin screw extruder in the amounts shown in Table 1, 180~ Melt extrusion at a rate of 450 rpm at a temperature of 230° C. to produce a polypropylene composite material in which a mixed powder of microfiber cellulose modified with ammonium ion and nanoclay composite material modified with ammonium ion is dispersed.

ingredient
(Unit: kg) Example Comparative example One 2 3 4 One 2 Polypropylene 94.0 91 88 85.0 97.0 82.0 With ammonium ion Modified Microfiber cellulose 5.0 7.5 10.0 12.5 2.5 15.0 With ammonium ion Modified Nano Clay 1.0 1.5 2.0 2.5 0.5 3.0

Evaluation example 1-composite material

The composite materials prepared in Examples 1, 2, 3 and 4, and Comparative Examples 1 and 2 were measured for physical properties by the method presented in the following measurement method, and the results are shown in Table 2 below.

1. Composite material tensile strength measurement

Tensile strength was measured using a universal tester by making a test specimen according to ASTM D 638 (Standard Test Method for Tensile Properties of Plastics).

(Tensile strength [Pa] = maximum load [N] / cross section of initial sample [m ² ])

2. Composite material impact strength measurement

A specimen for measurement was made according to ASTM D 256 (Standard Test Method for Tensile Properties of Plastics), and the impact strength value was measured using an Izod impactor.

3. Measurement of thermal deformation temperature of composite materials

Heat distortion temperature was measured by making a test specimen according to ASTM D 648 (Standard Test Method for Deflection Temperature of Plastics Under Flexural Load in the Edgewise Position).

4. Measurement of flexural strength of composite materials

According to ASTM D790 (Standard Test Method for FLEXURAL Properties of Plastics), the measuring specimen is placed on two points separated by a certain distance, and the specimen is placed in a vertical direction at a constant speed until the specimen breaks, and then pressed. Stress and distortion were measured.

(Bending strength = 3P × L/2b × d ² )

(P: applied force, L: length of support span, b: width of specimen, d: thickness of specimen)

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 IZOD impact strength
(kgfcm/cm ² ) 21 28 34 41 10 9 The tensile strength
(kgfcm/cm ² ) 270 384 450 508 185 131 Flexural strength
(kgfcm/cm ² ) 245 358 413 472 212 159 Heat deflection temperature (℃) 100 105 116 121 94 96

Referring to Table 2, it can be seen that the tensile strengths, flexural strengths, impact strengths, and thermal deformation temperatures of Examples 1 to 4 are all significantly higher than those of 1 and 2 in comparison.

Evaluation example 2-luggage board

The luggage boards were prepared using the composite materials prepared in Examples 1, 2, 3 and 4, and Comparative Examples 1 and 2, and the load bearing stiffness of the luggage board was measured, and the results are shown in Table 3 below. Did.

The load-bearing stiffness of the luggage board, after applying 80 kg of force at room temperature for 24 hours, measured the displacement in the vertical direction to the load.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Load bearing stiffness (mm) 9 7 5 2 15 17

Referring to Table 3, it was confirmed that the load supporting stiffness of the luggage boards made of the composite materials of Examples 1 to 4 was significantly lower than that of the luggage boards made of the composite materials 1 and 2 for comparison.

Features, structures, effects, and the like described in the above-described embodiments are included in at least one embodiment of the present invention, and are not necessarily limited to only one embodiment. Furthermore, features, structures, effects, and the like exemplified in each embodiment may be combined or modified for other embodiments by a person having ordinary knowledge in the field to which the embodiments belong. Therefore, the contents related to such combinations and modifications should be interpreted as being included in the scope of the present invention.

In addition, although the embodiments have been mainly described above, these are merely examples and do not limit the present invention, and those skilled in the art to which the present invention pertains are exemplified above in a range that does not depart from the essential characteristics of the present embodiment. It will be appreciated that various modifications and applications are possible. For example, each component specifically shown in the embodiments can be implemented by modification. And differences related to these modifications and applications should be construed as being included in the scope of the invention defined in the appended claims.

Claims (11)

Based on the total weight of the resin composition for luggage boards,
Greater than 85% by weight of polypropylene resin and up to 94% by weight; And
A resin composition for a luggage board comprising: 4% by weight or more and less than 15% by weight of a filler.
The filler includes a plate-shaped inorganic filler and a fibrous organic filler,
The plate-shaped inorganic filler and the fibrous organic filler are each modified with ammonium ions,
It includes the inorganic filler and the organic filler in a weight ratio of 1:1 to 1:5,
The plate-shaped inorganic filler and the fibrous organic filler are surface-modified with an ammonium ion having a weight average molecular weight of 300 to 10,000, a resin composition for a luggage board.
According to claim 1,
The polypropylene resin has a melt index (ASTM D-1238, 230°C) of 0.1 to 2.0 g/10 min (230°C, 2.16 kg), a resin composition for luggage boards.
According to claim 1,
The average thickness of the plate-shaped inorganic filler is 0.1 to 5 μm,
The average diameter of the fibrous organic filler is 0.1 to 5 ㎛ resin composition for luggage board, characterized in that.
According to claim 1,
A resin composition for a luggage board, wherein the filler has an aspect ratio of 10 to 100.
According to claim 1,
The inorganic filler is at least one kind selected from the group consisting of clay, talc, and calcium carbonate.
According to claim 1,
The organic filler is at least one selected from the group consisting of micronized cellulose, flax, hemp, jute, kenaf, abaca, and bamboo, Resin composition for luggage boards.
delete According to claim 1,
The plate-shaped inorganic filler is a nanoclay surface-modified with ammonium ions having a weight average molecular weight of 300 to 10,000,
The fibrous organic filler is a resin composition for a luggage board, characterized in that the non-oxidized microfibrous cellulose having a weight average molecular weight of 300 to 10,000.
A luggage board manufactured by blow molding the resin composition for a luggage board according to claim 1.
The method of claim 9,
Luggage board, characterized in that the load bearing stiffness is 2 mm to 9 mm. According to claim 1,
The content of ammonium ions in the plate-shaped inorganic filler or the fibrous organic filler is 0.1 to 5% by weight based on the total weight of the plate-shaped inorganic filler or the fibrous organic filler, the resin composition for luggage boards .