KR102130822B1 - A sheet product having micro powder of cellulose - Google Patents

Abstract

The sheet according to the present invention can be used to increase the amount of added fine cellulose powder and reduce the use of environmentally harmful substances by using a base material comprising a composition in which cellulose fine powder using paper as a raw material is mixed in a thermoplastic resin composition at a predetermined ratio or more. Compared with resin molded products including biodegradable resins and papers, it satisfies mechanical properties and maintains properties without breaking behaviors such as fracture and perforation, and has the advantage of being applicable to mass production and various products.
Through the above advantages, the molded article according to the present invention can be widely used in flooring, film, beverage tableware, various tableware other than beverage, containers, packages, and hollow bodies.

Description

A sheet product having micro powder of cellulose}

The present invention relates to a sheet containing a cellulose fine powder, in detail, by using a composition in which a thermoplastic resin composition is mixed with a cellulose fine powder using a paper as a base material of a sheet formed of a multi-layered sheet, the addition amount of the fine cellulose powder is increased, and fracture and puncture are performed. It relates to a sheet that maintains physical properties without such a fracture behavior.

Since industrialization, with the development of the industry, synthetic resins such as paper of various types and uses have been produced and supplied. As a result, the amount of paper waste, waste paper, waste paper generated as a by-product in the production process of paper, wallpaper, general paper, and various waste papers that are discarded after use has also increased rapidly, resulting in disposal problems of waste pulp and cost problems and environmental problems. Is emerging.

Therefore, studies on economical and eco-friendly treatment methods for recycling and use of waste pulp are actively being conducted, and research to produce synthetic resin or resin composite compositions that are more environmentally friendly, reduce costs and improve performance by using waste pulp Is going on.

However, the resin composite composition using the waste pulp decreases fluidity as the proportion of the waste pulp increases, so the processability decreases, and in particular, the physical properties, characteristics, and functionality of the final molded product are also poor due to poor physical properties of the waste pulp itself. There is a problem that is reduced than the general resin composite composition.

In particular, the biggest problem is that it is difficult to mix with synthetic resin due to agglomeration between pulp due to the nature of the waste pulp. In Korean Patent Publication No. 10-2006-0110500, the waste pulp and the synthetic resin are separately pulverized separately, and then the synthetic resin and additives are mixed and heated in the pulverized waste pulp and extruded to suppress the generation of static electricity between the pulp to prevent agglomeration. Methods of removing them are known.

However, despite these numerous studies, it is true that the resin composite composition in which the waste pulp is recycled has very poor physical properties and properties than the resin composite composition without waste pulp.

In particular, the main reason among the properties and properties of the resin composite composition using waste pulp is very deteriorated is the hydrophilicity of cellulose, the main component of pulp. As the hydrophilicity of the composition itself is high, the moisture content of the composition is greatly changed according to the humidity in the atmosphere, and this results in significantly deteriorating the mechanical properties of the molded body.

Republic of Korea Patent Publication No. 10-2006-0110500 (October 25, 2006)

The present invention has been devised to solve the above problems, and in detail, by using a composition in which a thermoplastic resin composition is mixed with a cellulose fine powder using paper as a raw material for a sheet formed of a multi-layered sheet, the amount of added fine cellulose powder is increased and the environment is increased. It is an object of the present invention to provide a resin molded body that reduces the use of harmful substances, satisfies mechanical properties, and at the same time maintains physical properties without breaking behavior such as fracture or puncture.

The present invention relates to a molded body containing fine cellulose powder.

An aspect of the present invention is a sheet containing a cellulose powder comprising a base material containing a cellulose fine powder component and a thermoplastic resin layer formed on both sides of the substrate, wherein the substrate has a melt mass flow measured at 230° C. and 2.16 kg ( mass flow rate) is 0.2 to 1.5 g/10min, water content is 0.1 to 0.5 wt%, specific gravity is 1.125 to 1.160, and the thermoplastic resin is polyethylene, polypropylene, polyester, polylactic acid, thermoplastic elastomer, polystyrene, acetylonitrile -Butadiene-relates to a sheet containing cellulose fine powder, characterized in that any one or a plurality selected from the group consisting of styrene copolymer resin.

In the present invention, the substrate has an average particle size of 10 to 50 μm, an apparent specific gravity of 0.25 to 0.35, and a cellulose fine powder having a water content of 2 to 6% by weight; Any one or a plurality of thermoplastic resins selected from the group consisting of polyethylene, polypropylene, polyester, polylactic acid, thermoplastic elastomer, polystyrene, acetylonitrile-butadiene-styrene copolymer resin; And additives.

In addition, the substrate may include 40 to 60% by weight of cellulose fine powder, 30 to 50% by weight of thermoplastic resin and 5 to 10% by weight of additive, and the thermoplastic resin is selected from polyethylene, polypropylene, polyester, polylactic acid, and polystyrene It may contain 10 to 40 parts by weight of a thermoplastic elastomer compared to 100 parts by weight of any one or a plurality of general polymers.

In addition, the thermoplastic elastomer is styrene-butadiene, styrene-isoprene, styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-(ethylene-butylene), styrene-(ethylene-propylene), styrene-(ethylene-butylene) -Styrene, styrene-(ethylene-propylene)-styrene, styrene-(ethylene-butylene)-styrene-(ethylene-butylene), styrene-(ethylene-propylene)-styrene-(ethylene-propylene) and styrene-ethylene -(Ethylene-propylene)-may be any one or a plurality of selected from styrene, the additive is an inner lubricant, anti-sparkling agent, inorganic particles, pigments, plasticizers, heat stabilizers, antioxidants, light stabilizers, scavenger (scavenger) , Any one or a plurality of dyes, fragrances, optical brighteners and flame retardants.

In addition, the cellulose fine powder is characterized in that the powder or any one or a plurality of paper selected from printing paper, writing paper, calligraphy paper, information paper, packaging paper, hygiene thin paper and miscellaneous paper as a raw material.

The sheet according to the present invention can be used to increase the amount of added fine cellulose powder and reduce the use of environmentally harmful substances by using a base material comprising a composition in which cellulose fine powder using paper as a raw material is mixed in a thermoplastic resin composition at a predetermined ratio or more. Compared with resin molded products including biodegradable resins and papers, it satisfies mechanical properties and maintains properties without breaking behaviors such as fracture and perforation, and has the advantage of being applicable to mass production and various products.

Through the above advantages, the molded article according to the present invention can be widely used in flooring, films, tableware for beverages, various tableware other than beverages, containers, packages, and hollow bodies.

Hereinafter, a sheet containing the cellulose fine powder according to the present invention will be described in more detail through specific examples or examples. However, the following specific examples or examples are only one reference for explaining the present invention in detail, and the present invention is not limited thereto, and may be implemented in various forms.

In addition, unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terms used in the description herein are for the purpose of effectively describing specific embodiments only and are not intended to limit the present invention.

Also, the singular form used in the specification and the appended claims may be intended to include the plural form unless otherwise indicated in the context.

The sheet containing the cellulose fine powder according to the present invention may include a substrate containing the cellulose fine powder component and a thermoplastic resin layer formed on both surfaces of the substrate.

In the present invention, the substrate is a composite composition containing cellulose fine powder, wherein the substrate is cellulose fine powder having an average particle size of 10 to 50 μm, an apparent specific gravity of 0.25 to 0.35, and a water content of 2 to 6% by weight; Any one or a plurality of thermoplastic resins selected from the group consisting of polyethylene, polypropylene, polyester, polylactic acid, thermoplastic elastomer, polystyrene, acetylonitrile-butadiene-styrene copolymer resin; And additives.

In the present invention, the cellulose fine powder is a powder of various kinds of materials containing cellulose as a main component, and specifically, may include pulp, cardboard, or paper fibers, etc., which are based on a number of tree species. Examples of these can be broadly divided into softwood and hardwood, and typical softwood species include various spruce (e.g. Sitka Spruce), fir (Douglas) Fir (Douglas fir), various hemlock (American Western hemlock), American larch (tamarack), larch (larch), various pines (Southern pine, White pine) , And Caribbean pine), cypress and redwood, or mixtures thereof. Examples of typical hardwood species are ash, aspen, cottonwood, basswood, birch, beech, chestnut, and rubberwood ( gum), elm, eucalyptus, maple oak, poplar, and sycamore, or mixtures thereof.

In the present invention, it is preferable to use paper dust generated while manufacturing papers such as pulp and cardboard as the cellulose fine powder. This occurs during roller mill work in the papermaking process, dryer blading work, and cleaning at work site blowing. In the papermaking process, impurities are effectively removed by releasing the chip-shaped pulp, and constant up to moisture during wire and press This is because it is easy to control the water content of the cellulose fine powder by being removed.

The phage may use at least one of a mixture of virgin paper and paper powder generated during the production of old paper or a mixture thereof. Newspaper notices, magazine notices, printed notices, packaging notices, corrugated notices, and OA notices can be used as notices. As virgin paper, it is also possible to use phage or finger paper that occurs when manufacturing it. As the paper powder, at least one of hardwood pulp and coniferous pulp may be used as a raw material, and a powder of a cellulosic material that pulverizes these pulp into powders by a grinding process may be used. have. The pulp may be any of mechanical pulp, chemical mechanical pulp, semichemical pulp, and chemical pulp. It is preferable to use paper or pulp that do not contain chlorine and fluorescent bleach. When paper or pulp contains chlorine or fluorescent bleach, chlorine and fluorescent bleach are excluded by dechlorination or defluorescence bleach treatment.

In the present invention, the cellulose fine powder can be prepared by grinding and drying the phage obtained as described above. Specifically, the process of crushing the phage is to make a fine powder having a uniform particle diameter through a preliminary crushing process and a fine grinding process. First, the phage is processed into paper powder of several tens of µm to hundreds of µm. At this time, as a coarse crusher that can be used, a jaw crusher, a gyratory crusher, a cone crusher, a hammer crusher, and a roll crusher can be used.

Next, the powdered phage may be finely pulverized through the coarse pulverizer. At this time, the average particle diameter of the finely ground phage is 50 μm or less, more preferably 10 to 50 μm. When the average particle diameter of the phage is less than 10 μm, it is difficult to control the water content, and the particles are not uniformly dispersed in the thermoplastic resin to be described later by agglomeration of particles by moisture in the air. The presence of fine particles in the thermoplastic resin can significantly degrade the mechanical properties of the sheet.

A ball mill, a medium stirring mill, and a roller mill may be used as the coarse grinder. As a ball mill, an electric ball mill, a vibration ball mill, a planetary ball mill, or a tower type ball mill can be used. As the medium stirring mill, a stirring tank mill or an annular mill can be used. As the roller mill, a centrifugal roller mill or a hydraulic roller mill can be used.

As described above, the powdered phage can be dried to adjust the water content to a predetermined range to complete the cellulose fine powder.

The drying method includes both a thermal drying method and a rotary separation dehydration method in which the container is rotated to dry after washing, and the dried phage dried by thermal drying or rotary separation is mixed with phosphorous pentoxide white powder. Therefore, it is also possible to put it in a certain amount of container and place it at a well-ventilated place at regular intervals to dry it so that moisture is absorbed.

In the present invention, it is preferable to adjust the apparent specific gravity and water content to a certain range in the cellulose fine powder through the above-described process. Specifically, the bulk density of the cellulose fine powder is preferably 0.25 to 0.35, and the moisture content is preferably 2 to 6% by weight. When the apparent specific gravity of the cellulose fine powder is less than the above range, back pressure may occur due to the pressure of the water vapor generated in the raw material mixing process, and when it is above the range, dispersibility decreases due to an increase in the aggregation frequency of the cellulose fine powder. By doing so, the physical properties of the final product may be deteriorated or the error range of the physical properties may be widened. In addition, when the moisture content of the cellulose fine powder is less than the above range, the generation of static electricity increases, which may significantly decrease productivity in the production of the second product, and when it is above the above range, the mechanical properties of the product may significantly decrease.

The cellulose fine powder may be included in 40 to 60% by weight of 100% by weight of the total composition. When the content of the cellulose fine powder is less than 40% by weight, it is difficult to achieve the purpose of recycling of the phage, and when it is added more than 60% by weight, the mechanical properties of the secondary molded product may be significantly reduced when manufacturing the secondary molded product using pellets.

In the present invention, the thermoplastic resin is mixed with the cellulose fine powder to maintain the shape of the pellet, and is selected from polyethylene, polypropylene, polyester, polylactic acid, thermoplastic elastomer, polystyrene, acetylonitrile-butadiene-styrene copolymer resin It may include any one or a plurality.

The thermoplastic resin is more preferably used by mixing polypropylene and a thermoplastic elastomer. Mixing of these compositions can develop and maintain excellent flexibility and show improved mechanical properties.

The polypropylene resin may be a polypropylene polymer or a copolymer of polypropylene and an aliphatic alpha-olefin or aromatic olefin. Here, the aliphatic alpha-olefin and the aromatic olefin may have 2 to 20 carbon atoms, and preferably 2 to 8 carbon atoms.

For example, the polypropylene-based resin may be a polypropylene polymer or a copolymer of propylene and one or more olefins selected from the group consisting of ethylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene, As another example, one or more selected from the group consisting of polypropylene polymer, polypropylene copolymer, propylene-alpha-olefin copolymer, propylene-ethylene copolymer, propylene-butene copolymer and propylene-ethylene-butene copolymer may be used. Can. Here, the copolymer may be a random or block copolymer.

It is preferable that the polypropylene-based resin satisfies a specific range in order to satisfy rigidity and impact resistance, and at the same time, formability such as flowability. Specifically, the melt index measured by ASTM D1238 is 0.5 to 10 g/10min, the density measured by ASTM D792 is 0.8 to 1.0 g/cm 3, and the heat distortion temperature (HDT) measured by ASTM D648 is 100 to It is good to satisfy 125°C. In the above range, mechanical properties such as stiffness and impact resistance described above, and moldability such as flowability and flexibility can be satisfied, which is preferable.

The thermoplastic elastomer is dispersed in the polypropylene resin to increase flexibility, crystallinity, and moldability, and can be prepared by dynamically cross-linking a part of a styrenic elastomer.

Examples of the thermoplastic elastomer are styrene-butadiene, styrene-isoprene, styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-(ethylene-butylene), styrene-(ethylene-propylene), styrene-(ethylene-butyl Styrene)-styrene, styrene-(ethylene-propylene)-styrene, styrene-(ethylene-butylene)-styrene-(ethylene-butylene), styrene-(ethylene-propylene)-styrene-(ethylene-propylene) and styrene -Ethylene-(ethylene-propylene)-styrene, and the like. These may be used alone or as a mixture of two or more.

In addition, the thermoplastic resin may further include one or more stabilizers as necessary. The stabilizer is easy to maintain the shape of the pellet by reducing the surface tackiness of the polypropylene resin or the thermoplastic elastomer, and processability can be improved.

In the present invention, the thermoplastic resin is preferably made of 10 to 40 parts by weight of thermoplastic elastomer compared to 100 parts by weight of any one or a plurality of general polymers selected from polyethylene, polypropylene, polyester, polylactic acid and polystyrene. When the thermoplastic elastomer is added less than 10 parts by weight, the flexibility and elasticity of the thermoplastic resin may decrease, resulting in poor moldability, and when added more than 40 parts by weight

The stabilizer may include a polyethylene-based wax, and the polyethylene-based wax may include a low-molecular-weight polyethylene-based wax obtained by polymerizing or copolymerizing ethylene and a low-molecular-weight polyethylene-based wax obtained by thermally decomposing these polymers or copolymers.

Specifically, the weight average molecular weight of the polyethylene-based wax may be 10,000 or less, more preferably 2,000 to 9,000, and the melting point may be 135°C to 150°C. In addition, the polyethylene wax has a density measured in accordance with JIS K7112 standard is 800 ㎏ / ㎥ to 1,000 ㎏ / ㎥.

The stabilizer is preferably added to 0.1 to 5 parts by weight relative to 100 parts by weight of the thermoplastic resin. When adding less than 0.1 parts by weight, the effect of improving the physical properties due to the addition of a stabilizer is insufficient, and when adding more than 5 parts by weight, the viscosity decreases and moldability may decrease.

In addition, the thermoplastic resin is preferably added to 30 to 50% by weight relative to the total composition 100% by weight. When adding less than 30% by weight, the addition of cellulose fine powder may be excessive and the mechanical properties of the molded product may decrease, and when it is added more than 50% by weight, the added amount of cellulose fine powder may be reduced, thereby impairing the object of the present invention.

In the present invention, the additive is added to supplement the mechanical-chemical properties of the above-mentioned thermoplastic resin, cellulose fine powder, internal lubricants, anti-snow agents, inorganic particles, pigments, plasticizers, heat stabilizers, antioxidants, light stabilizers, acid stabilizers , It may include any one or a plurality selected from scavengers, dyes, fragrances, optical brighteners and flame retardants.

In the present invention, the internal lubricant is added to increase the fluidity when molding the composition to facilitate processing, and is selected from the group consisting of a metal stearate-based lubricant, an amide-based lubricant, a paraffin-based lubricant, and an ester-based lubricant. Can be. Examples of commercial lubricants include Hi-Lube (Shinwon Chemical), Mg-St (Songwon), Ca-St (Songwon), Zn-St (Songwon), and AX-71 (ADEKA).

In the present invention, the anti-squatting agent is for suppressing the scab phenomenon occurring on the mold die, and examples of commercial anti-squatting agents include L-1000 (Mitsubishi) and the like.

In the present invention, the inorganic particles are to increase the heat resistance, quenching, impact resistance, dimensional stability, etc. of the composition, and to enable complex injection molding, in the form of a master batch mixed with a polymer resin in a matrix. Can be added.

The polymer resin contained in the inorganic particles can be used without limitation as long as it is similar to the physical properties of the thermoplastic resin, and specifically, low density polyethylene (LDPE), medium density polyethylene, high density polyethylene, or linear low density polyethylene (LLDPE) can be used.

The inorganic particles mixed with the polymer resin are not limited to the type as long as they are conventionally added in the art for the above purpose, and include, for example, titanium dioxide (TiO ₂ ), calcium carbonate (CaCO ₃ ), carbon black, and the like. Can be.

When the inorganic particles are added in the form of a masterbatch, it is preferable to add 30 to 80 parts by weight of inorganic particles relative to 100 parts by weight of the polymer resin, but the present invention is not limited thereto.

In the present invention, the plasticizer is to improve the moldability at high temperature by increasing the thermoplasticity of the composition, phthalate (phthalate) plasticizer, fatty acid (aliphate) plasticizer, trimellitate (trimellitate) plasticizer, polyester ( Polyester) plasticizer, epoxy (epoxy) plasticizer, phosphate (phosphate) plasticizer and glycol (glycol) plasticizer, any one or a plurality of selected from the can be used.

In the present invention, the antioxidant is for preventing oxidation of the composition, and a phosphorus-based antioxidant, a phenolic antioxidant, or the like can be used. At this time, examples of the phosphorus-based antioxidant include tris (2,4-di-t-butylphenyl) phosphite or bis (4,2,4-di-tert-butylphenyl) pentaerythritol diphosphite, and the like. Phenolic antioxidants are thiodiethylene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate or octadecyl-3-(3,5-di-t-butyl-4- And hydroxyphenyl) propionate. These may be used alone or in combination of two or more.

In the present invention, the heat stabilizer and the light stabilizer are used to suppress thermal decomposition of the compositions, and one or a plurality of halogen-based light stabilizers, benzotriazole-based light absorbers, and benzophenone-based light absorbers may be added.

In the present invention, the optical brightener is to increase the transparency of the secondary molded article when the secondary molded article is prepared using the composition, and to suppress the expression of a blue tint, bis-(benzooxazolyl) stilbene, Bis-(benzooxazolyl) naphthalene-based brightener, bis-(benzooxazolyl) thiophene-based brightener, coumarin-based brightener and pyrazoline-based brightener, and the like.

In the present invention, the flame retardant is intended to increase the flame retardancy of the composition, and may be any one or a plurality selected from melamine orthophosphate, melamine pyrophosphate, melamine polyphosphate, isolated (poly)ammonium phosphate or (poly)ammonium phosphate.

The additive according to the present invention may further include an auxiliary agent such as an acid scavenger, a pigment, a dye, and a fragrance in addition to the above-described components, and the amount of addition thereof can be freely adjusted within a range not impairing the object of the invention. .

In the present invention, the substrate may be prepared by first mixing the compositions and then melt-extruding the pellets prepared therefrom. At this time, the pellet does not limit the manufacturing method. As an example, after the composition is metered to a predetermined ratio, it is uniformly mixed using a Henschel mixer and the like, and is introduced into a kneader equipped with a hopper, a cylinder, etc. and homogenized by adding a temperature of 100 to 200°C. And it is preferable to continuously feed it to the feeder of the extruder and pelletize it.

In the present invention, the sheet preferably has a flow index (melt flow index) of 0.2 to 1.5 g/10min measured at 230°C and a load of 2.16 kg according to ASTM-D1238. If the flow index of the sheet is less than 0.2, a sheet having a thickness of 0.4 mm or less cannot be produced, and if it is more than 1.5, a sheet having a thickness of 0.3 mm can be produced, but physical properties may be lowered because PP having high flowability must be mixed.

In addition, the sheet preferably has a water content of 0.5% by weight or less, more preferably 0.001 to 0.5% by weight, and a specific gravity of 1.125 to 1.160. The lower the water content of the molded body, the better. Therefore, it is better to seal it by blocking it from the external environment to maintain the lowest water content. If the water content exceeds 0.5% by weight, physical properties may deteriorate and perforation may occur during sheet production.

In addition, considering the specific gravity (1.13) of the paper powder and considering that the paper powder contains more than 50% of the total raw material ratio, it cannot be lowered to less than 1.125. If the specific gravity is less than 1.125, it can be seen that the content of the paper powder is lowered, and if it is greater than 1.160, the paper powder content is increased, which may result in deterioration of physical properties. In addition, draw down may occur in the vacuum forming process, which is a post process of the sheet product, and thus difficulty in production of the final product may occur.

In the present invention, the thermoplastic resin layer laminated on the substrate may have the same or different composition than the thermoplastic resin included in the production of the sheet. Specifically, the thermoplastic resin layer is a sheet form by extruding a resin composition containing 10 to 40 parts by weight of thermoplastic elastomer compared to 100 parts by weight of any one or a plurality of general polymers selected from polyethylene, polypropylene, polyester, polylactic acid and polystyrene It can be produced by molding.

More preferably, the thermoplastic resin layer is preferably made of a mixture of polypropylene and a thermoplastic elastomer. In this case, the polypropylene has a melt index of 0.5 to 10 g/10min measured by ASTM D1238 and a density of 0.8 to 1.0 g/cm 3 measured by ASTM D792, ASTM D648, similar to the polypropylene included in the substrate. It is preferable that the heat distortion temperature (HDT) measured by satisfies 100 to 125°C. In the above range, it has properties similar to those of the base layer, and it is preferable because it can satisfy mechanical properties such as stiffness and impact resistance and formability such as flowability and flexibility.

In addition, the thermoplastic elastomer is also styrene-butadiene, styrene-isoprene, styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-(ethylene-butylene), styrene-(ethylene-propylene), styrene-(ethylene-butylene) -Styrene, styrene-(ethylene-propylene)-styrene, styrene-(ethylene-butylene)-styrene-(ethylene-butylene), styrene-(ethylene-propylene)-styrene-(ethylene-propylene) and styrene-ethylene It is preferable that it is any one or multiple selected from -(ethylene-propylene)-styrene.

The thermoplastic resin layer does not limit the bonding method with the base layer. For example, after forming an adhesive layer by applying a common adhesive to the surface of the substrate layer, it can be formed by bonding the thermoplastic resin layer to the adhesive layer. Alternatively, w may be formed by compressing the thermoplastic resin layer on both surfaces of the induction-heated base layer with a roller and then cooling it.

The sheet prepared as described above may be different depending on the place of use, but may have a thickness of 0.3 to 1.25 mm, and the composition of the base layer in the entire sheet may be maintained at about 50% by weight or volume%. However, the present invention is not limited to this.

Hereinafter, a molded body containing the cellulose fine powder according to the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the following examples and comparative examples are only examples for explaining the present invention in more detail, and the present invention is not limited by the following examples and comparative examples.

The physical properties of the specimens prepared through the following examples and comparative examples were measured as follows.

(Melt flow rate, specific gravity)

The melt flow rate was measured according to ISO 1133 (melt mass flow and melt volume flow of thermoplastic plastics), and specific gravity was measured according to ASTM D792 (Specific Gravity and Density Test of Molded Products).

(Water content)

To measure the water content, 5 g of a sample was placed in a water content meter and heated to 100° C. for 10 minutes to measure the evaporated water content at 100%.

(Apparent density)

It was measured according to KS M ISO 60: 2002 (apparent density measurement method).

(Mechanical properties-tensile strength, tensile modulus, elongation)

It measured according to JIS K7113 (tensile test method).

(Bending strength, flexural modulus)

It was measured in accordance with JIS K7203 (Measurement Method of Flexibility of Hard Plastic).

(IZOD impact strength)

It was measured according to ASTM D256 (Izod impact test on composite materials).

(Physical properties of secondary molded products)

① Mechanical properties-Tensile yield point strength, tensile break strength, tensile break elongation, elastic modulus: measured according to JIS K6251 (tensile stress-strain test of thermoplastic materials).

② Specific Gravity: Measured according to ASTM D792 (Specific Gravity and Density Test of Molded Products).

(Example 1)

First, glassine paper (MAPKA, ERI) was prepared from cellulose fine powder. At this time, the specifications of the glassine paper was an average particle diameter of 30㎛, an apparent specific gravity of 0.3, and a water content of 4% by weight. Here, polypropylene (J640, Hyosung Co.) was used as a thermoplastic resin, and an internal lubricant (Ca-St, Shinwon Chem.) as an additive. Anti-squatting agent (L-1000, manufactured by Mitsubishi), mixed with inorganic particles in a masterbatch form (Polyethylene-based, containing 70% by weight of TiO ₂ : Polyethylene-based, PNP), and when mixing, the composition ratio is 50% by weight of cellulose fine powder, thermoplastic resin It was 45% by weight and 5% by weight of the additive mixture. This was put into an extruder and pelletized to obtain a molded body containing cellulose fine powder.

(Example 2)

In the preparation of the molded body in Example 1, a resin in which polypropylene and a thermoplastic elastomer (Versify3401, Dow Chemical) were mixed was used as the thermoplastic resin. At this time, the mixing ratio was mixed so that 30 parts by weight of thermoplastic elastomer compared to 100 parts by weight of polypropylene, and the amount of the total thermoplastic resin added was the same as in Example 1. A molded body was manufactured with the same composition and method except for the above.

(Example 3)

When manufacturing the molded body in Example 1, the cellulose fine powder contained 55% by weight and the thermoplastic resin 38% by weight, except that the molded body was prepared in the same composition and method.

(Comparative Example 1)

A molded article was prepared in the same composition and method as in Example 3, except that the apparent specific gravity of the cellulose fine powder was adjusted to 0.22.

(Comparative Example 2)

A molded article was prepared in the same composition and method as in Example 3 except that the apparent specific gravity of the cellulose fine powder was adjusted to 0.37.

(Comparative Example 3)

In Example 3, a molded article was prepared with the same composition and method, except that the moisture content of the cellulose fine powder was adjusted to 1.5% by weight.

(Comparative Example 4)

In Example 3, a molded article was prepared in the same composition and method, except that the moisture content of the cellulose fine powder was adjusted to 6.5% by weight.

(Example 4)

A sheet was prepared using the molded body prepared through Example 3. At this time, the molded body had a melt mass flow of 1.0 g/10min measured at 230° C. and 2.16 kg, a water content of 0.3% by weight, and a specific gravity of 1.35 as measured by ISO 1133, and the sheet formed the molded body into a sheet shape having a thickness of 0.5 mm. After production, a polypropylene (HB240T, Hyosung Co.) film molded to a thickness of 0.25 mm was laminated on both sides. The laminated sheet was biaxially stretched by adjusting the elongation to 40%.

(Example 5)

The sheet was prepared in the same manner as in Example 4, except that the moisture content of the composition was adjusted to 0.05% by weight when preparing the molded body.

(Comparative Example 5)

In Example 4, a sheet was prepared in the same manner as in Example 4, except that the melt flow rate of the composition was adjusted to 1.55 by replacing polypropylene (HI828, Hanwha Total).

(Comparative Example 6)

The sheet was prepared in the same manner as in Example 4, except that the moisture content of the composition was adjusted to 0.55 when the molded body was prepared.

(Comparative Example 7)

The sheet was prepared in the same manner as in Example 4, except that the specific gravity of the composition was adjusted to 1.15 when manufacturing the molded body.

(Comparative Example 8)

The sheet was prepared in the same manner as in Example 4, except that the specific gravity of the composition was adjusted to 1.75 when manufacturing the molded body.

[Table 1]

[Table 2]

(In Table 2, MD is the Machine Direction, and TD means the Transverse Direction.)

As shown in Table 1, the pellets prepared according to the present invention satisfy mechanical properties despite containing fine cellulose powder. Particularly, in the case of Example 3 in which the contents of the cellulose fine powder and the thermoplastic resin were changed, the flexural modulus was slightly lower than that of Example 1, but the impact strength and elongation were much higher.

On the other hand, in Comparative Example 1 in which the apparent specific gravity was decreased, it can be seen that the elongation rate was significantly lowered due to the increase in the average particle diameter of the cellulose fine powders, and the Comparative Example 2 in which the apparent specific gravity increased, due to the increase in water vapor pressure in the extruder Due to this, a back pressure occurred and was not extruded properly.

In addition, in Comparative Examples 3 and 4 in which the water content of the cellulose fine powder exceeded the reference value, it was found that the flexural modulus and the impact strength were too low, so that it was difficult to secure mechanical properties even when manufactured as a secondary product.

When the sheet was manufactured using the pellets prepared according to the present invention, it was found that the desired properties were secured in terms of tensile strength, elongation, and elastic modulus. In particular, in the case of Example 5 in which the water content of the composition was adjusted to 0.05% by weight, it was found that the cause of defects generated during extrusion of the sheet, such as the warpage and excitation of the sheet, hardly occurs, and thus, it has the best mechanical properties.

On the other hand, in the case of Comparative Example 5 in which the melt mass flow was adjusted to 1.55, it was shown that stretching was difficult to use due to the increase in crystallinity of the sheet, and in the case of Comparative Example 6 in which the moisture content of the composition was outside the range, the elastic modulus increased. However, the elongation was significantly reduced. In Comparative Examples 7, 8 in which the specific gravity of the composition was adjusted to a specific range, the increase or decrease in crystallinity also influenced the mechanical properties of the entire sheet, so it was too hard or soft to show properties that were difficult to use as a final product.

As described above, the present invention has been described with reference to preferred embodiments and test examples, but those skilled in the art may vary the present invention without departing from the spirit and scope of the present invention as set forth in the claims below. You can understand that it can be modified and changed.

Claims (7)

Styrene-butadiene, which is formed on both sides of the substrate containing the cellulose fine powder component and the substrate, and is selected from the group consisting of polyethylene, polypropylene, polyester, polylactic acid, and polystyrene, 100 parts by weight of any one or a plurality of general polymers, Styrene-isoprene, styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-(ethylene-butylene), styrene-(ethylene-propylene), styrene-(ethylene-butylene)-styrene, styrene-(ethylene-propylene )-Styrene, styrene-(ethylene-butylene)-styrene-(ethylene-butylene), styrene-(ethylene-propylene)-styrene-(ethylene-propylene) and styrene-ethylene-(ethylene-propylene)-styrene A sheet containing a fine cellulose powder comprising a thermoplastic resin layer formed by extruding a resin composition containing 10 to 40 parts by weight of any one or a plurality of thermoplastic elastomers,
The above description,
The melt mass flow measured at 230° C. and 2.16 kg is 0.2 to 1.5 g/10min, and the water content is 0.1 to 0.5% by weight,
As a composition, cellulose fine powder having an average particle size of 10 to 50 µm and an apparent specific gravity of 0.25 to 0.35 is 40 to 60% by weight;
Styrene-butadiene, styrene-isoprene compared to 100 parts by weight of polypropylene having a melt mass flow of 0.5 to 10 g/10min, a density of 0.8 to 1.0 g/cm 2, and a heat distortion temperature of 100 to 125° C., measured at 230° C. and 2.16 kg, Styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-(ethylene-butylene), styrene-(ethylene-propylene), styrene-(ethylene-butylene)-styrene, styrene-(ethylene-propylene)-styrene, Any selected from styrene-(ethylene-butylene)-styrene-(ethylene-butylene), styrene-(ethylene-propylene)-styrene-(ethylene-propylene) and styrene-ethylene-(ethylene-propylene)-styrene Or 30 to 50% by weight of a thermoplastic resin mixed with 10 to 40 parts by weight of a plurality of thermoplastic elastomers;
And 5-10% by weight of additives;
Sheet containing a fine cellulose powder, characterized in that it comprises a.
delete delete delete delete According to claim 1,
The additive is any one or a plurality selected from internal lubricants, anti-scarring agents, inorganic particles, pigments, plasticizers, heat stabilizers, antioxidants, light stabilizers, acid scavengers, dyes, fragrances, optical brighteners and flame retardants A sheet containing fine cellulose powder, characterized in that.
According to claim 1,
The cellulosic fine powder is a sheet containing fine cellulose powder, characterized in that any one or a plurality of paper selected from printing paper, writing paper, calligraphy paper, information paper, packaging paper, hygiene thin paper, and miscellaneous paper as a raw material.