JP2011219715A - Resin compound material for molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin compound material for molding using a vegetable resource as a main raw material, and a molded body having excellent heat resistance and provided with flame retardancy and antibacterial properties.SOLUTION: The resin compound material for molding contains lignin, wherein the lignin is soluble in an organic solvent and contained therein in an amount of 5-90 mass%. The molded body is formed using the resin compound material.

Description

  The present invention relates to a resin compound material for compression, extrusion or injection molding and a molded body thereof.

  Conventionally, fossil resources such as petroleum have been used as raw materials for chemical products, but in recent years, demand for biomass plastics has increased due to the introduction of the concept of carbon neutral. Therefore, there is an active movement to replace plastic products around us, such as packaging materials, household appliance components, and automotive components, with plant-derived resins (bioplastics).

Specific examples of the plant-derived resin include polylactic acid: PLA (Polylactic Acid) produced by chemical polymerization using lactic acid obtained by fermenting sugars such as potato, sugarcane, and corn as a monomer. , Starch-based esterified starch, microorganism-produced resin that is a polyester produced by microorganisms in the body: PHA (PolyHydroxy Alkanoate), 1,3-propanediol obtained by fermentation, and petroleum-derived terephthalic acid as raw materials And PTT (Poly Trimethylene Telephthalate).
In addition, PBS (Poly Butylene Succinate) is currently used as a raw material derived from petroleum, but in the future, research to produce it as a plant-derived resin has been developed, and succinic acid, one of the main raw materials, has been developed. Developments have been made on technologies that are derived from plants.

  Resins using these plant-derived materials are introduced in a wide range of fields such as sanitary fields such as toilet seats, kitchens, and bathrooms, as well as miscellaneous goods and building materials, in addition to electrical / electronic parts, OA-related parts, and automobile parts. Has been. In particular, in electrical / electronic related parts, OA related parts, or automobile parts, heat resistance and flame retardancy are required for safety reasons. In addition, it has been pointed out that when bacteria and molds propagate in products used in the sanitary field, it has been pointed out to have an adverse effect on the human body, and it is preferable to impart antibacterial properties.

  All the plant-derived resins are thermoplastic (see Non-Patent Document 1). In order to use these thermoplastic resins as electrical / electronic related parts, OA related parts or automobile parts, high strength, heat resistance and flame retardancy are required. However, since the plant-derived resin has a low glass transition temperature, there are many problems in terms of heat resistance and flame retardancy.

  Moreover, compression molding, extrusion molding, and injection molding are mentioned as a method of manufacturing the electrical / electronic related parts, the OA related parts, or the automobile parts. In particular, injection molding is a molding method with excellent productivity, and is suitable for manufacturing a large number of molded articles.

  Lignin is attracting attention as a raw material for heat-resistant resin materials derived from plants, and composite materials obtained by adding lignin to biodegradable resin materials are known. Japanese Patent No. 4384949 discloses an injection molded body made of cellulose, lignin and a lactic acid resin. Japanese Patent Application Laid-Open No. 2008-37022 discloses a resin composition in which a biodegradable resin is kneaded with a lignocellulosic resin composition. However, in these composite materials, since the thermoplastic resin is composited, the heat resistance is not yet sufficient, which may cause problems in practice.

Japanese Patent No. 4384949 JP 2008-37022 A

Yoshiharu Tohi (Edition) Biodegradable polymer materials, Industrial Research Committee, published in 1990

  An object of this invention is to provide the resin compound material for shaping | molding and the molded object which utilized the woody material derived from a plant from a viewpoint of environmental load reduction. In particular, the object is to provide a molded article that uses plant-derived lignin as a main raw material, has excellent heat resistance, and imparts flame retardancy and antibacterial properties.

The present invention is as follows.
(1) A molding resin compound material for compression, extrusion or injection molding containing lignin, wherein the lignin is soluble in an organic solvent and contains 5 to 90% by mass of lignin. Compound material.
(2) The resin compound material for molding according to (1) above, wherein the lignin has a weight average molecular weight of 100 to 7000.
(3) The molding resin compound material according to (1) or (2), wherein the content of sulfur atoms in lignin is 2% by mass or less.
(4) The molding according to any one of (1) to (3), wherein the lignin is a lignin obtained by separating from a cellulose component and a hemicellulose component by a treatment method using only water, and dissolving the lignin in an organic solvent. Resin compound material.
(5) Lignin is obtained by injecting water vapor into the plant material and separating it from the cellulose component and hemicellulose component by a steam explosion method that explodes the plant material by instantaneously releasing the pressure and dissolving it in an organic solvent. The molding resin compound material according to any one of (1) to (3).
(6) The molding resin compound material according to any one of (1) to (5), further comprising at least one fiber selected from plant fibers, carbon fibers, synthetic fibers, and inorganic fibers.
(7) The molding resin according to any one of (1) to (6), wherein the molding resin has any shape or form of particles having an average particle diameter of 0.1 to 10 mm, a pulverized product, and a pellet. Compound material.
(8) The molding resin compound material according to any one of (1) to (7), further comprising at least one curing agent.
(9) The molding resin compound material according to (8), wherein the curing agent is an epoxy resin.
(10) The resin compound material for molding as described in (8) above, wherein the curing agent is isocyanate.
(11) The molding resin compound material according to (8), wherein the curing agent is a compound that generates aldehyde or formaldehyde.
(12) The molding resin compound material according to (8), wherein the curing agent is an acrylic resin.
(13) The molding resin compound material according to (8), wherein the curing agent is selected from one or more polyvalent carboxylic acids or polyvalent carboxylic anhydrides.
(14) A molded body obtained by molding the molding resin compound material according to any one of (1) to (13).

  ADVANTAGE OF THE INVENTION According to this invention, the molding resin compound material excellent in moldability can be provided, Thereby, the reduction effect of a fossil resource usage-amount and the reduction | decrease in the discharge | emission amount of a carbon dioxide is acquired, and the molding use excellent in productivity Resin compound material could be provided. Moreover, the molded object which has a high glass transition temperature was able to be provided by using lignin as the main raw material.

  According to the present invention, by using lignin as a main raw material, in addition to the above effects, a molding resin compound material (plant-derived molding resin material) excellent in flame retardancy can be provided.

  According to the present invention, by using lignin as a main raw material, it was possible to provide a molding resin compound material (plant-derived tree molding resin material) imparted with an antibacterial effect in addition to the above effects.

Hereinafter, the present invention will be described in more detail.
The present invention is a molding resin compound material for compression, extrusion or injection molding containing lignin, wherein the lignin is soluble in an organic solvent and contains 5 to 90% by mass of lignin. It is a compound material. The lignin is preferably contained in an amount of 30 to 90% by mass, and further preferably 40 to 80% by mass. If it exceeds 90% by mass, the strength of the molded product may deteriorate. On the other hand, if the amount is less than 5% by mass, the effect of reducing the amount of fossil resources used, flame retardancy, and antibacterial effect may not be obtained.

The weight average molecular weight of lignin is preferably 100 to 7000, more preferably 200 to 5000, and particularly preferably 500 to 4000 in terms of polystyrene. When the weight average molecular weight of lignin exceeds 7000, the solubility to an organic solvent will fall. If the molecular weight is too low, a molding resin compound material utilizing the structure of lignin cannot be obtained.
The weight average molecular weight was measured by gel permeation chromatography (GPC), and a value converted to standard polystyrene was used.

  The basic skeleton of lignin is generally a crosslinked polymer having a hydroxyphenylpropane unit as a basic unit. Trees form an interpenetrating network (IPN) structure of hydrophilic linear polymer polysaccharides (cellulose and hemicellulose) and hydrophobic cross-linked lignin. Lignin accounts for about 25% by weight of trees and has an irregular and extremely complex chemical structure of polyphenols.

  The present invention consists in using lignin as a main raw material and taking advantage of the complex chemical structure of lignin. When taking out lignin from a plant, if the molecular weight is low, a complicated polyphenol structure cannot be utilized, and high heat resistance cannot be obtained. Another object is to use a phenolic hydroxyl group and an alcoholic hydroxyl group possessed by lignin to form a three-dimensional crosslinked structure using a curing agent. Thereby, it became possible to obtain a resin material and a molded body having a high glass transition temperature. In addition, since the lignin obtained by the treatment method using sulfuric acid or the like has a hydroxyl group substituted with a sulfonate, the reaction with the curing agent is low and it is difficult to obtain a rigid skeleton.

  In addition, phenols are known to have excellent flame retardancy and antibacterial action because they easily form graphite upon combustion. The present invention provides a molding resin compound material having flame retardancy and antibacterial properties by utilizing the complicated structure obtained from plants as it is and using it as a resin raw material.

  There are no particular restrictions on the raw material of lignin. Conifers such as cedar, pine and cypress, broad-leaved trees such as beech, bamboo, rice straw, bagasse and the like are used. Examples of methods for separating and taking out lignin from trees include kraft method, sulfuric acid method, and explosion method. Many of the lignins currently produced in large quantities are obtained as residues during the production of cellulose, which is a raw material for paper and bioethanol. Examples of lignin that can be obtained include lignin sulfonate that is produced as a by-product mainly by the sulfuric acid method. Other examples include alkaline lignin, organosolv lignin, solvolysis lignin, filamentous fungus treated wood, dioxane lignin and milled wood lignin, and explosive lignin. The lignin described above can be used regardless of the method of taking out the lignin used in the present invention.

  When taking out, components other than lignin, such as cellulose and hemicellulose, may be contained to some extent. Also included are lignin derivatives prepared by acetylation, methylation, halogenation, nitration, sulfonation, reaction with sodium sulfide or hydrogen sulfide, and the like.

  As a method for obtaining lignin as a main raw material, a method using a separation technique using water is preferable. The lignin used is preferably a lignin obtained by separating it from a cellulose component and a hemicellulose component by a treatment method using only water and dissolving it in an organic solvent. Moreover, as a method for obtaining lignin, the steam explosion method is more preferable. The steam explosion method crushes plants in a short time by hydrolysis with high-temperature and high-pressure steam and a physical crushing effect by instantaneously releasing the pressure. This method is a clean separation method because only water is used without using sulfuric acid, sulfite or the like, compared with other separation methods such as sulfuric acid method and kraft method.

The conditions for steam explosion are not particularly limited. Usually, the raw material is placed in a pressure vessel for a steam explosion apparatus, 3-4 MPa of steam is injected, left to stand for 1-15 minutes, and then the pressure is instantaneously released for explosion. To do. The organic solvent-soluble lignin is also referred to as steam explosion lignin. The raw material is not particularly limited as long as lignin can be extracted. .
In this method, lignin containing no sulfur atom in the lignin or lignin having a low content of sulfur atoms can be obtained. Usually, the content of sulfur atoms in lignin is preferably 2% by mass or less, more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less. When the sulfur atom content is increased, hydrophilic sulfonic acid groups are increased, so that the solubility in an organic solvent is lowered. The present inventors have further found that the molecular weight of lignin can be controlled from the blasted product by extraction with an organic solvent.

  The organic solvent used in the extraction of lignin used in the present invention is one or a mixture of two or more kinds of alcohol solvents, a hydrous alcohol solvent in which alcohol and water are mixed, another organic solvent, or a hydrous organic solvent in which water is mixed. Can be used. It is preferable to use ion exchange water as water. The water content of the mixed solvent with water is preferably 0% by mass to 70% by mass. Since lignin has low solubility in water, it is difficult to extract lignin using only water as a solvent. Moreover, it is possible to control the weight average molecular weight of the lignin obtained by selecting the solvent to be used.

  One of the structures of the molding resin compound material of the present invention is composed of lignin and at least one curing agent. Furthermore, various desired additive components, curing accelerators, viscosity modifiers, mold release agents, plasticizers (mineral oil, silicone oil, etc.), lubricants, stabilizers, antioxidants, ultraviolet absorbers, antifungal agents, inorganic fillers Organic fillers can also be blended when polymer components are polymerized or when polymer molded bodies are molded. In addition, powder forms such as paper powder, wood powder, cellulose powder, rice husk powder, fruit husk powder, chitin powder, chitosan powder, protein, and starch may be added.

The molding resin compound material is fluidized by heating during molding, supplied to a mold, and further subjected to a curing reaction by heating to obtain a molded body. The fluidity of the molding resin compound material needs to be adjusted according to the molding method selected. As a method of adjusting the viscosity, there is a method of increasing the molecular weight by promoting curing by adding a viscosity modifier or heating and kneading in advance.
In addition, the molding resin compound material of the present invention has any shape or form of particles, pulverized products, and pellets having an average particle diameter of 0.1 to 10 mm from the viewpoint of ease of molding such as compression, extrusion or injection. It is preferable that Moreover, as an average particle diameter of particle | grains, Preferably it is 0.5-5 mm, More preferably, it is 1-3 mm. Further, the pulverized product is usually obtained by making the molding resin compound material semi-cured and pulverizing with a pulverizer. In addition, the resin compound material for molding in the form of pellets may be generally in a semi-cured state, molded by a molding machine, and formed into a cylindrical shape.

  One of the configurations of the molding resin compound material is composed of lignin, a curing agent, and at least one kind of fiber among plant fiber, carbon fiber, synthetic fiber, and inorganic fiber. The average fiber length of the fibers used is preferably 0.01 to 10 mm, more preferably 0.05 to 5 mm, and particularly preferably 0.1 to 3 mm at the stage after kneading with the resin. If the average fiber length of the fibers in the molding compound material is less than 0.01 mm, the mechanical strength is low, and if it exceeds 10 mm, molding becomes difficult.

  Plant fibers include cotton, bamboo, ramie, flax (linen), Manila hemp (avaca), sisal hemp, jute, kenaf, banana, coconut, straw, sugar cane, cedar, cypress, spruce, pine, Fir and larch fibers.

  There are pitch and PAN (polyacrylonitrile) types of carbon fiber, but PAN is preferred in terms of strength, elastic modulus, and thermal conductivity, because of its light weight, chemical resistance, heat resistance, and sliding properties. Is preferably a pitch system. In view of the environment, recycled carbon fiber taken out from CFRP (carbon fiber reinforced plastic) is preferable.

  Synthetic fibers include polyester fibers, polyamide fibers, acrylic fibers, urethane fibers, polyvinyl chloride fibers, polyvinylidene chloride fibers, acetate fibers, aramid fibers, nylon fibers, and vinylon fibers.

  Examples of inorganic fibers include amorphous fibers such as glass fibers and rock wool, alumina fibers, polycrystalline fibers such as zinc oxide, and single crystal fibers such as wollastonite and potassium titanate fibers.

  Examples of the organic solvent contained in the molding resin compound material or the organic solvent used for extraction of lignin include alcohol, toluene, benzene, N-methylpyrrolidone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ether, methyl cellosolve (ethylene glycol monomethyl). Ether), cyclohexanone, dimethylformamide, methyl acetate, ethyl acetate, acetone, tetrahydrofuran, and the like. These can be used in a mixture of two or more.

  Alcohols include monools such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, n-hexanol, benzyl alcohol, cynohexanol, ethylene glycol, diethylene glycol, 1,4-butanediol, Examples include polyols such as 1,6-hexanediol, trimethylolpropane, glycerin, and triethanolamine. Further, an alcohol obtained from a natural substance is more preferable from the viewpoint of reducing environmental load. Specifically, methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, ethylene obtained from natural substances Examples include glycol, glycerin, and hydroxymethylfurfural.

  An epoxy resin is mentioned as a hardening | curing agent used by this invention. Epoxy resins include bisphenol A glycidyl ether type epoxy, bisphenol F glycidyl ether type epoxy, bisphenol S glycidyl ether type epoxy, bisphenol AD glycidyl ether type epoxy, phenol novolac type epoxy, biphenyl type epoxy, and cresol novolac type epoxy. Further, an epoxy resin obtained from a naturally-derived substance is preferable from the viewpoint of reducing the environmental load. Specific examples include epoxidized soybean oil, epoxidized fatty acid esters, epoxidized linseed oil, and dimer acid-modified epoxy resin.

  An isocyanate is mentioned as a hardening | curing agent used by this invention. Isocyanates include aliphatic isocyanates, alicyclic isocyanates and aromatic isocyanates, as well as modified products thereof. Examples of the aliphatic isocyanate include hexamethylene diisocyanate, lysine diisocyanate, and lysine triisocyanate. Examples of the alicyclic isocyanate include isophorone diisocyanate. Examples of the aromatic isocyanate include tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, triphenylmethane triisocyanate, tris (isocyanatephenyl) thiophosphate, and the like. Examples of the modified isocyanate include urethane prepolymer, hexamethylene diisocyanate burette, hexamethylene diisocyanate trimer, and isophorone diisocyanate trimer.

  Examples of the curing agent used in the present invention include compounds that generate aldehyde or formaldehyde. The aldehyde is not particularly limited. For example, formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, chloral, furfural, glyoxal, n-butyraldehyde, caproaldehyde, allylaldehyde, benzaldehyde, crotonaldehyde, acrolein, phenylacetaldehyde , O-tolualdehyde, salicylaldehyde and the like. Moreover, hexamethylenetetramine is mentioned as a compound which produces | generates formaldehyde. Hexamethylenetetramine is particularly preferable. These may be used alone or in combination of two or more. Moreover, hexamethylenetetramine is preferable from the viewpoint of curability and heat resistance.

  An acrylic resin is mentioned as a hardening | curing agent used by this invention. As the acrylic resin, one or more monomers selected from acrylic acid, methacrylic acid, styrene, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, and fatty acid vinyl ester are used alone or Copolymerized products can be used.

  Examples of the curing agent used in the present invention include polyvalent carboxylic acids or polyvalent carboxylic acid anhydrides. Specific examples of the polycarboxylic acid include aliphatic polycarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, trimellitic acid, and pyromellitic acid. And aromatic polyvalent carboxylic acids such as isophthalic acid, terephthalic acid, phthalic acid, and 2,6-naphthalenedicarboxylic acid. Specific examples of the polyvalent carboxylic acid anhydride include, for example, malonic acid anhydride, succinic acid anhydride, glutaric acid anhydride, adipic acid anhydride, pimelic acid anhydride, suberic acid anhydride, azelaic acid anhydride, ethyl Aliphatic polycarboxylic acid anhydrides such as nadic acid anhydride, alkenyl succinic acid anhydride, hexahydrophthalic acid anhydride, trimellitic acid anhydride, pyromellitic acid anhydride, benzophenone tetracarboxylic acid anhydride, phthalic acid Aromatic polyvalent carboxylic acid anhydrides such as anhydrides may be mentioned. It is preferable that the polyvalent carboxylic acid or polyvalent carboxylic acid anhydride is obtained by reacting with the hydroxyl group of lignin.

  Examples of the curing agent used in the present invention include unsaturated polyvalent carboxylic acid or unsaturated polyvalent carboxylic acid anhydride. Specific examples of the unsaturated polycarboxylic acid include acrylic acid, crotonic acid, α-ethylacrylic acid, α-n-propylacrylic acid, α-n-butylacrylic acid, maleic acid, fumaric acid, citraconic acid, and mesacone. An acid, itaconic acid, etc. are mentioned. Specific examples of the unsaturated polyvalent carboxylic acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, cis-1,2,3,4-tetrahydrophthalic anhydride. It is preferable that the unsaturated polyvalent carboxylic acid or unsaturated polyvalent carboxylic acid anhydride is obtained by reacting with the hydroxyl group of lignin.

  The molding resin compound material and molded article of the present invention may contain a curing accelerator. Curing accelerators include cycloamidine compounds, quinone compounds, tertiary amines, organic phosphines, metal salts, 1-cyanoethyl-2-phenylimidazole, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4- Examples include imidazoles such as methylimidazole and 2-heptadecylimidazole.

The molded body of the present invention is manufactured (molded) by compressing, extruding, or injecting the resin compound material for molding, usually by a resin molding machine such as an injection molding machine or a compression molding machine. The production (molding) conditions are not particularly limited.
In addition, for example, the resin compound material for molding of the present invention is produced by an injection molding machine with a nozzle temperature of 80 to 200 ° C., an injection pressure of 1 to 30 MPa, a mold clamping pressure of 1 to 30 MPa, a mold temperature of 50 to 300 ° C., and a curing time of 1. It is injected and molded under the conditions of min to 100 min, further heat-treated at 50 to 300 ° C. for 1 to 8 hours, and sufficiently cured.
Further, for example, a mold of a compression molding machine heated to 80 to 250 ° C. is filled with the molding resin compound material of the present invention, pressed for 1 to 30 MPa, 1 to 100 minutes, cured, molded, and further 50 Heat cure at ~ 300 ° C for 1-8 hours and fully cure.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, the scope of the present invention is not limited to these Examples.

Example 1
(Extraction of lignin)
Bamboo was used as a lignin extraction raw material. Bamboo material cut to an appropriate size was placed in a 3 L pressure-resistant container of a steam explosion apparatus, 3.5 MPa of steam was injected, and held for 4 minutes. Thereafter, the valve was rapidly opened to obtain an explosion-treated product. The explosion-treated product obtained until the pH of the cleaning solution reached 6 or more was washed with water to remove water-soluble components. Thereafter, residual moisture was removed with a vacuum dryer. After adding 1000 ml of acetone to 100 g of the obtained dried product and stirring for 3 hours, the fiber material was removed by filtration. The extraction solvent (acetone) was removed from the obtained filtrate to obtain lignin. The obtained lignin was a brown powder at room temperature (25 ° C.).

(Lignin analysis)
The solvent solubility was evaluated by adding 1 g of the lignin to 10 ml of the solvent. When it melt | dissolved easily at normal temperature (25 degreeC), it evaluated as (circle), when it melt | dissolved at 50-70 degreeC, (triangle | delta), and the case where it did not melt | dissolve even if heated was evaluated. As a result of evaluating the solubility as acetone, cyclohexanone, tetrahydrofuran as the solvent group 1 and methanol, ethanol, and methyl ethyl ketone as the solvent group 2, the solvent group 1 was evaluated as ◯ and the solvent group 2 as △.

  The content of sulfur atoms in lignin was quantified by combustion decomposition-ion chromatography. As the apparatus, an automatic sample combustion apparatus (AQF-100) manufactured by Mitsubishi Chemical Analytech Co., Ltd. and an ion chromatograph (ICS-1600) manufactured by Nippon Dionex Co., Ltd. were used. The content rate of the sulfur atom in the said lignin was 0.2 mass%. Furthermore, the molecular weight of lignin was measured by gel permeation chromatography (GPC) equipped with a differential refractometer. Polystyrene having a low polydispersity was used as a standard sample, the mobile phase was used as tetrahydrofuran, and gel pack GL-A120S and GL-A170S manufactured by Hitachi High-Technologies Corporation were connected in series to perform molecular weight measurement. Its weight average molecular weight was 2400.

The hydroxyl equivalent of the lignin (organic solvent soluble lignin) obtained above was determined by measuring the hydroxyl value by acetic anhydride-pyridine method and the acid value by potentiometric titration (the units of hydroxyl equivalent and epoxy equivalent below are gram). / Equivalent, expressed below in g / eq.).
The hydroxyl equivalent of acetone-extracted bamboo-derived lignin is 140 g / eq. Met. The molar ratio (hereinafter P / A ratio) of the phenolic hydroxyl group and alcoholic hydroxyl group of lignin was determined by the following method. An acetylation treatment of 2 g of lignin was performed, the unreacted acetylating agent was distilled off, and the dried product was dissolved in deuterated chloroform and analyzed by 1H-NMR (manufactured by BRUKER, V400M, proton fundamental frequency 400.13 MHz). It was measured. Determine the molar ratio from the integral ratio of protons derived from acetyl groups (derived from acetyl groups bonded to phenolic hydroxyl groups: 2.2 to 3.0 ppm, derived from acetyl groups bonded to alcoholic hydroxyl groups: 1.5 to 2.2 ppm). As a result, the P / A ratio was 2.2 / 1.0.

[Production of resin compound material]
As a curing agent, 200 g of lignin and 150 g of cresol novolac type epoxy resin (YDCN-700-10, manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 210 g / eq.), Curazole 2PZ-CN 2 g (manufactured by Shikoku Kasei Kogyo Co., Ltd., 1-cyanoethyl- 2-phenylimidazole) was added and kneaded for 3 minutes with a heated roll (temperature 180 ° C.). The obtained semi-cured product was pulverized into particles (pulverized product) having an average particle diameter of 2 mm by a pulverizer to obtain a molding resin compound material containing 57% by mass of lignin.

(Production of molded body)
The molding resin compound material was molded by an injection molding machine. A good molded article was obtained at a nozzle temperature of 130 ° C., an injection pressure of 13 MPa, a mold clamping pressure of 14 MPa, a mold temperature of 180 ° C., and a curing time of 5 minutes. Furthermore, it processed at 200 degreeC for 4 hours, and was fully hardened.

(Flame retardancy test)
The evaluation of flame retardancy was performed according to UL flame resistance test standard (UL94). The molded body was dried as a test piece, and then crushed to produce a powder. The powder was filled in a mold having a thickness of 3 mm, a length of 130 mm, and a width of 13 mm, and was subjected to pressure heating molding at 180 ° C. for 2 hours. . In the horizontal combustion test, the HB level or higher was regarded as flame retardant. As a result of the evaluation, the HB level was satisfied.

(Antimicrobial test)
According to JIS Z2801, antibacterial activity against Staphylococcus aureus and Escherichia coli was evaluated. On the test piece, 0.4 mL of a bacterial solution (viable cells of 2.5 to 10 × 10 5 cells / mL) was inoculated, and the film was covered and cultured at 35 ° C. ± 1 ° C. for 24 hours. In order to measure the number of viable bacteria on the test piece, sampling was performed, the sample was appropriately diluted, and cultured in an agar plate culture at 35 ° C. ± 1 ° C. for 48 hours to obtain the viable cell count.
R = [Log (B / A) -log (C / A)] = [Log (B / C)]
R: antibacterial activity value A: average number of viable bacteria immediately after inoculation in unprocessed test pieces (pieces)
B: Average number of viable cells after 24 hours in unprocessed test piece
C: Average number of viable bacteria after 24 hours in antibacterial processed test piece
An antibacterial activity value of 2 or more was considered to be antibacterial. The antibacterial activity value of the molded product was 3.2 and 2.7 against Escherichia coli and Staphylococcus aureus, respectively.
Therefore, the obtained molded body was flame retardant and antibacterial.

(Glass transition temperature measurement)
In accordance with JIS K7244, the storage elastic modulus and loss tangent were measured using a viscoelastic spectrometer (EXTARDMS 6100, manufactured by SII Nano Technology Co., Ltd.) (sample size: length 40 mm, width 5 mm, thickness 1 mm, chuck) Between 20 mm, 25 ° C. to 350 ° C., heating rate 5 ° C./min, tension mode, composite wave (2 Hz, 1 Hz, 0.4 Hz, 0.2 Hz, 0.1 Hz), peak temperature of loss tangent at 1 Hz The glass transition temperature was taken. The glass transition temperature of the molded body was 160 ° C.

[Example 2]
(Extraction and analysis of lignin)
Lignin was obtained in the same manner as in Example 1 except that methanol was used as the extraction solvent. As a result of conducting elemental analysis and molecular weight measurement in the same manner as in Example 1, the sulfur atom content in the lignin was 0.2 mass%, and the weight average molecular weight was 1,900. As a result of evaluating the solvent solubility in the same manner as in Example 1, the solvent group 1 was evaluated as ◯ and the solvent group 2 as ◯. The molar ratio of the phenolic hydroxyl group and alcoholic hydroxyl group of lignin (hereinafter referred to as P / A ratio) was carried out in the same manner as in Example 1. The P / A ratio of the lignin obtained in Example 2 was 1.6 / 1.0. As a result of measuring the hydroxyl equivalent of the lignin (organic solvent-soluble lignin) obtained above in the same manner as in Example 1, the hydroxyl equivalent was 120 g / eq. Met.

[Production of resin compound material]
To 400 g of lignin is added 70 g of hexamethylene diisocyanate (Wako Pure Chemical Industries, Ltd.) as a curing agent and 4 g of dibutyltin dilaurate (IV) (Wako Pure Chemical Industries, Ltd.) as a curing accelerator, and 3 minutes with a 70 ° C. heating roll. Kneaded. The obtained semi-cured product was pulverized into particles (pulverized product) having an average particle diameter of 2 mm by a pulverizer to obtain a molding resin compound material containing 84% by mass of lignin.

(Production of molded body)
The molding resin compound material obtained above was filled into a mold of a compression molding machine heated to 180 ° C., pressurized at 15 MPa for 5 minutes, and cured to obtain a molded body. Further, it was cured at 200 ° C. for 4 hours and sufficiently cured. As a result of evaluating the flame retardancy of the molded body in the same manner as in Example 1, the HB level was satisfied. Moreover, as a result of evaluating antibacterial properties, the antibacterial activity values of the molded products were 4.3 and 3.0 for Escherichia coli and Staphylococcus aureus, respectively. The glass transition temperature was 230 ° C. Therefore, the obtained molded body was flame retardant and antibacterial.

Example 3
(Extraction and analysis of lignin)
Lignin was extracted with acetone as in Example 1. The sulfur atom content, molecular weight, solvent solubility, molar ratio of phenolic hydroxyl group to alcoholic hydroxyl group, and hydroxyl group equivalent of lignin were the same as in Example 1.

[Production of resin compound material]
40 g of hexamethylenetetramine as a curing agent, 2 g of magnesium oxide as a curing accelerator, 200 g of bamboo fiber, and 0.5 g of stearic acid as a release agent were added to 400 g of the lignin, and kneaded with a heating roll at 90 ° C. for 5 minutes. The obtained semi-cured product was pulverized into particles (pulverized product) having an average particle diameter of 2 mm by a pulverizer to obtain a molding resin compound material containing 62% by mass of lignin.

(Production of molded body)
As a result of molding under the same conditions as in Example 1, a good molded body was obtained. As a result of evaluating the flame retardancy of the molded body in the same manner as in Example 1, the HB level was satisfied. Moreover, as a result of evaluating antibacterial properties, the antibacterial activity values of the molded products were 5.5 and 4.7 against Escherichia coli and Staphylococcus aureus, respectively. Therefore, the obtained molded body was flame retardant and antibacterial.

Example 4
In a 100 ml four-necked separable flask equipped with a stirring blade, 36 g of lignin obtained in Example 1, 20 g of maleic anhydride as a curing agent and 1 g of diallyl phthalate were dissolved in 50 g of cyclohexanone and stirred at 120 ° C. for 3 hours. After removing cyclohexanone using an evaporator, the obtained semi-cured product was pulverized into particles (pulverized product) having an average particle diameter of 2 mm by a pulverizer to obtain a molding resin compound material containing 63% by mass of lignin.
As a result of evaluating the flame retardancy of the molded body in the same manner as in Example 1, the HB level was satisfied. Moreover, as a result of evaluating antibacterial properties, the antibacterial activity values were 2.5 and 2.2 for Escherichia coli and Staphylococcus aureus, respectively. Therefore, the obtained molded body was flame retardant and antibacterial.

[Comparative Example 1]
Using lignin sulfonate (Vanilex N, manufactured by Nippon Paper Industries Co., Ltd.) as lignin, production of a resin compound material for molding was attempted. The content of sulfur atoms in the lignin sulfonate measured by elemental analysis was 3% by mass. The weight average molecular weight was measured by high performance liquid chromatography (C-R4A) manufactured by Shimadzu Corporation and calculated by a calibration curve using standard polystyrene. The mobile phase was used as DMF + LiBr (0.06 mol / L) + phosphoric acid (0.06 mol / L), and two gel packs GL-S300MDT-5 manufactured by Hitachi High-Technologies Corporation were connected in series as a column for molecular weight measurement. went. Its weight average molecular weight was 11,000.
The solubility in organic solvents was evaluated in the same manner as in Example 1. As a result of evaluating the solubility using acetone, cyclohexanone, tetrahydrofuran, methanol, ethanol, and methyl ethyl ketone as the solvent, it was insoluble in all the solvents.

  In the same manner as in Example 1, 200 g of the lignin sulfonate, 150 g of cresol novolac type epoxy resin (YDCN-700-10, manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 210 g / eq.), 2 g of Curesol 2PZ-CN (Shikoku Kasei Kogyo Co., Ltd.) 1-cyanoethyl-2-phenylimidazole) was added and kneaded for 3 minutes with a heated roll (temperature 180 ° C.). As a result, the lignin sulfonic acid and the epoxy resin were phase-separated and a uniform resin compound material could not be obtained.

[Comparative Example 2]
An attempt was made to produce a molding resin compound material in the same manner as in Example 2 except that the above lignin sulfonate was used as the lignin. Prior to the production, the solubility in an organic solvent was evaluated in the same manner as in Example 1. As a result, it was insoluble in all solvents. As in Example 2, 70 g of hexamethylene diisocyanate (Wako Pure Chemical Industries, Ltd.) as a curing agent and 4 g of dibutyltin dilaurate (IV) (Wako Pure Chemical Industries, Ltd.) as a curing accelerator were added to 400 g of lignin sulfonate. The mixture was kneaded with a 70 ° C. heating roll for 3 minutes. As a result, lignin sulfonic acid and isocyanate were phase-separated and a uniform resin compound material could not be obtained.

[Comparative Example 3]
An attempt was made to produce a molding resin compound material in the same manner as in Example 3 except that the above lignin sulfonate was used as the lignin. Prior to the production, the solubility in an organic solvent was evaluated in the same manner as in Example 1. As a result, it was insoluble in all solvents. In the same manner as in Example 3, 40 g of hexamethylenetetramine as a curing agent, 2 g of magnesium oxide as a curing accelerator, 200 g of bamboo fiber, and 0.5 g of stearic acid as a release agent were added to 400 g of the lignin sulfonate at 90 ° C. The mixture was kneaded with a heating roll for 5 minutes. The obtained semi-cured product was pulverized into particles (pulverized product) having an average particle diameter of 2 mm by a pulverizer to obtain a molding resin compound material. As a result of producing a molded body in the same manner as in Example 3, a lignin sulfonate and hexamethylenetetramine had poor reactivity and a molded body with extremely low strength was obtained.

Claims (14)

  A molding resin compound material for compression, extrusion or injection molding containing lignin, wherein the lignin is soluble in an organic solvent and contains 5 to 90% by mass of lignin. .   The resin compound material for molding according to claim 1, wherein the weight average molecular weight of lignin is 100 to 7000.   The molding resin compound material according to claim 1 or 2, wherein the content of sulfur atoms in lignin is 2% by mass or less.   The resin compound material for molding according to any one of claims 1 to 3, wherein the lignin is a lignin obtained by separating from a cellulose component and a hemicellulose component by a treatment method using only water and dissolving the lignin in an organic solvent.   The lignin is a lignin obtained by injecting water vapor into a plant raw material and separating it from a cellulose component and a hemicellulose component by a steam explosion method in which the plant raw material is blasted by releasing the pressure instantaneously and dissolving it in an organic solvent. The molding resin compound material according to any one of 1 to 3.   Furthermore, at least 1 sort (s) of a vegetable fiber, carbon fiber, a synthetic fiber, and an inorganic fiber is included, The resin compound material for shaping | molding in any one of Claims 1-5 characterized by the above-mentioned.   The resin composition material for molding according to any one of claims 1 to 6, wherein the molding compound material has any shape or form of particles having an average particle diameter of 0.1 to 10 mm, a pulverized product, and a pellet.   Furthermore, at least 1 sort (s) of hardening | curing agent is included, The resin compound material for shaping | molding in any one of Claims 1-7 characterized by the above-mentioned.   The resin compound material for molding according to claim 8, wherein the curing agent is an epoxy resin.   The molding resin compound material according to claim 8, wherein the curing agent is an isocyanate.   The molding resin compound material according to claim 8, wherein the curing agent is a compound that generates aldehyde or formaldehyde.   The resin compound material for molding according to claim 8, wherein the curing agent is an acrylic resin.   9. The molding resin compound material according to claim 8, wherein the curing agent is one or more selected from polyvalent carboxylic acids or polyvalent carboxylic acid anhydrides.   The molded object formed by shape | molding the resin compound material for shaping | molding in any one of Claims 1-13.