WO2017006986A1 - Composition de résine ainsi que procédé de fabrication de celle-ci, et corps moulé - Google Patents

Composition de résine ainsi que procédé de fabrication de celle-ci, et corps moulé Download PDF

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Publication number
WO2017006986A1
WO2017006986A1 PCT/JP2016/070112 JP2016070112W WO2017006986A1 WO 2017006986 A1 WO2017006986 A1 WO 2017006986A1 JP 2016070112 W JP2016070112 W JP 2016070112W WO 2017006986 A1 WO2017006986 A1 WO 2017006986A1
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Prior art keywords
resin composition
resin
lignocellulose
mass
composition according
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PCT/JP2016/070112
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English (en)
Japanese (ja)
Inventor
舩岡　正光
有希 ▲徳▼永
野寺　明夫
めぐみ 藤本
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出光ライオンコンポジット株式会社
国立大学法人三重大学
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Priority to JP2017527491A priority Critical patent/JP6745446B2/ja
Publication of WO2017006986A1 publication Critical patent/WO2017006986A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse

Definitions

  • the present invention relates to a resin composition, a method for producing the same, and a molded body.
  • the fiber reinforced composite material whose strength and rigidity are greatly improved by blending various fibrous reinforcing materials with resin, is widely used in industrial fields such as electric / electronics, machinery, automobiles, and building materials.
  • the fibrous reinforcing material blended in the fiber-reinforced composite material glass fibers having excellent strength and lightness are mainly used.
  • the glass fiber reinforced material achieves high rigidity, but has a limitation in weight reduction because of its high specific gravity.
  • the glass fiber itself is non-flammable, which causes problems such as damage to the combustion furnace during incineration and low combustion efficiency, making it suitable for thermal recyclability. There was also the disadvantage of not.
  • fiber reinforcements made of organic materials such as polyester fibers, polyamide fibers, and aramid fibers have been studied, but fiber reinforcement materials containing these reinforcements can ensure light weight and thermal recyclability.
  • fiber reinforcement materials containing these reinforcements can ensure light weight and thermal recyclability.
  • mechanical reinforcement effect was not sufficient.
  • Patent Document 3 discloses a method in which cellulose fibers from pulp are modified in a solution, microfibrillated using a biaxial kneader, and uniformly dispersed in a matrix resin.
  • Patent Document 4 discloses a cellulose fiber coated with a lignophenol derivative and having an average fiber diameter of 2 nm or more and 200 nm or less, and a cellulose fiber composite material containing the cellulose fiber dispersed in a matrix resin. Yes.
  • the composite materials proposed in Patent Documents 1 and 2 are insufficient in mechanical properties such as tensile elastic modulus, their applications are limited. Moreover, in the invention described in Patent Document 3, the dispersion of cellulose fibers in the resin is still insufficient, and the resultant fiber composite material has insufficient mechanical strength.
  • the modified cellulose contains moisture and the like, and it becomes a problem in terms of productivity, or a resin (for example, polyamide or polyester) that is affected by moisture can produce a cellulose fiber composite material. There were problems such as being unable to do so. Furthermore, a modification step is necessary, which is disadvantageous in terms of cost.
  • Patent Document 4 the thermal decomposition temperature is improved by surface-coating cellulose fibers with a lignophenol derivative, but a process of coating with a lignophenol derivative is required, and this production method is There was a problem in terms of cost.
  • the problem to be solved by the present invention is that the manufacturing method is simple, the productivity is excellent, the production cost is low, the mechanical strength is high, and the molded product is excellent in flame retardancy, heat aging resistance, and weather resistance. It is providing the resin composition which can be obtained, its manufacturing method, and the molded object obtained from the said resin composition.
  • the inventors of the present invention include a lignophenol derivative and a cellulose component, blend a lignophenol-based mixture and a thermoplastic resin in a specific ratio, and a 1 mm or more irregularity is visually observed in a molded product.
  • a lignocellulosic mixture obtained by adding and mixing an acid to a lignocellulosic material to which a phenolic compound is added, and a thermoplastic resin at a specific ratio
  • the present inventors have found that the above problems can be solved.
  • the present invention provides the following.
  • a lignocellulose-based mixture and a thermoplastic resin are contained, and when the total of the lignocellulose-based mixture and the thermoplastic resin is 100% by mass, the lignocellulose-based mixture is contained in an amount of 0.5% by mass to 60% by mass.
  • the resin composition is characterized in that in the molded product, no defects of 1 mm or more are visually observed.
  • thermoplastic resin is at least one selected from the group consisting of polyolefin resins, polystyrene resins, polyamide resins, polyester resins, and polycarbonate resins.
  • thermoplastic resin is a polyolefin resin.
  • thermoplastic resin is at least one selected from the group consisting of polyethylene and polypropylene.
  • thermoplastic resin is at least one selected from the group consisting of polyethylene and polypropylene.
  • thermoplastic resin is at least one selected from the group consisting of polyethylene and polypropylene.
  • ⁇ 7> The resin composition according to ⁇ 5> or ⁇ 6>, wherein the obtained molded article has an elongation retention after exposure to light of 65% or more.
  • ⁇ 8> The resin composition according to any one of ⁇ 1> to ⁇ 7>, further comprising an antioxidant.
  • ⁇ 9> Contains a lignocellulose-based mixture and a thermoplastic resin, and when the total of the lignocellulose-based mixture and the thermoplastic resin is 100 mass%, the lignocellulose-based mixture is contained in an amount of 0.5 mass% to 60 mass%.
  • the lignocellulosic mixture is obtained by adding an acid to a lignocellulosic material to which a phenol compound has been added, and mixing the lignocellulosic material.
  • the lignocellulosic mixture comprises a lignophenol derivative and a cellulose component.
  • the resin composition as described in any one.
  • the phenol compound to be added to the lignocellulosic material has at least one substituent selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a hydroxyl group,
  • the resin composition according to any one of ⁇ 9> to ⁇ 11>, which is a phenol compound having an ortho position and / or a para position.
  • the lignocellulosic mixture is selected from the group consisting of p-cresol, 2,6-xylenol, 2,4-xylenol, 2-methoxyphenol, 2,6-dimethoxyphenol, catechol, homocatechol, and pyrogallol.
  • ⁇ 9> to ⁇ 12> which is obtained by adding and mixing phosphoric acid having a concentration of 90% by mass or more to a lignocellulosic material to which at least one phenol compound is added.
  • Resin composition. ⁇ 14> The resin composition according to any one of ⁇ 1> to ⁇ 13>, which is obtained by hot melt mixing a lignocellulose-based mixture and a thermoplastic resin.
  • ⁇ 15> A molded product obtained by molding the resin composition according to any one of ⁇ 1> to ⁇ 14>.
  • ⁇ 16> Step of obtaining a lignocellulose-based mixture comprising a lignophenol derivative and a cellulose component by adding an acid to the lignocellulosic material to which the phenol compound has been added, and the lignocellulose-based mixture and the thermoplastic resin.
  • Manufacturing method. ⁇ 17> The method for producing a resin composition according to ⁇ 16>, wherein the acid is at least one selected from the group consisting of phosphoric acid, formic acid, and trifluoroacetic acid.
  • the phenol compound to be added to the lignocellulosic material has at least one substituent selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a hydroxyl group,
  • the lignocellulose-based mixture is selected from the group consisting of p-cresol, 2,6-xylenol, 2,4-xylenol, 2-methoxyphenol, 2,6-dimethoxyphenol, catechol, homocatechol, and pyrogallol.
  • ⁇ 16> to ⁇ 19> obtained by adding and mixing phosphoric acid having a concentration of 90% by mass or more to a lignocellulosic material to which at least one phenol compound is added.
  • a method for producing the resin composition is produced by adding and mixing phosphoric acid having a concentration of 90% by mass or more to a lignocellulosic material to which at least one phenol compound is added.
  • thermoplastic resin is at least one selected from the group consisting of polyolefin resins, polystyrene resins, polyamide resins, polyester resins, and polycarbonate resins.
  • ⁇ 22> The method for producing a resin composition according to any one of ⁇ 16> to ⁇ 21>, wherein the thermoplastic resin is a polyolefin resin.
  • ⁇ 23> The method for producing a resin composition according to any one of ⁇ 16> to ⁇ 22>, wherein the thermoplastic resin is at least one selected from the group consisting of polyethylene and polypropylene.
  • ⁇ 24> The resin according to any one of ⁇ 16> to ⁇ 23>, wherein the step (2) is a step of heat-melting and mixing an antioxidant in addition to the lignocellulose-based mixture and the thermoplastic resin.
  • a method for producing the composition is a step of heat-melting and mixing an antioxidant in addition to the lignocellulose-based mixture and the thermoplastic resin.
  • a resin composition capable of producing a molded product with a simple manufacturing method, excellent productivity, low production cost, high mechanical strength, excellent flame resistance, heat aging resistance, and weather resistance. Articles, methods for producing the same, and molded articles obtained from the resin composition can be provided.
  • the first resin composition of the present invention contains a lignocellulose-based mixture and a thermoplastic resin, and when the total of the lignocellulose-based mixture and the thermoplastic resin is 100% by mass, the lignocellulose-based mixture is 0.5%. It is characterized by containing not less than 60% by mass and not visually confirming 1 mm or more in the molded product.
  • the second resin composition of the present invention contains a lignocellulosic mixture and a thermoplastic resin. When the total of the lignocellulosic mixture and the thermoplastic resin is 100% by mass, the lignocellulosic mixture is 0.
  • the lignocellulosic mixture is contained by adding an acid to a lignocellulosic material to which a phenol compound is added, and is composed of a lignophenol derivative and a cellulose component. It is characterized by.
  • the inventors have found that a high-strength material can be obtained and a heat aging resistance and a weather resistance are excellent by blending a specific amount of a lignocellulose-based mixture with a thermoplastic resin.
  • the cellulose component is uniformly dispersed in the resin by covering the cellulose component with a lignophenol derivative excellent in compatibility with the resin, and the resin is reinforced. It is presumed that this is a result of excellent aging resistance and weather resistance due to the lignophenol derivative that contributes to relaxation of stress and further has an antioxidant function and an ultraviolet absorbing ability.
  • the lignocellulose-based mixture is obtained by adding an acid to a lignocellulosic material to which a phenol compound has been added and mixing, and is composed of a lignophenol derivative and a cellulose component.
  • Lignocellulosic material examples include wooded materials, various materials mainly made of wood, such as wood flour, chips, waste materials, and scrap materials. Moreover, as wood to be used, any kind of wood such as conifers and hardwoods can be used. Furthermore, various herbaceous plants and related samples such as agricultural wastes can be used.
  • a lignocellulosic substance may be used individually by 1 type, and may use 2 or more types together.
  • the lignocellulosic material is preferably subjected to pretreatment such as pulverization and drying in advance, and it is preferable to perform a degreasing treatment as necessary.
  • the opening at the time of sieving after pulverization is preferably 5 mm or less, more preferably 2 mm or less, still more preferably 1 mm or less, and 0.5 mm. It is particularly preferable that it is not more than 0.3 mm, and most preferably not more than 0.3 mm.
  • the water content is preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less. It is preferable to perform drying so as to achieve the above moisture content. By setting the moisture content within the above range, clogging is suppressed during sieving and the yield of the raw material powder is improved, which is preferable.
  • a degreasing treatment By the degreasing treatment, unnecessary oil and fat can be removed.
  • a degreasing method for example, a lignocellulosic material and an organic solvent can be charged into a stirring tank, and sufficiently mixed and stirred. By degreasing with an organic solvent, an effect of removing water in the lignocellulosic material can also be obtained.
  • an organic solvent such as acetone or hexane.
  • the organic solvent for performing the degreasing treatment is not particularly limited, and an ethanol-benzene mixed solvent, an acetone-methanol mixed solvent and the like are preferably exemplified.
  • the amount of the organic solvent used is preferably 1 to 10 times the amount of lignocellulosic material.
  • the “double amount” defined here means the amount of the organic solvent (liters) relative to 1 kg of the raw material.
  • the “5-fold amount” means that 5 L of the organic solvent is added to 1 kg of the raw material. Means.
  • the mixture is preferably stirred for 1 to 120 hours, more preferably 1 to 60 hours. Before adding the phenol compound, it is preferable to remove the organic solvent used for degreasing, but if the phenol compound solvent and the organic solvent used for degreasing are the same, the removal step may be omitted. Good.
  • Phenol compound Although a phenol compound will not be specifically limited if it is a compound which has at least 1 OH group on an aromatic ring, It is preferable that it is a compound which has at least 1 OH group on a benzene ring. Specifically, a monovalent phenol compound, a divalent phenol compound, a trivalent phenol compound, or the like can be used as the phenol compound. Specific examples of the monovalent phenol compound include phenol that may have one or more substituents, naphthol that may have one or more substituents, and one or more substituents. Good antroll and the like.
  • divalent phenol compound examples include catechol which may have one or more substituents, resorcinol which may have one or more substituents, and one or more substituents. Examples include good hydroquinone.
  • trivalent phenol compound examples include pyrogallol, which may have one or more substituents.
  • a phenol compound may be used individually by 1 type and may use 2 or more types together.
  • the type of substituent that the monovalent to trivalent phenol compound may have is not particularly limited, and may have any substituent, but is preferably an electron donating group, for example, Alkyl groups having 1 to 6 carbon atoms (such as methyl, ethyl, and propyl groups), alkoxy groups having 1 to 6 carbon atoms (such as methoxy, ethoxy, and propoxy groups), aryl groups (such as phenyl groups), and the like. Can be mentioned.
  • the phenol compound preferably has at least one substituent selected from the group consisting of an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms.
  • the alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms.
  • the alkoxy group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms.
  • the alkyl group and alkoxy group may further have a substituent, and examples of the substituent include a hydroxyl group.
  • the phenol compound is preferably a phenol compound having one or more substituents at least in the ortho-position or para-position, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a hydroxyl group More preferably, it is a phenol compound having at least one substituent selected from the group consisting of at the ortho position and / or the para position. In the phenol compound, at least one of the ortho positions is preferably unsubstituted.
  • Preferred examples of the phenol compound include p-cresol, 2,6-xylenol, 2,4-xylenol, 2-methoxyphenol (Guaiacol), 2,6-dimethoxyphenol, catechol, resorcinol, homocatechol, pyrogallol, Loglucinol and the like, and p-cresol, 2,6-xylenol, 2,4-xylenol, 2-methoxyphenol, 2,6-dimethoxyphenol, catechol, homocatechol, and pyrogallol are more preferable.
  • the phenol compound used in the present invention is a phenol compound having a substituent at the 4-position (para-position), a phenol compound having a substituent at the 2-position (ortho-position), the 2-position (ortho-position) and the 4-position (para-position). Phenol compounds having a substituent at the position) are preferred.
  • the phenol compound having a substituent at the 4-position (para-position) is a phenol compound having no substituent at two ortho positions.
  • the phenol compound having a substituent at the 2-position (ortho position) and the 4-position (para-position) is a phenol compound having no substituent at the 6-position (one ortho position).
  • a crosslinkable lignophenol derivative having a crosslinkable functional group at the ortho position of the phenolic hydroxyl group in the lignophenol derivative is prepared. It is also possible to prepare and use a polymer material by crosslinking lignophenol. In this case, the frequency of introduction of the crosslinkable functional group can be adjusted by selecting the type of phenol compound to be used.
  • the phenol compound when a phenol compound having a substituent at the 2-position (ortho position) and the 4-position (para-position) is used, the phenol compound is a carbon atom at the 6-position and the carbon atom at the benzyl position of the phenylpropane unit of lignin. Will be bound to.
  • the introduced phenol compound since there are no free ortho-position and para-position, the introduced phenol compound does not have a crosslinkable functional group introduction site. Therefore, the crosslinkable functional group is introduced only on the lignin matrix side.
  • a phenol compound having a crosslinkable functional group introduction site with different reactivity, or a number of introduction sites, or one or two or more different phenol compounds are introduced into lignin to introduce a lignophenol derivative.
  • the number of crosslinkable functional group introduction sites in can be controlled, and as a result, the crosslink density of the crosslinkable lignin derivative can be controlled.
  • a substituent is located at the 2-position (ortho position) or the 4-position (para position).
  • the function of the lignophenol derivative or the use of a phenol compound having a substituent at the 2-position (ortho position) and 4-position (para-position) as a blocking switching element It is also possible to control the structure.
  • the phenol compound when a phenol compound having a substituent at the 2-position (ortho position) and the 6-position (ortho position) is used as the introduced phenol compound, the phenol compound is a benzyl of a phenylpropane unit of lignin at the 4-position carbon atom. To the carbon atom at the position. In this case, since there are no free ortho-position and para-position, the introduced phenol compound does not have a crosslinkable functional group introduction site. In addition, a phenol compound having a substituent at the 2-position (ortho position) and the 6-position (ortho position) does not exhibit a switching function, and thus functions as a stable control element.
  • a phenol compound having a substituent at the 4-position para-position
  • the 2-position (ortho-position) and the 6-position A phenol compound having a substituent at the ortho position can be appropriately selected and used depending on the purpose.
  • the addition amount of the phenol compound added to the lignocellulosic material is preferably 10 to 50 parts by mass, more preferably 15 to 45 parts by mass, with respect to 100 parts by mass of the lignocellulosic material. More preferably, it is 40 mass parts.
  • the phenylpropane unit of lignin is obtained as follows. Specifically, a formula for C9 units is calculated from the elemental analysis values, and this is used as the average basic skeleton (C9 units). The variation in conifers and hardwoods is not so great.
  • the molecular weight of conifer C9 units (all guaiacyl units, one OCH 3 per C9 unit) is 200, and the broad-leaved tree C9 units (guayacyl units (one OCH 3 )): syringyl
  • the lignocellulosic material more preferably, the acid added to the lignocellulosic material sorbed with the phenolic compound has an action of swelling cellulose and a low action of hydrolyzing cellulose. Is preferred.
  • the acid added to the lignocellulosic material is an acid excluding the above-mentioned phenolic compound. Specific examples include phosphoric acid, hydrochloric acid, p-toluenesulfonic acid, trifluoroacetic acid, trichloroacetic acid, formic acid and the like.
  • the concentration of phosphoric acid is preferably 85% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more.
  • the concentration of hydrochloric acid is preferably 38% by mass or more.
  • the phosphoric acid having the above concentration is preferably prepared from 99% phosphoric acid.
  • the hydrochloric acid having the above concentration is preferably prepared under cooling and pressure.
  • the amount of the acid added is preferably 10 to 50 parts by weight, more preferably 15 to 45 parts by weight, and more preferably 20 to 40 parts by weight with respect to 100 parts by weight of the lignocellulosic material treated with the phenol compound. More preferably, it is part by mass.
  • the lignocellulose-based mixture comprises a lignophenol derivative and a cellulose component, and an acid is added to and mixed with a lignocellulosic material to which a phenolic compound has been added.
  • lignophenol derivative in the present specification means a polymer containing a diphenylpropane unit in which a phenol compound is introduced by a C—C bond at the side chain ⁇ -position of the phenylpropane unit of lignin.
  • the amount and molecular weight of the introduced phenol compound in this polymer vary depending on the lignocellulosic material used as a raw material and the reaction conditions.
  • the lignocellulose-based mixture of the present invention In order to obtain the lignocellulose-based mixture of the present invention from the lignocellulosic material, it is necessary to treat the lignin in the lignocellulosic material with a phenol compound to obtain a lignophenol derivative.
  • a method for converting lignin in a lignocellulosic substance into a lignophenol derivative the following two methods may be mentioned.
  • the first method is to impregnate a lignocellulosic material such as wood flour with a liquid phenolic compound (as described above, such as p-cresol), solvate the lignin with the phenolic compound, A concentrated acid (what was demonstrated above, for example, 95 mass% phosphoric acid) is added and mixed with a lignocellulosic substance, and a cellulose component is melt
  • a phenol compound obtained by solvating lignin and a concentrated acid dissolving a cellulose component form a two-phase separation system.
  • the lignin solvated by the phenolic compound is contacted with the acid only at the interface where the phenolic compound phase is in contact with the concentrated acid phase, and the side chain ⁇ -position, which is a highly reactive site of the lignin basic structural unit generated by contact with the acid.
  • the (benzylic) cation is attacked by the phenolic compound.
  • the phenol compound is introduced into the ⁇ -position by a C—C bond, and the benzyl aryl ether bond is cleaved to reduce the molecular weight.
  • the molecular weight of lignin is reduced, and at the same time, a lignophenol derivative in which a phenol compound is introduced at the benzyl position of the basic structural unit is produced in the phenol compound phase.
  • a lignocellulosic material is infiltrated with a solvent (for example, ethanol, acetone, hexane, etc.) in which a solid or liquid phenol compound is dissolved, and then the solvent is distilled off (recovery of the phenol compound). Wearing process).
  • a solvent for example, ethanol, acetone, hexane, etc.
  • concentrated acid as described above, for example, 95% by mass phosphoric acid
  • the lignin solvated with the phenol compound is attacked by the phenol compound with the cation at the highly reactive site (side chain ⁇ -position) of the lignin generated upon contact with the concentrated acid.
  • a compound is introduced.
  • the benzyl aryl ether bond is cleaved to reduce the lignin molecular weight.
  • the second method it is preferable to add the phenol compound in a state in which the phenol compound is sufficiently dispersed or dissolved in the lignocellulosic material.
  • the phenol compound is mixed and dissolved in an organic solvent. It is preferable to add to the lignocellulosic material in a state of being dispersed or dissolved.
  • a solution in which the phenol compound is dispersed or dissolved in an organic solvent (hereinafter also referred to as a phenol compound solution) is added to 1 kg of the lignocellulosic substance.
  • the temperature of the phenol compound solution is not particularly limited, but is preferably 10 to 50 ° C., more preferably 15 to 40 ° C., and still more preferably 20 to 30 ° C.
  • stirring is performed, and it is preferable to impregnate the phenolic compound solution with the lignocellulosic material, preferably for 1 to 60 hours. It is more preferably 2 to 48 hours, and further preferably 4 to 36 hours.
  • a method of stirring with a glass rod or a method using a magnetic stirrer can be used for a small scale, and for a large scale, a method using a magnetic stirrer or a tank having a stirring blade. Etc. are used. Further, after the impregnation, it is preferable to remove the organic solvent and sorb the phenol compound.
  • the acid is preferably added at 10 to 50 ° C., more preferably at 20 to 40 ° C. Moreover, after adding an acid, in order to advance reaction uniformly, it is preferable to fully stir uniformly and a kneader may be used.
  • the treatment time with the acid is preferably 5 minutes to 2 hours, more preferably 10 minutes to 1 hour.
  • the entire reaction solution after concentrated acid treatment was poured into excess water, and the insoluble fraction was collected by centrifugation and deacidified. Then, it may be dried.
  • the lignophenol derivative and the cellulose component are uniformly present, that is, the cellulose component is uniformly present in the lignophenol matrix.
  • the lignocellulose-based mixture obtained by the above-described method is a composition that uniformly contains a lignophenol derivative and a cellulose component, and that the cellulose component is uniformly present in the matrix of the lignophenol derivative without being unevenly distributed.
  • cellulose fibers are not coated with a lignophenol derivative.
  • a crystalline cellulose component monodispersed in the lignophenol derivative is uniformly distributed by hydrolyzing the amorphous portion of cellulose.
  • the lignocellulose-based mixture is preferably a composition containing needle-like or cage-like crystals (crystalline cellulose).
  • the crystallinity of cellulose is a method in which only crystals are produced in production, but the crystallinity can be confirmed by X-ray analysis.
  • the average length in the major axis direction (average major axis length) of the lignocellulosic mixture is preferably 10 to
  • the average length (average minor axis length) in the direction perpendicular to the major axis is preferably 5 to 50 nm, more preferably 5 to 30 nm, still more preferably 500 nm, more preferably 20 nm or more, still more preferably 30 nm or more. 10 to 20 nm.
  • the major axis length / minor axis length is preferably 5 or more.
  • the average major axis length is determined by observing an electron microscope image of the lignocellulose-based mixture. Specifically, the major axis length and the minor axis length of each of 50 randomly selected lignocellulose-based mixtures are measured using an electron microscope, and the average major axis length and the average minor axis length are obtained from the average. be able to.
  • the uniaxial length when the cross section in the direction orthogonal to the major axis (uniaxial direction) is not circular, the length of the longest portion measured in the axial direction is defined as the uniaxial length.
  • Lignocellulosic mixtures are usually fluid. However, when the lignophenol derivative fraction in the mixture is extracted, the fluidity is lost. Therefore, in the lignocellulose-based mixture, it is considered that the lignophenol derivative fraction expresses an important plastic effect. Moreover, the fluidity
  • liquidity of this mixture can be improved by acylating (for example, acetylation etc.) the lignophenol derivative in the lignocellulose-type mixture which is a component of this invention. That is, in the present invention, in the lignocellulose mixture, the lignophenol derivatives tend to bind to each other or to the cellulose section through hydrogen bonding, and the materials tend to associate with each other.
  • the fluidity of the composition is not so high.
  • the acylation of the lignophenol derivative (for example, acetylation, etc.) can eliminate the association between the materials, thereby improving the fluidity of the entire lignocellulosic mixture, and processing into a molded product or the like. The processing energy at the time can be reduced.
  • the lignophenol derivative in the lignocellulose-based mixture may be used after being methylolated. When a methylolated material is used, a molded product having a relatively low density, a high water absorption rate, and excellent stability can be produced.
  • thermoplastic resin examples include the following.
  • Polyolefin resin examples of the polyolefin resin mainly include the following.
  • (1-1) Polypropylene Resin The polypropylene resin can be composed of one or more selected from a homopolymer of propylene, a copolymer containing propylene as a main component, and the like.
  • the propylene homopolymer is not particularly limited, but a propylene homopolymer having a melt mass flow rate at 230 ° C. of 0.1 to 200 g / 10 min is preferred from the viewpoint of obtaining light weight and excellent moldability.
  • the melt mass flow rate at 230 ° C. is more preferably 0.2 to 60 g / 10 minutes.
  • the copolymer containing propylene as a main component is not particularly limited.
  • a copolymer of propylene and ethylene, or a random copolymer of one or more ⁇ -olefins other than propylene and propylene is used.
  • a block copolymer of propylene and one or more ⁇ -olefins other than propylene is used.
  • the melt mass flow rate at 230 ° C. is more preferably 0.2 to 60 g / 10 minutes.
  • ⁇ -olefins other than propylene include 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene and 1-hexadecene. , 1-octadecene, 1-eicosene and the like.
  • the polyethylene resin can be composed of one or more selected from a homopolymer of ethylene and a copolymer containing ethylene as a main component.
  • the ethylene homopolymer include low-density polyethylene, linear low-density polyethylene, linear low-density polyethylene, and high-density polyethylene. From the viewpoint of obtaining light weight and excellent moldability, the density is 0. a .910 ⁇ 0.965g / cm 3, ethylene homopolymer preferably has a melt mass flow rate at 190 ° C. is 0.01 ⁇ 200 g / 10 min. If the melt mass flow rate at 190 ° C. is within the above range, there is no possibility of causing problems in the fluidity of the resin composition and the surface appearance of the molded body.
  • the melt mass flow rate at 190 ° C. is more preferably 0.01 to 60 g / 10 min.
  • Examples of the copolymer mainly composed of ethylene include a random copolymer of ethylene and an ⁇ -olefin other than ethylene, and a block copolymer of ethylene and an ⁇ -olefin other than ethylene.
  • copolymers having ethylene as a main component an ethylene copolymer having a melt mass flow rate at 190 ° C. of 0.01 to 200 g / 10 min from the viewpoint of obtaining a light weight and excellent resin composition. Is preferred.
  • the melt mass flow rate at 190 ° C. is within the above range, there is no possibility of causing problems in the fluidity of the resin composition and the surface appearance of the molded body.
  • ⁇ -olefins other than ethylene include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1 -Hexadecene, 1-octadecene, 1-eicocene and the like.
  • polystyrene resins examples include the series of polypropylene resins “Prime Polypro”, “Polyfine” and “Prime TPO” manufactured by Prime Polymer Co., Ltd., for example, product number: J-700GP, Idemitsu Kosan Co., Ltd. Polypropylene resin (product number: J-966HP) manufactured by Prime Polymer Co., Ltd. and various polyethylene resins “Hi-Zex”, “Neo-Zex”, “Ult-Zex”, “Moretech”, “Evolue” series (for example, high Density polyethylene resin, product number: 2200J), and low density polyethylene (for example, product number: Petrocene 190) manufactured by Tosoh Corporation.
  • Polystyrene resins are, for example, polystyrene, poly (p-methylstyrene), poly (m-methylstyrene), poly (p-tert-butylstyrene), poly (p-chlorostyrene), poly (M-chlorostyrene), poly (p-fluorostyrene), hydrogenated polystyrene, and copolymers containing these structural units. These polystyrene resins may be used alone or in combination of two or more.
  • polystyrene resins examples include PS Japan Co., Ltd., PSJ-polystyrene series (for example, product number: H8672), Toyo Styrene Co., Ltd., and Toyostyrene series.
  • polyester resin examples include polyol-polycarboxylic acid type polyester resin and hydroxycarboxylic acid type polyester resin.
  • polyol-polycarboxylic acid type polyester resin examples include polyethylene terephthalate resin, polybutylene terephthalate resin, and a copolymer of terephthalic acid and 1,3-propanediol or 1,4-butanediol.
  • hydroxycarboxylic acid type polyester resin examples include polylactic acid and / or a copolymer resin containing polylactic acid.
  • a polylactic acid resin and / or a copolymer resin containing polylactic acid is obtained by subjecting lactic acid or lactic acid and other hydroxycarboxylic acid to heat dehydration polymerization to obtain low molecular weight polylactic acid or a copolymer thereof.
  • Lactide which is a cyclic dimer of lactic acid or a copolymer thereof, is obtained by thermal decomposition under reduced pressure, and then lactide is polymerized in the presence of a catalyst such as a metal salt to produce polylactic acid resin and / or polylactic acid.
  • a copolymer resin containing is obtained. These polyester resins may be used alone or in combination of two or more.
  • Examples of commercially available polyol-polycarboxylic acid type polyester resins include Mitsui Chemicals, Mitsui PET TM series (for example, product number: Mitsui J125), Toyobo Co., Ltd., Byron series, and the like.
  • Examples of commercially available polylactic acid resins and / or copolymer resins containing polylactic acid include crystalline polylactic acid resins manufactured by Zhejiang Haisheng Biological Materials Co., Ltd.
  • Laissia series which is a polylactic acid resin (manufactured by lactic acid fermentation of plant starch) manufactured by Mitsui Chemicals, Inc.
  • polyamide resin examples include a ring-opening polymer of lactam, a polycondensate of diamine and dibasic acid, and a polycondensate of ⁇ -amino acid. These polyamide resins may be used alone or in combination of two or more. Examples of commercially available polyamide resins include nylon 6 and nylon 66 made by Toray Industries, Inc., Leona series made by Asahi Kasei Co., Ltd., and Teijin's n-nylon and n, m. -Nylon series and the like.
  • the polycarbonate resin may be an aromatic polycarbonate resin or an aliphatic polycarbonate resin. From the viewpoint of affinity with the lignocellulosic mixture and from the viewpoint of impact resistance and heat resistance, the polycarbonate resin It is more preferable to use a group polycarbonate resin.
  • the aromatic polycarbonate resin an aromatic polycarbonate resin usually produced by a reaction of a dihydric phenol and a carbonate precursor can be used.
  • the aromatic polycarbonate resin can be a main component of the resin composition because it has better heat resistance, flame retardancy, and impact resistance than other thermoplastic resins.
  • the flame retardancy and impact resistance at low temperatures are further improved. be able to.
  • the polyorganosiloxane constituting the copolymer is more preferably polydimethylsiloxane from the viewpoint of flame retardancy.
  • aromatic polycarbonate resin Idemitsu Kosan Co., Ltd. Toughlon series, Teijin Ltd. Panlite series, etc. are mentioned.
  • thermoplastic resin compatible ones may be appropriately mixed and used. For example, if an appropriate amount of a polyester resin is mixed with an aromatic polycarbonate resin generally considered to have poor fluidity, the fluidity is improved.
  • other thermoplastic resins compatible with them for example, AS resin (acrylonitrile-styrene resin), (meth) acrylic ester ( A suitable amount of (co) polymer may be mixed.
  • the thermoplastic resin is preferably at least one selected from the group consisting of polyolefin resins, polystyrene resins, polyamide resins, polyester resins, and polycarbonate resins, and more preferably polyolefin resins.
  • the resin composition of the present invention contains a lignocellulose-based mixture in an amount of 0.5% by mass to 60% by mass when the total of the lignocellulose-based mixture and the thermoplastic resin is 100% by mass. If the content of the lignocellulose-based mixture is less than 0.5% by mass, the strength and flame retardancy are insufficient, and if it exceeds 60% by mass, the fluidity is greatly reduced and the appearance of the molded product is greatly reduced.
  • the content of the lignocellulose-based mixture is preferably 2% by mass or more and 40% by mass or less, and more preferably 4% by mass or more and 30% by mass or less.
  • the resin composition of the present invention may contain components other than the lignocellulose-based mixture and the thermoplastic resin, for example, various additives, but the lignocellulose-based mixture in the resin composition.
  • the total content of the thermoplastic resin is preferably 70% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, and more preferably 95% by mass or more. Particularly preferred.
  • the resin composition of the present invention may contain various additives as necessary.
  • additives include ultraviolet absorbers, antioxidants, lubricants, crystal nucleating agents, softeners, antistatic agents, metal deactivators, antibacterial / antifungal agents, pigments and the like.
  • the resin composition of the present invention contains at least an antioxidant.
  • the ultraviolet absorber include benzophenone compounds, benzotriazole compounds, benzoate compounds, polyamide polyether block copolymers (providing permanent antistatic performance), and the like.
  • antioxidant A phenolic antioxidant, phosphorus antioxidant, thioether type antioxidant, etc. are mentioned.
  • antioxidants examples include Irganox 1010, Irganox 1076 (manufactured by BASF, phenolic antioxidant), Adekastab 2112 and Adekastab PEP36 (manufactured by ADEKA, phosphorous antioxidant). These may be used alone or in combination of two or more.
  • the lubricant is not particularly limited, and examples thereof include fatty acid amide lubricants, fatty acid ester lubricants, fatty acid lubricants, and fatty acid metal salt lubricants. These may be used alone or in combination of two or more.
  • the crystal nucleating agent is not particularly limited, and examples thereof include sorbitols, phosphorus nucleating agents, rosins, and petroleum resins.
  • the softening agent is not particularly limited, and examples thereof include liquid paraffin, mineral oil softener (process oil), and non-aromatic rubber mineral oil softener (process oil). These may be used individually by 1 type and may be used in combination of 2 or more type.
  • the antistatic agent is not particularly limited, and examples thereof include cationic antistatic agents, anionic antistatic agents, nonionic antistatic agents, amphoteric antistatic agents, and fatty acid partial esters such as glycerin fatty acid monoesters. Although it does not specifically limit as a metal deactivator, A hydrazine type metal deactivator, a nitrogen compound type metal deactivator, a phosphite ester type metal deactivator, etc. are mentioned. These may be used alone or in combination of two or more.
  • the antibacterial / antifungal agent is not particularly limited, and examples thereof include an organic compound antibacterial / antifungal agent, a natural organic antibacterial / antifungal agent, and an inorganic antibacterial / antifungal agent.
  • an inorganic pigment examples include titanium oxide, calcium carbonate, and carbon black.
  • organic pigments examples include azo pigments, acidic dye lakes, basic dye lakes, and condensed polycyclic pigments. These pigments may be used alone or in combination of two or more.
  • the amount of the additive component is not particularly limited as long as the properties of the resin composition of the present invention are not impaired.
  • the production method of the resin composition of the present invention is not particularly limited, but it is preferably obtained by hot melt mixing a lignocellulose-based mixture and a thermoplastic resin.
  • the resin composition of the present invention can be obtained by blending a lignocellulose-based mixture and a thermoplastic resin in the above proportions, and further adding various additives added as necessary, followed by hot melt mixing.
  • the compounding and kneading at this time are premixed with a commonly used equipment such as a ribbon blender or a drum tumbler, and then a Henschel mixer, a Banbury mixer, a single screw extruder, a twin screw extruder, a multi screw extruder.
  • This method can be performed by a method using a machine and a conider.
  • the heating temperature at the time of kneading is suitably selected in the range of usually 160 to 350 ° C. depending on the kind of the thermoplastic resin, but when the polyolefin resin is used as the thermoplastic resin, the temperature is in the range of 160 to 250 ° C.
  • the temperature is in the range of 170 to 280 ° C.
  • it is preferably selected in the range of 230 to 280 ° C.
  • a polyamide resin it is preferably selected in the range of 240 to 290 ° C.
  • a polycarbonate resin in the range of 270 to 350 ° C.
  • a polylactic acid resin it is preferably selected in the range of 190 to 250 ° C.
  • the resin composition of the present invention is made from the pellets obtained by the above-mentioned melt-kneading and pelletizing as raw materials, an injection molding method, an injection compression molding method, an extrusion molding method, a blow molding method, a press molding method, a vacuum molding method, and Various molded articles can be produced by a foam molding method or the like.
  • a pellet-shaped forming raw material is manufactured by the melt kneading method, and then this pellet is used suitably for manufacturing an injection molded body by injection molding or injection compression molding, and for manufacturing an extrusion molded body by extrusion molding. be able to.
  • after forming into an extrusion sheet by extrusion molding it is good also as a molded object by pressurizing and thermoforming.
  • the molded article obtained from the resin composition of this invention it is preferable that 1 mm or more of a lump (granular material) is not recognized visually.
  • the lignocellulose-based mixture is mixed with a thermoplastic resin, preferably when hot-melt mixed, the lignocellulose-based mixture is excellent in dispersibility in the thermoplastic resin, so that the occurrence of blisters (particulate matter) can be suppressed. This is because the lignocellulosic mixture is uniformly present in the matrix of lignophenolphenol derivative without the cellulose component being unevenly distributed.
  • the molded article obtained from the resin composition of this invention is excellent in tensile yield strength and a tensile elasticity modulus compared with the case where a lignocellulose type mixture is not added. Furthermore, it is preferable that the molded article obtained from the resin composition of the present invention has an improved elongation retention after exposure to light compared to the case where no lignocellulose-based mixture is added.
  • the elongation retention after exposure to light is preferably 65% or more, more preferably It is 70% or more, more preferably 80% or more, and still more preferably 85% or more.
  • the elongation retention after exposure to light is measured by the method described in the examples.
  • the molded article obtained from the resin composition of the present invention has an improved elongation retention after exposure to the oven as compared with the case where no lignocellulose-based mixture is added.
  • a polyolefin resin preferably at least one selected from the group consisting of polyethylene and polypropylene, more preferably polypropylene
  • the elongation retention after oven exposure is preferably 70% or more, more preferably 75% or more, more preferably 80% or more, and still more preferably 90 or more.
  • the elongation retention after exposure to the oven is measured by the method described in the examples and exposed to a temperature suitable for the thermoplastic resin.
  • the molded article obtained from the resin composition of this invention is excellent in a flame retardance (LOI) compared with the case where a lignocellulose-type mixture is not added.
  • LOI flame retardance
  • the resin composition of the present invention and the molded product obtained from the resin composition can be suitably used for OA materials, electrical / electronic materials, automotive materials, industrial materials, wire coating materials, films, fibers, and the like. .
  • the sample thus obtained contains the lignophenol derivative and the cellulose component uniformly because the cellulose component is once dissolved and recrystallized, that is, the cellulose component is uniformly distributed in the matrix of the lignophenol derivative.
  • It is a composition composed of acicular or cage crystals (also referred to herein as a lignocellulosic mixture).
  • Examples 1 to 9 and Comparative Examples 1 to 8 Each component was blended in the proportions shown in Tables 1 and 2, supplied to an extruder (model name: PCM-30, manufactured by Ikegai Co., Ltd.), melt-kneaded at 160 to 220 ° C., and pelletized.
  • 0.2 parts by mass of Irganox 1010 manufactured by BASF
  • 0.1 part by mass of ADK STAB 2112 manufactured by ADEKA
  • the obtained pellets were dried at 80 ° C.
  • the resulting lignophenol derivative-cellulose component mixture (lignocellulose-based mixture) is easy to manufacture without the steps of fibrillating cellulose or coating lignophenol, and the resulting mixture is powdery and thermoplastic. Even if it is melt-mixed with the resin, the dispersion is good and the molded appearance is not adversely affected. It was clarified that when the content ratio is within the range of the claims, the composition has high strength and is excellent in heat resistance, weather resistance, and flame retardancy.

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Abstract

L'invention concerne une composition de résine qui présente une fabrication simple, une excellente productivité, et un coût de fabrication faible, qui permet de fabriquer un article moulé de résistance mécanique élevée, résistant au feu, résistant au vieillissement thermique, et d'une excellente résistance aux intempéries. L'invention concerne également un procédé de fabrication de ladite composition de résine, et un corps moulé obtenu à partir de ladite composition de résine. La composition de résine de l'invention est caractéristique en ce qu'elle comprend un mélange à base de lignocellulose et une résine thermoplastique, elle comprend 0,5% en masse ou plus à 60% en masse ou moins du mélange à base de lignocellulose lorsque le total du mélange à base de lignocellulose et de la résine thermoplastique équivaut à 100% en masse, et aucun grumeau de 1mm ou plus ne peut être identifié visuellement dans l'article moulé.
PCT/JP2016/070112 2015-07-09 2016-07-07 Composition de résine ainsi que procédé de fabrication de celle-ci, et corps moulé WO2017006986A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001074949A1 (fr) * 2000-03-31 2001-10-11 Masamitsu Hunaoka Composition lignocellulosique comprenant un derive de lignophenol et un agent cellulosique
JP2005194314A (ja) * 2003-12-26 2005-07-21 Agri Future Joetsu Co Ltd 熱可塑性樹脂組成物、これを用いた複合材及びその製造方法
JP2007169612A (ja) * 2005-11-28 2007-07-05 Japan Polypropylene Corp 木質系材料配合樹脂組成物
JP2011038193A (ja) * 2009-08-07 2011-02-24 Konica Minolta Holdings Inc セルロース繊維及び繊維複合材料
WO2012176778A1 (fr) * 2011-06-22 2012-12-27 出光興産株式会社 Composition de résine thermoplastique et corps moulé
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WO2001074949A1 (fr) * 2000-03-31 2001-10-11 Masamitsu Hunaoka Composition lignocellulosique comprenant un derive de lignophenol et un agent cellulosique
JP2005194314A (ja) * 2003-12-26 2005-07-21 Agri Future Joetsu Co Ltd 熱可塑性樹脂組成物、これを用いた複合材及びその製造方法
JP2007169612A (ja) * 2005-11-28 2007-07-05 Japan Polypropylene Corp 木質系材料配合樹脂組成物
JP2011038193A (ja) * 2009-08-07 2011-02-24 Konica Minolta Holdings Inc セルロース繊維及び繊維複合材料
WO2012176778A1 (fr) * 2011-06-22 2012-12-27 出光興産株式会社 Composition de résine thermoplastique et corps moulé
WO2013069373A1 (fr) * 2011-11-07 2013-05-16 出光興産株式会社 Composition de résine thermoplastique et corps moulé

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MASAMITSU FUNAOKA ET AL.: "Cellulose Nanofiber/ Lignophenol Fukugo Sozai no Yudo to sono Kino", CONVERTECH, vol. 44, no. 3, 2016, pages 93 - 96 *
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