JP2011219571A - Method for producing cellulose-containing thermoplastic resin, the cellulose-containing thermoplastic resin, and molded body of the same - Google Patents

Abstract

A cellulose-containing thermoplastic resin that has high mechanical properties because it contains cellulose, does not warp or bend when formed into a molded product, and has flow properties that can be used for injection molding, extrusion molding, and the like. The present invention provides a method for producing a cellulose-containing thermoplastic resin, a cellulose-containing thermoplastic resin, and a molded article thereof. [MEANS FOR SOLVING PROBLEMS] Batch of fibrous cellulose, thermoplastic resin and acid anhydride defibrated by a dry defibrator In the method for producing a cellulose-containing thermoplastic resin that is melt-kneaded in a high-temperature high-pressure steam environment using a closed type kneading apparatus, the temperature range in the high-temperature high-pressure steam environment is 150 to 370 ° C., and the pressure range is 0.20 MPa or more. A method for producing a cellulose-containing thermoplastic resin characterized by being between the saturated water vapor pressure and the production method thereof Cellulose-containing thermoplastic resin.
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Description

  The present invention relates to a method for producing a cellulose-containing thermoplastic resin containing fibrous cellulose, a cellulose-containing thermoplastic resin produced by the production method, and a molded article thereof.

  The cellulose-containing thermoplastic resin has advantages such as improved mechanical properties, no residue remaining even after incineration, and light weight of the molded body made of the resin. The cellulose-containing thermoplastic resin in which fibrous cellulose and thermoplastic resin are mixed until they are uniform in appearance can be used industrially in the same way as the thermoplastic resin itself, and can be used for packaging, storage trays, pallets, and personal computers. And can be used for mobile phone housings, toys, stationery, etc.

  However, the affinity between the fibrous cellulose having a hydrophilic part and the thermoplastic resin having no hydrophilic part is not necessarily high, and even if the fibrous cellulose and the thermoplastic resin are melt-kneaded, the fluidity is low. In some cases, the fibrous cellulose burns with heat during molding to generate a strange odor, and during injection molding, problems such as weld lines, flow marks, and short shots may occur. Further, since the fiber lump cannot be completely unraveled, the fiber lump is present in the cellulose-containing thermoplastic resin as it is, and there may be a problem that the strength of the molded body is lowered or the appearance is deteriorated. Furthermore, if the affinity between the fibrous cellulose and the thermoplastic resin is low, when the molded body is stressed, peeling occurs at the interface between the fibrous cellulose and the thermoplastic resin, and the effect of improving the mechanical properties is lost. There was also.

  Therefore, in order to improve the fluidity at the time of melting, there has been proposed a resin composition containing a woody material in which an organic peroxide is blended with a propylene resin and vegetable fiber to improve uniformity and fluidity. (For example, refer to Patent Document 1). However, this proposal improves the fluidity of the resin composition and enables molding at low temperatures and eliminates problems during molding. Especially in injection molding, a small shape causes a short shot. In addition to the limitations on the shapes that can be formed, the blending ratio of the organic peroxide is small, so that fluidity nonuniformity may occur depending on the mixing method.

  On the other hand, fibrillated cellulose is used, and the fibrillated cellulose and thermoplastic resin are put into a mixer having rotating blades, stirred, and melt-mixed by the generated frictional heat to produce a cellulose-containing thermoplastic. A method for producing a resin has been proposed, but in this method, it takes a long time to melt and mix, and the problems of low uniformity and fluidity of the cellulose-containing thermoplastic resin have not been solved (for example, patents) Reference 2).

  Furthermore, cellulose and a thermoplastic resin are stirred at high speed with a rotary blade provided in a batch-type closed mixer, and melt-mixed in a high-pressure steam atmosphere with a pressure of 0.20 MPa or more by frictional heat accompanying high-speed stirring to cellulose. A method for producing the containing thermoplastic resin has also been proposed. In this method, compared with the conventional method, melt mixing was completed in a short time, and the uniformity of the resulting cellulose-containing thermoplastic resin was good. However, it has not been possible to completely solve the problem of inconvenience that causes problems during injection molding (see, for example, Patent Document 3).

  As a means for improving the affinity between the fibrous cellulose and the thermoplastic resin, for example, there is a method of adding an acid-modified thermoplastic resin such as maleic anhydride-modified polypropylene, but the problem of insufficient fluidity and mechanical strength is It cannot be solved completely (see, for example, Patent Document 4).

  On the other hand, a cellulose-containing thermoplastic resin having a wood texture by melting and mixing wood powder, wood chips and the like with a thermoplastic resin is also known. Also in this field, there is a problem that the affinity between wood flour and the thermoplastic resin is low. In order to increase this affinity, it has been proposed to use cellulose esterified with a polybasic acid anhydride as a woody filler for thermoplastic resins (see, for example, Patent Document 5). However, cellulose esterified with a polybasic acid anhydride in advance is necessary, and there is a problem that the number of production steps increases. In addition, a cellulose-containing resin composition obtained by heat-kneading wood powder, thermoplastic resin, and polybasic acid anhydride with a blender, kneader, mixing roll, Banbury mixer, uniaxial or biaxial extruder, etc. It has been proposed (see, for example, Patent Document 6). However, the cellulose-containing thermoplastic resin obtained by this method has a wood texture and is inferior in fluidity, uniformity, and mechanical properties. Was not available. In addition, a large amount of unreacted acid anhydride remained, which had an adverse effect on the fluidity, uniformity, mechanical properties, and appearance of the cellulose-containing thermoplastic resin.

JP-A 61-155436 JP 2009-001597 A International Publication No. 2004/076044 Pamphlet JP 2009-227806 A JP-A-10-329109 JP 2002-348416 A

  The object of the present invention is to provide cellulose-containing heat having high uniformity, high mechanical properties, no warping or bending when formed into a molded body, and fluidity that can be used for injection molding, extrusion molding, and the like. It is providing the manufacturing method of the cellulose containing thermoplastic resin which can manufacture a plastic resin simply, the cellulose containing thermoplastic resin manufactured by this manufacturing method, and its molded object.

As a result of intensive studies, the present inventors have found that the above-described problems can be solved by the present invention described below.
[1] In a method for producing a cellulose-containing thermoplastic resin in which a thermoplastic resin and cellulose are melt-mixed as a raw material in a batch-type closed kneading apparatus having a stirring chamber provided with a rotating shaft provided with rotating blades. , Cellulose is fibrous cellulose defibrated by a dry defibrator, the temperature in the stirring chamber at the time of melt mixing is 150 to 370 ° C, the pressure in the stirring chamber is 0.20 MPa or more up to the saturated water vapor pressure And a method for producing a cellulose-containing thermoplastic resin, wherein an acid anhydride is added as a raw material,
[2] The method for producing a cellulose-containing thermoplastic resin according to the above [1], wherein a polyhydric alcohol is further added as a raw material,
[3] The method for producing a cellulose-containing thermoplastic resin according to the above [1] or [2], wherein the cellulose content relative to the cellulose-containing thermoplastic resin is 5 to 70% by mass,
[4] The method for producing a cellulose-containing thermoplastic resin according to any one of the above [1] to [3], wherein the moisture content of the cellulose is 5 to 30% by mass,
[5] The method for producing a cellulose-containing thermoplastic resin according to any one of the above [1] to [4], wherein reheating and mixing are performed as a post-process,
[6] A cellulose-containing thermoplastic resin produced by the method for producing a cellulose-containing thermoplastic resin according to any one of [1] to [5],
[7] A molded article comprising the cellulose-containing thermoplastic resin as described in [6] above.

  According to the method for producing a cellulose-containing thermoplastic resin of the present invention, the uniformity is high, the mechanical properties are high, and when formed into a molded body, warping and bending do not occur, and it is possible to cope with injection molding, extrusion molding, etc. A cellulose-containing thermoplastic resin having excellent fluidity can be easily obtained in one step.

  The dry defibrating machine used in the method for producing a cellulose-containing thermoplastic resin of the present invention is a fluffy state of cellulose aggregates such as pulp sheets and waste paper, while leaving fibers (fibers) with physical force. A device that solves the problem. As the method, a plurality of claws are arranged on the surface of the cylinder, the cylinder is rotated at a high speed, and the fibers are unraveled by scratching the pulp sheet surface and the like. The rotating blades rotate at high speed to strike and unravel the fibrous cellulose aggregate, and the circular discs with grooves formed on the surface are separated by a small distance so that the surfaces with grooves are opposed to each other. Various methods can be used such as disposing the fibrous cellulose aggregates that are rotated in the opposite directions and unwinding between them by frictional force, and the method of fibrillation is not particularly limited.

  Examples of dry-type defibrators include Zuikou defibrator, Ikegami Kikai devitalizer, Ishikawa Prefectural Creative Development Cooperative Waste Paper Crusher, West Japan Technology Development Co., Ltd. Although the defibrator made from a corporation | Co., Ltd. can be mentioned, the dry type defibrator which can be used by this invention is not restricted to these.

  The cellulose used in the present invention is preferably fibrous cellulose obtained by defibrating chemical pulp with a dry defibrator. Chemical pulp has high color homogeneity, so the hue becomes uniform when formed into a molded product, and even when the molded product is colored by mixing a masterbatch or pigment during molding, the appearance of a uniform color It is possible to obtain a molded body having Chemical pulp, for example, natural cellulose such as wood (conifers, hardwoods), cotton linters, kenaf, manila hemp (avaca), sisal hemp, jute, sabygrass, esparto grass, bagasse, rice straw, straw, straw, bamboo, etc. Treated pulp (kraft pulp, sulfite pulp, etc.). It is more preferable to use kraft pulp (N-BKP, L-BKP, etc.) that is chemically bleached and white in color because the whiter background is easier to adjust the color of the molded body.

  The cellulose used in the present invention may be a fiber lump (for example, cotton-like) thereafter, as long as the fibers are unwound one by one by a dry defibrator. The dimension of the fibrillated fibrous cellulose is not particularly limited, but the fiber length is preferably 0.5 to 10 mm, more preferably 1 to 8 mm, and further preferably 1 to 5 mm, from the workability during molding. The fiber diameter is preferably 10 to 100 μm, more preferably 10 to 70 μm, and still more preferably 15 to 50 μm. In the dimension of the fibrillated fibrous cellulose, the aspect ratio (length / diameter) is particularly important in order to maintain the strength of the molded body. The aspect ratio of the fibrillated fibrous cellulose in the present invention is preferably 10 to 1000, more preferably 30 to 500, and still more preferably 50 to 100.

  The cellulose used in the present invention preferably has a water content of 5 to 30% by mass. When the moisture content of cellulose is within this range, the melt mixing time is shortened and the productivity is improved. On the other hand, if the water content is less than 5% by mass, the pressure in the stirring chamber may not increase even if it takes time. In addition, even if the pressure increases and melt kneading is performed, the interaction between cellulose or fibers increases and the dispersibility of cellulose deteriorates. As a result, the fiber mass increases, resulting in a decrease in strength of the molded body or molding. May deteriorate. In addition, when the water content exceeds 30% by mass, it takes time to dehydrate the cellulose, so that the melt-kneading time becomes long and the cellulose is likely to be decomposed. The water content is more preferably 8 to 25% by mass, and further preferably 10 to 20% by mass. In addition, the moisture content in this invention means the numerical value which remove | divided the absolute dry rate calculated | required with the operating method according to JISP8203 from 100 mass% by making drying temperature into 120 degreeC +/- 2 degreeC.

  The thermoplastic resin in the present invention is a resin that can be softened by heating to a glass transition temperature or a melting point, and can be molded into a desired shape. For example, polyethylene composed of high-density polyethylene, medium-density polyethylene, and low-density polyethylene. Polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate, polytetrafluoroethylene, acrylonitrile butadiene styrene resin, acrylonitrile styrene copolymer resin, acrylic resin, polyethylene terephthalate, polymethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate Examples thereof include polyester resins composed of phthalate, polybutylene naphthalate, and the like, but are not particularly limited as long as they are thermoplastic resins. Preferably, polyolefins such as polyethylene and polypropylene are used.

  Furthermore, a biodegradable resin can also be used as the thermoplastic resin. By using a biodegradable resin, it is expected that the molded product is decomposed by burying the molded product in the soil or the like at the time of disposal. The biodegradable resin is not particularly limited as long as it is an environmentally decomposed resin, particularly a resin that is decomposed by the action of microorganisms. For example, specific examples include polymeric polysaccharides, microbial polyesters, aliphatic polyesters, and more specifically, polylactic acid resin, polycaprolactone resin, polybutylene succinate adipate resin, polyethylene succinate resin, polyethylene. Succinate carbonate resin, polybutylene succinate resin, polybutylene adipate terephthalate resin, polyhydroxyalkanoate (eg, poly (3-hydroxybutyric acid) (PHB), poly (3-hydroxyvaleric acid) (PHV)), lactone resin And polyester resins obtained from low molecular weight aliphatic dicarboxylic acids and low molecular weight aliphatic diols, cellulose acetate-based composites, modified starch-modified polyvinyl alcohol composites, and other composites.

  When a biodegradable resin is used as the thermoplastic resin of the present invention, it is preferable to use a polylactic acid resin because of its versatility. The polylactic acid resin includes a lactic acid-based polymer such as a lactic acid copolymer and a blend polymer in addition to a polylactic acid homopolymer. The mass average molecular weight of the lactic acid polymer is generally 5 to 500,000. Further, the constituent molar ratio L / D of the L-lactic acid unit and the D-lactic acid unit in the polylactic acid resin may be any of 100/0 to 0/100, and is not particularly limited.

  The acid anhydride in the present invention is not limited to an acid anhydride composed of an organic acid, but may be an acid anhydride composed of an inorganic acid such as sulfuric acid, nitric acid, phosphoric acid, etc., as long as it is a compound obtained by dehydration condensation of two molecules of oxo acid. An acid anhydride having a structure in which the same type of acid is dehydrated and condensed may be used, or a mixed acid anhydride having a structure in which a different type of acid is dehydrated and condensed may be used.

  Examples of the acid anhydride in the present invention include the following. For example, acid anhydrides composed of inorganic acids include disulfuric acid (pyrosulfuric acid), dinitrogen pentoxide, pyrophosphoric acid (diphosphoric acid), diphosphorus pentoxide (phosphorus tetraoxide), diphosphorus trioxide, pentoxide Examples thereof include arsenic diarsenide and arsenic trioxide. Examples of acid anhydrides composed of organic acids include butyric anhydride, maleic anhydride, succinic anhydride, phthalic anhydride, methyl succinic anhydride, octenyl succinic anhydride, citraconic anhydride, glutaric anhydride, Styrene maleic anhydride, 2,4-diethylglutaric anhydride, itaconic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, methyltetrahydro Phthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, dichloromaleic anhydride, maleic anhydride modified rosin, tetrabromophthalic anhydride, het acid anhydride , Methylbicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride, bicyclo [2.2.1] heptane 2,3-dicarboxylic acid anhydride, methyl-5-norbornene-2,3-dicarboxylic acid anhydride, gallic acid anhydride, trimellitic acid anhydride, pyromellitic acid anhydride, benzophenone tetracarboxylic acid anhydride, methylcyclohexene Tetracarboxylic acid anhydride, polyazeline acid anhydride, etc. are mentioned. The acid anhydride in the present invention is not limited to those described above, and can be used.

  The acid anhydride in the present invention is preferably succinic anhydride, 4-methylhexahydrophthalic anhydride, 2,4-diethylglutaric anhydride, 4-methyl-1,2,3,6-tetrahydro. Phthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride can be used. By using these acid anhydrides, the surface of the fibrous cellulose is more efficiently esterified, and the amount added can be made smaller than that of other acid anhydrides.

  The addition amount of the acid anhydride is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 8 parts by mass, and still more preferably 0.2 to 4 parts by mass, when cellulose is 100 parts by mass.

  It has been known that an acid anhydride causes an esterification reaction with a hydroxyl group at a terminal of cellulose, so that the cellulose becomes hydrophobic, and as a result, the affinity with the thermoplastic resin is improved. When cellulose, acid anhydride, and thermoplastic resin are melt-kneaded at once, the reaction rate of the esterification reaction between cellulose and acid anhydride is reduced, so the affinity between cellulose and thermoplastic resin is sufficient. It will not be a thing. For this reason, conventionally, it has been necessary to perform the esterification step of cellulose in advance and then perform the kneading step of a thermoplastic resin and esterified cellulose in two steps.

  However, in the method for producing a cellulose-containing thermoplastic resin in the present invention, the temperature in the stirring chamber at the time of melt mixing is determined by a batch type closed kneading apparatus having a stirring chamber provided with a rotating shaft provided with rotating blades. 150 to 370 ° C., and melt kneading in a high-temperature and high-pressure steam environment where the pressure in the stirring chamber is 0.20 MPa or more and up to the saturated steam pressure, the high-temperature steam affects the esterification reaction. Therefore, even if cellulose, thermoplastic resin, and acid anhydride are melt-kneaded at the same time, the cellulose surface is selectively and efficiently esterified with acid anhydride, improving the affinity between cellulose and thermoplastic resin. It is possible to improve the fluidity and uniformity during melting of the cellulose-containing thermoplastic resin and improve the moldability and appearance such as injection molding and extrusion molding.

  The batch type closed kneading apparatus used in the present invention refers to a high-speed stirring apparatus provided with a sealed stirring chamber provided with a rotary blade inside. Specifically, the apparatus described in the pamphlet of International Publication No. 2004/076044 can be mentioned. In the agitation chamber, a plurality of agitation rotating blades are arranged on a rotatable rotating shaft connected to a motor as a drive source. The shape of the rotary blade is not particularly limited, and any shape such as a rectangular shape, a knife shape, or a saw shape may be used, but a rectangular rotary blade is preferable. Further, the number of rotating blades arranged on the rotating shaft is not particularly limited, and the mounting angle of the rotating blades on the rotating shaft is not particularly limited. In the method for producing a cellulose-containing thermoplastic resin in the present invention, the temperature in the stirring chamber rapidly rises due to the high-speed stirring of the rotating blades, water is vaporized and fills the stirring chamber, and the stirring chamber is heated to a high pressure. Since it is necessary to maintain the state, a high shearing force may be applied to the material to be kneaded in the stirring chamber by the rotating rotary blade.

  It is preferable that the stirring chamber of the batch type closed kneading apparatus used in the present invention is provided with a steam release mechanism for appropriately releasing the steam generated in the stirring chamber to the outside. As the water vapor release mechanism, a general mechanical seal, a labyrinth seal, or a simple openable / closable window can be used, but the present invention is not limited to these and can be used as appropriate. In particular, when a mechanical seal or labyrinth seal is installed as a water vapor release mechanism, the release mechanism portion melts in a state where the water vapor flowing out of the stirring chamber and the air flowing into the stirring chamber are balanced. It is preferable because it can be kneaded.

  The rotating shaft on which the rotating blades are arranged is connected to a motor which is a driving source. In the batch type closed kneading apparatus used in the present invention, a torque meter for measuring the rotating torque applied to the motor is installed. It is preferable. In the method for producing a cellulose-containing thermoplastic resin of the present invention, the change in the rotational torque of the rotary shaft provided with the rotary blades measured from the torque meter is measured to determine the end point of the melt kneading. Measures for the end operation according to the measured value of rotational torque are essential for materials handled for the first time, but when using the same material constantly, it is not always necessary to measure each time. It may be determined and the end point may be determined based on the determined melt-kneading time.

  In the production method of the present invention, when the cellulose contains moisture having a moisture content of 5 to 30% by mass, the temperature in the stirring chamber sealed by the shearing force and striking force to the material to be kneaded by the high-speed rotation of the rotating blades. Rises rapidly to a high temperature state, and the water vaporizes at a high temperature to become a water vapor state, which makes it easy to realize a high temperature and high pressure steam environment. As the high temperature and high pressure steam environment in the present invention, the high temperature range is preferably 150 to 370 ° C., and the high pressure range is preferably 0.20 MPa or more and up to the saturated water vapor pressure. By performing melt-kneading of the material to be kneaded in this high-temperature, high-pressure steam environment, the acid anhydride causes an esterification reaction on the cellulose surface more selectively, and the reaction efficiency is further improved. Improves.

  In the production method of the present invention, cellulose, a thermoplastic resin, and an acid anhydride may be premixed and then charged into a batch-type closed kneader, or each may be sequentially added to a batch-type closed kneader. May be. When sequentially charging, it is preferable that the rotating blades are charged while rotating at a low speed.

  In the present invention, when a polyhydric alcohol is further added, a competitive reaction occurs between the hydroxyl group of the polyhydric alcohol and the hydroxyl group of the cellulose, and the molecular weight chemically bonded to the cellulose surface increases, thereby increasing the affinity with the thermoplastic resin. The dispersibility of cellulose is improved, and the fluidity at the time of melting is further improved. Furthermore, in this invention, the fluidity | liquidity at the time of the fusion | melting of a cellulose containing thermoplastic resin can be controlled by adjusting the addition amount of a polyhydric alcohol. By adjusting the addition amount of the polyhydric alcohol, a cellulose-containing thermoplastic resin having flow characteristics suitable for various molding methods from extrusion molding to injection molding can be obtained.

  Examples of the polyhydric alcohol in the present invention include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butanediol, neopentyl glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2, 3-butylene glycol, 1,4-butylene glycol, pentadiol, 2,3-dimethylpropanediol, 1,6-hexanediol, 2,5-hexanediol, hydrogenated bisphenol A, cyclohexanedimethanol, trimethylene glycol, Examples include tetramethylene glycol, hexamethylene glycol, trimethylol ethane, trimethylol propane, glycerin, diglycerin, dipentaerythritol, and sorbitol. Kill.

  The addition amount of the polyhydric alcohol is not particularly limited, but is preferably 0.01 to 10 parts by mass when cellulose is 100 parts by mass. However, if it is introduced excessively, it may be replaced with water, and the water absorption characteristics may be deteriorated. Further, there is a problem that the surface oozes out after molding, so it is necessary to match the purpose of use. Furthermore, amines may be added to promote the reactivity with acid anhydrides.

  In the cellulose containing thermoplastic resin of this invention, it is preferable that the content rate of the cellulose with respect to a cellulose containing thermoplastic resin is 5-70 mass%. When the content is lower than 5% by mass, the effect of improving the mechanical properties of the molded article due to the inclusion of cellulose may not be remarkably exhibited. On the other hand, if it exceeds 70% by mass, the molding conditions may be limited depending on the molding method.

  In the present invention, various additives other than cellulose, thermoplastic resin, acid anhydride, and polyhydric alcohol can be appropriately added. Additives include compatibilizers, antioxidants, heat stabilizers, lubricants, mold release agents, plasticizers, UV absorbers, light stabilizers, pigments, dyes, antistatic agents, conductivity-imparting agents, dispersants, Additives such as transparent nucleating agents, antibacterial agents, antifungal agents, and flame retardants can be used alone or in combination of two or more, but are not limited thereto.

  In particular, the addition of an acid-modified polyolefin resin is preferable because the toughness of the molded body is increased. The acid-modified polyolefin resin refers to one obtained by modifying a polyethylene resin or a polypropylene resin with one or a mixture of two or more of unsaturated carboxylic acid and its derivative (monomer). Examples of unsaturated carboxylic acids and derivatives thereof include unsaturated carboxylic acids such as acrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, or derivatives thereof, such as, specifically, anhydrides, amides, imides, esters Etc. Among these, maleic anhydride-modified polyolefin is particularly preferable. The amount of maleic anhydride-modified polyolefin added to the cellulose-containing thermoplastic resin is preferably 0.1 to 10% by mass, more preferably 0.5 to 7% by mass, based on the content of the cellulose-containing thermoplastic resin. More preferred is mass%.

  Using the cellulose-containing thermoplastic resin of the present invention, a molded product can be produced by various molding methods. As a molding method, a general molding method can be used and is not particularly limited. Specific examples include injection molding methods, extrusion molding methods, compression molding methods, rotational molding methods, hollow molding methods (blow molding methods), T-die molding methods, inflation molding methods, and calendar molding methods. Yes, but you are not limited to these methods. Further, the shape of the molded body is not particularly limited, and an arbitrary shape can be produced by an arbitrary molding method.

  In order to realize the excellent moldability of the cellulose-containing thermoplastic resin of the present invention, it is preferable to obtain a molded body having a precise shape using an injection molding method. The cellulose-containing thermoplastic resin of the present invention not only has good flowability of the resin during molding, but also maintains uniform performance, and causes molding defects such as flow marks, weld lines, warpage, and twisting. There is nothing to do.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited to these at all.

(Example 1)
As a cellulose aggregate, prepared was a hardwood bleached kraft pulp (L-BKP) pulp sheet (dried in a drier whose temperature was set to 80 ° C. for 24 hours to dry the water), and a pulverizer ((stock) ) Coarsely pulverized with a product of Horai, trade name: BO-2572, 30 mm screen mounted). Next, the coarsely pulverized product was put into a defibrating machine (trade name: Turbo Mill T-250, manufactured by Turbo Kogyo Co., Ltd.), the pulp sheet was defibrated, and defibrated fibrous cellulose was obtained. The water content of the cellulose was 5% by mass.

  Cellulose (hereinafter referred to as a value converted to absolutely dry mass) 8 parts by mass, thermoplastic resin (manufactured by Prime Polymer Co., Ltd., trade name: Prime Polypro (registered trademark) F109V, MFR = 30 g / 10 min.) 92 parts by mass In addition, 1.5 parts by mass of acid anhydride (1,2,3,6-tetrahydrophthalic anhydride, manufactured by Shin Nippon Rika Co., Ltd., trade name: Rikacid (registered trademark) TH for 100 parts by mass of cellulose ) And 0.5 parts by mass of polyhydric alcohol (1,4-butanediol) with respect to 100 parts by mass of cellulose, and preliminarily mixed, and then described in International Publication No. 2004/076044 as a batch type closed kneading apparatus. In a kneading chamber of a high-speed stirring apparatus (manufactured by M & F Technology Co., Ltd.). Thereafter, the rotating blades were rotated at a rotational speed of 2000 rpm. Simultaneously with the start of rotation, water vapor leaked from the water vapor release mechanism, but after 1 minute, the leakage stopped, and melt mixing proceeded in a state where the water vapor was released in a balanced state. One minute after the leakage of water vapor stopped, the motor was turned off, the rotation of the rotating blade was stopped, and the cellulose-containing thermoplastic resin of the present invention was taken out. It should be noted that the temperature inside the kneading chamber was 150 ° C. and the pressure was 0.2 MPa after the water vapor leakage stopped until the motor was turned off.

(Example 2)
Cellulose / thermoplastic resin (manufactured by Prime Polymer Co., Ltd., trade name: Prime Polypro (registered trademark) F109V, MFR = 30 g / 10 min.) / Acid anhydride (1,2,3,6-tetrahydrophthal) Acid anhydride, manufactured by Shin Nippon Rika Co., Ltd., trade name: Ricacid (registered trademark) TH) / polyhydric alcohol (1,4-butanediol) = 10 / 89.7 / 0.2 / 0.1 A cellulose-containing thermoplastic resin of the present invention was obtained in the same manner as in Example 1 except that it was prepared as described above. It should be noted that the temperature inside the kneading chamber was 150 ° C. and the pressure was 0.2 MPa after the water vapor leakage stopped until the motor was turned off.

(Example 3)
Cellulose / thermoplastic resin (manufactured by Prime Polymer Co., Ltd., trade name: Prime Polypro (registered trademark) F109V, MFR = 30 g / 10 min.) / Acid anhydride (1,2,3,6-tetrahydrophthal) Acid anhydride, manufactured by Shin Nippon Rika Co., Ltd., trade name: Ricacid (registered trademark) TH) / polyhydric alcohol (1,4-butanediol) = 70/29 / 0.7 / 0.3 A cellulose-containing thermoplastic resin of the present invention was obtained in the same manner as in Example 1 except that it was prepared. It should be noted that the temperature inside the kneading chamber was 150 ° C. and the pressure was 0.2 MPa after the water vapor leakage stopped until the motor was turned off.

Example 4
Cellulose / thermoplastic resin (manufactured by Prime Polymer Co., Ltd., trade name: Prime Polypro (registered trademark) F109V, MFR = 30 g / 10 min.) / Acid anhydride (1,2,3,6-tetrahydrophthal) Acid anhydride, manufactured by Shin Nippon Rika Co., Ltd., trade name: Ricacid (registered trademark) TH) / polyhydric alcohol (1,4-butanediol) = 75/24 / 0.7 / 0.3 A cellulose-containing thermoplastic resin of the present invention was obtained in the same manner as in Example 1 except that it was prepared. It should be noted that the temperature inside the kneading chamber was 150 ° C. and the pressure was 0.2 MPa after the water vapor leakage stopped until the motor was turned off.

(Example 5)
Example 1 except that the water vapor release mechanism was adjusted so that the temperature in the kneading chamber after the water vapor leakage stopped until the motor was switched off showed 150 ° C. and the pressure showed 0.49 MPa. In the same manner as above, the cellulose-containing thermoplastic resin of the present invention was obtained. The pressure of 0.49 MPa corresponds to the saturated water vapor pressure at 150 ° C.

(Example 6)
Example 2 except that the water vapor release mechanism was adjusted so that the temperature in the kneading chamber after the water vapor leakage stopped until the motor was turned off showed 150 ° C. and the pressure showed 0.49 MPa. In the same manner as above, the cellulose-containing thermoplastic resin of the present invention was obtained. The pressure of 0.49 MPa corresponds to the saturated water vapor pressure at 150 ° C.

(Example 7)
Example 3 except that the steam release mechanism was adjusted so that the temperature in the kneading chamber after the steam leakage stopped until the motor was switched off showed 150 ° C. and the pressure showed 0.49 MPa. In the same manner as above, the cellulose-containing thermoplastic resin of the present invention was obtained. The pressure of 0.49 MPa corresponds to the saturated water vapor pressure at 150 ° C.

(Example 8)
Example 4 except that the water vapor release mechanism was adjusted so that the temperature in the kneading chamber after the water vapor leakage stopped until the motor was turned off showed 150 ° C. and the pressure showed 0.49 MPa. In the same manner as above, the cellulose-containing thermoplastic resin of the present invention was obtained. The pressure of 0.49 MPa corresponds to the saturated water vapor pressure at 150 ° C.

Example 9
Other than changing the rotation speed of the rotary blade to 3200 rpm so that the temperature in the kneading chamber rises to 370 ° C. and adjusting the water vapor release mechanism to maintain the pressure in the kneading chamber at 0.2 MPa Was the same as in Example 1 to obtain a cellulose-containing thermoplastic resin of the present invention.

(Example 10)
Other than changing the rotation speed of the rotary blade to 3200 rpm so that the temperature in the kneading chamber rises to 370 ° C. and adjusting the water vapor release mechanism to maintain the pressure in the kneading chamber at 0.2 MPa Obtained a cellulose-containing thermoplastic resin of the present invention in the same manner as in Example 2.

(Example 11)
Other than changing the rotation speed of the rotary blade to 3200 rpm so that the temperature in the kneading chamber rises to 370 ° C. and adjusting the water vapor release mechanism to maintain the pressure in the kneading chamber at 0.2 MPa Obtained a cellulose-containing thermoplastic resin of the present invention in the same manner as in Example 3.

(Example 12)
Other than changing the rotation speed of the rotary blade to 3200 rpm so that the temperature in the kneading chamber rises to 370 ° C. and adjusting the water vapor release mechanism to maintain the pressure in the kneading chamber at 0.2 MPa Obtained a cellulose-containing thermoplastic resin of the present invention in the same manner as in Example 4.

(Example 13)
The same as in Example 9 except that the temperature in the kneading chamber between the stop of the leakage of water vapor and the time the motor is switched off is 320 ° C., and the water vapor release mechanism is adjusted so that the pressure is 22 MPa. Thus, the cellulose-containing thermoplastic resin of the present invention was obtained. The pressure of 22 MPa corresponds to the saturated water vapor pressure at 320 ° C.

(Example 14)
The same as in Example 10 except that the temperature in the kneading chamber after the water vapor leakage stopped until the motor was switched off was 320 ° C., and the water vapor release mechanism was adjusted so that the pressure was 22 MPa. Thus, the cellulose-containing thermoplastic resin of the present invention was obtained. The pressure of 22 MPa corresponds to the saturated water vapor pressure at 320 ° C.

(Example 15)
The same as in Example 11 except that the temperature in the kneading chamber after the stoppage of the water vapor leak until the motor was switched off was 320 ° C., and the water vapor release mechanism was adjusted so that the pressure was 22 MPa. Thus, the cellulose-containing thermoplastic resin of the present invention was obtained. The pressure of 22 MPa corresponds to the saturated water vapor pressure at 320 ° C.

(Example 16)
The same as in Example 12 except that the temperature in the kneading chamber after the stoppage of the water vapor leak until the motor is switched off is 320 ° C., and the water vapor release mechanism is adjusted so that the pressure is 22 MPa. Thus, the cellulose-containing thermoplastic resin of the present invention was obtained. The pressure of 22 MPa corresponds to the saturated water vapor pressure at 320 ° C.

(Example 17)
As a cellulose aggregate, a hardwood bleached kraft pulp (L-BKP) pulp sheet was prepared, and coarsely pulverized with a pulverizer (trade name: BO-2572, 30 mm screen, manufactured by Horai Co., Ltd.). Next, the coarsely pulverized product was put into a defibrating machine (trade name: Turbo Mill T-250, manufactured by Turbo Kogyo Co., Ltd.), the pulp sheet was defibrated, and defibrated fibrous cellulose was obtained. The water content of the cellulose was 15% by mass.

  Cellulose / thermoplastic resin (manufactured by Prime Polymer Co., Ltd., trade name: Prime Polypro (registered trademark) F109V, MFR = 30 g / 10 min.) / Acid anhydride (1,2,3,6-tetrahydrophthal) Acid anhydride, manufactured by Shin Nippon Rika Co., Ltd., trade name: Ricacid (registered trademark) TH) / polyhydric alcohol (1,4-butanediol) = 8 / 91.7 / 0.2 / 0.1 After being prepared as described above and premixed, it was put into a kneading chamber of a high-speed stirring device (manufactured by M & F Technology Co., Ltd.) described in International Publication No. 2004/076044 as a batch type closed kneading device. Thereafter, the rotating blades were rotated at a rotational speed of 2700 rpm. Simultaneously with the start of rotation, water vapor leaked from the water vapor release mechanism, but after 1 minute, the leakage stopped, and the melt mixing proceeded in a state where equilibrium was maintained in the water vapor release mechanism. One minute after the leakage of water vapor stopped, the motor was turned off, the rotation of the rotating blade was stopped, and the cellulose-containing thermoplastic resin of the present invention was taken out. It should be noted that the temperature in the kneading chamber was 250 ° C. and the pressure was 2.0 MPa after the water vapor leakage stopped until the motor was turned off.

(Example 18)
Cellulose / thermoplastic resin (manufactured by Prime Polymer Co., Ltd., trade name: Prime Polypro (registered trademark) F109V, MFR = 30 g / 10 min.) / Acid anhydride (1,2,3,6-tetrahydrophthal) Acid anhydride, manufactured by Shin Nippon Rika Co., Ltd., trade name: Ricacid (registered trademark) TH) / polyhydric alcohol (1,4-butanediol) = 10/89 / 0.7 / 0.3 A cellulose-containing thermoplastic resin of the present invention was obtained in the same manner as in Example 17 except that it was prepared. It should be noted that the temperature in the kneading chamber was 250 ° C. and the pressure was 2.0 MPa after the water vapor leakage stopped until the motor was turned off.

(Example 19)
Cellulose / thermoplastic resin (manufactured by Prime Polymer Co., Ltd., trade name: Prime Polypro (registered trademark) F109V, MFR = 30 g / 10 min.) / Acid anhydride (1,2,3,6-tetrahydrophthal) Acid anhydride, manufactured by Shin Nippon Rika Co., Ltd., trade name: Ricacid (registered trademark) TH) / polyhydric alcohol (1,4-butanediol) = 60/39 / 0.7 / 0.3 A cellulose-containing thermoplastic resin of the present invention was obtained in the same manner as in Example 17 except that it was prepared. It should be noted that the temperature in the kneading chamber was 250 ° C. and the pressure was 2.0 MPa after the water vapor leakage stopped until the motor was turned off.

(Example 20)
The thermoplastic resin was MFR = 5 g / 10 min. In the same manner as in Example 19, except that the thermoplastic resin (made by Prime Polymer Co., Ltd., trade name: Prime Polypro (registered trademark) J113G, MFR = 3.0 g / min.) Was used. A thermoplastic resin was obtained.

(Example 21)
The cellulose-containing thermoplastic resin of the present invention produced in Example 20 was charged into a vented twin-screw extruder (with hot cut device) (trade name: PCM-30, manufactured by Ikekai Co., Ltd.), and the screw rotation speed was 150 rpm. The cellulose-containing thermoplastic resin of the present invention obtained by melt-mixing at a resin temperature of 200 ° C. to form a pellet was obtained.

(Example 22)
Cellulose / thermoplastic resin (manufactured by Prime Polymer Co., Ltd., trade name: Prime Polypro (registered trademark) F109V, MFR = 30 g / 10 min.) / Acid anhydride (1,2,3,6-tetrahydrophthal) Acid anhydride, manufactured by Shin Nippon Rika Co., Ltd., trade name: Ricacid (registered trademark) TH) / polyhydric alcohol (1,4-butanediol) = 60/39 / 0.06 / 0.94 A cellulose-containing thermoplastic resin of the present invention was obtained in the same manner as in Example 17 except that it was prepared. It should be noted that the temperature in the kneading chamber was 250 ° C. and the pressure was 2.0 MPa after the water vapor leakage stopped until the motor was turned off.

(Example 23)
Cellulose / thermoplastic resin (manufactured by Prime Polymer Co., Ltd., trade name: Prime Polypro (registered trademark) F109V, MFR = 30 g / 10 min.) / Acid anhydride (1,2,3,6-tetrahydrophthal) Acid anhydride, manufactured by Shin Nippon Rika Co., Ltd., trade name: Ricacid (registered trademark) TH) / polyhydric alcohol (1,4-butanediol) = 8/91 / 0.8 / 0.2 A cellulose-containing thermoplastic resin of the present invention was obtained in the same manner as in Example 17 except that it was prepared. It should be noted that the temperature in the kneading chamber was 250 ° C. and the pressure was 2.0 MPa after the water vapor leakage stopped until the motor was turned off.

(Example 24)
The cellulose-containing thermoplastic resin of the present invention is obtained in the same manner as in Example 19 except that the acid anhydride is changed to succinic anhydride (trade name: Ricacid (registered trademark) SA, manufactured by Shin Nippon Rika Co., Ltd.). It was.

(Example 25)
A cellulose-containing thermoplastic resin of the present invention was obtained in the same manner as in Example 19 except that the acid anhydride was changed to maleic anhydride (manufactured by Nippon Shokubai Co., Ltd.).

(Example 26)
A cellulose-containing thermoplastic resin of the present invention was obtained in the same manner as in Example 19, except that the acid anhydride was changed to maleic acid anhydride (manufactured by Nippon Shokubai Co., Ltd.) and the polyhydric alcohol was changed to glycerin.

(Example 27)
The cellulose-containing thermoplastic resin of the present invention was obtained in the same manner as in Example 19 except that the acid anhydride was changed to 2,4-diethylglutaric anhydride (Japan Epoxy Resin Co., Ltd., trade name: YH1120). .

(Example 28)
The cellulose-containing composition of the present invention was used in the same manner as in Example 19 except that the acid anhydride was changed to 4-methylhexahydrophthalic anhydride (trade name: Ricacid (registered trademark) MH, manufactured by Shin Nippon Rika Co., Ltd.). A thermoplastic resin was obtained.

(Example 29)
A cellulose-containing thermoplastic resin of the present invention was obtained in the same manner as in Example 19 except that the acid anhydride was changed to butyric anhydride.

(Example 30)
Acid anhydride, maleic anhydride-modified rosin (maleic anhydride-modified rosin is polymerized rosin (manufactured by Harima Chemicals Co., Ltd., 60% dimer), 12.5 parts maleic anhydride is stirred and refluxed. Prepared in a flask equipped with a condenser and a thermometer, heated and heated while blowing nitrogen gas, and reacted at 180 ° C. for 1 hour to synthesize.) In the same manner as in Example 19, the cellulose-containing composition of the present invention was used. A thermoplastic resin was obtained.

(Example 31)
A cellulose-containing thermoplastic resin of the present invention was obtained in the same manner as in Example 19 except that the acid anhydride was changed to styrene maleic anhydride (manufactured by Nova Chemical Co., Ltd., trade name: Dilark D332).

(Example 32)
The cellulose-containing thermoplastic resin of the present invention is obtained in the same manner as in Example 19 except that the acid anhydride is changed to octel succinic anhydride (manufactured by Shin Nippon Rika Co., Ltd., trade name: Ricacid (registered trademark) OSA). It was.

(Example 33)
A cellulose-containing thermoplastic resin of the present invention was obtained in the same manner as in Example 19 except that cellulose, a thermoplastic resin, and an acid anhydride were prepared so as to have a mass ratio of 60/39/1.

(Example 34)
Cellulose / thermoplastic resin (manufactured by Prime Polymer Co., Ltd., trade name: Prime Polypro (registered trademark) F109V, MFR = 30 g / 10 min.) / Acid anhydride (1,2,3,6-tetrahydrophthal) Acid anhydride, manufactured by Shin Nippon Rika Co., Ltd., trade name: Ricacid (registered trademark) TH) / polyhydric alcohol (1,4-butanediol) = 70/29 / 0.7 / 0.3 A cellulose-containing thermoplastic resin of the present invention was obtained in the same manner as Example 19 except that it was prepared. It should be noted that the temperature in the kneading chamber was 250 ° C. and the pressure was 2.0 MPa after the water vapor leakage stopped until the motor was turned off.

(Example 35)
Cellulose / thermoplastic resin (manufactured by Prime Polymer Co., Ltd., trade name: Prime Polypro (registered trademark) F109V, MFR = 30 g / 10 min.) / Acid anhydride (1,2,3,6-tetrahydrophthal) Acid anhydride, manufactured by Shin Nippon Rika Co., Ltd., trade name: Ricacid (registered trademark) TH) / polyhydric alcohol (1,4-butanediol) = 75/24 / 0.7 / 0.3 A cellulose-containing thermoplastic resin of the present invention was obtained in the same manner as Example 19 except that it was prepared. It should be noted that the temperature in the kneading chamber was 250 ° C. and the pressure was 2.0 MPa after the water vapor leakage stopped until the motor was turned off.

(Example 36)
A wet pulp sheet of hardwood bleached kraft pulp (L-BKP) was prepared as a cellulose aggregate and coarsely pulverized with a pulverizer (trade name: BO-2572, 30 mm screen mounted by Horai Co., Ltd.). Next, the coarsely pulverized product was put into a defibrating machine (trade name: Turbo Mill T-250, manufactured by Turbo Kogyo Co., Ltd.), the pulp sheet was defibrated, and defibrated fibrous cellulose was obtained. The water content of the cellulose was 30% by mass.

  Cellulose / thermoplastic resin (manufactured by Prime Polymer Co., Ltd., trade name: Prime Polypro (registered trademark) F109V, MFR = 30 g / 10 min.) / Acid anhydride (1,2,3,6-tetrahydrophthal) Acid anhydride, manufactured by Shin Nippon Rika Co., Ltd., trade name: Ricacid (registered trademark) TH) / polyhydric alcohol (1,4-butanediol) = 8 / 91.7 / 0.2 / 0.1 After being prepared as described above and premixed, it was put into a kneading chamber of a high-speed stirring device (manufactured by M & F Technology Co., Ltd.) described in International Publication No. 2004/076044 as a batch type closed kneading device. Thereafter, the rotating blades were rotated at a rotational speed of 2100 rpm. Simultaneously with the start of rotation, water vapor leaked from the water vapor release mechanism, but after 1 minute, the leakage stopped, and the melt mixing proceeded in a state where equilibrium was maintained at the water vapor release mechanism. One minute after the leakage of water vapor stopped, the motor was turned off, the rotation of the rotating blade was stopped, and the cellulose-containing thermoplastic resin of the present invention was taken out. It should be noted that the temperature inside the kneading chamber was 150 ° C. and the pressure was 0.2 MPa after the water vapor leakage stopped until the motor was turned off.

(Example 37)
Cellulose / thermoplastic resin (manufactured by Prime Polymer Co., Ltd., trade name: Prime Polypro (registered trademark) F109V, MFR = 30 g / 10 min.) / Acid anhydride (1,2,3,6-tetrahydrophthal) Acid anhydride, manufactured by Shin Nippon Rika Co., Ltd., trade name: Ricacid (registered trademark) TH) / polyhydric alcohol (1,4-butanediol) = 10/89 / 0.7 / 0.3 A cellulose-containing thermoplastic resin of the present invention was obtained in the same manner as Example 36 except that it was prepared. It should be noted that the temperature inside the kneading chamber was 150 ° C. and the pressure was 0.2 MPa after the water vapor leakage stopped until the motor was turned off.

(Example 38)
Cellulose / thermoplastic resin (manufactured by Prime Polymer Co., Ltd., trade name: Prime Polypro (registered trademark) F109V, MFR = 30 g / 10 min.) / Acid anhydride (1,2,3,6-tetrahydrophthal) Acid anhydride, manufactured by Shin Nippon Rika Co., Ltd., trade name: Ricacid (registered trademark) TH) / polyhydric alcohol (1,4-butanediol) = 70/29 / 0.7 / 0.3 A cellulose-containing thermoplastic resin of the present invention was obtained in the same manner as Example 36 except that it was prepared. It should be noted that the temperature inside the kneading chamber was 150 ° C. and the pressure was 0.2 MPa after the water vapor leakage stopped until the motor was turned off.

(Example 39)
Cellulose / thermoplastic resin (manufactured by Prime Polymer Co., Ltd., trade name: Prime Polypro (registered trademark) F109V, MFR = 30 g / 10 min.) / Acid anhydride (1,2,3,6-tetrahydrophthal) Acid anhydride, manufactured by Shin Nippon Rika Co., Ltd., trade name: Ricacid (registered trademark) TH) / polyhydric alcohol (1,4-butanediol) = 75/24 / 0.7 / 0.3 A cellulose-containing thermoplastic resin of the present invention was obtained in the same manner as Example 36 except that it was prepared. It should be noted that the temperature inside the kneading chamber was 150 ° C. and the pressure was 0.2 MPa after the water vapor leakage stopped until the motor was turned off.

(Example 40)
Example 36, except that the water vapor release mechanism was adjusted so that the temperature in the kneading chamber after the water vapor leakage stopped until the motor was switched off showed 150 ° C. and the pressure showed 0.49 MPa. In the same manner as above, the cellulose-containing thermoplastic resin of the present invention was obtained. The pressure of 0.49 MPa corresponds to the saturated water vapor pressure at 150 ° C.

(Example 41)
Example 37, except that the water vapor release mechanism was adjusted so that the temperature inside the kneading chamber after the water vapor leakage stopped until the motor was turned off showed 150 ° C. and the pressure showed 0.49 MPa. In the same manner as above, the cellulose-containing thermoplastic resin of the present invention was obtained. The pressure of 0.49 MPa corresponds to the saturated water vapor pressure at 150 ° C.

(Example 42)
Example 38, except that the water vapor release mechanism was adjusted so that the temperature in the kneading chamber after the water vapor leakage stopped until the motor was turned off showed 150 ° C. and the pressure showed 0.49 MPa. In the same manner as above, the cellulose-containing thermoplastic resin of the present invention was obtained. The pressure of 0.49 MPa corresponds to the saturated water vapor pressure at 150 ° C.

(Example 43)
Example 39, except that the water vapor release mechanism was adjusted so that the temperature in the kneading chamber after the water vapor leakage stopped until the motor was turned off showed 150 ° C. and the pressure showed 0.49 MPa. In the same manner as above, the cellulose-containing thermoplastic resin of the present invention was obtained. The pressure of 0.49 MPa corresponds to the saturated water vapor pressure at 150 ° C.

(Example 44)
Other than changing the number of revolutions of the rotating blades to 3300 rpm so that the temperature in the kneading chamber rises to 370 ° C., and adjusting the water vapor release mechanism to keep the pressure in the kneading chamber at 0.2 MPa In the same manner as in Example 36, the cellulose-containing thermoplastic resin of the present invention was obtained.

(Example 45)
Other than changing the number of revolutions of the rotating blades to 3300 rpm so that the temperature in the kneading chamber rises to 370 ° C., and adjusting the water vapor release mechanism to keep the pressure in the kneading chamber at 0.2 MPa Obtained a cellulose-containing thermoplastic resin of the present invention in the same manner as in Example 37.

(Example 46)
Other than changing the number of revolutions of the rotating blades to 3300 rpm so that the temperature in the kneading chamber rises to 370 ° C., and adjusting the water vapor release mechanism to keep the pressure in the kneading chamber at 0.2 MPa In the same manner as in Example 38, the cellulose-containing thermoplastic resin of the present invention was obtained.

(Example 47)
Other than changing the number of revolutions of the rotating blades to 3300 rpm so that the temperature in the kneading chamber rises to 370 ° C., and adjusting the water vapor release mechanism to keep the pressure in the kneading chamber at 0.2 MPa Produced a cellulose-containing thermoplastic resin of the present invention in the same manner as in Example 39.

(Example 48)
The same as in Example 44, except that the temperature in the kneading chamber after the stoppage of the water vapor leak until the motor was switched off was 320 ° C., and the water vapor release mechanism was adjusted so that the pressure was 22 MPa. Thus, the cellulose-containing thermoplastic resin of the present invention was obtained. The pressure of 22 MPa corresponds to the saturated water vapor pressure at 320 ° C.

(Example 49)
The same as in Example 45, except that the temperature inside the kneading chamber after the stoppage of the water vapor leak until the motor was switched off was 320 ° C., and the water vapor release mechanism was adjusted so that the pressure was 22 MPa. Thus, the cellulose-containing thermoplastic resin of the present invention was obtained. The pressure of 22 MPa corresponds to the saturated water vapor pressure at 320 ° C.

(Example 50)
The same as in Example 46, except that the temperature inside the kneading chamber after the water vapor leakage stopped and the motor was switched off showed 320 ° C. and the water vapor release mechanism was adjusted so that the pressure was 22 MPa. Thus, the cellulose-containing thermoplastic resin of the present invention was obtained. The pressure of 22 MPa corresponds to the saturated water vapor pressure at 320 ° C.

(Example 51)
The same as in Example 47, except that the temperature in the kneading chamber between the stop of the leakage of water vapor and the time the motor is turned off is 320 ° C., and the water vapor release mechanism is adjusted so that the pressure is 22 MPa. Thus, the cellulose-containing thermoplastic resin of the present invention was obtained. The pressure of 22 MPa corresponds to the saturated water vapor pressure at 320 ° C.

(Example 52)
Prepared pulp sheet of hardwood bleached kraft pulp (L-BKP) as a cellulose aggregate (dried with moisture kept in a dryer set at 90 ° C. for 24 hours) and defibrated fiber A cellulose-containing thermoplastic resin of the present invention was obtained in the same manner as in Example 19 except that the water content of the cellulose was 4% by mass.

(Example 53)
A wet pulp sheet of hardwood bleached kraft pulp (L-BKP) was prepared as the cellulose aggregate, and the moisture content of the fibrillated fibrous cellulose was 33% by mass, as in Example 19. The cellulose-containing thermoplastic resin of the present invention was obtained.

(Comparative Example 1)
By mass ratio, cellulose / thermoplastic resin (manufactured by Prime Polymer Co., Ltd., trade name: Prime Polypro (registered trademark) F109V, MFR = 30 g / 10 min.) / Polyhydric alcohol (1,4-butanediol) = 60 / A cellulose-containing thermoplastic resin was obtained in the same manner as in Example 19 except that it was adjusted to 39/1.

(Comparative Example 2)
Other than changing the rotational speed of the rotary blade to 2300 rpm so that the temperature in the kneading chamber rises to 135 ° C. and adjusting the water vapor release mechanism to maintain the pressure in the kneading chamber at 0.18 MPa In the same manner as in Example 19 to obtain a cellulose-containing thermoplastic resin.

(Comparative Example 3)
Other than changing the rotation speed of the rotary blade to 2700 rpm so that the temperature in the kneading chamber rises to 150 ° C. and adjusting the water vapor release mechanism to maintain the pressure in the kneading chamber at 0.18 MPa. In the same manner as in Example 19 to obtain a cellulose-containing thermoplastic resin.

(Comparative Example 4)
Other than changing the rotation speed of the rotary blade to 3300 rpm so that the temperature in the kneading chamber rises to 370 ° C. and adjusting the water vapor release mechanism to maintain the pressure in the kneading chamber at 0.18 MPa In the same manner as in Example 19 to obtain a cellulose-containing thermoplastic resin.

(Comparative Example 5)
Except for adjusting the rotation speed of the rotary blade to 3700 rpm so that the temperature in the kneading chamber rises to 400 ° C. and adjusting the water vapor release mechanism to maintain the pressure in the kneading chamber at 35 MPa. In the same manner as in Example 19, a cellulose-containing thermoplastic resin was obtained. The saturated water vapor pressure at 400 ° C. is 31 MPa.

(Comparative Example 6)
Other than changing the rotation speed of the rotary blade to 2300 rpm so that the temperature in the kneading chamber rises to 135 ° C. and adjusting the water vapor release mechanism to maintain the pressure in the kneading chamber at 0.20 MPa. In the same manner as in Example 19 to obtain a cellulose-containing thermoplastic resin.

(Comparative Example 7)
Implemented except that the rotational speed of the rotary blade was changed to 3700 rpm so that the temperature in the kneading chamber rose to 400 ° C., and the water vapor release mechanism was adjusted to maintain the pressure in the kneading chamber at 31 MPa. In the same manner as in Example 19, a cellulose-containing thermoplastic resin was obtained. 31 MPa corresponds to the saturated water vapor pressure at 400 ° C.

<MFR>
Melt mass flow rate (MFR) was measured according to JIS K7210. Test conditions were polypropylene test conditions (test temperature: 230 ° C., nominal load: 2.16 kg). However, since the flowability was low, MFR measurement was impossible under the above test conditions, and the MFR was measured at a test temperature of 230 ° C. and a nominal load of 10 kg. If the MFR can be measured at a nominal load of 10 kg, the molding process can be performed without any practical problem.

<Warpage>
A plate (150 mm × 80 mm × 1 mm) was injection molded by an injection molding machine (manufactured by Nippon Steel Works, Ltd., trade name: J55ELIII) using the cellulose-containing thermoplastic resin produced in the examples and comparative examples. During molding, the injection time was set to 0.3 seconds. The prepared plate was placed on a flat table and the lift amount was measured. In the measurement, when one of the four corners was brought into close contact with the table, the amount of lifting at the corner having the highest lifting amount was measured. It is considered that the smaller the amount of lift, the better the resin characteristics, because the more uniform the dispersibility of cellulose in the thermoplastic resin is, the less the warpage of the molded product is.

<Bending elastic modulus>
The bending elastic modulus was measured according to JIS K7171 using the cellulose-containing thermoplastic resin produced in the examples and comparative examples. However, the number of test pieces was set to 20, the measurement was performed 20 times, and the average value was taken as the flexural modulus. The larger the value, the higher the flexural modulus and the better. In addition, the test piece was cut out from the multipurpose test piece A form produced according to JISK7139.

<Variation in flexural modulus>
The standard deviation was calculated from the measurement results of the bending elastic modulus at 20 points, and used as a measure of the variation in bending elastic modulus. The smaller the standard deviation, the smaller the variation and the better the uniformity. The high degree of uniformity reflects the high degree of uniformity of the dispersed state of cellulose in the thermoplastic resin.

<Moisture content>
Ten test pieces that are the same as those used for the measurement of the flexural modulus are prepared, and the sample is left to stand at 23 ° C. and 50% RH to adjust the humidity, and then the mass (W1) of the entire ten pieces is measured. After the mass measurement, the sample is held for 6 hours in a hot air dryer set at 120 ° C. and dried, and then the mass (W2) of the entire sheet immediately after taking out from the dryer is measured. The (W1-W2) / W1 was defined as the moisture content of the molded body.

  The evaluation results are shown in Tables 1-3.

  As shown in Tables 1 and 2, it can be seen that the cellulose-containing thermoplastic resin of the present invention has excellent moldability because of its large MFR. Moreover, the molded object which consists of a cellulose containing thermoplastic resin of this invention does not generate | occur | produce a curvature, and it does not generate | occur | produce a curvature, and it corresponds to the low moisture content of the molded object measured together. Furthermore, it turns out that a bending elastic modulus is also high. On the other hand, in the comparative example shown in Table 3, these characteristics are inferior.

  The method for producing a cellulose-containing thermoplastic resin of the present invention, the cellulose-containing thermoplastic resin, and a molded product thereof can be used for packaging materials, storage trays, pallets, protective members, partition members, and the like. It can also be used for personal computers, mobile phone housings, automotive materials, building materials, furniture, play equipment, toys, stationery, and the like.

Claims (7)

  In a method for producing a cellulose-containing thermoplastic resin in which a thermoplastic resin and cellulose are melt-mixed as a raw material in a batch type closed kneading apparatus having a stirring chamber provided with a rotating shaft provided with rotating blades, Fibrous cellulose defibrated by a dry defibrator, the temperature in the stirring chamber at the time of melt mixing is 150 to 370 ° C, the pressure in the stirring chamber is 0.20 MPa or more up to the saturated water vapor pressure, And the manufacturing method of the cellulose containing thermoplastic resin characterized by adding the acid anhydride as a raw material.   The method for producing a cellulose-containing thermoplastic resin according to claim 1, wherein a polyhydric alcohol is further added as a raw material.   The method for producing a cellulose-containing thermoplastic resin according to claim 1 or 2, wherein the cellulose content relative to the cellulose-containing thermoplastic resin is 5 to 70 mass%.   The method for producing a cellulose-containing thermoplastic resin according to any one of claims 1 to 3, wherein the moisture content of the cellulose is 5 to 30% by mass.   The manufacturing method of the cellulose containing thermoplastic resin in any one of Claims 1-4 which performs reheating mixing as a post process.   A cellulose-containing thermoplastic resin produced by the method for producing a cellulose-containing thermoplastic resin according to claim 1.   A molded article comprising the cellulose-containing thermoplastic resin according to claim 6.