Method for producing resin composition

Abstract

Provided is a method for producing a resin composition with which it is possible to form a molded article having excellent tensile elongation and / or rigidity, and more preferably with which it is possible to form a molded article having both high-level and stable tensile elongation and rigidity. In one embodiment, provided is a method for producing a resin composition comprising a first component and a second component, the first component being a polymer, the second component being an organic fiber or a combination of an organic fiber and a polymer different from the first component, the method includes a kneading step in which a first component and a second component are kneaded by an extruder provided with a kneading zone including a plurality of high-pressure zones having a pressure of 0.1 MPa or more, the pressure P1 in the highest-pressure zone having the largest pressure among the plurality of high-pressure zones being 0.5 MPa or more, and the pressure P2 in the highest-pressure zone having the largest pressure among the plurality of high-pressure zones being 0.5 MPa or more. The ratio (P1 / P2) of the pressure (P1) to the average value (P2) of the pressure in a high-pressure region other than the highest-pressure region is greater than 1 and 100 or less.

Description

[0001] This application is a divisional application, and the Chinese national application number of the application it is directed to is 202280011357.2, the international application number is PCT / JP2022 / 004323, the application date is February 3, 2022, and the date of entry into China is July 24, 2023, and the invention title is "Method for manufacturing resin composition". Technical Field

[0002] The present invention relates to a method for manufacturing a resin composition. Background Art

[0003] Thermoplastic resins are widely used in various fields such as automotive parts, electrical and electronic parts, office equipment housings, and precision parts due to their light weight and excellent processing characteristics. However, in many cases, the mechanical properties, dimensional stability, etc. of the resin alone are insufficient. Therefore, a composite in which a filler is dispersed in a polymer continuous phase or a polymer dispersed phase is formed is usually used. As the above-mentioned filler, the use of organic fibers such as cellulose fibers has been studied in recent years. Cellulose fibers are materials with less environmental load, low specific gravity, and can have an excellent effect of improving the physical properties of the resin composition. Therefore, they are expected to be used as fillers for environmentally friendly resin compositions. However, organic fibers such as cellulose fibers are not necessarily easily and well dispersed in a polymer (resin). For example, when melt-kneading an organic fiber and a resin using an extruder, depending on the kneading conditions, sometimes the expected effect of improving the physical properties cannot be imparted to the resin composition. The same applies when forming a polymer alloy having a polymer continuous phase and a polymer dispersed phase. When melt-kneading using an extruder, depending on the kneading conditions, sometimes the desired effect of improving the physical properties cannot be obtained.

[0004] Regarding the kneading of a resin composition, for example, Patent Document 1 describes a method for manufacturing a resin composition in which the resin pressure in the kneading zone and the full-thread zone satisfies a specific relationship in the manufacture of a polyamide resin composition using a twin-screw extruder.

[0005] Prior Art Documents

[0006] Patent Documents

[0007] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2016-108547 Summary of the Invention

[0008] Problems to be Solved by the Invention

[0009] The method described in Patent Document 1 aims to obtain molded articles with excellent retention stability, heat aging resistance, surface appearance, etc. However, in resin compositions containing fillers such as organic fibers like cellulose fibers and / or polymer dispersed phases, no attention has been paid to methods for achieving the expected improvement in physical properties based on such fillers and / or dispersed phases. For resin compositions containing organic fibers such as cellulose fibers and / or polymer dispersed phases, due to their advantageous properties corresponding to their material compositions (e.g., light weight and dimensional stability in cellulose fibers), their applications in various uses such as automotive uses have been studied. For example, in uses where strict performance requirements are imposed such as automotive uses, it is desired to achieve a high level of balance between multiple properties (especially tensile elongation and rigidity) and stably exhibit these properties. However, in the prior art, no resin composition capable of forming a molded body having such excellent physical properties has been provided.

[0010] An object of one aspect of the present invention is to solve the above problems and provide a method for manufacturing a resin composition that can form a molded body having excellent tensile elongation and / or rigidity, and more preferably can form a molded body that achieves a high level of balance between tensile elongation and rigidity stably.

[0011] Means for Solving the Problems

[0012] The present disclosure includes the following aspects.

[0013] [1] A method for manufacturing a resin composition containing a first component and a second component, wherein,

[0014] The above first component is a polymer,

[0015] The above second component is an organic fiber, a polymer different from the above first component, or a combination thereof,

[0016] The above method includes a kneading step of kneading the first component and the second component using an extruder, and the extruder has a kneading zone including a plurality of narrow-gap zones where the gap between the inner wall of the barrel and the screw is 2 mm or less.

[0017] [2] The method according to the above aspect 1, wherein the ratio [G1 / G2] of the gap [G1] of the narrowest gap zone having the smallest gap among the plurality of narrow-gap zones to the average value [G2] of the gaps of the narrow-gap zones other than the narrowest gap zone is 0.001 or more and less than 1.

[0018] [3] The method according to the above aspect 1 or 2, wherein the ratio [G1 / G3] of the gap [G1] of the narrowest gap zone having the smallest gap among the plurality of narrow-gap zones to each of the gaps [G3] of the narrow-gap zones other than the narrowest gap zone is 0.001 or more and less than 1.

[0019] [4] The method according to any one of the above-described methods 1 to 3, wherein,

[0020] The above-described second component contains organic fibers,

[0021] The organic fibers supplied to the above-described extruder have an average fiber length of 1 μm to 10,000 μm,

[0022] The ratio of the gap [G1] of the narrowest gap region having the smallest gap among the above-described plurality of narrow gap regions to the above-described average fiber length is 0.001 to 10.

[0023] [5] The method according to any one of the above-described methods 1 to 4, wherein,

[0024] The above-described second component contains organic fibers,

[0025] The organic fibers supplied to the above-described extruder form particles having an average particle diameter of 1 μm to 10,000 μm,

[0026] The ratio of the gap [G1] of the narrowest gap region having the smallest gap among the above-described plurality of narrow gap regions to the above-described average particle diameter is 0.001 to 10.

[0027] [6] The method according to any one of the above-described methods 1 to 5, wherein the rate of increase in the flexural modulus per unit mass of the mixture in each of the above-described plurality of narrow gap regions is greater than the maximum value of the flexural modulus per unit mass of the mixture in the regions other than the narrow gap regions.

[0028] [7] The method according to any one of the above-described methods 1 to 6, wherein,

[0029] For each of the above-described narrow gap regions,

[0030] The pressure of the inflow material flowing into the above-described narrow gap region is 0.5 to 20 MPa, and

[0031] The ratio of the pressure of the outflow material flowing out of the above-described narrow gap region to the pressure of the inflow material flowing into the above-described narrow gap region is 0.2 or less.

[0032] [8] The method according to any one of the above-described methods 1 to 7, wherein, for each of the above-described narrow gap regions, the content of the above-described second component of the inflow material flowing into the above-described narrow gap region is 15 to 90% by mass.

[0033] [9] The method according to any one of the above-described methods 1 to 8, wherein, in the above-described kneading step, an additional polymer having a temperature lower than that of the mixture is added to the mixture after passing through the above-described plurality of narrow gap regions to cool the mixture.

[0034]

[10] A method for manufacturing a resin composition containing a first component and a second component, wherein,

[0035] The first component is a polymer,

[0036] The second component is an organic fiber, a polymer different from the first component, or a combination thereof,

[0037] The method includes a kneading step of kneading the first component and the second component using an extruder, and the extruder has a kneading zone including a pressure reduction zone,

[0038] The pressure reduction zone is a portion where the pressure of the inflow material flowing into the pressure reduction zone is 0.5 to 20 MPa, and the ratio of the pressure of the outflow material flowing out of the pressure reduction zone to the pressure of the inflow material flowing into the pressure reduction zone is 0.2 or less,

[0039] The content of the second component in the inflow material flowing into the pressure reduction zone is 15 to 90% by mass.

[0040]

[11] A method for manufacturing a resin composition containing a first component and a second component, wherein,

[0041] The first component is a polymer,

[0042] The second component is an organic fiber, a polymer different from the first component, or a combination thereof,

[0043] The method includes a kneading step of kneading the first component and the second component using an extruder, and the extruder has a kneading zone including a pressure reduction zone,

[0044] The pressure reduction zone is a portion where the pressure of the inflow material flowing into the pressure reduction zone is 0.5 to 20 MPa, and the ratio of the pressure of the outflow material flowing out of the pressure reduction zone to the pressure of the inflow material flowing into the pressure reduction zone is 0.2 or less,

[0045] In the kneading step, an additional polymer having a temperature lower than that of the mixture is added to the mixture after passing through the pressure reduction zone, and the mixture is cooled.

[0046]

[12] A method for manufacturing a resin composition containing a first component and a second component, wherein,

[0047] The first component is a polymer,

[0048] The second component is an organic fiber, a polymer different from the first component, or a combination thereof,

[0049] The above method includes a kneading step of kneading a first component and a second component using an extruder, the extruder having a kneading zone including a plurality of high-pressure zones with a pressure of 0.1 MPa or more.

[0050] The pressure [P1] of the highest-pressure zone with the maximum pressure among the plurality of high-pressure zones is 0.5 MPa or more, and the ratio [P1 / P2] of the pressure [P1] to the average value [P2] of the pressures of the high-pressure zones other than the highest-pressure zone is greater than 1 and 100 or less.

[0051]

[13] The method according to the above-described mode 12, wherein the ratio [P1 / P3] of the pressure [P1] to the pressure [P3] of each of the high-pressure zones other than the highest-pressure zone is greater than 1 and 100 or less.

[0052]

[14] The method according to the above-described mode 12 or 13, wherein the ratio of the zone length of each of the plurality of high-pressure zones to the inner diameter of the barrel is 1 to 30.

[0053]

[15] The method according to any one of the above-described modes 12 to 14, wherein the ratio of the zone length of the highest-pressure zone to the inner diameter of the barrel to the ratio of the zone length of each of the high-pressure zones other than the highest-pressure zone to the inner diameter of the barrel is 1 or more.

[0054]

[16] The method according to any one of the above-described modes 12 to 15, wherein the rate of increase in the flexural modulus per unit mass of the mixture in each of the plurality of high-pressure zones is greater than the maximum value of the rate of increase in the flexural modulus per unit mass of the mixture in the zones other than the high-pressure zones.

[0055]

[17] The method according to any one of the above-described modes 12 to 16, wherein

[0056] For each of the high-pressure zones,

[0057] The pressure of the inflow material flowing into the high-pressure zone is 0.5 to 20 MPa, and

[0058] The ratio of the pressure of the outflow material flowing out of the high-pressure zone to the pressure of the inflow material flowing into the high-pressure zone is 0.2 or less.

[0059]

[18] The method according to any one of the above-described modes 12 to 17, wherein, for each of the high-pressure zones, the content of the second component in the inflow material flowing into the high-pressure zone is 15 to 90% by mass.

[0060]

[19] The method according to any one of the above-described modes 12 to 18, wherein, in the above kneading step, an additional polymer having a temperature lower than that of the above mixture is added to the mixture after all the zones through which the above plurality of high-pressure zones pass, and the above mixture is cooled.

[0061]

[20] The method according to any one of the above-described modes 1 to 19, wherein, before the above kneading step, there is further included a step of adding the above second component to the melt of the above first component to obtain a premix, and the above premix is supplied to the above kneading zone.

[0062]

[21] A method for manufacturing a resin composition comprising a first component and a second component, wherein,

[0063] the above first component is a polymer,

[0064] the above second component is an organic fiber, a polymer different from the above first component, or a combination thereof,

[0065] the above method includes a dispersion mixing step of dispersing and mixing the first component and the second component in a dispersion mixing zone of an extruder,

[0066] the above dispersion mixing zone includes a first dispersion mixing zone and a second dispersion mixing zone, and the first dispersion mixing zone and the second dispersion mixing zone are different from each other in at least one selected from the group consisting of the ratio of the zone length to the barrel inner diameter, the mixture filling rate, the temperature, the pressure, and the space volume ratio,

[0067] The increment [E1] of the tensile elongation rate of the effluent flowing out from the above first dispersion mixing zone with respect to the tensile elongation rate of the influent flowing into the above first dispersion mixing zone and the increment [E2] of the tensile elongation rate of the effluent flowing out from the above second dispersion mixing zone with respect to the tensile elongation rate of the influent flowing into the above second dispersion mixing zone satisfy the relationship [E1] > [E2],

[0068] The increment [M1] of the flexural modulus of the effluent flowing out from the above first dispersion mixing zone with respect to the flexural modulus of the influent flowing into the above first dispersion mixing zone and the increment [M2] of the flexural modulus of the effluent flowing out from the above second dispersion mixing zone with respect to the flexural modulus of the influent flowing into the above second dispersion mixing zone satisfy the relationship [M1] < [M2].

[0069]

[22] A method for manufacturing a resin composition comprising a first component and a second component, wherein,

[0070] the above first component is a polymer,

[0071] the above second component is an organic fiber, a polymer different from the above first component, or a combination thereof,

[0072] The above method includes a dispersion mixing step of dispersing and mixing a first component and a second component in a dispersion mixing zone of an extruder,

[0073] In the above dispersion mixing zone, by making one or more selected from the group consisting of the ratio of zone length to barrel inner diameter, mixture filling rate, temperature, pressure, and space volume ratio different in the barrel length direction, the traveling length l (mm) of the mixture in the barrel is divided by the barrel inner diameter d (mm) to obtain l / d, and the ratio [ΔE / ΔM] of the change amount ΔE (%) of the tensile elongation rate per unit l / d to the change amount ΔM (GPa) of the flexural modulus per unit l / d changes in the barrel length direction.

[0074]

[23] A method for manufacturing a resin composition containing a first component and a second component, wherein,

[0075] The above first component is a polymer,

[0076] The above second component is an organic fiber, a polymer different from the above first component, or a combination thereof,

[0077] The above method includes the following steps:

[0078] A dispersion mixing step of dispersing and mixing the first component and the second component in a dispersion mixing zone of an extruder to obtain a dispersion mixing product; and

[0079] A distributive mixing step of distributively mixing at least the above dispersion mixing product in a distributive mixing zone of an extruder to obtain a resin composition,

[0080] The above dispersion mixing zone and the above distributive mixing zone are different from each other in one or more selected from the group consisting of the ratio of zone length to barrel inner diameter, mixture filling rate, temperature, pressure, and space volume ratio,

[0081] The increment [EA] of the tensile elongation rate of the effluent flowing out from the above dispersion mixing zone relative to the tensile elongation rate of the influent flowing into the above dispersion mixing zone and the increment [EB] of the tensile elongation rate of the effluent flowing out from the above distributive mixing zone relative to the tensile elongation rate of the influent flowing into the above distributive mixing zone satisfy the relationship [EA] > [EB],

[0082] The increment [MA] of the flexural modulus of the effluent flowing out from the above dispersion mixing zone relative to the flexural modulus of the influent flowing into the above dispersion mixing zone and the increment [MB] of the flexural modulus of the effluent flowing out from the above distributive mixing zone relative to the flexural modulus of the influent flowing into the above distributive mixing zone satisfy the relationship [MA] > [MB].

[0083]

[24] A method for manufacturing a resin composition comprising a first component and a second component, wherein,

[0084] The first component is a polymer,

[0085] The second component is an organic fiber, a polymer different from the first component, or a combination thereof,

[0086] The method includes the following steps:

[0087] A dispersion mixing step of dispersing and mixing the first component and the second component in the dispersion mixing zone of an extruder to obtain a dispersion mixed product; and

[0088] A distributive mixing step of distributively mixing at least the dispersion mixed product in the distributive mixing zone of the extruder to obtain a resin composition,

[0089] The concentration [CA] of the second component in the dispersion mixing zone is 10% by mass to 90% by mass, the concentration [CB] of the second component in the distributive mixing zone is 1% by mass to 50% by mass, and the ratio [CA] / [CB] is 2 to 90.

[0090]

[25] The method according to any one of the above aspects 1 to 20, wherein,

[0091] The method includes a dispersion mixing step of dispersing and mixing the first component and the second component in the dispersion mixing zone of an extruder,

[0092] The dispersion mixing zone includes a first dispersion mixing zone and a second dispersion mixing zone, and the first dispersion mixing zone and the second dispersion mixing zone are different from each other in at least one selected from the group consisting of the ratio of zone length to barrel inner diameter, mixture filling rate, temperature, pressure, and space volume ratio,

[0093] The increment [E1] of the tensile elongation rate of the effluent flowing out of the first dispersion mixing zone relative to the tensile elongation rate of the influent flowing into the first dispersion mixing zone and the increment [E2] of the tensile elongation rate of the effluent flowing out of the second dispersion mixing zone relative to the tensile elongation rate of the influent flowing into the second dispersion mixing zone satisfy the relationship [E1] > [E2],

[0094] The increment [M1] of the flexural modulus of the effluent flowing out of the first dispersion mixing zone relative to the flexural modulus of the influent flowing into the first dispersion mixing zone and the increment [M2] of the flexural modulus of the effluent flowing out of the second dispersion mixing zone relative to the flexural modulus of the influent flowing into the second dispersion mixing zone satisfy the relationship [M1] < [M2].

[0095]

[26] The method according to any one of the above aspects 1 to 20, wherein,

[0096] The above method includes a dispersion mixing step of dispersing and mixing a first component and a second component in a dispersion mixing zone of an extruder.

[0097] In the above dispersion mixing zone, by making one or more selected from the group consisting of the ratio of zone length to barrel inner diameter, mixture filling rate, temperature, pressure, and space volume ratio different in the barrel length direction, the traveling length l (mm) of the mixture in the barrel is divided by the barrel inner diameter d (mm) to obtain l / d, and the ratio [ΔE / ΔM] of the change amount ΔE (%) of the tensile elongation rate per unit l / d to the change amount ΔM (GPa) of the flexural modulus per unit l / d changes in the barrel length direction.

[0098]

[27] The method according to any one of the above modes 1 to 20, wherein

[0099] The above method includes the following steps:

[0100] A dispersion mixing step of dispersing and mixing a first component and a second component in a dispersion mixing zone of an extruder to obtain a dispersion mixed product; and

[0101] A distributive mixing step of distributively mixing at least the above dispersion mixed product in a distributive mixing zone of the extruder to obtain a resin composition,

[0102] The above dispersion mixing zone and the above distributive mixing zone are different from each other in one or more selected from the group consisting of the ratio of zone length to barrel inner diameter, mixture filling rate, temperature, pressure, and space volume ratio.

[0103] The increment [EA] of the tensile elongation rate of the effluent flowing out from the above dispersion mixing zone relative to the tensile elongation rate of the influent flowing into the above dispersion mixing zone and the increment [EB] of the tensile elongation rate of the effluent flowing out from the above distributive mixing zone relative to the tensile elongation rate of the influent flowing into the above distributive mixing zone satisfy the relationship [EA] > [EB].

[0104] The increment [MA] of the flexural modulus of the effluent flowing out from the above dispersion mixing zone relative to the flexural modulus of the influent flowing into the above dispersion mixing zone and the increment [MB] of the flexural modulus of the effluent flowing out from the above distributive mixing zone relative to the flexural modulus of the influent flowing into the above distributive mixing zone satisfy the relationship [MA] > [MB].

[0105]

[28] The method according to any one of the above modes 1 to 20, wherein

[0106] The above method includes the following steps:

[0107] A dispersion mixing step of dispersively mixing a first component and a second component in a dispersion mixing zone of an extruder to obtain a dispersion mixed product; and

[0108] A distributive mixing step of distributively mixing at least the above-mentioned dispersion mixed product in a distributive mixing zone of the extruder to obtain a resin composition,

[0109] The concentration [CA] of the second component in the dispersion mixing zone is 10% by mass to 90% by mass, the concentration [CB] of the second component in the distributive mixing zone is 1% by mass to 50% by mass, and the ratio [CA] / [CB] is 2 to 90.

[0110]

[29] The method according to any one of the above-mentioned modes 21 to 28, wherein, before the above-mentioned dispersion mixing step, a step of adding the second component to the melt of the first component to obtain a premix is further included, and the premix is supplied to the above-mentioned dispersion mixing zone.

[0111]

[30] The method according to any one of the above-mentioned modes 1 to 29, wherein the second component contains organic fibers.

[0112]

[31] The method according to the above-mentioned mode 30, wherein the organic fiber is a cellulose fiber.

[0113]

[32] The method according to the above-mentioned mode 30 or 31, wherein the organic fiber in the resin composition has an average fiber diameter of 1000 nm or less and an average fiber length / average fiber diameter ratio of 30 or more.

[0114]

[33] The method according to any one of the above-mentioned modes 30 to 32, wherein the organic fiber is supplied to the extruder in a dry state.

[0115] Effects of the invention

[0116] According to one mode of the present invention, a method for manufacturing a resin composition can be provided, and the resin composition can form a molded body having excellent tensile elongation and / or rigidity, and more preferably can form a molded body that can achieve both high-level and stable tensile elongation and rigidity. Description of the drawings

[0117] Figure 1 It is a diagram for explaining the steps of the method for manufacturing a resin composition according to the first embodiment of Mode A of the present invention.

[0118] Figure 2 It is a diagram for explaining the steps of the method for manufacturing a resin composition according to the second embodiment of Mode A of the present invention.

[0119] Figure 3This is a diagram for explaining the steps of the manufacturing method of the resin composition according to the third embodiment of Mode A of the present invention.

[0120] Figure 4 This is a diagram for explaining the steps of the manufacturing method of the resin composition according to the first embodiment of Mode B of the present invention.

[0121] Figure 5 This is a diagram for explaining the change behavior of the tensile elongation rate and the flexural modulus in the method according to the first embodiment of Mode B of the present invention.

[0122] Figure 6 This is a diagram for explaining the steps of the manufacturing method of the resin composition according to the second embodiment of Mode B of the present invention.

[0123] Figure 7 This is a diagram for explaining the change behavior of the tensile elongation rate and the flexural modulus in the method according to the second embodiment of Mode B of the present invention.

[0124] Figure 8 This is a diagram for explaining the steps of the manufacturing method of the resin composition according to Mode C of the present invention. Detailed Embodiments

[0125] The embodiments exemplified in the present invention (hereinafter simply referred to as "the present embodiments") will be described below. However, the present invention is not limited by any of these embodiments. In addition, regarding the characteristic values of the present disclosure, unless otherwise specified, they refer to the values measured by the methods described in the [Examples] section of the present disclosure or methods that those skilled in the art understand to be equivalent thereto.

[0126] One aspect of the present disclosure provides a method for manufacturing a resin composition containing a first component and a second component. In one aspect, the first component is a polymer, and the second component is an organic fiber, a polymer, or a combination thereof. In one aspect, the polymer in the second component is different from the first component. In one aspect, the first component forms a continuous phase in the resin composition. In one aspect, the organic fiber that the second component may contain is dispersed in the first component in the resin composition. In one aspect, the polymer that the second component may contain exists in the continuous phase of the first component in the form of a dispersed phase in the resin composition.

[0127] The method of the present disclosure includes a kneading step of kneading a first component and a second component using an extruder having a kneading zone. When manufacturing a resin composition by kneading the first component and the second component using an extruder, in order to uniformly and finely disperse the second component in the first component, it is necessary to refine the second component itself and improve the dispersion state of the second component in the first component. In order to refine the second component, a certain degree of strong force needs to be applied to the mixture, and such a force may cause damage to the second component (for example, when the second component contains organic fibers, the organic fibers break due to bending). Therefore, the kneading conditions are preferably designed in such a way that they are required for the refinement of the second component but do not impose an excessive load on the second component. In the method of the present disclosure, the first component and the second component are kneaded in a kneading zone controlled to specific kneading conditions.

[0128] For example, in the method of Mode A described later as an exemplary embodiment of the present disclosure, a part of the region in the kneading zone is made into a zone that applies a large force to the mixture.

[0129] In addition, in the method of Mode B described later as an exemplary embodiment of the present disclosure, a region that mainly increases the tensile elongation rate and a region that mainly increases the flexural modulus are provided in the dispersion mixing zone in the mixture.

[0130] In addition, in the method of Mode C described later as an exemplary embodiment of the present disclosure, the first component and the second component are dispersed and mixed and distributively mixed using a specific method.

[0131] It should be noted that in the present disclosure, dispersion mixing refers to a mixing form accompanied by a substantial size change of the second component (such as fragmentation, cutting, fibrillation, etc. of agglomerates), and distributive mixing refers to a change in the dispersion state of the second component in the first component, and on the other hand, a mixing form not accompanied by a substantial size change of the second component. In one mode, the substantial size change means a size change of 30% or more with respect to the original size in at least one size index.

[0132] According to the method of one mode of the present disclosure, through the contribution of the above-mentioned specific kneading form, it is possible to uniformly and finely disperse the second component in the first component while avoiding damage to the second component.

[0133] In the method of the present disclosure, when melt-mixing the first component and the second component using an extruder, the second component can be melt-kneaded with the first component in the form of a dry body or a slurry (such as an aqueous dispersion). In a preferred mode, the second component is supplied to the extruder in the form of a dry body. The heating temperature throughout the melt-kneading process is preferably above the glass transition point of the first component but not significantly higher than the glass transition point and / or the melting point of the first component.

[0134] It should be noted that in the present disclosure, the glass transition point refers to the temperature at the peak of the maximum loss modulus and a significant decrease in the storage modulus when measured at an application frequency of 10 Hz while heating from 23°C at a heating rate of 2°C / minute using a dynamic viscoelasticity measuring device. In the case where two or more peaks of the loss modulus appear, it refers to the peak temperature of the peak on the highest temperature side. In addition, in the present disclosure, the melting point refers to the peak temperature of the endothermic peak that appears when heating from 23°C at a heating rate of 10°C / minute using a differential scanning calorimeter (DSC). In the case where two or more endothermic peaks appear, it refers to the peak temperature of the endothermic peak on the highest temperature side.

[0135] The water content of the polymer to be melt-kneaded is preferably 0.2% by mass or less, or 0.1% by mass or less, or 0.07% by mass or less. From the aspect of ease of process management, the above water content can be, for example, 0.001% by mass or more.

[0136] In melt-kneading, a single-screw extruder or a twin-screw extruder can be used. In order to control the dispersibility of the second component, a twin-screw extruder is preferred. The ratio of the barrel length (L) to the screw diameter (D) of the extruder, L / D, is preferably 40 or more, particularly preferably 50 or more. In addition, the screw rotation speed during kneading is preferably in the range of 100 to 800 rpm, more preferably in the range of 150 to 600 rpm. They vary according to the screw design.

[0137] Each screw in the barrel of the extruder is optimized by combining a full-thread screw with an elliptical two-blade twisted shape, a kneading element called a kneading disk, etc. When optimizing, the screw element can have a cut or a split structure. In addition, a blocking structure called a sealing ring can also be arranged in the screw configuration. As one mode, the screw cross-section can be composed of multiple cross-sections such as 0, one, two, three, four, etc. In addition, these screw cross-sections can also be formed into an eccentric shape.

[0138] The following specifically describes Modes A to C as the exemplary embodiments of the present disclosure.

[0139] [Mode A]

[0140] In the method of Method A, a part of the kneading zone is made into a zone where a large force is applied to the mixture (also referred to as a high-load zone in the present disclosure) (more specifically, a narrow-gap zone, a pressure reduction zone, or a high-pressure zone described later). By providing a high-load zone and other zones in the kneading zone, the refinement of the second component can be achieved in the high-load zone (this can greatly contribute to improving the desired physical properties of the resin composition). On the other hand, in other zones, the mixing conditions can be relaxed in such a way that the force applied to the second component is minimized, avoiding damage to the second component. By using such a treatment, it is possible to uniformly and finely disperse the second component in the first component while avoiding damage to the second component. Therefore, in one aspect, it is possible to produce a resin composition that can form a molded body having excellent tensile elongation and / or flexural modulus, and more preferably a molded body that can form a high level and stably balance both tensile elongation and flexural modulus.

[0141] Method A more specifically includes the following first to third embodiments.

[0142] <<First Embodiment>>

[0143] The first embodiment provides a method including a kneading step of kneading a first component and a second component using an extruder, the extruder having a kneading zone including a plurality of narrow-gap zones where the gap between the inner wall of the barrel and the screw is 2 mm or less.

[0144] Figure 1 It is a diagram for explaining the steps of the method for producing the resin composition of the first embodiment. In the first embodiment, the extruder 100 includes a kneading zone 101 and may optionally include a melting zone 102. For example, in the method of the first embodiment, before the kneading step in the kneading zone 101, it may further include a step of melting the first component a1 in the melting zone 102, adding the second component a2 to the obtained melt to obtain a premix, and supplying the premix to the kneading zone 101. In conventional kneading using an extruder, strong shear is applied to the mixture in the initial melting zone. Therefore, when the second component is added to the molten first component from the addition port (side feeder), thermal degradation of the second component can be suppressed. The mixture is kneaded in the kneading zone 101 and taken out in the form of a resin composition b.

[0145] In one embodiment, the kneading zone 101 includes a plurality of narrow clearance zones N1, N2, and N3 where the clearance between the inner wall of the barrel and the screw (also referred to as the barrel clearance in the present disclosure) is 2 mm or less. It should be noted that in the present disclosure, the barrel clearance refers to the widest flow path clearance in the flow path through which the mixture can flow from the upstream to the downstream of the extruder. For example, in a screw element such as a double-threaded screw, the clearance in the short-axis direction of the cross-section in the screw diameter direction is taken as the barrel clearance. Additionally, for example, in a screw element such as a sealing ring, the clearance between the screw and the barrel is taken as the barrel clearance. Figure 1 An example showing the existence of 3 narrow clearance zones is presented, but the number of narrow clearance zones in the kneading zone can be selected according to the purpose. For example, it can be 2 or more, or 3 or more, and for example, it can be 10 or less, or 5 or less.

[0146] Among the plurality of narrow clearance zones N1, N2, and N3, regarding the ratio [G1 / G2] of the barrel clearance [G1] (hereinafter also simply referred to as [G1]) of the narrowest clearance zone with the smallest barrel clearance to the average value [G2] of the barrel clearances of the narrow clearance zones other than the narrowest clearance zone, from the aspect of well performing the micronization of the second component, in one embodiment, it is 0.001 or more, or 0.01 or more, or 0.1 or more, and from the aspect of suppressing damage to the second component, in one embodiment, it is less than 1, or 0.5 or less, or 0.3 or less. It should be noted that regarding the above average value [G2], if the corresponding zone is 1, it refers to the barrel clearance value of that zone, and if the corresponding zone is 2 or more, it refers to the arithmetic average of the barrel clearance values of that zone.

[0147] Regarding the ratio [G1 / G3] of the above [G1] to the barrel clearance [G3] of each zone of the narrow clearance zones other than the narrowest clearance zone, from the aspect of well performing the micronization of the second component, in one embodiment, it is 0.001 or more, or 0.01 or more, or 0.1 or more, and from the aspect of suppressing damage to the second component, in one embodiment, it is less than 1, or 0.5 or less, or 0.3 or less.

[0148] [G1] is preferably 0.001 mm or more, or 0.01 mm or more, or 0.05 mm or more, and preferably 2 mm or less, or 1 mm or less, or 0.5 mm or less.

[0149] [G2] is preferably 0.001 mm or more, or 0.01 mm or more, or 0.05 mm or more, and preferably 2 mm or less, or 1 mm or less, or 0.5 mm or less.

[0150] [G3] is preferably 0.001 mm or more, or 0.01 mm or more, or 0.05 mm or more, and preferably 2 mm or less, or 1 mm or less, or 0.5 mm or less.

[0151] When the second component contains organic fibers, in one embodiment, the organic fibers supplied to the extruder have an average fiber length of 1 μm to 10,000 μm. It should be noted that the average fiber length in the present disclosure is a value measured using a scanning electron microscope (SEM) as described below. Regarding the average fiber length, in one embodiment, it is 1 μm or more, or 10 μm or more, or 50 μm or more, and in one embodiment, it is 10,000 μm or less, or 1,000 μm or less, or 750 μm or less, or 600 μm or less. In one embodiment, regarding the ratio of the above [G1] to the average fiber length, from the aspect of suppressing damage to the organic fibers, it is preferably 0.001 or more, or 0.01 or more, or 0.1 or more, and from the aspect of favorably performing the refinement of the organic fibers, it is preferably 10 or less, or 5 or less, or 1 or less.

[0152] When the second component contains organic fibers, in one embodiment, the organic fibers supplied to the extruder form particles having an average particle diameter of 1 μm to 10,000 μm. The average particle diameter of the particles is 1 μm or more, or 10 μm or more, or 50 μm or more in one embodiment, and 10,000 μm or less, or 1,000 μm or less, or 750 μm or less, or 500 μm or less in one embodiment. In one embodiment, regarding the ratio of the above [G1] to the average particle diameter of the particles, from the aspect of suppressing damage to the organic fibers, it is preferably 0.001 or more, or 0.01 or more, or 0.1 or more, and from the aspect of favorably performing the refinement of the organic fibers, it is preferably 10 or less, or 5 or less, or 1 or less.

[0153] It should be noted that the average particle diameter in the present disclosure is the d50 particle diameter measured using a powder tester (for example, a powder tester manufactured by Hosokawa Micron Corporation, model: PT-X).

[0154] Regarding the content of the second component of the inflow material flowing into each narrow gap region, from the aspect of favorably obtaining the effect of improving the physical properties based on the second component by making the resin composition contain the second component at a desired concentration, the above content is preferably 15% by mass or more, or 20% by mass or more, or 30% by mass or more respectively, and from the aspect of favorably performing the refinement of the second component, it is preferably 90% by mass or less, or 80% by mass or less, or 70% by mass or less.

[0155] Regarding the pressure of the inflow into each narrow gap region, from the aspect of favorably performing the refinement of the second component, it is preferably 0.5 MPa or more, or 1 MPa or more, or 3 MPa or more. From the aspect of suppressing damage to the second component, it is preferably 20 MPa or less, or 15 MPa or less, or 10 MPa or less. It should be noted that in one embodiment, the pressure of the inflow into each narrow gap region is substantially equal to the pressure of the mixture within each narrow gap region.

[0156] Regarding the ratio of the pressure of the outflow from each narrow gap region to the pressure of the inflow into the narrow gap region for each narrow gap region, from the aspect of increasing the pressure of the inflow into the narrow gap region and favorably performing the refinement of the second component, it is preferably 0.2 or less, or 0.15 or less, or 0.1 or less. From the aspect of suppressing damage to the second component caused by a sharp pressure change in the mixture, it is preferably 0.0001 or more, or 0.001 or more, or 0.01 or more. It should be noted that in one embodiment, the pressure of the outflow from each narrow gap region is substantially equal to the pressure of the mixture within the region connected to each narrow gap region on the downstream side. It should be noted that the inflow into each region or the outflow from each region may be a mixture flowing into or out of each region. For example, the outflow is not limited to the case where a discharge flow path for discharging to the outside of the extruder is provided in the extrusion mechanism.

[0157] Regarding the pressure of the outflow from each narrow gap region, in one embodiment, it can be 0 MPa or more, or 0.001 MPa or more, or 0.01 MPa or more, and in one embodiment, it can be 4 MPa or less, or 2 MPa or less, or 1 MPa or less.

[0158] <<Second Embodiment>>

[0159] The second embodiment provides a method including a kneading step of kneading a first component and a second component using an extruder, and the extruder includes a kneading region including a pressure reduction region. The method of the second embodiment has the following characteristics. Except for these characteristics, one or more of the above-exemplified characteristics regarding the first embodiment can be combined.

[0160] The pressure reduction region is a part where the pressure of the inflow into the pressure reduction region is 0.5 to 20 MPa and the ratio of the pressure of the outflow from the pressure reduction region to the pressure of the inflow into the pressure reduction region is 0.2 or less.

[0161] Regarding the pressure of the inflow into the pressure reduction zone, from the aspect of facilitating the micronization of the second component, it is preferably 0.5 MPa or more, or 1 MPa or more, or 3 MPa or more. From the aspect of suppressing damage to the second component, it is preferably 20 MPa or less, or 15 MPa or less, or 10 MPa or less. It should be noted that in one embodiment, the pressure of the inflow into the pressure reduction zone is substantially equal to the pressure of the mixture within the pressure reduction zone.

[0162] In one embodiment, the content of the second component in the inflow into the pressure reduction zone is 15 to 90% by mass, and / or an additional polymer that is cooler than the temperature of the mixture is added to the mixture after it has passed through the pressure reduction zone in the kneading step, and the mixture is cooled.

[0163] In a specific embodiment, the content of the second component in the inflow into the pressure reduction zone is 15 to 90% by mass, the pressure of the inflow into the pressure reduction zone is 0.5 to 20 MPa, and the ratio of the pressure of the outflow from the pressure reduction zone to the pressure of the inflow into the pressure reduction zone is 0.2 or less.

[0164] In a specific embodiment, the pressure of the inflow into the pressure reduction zone is 0.5 to 20 MPa, the ratio of the pressure of the outflow from the pressure reduction zone to the pressure of the inflow into the pressure reduction zone is 0.2 or less, and in the kneading step, an additional polymer that is cooler than the temperature of the mixture is added to the mixture after it has passed through the pressure reduction zone, and the mixture is cooled.

[0165] Refer to Figure 2 , in the second embodiment, the extruder 200 includes a kneading zone 201 and optionally may include a melting zone 202. For example, in the method of the second embodiment, before the kneading step in the kneading zone 201, it may further include a step of melting the first component a1 in the melting zone 202 and adding the second component a2 to the resulting melt to obtain a premix, and the premix may be supplied to the kneading zone 201. In conventional kneading using an extruder, strong shear is applied to the mixture in the initial melting zone. Therefore, when the second component is added to the molten resin from the addition port (side feeder) after the resin as the first component has passed through the melting zone, thermal degradation of the second component can be suppressed. The mixture is kneaded in the kneading zone 201 and taken out in the form of the resin composition b.

[0166] The kneading zone 201 in the second embodiment includes a pressure reduction zone D1. It should be noted that in Figure 2An example in which there is one pressure reduction zone D1 is shown, but in the second embodiment, the number of pressure reduction zones can be selected according to the purpose, and in one mode, it is 1 or more, or 2 or more, or 3 or more, and in one mode, it is 10 or less, or 5 or less.

[0167] In one mode, the pressure reduction zone in the second embodiment can be the narrow gap zone described in the first embodiment. The barrel gap of this narrow gap zone can be the same as that exemplified in the first embodiment. The pressure reduction zone can be formed by adjusting one or more selected from the group consisting of the zone length / barrel inner diameter ratio, the mixture filling rate, the temperature, the pressure, the screw rotation speed, the feed rate, the resin composition, and the space volume ratio of the present disclosure.

[0168] <<Third Embodiment>>

[0169] Figure 3 It is a diagram for explaining the steps of the method for manufacturing the resin composition of the third embodiment. The method of the third embodiment has the following characteristics. Except for this characteristic, one or more of the above-exemplified characteristics for the first or second embodiment can be combined.

[0170] Refer to Figure 3 In the third embodiment, the extruder 300 includes a kneading zone 301 and optionally may include a melting zone 302. For example, in the method of the third embodiment, before the kneading step in the kneading zone 301, it may further include a step of melting the first component a1 in the melting zone 202 and adding the second component a2 to the obtained melt, for example, through side feeding, to obtain a premix, and the premix can be supplied to the kneading zone 301. From the aspect of suppressing the thermal deterioration of the second component, such an addition method is preferred. The mixture is kneaded in the kneading zone 301 and taken out in the form of the resin composition b.

[0171] In one mode, the kneading zone 301 includes a plurality of high-pressure zones H1, H2, H3 with a pressure of 0.1 MPa or more. Figure 3 An example in which there are 3 high-pressure zones is shown, but the number of high-pressure zones in the kneading zone can be selected according to the purpose, and for example, it can be 2 or more, or 3 or more, and for example, it can be 10 or less, or 5 or less.

[0172] Regarding the ratio [P1 / P2] of the pressure [P1] (hereinafter also simply referred to as [P1]) of the highest-pressure region, which has the maximum pressure among a plurality of high-pressure regions H1, H2, and H3, to the average value [P2] of the pressures of the high-pressure regions other than the highest-pressure region, from the aspect of favorably performing the refinement of the second component, in one mode, it is greater than 1, or 1.5 or more, or 2 or more, and from the aspect of suppressing damage to the second component, in one mode, it is 100 or less, or 50 or less, or 20 or less. It should be noted that regarding the above average value [P2], if the corresponding region is one, it refers to the pressure value of that region, and if the corresponding region is two or more, it refers to the arithmetic mean of the pressure values of those regions.

[0173] Regarding the ratio [P1 / P3] of [P1] to the pressure [P3] of each region of the high-pressure regions other than the highest-pressure region, from the aspect of favorably performing the refinement of the second component, in one mode, it is greater than 1, or 1.5 or more, or 2 or more, and from the aspect of suppressing damage to the second component, in one mode, it is 100 or less, or 50 or less, or 20 or less.

[0174] [P1] is 0.5 MPa or more in one mode, preferably 1 MPa or more, or 2 MPa or more, and preferably 20 MPa or less, or 15 MPa or less, or 10 MPa or less.

[0175] [P2] is preferably 0.1 MPa or more, or 0.3 MPa or more, or 0.5 MPa or more, and preferably 20 MPa or less, or 15 MPa or less, or 10 MPa or less.

[0176] [P3] is preferably 0.1 MPa or more, or 0.3 MPa or more, or 0.5 MPa or more, and preferably 20 MPa or less, or 15 MPa or less, or 10 MPa or less.

[0177] Regarding the ratio of the region length / cylinder inner diameter ratio of each region of a plurality of high-pressure regions, from the aspect of favorably performing the refinement of the second component, in one mode, it is 1 or more, or 2 or more, or 4 or more, and from the aspect of suppressing damage to the second component, in one mode, it is 30 or less, or 20 or less, or 15 or less.

[0178] Regarding the ratio of the region length / cylinder inner diameter ratio of the highest-pressure region to the region length / cylinder inner diameter ratio of each region of the high-pressure regions other than the highest-pressure region, from the aspect of favorably performing the refinement of the second component, in one mode, it is 1 or more, or 2 or more, or 4 or more, and from the aspect of suppressing damage to the second component, in one mode, it is 30 or less, or 20 or less, or 15 or less.

[0179] Regarding the pressure in the highest pressure zone, from the aspect of well refining the second component, in one mode it is 0.3 MPa or more, or 0.5 MPa or more, or 1 MPa or more, and from the aspect of suppressing damage to the second component, in one mode it is 50 MPa or less, or 20 MPa or less, or 15 MPa or less.

[0180] <<Other zones>>

[0181] Refer to Figures 1 to 3 , the kneading zones 101, 201, 301 may have a dispersion mixing zone and a distributive mixing zone. The narrow gap zones N1, N2, N3, the pressure reduction zone D1, and the high pressure zones H1, H2, H3 are dispersion mixing zones. On the other hand, each of the other zones 11, 12, 13, 14, 21, 22, 31, 32, 33, 34 may be a dispersion mixing zone or a distributive mixing zone. The kneading conditions of the other zones can be arbitrarily designed to be the same or different from each other as needed. In a preferred mode, the most downstream zone of the kneading zone is the other zone (for example Figures 1 to 3 the other zones 14, 22, 24), preferably a distributive mixing zone.

[0182] <<Addition of additional polymer>>

[0183] Refer to Figures 1 to 3 , in the method of Mode A, in the kneading zones 101, 201, 301, an additional polymer of the same or different type as the polymer in the mixture, preferably of the same type, can be added to the mixture (for example, side feeding). In a representative mode, the addition position of the additional polymer can be downstream of all the narrow gap zones N1, N2, N3 of the kneading zone 101, downstream of the pressure reduction zone D1 of the kneading zone 201, or downstream of all the high pressure zones H1, H2, H3 of the kneading zone 301.

[0184] The addition amount of the additional polymer can be determined according to kneading conditions, the desired concentration of the second component of the resin composition, etc. For example, it can be 10 parts by mass or more, or 20 parts by mass or more, or 30 parts by mass or more, or 50 parts by mass or more with respect to 100 parts by mass of the mixture, and can be 1000 parts by mass or less, or 500 parts by mass or less, or 400 parts by mass or less, or 300 parts by mass or less. In one embodiment, the concentration of the second component of the mixture before adding the additional polymer can be 10% by mass or more, or 15% by mass or more, or 20% by mass or more, or 25% by mass or more, or 30% by mass or more, and / or 90% by mass or less, or 80% by mass or less, or 70% by mass or less, or 60% by mass or less, or 50% by mass or less, and the concentration of the second component of the mixture after adding the additional polymer (equal to the concentration of the second component in the resin composition in one embodiment) can be 1% by mass or more, or 2% by mass or more, or 3% by mass or more, or 5% by mass or more, and / or 50% by mass or less, or 40% by mass or less, or 30% by mass or less, or 20% by mass or less.

[0185] (Based on the cooling of the additional polymer)

[0186] The additional polymer can be at a lower temperature than the mixture. That is, in the kneading process, the additional polymer at a lower temperature than the mixture can be added to the mixture after passing through all of the plurality of narrow gap regions of the first embodiment, or the pressure reduction region of the second embodiment (in the case where there are a plurality, all of them in one embodiment), or all of the plurality of high-pressure regions of the third embodiment to cool the mixture. Regarding the temperature of the additional polymer added for cooling, in one embodiment, it is 0°C or more, or 10°C or more, or 20°C or more, and in one embodiment, it is 300°C or less, or 200°C or less, or 100°C or less, or 50°C or less. Regarding the temperature of the mixture to which the additional polymer is added, in one embodiment, it is 100°C or more, or 150°C or more, or 200°C or more, and in one embodiment, it is 450°C or less, or 400°C or less, or 350°C or less.

[0187] (<Change in flexural modulus>)

[0188] In the method of Mode A, the rate of increase in the flexural modulus per unit mass of each of the plurality of high-load zones (i.e., the ratio of the flexural modulus of the effluent flowing out of each zone to the flexural modulus of the influent flowing into each zone) is greater than the maximum value of the rate of increase in the flexural modulus per unit mass of the zones other than the high-load zones (i.e., the ratio of the flexural modulus of the effluent flowing out of each zone to the flexural modulus of the influent flowing into each zone). In this case, the effect of increasing the flexural modulus in each high-load zone is good. On the other hand, in other zones, damage to the second component can be suppressed.

[0189] <<Change in Thixotropy Index>>

[0190] In the method of Mode A, regarding the ratio of the thixotropy index of the effluent flowing out of the kneading zone to the thixotropy index of the influent flowing into the kneading zone, from the aspect of uniform microdispersion of the second component based on the kneading zone, it is preferably 1 or more, or 2 or more, or 3 or more. From the aspect of suppressing damage to the second component, it is preferably 100 or less, or 50 or less, or 10 or less.

[0191] [Mode B]

[0192] The method of Mode B of the present disclosure includes a dispersion mixing step of dispersing and mixing a first component and a second component in a dispersion mixing zone of an extruder. The method of Mode B has the following characteristics. Except for these characteristics, one or more of the above-exemplified characteristics of Mode A can be combined. In one mode, the dispersion mixing zone of Mode B may include the high-load zone of Mode A (more specifically, a narrow clearance zone, a pressure reduction zone, or a high-pressure zone).

[0193] [1] A method for manufacturing a resin composition containing a first component and a second component, wherein,

[0194] The above method includes a dispersion mixing step of dispersing and mixing the first component and the second component in a dispersion mixing zone of an extruder,

[0195] The above dispersion mixing zone includes a first dispersion mixing zone and a second dispersion mixing zone, and the first dispersion mixing zone and the second dispersion mixing zone are different from each other in one or more selected from the group consisting of the ratio of zone length to barrel inner diameter, mixture filling rate, temperature, pressure, and space volume ratio,

[0196] The increment [E1] of the tensile elongation of the effluent flowing out of the above first dispersion mixing zone with respect to the tensile elongation of the influent flowing into the above first dispersion mixing zone and the increment [E2] of the tensile elongation of the effluent flowing out of the above second dispersion mixing zone with respect to the tensile elongation of the influent flowing into the above second dispersion mixing zone satisfy the relationship [E1] > [E2].

[0197] The increment [M1] of the flexural modulus of the effluent flowing out from the above-mentioned first dispersion mixing zone with respect to the flexural modulus of the influent flowing into the above-mentioned first dispersion mixing zone and the increment [M2] of the flexural modulus of the effluent flowing out from the above-mentioned second dispersion mixing zone with respect to the flexural modulus of the influent flowing into the above-mentioned second dispersion mixing zone satisfy the relationship of [M1]<[M2].

[0198] [2] The method according to the above-mentioned mode 1, wherein the above-mentioned first dispersion mixing zone and the above-mentioned second dispersion mixing zone are directly connected in such a way that the above-mentioned first dispersion mixing zone is on the upstream side.

[0199] [3] The method according to the above-mentioned mode 1, wherein the above-mentioned first dispersion mixing zone and the above-mentioned second dispersion mixing zone are directly connected in such a way that the above-mentioned second dispersion mixing zone is on the upstream side.

[0200] [4] The method according to any one of the above-mentioned modes 1 to 3, wherein,

[0201] The above-mentioned second component contains organic fibers, and the mass ratio of the component with a fiber diameter of 50 μm or more in the organic fibers in the influent flowing into the above-mentioned first dispersion mixing zone is 10% to 90%,

[0202] The ratio (1b / 1a) of the mass ratio (1b) of the component with a fiber diameter of 50 μm or more in the organic fibers in the effluent flowing out from the above-mentioned first dispersion mixing zone to the mass ratio (1a) of the component with a fiber diameter of 50 μm or more in the organic fibers in the influent flowing into the above-mentioned first dispersion mixing zone is 0 to 0.6,

[0203] The ratio (2b / 2a) of the mass ratio (2b) of the component with a fiber diameter of 50 μm or more in the organic fibers in the effluent flowing out from the above-mentioned second dispersion mixing zone to the mass ratio (2a) of the component with a fiber diameter of 50 μm or more in the organic fibers in the influent flowing into the above-mentioned second dispersion mixing zone is 0.6 to 1.

[0204] [5] The method according to any one of the above-mentioned modes 1 to 4, wherein the above-mentioned [E1] is 1% to 100%, the above-mentioned [E2] is 0% to 10%, the above-mentioned [M1] is 0 GPa to 1 GPa, the above-mentioned [M2] is 0.1 GPa to 20 GPa, the absolute value of the difference between the above-mentioned [E1] and [E2] is 0.1% to 100%, and the absolute value of the difference between the above-mentioned [M1] and [M2] is 0.1 GPa to 20 GPa.

[0205] [6] The method according to any one of the above-mentioned modes 1 to 5, wherein the ratio of the zone length to the barrel inner diameter of each of the above-mentioned first dispersion mixing zone and the above-mentioned second dispersion mixing zone is 1 to 30.

[0206] [7] The method according to any one of the above-described modes 1 to 6, wherein the mixture filling rate of each of the above-described first dispersion mixing zone and the above-described second dispersion mixing zone is 10% to 100%.

[0207] [8] The method according to any one of the above-described modes 1 to 7, wherein the temperature of each of the above-described first dispersion mixing zone and the above-described second dispersion mixing zone is 100°C to 400°C.

[0208] [9] The method according to any one of the above-described modes 1 to 8, wherein the pressure of the mixture in each of the above-described first dispersion mixing zone and the above-described second dispersion mixing zone is 0 MPa to 15 MPa.

[0209]

[10] A method for manufacturing a resin composition containing a first component and a second component, wherein,

[0210] The above method includes a dispersion mixing step of dispersing and mixing the first component and the second component in a dispersion mixing zone of an extruder,

[0211] In the above dispersion mixing zone, by making one or more selected from the group consisting of the ratio of the zone length to the barrel inner diameter, the mixture filling rate, the temperature, the pressure, and the space volume ratio different in the barrel length direction, the traveling length l (mm) of the mixture in the barrel is divided by the barrel inner diameter d (mm) to obtain l / d, and the ratio [ΔE / ΔM] of the change amount ΔE (%) of the tensile elongation rate per unit l / d to the change amount ΔM (GPa) of the flexural modulus per unit l / d changes in the barrel length direction.

[0212]

[11] The method according to the above mode 10, wherein the ratio [ΔE / ΔM] gradually decreases from the upstream side to the downstream side of the barrel.

[0213]

[12] The method according to the above mode 10, wherein the ratio [ΔE / ΔM] gradually increases from the upstream side to the downstream side of the barrel.

[0214]

[13] The method according to any one of the above-described modes 1 to 12, wherein the second component contains organic fibers, preferably contains cellulose fibers, and the organic fibers in the resin composition have an average fiber diameter of 1000 nm or less and an average fiber length / average fiber diameter ratio of 30 or more.

[0215]

[14] The method according to any one of the above-described modes 1 to 13, wherein before the above dispersion mixing step, a step of adding the second component to the melt of the first component to obtain a premix is further included, and the premix is supplied to the above dispersion mixing zone.

[0216] In the method of Mode B, in the dispersion mixing zone, there are provided a region that mainly increases the tensile elongation rate (also referred to as the tensile elongation rate increasing region in the present disclosure) and a region that mainly increases the flexural modulus (also referred to as the flexural modulus increasing region in the present disclosure) in the tensile elongation rate and flexural modulus of the mixture. In the tensile elongation rate increasing region, the coarse agglomerates of the second component are pulverized, whereby the tensile elongation rate of the mixture can be increased. On the other hand, the pulverization of the coarse agglomerates contributes little to increasing the flexural modulus (i.e., rigidity) of the mixture. On the other hand, in the flexural modulus increasing region, the second component is finely dispersed in the first component, whereby the flexural modulus of the mixture can be increased. On the other hand, the fine dispersion contributes little to increasing the tensile elongation rate of the mixture.

[0217] In the method of Mode B, instead of increasing the tensile elongation rate and the flexural modulus simultaneously, one of the tensile elongation rate and the flexural modulus is mainly increased in each of the tensile elongation rate increasing region and the flexural modulus increasing region. Surprisingly, according to the resin composition obtained through such treatment, compared with the resin composition obtained through the treatment of increasing the tensile elongation rate and the flexural modulus simultaneously, the tensile elongation rate and the flexural modulus can be balanced at a high level and stably. The above advantages can become significant when the second component contains organic fibers, particularly cellulose fibers.

[0218] Mode B more specifically includes the following first and second embodiments.

[0219] <<First Embodiment>>

[0220] Figure 4 is a diagram for explaining the steps of the manufacturing method of the resin composition of the first embodiment, Figure 5 is a diagram for explaining the change behavior of the tensile elongation rate and the flexural modulus in the method of the first embodiment. Refer to Figure 4, in the first embodiment, the extruder 400 has a dispersion mixing zone 401. The extruder 400 may further have a distributive mixing zone 402. The extruder 400 may further have a melting zone 403 upstream of the dispersion mixing zone 401 and / or a melting zone 404 downstream of the dispersion mixing zone 401. For example, the method of the present disclosure may further include a step of melting the first component a1 in the melting zone 403 and adding the second component a2 to the resulting melt to obtain a premix before the dispersion mixing step in the dispersion mixing zone 401, and the premix may be supplied to the dispersion mixing zone 401. In conventional kneading using an extruder, strong shear is applied to the mixture in the initial melting zone. Therefore, when the second component is added to the molten first component from the addition port (side feeder) after the resin has passed through the melting zone, thermal degradation of the second component can be suppressed. The mixture is subjected to dispersion mixing and optionally distributive mixing in the extruder 400 and taken out in the form of the resin composition b.

[0221] In addition, in the method of Mode B, a step of adding an additional polymer that is the same as or different from the first component in the dispersion mixing product, preferably the same, to the dispersion mixing product to obtain an additional polymer mixture is further included after the dispersion mixing step and before the distributive mixing step, and the additional polymer mixture may be supplied to the distributive mixing zone. For example, an additional polymer (e.g., by side feeding the additional polymer in the Figure 4 melting zone 404) may be added to the effluent flowing out from the dispersion mixing zone 401 and then supplied to the distributive mixing zone 402. The addition amount of the additional polymer can be determined according to kneading conditions, the desired concentration of the second component of the resin composition, etc. For example, it may be 10 parts by mass or more, or 20 parts by mass or more, or 30 parts by mass or more, or 50 parts by mass or more, and may be 1000 parts by mass or less, or 500 parts by mass or less, or 400 parts by mass or less, or 300 parts by mass or less, relative to 100 parts by mass of the dispersion mixing product. In one mode, the concentration of the second component in the dispersion mixing product may be 10% by mass or more, or 20% by mass or more, or 25% by mass or more, or 30% by mass or more, and / or 80% by mass or less, or 70% by mass or less, or 60% by mass or less, or 50% by mass or less, and the concentration of the second component in the additional polymer mixture (equal to the concentration of the second component in the resin composition in one mode) may be 1% by mass or more, or 2% by mass or more, or 3% by mass or more, or 5% by mass or more, and / or 50% by mass or less, or 40% by mass or less, or 30% by mass or less, or 20% by mass or less.

[0222] (Based on the cooling of the additional polymer)

[0223] The additional polymer can be at a lower temperature than the temperature of the dispersion mixed product, whereby the dispersion mixed product can be cooled. Regarding the temperature of the additional polymer added for cooling, in one embodiment, it is 0°C or higher, or 10°C or higher, or 20°C or higher, and in one embodiment, it is 300°C or lower, or 200°C or lower, or 100°C or lower, or 50°C or lower. Regarding the temperature of the dispersion mixed product to which the additional polymer is added, in one embodiment, it is 100°C or higher, or 150°C or higher, or 200°C or higher, and in one embodiment, it is 450°C or lower, or 400°C or lower, or 350°C or lower.

[0224] The dispersion mixing zone 401 includes a first dispersion mixing zone 41 and a second dispersion mixing zone 42 with different processing conditions. In one embodiment, the first dispersion mixing zone 41 and the second dispersion mixing zone 42 are directly connected to each other. In one embodiment, an additional dispersion mixing zone may exist upstream of the first dispersion mixing zone 41, between the first dispersion mixing zone 41 and the second dispersion mixing zone 42, and / or downstream of the second dispersion mixing zone 42. For example, the following configuration can be exemplified: A third dispersion mixing zone (not shown), which is the same as or different from the first dispersion mixing zone 41 or the second dispersion mixing zone 42, is arranged downstream of the second dispersion mixing zone 42, and the effluent flowing out from the third dispersion mixing zone is recovered in the form of the resin composition b.

[0225] In one embodiment, the processing conditions are one or more selected from the group consisting of the ratio of zone length to barrel inner diameter, mixture filling rate, temperature, pressure, and space volume ratio.

[0226] The above-mentioned zone length is the total length of the screw elements constituting the dispersion mixing zone and the distributive mixing zone, and depends on the screw configuration.

[0227] The above-mentioned mixture filling rate is the ratio of the actual filling amount (volume basis) of the mixture to the space volume of the extruder. After suddenly stopping the rotation of the screw and the raw material supply, the screw is pulled out, the mixture adhering to the screw surface is collected and measured, divided by the density of the mixture to calculate the volume filled with the mixture, and then the volume filled with the mixture is divided by the following-mentioned space volume to calculate the mixture filling rate. The mixture filling rate depends on the screw configuration and the extrusion conditions.

[0228] Regarding the above-mentioned space volume ratio, the space volume is calculated by subtracting the screw volume (the sum of the element volume and the shaft volume) from the barrel volume of the extruder, and the space volume ratio is calculated by dividing the space volume by the barrel volume. The space volume ratio depends on the screw configuration.

[0229] Refer to Figure 4 and Figure 5, the increment [E1] of the tensile elongation of the effluent 41b flowing out from the first dispersion mixing zone relative to the tensile elongation of the influent 41a flowing into the first dispersion mixing zone and the increment [E2] of the tensile elongation of the effluent 42b flowing out from the second dispersion mixing zone relative to the tensile elongation of the influent 42a flowing into the second dispersion mixing zone satisfy the relationship [E1] > [E2]. In addition, the increment [M1] of the flexural modulus of the effluent 41b flowing out from the first dispersion mixing zone relative to the flexural modulus of the influent 41a flowing into the first dispersion mixing zone and the increment [M2] of the flexural modulus of the effluent 42b flowing out from the second dispersion mixing zone relative to the flexural modulus of the influent 42a flowing into the second dispersion mixing zone satisfy the relationship [M1] < [M2]. That is, the first dispersion mixing zone is a region where the tensile elongation is increased, and the second dispersion mixing zone is a region where the flexural modulus is increased.

[0230] In one mode, as Figure 4 shown, the first dispersion mixing zone 41 and the second dispersion mixing zone 42 are connected in such a way that the first dispersion mixing zone 41 is on the upstream side (directly connected in one mode). Such a configuration is advantageous in further increasing the elastic modulus.

[0231] On the other hand, in another mode, the first and second dispersion mixing zones can be connected in such a way that the second dispersion mixing zone is on the upstream side (directly connected in one mode). Such a configuration is advantageous in further increasing the elongation.

[0232] It should be noted that the influent flowing into each zone or the effluent flowing out from each zone only needs to be a mixture flowing into or out from each zone. For example, the effluent is not limited to the case where a discharge flow path for discharging to the outside of the extruder is provided in the extrusion mechanism.

[0233] In one mode where the second component contains organic fibers, the mass ratio of the component with a fiber diameter of 50 μm or more in the organic fibers in the influent 41a flowing into the first dispersion mixing zone is preferably 10% or more, or 20% or more, or 30% or more, or 40% or more, and preferably 90% or less, or 80% or less, or 70% or less, or 60% or less. That is, the influent 41a can contain a considerable amount of coarse particles.

[0234] In one mode, the ratio (1b / 1a) of the mass ratio (1b) of the components with a fiber diameter of 50 μm or more in the organic fibers in the effluent 41b flowing out from the first dispersion mixing zone to the mass ratio (1a) of the components with a fiber diameter of 50 μm or more in the organic fibers in the influent 41a flowing into the first dispersion mixing zone is preferably 0 or more, or 0.1 or more, or 0.2 or more, and preferably 0.6 or less, or 0.5 or less, or 0.3 or less. In this case, in the first dispersion mixing zone 41, the coarse particles are crushed, and the coarse particles in the effluent 41b are significantly reduced.

[0235] In one mode, the ratio (2b / 2a) of the mass ratio (2b) of the components with a fiber diameter of 50 μm or more in the organic fibers in the effluent 42b flowing out from the second dispersion mixing zone to the mass ratio (2a) of the components with a fiber diameter of 50 μm or more in the organic fibers in the influent 42a flowing into the second dispersion mixing zone is preferably 0.6 or more, or 0.7 or more, or 0.8 or more, and preferably 1 or less, or 0.9 or less. In this case, in the second dispersion mixing zone 42, microdispersion is performed. On the other hand, the reduction of the coarse particles from the influent 42a to the effluent 42b is extremely small. It should be noted that in the present disclosure, when both of the above mass ratios (2a) and (2b) are 0%, the above ratio (2b / 2a) is treated as 1.

[0236] In one mode, [E1] is preferably 1% or more, or 2% or more, or 3% or more, and preferably 100% or less, or 50% or less, or 30% or less, [E2] is preferably 0% or more, and preferably 10% or less, or 5% or less, or 3% or less, [M1] is preferably 0 GPa or more, or 0.1 GPa or more, or 0.3 GPa or more, and preferably 1 GPa or less, or 0.7 GPa or less, or 0.5 GPa or less, [M2] is preferably 0.1 GPa or more, or 0.5 GPa or more, or 1 GPa or more, and preferably 20 GPa or less, or 10 GPa or less, or 5 GPa or less, the absolute value of the difference between [E1] and [E2] is preferably 0.1% or more, or 1% or more, or 5% or more, and preferably 100% or less, or 50% or less, or 30% or less, the absolute value of the difference between [M1] and [M2] is preferably 0.1 GPa or more, or 0.5 GPa or more, or 1 GPa or more, and preferably 20 GPa or less, or 10 GPa or less, or 5 GPa or less.

[0237] In one mode, the ratio of the zone length to the barrel inner diameter of each of the first and second dispersion mixing zones is preferably 1 or more, or 3 or more, or 4 or more, and preferably 30 or less, or 20 or less, or 10 or less.

[0238] In one mode, the mixture filling rate of each of the first and second dispersion mixing zones is preferably 10% or more, or 50% or more, or 70% or more, and preferably 100% or less, or 99% or less, or 95% or less.

[0239] In one mode, the temperature of each of the first and second dispersion mixing zones is preferably 100°C or more, or 150°C or more, or 200°C or more, and preferably 400°C or less, or 350°C or less, or 300°C or less.

[0240] In one mode, the pressure of the mixture in each of the first and second dispersion mixing zones is preferably 0 MPa or more, or 0.1 MPa or more, or 0.3 MPa or more, or 1 MPa or more, and preferably 15 MPa or less, or 10 MPa or less, or 5 MPa or less, or 3 MPa or less.

[0241] In one mode, the space volume ratio of each of the first and second dispersion mixing zones is preferably 10% or more, or 20% or more, or 30% or more, and preferably 70% or less, or 60% or less, or 50% or less.

[0242] The resin composition that has been dispersion-mixed in the dispersion mixing zone 401 can be introduced into the distributive mixing zone 402 with or without passing through other zones (such as the melting zone 404) to further perform distributive mixing. The mixing conditions in the distributive mixing zone are not particularly limited. For example, distributive mixing can be performed by arbitrarily combining kneading disks such as forward kneading disks and neutral kneading disks.

[0243] <<Second Embodiment>

[0244] Figure 6 is a diagram for explaining the steps of the method for manufacturing the resin composition of the second embodiment, Figure 7 is a diagram for explaining the change behavior of the tensile elongation and flexural modulus in the method of the second embodiment. The method of the second embodiment has the following characteristics. Except for these characteristics, the same steps and conditions as those described above for the first embodiment can be appropriately adopted.

[0245] Refer to Figure 6, In the second embodiment, the extruder 600 has a dispersion mixing zone 601, and optionally may further have a distributive mixing zone 602, and may further have a melting zone 603 upstream of the dispersion mixing zone 601 and / or a melting zone 604 downstream of the dispersion mixing zone 601. For example, in the method of Mode B, before the dispersion mixing step in the dispersion mixing zone 601, it may further include a step of melting the first component a1 in the melting zone 603 and adding the second component a2 to the obtained melt to obtain a premix, and the premix may be supplied to the dispersion mixing zone 601. When the second component a2 is added to the molten first component from the addition port (side feeder) after the first component a1 has passed through the melting zone 603, thermal degradation of the second component can be suppressed, which is preferable. The mixture is subjected to dispersion mixing and optionally distributive mixing by the extruder 600 and taken out in the form of the resin composition b.

[0246] Refer to Figure 6 and Figure 7 , In the dispersion mixing zone 601, by making the processing conditions different from each other, the barrel travel length l of the mixture (i.e., the flow length in the barrel length direction L when the mixture flows in the dispersion mixing zone 601) (mm) is divided by the barrel inner diameter d (mm) to obtain l / d, and the ratio [ΔE / ΔM] of the change amount ΔE (%) of the tensile elongation rate per unit l / d to the change amount ΔM (GPa) of the flexural modulus per unit l / d is changed in the barrel length direction L. In one mode, the processing conditions are one or more selected from the group consisting of the zone length / barrel inner diameter ratio, the mixture filling rate, temperature, pressure, and the space volume ratio.

[0247] In one mode, the ratio [ΔE / ΔM] is gradually decreased from the upstream side to the downstream side of the barrel. In such a mode, the relatively upstream side of the barrel corresponds to the tensile elongation rate increasing region, and the relatively downstream side corresponds to the flexural modulus increasing region, which is advantageous in terms of obtaining a resin composition with higher rigidity. In this mode, from the upstream side to the downstream side of the barrel, as ΔE gradually decreases, ΔM may gradually increase. For example, from the inlet to the outlet of the dispersion mixing zone 601, ΔE may gradually decrease from a range of 0.1% or more, or 1% or more, or 10% or more and 300% or less, or 200% or less, or 100% or less to a range of 0.01% or more, or 0.1% or more, or 0.5% or more and 10% or less, or 5% or less, or 2% or less, and ΔM may gradually increase from a range of 0.001 GPa or more, or 0.01 GPa or more, or 0.05 GPa or more and 10 GPa or less, or 5 GPa or less, or 2 GPa or less to a range of 0.02 GPa or more, or 0.05 GPa or more, or 0.1 GPa or more and 50 GPa or less, or 10 GPa or less, or 5 GPa or less.

[0248] On the other hand, in another mode, the ratio [ΔE / ΔM] is made to gradually increase from the upstream side to the downstream side of the barrel. In such a mode, the relatively upstream side of the barrel corresponds to the flexural modulus increasing region, and the relatively downstream side corresponds to the tensile elongation increasing region, which is advantageous in terms of obtaining a resin composition with a higher elongation. In this mode, from the upstream side to the downstream side of the barrel, as ΔE gradually increases, ΔM can gradually decrease. For example, from the inlet to the outlet of the dispersion mixing zone, ΔE can gradually increase from a range of 0.01% or more, or 0.1% or more, or 0.5% or more, and 10% or less, or 5% or less, or 2% or less to a range of 0.1% or more, or 1% or more, or 10% or more, and 300% or less, or 200% or less, or 100% or less, and ΔM can gradually decrease from a range of 0.02 GPa or more, or 0.05 GPa or more, or 0.1 GPa or more, and 50 GPa or less, or 10 GPa or less, or 5 GPa or less to a range of 0.001 GPa or more, or 0.01 GPa or more, or 0.05 GPa or more, and 10 GPa or less, or 5 GPa or less, or 2 GPa or less.

[0249] "Mode C"

[0250] The method of Mode C of the present disclosure includes a dispersion mixing step of dispersing and mixing a first component and a second component in a dispersion mixing zone of an extruder to obtain a dispersion mixed product; and a distributive mixing step of distributively mixing at least the dispersion mixed product in a distributive mixing zone of the extruder to obtain a resin composition. The method of Mode C has the following characteristics, and for those other than this, one or more of the above-exemplified characteristics of Mode A can be combined. In one mode, the dispersion mixing zone of Mode C may include the high load zone of Mode A (more specifically, the narrow gap zone, the pressure reduction zone, or the high pressure zone).

[0251] [1] A method for manufacturing a resin composition containing a first component and a second component, wherein,

[0252] The above method includes the following steps:

[0253] A dispersion mixing step of dispersing and mixing a first component and a second component in a dispersion mixing zone of an extruder to obtain a dispersion mixed product; and

[0254] A distributive mixing step of distributively mixing at least the above dispersion mixed product in a distributive mixing zone of the extruder to obtain a resin composition,

[0255] The above-mentioned dispersion mixing zone and the above-mentioned distribution mixing zone are different from each other in at least one selected from the group consisting of the ratio of zone length to barrel inner diameter, mixture filling rate, temperature, pressure, and space volume ratio.

[0256] The increment [EA] of the tensile elongation rate of the effluent flowing out of the above-mentioned dispersion mixing zone relative to the tensile elongation rate of the influent flowing into the above-mentioned dispersion mixing zone and the increment [EB] of the tensile elongation rate of the effluent flowing out of the above-mentioned distribution mixing zone relative to the tensile elongation rate of the influent flowing into the above-mentioned distribution mixing zone satisfy the relationship [EA] > [EB].

[0257] The increment [MA] of the flexural modulus of the effluent flowing out of the above-mentioned dispersion mixing zone relative to the flexural modulus of the influent flowing into the above-mentioned dispersion mixing zone and the increment [MB] of the flexural modulus of the effluent flowing out of the above-mentioned distribution mixing zone relative to the flexural modulus of the influent flowing into the above-mentioned distribution mixing zone satisfy the relationship [MA] > [MB].

[0258] [2] The method according to the above-mentioned mode 1, wherein the above-mentioned [EA] is 1% to 100%, the above-mentioned [EB] is 0% to 10%, the above-mentioned [MA] is 0.1 GPa to 20 GPa, the above-mentioned [MB] is 0 GPa to 1 GPa, the difference ([EA] - [EB]) between [EA] and [EB] is 0.01% to 100%, and the difference ([MA] - [MB]) between [MA] and [MB] is 0.001 GPa to 10 GPa.

[0259] [3] The method according to the above-mentioned mode 1 or 2, wherein in the region where the ratio of zone length to barrel inner diameter of the above-mentioned dispersion mixing zone is 1 or more and the ratio of zone length to barrel inner diameter of the above-mentioned distribution mixing zone is 5 or less, the pressure of the mixture is 0.3 MPa or more.

[0260] [4] A method for manufacturing a resin composition containing a first component and a second component, wherein

[0261] The above-mentioned method includes the following steps:

[0262] A dispersion mixing step of dispersing and mixing cellulose fibers and a resin in a dispersion mixing zone of an extruder to obtain a dispersion mixing product; and

[0263] A distribution mixing step of distributing and mixing at least the above-mentioned dispersion mixing product in a distribution mixing zone of the extruder to obtain a resin composition.

[0264] The concentration [CA] of the second component in the dispersion mixing zone is 10% by mass to 90% by mass, the concentration [CB] of the second component in the distribution mixing zone is 1% by mass to 50% by mass, and the ratio [CA] / [CB] is 2 to 90.

[0265] [5] The method according to any one of the above-described methods 1 to 4, wherein the increment [TA] of the thixotropic index of the effluent flowing out from the above-described dispersion mixing zone with respect to the thixotropic index of the inflow flowing into the above-described dispersion mixing zone and the increment [TB] of the thixotropic index of the effluent flowing out from the above-described distribution mixing zone with respect to the thixotropic index of the inflow flowing into the above-described distribution mixing zone satisfy the relationship [TA] > [TB].

[0266] [6] The method according to the above-described method 5, wherein the above [TA] is greater than 0.01 and 10 or less, the above [TB] is 0.01 or more and less than 10, and the [TA] / [TB] ratio is greater than 1 and 100 or less.

[0267] [7] The method according to any one of the above-described methods 1 to 6, wherein the rate of improvement in the physical properties per unit mass of the second component in the mixture is greater in the distribution mixing zone than in the dispersion mixing zone.

[0268] [8] The method according to any one of the above-described methods 1 to 7, further comprising a step of adding an additional polymer to the dispersion mixing product after the above-described dispersion mixing step and before the above-described distribution mixing step to obtain an additional polymer mixture, and supplying the above-described additional polymer mixture to the above-described distribution mixing zone.

[0269] [9] The method according to any one of the above-described methods 1 to 8, wherein the above-described second component contains organic fibers, preferably cellulose fibers, and the organic fibers in the resin composition have an average fiber diameter of 1000 nm or less and an average fiber length / average fiber diameter ratio of 30 or more.

[0270] In the method of Mode C, the tensile elongation and flexural modulus are not increased by dispersion mixing and distribution mixing. Instead, during dispersion mixing, a relatively large force is applied to the second component to significantly increase the tensile elongation and flexural modulus of the mixture. On the other hand, during distribution mixing, the mixing conditions are relaxed in such a way that the force applied to the second component is minimized, and the increase in tensile elongation and flexural modulus is small, but damage to the second component can be avoided. In the molded body formed from the resin composition obtained through such a processing step, it is possible to unexpectedly achieve a high level and stable balance between tensile elongation and flexural modulus.

[0271] Figure 8 is a diagram for explaining the steps of a method for manufacturing a resin composition according to one mode of the present invention. Refer to Figure 8 , the extruder 800 has a dispersion mixing zone 801 and a distribution mixing zone 802. In a representative mode, as Figure 8As shown, a distribution mixing zone 802 is disposed on the downstream side of the dispersion mixing zone 801. The extruder 800 may further have a melting zone 803 on the upstream side of the dispersion mixing zone 801 and / or a melting zone 804 on the downstream side of the dispersion mixing zone 801 and on the upstream side of the distribution mixing zone 802.

[0272] The method of Mode C may further include, before the dispersion mixing step in the dispersion mixing zone 801, a step of melting the first component a1 in the melting zone 803 and adding the second component a2 to the obtained melt to obtain a premix, and the premix may be supplied to the dispersion mixing zone 801. In conventional kneading using an extruder, strong shear is applied to the mixture in the initial melting zone. Therefore, when the second component is added to the molten first component from an addition port (side feeder), thermal degradation of the second component can be suppressed. The mixture is subjected to dispersion mixing and distribution mixing using the extruder 800 and taken out in the form of the resin composition b.

[0273] In addition, the method of Mode C may further include, after the dispersion mixing step and before the distribution mixing step, a step of adding an additional polymer that is the same as or different from the first component in the dispersion mixing product, preferably the same, to the dispersion mixing product to obtain an additional polymer mixture, and the additional polymer mixture may be supplied to the distribution mixing zone. For example, an additional polymer (e.g., by side feeding of the additional polymer in the melting zone 804) may be added to the effluent flowing out from the dispersion mixing zone 801 and then supplied to the distribution mixing zone 802. The addition amount of the additional polymer may be determined according to kneading conditions, the desired concentration of the second component of the resin composition, etc. For example, it may be 10 parts by mass or more, or 20 parts by mass or more, or 30 parts by mass or more, or 50 parts by mass or more, and may be 1000 parts by mass or less, or 500 parts by mass or less, or 400 parts by mass or less, or 300 parts by mass or less, relative to 100 parts by mass of the dispersion mixing product. In one mode, the concentration of the second component in the dispersion mixing product may be 10 mass% or more, or 20 mass% or more, or 25 mass% or more, or 30 mass% or more, and / or 80 mass% or less, or 70 mass% or less, or 60 mass% or less, or 50 mass% or less, and the concentration of the second component in the additional polymer mixture (equal to the concentration of the second component in the resin composition in one mode) may be 1 mass% or more, or 2 mass% or more, or 3 mass% or more, or 5 mass% or more, and / or 50 mass% or less, or 40 mass% or less, or 30 mass% or less, or 20 mass% or less. Figure 8 (Cooling based on the additional polymer)

[0274] (Based on additional polymer cooling)

[0275] The additional polymer can be at a temperature lower than that of the dispersion mixing product, whereby the dispersion mixing product can be cooled. Regarding the temperature of the additional polymer added for cooling, in one embodiment, it is 0°C or higher, or 10°C or higher, or 20°C or higher, and in one embodiment, it is 300°C or lower, or 200°C or lower, or 100°C or lower, or 50°C or lower. Regarding the temperature of the dispersion mixing product to which the additional polymer is added, in one embodiment, it is 100°C or higher, or 150°C or higher, or 200°C or higher, and in one embodiment, it is 450°C or lower, or 400°C or lower, or 350°C or lower.

[0276] Mode C more specifically includes the following first and second embodiments.

[0277] 《First Embodiment (Processing Condition Control)》

[0278] Referring again to Figure 8 , in the first embodiment, the processing conditions of the dispersion mixing zone 801 and the distributive mixing zone 802 are different from each other. In one embodiment, the processing conditions are one or more selected from the group consisting of the ratio of zone length to barrel inner diameter, mixture filling rate, temperature, pressure, and space volume ratio.

[0279] The above-mentioned zone length is the total length of the screw elements constituting the dispersion mixing zone and the distributive mixing zone, and depends on the screw configuration.

[0280] The above-mentioned mixture filling rate is the ratio of the actual filling amount (volume basis) of the mixture to the space volume of the extruder. After suddenly stopping the rotation of the screw and the raw material supply, the screw is pulled out, the mixture adhering to the screw surface is collected and measured, divided by the density of the mixture to calculate the volume filled with the mixture, and then the volume filled with the mixture is divided by the following space volume to calculate the mixture filling rate. The mixture filling rate depends on the screw configuration and extrusion conditions.

[0281] Regarding the above-mentioned space volume ratio, the space volume is calculated by subtracting the screw volume (the sum of the element volume and the shaft volume) from the barrel volume of the extruder, and the space volume ratio is calculated by dividing the space volume by the barrel volume. The space volume ratio depends on the screw configuration.

[0282] In one mode, the increment [EA] of the tensile elongation rate of the effluent flowing out from the dispersion mixing zone 801 relative to the tensile elongation rate of the influent flowing into the dispersion mixing zone 801 and the increment [EB] of the tensile elongation rate of the effluent flowing out from the distribution mixing zone 802 relative to the tensile elongation rate of the influent flowing into the distribution mixing zone 802 satisfy the relationship [EA] > [EB]. The increment [MA] of the flexural modulus of the effluent flowing out from the dispersion mixing zone 801 relative to the flexural modulus of the influent flowing into the dispersion mixing zone 801 and the increment [MB] of the flexural modulus of the effluent flowing out from the distribution mixing zone 802 relative to the flexural modulus of the influent flowing into the distribution mixing zone 802 satisfy the relationship [MA] > [MB].

[0283] It should be noted that the influent flowing into each zone or the effluent flowing out from each zone can be a mixture flowing into each zone or flowing out from each zone. For example, the effluent is not limited to the case where a discharge flow path for discharging to the outside of the extruder is preset in the extrusion mechanism.

[0284] [EA] is preferably 1% or more, or 2% or more, or 3% or more, and preferably 100% or less, or 50% or less, or 30% or less. [EB] is preferably 0% or more, or 0.1% or more, or 0.5% or more, and preferably 10% or less, or 5% or less, or 3% or less.

[0285] [MA] is preferably 0.1 GPa or more, or 0.5 GPa or more, or 1 GPa or more, and preferably 20 GPa or less, or 10 GPa or less, or 5 GPa or less. [MB] is preferably 0 GPa or more, or 0.1 GPa or more, or 0.3 GPa or more, and preferably 1 GPa or less, or 0.7 GPa or less, or 0.5 GPa or less.

[0286] The difference ([EA] - [EB]) between [EA] and [EB] is preferably 0.01% or more, or 0.1% or more, or 1% or more, and preferably 100% or less, or 50% or less, or 10% or less.

[0287] The difference ([MA] - [MB]) between [MA] and [MB] is preferably 0.001 GPa or more, or 0.01 GPa or more, or 0.1 GPa or more, and preferably 10 GPa or less, or 5 GPa or less, or 1 GPa or less.

[0288] In one mode, the ratio of the zone length to the barrel inner diameter of each of the dispersion mixing zone 801 and the distribution mixing zone 802 is preferably 1 or more, or 3 or more, or 4 or more, and preferably 30 or less, or 20 or less, or 10 or less.

[0289] In one mode, the mixture filling rate of each zone of the dispersion mixing zone 801 and the distribution mixing zone 802 is preferably 10% or more, or 50% or more, or 70% or more, and preferably 100% or less, or 99% or less, or 95% or less.

[0290] In one mode, the temperature of each zone of the dispersion mixing zone 801 and the distribution mixing zone 802 is preferably 100 °C or more, or 150 °C or more, or 200 °C or more, and preferably 400 °C or less, or 350 °C or less, or 300 °C or less.

[0291] In one mode, the pressure of the mixture to be processed in each zone of the dispersion mixing zone 801 and the distribution mixing zone 802 is preferably 0 MPa or more, or 0.1 MPa or more, or 0.3 MPa or more, or 1 MPa or more, and preferably 15 MPa or less, or 10 MPa or less, or 5 MPa or less, or 3 MPa or less.

[0292] In one mode, the space volume ratio of each zone of the dispersion mixing zone 801 and the distribution mixing zone 802 is preferably 10% or more, or 20% or more, or 30% or more, and preferably 70% or less, or 60% or less, or 50% or less.

[0293] In one mode, in a region where the ratio of the zone length to the barrel inner diameter of the dispersion mixing zone 801 is 1 or more, or 2 or more, or 5 or more, and the ratio of the zone length to the barrel inner diameter of the distribution mixing zone 802 is 5 or less, or 2 or less, or 1 or less, the pressure of the mixture to be processed is 0.1 MPa or more, or 0.2 MPa or more, or 0.3 MPa or more, or 0.5 MPa or more, or 1 MPa or more, or 3 MPa or more, or 5 MPa or more, or 7 MPa or more. From the aspect of suppressing damage to the second component, the pressure of the mixture to be processed can be preferably 20 MPa or less, or 15 MPa or less, or 10 MPa or less. In this case, the region where a high pressure is applied to the mixture to be processed can be made wider in the dispersion mixing zone 801 and narrower in the distribution mixing zone 802. Thus, in the dispersion mixing zone 801, the second component can be finely divided well, and on the other hand, in the distribution mixing zone 802, the dispersion state of the second component in the first component can be improved while avoiding damage to the second component. The region where the pressure of the mixture to be processed is in the above range can be a region where the ratio of the zone length to the barrel inner diameter of the dispersion mixing zone 801 is 30 or less, or 20 or less, or 10 or less.

[0294] In one mode, in a region where the ratio of the zone length to the barrel inner diameter of the dispersion mixing zone is 1 or more and the ratio of the zone length to the barrel inner diameter of the distribution mixing zone is 5 or less, the pressure of the mixture to be processed is 0.3 MPa or more.

[0295] In one mode, from the aspect of improving the dispersion of the second component and forming more practical properties, the rate of improvement in the physical properties per unit mass of the second component in the mixture is greater in the distributive mixing zone than in the dispersive mixing zone. The rate of improvement in the physical properties in the dispersive mixing zone is the ratio of the physical properties of the effluent flowing out of the dispersive mixing zone to the physical properties of the influent flowing into the dispersive mixing zone, and the rate of improvement in the physical properties in the distributive mixing zone is the ratio of the physical properties of the effluent flowing out of the distributive mixing zone to the physical properties of the influent flowing into the distributive mixing zone. In one mode, the physical properties are selected from the tensile elongation rate and the flexural modulus. Regarding the ratio of the distributive mixing zone to the dispersive mixing zone with respect to the above-mentioned rate of improvement in physical properties, from the above-mentioned aspect, it is preferably greater than 1, or 1.2 or more, or 1.5 or more, and from the aspect of ease of designing the processing conditions, it can be, for example, 100 or less, or 10 or less, or 5 or less.

[0296] 《Second Embodiment (Concentration Control of the Second Component)》

[0297] Refer again to Figure 8 , in the second embodiment, the concentration [CA] of the second component in the dispersive mixing zone 801 is 10% by mass to 90% by mass, and the concentration [CB] of the second component in the distributive mixing zone 802 is 1% by mass to 50% by mass, and the ratio [CA] / [CB] is 2 to 90. For example, the concentration of the second component can be adjusted to the above range by a method of adding an additional polymer (for example, by side-feeding the additional polymer in Figure 8 the melting zone 804) to the effluent flowing out of the dispersive mixing zone 801 and then supplying it to the distributive mixing zone 802. By adjusting the concentration of the second component in the dispersive mixing zone 801 and the distributive mixing zone 802 as described above, it is possible to achieve both the refinement of the second component in the dispersive mixing zone 801 and the improvement of the dispersed state of the second component while avoiding damage to the second component in the distributive mixing zone 802.

[0298] Regarding the above-mentioned concentration [CA], from the aspect of achieving good refinement of the second component, in one mode, it is 10% by mass or more, or 15% by mass or more, or 20% by mass or more, and from the aspect of suppressing damage to the second component, in one mode, it is 90% by mass or less, or 80% by mass or less, or 70% by mass or less.

[0299] Regarding the above-mentioned concentration [CB], from the aspect of adjusting the concentration of the second component in the resin composition according to various uses, in one mode, it is 1% by mass or more, or 5% by mass or more, or 10% by mass or more, and from the aspect of suppressing damage to the second component, in one mode, it is 50% by mass or less, or 40% by mass or less, or 30% by mass or less.

[0300] Regarding the above ratio [CA] / [CB], from the aspect of promoting the refinement in the dispersion mixing process of the second component and suppressing the damage in the distributive mixing process, in one embodiment, it is 2 or more, or 3 or more, or 4 or more. From the aspect of avoiding the damage of the second component caused by excessive concentration [CA] or the limitation of the application use of the resin composition due to too small concentration [CB], in one embodiment, it is 90 or less, or 50 or less, or 10 or less.

[0301] 《Change of Thixotropy Index》

[0302] In one embodiment, the increment [TA] of the thixotropy index of the effluent flowing out from the dispersion mixing zone 801 with respect to the thixotropy index of the influent flowing into the dispersion mixing zone 801 and the increment [TB] of the thixotropy index of the effluent flowing out from the distributive mixing zone 802 with respect to the thixotropy index of the influent flowing into the distributive mixing zone 802 satisfy the relationship of [TA] > [TB]. The larger the increment [TA], the more the refinement of the second component proceeds in the dispersion mixing zone 801. The larger the increment [TB], the more the refinement of the second component proceeds in the distributive mixing zone 802. [TA] > [TB] is an index indicating that the dispersion mixing zone 801 preferentially proceeds with the refinement of the second component compared to the distributive mixing zone 802.

[0303] Regarding the ratio [TA] / [TB], from the aspect of preferentially refining the second component in the dispersion mixing zone 801, it is preferably greater than 1, or 2 or more, or 3 or more. From the aspect of suppressing the damage of the second component caused by excessive refinement of the second component in the dispersion mixing zone 801, it is preferably 100 or less, or 50 or less, or 10 or less. The method for measuring the thixotropy index is as described below.

[0304] The increment [TA] is preferably greater than 0.01 and 10 or less, or 0.05 - 5, or 0.1 - 2.

[0305] The increment [TB] is preferably 0.01 or more and less than 10, or 0.05 - 5, or 0.1 - 2.

[0306] [Extrusion of Resin Composition]

[0307] In the methods of Modes A to C, the resin composition b that exits the kneading zones 101, 201, 301 (for Mode A), the distributive mixing zones 402, 602 (for Mode B), or the distributive mixing zone 802 (for Mode C) can be extruded out of the extruder in a desired shape. For example, from the perspective of ease of post-processing and transportation, a pellet form is preferred. Preferred examples of the pellet form include round, oval, cylindrical, etc., which vary depending on the cutting method during the extrusion process. As the size of the round pellets, diameters of 1 mm or more and 3 mm or less can be exemplified. As the size of the cylindrical pellets, diameters of 1 mm or more and 3 mm or less, and lengths of 2 mm or more and 10 mm or less can be exemplified. Regarding the above diameters and lengths, it is preferably above the lower limit from the perspective of operational stability during extrusion, and preferably below the upper limit from the perspective of bite-in performance into the molding machine during post-processing.

[0308] [Manufacture of Molded Bodies]

[0309] The resin composition produced by the methods of Modes A to C can be formed into molded bodies in various forms such as film, sheet, fiber, plate, powder, three-dimensional structure, etc. As molding methods, injection molding, extrusion molding, foam molding, insert molding, in-mold coating molding, mold molding, etc. can be exemplified. For example, various extrusion molding methods are suitable for the molding of sheets, films, fibers, etc. The molding temperature can be appropriately selected according to the composition of the resin composition, etc. For example, it can be above the melting point of the resin used, or above the melting point + 20°C, or above the melting point + 30°C, and can be below the melting point + 90°C, or below the melting point + 80°C, or below the melting point + 70°C.

[0310] [Material Components of Resin Composition]

[0311] The present disclosure, particularly the resin composition produced by the methods of Modes A to C, contains a first component that is a polymer, and a second component that is an organic fiber and / or a polymer different from the first component. Regarding the polymer different from the first component, in one mode, it refers to a polymer having a different molecular structure and / or molecular weight from the first component. The polymer in the first component, the organic fiber in the second component, and the polymer in the second component can each be one type or two or more types. In one mode, regarding the polymer in the first component and the polymer in the second component, the molecular structure and / or molecular weight of at least one polymer constituting them are different from each other. Regarding the second component, in one mode, it is an organic fiber, in one mode, it is a polymer, and in one mode, it is a combination of an organic fiber and a polymer. As the material components used to manufacture the resin composition and thus contained in the resin composition, the following components can be exemplified.

[0312] <<First Component》

[0313] The first component is a polymer in one embodiment. The polymer can be appropriately selected according to the intended use of the resin composition. For example, it can be a crystalline thermoplastic resin having a melting point in the range of 100°C to 350°C, an amorphous thermoplastic resin having a glass transition point in the range of 100 to 250°C, etc. Examples of the polymer include polyolefin resins, polyamide resins, polyester resins, polyacetal resins, polyphenylene ether resins, polyphenylene sulfide resins, and mixtures of two or more of them. From the aspects of processability and cost, preferred examples include polyolefin resins, polyamide resins, polyester resins, polyacetal resins, etc. More preferred are polyamide resins, polyolefin resins, and polyacetal resins, and particularly preferred are polyamide resins and polyacetal resins. From the aspect of improving the heat resistance of the resin composition, the melting point of the thermoplastic resin (especially the crystalline resin) is preferably 140°C or higher, or 150°C or higher, or 160°C or higher, or 170°C or higher, or 180°C or higher, or 190°C or higher, or 200°C or higher, or 210°C or higher, 220°C or higher, or 230°C or higher, or 240°C or higher, or 245°C or higher, or 250°C or higher.

[0314] As the melting point of the thermoplastic resin, for example, for resins with a relatively low melting point (such as polyolefin resins), examples include 150°C to 190°C, or 160°C to 180°C. Additionally, for example, for resins with a relatively high melting point (such as polyamide resins), examples include 220°C to 350°C, or 230°C to 320°C.

[0315] In the present disclosure, the melting point refers to the peak temperature of the endothermic peak that appears when heating from 23°C at a heating rate of 10°C / minute using a differential scanning calorimetry device (DSC). When two or more endothermic peaks appear, it refers to the peak temperature of the endothermic peak on the highest temperature side. Additionally, in the present disclosure, regarding the glass transition point, as described above, it refers to the temperature obtained using a dynamic viscoelasticity measuring device.

[0316] The preferred polyolefin resin as the polymer is a polymer obtained by polymerizing olefins (such as α-olefins) or using olefins as monomer units. Specific examples of the polyolefin resin include: ethylene-based (co)polymers exemplified by low-density polyethylene (such as linear low-density polyethylene), high-density polyethylene, ultra-low-density polyethylene, ultra-high-molecular-weight polyethylene, etc.; polypropylene-based (co)polymers exemplified by polypropylene, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, etc., and α-olefin copolymers represented by ethylene-acrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-glycidyl methacrylate copolymer, etc.

[0317] Here, as the most preferred polyolefin resin, polypropylene can be cited. Particularly preferred is polypropylene having a melt flow rate (MFR) of 3 g / 10 minutes or more and 30 g / 10 minutes or less as measured according to ISO1133 at 230°C and a load of 21.2 N. The lower limit value of the MFR is more preferably 5 g / 10 minutes, further more preferably 6 g / 10 minutes, and most preferably 8 g / 10 minutes. In addition, the upper limit value is more preferably 25 g / 10 minutes, further more preferably 20 g / 10 minutes, and most preferably 18 g / 10 minutes. Regarding the MFR, it is preferably not higher than the above upper limit value from the aspect of improving the toughness of the composition, and preferably not lower than the above lower limit value from the aspect of the fluidity of the composition.

[0318] In addition, in order to improve the affinity with cellulose, an acid-modified polyolefin resin can also be appropriately used. As the acid at this time, it can be appropriately selected from maleic acid, fumaric acid, succinic acid, phthalic acid and their anhydrides, and polycarboxylic acids such as citric acid. Among these, maleic acid or its anhydride is preferred from the aspect of the ease of improving the modification rate. There is no particular limitation on the modification method, and it is usually a method of melt-kneading by heating to above the melting point in the presence or absence of a peroxide. As the polyolefin resin subjected to acid modification, all of the above polyolefin resins can be used, and polypropylene can be preferably used among them. The acid-modified polypropylene can be used alone, but in order to adjust the modification rate of the whole resin, it is more preferably used in combination with unmodified polypropylene. At this time, the proportion of the acid-modified polypropylene relative to all polypropylene is 0.5% by mass to 50% by mass. The more preferred lower limit is 1% by mass, further preferably 2% by mass, further more preferably 3% by mass, particularly preferably 4% by mass, and most preferably 5% by mass. In addition, the more preferred upper limit is 45% by mass, further preferably 40% by mass, further more preferably 35% by mass, particularly preferably 30% by mass, and most preferably 20% by mass. In order to maintain the interfacial strength between the first component and the second component (in one mode, the interfacial strength between the resin and cellulose), it is preferably above the lower limit, and in order to maintain the ductility of the resin, it is preferably below the upper limit.

[0319] Regarding the melt flow rate (MFR) of the acid-modified polypropylene measured according to ISO1133 at 230°C and a load of 21.2 N, in order to improve the affinity of the interface between the first component and the second component (for example, the interface between cellulose and resin), it is preferably 50 g / 10 minutes or more. The more preferred lower limit is 100 g / 10 minutes, further more preferably 150 g / 10 minutes, and most preferably 200 g / 10 minutes. The upper limit is not limited, and it is 500 g / 10 minutes from the aspect of maintaining mechanical strength. By making the MFR within this range, the advantage of being easily present at the interface between the first component and the second component (in one mode, the interface between cellulose and resin) can be enjoyed.

[0320] Examples of polyamide resins include: polyamide 6, polyamide 11, and polyamide 12 obtained by polycondensation of lactams; polyamide 6,6, polyamide 6,10, polyamide 6,11, polyamide 6,12, polyamide 6,T, polyamide 6,I, polyamide 9,T, polyamide 10,T, polyamide 2M5,T, polyamide MXD,6, polyamide 6,C, polyamide 2M5,C, and copolymers formed by copolymerizing them respectively. As an example, copolymers such as polyamide 6,T / 6,I can be cited. These are copolymers obtained from diamines such as 1,6-hexanediamine, 2-methyl-1,5-pentanediamine, 1,7-heptanediamine, 2-methyl-1,6-hexanediamine, 1,8-octanediamine, 2-methyl-1,7-heptanediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecylamine, and m-xylylenediamine, and dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, benzene-1,2-dicarboxylic acid, benzene-1,3-dicarboxylic acid, benzene-1,4-dicarboxylic acid, cyclohexane-1,3-dicarboxylic acid, and cyclohexane-1,4-dicarboxylic acid.

[0321] Among these polyamide resins, aliphatic polyamides such as polyamide 6, polyamide 11, polyamide 12, polyamide 6,6, polyamide 6,10, polyamide 6,11, and polyamide 6,12 are more preferred; and alicyclic polyamides such as polyamide 6,C and polyamide 2M5,C are more preferred.

[0322] The terminal carboxyl group concentration of the polyamide resin is not particularly limited, and can preferably be 20 μmol / g or more, or 25 μmol / g or more, and can preferably be 150 μmol / g or less, or 100 μmol / g or less.

[0323] The terminal amino group concentration of the polyamide resin can preferably be 20 μmol / g or more, or 30 μmol / g or more, and can preferably be 150 μmol / g or less, or 100 μmol / g or less.

[0324] The total concentration of the terminal amino group and the terminal carboxyl group of the polyamide resin is not particularly limited, and can preferably be 10 μmol / g or more, or 50 μmol / g or more, or 100 μmol / g or more, or 135 μmol / g or more. From the aspects of preventing viscosity reduction caused by too low resin molecular weight and suppressing burr generation during molding, it can preferably be 500 μmol / g or less, or 300 μmol / g or less, or 135 μmol / g or less, or 100 μmol / g or less.

[0325] The ratio of the amino terminal groups to the carboxyl terminal groups ([NH 2 / [COOH]) of the polyamide resin is preferably greater than 1.00, or 1.01 or more, or 1.05 or more, or 1.10 or more. There is no particular limitation on the upper limit of the ratio of the amino terminal groups. From the aspect of maintaining the hue of the resin composition well, it can be preferably 10,000 or less, or 1,000 or less, or 100 or less, or 10 or less.

[0326] As a method for adjusting the terminal group concentration of the polyamide resin, known methods can be used. For example, a method can be cited in which a terminal modifier that reacts with the terminal groups, such as a diamine compound, a monoamine compound, a dicarboxylic acid compound, a monocarboxylic acid compound, an acid anhydride, a monoisocyanate, a monoacyl halide, a monoester, or a monoalcohol, is added to the polymerization solution so that a predetermined terminal group concentration is achieved during the polymerization of the polyamide.

[0327] The concentrations of the amino terminal groups and the carboxyl terminal groups of the polyamide resin can be determined by 1 H-NMR based on the integral values of the characteristic signals corresponding to each terminal group. Specifically, the method described in Japanese Patent Laid-Open No. 7-228775 is recommended.

[0328] The intrinsic viscosity [η] of the polyamide resin measured in concentrated sulfuric acid at 30 °C is preferably 0.6 to 2.0 dL / g, more preferably 0.7 to 1.4 dL / g, further preferably 0.7 to 1.2 dL / g, and particularly preferably 0.7 to 1.0 dL / g. When using a polyamide having an intrinsic viscosity within the above range, advantages such as improving the in-mold fluidity during injection molding of the resin composition and improving the appearance of the molded sheet can be obtained.

[0329] In the present disclosure, the "intrinsic viscosity" has the same meaning as the viscosity generally referred to as the limiting viscosity, and can be measured, for example, by the methods described on pages 291 to 294 of Polymer Process Engineering (Prentice-Hall, Inc 1994).

[0330] As the polyester resin, one or more selected from polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene succinate (PBS), polybutylene succinate / adipate (PBSA), polybutylene terephthalate / adipate (PBAT), polyhydroxyalkanoate (PHA), polylactic acid (PLA), polyarylate (PAR), polycarbonate (PC), etc. can be used. As the polyester resin, PET, PBS, PBSA, PBT, and PEN are more preferably cited, and PBS, PBSA, and PBT are further preferably cited.

[0331] In addition, the polyester resin can freely change the end groups according to the monomer ratio during polymerization, the addition or non-addition of the end stabilizer, and its addition amount. The ratio of the carboxyl end groups to all end groups ([COOH] / [all end groups]) of the polyester resin is more preferably 0.30 to 0.95. The lower limit of the carboxyl end group ratio is more preferably 0.35, further more preferably 0.40, and most preferably 0.45. In addition, the upper limit of the carboxyl end group ratio is more preferably 0.90, further more preferably 0.85, and most preferably 0.80. Regarding the above carboxyl end group ratio, it is preferably 0.30 or more from the aspect of the dispersibility of cellulose in the composition, and preferably 0.95 or less from the aspect of the hue of the resulting composition.

[0332] As the polyacetal resin, it is usually a homopolyacetal using formaldehyde as a raw material, and a copolymer acetal containing trioxane as a main monomer and 1,3-dioxolane as a comonomer component. Both can be used, and the copolymer acetal can be preferably used from the aspect of thermal stability during processing. In particular, the amount of the structure derived from the comonomer component (such as 1,3-dioxolane) is more preferably in the range of 0.01 to 4 mol%. The lower limit of the amount of the structure derived from the comonomer component is preferably 0.05 mol%, more preferably 0.1 mol%, and further more preferably 0.2 mol%. In addition, the upper limit amount is preferably 3.5 mol%, further preferably 3.0 mol%, further more preferably 2.5 mol%, and most preferably 2.3 mol%.

[0333] From the aspect of thermal stability during extrusion processing and molding processing, the lower limit is preferably within the above range, and from the viewpoint of mechanical strength, the upper limit is preferably within the above range.

[0334] As a polymer, from the aspect of affinity for cellulose, for example, a polymer having a hydrophilic group (for example, one or more selected from a hydroxyl group, an amino group, and a carboxyl group) is particularly preferred. Preferred examples of the polymer having a hydrophilic group are one or more selected from the group consisting of an acid-modified polyolefin resin, a polyacetal resin, a polycarbonate resin, a polyamide resin, a polyester resin, a polyphenylene ether resin, and an acrylic resin. Among them, a polyamide resin and maleated polypropylene are preferred.

[0335] <<Second Component》

[0336] The second component is an organic fiber and / or a polymer. In one mode, the second component is dispersed in the first component by mixing with the first component, and compared with the case where the second component is absent, the physical properties of the resin composition can be improved (in one mode, one or more selected from the group consisting of tensile elongation, flexural modulus, coefficient of thermal expansion, and physical property stability, preferably all of these physical properties). In the resin composition, the amount of the second component relative to 100% by mass of the entire resin composition, or the amount of the second component relative to 100% by mass of the total of the first component and the second component is preferably 0.1% by mass or more, or 0.5% by mass or more, or 1% by mass or more, or 3% by mass or more, and preferably 30% by mass or less, or 25% by mass or less, or 20% by mass or less, or 15% by mass or less. When the amount of the second component is in the above range, it is preferred from the aspects of high tensile elongation, high flexural modulus, low coefficient of thermal expansion, and / or good physical property stability.

[0337] Preferred examples of the organic fiber and the polymer will be described below.

[0338] <Organic Fiber>

[0339] The organic fiber is a fiber made of an organic material. The organic fiber is a polymer fiber in one mode, a fiber having a hydrogen bond-forming structure (for example, an OH structure and / or an NH structure) in one mode, and one or more selected from the group consisting of natural fibers (for example, cellulose fiber, cellulose nanocrystal, chitin fiber, chitosan fiber, wool, etc.) and synthetic fibers (for example, aramid fiber, nylon fiber, acrylic fiber, polyester fiber, vinylon fiber, rayon fiber, polyurethane fiber, etc.) in one mode. In the present disclosure, the cellulose fiber means cellulose having an L / D of 30 or more, and the cellulose nanocrystal means cellulose having an average fiber diameter of 1000 nm or less and an L / D of less than 30. The organic fiber having a hydrogen bond-forming structure has a tendency to substantially aggregate due to hydrogen bonds, and according to the method of the present disclosure, even such an organic fiber can be finely dispersed well in the first component.

[0340] In the resin composition, the amount of the organic fiber is preferably 0.1% by mass or more, or 0.5% by mass or more, or 1% by mass or more, or 3% by mass or more, and preferably 30% by mass or less, or 25% by mass or less, or 20% by mass or less, or 15% by mass or less, based on 100% by mass of the entire resin composition. The amount of the organic fiber within the above range is preferable in terms of high tensile elongation, high flexural modulus, low coefficient of thermal expansion, and / or good physical property stability.

[0341] [Cellulose fiber]

[0342] In one aspect, the organic fiber contains or is a cellulose fiber. As raw materials for the cellulose fiber, natural cellulose fibers and regenerated cellulose fibers can be cited. As the natural cellulose fiber, wood pulp obtained from wood (broad-leaved tree or coniferous tree), non-wood pulp obtained from non-wood (bamboo, hemp fiber, bagasse, kenaf, cotton linter, etc.), and their refined pulp (refined cotton linter, etc.) can be used. As the non-wood pulp, cotton source pulp containing cotton linter pulp, hemp source pulp, bagasse source pulp, kenaf source pulp, bamboo source pulp, rice straw source pulp, etc. can be used. Regarding the cotton source pulp, hemp source pulp, bagasse source pulp, kenaf source pulp, bamboo source pulp, and rice straw source pulp, cellulose fibers obtained by subjecting raw materials such as lint cotton, cotton linter, hemp-based abaca (e.g., abaca produced in Ecuador or the Philippines), sisal, bagasse, kenaf, bamboo, and rice straw to refining processes such as delignification based on cooking treatment and bleaching processes can be cited as raw materials respectively.

[0343] In one aspect, the cellulose fiber is cellulose nanofiber. Regarding the cellulose nanofiber, for example, the above-mentioned pulp can be treated with hot water at 100°C or higher to hydrolyze and embrittle the hemicellulose part, and then fibrillated by a pulverization method using a high-pressure homogenizer, microfluidizer, ball mill, disk mill, etc.

[0344] Regarding the number-average fiber diameter of the cellulose nanofiber, in one aspect, it is 2 to 1000 nm, preferably 4 nm or more, or 5 nm or more, or 10 nm or more, or 15 nm or more, or 20 nm or more, or 50 nm or more, or 100 nm or more, and preferably 500 nm or less, or 450 nm or less, or 400 nm or less, or 350 nm or less, or 300 nm or less, or 250 nm or less, or 200 nm or less.

[0345] Regarding the number-average fiber length / number-average fiber diameter ratio (L / D) of cellulose nanofibers, in one embodiment, it can be 30 or more, or 50 or more, or 80 or more, or 100 or more, and in one embodiment, it can be 5000 or less, or 4000 or less, or 3000 or less.

[0346] In one embodiment, the number-average fiber diameter (D), number-average fiber length (L), and L / D ratio of the cellulose fibers of the present disclosure are values measured using a scanning electron microscope (SEM) according to the following steps. Replace the aqueous dispersion of cellulose fibers with tert-butanol, dilute it to 0.001 to 0.1% by mass, disperse it using a high-shear homogenizer (e.g., manufactured by IKA, trade name “ULTRA-TURRAX T18”) under the treatment conditions of a rotation speed of 15,000 rpm for 3 minutes, pour it onto a silicon substrate that has been osmium-evaporated, air-dry it, and use it as a measurement sample, and measure it using a high-resolution scanning electron microscope (SEM) to obtain the values. Specifically, in an observation field of view where the magnification has been adjusted in such a way that at least 100 fibrous substances are observed, measure the length (L) and fiber diameter (D) of 100 randomly selected fibrous substances, and calculate the ratio (L / D). For cellulose fibers, calculate the number-average value of the length (L), the number-average value of the fiber diameter (D), and the number-average value of the ratio (L / D).

[0347] It should be noted that regarding the length, fiber diameter, and L / D ratio of cellulose fibers in the resin composition and the molded article, the polymer component can be dissolved in an organic or inorganic solvent capable of dissolving the polymer component, the cellulose fibers can be separated, thoroughly washed with the above solvent, replaced with tert-butanol, a 0.001 to 0.1% by mass dispersion is prepared, redispersed using a high-shear homogenizer (e.g., manufactured by IKA, trade name “ULTRA-TURRAX T18”), and the redispersed product is used to perform the measurement using the above method.

[0348] Regarding the crystallinity of cellulose fibers, from the aspect of obtaining a resin composition with excellent heat resistance, mechanical strength, and dimensional stability, it is preferably 55% or more, or 60% or more, or 70% or more, or 80% or more. When the crystallinity is within this range, the mechanical properties (heat resistance, strength, dimensional stability) of the cellulose fibers themselves are high. Therefore, when the cellulose fibers are dispersed in a polymer, the resin composition tends to have high heat resistance, strength, and dimensional stability. A high crystallinity is preferred, but from a production aspect, the upper limit of preference is 99%.

[0349] Regarding the crystallinity mentioned herein, in the case where the cellulose fiber is cellulose I type crystal (natural cellulose source), it is determined by the following formula according to the Segal method from the diffraction pattern (2θ / deg. is 10 to 30) when the sample is measured by wide-angle X-ray diffraction.

[0350] Crystallinity (%) = ([Diffraction intensity of (200) plane due to 2θ / deg. = 22.5] - [Diffraction intensity of amorphous state due to 2θ / deg. = 18]) / [Diffraction intensity of (200) plane due to 2θ / deg. = 22.5] × 100

[0351] In addition, regarding the crystallinity, in the case where the cellulose fiber is cellulose II type crystal (regenerated cellulose source), it is determined by the following formula based on the absolute peak intensity h0 at 2θ = 12.6° of the (110) plane peak attributed to cellulose II type crystal in wide-angle X-ray diffraction and the peak intensity h1 from the baseline at this plane spacing.

[0352] Crystallinity (%) = h1 / h0 × 100

[0353] As crystal forms of cellulose, I type, II type, III type, IV type, etc. are known. Among them, especially I type and II type are common. III type and IV type can be obtained on a laboratory scale, but are not common on an industrial scale. As the cellulose fiber of the present disclosure, the structural mobility is relatively high. For the reason that a resin composition with a lower coefficient of linear expansion and more excellent strength and elongation at break during stretching and bending deformation can be obtained by dispersing the cellulose fiber in a resin, cellulose fibers containing cellulose I type crystal or cellulose II type crystal are preferred, and cellulose fibers containing cellulose I type crystal and having a crystallinity of 55% or more are more preferred.

[0354] In addition, the degree of polymerization of the cellulose fiber is preferably 100 or more, more preferably 150 or more, more preferably 200 or more, more preferably 300 or more, more preferably 400 or more, preferably 3500 or less, more preferably 3300 or less, more preferably 3200 or less, more preferably 3100 or less, more preferably 3000 or less.

[0355] From the aspects of processability and manifestation of mechanical properties, it is preferred that the degree of polymerization of the cellulose fiber is within the above range. From the aspect of processability, it is preferred that the degree of polymerization is not too high. From the aspect of manifestation of mechanical properties, it is preferred that it is not too low.

[0356] The degree of polymerization of the cellulose fiber refers to the average degree of polymerization measured by the specific viscosity method using a copper ethylenediamine solution as described in the confirmation test (3) of "Explanation of the 15th Revision of the Japanese Pharmacopoeia (published by Hirokawa Shoten)".

[0357] In one embodiment, the cellulose fiber has a weight-average molecular weight (Mw) of 100,000 or more, more preferably 200,000 or more. The ratio of the weight-average molecular weight to the number-average molecular weight (Mn) (Mw / Mn) is 6 or less, preferably 5.4 or less. A larger weight-average molecular weight means a smaller number of end groups of the cellulose molecules. In addition, the ratio of the weight-average molecular weight to the number-average molecular weight (Mw / Mn) represents the width of the molecular weight distribution. Therefore, the smaller the Mw / Mn, the smaller the number of ends of the cellulose molecules. Since the ends of the cellulose molecules are the starting points of thermal decomposition, particularly highly heat-resistant cellulose fibers and resin compositions containing cellulose fibers and resins can be obtained when not only the weight-average molecular weight of the cellulose molecules is large, but also the weight-average molecular weight is large and the molecular weight distribution width is narrow at the same time. Regarding the weight-average molecular weight (Mw) of the cellulose fiber, from the aspect of the ease of obtaining the cellulose raw material, it can be, for example, 600,000 or less, or 500,000 or less. Regarding the ratio of the weight-average molecular weight to the number-average molecular weight (Mn) (Mw / Mn), from the aspect of the ease of manufacturing the cellulose fiber, it can be, for example, 1.5 or more, or 2 or more. By selecting a cellulose raw material having an Mw corresponding to the purpose and appropriately performing physical treatment and / or chemical treatment on the cellulose raw material within an appropriate range, etc., the Mw can be controlled within the above range. For Mw / Mn, it can also be controlled within the above range by selecting a cellulose raw material having an Mw / Mn corresponding to the purpose and appropriately performing physical treatment and / or chemical treatment on the cellulose raw material within an appropriate range. In both the control of Mw and the control of Mw / Mn, as the above physical treatment, physical treatments such as applying mechanical forces such as impact, shearing, cutting, and friction based on a microfluidizer homogenizer, ball mill, disk mill, etc. for dry or wet grinding, a kneader, a homogeneous mixer, a high-pressure homogenizer, an ultrasonic device, etc. can be exemplified. As the above chemical treatment, cooking, bleaching, acid treatment, regeneration of cellulose, etc. can be exemplified.

[0358] The weight-average molecular weight and number-average molecular weight of the cellulose fiber mentioned here refer to the values obtained by dissolving the cellulose fiber in N,N-dimethylacetamide added with lithium chloride and then performing gel permeation chromatography using N,N-dimethylacetamide as the solvent.

[0359] As a method for controlling the degree of polymerization (i.e., average degree of polymerization) or molecular weight of the cellulose fiber, hydrolysis treatment, etc. can be cited. By hydrolysis treatment, the amorphous cellulose inside the cellulose is depolymerized, and the average degree of polymerization decreases. At the same time, in addition to the above amorphous cellulose, impurities such as hemicellulose and lignin are also removed by hydrolysis treatment, so that the fiber mass becomes porous inside. As a result, in a process such as a kneading process described later where mechanical shear force is applied to the cellulose, the cellulose is easily subjected to mechanical treatment and is easily refined.

[0360] In addition to hemicellulose, the alkali-soluble polysaccharides that cellulose fibers can contain also include β-cellulose and γ-cellulose. For those skilled in the art, the alkali-soluble polysaccharides can be understood as the components obtained in the form of the alkali-soluble part in the holocellulose obtained by solvent extraction and chlorine treatment of plants (such as wood) (that is, the components obtained by removing α-cellulose from the holocellulose). The alkali-soluble polysaccharides are polysaccharides containing hydroxyl groups, and they have poor heat resistance, which will cause adverse conditions such as decomposition when heated, yellowing during thermal aging, and reduction in the strength of cellulose fibers. Therefore, it is preferable that the content of alkali-soluble polysaccharides in cellulose fibers is low.

[0361] In one aspect, from the perspective of obtaining good dispersibility of cellulose fibers, with respect to 100% by mass of cellulose fibers, the average content of alkali-soluble polysaccharides in cellulose fibers is preferably 20% by mass or less, or 18% by mass or less, or 15% by mass or less, or 12% by mass or less, or 11% by mass or less, or 8% by mass or less. Regarding the above content, from the perspective of the ease of manufacturing cellulose fibers, it can be 1% by mass or more, or 2% by mass or more, or 3% by mass or more, or 6% by mass or more. In one aspect, the average content of alkali-soluble polysaccharides in cellulose raw materials can be 13% by mass or less, or 12% by mass or less, or 11% by mass or less, or 8% by mass or less, and most preferably 0% by mass. From the perspective of the ease of obtaining cellulose raw materials, for example, it can be 3% by mass or more, or 6% by mass or more.

[0362] The average content of alkali-soluble polysaccharides can be determined by the method described in non-patent literature (Experimental Handbook of Wood Science, edited by the Japanese Wood Science Society, pages 92-97, 2000), which is obtained by subtracting the α-cellulose content from the holocellulose content (Wise method). It should be noted that this method is understood as a method for measuring the amount of hemicellulose in this field. The content of alkali-soluble polysaccharides is calculated three times for one sample, and the number average of the calculated alkali-soluble polysaccharide contents is taken as the average content of alkali-soluble polysaccharides.

[0363] In one aspect, from the perspective of avoiding the reduction in heat resistance of cellulose fibers and the accompanying discoloration, with respect to 100% by mass of cellulose fibers, the average content of acid-insoluble components in cellulose fibers is preferably 10% by mass or less, or 5% by mass or less, or 3% by mass or less. From the perspective of the ease of manufacturing cellulose fibers, the above content can be 0.1% by mass or more, or 0.2% by mass or more, or 0.3% by mass or more.

[0364] Regarding the average content of acid-insoluble components, the Klason method described in a non-patent document (Experimental Handbook of Wood Science, edited by the Japanese Wood Research Society, pages 92-97, 2000) was used to quantify the acid-insoluble components. It should be noted that this method is understood in the art as a method for measuring the amount of lignin. After stirring the sample in a sulfuric acid solution to dissolve cellulose and hemicellulose, etc., it is filtered using a glass fiber filter paper, and the resulting residue corresponds to the acid-insoluble components. The acid-insoluble component content is calculated from the weight of the acid-insoluble components, and the number average of the acid-insoluble component contents calculated for 3 samples is taken as the average content of acid-insoluble components.

[0365] Cellulose fibers can be chemically treated (such as oxidation or chemical modification using a modifier). As an example, microfibrillated cellulose fibers obtained by oxidizing cellulose using 2,2,6,6-tetramethylpiperidine-1-oxyl radical and then washing and mechanically fibrillating as shown in Cellulose (1998) 5, 153-164 can be used.

[0366] [Hydrophobization of cellulose fibers]

[0367] Cellulose fibers can be cellulose fibers hydrophobized using a hydrophobizing agent (also referred to as chemically modified cellulose fibers in the present disclosure). By hydrophobizing, the hydrogen bonds between cellulose fibers are weakened, which helps with fine dispersion, and as cellulose fibers, their heat resistance is improved, and deterioration caused by kneading with resin can be suppressed, and it has the effect that cellulose fibers are not easily the starting point of physical property defects. As the hydrophobizing agent (also referred to as a modifying agent in the present disclosure), a compound that reacts with the hydroxyl group of cellulose can be used, and examples include esterifying agents, etherifying agents, and silylating agents. An esterifying agent is particularly preferred. In a preferred mode, the hydrophobization is acylation using an esterifying agent. As the esterifying agent, acyl halides, acid anhydrides, and vinyl carboxylates are preferred. In a particularly preferred mode, the hydrophobization is acetylation. Among these esterification reagents, from the aspect of reaction efficiency, at least one selected from the group consisting of acetic anhydride, propionic anhydride, butyric anhydride, vinyl acetate, vinyl propionate, vinyl butyrate, and acetic acid is particularly preferred, especially acetic anhydride and vinyl acetate.

[0368] In the case of obtaining hydrophobized cellulose nanofibers, there is no particular limitation on the method of making the natural cellulose raw material finer and reducing the fiber diameter, and it is preferable to make the fibrillation treatment conditions (the method of imparting a shear field, the magnitude of the shear field, etc.) more efficient. In particular, by impregnating a fibrillation solution containing an aprotic solvent into a cellulose raw material having a cellulose purity of 85% by mass or more, swelling of cellulose occurs in a short time, and the cellulose can be refined only by applying slight stirring and shear energy. Moreover, by adding a cellulose modifier immediately after fibrillation, hydrophobized cellulose nanofibers can be obtained. From the viewpoints of production efficiency and purification efficiency (i.e., high cellulose purification of hydrophobized cellulose nanofibers) and the physical properties of the resin composition, this method is preferable.

[0369] Examples of the aprotic solvent include alkyl sulfoxides, alkylamides, pyrrolidones, etc., and they can be used alone or in combination of two or more. Among these aprotic solvents, if DMSO (29.8), DMF (26.6), DMAc (27.8), NMP (27.3) (the numbers in parentheses are donor numbers), etc., especially if DMSO is used, hydrophobized cellulose nanofibers having a high thermal decomposition start temperature can be produced more effectively. The mechanism of action is not necessarily clear, but it is presumed to be due to the uniform micro-swelling of the fiber raw material in the aprotic solvent.

[0370] The degree of hydrophobicity (modification degree) of cellulose fibers is expressed in terms of the average degree of substitution of hydroxyl groups (the average number of substituted hydroxyl groups per unit glucose, which is the basic structural unit of cellulose, also referred to as DS). In one embodiment, the DS of the chemically modified cellulose fibers is preferably 0.01 or more and 2.0 or less. If the DS is 0.01 or more, a resin composition containing chemically modified cellulose fibers having a high thermal decomposition start temperature can be obtained. On the other hand, if the DS is 2.0 or less, an unmodified cellulose skeleton remains in the chemically modified cellulose fibers, so the chemically modified cellulose fibers have both high tensile strength and dimensional stability derived from cellulose fibers and a high thermal decomposition start temperature derived from chemical modification, and a resin composition containing the chemically modified cellulose fibers can be obtained. The DS is more preferably 0.05 or more, further preferably 0.1 or more, particularly preferably 0.2 or more, most preferably 0.3 or more, more preferably 1.8 or less, further preferably 1.5 or less, particularly preferably 1.2 or less, and most preferably 1.0 or less.

[0371] In the reflection-type infrared absorption spectrum of hydrophobized cellulose fibers, the peak position of the absorption band changes according to the type of hydrophobization modification group. Based on the change in the peak position, it is possible to determine which absorption band the peak is based on and identify the modification group. In addition, the modification rate can be calculated from the peak intensity ratio of the peak derived from the modification group to the peak derived from the cellulose skeleton.

[0372] When the modifying group is an acyl group, the degree of substitution (DS) of the acyl group can be calculated from the reflection-type infrared absorption spectrum of the esterified cellulose fiber. The peak of the absorption band based on the C=O of the acyl group appears at 1730 cm -1 , and the peak of the absorption band based on the C-O of the cellulose backbone chain appears at 1030 cm -1 . Regarding the DS of the esterified cellulose, a correlation diagram of the DS obtained by solid NMR measurement of the esterified cellulose and the modification rate (IR index 1030) can be prepared, and the DS can be obtained using the calibration curve calculated from the correlation diagram. The above modification rate is defined by the ratio of the peak intensity of the absorption band based on the C=O of the acyl group to the peak intensity of the absorption band based on the C-O of the cellulose backbone chain.

[0373] Degree of substitution DS = 4.13 × IR index (1030)

[0374] It should be noted that in the case where it is difficult to perform appropriate measurement using the above reflection-type infrared absorption spectrum, solid NMR can be used. According to the area intensity (Inf) of the signal attributed to one carbon atom from the modifying group relative to the total area intensity (Inp) of the signals attributed to the carbon C1-C6 of the pyranose ring of cellulose appearing in the range of 50 ppm to 110 ppm, it can be obtained by the following formula.

[0375] DS = (Inf) × 6 / (Inp)

[0376] For example, when the modifying group is an acetyl group, the signal at 23 ppm attributed to -CH 3 can be used.

[0377] [Cellulose nanocrystals]

[0378] Cellulose nanocrystals can be crystalline cellulose remaining after dissolving the amorphous part of cellulose in acids such as hydrochloric acid and sulfuric acid, using pulp or the like as a raw material and cutting the raw material. The length / diameter ratio (L / D ratio) of the cellulose nanocrystals is less than 30 in one embodiment. The average diameter of the cellulose nanocrystals is 1000 nm or less in one embodiment, preferably 500 nm or less, or 200 nm or less, and preferably 10 nm or more, or 20 nm or more, or 30 nm or more. The above L / D ratio and average diameter are values measured by the same method as the average fiber diameter of the cellulose fiber.

[0379] The L / D of cellulose nanocrystals is less than 30 in one mode, preferably 25 or less, or 20 or less, or 15 or less, or 10 or less, or 5 or less. The lower limit is not particularly limited and can be greater than 1. Cellulose nanocrystals can improve the tensile elongation of the resin composition. In one mode, cellulose whiskers, aside from their size, can have the same properties as those of the above-described cellulose fibers (unmodified or modified modes, etc.).

[0380] [Chitin fiber, chitosan fiber]

[0381] Chitin fiber can be a fiber mainly composed of a polymer of N-acetylglucosamine obtained by using the chitin of crustaceans, etc. as a raw material and separating and refining the raw material, i.e., a fiber mainly composed of chitin. Chitosan fiber is a fiber obtained by deacetylating chitin fiber and can be a fiber mainly composed of a polymer of glucosamine, i.e., chitosan. In one mode, the average diameter of chitin fiber and chitosan fiber is respectively 2 to 1000 nm, preferably 500 nm or less, or 200 nm or less, and preferably 10 nm or more, or 20 nm or more, or 30 nm or more.

[0382] In one mode, the L / D of chitin fiber and chitosan fiber is respectively 30 or more, preferably 50 or more, or 100 or more, and in one mode, it can be 100000 or less, or 50000 or less, or 10000 or less, or 5000 or less.

[0383] [Aramid fiber]

[0384] Aramid fiber is a synthetic fiber mainly composed of aromatic polyamide and is roughly classified into para-aramid fiber and meta-aramid fiber according to the structure of the aromatic group. In one mode, the average diameter of aramid fiber is 2 to 1000 nm, preferably 500 nm or less, or 200 nm or less, and preferably 10 nm or more, or 20 nm or more, or 30 nm or more.

[0385] In one mode, the L / D of aramid fiber is 30 or more, preferably 50 or more, or 100 or more, and in one mode, it can be 100000 or less, or 50000 or less, or 10000 or less, or 5000 or less.

[0386] The fiber length, fiber diameter, and L / D of organic fibers other than cellulose fibers are measured by the same method as that for cellulose fibers.

[0387] <Polymer>

[0388] The second component contains a polymer in one mode. In one mode, with respect to the polymer in the first component and the polymer in the second component, the molecular structure and / or molecular weight of at least one polymer constituting them are different from each other. Regarding the polymer as the second component, for example, it contains one or more selected from the group consisting of polyolefin resins, polyamide resins, polyester resins, polyacetal resins, polyphenylene sulfide resins, polyvinyl alcohol resins, polyvinylidene chloride resins, polystyrene resins, polyvinyl chloride resins, polycarbonate resins, polymethyl methacrylate resins, polyurethane resins, fluorine resins, polyacrylonitrile resins, polybutene resins, polyimide resins, polyarylate resins, cellulose resins, polyphenylene ether resins, elastomers, and modified products thereof (such as modified products with maleic anhydride, etc.), or it can be one or more selected from the group consisting of them.

[0389] [Polyphenylene ether]

[0390] The polyphenylene ether has a structure represented by the following general formula (1).

[0391] [Chemical formula 1]

[0392]

[0393] (In formula (1), R 1 , R 2 , R 3 and R 4 are each independently a monovalent group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 7 carbon atoms, a phenyl group, a haloalkyl group, an aminoalkyl group, a hydrocarbonoxy group, or a haloalkoxy group in which at least 2 carbon atoms separate a halogen atom and an oxygen atom, and n is an integer of 20 or more.)

[0394] From the viewpoints of the bending characteristics of the resin composition, etc., it is advantageous to use polyphenylene ether as the second component.

[0395] In the above formula (1), as the halogen atom represented by R 1 , R 2 , R 3 and R 4 , fluorine atom, chlorine atom, bromine atom, etc. can be cited, and chlorine atom and bromine atom are preferred.

[0396] In the above formula (1), the "alkyl group" represented by R 1 , R 2 , R 3 and R 4 means a linear or branched alkyl group preferably having 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and examples thereof include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, etc. Methyl group and ethyl group are preferred, and methyl group is more preferred.

[0397] In the above formula (1), R 1 , R 2 , R 3 and R 4 The alkyl groups represented may be substituted by one or more substituents at the substitutable positions. Examples of such substituents include halogen atoms (e.g., fluorine atom, chlorine atom, bromine atom), alkyl groups having 1 to 6 carbon atoms (e.g., methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group), aryl groups (e.g., phenyl group, naphthyl group), alkenyl groups (e.g., vinyl group, 1-propenyl group, 2-propenyl group), alkynyl groups (e.g., ethynyl group, 1-propynyl group, 2-propynyl group), aralkyl groups (e.g., benzyl group, phenethyl group), alkoxy groups (e.g., methoxy group, ethoxy group), etc.

[0398] In the above formula (1), n may be 20 or more, or 100 or more, or 200 or more, and may be 2000 or less, or 1000 or less, or 400 or less.

[0399] There is no particular limitation on the polyphenylene ether, and known substances can be used. For example, poly(2,6-dimethyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), poly(2-methyl-6-phenyl-1,4-phenylene ether), poly(2,6-dichloro-1,4-phenylene ether), etc. can be cited. Furthermore, polyphenylene ether copolymers of 2,6-dimethylphenol and other phenols (e.g., 2,3,6-trimethylphenol or 2-methyl-6-butylphenol) can also be used. Among the above, poly(2,6-dimethyl-1,4-phenylene ether) and the copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferred, and poly(2,6-dimethyl-1,4-phenylene ether) is more preferred.

[0400] These polyphenylene ethers can be used alone or in combination of two or more.

[0401] Regarding the intrinsic viscosity [η] of the polyphenylene ether, from the aspect of obtaining a resin composition with high rigidity, it is preferably 0.1 dl / g or more, or 0.2 dl / g or more, or 0.3 dl / g or more. From the aspect of imparting good fluidity to the resin composition, it is preferably 1.0 dl / g or less, or 0.7 dl / g or less, or 0.6 dl / g or less, or 0.5 dl / g or less. The above intrinsic viscosity is a value measured in chloroform at 25°C.

[0402] In one embodiment, at least a part of the polyphenylene ether can be acid-modified. The acid modification can be achieved by reacting a modifier (e.g., α,β-unsaturated carboxylic acid and its derivatives, etc.) with the polyphenylene ether.

[0403] Examples of the α,β-unsaturated carboxylic acids include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, isocrotonic acid, furan carboxylic acid, pentenoic acid, vinylacetic acid, angelic acid, etc., dicarboxylic acids such as maleic acid, chloromaleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, endo-bicyclo[2,2,1]hept-5-ene-2,3-dicarboxylic acid (nadic acid), etc., and tricarboxylic acids such as citric acid, aconitic acid, etc.

[0404] Examples of the derivatives of the α,β-unsaturated carboxylic acids include acid halides, amides, imides, acid anhydrides, esters, etc. of the above-mentioned α,β-unsaturated carboxylic acids. For example, maleoyl chloride, acrylamide, maleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, maleic anhydride, itaconic anhydride, glutaconic anhydride, citraconic anhydride, nadic anhydride, aconic anhydride, (meth)acrylic acid methyl ester, monomethyl maleate, dimethyl maleate, diethyl itaconate, dibutyl citraconate, glycidyl (meth)acrylate, diglycidyl maleate, etc. can be exemplified. Among them, as examples of the preferred modifiers, maleic acid, citric acid, itaconic acid, itaconic anhydride, maleic anhydride can be mentioned, and citric acid and maleic anhydride are more preferably used.

[0405] Regarding the acid modification degree of the polyphenylene ether, from the aspect of enabling good fine dispersion of the second component, it is preferably 0.01% or more, or 0.1% or more, or 0.2% or more, or 0.25% or more, and from the aspect of obtaining the advantages brought by the use of the polyphenylene ether well, it is preferably 10% or less, or 5% or less, or 2% or less, or 1% or less, or 0.7% or less, or 0.6% or less. The polyphenylene ether of the present disclosure can be a mixture of two or more polymers having different acid modification degrees. In this case, the acid modification degree of the whole polyphenylene ether in the resin composition is preferably in the above range. The above acid modification degree is the addition rate calculated by infrared spectroscopic measurement. When the acidic functional group is derived from maleic anhydride, a mixture of polyphenylene ether and maleic anhydride is used, and for the peak at 1790 cm -1 from maleic acid, after preparing a calibration curve in advance, the addition rate is calculated based on the peak intensity at 1790 cm -1 of the maleic anhydride-modified polyphenylene ether.

[0406] As a method for acid-modifying polyphenylene ether, methods such as reacting a modifier with polyphenylene ether in a flowing state (e.g., by melting or dispersion or dissolution in a solvent) can be exemplified; a method of reacting a modifier with powdery polyphenylene ether at a temperature below the glass transition point of polyphenylene ether in the coexistence of the modifier; and so on. As an example of a method of reacting a modifier with polyphenylene ether in a flowing state, a method of melt-kneading polyphenylene ether and a modifier at 250°C to 350°C for 5 seconds to 30 minutes using a roll mill, Banbury mixer, extruder, etc. can be exemplified; a method of dissolving polyphenylene ether in an organic solvent (e.g., toluene, xylene, decalin, tetralin, etc.) and then adding a modifier and heating. In addition, as an example of a method of reacting a modifier with powdery polyphenylene ether, a method of charging a specified amount of polyphenylene ether and a modifier into a stirring device capable of high-speed stirring and maintaining the temperature of the content at 160°C to 200°C for at least 30 seconds or more by its shear heat generation during high-speed stirring and / or heat transfer from a jacket can be cited, etc.

[0407] The reaction can be carried out in the presence of a radical initiator. As the radical initiator, organic peroxides (benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, tert-butyl cumyl peroxide, cumene hydroperoxide, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hex-3-yne, etc.), azo compounds (azobisisobutyronitrile, dimethyl azoisobutyrate, etc.) can be cited. The amount of the radical initiator can be, for example, 0.01 parts by mass to 10 parts by mass relative to 100 parts by mass of polyphenylene ether.

[0408] In one mode, the polyphenylene ether can be a mixture of a polyphenylene ether having an acidic functional group and a polyphenylene ether not having an acidic functional group. Regarding the mixing ratio of the polyphenylene ether having an acidic functional group and the polyphenylene ether not having an acidic functional group, when the total of the two is 100% by mass, from the aspect of favorably obtaining the advantages brought by the polyphenylene ether having an acidic functional group, it is preferably 10% by mass or more, more preferably 20% by mass or more, further more preferably 30% by mass or more, and most preferably 40% by mass or more. The upper limit is not particularly limited, and substantially all of the polyphenylene ether can be a polyphenylene ether having an acidic functional group, but from the aspect that the fluidity during melting does not cause problems, it is preferably 80% by mass or less.

[0409] As the second component polymer, in one mode, it is an elastomer. In the present disclosure, an elastomer is a substance that is an elastomer at room temperature (23°C) (specifically, a natural or synthetic polymer substance). From the aspect of improving the toughness and elongation rate of the resin composition (especially the elongation rate in a low-temperature environment), the elastomer is advantageous.

[0410] As specific examples of the elastomer, natural rubber, conjugated diene compound polymers, aromatic compound-conjugated diene copolymers, hydrides of aromatic compound-conjugated diene copolymers, polyolefins, polyester-based elastomers, polyurethane-based elastomers, polyamide-based elastomers, elastomers having a core-shell structure, etc. can be cited. Among these, from the aspect of the ease of the modification reaction of the acidic functional group described later, aromatic compound-conjugated diene copolymers and their hydrides, polyolefins, and elastomers having a core-shell structure are preferred. As the above-mentioned aromatic compound-conjugated diene copolymers and their hydrides, aromatic compound-conjugated diene block copolymers and their hydrides are more preferred, and as the above-mentioned polyolefins, copolymers of ethylene and α-olefins are more preferred.

[0411] In one embodiment, the elastomer is one or more selected from the group consisting of ethylene-α olefin copolymers, block copolymers of aromatic vinyl compounds and conjugated diene compounds, and hydrides of block copolymers of aromatic vinyl compounds and conjugated diene compounds.

[0412] In the present disclosure, the aromatic compound-conjugated diene block copolymer is a block copolymer composed of a polymer block (A) mainly composed of an aromatic vinyl compound and a polymer block (B) mainly composed of a conjugated diene compound. From the aspect of exhibiting impact strength, a block copolymer in which the bonding form of each block is any one of AB type, ABA type, and ABAB type is preferred, and ABA type or ABAB type is more preferred.

[0413] In addition, the mass ratio of the aromatic vinyl compound unit to the conjugated diene compound unit in the block copolymer is preferably 10 / 90 to 70 / 30. More preferably, it is 15 / 85 to 55 / 45, and most preferably, it is 20 / 80 to 45 / 55. Further, they may also be substances obtained by blending two or more copolymers having different mass ratios of aromatic vinyl compounds and conjugated diene compounds. As specific examples of the aromatic vinyl compound, styrene, α-methylstyrene, vinyltoluene, etc. can be cited, and one or more compounds selected from them are used, and styrene is particularly preferred.

[0414] As specific examples of the conjugated diene compound, butadiene, isoprene, piperylene, 1,3-pentadiene, etc. can be cited, and one or more compounds selected from them are used, and among them, butadiene, isoprene, and their combination are preferred, and butadiene is particularly preferred. When butadiene is used as the conjugated diene compound of the block copolymer, as the microstructure of the polybutadiene block portion, from the aspect of suppressing the crystallization of the soft segment, the 1,2-vinyl content, or the total amount of the 1,2-vinyl content and the 3,4-vinyl content is preferably 5 to 80% in terms of molar basis, more preferably 10 to 50%, and most preferably 15 to 40%.

[0415] An aromatic compound-conjugated diene block copolymer is a block copolymer composed of a polymer block mainly composed of an aromatic vinyl compound and a polymer block mainly composed of a conjugated diene compound, and refers to a block copolymer that has not substantially undergone hydrogenation treatment. The hydride of the block copolymer of an aromatic vinyl compound and a conjugated diene compound refers to a substance in which the aliphatic double bonds of the polymer block mainly composed of a diene compound are controlled in the range of more than 0% to 100% by subjecting the block copolymer of the aromatic vinyl compound and the conjugated diene compound to hydrogenation treatment. From the aspect of suppressing thermal deterioration during processing, the hydrogenation rate of the hydride of this block copolymer is preferably 50% or more, more preferably 80% or more, and most preferably 98% or more. From the aspect of low-temperature toughness, it is preferably 50% or less, more preferably 20% or less, and most preferably 0% (that is, the block copolymer of an aromatic vinyl compound and a conjugated diene compound).

[0416] In addition, regarding the molecular weights of the block copolymer of an aromatic vinyl compound and a conjugated diene compound and its hydride respectively, from the aspect of balancing impact strength and fluidity, the number-average molecular weight (Mn) is preferably 10,000 to 500,000, and most preferably 40,000 to 250,000. In the present disclosure, unless otherwise specified, the number-average molecular weight refers to the value measured by using a gel permeation chromatography device, using chloroform as a solvent, and performing conversion with a polystyrene standard sample at a measurement temperature of 40°C.

[0417] These block copolymers of aromatic vinyl compounds-conjugated diene compounds can also be used by mixing two or more substances with different bonding forms, different molecular weights, different types of aromatic vinyl compounds, different types of conjugated diene compounds, substances with different 1,2-vinyl contents or different total amounts of 1,2-vinyl content and 3,4-vinyl content, substances with different aromatic vinyl compound component contents, substances with different hydrogenation rates, etc. In the mixture of substances with different hydrogenation rates, the preferred hydrogenation rate of the mixture is as described above.

[0418] In addition, as the polyolefin, from the aspect of exhibiting impact resistance, an ethylene-α-olefin copolymer can be preferably used. Examples of the monomer that can be copolymerized with the ethylene unit include aliphatic substituted vinyl monomers such as propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, isobutene, etc., aromatic vinyl monomers such as styrene and substituted styrene, ester vinyl monomers such as vinyl acetate, acrylate, methacrylate, glycidyl acrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, etc., nitrogen-containing vinyl monomers such as acrylamide, allylamine, vinyl-p-aminobenzene, acrylonitrile, etc., and dienes such as butadiene, cyclopentadiene, 1,4-hexadiene, isoprene, etc.

[0419] It is preferably a copolymer of ethylene and one or more α-olefins having 3 to 20 carbon atoms, more preferably a copolymer of ethylene and one or more α-olefins having 3 to 16 carbon atoms, and most preferably a copolymer of ethylene and one or more α-olefins having 3 to 12 carbon atoms. In addition, as the molecular weight of the ethylene-α-olefin copolymer, from the aspect of exhibiting impact resistance, the number average molecular weight (Mn) measured by a gel permeation chromatography apparatus using 1,2,4-trichlorobenzene as a solvent at 140 °C with polystyrene standards is preferably 10,000 or more, more preferably 10,000 to 100,000, and further preferably 20,000 to 60,000. In addition, from the aspect of balancing fluidity and impact resistance, the molecular weight distribution (weight average molecular weight / number average molecular weight: Mw / Mn) is preferably 3 or less, and more preferably 1.8 to 2.7.

[0420] In addition, from the aspect of processability during processing, the preferred content of the ethylene unit in the ethylene-α-olefin copolymer is 30 to 95% by mass based on the total amount of the ethylene-α-olefin copolymer.

[0421] These preferred ethylene-α-olefin copolymers can be produced, for example, by the production methods described in Japanese Patent Publication No. 4-12283, Japanese Patent Laid-Open No. 60-35006, Japanese Patent Laid-Open No. 60-35007, Japanese Patent Laid-Open No. 60-35008, Japanese Patent Laid-Open No. 5-155930, Japanese Patent Laid-Open No. 3-163088, U.S. Patent No. 5272236, etc.

[0422] In the present disclosure, as the elastomer having a core-shell structure, a core-shell type elastomer having a core of granular rubber and a shell of a graft layer made of a vitreous material formed outside the core can be cited. As the rubber component of the core, butadiene rubber, acrylic rubber, silicone-acrylic composite rubber, etc. can be preferably used. In addition,

[0423] As the shell, a vitreous polymer such as a styrene resin, acrylonitrile-styrene copolymer, or acrylic resin is preferred. For example, in the case where the first component contains polyamide, from the aspect of compatibility with polyamide, an elastomer having a core-shell structure with a core of butadiene rubber and a shell of an acrylic resin can be preferably used.

[0424] In one embodiment, at least a part of the elastomer has an acidic functional group. In the present disclosure, that the elastomer has an acidic functional group means that an acidic functional group is added by chemical bonding in the molecular skeleton of the elastomer. In addition, in the present disclosure, an acidic functional group refers to a functional group that can react with a basic functional group, etc. As specific examples, a hydroxyl group, a carboxyl group, a carboxylic acid ester group, a sulfo group, an acid anhydride group, etc. can be cited.

[0425] From the aspect of compatibility with the second polymer having an acidic functional group or polyphenylene ether having an acidic functional group, the addition amount of the acidic functional group in the elastomer is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, further preferably 0.2% by mass or more, based on 100% by mass of the elastomer, and preferably 5% by mass or less, more preferably 3% by mass or less, further preferably 2% by mass or less. It should be noted that the number of acidic functional groups is a value obtained as follows: The sample for calibration curve pre-mixed with an acidic substance is measured using an infrared absorption spectrometer, and based on the calibration curve made using the characteristic absorption band of the acid, the sample is measured, and the value obtained therefrom is the number of the acidic functional groups.

[0426] As the elastomer having an acidic functional group, an elastomer having a core-shell structure with a layer formed using acrylic acid or the like as a copolymerization component as the shell can be cited; an elastomer which is a modified product obtained by grafting an α,β-unsaturated dicarboxylic acid or its derivative onto an ethylene-α-olefin copolymer, polyolefin, aromatic compound-conjugated diene copolymer, or aromatic compound-conjugated diene copolymer hydride containing acrylic acid or the like as a monomer in the presence or absence of a peroxide, etc.

[0427] In a preferred embodiment, the elastomer is an acid anhydride-modified elastomer.

[0428] Among these, a modified product obtained by grafting an α,β-unsaturated dicarboxylic acid or its derivative onto a polyolefin, an aromatic compound-conjugated diene copolymer, or a hydrogenated aromatic compound-conjugated diene copolymer in the presence or absence of a peroxide is more preferred. Among them, a modified product obtained by grafting an α,β-unsaturated dicarboxylic acid and its derivative onto a copolymer of ethylene-α-olefin or a hydrogenated aromatic compound-conjugated diene block copolymer in the presence or absence of a peroxide is particularly preferred.

[0429] Specific examples of the α,β-unsaturated dicarboxylic acid and its derivative include maleic acid, fumaric acid, maleic anhydride, and fumaric anhydride. Among these, maleic anhydride is particularly preferred.

[0430] In one embodiment, the elastomer can be a mixture of an elastomer having an acidic functional group and an elastomer not having an acidic functional group. Regarding the mixing ratio of the elastomer having an acidic functional group and the elastomer not having an acidic functional group, from the aspect of maintaining the high toughness and physical property stability of the resin composition well, when the total of the two is 100% by mass, the elastomer having an acidic functional group is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, and most preferably 40% by mass or more. The upper limit is not particularly limited, and substantially all of the elastomers can be elastomers having an acidic functional group, but from the aspect that no problem will occur in fluidity, it is preferably 80% by mass or less.

[0431] When the second component contains a polymer or is a polymer, the polymer can form a particulate dispersed phase (dispersed particles) in the resin composition. In this case, the dispersed particle size is preferably 3 μm or less, more preferably 2 μm or less, and most preferably 1 μm or less in terms of number average particle size. The lower limit is not particularly limited, for example, it is 0.01 μm. From the aspects of high toughness and physical property stability, it is preferably within the above range.

[0432] In the resin composition, with respect to the entire resin composition of 100% by mass, the amount of the polymer as the second component is preferably 0.1% by mass or more, or 0.5% by mass or more, or 1% by mass or more, or 3% by mass or more, and is preferably 30% by mass or less, or 25% by mass or less, or 20% by mass or less, or 15% by mass or less. When the amount of the polymer is within the above range, it is preferred from the aspects of high tensile elongation, high flexural modulus, low thermal expansion coefficient, and / or good physical property stability.

[0433] 《Additional Components》

[0434] In the resin compositions of Modes A to C, additional components may be further included as needed to improve their properties. Examples of the additional components include: dispersants; filler components other than organic fibers; compatibilizers; plasticizers; polysaccharides such as starches and alginic acids; natural proteins such as gelatin, animal glue, and casein; inorganic compounds such as zeolites, ceramics, talc, silica, metal oxides, and metal powders; colorants; fragrances; pigments; flow regulators; leveling agents; conductive agents; antioxidants; antistatic agents; ultraviolet absorbers; ultraviolet dispersants; deodorants, etc. The content ratio of the optional additional components in the resin composition can be appropriately selected within a range that does not impair the desired effects of the present invention, for example, it can be 0.01 to 50% by mass, or 0.1 to 30% by mass.

[0435] As the dispersant, a compound that can react or interact with the second component is preferred. For example, when the second component has a hydrogen bond-forming structure (such as a hydroxyl group, etc.), as the dispersant, a compound that can react with or form a hydrogen bond with the hydrogen bond-forming structure is preferred. Preferred examples of the dispersant are one or more selected from the group consisting of cellulose derivatives, polyalkylene oxides, amides, and amines. Among them, when the second component contains cellulose, since the cellulose derivative is a cellulose-based substance, it has a high affinity for the cellulose. On the other hand, since it is also a thermoplastic resin, it has a high effect of improving the dispersion stability of cellulose in the resin composition and is preferred. As the dispersant, a dispersant having a boiling point higher than that of water is preferred. It should be noted that a boiling point higher than that of water means a boiling point higher than the boiling point at each pressure in the vapor pressure curve of water (for example, 100 °C at 1 atm).

[0436] In the resin composition, from the aspect of good dispersion of the second component and, in the case where the second component contains organic fibers, the formation of a network between the fibers, the amount of the dispersant is preferably 1 part by mass or more, or 5 parts by mass or more, or 10 parts by mass or more, or 20 parts by mass or more relative to 100 parts by mass of the second component. From the aspect of reducing the performance deviation of the resin composition, it is preferably 500 parts by mass or less, or 300 parts by mass or less, or 200 parts by mass or less.

[0437] 《Properties of the Resin Composition》

[0438] The resin composition obtained by the methods of Modes A to C can have the following properties.

[0439] <Average Fiber Diameter and L / D of Organic Fibers in the Resin Composition>

[0440] In one embodiment, the average fiber diameter of the organic fibers in the resin composition may be 1000 nm or less, or 500 nm or less, or 450 nm or less, or 400 nm or less, or 350 nm or less, or 300 nm or less, or 250 nm or less, or 200 nm or less, or 150 nm or less, or 100 nm or less, and may be 2 nm or more, or 4 nm or more, or 5 nm or more, or 10 nm or more, or 15 nm or more, or 20 nm or more, or 30 nm or more, or 40 nm or more, or 50 nm or more, or 100 nm or more.

[0441] Regarding the average fiber length / average fiber diameter ratio (L / D) of the organic fibers in the resin composition, in one embodiment, it may be 30 or more, or 50 or more, or 80 or more, or 100 or more, and in one embodiment, it may be 5000 or less, or 4000 or less, or 3000 or less.

[0442] <Thixotropy index>

[0443] In the resin composition obtained by the methods of Embodiments A to C, the second component may be uniformly dispersed. The thixotropy index of the resin composition is an index of the dispersion uniformity of the second component, and the thixotropy index increases when the dispersion uniformity is high. This phenomenon may be significant when the second component contains organic fibers, particularly cellulose fibers. Regarding the thixotropy index of the resin composition, from the aspect of good dispersion uniformity of the second component, it is preferably 2 or more, or 3 or more, or 4 or more, and from the aspect of ease of manufacture of the resin composition, it is preferably 10 or less, or 9 or less, or 8 or less. It should be noted that for the above thixotropy index, using a dynamic viscoelasticity measuring device, at a temperature of the melting point of the thermoplastic resin contained in the resin composition (when there are two or more thermoplastic resins, the melting point on the highest temperature side) + 25 °C, the viscosity at a shear rate of 1 second -1 is divided by the viscosity at a shear rate of 10 seconds -1 to obtain the value as the thixotropy index.

[0444] <Tensile elongation>

[0445] In one embodiment, the tensile elongation of the resin composition measured according to ISO527-1 may be 2% or more, or 3% or more, or 5% or more, and from the aspect of ease of manufacture of the resin composition, it may be 500% or less, or 300% or less, or 100% or less.

[0446] <Flexural modulus>

[0447] In one embodiment, the flexural modulus of the resin composition measured according to ISO 178 can be 1 GPa or more, or 2 GPa or more, or 3 GPa or more. From the perspective of ease of manufacturing the resin composition, it can be 20 GPa or less, or 15 GPa or less, or 10 GPa or less.

[0448] <Tensile strength>

[0449] In one embodiment, the tensile strength of the resin composition measured according to ISO 527-1 can be 10 MPa or more, or 20 MPa or more, or 50 MPa or more. From the perspective of ease of manufacturing the resin composition, it can be 300 MPa or less, or 250 MPa or less, or 150 MPa or less.

[0450] <Coefficient of linear thermal expansion>

[0451] In one embodiment, the coefficient of linear thermal expansion of the resin composition measured by thermomechanical analysis (TMA) according to ISO 11359-2 in the temperature range of 20°C to 100°C can be 140 ppm / K or less, or 100 ppm / K or less, or 70 ppm / K or less, or 60 ppm / K or less, or 50 ppm / K or less, or 45 ppm / K or less, or 40 ppm / K or less, or 35 ppm / K or less. From the perspective of ease of manufacturing the resin composition, it can be 5 ppm / K or more, or 10 ppm / K or more.

[0452] <<Use of the resin composition>>

[0453] The resin compositions of Embodiments A to C are useful as substitutes for steel plates, fiber-reinforced plastics (such as carbon fiber-reinforced plastics, glass fiber-reinforced plastics, etc.), resin composites containing inorganic fillers, etc. Preferred uses of the resin composition include industrial machine parts, general machine parts, automotive, railway, vehicle, ship, and aerospace-related parts, electronic and electrical parts, building and civil engineering materials, daily necessities, sports and leisure goods, wind power generation housing parts, container and packaging parts, etc.

[0454] Examples

[0455] Examples are given below to further illustrate the exemplary embodiments of the present invention, but the present invention is not limited to the following examples.

[0456] (1) Example A (Example of Embodiment A of the present disclosure)

[0457] <<Evaluation method>>

[0458] <Clearance between the inner wall of the barrel and the screw>

[0459] It is obtained by direct measurement using a vernier caliper. Specifically, in the flow path of the mixture, the gap between the inner wall of the barrel and the screw at the widest part of the flow path is measured. At the seal, the gap between the outer edge of the seal and the inner wall of the barrel is measured, and at the kneading disk and the thread, the gap between the outer edges in the short-axis direction and the inner wall of the barrel is measured.

[0460] <Tensile elongation at break and flexural modulus of the mixture and the resin composition>

[0461] Using an injection molding machine, under the conditions according to JIS K6920-2, a multipurpose test piece according to ISO294-3 is molded from the obtained mixture or resin composition. For the multipurpose test piece, the tensile elongation at break is measured according to ISO527, and the flexural modulus is measured according to ISO178. It should be noted that since the polyamide resin will change due to moisture absorption, it is immediately stored in an aluminum moisture-proof bag after molding to inhibit moisture absorption.

[0462] <Charpy impact strength of the resin composition>

[0463] Using the same multipurpose test piece prepared as above, the Charpy impact strength is measured by the method described in ISO179-1.

[0464] <The organic fibers used and the average fiber length, average fiber diameter, and L / D of the organic fibers in the resin composition>

[0465] The wet cake is diluted with tert-butanol to 0.01% by mass, dispersed using a high-shear homogenizer (manufactured by IKA, trade name “ULTRA-TURRAX T18”) under the treatment conditions of a rotation speed of 25,000 rpm for 5 minutes, poured on mica, air-dried, and then measured using a high-resolution scanning microscope. The magnification is adjusted so that at least 100 organic fibers are observed for measurement, and the length (L), major diameter (D), and their ratio of 100 randomly selected organic fibers are determined, and the arithmetic mean of the 100 organic fibers is calculated.

[0466] It should be noted that for the organic fibers in the resin composition, when the polymer is polyamide, the resin component is dissolved in hexafluoroisopropanol, and when the polymer is polypropylene, the resin component is dissolved in xylene. The organic fibers are separated, thoroughly washed with the above solvents, replaced with tert-butanol, and the obtained wet cake is used.

[0467] <Average particle size of the dried organic fibers used>

[0468] The d50 particle size is measured using a powder tester, model: PT-X, manufactured by Hosokawa Micron Corporation.

[0469] <Weight-average molecular weight (Mw), number-average molecular weight (Mn), and Mw / Mn ratio of cellulose fibers and chitosan fibers>

[0470] [Production of porous sheet]

[0471] First, the wet cake is added to tert-butanol, and then dispersed with a mixer or the like until the aggregates disappear. For 0.5 g of the organic fiber solid content weight, the concentration is adjusted to 0.5 mass%. 100 g of the obtained tert-butanol dispersion is filtered through filter paper, dried at 150 °C, and then the filter paper is peeled off to obtain a sheet. For every 10 g / m 2 of the sheet basis weight, a sheet with an air permeability resistance of 100 sec / 100 ml or less is used as the porous sheet and used as the measurement sample.

[0472] After measuring the basis weight W (g / m 2 ) of the sample that has been left standing in an environment of 23 °C and 50% RH for 1 day, the air permeability resistance R (sec / 100 ml) is measured using a Wangyan type air permeability resistance tester (manufactured by Asahi Seiko Co., Ltd., model EG01). At this time, the value of the basis weight per 10 g / m 2 is calculated according to the following formula.

[0473] Air permeability resistance per 10 g / m 2 basis weight (sec / 100 ml) = R / W × 10

[0474] [Measurement]

[0475] Weigh 0.88 g of the porous sheet, cut it into small pieces with scissors and gently stir, then add 20 mL of pure water and let it stand for 1 day. Then, the water and solid components are separated by centrifugation. Then add 20 mL of acetone, gently stir and let it stand for 1 day. Then, the acetone and solid components are separated by centrifugation. Then add 20 mL of N,N-dimethylacetamide, gently stir and let it stand for 1 day. After separating the N,N-dimethylacetamide and solid components by centrifugation again, add 20 mL of N,N-dimethylacetamide, gently stir and let it stand for 1 day. The N,N-dimethylacetamide and solid components are separated by centrifugation, and 19.2 g of an N,N-dimethylacetamide solution prepared by dissolving lithium chloride at 8 mass% is added to the solid components, stirred with a stirrer, and visually confirmed to be dissolved. The solution in which the organic fiber is dissolved is filtered through a 0.45 μm filter, and the filtrate is used as a sample for gel permeation chromatography. The equipment and measurement conditions used are as follows.

[0476] Equipment: Tosoh Corporation HLC-8120

[0477] Column: TSKgel SuperAWM-H (6.0 mm I.D. × 15 cm) × 2

[0478] Detector: RI detector

[0479] Eluent: N,N-dimethylacetamide (0.2% lithium chloride)

[0480] Flow rate: 0.6 mL / min

[0481] Calibration curve: in terms of pullulan

[0482] <Crystallinity of cellulose fiber>

[0483] The porous sheet is subjected to X-ray diffraction measurement, and the crystallinity is calculated by the following formula.

[0484] Crystallinity (%) = [I (200) - I (amorphous) / I (200) × 100

[0485] I (200) : Diffraction peak intensity of cellulose I crystal based on the 200 plane (2θ = 22.5°)

[0486] I (amorphous) : Halo peak intensity of cellulose I crystal based on the amorphous phase, which is the peak intensity on the angle side (2θ = 18.0°) 4.5° lower than the diffraction angle of the 200 plane

[0487] (X-ray diffraction measurement conditions)

[0488] Apparatus: MiniFlex (manufactured by Rigaku Corporation)

[0489] Operation axis: 2θ / θ

[0490] X-ray source: CuKα

[0491] Measurement method: continuous type

[0492] Voltage: 40 kV

[0493] Current: 15 mA

[0494] Start angle: 2θ = 5°

[0495] End angle: 2θ = 30°

[0496] Sampling width: 0.020°

[0497] Scanning speed: 2.0° / min

[0498] Sample: Paste the porous sheet on the sample holder

[0499] <Average content of alkali-soluble polysaccharides in cellulose fibers>

[0500] For the content of alkali-soluble polysaccharides, the method for cellulose described in the non-patent literature (Experimental Manual of Wood Science, edited by the Japanese Wood Science Society, pages 92 - 97, 2000) is used. It is obtained by subtracting the α-cellulose content from the total cellulose content (Wise method). The content of alkali-soluble polysaccharides is calculated 3 times for 1 sample, and the number average of the calculated alkali-soluble polysaccharide contents is taken as the average content of alkali-soluble polysaccharides in cellulose.

[0501] <Degree of substitution (DS) of cellulose fibers>

[0502] The infrared absorption spectra based on the ATR-IR method at 5 positions of the porous sheet are measured using a Fourier transform infrared spectrophotometer (FT / IR-6200 manufactured by JASCO Corporation). The infrared absorption spectra measurement is carried out under the following conditions.

[0503] Integration times: 64 times,

[0504] Wavenumber resolution: 4 cm -1 、

[0505] Measured wavenumber range: 4000 - 600 cm -1 、

[0506] ATR crystal: diamond,

[0507] Incident angle: 45°

[0508] The IR index is calculated from the obtained IR spectrum according to the following formula (1).

[0509] IR index = H1730 / H1030 ··· (1)

[0510] In the formula, H1730 and H1030 are the absorbances at 1730 cm -1 、1030 cm -1 (Absorption band of the C-O stretching vibration of the cellulose backbone chain). Here, it means that the lines connecting 1900 cm -1 and 1500 cm -1 and the lines connecting 800 cm -1 and 1500 cm -1 are used as the baseline, and the absorbance when this baseline is set to 0 absorbance.

[0511] After that, the average degree of substitution at each measurement position is calculated from the IR index according to the following formula (2), and its average value is taken as DS.

[0512] DS = 4.13 × IR index ··· (2)

[0513] <Content of particles with a particle size of 50 μm or more in the mixture and in the resin composition>

[0514] Using an injection molding machine, under the conditions according to JIS K6920-2, a multi-purpose test piece according to ISO294-3 was molded from the mixture or the resin composition. A specimen with a size of about 2 mm square was cut out from this test piece, and analysis of aggregates was performed using an X-CT (X-ray CT device) (manufactured by Bruker Japan, Skyscan1272). The measurement conditions are as described below.

[0515] Tube voltage: 40 kV

[0516] Tube current: 100 μA

[0517] Pixel resolution: 1.2 μm

[0518] Detector pixel number: 2452×1640 pixels

[0519] Integration times: 4 times

[0520] Measurement angle step: 0.2 degrees

[0521] Scanning range: 0 to 180 degrees

[0522] It should be noted that for the measured data, smoothing processing was applied using the Kuwahara filter between 2 pixels in the 3D direction to improve the image quality.

[0523] For the 3D data obtained in this way, automatic binarization based on the triangulation method was performed to extract only the pixels of the aggregates. The spherical equivalent volume in this aggregate is (4 / 3)×π×25 3 μm 3 The ratio of the sum of the pixels of the aggregates with a particle size of 50 μm or more to the sum of all pixels in the entire observation range was calculated to obtain the content (volume %) of particles with a particle size of 50 μm or more in the mixture or the resin composition. The content (volume %) of particles with a particle size of 50 μm or more was divided by the total content (volume %) of the organic fibers calculated from the compounding amount of the organic fibers in the mixture or the resin composition, and the value obtained thereby was regarded as the content (mass %) of particles with a particle size of 50 μm or more in the organic fibers.

[0524] <Particle size of the dispersed phase in the resin composition>

[0525] The particle size of the dispersed phase was measured by observing the cross-section of the resin composition using a scanning electron microscope. Dyeing of the styrene-based thermoplastic elastomer was carried out by immersion in an aqueous ruthenium tetroxide solution. Dyeing of the polyamide resin was carried out by immersion in an aqueous phosphotungstic acid solution.

[0526] <<Materials Used>>

[0527] <Component 1>

[0528] Polyamide 6 (PA6): (manufactured by Ube Industries, Ltd.: 1013B)

[0529] Polypropylene (PP): (manufactured by Prime Polymer Co., Ltd.: J105G)

[0530] Polyoxymethylene (POM): (manufactured by Asahi Kasei Corporation: HC450)

[0531] <Component 2>

[0532] [Acid-modified polyphenylene ether (m-PPE)]

[0533] Manufactured by Asahi Kasei Corporation: R4919

[0534] [Styrene-ethylene-butadiene-styrene copolymer (SEBS)]

[0535] Manufactured by Asahi Kasei Corporation: Tuftec H1052

[0536] [CNF-A]

[0537] Use the commercially available Celish KY100G (manufactured by Daicel Finechem Co., Ltd.) as the CNF-A cake.

[0538] [CNF-B] (acetylated CNF)

[0539] Use a single-screw mixer (DKV-1 manufactured by IMEX Co., Ltd. dissolver) to stir 1 part by mass of cotton linter pulp in 30 parts by mass of dimethyl sulfoxide (DMSO) at 500 rpm at room temperature for 1 hour. Then, feed it into a bead mill (NVM-1.5 manufactured by IMEX Co., Ltd.) using a hose pump and perform a 180-minute circulation operation with DMSO only to obtain a slurry S1 (DMSO solvent) with a solid content ratio of 3.2% by mass as the microfibrillated cellulose fiber slurry.

[0540] During the circulation operation, set the rotational speed of the bead mill to 2500 rpm and the circumferential speed to 12 m / s. The beads used are made of zirconia, and the filling rate is 70% (the gap between the beads in the bead mill is 0.6 mm). In addition, during the circulation operation, in order to absorb the heat generated by friction, use a cooler to manage the temperature so that the slurry temperature is 40°C.

[0541] After putting the slurry S1 into an explosion-proof dispersion tank, add 3.2 parts by mass of vinyl acetate and 0.49 parts by mass of sodium bicarbonate, set the temperature in the tank to 50°C, and stir for 120 minutes to obtain a slurry (DMSO solvent) with a solid content ratio of 2.9% by mass.

[0542] To stop the reaction, 30 parts by mass of pure water was added and stirred well, and then it was put into a dehydrator for concentration. The obtained wet cake was dispersed again in 30 parts by mass of pure water, stirred and concentrated, and this washing operation was repeated a total of 5 times to remove unreacted reagents and solvents, etc., to obtain 10 parts by mass of an acetylated microcrystalline cellulose fiber cake (CNF-B cake) (aqueous solvent) with a solid component ratio of 10 mass%. A porous sheet was made from this cake, and the degree of acyl substitution (DS) was determined, and the result was DS = 1.0.

[0543] [CNF-C] (CNF treated with a disk refiner)

[0544] 3 parts by mass of cotton linter pulp was impregnated in 27 parts by mass of water, and heat treatment was carried out at 130 °C for 4 hours in an autoclave. The obtained swollen pulp was washed with water to obtain refined pulp (30 parts by mass) containing water. Then, 170 parts by mass of water was added to 30 parts by mass of the refined pulp containing water to disperse it in water (solid component ratio: 1.5 mass%), and a SDR14 type Lab-Refiner (pressure type DISK type) manufactured by Aikawa Tekko Co., Ltd. was used as a disk refiner device, with the gap between the disks being 1 mm, and the aqueous dispersion was beaten for 20 minutes. After that, it was concentrated to a solid component ratio of 10 mass% using a dehydrator to obtain a CNF-C cake (aqueous solvent).

[0545] [CNF-D] (a substance obtained by further fibrillating CNF-C with a high-pressure homogenizer)

[0546] The CNF-C cake was thoroughly beaten under the condition that the gap was reduced to almost zero to obtain a beaten aqueous dispersion (solid component concentration: 1.5 mass%). The obtained beaten aqueous dispersion was directly subjected to 15 times of micronization treatment using a high-pressure homogenizer (NSO15H manufactured by Niro Soavi Co., Ltd. (Italy)) at an operating pressure of 100 MPa to obtain a cellulose fiber slurry (solid component concentration: 1.5 mass%). After that, it was concentrated to a solid component ratio of 10 mass% using a dehydrator to obtain a CNF-D cake (aqueous solvent).

[0547] [CNF-E] (acetylated CNF)

[0548] It was produced in the same manner as CNF-B except that the reaction time was 60 minutes. A porous sheet was made from this cake, and the degree of acyl substitution (DS) was determined, and the result was DS = 0.5.

[0549] [Cellulose nanocrystals]

[0550] Ceolus FD-301 (manufactured by Asahi Kasei Corporation) was used.

[0551] [Chitosan fiber]

[0552] Use Binfis Efo-08002 (manufactured by Sugino Machine).

[0553] [Aramid fiber]

[0554] Use Tiara KY400S (manufactured by Daicel Finechem).

[0555] The properties of the organic fibers are shown in Table 1.

[0556] [Dispersant]<

[0557] Polyoxyethylene-polyoxypropylene copolymer (PEG-PPG) (manufactured by Sanyo Chemical Industries: GL-3000)

[0558] [Mixing method]<<

[0559] [Screw configuration of the extruder]<

[0560] As described in Table 2, screws 1 to 6 are designed and configured with a high load zone 1, a high load zone 2, a high load zone 3, and a distributive mixing zone. It is designed to dispose a kneading element composed of any one of a split-thread screw, a slotted screw, a kneading disk, an eccentric multi-disk, and an eccentric multi-screw in the first half of the high load zone, and dispose a sealing ring with a specified gap downstream to block the mixture. Regarding the distributive mixing zone, it is configured in the barrel 11 in the order of two neutral kneading disks and one reverse screw.

[0561] [Mixing operation]<

[0562] [Example A1]

[0563] The preparation of the dried cellulose fiber body and the mixing of the dried cellulose fiber body and the resin are carried out according to the following steps to manufacture a resin composition.

[0564] (Manufacture of the dried cellulose fiber body)

[0565] A dispersant is added to the cellulose fiber cake (solid content mass 10%), and the addition amount is 43 mass parts relative to 100 mass parts of the cellulose solid content, and it is sufficiently stirred to obtain a cellulose fiber cake mixed with the dispersant. This is put into a drying device as a raw material, and drying is carried out at a specified shear rate, vacuum degree, and heating temperature (jacket temperature or hot air temperature). An infrared heating type moisture meter (MX-50 (manufactured by A&D)) is used to measure the moisture content, and the time when the moisture content reaches 7 mass% or less (solid content mass 93% or more) is taken as the end point of drying. The conditions are as described below.

[0566] Planetary mixer (PM)

[0567] Device: Planetary mixer (Model: ACM-5LVT: Hook type) manufactured by Kobayashi Seisakusho Co., Ltd.

[0568] Condition: Stir at 307 rpm while maintaining the jacket temperature at 60°C, and reduce the pressure to -90 kPa using a vacuum pump. Conduct vacuum drying until the product temperature reaches 50°C.

[0569] As the clearance, measure the minimum distance between the hook-shaped paddle (hook blade) (diameter 100 mm) and the jacket.

[0570] The drying time under these conditions is 180 minutes.

[0571] Regarding the drying temperature, measure the surface temperature of the jacket at three points and use the average value as the drying temperature.

[0572] (Dispersion mixing)

[0573] Feed 2 kg / h of polyamide 6 into the extruder, and feed 2.86 kg / h (2 kg / h in terms of cellulose) of the dried cellulose fiber into the extruder. Conduct heat melting and kneading in the dispersion mixing zone to obtain a dispersion mixture.

[0574] (Distribution mixing)

[0575] Add 15.14 kg / h of polyamide 6 to 4.86 kg / h of the dispersion mixture through side feeding, and then conduct heat melting and kneading in the distribution mixing zone to obtain a resin composition. Process the obtained resin composition into pellets using a pelletizer. Regarding the extrusion characteristics, record the situation where the screen is clogged within 1 hour after the start of the extruder operation during extrusion processing as "poor" in terms of running stability, and record the situation without clogging as "good" in terms of running stability.

[0576] [Examples A2 - A19, Comparative Examples A1 - A3]

[0577] Except for changing the composition of the resin composition and the set conditions of the extruder as shown in Tables 3 - 5, manufacture the resin composition using the same procedure as in Example A1 and conduct various evaluations. The results are shown in Tables 3 - 5.

[0578] [Table 1]

[0579]

[0580] [Table 2]

[0581]

[0582] [Table 3]

[0583]

[0584] [Table 4]

[0585]

[0586]

[0587] [Table 5]

[0588]

[0589] (2) Example B (Example of Mode B of the present disclosure)

[0590] 《Evaluation Method》

[0591] <Clearance between the inner wall of the barrel and the screw>

[0592] The measurement was carried out in the same manner as in Example A.

[0593] <Mixture filling rate>

[0594] During extrusion, after suddenly stopping the rotation of the screw and the supply of the raw material, the screw was pulled out, and the mixture adhering to the screw surface was collected and measured. Then, the volume filled with the mixture was calculated by dividing the measured value by the density of the mixture. Next, the mixture filling rate was calculated by dividing the volume filled with the mixture by the space volume described below.

[0595] <Space volume rate>

[0596] The space volume was calculated by subtracting the screw volume (the sum of the volume of the element and the volume of the shaft) from the barrel volume of the extruder, and the space volume rate was calculated by dividing the space volume by the barrel volume.

[0597] <Zone length>

[0598] The total length of the screw components constituting the dispersion mixing zone and the distributive mixing zone was taken as the zone length.

[0599] <Tensile elongation and flexural modulus of the mixture and the resin composition>

[0600] Using an injection molding machine, under the conditions according to JIS K6920-2, a multipurpose test piece according to ISO294-3 was molded from the obtained mixture or resin composition. For the multipurpose test piece, the tensile elongation at break was measured according to ISO527-1, and the flexural modulus was measured according to ISO178. It should be noted that polyamide resin changes due to moisture absorption, so it was immediately stored in an aluminum moisture-proof bag after molding to suppress moisture absorption.

[0601] <Content of particles with a particle size of 50 μm or more in the mixture and in the resin composition>

[0602] The measurement was carried out in the same manner as in Example A.

[0603] <Average fiber diameter and L / D of the organic fibers used and the organic fibers in the resin composition>

[0604] The measurement was carried out in the same manner as in Example A.

[0605] <Weight average molecular weight (Mw), number average molecular weight (Mn), and Mw / Mn ratio of cellulose fibers and chitosan fibers>

[0606] The measurement was carried out in the same manner as in Example A.

[0607] <Crystallinity of cellulose fibers>

[0608] The porous sheet was produced and measured in the same manner as in Example A.

[0609] <Average content of alkali-soluble polysaccharides in cellulose fibers>

[0610] The measurement was carried out in the same manner as in Example A.

[0611] <Degree of substitution (DS) of cellulose fibers>

[0612] The measurement was carried out in the same manner as in Example A.

[0613] 《Materials Used》

[0614] The same materials as those in Example A were used.

[0615] 《Mixing Method》

[0616] [Configuration of the Extruder]

[0617] Mixing was carried out using a twin-screw extruder (OMEGA30H manufactured by STEER Co., L / D = 72) with 15 barrel sections. It should be noted that in barrel 14, an exhaust port was provided at the upper part of the barrel to enable decompression suction for vacuum suction. A 50-mesh screen was installed between the die adapter and the die head.

[0618] <Screw configuration of the extruder>

[0619] As shown in Table 6, the screws 1 to 5 are designed and arranged with the first dispersive mixing zone, the second dispersive mixing zone, and the distribution mixing zone. The first dispersive mixing zone and the second dispersive mixing zone are respectively designed to be arranged with a mixing element composed of any one of a split-flow screw, a notched screw, a kneading disk, an eccentric multi-strip disk, and an eccentric multi-strip screw in the front half, and a seal ring and / or a reverse screw are combined in the rear half to retain the mixed material. As for the distribution mixing zone, two neutral kneading disks are arranged in the barrel 11, followed by a reverse screw.

[0620] <Mixed Operation>

[0621] [Example B1]

[0622] The preparation of a dried cellulose fiber body and the mixing of the dried cellulose fiber body and a resin were carried out in the following order to produce a resin composition.

[0623] (Manufacturing of Dried Cellulose Fibers)

[0624] A dispersant is added to a cellulose fiber cake (10% by weight of solid content) in an amount of 43 parts by weight relative to 100 parts by weight of cellulose solid content, and the mixture is stirred thoroughly to obtain a cellulose fiber cake mixed with a dispersant. It is put into a drying device as a raw material and dried at a specified shear rate, vacuum degree, and heating temperature (jacket temperature or hot air temperature). The moisture content is measured using an infrared heating moisture meter (MX-50 (manufactured by A&D)), and the time when the moisture content reaches 7% by weight or less (the solid content reaches 93% or more) is taken as the end point of drying. The conditions are as follows. It should be noted that after the dried cellulose fiber is loaded on agar, an X-CT analysis is performed using the above method, and the content of particles with a particle size of 50 μm or more formed by the aggregation of cellulose nanofibers exceeds 50% by weight.

[0625] Planetary mixer (PM)

[0626] Equipment: Planetary mixer manufactured by Kodaira Manufacturing Co., Ltd. (Model: ACM-5LVT: hook type)

[0627] Conditions: The pressure was reduced to -90 kPa using a vacuum pump while stirring at 307 rpm at a jacket temperature of 60°C. Drying under reduced pressure was performed until the product temperature reached 50°C.

[0628] As the gap, the minimum distance between the hook-shaped paddle (diameter 100 mm) and the jacket was measured.

[0629] The drying time in this condition is 180 minutes.

[0630] Regarding the drying temperature, the surface temperature of the jacket was measured at three points, and the average value was taken as the drying temperature.

[0631] (Dispersion mixing)

[0632] Polyamide 6 was fed into the extruder at 2 kg / h, and the dried cellulose fiber was fed into the extruder at 2.86 kg / h (2 kg / h in terms of cellulose). Heat melting and kneading were carried out in the first dispersion mixing zone to obtain the first dispersion mixture. Then, heat melting and kneading were carried out in the second dispersion mixing zone to obtain the second dispersion mixture.

[0633] (Distribution mixing)

[0634] Polyamide 6 was added to 4.86 kg / h of the second dispersion mixture at 15.14 kg / h through side feeding, and then heat melting and kneading were carried out in the distribution mixing zone to obtain the resin composition. The obtained resin composition was processed into pellets by a granulator. As the extrusion characteristics, the case where the screen was blocked within 1 hour after the start of the operation of the extruder during the extrusion process was recorded as "poor" in terms of running stability, and the case without blockage was recorded as "good" in terms of running stability.

[0635] [Examples B2 - B7, Comparative Example B1]

[0636] Except for changing the composition of the resin composition and the set conditions of the extruder as shown in Table 7, the resin composition was manufactured using the same steps as in Example B1, and various evaluations were carried out. The results are shown in Table 7.

[0637] [Table 6]

[0638]

[0639] [Table 7]

[0640]

[0641] (3) Example C (Example of Mode C of the present disclosure) "Evaluation Method"

[0642] <Clearance between the inner wall of the barrel and the screw>

[0643] The measurement was carried out in the same manner as in Example A.

[0644] <Mixture filling rate>

[0645] During the extrusion, after suddenly stopping the rotation of the screw and the raw material supply, the screw was pulled out, and the mixture adhering to the surface of the screw was collected and measured. Then, the volume filled with the mixture was calculated by dividing by the density of the mixture. Next, the volume filled with the mixture was divided by the space volume described below to calculate the mixture filling rate.

[0646] <Ratio of the length of the region where the mixture pressure is 0.3 MPa or more to the inner diameter of the barrel>

[0647] A plurality of resin pressure gauges are provided in the barrel of the extruder, and the resin pressure is monitored during extrusion, whereby the resin pressure in each zone is measured. The calculation is performed by dividing the total length of the zone where the mixture pressure exceeds 0.3 MPa by the inner diameter of the barrel.

[0648] <Space volume ratio>

[0649] The space volume is calculated by subtracting the screw volume (the sum of the element volume and the shaft volume) from the barrel volume of the extruder, and the space volume ratio is calculated by dividing the space volume by the barrel volume.

[0650] <Zone length>

[0651] The total length of the screw components constituting the dispersion mixing zone and the distributive mixing zone is taken as the zone length.

[0652] <Tensile elongation at break and flexural modulus of the mixture and the resin composition>

[0653] Using an injection molding machine, under the conditions according to JIS K6920-2, a multi-purpose test piece according to ISO294-3 is molded from the obtained mixture or resin composition. For the multi-purpose test piece, the tensile elongation at break is measured according to ISO527-1, and the flexural modulus is measured according to ISO178. It should be noted that polyamide resin will change due to moisture absorption, so it is immediately stored in an aluminum moisture-proof bag after molding to inhibit moisture absorption.

[0654] <Thixotropy index>

[0655] For the above multi-purpose test piece, the viscoelasticity during melting is measured under the following test conditions.

[0656] Device name: ARES G2TA Instruments·Japan Co., Ltd.

[0657] Measurement temperature: 250 °C (melting point of polyamide + 25 °C), 185 °C (melting point of polypropylene + 25 °C)

[0658] Shear rate: 1.0 - 40 s -1

[0659] Measurement is performed using a 25 mm / 40 mm parallel plate with a gap of 1 mm.

[0660] The thixotropy index is calculated from the measurement results at this time according to the following formula.

[0661] Thixotropy index = (viscosity at shear rate of 1 s -1 / viscosity at shear rate of 10 s -1 )

[0662] <Rate of improvement in physical properties per unit mass of cellulose fibers in the mixture (rate of improvement in flexural modulus)>

[0663] The concentration of cellulose fibers in the mixture is determined from the ratio of the feed amounts into the extruder during extrusion, and the rate of improvement in physical properties per unit mass of cellulose fibers in the mixture is calculated according to the following formula.

[0664] (Flexural modulus of the mixture - flexural modulus of the base resin) / cellulose fiber concentration (mass%)

[0665] <Charpy impact strength>

[0666] Measurement is carried out in the same manner as in Example A.

[0667] <Average fiber length, average fiber diameter, and L / D of the cellulose fibers used and the cellulose fibers in the resin composition>

[0668] Measurement is carried out in the same manner as in Example A.

[0669] <Weight-average molecular weight (Mw), number-average molecular weight (Mn), and Mw / Mn ratio of the cellulose fibers>

[0670] Measurement is carried out in the same manner as in Example A.

[0671] <Crystallinity of the cellulose fibers>

[0672] Production and measurement of the porous sheet are carried out in the same manner as in Example A.

[0673] <Average content of alkali-soluble polysaccharides in the cellulose fibers>

[0674] Measurement is carried out in the same manner as in Example A.

[0675] <Content of particles with a particle size of 50 μm or more in the resin composition>

[0676] Measurement is carried out in the same manner as in Example A.

[0677] <Particle size of the dispersed phase in the resin composition>

[0678] Measurement is carried out in the same manner as in Example A.

[0679] <<Materials Used>>

[0680] For the polymer, organic fiber, and dispersant, the same materials as in Example A are used.

[0681] <<Mixing Method>>

[0682] <Screw configuration of the extruder>

[0683] As shown in Table 8, screws 1 to 5 are designed and configured with zones 1 and 2. Zone 1 of screw 1 is a dispersive mixing zone, which is composed of a plurality of kneading zones, which are a combination of a kneading element composed of any one of a split-flow screw, a notched screw, a kneading disk, an eccentric multi-strip disk, and an eccentric multi-strip screw, and a retention element composed of a seal ring and / or a reverse screw. Zone 2 of screws 1 to 5 is a distributive mixing zone, and two neutral kneading disks are arranged in the barrel 11, followed by a reverse screw.

[0684] Zone 1 of the screw 2 is a distributive mixing zone designed as a combination of single and / or multiple kneading disks and single and / or multiple counter-rotating screws.

[0685] Zone 1 of screw 3 is a dispersive mixing zone, which is designed to have one more kneading zone than screw 1.

[0686] The zone length / barrel inner diameter ratio and space volume ratio of each screw are shown in Table 8.

[0687] <Mixed Operation>

[0688] [Example C1]

[0689] The preparation of a dried cellulose fiber body and the mixing of the dried cellulose fiber body and a polymer are carried out in the following steps to produce a resin composition.

[0690] (Manufacturing of Dried Cellulose Fibers)

[0691] A dispersant is added to a cellulose fiber cake (10% by weight of solid content) in an amount of 43 parts by weight relative to 100 parts by weight of cellulose solid content, and the mixture is stirred thoroughly to obtain a cellulose fiber cake mixed with a dispersant. The cake is put into a drying device as a raw material and dried at a specified shear rate, vacuum degree, and heating temperature (jacket temperature or hot air temperature). The moisture content is measured using an infrared heating moisture meter (MX-50 (manufactured by A&D)), and the time when the moisture content reaches 7% by weight or less (the solid content reaches 93% or more) is taken as the end point of drying. The conditions are as follows.

[0692] Planetary mixer (PM)

[0693] Equipment: Planetary mixer manufactured by Kodaira Manufacturing Co., Ltd. (Model: ACM-5LVT: hook type)

[0694] Conditions: The pressure was reduced to -90 kPa using a vacuum pump while stirring at 307 rpm at a jacket temperature of 60°C. Drying under reduced pressure was performed until the product temperature reached 50°C.

[0695] As the gap, the minimum distance between the hook-shaped paddle (diameter 100 mm) and the jacket was measured.

[0696] The drying time in these conditions is 180 minutes.

[0697] Regarding the drying temperature, the surface temperature of the jacket is measured at three points, and the average value thereof is taken as the drying temperature.

[0698] (Dispersion mixing)

[0699] Polyamide 6 is fed into the extruder at 2 kg / h, and the dried cellulose fiber is fed into the extruder at 2.86 kg / h (2 kg / h in terms of cellulose), and heat melting and kneading are carried out in the dispersion mixing zone, whereby a dispersion mixture is obtained.

[0700] (Distribution mixing)

[0701] Polyamide 6 is added to 4.86 kg / h of the dispersion mixture at 15.14 kg / h through side feeding, and then heat melting and kneading are carried out in the distribution mixing zone, whereby a resin composition is obtained. The obtained resin composition is processed into pellets by a granulator. As the extrusion characteristics, the case where the screen is clogged within 1 hour after the start of the operation of the extruder during extrusion processing is recorded as "poor" in terms of operation stability, and the case where there is no clogging is recorded as "good" in terms of operation stability.

[0702] [Examples C2 - C9, Comparative Example C1]

[0703] Except for changing the composition of the resin composition and the set conditions of the extruder as shown in Tables 9 and 10, resin compositions are manufactured using the same steps as in Example C1, and various evaluations are carried out. The results are shown in Tables 9 and 10.

[0704] [Table 8]

[0705]

[0706] [Table 9]

[0707]

[0708] [Table 10]

[0709]

[0710] Industrial applicability

[0711] The resin composition obtained by the manufacturing method of the resin composition of the present disclosure can be suitably applied in a wide range of uses such as industrial machine parts, general machine parts, automotive, railway, vehicle, ship, aerospace related parts, electronic and electrical parts, building and civil engineering materials, daily necessities, sports and leisure goods, wind power generation housing parts, container and packaging parts, etc.

[0712] Explanation of symbols

[0713] Extruders 100, 200, 300, 400, 600, 800

[0714] Mixing zones 101, 201, 301

[0715] Melting zones 102, 202, 302

[0716] Narrow clearance zones N1, N2, N3

[0717] Pressure reduction zone D1

[0718] High pressure zones H1, H2, H3

[0719] Other zones 11, 12, 13, 14, 21, 22, 31, 32, 33, 34

[0720] Dispersive mixing zones 401, 601, 801

[0721] Distributive mixing zones 402, 602, 802

[0722] Melting zones 403, 404, 603, 604, 803, 804

[0723] First dispersive mixing zone 41

[0724] Second dispersive mixing zone 42

[0725] Inflow to the first dispersive mixing zone 41a

[0726] Outflow from the first dispersive mixing zone 41b

[0727] Inflow to the second dispersive mixing zone 42a

[0728] Outflow from the second dispersive mixing zone 42b

[0729] First component a1

[0730] Second component a2

[0731] Resin composition b

[0732] Barrel length direction L

Claims

1. A method for manufacturing a resin composition comprising a first component and a second component, wherein, the first component is a polymer, the second component is an organic fiber or a combination of an organic fiber and a polymer different from the first component, the method includes a kneading step of kneading the first component and the second component using an extruder, and the extruder has a kneading zone including a plurality of high-pressure zones with a pressure of 0.1 MPa or more, the pressure P1 of the highest-pressure zone with the maximum pressure among the plurality of high-pressure zones is 0.5 MPa or more, and the ratio P1 / P2 of the pressure P1 to the average value P2 of the pressures of the high-pressure zones other than the highest-pressure zone is greater than 1 and 100 or less.

2. A method for manufacturing a resin composition comprising a first component and a second component, wherein, the first component is a polymer, the second component is an organic fiber or a combination of an organic fiber and a polymer different from the first component, the method includes a dispersion mixing step of dispersion mixing the first component and the second component in a dispersion mixing zone of an extruder, the dispersion mixing zone includes a first dispersion mixing zone and a second dispersion mixing zone, and the first dispersion mixing zone and the second dispersion mixing zone are different from each other in one or more selected from the group consisting of the ratio of zone length to barrel inner diameter, mixture filling rate, temperature, pressure, and space volume ratio, the increment E1 of the tensile elongation rate of the effluent flowing out from the first dispersion mixing zone relative to the tensile elongation rate of the influent flowing into the first dispersion mixing zone and the increment E2 of the tensile elongation rate of the effluent flowing out from the second dispersion mixing zone relative to the tensile elongation rate of the influent flowing into the second dispersion mixing zone satisfy the relationship E1>E2, the increment M1 of the flexural modulus of the effluent flowing out from the first dispersion mixing zone relative to the flexural modulus of the influent flowing into the first dispersion mixing zone and the increment M2 of the flexural modulus of the effluent flowing out from the second dispersion mixing zone relative to the flexural modulus of the influent flowing into the second dispersion mixing zone satisfy the relationship M1<M2.

3. A method for manufacturing a resin composition comprising a first component and a second component, wherein, the first component is a polymer, the second component is an organic fiber or a combination of an organic fiber and a polymer different from the first component, the method includes a dispersion mixing step of dispersion mixing the first component and the second component in a dispersion mixing zone of an extruder, in the dispersion mixing zone, by making one or more selected from the group consisting of the ratio of zone length to barrel inner diameter, mixture filling rate, temperature, pressure, and space volume ratio different in the barrel length direction, the traveling length l of the mixture in the barrel is divided by the barrel inner diameter d to obtain a 1 / d value, and the ratio ΔE / ΔM of the change amount ΔE of the tensile elongation rate per unit 1 / d to the change amount ΔM of the flexural modulus per unit 1 / d changes in the barrel length direction; the units of the l and the d are mm, the unit of the ΔE is %, and the unit of the ΔM is GPa.

4. A method for manufacturing a resin composition comprising a first component and a second component, wherein, The first component is a polymer, the second component is an organic fiber or a combination of an organic fiber and a polymer different from the first component, the method includes the following steps: a dispersion mixing step of dispersing and mixing the first component and the second component in a dispersion mixing zone of an extruder to obtain a dispersion mixed product; and a distributive mixing step of distributively mixing at least the dispersion mixed product in a distributive mixing zone of the extruder to obtain a resin composition, wherein at least one of the dispersion mixing zone and the distributive mixing zone is different from each other in terms of one or more selected from the group consisting of the ratio of the zone length to the barrel inner diameter, the mixture filling rate, the temperature, the pressure, and the space volume ratio, an increment EA of the tensile elongation rate of the effluent flowing out from the dispersion mixing zone relative to the tensile elongation rate of the influent flowing into the dispersion mixing zone and an increment EB of the tensile elongation rate of the effluent flowing out from the distributive mixing zone relative to the tensile elongation rate of the influent flowing into the distributive mixing zone satisfy the relationship EA > EB, an increment MA of the flexural modulus of the effluent flowing out from the dispersion mixing zone relative to the flexural modulus of the influent flowing into the dispersion mixing zone and an increment MB of the flexural modulus of the effluent flowing out from the distributive mixing zone relative to the flexural modulus of the influent flowing into the distributive mixing zone satisfy the relationship MA > MB.

5. A method for manufacturing a resin composition containing a first component and a second component, wherein, the first component is a polymer, the second component is an organic fiber or a combination of an organic fiber and a polymer different from the first component, the method includes the following steps: a dispersion mixing step of dispersing and mixing the first component and the second component in a dispersion mixing zone of an extruder to obtain a dispersion mixed product; and a distributive mixing step of distributively mixing at least the dispersion mixed product in a distributive mixing zone of the extruder to obtain a resin composition, the concentration CA of the second component in the dispersion mixing zone is 10% by mass to 90% by mass, the concentration CB of the second component in the distributive mixing zone is 1% by mass to 50% by mass, and the ratio CA / CB is 2 to 90.

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