WO2024014546A1 - Composition de résine et procédé de production de celle-ci - Google Patents

Composition de résine et procédé de production de celle-ci Download PDF

Info

Publication number
WO2024014546A1
WO2024014546A1 PCT/JP2023/026119 JP2023026119W WO2024014546A1 WO 2024014546 A1 WO2024014546 A1 WO 2024014546A1 JP 2023026119 W JP2023026119 W JP 2023026119W WO 2024014546 A1 WO2024014546 A1 WO 2024014546A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin composition
resin
cellulose
mass
less
Prior art date
Application number
PCT/JP2023/026119
Other languages
English (en)
Japanese (ja)
Inventor
敦志 馬場
亮介 小澤
Original Assignee
旭化成株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 旭化成株式会社 filed Critical 旭化成株式会社
Publication of WO2024014546A1 publication Critical patent/WO2024014546A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B62—LAND VEHICLES FOR TRAVELLING OTHERWISE THAN ON RAILS
    • B62D—MOTOR VEHICLES; TRAILERS
    • B62D29/00—Superstructures, understructures, or sub-units thereof, characterised by the material thereof
    • B62D29/04—Superstructures, understructures, or sub-units thereof, characterised by the material thereof predominantly of synthetic material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene

Definitions

  • the present invention relates to a resin composition containing a polypropylene resin and cellulose fibers, a method for producing the same, and a molded article formed from the resin composition.
  • Polypropylene (PP)-based resin has an excellent balance of various mechanical properties such as tensile strength and impact resistance, and has advantages such as transparency, ease of molding, light weight, and low environmental impact when disposed of. , is widely used in a wide range of applications.
  • PP Polypropylene
  • Styrenic elastomers are known as modifiers that improve the toughness and impact resistance of polypropylene resins.
  • the styrene elastomer is finely dispersed in the polypropylene resin, contributing to improved impact resistance.
  • Patent Document 1 describes a polypropylene resin composition suitable for use as an unpainted resin molding material because it has scratch resistance that is compatible with impact resistance.
  • a polypropylene resin composition containing 3 to 10% by weight of an elastomer (B) is described.
  • fillers are used in resin compositions to improve their mechanical properties.
  • various methods of reducing environmental impact are being studied, and the use of cellulose is being explored, focusing on its advantages of being a low specific gravity and recyclable material.
  • cellulose fiber is advantageous in that it has a good effect of improving physical properties per amount used.
  • Patent Document 2 discloses a cellulose composite resin in which a base resin, cellulose fibers, a dispersant, and a rubber-containing polymer are used for the purpose of providing a cellulose composite resin that has high impact strength and suppresses the coloring of the resin to the extent that there is no problem in coloring the desired color.
  • a cellulose composite resin is described, wherein the ⁇ -cellulose content in the cellulose fibers is 50% by mass or more and less than 80% by mass.
  • Patent Document 3 discloses a resin that has excellent environmental properties, less decrease in impact strength, low specific gravity, high rigidity, and excellent molded appearance by uniformly dispersing nano natural polymers in matrix components such as resin.
  • a molten mixture is described, which is characterized by containing a nano natural polymer and an oligomer having a vinyl aromatic compound as a main component.
  • WO 2005/000003 describes that the nano natural polymer may be a cellulose nanofiber and the oligomer may be a styrenic oligomer.
  • cellulose nanofibers When cellulose nanofibers are present as a filler in a molded article containing a polypropylene resin and a styrene elastomer, the effect of improving physical properties by cellulose nanofibers (for example, the effect of reducing the coefficient of linear expansion and the effect of improving the elastic modulus or toughness) does not occur. However, there was a problem in that the presence of cellulose nanofibers reduced the transparency of the molded product.
  • One aspect of the present invention solves the above problems and provides a resin composition containing a polypropylene resin and cellulose fibers and having excellent transparency, a method for producing the same, and a molded article formed from the resin composition.
  • Another aspect of the present invention is a resin composition that solves the above problems and has a low coefficient of linear expansion, high toughness, and excellent transparency, a method for producing the same, and a molded article formed from the resin composition. The purpose is to provide.
  • a resin composition containing a polypropylene resin, a styrene elastomer, and a cellulose fiber The polypropylene resin is molded into a sheet with a thickness of 0.2 mm, and the refractive index (P1) of the polypropylene resin is measured using the Abbe equation using the structural property correlation method based on the molecular structure of the cellulose fiber.
  • a resin composition in which the calculated ratio (C2/P1) of the refractive index (C2) of the cellulose fibers is 0.950 to 1.050.
  • a resin composition containing a polypropylene resin, a styrene elastomer, and a cellulose fiber was molded into a sheet with a thickness of 0.2 mm, and the refractive index (P1) of the polypropylene resin was measured using the Abbe method, and the structural property correlation method was used based on the molecular structure of the cellulose fiber.
  • ) from the refractive index (C2) of the cellulose fiber is 0.025 to 0.090.
  • the control composition is formed into a sheet with a thickness of 0.2 mm, and the refractive index (R1) of the sheet is measured using the Abbe formula, which is calculated by the structural property correlation method based on the molecular structure of the cellulose fiber.
  • the cellulose fiber has a refractive index (C2) ratio (C2/R1) of 0.970 to 1.050
  • the control composition consists of the same polypropylene resin and styrene elastomer as the polypropylene resin and styrene elastomer in the resin composition, and the mass ratio of the polypropylene resin and styrene elastomer in the control composition is The resin composition according to item 1 or 2, which is equal to the mass ratio of the polypropylene resin and the styrene elastomer in the resin composition.
  • the control composition is formed into a sheet with a thickness of 0.2 mm, and the refractive index (R1) of the sheet is measured by the Abbe formula, and the refractive index (R1) is calculated by the structural property correlation method based on the molecular structure of the cellulose fiber.
  • ) from the refractive index (C2) of the cellulose fiber is 0.001 to 0.100
  • the control composition consists of the same polypropylene resin and styrene elastomer as the polypropylene resin and styrene elastomer in the resin composition, and the mass ratio of the polypropylene resin and styrene elastomer in the control composition is The resin composition according to any one of items 1 to 3, which is equal to the mass ratio of polypropylene resin and styrene elastomer in the resin composition. [Item 5] The resin composition according to item 3 or 4, wherein the reference composition has a refractive index (R1) of 1.450 to 1.550.
  • a resin composition containing a polypropylene resin, a styrene elastomer, and a cellulose fiber The difference between the refractive index (P2) of the polypropylene resin calculated by the structural property correlation method based on the molecular structure and the refractive index (C2) of the cellulose fiber calculated by the structural property correlation method based on the molecular structure (
  • the cellulose fiber is a modified cellulose fiber, The resin composition according to item 9, wherein the refractive index (C2) of the cellulose fiber is 1.480 to 1.580.
  • the cellulose fiber is an acetylated cellulose fiber, The resin composition according to any one of items 1 to 10, wherein the acetylated cellulose fiber has a degree of acetyl substitution of 0.1 to 1.5.
  • [Item 14] The resin composition according to any one of items 1 to 13, wherein the ratio of the SP value of the cellulose fiber to the SP value of the polypropylene resin is 1.3 to 1.9.
  • [Item 15] The resin composition according to any one of items 1 to 14, wherein the polypropylene resin is homopolypropylene.
  • [Item 16] The resin composition according to any one of items 1 to 15, wherein the polypropylene resin has a melt mass flow rate (MFR) of 10 to 80 g/10 minutes at 230° C. and a load of 21.2 N.
  • MFR melt mass flow rate
  • the resin composition includes a styrenic resin containing the styrenic elastomer, The resin composition is 50% to 89.5% by mass of the polypropylene resin, 10% to 40% by mass of the styrenic elastomer, and 0.5% to 30% by mass of the cellulose fiber.
  • the mixing step is Obtaining an elastomer masterbatch containing a styrenic elastomer and cellulose fibers; kneading the elastomer masterbatch with the polypropylene resin;
  • the resin composition further includes one or more selected from the group consisting of liquid rubber and surfactant, and the method includes: Further comprising the step of obtaining a cellulose masterbatch containing cellulose fibers and one or more selected from the group consisting of liquid rubber and surfactant, The method according to item 25, wherein the elastomer masterbatch is obtained by mixing a styrenic elastomer and the cellulose masterbatch.
  • the resin composition includes a styrenic resin containing the styrenic elastomer, In the mixing step, the polypropylene resin, the styrene resin, and the cellulose fiber are mixed, The polypropylene resin is molded into a sheet with a thickness of 0.2 mm, and the styrene resin is molded into a sheet with a thickness of 0.2 mm with respect to the refractive index (P1) of the polypropylene resin when the sheet is measured by the Abbe formula.
  • P1 refractive index
  • a resin composition comprising a polypropylene resin, a styrene elastomer, and cellulose nanofibers, In the resin composition, the polypropylene resin forms a continuous phase, A dispersed phase composed of the cellulose nanofibers and a polymer covering the cellulose nanofibers is formed in the continuous phase, A resin composition in which the polymer includes the styrenic elastomer.
  • a method for producing a resin composition according to item 28 comprising: A method comprising a mixing step of mixing a polypropylene resin, a styrenic elastomer, and cellulose nanofibers.
  • a method for producing a resin composition containing a polypropylene resin, a styrene elastomer, and cellulose nanofibers the method comprising: a step of obtaining an elastomer masterbatch containing a styrene-based elastomer and cellulose nanofibers, and a step of kneading the elastomer masterbatch with the polypropylene-based resin; including methods.
  • An outer panel for an automobile comprising the resin composition according to any one of items 1 to 23 and 28.
  • a resin composition containing a polypropylene resin and cellulose fibers and having excellent transparency, a method for producing the same, and a molded article formed from the resin composition can be provided.
  • a resin composition having a low coefficient of linear expansion, high toughness, and excellent transparency, a method for producing the same, and a molded article formed from the resin composition can be provided.
  • FIG. 2 is a diagram showing a scanning electron microscope (SEM) image of a cross section of the resin composition obtained in Example 2-1.
  • the present embodiment exemplary embodiments of the present invention (hereinafter abbreviated as "the present embodiment”) will be described, but the present invention is not limited to these embodiments at all.
  • the characteristic values of the present disclosure are values measured by the method described in the [Examples] section of the present disclosure or a method understood by those skilled in the art to be equivalent thereto, unless otherwise specified.
  • ⁇ Resin composition including a polypropylene resin, a styrenic elastomer, and cellulose fibers.
  • the resin composition includes a styrenic resin containing the above styrenic elastomer.
  • the polypropylene resin may form a continuous phase and the styrene elastomer (or styrene resin) may form a dispersed phase in the resin composition.
  • cellulose is inherently hydrophilic due to its hydroxyl groups, if at least some of the hydroxyl groups of the cellulose fibers are modified, they may be more hydrophobic than unmodified cellulose fibers.
  • the styrene elastomer In a composite of a polypropylene resin and a styrene elastomer, the styrene elastomer not only improves the toughness of the polypropylene resin and improves its impact resistance, but also maintains the excellent transparency inherent in the polypropylene resin. It can also contribute to improvements.
  • the present inventors when further blending a filler for the purpose of improving mechanical properties, the present inventors achieved high transparency (i.e., high ultraviolet and visible light transmittance) while obtaining the desired reinforcing effect of the filler.
  • high transparency i.e., high ultraviolet and visible light transmittance
  • the present inventors have discovered that in a composition containing a polypropylene resin, a styrene elastomer, and a cellulose fiber, it is particularly important to control the refractive index ratio or refractive index difference between the polypropylene resin and the cellulose fiber. It is advantageous to control the refractive index of cellulose fibers by controlling the modified state of the cellulose fibers in order to achieve a high level of both mechanical properties and transparency of the resin composition. I found that.
  • the resin composition of the present embodiment can have high transparency in one aspect, and when such a resin composition is used as a base dye material, excellent color development and/or brightness can be exhibited. can be done.
  • the refractive index of the polypropylene resin is a refractive index evaluated by the following procedure 1 in one embodiment, and a refractive index evaluated by the following procedure 2 in one embodiment.
  • the refractive index of the styrene resin is the refractive index evaluated in Procedure 1 below.
  • the refractive index of the cellulose fiber is the refractive index evaluated in Procedure 2 below.
  • Step 1 In this procedure, 1 g of the material is preheated under vacuum at 200°C for 5 minutes, then pressed at 10 MPa and held for 1 minute, and then rapidly cooled at room temperature to form a sheet with a thickness of 0.2 mm. The index is measured using an Abbe refractometer.
  • the above-mentioned material is a charging material used for manufacturing a resin composition, but if evaluation using the charging material is not possible, the resin composition is prepared using an organic or inorganic solvent that dissolves polypropylene resin or styrene resin. A sample isolated by treating a substance to dissolve the resin, removing impurities by filtration and extraction, and distilling off the solvent from the resulting solution may be used.
  • Step 2 This procedure focuses on the molecular structure of the material (more specifically, monomer composition) for polypropylene resins, and the molecular structure of the material (more specifically, presence or absence of substitution, type of substituent, and degree of substitution) for cellulose fibers. Calculated using the structural property correlation method based on Specifically, the refractive index is determined by calculation using the Synthia module of Materials Studio manufactured by BIOVIA Corporation. Details of the calculation method will be described later in the [Examples] section of this disclosure.
  • the refractive index of the cellulose fibers is adjusted to a range close to that of the polypropylene resin.
  • interfacial reflection between the cellulose fibers and the polypropylene resin in the resin composition can be suppressed.
  • reflection that occurs locally at the interface between the resin component and the filler component causes increased light scattering of the entire resin composition, and therefore increases haze. Suppression of interfacial reflection contributes to improved transparency by reducing haze of the resin composition.
  • the refractive index (C2) of the cellulose fiber is 1.480 or more, or 1.500 or more, or 1.510 or more, or 1.520 or more; 600 or less, or 1.590 or less, or 1.580 or less, or 1.570 or less, or 1.560 or less.
  • the refractive index (C2) can typically be 1.480 to 1.580.
  • the refractive index of the cellulose fibers may be adjusted within a desired range by controlling the type and/or degree of substitution of the substituents on the cellulose fibers.
  • the refractive index (P1) of the polypropylene resin when evaluated in Procedure 1 of the present disclosure is 1.450 or more, or 1.490 or more, or 1.500 or more, and in one embodiment, 1. It is 550 or less, or 1.530 or less, or 1.520 or less.
  • the resin composition is treated with an organic or inorganic solvent that dissolves the polypropylene resin to dissolve the resin, and then the resin is dissolved by filtration and extraction.
  • a polypropylene resin isolated by distilling off the solvent from the solution obtained by removing impurities may be used to prepare a sample sheet and measure the refractive index according to Procedure 1.
  • the refractive index (P2) of the polypropylene resin when evaluated in Step 2 of the present disclosure is 1.410 or more, or 1.440 or more, or 1.450 or more; It is 510 or less, or 1.490 or less, or 1.480 or less.
  • the refractive index (S1) of the styrenic resin when evaluated in Step 1 of the present disclosure is: In one aspect, it is 1.450 or more, or 1.470 or more, or 1.480 or more, or 1.490 or more, and in one aspect, 1.550 or less, or 1.520 or less, or 1.510 or less, or 1.500 or less.
  • the ratio (C2/P1) of the refractive index (C2) of the cellulose fiber when evaluated according to the procedure 2 of the present disclosure to the refractive index (P1) of the polypropylene resin when evaluated according to the procedure 1 of the present disclosure is high transparency.
  • a resin composition with a It is .040 or less, or 1.035 or less, or 1.030 or less, or 1.025 or less, or 1.020 or less.
  • the ratio (C2/P2) of the refractive index (C2) of cellulose fibers when evaluated according to Step 2 of the present disclosure to the refractive index (P2) of the polypropylene resin when evaluated according to Step 2 of the present disclosure is high transparency.
  • a resin composition with a .080 or less, or 1.070 or less, or 1.065 or less, or 1.060 or less, or 1.055 or less, or 1.050 or less.
  • the difference between the refractive index (P1) of the polypropylene resin when evaluated in Step 1 of the present disclosure and the refractive index (C2) of the cellulose fiber when evaluated in Step 2 of the present disclosure (
  • ) between the refractive index (P2) of the polypropylene resin when evaluated in Step 2 of the present disclosure and the refractive index (C2) of the cellulose fiber when evaluated in Step 2 of the present disclosure is , from the viewpoint of obtaining a highly transparent resin composition, is preferably 0.100 or less, or 0.090 or less, or 0.080 or less. From the viewpoint of transparency of the resin composition, it is preferable that the difference is as small as possible, but from the viewpoint of simplifying the combination operation of cellulose fibers and polypropylene resin, in one embodiment, it is 0.050 or more, or 0.060 or more, or It may be 0.070 or more.
  • the refractive index of the mixture of the polypropylene resin and the styrene elastomer described below, when evaluated in Procedure 1 of the present disclosure is 1.45 or more, or 1.47 or more, or 1.48 or more, or 1. 49 or more, and in one embodiment, 1.55 or less, or 1.53 or less, or 1.52 or less, or 1.51 or less.
  • the resin composition is treated with an organic or inorganic solvent that dissolves the polypropylene resin and styrene elastomer to dissolve the resin.
  • an organic or inorganic solvent that dissolves the polypropylene resin and styrene elastomer to dissolve the resin.
  • the ratio (C2/R1) of the refractive index (C2) of the cellulose fibers when evaluated in Procedure 2 to the refractive index (R1) of the control composition when evaluated in Procedure 1 is 0.970 or more. , or 1.000 or more, or 1.020 or more, or 1.025 or more, or 1.030 or more, and in one embodiment, 1.050 or less, or 1.040 or less, or 1.035 or less.
  • control composition is composed of the same polypropylene resin and styrene elastomer as the polypropylene resin and styrene elastomer in the resin composition of the present disclosure, and is composed of the same polypropylene resin and styrene elastomer as the polypropylene resin and styrene in the control composition. It means a composition in which the mass ratio of the polypropylene resin and the styrene elastomer is equal to the mass ratio of the polypropylene resin and the styrene elastomer in the resin composition of the present disclosure.
  • ) between the refractive index of the control composition (R1) when evaluated in Step 1 and the refractive index (C2) of the cellulose fibers when evaluated in Step 2 is the From the viewpoint of obtaining a composition, it is preferably 0.100 or less, or 0.050 or less, or 0.030 or less, or 0.020 or less. From the viewpoint of transparency of the resin composition, it is preferable that the difference is as small as possible; however, from the viewpoint of simplifying the combination operation of the resin and cellulose fibers, in one embodiment, the difference is 0.001 or more, or 0.003 or more, or 0. 005 or more, or 0.007 or more.
  • the refractive index (R1) of the control composition when evaluated in Procedure 1 is 1.450 or more, or 1.480 or more, or 1.490 or more, and in one aspect, 1.550 or less, or 1.520 or less, or 1.510 or less.
  • the ratio (S1/P1) of the refractive index (S1) of the styrene resin when evaluated in Procedure 1 to the refractive index (P1) of the polypropylene resin when evaluated in Procedure 1 is preferably 0.950 or more. , or 0.970 or more, or 0.980 or more, or 0.990 or more, and preferably 1.050 or less, or 1.020 or less, or 1.010 or less, or 1.000 or less.
  • ) between the refractive index of the polypropylene resin (P1) when evaluated in step 1 and the refractive index (S1) of the styrene resin when evaluated in step 1 is the result of high transparency. From the viewpoint of obtaining a resin composition, it is preferably 0.100 or less, or 0.050 or less, or 0.030 or less, or 0.020 or less.
  • the above-mentioned difference is as small as possible; however, from the viewpoint of simplifying the operation of combining the polypropylene resin and the styrene resin, in one embodiment, the difference is 0.001 or more, or 0.003 or more, Or it may be 0.005 or more, or 0.007 or more.
  • the ratio (s1/P1) of the refractive index (s1) of the styrene elastomer when evaluated in procedure 1 to the refractive index (P1) of the polypropylene resin when evaluated in procedure 1 is The ratio of the refractive index of the styrene resin evaluated in Procedure 1 to the refractive index of the polypropylene resin is preferably in the same range as described above.
  • ) between the refractive index (P1) of the polypropylene resin when evaluated in Step 1 and the refractive index (s1) of the styrene elastomer when evaluated in Step 1 is the difference (
  • the cellulose fiber of the present disclosure has a modified group formed by partially modifying a hydroxyl group, such as an acetyl group, a propionyl group, a butyryl group, a carboxymethyl group, a methyl group, an ethyl group, a hydroxyethyl group, a hydroxypropyl group, and a carboxyl group. It may have one or more selected from the group consisting of groups. In one embodiment, hydrophobization by modification is advantageous for improving the heat resistance of cellulose fibers.
  • Cellulose fibers may be obtained from various cellulose fiber raw materials selected from natural cellulose and regenerated cellulose.
  • Natural cellulose includes wood pulp obtained from wood species (hardwood or softwood), non-wood pulp obtained from non-wood species (cotton, bamboo, hemp, bagasse, kenaf, cotton linters, sisal, straw, etc.), and animal (e.g. Cellulose fiber aggregates produced by sea squirts), algae, and microorganisms (eg, acetic acid bacteria) can be used.
  • animal e.g. Cellulose fiber aggregates produced by sea squirts
  • algae e.g. Cellulose fiber aggregates produced by sea squirts
  • microorganisms eg, acetic acid bacteria
  • regenerated cellulose regenerated cellulose fibers (viscose, cupra, tencel, etc.), cellulose derivative fibers, regenerated cellulose or cellulose derivative ultrafine threads obtained by electrospinning, etc.
  • linters are preferred from the viewpoint of heat resistance.
  • raw materials may be adjusted, as necessary, by mechanical beating, fibrillation, or micronization using a grinder, refiner, etc. to adjust the fiber diameter, fiber length, fibrillation degree, etc., or by bleaching or refining using chemicals.
  • the content of components other than cellulose can be adjusted.
  • Cellulose fibers are obtained by mechanically dry or wet pulverizing cellulose raw materials.
  • the modification may be performed before, during and/or after the refinement.
  • a single device may be used one or more times, or a plurality of devices may be used each one or more times.
  • Equipment used for micronization is not particularly limited, but examples include high-speed rotation type, colloid mill type, high-pressure type, roll mill type, and ultrasonic type equipment, including high-pressure or ultra-high pressure homogenizers, refiners, beaters, PFI Mills, kneaders, dispersers, high-speed defibrators, grinders (stone mills), ball mills, vibration mills, bead mills, conical refiners, disc refiners, single-, double-, or multi-shaft kneaders/extruders, high-speed rotation homomixer, refiner, defibrator, beater, friction grinder, high shear fibrilator (e.g.
  • cavitron rotor/starter device cavitron rotor/starter device
  • disperger disperger
  • homogenizer for example, a microfluidizer
  • pulp fibers to interact with metal or cutlery around a rotating shaft
  • a device that uses friction between pulp fibers can be used.
  • the cellulose fibers before or after modification can be obtained as a slurry.
  • Slurries can be prepared by dispersing and micronizing cellulosic fiber raw materials in water and/or other media (eg, organic solvents, inorganic acids, bases, and/or ionic liquids).
  • the organic solvent used in the micronization treatment is not particularly limited, but includes, for example, alcohols having 1 to 20 carbon atoms, preferably 1 to 4 carbon atoms, such as methanol, ethanol, and propanol; methyl cellosolve, propylene glycol monomethyl ether, and the like; Glycol ethers having 2 to 20 carbon atoms, preferably 2 to 6 carbon atoms; preferably 2 to 20 carbon atoms, such as propylene glycol monomethyl ether, 1,2-dimethoxyethane, diisopropyl ether, tetrahydrofuran, 1,4-dioxane, etc.
  • alcohols with 1 to 6 carbon atoms can be used alone or in combination of two or more, but from the viewpoint of operability in the refinement process, alcohols with 1 to 6 carbon atoms, glycol ethers with 2 to 6 carbon atoms, glycol ethers with 2 to 6 carbon atoms, 8 ethers, ketones with 3 to 6 carbon atoms, lower alkyl ethers with 2 to 5 carbon atoms, carboxylic acids with 1 to 8 carbon atoms, esters with 2 to 6 carbon atoms, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, Dimethyl sulfoxide and the like are preferred.
  • the inorganic acid examples include hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, and boric acid, but from the viewpoint of defibrating efficiency and ease of handling, it is preferably selected from the group consisting of hydrochloric acid, sulfuric acid, and phosphoric acid. One type or two or more types.
  • Examples of the base include hydroxides such as sodium hydroxide, potassium hydroxide, and calcium hydroxide, carbonates such as sodium carbonate, potassium carbonate, and calcium carbonate, and organic amines such as ammonia, triethylamine, and triethanolamine. From the viewpoint of defibrating efficiency and handleability, preferably one or more selected from the group consisting of hydroxides, carbonates, and organic amines.
  • the ionic liquid in the present disclosure refers to a liquid salt that contains an organic ion in at least one of a cation part and an anion part, and the melting point of only the ion is 100°C or less.
  • the ionic liquid has at least one cation selected from the group consisting of an imidazolium cation, a pyrrolidinium cation, a piperidinium cation, a morpholinium cation, a pyridinium cation, a quaternary ammonium cation, and a phosphonium cation. It is preferable to have.
  • ionic liquids having an imidazolium skeleton such as the following formula (1):
  • R 1 and R 2 each independently represent an alkyl group or an allyl group having 1 to 8 carbon atoms, and X represents an anion.
  • the imidazolium-based ionic liquid represented by is preferable because it has a relatively lower melting point than other ionic liquids, has a wide temperature range in which it exists as a liquid, has fluidity even at low temperatures, and has excellent thermal stability.
  • the number of carbon atoms in R 1 and R 2 is preferably 4 or less, further preferably 3 or less, and most preferably 2 or less from the viewpoint of fibrillating properties.
  • anion components include halide ions (Cl - , Br - , I -, etc.), carboxylic acid anions (for example, carboxylic acid anions having a total of 1 to 3 carbon atoms, such as C 2 H 5 CO 2 - , CH 3 CO 2 -). , HCO 2 -, etc.), pseudohalide ions (i.e., ions that are monovalent and have properties similar to halide ions, e.g.
  • sulfones Acid anions organic sulfonate anions (methanesulfonate anions, etc.), phosphate anions (ethyl phosphate anions, methyl phosphate anions, hexafluorophosphate anions, etc.), borate anions (tetrafluoroborate anions, etc.), perchloric acid
  • examples include anions, and from the viewpoint of fibrillating properties, halide ions and carboxylic acid anions are preferred.
  • imidazolium-based ionic liquids examples include 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium formate, 1-allyl-3-methylimidazolium chloride, and 1-allyl-3-methylimidazolium chloride.
  • Cellulose fiber raw materials can be defibrated using only ionic liquids, but if the dissolving power for cellulose is too high and there is a risk of dissolving cellulose fibers, water and/or an organic solvent may be added to the ionic liquids.
  • the type of organic solvent to be added may be selected appropriately taking into consideration the compatibility with the ionic liquid, the affinity with cellulose, the solubility of the mixed solvent in the cellulose fiber raw material, the viscosity, etc., but N,N-dimethylacetamide, N, One or more selected from the group consisting of N-dimethylformamide, 1-methyl-2-pyrrolidone, dimethyl sulfoxide, acetonitrile, methanol, and ethanol is preferred.
  • the total amount of water and/or other media used in the micronization treatment is not particularly limited as long as it is an effective amount that can disperse the cellulose fiber raw material, but is preferably 1 times or more by mass based on the cellulose fiber raw material. More preferably 10 times by mass or more, still more preferably 50 times by mass or more, preferably 10,000 times by mass or less, more preferably 5,000 times by mass or less, still more preferably 2,000 times by mass or less, particularly preferably 1,000 times by mass or less. .
  • Cellulose fiber raw materials contain alkali-soluble components and sulfuric acid-insoluble components (lignin, etc.), so even if the alkali-soluble components and sulfuric acid-insoluble components are reduced through a purification process such as delignification through cooking and a bleaching process. good.
  • purification processes such as delignification through cooking and bleaching processes break the molecular chains of cellulose and change the weight average molecular weight and number average molecular weight. It is desirable that the weight average molecular weight of the fibers and the ratio of the weight average molecular weight to the number average molecular weight be controlled within appropriate ranges.
  • cellulose fibers will have a lower molecular weight due to purification processes such as delignification through cooking and bleaching processes, and that the quality of the cellulose fiber raw materials will change and the proportion of alkali-soluble components will increase. Since alkali-soluble components have poor heat resistance, the refining and bleaching processes of cellulose fiber raw materials are controlled so that the amount of alkali-soluble components contained in cellulose fiber raw materials is within a certain range. This is desirable.
  • the cellulose fiber raw material may be modified (chemically modified), including inorganic esters such as nitric esters, sulfuric esters, phosphoric esters, silicate esters, and boric esters, and organic esters such as acetylation and propionylation.
  • inorganic esters such as nitric esters, sulfuric esters, phosphoric esters, silicate esters, and boric esters
  • organic esters such as acetylation and propionylation.
  • etherified products such as methyl ether, hydroxyethyl ether, hydroxypropyl ether, hydroxybutyl ether, carboxymethyl ether, and cyanoethyl ether
  • TEMPO oxide obtained by oxidizing the primary hydroxyl group of cellulose, etc.
  • the SP value of the cellulose fibers is preferably adjusted to a range close to that of the polypropylene resin.
  • the SP value of the cellulose fiber is preferably 22 or more, or 24 or more, or 26 or more, and preferably 32 or less, or 30 or less, or 28 or less.
  • the SP value is a value determined by the fedors method in the Synthia module of Materials Studio manufactured by BIOVIA Corporation.
  • the ratio of the SP value of the cellulose fiber to the SP value of the polypropylene resin is preferably 1.3 or more, or 1.4 or more, or 1.5 or more, and preferably 1.9 or less, or 1. 8 or less, or 1.7 or less.
  • the resin composition of the present embodiment includes a styrene elastomer, and the styrene elastomer has an SP value of about 15 to 20, for example, the SEBS (hydrogenated styrene-butadiene-styrene) elastomer has an SP value of about 16 to 18.
  • the number average fiber length of the cellulose fibers is preferably 30 ⁇ m or more, 50 ⁇ m or more, or 100 ⁇ m or more, from the viewpoint of obtaining a good effect of improving physical properties of the resin composition, and the number average fiber length of the cellulose fibers is preferably 30 ⁇ m or more, 50 ⁇ m or more, or 100 ⁇ m or more, and the number average fiber length of the cellulose fibers is preferably 30 ⁇ m or more, 50 ⁇ m or more, or 100 ⁇ m or more, and From the viewpoint of reducing the thickness and obtaining good transparency of the resin composition, it is preferably 750 ⁇ m or less, or 700 ⁇ m or less, or 650 ⁇ m or less, or 600 ⁇ m or less.
  • the number average fiber diameter of the cellulose fibers is 1000 nm or less, or 900 nm or less, or 800 nm or less, or 700 nm, from the viewpoint of reducing light scattering of the resin composition and obtaining good transparency of the resin composition. or 600 nm or less, or 500 nm or less, or 400 nm or less, or 300 nm or less, or 200 nm or less; It is 5 nm or more, or 10 nm or more, or 15 nm or more, or 20 nm or more.
  • the cellulose fibers may be nanofibers, and the average fiber diameter of the nanofibers is in one embodiment between 2 and 1000 nm.
  • the number average fiber length (L)/number average fiber diameter (D) ratio of the cellulose fibers is preferably 30 or more, or 50 or more, or 80 or more, from the viewpoint of obtaining a good effect of improving the physical properties of the resin composition. 100 or more, or 120 or more, or 150 or more, and from the viewpoint of reducing light scattering of the resin composition and obtaining good transparency of the resin composition, preferably 5000 or less, or 3000 or less, or 2000 or less, Or less than 1000.
  • the number average fiber diameter (D), number average fiber length (L), and L/D ratio of the cellulose fibers of the present disclosure are measured using a scanning electron microscope (SEM) according to the following procedure. It is a value.
  • the aqueous dispersion of cellulose fibers was replaced with tert-butanol, diluted to 0.001 to 0.1% by mass, and treated using a high shear homogenizer (for example, manufactured by IKA, trade name "Ultra Turrax T18") under the treatment conditions:
  • the measurement sample is obtained by dispersing at a rotational speed of 15,000 rpm for 3 minutes, casting onto a silicon substrate coated with osmium, and air drying, and measuring with a high-resolution scanning electron microscope (SEM).
  • the length (L) and diameter (D) of 100 fibrous substances were randomly selected in an observation field whose magnification was adjusted so that at least 100 fibrous substances could be observed. is measured and the ratio (L/D) is calculated.
  • the number average value of length (L), number average value of diameter (D), and number average value of ratio (L/D) are calculated.
  • the fiber length, fiber diameter, and L/D ratio of the cellulose fibers contained in the resin composition can be confirmed by measuring them using the above-mentioned measurement method as a measurement sample.
  • the fiber length, fiber diameter, and L/D ratio of the cellulose fibers contained in the resin composition can be determined by dissolving the polymer components contained in these in an organic or inorganic solvent that can dissolve the polymer components and separating the cellulose fibers. After thorough washing with the solvent, an aqueous dispersion was prepared by replacing the solvent with pure water, diluted with pure water to a cellulose fiber concentration of 0.1 to 0.5% by mass, and cast on mica. However, it can be confirmed by measuring an air-dried sample using the above-mentioned measuring method.
  • the cellulose fibers are preferably highly and uniformly finely divided.
  • the volume fraction of aggregates with a volume of 110 ⁇ m 3 or more in the resin composition is preferably 5% or less, or 4% or less, or 3% or less, or 2% or less, or 1.5 % or less.
  • the volume fraction of aggregates is a value measured for a resin composition by the following method using X-ray CT measurement.
  • the 3D data obtained by X-ray CT measurement is binarized and pixels containing only aggregates are extracted. Thereafter, the ratio of the total volume of aggregates larger than a cube with one side of 4.8 ⁇ m to the total volume of the observation range of X-ray CT is calculated as the volume fraction of aggregates.
  • the specific surface area of the cellulose fiber is preferably 40 m 2 /g or more, 45 m 2 /g or more, or 50 m 2 /g or more, or 55 m 2 /g or more, or 60 m 2 /g or more, or 70 m 2 /g or more, and preferably 200 m 2 /g or less, from the viewpoint of ease of manufacturing and handling of cellulose fibers. or 170 m 2 /g or less, or 160 m 2 /g or less.
  • the specific surface area is determined by drying approximately 0.2 g of a sample under vacuum at 120°C for 5 hours using a specific surface area/pore distribution measuring device (for example, Nova-4200e, manufactured by Quantachrome Instruments), and then drying it in liquid nitrogen.
  • the adsorption amount of nitrogen gas at the boiling point was measured at 5 points in the range of relative vapor pressure (P/P 0 ) from 0.05 to 0.2 (multipoint method), and the BET specific surface area (m 2 /g).
  • the crystallinity of the cellulose fibers is preferably 55% or more. When the degree of crystallinity is within this range, the mechanical properties (strength, dimensional stability) of cellulose itself are high, so when cellulose fibers are dispersed in a resin, the strength and dimensional stability of the resin composition tend to be high. .
  • the lower limit of the crystallinity is more preferably 60%, even more preferably 70%, and most preferably 80%.
  • the degree of crystallinity of the cellulose fibers is preferably higher in terms of the effect of improving physical properties, but from the viewpoint of easily adjusting the degree of substitution of the cellulose fibers so as to obtain a desired refractive index, it is preferably 99% or less, or 95% or less, or 90% or less.
  • Types I, II, III, and IV are known as crystalline polymorphs of cellulose. Among these, types I and II are particularly widely used, and types III and IV are not available on a laboratory scale. Although it has been obtained, it has not been widely used on an industrial scale.
  • the cellulose fibers of the present disclosure have relatively high structural mobility, and by dispersing the cellulose fibers in a resin, the resin has a lower linear expansion coefficient and has better strength and elongation during tensile and bending deformation. Since a composition can be obtained, cellulose fibers containing cellulose type I crystals or cellulose type II crystals are preferable, and cellulose fibers containing cellulose type I crystals and having a crystallinity of 55% or more are more preferable.
  • 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, more preferably 450 or more, and preferably 3500 or less. , more preferably 3300 or less, more preferably 3200 or less, more preferably 3100 or less, more preferably 3000 or less.
  • the degree of polymerization of cellulose fibers be within the above range. From the viewpoint of processability, it is preferable that the degree of polymerization is not too high, and from the viewpoint of developing mechanical properties, it is desirable that the degree of polymerization is not too low.
  • the degree of polymerization of cellulose fibers means the average degree of polymerization measured according to the reduced specific viscosity method using a copper ethylenediamine solution described in Confirmation Test (3) of the "15th Edition Japanese Pharmacopoeia Manual (published by Hirokawa Shoten)" .
  • the degree of polymerization of modified cellulose fibers may not be accurately calculated due to the presence of modifying groups.
  • the degree of polymerization of the cellulose fibers immediately before modification or the cellulose raw material immediately before modification, which is the raw material for cellulose fibers may be regarded as the degree of polymerization of the cellulose fibers.
  • the weight average molecular weight (Mw) of the cellulose fibers is 100,000 or more, or 200,000 or more.
  • the ratio of weight average molecular weight to number average molecular weight (Mn) (Mw/Mn) is 6 or less, or 5.4 or less. The larger the weight average molecular weight, the fewer the number of terminal groups in the cellulose molecule. Furthermore, since the ratio of the weight average molecular weight to the number average molecular weight (Mw/Mn) represents the width of the molecular weight distribution, it means that the smaller the Mw/Mn, the fewer the number of ends of the cellulose molecule.
  • the ends of cellulose molecules are the starting point for thermal decomposition, so if the weight average molecular weight of the cellulose molecules in the cellulose fiber is not only large, but also the weight average molecular weight is large and at the same time the width of the molecular weight distribution is narrow, especially high heat resistant cellulose Fiber is obtained.
  • the weight average molecular weight (Mw) of the cellulose fibers may be, for example, 600,000 or less, or 500,000 or less, from the viewpoint of availability of cellulose fiber raw materials.
  • the ratio of weight average molecular weight to number average molecular weight (Mn) (Mw/Mn) may be, for example, 1.5 or more, or 2 or more, from the viewpoint of ease of manufacturing cellulose fibers.
  • Mw can be controlled within the above range by selecting a cellulose fiber raw material having an Mw depending on the purpose, appropriately performing physical treatment and/or chemical treatment on the cellulose fiber raw material within an appropriate range, etc. .
  • Mw/Mn can also be controlled by selecting a cellulose fiber raw material having Mw/Mn according to the purpose, appropriately performing physical treatment and/or chemical treatment on the cellulose fiber raw material within a moderate range, etc. It can be controlled within the above range.
  • each of Mw and Mw/Mn of the cellulose raw material may be within the above ranges.
  • the above-mentioned physical processing includes dry pulverization or wet pulverization using a microfluidizer, ball mill, disc mill, etc., a crusher, a homomixer, a high-pressure homogenizer, and an ultrasonic device.
  • Physical treatments that apply mechanical forces such as impact, shearing, shearing, friction, etc. can be exemplified, and examples of the above-mentioned chemical treatments include cooking, bleaching, acid treatment, enzyme treatment, regenerated celluloseization, and the like. Note that Mw, Mn, and Mw/Mn of modified cellulose fibers may not be accurately calculated due to the presence of modifying groups.
  • the Mw, Mn, Mw/Mn of the cellulose fiber immediately before modification or the cellulose raw material immediately before modification, which is the raw material for the cellulose fiber may be regarded as the Mw, Mn, Mw/Mn of the cellulose fiber.
  • the weight average molecular weight and number average molecular weight of cellulose fibers referred to here mean that cellulose fibers are dissolved in N,N-dimethylacetamide to which lithium chloride is added, and then gel permeation is performed using N,N-dimethylacetamide as a solvent. This is a value determined by chromatography.
  • Examples of methods for controlling the degree of polymerization (ie, average degree of polymerization) or molecular weight of cellulose fibers include hydrolysis treatment and the like.
  • hydrolysis treatment depolymerization of amorphous cellulose inside the cellulose fibers progresses, and the average degree of polymerization decreases.
  • the hydrolysis treatment removes impurities such as hemicellulose and lignin in addition to the above-mentioned amorphous cellulose, so that the inside of the fiber becomes porous.
  • the method of hydrolysis is not particularly limited, and examples thereof include acid hydrolysis, alkaline hydrolysis, hydrothermal decomposition, steam explosion, and microwave decomposition. These methods may be used alone or in combination of two or more.
  • acid hydrolysis method for example, ⁇ -cellulose obtained as pulp from fibrous plants is used as a cellulose fiber raw material, and while this is dispersed in an aqueous medium, protonic acids, carboxylic acids, Lewis acids, heteropolyacids, etc. By adding an appropriate amount and heating while stirring, the average degree of polymerization can be easily controlled.
  • the reaction conditions such as temperature, pressure, time, etc.
  • the conditions include using an aqueous mineral acid solution of 2% by mass or less and treating cellulose fibers at 100° C. or higher under pressure for 10 minutes or longer. Under these conditions, catalyst components such as acids penetrate into the interior of the cellulose fibers, promoting hydrolysis, reducing the amount of catalyst components used, and facilitating subsequent purification.
  • the dispersion of the cellulose fiber raw material upon hydrolysis may contain, in addition to water, a small amount of an organic solvent within a range that does not impair the effects of the present invention.
  • Alkali-soluble polysaccharides and acid-insoluble components Alkali-soluble polysaccharides such as hemicellulose and acid-insoluble components such as lignin exist between microfibrils of cellulose fibers and between microfibril bundles.
  • Hemicellulose is a polysaccharide composed of sugars such as mannan and xylan, and it forms hydrogen bonds with cellulose and plays a role in connecting microfibrils.
  • lignin is a compound having an aromatic ring, and is known to be covalently bonded to hemicellulose in plant cell walls.
  • Alkali-soluble polysaccharides that cellulose fibers may contain include not only hemicellulose but also ⁇ -cellulose and ⁇ -cellulose.
  • Alkali-soluble polysaccharide is a component obtained as the alkali-soluble portion of holocellulose obtained by solvent extraction and chlorination of plants (for example, wood) (i.e., a component obtained by removing ⁇ -cellulose from holocellulose). It will be understood by those skilled in the art.
  • Alkali-soluble polysaccharides are polysaccharides containing hydroxyl groups and have poor heat resistance, resulting in disadvantages such as decomposition when exposed to heat, yellowing during heat aging, and a decrease in the strength of cellulose fibers. Therefore, it is preferable that the alkali-soluble polysaccharide content in the cellulose fibers be small.
  • the average alkali-soluble polysaccharide content in the cellulose fibers is preferably 20% by mass based on 100% by mass of the cellulose fibers, from the viewpoint of maintaining the mechanical strength of the cellulose fibers during melt-kneading and suppressing yellowing. It is not more than 18% by mass, or not more than 15% by mass, or not more than 12% by mass. From the viewpoint of ease of manufacturing cellulose fibers, the above content is 0.1% by mass or more, or 0.5% by mass or more, or 1% by mass or more, or 2% by mass or more, or 3% by mass or more. Good too.
  • the average alkali-soluble polysaccharide content can be determined by the method described in the non-patent literature (Wood Science Experiment Manual, edited by the Japan Wood Society, pp. 92-97, 2000), and the holocellulose content (Wise method) It is determined by subtracting the ⁇ -cellulose content from Note that this method is understood in the art as a method for measuring the amount of hemicellulose.
  • the alkali-soluble polysaccharide content is calculated three times for each sample, and the number average of the calculated alkali-soluble polysaccharide contents is taken as the average alkali-soluble polysaccharide content.
  • the alkali-soluble polysaccharide content of modified cellulose fibers may not be accurately calculated due to the presence of modifying groups.
  • the average alkali-soluble polysaccharide content of the cellulose fibers immediately before modification or the cellulose raw materials immediately before modification, which are the raw materials for cellulose fibers may be regarded as the average alkali-soluble polysaccharide content of the cellulose fibers.
  • Acid-insoluble components that cellulose fibers may contain are understood by those skilled in the art as insoluble components that remain after a defatted sample obtained by solvent extraction of a plant (for example, wood) is treated with sulfuric acid.
  • the acid-insoluble component is specifically aromatic-derived lignin, but is not limited thereto. Acid-insoluble components in cellulose fibers are often colored themselves, which impairs the appearance of the resin composition and can cause problems such as yellowing during heat aging. The lower the average content, the better.
  • the average content of acid-insoluble components in the cellulose fibers is preferably 10% by mass or less based on 100% by mass of the cellulose fibers, from the viewpoint of avoiding a decrease in the heat resistance of the cellulose fibers and the accompanying discoloration, or It is 5% by mass or less, or 3% by mass or less. From the viewpoint of ease of manufacturing cellulose fibers, the content may be 0.1% by mass or more, 0.2% by mass or more, or 0.3% by mass or more.
  • the average content of acid-insoluble components is determined by quantifying the acid-insoluble components using the Clason method described in a non-patent document (Wood Science Experiment Manual, edited by the Japan Wood Society, pp. 92-97, 2000). Note that this method is understood in the art as a method for measuring the amount of lignin.
  • the sample is stirred in a sulfuric acid solution to dissolve cellulose, hemicellulose, etc., and then filtered through glass fiber filter paper, and the resulting residue corresponds to acid-insoluble components.
  • the acid-insoluble component content is calculated from this acid-insoluble component weight, and the number average of the acid-insoluble component content calculated for the three samples is taken as the average acid-insoluble component content.
  • the average content of acid-insoluble components in modified cellulose fibers may not be accurately calculated due to the presence of modifying groups.
  • the average alkali-soluble polysaccharide content of the cellulose fibers immediately before modification or the cellulose raw materials immediately before modification, which are the raw materials for cellulose fibers may be regarded as the average alkali-soluble polysaccharide content of the cellulose fibers.
  • the thermal decomposition initiation temperature (T D ) of the cellulose fiber is preferably 250°C or higher, 260°C or higher, or 270°C from the viewpoint of avoiding thermal deterioration during melt-kneading and exhibiting mechanical strength. or above, or above 275°C, or above 280°C, or above 285°C.
  • the thermal decomposition start temperature is preferably as high as possible, but from the viewpoint of ease of manufacturing cellulose fibers, it may be, for example, 320°C or lower, 310°C or lower, or 300°C or lower.
  • the temperature at which the cellulose fiber loses 1 wt% weight (T 1% ) is preferably 260° C. or higher, or 270° C. or higher, from the viewpoint of avoiding thermal deterioration during melt-kneading and exhibiting mechanical strength. , or 275°C or higher, or 280°C or higher, or 285°C or higher, or 290°C or higher.
  • T 1% is preferably as high as possible, from the viewpoint of ease of manufacturing cellulose fibers, it may be, for example, 330°C or lower, 320°C or lower, or 310°C or lower.
  • the 250°C weight loss rate (T250 °C ) of the cellulose fiber is preferably 15% or less, 12% or less, or 10% or less, from the viewpoint of avoiding thermal deterioration during melt-kneading and exhibiting mechanical strength. % or less, or 8% or less, or 6% or less, or 5% or less, or 4% or less, or 3% or less.
  • the lower T250 °C is, the more preferable it is, but from the viewpoint of ease of manufacturing cellulose fibers, it is, for example, 0.1% or more, or 0.5% or more, or 0.7% or more, or 1.0% or more. Good too.
  • T D is a value determined from a graph in which the horizontal axis is temperature and the vertical axis is weight residual rate % in thermogravimetric (TG) analysis under nitrogen flow.
  • TG thermogravimetric
  • the 1% weight loss temperature (T 1% ) is the temperature at which the weight decreases by 1% by weight starting from the weight of 150° C. when the temperature is continued to increase by the method of T D described above.
  • the 250°C weight loss rate (T 250°C ) of cellulose fibers is the weight loss rate when cellulose fibers are held at 250°C under nitrogen flow for 2 hours in TG analysis.
  • Cellulose fibers were heated from room temperature to 150°C at a rate of 10°C/min in a nitrogen flow of 100ml/min, held at 150°C for 1 hour, and then heated from 150°C to 250°C at a rate of 10°C. The temperature was raised at 250°C for 2 hours. Starting from the weight W0 at the time when the temperature reaches 250°C, the weight after being maintained at 250°C for 2 hours is defined as W1, and is calculated from the following formula. 250°C weight change rate (%): (W0-W1)/W0 ⁇ 100
  • Porous sheet Characteristics of cellulose fibers (crystallinity, crystal polymorphism, degree of polymerization, Mw, Mn, Mw/Mn, average content of alkali-soluble polysaccharides, average content of acid-insoluble components, T D , T 1% , T 250 °C, etc.), the numerical value may vary greatly depending on the form of the measurement sample. In order to perform stable and reproducible measurements, a porous sheet with no distortion is used as the measurement sample. The method for producing the porous sheet is as follows.
  • a concentrated cake of cellulose fibers with a solid content of 10% by mass or more is added to tert-butanol, and further dispersed using a mixer or the like until there are no aggregates. The concentration is adjusted to 0.5% by mass based on 0.5g of cellulose fiber solid content.
  • 100 g of the obtained tert-butanol dispersion is filtered on filter paper. The filtered material is sandwiched together with the filter paper between two pieces of larger filter paper without being peeled off from the filter paper, and is dried in an oven at 150° C. for 5 minutes while pressing the edge of the larger filter paper with a weight. Thereafter, the filter paper is peeled off to obtain a porous sheet with little distortion.
  • a porous sheet having an air permeability resistance R of 100 sec/100 ml or less per sheet weight of 10 g/m 2 is used as a measurement sample.
  • Physical properties of cellulose fibers in resin composition Various physical properties of cellulose fibers in the resin composition (refractive index, number average fiber length, number average fiber diameter, L/D ratio, volume fraction of coarse aggregates, specific surface area, crystallinity, crystal polymorphism, degree of polymerization) , Mw, Mn, Mw/Mn, average content of alkali-soluble polysaccharides, average content of acid-insoluble components, T D , T 1% , T 250°C , and DS described below) are analyzed by the following methods.
  • the resin component in the resin composition is dissolved in an organic or inorganic solvent capable of dissolving the resin component in the resin composition, the cellulose fibers are separated, and after thoroughly washing with the solvent, the solvent is replaced with tert-butanol. Thereafter, the tert-butanol slurry of cellulose fibers is analyzed using a measurement method similar to the above method, and various physical properties of the cellulose fibers in the resin composition are calculated.
  • the cellulose fibers contained in the resin composition of the present embodiment may be modified, for example, at the stage of cellulose fiber raw material, during or after the fibrillation treatment, and preparation of a slurry as a dispersion containing cellulose fibers. It may be modified during or after the drying and granulation process.
  • the cellulose fibers may be subjected to acetylation using an acetylating agent as a modifier, and optionally a modification other than acetylation using a modifier other than the acetylating agent.
  • a compound that reacts with the hydroxyl group of cellulose can be used, such as an esterifying agent, an etherifying agent, a silylating agent, and the like.
  • Preferred esterifying agents for acetylation and optionally other esterifications are acid halides, acid anhydrides, carboxylic acid vinyl esters, and carboxylic acids.
  • the acid halide may be at least one selected from the group consisting of compounds represented by the following formula.
  • acid halides include acetyl chloride, acetyl bromide, acetyl iodide, propionyl chloride, propionyl bromide, propionyl iodide, butyryl chloride, butyryl bromide, butyryl iodide, benzoyl chloride, benzoyl bromide, and iodide.
  • acid chlorides can be preferably employed from the viewpoint of reactivity and ease of handling.
  • one or more alkaline compounds may be added for the purpose of acting as a catalyst and at the same time neutralizing by-product acidic substances.
  • the alkaline compound include, but are not limited to, tertiary amine compounds such as triethylamine and trimethylamine; and nitrogen-containing aromatic compounds such as pyridine and dimethylaminopyridine.
  • Any suitable acid anhydride can be used as the acid anhydride.
  • Saturated aliphatic monocarboxylic acid anhydrides such as acetic acid, propionic acid, (iso)butyric acid, and valeric acid
  • Unsaturated aliphatic monocarboxylic acid anhydrides such as (meth)acrylic acid and oleic acid
  • Alicyclic monocarboxylic acid anhydrides such as cyclohexanecarboxylic acid and tetrahydrobenzoic acid
  • Aromatic monocarboxylic acid anhydrides such as benzoic acid and 4-methylbenzoic acid
  • dibasic carboxylic anhydrides include saturated aliphatic dicarboxylic anhydrides such as succinic anhydride and adipic acid, unsaturated aliphatic dicarboxylic anhydrides such as maleic anhydride and itaconic anhydride, and 1-cyclohexene-1 anhydride.
  • 2-dicarboxylic acid alicyclic dicarboxylic acid anhydrides such as hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and aromatic dicarboxylic anhydrides such as phthalic anhydride and naphthalic anhydride;
  • polybasic carboxylic acid anhydrides having three or more bases include (anhydrous) polycarboxylic acids such as trimellitic anhydride and pyromellitic anhydride.
  • an acidic compound such as sulfuric acid, hydrochloric acid, phosphoric acid, or a Lewis acid (for example, a Lewis acid compound represented by MYn, where M is B, As, Ge, etc.) is used as a catalyst.
  • n is an integer corresponding to the valence of M, and 2 or 3 and Y represents a halogen atom, OAc, OCOCF 3 , ClO 4 , SbF 6 , PF 6 or OSO 2 CF 3 (OTf)), or one or more alkaline compounds such as triethylamine and pyridine are added. You may.
  • R-COO-CH CH 2
  • R is any one of an alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, a cycloalkyl group having 3 to 16 carbon atoms, or an aryl group having 6 to 24 carbon atoms.
  • Carboxylic acid vinyl esters are preferred.
  • Carboxylic acid vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl cyclohexanecarboxylate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, and pivalin.
  • alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, alkaline earth metal carbonates, alkali metal hydrogen carbonates, primary to tertiary metal hydrogen carbonates are used as catalysts.
  • One or more selected from the group consisting of amines, quaternary ammonium salts, imidazole and its derivatives, pyridine and its derivatives, and alkoxides may be added.
  • alkali metal hydroxide and alkaline earth metal hydroxide examples include sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, barium hydroxide, and the like.
  • alkali metal carbonates, alkaline earth metal carbonates, and alkali metal hydrogen carbonates include lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate, barium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, and carbonate. Examples include potassium hydrogen and cesium hydrogen carbonate.
  • Primary to tertiary amines refer to primary amines, secondary amines, and tertiary amines, and specific examples include ethylenediamine, diethylamine, proline, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethyl-1,3-propanediamine, N,N,N',N'-tetramethyl-1,6-hexanediamine, tris(3-dimethylaminopropyl)amine, Examples include N,N-dimethylcyclohexylamine and triethylamine.
  • imidazole and its derivatives examples include 1-methylimidazole, 3-aminopropylimidazole, carbonyldiimidazole, and the like.
  • pyridine and its derivatives examples include N,N-dimethyl-4-aminopyridine and picoline.
  • alkoxides include sodium methoxide, sodium ethoxide, potassium-t-butoxide, and the like.
  • Examples of the carboxylic acid include at least one selected from the group consisting of compounds represented by the following formula.
  • R-COOH (In the formula, R represents an alkyl group having 1 to 16 carbon atoms, an alkenyl group having 2 to 16 carbon atoms, a cycloalkyl group having 3 to 16 carbon atoms, or an aryl group having 6 to 16 carbon atoms.)
  • carboxylic acids include acetic acid, propionic acid, butyric acid, caproic acid, cyclohexanecarboxylic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, pivalic acid, methacrylic acid, crotonic acid, and octyl acid. At least one selected from the group consisting of acid, benzoic acid, and cinnamic acid.
  • carboxylic acids at least one selected from the group consisting of acetic acid, propionic acid, and butyric acid is preferred. In particular, it is preferable to use at least acetic acid from the viewpoint of reaction efficiency.
  • an acidic compound such as sulfuric acid, hydrochloric acid, phosphoric acid, or a Lewis acid (for example, a Lewis acid compound represented by MYn, where M is B, As, Ge, etc.) is used as a catalyst.
  • a Lewis acid compound represented by MYn, where M is B, As, Ge, etc. Represents a metalloid element, a base metal element such as Al, Bi, In, or a transition metal element such as Ti, Zn, Cu, or a lanthanoid element, where n is an integer corresponding to the valence of M, and 2 or 3.
  • Y represents a halogen atom, OAc, OCOCF 3 , ClO 4 , SbF 6 , PF 6 or OSO 2 CF 3 (OTf)
  • alkaline compounds such as triethylamine and pyridine are added. You can.
  • esterification reactants 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.
  • the degree of substitution (DS) of cellulose fibers is determined as the average degree of substitution. From the viewpoint of bringing the refractive index of the cellulose fibers close to that of the polypropylene resin, the degree of acetyl substitution when the cellulose fibers are acetylated cellulose fibers is preferably 0.1 or more, or 0.3 or more, or 0. .5 or more, or 0.6 or more, or 0.7 or more, or 0.8 or more, preferably 3.0 or less, or 2.0 or less, or 1.5 or less, or 1.0 or less. be.
  • the degree of carboxymethyl substitution is preferably 0.2 or more, or 0.6 or more, or 1.0 or more, and preferably 3 .0 or less, or 2.0 or less, or 1.5 or less.
  • the degree of butyryl substitution is preferably 0.1 or more, or 0.3 or more, or 0.5 or more, or 0.8 or more, Preferably, it is 3.0 or less, or 2.0 or less, or 1.5 or less, or 1.0 or less.
  • the degree of hydroxypropyl substitution is preferably 0.1 or more, or 0.5 or more, or 0.9 or more, and preferably 3 .0 or less, or 2.0 or less, or 1.0 or less.
  • the refractive index of unmodified cellulose fibers is about 1.551 in one embodiment
  • the refractive index of cellulose fibers with an acetyl substitution degree of 3 is about 1.551 in one embodiment.
  • the refractive index of cellulose fibers with a degree of carboxymethyl substitution of 3 is about 1.502 in one embodiment, and the refractive index of cellulose fibers with a degree of butyryl substitution of 3 is 1.490 in one embodiment.
  • the refractive index of cellulose fibers having a degree of hydroxypropyl substitution of 3 is about 1.506 in one embodiment.
  • Cellulose fibers having a degree of acetyl substitution, a degree of carboxymethyl substitution, a degree of butyryl substitution, or a degree of hydroxypropyl substitution within the above range are resins that have excellent transparency by bringing the refractive index of the cellulose fibers and the refractive index of the polypropylene resin close to each other.
  • degree, carboxymethyl substitution degree, butyryl substitution degree, or hydroxypropyl substitution degree is preferably 2.0 or less, or 1.8 or less, or 1.5 or less, or 1.2 or less, or 1.0 or less. It is advantageous that the degree of substitution is less than or equal to the upper limit value in terms of suppressing coloration of cellulose fibers.
  • the degree of substitution can be determined by reflection-type infrared absorption spectrum measurement and 13 C solid-state NMR measurement.
  • the degree of acyl substitution can be calculated from the reflection infrared absorption spectrum of the esterified cellulose fiber based on the peak intensity ratio between the peak derived from the acyl group and the peak derived from the cellulose skeleton. I can do it.
  • the peak of the C ⁇ O absorption band based on the acyl group appears at 1730 cm ⁇ 1
  • the peak of the C—O absorption band based on the cellulose backbone chain appears at 1030 cm ⁇ 1 .
  • a correlation graph with the denaturation rate (IR index 1030) defined by the ratio of is created, and the calibration curve substitution degree DS calculated from the correlation graph is 4.13 ⁇ IR index (1030) It can be found by using
  • the conditions for the 13 C solid-state NMR measurement used are, for example, as follows. Equipment: Bruker Biospin Avance500WB Frequency: 125.77MHz Measurement method: DD/MAS method Waiting time: 75 seconds NMR sample tube: 4mm ⁇ Accumulated number of times: 640 times (approx. 14 hours) MAS: 14,500Hz Chemical shift standard: Glycine (external standard: 176.03 ppm)
  • the amount of cellulose fibers per 100 parts by mass of the polypropylene resin in the resin composition is preferably 0.001 parts by mass or more, or 0.01 parts by mass or more, or 0.1 parts by mass, from the viewpoint of obtaining a good reinforcing effect. part or more, or 1 part or more by mass, and from the viewpoint of stably realizing good dispersion of cellulose fibers in the resin composition, preferably 100 parts by mass or less, or 80 parts by mass or less, or 70 parts by mass. or less, or 50 parts by mass or less, or 30 parts by mass or less.
  • the amount of cellulose fibers based on 100% by mass of the resin composition is preferably 0.001% by mass or more, or 0.01% by mass or more, or 0.1% by mass or more, or 0. .5% by mass or more, or 1% by mass or more, and from the viewpoint of stably realizing good dispersion of cellulose fibers in the resin composition, preferably 50% by mass or less, or 40% by mass or less, or It is 30% by mass or less, and 20% by mass or less.
  • the polypropylene resin may be a propylene homopolymer or a propylene unit-containing copolymer, and may have a modified group.
  • the propylene unit-containing copolymer include ethylene-propylene copolymer, ethylene-propylene-diene copolymer, and the like.
  • the polypropylene resin is homopolypropylene.
  • the SP value of the polypropylene resin is 16.5 or more, or 16.6 or more, or 16.7 or more, and in one embodiment, 17.5 or less, or 17.4 or less, or 17.3. It is as follows.
  • the weight average molecular weight of the polypropylene resin is preferably 10,000 or more, or 15,000 or more, or 20,000 or more, from the viewpoint of obtaining good mechanical properties, especially toughness, of the resin composition, and From the viewpoint of stably realizing the desired form of the dispersed phase, it is preferably 300,000 or less, or 200,000 or less, or 100,000 or less.
  • the melt mass flow rate (MFR) of the polypropylene resin measured at 230° C. and a load of 21.2 N according to ISO 1133 is preferably 0.1 g/10 minutes or more and 100 g/10 minutes or less.
  • the lower limit of MFR is more preferably 1 g/10 minutes, or 5 g/10 minutes, or 10 g/10 minutes, or 20 g/10 minutes, or 30 g/10 minutes, and the upper limit of MFR is more preferably 80 g/10 minutes. /10 minutes, or 70g/10 minutes, or 60g/10 minutes, or 50g/10 minutes.
  • MFR desirably does not exceed the above upper limit from the viewpoint of improving the toughness of the resin composition, and desirably does not fall below the above lower limit from the viewpoint of fluidity of the resin composition.
  • the glass transition temperature of the polypropylene is preferably -50°C or higher, 0°C or higher, or 50°C or higher, from the viewpoint of good mechanical properties of the resin composition; From the viewpoint of easy availability of polypropylene, the temperature is preferably 200°C or lower, 150°C or lower, or 100°C or lower.
  • the melting point refers to the peak top temperature of an endothermic peak that appears when the temperature is raised from 23°C at a temperature increase rate of 10°C/min using a differential scanning calorimeter (DSC). If two or more appear, it refers to the peak top temperature of the endothermic peak on the highest temperature side.
  • the enthalpy of the endothermic peak at this time is preferably 10 J/g or more, more preferably 20 J/g or more.
  • the glass transition temperature refers to the storage modulus when measured at an applied frequency of 10 Hz while increasing the temperature from 23° C. at a temperature increase rate of 2° C./min using a dynamic viscoelasticity measuring device. This is the temperature at the top of the peak at which the loss modulus decreases significantly and the loss modulus reaches its maximum. When two or more peaks of loss modulus appear, it refers to the peak top temperature of the peak on the highest temperature side.
  • the measurement frequency is preferably at least once every 30 seconds in order to improve measurement accuracy.
  • the content of the polypropylene resin in the resin composition is preferably 50% by mass or more, or 55% by mass or more, or 60% by mass or more, or 70% by mass or more, and preferably 99% by mass or less, or 95% by mass or less, or 94.5% by mass or less, or 94% by mass or less, or 93% by mass or less, or 92% by mass or less, or 91% by mass or less, or 90% by mass or less, or 89.5% by mass or less , or 85% by mass or less, or 80% by mass or less.
  • the resin composition includes a styrenic elastomer in one embodiment, and a styrenic resin including a styrene elastomer in one embodiment.
  • the styrenic resin may be a styrenic elastomer alone, or may be selected from the group consisting of a styrenic elastomer and another styrenic resin (e.g., polystyrene, acrylonitrile styrene copolymer, and acrylonitrile butadiene styrene copolymer). (one or more types).
  • an elastomer is, in one embodiment, a substance that is an elastic body at room temperature (23° C.). Further, in one embodiment, being an elastic body means that the storage elastic modulus at 23° C. and 10 Hz measured by dynamic viscoelasticity measurement is 1 MPa or more and 100 MPa or less.
  • the styrenic elastomer may be a hydrogenated product.
  • styrenic elastomers include SBS (styrene-butadiene-styrene), SEBS (hydrogenated styrene-butadiene-styrene), SIS (styrene-isoprene-styrene), SEPS (styrene-ethylene-propylene-styrene), and SBR (styrene-butadiene-styrene). rubber), and hydrogenated SBR, preferably SEBS, more preferably high vinyl SEBS.
  • the hydrogenation rate of the hydrogen additive is preferably 50% or more, or 80% or more, or 98% or more from the viewpoint of suppressing thermal deterioration during processing, and from the viewpoint of low temperature toughness, preferably 50% or more. % or less, or 20% or less.
  • the ratio of 1,2- or 3,4-bonds of butadiene is preferably 5 mol% or more, or 10 mol% or more, or 13 mol% or more, from the viewpoint of suppressing crystallization of the soft segment. or 15 mol% or more, preferably 80 mol% or less, or 75 mol% or less, or 65 mol% or less, or 50 mol% or less, or 40 mol% or less.
  • the number average molecular weight (Mn) of the styrene elastomer is preferably 10,000 or more, or 40,000 or more, or 100,000 or more, or 150,000 or more, from the viewpoint of obtaining a resin composition with excellent storage modulus etc. or more, or 200,000 or more, from the viewpoint of ease of dispersion of cellulose fibers into the styrenic elastomer, and from the viewpoint that the styrenic elastomer does not become too hard and the resin composition has good toughness, preferably: 800,000 or less, or 750,000 or less, or 700,000 or less, or 600,000 or less, or 500,000 or less, or 250,000 or less.
  • the number average molecular weight and weight average molecular weight of the elastomer or rubber of the present disclosure are values determined in terms of standard polystyrene using gel permeation chromatography at a measurement temperature of 40°C using chloroform as a solvent, unless otherwise specified. be.
  • the melt mass flow rate (MFR) of the styrene elastomer at 230°C and a load of 21.2N is determined from the viewpoint of ease of dispersion of cellulose fibers into the styrene elastomer, and from the viewpoint of the ease of dispersion of cellulose fibers into the styrene elastomer and the ability of the resin composition to prevent the styrene elastomer from becoming too hard.
  • MFR melt mass flow rate
  • the content of the styrene elastomer is preferably 25% by mass or more, 30% by mass or more, or 40% by mass in the total of 100% by mass of the styrene elastomer and cellulose fibers.
  • the content is preferably 99% by mass or less, or 95% by mass or less, or 90% by mass or less, from the viewpoint of satisfactorily expressing the reinforcing effect of cellulose fibers.
  • the content of the styrenic elastomer in the resin composition is preferably 5% by mass or more, or 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 preferably 50% by mass or less, or 45% by mass or less, or 40% by mass or less.
  • the resin composition may include liquid rubber.
  • the liquid rubber may form a dispersed phase in the resin composition in one embodiment.
  • liquid rubber refers to a substance that has fluidity at 23° C. and forms a rubber elastic body through crosslinking (more specifically, vulcanization) and/or chain extension. That is, in one embodiment, the liquid rubber is an uncured product.
  • having fluidity means that liquid rubber dissolved in cyclohexane is poured into a vial with a body diameter of 21 mm and a total length of 50 mm at 23° C., and then dried. This means that when a vial is filled to a height of 1 mm and sealed, and the vial is left standing upside down for 24 hours, movement of the substance by 0.1 mm or more in the height direction can be confirmed.
  • Liquid rubber can function as a dispersant to disperse cellulose fibers well in polypropylene resin, and tends to have superior ability to suppress cellulose fiber aggregation and heat resistance compared to, for example, liquid non-rubber materials. be.
  • the cellulose fibers can be well dispersed in the polypropylene resin since the resin composition can be sufficiently heat-kneaded without fear of thermal deterioration of each component during the production of the resin composition.
  • a molded article formed from the resin composition produced in this way has excellent mechanical properties and can also have excellent decorative properties and aesthetic appearance due to its high surface smoothness.
  • the liquid rubber may have a common rubber monomer composition, and preferably has a relatively low molecular weight from the viewpoint of ease of handling and good dispersibility of cellulose fibers.
  • the liquid rubber exhibits a liquid form by having a number average molecular weight (Mn) of 80,000 or less.
  • liquid rubber may be combined with cellulose fibers to form a masterbatch, and such masterbatch may be further combined with a styrenic elastomer to form a masterbatch.
  • the number average molecular weight (Mn) of the liquid rubber is preferably 1,000 or more, 1,500 or more, or 2,000 or more from the viewpoint of thermal stability and the effect of improving the dispersibility of cellulose fibers in the resin. and has high fluidity suitable for good dispersion when dispersing cellulose fibers in liquid rubber, preferably 80,000 or less, or 50,000 or less, or 40,000 or less, or 30, 000 or less, or 10,000 or less.
  • the weight average molecular weight (Mw) of the liquid rubber is preferably 1,000 or more, 2,000 or more, or 4,000 or more from the viewpoint of thermal stability and the effect of improving the dispersibility of cellulose fibers in the resin. It is preferably 240,000 or less, 150,000 or less, or 30,000 or less in terms of having high fluidity suitable for good dispersion when cellulose fibers are dispersed in liquid rubber.
  • the ratio of the number average molecular weight (Mn) to the weight average molecular weight (Mw) (Mw/Mn) of liquid rubber is determined by the fact that the molecular weights vary to a certain extent, so that a high degree of compatibility between multiple properties (in one embodiment, cellulose fiber It is preferably 1.5 or more, or 1.8 or more, or 2 or more, and the molecular weight From the viewpoint that the desired physical properties of the resin composition can be stably obtained without excessively large variations, for example, from the viewpoint of achieving both fluidity and impact resistance, preferably 10 or less, or 8 or less, or 5 or less, or 3 or less, or 2.7 or less.
  • Liquid rubber can have good thermal stability.
  • the thermal decomposition onset temperature (T D ) of the liquid rubber is 200° C. or higher, 250° C. or higher, or 300° C. or higher in terms of good thermal stability.
  • the thermal decomposition initiation temperature is preferably higher, but from the viewpoint of easy availability of liquid rubber, in one embodiment, it may be 500°C or lower, 450°C or lower, or 400°C or lower.
  • the glass transition temperature of the liquid rubber is preferably -150°C or higher, or -120°C or higher, or -100°C or higher, and in terms of good fluidity, preferably, The temperature is 25°C or lower, or 10°C or lower, or 0°C or lower.
  • the liquid rubber includes a diene rubber, and in one embodiment, a conjugated diene polymer, a non-conjugated diene polymer, or a hydrogenated product thereof.
  • the above polymer or its hydrogenated product may be an oligomer.
  • the monomers constituting the liquid rubber may be unmodified or modified (eg, acid-modified, hydroxyl-modified, etc.).
  • the liquid rubber may have a reactive group (for example, one or more selected from the group consisting of a hydroxyl group, a carboxy group, an isocyanato group, a thio group, an amino group, and a halo group) at both ends, Therefore, it may be bifunctional. These reactive groups contribute to crosslinking and/or chain extension of the liquid rubber.
  • the conjugated diene polymer may be a homopolymer, or a copolymer of two or more conjugated diene monomers or a conjugate of a conjugated diene monomer and another monomer. It may be a polymer.
  • the copolymer may be either random or block.
  • Conjugated diene monomers include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene, 1,3-heptadiene, and 1,3-hexadiene, and these may be used alone or in combination of two or more.
  • the conjugated diene polymer is a copolymer of the above conjugated diene monomer and aromatic vinyl monomer.
  • the aromatic vinyl monomer is not particularly limited as long as it is a monomer that can be copolymerized with a conjugated diene monomer, such as styrene, p-methylstyrene, ⁇ -methylstyrene, ethylstyrene, p-tert. -butylstyrene, vinylethylbenzene, vinylxylene, vinylnaphthalene, diphenylethylene, and divinylbenzene, which may be used alone or in combination of two or more. Styrene is preferred from the viewpoint of moldability of the resin composition and impact resistance of the molded article.
  • random copolymer examples include butadiene-isoprene random copolymer, butadiene-styrene random copolymer, isoprene-styrene random copolymer, and butadiene-isoprene-styrene random copolymer.
  • the compositional distribution of each monomer in the copolymer chain includes completely random copolymers that are close to statistically random compositions, and tapered (gradient) random copolymers that have a gradient in compositional distribution.
  • the bonding mode of the conjugated diene polymer ie, the composition of 1,4-bonds, 1,2-bonds, etc., may be uniform or different between molecules.
  • the block copolymer may be a copolymer consisting of two or more blocks.
  • a block A of an aromatic vinyl monomer and a block B of a conjugated diene monomer and/or a block of a copolymer of an aromatic vinyl monomer and a conjugated diene monomer are A It may be a block copolymer having a structure such as -B, ABA, ABAB, etc. Note that the boundaries of each block do not necessarily need to be clearly distinguished; for example, if block B is a copolymer of an aromatic vinyl monomer and a conjugated diene monomer, the aromatic vinyl monomer in block B
  • the particles may be distributed uniformly or tapered.
  • block B there may be a plurality of portions where the aromatic vinyl monomer is uniformly distributed and/or a plurality of portions where the aromatic vinyl monomer is distributed in a tapered shape.
  • block B may include a plurality of segments having different aromatic vinyl monomer contents.
  • the block copolymer is characterized by bond type, molecular weight, type of aromatic vinyl compound, type of conjugated diene compound, 1,2-vinyl content or total amount of 1,2-vinyl content and 3,4-vinyl content, aromatic vinyl It may be a mixture of two or more types that differ from each other in one or more of the compound component content, hydrogenation rate, etc.
  • the amount of vinyl bonds in the conjugated diene bond units in the conjugated diene polymer is preferably 10 mol% or more and 75 mol% or less, or 13 mol% or more and 65 mol% or more. It is less than mol%.
  • the amount of vinyl bonds in the conjugated diene bond unit (for example, the amount of 1,2-bonds in butadiene) can be determined by 13 C-NMR method (quantitative mode). That is, by integrating the peak areas appearing below in 13 C-NMR, a value proportional to the carbon content of each structural unit can be obtained, and the result can be converted into mass % of each structural unit.
  • the amount of the aromatic vinyl monomer bonded to the conjugated diene monomer is , preferably 5 mol% or more and 70 mol% or less, or 10 mol% or more and 50 mol% or less, based on 100% of the total mole of the conjugated diene polymer.
  • hydrogenated products of conjugated diene-based polymers include hydrogenated products of conjugated diene-based polymers exemplified above, such as butadiene homopolymer, isoprene homopolymer, styrene-butadiene copolymer, acrylonitrile- It may be a hydrogenated product of a butadiene copolymer.
  • the liquid rubber is one or more selected from the group consisting of polybutadiene, butadiene-styrene copolymer, polyisoprene, and polychloroprene. These may be derivatives (for example, maleic anhydride-modified products, methacrylic acid-modified products, terminal hydroxyl group-modified products, hydrogenated products, and combinations thereof).
  • Non-conjugated diene polymer may be a homopolymer, or a copolymer of two or more non-conjugated diene monomers or a non-conjugated diene monomer and other monomers. It may be a copolymer with a body. The copolymer may be either random or block.
  • Olefin polymers such as ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-butene-diene rubber, ethylene- ⁇ -olefin copolymer
  • examples include butyl rubber, brominated butyl rubber, acrylic rubber, fluororubber, silicone rubber, chlorinated polyethylene rubber, epichlorohydrin rubber, ⁇ , ⁇ -unsaturated nitrile-acrylic acid ester-conjugated diene copolymer rubber, urethane rubber, polysulfide rubber, etc. It will be done.
  • monomers that can be copolymerized with ethylene units include propylene, butene-1, pentene-1, 4-methylpentene-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, or eicosene-1, isobutylene, etc.
  • aliphatic substituted vinyl monomers and aromatic vinyl monomers such as styrene and substituted styrene, vinyl acetate, acrylic esters, methacrylic esters, glycidyl acrylic esters, glycidyl methacrylic esters, and hydroxyethyl methacrylic esters.
  • Nitrogen-containing vinyl monomers such as acrylamide, allylamine, vinyl-p-aminobenzene, and acrylonitrile, and dienes such as butadiene, cyclopentadiene, 1,4-hexadiene, and isoprene can be mentioned.
  • the ethylene- ⁇ -olefin copolymer is preferably a copolymer of ethylene and one or more ⁇ -olefins having 3 to 20 carbon atoms, more preferably ethylene and one or more ⁇ -olefins having 3 to 16 carbon atoms. Most preferably, it is a copolymer of ethylene and one or more ⁇ -olefins having 3 to 12 carbon atoms.
  • the molecular weight of the ethylene- ⁇ -olefin copolymer is determined by the number average measured using a gel permeation chromatography measuring device using 1,2,4-trichlorobenzene as a solvent at 140°C using a polystyrene standard.
  • the molecular weight (Mn) is preferably 10,000 or more, more preferably 10,000 to 100,000, more preferably 10,000 to 80,000, even more preferably 20,000 to 60. ,000.
  • the content of ethylene units in the ethylene- ⁇ -olefin copolymer is preferably 30 to 95% by mass based on the total amount of the ethylene- ⁇ -olefin copolymer from the viewpoint of ease of handling during processing.
  • Ethylene- ⁇ -olefin copolymers are disclosed, for example, in JP-A No. 4-12283, JP-A-60-35006, JP-A-60-35007, JP-A-60-35008, and JP-A-5. It can be manufactured by conventionally known manufacturing methods such as those described in Japanese Patent Application Laid-open No. 155930, Japanese Patent Application Laid-Open No. 3-163088, and US Pat. No. 5,272,236.
  • the liquid rubber includes one or more selected from the group consisting of diene rubber, silicone rubber, urethane rubber, polysulfide rubber, and hydrogenated products thereof.
  • the viscosity of the liquid rubber at 25° C. is preferably 1,000,000 mPa ⁇ s or less, 500,000 mPa ⁇ s or less, or 200,000 mPa ⁇ s or less from the viewpoint of dispersing cellulose fibers well in the liquid rubber. From the viewpoint of thermal stability, the effect of improving the dispersibility of cellulose fibers in the resin, and the mechanical properties of the resin composition, it is preferably 100 mPa ⁇ s or more, or 300 mPa ⁇ s or more, or 500 mPa ⁇ s or more. be.
  • the viscosity of the liquid rubber at 80°C is preferably 1,000,000 mPa ⁇ s or less from the viewpoint of dispersing cellulose fibers well in the liquid rubber and from the viewpoint of dispersing cellulose fibers well in the resin by heating and kneading. , or 500,000 mPa ⁇ s or less, or 250,000 mPa ⁇ s or less, or 100,000 mPa ⁇ s or less, and the thermal stability, the effect of improving the dispersibility of cellulose fibers in the resin, and the mechanical properties of the resin composition. From this viewpoint, it is preferably 50 mPa ⁇ s or more, 100 mPa ⁇ s or more, or 300 mPa ⁇ s or more.
  • the viscosity of the liquid rubber at 0° C. is preferably 2,000,000 mPa ⁇ s or less, 1,000,000 mPa ⁇ s or less, or 400,000 mPa ⁇ s from the viewpoint of dispersing cellulose fibers well in the liquid rubber. s or less, and from the viewpoint of thermal stability, the effect of improving the dispersibility of cellulose fibers in the resin, and the mechanical properties of the resin composition, preferably 200 mPa ⁇ s or more, or 600 mPa ⁇ s or more, or 1,000 mPa ⁇ S or more.
  • the temperature dependence of the viscosity of the liquid rubber is small because the cellulose fibers can be well dispersed in the liquid rubber over a wide mixing temperature range. From this point of view, it is particularly preferable that the viscosity of the liquid rubber at 80°C, 25°C and 0°C is within the above range.
  • the viscosity of the liquid rubber is a value measured at a rotation speed of 10 rpm using a B-type viscometer.
  • the liquid rubber may be combined with cellulose fibers to form a masterbatch.
  • the mass ratio of cellulose fiber/liquid rubber is 0.1/99.9 to 99.9/0.1, or 1/99 to 99/1, or 5/95 to 95/5, or 10 /90 to 90/10, or 20/80 to 80/20, or 30/70 to 70/30, or 40/60 to 60/40.
  • the masterbatch containing cellulose fibers and liquid rubber may or may not contain additional ingredients.
  • additional components include one or more of those exemplified in the present disclosure as additional components that may be included in the resin composition of the present embodiment.
  • the content of additional components in the masterbatch may be, for example, from 0.01 to 50% by weight, or from 0.1 to 30% by weight.
  • the amount of liquid rubber per 100 parts by mass of the polypropylene resin is preferably 0.001 parts by mass or more, 0.01 parts by mass or more, or 0.01 parts by mass or more, from the viewpoint of balance between processability and mechanical properties.
  • 1 part by weight or more, or 1 part by weight or more preferably 100 parts by weight or less, or 80 parts by weight or less, or 70 parts by weight or less, or 50 parts by weight or less, or 30 parts by weight or less, or 10 parts by weight or less, or It may be 8 parts by mass or less.
  • the content of cellulose fibers relative to 100% by mass of the total of cellulose fibers and liquid rubber is preferably 0.5% by mass or more, or 1% by mass or more, from the viewpoint of obtaining a good reinforcing effect by cellulose fibers. , or 3% by mass or more, and from the viewpoint of obtaining good benefits from the use of liquid rubber, preferably 80% by mass or less, or 60% by mass or less, or 33% by mass or less, or 30% by mass or less, or 20% by mass or less. % by mass or less, or 10% by mass or less.
  • the content of liquid rubber in the resin composition is preferably 0% by mass or more, or 0.5% by mass or more, or 1.0% by mass or more, or 1.4% by mass or more, or 1.8% by mass. or more, or 2.2% by mass or more, or 2.6% by mass or more, preferably 30% by mass or less, or 15% by mass or less, or 12% by mass or less, or 10% by mass or less, or 6.0 It is not more than 4.5% by mass, or not more than 4.0% by mass, or not more than 3.5% by mass, or not more than 3.0% by mass.
  • the resin composition typically includes a vulcanizing agent and may optionally include a vulcanization accelerator.
  • a vulcanizing agent and vulcanization accelerator conventionally known ones may be appropriately selected depending on the type of uncured rubber in the resin composition.
  • the vulcanizing agent organic peroxides, azo compounds, oxime compounds, nitroso compounds, polyamine compounds, sulfur, sulfur compounds, etc. can be used.
  • the sulfur compound include sulfur monochloride, sulfur dichloride, disulfide compounds, and polymeric polysulfur compounds.
  • the amount of the vulcanizing agent is preferably 0.01 parts by mass to 20 parts by mass, or 0.1 parts by mass to 15 parts by mass, based on 100 parts by mass of uncured rubber in the resin composition.
  • vulcanization accelerator examples include sulfenamide-based, guanidine-based, thiuram-based, aldehyde-amine-based, aldehyde-ammonia-based, thiazole-based, thiourea-based, and dithiocarbamate-based vulcanization accelerators.
  • zinc white, stearic acid, etc. may be used as a vulcanization aid.
  • the amount of the vulcanization accelerator is preferably 0.01 parts by mass to 20 parts by mass, or 0.1 parts by mass to 15 parts by mass, based on 100 parts by mass of uncured rubber in the resin composition.
  • the resin composition includes a surfactant.
  • the surfactant is a nonionic surfactant.
  • the nonionic surfactant can enter into the voids of the aggregate of cellulose fibers and make the aggregate porous. For example, if a nonionic surfactant is infiltrated into the aggregate in a wet state and then dried to form a dry body, it is different from a dry body obtained by drying the aggregate without using the nonionic surfactant. In comparison, shrinkage during drying can be reduced. Producing a resin composition using such a dried product is advantageous from the viewpoint of good dispersion of cellulose fibers.
  • the nonionic surfactant is preferably a compound having a hydrophilic group selected from the group consisting of a hydroxyl group, a carboxy group, a sulfonic acid group, and an amino group, and a hydrocarbon group.
  • the nonionic surfactant has an aliphatic group having 6 to 30 carbon atoms as a hydrophobic portion.
  • Such nonionic surfactants have good affinity with polypropylene resins and styrene elastomers due to the contribution of the carbon chain in the hydrophobic part, and also have good affinity with cellulose because the carbon chain in the hydrophobic part is not too long. It tends to easily enter the voids of the fiber aggregate.
  • the aliphatic group may be linear or cycloaliphatic or a combination thereof.
  • the number of carbon atoms in the aliphatic group is 6 or more, or 8 or more, or 10 or more, from the viewpoint of obtaining good dispersibility of the cellulose fibers in the resin, and the number of carbon atoms in the aliphatic group is 6 or more, or 8 or more, or 10 or more, and the number of carbon atoms in the aliphatic group is 6 or more, or 8 or more, or 10 or more. From the viewpoint of sex, in one embodiment, it is 30 or less, or 25 or less, or 20 or less.
  • the nonionic surfactant preferably has, as a hydrophilic portion, one or more structures selected from the group consisting of oxyethylene, glycerol, and sorbitan (specifically, a repeating structure having one or more of these as repeating units). ). These structures are preferable because they exhibit high hydrophilicity and can easily form various nonionic surfactants in combination with various hydrophobic moieties.
  • the nonionic surfactant having a hydrophilic portion the number of carbon atoms n in the hydrophobic portion and the number m of repeating units in the hydrophilic portion are determined from the viewpoint of obtaining good dispersibility of cellulose fibers in the resin.
  • the relationship of the following formula: n>m is satisfied.
  • the repeating number m of the hydrophilic portion is preferably 1 or more, or 2 or more, or 3 or more, or 5 or more, from the viewpoint of good penetration of the nonionic surfactant into the voids of the cellulose fiber aggregate. From the viewpoint of obtaining good dispersibility of cellulose fibers in the resin, it is preferably 30 or less, or 25 or less, or 20 or less, or 18 or less.
  • the nonionic surfactant is preferably General formula (1) below: R-(OCH 2 CH 2 ) m -OH (1) [In the formula, R represents a monovalent aliphatic group having 6 to 30 carbon atoms, and m is a natural number smaller than the number of carbon atoms in R. ], and the following general formula (2): R 1 OCH 2 -(CHOH) 4 -CH 2 OR 2 (2) [In the formula, R 1 and R 2 each independently represent a hydrogen atom, an aliphatic group having 1 to 30 carbon atoms, -COR 3 ⁇ wherein R 3 represents an aliphatic group having 1 to 30 carbon atoms].
  • R 4 represents a hydrogen atom or an aliphatic group having 1 to 30 carbon atoms, and y is an integer of 1 to 30.
  • ⁇ represents.
  • R corresponds to the above-mentioned hydrophobic moiety
  • (OCH 2 CH 2 ) ie, oxyethylene unit
  • the number of carbon atoms in R and the number m of repeating (OCH 2 CH 2 ) are preferably in the same ranges as described above for the number n of carbon atoms in the hydrophobic portion and the number m of repeating hydrophilic portions, respectively.
  • the number of carbon atoms in the aliphatic group having 1 to 30 carbon atoms is preferably 6 or more, or 8 or more, or 10 or more. Yes, 24 or less, or 20 or less, or 18 or less.
  • y is 1 or more, preferably 2 or more, or 4 or more, and preferably 30 or less, or 25 or less, or 20 or less.
  • the amount of surfactant in the resin composition is preferably 10 parts by mass or more, or 15 parts by mass or more, or 20 parts by mass or more, and preferably 200 parts by mass or less, based on 100 parts by mass of cellulose fibers. , or 150 parts by weight or less, or 100 parts by weight or less, or 90 parts by weight or less, or 80 parts by weight or less, or 70 parts by weight or less, or 60 parts by weight or less, or 50 parts by weight or less, or 45 parts by weight or less, or It is 40 parts by mass or less.
  • the content of the surfactant in the resin composition is preferably 0.1% by mass or more, or 0.5% by mass or more, or 1% by mass or more, and preferably 10% by mass or less, or 5% by mass. % or less, or 1% by mass or less.
  • the resin composition may further contain additional components in addition to the above-mentioned components.
  • Additional components include additional polymers, dispersants other than the surfactants mentioned above, organic or inorganic fillers, heat stabilizers, antioxidants, antistatic agents, colorants, and the like.
  • the content ratio of the optional additional component in the resin composition is appropriately selected within a range that does not impair the desired effects of the present invention, and for example, 0.01 to 50% by mass, or 0.1 to 30% by mass. It may be.
  • the resin composition does not contain a colorant.
  • the resin composition is useful as a dosing material in one embodiment because it is highly compatible with good mechanical properties and high transparency. That is, the resin composition according to one embodiment can constitute a dyed material by containing a colorant.
  • thermoplastic resins other than polypropylene resins such as one or more of polyamide resins, polyester resins, polyacetal resins, polyphenylene ether resins, and polyphenylene sulfide resins.
  • These thermoplastic resins may, in one embodiment, have a melting point of 100°C to 350°C, or a glass transition temperature of 100°C to 250°C. From the viewpoint of increasing the heat resistance of the resin composition, in one embodiment, the melting point is 100°C or higher, or 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.
  • the temperature may be 350°C or lower, or 320°C or lower.
  • the total content of polymer components in the resin composition is preferably 50% by mass or more, or 60% by mass or more, or 70% by mass or more, or 80% by mass or more, or 85% by mass or more, or 90% by mass or more, preferably 99.5% by mass or less, or 99% by mass or less, or 98% by mass or more. It is not more than 95% by mass, or not more than 90% by mass.
  • the mass ratio of cellulose fiber/total polymer components in the resin composition is preferably 1/99 to 50/50, 2/98 to 40/60, or 3/97 to 30/70.
  • the resin composition comprises: Polypropylene resin 50% by mass to 94.5% by mass, Styrenic elastomer 5% to 40% by mass, Cellulose fiber 0.5% to 30% by mass, As an optional component, liquid rubber 0% to 30% by mass, and as an optional component, surfactant 0% to 30% by mass, including.
  • the resin composition includes a styrenic resin containing a styrenic elastomer, and Polypropylene resin 50% by mass to 89.5% by mass, Styrenic elastomer 10% to 40% by mass, and cellulose fiber 0.5% to 30% by mass including.
  • ⁇ Resin composition second embodiment ⁇
  • One aspect of the present invention provides a resin composition including a polypropylene resin, a styrene elastomer, and cellulose nanofibers.
  • Cellulose nanofibers are inherently hydrophilic due to their hydroxyl groups, while polypropylene-based resins and styrenic elastomers are inherently hydrophobic.
  • the present inventors have developed a resin composition containing a polypropylene resin, a styrene elastomer, and cellulose nanofibers by dispersing the styrene elastomer and cellulose nanofibers in a unique form in the polypropylene resin, thereby achieving low linear expansion. It has been found that excellent mechanical properties such as high modulus and high toughness can be combined with high transparency.
  • the polypropylene resin forms a continuous phase in the resin composition, and in one embodiment, the continuous phase is composed of cellulose nanofibers and a polymer covering the cellulose nanofibers.
  • a dispersed phase (hereinafter also referred to as cellulose/polymer dispersed phase) is formed.
  • the polymer includes a styrenic elastomer.
  • the polymer covers the cellulose nanofibers means that the polymer is in contact with substantially the entire outer periphery of the cellulose nanofibers when observing the cross-sectional shape of the resin composition. Therefore, the polymer can coat the cellulose nanofibers in such a manner that the cellulose nanofibers do not come into contact with the polypropylene resin.
  • the area that is not in contact with the polymer may be 70% or less, 60% or less, or 50% or less of the outer circumferential length of the cellulose nanofibers may not be in contact with the polymer.
  • the above coating state can be determined by observing the cross-sectional form of the resin composition with a scanning electron microscope (SEM) at a magnification of 20,000 times or 50,000 times in one or more fields of view.
  • SEM scanning electron microscope
  • For each of the 30 cellulose nanofibers based on the measurement of the outer circumference length and the determination of the presence or absence of contact with the polymer, cellulose nanofibers that were in contact with the polymer over 30% or more of the outer circumference were coated with the polymer. It is determined that the cellulose nanofiber is When 15 or more of the 30 cellulose nanofibers are determined to be coated with a polymer, it is determined that the polymer coats the cellulose nanofibers in the resin composition.
  • the styrene elastomer In a composite of a polypropylene resin and a styrene elastomer, the styrene elastomer not only improves the toughness of the polypropylene resin and improves its impact resistance, but also maintains the excellent transparency inherent in the polypropylene resin. It can also contribute to improvements.
  • the present inventors have investigated various methods for obtaining the desired reinforcing effect of the filler without impairing the excellent transparency of the composite when adding filler to such a composite for the purpose of improving mechanical properties. .
  • the resin composition Since the polymer of the cellulose/polymer dispersed phase is interposed between the cellulose nanofibers and the polypropylene resin continuous phase and covers the cellulose nanofibers, the resin composition has good mechanical properties, especially a low coefficient of linear expansion. In addition to contributing to high toughness, light scattering is less likely to occur and contributes to low haze (that is, high transparency) of the resin composition. In addition, when attempting to simply disperse cellulose nanofibers in polypropylene resin, it is difficult to finely disperse cellulose nanofibers in polypropylene resin, which is essentially hydrophobic, and they form aggregates, which impair the mechanical properties and transparency of the resin composition. Although it may reduce properties, coating the cellulose nanofibers with a polymer is also advantageous for improving the mechanical properties and transparency of the resin composition by suppressing aggregation of the cellulose nanofibers.
  • the polymer constituting the cellulose/polymer dispersed phase may be only the styrene elastomer, or may further contain an additional polymer.
  • additional polymer include liquid rubber, which will be described later.
  • the polymer in the cellulose/polymer dispersed phase may cover the cellulose nanofibers as a whole.
  • the number average fiber length of the cellulose nanofibers can serve to disperse the polymer into an elongated shape in the cellulose/polymer dispersed phase.
  • the number average fiber length of the cellulose nanofibers is set as exemplified in the first embodiment, from the viewpoint of satisfactorily expressing the effect of improving physical properties by cellulose nanofibers and controlling the morphology of the cellulose/polymer dispersed phase. It is preferably at least the lower limit, and from the viewpoint of ease of controlling the morphology of the cellulose/polymer dispersed phase, it is preferably at most the upper limit exemplified in the first aspect.
  • the number average fiber diameter of the cellulose nanofibers is the same as that exemplified in the first embodiment, from the viewpoint of obtaining good physical properties improvement effect by cellulose nanofibers and from the viewpoint of making fine fibers advantageous for good coating with styrene elastomer. Preferably, they are the same.
  • the number-average fiber length (L)/number-average fiber diameter (D) ratio of cellulose nanofibers is determined from the viewpoint of good expression of the physical property improvement effect of cellulose nanofibers and good control of the morphology of the cellulose/polymer dispersed phase. , is preferably at least the lower limit value exemplified in the first aspect, and from the viewpoint of ease of controlling the morphology of the cellulose/polymer dispersed phase, is preferably at most the upper limit value exemplified in the first aspect.
  • Crystallinity The crystallinity of cellulose nanofibers is due to the high mechanical properties (strength, dimensional stability) of cellulose itself, so when cellulose nanofibers are dispersed in a resin, the strength and dimensional stability of the resin composition tends to be high. In this respect, it is preferable that it is equal to or higher than the lower limit value exemplified in the first aspect.
  • the upper limit of the crystallinity degree is not particularly limited, but from a production standpoint, it may be equal to or lower than the upper limit value exemplified in the first aspect.
  • Cellulose nanofibers may be chemically modified cellulose nanofibers (also referred to as chemically modified cellulose nanofibers).
  • Cellulose nanofibers may be chemically modified in advance, for example, at the stage of cellulose fiber raw material, during or after fibrillation treatment, or during or after the preparation of slurry as a dispersion, or during drying and manufacturing. Chemical modifications may be made during or after the graining process.
  • a compound that reacts with the hydroxyl group of cellulose can be used, such as an esterifying agent, an etherifying agent, a silylating agent, and the like.
  • the chemical modification is acylation using an esterifying agent, particularly preferably acetylation.
  • esterifying agent acid halides, acid anhydrides, carboxylic acid vinyl esters, and carboxylic acids are preferred. Details of the esterifying agent may be the same as in the first embodiment.
  • esterified cellulose nanofibers having a high thermal decomposition initiation temperature derived from modification, preferably 2.0 or less, or 1.8 or less, or 1.5 or less, or 1.2 or less, or 1.0 or less, or 0.8 or less, or 0.7 or less, or 0.6 or less, or 0.5 or less.
  • the degree of acyl substitution (DS) can be determined by the same method as described above in the first embodiment.
  • DS heterogeneity ratio defined as the ratio of the degree of modification (DSs) of the fiber surface to the degree of modification (DSt) of the entire fiber of chemically modified cellulose nanofibers (this is synonymous with the degree of acyl substitution (DS) described above) (DSs/DSt) is preferably 1.05 or more.
  • the larger the value of the DS heterogeneity ratio the more the sheath-core structure-like heterogeneous structure (i.e., the surface layer of the fiber is highly chemically modified, while the center of the fiber retains a cellulose structure close to the original unmodified cellulose structure).
  • the DS heterogeneity ratio is more preferably 1.1 or more, or 1.2 or more, or 1.3 or more, or 1.5 or more, or 2 or more, from the viewpoint of ease of manufacturing chemically modified cellulose nanofibers. , preferably 30 or less, or 20 or less, or 10 or less, or 6 or less, or 4 or less, or 3 or less.
  • the value of DSs varies depending on the degree of modification of the esterified cellulose nanofibers, but as an example, it is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, and even more preferably 0. 5 or more, preferably 3.0 or less, more preferably 2.5 or less, particularly preferably 2.0 or less, even more preferably 1.5 or less, particularly preferably 1.2 or less, most preferably 1.0 It is as follows.
  • the preferred range of DSt is as described above for the acyl substituent (DS).
  • the coefficient of variation is preferably 50% or less, or 40% or less, or 30% or less, or 20% or less.
  • the above coefficient of variation can be further reduced by, for example, a method in which chemically modified cellulose nanofibers are obtained by defibrating a cellulose fiber raw material and then chemically modifying it (i.e., a sequential method). can be increased in a method in which both are performed simultaneously (i.e., a simultaneous method).
  • the coefficient of variation (CV) of the DS heterogeneity ratio was determined by collecting 100 g of an aqueous dispersion (solid content of 10% by mass or more) of chemically modified cellulose nanofibers and freeze-pulverizing each 10 g of the sample. After calculating the DS non-uniformity ratio from DSs and DSs, it can be calculated using the following formula from the standard deviation ( ⁇ ) and arithmetic mean ( ⁇ ) of the DS non-uniformity ratio among the obtained 10 samples.
  • the method for calculating DSs is as follows. That is, esterified cellulose nanofibers pulverized by freeze-pulverization are placed on a 2.5 mm diameter dish-shaped sample stage, the surface is flattened, and measurement is performed using X-ray photoelectron spectroscopy (XPS).
  • XPS X-ray photoelectron spectroscopy
  • the XPS spectrum reflects the constituent elements and chemical bonding states only in the surface layer (typically about several nanometers) of the sample. Peak separation was performed on the obtained C1s spectrum, and the area intensity (Ixp) of the peak (289 eV, C-C bond) assigned to carbon C2-C6 derived from the pyranose ring of cellulose was determined to be assigned to one carbon atom derived from the modifying group.
  • the modifying group is an acetyl group
  • the 289ev peak will be in Ixp
  • the peak (286 eV) may be used.
  • the conditions for the XPS measurement used are, for example, as follows. Equipment used: ULVAC-phi VersaProbeII Excitation source: mono. AlK ⁇ 15kV ⁇ 3.33mA Analysis size: Approximately 200 ⁇ m ⁇ Photoelectron extraction angle: 45° Capture area Narrow scan: C 1s, O 1s Pass Energy: 23.5eV
  • the polypropylene resin may be the same as exemplified in the first embodiment except for the following.
  • the melt mass flow rate (MFR) of the polypropylene resin measured at 230° C. and a load of 21.2 N according to ISO 1133 is preferably 3 g/10 minutes or more and 30 g/10 minutes or less.
  • the lower limit of MFR is more preferably 5 g/10 minutes, or 6 g/10 minutes, or 8 g/10 minutes
  • the upper limit of MFR is more preferably 25 g/10 minutes, or 20 g/10 minutes, or 18 g. /10 minutes.
  • MFR desirably does not exceed the above upper limit from the viewpoint of improving the toughness of the resin composition, and desirably does not fall below the above lower limit from the viewpoint of fluidity of the resin composition.
  • the polypropylene resin may include or be a modified polypropylene.
  • the resin composition includes unmodified polypropylene and modified polypropylene.
  • Modified polypropylene can improve the dispersibility of cellulose nanofibers in the resin composition due to its good affinity with the styrenic elastomer and/or cellulose nanofibers.
  • the modified polypropylene is preferably acid-modified polypropylene.
  • mono- or polycarboxylic acids can be used, such as maleic acid, fumaric acid, succinic acid, phthalic acid, anhydrides thereof, and citric acid.
  • Maleic acid or its anhydride is particularly preferred since it is easy to increase the modification rate.
  • a common method is to heat polypropylene to a temperature above its melting point and melt-knead it in the presence or absence of peroxide.
  • the acid value of the acid-modified polypropylene is preferably 1 mgKOH/g or more, or 3 mgKOH/g or more, or 10 mgKOH/g or more, from the viewpoint of obtaining the advantages of using acid-modified polypropylene, and the acid value of the resin composition is From the viewpoint of maintaining good physical stability, it is preferably 200 mgKOH/g or less, 100 mgKOH/g or less, or 50 mgKOH/g or less.
  • the melt mass flow rate (MFR) of the acid-modified polypropylene measured at 230°C and a load of 21.2N according to ISO1133 is preferably 50 g/ 10 minutes or more, or 100g/10 minutes or more, or 150g/10 minutes or more, or 200g/10 minutes or more.
  • the upper limit is not particularly limited, but from the viewpoint of maintaining mechanical strength, it is preferably 500 g/10 minutes.
  • the MFR of the unmodified polypropylene may be within the range exemplified above as the MFR of the polypropylene resin.
  • the respective melting points of the unmodified polypropylene and the modified polypropylene are preferably 100°C or higher, or 140°C or higher, or 150°C or higher, or 160°C or higher, from the viewpoint of good mechanical properties of the resin composition. or 170°C or higher, and preferably 190°C or lower or 180°C or lower from the viewpoint of easy availability of polypropylene.
  • the glass transition temperature of each of the unmodified polypropylene and the modified polypropylene is preferably -50°C or higher, 0°C or higher, or 50°C or higher, from the viewpoint of good mechanical properties of the resin composition, From the viewpoint of easy availability of these polypropylenes, the temperature is preferably 200°C or lower, 150°C or lower, or 100°C or lower.
  • the styrenic elastomer and the styrene resin containing the same may be the same as those exemplified in the first embodiment except for the following.
  • the styrenic elastomer may be a modified product, such as an epoxy group, an acid anhydride group, a carboxy group, a carboxylate group, a sulfo group, an aldehyde group, a hydroxyl group, an alkoxy group, an amino group, A modifying group such as an amide group, an imide group, a nitro group, an isocyanate group, or a mercapto group may be introduced.
  • the amount of modifying groups based on 100 mol% of all monomer units is preferably 0.1 mol% or more, 0.2 mol% or more, or 0. .3 mol% or more, preferably 5 mol% or less, or 3 mol% or less.
  • the amount of modified groups is determined by FT-IR (Fourier transform infrared spectroscopy), solid-state NMR (nuclear magnetic resonance), solution NMR, or elemental analysis of the monomer composition specified in advance and elements not included in the unmodified substance. This can be confirmed by a method of calculating the molar ratio of modified groups in combination with quantitative determination.
  • the styrenic elastomer may have an acidic functional group.
  • the styrenic elastomer having an acidic functional group means that the acidic functional group is added to the molecular skeleton of the elastomer through a chemical bond.
  • an acidic functional group means a functional group that can react with a basic functional group, and specific examples thereof include an acid anhydride group, a carboxy group, a carboxylate group, a sulfo group, a hydroxyl group, etc. It will be done.
  • the amount of acidic functional groups added in the styrene elastomer is preferably 0.01% by mass or more, more preferably 0. .1% by mass or more, more preferably 0.2% by mass or more, preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 2% by mass or less.
  • the number of acidic functional groups is determined by measuring a calibration curve sample mixed with an acidic substance in advance using an infrared absorption spectrometer, and then determining the number of acidic functional groups based on the calibration curve prepared using the characteristic absorption band of the acid. This is a value obtained by measuring a sample.
  • the styrenic elastomer having an acidic functional group is a modified product in which an ⁇ , ⁇ -unsaturated dicarboxylic acid or a derivative thereof is grafted onto an unmodified styrene elastomer in the presence or absence of a peroxide.
  • examples include elastomers.
  • the styrenic elastomer is an acid anhydride-modified elastomer.
  • ⁇ , ⁇ -unsaturated dicarboxylic acids and derivatives thereof include maleic acid, fumaric acid, maleic anhydride, and fumaric anhydride, and among these, maleic anhydride is particularly preferred.
  • the styrenic elastomer may be a mixture of a styrenic elastomer having an acidic functional group and a styrenic elastomer not having an acidic functional group.
  • the mixing ratio of the styrene elastomer having an acidic functional group and the elastomer not having an acidic functional group is such that when the total of both is 100% by mass, the styrene elastomer having an acidic functional group has a high toughness of the resin composition.
  • the content is preferably 10% by mass or more, more preferably 20% by mass or more, even 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 styrene-based elastomers may be elastomers having acidic functional groups, but from the viewpoint of not causing problems in fluidity, it is preferably 80% by mass or less.
  • the content of the styrene elastomer in the total 100% by mass of the styrene elastomer and cellulose nanofibers is preferably 35% by weight, from the viewpoint of covering the cellulose nanofibers with the styrene elastomer and obtaining good toughness of the resin composition. % by mass or more, 40% by mass or more, 50% by mass or more, or 70% by mass or more, and preferably 99% by mass or less, or 95% by mass from the viewpoint of satisfactorily expressing the reinforcing effect by cellulose nanofibers. or below, or below 90% by mass.
  • the content of the styrene elastomer in the resin composition is preferably 10% by mass or more, or 11% by mass or more, or 13% by mass or more, or 15% by mass or more to improve the impact resistance of the resin composition. , preferably 50% by weight or less, or 45% by weight or less, or 40% by weight or less, or 35% by weight.
  • the resin composition may include liquid rubber.
  • the liquid rubber may be present as a polymer comprising a cellulose/polymer dispersed phase. Liquid rubber has the same meaning as described above in the first aspect. The liquid rubber may be the same as that exemplified in the first embodiment.
  • Liquid rubber can function as a dispersant to disperse cellulose nanofibers well in polypropylene resin, and has superior ability to suppress cellulose nanofiber aggregation and heat resistance compared to, for example, liquid non-rubber materials. Tend.
  • liquid rubber has a high affinity with styrene elastomers, it is suitable for coating cellulose nanofibers with styrene elastomers without agglomerating them into the styrene elastomers.
  • the cellulose nanofibers can be well dispersed in the polypropylene resin because heat kneading can be sufficiently carried out without fear of thermal deterioration of each component during the production of the resin composition.
  • a molded article formed from the resin composition produced in this way has excellent mechanical properties and can also have excellent decorative properties and aesthetic appearance due to its high surface smoothness.
  • the resin composition preferably includes: Polypropylene resin 50% by mass to 89.5% by mass, Styrenic elastomer 10% to 40% by mass, Cellulose nanofiber 0.5% by mass to 30% by mass, As an optional component, liquid rubber 0% to 30% by mass, and as an optional component, surfactant 0% to 30% by mass, including. .
  • the resin composition of the present embodiment is produced through a mixing step of mixing a polypropylene resin, a styrenic elastomer (in one embodiment, a styrene resin containing a styrene elastomer), and cellulose fibers (in one embodiment, cellulose nanofibers).
  • It can be manufactured by a method including Mixing is performed using a stirring means such as a rotation/revolution mixer, a planetary mixer, a homogenizer, a propeller-type stirrer, a rotary stirrer, an electromagnetic stirrer, an open roll, a Banbury mixer, a single-screw extruder, or a twin-screw extruder. It's okay. Further, in order to efficiently perform shearing, stirring may be performed under heating. Mixing using a homogenizer is preferred since dispersion can be promoted by applying high shearing force and pressure.
  • a mixing method in the mixing step for example, (1) A method of obtaining a resin composition by simultaneously adding and mixing cellulose fibers, a polypropylene resin, a styrene elastomer, and optionally additional components, (2) A method comprising the steps of obtaining an elastomer masterbatch containing a styrene elastomer and cellulose fibers, and kneading the elastomer masterbatch with a polypropylene resin; etc.
  • the method (2) above is useful for finely dispersing cellulose fibers in a polypropylene resin.
  • method (2) above is useful for forming the cellulose/polymer dispersed phase of the present disclosure.
  • the method for producing the elastomer masterbatch in (2) above is as follows: (a) After obtaining a cellulose masterbatch in which the resin composition further contains a surfactant and/or liquid rubber and contains cellulose fibers and the surfactant and/or liquid rubber, this is mixed with a styrenic elastomer, How to obtain elastomer masterbatch by optional drying, (b) The resin composition contains a surfactant and/or liquid rubber, and the cellulose fibers, the surfactant and/or liquid rubber, and the styrene elastomer are simultaneously mixed and optionally dried to form an elastomer masterbatch. how to get, can be mentioned.
  • the method for obtaining a cellulose masterbatch in (a) above is such that the resin composition contains a surfactant and a liquid rubber, and the surfactant is introduced into the voids of the cellulose fiber aggregate by mixing the cellulose fibers and the surfactant.
  • a preferred method is to infiltrate the voids, then add and mix liquid rubber to infiltrate the voids, and optionally dry the mixture to obtain a cellulose masterbatch.
  • Cellulose fibers or cellulose masterbatch may be used in the form of powder to produce a resin composition.
  • the powder may have one or more of the following properties.
  • the powder has excellent processing properties, and the cellulose fibers can exhibit an excellent dispersion state in the polypropylene resin.
  • a method for producing a powder includes a slurry preparation step of preparing a slurry containing cellulose fibers, a liquid medium, and optionally additional ingredients, and a drying step of drying the slurry to form a powder.
  • a slurry preparation step of preparing a slurry containing cellulose fibers, a liquid medium, and optionally additional ingredients and a drying step of drying the slurry to form a powder.
  • Liquid media include water-miscible organic solvents, such as: alcohols with a boiling point of 50° C. to 170° C., such as methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, s-butanol, t-butanol, butanol, etc.); ethers (e.g., propylene glycol monomethyl ether, 1,2-dimethoxyethane, diisopropyl ether, tetrahydrofuran, 1,4-dioxane, etc.); carboxylic acids (e.g., formic acid, acetic acid, lactic acid, etc.); esters (e.g., ethyl acetate, (vinyl acetate, etc.); ketones (eg, acetone, methyl ethyl ketone,
  • water-miscible organic solvents such as: alcohols with
  • the concentration of cellulose fibers in the slurry is preferably 5% by mass or more, or 10% by mass or more, or 15% by mass or more, or 20% by mass or more, or 25% by mass.
  • the above from the viewpoint of maintaining good handling properties by avoiding excessive increase in the viscosity of the slurry and solidification due to agglomeration, preferably 60% by mass or less, or 55% by mass or less, or 50% by mass or less, Or 45% by mass or less.
  • the concentration of cellulose fibers in the slurry may be adjusted to the above-mentioned preferred range by concentrating such a dilute dispersion.
  • methods such as suction filtration, pressure filtration, centrifugal deliquification, and heating can be used.
  • drying process In this step, the slurry is dried under controlled drying conditions to form powder.
  • the timing of adding components other than cellulose fibers may be before drying, during drying, and/or after drying of the slurry.
  • a drying device such as a spray dryer or an extruder can be used.
  • the drying device may be a commercially available product, and examples include a micro-mist spray dryer (manufactured by Fujisaki Electric), a spray dryer (manufactured by Okawara Kakoki), a twin-screw extruder (manufactured by Japan Steel Works), and the like.
  • the drying rate which is the amount (parts by mass) of the liquid medium desorbed per minute per 100 parts by mass of the slurry, is, for example, 10%/ or more, or 50%/min or more, or 100%/min or more, from the viewpoint of suppressing agglomeration of the cellulose fibers and obtaining good handleability by avoiding excessive pulverization of the cellulose fibers. , for example, 10000%/min or less, or 1000%/min or less, or 500%/min or less.
  • the start of drying is the point at which the slurry or cake to be dried is supplied to the device and the drying process begins at the desired drying temperature, degree of vacuum, and shear rate.
  • the drying time does not include the time for premixing when the material is different from the drying process.
  • the drying end point refers to the point in time when sampling is performed at intervals of at most 10 minutes from the start of drying, and the moisture content becomes 7% by mass or less for the first time.
  • the time required from the start of drying to the end of drying can be interpreted as residence time.
  • the residence time can be calculated by the heating air volume and the volume of the drying chamber.
  • the residence time can be calculated from the screw rotation speed and the total pitch number of the screw.
  • the drying temperature is, for example, 20° C. or higher, 30° C. or higher, 40° C. or higher, or 50° C. or higher, from the viewpoint of drying efficiency and appropriately agglomerating the cellulose fibers to form a powder with a desired particle size.
  • the temperature is, for example, 200°C or lower, or 150°C or lower, or 140°C or lower, or 130°C or lower. , or 100°C or less.
  • the drying temperature is the temperature of the heat source that comes into contact with the slurry, and is defined, for example, by the surface temperature of the temperature control jacket of the drying device, the surface temperature of the heating cylinder, and the temperature of hot air.
  • the degree of reduced pressure is -1 kPa or less, or -10 kPa or less, or -20 kPa or less, or -30 kPa or less, or -40 kPa from the viewpoint of drying efficiency and appropriately agglomerating cellulose fibers to form powder with a desired particle size.
  • the pressure may be -100 kPa or more, -95 kPa or more, or -90 kPa or more.
  • the residence time of the slurry at a temperature of 20° C. to 200° C. is preferably set to 0.01 minutes to 10 minutes, or 0.05 minutes to 5 minutes, or 0.1 minutes to 2 minutes. good. Drying under these conditions quickly dries the cellulose fibers and produces a powder with a desirable particle size.
  • the slurry when using a spray dryer, the slurry is sprayed into a drying chamber through which hot gas is circulated using a spraying mechanism (rotating disk, pressurized nozzle, etc.) and dried.
  • the slurry droplet size upon spray introduction may be, for example, from 0.01 ⁇ m to 500 ⁇ m, or from 0.1 ⁇ m to 100 ⁇ m, or from 0.5 ⁇ m to 10 ⁇ m.
  • the hot gas may be nitrogen, an inert gas such as argon, air, or the like.
  • the hot gas temperature may be, for example, from 50°C to 300°C, or from 80°C to 250°C, or from 100°C to 200°C.
  • Contact of the slurry droplets with the hot gas within the drying chamber may be cocurrent, countercurrent, or cocurrent.
  • the particulate powder produced by drying the droplets is collected using a cyclone, drum, etc.
  • the slurry when using an extruder, the slurry is introduced from a hopper into a kneading section equipped with a screw, and the slurry is dried by continuously transporting the slurry with a screw within the kneading section under reduced pressure and/or heating.
  • a conveying screw, a counterclockwise screw, and a kneading disk may be combined in any order.
  • the drying temperature may be, for example, 50°C to 300°C, or 80°C to 250°C, or 100°C to 200°C.
  • an elastomer masterbatch containing cellulose fibers, a styrenic elastomer or a styrenic resin containing the same, and optionally additional components may be used to produce a resin composition.
  • the amount of cellulose fibers in the elastomer masterbatch is preferably 10 parts by mass based on 100 parts by mass of the styrenic elastomer in one embodiment, or 100 parts by mass in total of the styrenic elastomer and liquid rubber in one embodiment. It is at least 15 parts by mass, or at least 20 parts by mass, and preferably at most 50 parts by mass, or at most 40 parts by mass, or at most 30 parts by mass.
  • the total content of cellulose fibers and any liquid rubber is preferably 5% by mass or more, or 15% by mass or more, or 30% by mass or more, or 40% by mass or more, or 50% by mass. In one embodiment, the content may be 80% by mass or less, 70% by mass or less, or 60% by mass or less.
  • the elastomer masterbatch may be formed by kneading a cellulose masterbatch, a styrenic elastomer or a styrenic resin containing the same, and optionally additional components.
  • the kneading temperature may be, for example, 100°C to 300°C. From the viewpoint of ease of processing, the temperature is preferably 150°C or higher, and from the viewpoint of suppressing decomposition of the resin and cellulose fibers, the temperature is preferably 270°C or lower.
  • an elastomer masterbatch containing cellulose nanofibers, a styrenic elastomer or a styrenic resin containing the same, and optionally additional components may be used to produce a resin composition.
  • the total content of cellulose nanofibers, styrenic elastomer, and any liquid rubber is preferably 50% by mass or more, or 60% by mass or more, or 70% by mass or more, or 80% by mass. or more, or 90% by mass or more, and in one embodiment, it may be 100% by mass or less, or 99% by mass or less, or 95% by mass or less.
  • the elastomer masterbatch may be formed by kneading a cellulose masterbatch, a styrenic elastomer or a styrenic resin containing the same, and optionally additional components.
  • the kneading temperature may be, for example, 150°C to 280°C.
  • the kneading means is not particularly limited, but includes, for example, an autorotation/revolution type mixer, a planetary mixer, a homogenizer, a propeller type stirring device, a rotary stirring device, an electromagnetic stirring device, an open roll, a Banbury mixer, a single Examples include stirring means such as a screw extruder and a twin screw extruder. Moreover, in order to perform shearing efficiently, stirring may be performed under heating.
  • a resin composition can be obtained by melt-kneading the elastomer masterbatch with a polypropylene resin.
  • the mass ratio of the elastomer masterbatch and the polypropylene resin is 1/99 to 99/1, or 5/95 to 95/5, or 10/90 to 90/ 10, or 20/80 to 80/20, or 30/70 to 70/30, or 40/60 to 60/40.
  • a common kneader such as a Banbury mixer or an open roll may be used for melt kneading.
  • the kneading temperature may be, for example, 100°C to 300°C. From the viewpoint of ease of processing, the temperature is preferably 150°C or higher, and from the viewpoint of suppressing decomposition of the resin and cellulose fibers, the temperature is preferably 270°C or lower.
  • the elastomer masterbatch may be kneaded with the polypropylene resin while the styrene elastomer remains in a fluid state.
  • melt-kneading may be performed using a twin-screw extruder.
  • the elastomer masterbatch transported to the polypropylene resin in a desired ratio may be introduced into the polypropylene resin and mixed, and then melt-kneaded.
  • the production of the elastomer masterbatch and the kneading of the elastomer masterbatch and the polypropylene resin are performed continuously in the same apparatus. Thereby, cellulose fibers, styrene elastomer, etc. can be well dispersed in the polypropylene resin.
  • the means for kneading the elastomer masterbatch and the polypropylene resin is preferably a single-screw extruder or a twin-screw extruder, but a twin-screw extruder is preferred from the viewpoint of controlling the dispersibility of cellulose fibers.
  • L is calculated by dividing the cylinder length (L) of the extruder through both processes by the screw diameter (D). /D is preferably 20 or more, particularly preferably 40 or more.
  • the screw rotation speed in both steps is preferably in the range of 50 to 800 rpm, more preferably in the range of 100 to 600 rpm.
  • Each screw in the cylinder of the extruder may be optimized by combining an oval two-wing screw-shaped conveying screw, a kneading element called a kneading disk, etc.
  • a common kneading machine such as a single-screw extruder, a twin-screw extruder, or a multi-screw extruder may be used for melt-kneading, for example.
  • the kneading temperature may be, for example, 150°C to 280°C.
  • the elastomer masterbatch may be kneaded with the polypropylene resin while the styrene elastomer remains in a fluid state.
  • a kneading machine such as a Banbury mixer or an open roll may be used.
  • a polypropylene resin and a styrene elastomer When a polypropylene resin and a styrene elastomer are mixed, generally one forms a continuous phase and the other forms a substantially spherical dispersed phase.
  • the styrene elastomer by appropriately adjusting the conditions when mixing the styrene elastomer mixed with cellulose nanofibers with the polypropylene resin, the styrene elastomer can be mixed into the continuous phase of the polypropylene resin. can be dispersed into
  • the elastomer masterbatch transported to the polypropylene resin in a desired ratio may be introduced into the polypropylene resin and mixed, and then melt-kneaded.
  • the production of the elastomer masterbatch and the kneading of the elastomer masterbatch and the polypropylene resin are performed continuously in the same apparatus. Thereby, a desired distribution state of cellulose nanofibers and a desired dispersed phase form of the styrene elastomer can be stably realized.
  • the means for kneading the elastomer masterbatch and the polypropylene resin is preferably a single-screw extruder or a twin-screw extruder, but a twin-screw extruder is preferred from the viewpoint of controlling the dispersibility of cellulose nanofibers.
  • L is calculated by dividing the cylinder length (L) of the extruder through both processes by the screw diameter (D). /D is preferably 30 or more, particularly preferably 40 or more.
  • the screw rotation speed in both steps is preferably in the range of 50 to 800 rpm, more preferably in the range of 100 to 600 rpm.
  • Each screw in the cylinder of the extruder may be optimized by combining an oval two-wing screw-shaped conveying screw, a kneading element called a kneading disk, etc.
  • the resin composition of this embodiment can be provided in various shapes such as pellets, sheets, fibers, plates, and rods.
  • the resin composition may be extruded into a strand and solidified by cooling in a water bath to form a pellet, or the resin composition may be extruded into a rod or cylinder and cooled to form an extrudate, or the resin composition may be extruded into a rod or cylinder and cooled to form an extrudate.
  • the composition may be extruded through a T-die to form a sheet or film.
  • a pellet shape is preferable from the viewpoint of ease of post-processing and ease of transportation.
  • Preferred pellet shapes include round, elliptical, and cylindrical shapes, and the shapes may vary depending on the cutting method used during extrusion processing. For example, pellets cut using a cutting method called underwater cutting are often round in shape, while pellets cut using a cutting method called hot cutting are often round or oval in shape. Pellets cut using the so-called cutting method often have a cylindrical shape.
  • a preferable pellet diameter of the round pellets is 1 mm or more and 3 mm or less.
  • the preferred diameter of the cylindrical pellet is 1 mm or more and 3 mm or less, and the preferred length is 2 mm or more and 10 mm or less.
  • the above diameter and length are desirably at least the lower limit from the viewpoint of operational stability during extrusion, and desirably at most the upper limit from the viewpoint of bite into the molding machine during post-processing.
  • a desired molded article may be produced by molding the resin composition alone or together with other components into a desired shape.
  • the method of combining the ingredients and the molding method are not particularly limited, and may be selected depending on the desired molded product.
  • Examples of the molding method include, but are not limited to, injection molding, extrusion molding, blow molding, inflation molding, foam molding, and the like. Among these, injection molding is particularly preferred from the viewpoints of design and cost.
  • the resin composition of this embodiment is useful as a substitute for steel plates, fiber-reinforced plastics (eg, carbon fiber-reinforced plastics, glass fiber-reinforced plastics, etc.), resin composites containing inorganic fillers, and the like.
  • Suitable uses for the resin composition include industrial mechanical parts, general mechanical parts, automobile/railroad/vehicle/vehicle/ship/aerospace related parts, electronic/electrical parts, architectural/civil engineering materials, household goods, sports/leisure goods, Examples include wind power generation housing members, containers/packaging members, and the like.
  • the resin composition of the first aspect has a high degree of both mechanical properties and transparency, and can have excellent color development and brightness even when colored, so it is used for applications that require high mechanical properties. It is particularly useful as a source-dyed material that can also be applied to (for example, automobile outer panels, etc.).
  • a source-dyed material that can also be applied to (for example, automobile outer panels, etc.).
  • One preferred embodiment provides an automobile outer panel comprising the resin composition of the present disclosure.
  • the resin composition of the second aspect is a doped material that can be applied to applications that require high mechanical properties (for example, outer panels for automobiles, etc.) because it can achieve both mechanical properties and transparency to a high degree. It is particularly useful as a
  • the refractive index of the resin composition (particularly the resin composition of the first embodiment) is such that the arithmetic average value when different points in the test piece are evaluated at five points in Step 1 of the present disclosure is 1. 500 or more, or 1.503 or more, or 1.505 or more, and in one embodiment, 1.515 or less, or 1.513 or less, or 1.510 or less.
  • the resin composition (especially the resin composition of the first embodiment) has a light transmittance of 1% or more, or 2% or more, or 3% or more, or 5% or more, or 8% or more, or 10% or more. % or more, or 15% or more.
  • the above transmittance is determined by kneading a resin composition in a small kneading machine (for example, Xplore instruments, product name "Xplore") and using an attached injection molding machine to obtain a 2 mm thick resin composition according to the ISO 37 type 3 standard.
  • This is the light transmittance at a wavelength of 780 nm measured using a UV-visible spectrophotometer (for example, V-670, manufactured by JASCO Corporation) for a dumbbell-shaped test piece.
  • the tensile yield strength of the resin composition (especially the resin composition of the first aspect) may be 20 MPa or more, or 21 MPa or more, or 22 MPa or more, and in one embodiment, 40 MPa or less, or 35 MPa or less, Or it may be 30 MPa or less.
  • the tensile elongation at break of the resin composition may be 100% or more, or 200% or more, or 300% or more, and in one embodiment, 1000% or less. , or 900% or less, or 800% or less.
  • the flexural modulus of the resin composition (particularly the resin composition of the second embodiment) may be 1.0 GPa or more, or 1.1 GPa or more, or 1.2 GPa or more, and 4.0 GPa or less, Alternatively, it may be 3.5 GPa or less, or 3.0 GPa or less.
  • ⁇ Cellulose fiber> The following evaluations were performed on acetylated and non-acetylated cellulose fibers.
  • [Preparation of porous sheet] First, the concentrated cake was added to tert-butanol, and further dispersed using a mixer or the like until there were no aggregates. The concentration was adjusted to 0.5% by mass based on 0.5g of cellulose fiber solid content. 100 g of the obtained tert-butanol dispersion was filtered on filter paper. The filtrate was sandwiched together with the filter paper between two larger filter papers without being peeled off from the filter paper, and was dried in an oven at 150° C. for 5 minutes while pressing the edges of the larger filter paper with weights.
  • N,N-dimethylacetamide After separating the N,N-dimethylacetamide and the solid content by centrifugation again, 20 mL of N,N-dimethylacetamide was added, stirred lightly, and left for one day. N,N-dimethylacetamide and solid content were separated by centrifugation, and 19.2 g of N,N-dimethylacetamide solution prepared so that the solid content contained 8% by mass of lithium chloride was added and stirred with a stirrer. Dissolution was confirmed visually. The solution in which cellulose fibers were dissolved was filtered through a 0.45 ⁇ m filter, and the filtrate was used as a sample for gel permeation chromatography. The equipment and measurement conditions used are as follows.
  • the alkali-soluble polysaccharide content was calculated from the holocellulose content (Wise method) using the method described in a non-patent document (Wood Science Experiment Manual, edited by the Japan Wood Society, pp. 92-97, 2000) for cellulose fibers. It was determined by subtracting the cellulose content. The alkali-soluble polysaccharide content was calculated three times for each sample, and the number average of the calculated alkali-soluble polysaccharide contents was taken as the average alkali-soluble polysaccharide content of the cellulose fibers. For CNF-3 and CNF-4, which are acetylated cellulose fibers, the average alkali-soluble polysaccharide content of CNF-1 and CNF-2, which are raw materials before acetylation, was used.
  • the acid-insoluble components were quantified using the Clason method for cellulose fibers as described in a non-patent literature (Wood Science Experiment Manual, edited by the Japan Wood Society, pp. 92-97, 2000). Precisely weigh the bone-dried cellulose fibers, place them in a designated container, add 72% by mass concentrated sulfuric acid, press appropriately with a glass rod to make the contents uniform, and then autoclave to dissolve cellulose and hemicellulose in an acid solution. dissolved in it. After cooling, the contents were filtered through glass fiber filter paper to obtain acid-insoluble components as a residue.
  • the acid-insoluble component content was calculated from the weight of the acid-insoluble component, and the number average of the acid-insoluble component content calculated for the three samples was taken as the average acid-insoluble component content.
  • CNF-3 and CNF-4 which are acetylated cellulose fibers
  • the average acid-insoluble component content of CNF-1 and CNF-2 which are raw materials before acetylation, was used.
  • the concentrated cake was diluted to 0.01% by mass with tert-butanol, and dispersed using a high shear homogenizer (manufactured by IKA, trade name "Ultra Turrax T18") under processing conditions: rotation speed 15,000 rpm x 3 minutes, It was cast onto a silicon substrate on which osmium was vapor-deposited, air-dried, and measured using a high-resolution scanning electron microscope (Regulus 8220, manufactured by Hitachi High-Technology). The measurement was performed by adjusting the magnification so that at least 100 cellulose fibers were observed, and the diameter (D) of 100 randomly selected cellulose fibers was measured, and the average of the 100 cellulose fibers was calculated. It was calculated as the number average fiber diameter.
  • a high shear homogenizer manufactured by IKA, trade name "Ultra Turrax T18”
  • Acyl substitution degree DS The degree of acetyl substitution was measured.
  • the infrared spectra of five locations on the porous sheet by ATR-IR method were measured using a Fourier transform infrared spectrophotometer (FT/IR-6200 manufactured by JASCO). Infrared spectroscopic measurements were performed under the following conditions. Accumulated number of times: 64 times, Wavenumber resolution: 4cm -1 , Measurement wave number range: 4000 to 600 cm -1 , ATR crystal: diamond, Incident angle: 45°
  • IR index H1730/H1030
  • H1730 and H1030 are absorbances at 1730 cm -1 and 1030 cm -1 (absorption bands of cellulose backbone chain CO stretching vibration).
  • the line connecting 1900 cm -1 and 1500 cm -1 and the line connecting 800 cm -1 and 1500 cm -1 are used as baselines, respectively, and it means the absorbance when the absorbance is set to 0 at this baseline.
  • Thermal decomposition start temperature ( TD ) Thermal analysis of the porous sheet was conducted using the following measurement method.
  • Device Rigaku, Thermo plus EVO2 Sample: A circular cutout from a porous sheet was placed in an aluminum sample pan in an amount of 10 mg.
  • Sample amount 10mg Measurement conditions: In a nitrogen flow of 100 ml/min, the temperature was raised from room temperature to 150°C at a rate of 10°C/min, held at 150°C for 1 hour, and then raised to 450°C at a rate of 10°C/min. The temperature was raised.
  • T D calculation method Calculated from a graph where the horizontal axis is temperature and the vertical axis is weight residual rate %.
  • the temperature was further increased to determine the temperature at 1 wt% weight loss and the temperature at 2 wt% weight loss. Obtained a straight line passing through. The temperature at the point where this straight line intersects with the horizontal line (baseline) passing through the starting point of the weight loss of 0 wt% was defined as the thermal decomposition start temperature (T D ).
  • [250°C weight loss rate] Device Rigaku, Thermo plus EVO2 Sample: A circular cutout from a porous sheet was placed in an aluminum sample pan in an amount of 10 mg. Sample amount: 10mg Measurement conditions: In a nitrogen flow of 100 ml/min, the temperature was raised from room temperature to 150°C at a rate of 10°C/min, held at 150°C for 1 hour, and then from 150°C to 250°C at a rate of 10°C. The temperature was raised at 250°C for 2 hours. Starting from the weight W0 at the time when the temperature reached 250°C, the weight after being maintained at 250°C for 2 hours was defined as W1, and was calculated from the following formula. 250°C weight loss rate (%): (W0-W1)/W0 ⁇ 100
  • Step 2 Refractive index calculated from molecular structure
  • the refractive index was calculated using the following procedure. Using the Synthia module of Materials Studio manufactured by BIOVIA, each polymer was calculated based on the structure-property correlation method from the chemical structure of the monomer, and a calibration curve was created. The detailed theory is based on the following formula described on page 303 of the following document, which is incorporated herein by reference: Jozef Bicerano, "Prediction of Polymer Properties, 3rd Edition” , published by Marcel Dekker.
  • the degree of acetyl group substitution DS A is 0 (that is, unmodified), 1.
  • the refractive index was determined for the cases of 0, 2.0, and 3.0, and the following formula was derived and calculated by linear regression using the least squares method.
  • Refractive index -0.0151 ⁇ DS A +1.55
  • RP 0 (that is, polyethylene homopolymer)
  • RE molar proportion of ethylene units
  • SP value Using the Synthia module of Materials Studio manufactured by BIOVIA, the chemical structure of each component was determined according to the Fedors method.
  • ⁇ Resin composition> [Light transmittance] A rectangular parallelepiped sample with a thickness of 2 mm, width of 4 mm, and length of 15 mm was cut out from a dumbbell-shaped test piece of ISO 37 type 3 standard using a precision cut saw, and was measured using an ultraviolet-visible spectrophotometer (manufactured by JASCO Corporation, V-670). The measured light transmittance at a wavelength of 780 nm was calculated as the light transmittance.
  • the 3D data obtained in this way was binarized and pixels containing only aggregates were extracted. Thereafter, the ratio of the total volume of aggregates larger than a cube with one side of 4.8 ⁇ m to the total volume of the observation range of X-ray CT was calculated as the volume fraction of aggregates.
  • Tensile yield strength and tensile breaking strain Tensile yield strength and tensile breaking strain were measured in accordance with ISO527-1. For molded pieces that broke before yielding, their maximum strength was used as a substitute.
  • PP polypropylene homopolymer (MA04A, available from Nippon Polypro Co., Ltd.), refractive index (P1) according to procedure 1: 1.510, refractive index (P2) according to procedure 2: 1.471, SP value: 16.06, MFR: 40g/10min
  • SEBS H1062 Product name "Tuftec H1062", manufactured by Asahi Kasei Corporation, MFR: 4.5 g/10 minutes
  • SEBS H1221 Product name "Tuftec H1221", manufactured by Asahi Kasei Corporation, MFR: 4.5 g/10 minutes
  • SEBS S1613 Product Product name "S.O.E S1613", manufactured by Asahi Kasei Corporation, MFR: 4.5 g/10 minutes
  • PS Polystyrene (PS) SX100: Product name "YS Resin SX100", manufactured by Yasuhara Chemical Co., Ltd.
  • Liquid rubber-1 butadiene-styrene random copolymer (RICON 184, available from Clay Valley), viscosity at 25°C 40,000 cP, number average molecular weight (Mn) 3,200, weight average molecular weight (Mw) 14,000, Mw/Mn 4.3, vinyl content 19 mol%, aromatic styrene content 8 mol%
  • Liquid rubber-2 butadiene-styrene random copolymer (RICON 100, available from Clay Valley), viscosity at 25°C 75,000 cP, number average molecular weight (Mn) 2,100, weight average molecular weight (Mw) 4,500, Mw/Mn2.1, vinyl amount 42 mol%, aromatic styrene amount 9 mol%
  • ⁇ Cellulose fiber> CNF-1 Unmodified cellulose fiber (finely refined) 3 parts by mass of cotton linter pulp was immersed in 27 parts by mass of water and dispersed using a pulper. An aqueous dispersion (solid content 1.5% by mass) obtained by adding 170 parts by mass of water to 30 parts by mass of pulped cotton linter pulp slurry (including 3 parts by mass of cotton linter pulp) and dispersing it in water, disk The aqueous dispersion was refined for 30 minutes using an SDR14 type laboratory refiner (pressure type DISK type) manufactured by Aikawa Tekko Co., Ltd. as a refiner device, with a clearance between disks of 1 mm.
  • SDR14 type laboratory refiner pressure type DISK type
  • CNF-2 Unmodified cellulose fiber CNF-2 was obtained in the same manner as CNF-1 except that the number of micronization treatments using a high-pressure homogenizer was changed to 10 times.
  • CNF-3 Acetylated cellulose fiber NETZSCH KAPPA VITA (registered trademark) manufactured by Vakumix Inc. Add 5 parts by mass of CNF-1 (solid content 20% by mass) and 95 parts by mass of DMSO to a homomixer (tank size 35L), and mix the homomixer. The slurry was dispersed at 2500 rpm (peripheral speed 12 m/s) to obtain 100 parts by mass of DMSO slurry (solid content 1.0% by mass). Subsequently, 2 parts by mass of vinyl acetate and 0.3 parts by mass of potassium carbonate were added, and the mixture was stirred at 40°C for 3 hours. In order to stop the reaction, 100 parts by mass of water was added with stirring.
  • CNF-4 Acetylated cellulose fiber CNF-4 was obtained by carrying out acetylation in the same manner as CNF-3 except that CNF-1 was changed to CNF-2.
  • CNF-5 Cellulose fiber Selish KY-100G (solid content concentration 10% by mass) manufactured by Daicel Millize Co., Ltd. was concentrated using a dehydrator so that the solid content concentration was 20% by mass. Table 1 shows the properties of cellulose fibers.
  • Surfactant-1 Sorbitan monolaurate (Rheodol SP-L10, available from Kao Corporation)
  • Surfactant-2 Polyoxyethylene (2) monolauryl ether (Emulgen 102KG, available from Kao Corporation) The number in parentheses is the number of repeating oxyethylene chains
  • Surfactant-3 Ethylene glycol-propylene glycol Polymer (PEG-PPG) (Sannix GL-3000, available from Sanyo Chemical Co., Ltd.)
  • ⁇ Preparation of resin composition 75 parts by mass of purified water was added to 25 parts by mass of cellulose fibers with a solid content of 20% by mass, and a nonionic surfactant and liquid rubber were added according to the composition shown in Table 2, and a rotation-revolution mixer manufactured by Shinky Co., Ltd. Mixing was carried out for 5 minutes using ARE-310 to obtain a dispersion of the cellulose fiber composition.
  • the obtained dispersion liquid was dried at 80° C. using SPH-201 manufactured by ESPEC Corporation.
  • the obtained dry body was pulverized using a mini speed mill MS-05 manufactured by Labnect Co., Ltd. to obtain CNF powder.
  • the obtained CNF powder and SEBS elastomer were circulated and kneaded for 3 minutes at 200°C and 200 rpm using a small kneader (manufactured by Xplore instruments, product name: "Xplore”) according to the composition shown in Table 3, and then discharged to form a masterbatch. I got it.
  • the obtained masterbatch and polypropylene resin were mixed in accordance with the composition shown in Table 5 using a small kneader (manufactured by Xplore instruments, product name "Xplore") at 200°C and 200 rpm for 3 minutes, and It was melted at 200°C using an injection molding machine to produce a dumbbell-shaped test piece of ISO 37 TYPE 3 standard.
  • Example 1 is a scanning electron microscope (SEM) image of a cross section of the resin composition obtained in Example 2-1, showing polypropylene (1), cellulose nanofiber (2), styrene elastomer (3), and liquid rubber (4) were observed.
  • SEM scanning electron microscope
  • the cellulose nanofibers that are in contact with the polymer at 30% or more are determined to be cellulose nanofibers coated with styrene elastomer, and the 30 cellulose nanofibers are If there are 15 or more cellulose nanofibers among the fibers that are determined to be coated with styrene-based elastomer, it is determined that the cellulose nanofibers are coated with the polymer in the resin composition, and the following evaluation is performed. did.
  • the resin composition pellets were molded using an injection molding machine under conditions compliant with JIS K6921-2 to form multipurpose test pieces compliant with ISO 294-3.
  • the molding temperature for injection molding was 200°C.
  • the flexural modulus was measured according to JIS K7171.
  • Linear expansion coefficient The coefficient of linear expansion was determined by cutting out a rectangular parallelepiped sample measuring 4 mm long, 4 mm wide, and 10 mm long from the center of the multipurpose test piece using a precision cut saw, and measuring the temperature range of -10°C to 80°C in accordance with ISO11359-2. The temperature was measured and the value between 0°C and 60°C was calculated.
  • Charpy impact strength was measured in accordance with JIS K7111 using a multipurpose test piece.
  • CNF-1 unmodified cellulose fiber
  • CNF-3 acetylated cellulose fiber (same as the first embodiment)
  • Nonionic surfactant Sorbitan monooleate (Rheodol SP-O10V, available from Kao Corporation)
  • Example 2-5 Using a twin-screw extruder, the dried CNF, SEBS elastomer, and polypropylene were melt-kneaded at 200° C. in the amounts listed in Table 7 to obtain resin pellets. Regarding the obtained resin pellets, multipurpose test pieces were produced using an injection molding machine, and various physical properties were evaluated.
  • ⁇ Comparative example 2-2> Using a twin-screw extruder, the dried CNF and polypropylene were melt-kneaded at 200° C. in the amounts listed in Table 7 to obtain resin pellets. Regarding the obtained resin pellets, multipurpose test pieces were produced using an injection molding machine, and various physical properties were evaluated.
  • the resin composition according to the present disclosure can form a molded body having good physical properties, it can be used in industrial machine parts, general machine parts, automobile/railway/vehicle/vehicle/ship/aerospace-related parts, electronic/electrical parts, etc. It can be suitably applied to a wide range of applications, such as construction/civil engineering materials, daily necessities, sports/leisure goods, wind power generation housing members, containers/packaging members, etc.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Transportation (AREA)
  • Combustion & Propulsion (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Un mode de réalisation de la présente invention concerne : une composition de résine qui contient une résine de polypropylène et des fibres de cellulose et présente une excellente transparence ; un procédé de production de cette composition de résine ; et un corps moulé qui est formé de cette composition de résine. Un autre mode de réalisation de la présente invention concerne : une composition de résine qui a un faible coefficient de dilatation linéaire et une résistance élevée tout en ayant une excellente transparence ; un procédé de production de cette composition de résine ; et un corps moulé qui est formé de cette composition de résine. Un autre mode de réalisation de la présente invention concerne : une composition de résine qui contient une résine de polypropylène, un élastomère de styrène et des fibres de cellulose. Si la résine de polypropylène est moulée en une feuille d'une épaisseur de 0,2 mm et la feuille est mesurée par un procédé d'Abbe, le rapport (C2/P1) de l'indice de réfraction (C2) des fibres de cellulose, tel que calculé par une relation structure-propriété sur la base de la structure moléculaire des fibres de cellulose, sur l'indice de réfraction (P1) de la résine de polypropylène, va de 0,950 à 1,050.
PCT/JP2023/026119 2022-07-15 2023-07-14 Composition de résine et procédé de production de celle-ci WO2024014546A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2022114023 2022-07-15
JP2022-113913 2022-07-15
JP2022113913 2022-07-15
JP2022-114023 2022-07-15

Publications (1)

Publication Number Publication Date
WO2024014546A1 true WO2024014546A1 (fr) 2024-01-18

Family

ID=89536891

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/026119 WO2024014546A1 (fr) 2022-07-15 2023-07-14 Composition de résine et procédé de production de celle-ci

Country Status (1)

Country Link
WO (1) WO2024014546A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01104636A (ja) * 1987-10-19 1989-04-21 Ube Ind Ltd 樹脂組成物
WO2019107449A1 (fr) * 2017-11-29 2019-06-06 花王株式会社 Composition de résine de polypropylène
WO2019220895A1 (fr) * 2018-05-17 2019-11-21 パナソニックＩｐマネジメント株式会社 Composition de résine
JP2020100714A (ja) * 2018-12-21 2020-07-02 ヤスハラケミカル株式会社 繊維強化熱可塑性樹脂組成物、およびそれから得られる成形体
CN112457585A (zh) * 2020-12-09 2021-03-09 金发科技股份有限公司 一种聚丙烯组合物及其制备方法
JP2021187885A (ja) * 2020-05-26 2021-12-13 旭化成株式会社 セルロース樹脂組成物及びその製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01104636A (ja) * 1987-10-19 1989-04-21 Ube Ind Ltd 樹脂組成物
WO2019107449A1 (fr) * 2017-11-29 2019-06-06 花王株式会社 Composition de résine de polypropylène
WO2019220895A1 (fr) * 2018-05-17 2019-11-21 パナソニックＩｐマネジメント株式会社 Composition de résine
JP2020100714A (ja) * 2018-12-21 2020-07-02 ヤスハラケミカル株式会社 繊維強化熱可塑性樹脂組成物、およびそれから得られる成形体
JP2021187885A (ja) * 2020-05-26 2021-12-13 旭化成株式会社 セルロース樹脂組成物及びその製造方法
CN112457585A (zh) * 2020-12-09 2021-03-09 金发科技股份有限公司 一种聚丙烯组合物及其制备方法

Similar Documents

Publication Publication Date Title
JP6688438B1 (ja) 化学修飾されたセルロース微細繊維を含む高耐熱性樹脂複合体
JP7385625B2 (ja) 複合粒子及び樹脂組成物
WO2021080010A1 (fr) Composition de résine de polyamide-cellulose
JP7411378B2 (ja) セルロース樹脂組成物
JP7488096B2 (ja) セルロース繊維乾燥体及びその製造方法、並びに樹脂複合体の製造方法
JP2023053377A (ja) セルロース微細繊維強化ポリアミド樹脂成形体
JP2022003120A (ja) セルロース樹脂組成物及びその製造方法
JP7444669B2 (ja) 微細セルロース繊維を含む複合粒子、及び複合粒子を含む樹脂組成物
JP2021187885A (ja) セルロース樹脂組成物及びその製造方法
JP2022169490A (ja) 乾燥体及びその製造方法、並びに樹脂組成物の製造方法
WO2024014546A1 (fr) Composition de résine et procédé de production de celle-ci
JP2021169578A (ja) セルロース繊維乾燥体の製造方法、及び樹脂複合体の製造方法
JP2021127383A (ja) セルロースナノファイバー乾固体、及びセルロースナノファイバーの再分散液の製造方法
JP6681499B1 (ja) 化学修飾されたセルロース微細繊維、及び化学修飾されたセルロース微細繊維を含む高耐熱性樹脂複合体
JP7417391B2 (ja) エステル化セルロース繊維の製造方法
JP2022001631A (ja) セルロース繊維の乾燥粉体の製造方法
WO2022260175A1 (fr) Composition de résine et son procédé de production
JP7342142B2 (ja) セルロース樹脂組成物
JP2024077608A (ja) 樹脂組成物及びその製造方法
JP2024031890A (ja) ３ｄプリント用造形材料及びその製造方法
WO2022177014A1 (fr) Composition contenant des nanofibres de cellulose
JP2022169489A (ja) 乾燥体及びその製造方法、並びに樹脂組成物の製造方法
JP6937817B2 (ja) セルロース組成物
WO2022177012A1 (fr) Composition contenant des nanofibres de cellulose
JP7209914B1 (ja) セルロース微細繊維及びその製造方法、不織布、並びに繊維強化樹脂及びその製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23839713

Country of ref document: EP

Kind code of ref document: A1