Patent Application
20190276637
This application is based on and claims priority under 35 USC 119 from Japanese Patent Application No. 2018-039555 filed Mar. 6, 2018.
The present invention relates to a resin composition and a resin molded body.
In the related art, various resin compositions are provided and used in a wide range of applications. In particular, resin compositions are used for, for example, various parts and housings of home appliances and automobiles. Thermoplastic resins are used for parts, such as housings, of office machines and electrical and electronic devices.
In recent years, plant-derived resins have been used, and one of plant-derived resins known in the art is cellulose acylate.
A resin composition containing cellulose acylate (A), a polyester resin (B), and an ester compound having a molecular weight of about 250 or more and about 2000 or less has high fluidity. The resin composition, however, tends to have low fluidity at low temperature. When the resin composition having low fluidity at low temperature is molded at low temperature, the obtained resin molded body tends to be colored brown.
According to an aspect of the invention, there is provided a resin composition containing cellulose acylate (A), a polyester resin (B), an ester compound (C) having a molecular weight of about 250 or more and about 2000 or less, and a cellulose fiber (D).
Exemplary embodiments of the present invention will be described below.
In this specification, the amount of each component in an object refers to, when there are several substances corresponding to each component in the object, the total amount or total proportion of the substances present in the object, unless otherwise specified.
The expression “polymer of A” encompasses a homopolymer of only A and a copolymer of A and a monomer other than A. Similarly, the expression “copolymer of A and B” encompasses a copolymer of only A and B (hereinafter referred to as a “homocopolymer” for convenience) and a copolymer of A, B, and a monomer other than A and B.
A cellulose acylate (A), a polyester resin (B), an ester compound (C), a cellulose fiber (D), a polymer (E), and a poly(meth)acrylate compound (F) are also referred to as a component (A), a component (B), a component (C), a component (D), a component (E), and a component (F), respectively.
A resin composition according to a first exemplary embodiment contains cellulose acylate (A), a polyester resin (B), an ester compound (C) having a molecular weight of about 250 or more and about 2000 or less, and a cellulose fiber (D). The resin composition according to the exemplary embodiment may also contain other components, such as a polymer (E) and a poly(meth)acrylate compound (F).
In the related art, cellulose acylate (A) (specifically, cellulose acylate in which one or more hydroxyl groups are substituted with one or more acyl groups) is derived from a non-edible source and is an environmentally friendly resin material because it is a primary derivative without a need of chemical polymerization. The cellulose acylate (A) has a high elastic modulus among resin materials due to its strong hydrogen bonds. Furthermore, the cellulose acylate (A) has high transparency because of its alicyclic structure.
The cellulose acylate (A) has strong intramolecular and intermolecular hydrogen bonds and thus has low fluidity when heated, which requires molding at a high temperature. This may cause decomposition of cellulose acylate itself or impurities to induce brown coloration.
In this respect, a resin composition containing cellulose acylate (A), a polyester resin (B), and an ester compound (C) having a molecular weight of about 250 or more and about 2000 or less may have high fluidity.
The resin composition, however, tends to have low fluidity at a low temperature (e.g., 200° C. or lower). When the resin composition having low fluidity at a low temperature is molded at a low temperature, the obtained resin molded body tends to be colored brown.
The resin composition according to the first exemplary embodiment containing the above-mentioned components provides a resin molded body that has undergone less brown coloration even when molded at a low temperature (e.g., 200° C. or lower) compared with a resin composition containing only cellulose acylate (A), a polyester resin (B), and an ester compound (C) having a molecular weight of about 250 or more and about 2000 or less. The reason for this is assumed as described below.
First, the ester compound (C) has high affinity for the cellulose acylate (A) and the polyester resin (B) and tends to be compatible substantially equally with both the cellulose acylate (A) and the polyester resin (B). The ester compound (C) has a low molecular weight and a low melt viscosity, and the cellulose fiber (D) tends to selectively enter the phase of the component (C). When the component (D) is mixed with a system containing the component (A) to the component (C), the phase of the component (C) which the component (D) has entered is substantially finely and uniformly dispersed in both the phase of the component (A) and the phase of the component (B). In other words, the component (D) is substantially uniformly dispersed in the entire system.
The cellulose fiber (D) is known to typically reduce the fluidity of the resin composition. This is because the fiber causes secondary aggregation to form large aggregates. When the component (D) is substantially uniformly dispersed in the entire system, the component (D) easily moves in response to external force because it is solid, thereby increasing fluidity. The resin composition may thus have high fluidity at a low temperature, and the obtained resin molded body may undergo less brown coloration.
As described above, a resin molded body according to the first exemplary embodiment is assumed to be a resin molded body that has undergone less brown coloration even when formed by molding at a low temperature.
A resin molded body according to a second exemplary embodiment includes cellulose acylate (A), a polyester resin (B), and an ester compound (C) having a molecular weight of about 250 or more and about 2000 or less and has a melt flow rate (MFR) of about 7 g/10 min or more at about 200° C. and under a load of about 21.6 kg.
As described above, a resin composition containing cellulose acylate (A), a polyester resin (B), and an ester compound (C) having a molecular weight of about 250 or more and about 2000 or less has low fluidity at a low temperature (e.g., 200° C. or lower). When the resin composition is molded at a low temperature, the obtained resin molded body tends to be colored brown.
The resin composition according to the second exemplary embodiment has a system containing the cellulose acylate (A), the polyester resin (B), and the ester compound (C) having a molecular weight of about 250 or more and about 2000 or less has a melt flow rate (MFR) of about 7 g/10 min or more at about 200° C. and under a load of about 21.6 kg. Because of this property, the resin composition may have high fluidity at a low temperature (e.g., 200° C. or lower) and, even when molded at a low temperature, may provide a resin molded body that has undergone less brown coloration.
When the resin composition having low fluidity at a low temperature (e.g., 200° C. or lower) is molded into a large resin molded body or a thin molded body, the obtained resin molded body tends to be colored brown. To suppress this brown coloration, the resin composition needs to be molded at a high temperature, which leads to a large environmental load from an energy viewpoint.
Since the resin compositions according to the first and second exemplary embodiments may have high fluidity at a low temperature, a large resin molded body or a thin molded body obtained even when formed by molding at a low temperature may undergo less brown coloration.
The components of the resin compositions according to the first and second exemplary embodiments (hereinafter collectively referred to as an exemplary embodiment) will be described below in detail.
The cellulose acylate (A) is, for example, a resin of a cellulose derivative in which at least one hydroxyl group in cellulose is substituted with an acyl group (acylation). Specifically, the cellulose acylate (A) is, for example, a cellulose derivative represented by general formula (CE).
In general formula (CE), RCE1, RCE2, and RCE3 each independently represent a hydrogen atom or an acyl group, and n represents an integer of 2 or more. It is noted that at least one of n RCE1's, n RCE2's, and n RCE3's represents an acyl group.
The acyl group represented by RCE1, RCE2, and RCE3 may be an acyl group having 1 or more and 6 or less carbon atoms.
In general formula (CE), n is preferably, but not necessarily, 200 or more and 1000 or less, and more preferably 500 or more and 1000 or less.
The expression “in general formula (CE), RCE1, RCE2, and RCE3 each independently represent an acyl group” means that at least one hydroxyl group in the cellulose derivative represented by general formula (CE) is acylated.
Specifically, n RCE1's in the molecule of the cellulose derivative represented by general formula (CE) may be all the same, partially the same, or different from each other. The same applies to n RCE2's and n RCE3's.
The cellulose acylate (A) may have, as an acyl group, an acyl group having 1 or more and 6 or less carbon atoms. In this case, a resin molded body in which a decrease in transparency may be suppressed and which may have high impact resistance is obtained easily compared with the case where the cellulose acylate (A) has an acyl group having 7 or more carbon atoms.
The acyl group has a structure represented by “—CO—RAC”, where RAC represents a hydrogen atom or a hydrocarbon group (may be a hydrocarbon group having 1 or more and 5 or less carbon atoms).
The hydrocarbon group represented by RAC may be a linear, branched, or cyclic hydrocarbon group, and is preferably a linear hydrocarbon group.
The hydrocarbon group represented by RAC may be a saturated hydrocarbon group or an unsaturated hydrocarbon group and is preferably a saturated hydrocarbon group.
The hydrocarbon group represented by RAC may have atoms (e.g., oxygen, nitrogen) other than carbon and hydrogen atoms, but is preferably a hydrocarbon group composed of carbon and hydrogen.
Examples of the acyl group include a formyl group, an acetyl group, a propionyl group, a butyryl group (butanoyl group), a propenoyl group, and a hexanoyl group.
Among these groups, the acyl group is preferably an acyl group having 2 or more and 4 or less carbon atoms and more preferably an acyl group having 2 or more and 3 or less carbon atoms in order to improve the moldability of the resin composition and to improve fluidity at low temperature and suppress brown coloration of the resin molded body in low-temperature molding.
Examples of the cellulose acylate (A) include cellulose acetates (cellulose monoacetate, cellulose diacetate (DAC), and cellulose triacetate), cellulose acetate propionate (CAP), and cellulose acetate butyrate (CAB).
The cellulose acylate (A) may be used alone or in combination of two or more.
Among these substances, the cellulose acylate (A) is preferably cellulose acetate propionate (CAP) or cellulose acetate butyrate (CAB) and more preferably cellulose acetate propionate (CAP) to improve fluidity at low temperature and suppress brown coloration of the resin molded body in low-temperature molding.
The weight-average degree of polymerization of the cellulose acylate (A) is preferably 200 or more and 1000 or less, and more preferably 500 or more and 1000 or less in order to improve the moldability of the resin composition and to improve fluidity at low temperature and suppress brown coloration of the resin molded body in low-temperature molding.
The weight-average degree of polymerization is calculated from the weight-average molecular weight (Mw) in the following manner.
First, the weight-average molecular weight (Mw) of the cellulose acylate (A) is determined on a polystyrene basis with a gel permeation chromatography system (GPC system: HLC-8320GPC available from Tosoh Corporation, column: TSKgel α-M) using tetrahydrofuran.
Next, the weight-average molecular weight of the cellulose acylate (A) is divided by the molecular weight of the structural unit of the cellulose acylate (A) to produce the degree of polymerization of the cellulose acylate (A). For example, when the substituent of the cellulose acylate is an acetyl group, the molecular weight of the structural unit is 263 at a degree of substitution of 2.4 and 284 at a degree of substitution of 2.9.
The degree of substitution of the cellulose acylate (A) is preferably 2.1 or more and 2.8 or less, more preferably 2.2 or more and 2.8 or less, still more preferably 2.3 or more and 2.75 or less, and yet still more preferably 2.35 or more and 2.75 or less in order to improve the moldability of the resin composition and to improve fluidity at low temperature and suppress brown coloration of the resin molded body in low-temperature molding.
In cellulose acetate propionate (CAP), the ratio (acetyl group/propionyl group) of the degree of substitution with the acetyl group to the degree of substitution with the propionyl group is preferably from 5/1 to 1/20 and more preferably from 3/1 to 1/15 in order to improve the moldability of the resin composition and to improve fluidity at low temperature and suppress brown coloration of the resin molded body in low-temperature molding.
In cellulose acetate butyrate (CAB), the ratio (acetyl group/butyryl group) of the degree of substitution with the acetyl group to the degree of substitution with the butyryl group is preferably from 5/1 to 1/20 and more preferably from 4/1 to 1/15 in order to improve the moldability of the resin composition and to improve fluidity at low temperature and suppress brown coloration of the resin molded body in low-temperature molding.
The degree of substitution indicates the degree at which the hydroxyl groups of cellulose are substituted with acyl groups. In other words, the degree of substitution indicates the degree of acylation of the cellulose acylate (A). Specifically, the degree of substitution means the average number of hydroxyl groups per molecule substituted with acyl groups among three hydroxyl groups of the D-glucopyranose unit of the cellulose acylate.
The degree of substitution is determined from the integration ratio between the peak from hydrogen of cellulose and the peak from the acyl groups using H1-NMR (JMN-ECA available from JEOL RESONANCE).
Examples of the polyester resin (B) include polymers of hydroxyalkanoates (hydroxyalkanoic acids), polycondensates of polycarboxylic acids and polyhydric alcohols, and ring-opened polycondensates of cyclic lactams.
The polyester resin (B) may be an aliphatic polyester resin. Examples of the aliphatic polyester include polyhydroxyalkanoates (polymers of hydroxyalkanoates) and polycondensates of aliphatic diols and aliphatic carboxylic acids.
Among these aliphatic polyesters, a polyhydroxyalkanoate is preferred as the polyester resin (B) to improve fluidity at low temperature and suppress brown coloration of the resin molded body in low-temperature molding.
Examples of the polyhydroxyalkanoate include a compound having a structural unit represented by general formula (PHA).
The compound having a structural unit represented by general formula (PHA) may include a carboxyl group at each terminal of the polymer chain (each terminal of the main chain) or may include a carboxyl group at one terminal and a different group (e.g., hydroxyl group) at the other terminal.
In general formula (PHA), RPHA1 represents an alkylene group having 1 or more and 10 or less carbon atoms, and n represents an integer of 2 or more.
In general formula (PHA), the alkylene group represented by RPHA1 may be an alkylene group having 3 or more and 6 or less carbon atoms. The alkylene group represented by RPHA1 may be a linear alkylene group or a branched alkylene group and is preferably a branched alkylene group.
The expression “RPHA1 in general formula (PHA) represents an alkylene group” indicates 1) having a [O—RPHA1—C(═O)—] structure where RPHA1 represents the same alkylene group, or 2) having plural [O—RPHA1—C(═O)—] structures where RPHA1 represents different alkylene groups (RPHA1 represents alkylene groups different from each other in branching or in the number of carbon atoms (e.g., a [O—RPHA1A—C(═O)—] [O—RPHA1B—C(═O)—] structure).
In other words, the polyhydroxyalkanoate may be a homopolymer of one hydroxyalkanoate (hydroxyalkanoic acid) or may be a copolymer of two or more hydroxyalkanoates (hydroxyalkanoic acids).
In general formula (PHA), the upper limit of n is not limited, and n is, for example, 20,000 or less. For the range of n, n is preferably 500 or more and 10,000 or less, and more preferably 1,000 or more and 8,000 or less.
Examples of the polyhydroxyalkanoate include homopolymers of hydroxyalkanoic acids (e.g., lactic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 2-hydroxy-3-methylbutyric acid, 2-hydroxy-3,3-dimethylbutyric acid, 3-hydroxyvaleric acid, 4-hydroxyvaleric acid, 5-hydroxyvaleric acid, 3-hydroxyhexanoic acid, 2-hydroxyhexanoic acid, 2-hydroxyisohexanoic acid, 6-hydroxyhexanoic acid, 3-hydroxypropionic acid, 3-hydroxy-2,2-dimethylpropionic acid, 3-hydroxyhexanoic acid, and 2-hydroxy-n-octanoic acid), and copolymers of two or more of these hydroxyalkanoic acids.
Among these, the polyhydroxyalkanoate is preferably a homopolymer of a branched hydroxyalkanoic acid having 2 or more and 4 or less carbon atoms, or a homocopolymer of a branched hydroxyalkanoic acid having 2 or more and 4 or less carbon atoms and a branched hydroxyalkanoic acid having 5 or more and 7 or less carbon atoms, more preferably a homopolymer of a branched hydroxyalkanoic acid having 3 carbon atoms (i.e., polylactic acid), or a homocopolymer of 3-hydroxybutyric acid and 3-hydroxyhexanoic acid (i.e., polyhydroxybutyrate-hexanoate), and still more preferably a homopolymer of a branched hydroxyalkanoic acid having 3 carbon atoms (i.e., polylactic acid) in order to suppress a decrease in the transparency of the obtained resin molded body and improve impact resistance.
The number of carbon atoms in hydroxyalkanoic acid is a number inclusive of the number of the carbon of the carboxyl group.
Polylactic acid is a polymer compound formed by polymerization of lactic acid through ester bonding.
Examples of polylactic acid include a homopolymer of L-lactic acid, a homopolymer of D-lactic acid, a block copolymer including a polymer of at least one of L-lactic acid and D-lactic acid, and a graft copolymer including a polymer of at least one of L-lactic acid and D-lactic acid.
Examples of a “compound copolymerizable with L-lactic acid or D-lactic acid” include glycolic acid, dimethyl glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 2-hydroxypropanoic acid, 3-hydroxypropanoic acid, 2-hydroxyvaleric acid, 3-hydroxyvaleric acid, and 4-hydroxyvaleric acid; polycarboxylic acids, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, and terephthalic acid, and anhydrides thereof; polyhydric alcohols, such as ethyleneglycol, diethyleneglycol, triethyleneglycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, neopentylglycol, tetramethyleneglycol, and 1,4-hexanedimethanol; polysaccharides, such as cellulose; aminocarboxylic acids, such as α-amino acid; hydroxycarboxylic acids, such as 5-hydroxyvaleric acid, 2-hydroxycaproic acid, 3-hydroxycaproic acid, 4-hydroxycaproic acid, 5-hydroxycaproic acid, 6-hydroxycaproic acid, 6-hydroxymethylcaproic acid, and mandelic acid; and cyclic esters, such as glycolide, β-methyl-δ-valerolactone, γ-valerolactone, and ε-caprolactone.
Polylactic acid is known to be produced by: a lactide method via lactide; a direct polymerization method involving heating lactic acid in a solvent under a reduced pressure to polymerize lactic acid while removing water; or other methods.
In polyhydroxybutyrate-hexanoate, the copolymerization ratio of 3-hydroxyhexanoic acid (3-hydroxyhexanoate) to a copolymer of 3-hydroxybutyric acid (3-hydroxybutyrate) and 3-hydroxyhexanoic acid (3-hydroxyhexanoate) is preferably 3 mol % or more and 20 mol % or less, more preferably 4 mol % or more and 15 mol % or less, and still more preferably 5 mol % or more and 12 mol % or less to improve fluidity at low temperature and suppress brown coloration of the resin molded body in low-temperature molding.
The copolymerization ratio of 3-hydroxyhexanoic acid (3-hydroxyhexanoate) is determined using H1-NMR such that the ratio of the hexanoate is calculated from the integrated values of the peaks from the hexanoate terminal and the butyrate terminal.
The weight-average molecular weight (Mw) of the polyester resin (B) may be 10,000 or more and 1,000,000 or less (preferably 50,000 or more and 800,000 or less, more preferably 100,000 or more and 600,000 or less) to improve fluidity at low temperature and suppress brown coloration of the resin molded body in low-temperature molding.
The weight-average molecular weight (Mw) of the polyester resin (B) is a value determined by gel permeation chromatography (GPC). Specifically, the determination of the molecular weight by GPC is carried out using HLC-8320GPC available from Tosoh Corporation as a measurement system, columns TSKgel GMHHR-M+TSKgel GMHHR-M (7.8 mm I.D., 30 cm) available from Tosoh Corporation, and a chloroform solvent. The weight-average molecular weight (Mw) is calculated from the molecular weight calibration curve created on the basis of the obtained measurement results using a monodisperse polystyrene standard sample.
The ester compound (C) is a compound having an ester group (—C(═O)O—) and a molecular weight of about 250 or more and about 2000 or less (preferably 250 or more and 1000 or less, more preferably 250 or more and 600 or less).
In combinational use of two or more ester compounds (C), ester compounds having a molecular weight of about 250 or more and about 2000 or less are used in combination.
Examples of the ester compound (C) include fatty acid ester compounds and aromatic carboxylic acid ester compounds.
Among these ester compounds, the ester compound (C) is preferably a fatty acid ester compound to improve fluidity at low temperature and suppress brown coloration of the resin molded body in low-temperature molding.
Examples of the fatty acid ester compound include aliphatic monocarboxylic acid esters (e.g., acetic acid ester), aliphatic dicarboxylic acid esters (e.g., succinic acid esters, adipic acid ester-containing compounds, azelaic acid esters, sebacic acid esters, stearic acid esters), aliphatic tricarboxylic acid esters (e.g., citric acid esters, isocitric acid esters), ester group-containing epoxidized compounds (epoxidized soybean oil, epoxidized linseed oil, epoxidized rapeseed fatty acid isobutyl, and epoxidized fatty acid 2-ethylhexyl), fatty acid methyl esters, and sucrose esters.
Examples of the aromatic carboxylic acid ester compound include dimethyl phthalate, diethyl phthalate, bis(2-ethylhexyl) phthalate, and terephthalic acid esters.
Among these compounds, the ester compound is preferably an aliphatic dicarboxylic acid ester or an aliphatic tricarboxylic acid ester, more preferably an adipic acid ester-containing compound or a citric acid ester, and still more preferably an adipic acid ester-containing compound to improve fluidity at low temperature and suppress brown coloration of the resin molded body in low-temperature molding.
The adipic acid ester-containing compound (a compound containing an adipic acid ester) refers to a compound of only an adipic acid ester or a mixture of an adipic acid ester and a component other than the adipic acid ester (a compound different from the adipic acid ester). The adipic acid ester-containing compound may contain 50 mass % or more of the adipic acid ester relative to the total mass of all components.
Examples of the adipic acid ester include adipic acid diesters. Specific examples include adipic acid diesters represented by general formula (AE) below.
In general formula (AE), RAE1 and RAE2 each independently represent an alkyl group or a polyoxyalkyl group [—(CxH2X—O)y—RA1] (where RA1 represents an alkyl group, x represents an integer of 1 or more and 10 or less, and y represents an integer of 1 or more and 10 or less).
The alkyl group represented by RAE1 and RAE2 in general formula (AE) is preferably an alkyl group having 1 or more and 6 or less carbon atoms, and more preferably an alkyl group having 1 or more and 4 or less carbon atoms. The alkyl group represented by RAE1 and RAE2 may be a linear, branched, or cyclic alkyl group, and is preferably a linear or branched alkyl group.
The alkyl group represented by RA1 in the polyoxyalkyl group [—(CxH2X—O)y—RA1] represented by RAE1 and RAE2 in general formula (AE) is preferably an alkyl group having 1 or more and 6 or less carbon atoms, and more preferably an alkyl group having 1 or more and 4 or less carbon atoms. The alkyl group represented by RA1 may be a linear, branched, or cyclic alkyl group, and is preferably a linear or branched alkyl group.
In general formula (AE), the group represented by each reference character is optionally substituted with a substituent. Examples of the substituent include an alkyl group, an aryl group, and a hydroxyl group.
Examples of the citric acid ester include citric acid alkyl esters having 1 or more and 12 or less carbon atoms (preferably 1 or more and 8 or less carbon atoms). The citric acid ester may be a citric acid ester acylated by an alkyl carboxylic anhydride (e.g., a linear or branched alkyl carboxylic anhydride having 2 or more and 6 or less carbon atoms (preferably 2 or more and 3 or less carbon atoms), such as acetic anhydride, propionic anhydride, butyric anhydride, or valeric anhydride).
Examples of the cellulose fiber include wood pulp, such as softwood pulp and hardwood pulp; cotton pulp, such as cotton linter and cotton lint; non-wood pulp, such as straw pulp and bagasse pulp; bacterial cellulose; cellulose isolated from sea squirt; and cellulose fibers isolated and spread from seaweed or the like.
Examples of the cellulose fiber also include surface-treated cellulose fibers, such as cellulose fibers having a reactive group introduced by using an acid treatment, cellulose fibers having a reactive group introduced by using a silane coupling agent, cellulose fibers having the surface treated with an amphiphilic polymer, cellulose fibers oxidized by using tetramethylpiperidine (TEMPO method), carboxyalkylated cellulose fibers, cellulose fibers having the surface treated with an epoxy compound, cellulose fibers having the surface treated with a glycidyl compound, and cellulose fibers having the surface treated with wood components, such as lignin or hemicellulose.
To improve fluidity at low temperature and suppress brown coloration of the resin molded body in low-temperature molding, in particular, the cellulose fiber may be at least one selected from an oxidized cellulose fiber in which some or all of primary hydroxyl groups are oxidized into carboxylic acids, and a substituted cellulose fiber in which some or all of hydroxyl groups are carboxylmethylated.
The oxidized cellulose fiber is a cellulose fiber in which some or all of primary hydroxyl groups (specifically, —CH2OH) of glucose are converted into carboxy groups (—COOH) or metal salts thereof (—COOM, where M represents a metal).
Examples of metal species of the metal salts include alkali metals and alkaline earth metals. Alkali metals (e.g., Na, Ca) are preferred, and Na is more preferred.
The oxidation percentage of the oxidized cellulose fiber may be 95% or more and preferably 97% or more to improve fluidity at low temperature and suppress brown coloration of the resin molded body in low-temperature molding. The maximum oxidation percentage of the oxidized cellulose fiber is ideally 100% but may be 75% or less from a manufacturing viewpoint.
The oxidation percentage of the cellulose fiber indicates the percentage at which primary hydroxyl groups (specifically, —CH2OH) of glucose are converted into carboxy groups or metal salts thereof.
The oxidation percentage of the oxidized cellulose fiber is determined by using the following method.
First, the target resin composition (or resin molded body) is dissolved in tetrahydrofuran, and insoluble cellulose fiber is collected. The collected cellulose fiber is analyzed by using H1-NMR (JMN-ECA available from JEOL RESONANCE Inc.,), and the peaks from the hydrogen atoms of the glucose primary hydroxyl groups and from the hydrogen atoms of the carboxyl groups or the metal salts thereof are classified. From the integrated values of the peaks, the oxidation percentage of the cellulose fiber is calculated.
To improve fluidity at low temperature and suppress brown coloration of the resin molded body in low-temperature molding, the ratio (oxidation percentage/molecular weight) of the oxidation percentage of the oxidized cellulose fiber to the molecular weight of the ester compound (C) is preferably about 70/2500 or more and about 100/200 or less, and more preferably about 70/1800 or more and about 98/300 or less.
The oxidized cellulose fiber is prepared by using a well-known method in which a cellulose fiber is oxidized in an aqueous medium solution containing an N-oxyl compound, which is a catalyst, an alkali halide, and an oxidizing agent.
The N-oxyl compound is a compound that may generate nitroxy radicals. Examples of the N-oxyl compound include 2,2,6,6-tetramethylpiperidyl-1-oxy radical (hereinafter also referred to as “TEMPO”) and TEMPO derivatives (e.g., TEMPO derivatives in which TEMPO is substituted with, at the C4-position, a substituent, such as an acetamide group, a carboxy group, a phosphonooxy group, or a hydroxyl group). Among these, TEMPO is preferably used as a catalyst.
Examples of the alkali halide include alkali fluorides, alkali bromides, alkali chlorides, and alkali iodides. Among these, sodium bromide is preferred.
Examples of the oxidizing agent include sodium hypochlorite, sodium chlorite, sodium hypobromite, and sodium bromide. Among these, sodium hypochlorite is preferred.
Examples of the aqueous medium include water and a mixed medium containing water and an organic solvent soluble in water. Among these, water is preferred. The organic solvent soluble in water means that 1 mass % or more of a target organic solvent is soluble in water at 25° C.
The substituted cellulose fiber is a cellulose fiber in which some or all of hydrogen atoms in hydroxyl groups (—OH) are substituted with carboxyalkyl groups (—RCOOH, where R represents an alkylene group) or metal salts thereof (—RCOOM, where R represents an alkylene group, and M represents a metal). In other words, it is a substituted cellulose fiber in which some or all of hydroxyl groups (—OH) are substituted with —ORCOOH or —ORCOOM.
Examples of the carboxyalkyl group include carboxyalkyl groups having an alkyl chain with 1 or more and 10 or less carbon atoms (preferably 1 or more and 5 or less carbon atoms) (excluding the carbon atom of the carboxyl group). The carboxyalkyl group may be a carboxymethyl group (that is, the substituted cellulose fiber may be a carboxymethylated cellulose fiber).
Examples of metal species of the metal salts include alkali metals and alkaline earth metals. Alkali metals (e.g., Na, Ca) are preferred, and Na is more preferred.
The degree of substitution of the substituted cellulose fiber may be 50% or more and preferably 70% or more to improve fluidity at low temperature and suppress brown coloration of the resin molded body in low-temperature molding. The maximum degree of substitution of the substituted cellulose fiber is ideally 100% but may be 95% or less from a manufacturing viewpoint.
The degree of substitution of the substituted cellulose fiber indicates the degree at which hydrogen atoms of hydroxyl groups are substituted with carboxyalkyl groups or metal salts thereof.
The degree of substitution of the substituted cellulose fiber is determined by using the following method.
First, the target resin composition (or resin molded body) is dissolved in tetrahydrofuran, and insoluble cellulose fiber is collected. The collected cellulose fiber is analyzed by using H1-NMR (JMN-ECA available from JEOL RESONANCE Inc.,), and the peaks from the hydroxy groups of the cellulose and from the carboxyalkyl groups or the metal salts thereof. From the integrated values of the peaks, the degree of substitution of the substituted cellulose fiber is determined.
To improve fluidity at low temperature and suppress brown coloration of the resin molded body in low-temperature molding, the ratio (degree of substitution/molecular weight) of the degree of substitution of the substituted cellulose fiber to the molecular weight of the ester compound (C) is preferably about 50/2500 or more and about 100/200 or less, and more preferably about 70/1800 or more and about 98/300 or less.
The substituted cellulose fiber is produced as follows: for example, mercerizing a cellulose fiber (preparing an alkali cellulose fiber) in an aqueous solvent containing a mercerizing agent; and then adding a carboxyl-alkylating agent to the solvent to cause carboxyalkylation of the cellulose fiber.
Examples of the mercerizing agent include alkali metal hydroxides (e.g., sodium hydroxide, potassium hydroxide).
Examples of the aqueous solvent include water, lower alcohols (e.g., methanol, ethanol, N-propyl alcohol, isopropyl alcohol, N-butanol, isobutanol, and tertiary butanol), and solvent mixtures thereof.
Examples of the carboxyl-alkylating agent include monochloroacetic acid, α-chloropropionic acid, β-chloropropionic acid, α-bromopropionic acid, β-bromopropionic acid, and alkali metal salts thereof.
The average fiber diameter of the cellulose fiber may be 1000 nm or less (preferably 100 nm or less).
To improve fluidity at low temperature and suppress brown coloration of the resin molded body in low-temperature molding, in particular, the average fiber diameter of the cellulose fiber is preferably about 30 nm or less, more preferably about 15 nm or less, still more preferably about 10 nm or less, and yet still more preferably about 8 nm or less. The minimum average fiber diameter of the cellulose fiber may be about 2 nm or more (preferably about 4 nm or more).
The average fiber length of the cellulose fiber may be 0.1 μm or more and 1000 μm or less.
To improve fluidity at low temperature and suppress brown coloration of the resin molded body in low-temperature molding, in particular, the average fiber length of the cellulose fiber is preferably 0.5 μm or more and 500 μm or less and more preferably 1 μm or more and 300 μm or less.
The average fiber diameter and average fiber length of the cellulose fiber are measured by using the following method.
The target resin composition (or resin molded body) is dissolved in tetrahydrofuran, and insoluble cellulose fiber is collected. The collected cellulose fiber is dispersed in methylene chloride by using a ball mill, and methylene chloride is evaporated. The cellulose fiber is then photographed with an electron microscope at a magnification of ×1000. From the photograph, 100 cellulose fibers are selected, and the width (diameter) and length of each fiber are measured. The average fiber diameter and the average fiber length are calculated on the basis of the arithmetic mean.
The polymer (E) is at least one polymer selected from core-shell structure polymers having a core layer and a shell layer formed on the surface of the core layer and containing a polymer of an alkyl (meth)acrylate, and olefin polymers including about 60 mass % or more of a structural unit derived from α-olefin.
The polymer (E) may be, for example, a polymer (thermoplastic elastomer) having, for example, elasticity at ordinary temperature (25° C.) and a property of softening at high temperature like thermoplastic resin.
When the resin composition contains the polymer (E), the resin composition may have high fluidity at low temperature, and the resin molded body may tend to undergo less brown coloration in low-temperature molding.
The core-shell structure polymer according to the exemplary embodiment is a core-shell structure polymer having a core layer and a shell layer on the surface of the core layer.
The core-shell structure polymer is a polymer having a core layer as the innermost layer and a shell layer as the outermost layer (specifically, a polymer in which a polymer of an alkyl (meth)acrylate is bonded to a polymer serving as a core layer by graft polymerization to form a shell layer).
The core-shell structure polymer may further include one or more other layers (e.g., 1 or more and 6 or less other layers) between the core layer and the shell layer. When further including other layers, the core-shell structure polymer is a polymer in which plural polymers are bonded to a polymer serving as a core layer by graft polymerization to form a multilayer polymer.
The core layer may be, but not necessarily, a rubber layer. Examples of the rubber layer include layers formed of (meth)acrylic rubber, silicone rubber, styrene rubber, conjugated diene rubber, α-olefin rubber, nitrile rubber, urethane rubber, polyester rubber, and polyamide rubber, and copolymer rubbers of two or more of these rubbers.
Among these rubbers, the rubber layer is preferably a layer formed of, for example, (meth)acrylic rubber, silicone rubber, styrene rubber, conjugated diene rubber, or α-olefin rubber, or a copolymer rubber of two or more of these rubbers.
The rubber layer may be a rubber layer formed by crosslinking through copolymerization using a crosslinker (e.g., divinylbenzene, allyl acrylate, butylene glycol diacrylate).
Examples of the (meth)acrylic rubber include a polymer rubber produced by polymerization of a (meth)acrylic component (e.g., a (meth)acrylic acid alkyl ester having 2 or more and 6 or less carbon atoms).
Examples of the silicone rubber include a rubber formed of a silicone component (e.g., polydimethylsiloxane, polyphenylsiloxane).
Examples of the styrene rubber include a polymer rubber produced by polymerization of a styrene component (e.g., styrene, α-methylstyrene).
Examples of the conjugated diene rubber include a polymer rubber produced by polymerization of a conjugated diene component (e.g., butadiene, isoprene).
Examples of the α-olefin rubber include a polymer rubber produced by polymerization of an α-olefin component (ethylene, propylene, 2-methylpropylene).
Examples of the copolymer rubber include a copolymer rubber produced by polymerization of two or more (meth)acrylic components; a copolymer rubber produced by polymerization of a (meth)acrylic component and a silicone component; and a copolymer of a (meth)acrylic component, a conjugated diene component, and a styrene component.
Examples of the alkyl (meth)acrylate for the polymer forming the shell layer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, and octadecyl (meth)acrylate. At least one hydrogen atom in the alkyl chain of the alkyl (meth)acrylate is optionally substituted with a substituent. Examples of the substituent include an amino group, a hydroxyl group, and a halogen group.
Among these, the polymer of an alkyl (meth)acrylate is preferably a polymer of an alkyl (meth)acrylate having an alkyl chain with 1 or more and 8 or less carbon atoms, more preferably a polymer of an alkyl (meth)acrylate having an alkyl chain with 1 or more and 2 or less carbon atoms, and still more preferably a polymer of an alkyl (meth)acrylate having an alkyl chain with one carbon atom to improve fluidity at low temperature and suppress brown coloration of the resin molded body in low-temperature molding. In particular, the polymer of an alkyl (meth)acrylate is preferably a copolymer of two or more alkyl acrylates in which the number of carbon atoms in the alkyl chain is different.
The polymer forming the shell layer may be a polymer produced by polymerizing at least one selected from glycidyl group-containing vinyl compounds and unsaturated dicarboxylic anhydrides, other than the alkyl (meth)acrylate.
Examples of glycidyl group-containing vinyl compounds include glycidyl (meth)acrylate, glycidyl itaconate, diglycidyl itaconate, allyl glycidyl ether, styrene-4-glycidyl ether, and 4-glycidylstyrene.
Examples of unsaturated dicarboxylic anhydrides include maleic anhydride, itaconic anhydride, glutaconic anhydride, citraconic anhydride, and aconitic anhydride. Among these anhydrides, maleic anhydride is preferred.
Examples of one or more other layers between the core layer and the shell layer include layers formed of the polymers described for the shell layer.
The amount of the polymer in the shell layer is preferably 1 mass % or more and 40 mass % or less, more preferably 3 mass % or more and 30 mass % or less, and still more preferably 5 mass % or more and 15 mass % or less relative to the total amount of the core-shell structure polymer.
The average primary particle size of the core-shell structure polymer is not limited but preferably 50 nm or more and 500 nm or less, more preferably 50 nm or more and 400 nm or less, still more preferably 100 nm or more and 300 nm or less, and yet still more preferably 150 nm or more and 250 nm or less to improve fluidity at low temperature and suppress brown coloration of the resin molded body in low-temperature molding.
The average primary particle size here refers to the value obtained by the following method. Provided that the maximum diameter of each primary particle is a primary particle size, the primary particle sizes of 100 particles are determined through observation of the particles with a scanning electron microscope and averaged out to a number-average primary particle size. Specifically, the average primary particle size is determined by observing the dispersion form of the core-shell structure polymer in the resin composition using a scanning electron microscope.
The core-shell structure polymer may be produced by using a known method.
Examples of the known method include an emulsion polymerization method. Specifically, the following method is illustrated as a production method. First, a monomer mixture is subjected to emulsion polymerization to produce a core particle (core layer). Next, another monomer mixture is subjected to emulsion polymerization in the presence of the core particle (core layer) to produce a core-shell structure polymer in which a shell layer is formed around the core particle (core layer).
When other layers are formed between the core layer and the shell layer, emulsion polymerization of other monomer mixtures is repeated to produce an intended core-shell structure polymer including the core layer, other layers, and the shell layer.
Examples of commercial products of the core-shell structure polymer include “Metablen” (registered trademark) available from Mitsubishi Chemical Corporation, “Kane Ace” (registered trademark) available from Kaneka Corporation, “Paraloid” (registered trademark) available from Dow Chemical Japan Ltd., “Staphyloid” (registered trademark) available from Aica Kogyo Co., Ltd., and “Paraface” (registered trademark) available from Kuraray Co., Ltd.
The olefin polymer is a polymer of an α-olefin and an alkyl (meth)acrylate and preferably an olefin polymer including about 60 mass % or more of the structural unit derived from the α-olefin.
Examples of the α-olefin for the olefin polymer include ethylene, propylene, and 2-methylpropylene. The α-olefin is preferably an α-olefin having 2 or more and 8 or less carbon atoms, and more preferably an α-olefin having 2 or more and 3 or less carbon atoms to improve fluidity at low temperature and suppress brown coloration of the resin molded body in low-temperature molding. Among these α-olefins, ethylene is still more preferred.
Examples of the alkyl (meth)acrylate polymerizable with the α-olefin include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, and octadecyl (meth)acrylate. To improve fluidity at low temperature and suppress brown coloration of the resin molded body in low-temperature molding, the alkyl (meth)acrylate is preferably an alkyl (meth)acrylate having an alkyl chain with 1 or more and 8 or less carbon atoms, more preferably an alkyl (meth)acrylate having an alkyl chain with 1 or more and 4 or less carbon atoms, and still more preferably an alkyl (meth)acrylate having an alkyl chain with 1 or more and 2 or less carbon atoms.
The olefin polymer here may be a polymer of ethylene and methyl acrylate to improve fluidity at low temperature and suppress brown coloration of the resin molded body in low-temperature molding.
The olefin polymer preferably includes about 60 mass % or more and about 97 mass % or less of a structural unit derived from the α-olefin and more preferably includes about 70 mass % or more and about 85 mass % or less of a structural unit derived from the α-olefin to improve fluidity at low temperature and suppress brown coloration of the resin molded body in low-temperature molding.
The olefin polymer may include structural units other than the structural unit derived from the α-olefin and the structural unit derived from the alkyl (meth)acrylate. The olefin polymer may include 10 mass % or less of other structural units relative to all structural units. Poly(meth)acrylate Compound (F): Component (F)
The poly(meth)acrylate compound (F) is a compound (resin) including about 50 mass % or more (preferably about 70 mass % or more, more preferably about 90 mass %, still more preferably about 100 mass %) of a structural unit derived from an alkyl (meth)acrylate.
When the resin composition contains the poly(meth)acrylate compound (F), the resin composition may have high fluidity at low temperature, and the resin molded body may tend to undergo less brown coloration in low-temperature molding. The obtained resin molded body may also tend to have high elastic modulus.
The poly(meth)acrylate compound (F) may be a compound (resin) including a structural unit derived from a monomer other than the (meth)acrylate.
The poly(meth)acrylate compound (F) may include one structural unit (monomer-derived unit) or two or more structural units.
Examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, n-decyl (meth)acrylate, isopropyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, isopentyl (meth)acrylate, amyl (meth)acrylate, neopentyl (meth)acrylate, isohexyl (meth)acrylate, isoheptyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, cyclohexyl (meth)acrylate, and dicyclopentanyl (meth) acrylate.
Among these, the alkyl (meth)acrylate may be an alkyl (meth)acrylate having an alkyl chain with 1 or more and 8 or less carbon atoms (preferably 1 or more and 4 or less carbon atoms, more preferably 1 or more and 2 or less carbon atoms, and still more preferably 1 carbon atom) to improve fluidity at low temperature and suppress brown coloration of the resin molded body in low-temperature molding.
As the poly(meth)acrylate compound (F) has a shorter alkyl chain, the poly(meth)acrylate compound (F) has a SP value closer to that of the polyester resin (B), which may result in better compatibility between the poly(meth)acrylate compound (F) and the polyester resin (B) and may ensure higher haze.
In other words, the poly(meth)acrylate compound (F) may be a polymer including about 50 mass % or more (preferably about 70 mass % or more, more preferably about 90 mass %, still more preferably about 100 mass %) of a structural unit derived from an alkyl (meth)acrylate having an alkyl chain with 1 or more and 8 or less carbon atoms (preferably 1 or more and 4 or less carbon atoms, more preferably 1 or more and 2 or less carbon atoms, and still more preferably 1 carbon atom).
The poly(meth)acrylate compound (F) may be a polymer including 100 mass % of a structural unit derived from an alkyl (meth)acrylate having an alkyl chain with 1 or more and 8 or less carbon atoms (preferably 1 or more and 4 or less carbon atoms, more preferably 1 or more and 2 or less carbon atoms, still more preferably 1 carbon atom). In other words, the poly(meth)acrylate compound (F) may be a poly(alkyl (meth)acrylate) having an alkyl chain with 1 or more and 8 or less carbon atoms (preferably 1 or more and 4 or less carbon atoms, more preferably 1 or more and 2 or less carbon atoms, still more preferably 1 carbon atom). The poly(alkyl (meth)acrylate) having an alkyl chain with 1 carbon atom may be poly(methyl methacrylate).
Examples of the monomer other than the (meth)acrylate in the poly(meth)acrylate compound (F) include styrenes [e.g., monomers having styrene skeletons, such as styrene, alkylated styrenes (e.g., α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene), halogenated styrenes (e.g., 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene), vinylnaphthalenes (e.g., 2-vinylnaphthalene), and hydroxystyrenes (e.g., 4-ethenylphenol)]; and unsaturated dicarboxylic anhydrides [e.g., compounds having an ethylenic double bond and a dicarboxylic anhydride group, such as maleic anhydride, itaconic anhydride, glutaconic anhydride, citraconic anhydride, and aconitic anhydride].
The weight-average molecular weight (Mw) of the poly(meth)acrylate compound (F) is not limited but may be 15,000 or more and 120,000 or less (preferably more than 20,000 and 100,000 or less, more preferably 22,000 or more and 100,000 or less, and still more preferably 25,000 or more and 100,000 or less).
To improve fluidity at low temperature and suppress brown coloration of the resin molded body in low-temperature molding, the weight-average molecular weight (Mw) of the poly(meth)acrylate compound (F) is preferably less than 50,000, more preferably 40,000 or less, and still more preferably 35,000 or less. The weight-average molecular weight (Mw) of the poly(meth)acrylate compound (F) is preferably 15,000 or more.
The weight-average molecular weight (Mw) of the poly(meth)acrylate compound (F) is a value determined by gel permeation chromatography (GPC). Specifically, the determination of the molecular weight by GPC is carried out using HLC-8320GPC available from Tosoh Corporation as a measurement system and using column TSKgel α-M available from Tosoh Corporation and a tetrahydrofuran solvent. The weight-average molecular weight (Mw) is calculated from the molecular weight calibration curve created on the basis of the obtained measurement results using a monodisperse polystyrene standard sample.
The amount or the mass ratio of each component will be described. The amount or the mass ratio of each component may be in the following range to improve fluidity at low temperature and suppress brown coloration of the resin molded body in low-temperature molding. The shortened name for each component is as described below.
Component (A)=cellulose acylate (A)
Component (B)=polyester resin (B)
Component (C)=ester compound (C)
Component (D)=cellulose fiber (D)
Component (E)=polymer (E)
Component (F)=poly(meth)acrylate compound (F)
The mass ratio (B/A) of the component (B) to the component (A) is preferably about 0.05 or more and about 0.5 or less, more preferably about 0.05 or more and about 0.25 or less, and still more preferably about 0.05 or more and about 0.2 or less.
The mass ratio (C/A) of the component (C) to the component (A) is preferably about 0.02 or more and about 0.15 or less, more preferably about 0.04 or more and about 0.15 or less, and still more preferably about 0.05 or more and about 0.1 or less.
The mass ratio (D/A) of the component (D) to the component (A) is preferably about 0.001 or more and about 0.2 or less, more preferably about 0.001 or more and about 0.1 or less, and still more preferably about 0.001 or more and about 0.05 or less.
The mass ratio (E/A) of the component (E) to the component (A) is preferably 0.05 or more and 0.5 or less, more preferably 0.05 or more and 0.25 or less, and still more preferably 0.05 or more and 0.2 or less.
The mass ratio (F/A) of the component (F) to the component (A) is preferably 0.03 or more and 0.2 or less, more preferably 0.05 or more and 0.2 or less, and still more preferably 0.05 or more and 0.1 or less.
The mass ratio (D/C) of the component (D) to the component (C) is preferably about 0.006 or more and about 10 or less, more preferably about 0.007 or more and about 9 or less, still more preferably about 0.01 or more and about 8 or less, and yet still more preferably about 0.01 or more and about 5 or less.
The amount of the component (A) relative to the resin composition is preferably 50 mass % or more, more preferably 60 mass % or more, and still more preferably 70 mass % or more.
The resin composition according to the exemplary embodiment may contain other components.
Examples of other components include a flame retardant, a compatibilizer, an antioxidant, a release agent, a light resisting agent, a weathering agent, a colorant, a pigment, a modifier, an anti-drip agent, an antistatic agent, a hydrolysis inhibitor, a filler, and reinforcing agents (e.g., glass fiber, carbon fiber, talc, clay, mica, glass flakes, milled glass, glass beads, crystalline silica, alumina, silicon nitride, aluminum nitride, and boron nitride).
As needed, components (additives), such as a reactive trapping agent and an acid acceptor for avoiding release of acetic acid, may be added. Examples of the acid acceptor include oxides, such as magnesium oxide and aluminum oxide; metal hydroxides, such as magnesium hydroxide, calcium hydroxide, aluminum hydroxide, and hydrotalcite; calcium carbonate; and talc.
Examples of the reactive trapping agent include epoxy compounds, acid anhydride compounds, and carbodiimides.
The amount of each of these components may be 0 mass % or more and 5 mass % or less relative to the total amount of the resin composition. The expression “0 mass %” means that the resin composition is free of a corresponding one of other components.
The resin composition according to the exemplary embodiment may contain resins other than the resins (the cellulose acylate (A), the polyester resin (B), the poly(meth)acrylate compound (F), and the like). When the resin composition contains other resins, the amount of other resins relative to the total amount of the resin composition may be 5 mass % or less and is preferably less than 1 mass %. More preferably, the resin composition is free of other resins (i.e., 0 mass %).
Examples of other resins include thermoplastic resins known in the related art. Specific examples include polycarbonate resin; polypropylene resin; polyester resin; polyolefin resin; polyester-carbonate resin; polyphenylene ether resin; polyphenylene sulfide resin; polysulfone resin; polyether sulfone resin; polyarylene resin; polyetherimide resin; polyacetal resin; polyvinyl acetal resin; polyketone resin; polyether ketone resin; polyether ether ketone resin; polyaryl ketone resin; polyether nitrile resin; liquid crystal resin; polybenzimidazole resin; polyparabanic acid resin; a vinyl polymer or a vinyl copolymer produced by polymerizing or copolymerizing at least one vinyl monomer selected from the group consisting of an aromatic alkenyl compound, a methacrylic acid ester, an acrylic acid ester, and a vinyl cyanide compound; a diene-aromatic alkenyl compound copolymer; a vinyl cyanide-diene-aromatic alkenyl compound copolymer; an aromatic alkenyl compound-diene-vinyl cyanide-N-phenylmaleimide copolymer; a vinyl cyanide-(ethylene-diene-propylene (EPDM))-aromatic alkenyl compound copolymer; polyvinyl chloride resin; and chlorinated polyvinyl chloride resin. These resins may be used alone or in combination of two or more.
The “melt flow rate (MFR) at about 200° C. and under a load of about 21.6 kg” of the resin composition according to the exemplary embodiment is about 7 g/10 min or more. When the “melt flow rate (MFR) at about 200° C. and under a load of about 21.6 kg” is about 7 g/10 min or more, the resin composition may have high fluidity at low temperature, and the resin molded body undergoes less brown coloration in low-temperature molding.
To improve fluidity at low temperature and suppress brown coloration of the resin molded body in low-temperature molding, the “melt flow rate (MFR) at about 200° C. and under a load of about 21.6 kg” is preferably about 7 g/10 min or more and more preferably about 9 g/10 min or more. To suppress burr generation and reduce cycle time in injection molding, the minimum “melt flow rate (MFR) at about 200° C. and under a load of about 21.6 kg” is, for example, about 30 g/10 min or less.
Examples of the method for bringing the “melt flow rate (MFR) at about 200° C.” in the above-mentioned range include a method for adding the cellulose fiber (D) to a system containing the cellulose acylate (A), the polyester resin (B), and the ester compound (C). It is noted that the method is not limited to this method.
The “melt flow rate (MFR) at about 200° C.” is a value obtained by using Melt indexer (model 2A available from Toyo Seiki Seisaku-sho, Ltd.) under the conditions of a temperature of about 200° C. and a load of about 21.6 kg in accordance with ISO 1133-1 (2011).
The resin composition according to the exemplary embodiment is produced by, for example, melt-kneading a mixture containing the cellulose acylate (A), the polyester resin (B), the ester compound (C), the cellulose fiber (D), and as needed, other components. Alternatively, the resin composition according to the exemplary embodiment is also produced by, for example, dissolving the above-described components in a solvent.
An apparatus used for melt kneading is, for example, a known apparatus. Specific examples of the apparatus include a twin-screw extruder, a Henschel mixer, a Banbury mixer, a single-screw extruder, a multi-screw extruder, and a co-kneader.
A resin molded body according to an exemplary embodiment contains the resin composition according to the exemplary embodiment. In other words, a resin molded body according to an exemplary embodiment has the same composition as the resin composition according to the exemplary embodiment.
A method for forming the resin molded body according to the exemplary embodiment may be injection molding from the viewpoint of a high degree of freedom in shaping. For this point, the resin molded body may be an injection-molded body formed by injection molding.
The cylinder temperature during injection molding is, for example, 160° C. or higher and 280° C. or lower, and preferably 180° C. or higher and 260° C. or lower. The mold temperature during injection molding is, for example, 40° C. or higher and 90° C. or lower, and preferably 60° C. or higher and 80° C. or lower.
Injection molding may be performed using a commercially available apparatus, such as NEX 500 available from Nissei Plastic Industrial Co., Ltd., NEX 150 available from Nissei Plastic Industrial Co., Ltd., NEX 70000 available from Nissei Plastic Industrial Co., Ltd., PNX 40 available from Nissei Plastic Industrial Co., Ltd., and SE50D available from Sumitomo Heavy Industries.
The molding method for producing the resin molded body according to the exemplary embodiment is not limited to injection molding described above. Examples of the molding method include extrusion molding, blow molding, heat press molding, calendar molding, coating molding, cast molding, dipping molding, vacuum molding, and transfer molding.
The resin molded body according to the exemplary embodiment is used in various applications, such as electrical and electronic devices, office machines, home appliances, automotive interior materials, toys, and containers. More specifically, the resin molded body is used in housings of electrical and electronic devices and home appliances; various parts of electrical and electronic devices and home appliances; automotive interior parts; block assembly toys; plastic model kits; cases for CD-ROMs, DVDs, and the like; tableware; drink bottles; food trays; wrapping materials; films; and sheets.
The present invention will be described below in more detail by way of Examples, but the present invention is not limited to these Examples. The unit “part(s)” refers to “part(s) by mass” unless otherwise specified.
The following materials are provided.
CA1: “CAP 482-20 (Eastman Chemical Company)”, cellulose acetate propionate
CA2: “CAP 482-0.5 (Eastman Chemical Company)”, cellulose acetate propionate
CA3: “CAP 504-0.2 (Eastman Chemical Company)”, cellulose acetate propionate
CA4: “CAB 171-15 (Eastman Chemical Company)”, cellulose acetate butylate
CA5: “CAB 381-20 (Eastman Chemical Company)”, cellulose acetate butylate
CA6: “CAB 551-0.2 (Eastman Chemical Company)”, cellulose acetate butylate
CA7: “L-50 (Daicel Corporation)”, diacetyl cellulose
CA8: “LT-35 (Daicel Corporation)”, triacetyl cellulose
PE1: “Ingeo 3001D (NatureWorks LLC)”, polylactic acid
PE2: “Terramac TE-2000 (Unitika, Ltd.)”, polylactic acid
PE3: “Lacea H-100 (Mitsui Chemicals, Inc.)”, polylactic acid
PE4: “Aonilex X151A (Kaneka Corporation)”, polyhydroxybutyrate-hexanoate
PE5: “Aonilex X131A (Kaneka Corporation)”, polyhydroxybutyrate-hexanoate
PE6: “Vylopet EMC-500 (Toyobo Co., Ltd.)”, polyethylene terephthalate
CE1: “Daifatty 101 (Daihachi Chemical Industry Co., Ltd.)”, adipic acid ester-containing compound, molecular weight of adipic acid ester=326 to 378
CE2: “DOA (Daihachi Chemical Industry Co., Ltd.,)” 2-ethylhexyl adipate, molecular weight=371
CE3: “D610A (Mitsubishi Chemical Corporation)”, di-n-alkyl adipate (C6, C8, and C10) mixture (R—OOC(CH2) 4COO—R, R=n-C6H13, n-C8H17, and n-C10H21), molecular weight=314 to 427
CE4: “HA-5 (Kao Corporation)”, adipic acid polyester, molecular weight=750
CE5: “D623 (Mitsubishi Chemical Corporation)”, adipic acid polyester, molecular weight=1800
CE6: “Citrofol AI (jungbunzlauer)”, triethyl citrate, molecular weight=276
CE7: “DBS (Daihachi Chemical Industry Co., Ltd.,)” dibutyl sebacate, molecular weight=314
CE8: “DESU (Daihachi Chemical Industry Co., Ltd.,)”, diethyl succinate, molecular weight=170
CE9: “D645 (Mitsubishi Chemical Corporation)”, adipic acid polyester, molecular weight=2200
CF1: carboxylic acid oxidized cellulose nanofiber produced by using the following method, average fiber diameter=4.5 nm, average fiber length=10 μm, oxidation percentage=98%
One point five kilograms (dry) of cellulose powder (KC flock W-400G available from Nippon Paper Chemicals Co., Ltd., average particle size: 24 μm) is added to 50 L of an aqueous solution in which 7 g (0.5 mmol) of TEMPO (available from Sigma Aldrich) and 75.5 g (7 mmol) of sodium bromide are dissolved. The mixture is stirred until the cellulose powder is uniformly dispersed. After 5 L of an aqueous sodium hypochlorite solution (5% available chlorine) is added to the system, the pH is adjusted to 10.3 with 0.5N aqueous hydrochloric acid solution to initiate the oxidation reaction. Since the pH of the system decreases during the reaction, the pH is kept at 10 by sequentially adding 0.5N aqueous sodium hydroxide solution. After the reaction for 2 hours, the oxidized cellulose powder is separated by centrifugation (6000 rpm, 30 minutes, 20° C.) and washed well with water. A 2% (weight/volume) slurry of the oxidized cellulose powder is processed with a mixer at 12,000 rpm for 15 min. The cellulose powder slurry is further processed with an ultra-high-pressure homogenizer 5 times under a pressure of 140 MPa to produce a transparent gel-like CF1 dispersion. The dispersion is vacuum-dried at 60° C. for 12 hours to yield a cellulose fiber (CF1).
CF2: carboxylic acid oxidized cellulose nanofiber produced by using the following method, average fiber diameter=6 nm, average fiber length=8 μm, oxidation percentage=98%
A cellulose fiber (CF2) is produced in the same manner as for the cellulose fiber CF1 except that the cellulose powder slurry is processed with an ultra-high-pressure homogenizer 5 times under a pressure of 120 MPa.
CF3: carboxylic acid oxidized cellulose nanofiber produced by using the following method, average fiber diameter=7.5 nm, average fiber length=20 μm, oxidation percentage=97%
A cellulose fiber (CF3) is produced in the same manner as for the cellulose fiber CF1 except that the amount of TEMPO added is changed to 30 mg.
CF4: commercially available carboxylmethylated cellulose nanofiber (BiNFi-s T Dry available from Sugino Machine Limited) is provided (fiber width: 16 nm, fiber length: 30 μm, percentage of carboxymethylation (degree of substitution)=95%).
CF5: “BiNFi-s Dry (available from Sugino Machine Limited)”, cellulose nanofiber, average fiber diameter=25 nm, average fiber length=300 μm
CF6: “Tencel (Lenzing AG)”, cellulose fiber, average fiber diameter=600 nm
CF7: carboxylic acid oxidized cellulose nanofiber produced by using the following method, average fiber diameter: 4.5 nm, average fiber length: 10 μm, oxidation percentage=75%
A cellulose fiber (CF7) is produced in the same manner as for the cellulose fiber CF1 except that the amount of TEMPO added is changed to 15 mg.
CF8: carboxylic acid oxidized cellulose nanofiber produced by using the following method, average fiber diameter: 4.5 nm, average fiber length: 10 μm, oxidation percentage=65%
Production of CF8
A cellulose fiber (CF8) is produced in the same manner as for the cellulose fiber CF1 except that the amount of TEMPO added is changed to 10 mg.
AE1: “Metablen W-600A (Mitsubishi Chemical Corporation)”, core-shell structure polymer (a polymer in which a “homopolymer rubber formed from methyl methacrylate and 2-ethylhexyl acrylate” is bonded to a “copolymer rubber formed from 2-ethylhexyl acrylate and n-butyl acrylate” serving as a core layer by graft polymerization to form a shell layer), average primary particle size=200 nm
AE2: “Metablen S-2006 (Mitsubishi Chemical Corporation)”, core-shell structure polymer (a polymer including a silicone-acrylic rubber as a core layer and a methyl methacrylate polymer as a shell layer), average primary particle size=200 nm
AE3: “Paraloid EXL-2315 (Dow Chemical Japan, Ltd.,)”, core-shell structure polymer (a polymer in which a “methyl methacrylate polymer” is bonded to a “rubber mainly composed of polybutyl acrylate” serving as a core layer by graft polymerization to form a shell layer), average primary particle size=300 nm
AE4: “Lotryl 29MA03 (Arkema K.K.)”, olefin polymer (an olefin polymer that is a copolymer of ethylene and methyl acrylate and includes 71 mass % of the structural unit derived from ethylene)
PM1: “Delpet 720V (Asahi Kasei Corporation)”, polymethyl methacrylate (PMMA), Mw=55,000
PM2: “Delpowder 500V (Asahi Kasei Corporation)”, polymethyl methacrylate (PMMA), Mw=25,000
PM3: “Sumipex MHF (Sumitomo Chemical Co., Ltd.)”, polymethyl methacrylate (PMMA), Mw=9,5000
PM4: “Delpet 980N (Asahi Kasei Corporation)”, homocopolymer of methyl methacrylate (MMA), styrene (St), and maleic anhydride (MAH) (mass ratio=MMA:St:MAH=67:14:19), Mw=110,000
A resin composition (pellets) is prepared by performing kneading with a twin-screw kneader (TEX 41SS available from Toshiba Machine Co., Ltd.) at the preparation composition ratio shown in Table 1 to Table 3 and the kneading temperature (cylinder temperature) shown in Table 1 to Table 3.
The produced pellets are molded into the following resin molded bodies (1) and (2) using an injection molding machine (NEX 500I available from Nissei Plastic Industrial Co., Ltd.) at an injection peak pressure of less than 180 MPa and the molding temperature (cylinder temperature) and the mold temperature shown in Table 1 to Table 3.
The produced pellets and molded bodies are subjected to the following evaluation. The evaluation results are shown in Table 1 to Table 3.
The “melt flow rate (MFR) at 180° C. and 200° C.” of the produced pellets is measured in accordance with the above-described method.
The Hazen scale (APHA) of the D2 molded body is determined by using a spectrophotometer (TZ 6000 available from Nippon Denshoku Industries, Co. Ltd.,) and evaluated as the degree of brown coloration.
The above-mentioned results indicate that the pellets (resin compositions) of Examples have higher fluidity at low temperatures than the pellets (resin compositions) of Comparative Examples.
The resin molded bodies of Examples are found to have undergone less brown coloration than the molded bodies of Comparative Examples, even when formed by molding at low temperatures.
In the “oxidation percentage or degree of substitution of (D)/molecular weight of (C)” in Table 1 to Table 3, the molecular weight of CE1 and CE3, which serve as the component (C), is a mean in the above-mentioned range.
The foregoing description of the exemplary embodiments of the present invention has been provided for the purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise forms disclosed. Obviously, many modifications and variations will be apparent to practitioners skilled in the art. The embodiments were chosen and described in order to best explain the principles of the invention and its practical applications, thereby enabling others skilled in the art to understand the invention for various embodiments and with the various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the following claims and their equivalents.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2018-039555 | Mar 2018 | JP | national |
