Resin composition and resin molded article
阅读说明：本技术 树脂组合物和树脂成型体 (Resin composition and resin molded article ) 是由 宫崎佳奈 田中凉 八百健二 于 2019-03-11 设计创作，主要内容包括：本发明涉及树脂组合物和树脂成型体。所述树脂组合物包含：纤维素酰化物(A)；热塑性弹性体(B)；和分子中含有两个以上氮原子的至少一种有机化合物的颗粒(C)。(The present invention relates to a resin composition and a resin molded article. The resin composition comprises: cellulose acylate (a); a thermoplastic elastomer (B); and particles (C) of at least one organic compound containing two or more nitrogen atoms in the molecule.)
1. A resin composition comprising:
cellulose acylate (a);
a thermoplastic elastomer (B); and
particles (C) of at least one organic compound containing two or more nitrogen atoms in the molecule.
2. The resin composition according to claim 1, wherein the thermoplastic elastomer (B) is at least one thermoplastic elastomer selected from the group consisting of:
a polymer (b1) having a core-shell structure comprising a core layer and a shell layer containing an alkyl (meth) acrylate on a surface of the core layer;
an olefin polymer (b2) which is a polymer of α -olefin and alkyl (meth) acrylate and contains 60 mass% or more of a monomer derived from the α -olefin;
a polymer (b3) having a core-shell structure, which comprises a core layer containing a butadiene polymer and a shell layer containing a polymer selected from styrene polymers and acrylonitrile-styrene polymers on the surface of the core layer;
styrene-ethylene-butadiene-styrene copolymer (b 4);
polyurethane (b 5); and
polyester (b 6).
3. The resin composition according to claim 1 or 2, wherein the cellulose acylate (a) is at least one selected from the group consisting of cellulose acetate, cellulose acetate propionate and cellulose acetate butyrate.
4. The resin composition according to claim 3, wherein the cellulose acylate (A) is at least one selected from the group consisting of cellulose acetate propionate and cellulose acetate butyrate.
5. The resin composition according to any one of claims 1 to 4, wherein the organic compound of the particles (C) contains at least one of a nitrogen-nitrogen double bond and a nitrogen-hydrogen bond.
6. The resin composition according to any one of claims 1 to 5, wherein the organic compound of the particles (C) is an organometallic compound.
7. The resin composition according to any one of claims 1 to 6, wherein the organic compound of the particles (C) has a molecular weight of 300 or more and 1300 or less.
8. The resin composition according to any one of claims 1 to 7, wherein the volume average diameter of the particles (C) is 10nm or more and 1,000nm or less.
9. The resin composition according to any one of claims 1 to 8, further comprising a plasticizer (D).
10. The resin composition according to any one of claims 1 to 9, wherein the plasticizer (D) contains at least one selected from the group consisting of a cardanol compound, a dicarboxylic acid diester, a citric acid ester, a polyether compound containing 1 or more unsaturated bonds in the molecule, a polyether ester compound, a glycol benzoate, a compound represented by the following general formula (6), and an epoxidized fatty acid ester:
wherein, in the general formula (6), R61Represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms, and R62Represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms.
11. The resin composition according to any one of claims 1 to 10, further comprising a polyester resin (E).
12. The resin composition according to claim 11, wherein the polyester resin (E) is polyhydroxyalkanoate.
13. The resin composition according to any one of claims 1 to 12, further comprising a poly (meth) acrylate compound (F).
14. A resin molded body comprising the resin composition according to any one of claims 1 to 13.
15. The resin molded body according to claim 14, wherein the resin molded body is an injection molded body.
Technical Field
The present invention relates to a resin composition and a resin molded article.
Background
Disclosure of Invention
When a resin composition containing cellulose acylate (a) is molded (for example, injection molding), an alignment layer is formed on the surface due to the molecular alignment of cellulose acylate (a), and therefore a molded article excellent in surface gloss is easily obtained. However, when the particles (C) of an organic compound are contained in the resin composition, since the particles (C) of an organic compound easily enter and are localized in the above-mentioned alignment layer, the surface glossiness may be lowered.
The purpose of the present invention is to provide a resin composition which can give a resin molded article having high surface gloss as compared with a resin composition containing at least one cellulose acylate (A) and particles (C) of at least one organic compound containing two or more nitrogen atoms in the molecule and not containing a thermoplastic elastomer (B), or as compared with a resin composition containing a cellulose acylate (A), a thermoplastic elastomer (B) and particles (C) of an organic compound containing only one or less nitrogen atoms in the molecule.
Specific means for solving the above technical problems include the following aspects.
<1> according to one aspect of the present invention, there is provided a resin composition comprising:
cellulose acylate (a);
a thermoplastic elastomer (B); and
particles (C) of at least one organic compound containing two or more nitrogen atoms in the molecule.
<2> the resin composition according to <1>, wherein the thermoplastic elastomer (B) is at least one thermoplastic elastomer selected from the group consisting of:
a polymer (b1) having a core-shell structure comprising a core layer and a shell layer containing an alkyl (meth) acrylate on a surface of the core layer;
an olefin polymer (b2) which is a polymer of α -olefin and alkyl (meth) acrylate and which contains 60 mass% or more of a monomer derived from α -olefin;
a polymer (b3) having a core-shell structure, which comprises a core layer containing a butadiene polymer and a shell layer containing a polymer selected from styrene polymers and acrylonitrile-styrene polymers on the surface of the core layer;
styrene-ethylene-butadiene-styrene copolymer (b 4);
polyurethane (b 5); and
polyester (b 6).
<3> the resin composition according to <1> or <2>, wherein the cellulose acylate (A) is at least one selected from the group consisting of cellulose acetate, cellulose acetate propionate and cellulose acetate butyrate.
<4> the resin composition according to <3>, wherein the cellulose acylate (A) is at least one selected from the group consisting of cellulose acetate propionate and cellulose acetate butyrate.
<5> the resin composition according to any one of <1> to <4>, wherein the organic compound of the particles (C) contains at least one of a nitrogen-nitrogen double bond and a nitrogen-hydrogen bond.
<6> the resin composition as stated in any one of <1> to <5>, wherein the organic compound of the particles (C) is an organometallic compound.
<7> the resin composition according to any one of <1> to <6>, wherein the organic compound of the particles (C) has a molecular weight of 300 or more and 1300 or less.
<8> the resin composition according to any one of <1> to <7>, wherein the volume average diameter of the particles (C) is 10nm or more and 1,000nm or less.
<9> the resin composition as stated in any one of <1> to <8>, which further contains a plasticizer (D).
<10> the resin composition according to any one of <1> to <9>, wherein the plasticizer (D) contains at least one selected from the group consisting of a cardanol compound, a dicarboxylic acid diester, a citric acid ester, a polyether compound containing 1 or more unsaturated bonds in the molecule, a polyether ester compound, a benzoic acid glycol ester, a compound represented by the following general formula (6), and an epoxidized fatty acid ester:
in the general formula (6), R61Represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms, and R62Represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms.
<11> the resin composition as stated in any one of <1> to <10>, which further contains a polyester resin (E).
<12> the resin composition <11>, wherein the polyester resin (E) is polyhydroxyalkanoate.
<13> the resin composition as stated in any one of <1> to <12>, which further contains a poly (meth) acrylate compound (F).
<14> a resin molded body comprising the resin composition <1> to <13 >.
<15> the resin molded body <14>, wherein the resin molded body is an injection molded body.
The invention has the advantages of
According to the invention described in <1>, <2>, <3>, <5>, <6>, <11>, <12> or <13>, there is provided a resin composition which can obtain a resin molded body having high surface glossiness as compared with a resin composition containing a cellulose acylate (a) and particles (C) of at least one organic compound containing two or more nitrogen atoms in the molecule and not containing a thermoplastic elastomer (B), or as compared with a resin composition containing a cellulose acylate (a), a thermoplastic elastomer (B) and particles (C) of an organic compound containing only one or less nitrogen atoms in the molecule.
According to the invention as described in <4>, there is provided a resin composition which can obtain a resin molded body having a high surface gloss as compared with a resin composition in which the cellulose acylate (A) is cellulose acetate.
According to the invention as described in <7>, there is provided a resin composition which can obtain a resin molded body having high surface gloss as compared with a resin composition in which the molecular weight of the organic compound in the particles (C) is less than 300 or more than 1300.
According to the invention as <8>, there is provided a resin composition which can obtain a resin molded body having high surface glossiness as compared with a resin composition in which the volume average diameter of the particles (C) is less than 10nm or more than 1000 nm.
According to the invention as described in <9>, there is provided a resin composition which can obtain a resin molded body having high surface gloss as compared with a resin composition comprising a cellulose acylate (a), a thermoplastic elastomer (B) and particles (C) of at least one organic compound containing two or more nitrogen atoms in the molecule but not containing a plasticizer (D).
According to the invention as <10>, there is provided a resin composition which can obtain a resin molded body having a high surface gloss as compared with a resin composition containing only polyethylene glycol as the plasticizer (D).
According to the invention as stated in <14> or <15>, there is provided a resin molded body having a high surface gloss as compared with the case where the resin composition used comprises the cellulose acylate (a) and the particles (C) of at least one organic compound containing two or more nitrogen atoms in the molecule and does not contain the thermoplastic elastomer (B), or as compared with the case where the resin composition used comprises the cellulose acylate (a), the thermoplastic elastomer (B) and the particles (C) of an organic compound containing only one or less nitrogen atoms in the molecule.
Detailed Description
Exemplary embodiments of the present invention are described below. These descriptions and examples depict exemplary embodiments and do not limit the scope of the exemplary embodiments.
In the present invention, the numerical range represented by "to" is meant to include a range between the numerical values described as the minimum value and the maximum value before and after "to", respectively.
In the numerical ranges described step by step in the present invention, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of the other numerical ranges described step by step. In addition, in the numerical ranges described in the present invention, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the embodiments, respectively.
In the present invention, the term "process (method)" is not only an independent process (method) but also a process (method) which cannot be clearly distinguished from other processes (methods) as long as the intended purpose of the process (method) can be achieved.
In the present invention, each component may contain a plurality of corresponding substances. In the present invention, when referring to the amount of each component in the composition, in the case where a plurality of substances corresponding to each component is present in the composition, it refers to the total amount of the plurality of substances present in the composition unless otherwise specified.
In the present invention, "(meth) acrylic acid" means at least one of acrylic acid and methacrylic acid, and "(meth) acrylate" means at least one of acrylate and methacrylate.
In the present invention, the cellulose acylate (a), the thermoplastic elastomer (B), the particles of at least one organic compound containing two or more nitrogen atoms in the molecule (C), the plasticizer (D), the polyester resin (E), and the 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.
< resin composition >
The resin composition of the present exemplary embodiment includes a cellulose acylate (a), a thermoplastic elastomer (B), and particles (C) of at least one organic compound containing two or more nitrogen atoms in a molecule.
The resin composition of the present exemplary embodiment may further include a plasticizer (D), a polyester resin (E), a poly (meth) acrylate compound (F), and other additives.
According to the resin composition of the present exemplary embodiment containing the above-described constituent components, high surface glossiness (gloss) can be obtained when a resin molded body is formed.
The reason for this is presumed as follows.
Conventionally, particles (C) of an organic compound are added to a resin composition containing a cellulose acylate (a) from various viewpoints (for example, for coloring, strength improvement, weather resistance improvement, and the like).
Here, when the resin composition containing the cellulose acylate (a) is molded, an alignment layer is formed on the surface due to the molecular orientation of the cellulose acylate (a), and a molded article excellent in surface gloss is obtained. In particular, in the case of forming a molded article by injection molding, the orientation layer becomes strong, and the gloss is more excellent. However, when the particles (C) of the organic compound are contained in the resin composition containing the cellulose acylate (a), the particles (C) of the organic compound tend to enter and localize among the molecules of the oriented cellulose acylate (a), which may lose gloss and reduce surface gloss.
In contrast, the resin composition of the present exemplary embodiment further includes a thermoplastic elastomer (B). The thermoplastic elastomer (B) tends to be localized more easily on the core layer side, that is, on the center side rather than the surface side of the resin molded body, as compared with the orientation layer.
Further, the thermoplastic elastomer (B) has a property of easily binding the particles (C) of the organic compound and a property of exhibiting adhesiveness to the particles (C) of the organic compound. In particular, in the case where the thermoplastic elastomer (B) is a polymer having a core-shell structure (for example, the polymer (B1) and the polymer (B2) described below), there is a tendency that the particles (C) of the organic compound are easily bonded as a property thereof, and in the case where the thermoplastic elastomer (B) is a linear or branched polymer (for example, an elastomer of the (B3) to (B6) described below), there is a strong tendency that the particles (C) of the organic compound have high adhesiveness as a property thereof. Therefore, when the resin composition of the present exemplary embodiment is kneaded, the particles (C) of the organic compound are dispersed to be attracted by the dispersion of the thermoplastic elastomer (B), and are more likely to be localized on the center side of the core layer (i.e., the resin molded body).
As a result, it is presumed that localization of the particles (C) of the organic compound in the alignment layer, i.e., the surface side is suppressed, and high surface glossiness (gloss) is obtained in the formed resin molded body.
It is considered that the gloss can be reduced by the particles (C) containing the organic compound "containing two or more nitrogen atoms in the molecule" as described above as the organic compound particles, in other words, it is considered that even the organic compound particles containing only one nitrogen atom in the molecule are hardly reduced in gloss.
The reason is presumed to be as follows.
In the organic compound particles having one nitrogen atom in the molecule, it is considered that since it is difficult to enter between the molecules of the cellulose acylate (a) as described above or the force pushing the particles apart when the particles move between the molecules of the cellulose acylate (a) is stronger than the entering force, the surface glossiness is not lowered.
Preferably, the resin composition of the present exemplary embodiment further includes a plasticizer (D). By containing the plasticizer (D), a resin molded article having high surface gloss can be easily obtained.
The reason is presumed to be as follows.
The plasticizer (D) has an effect of competing with the organic compound particles (C) into intermolecular cellulose acylate (a) in the alignment layer. Therefore, the plasticizer (D) enters before the particles (C) of the organic compound enter into the intermolecular of the oriented cellulose acylate (a), or the plasticizer (D) enters by pushing away the intermolecular particles (C) of the organic compound which previously entered into the cellulose acylate (a). Therefore, it is presumed that localization of the particles (C) of the organic compound on the surface side of the resin molded body is suppressed and high surface glossiness (gloss) can be obtained.
The components of the resin composition of the present exemplary embodiment are described in detail below.
[ cellulose acylate (A): component (A) ]
The cellulose acylate (a) is a cellulose derivative in which at least a part of the hydroxyl groups in the cellulose are substituted (acylated) with acyl groups. Acyl is of the formula-CO-RACGroup of the structure (R)ACRepresents a hydrogen atom or a hydrocarbon group).
The cellulose acylate (a) is, for example, a cellulose derivative represented by the following general formula (CA).
In the general formula (CA), A1，A2And A3Each independently represents a hydrogen atom or an acyl group, and n represents an integer of 2 or more. However, n is A1N number of A2And n is A3At least a part of (a) represents an acyl group. N number of A in molecule1May be all the same, some the same or different from each other. Similarly, n A's in the molecule2And n is A3May be all the same, some the same or different from each other.
From A1、A2And A3The hydrocarbyl group in the acyl group represented may be linear, branched or cyclic, preferably linear or branched, more preferably linear.
From A1、A2And A3The hydrocarbon group in the acyl group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and a saturated hydrocarbon group is more preferable.
From A1、A2And A3The acyl group represented is preferably an acyl group having 1 to 6 carbon atoms. That is, the cellulose acylate (A) is preferablyIs a cellulose acylate in which the acyl group has 1 to 6 carbon atoms (A). The cellulose acylate (a) having an acyl group with 1 to 6 carbon atoms is more likely to obtain a resin molded body having a high surface gloss than the cellulose acylate (a) having an acyl group with 7 or more carbon atoms.
From A1、A2And A3The hydrogen atom in the acyl group represented may be substituted with a halogen atom (for example, a fluorine atom, a bromine atom and an iodine atom), an oxygen atom, a nitrogen atom or the like, but is preferably unsubstituted.
From A1、A2And A3Examples of the acyl group represented include formyl, acetyl, propionyl, butyryl (butyryl group), acryloyl and hexanoyl. Among them, from the viewpoint of moldability of the resin composition and surface gloss of the resin molded body, the acyl group is preferably an acyl group having 2 to 4 carbon atoms, more preferably an acyl group having 2 or 3 carbons.
Examples of the cellulose acylate (a) include cellulose acetates (mono-, di-and tri-acetates), Cellulose Acetate Propionate (CAP) and Cellulose Acetate Butyrate (CAB).
The cellulose acylate (a) is preferably Cellulose Acetate Propionate (CAP) and Cellulose Acetate Butyrate (CAB), and more preferably Cellulose Acetate Propionate (CAP) from the viewpoint of the surface gloss of the resin molded body.
The cellulose acylate (a) may be used alone, or two or more thereof may be used in combination.
The weight-average degree of polymerization of the cellulose acylate (A) is preferably 200 to 1000, more preferably 500 to 1000, and still more preferably 600 to 1000, from the viewpoint of moldability of the resin composition and surface gloss of the resin molded product.
The weight-average polymerization degree of the cellulose acylate (a) is determined from the weight-average molecular weight (Mw) by the following procedure.
First, the weight average molecular weight (Mw) of the cellulose acylate (A) in terms of polystyrene was measured by a gel permeation chromatography apparatus (GPC apparatus: manufactured by Tosoh Corporation, HLC-8320GPC, column: TSK gel α -M) using tetrahydrofuran.
Subsequently, the polymerization degree of the cellulose acylate (a) is determined by dividing the weight-average molecular weight (Mw) of the cellulose acylate by the molecular weight of the structural unit of the cellulose acylate. For example, in the case where the substituent of the cellulose acylate is an acetyl group, the monomer molecular weight is 263 when the substitution degree is 2.4, and 284 when the substitution degree is 2.9.
The degree of substitution of the cellulose acylate (A) is preferably 2.1 to 2.9, more preferably 2.2 to 2.9, still more preferably 2.3 to 2.9, and particularly preferably 2.6 to 2.9, from the viewpoint of moldability of the resin composition and surface gloss of the resin molded article.
In the Cellulose Acetate Propionate (CAP), the substitution ratio of acetyl group to propionyl group (acetyl/propionyl group) is preferably 0.01 to 1, and more preferably 0.05 to 0.1, from the viewpoints of moldability of the resin composition and surface gloss of the resin molded article.
CAP preferably satisfies at least one of the following (1), (2), (3) and (4), more preferably satisfies the following (1), (3) and (4), still more preferably satisfies the following (2), (3) and (4) <1> <2> <3> <4> <1> < 0.14 > < 0.21 > of the weight average molecular weight (Mw) in terms of polystyrene, when measured by GPC method using tetrahydrofuran as a solvent, and < 0.14 > < 250,000 > of the ratio Mn/Mz of the number average molecular weight (Mn) in terms of polystyrene to the Z average molecular weight (Mz) in terms of polystyrene, <2> < 0.14 > < 0.21 > of the weight average molecular weight (Mn/Mz) in terms of polystyrene, when measured by GPC method using tetrahydrofuran as a solvent, and < 0.14 > < 0.21 > of the ratio Mn/Mz of the number average molecular weight (Mn) in terms of polystyrene to the Z average molecular weight (Mz) in terms of polystyrene, when measured by GPC method using tetrahydrofuran as a solvent, the ratio Mn/Mz) to the Z average molecular weight (Mz) in terms of polystyrene, the test piece < 0.21 </6 > < 0.21 > of the weight (Mw) in terms of polystyrene, when measured by injection molding temperature is measured by a relative expansion coefficient of a <1> of a die under a pressure of a pressure measured by a pressure in the MD <1> of a pressure in the MD < 3.42 <3> 0.42 <3> of a <3> 0.42 </35 > of a pressure in the MD <3> of a CD-19 > of a <3> of a cross-19 > of a cross-direction, when measured by a cross-flow rate of a <3> of a <2 < 20 <8 <3> of a pressure under a pressure, when measured by a pressure, a.
In the Cellulose Acetate Butyrate (CAB), the ratio of the degree of substitution of acetyl groups to butyryl groups (acetyl/butyryl groups) is preferably 0.05 to 3.5, and more preferably 0.5 to 3.0, from the viewpoints of moldability of the resin composition and surface gloss of the resin molded article.
The degree of substitution of the cellulose acylate (a) is an index indicating the degree of substitution of the hydroxyl group of the cellulose with the acyl group. That is, the degree of substitution is an index indicating the degree of acylation of the cellulose acylate (a). Specifically, the degree of substitution refers to the intramolecular average of the number of substitutions by acyl groups of three hydroxyl groups in the D-glucopyranose unit of the cellulose acylate. Use of1H-NMR (JMN-ECA, JEOL RESONANCE co., ltd.) determines the degree of substitution from the integral ratio of cellulose-derived hydrogen to acyl-derived peaks.
[ thermoplastic elastomer (B): component (B) ]
Examples of the thermoplastic elastomer (B) include at least one thermoplastic elastomer (B) selected from the group consisting of:
a polymer (b1) having a core-shell structure comprising a core layer and a shell layer containing an alkyl (meth) acrylate on a surface of the core layer;
an olefin polymer (b2) which is a polymer of α -olefin and alkyl (meth) acrylate and which contains 60 mass% or more of a monomer derived from α -olefin;
a polymer (b3) having a core-shell structure comprising a core layer containing a butadiene polymer and a shell layer containing a polymer selected from a styrene polymer and an acrylonitrile-styrene polymer on the surface of the core layer;
styrene-ethylene-butadiene-styrene copolymer (b 4);
polyurethane (b 5); and
polyester (b 6).
The thermoplastic elastomer (B) is, for example, a thermoplastic elastomer having elasticity at normal temperature (25 ℃) and having the same softening property as the thermoplastic resin at high temperature.
(Polymer having core-Shell Structure (b 1): component (b1))
The polymer (b1) having a core-shell structure comprises a core layer and a shell layer on a surface of the core layer.
The polymer having a core-shell structure (b1) is a polymer in which a core layer is provided as an innermost layer and a shell layer is provided as an outermost layer (specifically, a polymer in which a shell layer is obtained by graft-polymerizing a polymer of alkyl (meth) acrylate on the polymer as the core layer).
More than one other layer (e.g., 1 to 6 other layers) may be provided between the core layer and the shell layer. In the case where other layers are provided between the core layer and the shell layer, the polymer having a core-shell structure (b1) is a polymer in which a plurality of polymers are graft-polymerized to form a plurality of layers on the polymer as the core layer.
Examples of the rubber layer include layers of (meth) acrylic rubber, silicone rubber, styrene rubber, conjugated diene rubber, α -olefin rubber, nitrile rubber, urethane rubber, polyester rubber, polyamide rubber, and copolymer rubbers of two or more thereof.
Among them, the rubber layer is preferably a layer of (meth) acrylic rubber, silicone rubber, styrene rubber, conjugated diene rubber, α -olefin rubber, or a copolymer rubber of two or more thereof.
The rubber layer may be a rubber layer obtained by copolymerizing and crosslinking a crosslinking agent (divinylbenzene, allyl acrylate, butylene diacrylate, or the like).
Examples of the (meth) acrylic rubber include polymer rubbers obtained by polymerizing a (meth) acrylic component (for example, an alkyl (meth) acrylate in which an alkyl group has 2 to 8 carbon atoms).
Examples of the silicone rubber include rubbers composed of a silicon component (polydimethylsiloxane or polyphenylsiloxane, etc.).
Examples of the styrene rubber include polymer rubbers obtained by polymerizing styrene components (styrene or α -methylstyrene or the like).
Examples of the conjugated diene rubber include polymer rubbers obtained by polymerizing a conjugated diene component (butadiene or isoprene or the like).
α -olefin rubber examples include polymer rubbers obtained by polymerizing α -olefin components (ethylene, propylene, 2-methylpropylene).
Examples of the copolymer rubber include a copolymer rubber obtained by polymerizing two or more (meth) acrylic components, a copolymer rubber obtained by polymerizing 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 in the polymer constituting 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, octadecyl (meth) acrylate, and the like. In the alkyl (meth) acrylate, at least a part of hydrogen of the alkyl chain may be substituted. Examples of substituents for hydrogen include amino, hydroxyl, or halo, and the like.
Among them, the polymer of an alkyl (meth) acrylate is preferably a polymer of an alkyl (meth) acrylate in which an alkyl chain has 1 to 8 carbon atoms, more preferably a polymer of an alkyl (meth) acrylate in which an alkyl chain has 1 or 2 carbon atoms, and more preferably a polymer of an alkyl (meth) acrylate in which an alkyl chain has 1 carbon atom, from the viewpoint of the surface gloss of the resin molded body.
The polymer constituting the shell layer may be a polymer obtained by polymerizing at least one selected from the group consisting of a glycidyl group-containing vinyl compound and an unsaturated dicarboxylic anhydride other than the alkyl (meth) acrylate.
Examples of the glycidyl group-containing vinyl compound include glycidyl (meth) acrylate, glycidyl itaconate, allyl glycidyl ether, styrene-4-glycidyl ether, and 4-glycidyl styrene.
Examples of the unsaturated dicarboxylic acid anhydride include maleic anhydride, itaconic anhydride, glutaconic anhydride, citraconic anhydride and aconitic anhydride. Among them, maleic anhydride is preferable.
One or more other layers between the core layer and the shell layer include layers comprising the polymers described with respect to the shell layer.
The mass proportion of the shell layer is preferably 1 to 40 mass%, more preferably 3 to 30 mass%, and still more preferably 5 to 15 mass% with respect to the entire core-shell structure.
The polymer (b1) having a core-shell structure can be produced by a known method.
Examples of known methods include emulsion polymerization. Specifically, the following methods may be mentioned as the production method. First, a monomer mixture is emulsified and polymerized to form a core particle (core layer), and then another monomer mixture is emulsified and polymerized in the presence of the core particle (core layer) to manufacture a polymer having a core-shell structure forming a shell layer around the core particle (core layer).
In the case where another layer is formed between the core layer and the shell layer, the emulsion polymerization of the other monomer mixture is repeated to obtain the objective polymer having a core-shell structure composed of the core layer, the other layer and the shell layer.
Examples of commercially available products of the polymer having a core-shell structure (b1) include "metabelt" (registered trademark) manufactured by Mitsubishi Chemical Corporation, "KANE ACE" (registered trademark) manufactured by Kaneka Corporation, "PARALOID" (registered trademark) manufactured by Dow Chemical Japan ltd., "stafild" (registered trademark) manufactured by Aica Kogyo co.
(olefin Polymer (b 2): component (b2))
The olefin polymer (b2) is preferably a polymer of α -olefin and alkyl (meth) acrylate, and contains 60 mass% or more of a monomer derived from α -olefin.
Among olefin polymers, α -olefin examples include ethylene, propylene, 2-methylpropene and the like, from the viewpoint of surface gloss of the resin molded body, α -olefin preferably has 2 to 8 carbon atoms, and more preferably has 2 or 3 carbon atoms, of which ethylene is still more preferred.
Meanwhile, examples of the alkyl (meth) acrylate polymerized with 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, or octadecyl (meth) acrylate examples of the alkyl (meth) acrylate polymerized with 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, or octadecyl (meth) acrylate, and the like.
The olefin polymer is preferably a polymer of ethylene and methyl acrylate from the viewpoint of the surface gloss of the resin molded article.
The olefin polymer contains from 60 to 97 mass%, and more preferably from 70 to 85 mass% of a monomer derived from α -olefin from the viewpoint of the surface gloss of the resin molded article.
The olefin polymer may have a monomer derived from α -olefin and a monomer other than a monomer derived from alkyl (meth) acrylate, however, the other monomer is preferably 10% by mass or less with respect to all the monomers in the olefin polymer.
(Polymer having core-Shell Structure (b 3): component (b3))
The polymer (b3) having a core-shell structure comprises a core layer and a shell layer on a surface of the core layer.
The polymer having a core-shell structure (b3) is a polymer in which a core layer is provided as an innermost layer and a shell layer is provided as an outermost layer (specifically, a polymer in which a shell layer is obtained by graft polymerizing a styrene polymer or an acrylonitrile-styrene polymer on a core layer containing a butadiene polymer).
More than one other layer (e.g., 1 to 6 other layers) may be provided between the core layer and the shell layer. In the case where other layers are provided, the polymer having a core-shell structure (b3) is a polymer in which a plurality of polymers are graft-polymerized to form a multilayer polymer on the polymer as a core layer.
In the case where the core layer is a copolymer of butadiene and other monomers, examples of the other monomers include vinyl aromatic monomers, which may be a styrene component (e.g., alkyl-substituted styrene (e.g., α -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, etc.) and halogen-substituted styrene (e.g., 2-chlorostyrene, 3-chlorostyrene, and 4-chlorostyrene)). the styrene component may be used alone or may be used in combination of two or more.
Specific examples of the core layer containing a butadiene polymer may include a homopolymer of butadiene, a copolymer of butadiene and styrene, or a terpolymer of butadiene, styrene, and divinylbenzene.
The butadiene polymer contained in the core layer preferably contains 60 to 100 mass% (preferably 70 to 100 mass%) of a monomer derived from butadiene, and 0 to 40 mass% (preferably 0 to 30 mass%) of a monomer derived from other monomers (preferably a styrene component). For example, as the monomer derived from the monomer constituting the butadiene polymer, the proportions of butadiene and styrene are preferably each 60 to 100 mass% and 0 to 40 mass%; and divinylbenzene may be 0 to 5 mass% with respect to the total amount of styrene and divinylbenzene.
The shell layer containing the styrene polymer is not particularly limited as long as the shell layer contains a polymer obtained by polymerizing a styrene component. The shell layer may comprise a homopolymer of styrene, or may comprise a copolymer of styrene and other monomers. Examples of the styrene component include components similar to the styrene component exemplified in the core layer. Examples of the other monomers include alkyl (meth) acrylates (e.g., 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, or octadecyl (meth) acrylate), and the like. In the alkyl (meth) acrylate, at least a part of hydrogen of the alkyl chain may be substituted. Examples of the substituent for hydrogen include amino, hydroxyl, halogen, or the like. The alkyl (meth) acrylate may be used alone, or two or more kinds may be used in combination. In addition, polyfunctional monomers such as allyl (meth) acrylate, triallyl isocyanurate, and divinylbenzene may be used as the other monomers. The styrene polymer contained in the shell layer is preferably a copolymer of 85 to 100 mass% of a styrene component and 0 to 15 mass% of other monomer components (preferably alkyl (meth) acrylates).
Among them, the styrene polymer contained in the shell layer is preferably a copolymer of styrene and an alkyl (meth) acrylate from the viewpoint of the surface gloss of the resin molded article. From the same viewpoint, preferred are copolymers of styrene with alkyl (meth) acrylates having an alkyl chain of 1 to 8 carbon atoms, and more preferred are polymers of alkyl (meth) acrylates having an alkyl chain of 1 to 4 carbon atoms.
The shell layer containing the acrylonitrile-styrene polymer comprises a copolymer of an acrylonitrile component and a styrene component. The acrylonitrile-styrene polymer is not particularly limited, and examples thereof include known acrylonitrile-styrene polymers. Examples of the acrylonitrile-styrene polymer include a copolymer of 10 to 80 mass% of an acrylonitrile component and 20 to 90 mass% of a styrene component. Examples of the styrene component copolymerized with the acrylonitrile component include components similar to the styrene component exemplified in the core layer. In addition, polyfunctional monomers such as allyl (meth) acrylate, triallyl isocyanurate, and divinylbenzene may also be used for the acrylonitrile-styrene polymer contained in the shell layer.
One or more other layers between the core layer and the shell layer include layers comprising the polymers described with respect to the shell layer.
The mass proportion of the shell layer is preferably 1 to 40 mass%, more preferably 3 to 30 mass%, and still more preferably 5 to 15 mass% with respect to the entire core-shell structure.
Among the components (b3), examples of commercially available products of the polymer having a core-shell structure (b3) including a core layer containing a butadiene polymer and a shell layer containing a styrene polymer on the surface of the core layer include "metabelen" (registered trademark) manufactured by mitsubishi chemical Corporation, "KANE ACE" (registered trademark) manufactured by Kaneka Corporation, "CLEARSTRENGTH" (registered trademark) manufactured by Arkema, and "PARALOID" (registered trademark) manufactured by Dow chemical japan ltd.
In addition, among the component (b3), examples of commercially available products of the polymer having a core-shell structure (b3) including a core layer containing a butadiene polymer and a shell layer containing an acrylonitrile-styrene polymer on a surface of the core layer include "BLENDEX" (registered trademark) manufactured by Galata Chemicals and "ELIX" manufactured by ELIX POLYMERS.
The average primary particle diameter of the polymer having a core-shell structure (b1, b3) is not particularly limited, but is preferably 50nm to 500nm, more preferably 50nm to 400nm, still more preferably 100nm to 300nm, and particularly preferably 150nm to 250nm, from the viewpoint of the surface gloss of the resin molded body.
The average primary particle diameter refers to a value measured by the following method. The number average primary particle size is obtained by the following method: observing the particles with a scanning electron microscope; setting the maximum diameter of the primary particles as a primary particle diameter; and the primary particle diameters of 100 particles were measured and averaged. Specifically, the number average primary particle diameter is determined by observing the polymer having a core-shell structure in a dispersed form in the resin composition with a scanning electron microscope.
(styrene-ethylene-butadiene-styrene copolymer (b 4): component (b4))
The copolymer (b4) is not particularly limited as long as the copolymer (b4) is a thermoplastic elastomer, and examples thereof include well-known styrene-ethylene-butadiene-styrene copolymers. The copolymer (b4) may be a styrene-ethylene-butadiene-styrene copolymer and a hydrogenated product thereof.
The copolymer (b4) is preferably a hydrogenated product of a styrene-ethylene-butadiene-styrene copolymer from the viewpoint of the surface gloss of the resin molded article. From the same viewpoint, the copolymer (b4) may be a block copolymer, for example, a copolymer (styrene-ethylene/butylene-styrene triblock copolymer) preferably comprising a block having a styrene moiety at both ends and a block having an ethylene/butylene moiety in the center, which is obtained by hydrogenating at least a part of the double bonds of a butadiene moiety. The ethylene/butylene block portion of the styrene-ethylene/butylene-styrene copolymer may be a random copolymer.
The copolymer (b4) can be obtained by a known method. In the case where the copolymer (b4) is a hydrogenated product of a styrene-ethylene-butadiene-styrene copolymer, for example, the copolymer (b4) can be obtained by hydrogenating the butadiene moiety of a styrene-butadiene-styrene block copolymer whose conjugated diene moiety is composed of 1,4 bonds.
Examples of commercially available products of the copolymer (b4) include "KRATON" (registered trademark) manufactured by Clayton co.
(polyurethane (b 5): component (b5))
The polyurethane (b5) is not particularly limited as long as the polyurethane (b5) is a thermoplastic elastomer, and examples thereof include well-known polyurethanes. The polyurethane (b5) is preferably a linear polyurethane. The polyurethane (b5) is obtained, for example, by reacting a polyol component (polyether polyol, polyester polyol, polycarbonate polyol, or the like) with an organic isocyanate component (aromatic diisocyanate, aliphatic (including alicyclic) diisocyanate, or the like) and, if necessary, a chain extender (aliphatic (including alicyclic) diol, or the like). The polyol component and the organic isocyanate component may each be used alone, or two or more may be used in combination.
The polyurethane (b5) is preferably an aliphatic polyurethane from the viewpoint of the surface gloss of the resin molded product. The aliphatic polyurethane is preferably an aliphatic polyurethane obtained by, for example, reacting a polyol component containing a polycarbonate polyol with an isocyanate component containing an aliphatic diisocyanate.
The polyurethane (b5) can be obtained, for example, by reacting a polyol component with an organic isocyanate component, provided that the NCO/OH ratio of the raw materials at the time of synthesizing the polyurethane is from 0.90 to 1.5. The polyurethane (b5) can be obtained by a known method such as a one-shot method and a prepolymerization method.
Examples of commercially available products of the polyurethane (b5) include "ESTANE" (registered trademark) manufactured by Lubrizol Corporation or "ELASTOLLAN" (registered trademark) manufactured by BASF SE. Examples thereof also include "Desmopan" (registered trademark) manufactured by Bayer Corporation.
(polyester (b 6): component (b6))
The polyester (b6) is not particularly limited as long as the polyester (b6) is a thermoplastic elastomer, and examples thereof include known polyesters. The polyester (b6) is preferably an aromatic polyester from the viewpoint of obtaining the surface gloss of the resin molded article. In the present exemplary embodiment, the aromatic polyester means a polyester having an aromatic ring in its structure.
Examples of the polyester (b6) include polyester copolymers (polyether esters or polyester esters, etc.). Examples of the polyester (b6) specifically include: a polyester copolymer comprising a hard segment composed of polyester units and a soft segment composed of polyester units; a polyester copolymer comprising a hard segment composed of polyester units and a soft segment composed of polyether units; and a polyester copolymer having a hard segment composed of polyester units and a soft segment composed of polyether units and polyester units. The mass ratio of the hard segment to the soft segment (hard segment/soft segment) of the polyester copolymer is, for example, preferably 20/80 to 80/20. The polyester units constituting the hard segment and the polyester units and polyether units constituting the soft segment may be aromatic or aliphatic (including alicyclic).
The polyester copolymer as the polyester (b6) can be obtained by a known method. The polyester copolymer is preferably a linear polyester copolymer. The polyester copolymer can be obtained by: a method of esterifying or transesterifying a dicarboxylic acid component having 4 to 20 carbon atoms, a diol component having 2 to 20 carbon atoms, and a polyalkylene glycol component (alkylene oxide adduct containing polyalkylene glycol) having a number-average molecular weight of 300 to 20,000; and a method of polycondensing the oligomer after the oligomer is produced by esterifying or transesterifying the above components. In addition, examples of the method include a method of esterifying or transesterifying a dicarboxylic acid component having 4 to 20 carbon atoms, a diol component having 2 to 20 carbon atoms, and an aliphatic polyester component having a number average molecular weight of 300 to 20,000. The dicarboxylic acid component is an aromatic or aliphatic dicarboxylic acid or an ester derivative thereof. The diol component is an aromatic or aliphatic diol. The polyalkylene glycol component is an aromatic or aliphatic polyalkylene glycol.
Among these components, the dicarboxylic acid component of the polyester copolymer is preferably a dicarboxylic acid component having an aromatic ring, from the viewpoint of surface gloss of the resin molded article. In addition, the diol component and the polyalkylene glycol component preferably use an aliphatic diol component and an aliphatic polyalkylene glycol component, respectively.
Examples of commercially available products of the polyester (b6) include "perprene" (registered trademark) manufactured by Toyobo co.
[ particles (C) of at least one organic compound containing two or more nitrogen atoms in the molecule: component (C) ]
The structure of the organic compound in the particles (C) is not particularly limited as long as the organic compound has a structure containing two or more nitrogen atoms in the molecule.
However, from the viewpoint of the surface gloss of the resin molded product, a compound containing a nitrogen-nitrogen double bond (-N ═ N-) and/or a nitrogen-hydrogen bond (N-H) in the molecular structure is preferable. Further, an organometallic compound is also preferable from the viewpoint of the surface gloss of the resin molded product.
As the compound having a nitrogen-nitrogen double bond (-N ═ N-) and/or a nitrogen-hydrogen bond (N-H) in the molecular structure, for example, a compound having the following structure is preferable:
quinacridone skeleton (dichloroquinacridone, quinacridone, or the like), azo group (-N ═ N-) (monoazo compounds, disazo compounds, or the like), oxazine skeleton (six-membered heterocyclic structure containing one oxygen atom, one nitrogen atom, and a double bond therebetween) (dioxazine, or the like), perylene skeleton (perylene, or the like), quinophthalone skeleton (quinophthalone yellow, or the like), isoindoline skeleton, isoindolinone skeleton, diketopyrrolopyrrole skeleton, and aminoanthraquinone skeleton.
The organometallic compound is preferably, for example, a compound having the following structure:
phthalocyanine skeleton (copper phthalocyanine, etc.) and porphyrin skeleton (iron porphyrin, etc.).
Examples of the particles (C) of the organic compound (component (C)) include, for example, the following organic compound particles.
The molecular weight of the organic compound in the particles (C) is preferably 300 to 1,500, more preferably 300 to 1,200, and further preferably 300 to 1,000 from the viewpoint of the surface gloss of the resin molded body.
The volume average diameter of the particles (C) is preferably from 10nm to 1,000nm, more preferably from 30nm to 800nm, and further preferably from 50nm to 600nm, from the viewpoint of the surface gloss of the resin molded body.
The volume average diameter of the particles means a value measured by the following method.
The volume average particle diameter was measured using a laser diffraction particle size distribution measuring apparatus (LS 13320: manufactured by Beckman Coulter inc.). As a measurement method, the organic compound particles (C) were adjusted to a dispersion liquid having a solid content of 1 mass% by ion-exchanged water, and charged into a sample cell to an appropriate concentration (exhibiting a density value of 40 to 45), and after waiting for 10 seconds, the volume average particle diameter at a stable concentration in the sample cell was measured. The measured particle size cumulative distribution is plotted from the small diameter side with respect to the divided particle size range (channel) in volume, and the particle size at which the cumulative becomes 50% is defined as a volume average particle size.
[ plasticizer (D): component (D) ]
Examples of the plasticizer (D) include cardanol compounds, ester compounds other than the ester compound (H) described below, camphor, metal soaps, polyhydric alcohols, and polyalkylene oxides. The plasticizer (D) is preferably a cardanol compound or an ester compound other than the ester compound (H) described below, from the viewpoint of the surface gloss of the resin molded article.
The plasticizer (D) may be used alone or in combination of two or more.
The plasticizer (D) is preferably an anacardol compound or an ester compound other than the ester compound (H) described below, from the viewpoint of facilitating the effect of improving toughness by adding the ester compound (H). Cardanol compounds and ester compounds suitable as the plasticizer (D) are specifically described below.
-anacardol compounds
The cardanol compound refers to a component (for example, a compound represented by the following structural formulae (c-1) to (c-4)) contained in a compound of natural origin using a cardanol as a raw material or a derivative of the above component.
The cardanol compound may be used alone or in combination of two or more.
The resin composition of the present exemplary embodiment may include a mixture of compounds of natural origin using cashew nuts as a raw material (hereinafter, simply referred to as "cashew nut-derived mixture") as the cardanol compound.
The resin composition of the present exemplary embodiment may include a derivative derived from a mixture derived from cashew nuts as a cardanol compound. Examples of the derivatives from the mixture derived from cashew nuts include the following mixtures or monomers, and the like.
A mixture obtained by adjusting the composition ratio of each component in the mixture derived from cashew nuts;
monomers obtained by separating only specific components from mixtures derived from cashew nuts;
a mixture containing a modified product obtained by modifying components in the mixture derived from cashew nuts;
a mixture containing a polymer obtained by polymerizing components in the cashew nut-derived mixture;
a mixture containing a modified polymer obtained by modifying and polymerizing components in a mixture derived from cashew nuts;
a mixture containing a modified product obtained by further modifying the components in the mixture obtained by adjusting the composition ratio;
a mixture containing a polymer obtained by further polymerizing the components in the mixture obtained by adjusting the composition ratio;
a mixture containing a modified polymer obtained by further modifying and polymerizing the components in the mixture obtained by adjusting the composition ratio;
modified products obtained by further modifying the isolated monomers;
a polymer obtained by further polymerizing the separated monomer;
modified polymers obtained by further modifying and polymerizing the isolated monomers.
Here, the monomer includes multimers such as dimers and trimers.
The cardanol compound is preferably at least one compound selected from the group consisting of a compound represented by general formula (CDN1) and a polymer obtained by polymerizing a compound represented by general formula (CDN1) from the viewpoint of the surface gloss of the resin molded body.
In the general formula (CDN1), R1Represents an alkyl group which may have a substituent, or an unsaturated aliphatic group which has a double bond and may have a substituent. R2Represents a hydroxyl group, a carboxyl group, an alkyl group which may have a substituent, orAn unsaturated aliphatic group having a double bond and may have a substituent. P2 represents an integer of 0 to 4. When P2 is 2 or more, plural Rs2May be the same group or different groups.
In the general formula (CDN1), R is represented by1The alkyl group which may have a substituent(s) represented is preferably an alkyl group having 3 to 30 carbon atoms, more preferably an alkyl group having 5 to 25 carbon atoms, and still more preferably an alkyl group having 8 to 20 carbon atoms.
Examples of the substituent include: a hydroxyl group; ether bond-containing substituents such as epoxy and methoxy; and substituents containing ester bonds, such as acetyl and propionyl.
Examples of the alkyl group which may have a substituent include pentadecan-1-yl, heptane-1-yl, octane-1-yl, nonane-1-yl, decan-1-yl, undecane-1-yl, dodecane-1-yl or tetradecan-1-yl and the like.
In the general formula (CDN1), R is represented by1The unsaturated aliphatic group having a double bond and which may have a substituent represented is preferably an unsaturated aliphatic group having 3 to 30 carbon atoms, more preferably an unsaturated aliphatic group having 5 to 25 carbon atoms, and still more preferably an unsaturated aliphatic group having 8 to 20 carbon atoms.
The number of double bonds contained in the unsaturated aliphatic group is preferably 1 to 3.
Examples of the substituent of the unsaturated aliphatic group are the same as those of the substituent of the alkyl group.
Examples of the unsaturated aliphatic group which has a double bond and may have a substituent include pentadec-8-en-1-yl, pentadec-8, 11-dien-1-yl, pentadec-8, 11, 14-trien-1-yl, pentadec-7-en-1-yl, pentadec-7, 10-dien-1-yl or pentadec-7, 10, 14-trien-1-yl and the like.
In the general formula (CDN1), R1Preferably pentadec-8-en-1-yl, pentadec-8, 11-dien-1-yl, pentadec-8, 11, 14-trien-1-yl, pentadec-7-en-1-yl, pentadec-7, 10-dien-1-yl or pentadec-7, 10, 14-trien-1-yl, etc.
In the general formula (CDN1), R is represented by2Can representPreferred examples of the alkyl group having a substituent and the unsaturated aliphatic group having a double bond and which may have a substituent are represented by the formula1Preferable examples of the alkyl group which may have a substituent and the unsaturated aliphatic group which may have a double bond and may have a substituent are the same.
The compound represented by formula (CDN1) may be further modified. For example, a compound represented by formula (CDN1), specifically, a compound having a structure in which a hydroxyl group of a compound represented by formula (CDN1) is substituted with the following group (EP), that is, a compound represented by the following general formula (CDN1-e), may be epoxidized.
In the group (EP) and the formula (CDN1-e), LEPRepresents a single bond or a divalent linking group. R in the general formula (CDN1-e)1、R2And P2 has the same general formula as R in (CDN1)1、R2The same meaning as P2.
In the group (EP) and the general formula (CDN1-e), from LEPExamples of the divalent linking group represented include an alkylene group (preferably an alkylene group having 1 to 4 carbon atoms, more preferably an alkylene group having 1 carbon atom) which may have a substituent, and-CH2CH2OCH2CH2-a group.
Examples of substituents are with R of formula (CDN1)1The substituents in (1) are the same as examples.
LEPMethylene is preferred.
The polymer obtained by polymerizing the compound represented by the general formula (CDN1) refers to a polymer in which at least two compounds represented by the general formula (CDN1) are polymerized with or without a linking group.
Examples of the polymer obtained by polymerizing the compound represented by the general formula (CDN1) include a compound represented by the following general formula (CDN 2).
In the general formula (CDN2), R11、R12And R13Each independently represents an alkyl group which may have a substituent, or an unsaturated aliphatic group which has a double bond and may have a substituent. R21、R22And R23Each independently represents a hydroxyl group, a carboxyl group, an alkyl group which may have a substituent, or an unsaturated aliphatic group which may have a double bond and may have a substituent. P21 and P23 each independently represent an integer of 0 to 3, and P22 represents an integer of 0 to 2. L is1And L2Each independently represents a divalent linking group. n represents an integer of 0 to 10. Plural R's when P21 is 2 or more21And a plurality of R's when P22 is 2 or more22And a plurality of R when P23 is 2 or more23May be the same group or different groups, respectively. When n is 2 or more, a plurality of R12、R22And L1May be the same group or different groups, respectively. In the case where n is 2 or more, the plurality of P22 may be the same number or different numbers.
By R in the general formula (CDN2)11、R12、R13、R21、R22And R23Preferred examples of the alkyl group which may have a substituent and the unsaturated aliphatic group which may have a double bond and may have a substituent represented by the formula (CDN1) and R1The preferred examples of (3) are the same.
In the general formula (CDN2) represented by L1And L2Examples of the divalent linking group represented include alkylene groups (preferably alkylene groups having 2 to 30 carbon atoms, more preferably alkylene groups having 5 to 20 carbon atoms) which may have a substituent.
Examples of substituents are with R of formula (CDN1)1The substituents in (1) are the same as examples.
In the general formula (CDN2), n is preferably 1 to 10, and more preferably 1 to 5.
The compound represented by the general formula (CDN2) may be further modified. For example, a compound represented by the general formula (CDN2), specifically, a compound having a structure in which a hydroxyl group of a compound represented by the formula (CDN1) is substituted with a group (EP), that is, a compound represented by the following general formula (CDN2-e), may be epoxidized.
R in the general formula (CDN2-e)11、R12、R13、R21、R22、R23、P21、P22、P23、L1、L2And n is independently selected from the group consisting of R in formula (CDN2)11、R12、R13、R21、R22、R23、P21、P22、P23、L1、L2And n have the same meaning.
In the general formula (CDN2-e), LEP1、LEP2And LEP3Each independently represents a single bond or a divalent linking group. When n is 2 or more, a plurality of LEP2May be the same group or different groups.
General formula (CDN2-e) represented by LEP1、LEP2And LEP3Preferred examples of the divalent linking group represented by the formula (CDN1-e) represented by LEPPreferred examples of the divalent linking groups represented are the same.
The polymer obtained by polymerizing the compound represented by the general formula (CDN1) may be, for example, a polymer in which at least three or more compounds represented by the general formula (CDN1) are three-dimensionally crosslinked and polymerized with or without a linking group. Examples of the polymer obtained by three-dimensionally crosslinking and polymerizing the compound represented by the general formula (CDN1) include, for example, compounds represented by the following structural formulae.
In the above structural formula, R10、R20And P20Respectively having the general formula (CDN1) as R1、R2And P2The same meaning is used. L is10Represents a single bond or a divalent linking group. Plural R10、R20And L10May be the same group or different groups, respectively. The plurality of P20 may be the same number or different numbers.
In the above formula, from L10Examples of the divalent linking group represented include alkylene groups (preferably alkylene groups having 2 to 30 carbon atoms, more preferably alkylene groups having 5 to 20 carbon atoms) which may have a substituent.
Examples of substituents are with R of formula (CDN1)1The substituents in (1) are the same as examples.
The compound represented by the above structural formula may be further modified and, for example, may be epoxidized. Specifically, a compound having a structure in which a hydroxyl group of a compound represented by the above structural formula is substituted with a group (EP) may be used, and examples thereof include a compound represented by the following structural formula, that is, a polymer obtained by three-dimensionally crosslinking and polymerizing a compound represented by the general formula (CDN 1-e).
In the above structural formula, R10、R20And P20 has the same general formula as R in (CDN1-e) respectively1、R2The same meaning as P2. L is10Represents a single bond or a divalent linking group. Plural R10、R20And L10May be the same group or different groups, respectively. The plurality of P20 may be the same number or different numbers.
In the above structural formula, from L10Examples of the divalent linking group represented include alkylene groups (preferably alkylene groups having 2 to 30 carbon atoms, more preferably alkylene groups having 5 to 20 carbon atoms) which may have a substituent.
Examples of substituents are with R of formula (CDN1)1The substituents in (1) are the same as examples.
The cardanol compound preferably contains a cardanol compound having an epoxy group, and more preferably a cardanol compound having an epoxy group, from the viewpoint of improving the surface gloss of the resin molded body.
As the cardanol compound, a commercially available product can be used. Examples of commercially available products include NX-2024, Ultra LITE 2023, NX-2026, GX-2503, NC-510, LITE 2020, NX-9001, NX-9004, NX-9007, NX-9008, NX-9201, NX-9203, or LB-7000, LB-7250, CD-5L, and the like, manufactured by CARDOLITE Corp. Examples of commercially available products of cardanol compounds with epoxy groups include NC-513, NC-514S, NC-547, LITE513E, or Ultra LTE 513, manufactured by CARDOLITE Corp.
The hydroxyl value of the cardanol compound is preferably 100mgKOH/g or more, more preferably 120mgKOH/g or more, and still more preferably 150mgKOH/g or more, from the viewpoint of the surface gloss of the resin molded product. The hydroxyl value of the cardanol compound was measured according to method a of ISO 14900.
In the case of the cardanol compound having an epoxy group, the epoxy equivalent of the cardanol compound is preferably 300 to 500, more preferably 350 to 480, and still more preferably 400 to 470 from the viewpoint of improving the surface gloss of the resin molded body. The epoxy equivalent of the cardanol compound having an epoxy group is measured according to ISO 3001.
The molecular weight of the cardanol compound is preferably 250 to 1000, more preferably 280 to 800, and still more preferably 300 to 500, from the viewpoint of easily obtaining the effect of improving toughness by adding component (B).
Ester compounds
The ester compound contained as the plasticizer (D) in the resin composition of the present exemplary embodiment is not particularly limited as long as the ester compound is an ester compound other than the compounds represented by the general formulae (1) to (5).
Examples of the ester compound contained as the plasticizer (D) include dicarboxylic acid diesters, citric acid esters, polyether ester compounds, benzoic acid glycol esters, compounds represented by the general formula (6), and epoxidized fatty acid esters. Examples of esters include monoesters, diesters, triesters, and polyesters.
In the general formula (6), R61Represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms, R62Represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms.
As a group consisting of R61Specific forms and preferred forms of the group represented are exemplified by R in the formula (1)11The groups represented are in the same form.
R62The group represented may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, and is preferably a saturated aliphatic hydrocarbon group. R62The group represented may be a straight-chain aliphatic hydrocarbon group, a branched-chain aliphatic hydrocarbon group, or an aliphatic hydrocarbon group containing an alicyclic ring, and is preferably a branched-chain aliphatic hydrocarbon group. R62The group represented may be a group in which a hydrogen atom in the aliphatic hydrocarbon group is substituted with a halogen atom (e.g., a fluorine atom, a bromine atom, and an iodine atom), an oxygen atom, a nitrogen atom, or the like, and is preferably an unsubstituted group. R62The group represented preferably has 2 or more carbon atoms, more preferably 3 or more carbon atoms, and further preferably 4 or more carbon atoms.
Examples of the ester compound contained as the plasticizer (D) include adipates, citrates, sebacates, azelates, phthalates, acetates, dibasic esters, phosphates, condensed phosphates, glycol esters (e.g., benzoic acid glycol esters), and modified products of fatty acid esters (e.g., epoxidized fatty acid esters). Examples of the above esters include monoesters, diesters, triesters, and polyesters. Among them, dicarboxylic acid diesters (adipic acid diester, sebacic acid diester, azelaic acid diester, phthalic acid diester, etc.) are preferable.
The molecular weight (or weight average molecular weight) of the ester compound contained as the plasticizer (D) in the resin composition of the present exemplary embodiment is preferably 200 to 2000, more preferably 250 to 1500, and further preferably 280 to 1000. The weight average molecular weight of the ester compound is a value determined according to the measurement method for measuring the weight average molecular weight of the cellulose acylate (a), unless otherwise specified.
The plasticizer (D) is preferably an adipate. The adipic acid ester has high affinity with the resin, particularly the cellulose acylate (a), and is dispersed in an almost uniform state with respect to the cellulose acylate (a), and therefore the heat fluidity of the adipic acid ester is more improved than that of the other plasticizer (D).
Examples of adipic acid esters include adipic acid diesters and adipic acid polyesters. Specific examples include adipic diesters represented by the following general formula (AE) and adipic polyesters represented by the following general formula (APE).
In the general formula (AE), RAE1And RAE2Each independently represents an alkyl group or a polyoxyalkyl [ - (C)xH2x-O)y-RA1](wherein R isA1Represents an alkyl group, x represents an integer of 1 to 10, and y represents an integer of 1 to 10).
In the general formula (APE), RAE1And RAE2Each independently being alkyl or polyoxyalkyl [ - (C)xH2x-O)y-RA1](wherein R isA1Represents an alkyl group, x represents an integer of 1 to 10, and y represents an integer of 1 to 10), RAE3Represents an alkylene group. m1 represents an integer of 1 to 10, and m2 represents an integer of 1 to 20.
In the general formulae (AE) and (APE), RAE1And RAE2The alkyl group represented is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 4 to 10 carbon atoms, and further preferably an alkyl group having 8 carbon atoms. RAE1And RAE2The alkyl groups represented may be linear, branched and cyclic, and are preferably linear or branched.
In the general formulae (AE) and (APE), in RAE1And RAE2Polyoxyalkyl [ - (C) ofxH2x-O)y-RA1]In, RA1The alkyl group represented is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. RA1The alkyl groups represented may be linear, branched and cyclic, and are preferably linear or branched.
In the general formula (APE), RAE3The alkyl group represented is preferably an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 1 to 4 carbon atoms. The alkylene group may be linear, branched and cyclic, and is preferably linear or branched.
In the general formula (APE), m1 is preferably an integer of 1 to 5, and m2 is preferably an integer of 1 to 10.
In the general formulae (AE) and (APE), the group represented by each symbol may be substituted with a substituent. Examples of the substituent include an alkyl group, an aryl group and a hydroxyl group.
The molecular weight (or weight average molecular weight) of the adipate is preferably 250 to 2000, more preferably 280 to 1500, still more preferably 300 to 1000. The weight average molecular weight of adipate is a value determined according to the measurement method for measuring the weight average molecular weight of cellulose acylate (a).
Adipate esters may be used as a mixture with other components. A commercial product of this mixture includes daicatty 101 prepared by Daihachi Chemical Industry co., ltd.
The hydrocarbon group at the terminal of the fatty acid ester (e.g., citrate ester, sebacate ester, azelate diester, phthalate ester, and acetate ester) is preferably an aliphatic hydrocarbon group, preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 4 to 10 carbon atoms, and still more preferably an alkyl group having 8 carbon atoms. The alkyl group may be linear, branched and cyclic, and is preferably linear or branched.
Examples of fatty acid esters (e.g., citric acid esters, sebacic acid esters, azelaic acid diesters, phthalic acid esters, and acetic acid esters) include esters formed from fatty acids and alcohols. Examples of alcohols include: monohydric alcohols such as methanol, ethanol, propanol, butanol and 2-ethylhexanol; polyhydric alcohols, for example glycerol, polyglycerols (such as diglycerol), pentaerythritol, ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, trimethylolpropane, trimethylolethane and sugar alcohols.
Examples of the diol in the glycol benzoate include ethylene glycol, diethylene glycol, and propylene glycol.
The epoxidized fatty acid ester is an ester compound having a structure in which the carbon-carbon unsaturated bond of the unsaturated fatty acid ester is epoxidized (i.e., oxetane). Examples of epoxidized fatty acid esters include esters of fatty acids and alcohols in which some or all of the carbon-carbon unsaturation in the unsaturated fatty acids (e.g., oleic, palmitoleic, vaccenic, linoleic, linolenic, and nervonic acids) is epoxidized. Examples of alcohols include: monohydric alcohols such as methanol, ethanol, propanol, butanol and 2-ethylhexanol; polyhydric alcohols, for example glycerol, polyglycerols (such as diglycerol), pentaerythritol, ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, trimethylolpropane, trimethylolethane and sugar alcohols.
Examples of commercially available products of epoxidized fatty acid esters include ADK CIZER D-32, D-55, O-130P and O-180A (manufactured by ADEKA CORPORATION), SANSOSAIZA E-PS, nE-PS, E-PO, E-4030, E-6000, E-2000H and E-9000H (manufactured by New Japan Chemical Co., Ltd.).
The respective polyester units and polyether units of the polyetherester compound may be aromatic or aliphatic (including alicyclic). The mass ratio of the polyester unit to the polyether unit is, for example, 20:80 to 80: 20. The molecular weight (or weight average molecular weight) of the polyetherester compound is preferably 250 to 2000, more preferably 280 to 1500, and still more preferably 300 to 1000. Examples of commercially available products of polyetherester compounds include ADK CIZER RS-1000 (ADEKA).
Examples of the polyether compound having one or more unsaturated bonds in the molecule include polyether compounds having allyl groups at the terminals, and polyalkylene glycol allyl ethers are preferred. The molecular weight (or weight average molecular weight) of the polyether compound having one or more unsaturated bonds in the molecule is preferably 250 to 2000, more preferably 280 to 1500, and the sea ridge is preferably 300 to 1000. Examples of commercially available products of polyether compounds having more than one unsaturated bond in the molecule include polyalkylene glycol allyl ethers such as UNIOX PKA-5006, UNIOX PKA-5008, UNIOL PKA-5014 and UNIOL PKA-5017 (NOFCORPORATION).
[ polyester resin (E): component (E) ]
Examples of the polyester resin (E) include polymers of hydroxyalkanoates (hydroxyalkanoic acids), polycondensates of polycarboxylic acids and polyhydric alcohols, and ring-opening polycondensates of cyclic lactams.
The polyester resin (E) 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 them, the polyester resin (E) is preferably polyhydroxyalkanoate from the viewpoint of the surface gloss of the obtained resin molded article.
The polyester resin (E) may be used alone or in combination of two or more.
Examples of the polyhydroxyalkanoate include a compound having a structural unit represented by the general formula (PHA).
In the compound having the structural unit represented by the general formula (PHA), both ends of the polymer chain (ends of the main chain) may be carboxyl groups, or only one end may be carboxyl groups and the other end may be other groups (for example, hydroxyl groups).
R in the general formula (PHA)PHA1Represents an alkylene group having 1 to 10 carbon atoms. n represents an integer of 2 or more.
In the general formula (PHA) represented by RPHA1The alkylene group represented is preferably an alkylene group having 3 to 6 carbon atoms. From RPHA1The alkylene groups represented may be linear or branched, preferably branched.
Here, R in the general formula (PHA) represents an alkylene groupPHA1The method comprises the following steps: 1) containing [ O-RPHA1-C(＝O)-]Structure (II) wherein RPHA1Represent the same alkylene group; 2) comprising a plurality of [ O-RPHA1-C(＝O)-]Structure (i.e., [ O-R ]PHA1A-C(＝O)-]And [ O-RPHA1B-C(＝O)-]Structure) wherein RPHA1Represents different alkylene radicals (R)PHA1Are of different carbon numbers or are differentBranched alkylene).
That is, the polyhydroxyalkanoate may be a homopolymer of one kind of hydroxyalkanoate (hydroxyalkanoic acid), or may be a copolymer of two or more kinds of hydroxyalkanoates (hydroxyalkanoic acids).
In the general formula (PHA), the upper limit of n is not particularly limited, but is, for example, 20,000 or more. n preferably ranges from 500 to 10,000, more preferably from 1,000 to 8,000.
Examples of the polyhydroxyalkanoate include homopolymers of hydroxyalkanoic acids (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-hydroxyisocaproic acid, 6-hydroxyhexanoic acid, 3-hydroxypropionic acid, 3-hydroxy-2, 2-dimethylpropionic acid, 3-hydroxyhexanoic acid, 2-hydroxy-n-octanoic acid, etc.), or copolymers of 2 or more of these hydroxyalkanoic acids.
Among them, the polyhydroxyalkanoate may be preferably a homopolymer of a branched hydroxyalkanoic acid having 2 to 4 carbon atoms, and a homopolymer of a branched hydroxyalkanoic acid having 2 to 4 carbon atoms and a branched hydroxyalkanoic acid having 5 to 7 carbon atoms, more preferably a homopolymer of a branched hydroxyalkanoic acid having 3 carbon atoms (i.e., polylactic acid) and a homopolymer 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), from the viewpoint of surface gloss of the resin molded article and suppressing a decrease in transparency of the resulting resin molded article.
The number of carbons in hydroxyalkanoic acids is a number including also the number of carbons in carboxyl groups.
Polylactic acid is a polymeric compound in which lactic acid is polymerized through an ester bond.
Examples of the polylactic acid include homopolymers of L-lactic acid, homopolymers of D-lactic acid, block copolymers containing at least one polymer of L-lactic acid and D-lactic acid, and graft copolymers containing at least one polymer of L-lactic acid and D-lactic acid.
Examples of the "compound copolymerizable with L-lactic acid or D-lactic acid" include polycarboxylic acids such as glycolic acid, dimethylglycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 2-hydroxypropionic acid, 3-hydroxypropionic acid, 2-hydroxypentanoic acid, 3-hydroxypentanoic acid, 4-hydroxypentanoic acid, 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, polyols such as ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propanediol, 1, 3-butanediol, 1, 4-butanediol, 2, 3-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 9-nonanediol, 3-methyl-1, 5-pentanediol, neopentyl glycol, tetramethylene glycol and 1, 4-hexanedimethanol, polysaccharides such as cellulose, amino carboxylic acids such as α -amino acids, hydroxycarboxylic acids such as 5-hydroxymandelic acid, 2-hydroxyhexanoic acid, 3-hydroxyhexanoic acid, 4-hydroxyvalerolactone, gamma-hydroxyvalerolactone and β, and delta-hydroxycaprolactone.
Polylactic acid is known to be produced by the following method: lactide process via lactide; a direct polymerization method in which lactic acid is heated under reduced pressure and polymerized while removing water in a solvent; and so on.
In the polyhydroxyhexanoate ester, the copolymerization ratio of 3-hydroxyhexanoic acid (3-hydroxyhexanoate ester) to the copolymer of 3-hydroxybutyric acid (3-hydroxybutyrate) and 3-hydroxyhexanoic acid (3-hydroxyhexanoate ester) is preferably 3 to 20 mol%, more preferably 4 to 15 mol%, still more preferably 5 to 12 mol%, from the viewpoint of the surface gloss of the resulting resin molded body.
In the method for measuring the copolymerization ratio of 3-hydroxycaproic acid (3-hydroxycaproic ester), use is made of1H-NMR the hexanoate ratio was calculated from the integral values of the peaks derived from the hexanoate and butyrate ends.
The weight average molecular weight (Mw) of the polyester resin (E) may be 10,000 to 1,000,000 (preferably 50,000 to 800,000, more preferably 100,000 to 600,000) from the viewpoint of surface gloss of the resulting resin molded article.
The weight average molecular weight (Mw) of the polyester resin (E) is a value measured by Gel Permeation Chromatography (GPC). Specifically, GPC molecular weight measurement HLC-8320GPC manufactured by Tosoh Corporation was used as a measurement device in a chloroform solvent and a column was used: TSKgel GMHHR-M + TSKgel GMHHR-M (7.8mm I.D.30cm).
From the measurement results, the weight average molecular weight (Mw) was calculated by using a molecular weight calibration curve prepared from monodisperse polystyrene standard samples.
[ poly (meth) acrylate compound (F): compound (F) ]
The poly (meth) acrylate compound (F) is a compound containing 50% by mass or more (preferably 70% by mass or more, more preferably 90% by mass, more preferably 100% by mass) of a monomer derived from an alkyl (meth) acrylate.
The poly (meth) acrylate compound (F) may be a compound (resin) containing a monomer derived from a monomer other than (meth) acrylate.
The monomers contained in the poly (meth) acrylate compound (F) may be used alone or in combination of two or more.
The poly (meth) acrylate compound (F) may be used alone or in combination of two or more.
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, tert-butyl (meth) acrylate, isoamyl (meth) acrylate, pentyl (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 dicyclopentyl (meth) acrylate.
Among them, the alkyl (meth) acrylate may be an alkyl (meth) acrylate having an alkyl chain of 1 to 8 carbon atoms (preferably 1 to 4, more preferably 1 to 2, and still more preferably 1) from the viewpoint of the surface gloss of the resulting resin molded body.
That is, the poly (meth) acrylate compound (F) may be a polymer containing 50% by mass or more (preferably 70% by mass or more, more preferably 90% by mass, still more preferably 100% by mass) of a monomer derived from an alkyl (meth) acrylate having an alkyl chain of 1 to 8 carbon atoms (preferably 1 to 4, more preferably 1 to 2, still more preferably 1).
The poly (meth) acrylate compound (F) may be a polymer containing 100 mass% of a monomer derived from an alkyl (meth) acrylate in which the alkyl chain has 1 to 8 carbon atoms (preferably 1 to 4, more preferably 1 to 2, and still more preferably 1). That is, the poly (meth) acrylate compound (F) may be a polyalkyl (meth) acrylate in which the alkyl chain has 1 to 8 carbon atoms (preferably 1 to 4, more preferably 1 to 2, still more preferably 1). The polyalkyl (meth) acrylate in which the alkyl chain has one carbon atom is preferably polymethyl methacrylate.
Examples of the monomer other than (meth) acrylate in the poly (meth) acrylate compound (F) include:
styrene compounds [ monomers having a styrene skeleton, such as styrene, alkyl-substituted styrenes (such as α -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-ethylstyrene, 3-ethylstyrene and 4-ethylstyrene), halogen-substituted styrenes (such as 2-chlorostyrene, 3-chlorostyrene and 4-chlorostyrene), vinylnaphthalene (2-vinylnaphthalene and the like) and hydroxystyrene (4-vinylphenol and the like) ], and
unsaturated dicarboxylic anhydrides [ "compounds having an ethylenic double bond and a dicarboxylic anhydride group", such as maleic anhydride, itaconic anhydride, glutaric anhydride, citraconic anhydride and aconitic anhydride ].
The weight average molecular weight (Mw) of the poly (meth) acrylate compound (F) is not particularly limited, but may be 15,000 to 120,000 (preferably, more than 20,000 to 100,000, more preferably, 22,000 to 100,000, more preferably, 25,000 to 100,000).
In particular, the weight average molecular weight (Mw) of the poly (meth) acrylate compound (F) is preferably less than 50,000 (i.e., less than 5 ten thousand), more preferably 40,000 or less, and still more preferably 35,000 or less, from the viewpoint of the surface gloss of the resulting resin molded article. However, the weight average molecular weight (Mw) of the poly (meth) acrylate compound (F) may be 15,000 or more.
Specifically, GPC molecular weight measurement was performed in a tetrahydrofuran solvent using HLC-8320GPC manufactured by Tosoh Corporation as a measurement device and using column TSKgel α -M manufactured by Tosoh Corporation.
[ other additives ] (at least one compound (G) selected from the group consisting of hindered phenol compound, tocopherol compound, tocotrienol compound, phosphite compound and hydroxylamine compound: component (G))
The resin composition of the present exemplary embodiment may further include a compound (G).
The compound (G) is at least one selected from the group consisting of a hindered phenol compound, a tocopherol compound, a tocotrienol compound, a phosphite compound and a hydroxylamine compound.
Hindered phenol compounds
In the present exemplary embodiment, the hindered phenol compound refers to a compound in which at least one of the ortho positions to the phenolic hydroxyl group is substituted with an alkyl group. The alkyl group is preferably a bulky alkyl group such as a tert-butyl group and a tert-amyl group (1, 1-dimethylpropyl group).
Examples of the hindered phenol compound include compounds represented by the following general formula (HP 1).
In the general formula (HP1), R11And R12Each independently represents an alkyl group having 1 to 6 hydrogen atoms or carbon atoms, L11Represents a single bond orDivalent linking group, X11Represents a single bond or an n-valent group, and n represents 1,2, 3 or 4.
From R11The alkyl group having 1 to 6 carbon atoms represented is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. From R11The alkyl groups represented having 1 to 6 carbon atoms may be linear, branched or cyclic, but are preferably linear or branched alkyl groups.
Specifically, from R11The alkyl group having 1 to 6 carbon atoms represented is preferably a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a n-hexyl group or a1, 1-dimethylbutyl group, more preferably a methyl group, a tert-butyl group or a tert-pentyl group, and still more preferably a methyl group or a tert-butyl group.
From R12The alkyl group having 1 to 6 carbon atoms represented is preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms. From R12The alkyl groups represented having 1 to 6 carbon atoms may be linear, branched or cyclic, but are preferably linear or branched alkyl groups.
Specifically, from R12The alkyl group having 1 to 6 carbon atoms represented is preferably a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a n-hexyl group or a1, 1-dimethylbutyl group, more preferably a methyl group, an ethyl group, a n-propyl group or an isopropyl group, and still more preferably a methyl group or an ethyl group.
From R11The group represented is preferably a hydrogen atom, a methyl group, a tert-butyl group or a tert-pentyl group.
From R12The group represented is preferably a hydrogen atom, a methyl group or an ethyl group.
R11And R12May be connected to each other to form a ring.
From R11Examples of the divalent linking group represented include an alkylene group having 1 to 6 carbon atoms (preferably an alkylene group having 1 to 4 carbon atoms) and-R-C (═ O) O-R' -. Wherein R and R' each independently represent an alkylene group having 1 to 6 carbon atoms(preferably an alkylene group having 1 to 4 carbon atoms, more preferably an alkylene group having 1 or 2 carbon atoms) or a phenylene group.
-R-C (═ O) O-R' -is preferably-CH2CH2-C(＝O)O-CH2-。
From X11Examples of the monovalent group represented include aliphatic hydrocarbon groups.
The aliphatic hydrocarbon group may be linear, branched or alicyclic. The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having an alicyclic ring (i.e., a chain aliphatic hydrocarbon group), and more preferably a linear aliphatic hydrocarbon group, from the viewpoint that the compound represented by the general formula (HP1) is easily dispersed in the cellulose acylate (a).
The aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. The aliphatic hydrocarbon group is preferably a saturated aliphatic hydrocarbon group from the viewpoint that the compound represented by the general formula (HP1) is easily dispersed in the cellulose acylate (a).
The aliphatic hydrocarbon group preferably has 1 to 24 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 12 to 18 carbon atoms, from the viewpoint that the compound represented by the general formula (HP1) is easily dispersed in the cellulose acylate (a).
Specific examples of the aliphatic hydrocarbon group include those related to Y in the general formula (P1) described below41The same groups as the specific examples of (1).
Specific examples of the aliphatic hydrocarbon group are preferably a straight-chain alkyl group having 6 to 20 carbon atoms, more preferably a straight-chain alkyl group having 12 to 18 carbon atoms, and still more preferably a straight-chain alkyl group having 16 to 18 carbon atoms.
From X11Examples of the divalent groups represented include a group obtained by removing two hydrogen atoms from an alkane having 1 to 6 carbon atoms (preferably an alkane having 1 to 4 carbon atoms) (alkanediyl) and- (R-O-R')m-. Here, R and R' each independently represent an alkylene group or a phenylene group having 1 to 4 carbon atoms, and m represents 1,2, 3 or 4 (preferably 1 or 2).
-(R-O-R')m-is preferably-CH2-O-CH2-and- (CH)2-O-CH2)2-。
From X11Examples of the divalent group represented also include the following group (HP 1-a). Denotes L11The binding site of (a).
In the group (HP1-a), R111、R112、R113And R114Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, or a tert-butyl group, more preferably a methyl group or an ethyl group, and still more preferably a methyl group.
From X11Examples of the trivalent group represented include a group (alkanetriyl) obtained by removing three hydrogen atoms from an alkane having 1 to 6 carbon atoms (preferably an alkane having 1 to 4 carbon atoms).
From X11Examples of trivalent groups represented also include the following groups (HP1-b) and groups (HP 1-c). Denotes L11The binding site of (a).
In the group (HP1-b), R115、R116And R117Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, or a tert-butyl group, more preferably a methyl group or an ethyl group, and still more preferably a methyl group.
From X11Examples of the tetravalent group represented include a group (alkanetetrayl) obtained by removing four hydrogen atoms from an alkane having 1 to 6 carbon atoms (preferably an alkane having 1 to 4 carbon atoms), of which methanetetrayl is preferable.
In case n is 2,3 or 4, a plurality of R11、R12And L11May be the same or different groups, respectively.
Specific examples of the compound represented by the general formula (HP1) include "Irganox 1010", "Irganox 245" and "Irganox 1076" manufactured by BASF SE; "ADK STAB AO-60", "ADKSTAB AO-50", "ADK STAB AO-40", "ADK STAB AO-30", "ADK STAB AO-20", and "ADK STAB AO-330", manufactured by ADEKA Corporation; and "Sumilizer GA-80" manufactured by Sumitomo Chemical Co., Ltd.
Examples of the hindered phenol compound include compounds represented by the following general formula (HP 2).
In the general formula (HP2), R21、R22、R23、R24And R25Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
From R21The alkyl group having 1 to 6 carbon atoms represented is preferably an alkyl group having 4 to 6 carbon atoms, more preferably an alkyl group having 4 or 5 carbon atoms. From R21The alkyl group having 1 to 6 carbon atoms represented may be linear, branched or cyclic, but is preferably a linear or branched alkyl group, more preferably a branched alkyl group.
Specifically, from R21The alkyl group having 1 to 6 carbon atoms represented is preferably a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a n-hexyl group or a1, 1-dimethylbutyl group, more preferably a tert-butyl group, a tert-pentyl group or a1, 1-dimethylbutyl group, and still more preferably a tert-butyl group or a tert-pentyl group.
From R22The alkyl group having 1 to 6 carbon atoms represented is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. From R22The alkyl groups represented having 1 to 6 carbon atoms may be linear, branched or cyclic, but are preferably linear or branched alkyl groups.
Specifically, from R22The alkyl group having 1 to 6 carbon atoms represented is preferably a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a n-hexyl group or a1, 1-dimethylbutyl group, more preferably a methyl group, a tert-butyl group or a tert-pentyl group.
From R23The specific and preferred forms of the radicals indicated and the pairs R21Those described are the same.
From R24The specific and preferred forms of the radicals indicated and the pairs R22Those described are the same.
From R25The alkyl group having 1 to 6 carbon atoms represented is preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms. From R25The alkyl groups represented having 1 to 6 carbon atoms may be linear, branched or cyclic, but are preferably linear or branched alkyl groups.
Specifically, from R25The alkyl group having 1 to 6 carbon atoms represented is preferably a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a n-hexyl group or a1, 1-dimethylbutyl group, more preferably a methyl group, an ethyl group, a n-propyl group or an isopropyl group, and still more preferably a methyl group or an ethyl group.
From R21The group represented is preferably a tert-butyl group or a tert-amyl group.
From R22The radicals indicated are preferably methyl, tert-butyl or tert-pentyl.
From R23The group represented is preferably a tert-butyl group or a tert-amyl group.
From R24The radicals indicated are preferably methyl, tert-butyl or tert-pentyl.
From R25The group represented is preferably a hydrogen atom, a methyl group or an ethyl group.
Specific examples of the compound represented by the general formula (HP2) include "Sumilizer GM" and "Sumilizer GS" manufactured by Sumitomo Chemical co.
Tocopherol compounds, tocotrienol compounds
Examples of the tocopherol compound or the tocotrienol compound include compounds represented by the following general formula (T1).
In the general formula (T1), R31、R32And R33Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
From R31The alkyl group having 1 to 3 carbon atoms represented may be linear, branched or cyclic, but is preferably a linear or branched alkyl group.
Specifically, from R31The alkyl group having 1 to 3 carbon atoms represented is preferably a methyl group, an ethyl group, an n-propyl group or an isopropyl group, more preferably a methyl group or an ethyl group, and still more preferably a methyl group.
From R31The group represented is particularly preferably a hydrogen atom or a methyl group.
From R32The specific and preferred forms of the radicals indicated and the pairs R31Those described are the same.
From R33The specific and preferred forms of the radicals indicated and the pairs R31Those described are the same.
Specific examples of the tocopherol compound include the following compounds.
Specific examples of the tocotrienol compound include the following compounds.
Phosphite compounds
Examples of the phosphite ester compound include compounds represented by the following general formula (P1).
In the general formula (P1), R41、R42And R43Each independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, Y41And Y42Each independently represents an aliphatic hydrocarbon group, n41Represents 1,2 or 3, m41Represents 0 or 1, and m42Represents 0 or 1, provided that n41+m41+m42＝3。
From R41The alkyl group having 1 to 12 carbon atoms represented is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 9 carbon atoms. From R41The alkyl groups represented having from 1 to 12 carbon atoms may be linear, branched or cyclic, but are preferably linear or branched alkyl groups.
From R41Specific examples of the alkyl group having 1 to 12 carbon atoms represented include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, n-heptyl group, isoheptyl group, sec-heptyl group, tert-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, sec-nonyl group, tert-nonyl group, n-decyl group, isodecyl group, tert-decyl group, n-undecyl group, isoundecyl group, sec-dodecyl group, tert-dodecyl group, n-dodecyl group.
From R42Examples of the alkyl group having 1 to 12 carbon atoms include the alkyl group represented by the formula and p-R41The alkyl groups described are in the same form.
From R43Examples of the alkyl group having 1 to 12 carbon atoms include the alkyl group represented by the formula and p-R41The alkyl groups described are in the same form.
From R41The group represented is preferably a hydrogen atom, a methyl group or a tert-butyl group.
From R42The group represented is preferably an alkyl group having 1 to 9 carbon atoms, more preferably a methyl group or a tert-butyl group, and still more preferably a tert-butyl group.
From R43The group represented is preferably a hydrogen atom, a methyl group or a tert-butyl group.
At n41In the case of 2 or 3, a plurality of R41、R42And R43May be the same group or different groups, respectively.
At n41In the case of 2 or 3, a plurality of R41A plurality of R43Or a plurality of R41And R43May be joined to form a ring.
From Y41The aliphatic hydrocarbon groups represented may be linear, branched or alicyclic. From the viewpoint that the groups easily enter the molecular chain of the resin, from Y41The group represented is preferably an aliphatic hydrocarbon group having no alicyclic ring (i.e., a chain aliphatic hydrocarbon group), and more preferably a linear aliphatic hydrocarbon group.
From Y41The aliphatic hydrocarbon group represented may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. From the viewpoint that the compound represented by the general formula (P1) is easily dispersed in the cellulose acylate (A), Y represents41The aliphatic hydrocarbon group represented is preferably a saturated aliphatic hydrocarbon group.
From the viewpoint that the compound represented by the general formula (P1) is easily dispersed in the cellulose acylate (A), Y41The aliphatic hydrocarbon group represented preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 2 to 8 carbon atoms.
From Y42The specific and preferred forms of the aliphatic hydrocarbon groups represented and the para-Y41Those described are the same.
From Y41And Y42Specific examples of the aliphatic hydrocarbon group are shown below.
n41Represents 1,2 or 3, preferably 2 or 3, more preferably 3.
In the formula (P1), n41In the case of 2, specific examples of the compound include "Irgafos38" (bis (2, 4-di-tert-butyl-6-methylphenyl) -ethyl-phosphite) manufactured by BASF SE.
In the formula (P1), n41In the case of 3, the compound represented by the general formula (P1) is a compound represented by the following general formula (P1-a).
R in the formula (P1-a)41、R42And R43Having the formula (P1) as R41、R42And R43The same meaning is used.
Specific examples of the compound represented by the general formula (P1) include "Irgafos38" manufactured by BASF SE and "Irgafos TNPP" manufactured by BASF SE.
Examples of the phosphite ester compound include compounds represented by the following general formula (P2).
In the general formula (P2), R51、R52、R53、R54、R55And R56Each independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, L51Represents a single bond or a divalent linking group.
From R51The alkyl group having 1 to 12 carbon atoms represented is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 9 carbon atoms. From R51The alkyl groups represented having from 1 to 12 carbon atoms may be linear, branched or cyclic, but are preferably linear or branched alkyl groups.
From R51Specific examples of the alkyl group having 1 to 12 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, isohexyl, sec-hexyl, tert-hexylAn alkyl group, an n-heptyl group, an isoheptyl group, a secondary heptyl group, a tertiary heptyl group, an n-octyl group, an isooctyl group, a secondary octyl group, a tertiary octyl group, an n-nonyl group, an isononyl group, a secondary nonyl group, a tertiary nonyl group, an n-decyl group, an isodecyl group, a tertiary decyl group, an n-undecyl group, an isoundecyl group, a secondary dodecyl group, a tertiary dodecyl group, an n-dodecyl group, an isododecyl group, a secondary dodecyl group and a tertiary dodecyl.
From R52Examples of the alkyl group having 1 to 12 carbon atoms include the alkyl group represented by the formula and p-R51The alkyl groups described are in the same form.
From R53Examples of the alkyl group having 1 to 12 carbon atoms include the alkyl group represented by the formula and p-R51The alkyl groups described are in the same form.
From R54Examples of the alkyl group having 1 to 12 carbon atoms include the alkyl group represented by the formula and p-R51The alkyl groups described are in the same form.
From R55Examples of the alkyl group having 1 to 12 carbon atoms include the alkyl group represented by the formula and p-R51The alkyl groups described are in the same form.
From R56Examples of the alkyl group having 1 to 12 carbon atoms include the alkyl group represented by the formula and p-R51The alkyl groups described are in the same form.
From R51The group represented is preferably a hydrogen atom, a methyl group or a tert-butyl group.
From R52The group represented is preferably an alkyl group having 1 to 9 carbon atoms, more preferably a methyl group or a tert-butyl group, and still more preferably a tert-butyl group.
From R53The group represented is preferably a hydrogen atom, a methyl group or a tert-butyl group.
From R54The group represented is preferably a hydrogen atom, a methyl group or a tert-butyl group.
From R55The group represented is preferably an alkyl group having 1 to 9 carbon atoms, more preferably a methyl group or a tert-butyl group, and still more preferably a tert-butyl group.
From R56The group represented is preferably a hydrogen atom, a methyl group or a tert-butyl group.
From L51Examples of the divalent linking groups include alkylene and aryleneThe group is preferably an alkylene group or a phenylene group having 1 to 6 carbon atoms, and more preferably an alkylene group or a phenylene group having 1 to 4 carbon atoms.
Specific examples of the compound represented by the general formula (P2) include "Irgafos P-EPQ" manufactured by BASF SE.
Examples of the phosphite ester compound include compounds represented by the following general formula (P3).
In the general formula (P3), R61、R62、R63、R64、R65And R66Each independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, L61And L62Each independently represents a single bond or a divalent linking group.
From R61The alkyl group having 1 to 12 carbon atoms represented is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 9 carbon atoms. From R61The alkyl groups represented having from 1 to 12 carbon atoms may be linear, branched or cyclic, but are preferably linear or branched alkyl groups.
From R61Specific examples of the alkyl group having 1 to 12 carbon atoms represented include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, n-heptyl group, isoheptyl group, sec-heptyl group, tert-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, sec-nonyl group, tert-nonyl group, n-decyl group, isodecyl group, tert-decyl group, n-undecyl group, isoundecyl group, sec-dodecyl group, tert-dodecyl group, n-dodecyl group.
From R62Examples of the alkyl group having 1 to 12 carbon atoms include the alkyl group represented by the formula and p-R61The alkyl groups described are in the same form.
From R63Examples of the alkyl group having 1 to 12 carbon atoms includeAnd to R61The alkyl groups described are in the same form.
From R64Examples of the alkyl group having 1 to 12 carbon atoms include the alkyl group represented by the formula and p-R61The alkyl groups described are in the same form.
From R65Examples of the alkyl group having 1 to 12 carbon atoms include the alkyl group represented by the formula and p-R61The alkyl groups described are in the same form.
From R66Examples of the alkyl group having 1 to 12 carbon atoms include the alkyl group represented by the formula and p-R61The alkyl groups described are in the same form.
From R61The group represented is preferably a hydrogen atom, a methyl group or a tert-butyl group.
From R62The group represented is preferably an alkyl group having 1 to 9 carbon atoms, more preferably a methyl group or a tert-butyl group, and still more preferably a tert-butyl group.
From R63The group represented is preferably a hydrogen atom, a methyl group or a tert-butyl group.
From R64The group represented is preferably an alkyl group having 1 to 9 carbon atoms, more preferably a methyl group or a tert-butyl group, and still more preferably a tert-butyl group.
From R65The group represented is preferably a hydrogen atom, a methyl group, a tert-butyl group or a tert-pentyl group.
From R66The group represented is preferably a hydrogen atom, a methyl group, a tert-butyl group or a tert-pentyl group.
R65And R66At least one of (a) and (b) is preferably an alkyl group, and the alkyl group is preferably a tert-butyl group or a tert-pentyl group.
From L61Examples of the divalent linking group represented include alkylene groups, preferably alkylene groups having 1 to 3 carbon atoms, more preferably alkylene groups having 1 or 2 carbon atoms.
L61Particularly preferred is a single bond or a methylene group.
From L62Examples of the divalent linking group represented include alkylene groups and arylene groups, preferably alkylene groups or phenylene groups having 1 to 6 carbon atoms, and more preferably alkylene groups or phenylene groups having 1 to 4 carbon atoms.
Specific examples of the compound represented by the general formula (P3) include "Sumilizer GP" manufactured by Sumitomo Chemical co.
-hydroxylamine compounds-
In the present exemplary embodiment, the hydroxylamine compound refers to a compound having a structure in which at least one hydroxyl group is directly bonded to a nitrogen atom of an amine. The hydroxylamine compound is preferably an N, N-dialkylhydroxylamine.
Examples of the hydroxylamine compound include compounds represented by the following general formula (HA 1).
R in the formula (HA1)71And R72Each independently represents an alkyl group having 14 to 20 carbon atoms.
From R71The alkyl group having 14 to 20 carbon atoms represented may be a straight-chain alkyl group, a branched-chain alkyl group or an alicyclic alkyl group, but is preferably a straight-chain or branched-chain alkyl group, more preferably a straight-chain alkyl group.
In the reaction of R71In the case where the alkyl group having 14 to 20 carbon atoms represented is a branched chain, the number of branches in the group is preferably 1 to 3, more preferably 1 or 2, and still more preferably 1.
From R71The alkyl group having 14 to 20 carbon atoms represented is preferably a straight-chain or branched alkyl group having 16 to 18 carbon atoms, particularly preferably a straight-chain alkyl group having 16 to 18 carbon atoms.
From R72The specific and preferred forms of the radicals indicated and the pairs R71Those described are the same.
From R71And R72Specific examples of the alkyl group having 14 to 20 carbon atoms represented are shown below.
Specific examples of the compound represented by the general formula (HA1) include "Irgastab FS-042" manufactured by BASF SE.
The compound (G) may be used alone or in combination of two or more. The form in which two or more species are used in combination may be a form in which two or more species in the same class (e.g., hindered phenol compounds) are used in combination, or a form in which two or more species in different classes (e.g., hindered phenol compounds and tocopherol compounds) are used in combination.
The form in which two or more kinds are used in combination is preferably a form in which at least one selected from the group consisting of a hindered phenol compound and a hydroxylamine compound and at least one selected from phosphite compounds are used in combination.
(ester Compound (H): component (H))
The resin composition of the present exemplary embodiment may further include a specific ester compound (H).
The resin composition of the present exemplary embodiment is at least one selected from the group consisting of a compound represented by general formula (1), a compound represented by general formula (2), a compound represented by general formula (3), a compound represented by general formula (4), and a compound represented by general formula (5).
In the general formula (1), R11Represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms, R12Represents an aliphatic hydrocarbon group having 9 to 28 carbon atoms.
In the general formula (2), R21And R22Each independently represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms.
In the general formula (3), R31And R32Each independently represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms.
In the general formula (4), R41、R42And R43Each independently represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms.
In the general formula (5), R51、R52、R53And R54Each independently represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms.
R11Represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms. From R11The group represented by (a) is preferably an aliphatic hydrocarbon group having 9 or more carbon atoms, more preferably an aliphatic hydrocarbon group having 10 or more carbon atoms, and still more preferably an aliphatic hydrocarbon group having 15 or more carbon atoms. From R11The group represented by (a) is preferably an aliphatic hydrocarbon group having 24 or less carbon atoms, more preferably an aliphatic hydrocarbon group having 20 or less carbon atoms, and still more preferably an aliphatic hydrocarbon group having 18 or less carbon atoms. From R11The radicals indicated are particularly preferably aliphatic hydrocarbon radicals having 17 carbon atoms.
From R11The groups represented may be saturated aliphatic hydrocarbon groups and unsaturated aliphatic hydrocarbon groups. From R11The group represented is preferably a saturated aliphatic hydrocarbon group.
From R11The group represented may be a straight-chain aliphatic hydrocarbon group, a branched-chain aliphatic hydrocarbon group, or an aliphatic hydrocarbon group having an alicyclic ring. From R11The group represented is preferably an aliphatic hydrocarbon group (i.e., a chain aliphatic hydrocarbon group) free of alicyclic group, more preferably a straight chain aliphatic hydrocarbon group.
In the reaction of R11When the group represented by (A) is an unsaturated aliphatic hydrocarbon group, the compound represented by (B) is represented by11The number of unsaturated bonds in the group represented is preferably 1 to 3, more preferably 1 or 2, and further preferably 1.
In the reaction of R11In the case where the group represented is an unsaturated aliphatic hydrocarbon group, among the groups, preferred is a straight-chain saturated hydrocarbon chain having 5 to 24 carbon atoms, more preferred is a straight-chain saturated hydrocarbon chain having 7 to 22 carbon atoms, still more preferred is a straight-chain saturated hydrocarbon chain having 9 to 20 carbon atoms, and particularly preferred is a straight-chain saturated hydrocarbon chain having 15 to 18 carbon atoms.
In the reaction of R11When the group represented is a branched aliphatic hydrocarbon group, the number of branches in the group is preferably 1 to 3, more preferably 1 or 2, and further preferably 1.
In the reaction of R11In the case where the group represented is a branched aliphatic hydrocarbon group, the main chain of the group preferably contains 5 to 24 carbon atoms, more preferablyContains 7 to 22 carbon atoms, further preferably contains 9 to 20 carbon atoms, and particularly preferably contains 15 to 18 carbon atoms.
In the reaction of R11When the group represented is an aliphatic hydrocarbon group having an alicyclic ring, the number of alicyclic rings in the group is preferably 1 or 2, and more preferably 1.
In the reaction of R11When the group represented is an aliphatic hydrocarbon group having an alicyclic ring, the alicyclic ring in the group is preferably an alicyclic ring having 3 or 4 carbon atoms, and more preferably an alicyclic ring having 3 carbon atoms.
From the viewpoint of surface gloss of the resin molded article, R is11The group represented is preferably a linear saturated aliphatic hydrocarbon group, a linear unsaturated aliphatic hydrocarbon group, a branched saturated aliphatic hydrocarbon group or a branched unsaturated aliphatic hydrocarbon group, and particularly preferably a linear saturated aliphatic hydrocarbon group. The number of carbon atoms in these aliphatic hydrocarbon groups is preferably as described above.
From R11The group represented may be a group in which a hydrogen atom in the aliphatic hydrocarbon group is substituted with a halogen atom (for example, a fluorine atom, a bromine atom, and an iodine atom), an oxygen atom, a nitrogen atom, or the like, and is preferably an unsubstituted group.
R12Represents an aliphatic hydrocarbon group having 9 to 28 carbon atoms. From R12Examples of the radicals represented include the radicals represented by the formula11Those described are the same groups. However, from R12The number of carbon atoms of the group represented is preferably as follows.
From R12The group represented by (a) is preferably an aliphatic hydrocarbon group having 10 or more carbon atoms, more preferably an aliphatic hydrocarbon group having 11 or more carbon atoms, and still more preferably an aliphatic hydrocarbon group having 16 or more carbon atoms. From R12The group represented by (a) is preferably an aliphatic hydrocarbon group having 24 or less carbon atoms, more preferably an aliphatic hydrocarbon group having 20 or less carbon atoms, and still more preferably an aliphatic hydrocarbon group having 18 or less carbon atoms. From R12The radicals indicated are particularly preferably aliphatic hydrocarbon radicals having 18 carbon atoms.
From the viewpoint of surface gloss of the resin molded article, R is12The group represented is preferably a linear saturated aliphatic hydrocarbon group, a linear unsaturated aliphatic hydrocarbon group, a branched saturated aliphatic hydrocarbon group or a branched unsaturated aliphatic hydrocarbon group, and particularly preferably a linear saturated aliphatic hydrocarbon group. The number of carbon atoms in these aliphatic hydrocarbon groups is preferably as described above.
R21、R22、R31、R32、R41、R42、R43、R51、R52、R53And R54The specific and preferred forms of the radicals indicated and the pairs R11Those described are the same.
From R11、R21、R22、R31、R32、R41、R42、R43、R51、R52、R53And R54Specific examples of the aliphatic hydrocarbon group having 7 to 28 carbon atoms represented and represented by R12Specific examples of the represented aliphatic hydrocarbon group having 9 to 28 carbon atoms are shown below, but the present exemplary embodiment is not limited thereto.
The ester compound (H) may be used alone or in combination of two or more.
[ content or content ratio of component (A) to component (F) ]
The resin composition of the present exemplary embodiment includes component (a), component (B), and component (C), and if necessary, component (D), component (E), and component (F). The content or content ratio (both based on mass) of each component in the resin composition of the present exemplary embodiment is preferably within the following range from the viewpoint of the surface gloss of the resin molded body.
Abbreviations for the respective components are as follows.
Cellulose acylate (a): component (A)
Thermoplastic elastomer (B): component (B)
Particles (C) of an organic compound containing two or more nitrogen atoms in the molecule: component (C)
Plasticizer (D): component (D)
Polyester resin (E): component (E)
Poly (meth) acrylate compound (F): component (F)
The content of the component (a) in the resin composition of the present exemplary embodiment is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass or more, relative to the total mass of the resin composition.
The content of the component (B) in the resin composition of the present exemplary embodiment is preferably 0.5 to 20 mass%, more preferably 3 to 20 mass%, and still more preferably 5 to 9 mass%, with respect to the total mass of the resin composition.
The content of the component (C) in the resin composition of the present exemplary embodiment is preferably 0.03 to 5% by mass, more preferably 0.1 to 3.0% by mass, and still more preferably 0.3 to 1.5% by mass, relative to the total mass of the resin composition.
The content of the component (D) in the resin composition of the present exemplary embodiment is preferably 0 to 25 mass%, more preferably 3 to 15 mass%, and still more preferably 5 to 10 mass%, with respect to the total mass of the resin composition.
The content of the component (E) in the resin composition of the present exemplary embodiment is preferably 0 to 15 mass%, more preferably 0 to 10 mass%, and still more preferably 0 to 6 mass%, with respect to the total mass of the resin composition.
The content of the component (F) in the resin composition of the present exemplary embodiment is preferably 0 to 15 mass%, more preferably 0 to 10 mass%, and still more preferably 0 to 6 mass%, with respect to the total mass of the resin composition.
The content ratio of the component (B) to the component (A) is preferably 0.025. ltoreq. B)/(A. ltoreq.0.3, more preferably 0.04. ltoreq. B)/(A. ltoreq.0.2, still more preferably 0.07. ltoreq. B)/(A. ltoreq.0.15.
The content ratio of the component (C) to the component (A) is preferably 0.001. ltoreq. C)/(A. ltoreq.0.06, more preferably 0.002. ltoreq. C)/(A. ltoreq.0.04, still more preferably 0.004. ltoreq. C)/(A. ltoreq.0.02.
The content ratio of the component (D) to the component (A) is preferably 0. ltoreq. D)/(A). ltoreq.0.35, more preferably 0.025. ltoreq. D)/(A). ltoreq.0.2, still more preferably 0.05. ltoreq. D)/(A). ltoreq.0.15.
The content ratio of the component (E) to the component (A) is preferably 0. ltoreq. E)/(A). ltoreq.0.15, more preferably 0. ltoreq. E)/(A). ltoreq.0.10, still more preferably 0. ltoreq. E)/(A.ltoreq.0.06.
The content ratio of the component (F) to the component (A) is preferably 0. ltoreq. F)/(A). ltoreq.0.15, more preferably 0. ltoreq. F)/(A). ltoreq.0.10, still more preferably 0. ltoreq. F)/(A.ltoreq.0.06.
The content or content ratio of the other additives is preferably within the following range. Abbreviations for the respective components are as follows.
Ester compound (G): component (G)
At least one compound (G) selected from the group consisting of hindered phenol compounds, tocopherol compounds, tocotrienol compounds, phosphite compounds and hydroxylamine compounds: component (G)
The content of the component (G) in the resin composition of the present exemplary embodiment is preferably 0.1 to 15 mass%, more preferably 0.5 to 10 mass%, and still more preferably 1 to 5 mass%, with respect to the total mass of the resin composition.
The content ratio of the component (G) to the component (A) is preferably 0.001. ltoreq. G)/(A. ltoreq.0.15, more preferably 0.005. ltoreq. G)/(A. ltoreq.0.15, still more preferably 0.01. ltoreq. G)/(A. ltoreq.0.07.
The content of the component (H) in the resin composition of the present exemplary embodiment is preferably 0.01 to 5% by mass, more preferably 0.05 to 2% by mass, and still more preferably 0.1 to 1% by mass, relative to the total mass of the resin composition.
The content ratio of component (H) to component (A) is preferably 0.0001. ltoreq. H)/(A. ltoreq.0.075, more preferably 0.0005. ltoreq. H)/(A. ltoreq.0.03, still more preferably 0.010. ltoreq. H)/(A. ltoreq.0.015.
[ other Components ]
The resin composition of the present exemplary embodiment may include other components.
Examples of the other components include flame retardants, compatibilizers, antioxidants, antiblocking agents, light-proofing agents, weather-resistant agents, colorants, pigments, modifiers, drip inhibitors, antistatic agents, hydrolysis inhibitors, fillers, and reinforcing agents (such as glass fibers, carbon fibers, talc, clay, mica, glass flakes, ground glass, glass beads, crystalline silica, alumina, silicon nitride, aluminum nitride, and boron nitride).
If necessary, components (additives) such as an acid acceptor and a reactive trapping agent for preventing the release of acetic acid may be added. Examples of acid acceptors 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 reactive capture agents include epoxy compounds, anhydride compounds, and carbodiimides.
The content of each component is preferably 0 to 5% by mass with respect to the total mass of the resin composition. Here, "0 mass%" means that no other component is contained.
The resin composition of the present exemplary embodiment may contain other resins than the resin (cellulose acylate (a) and the like). However, in the case of containing another resin, the content of the other resin may be 5% by mass or less, and preferably less than 1% by mass, relative to the total mass of the resin composition. More preferably, no other resin is contained (i.e., 0 mass%).
Examples of the other resins include known thermoplastic resins, specifically including: a polycarbonate resin; a polypropylene resin; a polyester resin; a polyolefin resin; a polyester carbonate resin; a polyphenylene ether resin; polyphenylene sulfide resin; polysulfone resin; polyether sulfone resin; a polyarylene resin; a polyetherimide resin; a polyacetal resin; a polyvinyl acetal resin; a polyketone resin; a polyetherketone resin; polyether ether ketone resin; a polyaryl ketone resin; a polyether nitrile resin; a liquid crystal resin; a polybenzimidazole resin; a polyoxamide resin; a vinyl polymer or copolymer obtained by polymerizing or copolymerizing one or more vinyl monomers selected from the group consisting of an aromatic alkenyl compound, a methacrylate acrylate, and a vinyl cyanide compound; a diene-aromatic alkenyl compound copolymer; vinyl cyanide-diene-aromatic alkenyl compound copolymers; aromatic alkenyl compound-diene-vinyl cyanide-N-phenyl maleimide copolymer; vinyl cyanide- (ethylene-diene-propylene (EPDM)) -aromatic alkenyl compound copolymers; vinyl chloride resins and chlorinated vinyl chloride resins. These resins may be used alone or in combination of two or more.
[ method for producing resin composition ]
The resin composition of the present exemplary embodiment is produced by the following method: a mixture comprising a cellulose acylate (a), a thermoplastic elastomer (B), particles of an organic compound having two or more nitrogen atoms in the molecule (C), and other additives (a plasticizer (D), a polyester resin (E), a poly (meth) acrylate compound (F), etc.), and other components as necessary, is melt-kneaded. In addition, the resin composition of the present exemplary embodiment is also produced, for example, by dissolving the above components in a solvent.
Examples of the unit for melt-kneading include known units, specifically including a twin-screw extruder, a henschel mixer, a banbury mixer, a single-screw extruder, a multi-screw extruder, and a co-mixer.
< resin molded article >
The resin molded body of the present exemplary embodiment includes the resin composition of the present exemplary embodiment. That is, the resin molded body of the present exemplary embodiment has the same composition as the resin composition of the present exemplary embodiment.
The molding method of the resin molded body of the present exemplary embodiment is preferably injection molding from the viewpoint of a high degree of freedom in shape. In this regard, the resin molded body is preferably an injection molded body obtained by injection molding.
The cylinder temperature at the time of injection molding is, for example, 160 ℃ to 280 ℃, and preferably 180 ℃ to 260 ℃. The mold temperature at the time of injection molding is, for example, 30 ℃ to 90 ℃, and more preferably 40 ℃ to 60 ℃.
Injection molding can be performed using, for example, commercially available equipment such as NEX500 manufactured by Nissei Plastic Industrial co., ltd, NEX150 manufactured by Nissei Plastic Industrial co., ltd, NEX7000 manufactured by Nissei Plastic Industrial co., ltd, PNX40 manufactured by Nissei Plastic Industrial co, ltd, and SE50D manufactured by Sumitomo Machinery corp.
The molding method for obtaining the resin molded body of the present exemplary embodiment is not limited to the above-described injection molding, and extrusion molding, blow molding, hot press molding, calendar molding, coating molding, casting molding, dip molding, vacuum molding, transfer molding, or the like may be applied.
The resin molded body of the present exemplary embodiment is suitable for applications such as electronic/electrical equipment, office machines, home appliances, automotive interior materials, toys, containers, vehicles, absorbents, and separation films. More specifically, a housing of an electronic/electric appliance or a home appliance; various components of electronic/electric devices or home appliances; an automotive interior trim part; a building block toy; a plastic model kit; a storage case for CD-ROM or DVD; tableware; beverage bottles; a food tray; a packaging material; a film; a sheet material; a catalyst support; a water absorbing material and a humidity adjusting material.
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