阅读说明：本技术 树脂组合物和树脂成型品 (Resin composition and resin molded article ) 是由 宫崎佳奈 田中凉 八百健二 于 2019-03-12 设计创作，主要内容包括：本发明提供一种树脂组合物和树脂成型品,所述树脂组合物包含具有源自生物质的碳原子的树脂(A),其中在JIS K7244-3:1999所定义的动态粘弹性测量中,在频率为1Hz和温度为80℃时储能模量E’f80与损耗模量E”f80之比(E’f80/E”f80)为5至15。(The present invention provides a resin composition comprising a resin (A) having a carbon atom derived from a biomass, wherein the ratio of the storage modulus E 'f 80 to the loss modulus E' f80 (E 'f 80/E' f80) at a frequency of 1Hz and a temperature of 80 ℃ is 5 to 15 in the dynamic viscoelasticity measurement defined in JIS K7244-3:1999, and a resin molded article.)

1. A resin composition, the resin composition comprising:

a resin (A) having a biomass-derived carbon atom,

wherein, in the dynamic viscoelasticity measurement defined in JIS K7244-3:1999, the ratio E 'f 80/E "f 80 of the storage modulus E' f80 to the loss modulus E" f80 at a frequency of 1Hz and a temperature of 80 ℃ is 5 to 15.

2. The resin composition according to claim 1, wherein,

wherein the content of biomass-derived carbon atoms in the resin composition as defined in ASTM D6866:2012 is 30% or more relative to the total amount of carbon atoms in the resin composition.

3. The resin composition according to claim 1 or 2,

wherein the resin (a) is at least one selected from the group consisting of cellulose acylate and aliphatic polyester resin.

4. The resin composition according to claim 3, wherein,

wherein the resin (a) is at least one selected from the group consisting of cellulose acetate propionate and cellulose acetate butyrate.

5. The resin composition according to claim 3, wherein,

wherein the resin (A) is polyhydroxyalkanoate.

6. The resin composition according to any one of claims 1 to 5, further comprising:

a plasticizer (B); and

a compound (C) which 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,

wherein the resin (A) is a cellulose acylate.

7. The resin composition according to any one of claims 1 to 6,

wherein, in the dynamic viscoelasticity measurement defined in JIS K7244-3:1999, the ratio E 'f 80/E "f 80 of the storage modulus E' f80 to the loss modulus E" f80 at a frequency of 1Hz and a temperature of 80 ℃ is 6.5 to 13.

8. The resin composition according to any one of claims 1 to 7,

wherein, in the dynamic viscoelasticity measurement defined in JIS K7244-3:1999, the ratio E 'f 90/E "f 90 of the storage modulus E' f90 to the loss modulus E" f90 at a frequency of 1Hz and a temperature of 90 ℃ is 3 to 12.

9. The resin composition according to any one of claims 1 to 8,

wherein, in the dynamic viscoelasticity measurement defined by JIS K7244-3:1999, the ratio of the ratio E 'f 80/E "f 80 of the storage modulus E' f80 to the loss modulus E" f80 at a frequency of 1Hz and a temperature of 80 ℃ to the ratio E 'f 90/E "f 90 of the storage modulus E' f90 to the loss modulus E" f90 at a frequency of 1Hz and a temperature of 90 ℃ (E 'f 80/E "f 80)/(E' f 90/E" f90) is 1.15 to 1.35.

10. The resin composition according to any one of claims 1 to 9,

wherein, in the dynamic viscoelasticity measurement defined by JIS K7244-3:1999, the ratio of the ratio E 'f 25/E "f 25 of the storage modulus E' f25 to the loss modulus E" f25 at a frequency of 1Hz and a temperature of 25 ℃ to the ratio E 'f 80/E "f 80 of the storage modulus E' f80 to the loss modulus E" f80 at a frequency of 1Hz and a temperature of 80 ℃ (E 'f 25/E "f 25)/(E' f 80/E" f80) is 1.4 to 3.5.

11. A resin molded article comprising the resin composition according to any one of claims 1 to 10.

12. The resin molded article according to claim 11, which is an injection molded article.

Technical Field

The present invention relates to a resin composition and a resin molded article.

Background

In the related art, various resin compositions have been provided and used for various purposes. The resin composition has been used particularly for household appliances and various automobile parts, housings, and the like. In addition, thermoplastic resins are also used for parts such as housings of office equipment and electronic and electrical equipment.

In recent years, plant-derived resins have been used, and, as one of the plant-derived resins known in the related art, resins having a carbon atom derived from biomass, such as cellulose acylate, can be cited.

For example, JP-A-2016-23273 discloses that "the resin composition comprises at least one compound selected from the group consisting of an aromatic polyester resin, ｃA polylactic acid resin, ｃA carbodiimide compound, an epoxy compound, an oxazoline compound, an oxazine compound and an aziridine compound, wherein ｃA tan deltｃA peak obtained by viscoelasticity measurement indicates ｃA single peak in the range of 60 ℃ to 90 ℃. "

Disclosure of Invention

Meanwhile, when a resin molded article is molded from the resin composition, a step of applying pressure (so-called holding pressure) is performed to compensate for volume shrinkage when the molten resin is cooled and hardened. When the pressure is low while the pressure is maintained, a sink mark (sink mark) is generated; at higher pressures, however, residual stresses are created and deformation is induced in some cases. In view of this, it is desirable to obtain a resin molded article that prevents such a sink mark and deformation and has high dimensional accuracy.

Aspects of certain non-limiting embodiments of the present disclosure relate to a resin composition comprising a resin (a) having carbon atoms derived from biomass from which a resin molded article having high dimensional accuracy can be obtained, as compared to a case where the ratio (E ' f80/E "f 80) of the storage modulus (storagemodule) E ' f80 to the loss modulus (loss module) E" f80 at a frequency of 1Hz and a temperature of 80 ℃ (E ' f80/E "f 80) is less than 5 or more than 15.

<1> according to an aspect of the present disclosure, there is provided a resin composition comprising: a resin (A) having carbon atoms derived from biomass, wherein the ratio of the storage modulus E 'f 80 to the loss modulus E "f 80 (E' f 80/E" f80) at a frequency of 1Hz and a temperature of 80 ℃ is 5 to 15 in the dynamic viscoelasticity measurement defined in JIS K7244-3: 1999.

<2> the resin composition according to <1>, wherein a content of the biomass-derived carbon atoms in the resin composition as defined in ASTM D6866:2012 is 30% or more relative to a total amount of the carbon atoms in the resin composition.

<3> the resin composition according to <1> or <2>, wherein the resin (A) is at least one selected from the group consisting of cellulose acylate and aliphatic polyester resin.

<4> the resin composition according to <3>, wherein the resin (A) is at least one selected from the group consisting of cellulose acetate propionate and cellulose acetate butyrate.

<5> the resin composition according to <3>, wherein the resin (A) is polyhydroxyalkanoate ().

<6> the resin composition according to any one of <1> to <5>, further comprising a plasticizer (B) and a compound (C), the compound (C) being 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, wherein the resin (a) is a cellulose acylate.

<7> the resin composition according to any one of <1> to <6>, wherein, in the dynamic viscoelasticity measurement defined in JIS K7244-3:1999, the ratio of the storage modulus E 'f 80 to the loss modulus E "f 80 (E' f 80/E" f80) at a frequency of 1Hz and a temperature of 80 ℃ is from 6.5 to 13.

<8> the resin composition according to any one of <1> to <7>, wherein, in the dynamic viscoelasticity measurement defined in JIS K7244-3:1999, the ratio (E 'f 90/E "f 90) of the storage modulus E' f90 to the loss modulus E" f90 at a frequency of 1Hz and a temperature of 90 ℃ is from 3 to 12.

<9> the resin composition according to any one of <1> to <8>, wherein, in the dynamic viscoelasticity measurement defined in JIS K7244-3:1999, a ratio [ (E 'f 80/E' f80)/(E 'f 90/E' f90) ] of a ratio of the storage modulus E 'f 80 to the loss modulus E' f80 (E 'f 80/E' f80) at a frequency of 1Hz and a temperature of 80 ℃ to a ratio of the storage modulus E 'f 90 to the loss modulus E' f90 (E 'f 90/E' f90) at a frequency of 1Hz and a temperature of 90 ℃ is 1.15 to 1.35.

<10> the resin composition according to any one of <1> to <9>, wherein, in the dynamic viscoelasticity measurement defined in JIS K7244-3:1999, a ratio [ (E 'f 25/E' f25)/(E 'f 80/E' f80) ] of a ratio of the storage modulus E 'f 25 to the loss modulus E' f25 (E 'f 25/E' f25) at a frequency of 1Hz and a temperature of 25 ℃ to a ratio of the storage modulus E 'f 80 to the loss modulus E' f80 (E 'f 80/E' f80) at a frequency of 1Hz and a temperature of 80 ℃ is 1.4 to 3.5.

<11> according to another aspect of the present disclosure, there is provided a resin molded article comprising the resin composition of any one of <1> to <10 >.

<12> the resin molded article according to <11>, which is an injection molded article.

According to the invention of <1>, <2>, <3>, <4>, <5> or <6>, there is provided a resin composition containing a resin (a) having a carbon atom derived from a biomass, which is capable of obtaining a resin molded article having high dimensional accuracy, as compared with the case where the ratio (E 'f 80/E "f 80) of the storage modulus E' f80 to the loss modulus E" f80 is less than 5 or more than 15 at a frequency of 1Hz and a temperature of 80 ℃.

According to the invention of <7>, there is provided a resin composition capable of obtaining a resin molded article with high dimensional accuracy, as compared with the case where the ratio of the storage modulus E 'f 80 to the loss modulus E' f80 (E 'f 80/E' f80) is less than 6.5 or more than 13 at a frequency of 1Hz and a temperature of 80 ℃.

According to the invention of <8>, there is provided a resin composition capable of obtaining a resin molded article with high dimensional accuracy, as compared with the case where the ratio of the storage modulus E 'f 90 to the loss modulus E' f90 (E 'f 90/E' f90) is less than 3 or more than 12 at a frequency of 1Hz and a temperature of 90 ℃.

According to the invention of <9>, there is provided a resin composition capable of obtaining a resin molded article with high dimensional accuracy, as compared with the case where the ratio [ (E 'f 80/E "f 80)/(E' f 90/E" f90) ] of the ratio of the storage modulus E 'f 80 to the loss modulus E "f 80 (E' f 80/E" f80) at a frequency of 1Hz and a temperature of 80 ℃ to the ratio of the storage modulus E 'f 90 to the loss modulus E "f 90 (E' f 90/E" f90) at a frequency of 1Hz and a temperature of 90 ℃ is less than 1.15 or more than 1.35.

According to the invention of <10>, there is provided a resin composition capable of obtaining a resin molded article with high dimensional accuracy, as compared with the case where the ratio [ (E 'f 25/E "f 25)/(E' f 80/E" f80) ] of the ratio of the storage modulus E 'f 25 to the loss modulus E "f 25 (E' f 25/E" f25) at a frequency of 1Hz and a temperature of 25 ℃ to the ratio of the storage modulus E 'f 80 to the loss modulus E "f 80 (E' f 80/E" f80) at a frequency of 1Hz and a temperature of 80 ℃ is less than 1.4 or more than 3.5.

According to the invention of <11> or <12>, compared with the case of using a resin composition in which the ratio of the storage modulus E 'f 80 to the loss modulus E "f 80 (E' f 80/E" f80) is less than 5 or more than 15 at a frequency of 1Hz and a temperature of 80 ℃, there is provided a resin molded article capable of obtaining a resin molded article with high dimensional accuracy from a resin composition containing a resin (a) having a carbon atom derived from a biomass.

Detailed Description

Exemplary embodiments will be described below as examples of the present invention.

In the present specification, if there are a plurality of substances corresponding to each component in the body, the amount of each component in the body refers to the content ratio or content of the total amount of the plurality of substances in the body unless otherwise specified.

In addition, the expression "polymer of X" means a copolymer comprising X and non-X monomers in addition to a homopolymer comprising only X. Also, the expression "a copolymer of X and Y" means that X, Y including a copolymer with a monomer other than X and Y in addition to a copolymer containing only X and Y (hereinafter simply referred to as "single copolymer" for convenience) is included.

In addition, the resin (a), the plasticizer (B), and the compound (C) having a carbon atom derived from biomass are also referred to as a component (a), a component (B), and a component (C), respectively.

< resin composition >

The resin composition of the exemplary embodiment contains a resin (a) having a carbon atom derived from biomass (hereinafter also simply referred to as "bio-resin (a)").

In the dynamic viscoelasticity measurement defined in JIS K7244-3:1999, the ratio of the storage modulus E 'f 80 to the loss modulus E "f 80 (E' f 80/E" f80) at a frequency of 1Hz and a temperature of 80 ℃ is 5 to 15.

Generally, in the case of molding a resin molded article by melting a resin composition to mold the molten resin composition and then solidifying (for example, injection molding or the like), a step of applying pressure (so-called holding pressure) is performed to compensate for volume shrinkage when the molten resin is cooled and solidified. In the case where the pressure is low while maintaining the pressure, a sink mark, that is, a depression caused by molding shrinkage is generated. On the other hand, when the pressure is high, residual stress is generated, and therefore, deformation of the resin molded product is induced.

In contrast, according to the resin composition of the exemplary embodiment having the above constitution, there is provided a resin composition capable of obtaining a resin molded article with high dimensional accuracy.

The reason is presumed to be as follows.

When the molten resin composition is molded (e.g., poured into a mold) and further cooled, a temperature gradient is generated from the center of the molded resin composition to the surface, and the fluidity is lower on the surface side than at the center. When a holding pressure is applied in this state, the center side of the molded resin composition is filled with the resin, and the cured surface is stretched. At this time, when the elasticity of the resin composition is excessively high, stretching at the surface side (i.e., in the stretched region) is less likely to occur, and a high holding pressure is required to eliminate the sink mark, so that an excessive residual stress is generated in the molded article, and deformation is likely to occur. In contrast, if the viscosity of the resin composition is too high, the surface is not sufficiently cured, and thus the resin is likely to leak out from the mold without removing the sink marks in the pressure-holding step, and burrs may occur.

Here, the ratio of the storage modulus E 'f 80 to the loss modulus E "f 80 (E' f 80/E" f80) at a temperature of 80 ℃ is an index indicating that the ratio is large, the elasticity is strong, and the ratio is small, the viscosity is strong. That is, setting the ratio E' f80/E "f 80 in the resin composition of the exemplary embodiment within the above range means that the viscosity and elasticity are within suitable ranges at a temperature of 80 ℃ (at which curing of the glass state in the resin is nearly completed).

In view of this, it is considered that when the molded resin composition is cooled and cured, stretching of the surface side is favorably performed to prevent generation of a sink mark while preventing generation of a residual stress, so that deformation hardly occurs.

As described above, in the exemplary embodiments, it is considered to provide a resin composition capable of obtaining high dimensional accuracy in forming a resin molded article.

The ratio at a temperature of 80 ℃ (E' f80/E "f 80)

The ratio of the storage modulus E 'f 80 to the loss modulus E' f80 (E 'f 80/E' f80) at a frequency of 1Hz and a temperature of 80 ℃ is from 5 to 15, preferably from 6.5 to 13, more preferably from 7 to 11.

When the ratio (E 'f 80/E' f80) is 5 or more at 80 ℃, the resin composition has appropriate elasticity, and therefore, the mold can be effectively filled with the resin by holding the pressure, and the occurrence of sink marks is prevented without burrs. On the other hand, when the ratio (E' f80/E "f 80) at a temperature of 80 ℃ is 15 or less, the resin composition has an appropriate viscosity, and therefore, generation of sink marks is prevented, and excessive residual stress is not generated. Thus, a resin molded article having high dimensional accuracy can be formed.

The ratio at a temperature of 90 ℃ (E' f90/E "f 90)

The ratio of the storage modulus E 'f 90 to the loss modulus E' f90 (E 'f 90/E' f90) at a frequency of 1Hz and a temperature of 90 ℃ is preferably from 3 to 12, more preferably from 4 to 11, and even more preferably from 5 to 10.

The storage modulus E' f90 and loss modulus E "f 90 at higher temperatures of 90 ℃ indicate the viscoelasticity of the resin composition, where the resin is more glassy.

When the ratio (E' f90/E "f 90) at a temperature of 90 ℃ is 3 or more, the resin composition has moderate elasticity, and therefore, the mold can be efficiently filled with the resin by virtue of the holding pressure, and it is highly possible to prevent the generation of sink marks without burrs. On the other hand, when the ratio (E' f90/E "f 90) at a temperature of 90 ℃ is 12 or less, the resin composition has an appropriate viscosity, and therefore, generation of sink marks is prevented, and excessive residual stress is not generated. Thereby making it possible to form a resin molded article with high dimensional accuracy.

·[(E’f80/E”f80)/(E’f90/E”f90)]

The ratio [ (E 'f 80/E "f 80)/(E' f 90/E" f90) ] of the ratio (E 'f 80/E "f 80) at a temperature of 80 ℃ to the ratio (E' f 90/E" f90) at a temperature of 90 ℃ is preferably 1.15 to 1.35, more preferably 1.16 to 1.3, and still more preferably 1.17 to 1.28.

The ratio of the ratio indicating viscoelasticity at a temperature of 90 ℃ (E 'f 90/E "f 90) to the ratio indicating viscoelasticity at a temperature of 80 ℃ (E' f 80/E" f80) is an index of the rate of change in viscoelasticity in the resin composition when the temperature is decreased from 90 ℃ to 80 ℃. Thus, setting the ratio (E 'f 80/E "f 80)/(E' f 90/E" f90) within the above range means that the change in viscoelasticity in the resin composition is moderate when the temperature is decreased from 90 ℃ to 80 ℃.

When the ratio (E 'f 80/E "f 80)/(E' f 90/E" f90) is 1.35 or less, it is shown that the elasticity does not become excessively strong due to a temperature drop, and the resin composition has moderate viscosity and elasticity, it is possible to prevent generation of sink marks and not generate excessive residual stress when the mold is filled with the resin by holding pressure. In addition, when the ratio (E 'f 80/E "f 80)/(E' f 90/E" f90) is 1.15 or more, it is shown that the elasticity becomes stronger with a decrease in temperature, and since the resin composition has moderate elasticity, the mold can be effectively filled with the resin by virtue of the holding pressure, and generation of sink marks can be prevented without burrs. Thus, a resin molded article having high dimensional accuracy can be formed.

·[(E’f25/E”f25)/(E’f80/E”f80)]

The ratio (E 'f 25/E "f 25)/(E' f 80/E" f80) of the ratio (E 'f 25/E "f 25) at a temperature of 25 ℃ to the ratio (E' f 80/E" f80) at a temperature of 80 ℃ is preferably 1.4 to 3.5, more preferably 1.5 to 3, and still more preferably 1.6 to 2.5.

The ratio of the ratio indicating viscoelasticity at a temperature of 80 ℃ (E 'f 80/E "f 80) to the ratio indicating viscoelasticity at a temperature of 25 ℃ (E' f 25/E" f25) is an index of the rate of change in viscoelasticity in the resin composition when the temperature is decreased from 80 ℃ to 25 ℃. Thus, setting the ratio (E 'f 25/E "f 25)/(E' f 80/E" f80) within the above range means that the change in viscoelasticity in the resin composition is moderately mild when the temperature is decreased from 80 ℃ to 25 ℃ (i.e., the temperature at which curing is completed).

Setting the ratio (E 'f 25/E "f 25)/(E' f 80/E" f80) to 3.5 or less means that the elasticity at a temperature of 80 ℃ is not too small and the viscosity is not too large with respect to the viscoelasticity at a temperature of 25 ℃ (temperature at which curing is completed), in other words, means that excessive curing does not occur during cooling from 80 ℃ to 25 ℃. Thus, the mold can be efficiently filled with the resin by virtue of the holding pressure, the generation of the sink mark without burrs is likely to be prevented, and the generation of the sink mark without excessive residual stress is likely to be prevented, thereby forming the resin molded article with high dimensional accuracy. In addition, setting the ratio (E 'f 25/E "f 25)/(E' f 80/E" f80) to 1.4 or more means that the elasticity is sufficiently increased and the viscosity is sufficiently decreased at the temperature (25 ℃) at which curing is completed. Thereby, it is possible to prevent the resin molded article from being deformed when taken out of the mold.

Note that the above-mentioned "storage modulus E ' f80 and loss modulus E" f80 at a frequency of 1Hz and a temperature of 80 ℃ "," storage modulus E ' f90 and loss modulus E "f 90 at a frequency of 1Hz and a temperature of 90 ℃", and "storage modulus E ' f25 and loss modulus E" f25 at a frequency of 1Hz and a temperature of 25 ℃ were measured by the following methods.

A strip-shaped test piece (width 13mm, length 50mm, thickness 2mm) was prepared as a measurement sample, and a dynamic viscoelasticity measuring apparatus (DMS 6100, manufactured by Hitachi High-Technologies Corporation) was used. "Plastic-dynamic mechanical Properties measurement-part 5, based on JIS K7244-5: 1999: "figure 1a) test method using a fixed-holder test piece" in flexural vibration-non-resonance method ", measurement was performed under conditions of sinusoidal vibration, a measurement frequency of 1Hz, and a nitrogen flow, with a temperature increased from 10 ℃ to the highest achievable temperature (set in the range of 100 ℃ to 180 ℃) at a heating rate of 2 ℃/min. The values at 25 ℃, 80 ℃ and 90 ℃ were determined from the obtained curves of the storage modulus and the loss modulus, respectively, whereby the storage modulus E' f and the loss modulus E ″ f were obtained.

The method of controlling the ranges of "storage modulus E ' f80 and loss modulus E" f80 at a frequency of 1Hz and a temperature of 80 ℃ "," storage modulus E ' f90 and loss modulus E "f 90 at a frequency of 1Hz and a temperature of 90 ℃", and "storage modulus E ' f25 and loss modulus E" f25 at a frequency of 1Hz and a temperature of 25 ℃ as described above is not particularly limited, and examples thereof include the following methods.

For example, there may be mentioned a method of selecting the kind of the bio-resin (a), adjusting the kind and the addition amount of an additive (for example, 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) and adjusting the kind and the addition amount of other additives (for example, the thermoplastic elastomer (D) and the ester compound (E)) other than the aforementioned additives.

The components of the resin composition of the exemplary embodiment will be described in detail below.

[ resin (a) having a biomass-derived carbon atom: component (A) ]

The resin composition of the exemplary embodiment includes a resin (a) having a carbon atom derived from biomass.

The resin (a) having a biomass-derived carbon atom is not particularly limited, and a known resin having a biomass-derived carbon atom is used.

In addition, as the resin (a) having a carbon atom derived from biomass, not all of the resins need to be derived from biomass, and at least a part thereof may have a structure derived from biomass. Specifically, the cellulose acylate described below may have a cellulose structure derived from biomass and an acylate structure derived from petroleum.

Note that, in an exemplary embodiment, the "resin having a biomass-derived carbon atom" is a resin having at least a carbon atom derived from an organic resource of an organism other than a fossil resource, and as described below, the presence of a biomass-derived carbon atom is specified based on ASTM D6866:2012By¹⁴Abundance of C indicates.

From the viewpoint of dimensional accuracy of the resulting resin molded article, in the resin composition of the exemplary embodiment, the content of the biomass-derived carbon defined by ASTM D6866:2012 is preferably 20% by weight or more, more preferably 30% by weight or more, further preferably 35% by weight or more, and particularly preferably 40% by weight to 100% by weight, relative to the total amount of carbon atoms in the resin composition.

Further, in exemplary embodiments, the method of measuring the content of biomass-derived carbon atoms of the resin composition is by measuring of total carbon atoms of the resin composition based on the provisions of ASTM D686: 2012¹⁴The C abundance is used to calculate the content of carbon atoms derived from the biomass.

Examples of the resin (a) having a biomass-derived carbon atom include cellulose acylate, biomass-derived polyester, biomass-derived polyolefin, biomass-derived polyethylene terephthalate, biomass-derived polyamide, polytrimethylene terephthalate (PTT), polybutylene succinate (PBS), Phosphatidylglycerol (PG), isosorbide polymer, and acrylic-modified rosin.

Among them, the resin (a) having carbon atoms derived from biomass is preferably at least one selected from the group consisting of cellulose acylate and aliphatic polyester, and more preferably cellulose acylate, from the viewpoint of dimensional accuracy in the resin molded article to be obtained.

Cellulose acylate-

Cellulose acylate is a cellulose derivative in which at least a part of hydroxyl groups in cellulose are substituted (acylated) with acyl groups. Acyl is of the formula-CO-R^ACGroup of the structure (R)^ACRepresents a hydrogen atom or a hydrocarbon group).

The cellulose acylate is a cellulose derivative represented by the formula (CA).

In the formula (CA), A¹、A²And A³Independent earth surfaceRepresents a hydrogen atom or an acyl group, and n represents an integer of 2 or more. Here, n are A¹N number of A²And n is A³At least a part of (a) represents an acyl group. All n A's in the molecule¹May be the same, partially the same or different from each other. Similarly, all n A's in a molecule²May be the same as, partially the same as or different from each other, and n A's in the molecule³May be the same, partially the same or different from each other.

In the reaction of A¹、A²And A³In the acyl group, the hydrocarbon group in the acyl group may be linear, branched or cyclic, but is preferably linear or branched, more preferably linear.

In the reaction of A¹、A²And A³In the acyl group represented, the hydrocarbon group in the acyl group may be a saturated hydrocarbon group or may be an unsaturated hydrocarbon group, and is more preferably a saturated hydrocarbon group.

From A¹、A²And A³The acyl group represented is preferably an acyl group having 1 to 6 carbon atoms. That is, as the cellulose acylate, a cellulose acylate containing an acyl group having 1 to 6 carbon atoms is preferable. With the use of a cellulose acylate containing an acyl group having 1 to 6 carbon atoms, a resin molded article more excellent in dimensional accuracy is easily obtained as compared with the case of a cellulose acylate containing an acyl group having 7 or more carbon atoms.

From A¹、A²And A³The acyl group represented may be a group in which a hydrogen atom in the acyl 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, and is preferably an unsubstituted group.

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 dimensional accuracy of the resin molded article, the acyl group is more preferably an acyl group having 2 to 4 carbon atoms, and still more preferably an acyl group having 2 or 3 carbon atoms.

Examples of the cellulose acylate include cellulose acetate (mono-acetate, cellulose Diacetate (DAC) and cellulose triacetate), Cellulose Acetate Propionate (CAP) and Cellulose Acetate Butyrate (CAB).

From the viewpoint of dimensional accuracy of the obtained resin molded product, the cellulose acylate is preferably Cellulose Acetate Propionate (CAP) and Cellulose Acetate Butyrate (CAB), and more preferably Cellulose Acetate Propionate (CAP).

The cellulose acylate may be used alone, or two or more kinds may be used in combination.

From the viewpoint of moldability of the resin composition and dimensional accuracy of a resin molded article to be obtained, the weight-average polymerization degree of the cellulose acylate is preferably from 200 to 1000, more preferably from 500 to 1000, and further preferably from 600 to 1000.

The weight-average degree of polymerization of cellulose acylate was determined from the weight-average molecular weight (Mw) by the following procedure.

First, the weight average molecular weight (Mw) of the cellulose acylate was measured with reference to polystyrene using a gel permeation chromatography apparatus (GPC apparatus: manufactured by TOSOH CORPORATION, HLC-8320GPC, column: TSKgel α -M) using tetrahydrofuran.

Next, the weight average molecular weight (Mw) of the cellulose acylate is divided by the molecular weight of the structural unit of the cellulose acylate to determine the degree of polymerization of the cellulose acylate. For example, in the case where the substituent of the cellulose acylate is an acetyl group, the molecular weight of the structural unit is 263 when the substitution degree is 2.4, and 284 when the substitution degree is 2.9.

The weight average molecular weight (Mw) of the resin in the exemplary embodiment is also measured by the same method as the method of measuring the weight average molecular weight of the cellulose acylate.

The substitution degree of the cellulose acylate is preferably 2.1 to 2.9, more preferably 2.2 to 2.9, further preferably 2.3 to 2.9, particularly preferably 2.6 to 2.9, from the viewpoint of moldability of the resin composition and high dimensional accuracy of the resin molded article to be obtained.

In the Cellulose Acetate Propionate (CAP), the ratio of the substitution degree of acetyl group to propionyl group (acetyl group/propionyl group) is preferably 0.01 to 1, more preferably 0.05 to 0.1, from the viewpoints of moldability of the resin composition and dimensional accuracy of a resin molded article to be obtained.

As the CAP, a CAP satisfying at least one of the following (1), (2), (3) and (4) is preferable, a CAP satisfying the following (1), (3) and (4) is more preferable, a CAP satisfying the following (2), (3) and (4) is further preferable: (1) when measured by a GPC method using tetrahydrofuran as a solvent, the weight average molecular weight (Mw) of the reference polystyrene is 160,000 to 250,000, and the ratio Mn/Mz of the number average molecular weight (Mn) of the reference polystyrene to the Z average molecular weight (Mz) of the reference polystyrene is 0.14 to 0.21. (2) when measured by a GPC method using tetrahydrofuran as a solvent, the weight average molecular weight (Mw) of the reference polystyrene is 160,000 to 250,000, the ratio Mn/Mz of the number average molecular weight (Mn) of the reference polystyrene to the Z average molecular weight (Mz) of the reference polystyrene is 0.14 to 0.21, and the ratio Mn/Mz of the Z of the number average molecular weight (Mn) of the reference polystyrene to the Z average molecular weight (Mz) of the polystyrene is 0.14 to 0.21, and the ratio Mn/Mz of the Z of the weight (Mn/Mz) of the polystyrene to the Z average molecular weight (Mz) of the reference polystyrene is 0.6, when measured by a GPC method using tetrahydrofuran as a GPC method, the perpendicular to the die is 0.7, the viscosity of the die is 0.7.7 mm, the perpendicular to the 0.7 mm, the MD 8mm, 19 mm, the MD 8mm, the MD 8mm, the MD.

In 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, more preferably 0.5 to 3.0, from the viewpoints of moldability of the resin composition and high dimensional accuracy of a resin molded article to be obtained.

The degree of substitution of cellulose acylate is an index indicating the degree of substitution of hydroxyl groups of cellulose with acyl groups. In other words, the degree of substitution is an index indicating the degree of acylation of cellulose acylate. Specifically, the degree of substitution refers to D-glucopyranose units of cellulose acylateThe number of substitutions of three hydroxyl groups in the unit by acyl groups is an intramolecular average. Degree of substitution is given by¹The ratio of the peak integral of the hydrogen atom derived from cellulose to the peak integral of the hydrogen atom derived from acyl group in H-NMR (JMN-ECA, produced by JEOL RESONANCE).

Polyesters derived from biomass

Examples of the biomass-derived polyester (hereinafter also simply referred to as "polyester resin") include polymers of hydroxyalkanoates (hydroxyalkanoic acids), polycondensates of polycarboxylic acids and polyhydric alcohols, and ring-opening polycondensates of lactams.

The polyester resin is preferably an aliphatic polyester resin. Examples of the aliphatic polyester resin include polyhydroxyalkanoate (polymer of hydroxyalkanoate) and a polycondensate of an aliphatic diol and an aliphatic carboxylic acid.

Among them, polyhydroxyalkanoate is preferable as the polyester resin from the viewpoint of high dimensional accuracy of the resin molded article to be obtained.

The polyester resins may be used alone or in combination of two or more.

Examples of the polyhydroxyalkanoate include a compound having a structural unit represented by formula (PHA).

Note that in the compound having a structural unit represented by the formula (PHA), both ends of the polymer chain (main chain ends) may be carboxyl groups, or only one end of the polymer chain may be a carboxyl group and the other end of the polymer chain may be another group (for example, a hydroxyl group).

In the formula (PHA), R^PHA1Represents an alkylene group having 1 to 10 carbon atoms. n represents an integer of 2 or more.

In the formula (PHA), from R^PHA1The alkylene group represented is preferably an alkylene group having 3 to 6 carbon atoms. From R^PHA1The alkylene group represented may be any of a linear alkylene group and a branched alkylene group, and a branched alkylene group is preferable.

Here, in the formula (PHA), R^PHA1An alkylene group of the formula, which means 1) R^PHA1Having [ O-R ] representing the same alkylene group^PHA1-C(＝O)-]Structure, 2) R^PHA1Having a plurality of [ O-R ] s representing different alkylene groups^PHA1-C(＝O)-]Structure (R)^PHA1Represents an alkylene group having different carbon atoms or branches) (i.e., [ O-R ]^PHA1A-C(＝O)-][O-R^PHA1B-C(＝O)-]Structure).

That is, the polyhydroxyalkanoate may be a homopolymer of one hydroxyalkanoate (hydroxyalkanoic acid), or a copolymer of two or more hydroxyalkanoates (hydroxyalkanoic acids).

In the formula (PHA), the upper limit of n is not particularly limited, and is, for example, 20000 or less. n preferably ranges from 500 to 10000, more preferably from 1000 to 8000.

Examples of polyhydroxyalkanoates 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 two or more of these hydroxyalkanoic acids.

Among them, from the viewpoint of suppressing the decrease in transparency of the resin molded article to be obtained and improving the dimensional accuracy thereof, the polyhydroxyalkanoate is preferably a homopolymer of a branched hydroxyalkanoic acid having 2 to 4 carbon atoms, a single copolymer 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 single copolymer of 3-hydroxybutyric acid and 3-hydroxyhexanoic acid (i.e., polyhydroxybutyric acid hexanoic acid), and still more preferably a homopolymer of a branched hydroxyalkanoic acid having 3 carbon atoms (i.e., polylactic acid).

Note that the number of carbon atoms of hydroxyalkanoic acid is the number of carbon atoms including carboxyl group.

Polylactic acid is a polymer compound obtained by polymerizing lactic acid through an ester bond.

Examples of the polylactic acid include homopolymers of L-lactic acid, homopolymers of D-lactic acid, block copolymers comprising at least one polymer of L-lactic acid and D-lactic acid, and graft copolymers comprising 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-hydroxyvaleric acid, 3-hydroxyvaleric acid, 4-hydroxyvaleric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, 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, tetramethylenediol and 1, 4-hexanedimethanol, polysaccharides such as cellulose, aminocarboxylic acids such as α -amino acids, hydroxycarboxylic acids such as 5-hydroxyvaleric acid, 2-hydroxyhexanoic acid, 3-hydroxyhexanoic acid, 4-hydroxyvalerolactone, 5-hydroxyvalerolactone, delta-and β, and delta-hydroxycaprolactone.

It is known that polylactic acid can be produced using the following method: lactide process via lactide; a direct polymerization method in which lactic acid is heated in a solvent under reduced pressure and polymerized while removing water; and so on.

In polyhydroxybutyrate caproic acid, the copolymerization ratio of 3-hydroxyhexanoic acid (3-hydroxyhexanoate ester) to a copolymer of 3-hydroxybutyrate (3-hydroxybutyrate) and 3-hydroxyhexanoic acid (3-hydroxyhexanoate ester) is preferably 3 to 20 mol%, more preferably 4 to 15 mol%, and still more preferably 5 to 12 mol%, from the viewpoint of the dimensional accuracy of a resin molded article to be obtained.

In the method of measuring the copolymerization ratio of 3-hydroxycaproic acid (3-hydroxycaproic ester), the ratio of caproic ester is used¹H-NMR was calculated from the integrated value of the peak derived from the hexanoate terminus and the integrated value of the peak derived from the butyrate terminus.

The weight average molecular weight (Mw) of the polyester resin 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 the dimensional accuracy of the resin molded article to be obtained.

The weight average molecular weight (Mw) of the polyester resin is a value measured by Gel Permeation Chromatography (GPC). Specifically, GPC molecular weight measurement was performed using HLC-8320GPC (manufactured by Tosoh Corporation) as a measurement device, chloroform as a solvent, and column/TSK gel GMHHR-M + TSK gel GMHHR-M (7.8mml.D.30cm) manufactured by TosohCurtion. The weight average molecular weight (Mw) was calculated from the above measurement results using a molecular weight calibration curve prepared from monodisperse polystyrene standard samples.

The resin (a) having a carbon atom derived from biomass may be used alone, or two or more kinds may be used in combination.

[ plasticizer (C): component (C) ]

Examples of the plasticizer (C) include cardanol compounds, ester compounds other than the ester compound (E) described below, camphor, metal soaps, polyhydric alcohols, and polyalkylene oxides. The plasticizer (C) is preferably a cardanol compound or an ester compound other than the ester compound (E) described below, from the viewpoint of dimensional accuracy of the resin molded product.

The plasticizer (C) may be used alone, or two or more thereof may be used in combination.

The plasticizer (C) is preferably a cardanol compound or an ester compound other than the ester compound (E) in view of easily obtaining a toughness-improving effect by adding the ester compound (E). Hereinafter, cardanol compounds and ester compounds suitable as the plasticizer (C) will be specifically described.

-Cardanol Compound-

The cardanol compound refers to a component (for example, a compound represented by formulae (c-1) to (c-4)) contained in a compound derived from a natural source of cashew nuts or a derivative of the above component.

The cardanol compound may be used alone, or two or more thereof may be used in combination.

The resin composition of the exemplary embodiment may include a mixture of compounds derived from natural sources of cashews as the cardanol compound (hereinafter, also referred to as "cashew-source mixture").

The resin composition of the exemplary embodiment may include a derivative from a cashew source mixture as a cardanol compound. As the derivative derived from the cashew nut-derived mixture, for example, the following mixture and pure substance can be exemplified.

Mixtures prepared by adjusting the composition ratio of the components in the cashew source mixture

Pure substance, which is a specific component separated from the cashew source mixture

Mixtures containing modified products obtained by modifying the components of the cashew source mixture

Mixtures comprising polymers obtained by polymerising components of cashew source mixtures

A mixture comprising a modified polymer obtained by modifying and polymerizing components of the cashew source mixture

A mixture comprising a modified product obtained by: preparing a mixture by adjusting the composition ratio of each component in the cashew source mixture, and further modifying the components in the mixture

A mixture comprising a polymer obtained by the following process: preparing a mixture by adjusting the composition ratio of each component in the cashew source mixture, and polymerizing the components in the mixture

A mixture comprising a modified polymer obtained by the following process: preparing a mixture by adjusting the composition ratio of the components in the cashew source mixture, modifying the components in the mixture and polymerizing

Modified products obtained by further modification of the pure substances

Polymers obtained by further polymerizing the pure substances

Modified polymers obtained by further modifying the pure substances and polymerizing them

Here, the single substance includes multimers such as dimers and trimers.

From the viewpoint of dimensional accuracy of the resin molded article, the cardanol compound is preferably at least one compound selected from the group consisting of a polymer obtained by polymerizing a compound represented by formula (CDN1) and a compound represented by formula (CDN 1).

In formula (CDN1), R¹Represents an alkyl group which may have a substituent, or an unsaturated aliphatic group which may have a double bond and may have a substituent. R²Represents 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 a substituent. P2 represents an integer of 0 to 4. When P2 is 2 or more, a plurality of R's are present²Each may be the same group or different groups.

In formula (CDN1), R¹The 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 further 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 group and methoxy group; and substituents containing an ester bond such as acetyl and propionyl.

Examples of the alkyl group which may have a substituent include pentadecn-1-yl, hept-1-yl, oct-1-yl, non-1-yl, decan-1-yl, undecane-1-yl, dodecane-1-yl and tetradecan-1-yl.

In formula (CDN1), R¹The unsaturated aliphatic group having a double bond and which may have a substituent(s) represented by (a) is preferably an unsaturated aliphatic group having 3 to 30 carbon atoms, more preferably an unsaturated aliphatic group havingAn unsaturated aliphatic group having 5 to 25 carbon atoms, and 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 include the same substituents 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 and pentadec-7, 10, 14-trien-1-yl.

In the formula (CDN1), R is¹Pentadecan-8-en-1-yl, pentadecan-8, 11-dien-1-yl, pentadecan-8, 11, 14-trien-1-yl, pentadecan-7-en-1-yl, pentadecan-7, 10-dien-1-yl and pentadecan-7, 10, 14-trien-1-yl are preferred.

In formula (CDN1), represented by R²Examples 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 R¹The alkyl group which may have a substituent and the unsaturated aliphatic group which has a double bond and may have a substituent are the same as those represented.

The compound represented by formula (CDN1) may be further modified. For example, it may be epoxidized, and specifically, it may be a compound having the following structure: wherein the hydroxyl group of the compound represented by the formula (CDN1) is replaced with the following group (EP), that is, a compound represented by the following formula (CDN 1-e).

In the radicals (EP) and formula (CDN1-e), L_EPRepresents a single bond or a divalent linking group. In the formula (CDN1-e), R¹、R²And P2 each independently with R in formula (CDN1)¹、R²As with P2.

In the radicals (EP) and formula (CDN1-e), L_EPExamples of the divalent linking groups represented includeAlkylene which may have a substituent (preferably alkylene having 1 to 4 carbon atoms, more preferably alkylene having 1 carbon atom) and-CH₂CH₂OCH₂CH₂-a group.

Examples of substituents include R with formula (CDN1)¹The same substituents as in (1).

As L_EPMethylene is preferred.

The polymer obtained by polymerizing the compound represented by the formula (CDN1) is a polymer obtained by polymerizing at least two or more compounds represented by the formula (CDN1) with or without a linking group.

Examples of the polymer obtained by polymerizing the compound represented by the formula (CDN1) include a compound represented by the formula (CDN 2).

In 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. When P21 is 2 or more, a plurality of R's are present²¹May be the same group or different groups; when P22 is 2 or more, a plurality of R's are present²²May be the same group or different groups; when P23 is 2 or more, a plurality of R's are present²³May be the same group or different groups. In the case where n is 2 or more, a plurality of R's are present¹²May be the same group or different groups; in the case where n is 2 or more, a plurality of R's are present²²May be the same group or different groups; in the case where n is 2 or moreLower, plural of L¹May be the same group or different groups; in the case where n is 2 or more, the plural P22 present may be the same number or different numbers.

In the formula (CDN2), as represented by R¹¹、R¹²、R¹³、R²¹、R²²And R²³The alkyl group which may have a substituent and the unsaturated aliphatic group which may have a double bond and may have a substituent are represented by R in the formula (CDN1), and R is preferably exemplified¹The same groups are exemplified.

In formula (CDN2), 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 include R with formula (CDN1)¹The substituents in (1) are the same as the substituents in (2).

In formula (CDN2), n is preferably 1 to 10, more preferably 1 to 5.

The compound represented by formula (CDN2) may be further modified. For example, it may be epoxidized, and specifically, it may be a compound having the following structure: wherein the hydroxyl group of the compound represented by the formula (CDN2) is replaced with the following group (EP), that is, a compound represented by the following formula (CDN 2-e).

In the formula (CDN2-e), R¹¹、R¹²、R¹³、R²¹、R²²、R²³、P21、P22、P23、L¹、L²And n is each independently related to R in formula (CDN2)¹¹、R¹²、R¹³、R²¹、R²²、R²³、P21、P22、P23、L¹And L²And n are respectively the same.

In the formula (CDN2-e), L_EP1、L_EP2And L_EP3Each independently represents a single bond or a divalent linking group. When n is 2 or morePlural of L present_EP2Each may be the same group or different groups.

In the formula (CDN2-e), as represented by L_EP1、L_EP2And L_EP3The divalent linking group represented is preferably exemplified by the group represented by L in the formula (CDN1-e)_EPThe divalent linking groups represented are exemplified by the same groups.

The polymer obtained by polymerizing the compound represented by formula (CDN1) may be, for example, a polymer obtained by three-dimensionally crosslinking and polymerizing at least three or more compounds represented by formula (CDN1) with or without a linking group. Examples of the polymer obtained by three-dimensionally crosslinking and polymerizing the compound represented by formula (CDN1) include a compound represented by the following formula.

In the above formula, R¹⁰、R²⁰And P20 are each related to R in formula (CDN1)¹、R²As with P2. L is¹⁰Represents a single bond or a divalent linking group. Multiple existence of R¹⁰May be the same group or different groups, a plurality of R being present²⁰May be the same group or different groups, and a plurality of L's present¹⁰May be the same group or different groups. The plurality of P20 present may be the same number or a different number.

In the above formula, 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 include R with formula (CDN1)¹The substituents in (1) are the same as the substituents in (2).

The compound represented by the above formula may be further modified, for example, it may be epoxidized. Specifically, it may be a compound having the following structure: wherein a hydroxyl group of the compound represented by the above formula is replaced with a group (EP), and examples thereof include a compound represented by the following formula, that is, a polymer obtained by three-dimensionally crosslinking and polymerizing a compound represented by the formula (CDN 1-e).

In the above formula, R¹⁰、R²⁰And P20 are each related to R in formula (CDN1-e)¹、R²And P2 are the same. L is¹⁰Represents a single bond or a divalent linking group. Multiple existence of R¹⁰May be the same group or different groups, a plurality of R being present²⁰May be the same group or different groups, and a plurality of L's present¹⁰May be the same group or different groups. The plurality of P20 present may be the same number or a different number.

In the above formula, 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 include R with formula (CDN1)¹The substituents in (1) are the same as the substituents in (2).

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 dimensional accuracy of the resin molded product.

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, and NX-9203, prepared by Cardolite, and LB-7000, LB-7250, and CD-5L, prepared by Tohoku Chemical Industries, Ltd. Examples of commercially available products of cardanol compounds with epoxy groups include NC-513, NC-514S, NC-547, LITE513E and Ultra LTE 513 prepared from Cardolite. .

From the viewpoint of dimensional accuracy of the resin molded product, the hydroxyl value of the cardanol compound is preferably 100mgKOH/g or more, more preferably 120mgKOH/g, and still more preferably 150 mgKOH/g. The hydroxyl value of the cardanol compound was measured according to method a of ISO 14900.

In the case of using a cardanol compound having an epoxy group as the cardanol compound, the epoxy equivalent weight is preferably 300 to 500, more preferably 350 to 480, and even more preferably 400 to 470, from the viewpoint of improving the dimensional accuracy of the resin molded product. The measurement of the epoxy equivalent of the cardanol compound having an epoxy group was performed according to ISO 3001.

The molecular weight of the cardanol compound is preferably 250 to 1,000, more preferably 280 to 900, and still more preferably 300 to 800, from the viewpoint that the toughness-improving effect is easily obtained by adding component (B).

-ester compound-

The ester compound as the plasticizer (C) contained in the resin composition of the exemplary embodiment is not particularly limited as long as it is an ester compound other than the compounds represented by formulae (1) to (5).

Examples of the ester compound contained as the plasticizer (C) include dicarboxylic acid diesters, citric acid esters, polyether ester compounds, benzoic acid glycol esters, compounds represented by formula (6), and epoxidized fatty acid esters. Examples of such esters include monoesters, diesters, triesters, and polyesters.

In the 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 specific form and preferred form of the group represented are the same.

R⁶²The group represented may be a saturated aliphatic hydrocarbon group or may be an unsaturated aliphatic hydrocarbon group, and is preferably a saturated aliphatic hydrocarbon group. R⁶²The group represented may be a straight-chain aliphatic hydrocarbon group, may be a branched aliphatic hydrocarbon group, may be an aliphatic hydrocarbon group containing an alicyclic ring, and is preferably a branched aliphatic hydrocarbon group. R⁶²Of the representationThe group 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, 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.

Specific examples of the ester compound contained as the plasticizer (C) include adipates, citrates, sebacates, azelates, phthalates, acetates, dibasic esters, phosphates, condensed phosphates, glycol esters (e.g., benzoic acid glycol esters), and modifications 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.

In the ester compound contained as the plasticizer (C) in the resin composition of the exemplary embodiment, the molecular weight (or weight average molecular weight) 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 measured according to the method for measuring the weight average molecular weight of the cellulose acylate (a), unless otherwise specified.

As the plasticizer (C), adipate is preferable. The adipic acid ester has high affinity with the cellulose acylate (a) and is dispersed in a state almost uniform with the cellulose acylate (a), and therefore the thermal fluidity is improved more than that of the other plasticizer (C).

Examples of adipic acid esters include adipic acid diesters and adipic acid polyesters. Specific examples thereof include adipic acid diesters represented by the formula (AE) and adipic acid polyesters represented by the formula (APE).

In formula (AE), R^AE1And R^AE2Each independently represents an alkyl group or a polyoxyalkyl [ - (C)_xH_2x-O)_y-R^A1](where R is^A1Represents an alkyl group, x represents an integer of 1 to 10, and y represents an integer of 1 to 10).

In formula (APE), R^AE1And R^AE2Each independently being alkyl or polyoxyalkyl [ - (C)_xH_2x-O)_y-R^A1](where R is^A1Represents an alkyl group, x represents an integer of 1 to 10, and y represents an integer of 1 to 10), R^AE3Represents an alkylene group. m1 represents an integer of 1 to 10, and m2 represents an integer of 1 to 20.

In the formulae (AE) and (APE), R^AE1And R^AE2The 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. R^AE1And R^AE2The alkyl group represented may be any of a straight-chain alkyl group, a branched alkyl group, and a cyclic alkyl group, and is preferably a straight-chain alkyl group or a branched alkyl group.

In the formulae (AE) and (APE), in R^AE1And R^AE2Polyoxyalkyl [ - (C) of_xH_2x-O)_y-R^A1]In, R^A1The 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. R^A1The alkyl group represented may be any of a straight-chain alkyl group, a branched alkyl group, and a cyclic alkyl group, and is preferably a straight-chain alkyl group or a branched alkyl group.

In formula (APE), R^AE3The alkylene 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 any of a linear alkylene group, a branched alkylene group, and a cyclic alkylene group, and is preferably a linear alkylene group or a branched alkylene group.

In formula (APE), m1 is preferably an integer of 1 to 5, and m2 is preferably an integer of 1 to 10.

In the 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, and further preferably 300 to 1000. The weight average molecular weight of adipate is a value measured according to the method of measuring the weight average molecular weight of cellulose acylate (a).

As the adipate ester, a mixture of the adipate ester with other components may be used. Examples of commercially available products of the mixture include daicatty 101 manufactured by Daihachi Chemical Industry co., ltd.

As the hydrocarbon group at the terminal of the fatty acid ester (e.g., citrate ester, sebacate ester, azelate ester, phthalate ester, and acetate ester), an aliphatic hydrocarbon group is preferable, and an alkyl group having 1 to 12 carbon atoms is preferable, an alkyl group having 4 to 10 carbon atoms is more preferable, and an alkyl group having 8 carbon atoms is further preferable. The alkyl group may be any of a straight-chain alkyl group, a branched alkyl group, and a cyclic alkyl group, and is preferably a straight-chain alkyl group or a branched alkyl group.

Examples of fatty acid esters (e.g., citrate, sebacate, azelate, phthalate, and acetate) include esters of fatty acids and alcohols. Examples of alcohols include: monohydric alcohols such as methanol, ethanol, propanol, butanol and 2-ethylhexanol; polyhydric alcohols such as glycerin, polyglycerin (diglycerin and the like), 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 acid, palmitoleic acid, vaccenic acid, linoleic acid, linolenic acid, and nervonic acid) is epoxidized. Examples of alcohols include: monohydric alcohols such as methanol, ethanol, propanol, butanol and 2-ethylhexanol; polyhydric alcohols such as glycerin, polyglycerin (diglycerin and the like), 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 ADEKA CIZER D-32, D-55, O-130P and O-180A (manufactured by ADEKA CORPORATION), SANSO CIZER E-PS, nE-PS, E-PO, E-4030, E-6000, E-2000H and E-9000H (manufactured by New Japan Chemical Co., Ltd.).

The polyester unit of the polyetherester compound may be aromatic or aliphatic (including alicyclic), and the polyether unit of the polyetherester compound may be aromatic or aliphatic (including alicyclic). The weight ratio of polyester units to polyether units 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 further preferably 300 to 1000. Examples of commercially available products of polyether ester compounds include ADEKA CIZER RS-1000 (manufactured by ADEKA CORPORATION).

As the polyether compound having at least one unsaturated bond in the molecule, a polyether compound having an allyl group at the terminal is exemplified, and a polyalkylene glycol allyl ether is preferable. The molecular weight (or weight average molecular weight) of the polyether compound having at least one unsaturated bond in the molecule is preferably 250 to 2000, more preferably 280 to 1500, and further preferably 300 to 1000. Examples of commercially available products of polyether compounds having at least 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 (manufactured by NOF CORPORATION).

< Compound (C) of at least one selected from the group consisting of hindered phenol compound, tocopherol compound, tocotrienol compound, phosphite compound and hydroxylamine compound: component (C) >

The resin composition of the exemplary embodiment further includes a compound (C).

The compound (C) 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.

When various additives are mixed in the bio-resin (a), these compounds (C) are used as, for example, a stabilizer (mixing stabilizer), so that the dimensional accuracy of the resin molded article can be more easily improved.

Hindered phenol compounds

The hindered phenol compound in the exemplary embodiment refers to a compound in which at least one of the ortho positions to the hydroxyl group of phenol is substituted with an alkyl group. The alkyl group is preferably a bulky alkyl group such as a tert-butyl or tert-amyl (1, 1-dimethylpropyl) group.

Examples of the hindered phenol compound include compounds represented by the formula (HP 1).

In the formula (HP1), R¹¹And R¹²Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, L¹¹Represents a single bond or a divalent linking group, X¹¹Represents a single bond or an n-valent group, and n represents 1,2, 3 or 4.

As a group consisting of 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 group having 1 to 6 carbon atoms represented may be linear, branched or cyclic, and is preferably a linear or branched alkyl group.

As a group consisting of R¹¹The alkyl group having 1 to 6 carbon atoms represented by (a) is, specifically, 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 and a1, 1-dimethylbutyl group, more preferably a methyl group, a tert-butyl group or a tert-pentyl group, and further preferably a methyl group or a tert-butyl.

As a group consisting of 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 group having 1 to 6 carbon atoms represented may be linear, branched or cyclic, and is preferably a linear or branched alkyl group.

As a group consisting of R¹²The alkyl group having 1 to 6 carbon atoms represented by (a) is, specifically, 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 and a1, 1-dimethylbutyl group, more preferably a methyl group, an ethyl group, a n-propyl group or an isopropyl group, and further preferably a methyl group or an ethyl group.

As a group consisting of R¹¹The group represented is preferably a hydrogen atom, a methyl group, a tert-butyl group or a tert-pentyl group.

As a group consisting of R¹²The group represented is preferably a hydrogen atom, a methyl group or an ethyl group.

R¹¹And R¹²May be bonded to each other to form a ring.

As a result of L¹¹Examples of the divalent linking group include an alkylene group having 1 to 6 carbon atoms (preferably an alkylene group having 1 to 4 carbon atoms), -R-C (═ O) O-R' -, and the like. Here, 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-。

As a result of X¹¹Examples of the monovalent group include aliphatic hydrocarbon groups.

The aliphatic hydrocarbon group may be straight-chain, branched, or contain an alicyclic ring. From the viewpoint of ease of dispersion of the compound represented by formula (HP1) in the bio-resin (a) and from the viewpoint of high dimensional accuracy, the aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group containing no alicyclic ring (i.e., a chain aliphatic hydrocarbon group), and more preferably a linear aliphatic hydrocarbon group.

The aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group, as well as an unsaturated aliphatic hydrocarbon group. The aliphatic hydrocarbon group is preferably a saturated aliphatic hydrocarbon group from the viewpoint of easy dispersion of the compound represented by the formula (HP1) in the bio-resin (a) and from the viewpoint of high dimensional accuracy.

From the viewpoint of ease of dispersion of the compound represented by the formula (HP1) in the bio-resin (a) and from the viewpoint of high dimensional accuracy, the number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 24, more preferably 6 to 20, and further more preferably 12 to 18.

Specific examples of the aliphatic hydrocarbon group include those for Y in the formula (P1) described below⁴¹Those mentioned are the same groups.

As specific examples of the aliphatic hydrocarbon group, a straight-chain alkyl group having 6 to 20 carbon atoms is preferable, a straight-chain alkyl group having 12 to 18 carbon atoms is more preferable, and a straight-chain alkyl group having 16 to 18 carbon atoms is even more preferable.

As a result of X¹¹As the divalent group represented, there may be mentioned 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 group) 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-or- (CH)₂-O-CH₂)₂-。

As a result of X¹¹The divalent group represented by (A) may be the following group (HP 1-a). Is represented by¹¹The bonding position of (2).

In (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.

As a result of X¹¹As the trivalent group represented, a group obtained by removing three hydrogen atoms from an alkane having 1 to 6 carbon atoms (preferably an alkane having 1 to 4 carbon atoms) (an alkanetriyl group) can be mentioned.

As a result of X¹¹Examples of the trivalent group include the following (HP1-b) and (HP1)-c). Is represented by¹¹The bonding position of (2).

In (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.

As a result of X¹¹As the tetravalent group represented, there may be mentioned a group (an alkanetetrayl group) 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 group is preferred.

In case n is 2,3 or 4, a plurality of R's are present¹¹R, which may be the same or different, being present in a plurality¹²Can be the same group or different groups, a plurality of L being present¹¹May be the same group or different groups.

Specific examples of the compound represented by the formula (HP1) include: "Irganox 1010", "Irganox 245", and "Irganox 1076", manufactured by BASF; "ADK STAB AO-80", "ADK STAB AO-60", "ADK STAB AO-50", "ADK STAB AO-40", "ADK STAB AO-30", "ADK STAB AO-20" and "ADK STAB AO-330", manufactured by ADEKACORPORATION; and "Sumilizer GA-80", "Sumilizer GM", and "Sumilizer GS", manufactured by Sumitomo Chemical Company, Limited.

Examples of the hindered phenol compound include compounds represented by the formula (HP 2).

In formula (HP2), R²¹、R²²、R²³、R²⁴And R²⁵Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

As a group consisting of R²¹Alkyl groups having 1 to 6 carbon atoms, preferably 4 to 6 carbon atoms, more preferably 4 or 5 carbon atoms are represented. From R²¹The alkyl group having 1 to 6 carbon atoms represented may be linear, branched or cyclic, and is preferably a linear or branched alkyl group, more preferably a branched alkyl group.

As a group consisting of R²¹The alkyl group having 1 to 6 carbon atoms represented by (a) is, specifically, 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 and 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.

As a group consisting of 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 group having 1 to 6 carbon atoms represented may be linear, branched or cyclic, and is preferably a linear or branched alkyl group.

As a group consisting of R²²The alkyl group having 1 to 6 carbon atoms represented is, specifically, 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 and a1, 1-dimethylbutyl group, more preferably a methyl group, a tert-butyl group or a tert-pentyl group.

From R²³The particular and preferred forms of the radicals indicated and for R²¹Those described are the same.

From R²⁴The particular and preferred forms of the radicals indicated and for R²²Those described are the same.

As a group consisting of 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 group having 1 to 6 carbon atoms represented may be linear, branched or cyclic, and is preferably a linear or branched alkyl group.

As byR²⁵The alkyl group having 1 to 6 carbon atoms represented by (a) 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 and 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.

As a group consisting of R²¹The group represented is preferably a tert-butyl group or a tert-pentyl group.

As a group consisting of R²²The group represented is preferably a methyl group, a tert-butyl group or a tert-pentyl group.

As a group consisting of R²³The group represented is preferably a tert-butyl group or a tert-pentyl group.

As a group consisting of R²⁴The group represented is preferably a methyl group, a tert-butyl group or a tert-pentyl group.

As a group consisting of R²⁵The group represented is preferably a hydrogen atom, a methyl group or an ethyl group.

Specific examples of the compound represented by the formula (HP2) include "Sumilizer GM" and "Sumilizer GS" manufactured by Sumitomo Chemical Company, Limited.

Tocopherol compounds and tocotrienol compounds

Examples of the tocopherol compound or the tocotrienol compound include compounds represented by the following formula (T1).

In the 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, and is preferably a linear or branched alkyl group.

As a group consisting of R³¹The alkyl group having 1 to 3 carbon atoms represented by (a) is, specifically, preferably a methyl group, an ethyl group, an n-propyl group and an isopropyl group, more preferably a methyl group or an ethyl group, and still more preferably a methyl group.

As a group consisting of R³¹The group represented is particularly preferably a hydrogen atom or a methyl group.

From R³²The particular and preferred forms of the radicals indicated and for R³¹Those described are the same.

From R³³The particular and preferred forms of the radicals indicated and for 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 formula (P1).

In the 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, m₄₂Represents 0 or 1. Here, n is₄₁+m₄₁+m₄₂＝3。

As a group consisting of 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 group having 1 to 12 carbon atoms represented may be linear, branched or cyclic, and is preferably a linear or branched alkyl group.

As a group consisting of R⁴¹Specific examples of the alkyl group having 1 to 12 carbon atoms include methyl group,Ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, isohexyl, sec-hexyl, tert-hexyl, n-heptyl, isoheptyl, sec-heptyl, tert-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, sec-nonyl, tert-nonyl, n-decyl, isodecyl, sec-decyl, tert-decyl, n-undecyl, isoundecyl, sec-dodecyl, tert-dodecyl, n-dodecyl, isododecyl, sec-dodecyl and tert-dodecyl.

As a group consisting of R⁴²As the alkyl group having 1 to 12 carbon atoms, those represented by the formula⁴¹Those same forms of alkyl are described.

As a group consisting of R⁴³As the alkyl group having 1 to 12 carbon atoms, those represented by the formula⁴¹The same forms as those described.

As a group consisting of R⁴¹The group represented is preferably a hydrogen atom, a methyl group or a tert-butyl group.

As a group consisting of 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.

As a group consisting of 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 R's are present⁴¹R, which may be the same or different, being present in a plurality⁴²R, which may be the same or different, being present in a plurality⁴³May be the same group or different groups.

At n₄₁In the case of 2 or 3, a plurality of R's are present⁴¹May be linked to each other to form a ring, a plurality of R's being present⁴³May be linked to each other to form a ring, or R⁴¹And R⁴³May be connected to each other to form a ring.

From Y⁴¹The aliphatic hydrocarbon groups represented may be linear, branched or cycloaliphatic. From the viewpoint of easy dispersion of the compound represented by the formula (P1) in the bio-resin (A) and from the viewpoint of high dimensional accuracyFrom Y⁴¹The group represented is preferably an aliphatic hydrocarbon group containing no alicyclic group (i.e., a chain aliphatic hydrocarbon group), and more preferably a straight-chain 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 of easy dispersion of the compound represented by the formula (P1) in the bio-resin (A) and from the viewpoint of high dimensional accuracy, by Y⁴¹The aliphatic hydrocarbon group represented is preferably a saturated aliphatic hydrocarbon group.

From the viewpoint of easy dispersion of the compound represented by the formula (P1) in the bio-resin (A) and from the viewpoint of high dimensional accuracy, by Y⁴¹The number of carbon atoms of the aliphatic hydrocarbon group represented is preferably 1 to 20, more preferably 1 to 12, and still more preferably 2 to 8.

From Y⁴²Specific and preferred forms of the aliphatic hydrocarbon groups represented with respect to 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 "Irgafos 38" (bis (2, 4-di-tert-butyl-6-methylphenyl) -ethyl-phosphite) manufactured by BASF.

In the formula (P1), n₄₁In the case of 3, the compound represented by formula (P1) is a compound represented by formula (P1-a).

R in the formula (P1-a)⁴¹、R⁴²And R⁴³And R in the formula (P1)⁴¹、R⁴²And R⁴³The same is true.

Specific examples of the compound represented by the formula (P1-a) include "Irgafos 168" manufactured by BASF and "Irgafos TNPP" manufactured by BASF.

Examples of the phosphite ester compound include compounds represented by the formula (P2).

In the 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.

As a group consisting of 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 group having 1 to 12 carbon atoms represented may be linear, branched or cyclic, and is preferably a linear or branched alkyl group.

As a group consisting of R⁵¹Specific examples of the alkyl group having 1 to 12 carbon atoms 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, sec-decyl group, tert-decyl group, n-undecyl group, isoundecyl group, sec-dodecyl group, tert-dodecyl group, n-dodecyl group.

As a group consisting of R⁵²As the alkyl group having 1 to 12 carbon atoms, those represented by the formula⁵¹The same forms as those described.

As a group consisting of R⁵³The alkyl group having 1 to 12 carbon atoms represented by the formulaFor R⁵¹The same forms as those described.

As a group consisting of R⁵⁴As the alkyl group having 1 to 12 carbon atoms, those represented by the formula⁵¹The same forms as those described.

As a group consisting of R⁵⁵As the alkyl group having 1 to 12 carbon atoms, those represented by the formula⁵¹The same forms as those described.

As a group consisting of R⁵⁶As the alkyl group having 1 to 12 carbon atoms, those represented by the formula⁵¹The same forms as those described.

As a group consisting of R⁵¹The group represented is preferably a hydrogen atom, a methyl group or a tert-butyl group.

As a group consisting of 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.

As a group consisting of R⁵³The group represented is preferably a hydrogen atom, a methyl group or a tert-butyl group.

As a group consisting of R⁵⁴The group represented is preferably a hydrogen atom, a methyl group or a tert-butyl group.

As a group consisting of 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.

As a group consisting of R⁵⁶The group represented is preferably a hydrogen atom, a methyl group or a tert-butyl group.

As a result of L⁵¹The divalent linking group represented is exemplified by alkylene and arylene groups, preferably alkylene or phenylene groups having 1 to 6 carbon atoms, and more preferably alkylene or phenylene groups having 1 to 4 carbon atoms.

Specific examples of the compound represented by the formula (P2) include "Irgafos P-EPQ" manufactured by BASF.

Examples of the phosphite ester compound include compounds represented by the formula (P3).

In the 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.

As a group consisting of 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 group having 1 to 12 carbon atoms represented may be linear, branched or cyclic, and is preferably a linear or branched alkyl group.

As a group consisting of R⁶¹Specific examples of the alkyl group having 1 to 12 carbon atoms 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, sec-decyl group, tert-decyl group, n-undecyl group, isoundecyl group, sec-dodecyl group, tert-dodecyl group, n-dodecyl group.

As a group consisting of R⁶²As the alkyl group having 1 to 12 carbon atoms, those represented by the formula⁶¹The same forms as those described.

As a group consisting of R⁶³As the alkyl group having 1 to 12 carbon atoms, those represented by the formula⁶¹The same forms as those described.

As a group consisting of R⁶⁴As the alkyl group having 1 to 12 carbon atoms, those represented by the formula⁶¹The same forms as those described.

As a group consisting of R⁶⁵As the alkyl group having 1 to 12 carbon atoms, those represented by the formula⁶¹The same forms as those described.

As a group consisting of R⁶⁶As the alkyl group having 1 to 12 carbon atoms, there may be mentionedAnd for R⁶¹The same forms as those described.

As a group consisting of R⁶¹The group represented is preferably a hydrogen atom, a methyl group or a tert-butyl group.

As a group consisting of 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.

As a group consisting of R⁶³The group represented is preferably a hydrogen atom, a methyl group or a tert-butyl group.

As a group consisting of 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.

As a group consisting of R⁶⁵The group represented is preferably a hydrogen atom, a methyl group, a tert-butyl group or a tert-pentyl group.

As a group consisting of 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 them is preferably an alkyl group, and the alkyl group is preferably a tert-butyl group or a tert-amyl group.

As a result of L⁶¹The divalent linking group represented is exemplified by alkylene groups, and preferably alkylene groups having 1 to 3 carbon atoms, more preferably alkylene groups having either 1 or 2 carbon atoms.

As L⁶¹Particularly preferred is a single bond or a methylene group.

As a result of L⁶²The divalent linking group represented is exemplified by alkylene and arylene, and alkylene or phenylene having 1 to 6 carbon atoms is preferable, and alkylene or phenylene having 1 to 4 carbon atoms is more preferable.

Specific examples of the compound represented by the formula (P3) include "Sumilizer GP" manufactured by Sumitomo Chemical Company, Limited.

Hydroxylamine compounds

The hydroxylamine compounds in exemplary embodiments are compounds having the following structure: wherein at least one hydroxyl group is directly bonded to the nitrogen atom of the amine. As the hydroxylamine compound, N-dialkylhydroxylamine is preferable.

Examples of the hydroxylamine compound include compounds represented by the formula (HA 1).

In formula (HA1), R⁷¹And R⁷²Each independently represents an alkyl group having 14 to 20 carbon atoms.

As a group consisting of R⁷¹The alkyl group having 14 to 20 carbon atoms represented may use any of a straight-chain alkyl group, a branched alkyl group and an alicyclic group-containing alkyl group, preferably a straight-chain or branched 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 alkyl group, the number of branches in the alkyl group is preferably 1 to 3, more preferably 1 or 2, and still more preferably 1.

As a group consisting of R⁷¹The alkyl groups represented have 14 to 20 carbon atoms, preferably straight-chain or branched alkyl groups having 16 to 18 carbon atoms, particularly preferably straight-chain alkyl groups having 16 to 18 carbon atoms.

From R⁷²The particular and preferred forms of the radicals indicated and for 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 formula (HA1) include "Irgastab FS-042" manufactured by BASF.

The compound (C) may be used alone or in combination of two or more. The form in which two or more kinds are used in combination may be any of the following forms: the form of using two or more (e.g., two or more hindered phenol compounds) in the same class in combination, and the form of using two or more (e.g., hindered phenol compound and tocopherol compound) in different classes in combination.

A form in which at least one selected from the group consisting of hindered phenol compounds and hydroxylamine compounds is used in combination with at least one selected from phosphite compounds is preferable.

[ other additives ]

< < thermoplastic elastomer (D): component (D) >

The resin composition of the exemplary embodiment may further include a thermoplastic elastomer (D).

The thermoplastic elastomer (D) is at least one thermoplastic elastomer selected from the group consisting of a polymer (D1) having a core-shell structure, a polymer (D2) having a core-shell structure, an olefin polymer (D3), a styrene-ethylene-butadiene-styrene copolymer (D4), polyurethane (D5) and polyester (D6), the polymer (D1) has a core layer comprising a butadiene polymer and a shell layer comprising a polymer selected from a styrene polymer and an acrylonitrile-styrene polymer on the surface of the core layer, the polymer (D2) has a core layer and a shell layer comprising a polymer containing an alkyl (meth) acrylate on the surface of the core layer, and the olefin polymer (D3) is a polymer of an α -olefin and an alkyl (meth) acrylate and contains 60% by weight or more of structural units derived from the α -olefin.

The thermoplastic elastomer (D) is, for example, a thermoplastic elastomer having elasticity at normal temperature (25 ℃) and softening properties similar to those of a thermoplastic resin at high temperature.

(Polymer having core-Shell Structure (d 1): component (d1))

The polymer having a core-shell structure (d1) is a polymer having a core-shell structure having a core layer and a shell layer located on the surface of the core layer.

The polymer having a core-shell structure (d1) is a polymer having a core layer as an innermost layer and a shell layer as an outermost layer (specifically, a polymer obtained by graft polymerizing a styrene polymer or an acrylonitrile-styrene polymer to a core layer containing a butadiene polymer to form a shell layer).

One or more other layers (e.g., 1 to 6 other layers) may be provided between the core layer and the shell layer. The polymer having a core-shell structure (d1) is a polymer obtained by graft-polymerizing a plurality of polymers onto a polymer serving as a core layer to form a multilayered polymer in the case of containing other layers.

The core layer containing a butadiene polymer is not particularly limited as long as it is a polymer obtained by polymerizing a butadiene-containing component, and may be a core layer of a butadiene homopolymer, but also a core layer of a copolymer of butadiene and other monomers, examples of the other monomers include vinyl aromatic compounds, among vinyl aromatic compounds, styrene components such as styrene, alkyl-substituted styrene (e.g., α -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-ethylstyrene, 3-ethylstyrene and 4-ethylstyrene) and halogen-substituted styrene (e.g., 2-chlorostyrene, 3-chlorostyrene and 4-chlorostyrene) may be used, styrene components may be used alone or in combination of two or more.

In particular, the core layer containing a butadiene polymer may be, for example, a homopolymer of butadiene, may be a copolymer of butadiene and styrene, or may be a terpolymer of butadiene, styrene and divinylbenzene.

In the butadiene polymer contained in the core layer, the proportion of the structural unit derived from butadiene is preferably 60 to 100% by weight (preferably 70 to 100% by weight), and the proportion of the structural unit derived from the other monomer (preferably styrene component) is 0 to 40% by weight (preferably 0 to 30% by weight). For example, as the proportion of the structural unit derived from each monomer constituting the butadiene polymer, butadiene is 60 to 100% by weight, styrene is 0 to 40% by weight, and divinylbenzene may be contained in an amount of 0 to 5% by weight of 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, and may be a shell layer of a styrene homopolymer or a copolymer of styrene and other monomers. Examples of the styrene component include the same components as those exemplified for 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, and octadecyl (meth) acrylate). In the alkyl (meth) acrylate, at least a part of hydrogen of the alkyl chain may be substituted. Examples of the substituent include amino, hydroxyl and halogen groups. The alkyl (meth) acrylate may be used alone or in combination of two or more. As other monomers, polyfunctional monomers such as allyl (meth) acrylate, triallyl isocyanurate, and divinylbenzene may be used. The styrene polymer contained in the shell layer may be a copolymer of 85 to 100% by weight of a styrene component and 0 to 15% by weight of other monomer components (preferably, alkyl (meth) acrylate).

Among them, the styrene polymer contained in the shell layer is preferably a copolymer of styrene and an alkyl (meth) acrylate. From the same viewpoint, a copolymer of styrene and an alkyl (meth) acrylate having an alkyl chain of 1 to 8 carbon atoms is preferable, and a polymer of an alkyl (meth) acrylate having an alkyl chain of 1 to 4 carbon atoms is more preferable.

The shell layer containing the acrylonitrile-styrene polymer is a shell layer containing 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% by weight of an acrylonitrile component and 20 to 90% by weight of a styrene component. Examples of the styrene component copolymerized with the acrylonitrile component include the same components as the styrene component exemplified for the core layer. As the acrylonitrile-styrene polymer contained in the shell layer, polyfunctional monomers such as allyl (meth) acrylate, triallyl isocyanurate, and divinylbenzene can be used.

Examples of one or more other layers disposed between the core layer and the shell layer include the polymer layers described for the shell layer.

The weight ratio of the shell layer is preferably 1 to 40% by weight, more preferably 3 to 30% by weight, and further preferably 5 to 15% by weight, relative to the entire core-shell structure.

Among the components (d1), examples of commercially available products of the core-shell structured polymer (d1) having a core layer comprising a butadiene polymer and a shell layer containing a styrene polymer on the core layer include "METABLEN" (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 Limited.

Among the components (d1), examples of commercially available products of the core-shell structured polymer (d1) having a core layer comprising a butadiene polymer and a shell layer containing an acrylonitrile-styrene polymer on the surface of the core layer include "blendex" (registered trademark) prepared by Galata Chemicals and "ELIX" prepared by ELIX POLYMERS.

(Polymer having core-Shell Structure (d 2): component (d2))

The polymer having a core-shell structure (d2) is a polymer having a core-shell structure having a core layer and a shell layer on the surface of the core layer.

The polymer having a core-shell structure (d2) is a polymer having a core layer as the innermost layer and a shell layer as the outermost layer (in particular, a polymer in which a shell layer is formed by graft polymerizing an alkyl (meth) acrylate polymer onto a polymer serving as a core layer).

One or more other layers (e.g., 1 to 6 other layers) may be provided between the core layer and the shell layer. The polymer having a core-shell structure (d2) is a polymer obtained by graft polymerizing a plurality of polymers onto a polymer serving as a core layer to form a multilayered polymer, in the case where other layers are included.

Examples of the rubber layer include a (meth) acrylic rubber layer, a silicone rubber layer, a styrene rubber layer, a conjugated diene rubber layer, an α -olefin rubber layer, a nitrile rubber layer, a polyurethane rubber layer, a polyester rubber layer, a polyamide rubber layer, and a copolymer rubber layer of two or more of these rubbers.

Among them, the rubber layer is preferably a (meth) acrylic rubber layer, a silicone rubber layer, a styrene rubber layer, a conjugated diene rubber layer, an α -olefin rubber layer, and a copolymer rubber layer of two or more of these rubbers.

The rubber layer may be a rubber layer obtained by copolymerizing and crosslinking a crosslinking agent (divinylbenzene, allyl acrylate, butylene glycol diacrylate, or the like).

Examples of the (meth) acrylic rubber include polymer rubbers obtained by polymerizing (meth) acrylic components (alkyl esters of (meth) acrylic acid having 2 to 8 carbon atoms, and the like).

Examples of silicone rubbers include rubbers made from polysiloxane components (polydimethylsiloxane, polyphenylsiloxane, etc.).

Examples of the styrene rubber include polymer rubbers obtained by polymerizing styrene components (styrene, α -methylstyrene, etc.).

Examples of the conjugated diene rubber include polymer rubbers obtained by polymerizing conjugated diene components (butadiene, isoprene, etc.).

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 polysiloxane component, a copolymer rubber obtained by polymerizing a (meth) acrylic component, a conjugated diene, and a styrene component.

Examples of the alkyl (meth) acrylate among the polymers 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, and octadecyl (meth) acrylate. In the alkyl (meth) acrylate, at least a part of hydrogen of the alkyl chain may be substituted. Examples of the substituent include amino, hydroxyl and halogen groups.

Among these, the polymer of the alkyl (meth) acrylate is preferably a polymer of an alkyl (meth) acrylate having an alkyl chain with 1 to 8 carbon atoms, more preferably a polymer of an alkyl (meth) acrylate having an alkyl chain with 1 or 2 carbon atoms, and still more preferably a polymer of an alkyl (meth) acrylate having an alkyl chain with 1 carbon atom.

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, and an alkyl (meth) acrylate.

Examples of the glycidyl group-containing vinyl compound include glycidyl (meth) acrylate, glycidyl itaconate, diglycidyl itaconate, allyl glycidyl ether, styrene-4-glycidyl ether, and 4-glycidylstyrene.

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.

Examples of one or more other layers provided between the core layer and the shell layer include the polymer layers described for the shell layer.

The weight ratio of the shell layer is preferably 1 to 40% by weight, more preferably 3 to 30% by weight, and further preferably 5 to 15% by weight, relative to the entire core-shell structure.

The polymer having a core-shell structure (d2) can be prepared by known methods.

An emulsion polymerization method is a known method. Specifically, the following method is exemplified as the preparation method. First, a core particle (core layer) is prepared by emulsion polymerization of a monomer mixture, and then a mixture of other monomers is emulsion polymerized in the presence of the core particle (core layer) to form a polymer having a core-shell structure in which a shell layer is formed around the core particle (core layer).

In the case where other layers are formed between the core layer and the shell layer, emulsion polymerization of a mixture of other monomers is repeatedly performed to obtain a polymer having a core-shell structure composed of the objective core layer, other layers, and shell layer.

Examples of commercially available products of the polymer having a core-shell structure (d2) include "METABLEN" (registered trademark) manufactured by Mitsubishi Chemical Corporation, "KANE ACE" (registered trademark) manufactured by Kaneka Corporation, "PARALOID" (registered trademark) manufactured by Dow Chemical Japan Limited, "STAPHYLOID" (registered trademark) manufactured by Aica Kogyo company Limited, and "PARAFACE" (registered trademark) manufactured by KURAY Co., Ltd.

The average primary particle diameter of the polymer having a core-shell structure (d1) and the polymer having a core-shell structure (d2) is not particularly limited, and it is preferably from 50nm to 500nm, more preferably from 50nm to 400nm, further preferably from 100nm to 300nm, particularly preferably from 150nm to 250 nm.

The average primary particle diameter refers to a value measured by the following method. The average primary particle diameter is a number average primary particle diameter, which is an average of primary particle diameters of 100 particles. Each primary particle diameter is the maximum diameter in each primary particle, and is measured by observing the particles with a scanning electron microscope. Specifically, the average primary particle diameter is obtained by observing the polymer having a core-shell structure in a dispersed form in the resin composition with a scanning electron microscope.

(olefin Polymer (d 3): component (d3))

The olefin polymer (d3) is a polymer of α -olefin and alkyl (meth) acrylate, and is preferably an olefin polymer containing 60% by weight or more of a structural unit derived from α -olefin.

Among the olefin polymers, α -olefins are exemplified by ethylene, propylene and 2-methylpropene, α -olefins having 2 to 8 carbon atoms are preferable, α -olefins having 2 or 3 carbon atoms are more preferable, and among them, ethylene is more preferable.

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, and octadecyl (meth) acrylate, preferred are alkyl (meth) acrylates having an alkyl chain with a carbon number of 1 to 8, more preferred are alkyl (meth) acrylates having an alkyl chain with a carbon number of 1 to 4, and further preferred are alkyl (meth) acrylates having an alkyl chain with a carbon number of 1 or 2.

The olefin polymer is preferably a polymer of ethylene and methyl acrylate.

In the olefin polymer, the structural unit derived from α -olefin is preferably 60 to 97% by weight, more preferably 70 to 85% by weight.

The olefin polymer may have other structural units in addition to the structural unit derived from α -olefin and the structural unit derived from alkyl (meth) acrylate, here, the other structural units may be 10% by weight or less with respect to the entire structural units in the olefin polymer.

(styrene-ethylene-butadiene-styrene copolymer (d 4): component (d4))

The copolymer (d4) is not particularly limited as long as it is a thermoplastic elastomer, and examples thereof include known styrene-ethylene-butadiene-styrene copolymers. The copolymer (d4) may be a styrene-ethylene-butadiene-styrene copolymer and a hydrogenated product thereof.

The copolymer (d4) is preferably a styrene-ethylene-butadiene-styrene copolymer and a hydrogenated product thereof. The copolymer (d4) may be a block copolymer, for example, it is preferably a copolymer having styrene block portions at both ends and having an ethylene/butylene block portion in the middle due to hydrogenation of at least a part of the double bonds of the butadiene portion (a triblock copolymer of styrene-ethylene/butylene-styrene). The ethylene/butylene block portion of the styrene-ethylene/butylene-styrene copolymer may be a random copolymer.

The copolymer (d4) is obtained by known methods. In the case where the copolymer (d4) is a hydrogenated product of a styrene-ethylene-butadiene-styrene copolymer, for example, the copolymer is obtained by hydrogenating the butadiene moiety of a styrene-butadiene-styrene block copolymer in which the conjugated diene moiety is composed of 1,4 bonds.

Examples of commercially available products of the copolymer (d4) include "Kraton" (registered trademark) manufactured by Kraton Corporation and "Septon" (registered trademark) manufactured by KURARAY co.

(polyurethane (d 5): component (d5))

The polyurethane (d5) is not particularly limited as long as it is a thermoplastic elastomer, and examples thereof include known polyurethanes. The polyurethane (d5) is preferably a linear polyurethane. The polyurethane (d5) can be obtained, for example, by reacting a polyol component (polyether polyol, polyester polyol, polycarbonate polyol, etc.), an organic isocyanate component (aromatic diisocyanate, aliphatic (including alicyclic) diisocyanate, etc.), and, if necessary, a chain extender (aliphatic (including alicyclic) diol, etc.). The polyol component may be used alone or in combination of two or more; the organic isocyanate component may be used alone or in combination of two or more.

The polyurethane (d5) is preferably an aliphatic polyurethane. As the aliphatic polyurethane, for example, an aliphatic polyurethane obtained by reacting a polyol component containing a polycarbonate polyol with an isocyanate component containing an aliphatic diisocyanate is preferable.

The polyurethane (d5) can be obtained by the following process: the polyol component is reacted with the organic isocyanate component such that the NCO/OH ratio in the raw materials when synthesizing the polyurethane is in the range of, for example, 0.90 to 1.5. The polyurethane (d5) is obtained by known methods, such as the one shot (one shot) method and the prepolymerization method.

Examples of commercially available products of polyurethane (d5) include "Estane" (registered trademark) manufactured by Lubrizol and "Elastollan" (registered trademark) manufactured by BASF. Also exemplified is "Desmopan" (registered trademark) manufactured by Bayer corporation.

(polyester (d 6): component (d6))

The polyester (d6) is not particularly limited as long as it is a thermoplastic elastomer, and examples thereof include known polyesters. The polyester (d6) is preferably an aromatic polyester. In an exemplary embodiment, the aromatic polyester means a polyester having an aromatic ring in its structure.

Examples of the polyester (d6) include polyester copolymers (polyetheresters, polyesteresters, etc.). Specific examples thereof include: a polyester copolymer having a hard segment composed of a polyester unit and a soft segment composed of a polyester unit; a polyester copolymer having 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 weight ratio of the hard segment to the soft segment (hard segment/soft segment) of the polyester copolymer may be, for example, 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 (d6) is obtained using a known method. The polyester copolymer is preferably a linear polyester copolymer. The polyester copolymer is obtained, for example, by the following method: 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 having a number-average molecular weight of 300 to 20000 (including alkylene oxide adducts of polyalkylene glycols); and a method of esterifying or transesterifying these components to produce an oligomer and then polycondensing the oligomer. Further, for example, there can be exemplified 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 20000. 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, and the polyalkylene glycol component is an aromatic or aliphatic polyalkylene glycol.

Among them, the dicarboxylic acid component of the polyester copolymer is preferably a dicarboxylic acid component having an aromatic ring. The diol component and the polyalkylene glycol component each preferably use an aliphatic diol component and an aliphatic polyalkylene glycol component.

Examples of commercially available products of the polyester (d6) include "perprene" (registered trademark) manufactured by Toyobo co., ltd., and "HYTREL" (registered trademark) manufactured by Du Pont-Toray co., ltd.).

< ester compound (E): component (E) >

The resin composition of the exemplary embodiment may further include a specific ester compound (E).

The specific ester compound (E) is at least one selected from the group consisting of a compound represented by formula (1), a compound represented by formula (2), a compound represented by formula (3), a compound represented by formula (4), and a compound represented by formula (5).

In the 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 formula (2), R²¹And R²²Each independently represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms.

In the formula (3), R³¹And R³²Each independently represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms.

In the formula (4), R⁴¹、R⁴²And R⁴³Each independently represents an aliphatic hydrocarbon group having 7 to 28 carbon atoms.

In the 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. 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. 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. R¹¹The radicals indicated are particularly preferably aliphatic hydrocarbon radicals having 17 carbon atoms.

R¹¹The groups represented may be saturated aliphatic hydrocarbon groups and unsaturated aliphatic hydrocarbon groups. R¹¹The group represented is preferably a saturated aliphatic hydrocarbon group.

R¹¹The group represented may be a straight-chain aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group or an aliphatic hydrocarbon group containing an alicyclic ring. R¹¹The group represented is preferably an aliphatic hydrocarbon group (i.e., a chain aliphatic hydrocarbon group) free of alicyclic group, and more preferably a linear aliphatic hydrocarbon group.

At R¹¹When the group represented by (A) is an unsaturated aliphatic hydrocarbon group, R¹¹The number of unsaturated bonds in the group represented is preferably 1 to 3, more preferably 1 or 2, and further preferably 1.

At R¹¹When the group represented by (A) is an unsaturated aliphatic hydrocarbon group, R¹¹The group represented preferably contains a straight-chain saturated hydrocarbon chain having 5 to 24 carbon atoms, more preferably contains a straight-chain saturated hydrocarbon chain having 7 to 22 carbon atoms, further preferably contains a straight-chain saturated hydrocarbon chain having 9 to 20 carbon atoms, and particularly preferably contains a straight-chain saturated hydrocarbon chain having 15 to 18 carbon atoms.

At R¹¹In the case where the group represented is a branched aliphatic hydrocarbon group, R¹¹The number of branches in the group represented is preferably 1 to 3, more preferably 1 or 2, and further preferably 1.

At R¹¹In the case where the group represented is a branched aliphatic hydrocarbon group, R¹¹The main chain of the group represented by (a) preferably contains 5 to 24 carbon atoms, more preferably contains 7 to 22 carbon atoms, further preferably contains 9 to 20 carbon atoms, and particularly preferably contains 15 to 18 carbon atoms.

At R¹¹When the group represented is an alicyclic-containing aliphatic hydrocarbon group, R¹¹Of the representationThe number of alicyclic rings in the group is preferably 1 or 2, more preferably 1.

At R¹¹When the group represented is an alicyclic-containing aliphatic hydrocarbon group, R¹¹The number of carbon atoms of the alicyclic ring in the group represented by (a) is preferably 3 or 4, and more preferably 3.

From the viewpoint of further improving the high dimensional accuracy of the resin molded article, R¹¹The group represented is preferably a straight-chain saturated aliphatic hydrocarbon group, a straight-chain unsaturated aliphatic hydrocarbon group, a branched saturated aliphatic hydrocarbon group or a branched unsaturated aliphatic hydrocarbon group, and particularly preferably a straight-chain saturated aliphatic hydrocarbon group. The number of carbon atoms in these aliphatic hydrocarbon groups is preferably as described above.

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, and is preferably an unsubstituted group.

R¹²Represents an aliphatic hydrocarbon group having 9 to 28 carbon atoms. As R¹²The group represented by (A) is exemplified by a group represented by R¹¹The same forms as those described. Here, R¹²The number of carbon atoms in the group represented is preferably as follows.

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. 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. R¹²The radicals indicated are particularly preferably aliphatic hydrocarbon radicals having 18 carbon atoms.

From the viewpoint of further improving the high dimensional accuracy of the resin molded article, R¹²The group represented is preferably a straight-chain saturated aliphatic hydrocarbon group, a straight-chain unsaturated aliphatic hydrocarbon group, a branched saturated aliphatic hydrocarbon group or a branched unsaturated aliphatic hydrocarbon group, and particularly preferably a straight-chain saturated aliphatic hydrocarbon group. Preferred carbon of these aliphatic hydrocarbon groupsThe atomic number is as described above.

R²¹、R²²、R³¹、R³²、R⁴¹、R⁴²、R⁴³、R⁵¹、R⁵²、R⁵³And R⁵⁴The particular and preferred forms of the radicals indicated and for R¹¹Those described are the same.

Hereinafter, the compound represented by R will be described¹¹、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 aliphatic hydrocarbon group having 9 to 28 carbon atoms are shown, but the exemplary embodiments are not limited thereto.

The ester compound (E) may be used alone, or two or more thereof may be used in combination.

[ contents or weight ratios of Components (A) to (E) ]

The contents or weight ratios of the respective components will now be described. From the viewpoint of improving the dimensional accuracy of the resin molded article, the content or weight ratio of each component is preferably in the following range. Note: abbreviations for the respective components are as follows.

Component (a) ═ resin (a) having carbon atoms derived from biomass

Component (B) is a plasticizer (B)

Component (C) ═ a compound (F) of at least one selected from the group consisting of hindered phenol compounds, tocopherol compounds, tocotrienol compounds, phosphite compounds and hydroxylamine compounds

In the resin composition of the exemplary embodiment, the content of the component (a) is preferably 50% by weight or more, more preferably 60% by weight or more, and further preferably 70% by weight or more, relative to the total weight of the resin composition.

In the resin composition of the exemplary embodiment, the content of the component (B) is preferably 1 to 25% by weight, more preferably 3 to 20% by weight, and further preferably 5 to 15% by weight, relative to the total weight of the resin composition.

In the resin composition of the exemplary embodiment, the content of the component (C) is preferably 0.01 to 5% by weight, more preferably 0.05 to 2% by weight, and further preferably 0.1 to 1% by weight, relative to the total weight of the resin composition.

The content ratio (B/A) of the component (B) to the component (A) is preferably 0.03. ltoreq. B/A.ltoreq.0.3, more preferably 0.05. ltoreq. B/A.ltoreq.0.2, further preferably 0.07. ltoreq. B/A.ltoreq.0.15.

The ratio of the component (C) to the total amount of the component (a), the component (B) and the component (C) is preferably 0.05 to 5% by weight, more preferably 0.1 to 5% by weight, further preferably 0.1 to 1% by weight.

The content or weight ratio of the other additives is preferably within the following range. Note: abbreviations for the respective components are as follows.

Component (D) ═ thermoplastic elastomer (D)

Component (E) ═ ester compound (E)

In the resin composition of the exemplary embodiment, the content of the component (D) is preferably 1 to 20% by weight, more preferably 3 to 15% by weight, and further preferably 5 to 10% by weight, relative to the total weight of the resin composition.

The content ratio (D/A) of the component (D) to the component (A) is preferably 0.025. ltoreq. D/A.ltoreq.0.3, more preferably 0.05. ltoreq. D/A.ltoreq.0.2, further preferably 0.06. ltoreq. D/A.ltoreq.0.15.

In the resin composition of the exemplary embodiment, the content of the component (E) is preferably 0.1 to 15% by weight, more preferably 0.5 to 10% by weight, and further preferably 1 to 5% by weight, relative to the total weight of the resin composition.

The content ratio (E/A) of the component (E) to the component (A) is preferably 0.0025. ltoreq. E/A.ltoreq.0.1, more preferably 0.003. ltoreq. E/A.ltoreq.0.095, further preferably 0.005. ltoreq. E/A.ltoreq.0.05.

[ other Components ]

The resin composition of the exemplary embodiment may include other components.

Examples of the other components include flame retardants, compatibilizers, antioxidants, stabilizers, antiblocking agents, light stabilizers, weather-resistant agents, colorants, pigments, modifiers, drip inhibitors, antistatic agents, hydrolysis inhibitors, fillers, reinforcing agents (glass fibers, carbon fibers, talc, clay, mica, glass flakes, ground glass, glass beads, crystalline silica, alumina, silicon nitride, aluminum nitride, boron nitride, and the like).

Further, components (additives) for preventing acetic acid release, such as an acid acceptor and a reactive trapping agent, may be added as necessary. Examples of acid acceptors include: oxides such as magnesium oxide and aluminum oxide; metal hydroxides such as magnesium hydroxide, calcium hydroxide, aluminum hydroxide and aluminum magnesium carbonate; calcium carbonate; and talc.

Examples of reactive capture agents include epoxy compounds, anhydride compounds, and carbodiimides.

The content of these other components is preferably 0 to 5% by weight with respect to the total amount of the resin composition. Here, "0 wt%" means that no other component is contained.

The resin composition of the exemplary embodiment may contain other resins than the above-described resins (the bio-resin (a) and the like). However, when other resin is contained, the content of the other resin may be 5% by weight or less, more preferably 1% by weight or less, relative to the total amount of the resin composition. More preferably, no other resin is present in the resin composition (i.e., 0 wt%).

Examples of the other resins include thermoplastic resins in the related art, and specific examples thereof include: 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 polyaspartic acid resin; a vinyl polymer or copolymer obtained by polymerizing or copolymerizing one or more vinyl monomers selected from the group consisting of aromatic alkenyl compounds, methacrylates, acrylates, and vinyl cyanide compounds; a diene-aromatic alkenyl compound copolymer; vinyl cyanide-diene-aromatic alkenyl compound copolymer; aromatic alkenyl-diene-vinyl cyanide-N-phenylmaleimide copolymer; ethylene cyanide- (ethylene-diene-propylene (EPDM)) -aromatic alkenyl compound copolymers; vinyl chloride resin; 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 exemplary embodiment is prepared by melt-kneading a mixture containing, for example, the bio-resin (a) and, if necessary, the plasticizer (B), the compound (C), other additives (the thermoplastic elastomer (D), the ester compound (E), and the components thereof). In addition to this, the resin composition of the exemplary embodiment is also prepared by, for example, dissolving the above components in a solvent.

Examples of the apparatus for melt-kneading include known apparatuses such as a twin-screw extruder, a HENSCHEL mixer, a BANBURY mixer, a single-screw extruder, a multi-screw extruder, and a co-kneader.

< resin molded article >

The resin molded article of the exemplary embodiment includes the resin composition of the exemplary embodiment. That is, the resin molded article of the exemplary embodiment has the same composition as the resin composition of the exemplary embodiment.

Injection molding is preferable as a molding method of the resin molded article of the exemplary embodiment from the viewpoint of high degree of freedom in shape. In this regard, the resin molded article is preferably an injection molded article obtained by injection molding.

The barrel temperature for injection molding is, for example, 160 ℃ to 280 ℃, preferably 180 ℃ to 260 ℃. The mold temperature for injection molding is, for example, 40 ℃ to 90 ℃, preferably 60 ℃ to 80 ℃.

Injection molding can be performed using commercially available equipment, such as NEX500(Nissei Plastic Industrial co., Ltd.), NEX150(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 Heavy Industries, Ltd.).

The molding method for obtaining the resin molded article of the exemplary embodiment is not limited to the above injection molding, and for example, extrusion molding, blow molding, hot press molding, calender molding, coating molding, cast molding, dip molding, vacuum molding, transfer molding, and the like may also be used.

The resin molded article of the exemplary embodiment is suitable for applications such as electronic and electrical equipment, office equipment, home appliances, automobile interior materials, toys, containers, carriers, absorbents, and separation films. More specifically: housings for electronic and electrical equipment or household appliances; various components of electronic and electrical equipment or household appliances; an automotive interior component; assembling the toy; a plastic mold kit; a storage case for CD-ROM or DVD; tableware; beverage bottles; a food tray; a wrapping material; a film; a sheet material; a catalyst support; a water-absorbing material; and a humidity adjusting material.