JP2012052007A - Cyclic phosphorus carbonate compound, flame retardant, resin composition, and housing for electric and electronic equipment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel cyclic phosphorus carbonate compound which is excellent in flame retardancy, hardly bleeds out, and when used for a resin composition, is excellent in moldability, and further has improved heat resistance and improved bending elastic modulus.SOLUTION: The compound is a cyclic phosphorus oligomer having a carbonate bond such as a compound represented by formula.

Description

  The present invention relates to a cyclic phosphate compound, a flame retardant, a resin composition, and a casing for electric and electronic equipment.

Resin compositions used for electrical and electronic equipment casings and the like are required to be provided with flame retardancy in order to prevent exothermic ignition and the like, and various flame retardants are used.
Phosphorus-containing compounds are widely used in resin compositions as flame retardants or plasticizers.
Patent Document 1 describes that a cyclic phosphorus compound having a specific structure can be used as a flame retardant.
Patent Document 2 describes a flame retardant resin composition containing a cyclic phosphorus compound having a specific structure and a resin such as polycarbonate.

JP 2010-59145 A JP 2010-53195 A

However, there is a need for a flame retardant that can further improve the heat resistance and flame retardancy of the resin composition than the cyclic phosphorus compound described in Patent Document 1 or 2.
The resin composition containing the cyclic phosphorus compound described in Patent Document 1 or 2 and the molded article made of the resin composition have problems in moldability, have a low bending elastic modulus, and are likely to be distorted or deformed. There is.
Moreover, the cyclic phosphorus compound described in Patent Document 1 or 2 has a problem that it tends to bleed out.

The present invention is excellent in flame retardancy, is difficult to bleed out, has excellent moldability when used in a resin composition, can further contribute to improvement in heat resistance and bending elastic modulus, An object is to provide a cyclic phosphorus carbonate compound and a flame retardant.
Another object of the present invention is a resin that can be used for various applications, and can obtain a molded article having excellent moldability and excellent bending elastic modulus, heat resistance, flame retardancy, and bleed-out resistance. It is to provide a composition.
Furthermore, another object of the present invention is to provide a housing for electrical and electronic equipment composed of a molded body obtained by molding the resin composition.

  As a result of intensive studies, the present inventors have found that the above problems can be achieved by the following means.

  [1] A compound comprising a structural unit represented by the following general formula (I) and a structural unit represented by the following general formula (II).

In general formula (I), R ¹ , R ² , R ³ , and R ⁴ each independently represent a halogen atom, a hydroxyl group, a substituted or unsubstituted amino group, a nitro group, a cyano group, a substituted or unsubstituted group. It represents an alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a sulfonic acid group.
R ⁵ represents a hydrogen atom, a substituted or unsubstituted aryl group, or a group represented by the following general formula (III).
n1, n2, n3, and n4 each independently represents an integer of 0 to 4.

In general formula (III), R ⁶ and R ⁷ are each independently a halogen atom, hydroxyl group, substituted or unsubstituted amino group, nitro group, cyano group, substituted or unsubstituted alkyl group, substituted or unsubstituted A cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a sulfonic acid group.
n6 and n7 each independently represents an integer of 0 to 4.
* Represents a binding site.
In general formula (II), L represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted divalent heterocyclic group, and the following general formula It represents a divalent linking group represented by (L-1) or a divalent linking group formed by combining these groups.

In general formula (L-1), X represents an oxygen atom or a sulfur atom.
m1 and m3 each independently represents an integer of 1 to 8.
m2 represents an integer of 1 to 30.
Each ** represents a binding site.
[2] The compound according to [1] above, wherein, in the general formula (I), R ⁵ represents a substituted or unsubstituted aryl group or a group represented by the general formula (III).
[3] The molar ratio of the content of the structural unit represented by the general formula (I) and the content of the structural unit represented by the general formula (II) is 30:70 to 70:30. And [1] or [2].
[4] The compound according to any one of [1] to [3], wherein the mass average molecular weight is in the range of 500 to 10,000.
[5] A flame retardant which is the compound according to any one of [1] to [4].
[6] A resin composition containing the compound according to any one of [1] to [4].
[7] The resin composition according to [6], containing the compound according to any one of [1] to [4] in an amount of 4 to 20% by mass with respect to the total solid content of the resin composition. .
[8] The resin composition according to [6] or [7], further containing a cellulose resin.
[9] The resin composition according to [8], wherein the cellulose resin is contained in an amount of 41 to 61% by mass with respect to the total solid content of the resin composition.
[10] The resin composition according to [8] or [9], further including a thermoplastic resin other than the cellulose resin.
[11] The resin composition according to [8] or [9], wherein the cellulose resin is a cellulose ester.
[12] The resin composition according to [11], wherein the cellulose ester is cellulose diacetate or cellulose acetate propionate.
[13] The resin composition according to [10], wherein the thermoplastic resin other than the cellulose resin is at least one of polyester and polycarbonate.
[14] Further, containing one or more flame retardants selected from the group consisting of brominated flame retardants, phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, metal oxides and metal hydroxide flame retardants The resin composition according to any one of [6] to [13] above.
[15] The resin composition according to any one of [6] to [14], further containing a fluororesin.
[16] A housing for an electric and electronic device comprising a molded body obtained by thermoforming the resin composition according to any one of [6] to [15].

According to the present invention, excellent in flame retardancy, difficult to bleed out, when used in a resin composition, it is excellent in moldability, can further contribute to improvement in heat resistance and improvement in flexural modulus, Novel cyclic phosphorus carbonate compounds and flame retardants can be provided.
In addition, according to the present invention, the resin composition can be used for various applications, and can provide a molded article having excellent moldability and excellent bending elastic modulus, heat resistance, flame retardancy, and bleed-out resistance. Can be provided.
Furthermore, according to this invention, the housing | casing for electric and electronic devices comprised from the molded object obtained by shape | molding this resin composition can be provided.

  The present invention relates to a structural unit represented by the following general formula (I) and a compound containing a structural unit represented by the following general formula (II) (hereinafter also referred to as a cyclic phosphate compound). The cyclic phosphate compound is typically a polymer and may be an oligomer or a polymer.

In general formula (I), R ¹ , R ² , R ³ , and R ⁴ each independently represent a halogen atom, a hydroxyl group, a substituted or unsubstituted amino group, a nitro group, a cyano group, a substituted or unsubstituted group. It represents an alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a sulfonic acid group.
R ⁵ represents a hydrogen atom, a substituted or unsubstituted aryl group, or a group represented by the following general formula (III).
n1, n2, n3, and n4 each independently represents an integer of 0 to 4.

In general formula (III), R ⁶ and R ⁷ are each independently a halogen atom, hydroxyl group, substituted or unsubstituted amino group, nitro group, cyano group, substituted or unsubstituted alkyl group, substituted or unsubstituted A cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a sulfonic acid group.
n6 and n7 each independently represents an integer of 0 to 4.
* Represents a binding site.

  In general formula (II), L represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted divalent heterocyclic group, and the following general formula It represents a divalent linking group represented by (L-1) or a divalent linking group formed by combining these groups.

In general formula (L-1), X represents an oxygen atom or a sulfur atom.
m1 and m3 each independently represents an integer of 1 to 8.
m2 represents an integer of 1 to 30.
Each ** represents a binding site.

1. Cyclic phosphate compound The cyclic phosphate compound in this invention contains the structural unit represented by the said general formula (I), and the structural unit represented by the said general formula (II).
The cyclic phosphorus carbonate compound in the present invention is excellent in flame retardancy because it is a skeleton having a high phosphorus content, excellent in heat resistance because of its high melting point (crystallinity), and has heat resistance and rigidity because it has a rigid cyclic phosphorus structure. Excellent. Since the cyclic phosphate compound has these characteristics, for example, it can be expected to have a wide range of uses as an additive for imparting various functions to the resin composition, but it is preferably a flame retardant or a plasticizer, more preferably difficult. Can be used as a flame retardant.

In general formula (I), R ¹ , R ² , R ³ , and R ⁴ each independently represent a halogen atom, a hydroxyl group, a substituted or unsubstituted amino group, a nitro group, a cyano group, a substituted or unsubstituted group. It represents an alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a sulfonic acid group.

When R ¹ , R ² , R ³ , and R ⁴ represent a halogen atom, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and a fluorine atom is preferable.

When R ¹ , R ² , R ³ , and R ⁴ represent an alkyl group, the alkyl group may have a linear or branched structure and may have an unsaturated bond. As this alkyl group, Preferably it is a C1-C30 alkyl group, More preferably, it is a C1-C20 alkyl group, More preferably, it is a C1-C10 alkyl group. Specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, neopentyl group, hexyl group, 2-ethylhexyl group, tert-butyl group, isoheptyl group, octyl group, nonyl group , A decyl group, a stearyl group, and the like. A methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group are preferable, a methyl group and an ethyl group are more preferable, and a methyl group is particularly preferable.

When R ¹ , R ² , R ³ and R ⁴ represent a cycloalkyl group, the cycloalkyl group preferably has 3 to 20 carbon atoms, more preferably 5 to 10 carbon atoms, still more preferably 6 carbon atoms. ˜8 cycloalkyl groups. Specific examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like. A cyclohexyl group or a cycloheptyl group is preferable, and a cyclohexyl group is more preferable.

When R ¹ , R ² , R ³ , and R ⁴ represent an aryl group, the aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 10 carbon atoms. Of the aryl group. Specific examples include a phenyl group, a naphthyl group, a biphenyl group, a fluorenyl group, a phenanthryl group, a triphenylenyl group, and an anthryl group, particularly preferably a phenyl group, a naphthyl group, or a biphenyl group, and most preferably a phenyl group. It is.

When R ¹ , R ² , R ³ , and R ⁴ represent an alkoxy group, the preferred range of the alkyl group moiety in the alkoxy group is that the R ¹ , R ² , R ³ , and R ⁴ represent an alkyl group. It is the same as the preferable range in the case.

When R ¹ , R ² , R ³ , and R ⁴ represent a heterocyclic group, the heterocyclic group is preferably an aromatic heterocyclic group, and is an aromatic heterocyclic group having 4 to 20 carbon atoms. Is more preferable. Specifically, the heterocyclic group is preferably a pyridyl group or a thienyl group.

When R ¹ , R ² , R ³ , and R ⁴ represent an amino group, an alkyl group, a cycloalkyl group, an alkoxy group, an aryl group, or a heterocyclic group, these may be further substituted, Examples of the substituent include a halogen atom, hydroxyl group, amino group, nitro group, cyano group, alkyl group, cycloalkyl group, alkoxy group, aryl group, heterocyclic group, or sulfonic acid group.

When a plurality of R ¹ , R ² , R ³ , and R ⁴ are present, they may be the same as or different from each other.

In general formula (I), R ¹ , R ² , R ³ , and R ⁴ are preferably hydrogen atoms from the viewpoint of improving heat resistance.

  In general formula (I), n1, n2, n3 and n4 each independently represents an integer of 0 to 4. From the viewpoint of improving heat resistance, n1, n2, n3, and n4 are preferably 0 or 1, and more preferably 0.

In the general formula (I), R ⁵ represents a hydrogen atom, a substituted or unsubstituted aryl group, or a group represented by the following general formula (III).

In general formula (III), R ⁶ and R ⁷ are each independently a halogen atom, hydroxyl group, substituted or unsubstituted amino group, nitro group, cyano group, substituted or unsubstituted alkyl group, substituted or unsubstituted A cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a sulfonic acid group.
n6 and n7 each independently represents an integer of 0 to 4.
* Represents a binding site.

When R ⁵ represents an aryl group, the preferred range of the aryl group is the same as the preferred range when R ¹ , R ² , R ³ , and R ⁴ represent an aryl group.
When R ⁵ represents an aryl group, it may further have a substituent, and as the substituent, when R ¹ , R ² , R ³ , and R ⁴ represent an alkyl group or an aryl group, The thing similar to the substituent which you may have is mentioned.

In general formula (III), R ⁶ and R ⁷ are each independently a halogen atom, hydroxyl group, substituted or unsubstituted amino group, nitro group, cyano group, substituted or unsubstituted alkyl group, substituted or unsubstituted A cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a sulfonic acid group. Specific examples and preferred ranges of R ⁶ and R ⁷ are the same as the specific examples and preferred ranges of R ¹ , R ² , R ³ , and R ⁴ . Moreover, the substituent which these may have is also the same.
When a plurality of R ⁶ and R ⁷ are present, they may be the same as or different from each other.

  In general formula (III), n6 and n7 represent the integer of 0-4 each independently. From the viewpoint of improving heat resistance, n6 and n7 are preferably 0 or 1, and more preferably 0.

R ⁵ in the general formula (I) is a hydrogen atom, a substituted or unsubstituted aryl group, or a group represented by the general formula (III). From the viewpoint of improving rigidity and heat resistance, substituted or unsubstituted aryl A group or a group represented by the general formula (III) is preferable, and a group represented by the general formula (III) is more preferable. The reason why these are preferable is presumed that the rigidity of the cyclic phosphate compound itself is increased by having a substituted or unsubstituted aryl group or a group represented by the general formula (III) as R ^5. It is thought that it contributes to the improvement of heat resistance and flexural modulus.
In the above range, the substituted or unsubstituted aryl group is preferably an unsubstituted aryl group.

In addition, R ⁵ may be an embodiment in which a hydroxyl group is substituted on an aryl group, the hydroxyl group undergoes a condensation reaction, and is bonded to a structural unit represented by the general formula (II) (a specific example compound described later) 29).

  Next, general formula (II) will be described.

  In general formula (II), L represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted divalent heterocyclic group, and the following general formula It represents a divalent linking group represented by (L-1) or a divalent linking group formed by combining these groups.

In general formula (L-1), X represents an oxygen atom or a sulfur atom.
m1 and m3 each independently represents an integer of 1 to 8.
m2 represents an integer of 1 to 30.
Each ** represents a binding site.

  In the general formula (II), when L represents an alkylene group, the alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and still more preferably 2 to 8 carbon atoms. is there. Specifically, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, pentylene group, 2,2-dimethylpropylene group, hexylene group, heptylene group, 2-ethylhexylene group, tert- A butylene group, an isoheptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tridecylene group, a tetradecylene group, a stearylene group, and the like. From the viewpoint of improving compatibility with other resins, an ethylene group, A propylene group, an isopropylene group, a butylene group, a pentylene group, a 2,2-dimethylpropylene group, a hexylene group, a heptylene group, and an octylene group, more preferably a hexylene group.

  When L represents a cycloalkylene group, the cycloalkylene group is preferably a cycloalkylene group having 3 to 20 carbon atoms, more preferably 5 to 12 carbon atoms, and still more preferably 6 to 8 carbon atoms. Specific examples include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, and a cyclooctylene group. From the viewpoint of improving compatibility with other resins, a cyclohexylene group is preferable. It is.

When L represents an arylene group, the arylene group is preferably an arylene group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 10 carbon atoms. Specific examples include a phenylene group, a naphthylene group, and a biphenylene group, and a phenylene group is preferable from the viewpoint of improving compatibility with other resins.
When L represents a divalent heterocyclic group, the divalent heterocyclic group is preferably a divalent aromatic heterocyclic group, and is a C 4-20 divalent aromatic heterocyclic group. It is more preferable. Specific examples of the divalent heterocyclic group include a pyridylene group and a thienylene group.

  The alkylene group, cycloalkylene group, arylene group, and divalent heterocyclic group represented by L may further have a substituent. Examples of the substituent include halogen atoms (for example, chlorine, bromine, fluorine and iodine), alkyl groups, cycloalkyl groups, halogenated alkyl groups, aryl groups, alkoxy groups, aryloxy groups, acyl groups, alkoxycarbonyl groups, aryls. Examples thereof include an oxycarbonyl group, an acyloxy group, a sulfonylamino group, a hydroxy group, a silyl group, a cyano group, an amino group, and an acylamino group. These substituents may be further substituted if possible, and examples of the further substituents are the same as those described above. The substituent that L may have is preferably an alkyl group, an aryl group, a hydroxy group, or a halogen atom, more preferably a halogen atom, and still more preferably a fluorine atom. 0-30 are preferable and, as for carbon number of this substituent, 0-20 are more preferable.

In general formula (L-1), X represents an oxygen atom or a sulfur atom. From the viewpoint of the stability of the compound, X is preferably an oxygen atom.
m1 and m3 each independently represents an integer of 1 to 8. From the viewpoint of improving compatibility with other resins, m1 and m3 are each independently preferably an integer of 1 to 6, and more preferably an integer of 1 to 3.
m2 represents an integer of 1 to 30. From the viewpoint of improving compatibility with other resins, m2 is preferably an integer of 1 to 15, and more preferably an integer of 1 to 8.
Each ** represents a binding site. Each ** is preferably a bonding site with an oxygen atom adjacent to L in the general formula (II).

L represents the substituted or unsubstituted alkylene group, the substituted or unsubstituted cycloalkylene group, the substituted or unsubstituted arylene group, the substituted or unsubstituted divalent heterocyclic group, and the general formula (L It may be a divalent linking group formed by combining at least two selected from the group consisting of divalent linking groups represented by -1). The divalent linking group is obtained by combining at least two selected from the group consisting of the aforementioned groups with —O—, —S—, —NR ¹⁰ —, —CO—, —SO ₂ —, and combinations thereof. divalent group ^{(e.g., -COO -, - NR 10 CO} -, - NR 10 COO -, - NR 10 CONR 10 -, - SO 2 NR 10 -) (R 10 is a hydrogen atom, or a substituent A divalent group selected from the group consisting of a plurality of R ^{10 s} , which may be the same or different. It may be a divalent linking group having one or more of them.
When L is a divalent linking group formed by combining at least two selected from the group consisting of the aforementioned groups, the total number of carbon atoms of L is preferably 2 to 30, and more preferably 2 to 20. When L is a divalent linking group formed by combining at least two selected from the group consisting of the aforementioned groups, one or two substituted or unsubstituted alkylene groups and one or two substituted or unsubstituted groups Preferably, the divalent linking group is a combination of one arylene group and a divalent linking group formed by combining one substituted or unsubstituted alkylene group and two substituted or unsubstituted arylene groups. More preferably. In the divalent linking group, the alkylene group and the arylene group may be linked via an ester bond (—COO—).

L is preferably an arylene group or a divalent linking group formed by combining the above-described groups from the viewpoint of improving rigidity and heat resistance, and includes at least one arylene group. The reason why these are preferable is presumed that the rigidity of the cyclic phosphorus carbonate compound itself is increased by having an arylene group as L, which is considered to contribute to the improvement of heat resistance and flexural modulus.
A divalent linking group formed by combining the above-mentioned groups, and the linking group containing at least one arylene group is a divalent linking group formed by combining at least two selected from the group consisting of the above-described groups. This is the same as the preferred range, and among them, when a combination resin is present, it is preferable that the structural similarity with the resin used in combination is high because of high compatibility. For example, when a commercially available polycarbonate is used in combination, a divalent linking group derived from bisphenol A is preferably used because of high structural similarity and high compatibility.

  In the cyclic phosphate compound in the present invention, the content of the structural unit represented by the general formula (I) is 30 to 70 mol% with respect to the total structural unit from the viewpoint of improving heat resistance and high bending elastic modulus. Is preferable, and 40 to 65 mol% is more preferable.

  In the cyclic phosphate compound in the present invention, the content of the structural unit represented by the general formula (II) is 30 to 70 mol% with respect to the total structural unit from the viewpoint of improving compatibility with other resins. Is preferable, and 40 to 65 mol% is more preferable.

  In the cyclic phosphorus carbonate compound in the present invention, the ratio of the content of the structural unit represented by the general formula (I) and the content of the structural unit represented by the general formula (II) is the same as that of other resins. From the viewpoint of achieving both solubility and heat resistance, the molar ratio is preferably 30:70 to 70:30, more preferably 40:60 to 60:40, and even more preferably 1: 1.

  The cyclic phosphate compound in the present invention preferably contains a structural unit represented by the following general formula (IV).

In general formula (IV), R ¹ , R ² , R ³ , and R ⁴ are each independently a halogen atom, hydroxyl group, substituted or unsubstituted amino group, nitro group, cyano group, substituted or unsubstituted It represents an alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a sulfonic acid group.
R ⁵ represents a hydrogen atom, a substituted or unsubstituted aryl group, or a group represented by the following general formula (III).
n1, n2, n3, and n4 each independently represents an integer of 0 to 4.

In general formula (III), R ⁶ and R ⁷ are each independently a halogen atom, hydroxyl group, substituted or unsubstituted amino group, nitro group, cyano group, substituted or unsubstituted alkyl group, substituted or unsubstituted A cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a sulfonic acid group.
n6 and n7 each independently represents an integer of 0 to 4.
* Represents a binding site.

  L represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted divalent heterocyclic group, represented by the following general formula (L-1). Represents a divalent linking group formed by combining these groups.

In general formula (L-1), X represents an oxygen atom or a sulfur atom.
m1 and m3 each independently represents an integer of 1 to 8.
m2 represents an integer of 1 to 30.
Each ** represents a binding site.

^{R 1,} R ^{2, R} 3 in the general formula ^{(IV), R 4, R} 5, n1, n2, n3, n4, and L, ^R 1 in the general formula (I) or ^{(II), R 2,} R ^3, is ^{R 4, R 5, n1,} n2, n3, n4, and synonymous with L, and also specific examples and preferred ranges.
Specific examples and preferred ranges of R ⁶ , R ⁷ , n6 and n7 in the general formula (III) are the same as described above.
Specific examples and preferred ranges of X, m1, m2, m3, and ** in formula (L-1) are the same as described above.
In the cyclic phosphoric acid carbonate compound in the present invention, the content of the structural unit represented by the general formula (IV) is 30 to 100 mol% with respect to all the structural units from the viewpoint of improving heat resistance and high bending elastic modulus. Is preferable, 60 to 100 mol% is more preferable, and 100 mol% is most preferable.

  The terminal of the main chain of the cyclic phosphorus carbonate compound in the present invention is preferably a hydroxyl group or an acyloxy group (an aliphatic acyloxy group or an aromatic acyloxy group). That is, it is preferable that a hydrogen atom, an alkyl group, or an aryl group is bonded to the terminal general formula (I) or (II). The alkyl group is preferably an alkyl group having 1 to 11 carbon atoms, preferably a methyl group or an ethyl group. From the viewpoint of improving compatibility with other resins, a methyl group (that is, the terminal of the cyclic phosphate compound is an acetyloxy group). ) Is more preferable. The aryl group is preferably an aryl group having 6 to 10 carbon atoms, preferably a phenyl group or a naphthyl group, and a phenyl group (that is, a terminal of a cyclic phosphate compound) from the viewpoint of achieving both heat resistance and compatibility with other resins. Is more preferably a benzoyloxy group.

The cyclic phosphorus carbonate compound in the present invention may contain other structural units other than the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II). Examples of the other structural unit include a structural unit derived from alkylene glycol, a structural unit derived from amine, a structural unit derived from isocyanate, and a structural unit derived from dicarboxylic acid.
The cyclic phosphate compound in the present invention does not include the structural unit represented by the general formula (I) and other structural units other than the structural unit represented by the general formula (II). However, when it is included, the content of other structural units in the cyclic phosphate compound in the present invention is preferably 5 to 40 mol% from the reason that high formability is maintained with respect to all structural units, 10-30 mol% is more preferable.

  The structure and ratio (copolymerization ratio) of the structural unit contained in the cyclic phosphate compound in the present invention can be determined by a nuclear magnetic resonance apparatus (NMR) or the like.

The molecular weight of the cyclic phosphate compound in the present invention is preferably in the range of 500 to 10,000, more preferably 600 to 7000 in terms of mass average molecular weight (Mw), from the viewpoint of compatibility with other resins and heat resistance. ˜5500 is more preferred.
More specifically, the mass average molecular weight is obtained using a converted molecular weight calibration curve obtained in advance from a constituent curve of standard monodispersed polystyrene using tetrahydrofuran as a solvent and a polystyrene gel. As the GPC apparatus, HLC-8220 GPC (manufactured by Tosoh Corporation) can be used.

  Specific examples of the cyclic phosphorus carbonate compound in the present invention are shown below, but are not limited thereto.

  The cyclic phosphorus carbonate compound in the present invention can be obtained by polymerizing monomers corresponding to the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II).

As a monomer corresponding to the structural unit represented by the general formula (I), a compound represented by the following general formula (IM) is preferable.
In this invention, 1 type of compounds represented by general formula (IM) may be used, and 2 or more types may be used.

In general formula (IM), R ¹ , R ² , R ³ and R ⁴ are each independently a halogen atom, a hydroxyl group, a substituted or unsubstituted amino group, a nitro group, a cyano group, a substituted or unsubstituted group. It represents an alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a sulfonic acid group.
R ⁵ represents a hydrogen atom, a substituted or unsubstituted aryl group, or a group represented by the following general formula (III).
n1, n2, n3, and n4 each independently represents an integer of 0 to 4.

In general formula (III), R ⁶ and R ⁷ are each independently a halogen atom, hydroxyl group, substituted or unsubstituted amino group, nitro group, cyano group, substituted or unsubstituted alkyl group, substituted or unsubstituted A cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a sulfonic acid group.
n6 and n7 each independently represents an integer of 0 to 4.
* Represents a binding site.

^R 1 in the general formula ^{(IM), R 2, R} 3, R 4, R 5, n1, n2, n3, and ^{n4, R 1, R 2, R} 3 in Formula ^{(I), R 4,} R ^5, n1, n2, n3, and n4 in the above formula, the same applies to specific examples and preferred ranges.
Specific examples and preferred ranges of R ⁶ , R ⁷ , n6 and n7 in the general formula (III) are the same as described above.
The compound represented by the general formula (IM) can be synthesized by a known method described in JP 2010-59145 A, JP 2010-53195 A, or the like, or a commercially available one can be used. You can also.

The monomer corresponding to the structural unit represented by the general formula (II) is preferably divalent chloroformate.
In the present invention, one kind of divalent chloroformate may be used, or two or more kinds thereof may be used.

Examples of the divalent dichloroformate include aliphatic dichloroformate and aromatic dichloroformate.
The aliphatic dichloroformate preferably used in the present invention is preferably an aliphatic dichloroformate having 1 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and still more preferably 2 to 8 carbon atoms. For example, ethyl dichloroformate, 1,3-propyldichloroformate, 1,4-butyldichloroformate, 1,5-pentyldichloroformate, 1,6-hexyldichloroformate and the like can be mentioned. From the viewpoint of compatibility between heat resistance and compatibility with other resins, ethyldichloroformate, 1,3-propyldichloroformate, and 1,4-butyldichloroformate are preferable, and ethyldichloroformate is more preferable. 1,3-propyldichloroformate.

  The aromatic dichloroformate preferably used in the present invention is preferably an aromatic dichloroformate having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, still more preferably 6 to 10 carbon atoms. 1,3-phenyldichloroformate, 1,4-phenyldichloroformate, bisphenol A bischloroformate, 1,5-naphthyldichloroformate, 4,4′-biphenyldichloroformate and the like are preferably used. From the viewpoint of improving heat resistance, 1,3-phenyldichloroformate, 1,4-phenyldichloroformate, and bisphenol A bischloroformate are more preferable, and bisphenol A bischloroformate is more preferable.

2. Resin Composition The resin composition of the present invention contains the cyclic phosphate compound.
Since the cyclic phosphorus carbonate compound is a skeleton having a high phosphorus content, it is considered that the cyclic phosphorus carbonate compound can contribute to the improvement of the flame retardancy of the resin composition and a molded product obtained from the resin composition.
It is considered that the cyclic phosphorus carbonate compound can contribute to the improvement of the heat resistance of the resin composition and the molded article because of its high melting point (crystallinity).
Since the cyclic phosphorus carbonate compound includes a hydrophilic carbonate bond composed of the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II), molding of the resin composition It is thought that it can contribute to the improvement of property.
In addition, the cyclic phosphate compound has a rigid cyclic phosphorus structure, and it is considered that the cyclic phosphate compound can contribute to improvement in rigidity by entering the gaps of the resin constituting the molded body.

The resin composition of the present invention may further contain a resin other than the cyclic phosphate compound.
As the resin other than the cyclic phosphate compound that the resin composition of the present invention may contain, a cellulose resin or a thermoplastic resin other than the cellulose resin is preferable.
The resin composition of the present invention preferably contains a cyclic phosphate compound, a cellulose resin, and a thermoplastic resin other than the cellulose resin.

  The content of the cyclic phosphorus carbonate compound contained in the resin composition of the present invention is not particularly limited. Preferably, the cyclic phosphate compound is 4 to 20% by mass, more preferably 6 to 20% by mass, still more preferably 7 to 16% by mass, particularly preferably 7.5 to 15%, based on the total solid content of the resin composition. Contains by mass%. By setting it as this range, since the resin composition and molded object which are excellent in heat resistance, a bending elastic modulus, a moldability, and bleed-out resistance can be obtained, it is preferable.

3. Cellulose-based resin The resin composition of the present invention preferably further contains a cellulose-based resin.
Since the cyclic phosphorus carbonate compound in the present invention includes a carbonate bond composed of the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II), a cellulose resin (preferably cellulose) It is considered that a resin composition excellent in heat resistance, flexural modulus, moldability, and bleed-out resistance can be obtained.
Although it does not specifically limit as a cellulose resin in this invention, A cellulose ether (for example, ethyl cellulose etc.), a cellulose ester, or a cellulose ether ester (for example, A) hydrocarbon group mentioned later, B) Acyl group: -CO-R _B1 And a group containing an alkyleneoxy group: —R _B2 —O— (R _B1 represents a hydrocarbon group, R _B2 represents an alkylene group having 3 carbon atoms), and C) an acyl group: —CO—R _C (wherein R _C represents a cellulose group) is preferable, and a cellulose ester is preferable from the viewpoint of compatibility with the cyclic phosphate compound, high heat resistance, and high flexural modulus. Cellulose esters are usually produced by esterifying cellulose such as wood pulp (conifer pulp, hardwood pulp) and cotton linter pulp.
The cellulose resin in the present invention may be used alone or in combination of two or more.

  The cellulose ester can be produced by a conventional esterification method in which cellulose is reacted with an acylating agent, and can be produced through a saponification or aging step as necessary. Cellulose esters are usually prepared by activating pulp (cellulose) with an activating agent (activation step) and then preparing an ester (such as a triester) with an acylating agent using a catalyst such as sulfuric acid (acylation step). ), Saponification (hydrolysis) and aging to adjust the degree of esterification (saponification and aging step). In the case of cellulose acetate, it can be produced by a conventional method such as a sulfuric acid catalyst method, an acetic acid method, or a methylene chloride method.

  The ratio of the acylating agent in the acylation step can be selected within a range where the desired degree of acylation (eg, degree of acetylation) can be selected. For example, 230 to 300 parts by weight, preferably 240 parts per 100 parts by weight of pulp (cellulose). It is about 290 mass parts, More preferably, it is about 250-280 mass parts. In the case of cellulose acetate, for example, acetic anhydride can be used as the acylating agent.

As the acylation or aging catalyst, sulfuric acid is usually used. The usage-amount of a sulfuric acid is 0.5-15 mass parts normally with respect to 100 mass parts of cellulose, Preferably it is 5-15 mass parts, More preferably, it is about 5-10 mass parts. The saponification / ripening temperature can be selected from the range of 40 to 160 ° C, and is, for example, about 50 to 70 ° C.
Furthermore, in order to neutralize the remaining sulfuric acid, it may be treated with an alkali.

Examples of the cellulose ester include organic acid esters [cellulose acetate (cellulose acetate), cellulose propionate, cellulose butyrate, etc., cellulose and carboxylic acid ester having 2 to 6 carbon atoms, etc.], mixed esters (cellulose acetate propionate). , Cellulose such as cellulose acetate butyrate and dicarboxylic acid esters having 2 to 6 carbon atoms), grafts (polycaprolactone-grafted cellulose acetate, etc.), inorganic acid esters (cellulose nitrate, cellulose sulfate, cellulose phosphate, etc.), organic Examples include acid / inorganic acid mixed esters (such as cellulose nitrate acetate).
In the present invention, among these cellulose esters, a cellulose organic acid ester modified with an organic acid is preferable, and a cellulose organic acid ester modified with an organic acid having 2 to 12 carbon atoms is more preferable. Specifically, cellulose acetate, cellulose propionate, cellulose butyrate, and the like are preferable, cellulose acetate is more preferable, cellulose triacetate, cellulose acetate propionate, and cellulose diacetate are more preferable. From the viewpoint of volatility, cellulose acetate pro Pionate and cellulose diacetate are particularly preferable.

The acyl substitution degree of the cellulose ester is preferably 2.7 or less, more preferably 2.65 or less, and even more preferably 2.6 or less from the viewpoint of impact resistance. The acyl substitution degree is preferably 1 to 2.7, more preferably 1.3 to 2.65, and still more preferably 1.5 to 2.6.
In the case of cellulose acetate, it can be selected from the range of an average degree of acetylation of about 30 to 62.5%, and usually an average degree of acetylation of 43.7 to 62.5% (average substitution degree of acetyl group of 1.7 to 3), Preferably it is 45-62.5% (average substitution degree 1.8-3), More preferably, it is about 48-62.5% (average substitution degree 2-3).

  The polymerization degree of the cellulose ester is not particularly limited, and is a viscosity average polymerization degree of 200 to 400, preferably 250 to 400, and more preferably about 270 to 350. The viscosity average degree of polymerization can be measured by the method described in JP-A-9-77801, [0018] to [0019].

  The cellulose ester in the present invention can be produced by a known method. Moreover, a commercial item can also be used. For example, as cellulose acetate propionate, “482-20 (acetyl substitution degree: 0.1, propionyl substitution degree: 2.5, Mn: 73000, Mw: 234000)” manufactured by Eastman Chemical Co., Ltd. is cellulose diacetate. As Daicel Chemical, “L-70 (acetyl substitution degree: 2.45, Mn: 65000, Mw: 200000)”, “L-40 (acetyl substitution degree: 2.45)”, cellulose triacetate, Daicel Chemical “FRM (acetyl substitution degree: 2.79, Mn: 66000, Mw: 186000)”, etc.

In the present invention, the cellulose resin may be a cellulose derivative containing the following A), B) and C).
A) a hydrocarbon group,
B) A group containing an acyl group: —CO—R _B1 and an alkyleneoxy group: —R _B2 —O— (R _B1 represents a hydrocarbon group, and R _B2 represents an alkylene group having 3 carbon atoms), as well as,
C) Acyl group: —CO—R _C (R _C represents a hydrocarbon group).
That is, in the cellulose derivative in the present invention, at least a part of the hydrogen atoms of the hydroxyl group contained in cellulose {(C ₆ H ₁₀ O ₅ ) _n } is A) a hydrocarbon group, B) an acyl group (—CO—). R _B1 ) and an alkyleneoxy group (—R _B2 —O—) and the above C) acyl group (—CO—R _C ).
More specifically, the cellulose derivative has a repeating unit represented by the following general formula (A).

In the above formula, R ^2A , R ^3A and R ^6A are each independently a hydrogen atom, A) a hydrocarbon group, B) an acyl group (—CO—R _B1 ) and an alkyleneoxy group (—R _B2 —O—). Or C) an acyl group (—CO—R _C ). R _B1 and R _C each independently represents a hydrocarbon group. R _B2 represents an alkylene group having 3 carbon atoms. ^{However, R 2A,} R ^3A, and at least a portion of ^{R 6A} represents a hydrocarbon ^{group, R 2A,} R ^3A, and at least part of an acyl group _{(-CO-R B1)} and an alkyleneoxy group of ^{R 6A} ( -R _B2 -O-), and at least a part of R ^2A , R ^3A , and R ^6A represents an acyl group (-CO- _RC ).

As described above, in the cellulose derivative, at least a part of the hydroxyl groups of the β-glucose ring are A) a hydrocarbon group, B) an acyl group (—CO—R _B1 ), an alkyleneoxy group (—R _B2 —O—). And _C ) etherification and esterification with an acyl group (—CO—R _C ) can exhibit thermoplasticity and can be made suitable for molding.
Further, this cellulose derivative is insoluble in water, and can exhibit excellent strength and heat resistance as a molded body. Furthermore, since cellulose is a completely plant-derived component, it is carbon neutral and can greatly reduce the burden on the environment.
Here, “insoluble in water” as used in the present invention means that the solubility in 100 parts by mass of water at 25 ° C. is 5 parts by mass or less.

  The “cellulose” is a polymer compound in which a large number of glucoses are bonded by β-1,4-glycosidic bonds and bonded to carbon atoms at the 2nd, 3rd and 6th positions in the glucose ring of cellulose. Means that the hydroxyl group is unsubstituted. Further, “hydroxyl group contained in cellulose” refers to a hydroxyl group bonded to carbon atoms at the 2nd, 3rd and 6th positions in the glucose ring of cellulose.

The cellulose derivative has a group containing A) a hydrocarbon group, B) an acyl group (—CO—R _B1 ) and an alkyleneoxy group (—R _B2 —O—) in any part of the whole, and C ) An acyl group (—CO—R _C ) may be contained, and may be composed of the same repeating unit, or may be composed of a plurality of types of repeating units. Further, the cellulose derivative need not contain all the substituents of A) to C) in one repeating unit.
More specific embodiments include the following embodiments.
(1) A part of R ^2A , R ^3A and R ^6A is A) a repeating unit substituted with a hydrocarbon group, and part of R ^2A , R ^3A and R ^6A is B) an acyl group (—CO A repeating unit substituted with a group containing -R _B1 ) and an alkyleneoxy group (-R _B2 -O-), and a part of R ^2A , R ^3A and R ^6A is C) an acyl group (-CO- And a repeating unit substituted with R _C ).
(2) One of R ^2A , R ^3A and R ^6A of one repeating unit is A) a hydrocarbon group, B) an acyl group (—CO—R _B1 ) and an alkyleneoxy group (—R _B2 —O—) And C) the same type of repeating unit substituted with an acyl group (—CO—R _C ) (that is, having all of the substituents A) to C) in one repeating unit) Cellulose derivative.
(3) A cellulose derivative in which repeating units having different substituent positions and different types of substituents of A) to C) are bonded at random.
Further, a part of the cellulose derivative may contain an unsubstituted repeating unit (that is, a repeating unit in which R ^2A , R ^3A and R ^6A are all hydrogen atoms in the general formula (1)).

A) The hydrocarbon group may be either an aliphatic group or an aromatic group. In the case of an aliphatic group, it may be linear, branched or cyclic, and may have an unsaturated bond. Examples of the aliphatic group include an alkyl group, a cycloalkyl group, an alkenyl group, and an alkynyl group. Examples of the aromatic group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group.
A) The hydrocarbon group is preferably an aliphatic group, more preferably an alkyl group, and still more preferably an alkyl group having 1 to 4 carbon atoms (lower alkyl group). Specific examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, tert-butyl group, isoheptyl group, and the like. Group or ethyl group is preferred.

In the acyl group (—CO—R _B1 ), R _B1 represents a hydrocarbon group. R _B1 may be either an aliphatic group or an aromatic group. In the case of an aliphatic group, it may be linear, branched or cyclic, and may have an unsaturated bond. Examples of the aliphatic group include an alkyl group, a cycloalkyl group, an alkenyl group, and an alkynyl group. Examples of the aromatic group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group.
R _B1 is preferably an alkyl group or an aryl group. R _B1 is more preferably an alkyl group having 1 to 12 carbon atoms or an aryl group, still more preferably an alkyl group having 1 to 12 carbon atoms, still more preferably an alkyl group having 1 to 4 carbon atoms, Most preferred is an alkyl group having 1 or 2 carbon atoms (that is, a methyl group or an ethyl group).
Specifically, as R _B1 , methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, tert-butyl group, isoheptyl group and the like Is mentioned. Preferably, R _B1 is a methyl group, an ethyl group, or a propyl group.

In the alkyleneoxy group (—R _B2 —O—), the alkylene group portion (R _B2 ) having 3 carbon atoms may be linear, branched or cyclic, but may be linear or branched. The branched shape is preferable.
Specifically, examples of the alkyleneoxy group (—R _B2 —O—) include the following structures.

  Among these, a group represented by the following formula (1) or (2) in which the alkylene group portion is branched is preferable.

A plurality of the alkyleneoxy groups may be contained in the group B), but 1 is preferred. When two or more are included, the structure of the alkylene group having 3 carbon atoms may be the same or different.
Further, the bonding direction of the alkyleneoxy group to the cellulose derivative is not particularly limited, but the alkylene group part of the alkyleneoxy group is preferably bonded to the cellulose derivative molecule side (glucose ring side).

The B) group containing an acyl group (—CO—R _B1 ) and an alkyleneoxy group (—R _B2 —O—) is preferably a group containing a structure represented by the following general formula (3).
General formula (3)

In the formula, R _B1 and R _B2 have the same _{meanings as} described above, and preferred ranges thereof are also the same.
The group B) may contain a plurality of alkyleneoxy groups or only one alkyleneoxy group. More specifically, the group B) can be represented by the following general formula (1 ′).
General formula (1 ')

In the formula, R _B1 and R _B2 have the same _{meanings as} described above, and preferred ranges thereof are also the same. n is 1 or more. The upper limit of n is not particularly limited, and varies depending on the amount of alkyleneoxy group introduced, but is about 10, for example.
Further, in the cellulose derivative, the group of B) containing only one alkyleneoxy group (the group in which n is 1 in the above general formula (1 ′)) and the group of B) containing two or more alkyleneoxy groups (A group in which n is 1 in the above formula (1 ′)) may be mixed and contained.

C) In the acyl group (—CO—R _C ), R _C represents a hydrocarbon group. As the hydrocarbon group represented by R _{C, the same} groups as those described above for R _B1 can be used. The preferred range of R _C is the same as R _B1 .

The A) hydrocarbon group, the hydrocarbon group represented by R _B1 and R _C, and the alkylene group represented by R _B2 having 3 carbon atoms may have a further substituent or may be unsubstituted. It is preferably unsubstituted.
In particular, when R _B1 and R _C have a further substituent, it is preferable not to include a substituent that imparts water solubility, such as a sulfonic acid group or a carboxyl group. By not containing these groups, a cellulose derivative insoluble in water and a molding material comprising them are obtained. Moreover, when it has a sulfonic acid group, a carboxyl group, etc., it is known that a compound stability will be deteriorated, and since especially thermal decomposition is accelerated | stimulated, it is preferable not to contain these groups.

When the A) hydrocarbon group, R _B1 , R _C , and R _B2 have a further substituent, examples of the further substituent include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), hydroxy Group, an alkoxy group (the carbon number of the alkyl group is preferably 1 to 5), an alkenyl group, and the like. In addition, when said A) hydrocarbon group, R _<B1> , R _{< C >} , and R _<B2> are other than an alkyl group, it can also have an alkyl group (preferably C1-C5) as a substituent.

Moreover, it is preferable that the said cellulose derivative does not have substantially water-soluble substituents, such as a carboxyl group. When the cellulose derivative does not substantially have a carboxyl group, the resin composition can be made water-insoluble and the moldability can be improved.
Note that “substantially has no carboxyl group” means not only the case where the cellulose derivative has no carboxyl group, but also the case where the cellulose derivative has a trace amount of carboxyl groups in a range insoluble in water. It shall be included. For example, a cellulose which is a raw material may contain a carboxyl group, and a cellulose derivative in which the substituents A) to C) are introduced using this may contain a carboxyl group. In a cellulose derivative substantially free of

A) a hydrocarbon group, B) a group containing an acyl group (—CO—R _B1 ) and an alkyleneoxy group (—R _B2 —O—), and C) an acyl group (—CO—R _C ) in the cellulose derivative. There are no particular restrictions on the position of substitution and the number of substitution groups (substitution degree) per β-glucose ring unit.

For example, A) the degree of substitution DSa of the hydrocarbon group (A) the number of hydrocarbon groups with respect to the hydroxyl groups at the 2nd, 3rd and 6th positions of the β-glucose ring in the repeating unit) is 1.0 <DSa. Is preferable, and 1.0 <DSa <2.5 is more preferable.
B) Degree of substitution DSb of the group containing an acyl group (—CO—R _B1 ) and an alkyleneoxy group (—R _B2 —O—) (in the repeating unit, the 2nd, 3rd and 3rd positions of the cellulose structure of the β-glucose ring) The number B) of the group containing an acyl group and an alkyleneoxy group with respect to the hydroxyl group at the 6-position is preferably 0 <DSb, and more preferably 0 <DSb <1.0. Since 0 <DSb, the melting start temperature can be lowered, so that thermoforming can be performed more easily.
C) Degree of substitution DSc of the acyl group (—CO—R _C ) ( _C ) in the repeating unit, C) the number of acyl groups with respect to the hydroxyl groups at the 2nd, 3rd and 6th positions of the cellulose structure of the β-glucose ring. 1 <DSc is preferable, and 0.1 <DSc <2.0 is more preferable.
By setting the degree of substitution within the above range, mechanical strength, moldability, and the like can be improved.

  Further, the number of unsubstituted hydroxyl groups present in the cellulose derivative is not particularly limited. The degree of substitution DSh of hydrogen atoms (ratio in which the hydroxyl groups at the 2nd, 3rd and 6th positions in the repeating unit are unsubstituted) can be in the range of 0 to 1.5, preferably 0 to 0.6. do it. By setting DSh to 0.6 or less, it is possible to improve the fluidity of the thermoforming material, or to accelerate the thermal decomposition and suppress foaming due to water absorption of the thermoforming material during molding.

The cellulose derivative includes A) a hydrocarbon group, B) a group containing an acyl group (—CO—R _B1 ) and an alkyleneoxy group (—R _B2 —O—), and C) an acyl group (—CO). -R _C) may have a substituent other than. Examples of the substituent that may be included include a hydroxyethyl group, a hydroxypropyl group, a hydroxyethoxyethyl group, a hydroxypropoxypropyl group, a hydroxyethoxyethoxyethyl group, and a hydroxypropoxypropoxypropyl group. Therefore, the total sum of the degree of substitution of all substituents of the cellulose derivative is 3, but (DS _a + DS _b + DS _c + DS _h ) is 3 or less.

  The amount of alkyleneoxy group introduced in the group B) is expressed in terms of molar substitution (MS: number of moles of substituent introduced per glucose residue) (edited by Cellulose Society, Cellulose Dictionary P142). The molar substitution degree MS of the alkyleneoxy group is preferably 0 <MS, more preferably 0 <MS ≦ 1.5, and still more preferably 0 <MS <1.0. When MS is 1.5 or less (MS ≦ 1.5), heat resistance, moldability and the like can be improved, and a cellulose derivative suitable for a thermoforming material can be obtained.

The molecular weight of the cellulose derivative is preferably a number average molecular weight (Mn) in the range of 5 × 10 ^{3 to} 1000 × 10 ³ , more preferably in the range of 10 × 10 ^{3 to} 500 × 10 ³ , and 10 × 10 ³ to 200 ×. 10 ³ ranges are most preferred. The weight average molecular weight (Mw) is preferably in the range of 7 × 10 ^{3 to} 10000 × 10 ³ , more preferably in the range of 15 × 10 ^{3 to} 5000 × 10 ³ , and in the range of 100 × 10 ^{3 to} 3000 × 10 ³ . Is most preferred. By setting the average molecular weight within this range, it is possible to improve the moldability and mechanical strength of the molded body.
The molecular weight distribution (MWD) is preferably in the range of 1.1 to 10.0, and more preferably in the range of 1.5 to 8.0. By setting the molecular weight distribution within this range, moldability and the like can be improved.
The number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (MWD) can be measured using gel permeation chromatography (GPC). Specifically, N-methylpyrrolidone can be used as a solvent, a polystyrene gel can be used, and the molecular weight can be obtained using a conversion molecular weight calibration curve obtained in advance from a constituent curve of standard monodisperse polystyrene.

Among the cellulose derivatives described above, the following cellulose derivatives (1) and (2) are particularly excellent in thermoplasticity and mechanical strength (particularly toughness), and are particularly useful as thermoforming materials.
(1) a1) ethyl group, b1) acyl group: -CO-Rb1 (Rb1 represents a hydrocarbon group) and alkyleneoxy group: -Rb2-O- (Rb2 represents an alkylene group having 3 carbon atoms. ) And a c1) acyl group: -CO-Rc (Rc represents a hydrocarbon group) and a water-insoluble cellulose derivative.
(2) a2) methyl group, b2) acyl group: —CO—Rb1 (Rb1 represents a hydrocarbon group) and alkyleneoxy group: —Rb2-O— (Rb2 represents an alkylene group having 3 carbon atoms). ), And c2) an acyl group: —CO—Rc (Rc represents a hydrocarbon group), wherein the degree of substitution of the methyl group in the cellulose derivative is 1.1 or more. A cellulose derivative having a molar substitution degree (MS) of the alkyleneoxy group of 1.5 or less and insoluble in water.

Hydrocarbon group in which the Rb1 and Rc represent can be applied the same as those described in the above R _B1. The preferable ranges of Rb1 and Rc are the same as those of R _B1 . Further, an alkylene group having a carbon number of 3 represented by Rb2 may apply the same as those described in the above R _B2. A preferred range of Rb2 is the same as the _{R B2.}
In the aspect (1), the degree of substitution and the like are not particularly limited, and the range described above can be applied as a preferable range of the degree of substitution.
In the aspect (2), the substitution degree of the a2) methyl group is preferably 1.1 or more and 2.5 or less, more preferably 1.1 or more and 2.0 or less. Further, the molar substitution degree (MS) of the alkyleneoxy group is preferably more than 0 and 1.5 or less, and more preferably 0.1 or more and 1.2 or less. Other substitution degrees are not particularly limited, and the above-described ranges can be applied as preferable ranges.

The method for producing the cellulose derivative is not particularly limited, and the cellulose derivative can be produced by using cellulose as a raw material and etherifying and esterifying the cellulose. The raw material for cellulose is not limited, and examples thereof include cotton, linter, and pulp.
A preferred embodiment of the production method is performed by a method including a step of esterification (acylation) by reacting a hydroxypropyl cellulose ether having a hydrocarbon group and a hydroxypropyl group with an acid chloride or an acid anhydride. .
Further, as another embodiment, for example, after etherification with cellulose ether such as methyl cellulose or ethyl cellulose with propylene oxide or the like, alkyl chloride such as methyl chloride or ethyl chloride / alkylene oxide having 3 carbon atoms or the like is allowed to act on cellulose. Furthermore, a method including a step of esterification by reacting an acid chloride or an acid anhydride is also included.
As a method for reacting acid chloride, for example, the method described in Cellulose 10; 283-296, 2003 can be used.

  Specific examples of the cellulose ether having a hydrocarbon group and a hydroxypropyl group include hydroxypropylmethylcellulose, hydroxypropylethylcellulose, hydroxypropylpropylcellulose, hydroxypropylallylcellulose, hydroxypropylbenzylcellulose, and the like. Preferred are hydroxypropylmethylcellulose and hydroxypropylethylcellulose.

  As the acid chloride, an acyl group contained in B) and a carboxylic acid chloride corresponding to C) an acyl group can be used. Examples of the carboxylic acid chloride include acetyl chloride, propionyl chloride, butyryl chloride, isobutyryl chloride, pentanoyl chloride, 2-methylbutanoyl chloride, 3-methylbutanoyl chloride, pivaloyl chloride, hexanoyl chloride, 2-methylpentanoyl chloride, 3-methylpentanoyl chloride, 4-methylpentanoyl chloride, 2,2-dimethylbutanoyl chloride, 2,3-dimethylbutanoyl chloride, 3,3-dimethylbutanoyl chloride, 2- Ethylbutanoyl chloride, heptanoyl chloride, 2-methylhexanoyl chloride, 3-methylhexanoyl chloride, 4-methylhexanoyl chloride, 5-methylhexanoyl chloride, 2,2-dimethylpentanoyl chloride, , 3-dimethylpentanoyl chloride, 3,3-dimethylpentanoyl chloride, 2-ethylpentanoyl chloride, cyclohexanoyl chloride, octanoyl chloride, 2-methylheptanoyl chloride, 3-methylheptanoyl chloride, 4-methyl Heptanoyl chloride, 5-methylheptanoyl chloride, 6-methylheptanoyl chloride, 2,2-dimethylhexanoyl chloride, 2,3-dimethylhexanoyl chloride, 3,3-dimethylhexanoyl chloride, 2-ethylhexanoyl Chloride, 2-propylpentanoyl chloride, nonanoyl chloride, 2-methyloctanoyl chloride, 3-methyloctanoyl chloride, 4-methyloctanoyl chloride, 5-methyloctanoyl chloride, 6-methyloctanoy Chloride, 2,2-dimethylheptanoyl chloride, 2,3-dimethylheptanoyl chloride, 3,3-dimethylheptanoyl chloride, 2-ethylheptanoyl chloride, 2-propylhexanoyl chloride, 2-butylpentanoyl chloride, Decanoyl chloride, 2-methylnonanoyl chloride, 3-methylnonanoyl chloride, 4-methylnonanoyl chloride, 5-methylnonanoyl chloride, 6-methylnonanoyl chloride, 7-methylnonanoyl chloride, 2,2- Examples include dimethyloctanoyl chloride, 2,3-dimethyloctanoyl chloride, 3,3-dimethyloctanoyl chloride, 2-ethyloctanoyl chloride, 2-propylheptanoyl chloride, 2-butylhexanoyl chloride and the like.

As the acid anhydride, for example, a carboxylic acid anhydride corresponding to the acyl group contained in B) and the C) acyl group can be used. Examples of such carboxylic anhydrides include acetic anhydride, propionic anhydride, butyric anhydride, valeric anhydride, hexanoic anhydride, heptanoic anhydride, octanoic anhydride, 2-ethylhexanoic acid. An anhydride, nonanoic acid anhydride, etc. are mentioned.
As described above, since the cellulose derivative preferably has no carboxylic acid as a substituent, for example, a dicarboxylic acid such as phthalic anhydride or maleic anhydride is used, and a compound that generates a carboxyl group by reacting with cellulose is used. Preferably it is not.

  Other specific production conditions and the like can follow conventional methods. For example, a method described in “Encyclopedia of Cellulose” pages 131 to 164 (Asakura Shoten, 2000) can be referred to.

  When the resin composition of the present invention contains a cellulose resin, the content of the cellulose resin is not particularly limited. Preferably, the cellulose resin is contained in an amount of 41 to 61% by mass, more preferably 41 to 60% by mass, still more preferably 41 to 52% by mass, and particularly preferably 42 to 50% by mass, based on the total solid content of the resin composition. To do. By setting it as the above range, the resin composition of the present invention has a significance as a carbon neutral material, and obtains a molded product excellent in terms of heat resistance, bending elastic modulus, moldability, and bleed-out resistance. be able to.

  Since the cellulose resin is a plant-derived resin produced using carbon dioxide and water in the atmosphere as raw materials, it can be replaced with a conventional petroleum-derived resin as a material that can contribute to prevention of global warming. Further, by containing a cellulose resin, it is expected to be used as a resin composition that exhibits biodegradability and has a small environmental load, and a molding material.

4). Thermoplastic Resin Other than Cellulose Resin The resin composition of the present invention contains the cyclic phosphate compound, but preferably further contains a thermoplastic resin other than the cellulose resin. By containing the thermoplastic resin, the moldability and the flexural modulus can be further improved.
Specific examples of the thermoplastic resin include low density polyethylene, linear low density polyethylene, high density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-propylene-nonconjugated diene copolymer, ethylene-butene- 1 copolymer, polyolefin such as polypropylene, polybutene-1 and poly-4-methylpentene-1, polyester such as polybutylene terephthalate, polyethylene terephthalate and other aromatic polyesters, nylon 6, nylon 46, nylon 66, nylon 610 , Polyamides such as nylon 612, nylon 6T, nylon 12, polystyrene, high impact polystyrene, polyacetal (including homopolymers and copolymers), polyurethane, aromatic and aliphatic polyketones, polyphenylene Rufide, polyether ether ketone, thermoplastic starch resin, polymethyl methacrylate and acrylic resins such as methacrylic acid ester-acrylic acid ester copolymer, AS resin (acrylonitrile-styrene copolymer), ABS resin, AES resin (ethylene) Rubber reinforced AS resin), ACS resin (chlorinated polyethylene reinforced AS resin), ASA resin (acrylic rubber reinforced AS resin), polyvinyl chloride, polyvinylidene chloride, vinyl ester resin, maleic anhydride-styrene copolymer , MS resin (methyl methacrylate-styrene copolymer), polycarbonate, polyarylate, polysulfone, polyethersulfone, phenoxy resin, polyphenylene ether, modified polyphenylene ether, polyvinyl alcohol, unsaturated polyester, polyester Or the like can be mentioned lactic acid.
Of these, polypropylene, polycarbonate, polyester, and polylactic acid are preferable, polyester and polycarbonate are more preferable, and polycarbonate is particularly preferable. When polycarbonate is used in combination, the heat resistance is further improved. Moreover, it is excellent also in performance, such as a bending elastic modulus, a moldability, and water absorption resistance.
Since the cyclic phosphorus carbonate compound in the present invention contains a carbonate bond composed of the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II), the ester having a hydrophilic structure It is considered that the compatibility with the polyester or polycarbonate having a bond or a carbonate bond is excellent, and the improvement in heat resistance and bending elastic modulus, which could not be obtained with a conventional cyclic phosphorus compound, can be achieved.

  The thermoplastic resin other than the cellulose resin in the present invention can be produced by a known method. Moreover, a commercial item can also be used. For example, “NOVATEC PP MA3” manufactured by Nippon Polypro Co., Ltd. as the polypropylene, BASF manufactured by “BASF”, “Ecoflex” as the polyester, and “Panlite” manufactured by Teijin Chemicals Ltd. as the polycarbonate. L-1225Y ".

In the present invention, any of an aromatic polycarbonate, an aliphatic polycarbonate, and an aromatic-aliphatic polycarbonate can be used as the polycarbonate. Of these, aromatic polycarbonates are preferred because they are compatible with cellulose esters and are excellent in the balance of rigidity, impact resistance, and heat resistance of resins obtained by combining them with cellulose esters.
The molecular weight of the thermoplastic resin other than the cellulose resin in the present invention is in the range of 5,000 to 400,000 in terms of number average molecular weight, preferably 8,000 to 100,000, and more preferably 10,000 to 100,000. If the number average molecular weight is 10,000 or more, the mechanical strength is improved, and if it is 100,000 or less, the moldability is improved. More specifically, the number average molecular weight is obtained using N-methylpyrrolidone as a solvent, using a polystyrene gel, and using a conversion molecular weight calibration curve obtained in advance from a constituent curve of standard monodisperse polystyrene. As the GPC apparatus, HLC-8220 GPC (manufactured by Tosoh Corporation) can be used.

  The content of the thermoplastic resin other than the cellulose resin in the resin composition of the present invention is not particularly limited. Preferably, the thermoplastic resin is preferably 23 to 55% by mass, more preferably 30% to 55% by mass, still more preferably 32 to 55% by mass, particularly preferably 40%, based on the total solid content of the resin composition. Contains ~ 50% by mass. By setting it as the said range, the water absorption of a molded object and bleed-out-proof property can further be improved.

5). Flame retardant The resin composition of the present invention may further contain a flame retardant. The flame retardant is selected from the group consisting of brominated flame retardants, phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants and other inorganic flame retardants (preferably metal oxides or metal hydroxide flame retardants). It is preferable to include one or more flame retardants. Thereby, the flame-retardant effect, such as a reduction or suppression of a combustion rate, can be improved.
Among the flame retardants, brominated flame retardants and phosphorus flame retardants are preferable, and phosphorus flame retardants are particularly preferable.

The brominated flame retardant is not particularly limited, and a commonly used one can be used. For example, decabromodiphenyl oxide, octabromodiphenyl oxide, tetrabromodiphenyl oxide, tetrabromophthalic anhydride, tetrabromophthalate ester, hexabromocyclododecane, bis (2,4,6-tribromophenoxy) ethane, ethylenebistetrabromo Phthalimide, hexabromobenzene, 1,1-sulfonyl [3,5-dibromo-4- (2,3-dibromopropoxy)] benzene, polydibromophenylene oxide, tetrabromobisphenol-S, tris (2,3-dibromopropyl -1) Isocyanurate, tribromophenol, tribromophenyl allyl ether, octabromodiphenyl ether, tribromoneopentyl alcohol, brominated polystyrene, brominated polyethylene Tetrabromobisphenol-A, tetrabromobisphenol A or derivatives thereof, tetrabromobisphenol A epoxy oligomer or polymer, brominated epoxy oligomer or polymer such as brominated phenol novolac epoxy, tetrabromobisphenol A carbonate oligomer or polymer, tetrabromobisphenol -A-bis (2-hydroxydiethyl ether), tetrabromobisphenol-A-bis (2,3-dibromopropyl ether), tetrabromobisphenol-A-bis (allyl ether), tetrabromocyclooctane, ethylenebispentabromo Diphenyl, tris (tribromoneopentyl) phosphate, poly (pentabromobenzyl) acrylate, octabromotrimethylphenyl Ndan, dibromoneopentyl glycol, pentabromobenzyl polyacrylate and its reactant, dibromocresyl glycidyl ether, N, N′-ethylene-bis-tetrabromoterephthalimide, brominated triazine, tribromostyrene and its reactant, Examples include bromophenylmaleimide and its reactants.
These brominated flame retardants may be used singly or in combination of two or more.

The phosphorus-based flame retardant has an advantage that a decrease in flexural modulus and impact resistance is suppressed as compared with other flame retardants.
The phosphorus-based flame retardant is not particularly limited, and a commonly used one can be used. Examples thereof include organic phosphorus compounds such as phosphate esters, phosphate condensation esters, and polyphosphates.

  Specific examples of phosphate esters include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (isopropylphenyl) Phosphate, tris (phenylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropylphenyl) phenyl phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl Acid phosphate, 2-methacryloyloxyethyl acid phosphate, diphenyl Examples include 2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methanephosphonate, diethyl phenylphosphonate be able to.

  Examples of phosphoric acid condensed esters include resorcinol polyphenyl phosphate, resorcinol poly (di-2,6-xylyl) phosphate, bisphenol A polycresyl phosphate, hydroquinone poly (2,6-xylyl) phosphate, and condensates thereof. Aromatic phosphoric acid condensed ester and the like.

  Moreover, the polyphosphate which consists of a salt of phosphoric acid, polyphosphoric acid, a periodic table group 1-14 group metal, ammonia, an aliphatic amine, and an aromatic amine can also be mentioned. As typical salts of polyphosphates, lithium salts, sodium salts, calcium salts, barium salts, iron (II) salts, iron (III) salts, aluminum salts and the like as metal salts, methylamine salts as aliphatic amine salts, Examples include ethylamine salts, diethylamine salts, triethylamine salts, ethylenediamine salts, piperazine salts, and examples of aromatic amine salts include pyridine salts and triazines.

In addition to the above, halogen-containing phosphate esters such as trischloroethyl phosphate, trisdichloropropyl phosphate, tris (β-chloropropyl) phosphate), and structures in which a phosphorus atom and a nitrogen atom are connected by a double bond Phosphazene compounds having phosphoric acid and phosphoric ester amides.
These phosphorus flame retardants may be used singly or in combination of two or more.

  These phosphorus flame retardants can be produced by a known method. Moreover, a commercial item can also be used, for example, "PX-200, 1,3-phenylenebis (di-2,6-xylenyl phosphate) (made by Daihachi Chemical)" can be mentioned.

Examples of the nitrogen-based flame retardant include nitrogen-containing sulfate, sulfamate, and melamine cyanurate.
Examples of the nitrogen-containing sulfate include ammonium sulfate, dimethylamine sulfate, trimethylamine sulfate, diethylamine sulfate, triethylamine sulfate, diphenylamine sulfate, triphenylamine sulfate, guanidine sulfate, guanylurea sulfate, melamine sulfate, and combinations thereof. Guanidine sulfate, guanyl urea sulfate, melamine sulfate, or combinations thereof. Of these, melamine sulfate and guanidine sulfate are more preferable, and melamine sulfate is more preferable.
Examples of the sulfamate include those having 2 or more nitrogen atoms in the molecule. Specific examples include ammonium sulfamate, guanidine sulfamate, guanylurea sulfamate, melamine sulfamate, dimethylamine sulfamate, trimethylamine sulfamate, diethylamine sulfamate, triethylamine sulfamate, triphenylamine sulfamate, or combinations thereof. Among them, guanidine sulfamate, guanylurea sulfamate, melamine sulfamate or a combination thereof is preferable, guanidine sulfamate, guanylurea sulfamate, diethylamine sulfamate, triethylamine sulfamate is more preferable, and guanidine sulfamate and guanylurea sulfamate are preferable. Further preferred.
These nitrogen-based flame retardants may be used singly or in combination of two or more.

Examples of the silicone flame retardant include a two-dimensional or three-dimensional organosilicon compound, polydimethylsiloxane, or a methyl group at a side chain or a terminal of polydimethylsiloxane, a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, Examples thereof include those substituted or modified with an aromatic hydrocarbon group, so-called silicone oils, or modified silicone oils.
Examples of the substituted or unsubstituted aliphatic hydrocarbon group and aromatic hydrocarbon group include an alkyl group, a cycloalkyl group, a phenyl group, a benzyl group, an amino group, an epoxy group, a polyether group, a carboxyl group, a mercapto group, Examples include a chloroalkyl group, an alkyl higher alcohol ester group, an alcohol group, an aralkyl group, a vinyl group, or a trifluoromethyl group.
These silicon-containing flame retardants may be used alone or in combination of two or more.

  In addition to the brominated flame retardant, phosphorus-based flame retardant, nitrogen-based flame retardant, and silicone-based flame retardant, an inorganic flame retardant is preferable, and a metal oxide or a metal hydroxide flame retardant is more preferable. preferable. For example, magnesium hydroxide, aluminum hydroxide, antimony trioxide, antimony pentoxide, sodium antimonate, zinc hydroxystannate, zinc stannate, metastannic acid, tin oxide, tin oxide salt, zinc sulfate, zinc oxide, first oxide Iron, ferric oxide, stannous oxide, stannic oxide, zinc borate, ammonium borate, ammonium octamolybdate, metal salt of tungstic acid, complex oxide of tungsten and metalloid, ammonium sulfamate, odor Inorganic flame retardants such as ammonium fluoride, zirconium compounds, guanidine compounds, fluorine compounds, graphite, and swellable graphite can be used. These other flame retardants may be used alone or in combination of two or more.

  In the resin composition of the present invention, the content of the flame retardant is not limited, but is preferably 5 to 15% by mass, and preferably 7 to 10% by mass with respect to the total solid content of the resin composition. More preferred. When the content is within this range, it is preferable from the viewpoint of improving the flexural modulus in addition to flame retardancy.

6). Fluorine-based resin The resin composition of the present invention preferably further contains a fluorine-based resin. This is to prevent drip when the molded body burns and to obtain higher flame retardancy.
Fluorine-based resin is a resin containing fluorine in a substance molecule. Specifically, polytetrafluoroethylene, polyhexafluoropropylene, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / perfluoro Examples include alkyl vinyl ether copolymers, tetrafluoroethylene / ethylene copolymers, hexafluoropropylene / propylene copolymers, polyvinylidene fluorides, vinylidene fluoride / ethylene copolymers, among which polytetrafluoroethylene, tetra Fluoroethylene / perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / ethylene copolymer, and polyvinylidene fluoride are preferred. In particular, polytetrafluoroethylene and a tetrafluoroethylene / ethylene copolymer are preferable, polytetrafluoroethylene is more preferable, and a polytetrafluoroethylene-containing mixed powder composed of polytetrafluoroethylene particles and an organic polymer is also preferable. Used. The molecular weight of the fluororesin such as polytetrafluoroethylene is preferably in the range of 100,000 to 10,000,000, more preferably in the range of 100,000 to 1,000,000, particularly for the extrudability and flame retardancy of the present invention. effective. Commercially available products of polytetrafluoroethylene include “Teflon (registered trademark)” 6-J, “Teflon (registered trademark)” 6C-J, and “Teflon (registered trademark)” 62 manufactured by Mitsui DuPont Fluorochemical Co., Ltd. -J, “Full-on” CD1 and CD076 manufactured by Asahi IC Fluoropolymers Co., Ltd. are commercially available. In addition, as a commercial product of a polytetrafluoroethylene-containing mixed powder composed of polytetrafluoroethylene particles and an organic polymer, it is commercially available as “Metabrene (registered trademark)” A series from Mitsubishi Rayon Co., Ltd. METABLEN (registered trademark) “A-3000”, “METABBRENE (registered trademark)” A-3800, and the like are commercially available. In addition, polytetrafluoroethylene “Teflon (registered trademark)” 6-J and the like are prone to agglomerate, so if they are mechanically strongly mixed with other resin compositions using a Henschel mixer or the like, agglomeration may occur due to aggregation. There are problems in handling and dispersibility depending on conditions. On the other hand, a polytetrafluoroethylene-containing mixed powder composed of polytetrafluoroethylene particles and an organic polymer is excellent in handling properties and dispersibility, and is particularly preferably used. The polytetrafluoroethylene-containing mixed powder composed of the polytetrafluoroethylene particles and the organic polymer is not limited, but polytetrafluoroethylene disclosed in Japanese Patent Application Laid-Open No. 2000-226523. Examples thereof include polytetrafluoroethylene-containing mixed powder composed of particles and an organic polymer. Examples of the organic polymer include aromatic vinyl monomers, acrylate monomers, and vinyl cyanide. An organic polymer containing 10% by mass or more of a monomer, and a mixture thereof. The content of polytetrafluoroethylene in the polytetrafluoroethylene-containing mixed powder is 0.1% by mass to 90%. It is preferable that it is mass%.

  The content of the fluororesin in the resin composition of the present invention is preferably 0.01 to 1% by mass, more preferably 0.05 to 0.5% by mass, based on the total solid content of the resin composition. It is. By setting it as this range, a flame retardance can be improved more, suppressing the influence on a moldability.

7). Antioxidant It is preferable that the resin composition of the present invention further contains an antioxidant.
Examples of antioxidants include hindered phenolic antioxidants, phosphorus antioxidants, amine antioxidants, sulfur antioxidants, calcium carbonate antioxidants, and hindered phenolic agents. It is possible to use an antioxidant (for example, “Irganox 1010” manufactured by Ciba Specialty Chemicals, “Sumilyzer GP” manufactured by Sumitomo Chemical Co., Ltd.) and a phosphorus-based antioxidant (“PEP-36” manufactured by Asahi Denka). preferable.
The content of the antioxidant in the resin composition of the present invention is not limited, but is preferably 30% by mass or less, more preferably 0.01 to 10% by mass with respect to the total solid content of the resin composition. It is. By setting it as this range, it is preferable from a viewpoint of coloring property improvement.

8). Plasticizer It is preferable that the resin composition of the present invention further contains a plasticizer. Thereby, a moldability can be improved.
As the plasticizer, those commonly used for polymer molding can be used. Examples thereof include polyester plasticizers, glycerin plasticizers, polycarboxylic acid ester plasticizers, polyalkylene glycol plasticizers, and epoxy plasticizers.

  Specific examples of the polyester plasticizer include acid components such as adipic acid, sebacic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, rosin, propylene glycol, 1,3-butanediol, 1,4 -Polyesters composed of diol components such as butanediol, 1,6-hexanediol, ethylene glycol and diethylene glycol, and polyesters composed of hydroxycarboxylic acids such as polycaprolactone. These polyesters may be end-capped with a monofunctional carboxylic acid or monofunctional alcohol, or may be end-capped with an epoxy compound or the like.

  Specific examples of the glycerin plasticizer include glycerin monoacetomonolaurate, glycerin diacetomonolaurate, glycerin monoacetomonostearate, glycerin diacetomonooleate, glycerin monoacetomonomontanate, and glycerin tribenzoate.

  Specific examples of polycarboxylic acid ester plasticizers include phthalates such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diheptyl phthalate, dibenzyl phthalate, and butyl benzyl phthalate. Tributyl acid, trioctyl trimellitic acid, trihexyl trimellitic acid, trimellitic acid ester such as tri (2-ethylhexyl) trimellitic acid, diisodecyl adipate, n-octyl-n-decyl adipate, methyl diglycol butyldidipate Adipic acid ester such as glycol, benzyl methyl diglycol adipate, benzyl butyl diglycol adipate, citrate ester such as triethyl acetyl citrate, tributyl acetyl citrate, di-2-azelineate Azelaic acid esters such as hexyl, dibutyl sebacate, and di-2-ethylhexyl sebacate, and the like.

  Specific examples of the polyalkylene glycol plasticizer include polyethylene glycol, polypropylene glycol, poly (ethylene oxide / propylene oxide) block and / or random copolymer, polytetramethylene glycol, ethylene oxide addition polymer of bisphenols, and bisphenols. And a polyalkylene glycol such as a propylene oxide addition polymer, a tetrahydrofuran addition polymer of bisphenol, or a terminal epoxy-modified compound thereof, a terminal ester-modified compound, a terminal ether-modified compound, and the like.

  The epoxy plasticizer generally refers to an epoxy triglyceride composed of an alkyl epoxy stearate and soybean oil, but there are also so-called epoxy resins mainly made of bisphenol A and epichlorohydrin. Can be used.

  Specific examples of other plasticizers include benzoic acid esters of aliphatic polyols such as ethylene glycol, neopentyl glycol dibenzoate, diethylene glycol dibenzoate, and triethylene glycol di-2-ethylbutyrate, and fatty acid amides such as stearamide. And aliphatic carboxylic acid esters such as butyl oleate, oxyacid esters such as methyl acetylricinoleate and butyl acetylricinoleate, pentaerythritol, and various sorbitols.

  As a plasticizer, 500 or more are preferable, as for a mass average molecular weight, 600-4000 are more preferable, and 800-2000 are especially preferable. When the average molecular weight of the plasticizer is within this range, the compatibility with the cellulose ester is enhanced, the dispersibility is improved, and the bleed-out suppressing effect is high.

  The content of the plasticizer in the resin composition of the present invention is preferably 10 to 30% by mass, more preferably 12 to 25% by mass, and particularly preferably 15 to 20% by mass with respect to the total solid content of the resin composition. . When the content is within this range, it is preferable from the viewpoint of improving the flexural modulus, heat resistance, and moisture absorption resistance.

9. Other Additives and Molded Body The resin composition of the present invention may contain various additives such as a filler (reinforcing material) as necessary in addition to the above-described components.

The resin composition of the present invention may contain a filler (reinforcing material). By containing the filler, the mechanical properties of the molded body formed from the resin composition can be enhanced.
A well-known thing can be used as a filler. The shape of the filler may be any of fibrous, plate-like, granular, powdery and the like. Further, it may be inorganic or organic.
Specifically, as the inorganic filler, glass fiber, carbon fiber, graphite fiber, metal fiber, potassium titanate whisker, aluminum borate whisker, magnesium whisker, silicon whisker, wollastonite, sepiolite, slag fiber, zonolite, Elastadite, gypsum fiber, silica fiber, silica-alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber and boron fiber, and other inorganic fillers; glass flakes, non-swellable mica, carbon black, graphite, metal foil , Ceramic beads, talc, clay, mica, sericite, zeolite, bentonite, dolomite, kaolin, fine silicate, feldspar, potassium titanate, shirasu balloon, calcium carbonate, magnesium carbonate, barium sulfate, calcium oxide Beam, aluminum oxide, titanium oxide, magnesium oxide, aluminum silicate, silicon oxide, aluminum hydroxide, magnesium hydroxide, gypsum, novaculite, dawsonite, and a plate-like or granular inorganic fillers of clay or the like.

  Organic fillers include synthetic fibers such as polyester fiber, nylon fiber, acrylic fiber, regenerated cellulose fiber, and acetate fiber, and natural fibers such as kenaf, ramie, cotton, jute, hemp, sisal, Manila hemp, flax, linen, silk, and wool. Examples thereof include fibrous organic fillers obtained from microcrystalline cellulose, sugar cane, wood pulp, paper waste, waste paper and the like, and granular organic fillers such as organic pigments.

  When the resin composition contains a filler, the content is not limited, but is preferably 30% by mass or less, and more preferably 5 to 10% by mass with respect to the total solid content of the resin composition.

In addition to those described above, the resin composition of the present invention may contain other components for the purpose of further improving various properties such as moldability and flame retardancy, as long as the object of the present invention is not impaired. Good.
Other components include, for example, release agents (fatty acids, fatty acid metal salts, oxy fatty acids, fatty acid esters, aliphatic partially saponified esters, paraffins, low molecular weight polyolefins, fatty acid amides, alkylene bis fatty acid amides, aliphatic ketones, fatty acid lowers. Alcohol ester, fatty acid polyhydric alcohol ester, fatty acid polyglycol ester, modified silicone), antistatic agent, flame retardant aid, processing aid, antibacterial agent, antifungal agent and the like. Further, a coloring agent containing a dye or a pigment can be added.

The resin composition of the present invention can be used for various applications.
The resin composition of the present invention is preferably a resin composition having thermoplasticity. Moreover, it is preferable that the resin composition of this invention is a resin composition for injection molding.

The molded product of the present invention can be obtained by molding the resin composition of the present invention. Preferably, the molded article of the present invention is obtained by thermoforming the resin composition.
The manufacturing method of the molded object of this invention includes the process of heating and shape | molding the resin composition of this invention.
Examples of the molding method include injection molding, extrusion molding, blow molding and the like.
The heating temperature is preferably 160 to 300 ° C, more preferably 180 to 260 ° C.
The manufacturing method of the molded object of this invention includes the process of heating and shape | molding the resin composition of this invention.

  The use of the molded product of the present invention is not particularly limited. For example, interior or exterior parts of electrical and electronic equipment (home appliances, OA / media related equipment, optical equipment, communication equipment, etc.), automobiles, mechanical parts, etc. , Housing / building materials, films, etc. Among these, from the viewpoint of having excellent heat resistance and impact resistance and low environmental impact, for example, exterior parts (especially casings) for electrical and electronic equipment such as copiers, printers, personal computers, and televisions. ) Can be suitably used.

  EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the scope of the present invention is not limited to the examples shown below.

  An example of a method for synthesizing a cyclic phosphorus carbonate compound is shown below.

<Synthesis Example 1 (Synthesis of Compound 43)>

In a 200 mL eggplant flask, compound 43a: 2.4 g (3.8 mmol), NMP (N-methylpyrrolidone) 30 mL, triethylamine 0.77 g (7.6 mmol), DMAP (N, N-dimethyl-4-aminopyridine) in small quantities Was added and cooled to 0 ° C. Thereto, 1.34 g (3.8 mmol) of bisphenol A bis (chloroformate) (compound 43b) was slowly added dropwise, the temperature was slowly raised to 140 ° C., and the mixture was heated and stirred for 5 hours. After cooling, the reaction solution was slowly poured into 300 mL of water, suction filtered, and washed with methanol and water to obtain 1.5 g of a white solid. The 1H-NMR measurement result of compound 43 and the molecular weight measurement value by GPC (apparatus: HLC-8220 GPC (manufactured by Tosoh Corporation), solvent tetrahydrofuran, polystyrene conversion value) are shown below. From the 1H-NMR measurement results, it was found that the copolymerization ratio in Compound 43 was 50:50.
1H-NMR (deuterated chloroform): δ = 1.5-1.8 (m, 6H); 6.5-6.9 (m, 5H); 6.9-7.1 (m, 3H); 7 1-7.4 (m, 11H); 7.4-7.8 (m, 8H); 7.8-8.0 (m, 3H); 8.0-8.2 (m, 1H) 8.4-8.7 (m, 1H)
Mn (number average molecular weight): 5000 Mw (mass average molecular weight): 5400
Compound 43a was synthesized by a known method (for example, Journal of Polymer Science, Part A: Polymer Chemistry, 40, P359, 2001). Further, other cyclic phosphorus carbonate compounds used in the examples can be synthesized in the same manner.

<Examples 1 to 13, Comparative Examples 1 and 2>
[Production of molded body]
Cellulosic resins, cyclic phosphorus compounds, thermoplastic resins, antioxidants, flame retardants, fluororesins, and other components were mixed at a blending ratio (parts by mass) shown in Tables 1 and 2 to prepare a resin composition. . This resin composition is supplied to a twin-screw kneading extruder (manufactured by Technobel Co., Ltd., Ultrano) to produce pellets, and then the obtained pellets are injected into an injection molding machine (manufactured by Imoto Seisakusho, semi-automatic injection molding machine). And 4 × 10 × 80 mm multipurpose test pieces (impact test pieces and thermal deformation test pieces) were molded at a cylinder temperature of 190 ° C., a mold temperature of 30 ° C., and an injection pressure of 1.5 kgf / cm ² .
The cylinder temperature in the polymer molding was set to a temperature at which the melt flow rate was in the range of 6 to 9 g / 10 min. The mold temperature was 30 ° C.

In Tables 1 and 2, each component indicates the following.
Cellulose diacetate: Daicel Chemical Industries, L-70 (degree of substitution: 2.45, Mn: 65000, Mw: 200000)
Cellulose acetate propionate: manufactured by Eastman Chemical Co., 482-20 (propionyl substitution degree: 2.5 / acetyl substitution degree: 0.1, Mn: 73000, Mw: 234000)
-Cyclic phosphate compounds 14, 28, 32, 43:

  The numbers appended to each structural unit in each structural formula of the cyclic phosphorus carbonate compound represent the composition ratio (molar ratio) of the structural unit.

  As a comparative compound, Comparative Compound 1 having the following structure described in JP 2010-59145 A was used.

・ Polyester: Ecoflex (manufactured by BASF)
Polycarbonate: (Teijin Chemicals Ltd., “Panlite L-1225Y”)
・ Flame retardant 1: (bromine-based) octabromodiphenyl ether Product name: Prasafety (R) EB-8 (manac)
Flame retardant 2: (Silicone-based) X-22-343 (manufactured by Shin-Etsu Chemical Co., Ltd.)
-Flame retardant 3: (Nitrogen) Apinone 901 (Melamine sulfate, manufactured by Sanwa Chemical Co., Ltd.)
・ Flame retardant 4: TPP (triphenyl phosphate) (Daihachi Chemical Industry Co., Ltd.)
Flame retardant 5: (Inorganic) Kisuma 5L (magnesium hydroxide, manufactured by Kyowa Chemical Industry Co., Ltd.)
Flame retardant 6: (Phosphorus) PX-200 (Daihachi Chemical Co., Ltd.)
PEP-36: Phosphorous antioxidant, manufactured by Asahi Denka Co., Ltd. Irganox 1010: Phenol antioxidant, “Irganox 1010”, Ciba Specialty Chemicals Co., Ltd.
・ CaCO ₃ (Wako Pure Chemical Industries, Ltd.)
Teflon (registered trademark) 6-J: Mitsui DuPont Fluorochemical Co., Ltd. polytetrafluoroethylene

[Evaluation]
The following items were evaluated using the obtained resin composition and multipurpose test piece. The evaluation results are shown in Tables 1 and 2.

(Heat deformation temperature (HDT))
In accordance with ISO75, a constant bending load (1.8 MPa) is applied to the center of the test piece (in the flatwise direction), the temperature is increased at a constant speed, and the temperature when the strain at the center reaches 0.34 mm ( ° C). As a heat distortion temperature measuring device, HDT tester 6M-2 manufactured by Toyo Seiki Seisakusho Co., Ltd. was used. The measurement is an average of three measurements.

(Flexural modulus)
In accordance with ISO178, after adjusting the test piece molded by injection molding for 48 hours or more at 23 ° C ± 2 ° C, 50% ± 5% RH, the distance between fulcrums by Instron (Toyo Seiki, Strograph V50) The flexural modulus was measured at 64 mm and a test speed of 2 mm / min. The measurement is an average of three measurements.

(Formability)
The moldability evaluation indicates moldability in an injection molding machine. Good molding transportability means that the resin composition can be stably supplied when charged into the molding machine, and the load is not excessive. Also, good injection means that the resin can be molded into a desired shape without deterioration such as coloring. A resin composition having good molding transportability and injection property was marked with ◎, a resin composition with problems on either side was marked with ◯, a resin composition with problems on both sides was marked with △, and a resin composition that could not be molded was marked with x.

(Flame retardance)
As a flame retardant index, a vertical combustion test based on UL94 was performed. The number of tests is five. V-not for non-self-extinguishing material, drip of resin composition during combustion test, V-2 for self-extinguishing within a predetermined time (within 30 seconds of combustion time), no drip of resin composition during combustion Those that self-extinguish within a predetermined time were designated as V-1 (combustion time within 30 seconds) and V-0 (combustion time within 10 seconds).

(Bleed-out resistance)
Letters (ABC) were written with oil-based ink on the surface of the test piece obtained by molding, and this test piece was left under conditions of 65 ° C. and 90% RH for 4 hours. Then, the bleed-out state of the additive component on the surface of the test piece was visually judged based on the following criteria.
A: Bleed-out is not seen at all, and there is no bleeding of ink characters.
○: Bleed-out is hardly seen, and ink characters are hardly blotted.
Δ: Bleed-out is slightly observed and ink characters are blurred.
X: The bleed-out is remarkable and the ink character is blurred to a level where it cannot be recognized.

  From the above results, the resin composition containing the cyclic phosphate compound in the present invention is excellent in heat resistance, moldability and flame retardancy, has a high bending elastic modulus, and can obtain a molded article excellent in bleed-out resistance. I understand. On the other hand, in Comparative Example 1 which does not contain the cyclic phosphate compound in the present invention and uses TPP which is a conventional flame retardant, and Comparative Example 2 which uses Comparative Compound 1 described in JP 2010-59145 A, Bleed-out resistance, heat resistance, flexural modulus, moldability and difficulty compared to Example 11 using the cyclic phosphate compound in the present invention instead of TPP in Comparative Example 1 or Comparative Compound 1 in Comparative Example 2 It was inferior to all of flammability.

Claims (16)

A compound comprising a structural unit represented by the following general formula (I) and a structural unit represented by the following general formula (II).

In general formula (I), R ¹ , R ² , R ³ , and R ⁴ each independently represent a halogen atom, a hydroxyl group, a substituted or unsubstituted amino group, a nitro group, a cyano group, a substituted or unsubstituted group. It represents an alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a sulfonic acid group.
R ⁵ represents a hydrogen atom, a substituted or unsubstituted aryl group, or a group represented by the following general formula (III).
n1, n2, n3, and n4 each independently represents an integer of 0 to 4.

In general formula (III), R ⁶ and R ⁷ are each independently a halogen atom, hydroxyl group, substituted or unsubstituted amino group, nitro group, cyano group, substituted or unsubstituted alkyl group, substituted or unsubstituted A cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a sulfonic acid group.
n6 and n7 each independently represents an integer of 0 to 4.
* Represents a binding site.
In general formula (II), L represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted divalent heterocyclic group, and the following general formula It represents a divalent linking group represented by (L-1) or a divalent linking group formed by combining these groups.

In general formula (L-1), X represents an oxygen atom or a sulfur atom.
m1 and m3 each independently represents an integer of 1 to 8.
m2 represents an integer of 1 to 30.
Each ** represents a binding site. The compound according to claim 1, wherein, in the general formula (I), R ⁵ represents a substituted or unsubstituted aryl group or a group represented by the general formula (III).   The ratio of the content of the structural unit represented by the general formula (I) and the content of the structural unit represented by the general formula (II) is 30:70 to 70:30 in molar ratio. The compound according to 1 or 2.   The compound of any one of Claims 1-3 whose mass mean molecular weight is in the range of 500-10000.   The flame retardant which is a compound of any one of Claims 1-4.   The resin composition containing the compound of any one of Claims 1-4.   The resin composition of Claim 6 which contains 4-20 mass% of the compounds of any one of Claims 1-4 with respect to the total solid of a resin composition.   Furthermore, the resin composition of Claim 6 or 7 containing a cellulose resin.   The resin composition of Claim 8 which contains 41-61 mass% of the said cellulose resin with respect to the total solid of a resin composition.   Furthermore, the resin composition of Claim 8 or 9 containing thermoplastic resins other than a cellulose resin.   The resin composition according to claim 8 or 9, wherein the cellulose resin is a cellulose ester.   The resin composition according to claim 11, wherein the cellulose ester is cellulose diacetate or cellulose acetate propionate.   The resin composition according to claim 10, wherein the thermoplastic resin other than the cellulose resin is at least one of polyester and polycarbonate.   Furthermore, it contains one or more flame retardants selected from the group consisting of brominated flame retardants, phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, metal oxides and metal hydroxide flame retardants. The resin composition according to any one of 6 to 13.   Furthermore, the resin composition of any one of Claims 6-14 containing a fluorine resin.   The housing | casing for electric and electronic devices comprised from the molded object obtained by heat-molding the resin composition of any one of Claims 6-15.