JP6075776B2 - Polyester plasticizer and cellulose resin composition - Google Patents

Description

  The present invention relates to a polyester-based plasticizer and a cellulose-based resin composition containing the polyester-based plasticizer, and more specifically, a polyester-based plasticizer capable of suppressing contamination of a processing machine during processing and a decrease in productivity. The present invention relates to a cellulose resin composition containing the same.

  Cellulosic resins have attracted attention in recent years as resins with low environmental impact. In general, it is tougher than other synthetic resins, has excellent characteristics such as excellent transparency, gloss and gloss, and a smooth surface and good touch. For this reason, the use of the cellulose-based resin is very diverse, for example, a sheet, a film, a wire coating, a toy, a medical device or a food packaging material.

  However, cellulosic resins do not have thermoplasticity, and must be melted or melted in a solvent at the time of processing and molding, but when they are melted at a high temperature, they simultaneously undergo thermal decomposition and become colored. There is. In order to avoid this, it is necessary to add an appropriate plasticizer to lower its softening point.

  For the above purpose, conventionally, for example, triphenyl phosphate, tricresyl phosphate, diphenyl phosphate, triethyl phosphate, tributyl phosphate, dimethyl phthalate, diethyl phthalate, dimethoxyethyl phthalate, ethyl phthalyl ethyl glycolate, butyl phthalyl butyl Glycolate, toluenesulfonamide, triacetin, pentaerythritol tetraacetate and the like have been used.

However, the above plasticizers can satisfy a wide range of performances such as compatibility with cellulosic resins, plasticization efficiency, non-volatility, stability to heat and light, non-migration, non-extractability, and water resistance. There is nothing, and the current situation is that it hinders further expansion of the use of the cellulose resin composition.
For this reason, Patent Documents 1 to 4 propose cellulose-based resin compositions obtained by blending various polyester-based plasticizers.

JP 2009-173740 A JP 2009-173741 A JP 2009-173742 A JP 2009-191219 A

  However, the cellulosic resin composition described in the above-mentioned patent document still has room for improvement in terms of contamination of the processing machine due to volatilization during the processing of the contained components and the resulting decrease in product yield.

  Accordingly, an object of the present invention is to provide a polyester plasticizer capable of suppressing contamination of a processing machine during processing, and a decrease in productivity caused thereby, and a cellulose resin composition obtained by adding the polyester plasticizer. Is to provide.

  As a result of intensive studies in order to solve the above problems, the present inventors have found that a specific polyester plasticizer can solve the above problems, and have completed the present invention.

（式（１）中、ｎは平均重合度を表し、１．９５＜ｎ≦６であり、Ａはエチレン基およびフェニレン基を、Ｇはエチレングリコールおよび１，２−プロピレングリコールから２つのヒドロキシル基を除いた基を、Ｅはアセチル基またはベンゾイル基を表す。） That is, the polyester plasticizer of the present invention is characterized in that the component represented by the following general formula (1) and having a polymerization degree of 1 is 0.7 to 1.3% by mass. .

(In the formula (1), n represents an average degree of polymerization, 1.95 <n ≦ 6, A represents an ethylene group and a phenylene group, and G represents two hydroxyl groups from ethylene glycol and 1,2-propylene glycol. E represents an acetyl group or a benzoyl group.

  The method for producing a polyester plasticizer according to the present invention is characterized in that a component having a polymerization degree of 1 is 0.7 to 1.3% by mass by thin film distillation in producing the polyester plasticizer. Is.

  The cellulose resin composition of the present invention is characterized by containing 1 to 50 parts by mass of any one of the above polyester plasticizers with respect to 100 parts by mass of the cellulose resin.

  In the cellulose resin composition of the present invention, the cellulose resin is preferably cellulose acylate.

  According to the present invention, it is possible to provide a polyester plasticizer in which contamination of a processing machine during processing and a decrease in productivity caused thereby are suppressed, and a cellulose resin composition obtained by adding the polyester plasticizer. It becomes possible.

Hereinafter, the polyester plasticizer of the present invention will be described in detail.
The polyester plasticizer of the present invention is characterized in that the component represented by the general formula (1) and having a polymerization degree of 1 is less than 5% by mass.
The component having a polymerization degree of 1 is a compound in which n is 1 in the general formula (1). Thereby, it becomes possible to suppress the contamination of the processing machine at the time of processing due to the volatilization component, and the resulting decrease in productivity.
The polyester plasticizer of the present invention is usually used as a mixture of compounds represented by the above general formula (1).

  In the general formula (1), examples of the linear or branched alkylene group having 1 to 18 carbon atoms that A can take include, for example, removing any one hydrogen atom from the following alkyl group having 1 to 18 carbon atoms. Groups. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert- Amyl group, 1,2-dimethylpropyl group, n-hexyl group, 1,2-dimethylbutyl group, 1-isopropylpropyl group, 1,3-dimethylbutyl group, n-heptyl group, 2-heptyl group, 1, 4-dimethylpentyl group, tert-heptyl group, 2-methyl-1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, tert-octyl group, 2-methylhexyl group, 2-ethylhexyl group 2-propylhexyl group, n-nonyl group, isononyl group, n-decyl group, isodecyl group, n-undecyl group, Undecyl group, n-dodecyl group, isododecyl group, n-tridecyl group, isotridecyl group, n-tetradecyl group, isotetradecyl group, n-pentadecyl group, isopentadecyl group, n-hexadecyl group, isohexadecyl group, n -Heptadecyl group, isoheptadecyl group, n-octadecyl group, isooctadecyl group, etc. are mentioned. Among these, an alkylene group having 2 to 5 carbon atoms is preferable.

  In the general formula (1), examples of the cycloalkylene group having 5 to 12 carbon atoms that A can take include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclododecyl group, and a 4-methylcyclohexyl group. And a group in which any one hydrogen atom is removed.

  In said general formula (1), as a C6-C18 aromatic group which A can take, a phenyl group, a naphthyl group, anthracen-1-yl group, a phenanthren-1-yl group etc. are mentioned, for example. Of these, a phenyl group and a naphthyl group are preferable.

  The polyester plasticizer of the present invention can also be used as a mixture of compounds having different A in the general formula (1).

  In the general formula (1), as the linear or branched alkylene group having 2 to 12 carbon atoms or the linear or branched alkylene group having 4 to 12 carbon atoms that can be taken by G, for example, Examples include groups obtained by removing two hydroxyl groups from the following glycols. As glycol, ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2 -Diethyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1 , 5-pentanediol, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, and the like. In addition, a group obtained by removing two hydroxyl groups from a trihydric or higher polyhydric alcohol such as glycerin, trimethylolpropane, trimethylolethane, dipentaerythritol, and pentaerythritol may be used.

  Among the groups obtained by removing two hydroxyl groups from the glycol, selected from the group consisting of ethylene glycol, 1,2-propylene glycol, butanediol, neopentyl glycol, diethylene glycol, triethylene glycol, cyclohexanediol, and cyclohexanedimethanol. A group obtained by removing two hydroxyl groups from one or more selected from the group consisting of one or more selected from the group consisting of ethylene glycol, 1,2-propylene glycol, 1,3-butanediol, and 1,4-butanediol. A group in which two hydroxyl groups are removed is more preferable.

  In the general formula (1), examples of the cycloalkylene group having 5 to 12 carbon atoms that G can take include any one of a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclododecyl group, a 4-methylcyclohexyl group, and the like. And a group in which two hydrogen atoms are removed.

  The polyester plasticizer of the present invention can also be used as a mixture of compounds having different G in the general formula (1).

  In the general formula (1), the aliphatic acyl group having 2 to 10 carbon atoms that E can take is acetyl group, propanoyl group, butanoyl group, pentanoyl group, hexanoyl group, heptanoyl group, octanoyl group, nonanoyl group, decanoyl group Groups.

  In the general formula (1), the aromatic acyl group having 7 to 13 carbon atoms that E can take includes a benzoyl group which may have a substituent, a cinnamoyl group which may have a substituent, and the like. Can be mentioned.

  The polyester plasticizer of the present invention can also be used as a mixture of compounds having different E in the general formula (1).

  The acid value (AV) of the polyester plasticizer of the present invention is preferably 1 or less.

The polyester plasticizer of the present invention can be produced by performing polycondensation by a known method and then removing the component having a polymerization degree of 1 to less than 5% by mass by a known method.
For example, a polyhydric alcohol and a polyvalent carboxylic acid may be esterified with an esterification catalyst such as an acid catalyst, a titanium compound, or a tin compound, or an acid chloride corresponding to the polyvalent carboxylic acid is reacted with a polyhydric alcohol to form an ester. The raw material and the production method are not particularly limited, and may be obtained by transesterification of a polycarboxylic acid ester and a polyhydric alcohol in the presence of a transesterification catalyst. Moreover, it is preferable to refine | purify by various methods as needed.

In the general formula (1), a compound in which n is larger than 6 has a high viscosity and poor compatibility with the resin, and may cause problems such as bleeding of a molded product and clouding of a product when a transparent product is molded. is there.
Therefore, in addition to the fact that the component having a polymerization degree of 1 is less than 5% by mass, by setting 1.95 <n ≦ 6 in the general formula (1), there is less contamination of the processing machine, volatilization resistance and It can be set as the polyester plasticizer which is excellent also in compatibility. In addition, n = 1.95 is a case where the ratio of the component with a polymerization degree of 1 is 5 mass%, and the component with a polymerization degree of 2 is 95 mass%.

Examples of a method for removing a component having a polymerization degree of 1 include, but are not limited to, distillation (simple distillation, thin film distillation, flash distillation, etc.), extraction, column, filtration, and membrane permeation. Among these, thin film distillation is preferable because a component having a polymerization degree of 1 can be effectively removed. That is, the polyester plasticizer of the present invention is preferably a component having a polymerization degree of 1 less than 5% by thin film distillation. In the thin film distillation, the degree of vacuum is preferably 70 Pa or less, more preferably 50 Pa or less, and further preferably 1 to 50 Pa. The outside temperature is preferably 300 ° C. or less, more preferably 270 ° C. or less, and further preferably 180 to 270 ° C. In simple distillation, a heat history is applied during production, and there is a concern that the acid value (AV) increases due to coloring or thermal decomposition.
Here, the content of a component having a polymerization degree of 1 can be easily measured by using gas chromatographic analysis (GC). The analysis method for the composition satisfying 1.95 <n ≦ 6 is, for example, hydrolyzing the synthesized polyester plasticizer, and the acid value (A.V) and hydroxyl value of the chemical product of JIS K 0070: 1992. It can be easily measured by obtaining the molar ratio from the value calculated in accordance with the (OH.V) test method or by using high performance liquid chromatographic analysis (HPLC) using a GPC column.

  The analysis method for the average degree of polymerization n is not limited to the above method, and an optimal method can be used as appropriate for the column, temperature, flow rate, and the like.

The addition amount of the polyester plasticizer in the present invention is 1 to 50 parts by mass, preferably 5 to 30 parts by mass with respect to 100 parts by mass of the cellulose resin.
If the amount added is less than 1 part by mass, the plasticity and flexibility imparting effects may not be obtained, and if it exceeds 50 parts by mass, bleeding may occur, which is not preferable.

Hereinafter, the cellulose resin composition of the present invention will be described in detail.
The cellulose resin is not particularly limited, and various known cellulose derivatives can be used. For example, cellulose esters such as triacetyl cellulose (TAC), diacetyl cellulose (DAC), cellulose acetate propionate (CAP), cellulose acetate butyrate (CAB), cellulose acetate phthalate, cellulose acetate trimellitate, cellulose nitrate, etc. Cellulose carbamates such as cellulose phenyl carbamate and the like, and cellulose ethers such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and cyanoethyl cellulose are exemplified, and cellulose esters are preferable.

As the cellulose esters, for example, cellulose esters synthesized using cotton linter, wood pulp, kenaf and the like as raw materials can be used alone or in combination. In particular, it is preferable to use a cellulose ester synthesized from cotton linter (hereinafter sometimes simply referred to as linter) alone or in combination.
The number of unsubstituted hydroxyl groups present in the cellulose resin is not particularly limited.

  Among cellulose esters, a lower fatty acid ester of cellulose (cellulose acylate) is preferable. The lower fatty acid in the lower fatty acid ester of cellulose means a fatty acid having 6 or less carbon atoms. Examples of the lower fatty acid ester of cellulose include, for example, cellulose acetate, cellulose propionate, cellulose butyrate, JP-A-10-45804, JP-A-8-231761, and U.S. Pat. No. 2,319,052. Examples thereof include mixed fatty acid esters such as cellulose acetate propionate and cellulose acetate butyrate as described in the literature. Among the lower fatty acid esters of cellulose described above, particularly preferred lower fatty acid esters of cellulose are cellulose triacetate and cellulose acetate propionate.

  When cellulose triacetate is used as the cellulose resin, those having a polymerization degree of 250 to 400 and an average degree of acetylation (amount of bound acetic acid) of 54.0 to 62.5 mol% are preferable from the viewpoint of product strength, and the average degree of acetylation More preferably 58.0 to 62.5 mol%.

A particularly preferred lower fatty acid ester of cellulose has an acyl group having 2 to 4 carbon atoms as a substituent, the substitution degree of acetyl group is X, and the substitution degree of propionyl group or butyryl group is Y, It is a cellulose ester containing the cellulose ester which satisfy | fills (I) and (II) simultaneously.
Formula (I) 2.6 ≦ X + Y ≦ 3.0
Formula (II) 0 ≦ X ≦ 2.5

When cellulose acetate propionate is used as the cellulose ester, 1.9 ≦ X ≦ 2.5 and preferably 0.1 ≦ Y ≦ 0.9 in the above formulas (I) and (II). . The portion not substituted with an acyl group usually exists as a hydroxyl group. These can be synthesized by known methods.
However, it is not necessarily limited to the above cellulose resin, and other cellulose resins can be used.

  Cellulosic resins may be used alone or in combination of two or more. The molecular weight and molecular weight distribution of the cellulosic resin can be appropriately selected depending on the application and molding method.

  The cellulose resin composition of the present invention may further contain various additives such as phosphorus, phenol or sulfur antioxidants, ultraviolet absorbers, hindered amine light stabilizers and the like.

  Examples of the phosphorus antioxidant include triphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris ( Mono-, di-mixed nonylphenyl) phosphite, bis (2-tert-butyl-4,6-dimethylphenyl) -ethyl phosphite, diphenyl acid phosphite, 2,2'-methylene bis (4,6-di-tert-butyl) Phenyl) octyl phosphite, diphenyl decyl phosphite, phenyl diisodecyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, dibutyl acid phosphite, dilauryl acid phosphite, bird Uril trithiophosphite, bis (neopentyl glycol) 1,4-cyclohexanedimethyl diphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl) -4-methylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, phenyl-4,4'-isopropylidenediphenol pentaerythritol diphosphite, tetra (C12-15 mixed alkyl) -4,4 '-Isopropylidene diphenyl phosphite, bis [2,2'-methylenebis (4,6-diamilphenyl)]-isopropylidene diphenyl phosphite, hydrogenated-4,4'-isopropylidenediphenol polyphosphite, bis (Octylfe ) Bis [4,4'-n-butylidenebis (2-tert-butyl-5-methylphenol)] 1,6-hexanediol diphosphite, tetratridecyl4,4'-butylidenebis Tributyl-5-methylphenol) diphosphite, hexa (tridecyl) 1,1,3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butane-triphosphonite, 9,10-dihydro- 9-oxa-10-phosphaphenanthrene-10-oxide, 2-butyl-2-ethylpropanediol, 2,4,6-tritert-butylphenol monophosphite, tetrakis (2,4-ditert-butyl Phenyl) biphenylphosphonite and the like.

  Examples of the phenol-based antioxidant include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-ditert-butyl-4- Hydroxyphenyl) propionate, distearyl (3,5-ditert-butyl-4-hydroxybenzyl) phosphonate, tridecyl 3,5-ditert-butyl-4-hydroxybenzylthioacetate, thiodiethylenebis [(3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6-tert-butyl-m-cresol), 2-octylthio-4,6-di (3,5-di-tert-butyl) -4-hydroxyphenoxy) -s-triazine, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), bis [3,3- (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4,4′-butylidenebis (4,6-ditert-butylphenol), 2,2′-ethylidenebis (4,6-di) Tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3) -Tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris ( 3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) -2,4,6-to Methylbenzene, 1,3,5-tris [(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3,5-ditert-butyl-4) -Hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propanoyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycol And bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate].

  Examples of the sulfur-based antioxidant include dialkylthiodipropionates such as dilauryl, dimyristyl, myristyl stearyl, and distearyl esters of thiodipropionic acid and polyols such as pentaerythritol tetra (β-dodecyl mercaptopropionate). And β-alkyl mercaptopropionic acid esters.

  Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-tert-butyl-4 ′-(2 -Methacryloyloxyethoxyethoxy) benzophenone, 2-hydroxybenzophenones such as 5,5'-methylenebis (2-hydroxy-4-methoxybenzophenone); 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- ( 2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-ditert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-tert-butyl) -5-methylphenyl) -5-chlorobenzotriazole 2- (2-hydroxy-3-dodecyl-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3-tert-butyl-5-C7-9mixed alkoxycarbonylethylphenyl) triazole, 2- (2- Hydroxy-3,5-dicumylphenyl) benzotriazole, 2,2′-methylenebis (4-tert-octyl-6-benzotriazolylphenol), 2- (2-hydroxy-3-tert-butyl-5) 2- (2-hydroxyphenyl) benzotriazoles such as polyethylene glycol esters of carboxyphenyl) benzotriazole; 2- (2-hydroxy-4-hexyloxyphenyl) -4,6-diphenyl-1,3,5-triazine 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3 -Triazine, 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-acryloyloxy) 2- (2-hydroxyphenyl) -1,3,5-triazines such as ethoxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine; phenyl salicylate, resorcinol mono Benzoate, 2,4-ditert-butylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, 2,4-ditert-amylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, Benzoates such as hexadecyl-3,5-ditert-butyl-4-hydroxybenzoate; 2-ethyl-2′-ethoxyoxanilide, 2-eth Substituted oxanilides such as xy-4′-dodecyloxanilide; cyano such as ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate Acrylates, 2- (2-hydroxy-4- (2- (2-ethylhexanoyloxy) ethyloxy) -4,6-diphenyl-1,3,5-triazine, 2,4,6-tris (2- Hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2,4,6-tris (2-hydroxy-3-methyl-4- (2-octanoyloxyethyl) phenyl) -1,3 5-triazine, tetrakis (α-cyano-β, β-diphenylacryloyloxymethyl) methane and the like can be mentioned.

Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2, 6,6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate Bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4 Butanetetracarboxylate, tetrakis (1
, 2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl) bis (tridecyl) ) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) .bis (tridecyl) -1,2,3,4-butanetetracarboxylate Bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-ditert-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxy Ethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / dibromoe Polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6- Bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [ 2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraaza Dodecane, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N-
(1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,6,11-tris [2 , 4-Bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino-s-triazin-6-ylamino] undecane, 1,6,11-tris [2,4 -Bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino-s-triazin-6-ylamino] undecane, 3,9-bis [1,1-dimethyl- 2- {tris (2,2,6,6-tetramethyl-4-piperidyloxycarbonyl) butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9 -Bis [1,1-dimethyl 2- {tris (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl) butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, bis ( 1-undecyloxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate and the like.

  In addition, other additives such as a filler, a colorant, a crosslinking agent, an antistatic agent, a plate-out preventing agent, a surface treatment agent, a lubricant, a flame retardant, and a fluorescent agent are added to the composition of the present invention as necessary. Antifungal agents, bactericides, metal deactivators, mold release agents, pigments, processing aids, antioxidants, light stabilizers, foaming agents, and the like can be blended.

  The cellulose resin composition of the present invention can be processed by known processing methods and used for various applications.

  The cellulose resin composition obtained by adding the polyester plasticizer of the present invention can be used without being limited to the processing method, and for example, roll processing, extrusion molding processing, melt rolling method, melting It can be suitably used for casting, solution casting, injection molding, pressure molding, powder molding, and the like.

Hereinafter, the cellulose resin composition of the present invention will be described in more detail with reference to production examples and examples, but the present invention is not limited thereto.
Polyester plasticizers (compounds No. 1 to No. 8) were produced according to the formulation shown below. The inside of () of a mixture shows molar ratio.

Example compounds
Compound No. 1: Succinic acid (50) and terephthalic acid (50) as polyvalent carboxylic acid component A, ethylene glycol (50) and 1,2-propylene glycol (50) as polyhydric alcohol component G, and terminal E is acetyl N = 2 polyester compounds comprising a group.
Compound No. 2: Succinic acid (50) and terephthalic acid (50) as polyvalent carboxylic acid component A, ethylene glycol (50) and 1,2-propylene glycol (50) as polyhydric alcohol component G, and terminal E is acetyl A polyester compound of n = 3.1 consisting of groups.
Compound No. 3: Adipic acid (100) as the polyhydric carboxylic acid component A, ethylene glycol (100) as the polyhydric alcohol component G, and n = 2.3 polyester compound in which the terminal E is an acetyl group.
Compound No. 4: Adipic acid (100) as the polyvalent carboxylic acid component A, ethylene glycol (100) as the polyhydric alcohol component G, and an n = 5.6 polyester compound in which the terminal E is an acetyl group.
Compound No. 5: Succinic acid (50) and terephthalic acid (50) as polyvalent carboxylic acid component A, ethylene glycol (50) and 1,2-propylene glycol (50) as polyhydric alcohol component G, and terminal E is benzoyl A polyester compound of n = 4.1 consisting of groups.

≪Comparative Example Compound≫
Compound No. 6: Succinic acid (50) and terephthalic acid (50) as polyvalent carboxylic acid component A, ethylene glycol (50) and 1,2-propylene glycol (50) as polyhydric alcohol component G, and terminal E is acetyl N = 0.5 polyester compound comprising a group.
Compound No. 7: Succinic acid (50) and terephthalic acid (50) as polyvalent carboxylic acid component A, ethylene glycol (50) and 1,2-propylene glycol (50) as polyhydric alcohol component G, and terminal E is acetyl A polyester compound of n = 8.3 consisting of a group.
Compound No. 8: Succinic acid (50) and terephthalic acid (50) as polyvalent carboxylic acid component A, ethylene glycol (50) and 1,2-propylene glycol (50) as polyhydric alcohol component G, and terminal E is acetyl A polyester compound of n = 3.1 consisting of a group.

In the production method, a polycarboxylic acid, a polyhydric alcohol, and a stopper were charged in a reaction vessel, tetraisopropyl titanate was added as a catalyst, a solvent was added if necessary, and the temperature was increased while stirring. By-product water was removed under normal pressure and reduced pressure, and finally the temperature was raised to 220 to 230 ° C. to complete the dehydration condensation reaction. When batch synthesis is difficult, the reaction of the polyvalent carboxylic acid / polyhydric alcohol and the reaction with the stopper were separated.
About the obtained polyester plasticizer, using a thin film distillation apparatus, compound No. 1-5 and no. For compound No. 7, at a pressure of 4 Pa / mantle temperature of 250 ° C., compound no. For No. 6, thin film distillation was performed at a pressure of 80 Pa / outside temperature of 250 ° C. No thin film distillation was performed on 8.

<Measurement of a component having a polymerization degree of 1>
Gas chromatographic analysis (GC) was performed using PEG-HT manufactured by GL Sciences Inc. as a carrier, nitrogen (50 ml / min) as a carrier, temperature of both injector and detector at 300 ° C., and temperature program at 150 ° C. to 300 ° C., 5 ° C. / Min and held at 300 ° C. for 15 minutes. Using dimethyl terephthalate as an internal standard, the content of a component with a degree of polymerization of 1 is measured from a calibration curve of n = 1 compound (comprising a single glycol and a single dibasic acid) synthesized in advance. (Mass%).

  Compound no. 1, no. 2, no. 5, no. 6, no. 7, no. For compound No. 8, the peak of the compound consisting of a single glycol and a single dibasic acid and the retention time of each of the compounds in which ethylene glycol and propylene glycol reacted with a single acid are different. The content of each component was calculated from a calibration curve created based on each area ratio.

<Measurement of average degree of polymerization>
The average degree of polymerization n and molecular weight (M.w) of the polyester plasticizer are obtained by hydrolyzing the synthesized polyester plasticizer, and the acid value (A.V) and hydroxyl value (OH) of the chemical product of JIS K 0070: 1992. V) was determined from the calculated molar ratio in accordance with the test method, and the measurement results are shown in Table 1.

<Cutability>
In the case of film use, since a cutting process is required at the time of processing, the cutting property was evaluated.
Acetylcellulose (acetylation degree 61.5 mol%, polymerization degree 260) was dissolved in a mixed solvent consisting of 90 parts by mass of methylene chloride and 10 parts by mass of methyl alcohol with stirring to obtain a solution having a concentration of 15% by mass. The plasticizer shown in Table 1 was mixed with the addition amount (parts by mass) shown in Tables 2 to 6 with respect to acetylcellulose, and the solution was cast on a petri dish to form a film having a thickness of about 0.1 mm. And made a film. When the film was cut using scissors, the cut portion was visually determined, and the following evaluation was made.
○: Good cutting property ×: Cracking occurs from the cutting part

<Compatibility>
A film was prepared by the above method, and the compatibility was determined by the presence or absence of cloudiness of the film, and the following evaluation was made.
○: No cloudiness ×: Cloudiness

<Processing machine contamination>
Acetylcellulose (acetylation degree 61.5 mol%, polymerization degree 260) was dissolved in a mixed solvent consisting of 90 parts by mass of methylene chloride and 10 parts by mass of methyl alcohol with stirring to obtain a solution having a concentration of 15% by mass. The plasticizer shown in Table 1 was mixed with the addition amount (parts by mass) shown in Tables 2 to 6 with respect to acetylcellulose, and the solution was cast on a metal support to a thickness of about 0.1 mm. A film was formed to form a film. After peeling off the film from the metal support, the metal support was visually checked for dirt, and the following evaluation was made.
◎: No dirt ○: Almost no dirt △: Dirt *: Severe dirt

From the above Tables 2 to 6, it is clear that Comparative Examples 11 to 13 have poor processing machine contamination and compatibility. On the other hand, in Examples 1-9 and Reference Examples 1-6, since there is almost no contamination of the processing machine, polyester plasticization that can be used for a wide range of processing can be provided without reducing production efficiency. It was. Also, when used as a film, it is clear that cutting properties and compatibility are excellent. Therefore, it is clear that the specific polyester plasticizer in the present invention is excellent in reducing processing machine contamination, cutting properties, and compatibility, and by providing a predetermined amount, it is possible to provide a resin composition having the performance. It has become possible.

Claims (4)

A polyester plasticizer represented by the following general formula (1) and having a polymerization degree of 1 is 0.7 to 1.3% by mass .

(In the formula (1), n represents an average degree of polymerization, 1.95 <n ≦ 6, A represents an ethylene group and a phenylene group , and G represents two hydroxyl groups from ethylene glycol and 1,2-propylene glycol. the group excluding, E is represents an acetyl group or a benzoyl group.) A process for producing a polyester plasticizer according to claim 1, wherein the component having a polymerization degree of 1 is 0.7 to 1.3% by mass by thin-film distillation when producing the polyester plasticizer according to claim 1 . Relative to 100 parts by mass of cellulose resin, cellulose resin composition characterized by containing 1 to 50 parts by weight of a polyester plasticizer according to claim 1, wherein. The cellulose resin composition according to claim 3 , wherein the cellulose resin is cellulose acylate.