TWI490257B - Polylactic resin composition - Google Patents

Description

Polylactic acid resin composition

The present invention relates to a crystal nucleating agent for a polylactic acid resin and a polylactic acid resin composition. In recent years, from the standpoint of natural environmental protection, biodegradable resins and their molded bodies which can be decomposed in the natural environment are required. Among them, polylactic acid resins are formed in addition to the manufacturing technology using crops as raw materials. It is also excellent in heat resistance and is therefore the most eye-catching. However, although the nature of the polylactic acid resin is a crystalline resin, the crystallization is slow, and the behavior of the amorphous resin is exhibited at the time of actual molding, and there are many aspects in terms of formability and physical properties of the obtained molded body. Difficulties. In order to improve the difficulty, the polylactic acid resin is generally added with a crystal nucleating agent, and even if other additives are added in combination with a specific purpose, the composition is provided after being prepared into a polylactic acid resin composition. The present invention relates to a crystal nucleating agent for a polylactic acid resin and a polylactic acid resin composition using the same.

The crystal nucleating agent for polylactic acid resin as described above is known as follows: 1) selected from aliphatic carboxylic acid decylamines, aliphatic dicarboxylic acid decyl amines, N-substituted aliphatic carboxylic acid bis guanamines a compound having a melting point of 40 to 300 ° C in the class of N-substituted ureas (for example, refer to Patent Document 1); 2) such as: trimesic acid tris(t-butyldecylamine), 1,4-cyclohexane Diphenylamine dicarboxylate, dicyclohexyldecylamine 2,6-naphthalene dicarboxylate, N,N'-dibenridyl-1,4-diaminocyclohexane, N,N'-bicyclohexane An aromatic decylamine compound such as an alkylcarbonyl-1,5-diaminonaphthalene (for example, refer to Patent Document 2); 3) a phosphate metal salt and a basic inorganic aluminum compound (for example, refer to Patent Document 3); 4) such as talc; Inorganic particles (for example, refer to Patent Document 4). However, these conventional nucleating agents for polylactic acid resins are still too slow to be crystallized by using the polylactic acid resin composition prepared therefrom, and thus it takes a long time to form, and in this case, the problem of deterioration in productivity is caused.

Therefore, a crystal nucleating agent for a polylactic acid resin which has been improved to the above problems is known, such as an aromatic sulfonate (see, for example, Patent Document 5). However, the crystal nucleating agent for polylactic acid resin actually has a large difference in performance depending on the average particle diameter, and when a larger average particle diameter is used, it is used for a constituent unit formed of L-lactic acid or by D. - When the polylactic acid resin is formed in a unit of 99% by mole or more of the total constituent unit, the same effect can be exerted on the constituent unit formed by L-lactic acid or by D. - When the lactic acid is formed as a constituent unit and the polylactic acid resin is less than 99 mol% of the total constituent unit, the crystallization is still slow, and it takes a long time to form, which may cause poor productivity; and, conversely, if used When the average particle diameter is too small, not only the work environment due to the dust during the treatment is deteriorated, but also the kneading property to the polylactic acid resin is deteriorated, and as a result, there is a problem that the crystallization cannot be sufficiently improved.

[Patent Document 1] Japanese Patent Laid-Open No. Hei 9-278991

[Patent Document 2] Japanese Patent Laid-Open No. Hei 10-87975

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2003-192883

[Patent Document 4] Japanese Patent Laid-Open No. Hei 8-3432

[Patent Document 5] WO2005/068554

An object of the present invention is to provide a polylactic acid resin having a low content ratio (i.e., a polylactic acid resin having a low optical purity) which is used in a constituent unit formed of L-lactic acid or a constituent unit formed of D-lactic acid. In addition, it is possible to sufficiently enhance the crystallization, and it is also excellent in workability at the time of disposal, and does not cause a crystal nucleating agent for polylactic acid resin and a polylactic acid resin composition which deteriorates the working environment.

In order to solve the above problems, the inventors of the present invention have intensively studied and found that the specific aromatic sulfonate is adjusted to a specific average particle diameter, and it can be suitably applied as a crystal nucleating agent of a polylactic acid resin.

In other words, the crystal nucleating agent for a polylactic acid resin of the present invention is composed of an aromatic sulfonate represented by the following formula 1, and is composed of an average particle diameter of 0.1 to 10 μm.

In 1, 1

X: removal of residues of 3 hydrogen atoms from benzene

R ¹ , R ² : a hydrocarbon group having 1 to 6 carbon atoms

M: alkali metal atom or alkaline earth metal atom

n: 1 or 2, when M is an alkali metal atom, n = 1, and when M is an alkaline earth metal atom, n = 2

In addition, the polylactic acid resin composition of the present invention contains a constituent unit formed of L-lactic acid or a constituent unit formed of D-lactic acid, and contains 95 to 99 mol% of the total constituent unit of polylactic acid resin. And the above-mentioned crystal nucleating agent for polylactic acid resin of this invention is comprised.

First, the crystal nucleating agent for polylactic acid resin (hereinafter referred to as "the crystal nucleating agent of the present invention") of the present invention will be described. The crystal nucleating agent of the present invention is composed of the aromatic sulfonate represented by Chemical Formula 1. The aromatic sulfonate represented by Formula 1 includes: 1) an alkali metal salt of a dialkyl sulfophthalate, 2) an alkali metal salt of a dialkyl sulfoisophthalate, and 3) a sulfo pair. Alkali metal salt of dialkyl phthalate, 4) alkaline earth metal salt of dialkyl sulfophthalate, 5) alkaline earth metal salt of dialkyl sulfoisophthalate, 6) sulfo pair An alkaline earth metal salt of a dialkyl phthalate, and 7) any mixture of the above 1) to 6).

In the aromatic sulfonate represented by the formula 1, the X in the compound 1 removes the residue of three hydrogen atoms from the benzene. Further, R ¹ and R ² in the formula ¹ are as follows: methyl, ethyl, propyl, isopropyl, isobutyl, pentyl, hexyl, cyclopentyl, cyclohexyl, allyl, cyclohexene. The hydrocarbon group having 1 to 6 carbon atoms, and the like, preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably a methyl group.

In the aromatic sulfonate represented by Formula 1, the M system in Chemical Formula 1 has, for example, 1) an alkali metal atom such as a lithium atom, a sodium atom, a potassium atom, a ruthenium atom or a ruthenium atom, and 2) a ruthenium atom, a magnesium atom, and a calcium atom. An alkaline earth metal atom such as a ruthenium atom or a ruthenium atom is preferably a potassium atom, a ruthenium atom, a ruthenium atom, a ruthenium atom or a calcium atom, more preferably a potassium atom and a ruthenium atom.

In the aromatic sulfonate represented by the formula 1, the alkali metal salt of the dialkyl sulfophthalate is exemplified by, for example, 1) 4-sulfophthalic acid dimethyl group = lithium, 4- Diethyl sulfophthalate = lithium, di-n-propyl 4-sulfophthalate = lithium, diisopropyl 4-sulfophthalate = lithium, 4-sulfophthalic acid Di-n-butyl = lithium, diisobutyl 4-sulfophthalate = lithium, di-t-butyl 4-sulfophthalate = lithium, 4-sulfophthalic acid di-2- Methyl propyl=lithium, di-n-pentyl 4-sulfophthalate=lithium, 2--3-methylbutyl 4-sulfophthalate=lithium, 4-sulfophthalic acid -2-methylbutyl=lithium, 4-sulfophthalic acid di-2,2-dimethylpropyl=lithium, 4-sulfophthalic acid di-n-hexyl=lithium, 4-sulfoyl Di-4-methylpentyl phthalate = lithium, 4-sulfophthalic acid di-3,3-dimethylbutyl=lithium, 4-sulfophthalic acid di-2,3 - dimethyl butyl = lithium, 4-sulfophthalic acid dicyclohexyl = lithium sulfophthalic acid dialkyl lithium salt; 2) 4-sulfophthalic acid dimethyl = Sodium, 4-sulfophthalic acid diethyl = sodium , 4-sulfophthalic acid di-n-propyl = sodium, 4-sulfophthalic acid diisopropyl = sodium, 4-sulfophthalic acid di-n-butyl = sodium, 4-sulfo Diisobutyl phthalate = sodium, dibutylbutyl 4-sulfophthalate = sodium, 4-sulfophthalic acid di-2-methylpropyl = sodium, 4-sulfo Di-n-pentyl phthalate = sodium, 4-trimethylbutyl 4-sulfophthalate = sodium, 2-sulfophthalic acid di-2-methylbutyl = sodium, 4 - sulfophthalic acid di-2,2-dimethylpropyl=sodium, 4-sulfophthalic acid di-n-hexyl=sodium, 4-sulfophthalic acid di-2-methylpentyl Base = sodium, 4-sulfophthalic acid bis-3-methylpentyl = sodium, 4-sulfophthalic acid di-4-methylpentyl = sodium, 4-sulfophthalic acid Di-3,3-dimethylbutyl=sodium, 4-sulfophthalic acid di-2,3-dimethylbutyl=sodium, 4-sulfophthalic acid dicyclohexyl=sodium, etc. Sodium salt of sulfophthalic acid dialkyl; 3) 4-sulfophthalic acid dimethyl=potassium, 4-sulfophthalic acid diethyl-potassium, 4-sulfo-o-phenylene Di-n-propyl formate = potassium, 4-sulfophthalic acid diisopropyl = potassium, 4- Di-n-butyl phthalate = potassium, diisobutyl 4-sulfophthalate = potassium, di-tert-butyl 4-sulfophthalate = potassium, 4-sulfo-o-phenyl Di-2-methylpropyl formate = potassium, di-n-pentyl 4-sulfophthalate = potassium, 4-sulfophthalic acid bis-3-methylbutyl = potassium, 4-sulfo Di-2-methylbutyl phthalate = potassium, 2-sulfophthalic acid di-2,2-dimethylpropyl = potassium, 4-sulfophthalic acid n-hexyl = potassium, 4-sulfophthalic acid di-2-methylpentyl=potassium, 4-sulfophthalic acid di-3-methylpentyl=potassium, 4-sulfophthalic acid di-4--4- Methylpentyl=potassium, 4-sulfophthalic acid di-3,3-dimethylbutyl=potassium, 4-sulfophthalic acid di-2,3-dimethylbutyl=potassium , 4-sulfophthalic acid dicyclohexyl=potassium salt of sulfophthalic acid dialkyl; 4) 4-sulfophthalic acid dimethyl = anthracene, 4-sulfo-o-benzene Diethyl dicarboxylate = hydrazine, di-n-propyl 4-sulfophthalate = hydrazine, diisopropyl 4-sulfophthalate = hydrazine, di-n-butyl 4-sulfophthalate =铯, diisobutyl 4-sulfophthalate = hydrazine, 4-sulfo-o-benzene Di-tert-butyl dicarboxylate = hydrazine, di-2-methylpropyl 4-sulfophthalate = hydrazine, di-n-pentyl 4-sulfophthalate = hydrazine, 4-sulfo-o-benzene Di-3-methylbutyl dicarboxylate = hydrazine, di-2-methylbutyl 4-sulfophthalate = hydrazine, di-2,2-dimethylpropane 4-sulfophthalate Base = fluorene, 4-sulfophthalic acid di-2-methylpentyl = hydrazine, 4-sulfophthalic acid bis-3-methylpentyl = hydrazine, 4-sulfophthalic acid Di-4-methylpentyl=anthracene, 4-sulfophthalic acid di-3,3-dimethylbutyl=anthracene, 4-sulfophthalic acid di-2,3-dimethyl Butyl = hydrazine, 4-sulfophthalic acid dicyclohexyl = hydrazine sulfonate phthalic acid dialkyl sulfonium salt and the like.

In the aromatic sulfonate represented by the formula 1, the alkali metal salt of the dialkyl sulfoisophthalate is exemplified by, for example, 1) 5-sulfoisophthalic acid dimethyl group = lithium, 5- Diethyl sulfoisophthalate = lithium, di-n-propyl 5-sulfoisophthalate = lithium, diisopropyl 5-sulfoisophthalate = lithium, 5-sulfoisophthalic acid Di-n-butyl = lithium, diisobutyl 5-sulfoisophthalate = lithium, di-t-butyl 5-sulfoisophthalate = lithium, 5-sulfoisophthalic acid di-2- Methyl propyl=lithium, di-n-pentyl 5-sulfoisophthalate=lithium, bis-3-methylbutyl 5-sulfoisophthalate=lithium, 5-sulfoisophthalic acid -2-methylbutyl=lithium, 5-sulfoisophthalic acid di-2,2-dimethylpropyl=lithium, 5-sulfoisophthalic acid di-4-methylpentyl=lithium , 5-sulfoisophthalic acid di-3,3-dimethylbutyl=lithium, 5-sulfoisophthalic acid di-2,3-dimethylbutyl=lithium, 5-sulfo Dicyclohexyl phthalate = lithium salt of dialkyl sulfoisophthalate such as lithium; 2) dimethyl 5-sulphonate isophthalate, diethyl 5-sulfoisophthalate = Sodium, 5-sulfoisophthalate di-n-propyl = sodium , 5-sulfoisophthalic acid diisopropyl = sodium, 5-sulfoisophthalic acid di-n-butyl = sodium, 5-sulfoisophthalic acid diisobutyl = sodium, 5-sulfo Di-tert-butyl isophthalate = sodium, di-2-methylpropyl 5-sulfoisophthalate = sodium, di-n-pentyl 5-sulfoisophthalate = sodium, 5-sulfo Di-3-methylbutyl isophthalate = sodium, 2-sulfoisophthalic acid di-2-methylbutyl=sodium, 5-sulfoisophthalic acid di-2,2-dimethyl Propyl group = sodium, 5-sulfoisophthalic acid di-2-methylpentyl = sodium, 5-sulfoisophthalic acid bis-3-methylpentyl = sodium, 5-sulfoisophthalic acid Di-4-methylpentyl dicarboxylate = sodium, 5-sulfoisophthalic acid di-3,3-dimethylbutyl=sodium, 5-sulfoisophthalic acid di-2,3-di a sodium salt of a dialkyl sulfoisophthalate such as methyl butyl = sodium, 5-sulfoisophthalic acid dicyclohexyl = sodium; 3) dimethyl 5-potassium 5-sulfoisophthalate, 5-sulfoisophthalic acid diethyl = potassium, 5-sulfoisophthalic acid di-n-propyl = potassium, 5-sulfoisophthalic acid diisopropyl = potassium, 5-sulfoisophthalic acid Di-n-butyl dicarboxylate = potassium, diisobutyl 5-sulfoisophthalate = potassium, 5- Di-tert-butyl isophthalate = potassium, 5-sulfoisophthalic acid di-2-methylpropyl = potassium, 5-sulfoisophthalic acid di-n-pentyl = potassium, 5-sulfonate Di-3-methylbutyl = potassium, 5-sulfoisophthalic acid di-2-methylbutyl = potassium, 5-sulfoisophthalic acid di-2, 2-di Methyl propyl = potassium, 5-sulfoisophthalic acid di-2-methylpentyl = potassium, 5-sulfoisophthalic acid bis-3-methylpentyl = potassium, 5-sulfo Di-4-methylpentyl phthalate = potassium, 5-sulfoisophthalic acid di-3,3-dimethylbutyl=potassium, 5-sulfoisophthalic acid di-2,3- Potassium salt of dialkyl sulfoisophthalate such as dimethyl butyl group = potassium, 5-sulfoisophthalic acid dicyclohexyl group = potassium; 4) dimethyl 5-sulfoisophthalate = 铯, 5-sulfoisophthalic acid diethyl = hydrazine, 5-sulfoisophthalic acid di-n-propyl = hydrazine, 5-sulfoisophthalic acid diisopropyl = hydrazine, 5-sulfo Di-n-butyl phthalate = hydrazine, diisobutyl 5-sulfoisophthalate = hydrazine, di-tert-butyl 5-sulfoisophthalate = hydrazine, 5-sulfoisophthalic acid -2-methylpropyl=铯, 5-sulfoisophthalate di-n-pentyl=铯, 5- Sulfophenylisophthalate bis-3-methylbutyl=anthracene, 5-sulfoisophthalic acid di-2-methylbutyl=anthracene, 5-sulfoisophthalic acid di-2,2- Dimethylpropyl = hydrazine, 5-sulfoisophthalic acid di-2-methylpentyl = hydrazine, 5-sulfoisophthalic acid bis-3-methylpentyl = hydrazine, 5-sulfo Di-4-methylpentyl isophthalate = anthracene, 5-sulfoisophthalic acid di-3,3-dimethylbutyl=anthracene, 5-sulfoisophthalic acid di-2,3 - dimethyl butyl = hydrazine, 5-sulfoisophthalic acid dicyclohexyl = sulfonium salt of a dialkyl sulfoisophthalate or the like.

Specific examples of the alkali metal salt of a dialkyl sulfophthalate in the aromatic sulfonate represented by the formula 1 include, for example, 1) sulfophthalic acid dimethyl group; lithium, sulfo-p-benzene. Diethyl diformate = lithium, di-n-propyl sulfophthalate = lithium, diisopropyl sulfophthalate = lithium, di-n-butyl sulfophthalate = lithium, sulfo pair Diisobutyl phthalate = lithium, di-tert-butyl sulfophthalate = lithium, di-2-methylpropyl sulfophthalate = lithium, di-n-pentyl sulfophthalate Base = lithium, sulfo-terephthalic acid bis-3-methylbutyl = lithium, sulfo-terephthalic acid di-2-methylbutyl = lithium, sulfophthalic acid di-2,2- Dimethyl propyl = lithium, sulfo-terephthalic acid di-4-methylpentyl = lithium, sulfo-terephthalic acid di-3,3-dimethylbutyl = lithium, sulfo-p-phenylene Di- 2,3-dimethylbutyl formate = lithium, sulfo-terephthalic acid dicyclohexyl = lithium salt of sulfo-terephthalic acid dialkyl such as lithium; 2) sulfoisophthalate Base = sodium, sulfo-terephthalic acid diethyl = sodium, sulfo-terephthalic acid di-n-propyl = sodium, sulfo-terephthalic acid diisopropyl = sodium , di-n-butyl sulfo-terephthalate = sodium, diisobutyl sulfo-terephthalate = sodium, di-t-butyl sulfo-terephthalate = sodium, sulfo-terephthalic acid di-2 -Methylpropyl group = sodium, di-n-pentyl sulfophthalate = sodium, bis-trimethylmethyl sulfophthalate = sodium, di-2-methyl sulfophthalate Butyl = sodium, sulfophthalic acid di-2,2-dimethylpropyl = sodium, sulfobutylene di-2-methylpentyl = sodium, sulfophthalic acid di- 3-methylpentyl=sodium, sulfo-terephthalic acid di-4-methylpentyl=sodium, sulfo-terephthalic acid di-3,3-dimethylbutyl=sodium, sulfo-p-benzene Sodium di-2,3-dimethylbutyl=dicarboxylate, sodium sulfo-terephthalate such as dicyclohexyl sulfophthalate; sodium; 3) sulfophthalic acid Methyl=potassium, sulfobutyl terephthalate diethyl=potassium, sulfoisophthalate di-n-propyl=potassium, sulfoisophthalate diisopropyl=potassium, sulfophthalic acid II n-Butyl = potassium, diisobutyl sulfo-terephthalate = potassium, di-t-butyl sulfo-terephthalate = potassium, sulfo-terephthalic acid di-2-methylpropyl = potassium Di-n-pentyl sulfophthalate = potassium, bis-3-methylbutyl sulfo-terephthalate = potassium, sulfo-terephthalic acid di-2-methylbutyl = potassium, sulfo pair Di-2,2-dimethylpropyl phthalate = potassium, di-n-hexyl sulfophthalate = potassium, sulfo-terephthalic acid di-2-methylpentyl = potassium, sulfo-p-benzene Di-3-methylpentyl dicarboxylate = potassium, sulfobutyl terephthalate di-4-methylpentyl = potassium, sulfobutyl terephthalate di-3,3-dimethylbutyl = potassium, Potassium salt of sulfo-terephthalic acid dialkyl such as sulfo-terephthalic acid di-2,3-dimethylbutyl=potassium; sulfo-terephthalic acid dicyclohexyl=potassium; 4) sulfo pair Dimethyl phthalate = hydrazine, sulfobutyl terephthalate diethyl = hydrazine, sulfo-terephthalic acid di-n-propyl = hydrazine, sulfo-terephthalic acid diisopropyl = hydrazine, sulfo pair Di-n-butyl phthalate = hydrazine, diisobutyl sulfo-terephthalate = hydrazine, di-tert-butyl sulfophthalate = hydrazine, di-2-methyl propyl sulfophthalate Base = hydrazine, di-n-pentyl sulfophthalate = hydrazine, bis-methyl methyl butyl terephthalate = hydrazine, di-2-methyl butyl sulfophthalate = , 2,2-dimethylpropyl sulfophthalate = hydrazine, di-2-methylpentyl sulfophthalate = hydrazine, bis-methyl sulfophthalate Pentyl = hydrazine, sulfobutylene terephthalate di-4-methylpentyl = hydrazine, sulfophthalic acid di-3,3-dimethylbutyl = hydrazine, sulfophthalic acid di- 2,3-Dimethylbutyl=anthracene, sulfobutylene terephthalate=dicyclohexyl=anthracene salt of dialkyl sulfophthalate or the like.

Specific examples of the alkaline earth metal salt of the sulfophthalic acid dialkyl group in the aromatic sulfonate represented by the formula 1 include, for example, 1) bis(4-sulfophthalic acid dimethyl)= Magnesium, bis(4-sulfophthalic acid diethyl)=magnesium, bis(4-sulfophthalic acid di-n-propyl)=magnesium, bis(4-sulfophthalic acid diisopropyl Base) = magnesium, bis(4-sulfophthalic acid di-n-butyl) = magnesium, bis(4-sulfophthalic acid diisobutyl) = magnesium, bis(4-sulfo-o-phenylene) Di-tert-butyl formate) = magnesium, bis(4-sulfophthalic acid di-2-methylpropyl) = magnesium, bis(4-sulfophthalic acid di-n-pentyl) = magnesium, Bis(4-sulfophthalic acid bis-3-methylbutyl)=magnesium, bis(4-sulfophthalic acid di-2-methylbutyl)=magnesium, bis(4-sulfoyl) Di-2,2-dimethylpropyl phthalate=magnesium, bis(4-sulfophthalic acid di-4-methylpentyl)=magnesium, bis(4-sulfo-o-phenylene) Di-3,3-dimethylbutyl formate = magnesium, bis(4-sulfophthalic acid di-2,3-dimethylbutyl)=magnesium, bis(4-sulfo-o-phenylene) Dicyclohexyl formate) = magnesium salt of dialkyl sulfophthalate such as magnesium; 2) bis(4-sulfophthalic acid dimethyl Base) = calcium, bis(4-sulfophthalic acid diethyl) = calcium, bis(4-sulfophthalic acid di-n-propyl) = calcium, bis (4-sulfophthalic acid) Diisopropyl)=calcium, bis(4-sulfophthalic acid di-n-butyl)=calcium, bis(4-sulfophthalic acid diisobutyl)=calcium, bis(4-sulfoyl) Di-tert-butyl phthalate = calcium, bis(4-sulfophthalic acid di-2-methylpropyl) = calcium, bis(4-sulfophthalic acid di-n-pentyl) = calcium, bis(4-sulfophthalic acid bis-3-methylbutyl) = calcium, bis(4-sulfophthalic acid di-2-methylbutyl) = calcium, double (4 - sulfophthalic acid di-2,2-dimethylpropyl)=calcium, bis(4-sulfophthalic acid di-2-methylpentyl)=calcium, bis(4-sulfoyl) Di-3-methylpentyl phthalate)=calcium, bis(4-sulfophthalic acid di-4-methylpentyl)=calcium, bis(4-sulfophthalic acid di- 3,3-dimethylbutyl)=calcium, bis(4-sulfophthalic acid di-2,3-dimethylbutyl)=calcium, bis(4-sulfophthalic acid bicyclic ring Hexyl) = calcium salt of dialkyl sulfophthalate such as calcium; 3) bis(4-sulfophthalic acid dimethyl) = hydrazine, bis(4-sulfophthalic acid diethyl Base)=钡, bis(4-sulfophthalic acid di-n-propyl)=钡, bis(4-sulfophthalic acid diisopropyl)=钡, bis(4-sulfo-o-phenylene) Di-n-butyl formate) = bismuth, bis(4-sulfophthalic acid diisobutyl) = hydrazine, bis(4-sulfophthalic acid di-tert-butyl) = hydrazine, bis (4- Sulfhydryl phthalate di-2-methylpropyl)=indole, bis(4-sulfophthalic acid di-n-pentyl)=indole, bis(4-sulfophthalic acid di-3-) Methyl butyl)=钡, bis(4-sulfophthalic acid di-2-methylbutyl)=钡, bis(4-sulfophthalic acid di-2,2-dimethylpropane Base)=钡, bis(4-sulfophthalic acid di-2-methylpentyl)=钡, bis(4-sulfophthalic acid di-3-methylpentyl)=钡, double (4-sulfophthalic acid di-4-methylpentyl)=indole, bis(4-sulfophthalic acid di-3,3-dimethylbutyl)=钡, double (4- Sulfhydryl phthalic acid di-2,3-dimethylbutyl)=indole, bis(4-sulfophthalic acid dicyclohexyl=fluorene sulfonate phthalic acid dialkyl sulfonium salt, etc. Wait.

In the aromatic sulfonate represented by the formula 1, the alkaline earth metal salt of the dialkyl sulfoisophthalate is exemplified by, for example, 1) bis(5-sulfoisophthalic acid dimethyl)= Magnesium, bis(5-sulfoisophthalic acid diethyl)=magnesium, bis(5-sulfoiso-diphenyl)-magnesium, bis(5-sulfoisophthalate diisopropyl Base) = magnesium, bis(di-butyl 5-sulfoisophthalate) = magnesium, bis(diisobutyl 5-sulfoisophthalate) = magnesium, bis(5-sulfoisophthalate) Di-tert-butyl formate) = magnesium, bis(5-sulfoisophthalic acid di-2-methylpropyl) = magnesium, bis(5-sulfoisophthalic acid di-n-pentyl) = magnesium, Bis(5-sulfoisophthalic acid bis-3-methylbutyl)=magnesium, bis(5-sulfoisophthalic acid di-2-methylbutyl)=magnesium, bis(5-sulfo) Di- 2,2-dimethylpropyl isophthalate = magnesium, bis(5-sulfoisophthalic acid di-4-methylpentyl)=magnesium, bis(5-sulfoisophthalene) Di-3,3-dimethylbutyl formate = magnesium, bis(5-sulfoisophthalic acid di-2,3-dimethylbutyl)=magnesium, bis(5-sulfoisophthalene) Dicyclohexyl formate) = magnesium salt of dialkyl sulfoisophthalate such as magnesium; 2) bis(5-sulfoisophthalate Base) = calcium, bis(5-sulfoisophthalic acid diethyl) = calcium, bis(di-propyl 5-sulfoisophthalate) = calcium, bis(5-sulfoisophthalic acid) Diisopropyl)=calcium, bis(di-butyl 5-sulfoisophthalate)=calcium, bis(diisobutyl 5-sulfoisophthalate)=calcium, bis(5-sulfo) Di-tert-butyl isophthalate) = calcium, bis(5-sulfoisophthalic acid di-2-methylpropyl) = calcium, bis(5-sulfoisophthalic acid di-n-pentyl) = calcium, bis(5-sulfoisophthalate bis-3-methylbutyl) = calcium, bis(5-sulfoisophthalate di-2-methylbutyl = calcium, double (5- Sulfhydryl isophthalate di-2,2-dimethylpropyl)=calcium, bis(5-sulfoisophthalic acid di-2-methylpentyl)=calcium, bis(5-sulfo) Di-3-methylpentyl phthalate) = calcium, bis(5-sulfoisophthalic acid di-4-methylpentyl) = calcium, bis(5-sulfoisophthalic acid di-3 ,3-dimethylbutyl)=calcium, bis(5-sulfoisophthalic acid di-2,3-dimethylbutyl)=calcium, bis(5-sulfoisophthalic acid dicyclohexyl) ) = calcium salt of dialkyl sulfoisophthalate such as calcium; 3) bis(5-sulfoisophthalic acid dimethyl) = hydrazine, bis(5-sulfoisophthalate diethyl )=钡, bis(di-propyl 5-sulfoisophthalate)=钡, bis(5-sulfoisophthalic acid diisopropyl)=钡, bis(5-sulfoisophthalic acid) Di-n-butyl)=钡, bis(diisobutyl 5-sulfoisophthalate)=钡, bis(di-t-butyl 5-sulfoisophthalate)=钡, bis(5-sulfonate) Di-2-methylpropyl)isophthalic acid=钡, bis(di-pentyl 5-sulfoisophthalate)=钡, bis(5-sulfoisophthalate di-3-methyl) Butyl) = hydrazine, bis(5-sulfoisophthalic acid di-2-methylbutyl) = hydrazine, bis(5-sulfoisophthalic acid di-2,2-dimethylpropyl = 钡, bis (5-sulfoisophthalic acid di-2-methylpentyl) = hydrazine, bis(5-sulfoisophthalic acid bis-3-methylpentyl) = hydrazine, double ( 5-sulfoisophthalate di-4-methylpentyl)=indole, bis(5-sulfoisophthalic acid di-3,3-dimethylbutyl)=钡, bis(5-sulfonate) Isophthalic acid di-2,3-dimethylbutyl)=anthracene, bis(5-sulfoisophthalic acid dicyclohexyl)=antimony salt of dialkyl sulfoisophthalate, etc. Wait.

In the aromatic sulfonate represented by the formula 1, the alkaline earth metal salt of the dialkyl sulfophthalate is exemplified by, for example, 1) bis(sulfo-terephthalate dimethyl)=magnesium. Bis(diethyl sulfoteate terephthalate) = magnesium, di(n-propyl sulfo-terephthalate) = magnesium, bis(sulfo-terephthalate diisopropyl) = magnesium, bis (sulfonate) Di-n-butyl terephthalate = magnesium, di(isobutyl) sulfo-terephthalate = magnesium, di-tert-butyl sulfo-terephthalate = magnesium, bis(sulfo) Di-2-methylpropyl terephthalate = magnesium, di(n-pentyl) sulfo-terephthalate = magnesium, bis(sulfo-terephthalic acid bis-3-methylbutyl) = Magnesium, bis(sulfobutylene terephthalate)-2-magnesium, bis(sulfo-terephthalic acid di-2,2-dimethylpropyl)=magnesium, bis(sulfo pair) Di-4-methylpentyl phthalate) = magnesium, bis(sulfophthalic acid di-3,3-dimethylbutyl) = magnesium, bis(sulfophthalic acid di-2, 3-dimethylbutyl)=magnesium, bis(sulfo-terephthalate dicyclohexyl)=magnesium salt of dialkyl sulfophthalate, etc.; 2) bis(sulfophthalic acid II) Methyl) = calcium, bis(sulfo-p-xylylene) Diethyl)=calcium, bis(di-propylsulfonate terephthalate)=calcium, bis(sulfoisophthalate diisopropyl)=calcium, bis(sulfobutylene di-n-butylate) Base) = calcium, bis(sulfisobutylene terephthalate) = calcium, bis(sulfobutyl terephthalate) = calcium, bis(sulfophthalic acid di-2-) Methylpropyl)=calcium, bis(sulfanyldi-n-pentyl)-calcium, bis(sulfo-terephthalic acid bis-3-methylbutyl)=calcium, bis(sulfo-p-benzene) Di-2-methylbutyl dicarboxylate=calcium, bis(sulfophthalic acid di-2,2-dimethylpropyl)=calcium, bis(sulfophthalic acid di-2-methyl) Lymeyl) = calcium, bis(sulfophthalic acid bis-3-methylpentyl) = calcium, bis(sulfo-terephthalate di-4-methylpentyl) = calcium, bis (sulfonate) Di-terophthalic acid di-3,3-dimethylbutyl)=calcium, bis(sulfophthalic acid di-2,3-dimethylbutyl)=calcium, bis(sulfo-p-phenylene) Dicyclohexyl formate) = calcium salt of sulfo-terephthalic acid dialkyl such as calcium; 3) bis(sulfo-terephthalate dimethyl)=钡, bis(sulfo-terephthalate diethyl) =钡, bis(di-n-propyl sulfophthalate)=钡, bis(sulfo-p-benzene) Diisopropyl)dicarboxylate=钡, bis(di-n-butyl sulfoteate terephthalate=bis, bis(sulfisobutylene terephthalate)=钡, bis(sulfophthalic acid II) Third butyl)=钡, bis(sulfo-terephthalic acid di-2-methylpropyl)=钡, bis(sulfo-p-butylene terephthalate)=钡, bis(sulfo-p-benzene) Di-3-methylbutyl dicarboxylate = hydrazine, bis(sulfo-terephthalic acid di-2-methylbutyl)=indole, bis(sulfo-terephthalic acid di-2,2-dimethyl Propyl) = hydrazine, bis(sulfophthalic acid di-2-methylpentyl) = hydrazine, bis(sulfophthalic acid bis-3-methylpentyl) = hydrazine, bis (sulfonate) Di-4-methylpentyl terephthalate)=钡, bis(sulfo-terephthalic acid di-3,3-dimethylbutyl)=钡, bis(sulfo-terephthalic acid di- 2,3-Dimethylbutyl)=anthracene, bis(sulfo-terephthalic acid dicyclohexyl)=phosphonium sulfonate tert-butyl dialkyl sulfonium salt and the like.

The aromatic sulfonate represented by the above 1 described above can be synthesized by a known method. For example, the method described in Japanese Patent Publication No. Sho 34-10497 can be used.

The crystal nucleating agent of the present invention is an aromatic sulfonate as described above, and the average particle diameter is adjusted in the range of 0.1 to 10 μm, preferably in the range of 0.5 to 5.0 μm, more preferably in the range of 0.8 to 3.0 μm. Here, the "average particle diameter" means a 50% by volume particle diameter (intermediate particle diameter) measured by a laser diffraction ‧ scattering method. When the average particle diameter of the aromatic sulfonate is more than 10 μm, it is used in a constituent unit formed of L-lactic acid or a constituent unit formed by D-lactic acid, and accounts for 95 to 99 mol% of the total constituent unit. In the polylactic acid resin, crystallization cannot be sufficiently improved. On the other hand, when the average particle diameter of the aromatic sulfonate is less than 0.1 μm, even if it is used in the same polylactic acid resin, not only the working environment is deteriorated due to dust during the treatment, but also the kneading with the polylactic acid resin. The result is also poor, and as a result, crystallization cannot be sufficiently enhanced.

The method for adjusting the average particle diameter of the aromatic sulfonate used as the crystal nucleating agent to 0.1 to 10 μm is, for example, providing the aromatic sulfonate, 1) to a jet mill, a ball mill, a bead mill, a method of adjusting the average particle size by a dry pulverizer such as a cyclone; 2) using a mixture such as water, an organic solvent, or a mixture of water and an organic solvent, etc., and supplying it to a wet machine such as a grinder, a ball mill, a bead mill, or the like. In the pulverizer, the method of adjusting the average particle diameter is preferred, but from the viewpoint of productivity, the method of the above 1) is preferred.

Next, the polylactic acid resin composition (hereinafter referred to as "the composition of the present invention") of the present invention will be described. The composition of the present invention comprises: a constituent unit formed of L-lactic acid or a constituent unit formed of D-lactic acid, and a polylactic acid resin of 95 to 99 mol% in the total constituent unit, and the above-described crystal nucleating agent of the present invention. . From the viewpoint of the physical properties of the obtained polylactic acid resin composition, it is preferable that the constituent unit composed of L-lactic acid accounts for 96 to 99 mol% of the total constituent unit of the polylactic acid resin, and more preferably is formed of L-lactic acid. The constituent unit accounts for 98 to 99 mol% of the polylactic acid resin in the entire constituent unit.

The polylactic acid resin itself can be synthesized in accordance with a known method. For example, Japanese Laid-Open Patent Publication No. Hei 7-33861, JP-A-59-96123, and Polymer Review No. 44, pages 3198-3199, 1) direct dehydration condensation reaction of lactic acid Method; 2) a method of subjecting lactide of lactic acid to ring-opening polymerization. The method of the above 1) may be L-lactic acid, D-lactic acid, DL-lactic acid, or any of these mixtures. The method of the above 2) may be the use of L-lactide, D-lactide, DL-lactide, meso-lactide, or any of these mixtures. A method of synthesizing, refining, and polymerizing a raw material lactide is also applicable to a known method. For example, the method described in U.S. Patent No. 4,057,537, the disclosure of European Patent Application No. 261,572, Polymer Bulletin, 14, 491-495 (1985), Macromol. Chem., 187, 1611-1628 (1986), and the like.

The polylactic acid resin to be used in the composition of the present invention is preferably a mass average molecular weight (polystyrene equivalent value analyzed by a gel permeation chromatography layer analyzer, the same applies hereinafter) of 80,000 or more, more preferably 100,000 or more. It is especially suitable for 110000~200000. When the mass average molecular weight of the polylactic acid resin is less than 80,000, mechanical properties such as strength and elastic modulus of the obtained molded article tend to be insufficient, and the higher the mass average molecular weight, the higher the mechanical properties tend to be. Further, when the mass average molecular weight of the polylactic acid resin is 200,000 or less, fluidity suitable for molding is exhibited.

The polylactic acid resin used in the composition of the present invention is preferably 5,000 ppm or less, more preferably 4,000 ppm or less, and particularly preferably 3,000 ppm or less. If the amount of residual monomers in the polylactic acid resin exceeds 5,000 ppm, since the residual monomer has a catalytic function of hydrolysis, even if a compound such as a carbodiimide compound is added, A known hydrolysis inhibitor such as an oxazoline-based compound or an isocyanate-based compound does not sufficiently exhibit an effect, and is liable to cause insufficient wet heat aging resistance and heat resistance. Further, the lower the residual monomer in the polylactic acid, the higher the resistance to moist heat aging and heat resistance.

In the composition of the present invention, the content ratio of the crystal nucleating agent of the present invention is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, particularly preferably 0.5 to 3 parts by mass per 100 parts by mass of the polylactic acid resin. . In any case, the effect of adding an aromatic sulfonate represented by Formula 1 of a crystal nucleating agent to a polylactic acid resin can be sufficiently exhibited.

The composition of the present invention may contain the aromatic sulfonate represented by Formula 1 together with the above-mentioned known organic nucleating agent and/or inorganic nucleating agent. The organic nucleating agent is preferably an aliphatic decylamine or an aromatic decylamine, and the content thereof is preferably equal to or lower than the content of the aromatic sulfonate represented by Chemical Formula 1. Further, the inorganic crystal nucleating agent is preferably talc, and the content ratio is preferably 1 to 20 parts by mass per 100 parts by mass of the polylactic acid resin.

The composition of the present invention may contain other resins from the viewpoint of improving physical properties such as rigidity, flexibility, heat resistance, and durability. Specific examples of the other resin include a polyester such as polycarbonate, polyethylene terephthalate, polybutylene terephthalate or polyethylene naphthalate; and polyphenylene; Polystyrene resin such as ether, polyethylene, polypropylene, polyvinyl chloride, polyacetal, polyphenylene sulfide, ABS resin, AS resin, HIPS; acrylic resin such as polymethyl methacrylate; and polyamine . These may be used alone or in combination of two or more. Among them, from the viewpoint of compatibility with the polylactic acid resin, it is preferred to have a carbonyl group-containing resin such as an ester bond or a carbonate bond, and more preferably an ABS resin or a polybutylene terephthalate. Polycarbonate.

The compositions of the present invention may contain other additives in conjunction with specific purposes. The other additives may, for example, be plasticizers, antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, pigments, colorants, various fillers, antistatic agents, mold release agents, perfumes, lubricants, flame retardants , foaming agent, filler, antibacterial, anti-fungal agent, etc.

The composition of the present invention described above can be prepared in accordance with a known method. For example, 1) a powder or granular polylactic acid resin, a crystal nucleating agent, and optionally other additives may be simultaneously subjected to dry blending, followed by a kneading method; 2) powder or granular polylactic acid resin, Pre-blending with the crystal nucleating agent, and further drying the other additives as needed, and then performing the kneading method. The dry blending apparatus may, for example, be a mill roll, a Banbury mixer, a super mixer or the like. Further, the kneading machine may be, for example, a single screw or a twin screw extruder. The kneading temperature of the kneading machine is usually set to about 120 to 220 °C. In the polymerization stage of the polylactic acid resin, a crystal nucleating agent or other additives as needed may be added, and a concentrate containing a crystal nucleating agent or other additives as needed may be prepared in advance, and then added. In polylactic acid resin.

(effect of the invention)

When the crystal nucleating agent of the present invention is used, even a polylactic acid resin having a low content ratio of a constituent unit formed of L-lactic acid or a constituent unit formed of D-lactic acid (that is, a polylactic acid resin having a low optical purity) is still used. The crystallization can be sufficiently improved, and the workability at the time of handling is excellent, and the working environment is not deteriorated.

Hereinafter, the embodiments and the like are exemplified by embodying the configuration and effects of the present invention, but the present invention is not limited to the embodiments. In the following examples and comparative examples, "parts" means "parts by mass" and "%" means "mass%".

[Examples]

Test Classification 1 (Synthesis and Adjustment of Crystal Nucleating Agent for Polylactic Acid Resin) The crystal nucleating agent for polylactic acid resin was synthesized and adjusted as follows. The contents are summarized in Table 1. Further, the average particle diameter of the crystalline nucleating agent for polylactic acid resin was measured as follows.

‧The average particle size

The polylactic acid resin was filled in a beaker with 0.01 g of a crystal nucleating agent and 200 g of isopropyl alcohol, and subjected to ultrasonic treatment for 10 minutes, and then subjected to a laser diffraction type particle size distribution analyzer (LA-920, manufactured by Horiba, Ltd.). The polylactic acid resin was measured by the average particle diameter (50% by volume) of the crystal nucleating agent.

‧Example 1 {Synthesis and Adjustment of Crystal Nucleating Agent (C-1) for Polylactic Acid Resin}

In a 1 L separable flask equipped with a cooling tube, 85.8 g (0.29 mol) of 5-sulfoisophthalic acid dimethyl=sodium and 772.0 g of ion-exchanged water were charged, and heated while stirring. Temperature 80 ° C. Further, 35.7 g (0.15 mol) of ruthenium chloride ‧ dihydrate was dissolved in 94.2 g of ion-exchanged water while heating. After confirming that dimethyl 5-sulfoisophthalate was dissolved, the aqueous solution of ruthenium chloride was dropped for 35 minutes while maintaining the internal temperature at 80 ° C, and stirring was carried out while maintaining the internal temperature at 80 ° C. After 3 hours, a solid slurry containing bis(5-sulfoisophthalic acid dimethyl)=ruthenium was obtained. After quenching to an internal temperature of 30 ° C or lower, the solid portion was filtered from the slurry, and 100 g of ion-exchanged water was further added thereto to carry out a water washing treatment. Next, 430 g of the water-treated solid component and ion-exchanged water were placed in a 1 L separable flask, and stirred at an internal temperature of 80 ° C for 3 hours. After quenching to an internal temperature of 30 ° C or lower, the solid portion was filtered from the slurry, and subjected to a water washing treatment using 100 g of ion-exchanged water. The washed solid portion was dried by a 105 ° C hot air dryer for 4 hours to obtain 90.1 g of a white powder. Finally, the obtained white powder was subjected to a pulverization treatment using a jet mill (trade name SINGLE TRACK jet mill STJ-200, manufactured by SEISHIN CORPORATION) under the conditions of a crushing pressure of 0.7 Mpa. This was designated as the crystal nucleating agent (C-1) for polylactic acid resin of Example 1.

‧Examples 2 to 5 {Synthesis and adjustment of crystal nucleating agents (C-2) to (C-5) for polylactic acid resin}

The crystal nucleating agents (C-2) to (C-5) for polylactic acid resins of Examples 2 to 5 were obtained as in the case of the crystalline nucleating agent (C-1) for polylactic acid resin of Example 1.

‧Comparative Examples 1, 3 and 5 {Synthesis of Crystal Nucleating Agents (R-1), (R-3) and (R-5) for Polylactic Acid Resins}

The nucleating agents (C-1), (C-3) and (C-5) for polylactic acid resins of Examples 2, 3 and 5 were used except that the pulverization treatment by the jet mill was not carried out. The crystal nucleating agents (R-1), (R-3) and (R-5) for polylactic acid resins of Comparative Examples 1, 3 and 5 were obtained.

‧Comparative Example 2 {Synthesis of Crystal Nucleating Agent (R-2) for Polylactic Acid Resin}

In a 1 L separable flask equipped with a cooling tube, 85.7 g (0.29 mol) of 5-sulfoisophthalic acid dimethyl=sodium and 772.0 g of ion-exchanged water were charged, and heated while stirring. Temperature 80 ° C. Further, 35.7 g (0.15 mol) of ruthenium chloride ‧ dihydrate was dissolved in 94.2 g of ion-exchanged water while heating. After confirming that dimethyl 5-sulfoisophthalate was dissolved, the aqueous solution of ruthenium chloride was dropped for 35 minutes while maintaining the internal temperature at 80 ° C, and stirring was carried out while maintaining the internal temperature at 80 ° C. After 3 hours, a solid slurry containing bis(5-sulfoisophthalic acid dimethyl)=ruthenium was obtained. After quenching to an internal temperature of 30 ° C or less, the slurry was subjected to a pulverization treatment using a bead mill (manufactured by IMEX Co., Ltd.). The solid fraction was filtered from the pulverized slurry, and 100 g of ion-exchanged water was further added thereto to carry out a water washing treatment. Next, 430 g of the water-treated solid component and ion-exchanged water were placed in a 1 L separable flask, and stirred at an internal temperature of 80 ° C for 3 hours. After quenching to an internal temperature of 30 ° C or lower, the solid portion was filtered from the slurry, and subjected to a water washing treatment using 100 g of ion-exchanged water. The washed solid portion was dried by a 105 ° C hot air dryer for 4 hours to obtain 83.2 g of a white powder. Finally, the obtained white powder was subjected to a pulverization treatment using a jet mill (trade name SINGLE TRACK jet mill STJ-200, manufactured by SEISHIN CORPORATION) under the conditions of a crushing pressure of 0.7 Mpa. This was designated as a crystal nucleating agent (R-2) for a polylactic acid resin of Comparative Example 2.

‧Comparative Example 4 {Synthesis of Crystal Nucleating Agent (R-4) for Polylactic Acid Resin}

The crystal nucleating agent (R-4) for polylactic acid resin of Comparative Example 4 was obtained as in the case of the polynuclear resin of Comparative Example 2 (R-2).

Test Category 2 (Modulation of Polylactic Acid Resin Composition and Evaluation of Its Workability) ‧Examples 6 to 25, Comparative Examples 6 to 10, and Reference Examples 8, 11 to 17, 23, and 26

The constituent unit formed of L-lactic acid accounts for 98.6% of the total constituent units of polylactic acid resin (polylactic acid resin having an optical purity of 98.6%, mass average molecular weight of 160,000), 20 kg, and bis(sulfoisophthalic acid dimethyl)=钡 0.1 kg was placed in a 200 L transfer barrel, and after 15 minutes of rotation, the mixture was taken out from the raw material discharge port. The workability of the mixing operation of the poly-L-lactic acid resin and the crystal nucleating agent was evaluated according to the following criteria. The results are summarized in Table 2.

‧Operational assessment

AA: The dust is scattered and the working environment is good.

A: Although the dust is scattered, the working environment is generally good.

B: The dust is scattered and the working environment is deteriorated.

Test Category 3 (Evaluation of Crystallinity of Polylactic Acid Resin Composition)

According to the content of Table 2, the polylactic acid resin and the aromatic sulfonate represented by the chemical nucleating agent of the polylactic acid resin obtained by the test classification 1 were put into an experimental plastic impact grinding machine (manufactured by Toyo Seiki Co., Ltd.). The polylactic acid resin composition was prepared by kneading at 200 ° C for 5 minutes. The prepared polylactic acid resin composition was molded at 200 ° C by a hot press (manufactured by Toyo Seiki Co., Ltd.), and then quenched by water to obtain a sheet having a thickness of 2 mm. For the obtained sheet, the crystallization peak temperature of the degree of crystallization (degree of crystallization and the degree of crystallization) was determined. Specifically, the obtained sheet was subjected to dehumidifying and drying at 100 ° C for 2 hours to be in a dry state, and then a sample was taken, and the crystallization peak temperature was determined under the conditions of the following differential scanning calorimeter. Then, the evaluation is carried out according to the following criteria. The results are summarized in Table 2.

‧ Conditions for differential scanning calorimeter

Using a differential scanning calorimeter (DSC-6200 manufactured by Seiko Instruments Co., Ltd.), 3 mg of the sample was filled in an aluminum bath, and the temperature was raised from room temperature to 200 ° C at 30 ° C / min. After 5 minutes, the temperature was further adjusted to 30 ° C / min. The cooling rate is measured.

‧Evaluation of crystallization peak temperature

AAA: The crystallization peak temperature is above 110 °C.

AA: The crystallization peak temperature is 100 ° C or more and less than 110 ° C.

A: The crystallization peak temperature is 80 ° C or more and less than 100 ° C.

B: The crystallization peak temperature is 60 ° C or more and less than 80 ° C.

In Table 2,

C-1~C-5, R-1~R-5: the contents listed in Table 1

D-1: guanamine-based crystal nucleating agent (trade name SLIPAXH manufactured by Nippon Kasei Co., Ltd.: ethylene bis-12-hydroxystearic acid decylamine)

D-2: talc crystal nucleating agent (product name MicroAceP-6, manufactured by Nippon Talc Co., Ltd., average particle size 4 μm)

D-3: ABS resin (TOYOLAC manufactured by TORAY Corporation) 250)

D-4: Polybutylene terephthalate (trade name NOVADURAN manufactured by Mitsubishi Engineering Plastics Co., Ltd.) 5010TRXA)

D-5: Polycarbonate (product name JUPILON S-3000 manufactured by Mitsubishi Engineering Plastics Co., Ltd.)

As is apparent from Table 2, when the crystal nucleating agent of the present invention is used, even when it is used in a polylactic acid resin having an optical purity of 95 to 99%, crystallization can be sufficiently enhanced, workability is good, and the working environment is also good.

Claims (1)

A polylactic acid resin composition is a ratio of 0.5 to 3 parts by mass per 100 parts by mass of the polylactic acid resin having a constituent unit of L-lactic acid having 98 to 99 mol% in the total constituent unit. The crystal nucleating agent is a nucleating agent for a polylactic acid resin, and the nucleating agent is composed of a pulverized product of an aromatic sulfonate represented by the following formula 1, and a pulverized material having an average particle diameter adjusted to a range of 0.8 to 3.0 μm. ; (In Formula 1, X: a residue from which three hydrogen atoms are removed from benzene; R ¹ , R ² : an aliphatic hydrocarbon group having 1 to 3 carbon atoms; M: a potassium atom or a halogen atom; n: 1 or 2, when The case where M is a potassium atom is n=1, and the case where M is a germanium atom is n=2).