JP5155643B2 - Polylactic acid resin, polylactic acid resin composition, and molded article thereof - Google Patents

Description

  The present invention relates to a novel polylactic acid resin having improved transparency, crystallization speed and heat resistance. The present invention also relates to a polylactic acid resin composition comprising the polylactic acid-based resin as a main component and a molded body comprising the same.

  As awareness of global environmental issues increases, depletion of fossil raw materials and petroleum resources, and an increase in carbon dioxide are regarded as problems. For this reason, research and development of biodegradable resins such as aliphatic polyesters and resins synthesized from plants as raw materials have been actively conducted. Among aliphatic polyesters, polylactic acid having excellent moldability has been attracting attention as a plant-derived resin that uses lactic acid obtained by fermentation from cereal resources such as corn as a raw material.

  However, polylactic acid has a limitation in application development because it is hard and brittle, and has a low crystallization rate and low heat resistance. In particular, in the case of a polylactic acid amorphous molded article, since the softening temperature is less than 60 ° C., it has been pointed out that it tends to cause whitening, deformation, and the like in an everyday use environment.

  Further, when heat treatment (annealing) is performed to improve the heat resistance of polylactic acid by increasing the crystallinity, crystals having a size equal to or larger than the wavelength of light that normally causes light scattering (for example, , Spherulites) grow rapidly and become opaque.

In order to solve such problems, many attempts have been made to improve heat resistance and transparency by adding various additives to polylactic acid.
Patent Document 1 describes that addition of a phosphoric acid ester metal salt, hydrous magnesium silicate, or the like as a nucleating agent is effective. However, when such a nucleating agent is used, there is a drawback that transparency is impaired. In addition, talc generally used is within the practical range from the viewpoint of crystallization speed, but for that purpose, an addition amount of 1% or more is often required, which is a characteristic characteristic of polylactic acid. There are drawbacks that impair the performance.

  Patent Document 2 describes a method in which at least one selected from an aliphatic carboxylic acid amide, an aliphatic carboxylate, an aliphatic alcohol, and an aliphatic carboxylic acid ester as a nucleating agent is added as a transparent nucleating agent. However, in this case, the crystallinity was 33% and the haze was 6.5%, and a result having sufficient crystallinity and transparency was not obtained.

  Patent Document 3 describes a method of using polylactic acid and an inorganic filler using a compound having a specific functional group as an initiator. However, in this method, although slip property was improved, transparency could not be ensured by adding an inorganic filler.

  On the other hand, Patent Document 4 describes an example in which a silicone compound is added to a polylactic acid-based resin composition, but there is no description regarding the degree of crystallinity and transparency. Although some have functional groups copolymerizable with lactic acid units, the amount of use is limited in order to cause bleed out, and because silicone oils without functional groups are presented, It is the purpose of addition for improving impact resistance, and it is clear that the structure and purpose are different from those of the present invention.

Patent Document 5 discloses that in a polylactic acid resin composition, a lactic acid resin obtained by copolymerizing a lactic acid unit and a silicone unit is added to an ordinary polylactic acid resin for the purpose of adding flame retardancy and impact resistance. It has been shown to be added and used.
However, in the copolymer consisting of lactic acid units and silicone units, it is described that the silicon content is preferably 1 to 40% by weight, and more preferably 5 to 20% by weight. Even when calculated as dimethylsiloxane ((CH3) 2-SiO-) as a unit, the content (% by weight) of the silicone resin in the copolymer is in the range of 2.7% to 105.8%, more preferably. It contains 13.2% -52.9% and a fairly large amount of silicone moieties.
Further, there is a description that a more preferable molecular weight range is 5,000 to 50,000 in Mw, and that flame retardancy is lowered at a molecular weight exceeding this, on the other hand, regarding the relationship between crystallinity and transparency, what is Since there is no description, in order to improve the flame retardancy and impact resistance, a low molecular weight polylactic acid-silicone resin copolymer is produced at a high concentration of silicone resin and added to general polylactic acid. The purpose is to prevent bleeding out.
Japanese Patent Laid-Open No. 2003-192848 JP-A-9-278991 JP 2004-285121 A JP 2007-262200 A JP 2004-277575 A

  An object of the present invention is to provide a novel polylactic acid resin having improved heat resistance (high crystallization property) and transparency without impairing the rigidity inherent to the polylactic acid resin, Another object of the present invention is to provide a polylactic acid-based resin composition containing the polylactic acid-based resin as a main component and a molded body made of the same.

The present inventors have intensively studied to solve the above problems. As a result, it has been found that the above problem can be solved by using a polylactic acid resin having a specific site.
That is, the polylactic acid-based resin according to the present invention has a portion having a weight average molecular weight (Mw) composed of a repeating unit represented by the following formula (1) of 100 to 10,000 and has an overall weight average molecular weight (Mw). Is 5,000-500,000 polylactic acid resin (A).

(In Formula (1), R ₁ and R ₂ each independently represent a linear or branched alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms, May be different.)
The polylactic acid resin composition according to the present invention also relates to a polylactic acid resin composition containing 5 to 95 parts by weight of the polylactic acid resin (A).

The polylactic acid resin composition of the present invention may further contain other polylactic acid resin (B) excluding the polylactic acid resin (A).
The polylactic acid resin (B) may be polylactic acid,
Furthermore, the following general formula (2)
-X ₁ -R ₃ -X _2- (2)
(In formula (2), X ₁ and X ₂ each independently represent an O atom, an S atom or an NH group, R ₃ represents a divalent group containing at least one aromatic ring or aliphatic ring, The hydrocarbon group is O,
N or S atoms may be included. When R ₃ is a group other than a group consisting of a dicarboxylic acid and a diol, R ₃ preferably has 5 to 50 carbon atoms. )
Or a polylactic acid resin having a weight average molecular weight (Mw) in the range of 5,000 to 500,000, or the following general formula (3):
-X ¹ -R ₄ -X ^2- (3)
(In Formula (3), X ¹ and X ² each independently represent an O atom, an S atom or an NH group, and R ₄ is an aliphatic hydrocarbon having a weight average molecular weight of 25 to 50,000 and not containing a ring structure. Represents a group,
The hydrocarbon group may contain O, N or S atoms. )
And a polylactic acid resin having a weight average molecular weight (Mw) in the range of 5,000 to 500,000.

  The polylactic acid resin composition of the present invention comprises a total of 100 weights of the polylactic acid resin (A) or the polylactic acid resin (A) and other polylactic acid resin (B) used as necessary. May further include 0.1 to 10 parts by weight of at least one transparent nucleating agent (C) selected from carboxylic acid amides, aliphatic alcohols and aliphatic carboxylic acid esters.

  In the polylactic acid-based resin composition of the present invention, the composition is melted at 220 ° C. for 3 minutes, then cooled to 100 ° C. at a cooling rate of 99 ° C./min, and maintained at 100 ° C. for isothermal crystallization time Is preferably within 5 minutes.

The transparent nucleating agent (C) is preferably a carboxylic acid amide, which is a lauric acid amide, palmitic acid amide, stearic acid amide, erucic acid amide, behenic acid amide, ricinoleic acid amide, hydroxystearic acid Amide, N-oleyl palmitic acid amide, N-stearyl erucic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, ethylene bis stearic acid amide, ethylene bis oleic acid amide, ethylene bis-12-hydroxy stearic acid amide, Hexamethylene biscapric amide, hexamethylene bis lauric acid amide, hexamethylene bis stearic acid amide, hexamethylene bis oleic acid amide, hexamethylene bis-12-hydroxystearic acid amide, m-xylylene bis At least one selected from the group consisting of capric acid amide, m-xylylene bislauric acid amide, m-xylylene bis stearic acid amide, m-xylylene bis oleic acid amide and m-xylylene bis-12-hydroxystearic acid amide More preferably.

  The molded body according to the present invention comprises the polylactic acid resin (A) or the polylactic acid resin composition of the present invention described above, has a haze of 0.1 to 15% at a thickness of 100 μm, and is crystallized. The degree is preferably 35% or more.

  According to the present invention, the crystallization speed and transparency are improved, and it becomes possible to apply to a product that requires a molding cycle shortening, heat resistance and transparency, which has been difficult in the past, and is represented by a conventional polylactic acid resin. Contributes to the expansion of the use of green plastic.

Hereinafter, a polylactic acid resin according to the present invention, a polylactic acid resin composition containing the same as a main component, and a molded product thereof will be described in detail.
First, each component which can be used for the polylactic acid-type resin composition of this invention is demonstrated.

<Polylactic acid resin (A)>
The polylactic acid resin (A) of the present invention has a portion having a weight average molecular weight (Mw) composed of repeating units represented by the following formula (1) in the range of 100 to 10,000, and a polylactic acid resin ( A) The total weight average molecular weight (Mw) is in the range of 5,000 to 500,000.

  In addition, the weight average molecular weight (Mw) shown by this invention means the value of polystyrene conversion calculated | required by gel permeation chromatography (GPC) (column temperature 40 degreeC, chloroform solvent).

  In the present invention, “polylactic acid-based resin” refers to a polymer containing L-lactic acid units and / or D-lactic acid units in an amount of 50 mol% or more, preferably 75 mol% or more, and a mixture of these polymers.

In the above formula (1), R ₁ and R ₂ each independently represent a linear or branched alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms, and may be the same It may be different.

Examples of the linear or branched alkyl group having 1 to 5 carbon atoms of R ₁ and R ₂ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and t-butyl. Group, n-pentyl group, isopentyl group, neopentyl group and the like.

Among the alkyl groups, a methyl group is preferable.
Examples of the aryl group having 6 to 10 carbon atoms of R ₁ and R ₂ include a phenyl group, a tolyl group, a xylyl group, a mesityl group, an ethylphenyl group, and a t-butylphenyl group.

Of the aryl groups, a phenyl group is preferable.
R ₁ and R ₂ may be the same or different.
The content of the site of the general formula (1) in the polylactic acid resin (A) is preferably in the range of 0.1 wt% to 10 wt%, more preferably in the range of 0.5 wt% to 5 wt%.

  The actual content is unreacted when the polylactic acid resin (A) is obtained by reacting a modified silicone compound having active hydrogen and a lactic acid monomer, having the structure of the following general formula (1). By quantifying the amount of monomer, the amount of the moiety of the general formula (1) in the resin can be determined.

  The polylactic acid-based resin (A) has, for example, a modified silicone compound having a structure represented by the general formula (1) and a group having active hydrogen such as a hydroxyl group and an amino group, and lactide or lactic acid as a main component. It can be obtained by copolymerizing with the monomer to be used.

In the copolymerization, when lactide is used as a monomer, lactide is sequentially polymerized from the active hydrogen portion of the modified silicone compound, so that a regular polymer in which one silicone unit is introduced into the polymer chain is obtained.

Further, when lactic acid is used as a monomer during copolymerization, a polymer in which silicone units are randomly introduced into the polymer chain is obtained.
The group having active hydrogen in the modified silicone compound may be directly bonded to a silicon atom, or may be bonded via a linking group such as an alkyl group, an alkoxy group, an aryl group, or an aralkyl group.

Examples of the modified silicone compound include:
Both-end-modified hydroxyl-modified silicone compounds such as KF-6001, KF-6002, KF-6003 (manufactured by Shin-Etsu Chemical Co., Ltd.); X-22-170BX, X-22-170DX (manufactured by Shin-Etsu Chemical Co., Ltd.) One-end modified hydroxyl group-modified silicone such as X-22-176DX, X-22-176F (manufactured by Shin-Etsu Chemical Co., Ltd.), etc .; X-22-4039, X-22-4015 (Shin-Etsu Chemical Co., Ltd.) and other side chain-modified hydroxyl group-containing silicones; X-22-167B (Shin-Etsu Chemical Co., Ltd.) and other terminal-modified mercapto group-containing silicones; KF-2001, KF-2004 ( Side chain modified mercapto-containing silicone such as Shin-Etsu Chemical Co., Ltd .; PAM-E, KF-8010, KF-8008, X-22-161A, X-22- Both-end modified amino group-containing silicone such as 660B-3 (manufactured by Shin-Etsu Chemical Co., Ltd.); Both-end modified amino group-containing silicone such as X-22-162C (manufactured by Shin-Etsu Chemical Co., Ltd.); X-21- 5841, KF-9701 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like, both-end-modified silanol group-containing silicones and the like can be mentioned.

The weight average molecular weight (Mw) of the modified silicon compound is preferably in the range of 100 to 10000, and more preferably in the range of 100 to 6000.
The optical purity of lactide or lactic acid used for the production of the polylactic acid resin (A) is preferably 95% or more, more preferably 97% or more in the L-form or D-form.

  Other monomers other than lactide and lactic acid used in the production of the polylactic acid resin (A) include cyclic esters (lactones) such as caprolactone, propiolactone and butyrolactone, and hydroxy such as hydroxybutanoic acid and hydroxypropanoic acid. And alkanoic acids.

  The ratio of lactide and lactic acid used for the production of the polylactic acid resin (A) and other monomers is preferably 75 to 100% by weight for lactide and lactic acid, and 25 to 0% by weight for other monomers. Is more preferably in the range of 80 to 100% by weight and other monomers in the range of 20 to 0% by weight, more preferably in the range of 90 to 100% by weight of lactide and lactic acid and in the range of 10 to 0% by weight of other monomers.

The polymerization of the polylactic acid resin (A) may be carried out without a solvent or a solvent may be used. In the polymerization, a solvent that is substantially inert to the polymerization reaction can be used.
Examples of the solvent include aliphatic hydrocarbons such as hexane, heptane, and decane; aromatic halogenated hydrocarbons such as chlorobenzene and o-dichlorobenzene; alicyclic hydrocarbons such as cyclopentane and cyclohexane; benzene, toluene, Aromatic hydrocarbons such as xylene, mesitylene, ethylbenzene and diethylbenzene; ether solvents such as diethyl ether, dioxane, tetrahydrofuran (THF) and diglyme.

These solvents may be used alone or in combination of two or more.
Aromatic hydrocarbons, aromatic halogenated hydrocarbons and ether solvents are preferred from the standpoints of solubility of lactide and lactic acid, reaction temperature, reaction rate, and ease of solvent removal after completion of the reaction. Xylene, toluene, chlorobenzene , O-dichlorobenzene and diglyme are particularly preferred.

  When a solvent is used for the polymerization, the amount used is 0.1 to 20 times the total amount of monomer and modified silicone compound used for the production of the polylactic acid resin (A), preferably 0.8. It is selected in the range of 5 to 10 times, more preferably 1.0 to 5 times.

The production of the polylactic acid resin (A) may be carried out in the presence of a catalyst.
The catalyst is not particularly limited as long as the polylactic acid resin (A) can be produced. Examples of the catalyst include tin catalysts such as tin octoate (tin 2-ethylhexanoate), dibutyltin dilaurate and tin chloride, titanium catalysts such as titanium chloride and titanium tetraisopropoxide, zinc chloride and zinc acetate. And other known catalysts.

Among these catalysts, tin-based catalysts are preferable, and tin octoate is more preferable.
The amount of the catalyst used is usually 0.001 to 5 parts by weight, preferably 0.003 to 1 part by weight, and more preferably 0 to 100 parts by weight of all monomers used for the production of the resin (A). 0.005 to 0.1 part by weight.

  The polymerization temperature is usually 60 ° C to 250 ° C, preferably 100 ° C to 230 ° C. When the polymerization is carried out without using a solvent, the polymerization temperature is more preferably about 150 to 200 ° C. Moreover, when using xylene as a solvent and tin octoate as a catalyst and further reacting a polymerization initiator with lactide, the polymerization temperature is more preferably about 110 to 150 ° C.

The polymerization time varies depending on the type of monomer used, the polymerization temperature, the amount of catalyst, and the like, but is usually 0.1 to 24 hours, preferably 0.5 to 12 hours, and more preferably 1 to 6 hours.
The actual polymerization time can be determined, for example, by measuring the molecular weight by GPC (gel permeation chromatography) or the like and determining when the desired molecular weight is reached as the reaction end point. The polylactic acid compound (A) has a weight average molecular weight (Mw) in the range of 5,000 to 500,000, preferably 10,000 to 500,000, more preferably 100,000 to 500,000. More preferably, it is in the range of 120,000 to 500,000.

The weight average molecular weight (Mw) can be controlled by controlling the quantity ratio between the monomer and catalyst used, the presence or absence or type of reaction solvent, the polymerization temperature, the polymerization time, and the like.
Although the weight average molecular weight (Mw) of the site | part consisting of the repeating unit represented by the said Formula (1) contained in the said polylactic acid-type resin (A) is the range of 100-10000, Preferably it is the range of 100-6000. is there.

  The weight average molecular weight of the site consisting of the repeating unit represented by the above formula (1) is a modified silicon having a desired weight average molecular weight when the polylactic acid resin (A) is produced using the modified silicon compound as a raw material. It can be controlled by using a compound.

<Polylactic acid resin (B)>
The polylactic acid-based resin composition of the present invention uses the polylactic acid-based resin (A) as an essential component, and if necessary, a polylactic acid-based resin (B) other than the polylactic acid-based resin (A). It may contain.

  The polylactic acid-based resin (B) is, for example, homopolymerization of lactic acid or lactide, or lactic acid or lactide and a compound such as other monomer or polymer copolymerizable with lactic acid or lactide, excluding the modified silicone compound. Obtained by copolymerization.

  The polylactic acid resin (B) has a weight average molecular weight (Mw) of 5,000 to 500,000, preferably 10,000 to 400,000, more preferably 50,000 to 300,000.

A polylactic acid resin composition using polylactic acid having 100 mol% of lactic acid units as the polylactic acid resin (B) is a preferred embodiment of the present invention.
As the polylactic acid, polylactic acid having a structural unit derived from L-lactic acid or D-lactic acid of 95 mol% or more, more preferably 97 mol% or more is desirable.

The polylactic acid is obtained by polycondensation of lactic acid or ring-opening polymerization of lactide, which is a cyclic dimer of lactic acid.
As the polylactic acid resin (B), as described above, a copolymer obtained by copolymerization of lactic acid and other monomers excluding the modified silicone compound can be used.

Examples of monomers copolymerizable with lactic acid (excluding the modified silicone compound) include hydroxycarboxylic acids such as glycolic acid and caproic acid; ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, Ethylene glycol / propylene glycol copolymer, 1,3-butanediol, 1,4-butanediol, 3-methyl-1,5-pentanediol,
, 6-hexanediol, 1,9-nonanediol, neopentyl glycol, polytetramethylene glycol, glycerin, trimethylolpropane and other polyfunctional alcohols such as succinic acid and adipic acid Examples include acids; polyvalent isocyanates such as xylylene diisocyanate and 2,4-tolylene diisocyanate; polysaccharides such as cellulose, acetyl cellulose and ethyl cellulose.

  The copolymer may be a random copolymer, an alternating copolymer, a block copolymer, or a graft copolymer. Further, at least a part of the copolymer may have any structure such as a linear shape, a cyclic shape, a branched shape, a star shape, and a three-dimensional network structure.

  As the polylactic acid resin (B), a polylactic acid resin having a site represented by the following general formula (2) and having an overall weight average molecular weight (Mw) of 5,000 to 500,000 was used. A polylactic acid resin composition is a preferred embodiment of the present invention.

-X ₁ -R ₃ -X _2- (2)
In the above formula (2), X ₁ and X ₂ each independently represent an O atom, an S atom or an NH group, and R ₃ represents a divalent hydrocarbon group containing at least one aromatic ring or aliphatic ring. And the hydrocarbon group may contain O, N or S atoms.

In addition, when R ₃ is a group other than a group consisting of a dicarboxylic acid and a diol, R ₃ preferably has 5 to 50 carbon atoms.
Examples of the polylactic acid-based resin (B) having the site represented by the above formula (2) include the following polylactic acid-based resins (B1) to (B5). [1] Represented by the formula (2) The polylactic acid resin (B1) represented by the following formula (4)

In Formula (4), X ₁ and X ₂ each independently represent an O atom, an S atom or an NH group, R ₅ represents a single bond or a hydrocarbon group having 1 to 10 carbon atoms, and the hydrocarbon group is It may be linear, branched or cyclic. Y ₁ and Y ₂ each independently represent a saturated hydrocarbon group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or a hydrogen atom, and does not exist when R ₅ is a single bond. L ₁ and L ₂ each independently represent an alkylene group having 1 to 8 carbon atoms or an oxyalkylene group having 1 to 8 carbon atoms. Z ₁ and Z ₂ each independently represent a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom. Y ₁ and Y ₂ , Y ₁ and Z ₁ , and Y ₂ and Z ₂ may be bonded to each other to form a ring. m represents an integer of 0 to 5.

  [2] A polylactic acid resin (B2) in which the site represented by the formula (2) is represented by the following formula (5)

In formula (5), X ₁ and X ₂ each independently represent an O atom, an S atom or an NH group, Y ₃ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 8 carbon atoms, or a 6 to 8 carbon atom. It represents an aryl group or an aralkyl group having 7 to 8 carbon atoms, and the saturated hydrocarbon group may be linear, branched or cyclic. r represents an integer of 0 to 4. L ₃ and L ₄ each independently represents an alkylene group having 2 to 8 carbon atoms or a cycloalkylene group having 3 to 8 carbon atoms. n represents an integer of 1 to 100.

  [3] A polylactic acid resin (B3) in which the site represented by the formula (2) is represented by the following formula (6)

In Formula (6), X ₁ and X ₂ each independently represent an O atom, an S atom or an NH group, Y ₄ represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and the hydrocarbon group is It may be linear, branched or cyclic. R ₆ , L ₅ and L ₆ each independently represent a single bond or an alkylene group having 1 to 8 carbon atoms. p represents an integer of 0 to 4. q represents an integer of 0 to 5.

  [4] The polylactic acid resin (B4) in which the site represented by the formula (2) is represented by the following formula (7)

In formula (7), X ₁ and X ₂ each independently represent an O atom, an S atom or an NH group.
[5] A polylactic acid resin (B5) in which the site represented by the formula (2) is represented by the following formula (8)

In formula (8), X ₁ and X ₂ each independently represent an O atom, an S atom or an NH group.
The polylactic acid resin (B) can be obtained by a publicly known method. For example, it can be obtained by copolymerizing a compound having the sites shown in the above (B1) to (B5) and a monomer mainly composed of lactide or lactic acid.

  Examples of the compound having the moiety shown in (B1) above include compounds having a hydroxyl group, a thiol group or an amino group represented by the following formula (4a).

In the formula (4a), X ₁ , X ₂ , R ₄ , Y ₁ , Y ₂ , L ₁ , L ₂ , Z ₁ , Z ₂ and m are the above formulas (
It is synonymous with X ₁ , X ₂ , R ₅ , Y ₁ , Y ₂ , L ₁ , L ₂ , Z ₁ , Z ₂ and m in 4).
In the formula (4a), X ₁ and X ₂ are preferably O atoms or NH groups, and L ₁ and L ₂ are methylene group, oxymethylene group, ethylene group, oxyethylene group, 1,2-propylene group, oxy-1 , 2-propylene group, trimethylene group, oxytrimethylene group, 2,3-butylene group, oxy-2,3-butylene group, tetramethylene group, oxytetramethylene group, cyclohexylene group, and oxycyclohexylene group are preferable, Z ₁ and Z ₂ are preferably a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, or a t-butyl group, and Y ₁ and Y ₂ are a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a phenyl group, or a cyclohexyl group. R ₅ is preferably a single bond, a methyl group, a methylene group or a methine group.

  Examples of the compound having the moiety shown in (B2) above include compounds having a hydroxyl group, a thiol group or an amino group represented by the following formula (5a).

In the formula (5a), X ₁ , X ₂ , Y ₃ , L ₃ , L ₄ , r and n are the same as X ₁ , X _{2 in the} above formula (5).
, Y ₃ , L ₃ , L ₄ , r and n.
In the formula (5a), X ₁ and X ₂ are preferably O atoms or NH groups, and L ₃ and L ₄ are methylene group, ethylene group, 1,2-propylene group, trimethylene group, 2,3-butylene group, tetra , pentamethylene, hexamethylene group, heptamethylene group, octamethylene group, cyclohexylene group preferably, Y ₃ is a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a phenyl group, a benzyl group, a cyclohexyl group are preferable .

    Examples of the compound having the site represented by B3 include compounds having a hydroxyl group, a thiol group or an amino group represented by the following formula (6a).

In the formula (6a), X ₁ , X ₂ , Y ₄ , R ₆ , L ₅ , L ₆ , p and q are the same as X ₁ in the above formula (6).
, X ₂ , Y ₄ , R ₆ , L ₅ , L ₆ , p and q.
In the formula (6a), X ₁ and X ₂ are preferably O atoms or NH groups, L ₅ and L ₆ are preferably single bonds, methylene groups and ethylene groups, and R ₆ is a single bond, methylene group, ethylene group and isopropylidene. Group is preferred, Y ₄ is a hydrogen atom, methyl group, ethyl group, isopropyl group,
A cyclohexyl group is preferred.

  Examples of the compound having the moiety shown in (B4) above include compounds having a hydroxyl group, a thiol group or an amino group represented by the following formula (7a).

In formula (7a), X ₁ and X ₂ each independently represent an O atom, an S atom or an NH group, and preferably an O atom or an NH group.
Examples of the compound having the site shown in (B5) above include compounds having a hydroxyl group, a thiol group or an amino group represented by the following formula (8a).

In formula (8a), X ₁ and X ₂ each independently represent an O atom, an S atom or an NH group, preferably an O atom or an NH group.
Preferable specific examples of the compound having the sites shown in the above (4a) to (8a) include aliphatic ring-containing diols and aromatic ring-containing diols.

Examples of the aliphatic ring-containing diols include:
1,4-cyclohexanediol:

1,3-cyclohexanediol:

4,4'-bicyclohexanol:

4,4'-Isopropylidenedicyclohexanol (2,2-bis (4-hydroxycyclohexyl) propane):

4,4'-methylenedicyclohexanol:

4,8-bis (hydroxymethyl) tricyclo (5.2.1.0 2,6) decane:

Etc.
Examples of the aromatic ring-containing diols include:
4,4'-Xylylene glycol:

4,4'-biphenylene glycol:

6,6'-bis (2-hydroxyethoxy) -3,3,3 ', 3'-tetramethyl-1,1-spirobiindane:

4,4 '-(Fluoronylidene) bis (2-phenoxyethanol):

N, N'-bis (2-hydroxyethyl) -pyromellitimide:

2,2-bis (4- (2-hydroxyethoxy) phenyl) propane:

Etc.
Other than the above compounds, the compounds having the sites shown in formulas (4a) to (8a) include polyesters having hydroxyl groups at both ends.

  Polyesters having hydroxyl groups at both ends are polycondensation of aromatic dicarboxylic acid, esters of aromatic dicarboxylic acid, or acid halides of aromatic dicarboxylic acid and alkylene diol or cycloalkylene diol having 2 to 8 carbon atoms. Obtained by.

  Examples of the aromatic dicarboxylic acids, aromatic dicarboxylic acid esters or aromatic dicarboxylic acid acid halides include terephthalic acid, dimethyl terephthalate, terephthalic acid chloride, isophthalic acid, dimethyl isophthalic acid, and isophthalic acid chloride. Can be mentioned.

Examples of the alkylene diol or cycloalkylene diol having 2 to 8 carbon atoms include ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1, Examples include 6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,4-cyclohexane-di-methanol and the like.

The above polyesters having hydroxyl groups at both ends can be obtained by using an excessive amount of diol and condensing it by a conventional method, and then removing the excessive amount of diol.
The weight average molecular weight (Mw) of the polyesters having hydroxyl groups at both ends is preferably in the range of 500 to 10,000, more preferably in the range of 1000 to 7000.

In addition, the weight average molecular weight (Mw) in this case should just be calculated | required by comparison with a standard polystyrene by the measurement by GPC (gel permeation chromatography) like the above.
In the compound having the above-described site, the aromatic ring, aliphatic ring, side chain, and the like may have a substituent.

  When a copolymer of lactic acid or lactide and another monomer is produced as the polylactic acid resin (B), the amount of the compound having the above-mentioned site is particularly limited as long as it becomes a polylactic acid resin However, it is preferably 0.001 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, still more preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of the monomer mainly composed of lactide or lactic acid. Part.

In addition, regarding the detail of manufacture of the polylactic acid-type resin which has the said site | part, it applies to manufacture of the polylactic acid-type resin (A) of this invention.
Further, as the polylactic acid-based resin (B), a polylactic acid-based resin having a portion represented by the following general formula (3) and having an overall weight average molecular weight (Mw) of 5,000 to 500,000 The used polylactic acid resin composition is a preferred embodiment of the present invention.

-X ¹ -R ₄ -X ^2- (3)
In the above formula (3), X ¹ and X ² each independently represent an O atom, an S atom or an NH group, and R ₄ is an aliphatic hydrocarbon having a weight average molecular weight of 25 to 50,000 and containing no ring structure The hydrocarbon group may contain O, N or S atoms.

  The site represented by the above formula (3) is preferably a site derived from at least one selected from diols, polyesters having both ends hydroxyl groups, and polycarbonates having both ends hydroxyl groups, The diol is preferably at least one selected from alkylene glycols, polymethylene glycols and polyalkylene glycols.

The method for obtaining the polylactic acid resin having these sites is also in accordance with the polylactic acid resin (A) of the present invention.
In the polylactic acid resin composition of the present invention, when the polylactic acid resin (B) is used, the content thereof is not particularly limited, but the content of the polylactic acid resin (B) is polylactic acid resin Usually in the range of 5 to 95 parts by weight, preferably in the range of 10 to 80 parts by weight, more preferably in the range of 20 to 50 parts by weight with respect to 100 parts by weight of the total of the resin (A) and the polylactic acid resin (B). It is. When the content of the polylactic acid resin (B) is within the above range, a composition having excellent heat resistance and transparency can be obtained.

<Transparent nucleating agent (C)>
The polylactic acid-type resin composition of this invention may contain a transparent nucleating agent (C) as needed. Here, the “transparent nucleating agent” is a nucleating agent that is added to the polylactic acid-based resin (A) during crystallization and maintains transparency. Examples of the transparent nucleating agent (C) include carboxylic acid amides, aliphatic alcohols, and aliphatic carboxylic acid esters. These may be used alone or in combination of two or more.

Specific examples of the carboxylic acid amide include aliphatic carboxylic acid amides such as lauric acid amide, palmitic acid amide, oleic acid amide, stearic acid amide, erucic acid amide, behenic acid amide, ricinoleic acid amide, and hydroxy stearic acid amide. Kind;
N-oleyl palmitic acid amide, N-oleyl oleic acid amide, N-oleyl stearic acid amide, N-stearyl oleic acid amide, N-stearyl stearic acid amide, N-
N-substituted aliphatic monocarboxylic amides such as stearyl erucamide, methylol stearamide, methylol behenic acid amide;
Methylenebisstearic acid amide, ethylene bisstearic acid amide, ethylene bislauric acid amide, ethylene biscapric acid amide, ethylene biserucic acid amide, ethylene bisbehenic acid amide, ethylene bisisostearic acid amide, ethylene bishydroxystearic acid amide , Butylene bis stearic acid amide, hexamethylene bis oleic acid amide, hexamethylene bis stearic acid amide, hexamethylene bis behenic acid amide, hexamethylene bis hydroxy stearic acid amide, m-xylylene bis oleic acid amide, m-xyl Aliphatic biscarboxylic amides such as lenbis stearic acid amide, m-xylylene bisbehenic acid amide, m-xylylene bishydroxy stearic acid amide;
N, N′-dioleyl sebacic acid amide, N, N′-dioleyl adipic acid amide, N, N′-distearyl adipic acid amide, N, N′-distearyl sebacic acid amide, N, N′-di N-, such as stearyl isophthalamide, N, N'-distearyl terephthalamide
Substituted aliphatic carboxylic acid bisamides;
N-butyl-N'-stearyl urea, N-propyl-N'-stearyl urea, N-stearyl-N'-stearyl urea, N-phenyl-N'-stearyl urea, xylylene bisstearyl urea, xylylene bisstearyl Examples include N-substituted ureas such as urea, toluylene bisstearyl urea, hexamethylene bisstearyl urea, diphenylmethane bisstearyl urea, and diphenylmethane bislauryl urea.

Among these carboxylic acid amides, biscarboxylic acid amides are preferably used, and in particular, ethylene bislauric acid amide, ethylene bisoleic acid amide, ethylene bis stearic acid amide, ethylene bis-12-hydroxystearic acid amide, hexamethylene bis Lauric acid amide, hexamethylene bis oleic acid amide, hexamethylene bis-12-hydroxy stearic acid amide, m-xylylene bis lauric acid amide, m-xylylene bis oleic acid amide, m-xylylene bis-12-hydroxy stearic acid amide Is preferred. In particular, ethylene bis lauric acid amide, ethylene bis oleic acid amide, ethylene bis-12-hydroxy stearic acid amide, ethylene bis stearic acid amide, hexamethylene bis lauric acid amide, hexamethylene bis oleic acid which does not have an aromatic ring in the molecule Amides and hexamethylene bis-12-hydroxystearic acid amide are preferred from the viewpoint of excellent crystallization speed.

  Specific examples of the aliphatic alcohol include pentadecyl alcohol, cetyl alcohol, heptadecyl alcohol, 1,6-hexanediol, 1,8-octanediol, cyclohexane1,2-diol, cyclohexane1,4-diol and the like. It is done.

  Specific examples of the aliphatic carboxylic acid ester include lauric acid cetyl ester, palmitic acid cetyl ester, stearic acid cetyl ester, dilauric acid glycol, dipalmitic acid glycol, monolauric acid glycerin ester, and monostearic acid glycerin ester.

Among the transparent nucleating agents (C), a carboxylic acid amide is preferable from the viewpoint of a balance between the nucleating agent effect and transparency.
The transparent nucleating agent (C) is used in a total of 100 parts by weight of the polylactic acid resin (A) or the polylactic acid resin (A) and the polylactic acid resin (B) used as necessary. 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, more preferably 0.3 to 3 parts by weight. When the content of the transparent nucleating agent (C) is within the above range, the effect as a transparent nucleating agent is greatly expressed, and a resin composition having both high crystallization speed and transparency can be obtained.

<Various additives>
The polylactic acid resin composition of the present invention may contain other resins, additives, and the like as long as the properties of the present invention are not impaired.

  In addition, the polylactic acid resin composition of the present invention has a purpose (for example, improvement of moldability, secondary processability, decomposability, tensile strength, heat resistance, storage stability, weather resistance, flame retardancy, etc.). Depending on the above, other resins or polymers other than the components (A) to (C) and various additives may be added.

Other resins or polymers include polycarbonate resin, unmodified polyolefin, vinyl resin, polystyrene, polyamide, acrylic resin, polyphenylene sulfide resin, polyether ether ketone resin, polyester, polysulfone, polyphenylene oxide, polyimide, polyetherimide, Examples include acrylonitrile / butadiene / styrene copolymer (ABS), ethylene / α-olefin copolymer rubber, conjugated diene rubber, styrene rubber, phenol resin, melamine resin, polyester resin, silicone resin, and epoxy resin. These may be used alone or in combination of two or more.

  Various additives include, for example, plasticizers, antioxidants, ultraviolet absorbers, heat stabilizers, flame retardants, internal mold release agents, inorganic additives, organic additives, antistatic agents, surface wetting improvers, and incineration aids. Agents, pigments, dyes, nucleating agents, lubricants, natural products and the like, preferably plasticizers.

  Examples of the plasticizer include triacetin, triethylene glycol diacetate, triethyl acetyl citrate, tributyl acetyl citrate, and dibutyl sebacate.

  Inorganic additives and lubricants can be used to improve anti-blocking and slipperiness of the film or sheet. As inorganic additives, silica, mica, talc, glass fiber, glass beads, kaolin, kaolinite, barium sulfate, calcium sulfate, magnesium hydroxide, wollastonite, carbon fiber, calcium silicate fiber, magnesium oxysulfate fiber, Examples include potassium titanate fiber, calcium sulfite, white carbon, clay, montmorillonite, titanium oxide, and zinc oxide. These may be used alone or in combination of two or more. In particular, the use of glass fiber as an inorganic additive can be expected to improve the heat resistance of the resin composition.

Organic additives include starch and its derivatives, cellulose and its derivatives, pulp and its derivatives, paper and its derivatives, flour, okara, bran, coconut husk, coffee cake, protein, phthalic acid, aliphatic polybasic acid Low molecular weight materials such as polyethylene, glycerin, citric acid, glycol, and olefin, polyethylene terephthalate fiber, polyethylene naphthalate fiber, and aramid fiber. These may be used alone or in combination of two or more.

The amount of other resin, polymer or additive added is appropriately selected according to the application within a range not impairing the object of the present invention.
<Method for producing polylactic acid-based resin composition>
As a method for producing the polylactic acid resin composition of the present invention, a known production method can be appropriately employed. For example, using a high-speed stirrer or a low-speed stirrer, etc., each component is mixed in advance in advance, and then melt-kneaded with a single-screw or multi-screw extruder having sufficient kneading ability above the melting point of the resin. Sometimes a method of mixing and kneading, a method of removing the solvent after mixing in a solution, and the like can be employed.

  Manufacture of a polylactic acid-type resin composition may be performed before shaping | molding of a molded object, and manufacture and shaping | molding of a composition may be performed simultaneously. When manufacturing a composition before shaping | molding, the shape of a resin composition has a preferable pellet, rod shape, or powder.

<Polylactic acid resin composition>
The polylactic acid resin composition of the present invention is excellent in that the crystallization speed is high. Here, the “crystallization rate” in the present invention is a differential scanning calorimetry (DSC) analysis, where the polymer is heated to melt and then cooled to a predetermined temperature at a constant rate and held at the predetermined temperature. The time from when the temperature is maintained at the predetermined temperature to the time when the exothermic peak for crystallization reaches the maximum value (hereinafter also referred to as “isothermal crystallization time”) is obtained. If this time is short, the crystallization speed is fast. The predetermined temperature is appropriately selected depending on the polymer to be measured.

  Specifically, when the resin is composed of units derived from lactic acid as in the present invention, the above isothermal crystallization time is measured by weighing 5 to 6 mg of a film-like polymer into a nitrogen-sealed pan, After charging the sealed DSC measuring unit set at 30 ° C in advance, the temperature was raised at a rate of 100 ° C / min, melted at 220 ° C for 3 minutes, and then predetermined at a rate of 99 ° C / min. When it is cooled and held at a crystallization temperature (for example, 100 ° C.), the time from when it is cooled to a predetermined temperature until the exothermic peak for crystallization reaches the maximum value is obtained.

The isothermal crystallization time of the polylactic acid resin composition of the present invention is within 5 minutes, preferably 0.1 to 4 minutes, and more preferably 1 to 3 minutes.
<Molded body>
The molded product of the present invention comprises the above-described polylactic acid resin composition of the present invention. The molded article of the present invention can be produced by a publicly known method, for example, the following method.

(1) In extrusion molding, a film or sheet can be formed by molding the polylactic acid resin composition of the present invention with a general T-die extrusion molding machine.
(2) In injection molding, the pellets of the polylactic acid resin composition of the present invention are melt-softened and filled into a mold, and a molded product is obtained in a molding cycle of 20 to 300 seconds.

  (3) In blow molding (injection blow molding, stretch blow molding, direct blow molding), for example, in the case of injection blow molding, pellets of the polylactic acid-based resin composition of the present invention are used with a general injection blow molding machine. A preform is obtained by melting and filling the mold. After the obtained preform is reheated in an oven (heating furnace), it is placed in a mold maintained at a constant temperature, and a blow bottle can be formed by sending and blowing pressure air. .

  (4) In vacuum forming / vacuum / pressure forming, a film or sheet formed by the same method as the extrusion forming in (1) above is used as a preform. The obtained preform is heated and softened once, and then, using a general vacuum forming machine, by vacuum forming or vacuum / pressure forming in a mold held at a constant temperature, A molded body can be obtained.

  (5) In laminate molding, a method of laminating a film or sheet obtained by the extrusion molding method of the above (1) and another substrate with an adhesive or heat; a method of extrusion molding of the above (1) Extrusion lamination method in which the molten resin is extruded directly onto a substrate such as paper, metal, plastic, etc. by the same method as above; the resin composition of the present invention is melted with a separate extruder, and the die head is used. A laminated molded body can be obtained by a coextrusion method in which they are merged and extruded simultaneously; a method such as a coextrusion lamination in which these are combined.

  (6) In tape yarn forming, a film or sheet formed by the same method as the extrusion forming in (1) above is slit to a specific width, and is uniaxially heated in a temperature range of 60 ° C to 140 ° C and necessary. Depending on the above, it is possible to obtain a molded body by further heat setting in a temperature range of 80 ° C to 160 ° C.

  (7) In yarn forming, the polylactic acid-based resin composition of the present invention can be obtained by a melt spinning method in which an extruder is used to melt at a temperature of 150 to 240 ° C. and discharged from a spinneret. . If necessary, the yarn can be formed by uniaxially heating in a temperature range of 60 ° C. to 100 ° C. and, in some cases, further heat fixing in a temperature range of 80 ° C. to 140 ° C.

  (8) In the nonwoven fabric molding, a molded body can be molded by a spunbond method or a melt blown method. In the spunbond method, a web is formed by melt spinning using a porous spinneret and drawing using an air sucker installed at the bottom of the spinneret in the same manner as the yarn forming in (7) above. The non-woven fabric can be obtained by depositing on the collecting surface and further pressure-bonding or heat-sealing it with an embossing roll and a smooth roll. In the melt blown method, the molten resin discharged from a porous spinneret contacts with a high-speed heated gas blown from a heated gas blower outlet, is fiberized into fine fibers, and is further deposited on a moving support. Thus, a nonwoven fabric can be obtained.

  The molded body of the present invention has a haze at a thickness of 100 μm after heat treatment at 80 ° C. to 120 ° C. for 1 to 300 seconds, 0.1 to 15%, preferably 0.1 to 12%, more preferably 0.1 to 0.1%. 11% and the crystallinity is 35% or more, preferably 38 to 60%. More preferably, it is 42 to 55%.

The “crystallinity” in the present invention is determined by differential scanning calorimetry (DSC). Specifically, first, a non-oriented film obtained by press molding is heat-treated in an oven at 105 ° C. for a predetermined time. 5-6 mg of the heat-treated film was weighed, weighed into a nitrogen-sealed pan, charged into a nitrogen-sealed DSC measuring unit set in advance at 30 ° C., and 10 ° C./mi
The temperature is increased at a temperature increase rate of n and the temperature is increased to 220 ° C. Crystallization enthalpy (ΔHc) and crystal melting enthalpy (ΔHm) are measured to obtain [{(ΔHm−ΔHc) / (ΔH ₀ )} × 100], which is defined as crystallinity. Where ΔH ₀ represents the perfect ideal crystal melting enthalpy,
For example, ΔH ₀ of polylactic acid is 93 J / g. The “haze” in the present invention is a value measured with a haze meter.

<Application>
The polylactic acid-based resin composition of the present invention can be molded by the various molding methods described above, and can be suitably used for various applications without any particular limitation. In addition, these molded products are foams suitable for automobile parts, home appliance material parts, electrical / electronic parts, building members, civil engineering members, agricultural materials and daily necessities, various films, breathable films and sheets, general industrial applications and recreational applications. It can be used for various applications such as body, thread, textile, medical or sanitary goods, and preferably used for automobile material parts, home appliance material parts, electrical / electronic material parts that require heat resistance and impact resistance. be able to.

  Specifically, in automotive parts materials applications, it has expanded to parts that have been used in resin parts such as front doors and foil caps, and in household appliance material parts applications, housings for products such as personal computers, headphone stereos, and mobile phones. In the development of parts and electrical / electronic parts, examples include the development of reflective material films and sheets and polarizing films and sheets.

EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited to these Examples at all.
<Weight average molecular weight>
The weight average molecular weight of the raw material used for the reaction and the obtained resin was determined by gel permeation chromatography (GPC) [“Shodex GPC-101” manufactured by Showa Denko KK, column: “PLgel mixed c” manufactured by Polymer Lab. ”× 2 in series, column temperature: 40 ° C. (80 ° C. only for the polyesters of Synthesis Examples 1 and 2), mobile phase: chloroform (p-chlorophenol only for the polyesters of Synthesis Examples 1 and 2), flow rate: 1 ml / min]. The analysis was performed by GPC analysis software, Data Station 480II [manufactured by System Instruments Co., Ltd.].

The lactide content was quantified by an absolute calibration curve method based on area percentage.
<Crystalization rate (isothermal crystallization time)>
It was determined by DSC (“DSC-60” manufactured by Shimadzu Corporation). 5-6 mg of non-oriented film obtained by press molding was weighed, weighed into a nitrogen-sealed pan, and placed in a DSC measuring section previously set at 30 ° C. that had been nitrogen-sealed, and then increased at 100 ° C./min. The temperature was raised at a temperature rate and melted at 220 ° C. for 3 minutes. After melting, the mixture was cooled to 100 ° C. at a cooling rate of 99 ° C./min, and the time at which the crystallization peak was maximized was determined with the time when it was cooled to 100 ° C. as the start time.

<Crystallinity>
It was determined by DSC (“DSC-60” manufactured by Shimadzu Corporation). The non-oriented film obtained by press molding was heat-treated in an oven at 105 ° C. for a predetermined time, 5 to 6 mg of the treated film was weighed, weighed into a nitrogen-sealed pan, and preset at 25 ° C. that was nitrogen-sealed. After charging the DSC measurement unit, the temperature was raised to 220 ° C. at a rate of 10 ° C./min. Crystallization enthalpy (ΔHc) and crystal melting enthalpy (ΔHm) were measured to obtain [{(ΔHm−ΔHc) / (ΔH ₀ )} × 100], which was defined as crystallinity. Here, ΔH ₀ represents a perfect ideal crystal melting enthalpy, and a numerical value of 93 J / g of polylactic acid was used.

<Transparency (HAZE)>
Based on JISK7105, it calculated | required with the haze meter (Nippon Denshoku Co., Ltd. "NDH2000").

<Synthesis Example 1>
In a 200 mL glass reactor equipped with a stirrer, a thermometer and a condenser, 142.3 g (0.988 mol) of L-lactide, 1.7 g (0.122 mol) of D-lactide, terephthalic acid chloride and 1,4- Polyester having hydroxyl groups at both ends, obtained by reacting with butanediol (hydroxyl equivalent: 770 g / eq, weight average molecular weight: 2810)
2.2 g (0.00143 mol) and 11.5 mg of tin octoate were charged, and the temperature was raised to 190 ° C. with stirring at a rotation speed of 150 rpm in a nitrogen atmosphere. Polymerization was carried out at 190 ° C. to 200 ° C. for 2 hours with continuous stirring. During polymerization, as the viscosity of the polymer increased, stirring became difficult, so the rotational speed was reduced to 50 rpm while observing the state. The polymerization was completed after confirming that the viscosity of the produced polymer was sufficiently increased and the molecular weight (Mw) by GPC was 203,000. At this time, the amount of unreacted residual lactide was 3.2% by weight.

  After completion of the polymerization, the polymer was once discharged into a vat and cooled, and then dissolved in 2000 mL of chloroform. While stirring this chloroform solution, methanol was added little by little. Since about 2000 mL of methanol was added and clouded, the temporary methanol addition was stopped and the polymer was gradually precipitated while stirring. After 2 hours, the polymer was sufficiently precipitated, so about 4000 mL of methanol was further added and stirred for 1 hour to remove the remaining lactide, and then the polymer was separated by suction filtration. The filter cake was rinsed with a small amount of methanol, and further stirred in 3000 mL of methanol for 1 hour, followed by suction filtration to completely remove the remaining lactide. The polymer thus obtained was dried in a dryer under a nitrogen stream at 40 ° C. for 24 hours to obtain a polylactic acid having a partial structure derived from polyester obtained from terephthalic acid and 1,4-butanediol ( B-1) 135.2 g was obtained. The obtained polylactic acid (B-1) had a weight average molecular weight (Mw) of 206,000, and no unreacted lactide was detected.

<Synthesis Example 2>
Polyester having hydroxyl groups at both ends (hydroxyl equivalent: 770 g / eq) obtained by reacting terephthalic acid chloride and 1,4-butanediol using the same reaction apparatus as in Synthesis Example 1 2.2 g (0 .00143 mol) obtained by reacting terephthalic acid chloride with 1,8-octanediol, 1.8 g of a polyester having hydroxyl groups at both ends (hydroxyl equivalent: 1230 g / eq, weight average molecular weight: 4238) Except for changing to 0.00143 mol), 135.8 g of polylactic acid (B-2) having a partial structure derived from polyester obtained from terephthalic acid and 1,8-octanediol was obtained in the same manner as in Synthesis Example 1. It was. The obtained polylactic acid (B-2) had a weight average molecular weight (Mw) of 27,000.

<Synthesis Example 3>
Polyester having hydroxyl groups at both ends (hydroxyl equivalent: 770 g / eq) obtained by reacting terephthalic acid chloride and 1,4-butanediol using the same reaction apparatus as in Synthesis Example 1 2.2 g (0 .00143 mol) was changed to PPG # 2000 (Mw = 2200, reagent grade manufactured by Kanto Chemical Co., Ltd.) 3.1 g (0.00143 mol as a hydroxyl group) in the same manner as in Synthesis Example 1, except that PPG # 2000 133.2 g of polylactic acid (B-3) having a partial structure derived from was obtained. The obtained polylactic acid (B-3) had a weight average molecular weight (Mw) of 18,000.

[ Synthesis Example 4 ]
In a 200 mL glass reactor equipped with a stirrer, a thermometer and a condenser, L-lactide 142.3 g (0.988 mol), D-lactide 1.7 g (0.122 mol), alkyl groups having hydroxyl groups at both ends Modified with a silicone compound (manufactured by Shin-Etsu Chemical Co., Ltd., product name: KF-6002, hydroxyl equivalent: 1648 g / eq, weight average molecular weight: 6095): 4.7 g (0.00143 mol) and tin octoate 11.5 mg was charged, and the temperature was raised to 190 ° C. with stirring at 150 rpm in a nitrogen atmosphere. The polymerization was carried out for 2 hours with subsequent stirring. As the polymerization progressed, the internal temperature rose due to heat generation, reaching a maximum of 203 ° C. The polymerization was completed after confirming that the viscosity of the produced polymer was sufficiently increased and the molecular weight (Mw) by GPC was 203,000.

  At this time, it was confirmed by GPC measurement that no silicone compound remained and the amount of unreacted residual lactide was 3.5% by weight. Therefore, the content of the silicone compound in the polymer is 3.28 wt% calculated from the weight of the silicone compound used in the reaction and the weight of the lactide involved in the reaction, and is 0.148 mol%.

  After completion of the polymerization, the polymer was once discharged into a vat and cooled, and then dissolved in 2000 mL of chloroform. While stirring this chloroform solution, methanol was added little by little. Since about 2000 mL of methanol was added and clouded, the temporary methanol addition was stopped and the polymer was gradually precipitated while stirring. After 2 hours, the polymer was sufficiently precipitated, so about 4000 mL of methanol was further added and stirred for 1 hour to remove the remaining lactide, and then the polymer was separated by suction filtration. The filter cake was rinsed with a small amount of methanol, and further stirred in 3000 mL of methanol for 1 hour, followed by suction filtration to completely remove the remaining lactide. The polymer thus obtained was dried at 40 ° C. for 24 hours in a dryer under a nitrogen stream to obtain 135.2 g of polylactic acid having a partial structure of the general formula (1). The obtained polylactic acid (A-1) had a weight average molecular weight (Mw) of 20,000,000, and no unreacted lactide was detected.

[ Synthesis Example 5 ]
Using the same reaction apparatus as in Synthesis Example 4 , a silicone compound modified with an alkyl group having hydroxyl groups at both ends (manufactured by Shin-Etsu Chemical Co., Ltd., product name: KF-6002, hydroxyl group equivalent: 1648 g / eq, weight) Average molecular weight: 6095): 4.7 g (0.00143 mol) of silicone compounds having the same structure and different molecular weight (manufactured by Shin-Etsu Chemical Co., Ltd., product name: KF-6003, hydroxyl group equivalent: 2545 g / eq, weight average molecular weight: 9410): The reaction was carried out in the same manner except that the weight was changed to 7.3 g (0.00143 mol), and polymerization was conducted after confirming that the molecular weight (Mw) by GPC was 204,000. finished.

At this time, it was confirmed by GPC measurement that no silicone compound remained and the amount of unreacted residual lactide was 3.1% by weight. Therefore, the content of the silicone compound in the polymer is 4.98 wt% and 0.150 mol% calculated from the weight of the silicone compound used in the reaction and the weight of the lactide involved in the reaction.
After completion of the polymerization, the same operation as in Synthesis Example 4 was further performed to obtain 136.3 g of polylactic acid having a partial structure of the general formula (1). The obtained polylactic acid (A-2) had a weight average molecular weight (Mw) of 216,000, and no unreacted lactide was detected.

[ Synthesis Example 6 ]
Using the same reaction apparatus as in Synthesis Example 4 , a silicone compound modified with an alkyl group having hydroxyl groups at both ends (manufactured by Shin-Etsu Chemical Co., Ltd., product name: KF-6002, hydroxyl group equivalent: 1648 g / eq, weight) Average molecular weight: 6095): 4.7 g (0.00143 mol) of a silicone compound modified with an alkyl group having a hydroxyl group at one end (manufactured by Shin-Etsu Chemical Co., Ltd., product name: X-22-170BX, Hydroxyl equivalent: 2800 g / eq, weight average molecular weight: 5860, number average molecular weight: 2985): The reaction was carried out in the same manner except that it was changed to 4.0 g (0.00143 mol), and the molecular weight (Mw) by GPC was 18. The polymerization was terminated after confirming that it was 90,000.

  At this time, it was confirmed by GPC measurement that no silicone compound remained and the amount of unreacted residual lactide was 3.8% by weight. Therefore, the content of the silicone compound in the polymer is 2.81 wt% and 0.147 mol% calculated from the weight of the silicone compound used in the reaction and the weight of the lactide involved in the reaction.

After completion of the polymerization, the same operation as in Synthesis Example 4 was further performed to obtain 135.7 g of polylactic acid having a partial structure of the general formula (1). The resulting polylactic acid (A-3) had a weight average molecular weight (Mw) of 201,000, and no unreacted lactide was detected.

[ Synthesis Example 7 ]
Using the same reaction apparatus as in Synthesis Example 4 , a silicone compound modified with an alkyl group having hydroxyl groups at both ends (manufactured by Shin-Etsu Chemical Co., Ltd., product name: KF-6002, hydroxyl group equivalent: 1648 g / eq, weight) Average molecular weight: 6095): 4.7 g (0.00143 mol) of a branched modified silicone compound modified with an alkyl group having a hydroxyl group in the molecular chain (manufactured by Shin-Etsu Chemical Co., Ltd., product name: X- 22-4015, hydroxyl equivalent: 1930 g / eq, weight average molecular weight: 3468): The reaction was conducted in the same manner except that the weight was changed to 2.7 g (0.00143 mol), and the molecular weight (Mw) by GPC was 219,000. Then, the polymerization was terminated.

  At this time, it was confirmed by GPC measurement that no silicone compound remained and the amount of unreacted residual lactide was 3.1% by weight. Therefore, the content of the silicone compound in the polymer is 1.90 wt% and 0.146 mol% calculated from the weight of the silicone compound used in the reaction and the weight of the lactide involved in the reaction.

After completion of the polymerization, the same operation as in Synthesis Example 4 was further performed to obtain 136.1 g of polylactic acid having a partial structure of the general formula (1). The obtained polylactic acid (A-4) had a weight average molecular weight (Mw) of 225,000, and no unreacted lactide was detected.

[ Reference Examples 5 to 8]
The polylactic acid (A-1) to (A-4) synthesized in Synthesis Examples 4 to 7 and the transparent nucleating agent (C) were used at a temperature of 200 ° C., a time of 5 minutes, and a rotation speed of 50 rpm using a lab plast mill. It knead | mixed by the weight part shown in Table 1 on conditions. The kneaded product was pressed under the conditions of 200 ° C. and 10 MPa for 5 minutes to obtain a film having a thickness of 100 μm. The isothermal crystallization time of the obtained film was measured as described above. The film was annealed (heat treatment) in a 105 ° C. oven for 20 seconds and 60 seconds, and the crystallinity and transparency (haze) before and after annealing were measured as described above. The results are shown in Table 1.

[ Reference Example 9, Examples 10 to 12]
Polylactic acids (A-1) to (A-4) synthesized in Synthesis Examples 4 to 7 and commercially available polylactic acid (B-0) [manufactured by Mitsui Chemicals, registered trademark LACEEA, grade H-100, weight average molecular weight: 182,000, L / D ratio: 98.8 / 1.2] and a clear nucleating agent (C) using a lab plast mill at a temperature of 200 ° C., a time of 5 minutes, and a rotation speed of 50 rpm. It knead | mixed in the weight part shown in Table 1. The kneaded product was pressed under the conditions of 200 ° C. and 10 MPa for 5 minutes to obtain a film having a thickness of 100 μm. The isothermal crystallization time of the obtained film was measured as described above. The film was annealed (heat treatment) in a 105 ° C. oven for 20 seconds and 60 seconds, and the crystallinity and transparency (haze) before and after annealing were measured as described above. The results are shown in Table 1 .

[Examples 13 to 15]
The polylactic acid (A1) synthesized in Synthesis Example 4 and the polylactic acids (B1) to (B3) and the transparent nucleating agent (C) synthesized in Synthesis Examples 1 to 3 were heated at a temperature of 200 ° C. using a lab plastmill. The mixture was kneaded in parts by weight shown in Table 1 under the conditions of time 5 minutes and rotation speed 50 rpm. The kneaded product was pressed under the conditions of 200 ° C. and 10 MPa for 5 minutes to obtain a film having a thickness of 100 μm. The isothermal crystallization time of the obtained film was measured as described above. The film was annealed (heat treatment) in a 105 ° C. oven for 20 seconds and 60 seconds, and the crystallinity and transparency (haze) before and after annealing were measured as described above. The results are shown in Table 1.

[Comparative Example 1]
Commercially available polylactic acid (B-0) [manufactured by Mitsui Chemicals, registered trademark LACEA, grade H-100] and transparent nucleating agent (C) were mixed in the parts by weight shown in Table 1 in the same manner as in Example 12. Films were prepared and the isothermal crystallization time, crystallinity and transparency were measured. The results are shown in Table 1.

Claims (7)

The weight average molecular weight (Mw) composed of repeating units represented by the following formula (1) has a portion in the range of 100 to 10,000, and the entire weight average molecular weight (Mw) is in the range of 5,000 to 500,000. 20 to 95 parts by mass of the polylactic acid resin (B) with respect to a total of 100 parts by weight of the polylactic acid resin (A) and the other polylactic acid resin (B) excluding the polylactic acid resin (A). And at least one transparent nucleus selected from carboxylic acid amides, aliphatic alcohols and aliphatic carboxylic acid esters in a total of 100 parts by weight of the polylactic acid resin (A) and the polylactic acid resin (B) A polylactic acid resin composition comprising 0.1 to 10 parts by weight of an agent (C).

(In Formula (1), R ₁ and R ₂ each independently represent a linear or branched alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms, May be different.) The weight average molecular weight (Mw) of the entire polylactic acid resin (A) is in the range of 100,000 to 500,000, and the content of the site consisting of the repeating unit represented by the above formula (1) is 0.00. The polylactic acid resin composition according to claim 1, which is in the range of 1 to 10% by weight. The polylactic acid resin composition according to claim 1 or 2 , wherein the polylactic acid resin (B) is polylactic acid. Upper Kipo polylactic acid based resin (B) is represented by the following general formula (2)
-X ₁ -R ₃ -X _2- (2)
(In the formula (2), X ₁ and X ₂ each independently represents an O atom, an S atom or an NH group, and R ₃ represents a divalent hydrocarbon group containing at least one aromatic ring or aliphatic ring. And the hydrocarbon group may contain O, N or S atoms.)
The polylactic acid-type resin composition of Claim 1 or 2 which has the site | part represented by these, and the weight average molecular weight (Mw) of the whole is the range of 5,000-500,000. The polylactic acid resin (B) is represented by the following general formula (3)
-X ₁ -R ₄ -X _2- (3)
(Wherein, X ₁ and X ₂ each independently represents an O atom, an S atom or an NH group, and R ₄ represents an aliphatic hydrocarbon group having a weight average molecular weight of 25 to 50,000 and not containing a ring structure. The hydrocarbon group may contain O, N or S atoms.)
The polylactic acid-type resin composition of Claim 1 or 2 which has the site | part represented by these, and the weight average molecular weight (Mw) of the whole is the range of 5,000-500,000. The transparent nucleating agent (C) is lauric acid amide, palmitic acid amide, stearic acid amide, erucic acid amide, behenic acid amide, ricinoleic acid amide, hydroxystearic acid amide, N-oleyl palmitic acid amide, N-stearyl erucic acid Amide, ethylene biscapric amide, ethylene bis lauric acid amide, ethylene bis stearic acid amide, ethylene bis oleic acid amide, ethylene bis-12-hydroxystearic acid amide, hexamethylene bis capric acid amide, hexamethylene bis lauric acid amide, Hexamethylene bis stearic acid amide, hexamethylene bis oleic acid amide, hexamethylene bis-12-hydroxystearic acid amide, m-xylylene biscapric acid amide, m-xylylene bis lauric acid amide, m-ki Li Ren acid amide is at least one carboxylic acid amide selected from the group consisting of m- xylylene bis oleamide and m- xylylenebis-12-hydroxystearic acid amide, any of claims 1 to 5 1 polylactic acid resin composition according to item. It consists of the polylactic acid-type resin composition of any one of Claims 1-6, haze in thickness of 100 micrometers is 0.1 to 15% of range, and crystallinity is 35% or more. A molded product characterized by that.