Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
  • C08G63/08—Lactones or lactides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/78—Preparation processes
  • C08G63/82—Preparation processes characterised by the catalyst used
  • C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/06—Biodegradable
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
  • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

• the present invention relates to a resin composition containing a polylactic acid-based polymer and a ⁇ -methyl- ⁇ -valerolactone-based polymer.
• Patent Document 1 discloses a biodegradable cord containing a lactic acid-based polymer, a biodegradable aliphatic polyester other than the lactic acid-based polymer, and a lubricant. It is described that the biodegradable cord is biodegradable and can be continuously bound with a current binding machine.
• Patent Document 2 discloses a biodegradable plastic or sheet comprising a polylactic acid polymer and a biodegradable aliphatic polyester. It is described that the biodegradable plastic or sheet has excellent impact resistance.
• Patent Document 3 discloses a heat-stable and liquid alkyl- ⁇ -valerolactone-based polyester. Furthermore, Patent Document 3 describes that a composition comprising an alkyl- ⁇ -valerolactone-based polyester and an organic carbodiimide compound is known as a plasticizer for resins such as polyvinyl chloride.
• JP-A-9-111107 Japanese Patent Application Laid-Open No. 2001-115350 JP-A-3-181516
• Patent Documents 1 and 2 describe that an aliphatic polyester obtained by ring-opening polymerization of cyclic lactones can be used as a biodegradable aliphatic polyester. However, there is no detailed disclosure of the molecular weight, viscosity, specific structure, etc. of the aliphatic polyester. In addition, there is no specific disclosure of a resin composition containing the aliphatic polyester and polylactic acid. Moreover, Patent Document 3 makes no reference to the modification effect of the alkyl- ⁇ -valerolactone-based polyester on polylactic acid.
• the present invention provides a resin composition containing a polylactic acid-based polymer with improved tensile elongation at break and suppressed decrease in glass transition temperature.
• a resin composition containing a polylactic acid-based polymer and a ⁇ -methyl- ⁇ -valerolactone-based polymer [1] A resin composition containing a polylactic acid-based polymer and a ⁇ -methyl- ⁇ -valerolactone-based polymer. [2] The resin composition according to [1] above, wherein the ⁇ -methyl- ⁇ -valerolactone-based polymer is represented by the following general formula (I).
• R 1 is a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 2 to 20 carbon atoms, aryl group, arylalkyl group having 7 to 12 carbon atoms, and linear alkyl group having 1 to 20 carbon atoms, one hydrogen atom bonded to the terminal carbon atom is substituted with a group represented by the following formula (X) one hydrogen atom bonded to at least one terminal carbon atom of the oxygen atom-containing hydrocarbon group or branched alkyl group having 3 to 20 carbon atoms is substituted with a group represented by the following formula (X) represents an oxygen atom-containing hydrocarbon group.
• R 2 is a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, or 7 to 12 carbon atoms. represents an arylalkyl group of n is an integer from 8 to 1,000 and m is an integer from 8 to 1,000. When two or more R 2 and m are present, they may be the same or different from each other.
• [5] Containing 0.5 parts by mass or more and 2 parts by mass or less of the ⁇ -methyl- ⁇ -valerolactone polymer with respect to 100 parts by mass of the polylactic acid polymer,
• [6] Containing 2 parts by mass or more and 50 parts by mass or less of the ⁇ -methyl- ⁇ -valerolactone polymer with respect to 100 parts by mass of the polylactic acid polymer,
• the polylactic acid-based polymer is a homopolymer of L-lactic acid, a homopolymer of D-lactic acid, or a copolymer of L-lactic acid and D-lactic acid.
• a modifier for a polylactic acid-based polymer comprising a ⁇ -methyl- ⁇ -valerolactone-based polymer represented by the following general formula (I).
• R 1 is a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 2 to 20 carbon atoms, aryl group, arylalkyl group having 7 to 12 carbon atoms, and linear alkyl group having 1 to 20 carbon atoms, one hydrogen atom bonded to the terminal carbon atom is substituted with a group represented by the following formula (X) one hydrogen atom bonded to at least one terminal carbon atom of the oxygen atom-containing hydrocarbon group or branched alkyl group having 3 to 20 carbon atoms is substituted with a group represented by the following formula (X) represents an oxygen atom-containing hydrocarbon group.
• R 2 is a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, or 7 to 12 carbon atoms. represents an arylalkyl group of n is an integer from 8 to 1,000 and m is an integer from 8 to 1,000. When two or more R 2 and m are present, they may be the same or different from each other.
• R 1 is a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 2 to 20 carbon atoms, aryl group, arylalkyl group having 7 to 12 carbon atoms, and linear alkyl group having 1 to 20 carbon atoms, one hydrogen atom bonded to the terminal carbon atom is substituted with a group represented by the following formula (X) one hydrogen atom bonded to at least one terminal carbon atom of the oxygen atom-containing hydrocarbon group or branched alkyl group having 3 to 20 carbon atoms is substituted with a group represented by the following formula (X) represents an oxygen atom-containing hydrocarbon group.
• R 2 is a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, or 7 to 12 carbon atoms. represents an arylalkyl group of n is an integer from 8 to 1,000 and m is an integer from 8 to 1,000. When two or more R 2 and m are present, they may be the same or different from each other. ]
• a resin composition containing a polylactic acid-based polymer with improved tensile elongation at break and suppressed decrease in glass transition temperature a polylactic acid-based polymer with improved tensile elongation at break and suppressed decrease in glass transition temperature.
• polylactic acid polymer examples include L-lactic acid homopolymer, D-lactic acid homopolymer, L-lactic acid and D-lactic acid copolymer, DL-lactic acid homopolymer, DL -At least one selected from the group consisting of a copolymer of lactic acid and L-lactic acid, a copolymer of DL-lactic acid and D-lactic acid, and a polymer of lactide, which is a cyclic dimer of lactic acid. .
• the polylactic acid-based resin may also be a copolymer of lactic acid and other aliphatic hydroxycarboxylic acids, aliphatic dicarboxylic acids, aliphatic diols, aromatic dicarboxylic acids, and the like.
• the above copolymer preferably contains 70 mol % or more, more preferably 90 mol % or more, of structural units derived from lactic acid.
• the polylactic acid-based resin is preferably a homopolymer of L-lactic acid, a homopolymer of D-lactic acid, or a copolymer of L-lactic acid and D-lactic acid, and more preferably a homopolymer of L-lactic acid.
• Polylactic acid-based resins may be used singly or in combination of two or more.
• a commercially available product may be used as the polylactic acid polymer.
• Commercially available products include, for example, NatureWorks' “product name INGEO series”, TOTAL CORBION company's “product name Luminy series”, Zhejiang Hisun Biomaterials Co., Ltd. , Ltd. "Revode” series, SUPLA Material Technology Co., Ltd. , Ltd. under the trade name SUPLA.
• the weight average molecular weight of the polylactic acid resin is preferably 50,000 or more, more preferably 100,000 or more, and still more preferably 200,000 or more. It is preferably 600,000 or less, more preferably 550,000 or less, still more preferably 500,000 or less, from the viewpoint of moldability and compatibility with the ⁇ -methyl- ⁇ -valerolactone polymer. That is, the weight average molecular weight of the polylactic acid resin is preferably 50,000 or more and 600,000 or less.
• the weight average molecular weight of the polylactic acid resin can be obtained by gel permeation chromatography (GPC) measurement in terms of standard polystyrene. Moreover, when using a commercial item, you may employ
• polymer As the ⁇ -methyl- ⁇ -valerolactone-based polymer (hereinafter sometimes simply referred to as "polymer") used in this embodiment, a polymer represented by the following general formula (I) is preferable.
• the following polymer has a structure represented by the general formula (I) and is therefore an excellent modifier for polylactic acid-based polymers.
• the polymer below is a polymer obtained by ring-opening polymerization of ⁇ -methyl- ⁇ -valerolactone, and at least one hydroxyl group at the end of the molecule has been modified with another functional group. It becomes a suppressed polymer, and can suppress the decrease in the glass transition temperature of the resin composition.
• the polymer can improve the tensile elongation at break of the resin composition depending on the structure and number of the molecular terminals, and also improve the crystallization rate, impact resistance, and hydrolysis resistance. , and other functions, and it is expected that properties with a good balance of handling properties can be expressed. Furthermore, since the raw material of the polymer is ⁇ -methyl- ⁇ -valerolactone, the resin composition of this embodiment is considered to have good biodegradability.
• R 1 is a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 2 to 20 carbon atoms, a It represents an aryl group or an arylalkyl group having 7 to 12 carbon atoms.
• the "branched alkyl group” has 3 to 20 carbon atoms
• the "branched alkenyl group” has 3 to 20 carbon atoms.
• Linear alkyl groups having 1 to 20 carbon atoms include, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group and n-octyl.
• n-nonyl group n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-icosyl group and the like.
• Examples of branched alkyl groups having 3 to 20 carbon atoms include isopropyl group, 1-methylpropyl group, 2-methylpropyl group, t-butyl group, 1,1-dimethylpropyl group and 2,2-dimethylpropyl group.
• the linear or branched alkyl group having 1 to 20 carbon atoms is preferably a linear or branched alkyl group having 1 to 16 carbon atoms, more preferably 1 to 10 carbon atoms, from the viewpoint of handleability. It is a linear or branched alkyl group, more preferably a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 1-methylbutyl group, 3-methylbutyl group, n-pentyl group and 2,2-dimethylpropyl group are preferred.
• linear alkenyl groups having 2 to 20 carbon atoms include ethenyl, n-propenyl, n-butenyl (e.g., 2-butenyl and 3-butenyl), n-pentenyl (e.g., 3 -pentenyl group and 4-pentenyl group), n-hexenyl group (e.g., 1-hexenyl group and 5-hexenyl group), n-heptenyl group (e.g., 1-heptenyl group and 1,3-heptadienyl group), n- Octenyl group (e.g., 7-octenyl group and 2,7-octadienyl group), n-nonenyl group (e.g., 3-nonenyl group and 3,6-nonadienyl group), n-decenyl group (e.g., 1,3-decadienyl group) and 1,3,5-dec
• Examples of branched alkenyl groups having 3 to 20 carbon atoms include isopropenyl, 1-methylpropenyl, 2-methylpropenyl, t-butenyl, 1,1-dimethylpropenyl and 2,2-dimethylpropenyl.
• the linear or branched alkenyl group having 2 to 20 carbon atoms is preferably a linear or branched alkenyl group having 2 to 15 carbon atoms, more preferably a linear or branched alkenyl group having 3 to 10 carbon atoms, from the viewpoint of handleability. It is a linear or branched alkenyl group, more preferably a linear or branched alkenyl group having 3 to 6 carbon atoms.
• the aryl group having 6 to 12 carbon atoms includes a phenyl group, 2-methylphenyl group, 4-methylphenyl group, 2,4-dimethylphenyl group, 2-naphthyl group and the like.
• a phenyl group is preferred.
• Examples of arylalkyl groups having 7 to 12 carbon atoms include phenylmethyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl, phenylhexyl, naphthylmethyl and naphthylethyl groups.
• a phenylmethyl group is preferred.
• R 1 is a linear alkyl group having 1 to 20 carbon atoms and one hydrogen atom bonded to the terminal carbon atom is represented by the following formula (X).
• One hydrogen atom bonded to at least one terminal carbon atom of an oxygen atom-containing hydrocarbon group substituted with the represented group or a branched alkyl group having 3 to 20 carbon atoms is represented by the following formula (X) represents an oxygen atom-containing hydrocarbon group substituted with a group.
• the bond indicated by * binds to a linear alkyl group having 1 to 20 carbon atoms or a branched alkyl group having 3 to 20 carbon atoms.
• R 2 in the above formula (X) has the same meaning as R 2 described later.
• the straight-chain alkyl group having 1 to 20 carbon atoms that bonds to the above formula (X) the groups exemplified as the "linear alkyl group having 1 to 20 carbon atoms” can be similarly exemplified.
• the linear alkyl group having 1 to 20 carbon atoms that bonds to the above formula (X) is preferably a linear alkyl group having 1 to 15 carbon atoms, more preferably a linear alkyl group having 1 to 10 carbon atoms. group, more preferably a straight-chain alkyl group having 2 to 10 carbon atoms, and even more preferably a straight-chain alkyl group having 2 to 5 carbon atoms.
• the branched alkyl group having 3 to 20 carbon atoms that bonds to the above formula (X) can be similarly exemplified as the above-mentioned "branched alkyl group having 3 to 20 carbon atoms".
• the branched alkyl group having 3 to 20 carbon atoms that bonds to the above formula (X) is preferably a branched alkyl group having 3 to 15 carbon atoms, more preferably a branched alkyl group having 3 to 10 carbon atoms. , more preferably a branched alkyl group having 3 to 6 carbon atoms, and may be a branched alkyl group having 3 to 5 carbon atoms.
• one hydrogen atom bonded to all terminal carbon atoms of the branched alkyl group having 3 to 20 carbon atoms is an oxygen atom-containing hydrocarbon group substituted with a group represented by the above formula (X).
• m represents the average number of repetitions and is an integer of 8 to 1,000, preferably 8 to 800, more preferably 10 to 500, still more preferably 10 to 300, and may be 10 to 100, 10 ⁇ 80, or 10-60. If m is an integer of 8 or more, a more excellent modification effect can be obtained. Moreover, when m is an integer of 1,000 or less, good moldability and productivity can be obtained.
• R 1 when there are a plurality of groups represented by the above formula (X), these may be the same or different.
• a plurality of R 2 and m may be present. When two or more R 2 are present, they may be the same or different from each other. Moreover, when there are a plurality of m, these may be the same or different from each other.
• R 1 represents an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to a terminal carbon atom in a linear alkyl group having 1 to 20 carbon atoms is substituted with a group represented by the above formula (X);
• the following structures can be specifically exemplified as the general formula (I).
• R 1 represents an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to a terminal carbon atom in a linear alkyl group having Q carbon atoms is replaced with a group represented by the above formula (X)
• the above general formula (I) is represented by the following general formula (Ia).
• Q is an integer of 1-20.
• R 1 is an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to at least one terminal carbon atom of a branched alkyl group having 3 to 20 carbon atoms is substituted with a group represented by the above formula (X).
• the following structures can be specifically exemplified as the general formula (I).
• R 1 is an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to the above carbon atoms at all terminal carbon atoms of a 2-methylpropyl group is replaced with a group represented by the above formula (X);
• the above general formula (I) is represented by the following general formula (Ic).
• R 1 is an oxygen atom-containing hydrocarbon in which one hydrogen atom bonded to the carbon atoms at the two terminal carbon atoms of the 2,2-dimethylpropyl group is replaced with a group represented by the above formula (X)
• the above general formula (I) is represented by the following general formula (Id).
• R 1 is an oxygen atom-containing hydrocarbon in which one hydrogen atom bonded to the carbon atoms at the two terminal carbon atoms of the 2,2-dimethylbutyl group is replaced with a group represented by the above formula (X).
• the above general formula (I) is represented by the following general formula (Ie).
• R 1 is an oxygen atom-containing hydrocarbon in which one hydrogen atom bonded to the above carbon atoms at all terminal carbon atoms of a 2,2-dimethylpropyl group is substituted with a group represented by the above formula (X)
• the above general formula (I) is represented by the following general formula (If).
• R 1 is a linear or branched alkyl group having 1 to 20 carbon atoms, a linear alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, from the viewpoint of easily obtaining a modifying effect.
• An oxygen atom in which one hydrogen atom bonded to a terminal carbon atom in an arylalkyl group having 7 to 12 carbon atoms or a linear alkyl group having 1 to 20 carbon atoms is substituted with a group represented by the above formula (X).
• a hydrocarbon group is preferred.
• R 2 is a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, Alternatively, it represents an arylalkyl group having 7 to 12 carbon atoms.
• the "branched alkyl group” has 3 to 20 carbon atoms
• the "branched alkenyl group” has 3 to 20 carbon atoms.
• the linear or branched alkyl group having 1 to 20 carbon atoms represented by R 2 can be similarly exemplified as the above-mentioned "linear or branched alkyl group having 1 to 20 carbon atoms".
• the linear or branched alkyl group having 1 to 20 carbon atoms represented by R 2 is preferably a linear or branched alkyl group having 1 to 15 carbon atoms, more preferably carbon It is a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 1-methylbutyl group, n-pentyl group and 2,2-dimethylpropyl group are preferred.
• the straight-chain or branched alkenyl group having 2 to 20 carbon atoms represented by R 2 can be similarly exemplified as the above-mentioned "straight-chain or branched alkenyl group having 2 to 20 carbon atoms".
• the linear or branched alkenyl group having 2 to 20 carbon atoms represented by R 2 is preferably a linear or branched alkenyl group having 2 to 15 carbon atoms, more preferably 3, from the viewpoint of handleability. It is a linear or branched alkenyl group having up to 10 carbon atoms, more preferably a linear or branched alkenyl group having 3 to 6 carbon atoms.
• the aryl group having 6 to 12 carbon atoms represented by R 2 can be similarly exemplified as the above-mentioned "aryl group having 6 to 12 carbon atoms".
• the aryl group having 6 to 12 carbon atoms represented by R 2 is preferably a phenyl group.
• the arylalkyl group having 7 to 12 carbon atoms represented by R 2 can be exemplified in the same manner as the groups exemplified as the "arylalkyl group having 7 to 12 carbon atoms”.
• the arylalkyl group having 7 to 12 carbon atoms represented by R 2 is preferably a phenylmethyl group.
• R 2 is preferably a linear alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, from the viewpoint of easily obtaining a modifying effect.
• n represents the average repetition number and is an integer of 8 to 1,000, preferably 8 to 800, more preferably 10 to 600, still more preferably 10 to 500, still more preferably 10 to 300. If n is an integer of 8 or more, a more excellent modification effect can be obtained. Moreover, when n is an integer of 1,000 or less, good moldability and productivity can be obtained.
• the number average molecular weight of the polymer is preferably 1,000 or more, more preferably 1,500 or more, and still more preferably 2,000 or more, from the viewpoint of easily obtaining a more excellent modification effect.
• the number average molecular weight of the polymer is preferably 100,000 or less, more preferably 80,000 or less, and even more preferably 50,000 or less. That is, the number average molecular weight of the polymer is preferably 1,000 or more and 100,000 or less.
• the number average molecular weight of the ⁇ -methyl- ⁇ -valerolactone polymer is the standard polystyrene-equivalent number average molecular weight obtained by gel permeation chromatography (GPC) measurement. A detailed measurement method can follow the method described in Examples.
• the weight average molecular weight of the polymer is preferably 1,500 or more and 200,000 or less. If the weight-average molecular weight is 1,500 or more, a more excellent modification effect is likely to be exhibited. If the weight-average molecular weight is 200,000 or less, it tends to be excellent in handleability and productivity during molding.
• the weight average molecular weight of the polymer is more preferably 2,200 or more, and still more preferably 3,000 or more. Also, the number average molecular weight of the polymer is more preferably 160,000 or less, still more preferably 125,000 or less, and even more preferably 100,000 or less.
• the weight average molecular weight of the ⁇ -methyl- ⁇ -valerolactone polymer is the weight average molecular weight in terms of standard polystyrene determined by gel permeation chromatography (GPC) measurement. A detailed measurement method can follow the method described in Examples.
• viscosity is the viscosity of a polymer measured with an E-type viscometer.
• the measurement temperature can be optimized according to the molecular weight and the like.
• the viscosity of the polymer is preferably 400 mPa ⁇ s or more at 80°C, more preferably 1,000 mPa ⁇ s or more at 80°C, from the viewpoint of exhibiting a more excellent modifying effect. From the viewpoint of moldability and productivity, it is preferably 200,000 mPa ⁇ s or less at 80°C, and more preferably 150,000 mPa ⁇ s or less at 80°C.
• the viscosity of the polymer is preferably 400 mPa ⁇ s or more and 200,000 mPa ⁇ s or less at a measurement temperature of 80°C.
• the measurement temperature can be set according to the molecular weight and the like.
• the polymer preferably has a viscosity of, for example, 3,500 to 150,000 mPa ⁇ s, more preferably 4,000 to 150,000 mPa ⁇ s at 30°C.
• the polymer preferably has a viscosity of, for example, 650 to 150,000 mPa ⁇ s at 60° C., more preferably 800 to 150,000 mPa ⁇ s.
• the method for producing the ⁇ -methyl- ⁇ -valerolactone polymer is not particularly limited. On the other hand, from the viewpoint of productivity and convenience, or in the case of producing a high-molecular-weight polymer, ⁇ -methyl- ⁇ -valerolactone, an alcohol compound or water, and a base catalyst are reacted to form a reaction solution, It is preferable to employ a production method including a step of adding a terminal modifier to carry out a terminal modification reaction (hereinafter also referred to as a “reaction step”).
• the above production method is characterized by adding a terminal modifying agent directly to a reaction solution obtained by reacting ⁇ -methyl- ⁇ -valerolactone, an alcohol compound or water, and a basic catalyst. That is, after the ring-opening polymerization of ⁇ -methyl- ⁇ -valerolactone, a terminal modifier is added to the reactor in which the ring-opening polymerization was performed without taking out the ring-opening polymer once, and the end of the ring-opening polymer is Denaturation can be performed. In the reaction process, the ring-opening polymerization reaction and the terminal modification reaction are performed in one pot, so the above production method can be said to be a simplified process. In addition, the polymer is not limited to the production method described above.
• the terminal modification of the ring-opened polymer once taken out is performed at a relatively high temperature (about 100°C), so the thermal decomposition rate tends to increase, and the ring-opened polymer depolymerizes and the molecular weight decreases. Conceivable.
• the production method described above can produce a high-molecular-weight polymer without lowering the molecular weight even though the terminal is modified.
• Alcohol compounds include, for example, linear or branched aliphatic hydrocarbon alcohols having 1 to 20 carbon atoms, alcohols of aromatic hydrocarbons having 6 to 12 carbon atoms, and alkyl aromatic hydrocarbons having 7 to 12 carbon atoms. Alcohol etc. are mentioned. These alcohol compounds may have saturated or unsaturated hydrocarbon groups. In the case of the above-mentioned "alcohol of branched aliphatic hydrocarbon", the number of carbon atoms is 3-20. Also, the alcohol compound may be a monohydric alcohol or a polyhydric alcohol such as a dihydric alcohol and a trihydric alcohol. Water that can be used in this embodiment is not particularly limited as long as the effects of the present invention can be obtained. For example, tap water, distilled water, ion-exchanged water, industrial water, deionized water, etc. can be used.
• Base catalysts that can be used in the present embodiment include metal catalysts such as alkali metals and alkali metal compounds, organic base compounds, and the like.
• the basic catalyst may be used alone or in combination of two or more.
• the alkali metal compound include organic alkali metal compounds, alkali metal hydroxide compounds, and alkali metal hydride compounds. Among them, organic lithium compounds such as butyllithium are preferred.
• organic base compounds include amine compounds having an amidine skeleton or a guanidine skeleton.
• Metal catalysts such as organomagnesium compounds and organozinc compounds can also be used as basic catalysts.
• a base catalyst in an amount of 0.005 to 1.5 molar equivalents relative to the hydroxyl group of the alcohol compound.
• a basic catalyst it is preferable to add 0.005 to 3.0 molar equivalents of a basic catalyst to water.
• ⁇ -methyl- ⁇ -valerolactone As ⁇ -methyl- ⁇ -valerolactone that can be used in this embodiment, one produced by a known method can be used. For example, it can be produced by a known method using 2-hydroxy-4-methyltetrahydropyran or the like as a raw material (JP-B-6-53691, etc.). Also, ⁇ -methyl- ⁇ -valerolactone can be used as a commercial product, and can be used regardless of whether it is derived from petrochemicals or bio-derived. In the reaction step, it is preferable to add 5 to 1,500 molar equivalents of ⁇ -methyl- ⁇ -valerolactone to the hydroxyl groups of the alcohol compound. When water is used, it is preferable to add 5 to 1,500 molar equivalents of ⁇ -methyl- ⁇ -valerolactone to water.
• Terminal modifiers that can be used in this embodiment include acid anhydrides and acid halides (acid halides are also referred to as “halogenated esters”). Acid anhydrides and acid halides are not particularly limited as long as the effects of the present invention can be obtained. For example, linear or branched alkyl groups having 1 to 20 carbon atoms, linear or branched alkenyl groups having 2 to 20 carbon atoms, aryl groups having 6 to 12 carbon atoms, and arylalkyl groups having 7 to 12 carbon atoms. Acid anhydrides and acid halides having at least one group selected from the group consisting of groups can be used. The "branched alkyl group” has 3 to 20 carbon atoms, and the "branched alkenyl group” has 3 to 20 carbon atoms.
• acid anhydrides include acetic anhydride, oxalic anhydride, propionic anhydride, succinic anhydride, maleic anhydride, benzoic anhydride, phthalic anhydride, glutaric anhydride, methacrylic anhydride, butyric anhydride, and isobutyric anhydride. , 1,8-naphthalic anhydride, trifluoroacetic anhydride, cyclohexanecarboxylic anhydride and the like.
• acid halides include acetyl chloride, propionyl chloride, butyroyl chloride, trifluoroacetyl chloride, benzoyl chloride, 2-furoyl chloride, hexanoyl chloride, phenylacetyl chloride, acetyl bromide, propionyl bromide, and bromide. benzoyl and the like.
• the reaction step it is preferable to add 1 to 20.0 molar equivalents of the terminal modifier to the hydroxyl group of the alcohol compound.
• water it is preferable to add 1.0 to 20.0 molar equivalents of a terminal modifier to water.
• a co-catalyst may be added in the reaction step, if necessary.
• cocatalysts that can be used include amine compounds such as triethylamine, tributylamine, trioctylamine, imidazole, pyridine, aminopyridine and 4-dimethylaminopyridine.
• the cocatalyst can be added in an amount of 0.001 to 10 molar equivalents relative to the hydroxyl group of the alcohol compound.
• water when water is used, the co-catalyst can be added in an amount of 0.001 to 10 molar equivalents relative to water.
• the reaction step can be performed in the presence of a solvent inert to the ring-opening polymerization reaction.
• solvents include aliphatic hydrocarbons such as cyclohexane, methylcyclohexane, n-hexane and n-pentane; aromatic hydrocarbons such as benzene, toluene and xylene.
• the reaction temperature for reacting ⁇ -methyl- ⁇ -valerolactone, the alcohol compound or water, and the base catalyst is usually 20 to 100° C., and the reaction time is usually 1 minute to 24 hours. is.
• the reaction temperature for performing the terminal modification reaction is usually 20 to 80° C., and the reaction time is usually 1 minute to 24 hours.
• the polymer represented by the general formula (I) can be produced.
• a post-treatment step may be performed to isolate the polymer produced.
• a suitable method can be adopted from known methods.
• the reaction mixture after the reaction step can be washed with a reaction solvent and water, concentrated, and purified by a method commonly used for separation and purification of organic compounds, such as distillation.
• the resin composition of this embodiment preferably contains 0.1 parts by mass or more and 50 parts by mass or less, more preferably 0 parts by mass of ⁇ -methyl- ⁇ -valerolactone polymer with respect to 100 parts by mass of polylactic acid polymer. .5 to 30 parts by mass, more preferably 1.0 to 15 parts by mass. With the above content ratio, it is possible to obtain a resin composition that is even more excellent in both improving the tensile elongation at break and suppressing the decrease in the glass transition temperature.
• the resin composition of the present embodiment contains ⁇ -methyl- ⁇ -valerolactone-based polymer with respect to 100 parts by mass of the polylactic acid-based polymer.
• the amount can also be 2.0 parts by mass or more and 15 parts by mass or less.
• ⁇ -methyl- ⁇ -valerolactone polymer 0.5 parts by mass or more and 2 parts by mass or less of ⁇ -methyl- ⁇ -valerolactone polymer is contained in 100 parts by mass of the polylactic acid polymer, and ⁇ -methyl
• the above resin composition is more excellent in both improvement of tensile elongation at break and suppression of decrease in glass transition temperature, and can exhibit improvement in crystallization rate.
• 2 parts by mass or more and 50 parts by mass or less (more preferably 2 parts by mass or more) of ⁇ -methyl- ⁇ -valerolactone polymer is added to 100 parts by mass of polylactic acid polymer. 30 parts by mass or less, more preferably 2 parts by mass or more and 15 parts by mass or less), and the number average molecular weight of the ⁇ -methyl- ⁇ -valerolactone polymer is 1,000 or more and 100,000 or less (more preferably 2, 000 or more and 50,000 or less).
• the above resin composition is more excellent in terms of both improvement in tensile elongation at break and suppression of lowering of the glass transition temperature, and can exhibit improved impact resistance.
• the total content of the polylactic acid-based polymer and the ⁇ -methyl- ⁇ -valerolactone-based polymer in the resin composition of the present embodiment is preferably 80% by mass or more, more preferably 85% by mass or more, and further It is preferably 90% by mass or more, still more preferably 95% by mass or more, and even more preferably 98% by mass or more.
• the total content of the polylactic acid-based polymer and the ⁇ -methyl- ⁇ -valerolactone-based polymer in the resin composition of this embodiment may be 100% by mass or less. If it is the said content rate, the effect of this invention will be exhibited more notably.
• the resin composition of this embodiment may contain additives other than the polylactic acid-based polymer and the ⁇ -methyl- ⁇ -valerolactone-based polymer.
• Additives include inorganic fillers, softening agents, heat antioxidants, antioxidants, hydrolysis inhibitors, light stabilizers, antistatic agents, release agents, flame retardants, foaming agents, pigments, dyes, and brightening agents. agents, UV absorbers, lubricants, and the like. These may be used individually by 1 type, and may use 2 or more types together. When the above additive is used, the content of the additive in the resin composition may be appropriately determined according to the desired physical properties of the resin composition.
• the method for producing the resin composition of this embodiment is not particularly limited, and the polylactic acid-based polymer, the ⁇ -methyl- ⁇ -valerolactone-based polymer, and, if necessary, additives may be uniformly mixed.
• a mixing method a method of melt-kneading using a single-screw extruder, a multi-screw extruder, a Banbury mixer, a heating roll, Brabender, various kneaders, etc., or a method of supplying each component from a separate charging port and melt-kneading. methods and the like.
• pre-blending may be performed before melt-kneading.
• Examples of the pre-blending method include a method using a mixer such as a Henschel mixer, a high speed mixer, a V blender, a ribbon blender, a tumbler blender and a conical blender.
• the temperature during melt-kneading can be arbitrarily selected, preferably within the range of 140 to 220° C., taking into account the melting point and decomposition temperature of the polylactic acid polymer.
• the present invention also provides a molded article made of the resin composition.
• the shape of the molded article may be any molded article that can be produced using the resin composition of the present embodiment.
• molded bodies include molded bodies of various shapes such as pellets, films, sheets, plates, pipes, tubes, bottles, fibrous bodies, rod-shaped bodies, microparticles, particulate bodies, and foams.
• the method for producing this molded article is not particularly limited, and various molding methods such as injection molding, blow molding, press molding, extrusion molding, calender molding, and molding using a 3D printer can be used.
• the polylactic acid-based polymer is mixed with the ⁇ -methyl- ⁇ -valerolactone-based polymer represented by the general formula (I) to form a resin composition, thereby improving the tensile elongation at break and lowering the glass transition temperature can be suppressed.
• the present invention provides a polylactic acid-based polymer modifier comprising the ⁇ -methyl- ⁇ -valerolactone-based polymer represented by the general formula (I).
• a preferred embodiment is the use of the ⁇ -methyl- ⁇ -valerolactone-based polymer represented by the general formula (I) as a modifier for polylactic acid-based polymers.
• the resin composition of this embodiment can be used for various purposes.
• Applications of the resin composition include: Food utensils such as edible bags, edible caps, edible trays, straws, cutlery and food containers; Closures and cap liners for containers storing food, beverages, medicines, etc.; Single-layer or multi-layer films and sheets such as electronic component packaging materials, pharmaceutical packaging materials, food packaging materials, agricultural materials, civil engineering and construction materials, and industrial materials; Fibers such as fabrics and nonwovens; Adhesive (imparting) agents and adhesive (imparting) agents such as solvent-type, hot-melt, and heat-stretching types; Aqueous-type, solution-type, emulsion-type, dispersion-type coating agents; Filament for 3D printer; developing toner; Support material for hydraulic fracturing and water loss prevention agent for excavation; Various anti-vibration and damping materials such as anti-vibration rubber, mats, seats, cushions, dampers, pads, mounting rubber; Household appliances such as televisions, stereos
• Glass transition temperature (Tg) and melting point (Tm) The resin compositions and resin composition sheets obtained in Examples 1 to 31 and Comparative Examples 1 to 12 were measured using a differential scanning calorimeter ("DSC25" manufactured by TA Instruments) under a nitrogen flow rate (100 mL/min). The temperature was raised from 30°C to 220°C at a rate of 10°C/min, held at 220°C for 5 minutes, and then lowered to -70°C at a rate of 10°C/min. After holding at -70°C for 5 minutes, the temperature was raised to 220°C at a rate of 10°C/min, and the glass transition temperature and melting point were evaluated.
• DSC25 differential scanning calorimeter
• a strip piece of 80 ⁇ 10 mm was cut out from the obtained pressed plate and subjected to crystallization treatment in a constant temperature bath of 80° C. for 16 hours.
• V notch processing (remaining width 8 mm, tip radius 0.25 mm) was performed on the center of the long side to prepare a notched strip test piece.
• the resin compositions obtained in Examples 25 to 28 and Comparative Example 10 were molded using an injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd., mold clamping force: 80 tons, screw diameter: ⁇ 26 mm), and a cylinder temperature of 190 to 210 ° C.
• a multi-purpose test piece type A1 (dumbbell-shaped test piece described in JIS K7139; 4 mm thickness, total length 170 mm, parallel part length 80 mm, parallel part width 10 mm) were produced.
• the obtained test piece was crystallized in a constant temperature bath at 80 ° C. for 16 hours, cut into a strip of 80 ⁇ 10 mm, and V-notched at the center of the long side (remaining width 8 mm, tip radius 0.25 mm).
• a notched strip test piece was produced. Square pieces of 50 ⁇ 50 mm were cut out from the resin composition sheets obtained in Examples 29-31 and Comparative Examples 11-12.
• dumbbell-shaped test piece was punched out from the obtained pressed plate and subjected to crystallization treatment in a constant temperature bath of 80° C. for 16 hours.
• the resin compositions obtained in Examples 25 to 28 and Comparative Example 10 were molded using an injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd., mold clamping force: 80 tons, screw diameter: ⁇ 26 mm), and a cylinder temperature of 190 to 210 ° C.
• dumbbell-shaped test piece described in JIS K7139; 4 mm thickness, total length 170 mm, parallel part length 80 mm, parallel part width 10 mm .
• the obtained dumbbell-shaped specimen was subjected to crystallization treatment in a constant temperature bath of 80° C. for 16 hours.
• JIS No. 3 dumbbell-shaped specimens were punched out from the resin composition sheets prepared in Examples 29-31 and Comparative Examples 11-12.
• Tensile test The prepared dumbbell-shaped test piece was stored at 23 ° C.
• Total light transmittance Square pieces (test pieces) of 50 ⁇ 50 mm were cut out from the resin composition sheets prepared in Examples 29-31 and Comparative Examples 11-12. Using a spectroscopic haze meter ("Spectral Haze Meter SH7000" manufactured by Nippon Denshoku Industries Co., Ltd., light source D65), the total light transmittance of the test piece was measured according to JIS-K7361-1.
• ⁇ Resin composition The following polylactic acid-based polymer, ⁇ -methyl- ⁇ -valerolactone-based polymer, and other components were used in Examples and Comparative Examples.
• Polylactic acid polymer ⁇ Nature Works, trade name “INGEO 2500HP” (weight average molecular weight: 200,000) ⁇ Nature Works, trade name “INGEO 3001D” (weight average molecular weight: 150,000) ⁇ Nature Works, trade name “INGEO 2003D” (weight average molecular weight: 220,000)
• Polymer - ⁇ -methyl- ⁇ -valerolactone polymer produced in Production Examples 1 to 19
• the resulting reaction solution containing the polymer was extracted with toluene and water and purified by a thin film evaporator to obtain 135 g (0.04 mmol) of the polymer.
• the obtained polymer (hereinafter sometimes referred to as “PMVL-17”) is represented by the following structural formula (II), where n and m are as shown in Table 1.
• the resulting reaction solution containing the ring-opened polymer was purified by extraction with toluene and water, reprecipitation in a large amount of hexane, and drying under reduced pressure at 80°C. After putting 1500 mL of dichloromethane as a solvent into a 3,000 mL internal volume glass 4-necked flask, the above purified ring-opening polymer, 22.7 g (270 mmol) of 3,4-dihydro-2H-pyran, and p-toluenesulfone 0.9 g (3.6 mmol) of pyridinium acid was added and stirred at 25° C. for 5 hours to obtain a reaction solution containing a polymer.
• the resulting reaction solution containing the polymer was purified by extraction with dichloromethane and water and distillation to obtain 114 g (0.06 mmol) of the polymer.
• the obtained polymer (hereinafter sometimes referred to as “PMVL-18”) is represented by the following structural formula (III), where n and m are as shown in Table 1.
• Table 1 shows the measured values of the aforementioned number average molecular weight, weight average molecular weight, and viscosity for the polymers obtained in Production Examples.
• Examples 1 to 24 and Comparative Examples 1 to 9 The polylactic acid-based polymer "INGEO 2500HP", the polymers obtained in the production examples, and other components were mixed in the formulations shown in Tables 2 to 4, using a kneader Labo Plastomill (manufactured by Toyo Seiki Seisakusho Co., Ltd., product name "3S150"), melted and kneaded for 5 minutes at a cylinder temperature of 210° C. and a screw rotation speed of 50 rpm, extruded into strands and cut to obtain a resin composition. The obtained resin composition was evaluated as described above. The results are shown in Tables 2-4.
• Examples 1, 5, 8 and Comparative Example 1 it can be seen that the examples are resin compositions with improved tensile elongation at break and suppressed decrease in glass transition temperature, and good crystallization speed. . From the comparison between Examples 2, 3, 6, 7, 9, 10, 12 to 24 and Comparative Examples 3 and 4, the above examples significantly improved the tensile elongation at break and suppressed the decrease in the glass transition temperature. It can be seen that the resin composition has good impact resistance. From the comparison between Example 11 and Comparative Example 5, it can be seen that the above Examples are resin compositions in which the tensile elongation at break is improved well and the decrease in the glass transition temperature is suppressed.
• Example 4 and Comparative Example 6 From the comparison between Example 4 and Comparative Example 6, it can be seen that the tensile elongation at break is favorably improved in the above Examples. From the comparison between Example 3 and Comparative Example 9, and between Example 14 and Comparative Examples 7 and 8, it can be seen that the Examples are resin compositions with improved tensile elongation at break and good impact resistance. I understand. From Examples 1 to 24 and Comparative Example 1, Examples are resin compositions with improved tensile elongation at break and suppressed decrease in glass transition temperature, and Examples 1 to 24 and Comparative Examples 2 to 9. shows the excellent modifying effect of the polymer on polylactic acid.
• the resin composition of this embodiment has improved tensile elongation at break and reduced decrease in glass transition temperature compared to polylactic acid, and is useful for applications requiring these physical properties.
• the resin composition of this embodiment includes, for example, food utensils, plugs, cap liners, films and sheets, fibers, adhesive (applying) agents, adhesive (applying) agents, coating agents, filaments for 3D printers, developing toners, hydraulic It can be used as a support material for crushing, a water loss prevention agent for excavation, a vibration isolating member, a vibration damping member, automobile interior and exterior parts, various grips, and the like.

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• 2022
  • 2022-10-20 CN CN202280070734.XA patent/CN118139926A/zh active Pending
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