WO2011074328A1 - ポリ乳酸系ポリオール組成物、その製造方法、ウレタン樹脂組成物、その製造方法及び成形体 - Google Patents
ポリ乳酸系ポリオール組成物、その製造方法、ウレタン樹脂組成物、その製造方法及び成形体 Download PDFInfo
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- WO2011074328A1 WO2011074328A1 PCT/JP2010/068852 JP2010068852W WO2011074328A1 WO 2011074328 A1 WO2011074328 A1 WO 2011074328A1 JP 2010068852 W JP2010068852 W JP 2010068852W WO 2011074328 A1 WO2011074328 A1 WO 2011074328A1
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- polylactic acid
- based polyol
- compound
- silica compound
- polyol composition
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/428—Lactides
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
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- 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
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- 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
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
Definitions
- the present invention relates to a polylactic acid-based polyol composition in which a catalyst remaining in a polylactic acid-based polyol obtained by a transesterification reaction is deactivated, a production method thereof, and a urethane resin composition obtained using the same, and production thereof
- the present invention relates to a method and a molded body.
- Polyurethane has long been used in a wide range of fields such as plastics materials, fibers, paints, and adhesives.
- polyurethane made from a polylactic acid-based polyol having biodegradability and biocompatibility has attracted attention.
- polyurethane made from a polylactic acid-based polyol having shape memory properties is known. (Patent Document 1), and application to electronic materials and medical materials is being studied.
- the polylactic acid-based polyol used for the production of the urethane resin is a ring-opening polymerization of lactide using a compound having two or more hydroxyl groups as an initiator, or a transesterification reaction between a compound having two or more hydroxyl groups and a commercially available polylactic acid resin. Obtained by.
- lactide is expensive, and if the purity is low, a high molecular weight polymer cannot be obtained, so that purification of lactide is necessary.
- the transesterification reaction is a synthetic method with higher productivity than ring-opening polymerization because a polylactic acid-based polyol can be obtained only by melt mixing.
- the polylactic acid-based polyol obtained by the transesterification reaction includes an oligomer of a by-product of the transesterification reaction and a polymerization catalyst used for the synthesis of the polylactic acid-based compound used as a raw material in the transesterification reaction. It is. If these remain in the polylactic acid-based polyol, the urethane reaction is affected, so purification is necessary.
- As a purification method after dissolving polylactic acid-based polyol in chloroform or the like, it is precipitated by dropping in a poor solvent such as methanol, and reduced pressure by removing the oligomer by reducing the pressure inside the system after completion of the esterification reaction. There is a law.
- the reprecipitation method can remove oligomers and catalysts, but uses a large amount of solvent, and therefore has high environmental load and low productivity.
- the depressurization method is a method of reducing the pressure by attaching a distiller or the like to the reaction vessel, and is a simple and highly productive purification method.
- the decompression method can remove oligomers having a low boiling point, but the polymerization catalyst remains in the polylactic acid-based polyol because it has a high boiling point. Since the polymerization catalyst also has a catalytic action on the urethanization reaction of polylactic acid-based polyol, when synthesizing polyurethane using polylactic acid-based polyol purified by the reduced pressure method, the urethanation reaction proceeds by the remaining polymerization catalyst, and urethane It may be difficult to uniformly mix the raw materials to be subjected to the chemical reaction, and a uniform molded body may not be obtained. For this reason, phosphoric acid, citric acid, a phenol compound, a polyvalent amine compound, etc.
- Patent Document 2 a deactivator that forms a chelate with a polymerization catalyst in polylactic acid and deactivates it.
- this deactivator is an acid or a basic compound, there is a possibility of decomposing polylactic acid or reacting with an isocyanate group to inhibit the urethane reaction.
- the acid reacts with isocyanate to generate carbon dioxide, a uniform molded product cannot be obtained.
- survives by a hot water process is also reported, water may cause the decomposition
- a silica compound is known as a catalyst adsorbing material (Patent Document 5).
- a solid catalyst is synthesized in advance by reacting a tin catalyst used for polymer synthesis with a silanol group on the surface of a silica compound, and this is used as a catalyst for the urethanization reaction. That is, the adsorbed tin catalyst is said to have a catalytic action and is not aimed at deactivating the catalytic ability.
- the synthesis of the solid catalyst requires 3 hours for heating the silica compound and the tin catalyst, and a method for synthesizing the solid catalyst under the same reaction conditions was obtained by the transesterification reaction.
- the tin catalyst adsorbed on the silica compound surface has a low dispersibility in the urethane raw material, and it is difficult to obtain a uniform molded body.
- An object of the present invention is to easily deactivate a catalyst that remains in a polylactic acid-based polyol and also functions as a catalyst for a urethanization reaction, suppresses the influence of the catalyst on the urethanization reaction, and is used as a raw material for a urethane resin.
- the present invention is to provide a polylactic acid-based polyol composition capable of obtaining a uniform molded body even when it is present, and a method for producing the same. Furthermore, it is providing the urethane resin composition obtained using a polylactic acid-type polyol composition, its manufacturing method, and a molded object.
- the present inventors have added a silica compound having a specific surface area to a polylactic acid-based polyol obtained by the transesterification reaction, and mixed it to produce a polyester provided as a raw material for the transesterification reaction.
- the present inventors have found that the catalytic action of the polymerization catalyst used in the synthesis remaining in the lactic acid compound can be deactivated. It was found that a uniform urethane resin can be obtained by reacting with a polyisocyanate compound using this polylactic acid-based polyol composition, and further, a uniform molded product can be obtained. Based on this finding, the present invention has been completed.
- the present invention includes a polylactic acid-based polyol obtained by transesterification and a silica compound, and the silica compound has a surface area of 40 m 2 or more with respect to 100 g of the polylactic acid-based polyol, and the silica compound It is related with the polylactic acid-type polyol composition characterized by the content of being 70 mass% or less.
- the present invention also relates to a urethane resin composition
- a urethane resin composition comprising a urethane raw material containing the polylactic acid-based polyol composition and a polyisocyanate compound.
- the present invention also provides a crude polylactic acid-based polyol obtained by transesterifying a polylactic acid-based compound and a polyol obtained using a catalyst with a surface area of 40 m 2 or more with respect to 100 g of the crude polylactic acid-based polyol. It is related with the manufacturing method of the polylactic acid-type polyol composition characterized by mixing the silica compound which has so that content may become the range of 70 mass% or less.
- this invention uses the manufacturing method of the urethane resin composition characterized by adding a catalyst when adding a polyisocyanate compound to the said polylactic acid-type polyol composition, and the said urethane resin composition.
- the present invention relates to a molded body characterized by being molded.
- the polylactic acid-based polyol composition of the present invention is obtained by simply mixing a silica compound having a specific surface area with a polylactic acid-based polyol obtained by a transesterification reaction, and remaining in the polylactic acid-based polyol.
- the catalytic action of the urethanization reaction of the polymerization catalyst used in the synthesis of is deactivated.
- this polylactic acid-based polyol composition is used as a raw material for polyurethane synthesis, the influence of the polymerization catalyst on the urethanization reaction is suppressed, and a uniform molded product can be obtained.
- the silica compound does not decompose the polylactic acid-based polyol
- the urethane resin obtained using the polylactic acid-based polyol composition has excellent physical properties, electronic materials, medical materials, packaging materials, fibers, paints, adhesives, industrial use It can be widely used in the field of materials and the like.
- the polylactic acid-based polyol composition of the present invention includes a polylactic acid-based polyol obtained by a transesterification reaction and a silica compound, and the silica compound has a surface area of 40 m 2 or more with respect to 100 g of the polylactic acid-based polyol.
- the content of the silica compound is 70% by mass or less.
- polylactic acid-based polyol examples of the polylactic acid-based polyol contained in the polylactic acid-based polyol composition of the present invention include those obtained by a transesterification reaction between a polylactic acid-based compound synthesized using a polymerization catalyst and a polyol.
- Such polylactic acid compounds include L-lactic acid and D-lactic acid polymers, copolymers thereof (poly DL-lactic acid), and copolymers of these lactic acids with other monomers capable of forming esters. There may be.
- monomers include hydroxycarboxylic acids such as glycolic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxypentanoic acid, and hydroxycaproic acid.
- the polylactic acid compound can also be produced by ring-opening copolymerization of lactide or a cyclic product of lactide and the above hydroxycarboxylic acid.
- polylactic acid compounds may be monomers, oligomers, polymers obtained from biomass raw materials, or polycondensation products synthesized using a polymerization catalyst using these derivatives or modified materials as raw materials.
- a synthetic product synthesized using a polymerization catalyst using a synthetic material other than a biomass raw material as a raw material may be used. These are particularly excellent in biodegradability in order to reduce the environmental load during disposal.
- the polymerization catalyst for the lactic acid compound is not particularly limited, but can include tin or a tin compound.
- tin compounds such as tin octylate, tin lactate, tin tartrate, tin dicaprylate, tin dilaurate, tin dipalmitate, tin distearate, tin dioleate, tin ⁇ -naphthoate, tin ⁇ -naphthoate, Examples thereof include powdered tin and tin oxide.
- tin octylate is preferable because of its high safety and high activity.
- Catalysts other than the above include zinc powder, zinc halide, zinc oxide, organic zinc compounds, titanium compounds such as tetrapropyl titanate, zirconium compounds such as zirconium isopropoxide, antimony compounds such as antimony trioxide, oxidation Examples thereof include bismuth compounds such as bismuth (III) and aluminum compounds such as aluminum oxide and aluminum isopropoxide.
- the polyol for transesterification with the polylactic acid compound is not particularly limited, and specifically includes ethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butane.
- Dihydric alcohol such as diol, 1,6-hexanediol
- trihydric alcohol such as glycerin, trimethylolpropane, trimethylolethane, hexanetriol
- tetrahydric alcohol such as pentaerythritol, methylglycoside, diglycerin, triglycerin, tetra Polyglycerin such as glycerin, polypentaerythritol such as dipentaerythritol, tripentaerythritol, cycloalkane polyol such as tetrakis (hydroxymethyl) cyclohexanol, and polyvinyl alcohol It is possible.
- sugar alcohols such as adonitol, arabitol, xylitol, sorbitol, mannitol, iditol, tallitol, dulcitol, and sugars such as glucose, mannose glucose, mannose, fructose, sorbose, sucrose, lactose, raffinose, and cellulose.
- polyhydric phenol examples include monocyclic polyhydric phenols such as pyrogallol, hydroquinone and phloroglucin, bisphenols such as bisphenol A and bisphenol sulfone, and phenol / formaldehyde condensates (novolaks). These can be used alone or in combination of two or more.
- transesterification reactions can be performed without using a catalyst.
- a catalyst for example, compounds containing elements such as Ti, Sn, Zn, Mg, and Al, specifically, titanium tetraisopropoxide or titanium tetrabutoxide. Etc. can also be used.
- the amount of the catalyst used may be, for example, 10 ppm to 1000 ppm with respect to the total mass of the polylactic acid compound used as a raw material for the transesterification reaction and the polyol.
- the number average molecular weight of the polylactic acid-based polyol obtained by the transesterification reaction can be in the range of 100 to 1,000,000, preferably 500 to 20,000, more preferably 1, 000 to 10,000. If the number average molecular weight of the polylactic acid-based polyol is 100 or more, the molded product of polyurethane obtained by a crosslinking reaction with polyisocyanate exhibits excellent mechanical properties, and if it is 1,000,000 or less, the viscosity is It is possible to obtain a molded article that suppresses the increase and is easy to handle, has a high crosslinking density, and good physical properties such as heat resistance and shape memory.
- the crude polylactic acid-based polyol obtained by the transesterification reaction contains an oligomer of a polylactic acid-based compound as a reaction byproduct.
- a polylactic acid-based polyol containing an oligomer is used for forming a polyurethane, gas generation, a decrease in strength of the urethane resin, decomposition of the polylactic acid, and the like occur. Therefore, it is preferable to remove the oligomer from the crude polylactic acid-based polyol.
- the removal of oligomers and the like from the polylactic acid-based polyol is preferably carried out by a reduced pressure method. Specifically, a method of attaching a distiller to the reaction vessel and reducing the pressure can be mentioned.
- the concentration of the carboxylic acid in the crude polylactic acid-based polyol obtained by the transesterification reaction is preferably 500 ⁇ mol / g or less, more preferably 300 ⁇ mol / g or less, and still more preferably 100 ⁇ mol / g or less.
- the carboxylic acid concentration can be determined by dissolving a polylactic acid-based polyol in chloroform and a methanol solution, adding an indicator such as phenol red, and titrating with an aqueous sodium hydroxide solution.
- the concentration of carboxylic acid in the crude polylactic acid-based polyol can be reduced by removing the oligomer contained in the crude polylactic acid-based polyol by the reduced pressure method. .
- the carboxylic acid concentration can be lowered by adding a carboxylic acid scavenger to the crude polylactic acid-based polyol.
- the carboxylic acid scavenger known materials can be used, and examples thereof include a monocarbodiimide compound having one functional group and a polycarbodiimide compound having two or more functional groups.
- an oxazoline compound, an oxazine compound, an epoxy compound, or the like can be used.
- the monocarbodiimide compound has one carbodiimide group in one molecule, and specifically includes diphenylcarbodiimide, di-2,6-dimethylphenylcarbodiimide, di-2,6-diethylphenylcarbodiimide, di-2, 6-diisopropylphenylcarbodiimide, di-2,6-ditert-butylphenylcarbodiimide, di-o-tolylcarbodiimide, di-p-tolylcarbodiimide, di-2,4,6-trimethylphenylcarbodiimide, di-2,4 Aromatic monocarbodiimides such as 1,6-triisopropylphenylcarbodiimide, di-2,4,6-triisobutylphenylcarbodiimide; alicyclic monocarbodiimides such as di-cyclohexylcarbodiimide; di-isopropylcarbodiimide, di-octadecy
- aromatic monocarbodiimide is preferable from the viewpoint of showing good reactivity with a carboxy group, and di-2,6-diisopropylphenylcarbodiimide and di-2,6-dimethylphenylcarbodiimide are more preferable.
- a polycarbodiimide compound is a compound having two or more carbodiimide groups in one molecule, and is obtained by subjecting diisocyanate to a condensation reaction using a catalyst such as 3-methyl-1-phenyl-2-phospholene-1-oxide. It is done.
- the diisocyanate used as a raw material include aromatic diisocyanate compounds, aliphatic diisocyanate compounds, alicyclic diisocyanate compounds, and mixtures thereof.
- polycarbodiimide compounds include Carbodilite LA-1 (Nisshinbo, Aliphatic), Carbodilite V-05 (Nisshinbo, Aromatic), Carbodilite V-02B (Nisshinbo, isocyanate-blocked) ), Stabaxol P (manufactured by Rhein Chemie, aromatic) and the like.
- the addition amount of the carboxylic acid scavenger is preferably such that the molar ratio of the functional group of the carboxylic acid scavenger to the carboxylic acid is 0.9 or more, since the functional group can be generally bonded to the carboxylic acid.
- the amount is more preferably 1.0 or more, still more preferably 1.1 or more and // or less.
- the silica compound contained in the polylactic acid-based polyol composition of the present invention is a crude polylactic acid-based polyol, a polymerization catalyst used for the synthesis of the polylactic acid-based compound remaining in the raw polylactic acid-based compound, for example, Since tin catalysts are contained, they are used to adsorb and deactivate these catalysts.
- the silica compound either natural silica or synthetic silica can be used.
- examples of natural silica include amorphous types such as diatomaceous earth and acid clay, and crystalline types such as quartz, quartz and quartz sand, which are used alone or in combination of two or more. You can also.
- amorphous silica compounds having no crystal structure are preferable because of their high safety to human bodies.
- the synthetic silica include dry silica, wet silica, silica gel, aerosil, zeolite and the like, and these can be used alone or in combination of two or more.
- These synthetic silicas may be produced by either a wet method or a dry method, but a silica compound produced by a wet method is preferred in that an aggregated structure can be easily obtained.
- the silica compound is added so that the surface area per 100 g of the crude polylactic acid-based polyol is 40 m 2 or more, preferably 80 m 2 or more, more preferably 100 m 2 or more, and further preferably 200 m 2 or more. If the surface area of the silica compound per 100 g of the crude polylactic acid-based polyol is 40 m 2 or more, the catalyst used for the synthesis of the polylactic acid-based compound is sufficiently adsorbed, and the catalyst of this catalyst for the urethanization reaction of the polylactic acid-based polyol The action can be deactivated, and the deterioration of the properties of the molded article molded using this can be suppressed.
- the surface area per crude polylactic acid polyol 100g silica compound is 233000M 2 or less, preferably not 100000 2 or less, more preferably 70000M 2 or less, more preferably 30000 m 2 or less. If the surface area of the silica compound per 100 g of the crude polylactic acid-based polyol is 233,000 m 2 or less, it is possible to suppress difficulty in handling due to an increase in the viscosity of the resin.
- the surface area of the silica compound is obtained by multiplying the specific surface area of the silica compound by the content (g) of the silica compound with respect to 100 g of the crude polylactic acid-based polyol.
- the specific surface area of the silica compound is preferably not more than 10 m 2 / g or more 1000 m 2 / g, more preferably, 40 m 2 / g or more 800 m 2 / g or less, more preferably, 200 meters 2 / g or more 500 meters 2 / g or less.
- the specific surface area is 10 m 2 / g or more, the polymerization catalyst used for the synthesis of the polylactic acid compound can be adsorbed with a small amount of addition, and when the specific surface area is 1000 m 2 / g or less, an increase in the viscosity of the resin can be suppressed.
- the specific surface area of the silica compound is measured with a specific surface area measuring device, and a measurement value calculated by the BET method can be adopted.
- the content of the silica compound in the polylactic acid-based polyol composition is 70% by mass or less, preferably 50% by mass or less, more preferably 30% by mass, based on the total mass of the polylactic acid-based polyol and the silica compound. Hereinafter, it is more preferably 10% by mass or less. If the content of the silica compound is 70% by mass or less, an increase in the viscosity of the polylactic acid-based polyol composition can be suppressed, and a molded product obtained using the polylactic acid-based polyol composition is fragile. It can be suppressed that the elastic modulus of the molded body is increased and the shape memory property is decreased.
- the content of the silica compound in the polylactic acid-based polyol composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, and further preferably 2% by mass or more.
- the content of the silica compound is 0.1% by mass or more, the adsorption effect of the polymerization catalyst used for the synthesis of the polylactic acid compound as a raw material for synthesizing the polylactic acid polyol can be obtained in a short time.
- the average primary particle diameter of the silica compound is preferably 30 ⁇ m or less, more preferably 10 ⁇ m or less, still more preferably 5 ⁇ m or less, and further preferably 3 ⁇ m or less.
- the silica compound having such a primary particle diameter is preferably one that forms strong aggregates as secondary particles in the polylactic acid-based polyol composition. As the specific surface area of the silica compound increases, the viscosity of the polylactic acid-based polyol composition also increases.
- the average particle size of such secondary particle aggregates is preferably 0.05 ⁇ m or more and 30 ⁇ m or less, more preferably 0.1 ⁇ m or more and 10 ⁇ m or less, and further preferably 0.5 ⁇ m or more and 5 ⁇ m or less. And more preferably 0.1 ⁇ m or more and 3 ⁇ m or less.
- a measurement value measured using an electron microscope, a laser diffraction particle size distribution analyzer, a Coulter counter, or the like can be employed.
- Such a silica compound is preferably a silica compound having a porous structure, and examples thereof include nano, meso and macroporous silica, xerogel, and silica aerogel.
- Specific examples that can be obtained industrially include NIPGEL (Tosoh Silica Co., Ltd.) and Siricia (Fuji Silysia Chemical Co., Ltd.).
- the surface of the silica compound is preferably hydrophilic.
- hydrophilic By being hydrophilic, the compatibility with the polylactic acid-based polyol is improved, and a polylactic acid-based polyol composition in which the silica compound is highly dispersed is obtained. Furthermore, even if the addition amount of the silica compound is small, the adsorption effect of the tin catalyst is high, and the transparency of the resulting urethane resin is not lost.
- the silica compound is hydrophilic as it is, but surface treatment may be performed with a hydrophilic compound.
- the pH value of the silica compound is preferably 3.5 or more and 9 or less because decomposition of the polylactic acid-based polyol is suppressed, and more preferably 4 or more and 8 or less.
- the pH value can be obtained by preparing an aqueous solution of a silica compound and measuring it with a pH meter.
- the polylactic acid-based polyol composition preferably contains a polyol having a glass transition temperature (Tg) of less than 30 ° C.
- a polyol having a glass transition temperature (Tg) of less than 30 ° C. (hereinafter also referred to as a soft polyol) reduces the viscosity of the polylactic acid-based polyol composition and improves workability, and the toughness and impact resistance of the resulting urethane resin. Can be improved.
- the soft polyol preferably has a Tg of less than 10 ° C, more preferably 0 ° C or less, and further preferably -20 ° C or less.
- the soft polyol is a polycondensate synthesized using a monomer, oligomer, polymer, or a derivative or modified product thereof derived from a biomass raw material, or a natural product extract or a derivative or modified product thereof, or other than a biomass raw material. It is also possible to use a synthetic material using as a raw material. It is preferable that the soft polyol is biodegradable because it can reduce the environmental burden during disposal. Specific examples of the soft polyol include polyesters obtained from dicarboxylic acids and diols such as polybutylene succinate, polybutylene adipate, polyethylene succinate, and polyethylene adipate, castor oil, castor hardened oil, and castor oil-modified polyol.
- the soft polyol is a polyester synthesized from a dicarboxylic acid and a diol
- the molar ratio of diol to dicarboxylic acid used in the synthesis of the polyester is set to a molar ratio of diol / dicarboxylic acid greater than 1, so that all end groups are converted to hydroxyl groups. can do.
- the soft polyol can be obtained by introducing a hydroxyl group at the terminal by a transesterification reaction between a polyol and a compound having two or more hydroxyl groups, and further by reaction with a trifunctional or higher polyisocyanate or an epoxy compound, What increased the number of functional groups of a hydroxyl group is obtained.
- the number average molecular weight of the soft polyol can be in the range of 100 to 1,000,000, preferably 500 to 100,000, and more preferably 1,000 to 20,000. If the number average molecular weight of the soft polyol is 100 or more, a polyurethane excellent in mechanical properties and processability can be obtained. If the number average molecular weight is 1,000,000 or less, the resulting molded article has a reduced crosslinking density and strength. It can suppress that physical properties fall.
- the addition amount of the soft polyol is preferably such that the mass ratio of the polylactic acid-based polyol to the soft polyol is 100: 0 to 50:50, more preferably 95: 5 to 60:40, and still more preferably 90:10. This is an amount of 70:30.
- the mass ratio of the polylactic acid-based polyol and the soft polyol is in the above range, a high-strength molded product can be obtained, and even when the soft polyol is a crystalline polymer, a decrease in transparency due to crystallization can be suppressed.
- a crude polylactic acid-based polyol obtained by transesterifying a polylactic acid-based compound obtained by using a catalyst with a polyol is added to 100 g of the crude polylactic acid-based polyol.
- the silica compound having a surface area of 40 m 2 or more may be mixed so that the content is in the range of 70% by mass or less, and the silica compound may be added when the crude polylactic acid-based polyol is in a molten state.
- the mixing temperature is preferably 130 ° C. or higher and 230 ° C. or lower because decomposition of the polylactic acid-based polyol can be suppressed and mixing can be performed efficiently.
- the mixing time is preferably from 1 minute to 1 hour, more preferably from 3 minutes to 30 minutes, still more preferably from 5 minutes to 10 minutes.
- the mixing of the silica compound is preferably performed after removing the oligomer of the polylactic acid compound after the transesterification reaction.
- the oligomer is preferably removed by a reduced pressure method from the viewpoint of productivity. Examples of the depressurization method include a method in which a distillation apparatus is attached to the reaction vessel and the pressure is reduced to 15 mmHg or less.
- the urethane resin composition of the present invention includes a urethane raw material containing the polylactic acid-based polyol composition and a polyisocyanate compound.
- the polyisocyanate compound contained in the urethane raw material together with the polylactic acid-based polyol composition and urethanizes the polylactic acid-based polyol has at least two isocyanate groups. Specific examples include carbodiimide-modified MDI, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, tolylene diisocyanate, naphthylene diisocyanate, lysine diisocyanate, and lysine triisocyanate.
- amino acid-derived lysine diisocyanate and lysine triisocyanate are particularly preferred linkers derived from natural products.
- the amount of the polyisocyanate compound used is such that the molar ratio of the hydroxyl group to the isocyanate group in the polylactic acid-based polyol is in the range of 0.9 to 1.1: 1. preferable.
- the urethane resin composition preferably contains a catalyst for urethanization reaction.
- the catalyst makes it possible to adjust the gelation time of the urethane raw material and adjust the urethanization reaction rate to obtain a uniform molded body.
- the gelation time is the time required for the urethane raw material to gel after mixing the polylactic acid-based polyol composition, the polyisocyanate compound, and the catalyst.
- the gelation time is remarkably short, the viscosity of the urethane raw material increases and crosslinks to make it impossible to form a molded product.
- the gelation time is remarkably long, the molding cycle becomes long and the productivity is lowered.
- the optimum gelling time varies depending on the molding method.
- the urethanization reaction catalyst is preferably one that is not adsorbed by the silica compound contained in the polylactic acid-based polyol composition and can adjust the gelation time.
- dibutyltin dilaurate tin dioctyl dilaurate, dibutyltin diacetate, dibutyltin maleate, bis (neodecanoate) tin, di-n-butylbis (2-ethylhexylmalate) tin, n-butylbis (2, 4-pentanedionate) tin, di-n-butylbutoxychlorotin, dimethylhydroxy (oleate) tin, dimethyldinedecanoatetin, di-n-butyldiacetoxytin, tin chloride, iron chloride, bismuth nitrate, etc.
- an organic catalyst such as triethylamine, triethylenediamine, or dimethylethanolamine can be used.
- tetravalent tin catalysts such as dibutyltin dilaurate are particularly preferable because they are highly safe and difficult to be adsorbed by the silica compound.
- the addition amount of a catalyst is dependent on each catalyst activity, 1 mass ppm or more and 1 mass% or less are preferable with respect to the total mass of a polylactic acid-type polyol and a polyisocyanate compound.
- the addition amount of the urethanization catalyst is 1 mass ppm or more, the reactivity of the terminal hydroxyl group of the polylactic acid-based polyol is improved, and if it is 1 mass% or less, the molded article can be molded.
- the urethanization catalyst can be prevented from adsorbing to the silica compound.
- a master batch in which a polylactic acid-based polyol and a urethanization catalyst are mixed in advance is prepared, and the work efficiency can be further improved by adding the master batch when the polylactic acid-based polyol composition and the isocyanate compound are mixed. It is possible and preferable.
- the inorganic filler in the urethane raw material, the inorganic filler, organic filler, reinforcing material, coloring agent, stabilizer (radical scavenger, antioxidant, etc.), antibacterial agent, You may contain additives, such as a fungicide and a flame retardant.
- the inorganic filler talc, sand, ore, etc. can be used.
- organic filler organic fibers such as polyamide fibers and plant fibers can be used.
- the reinforcing material glass fiber, carbon fiber, polyamide fiber, polyarylate fiber, acicular inorganic material, fibrous fluororesin, or the like can be used.
- antibacterial agent silver ions, copper ions, zeolites containing these, and the like can be used.
- flame retardant silicone flame retardant, bromine flame retardant, phosphorus flame retardant, inorganic flame retardant and the like can be used.
- a carbodiimide modifier or the like can be used as a hydrolysis-resistant stabilizer.
- the molded body of the present invention is molded using the urethane resin composition, and is molded and cured from an uncured urethane raw material containing the polylactic acid-based polyol composition, a polyisocyanate compound, and a catalyst. Can be formed. Further, a prepolymer can be prepared by proceeding with a part of reaction in a urethane raw material and crosslinking to form a prepolymer, which can be molded, crosslinked and cured to form a molded body. Moreover, a polyurethane film can be formed by dissolving and casting these uncured urethane raw materials and prepolymers in a solvent such as chloroform. The urethane raw material can be molded using a method such as transfer molding, RIM molding, compression molding, foam molding, and photo-curing molding at a temperature lower than the decomposition temperature of the polylactic acid-based polyol.
- the molded body can be applied to electronic materials, medical materials, packaging materials, fibers, paints, adhesives, industrial materials, and the like, and is particularly suitable for electronic materials, medical materials, and the like. When it is discarded, it is taken into the action of sunlight and water or the biocycle by being left in the environment without firing, and is easily biodegraded.
- Example 1 [Preparation of polylactic acid-based polyol] 318 g of polylactic acid (Teramac: manufactured by Unitika Co., Ltd.) and 11.0 g of D-sorbitol were weighed into a 1 L separable flask and melt-mixed in a nitrogen atmosphere at 210 ° C. for 5 hours to conduct a transesterification reaction.
- the obtained polylactic acid-based polyol has a number average molecular weight calculated from the concentration of OH groups measured by NMR of 7098, measured by gel permeation chromatogram method, and converted by using standard polystyrene. The molecular weight was 6413.
- [Concentration of carboxylic acid in polylactic acid polyol] 1 g of the obtained polylactic acid-based polyol was dissolved in a mixed solution of chloroform (50 mL) / methanol (50 mL), and titrated with a 0.1N sodium aqueous solution using phenol red as an indicator.
- the carboxylic acid concentration in the polylactic acid-based polyol was 69.7 ⁇ mol / g.
- Preparation of polylactic acid-based polyol composition 10 g of the obtained polylactic acid-based polyol and 0.5 g (5 parts by mass) of a silica compound were heated and mixed at 180 ° C. for 10 minutes to obtain a polylactic acid-based polyol composition. 1.54 g of isocyanate (R2) was added to the obtained polylactic acid-based polyol composition, stirred at 180 ° C. for 1 minute, and then air-cooled to obtain a urethane resin composition.
- R2 isocyanate
- the obtained molded body was heated to 80 ° C., the center of the molded body was bent at 90 °, deformed for 5 seconds, and then cooled to room temperature.
- the shape retention of the molded body was evaluated according to the following criteria based on the angle (A1) at this time.
- the results are shown in Table 1.
- the molded body was heated again at 80 ° C. for 3 minutes, and then the shape restoration property of the molded body was evaluated based on the angle (A2) of the bent portion.
- the results are shown in Table 1.
- Example 2 to 6 Except having changed into the raw material shown in Table 1, the polylactic acid-type polyol composition was prepared like Example 1, the molded object was produced, and the molded object was evaluated. The results are shown in Table 1.
- Example 1 A polylactic acid-based polyol composition was prepared in the same manner as in Example 1 except that the silica compound was not used, and an attempt was made to produce a molded product. However, the gelation time of the urethane raw material was short, and it was not possible to form a molded product. It was possible. The results are shown in Table 1.
- Example 7 A polylactic acid-based polyol composition was prepared in the same manner as in Example 1 except that the raw materials shown in Table 1 were changed, and a molded body was tried.
- the urethane raw material of Comparative Example 2 had a short gel time, and it was impossible to form a molded body.
- the results are shown in Table 1.
- Example 7 [Preparation of polylactic acid-based polyol] The polylactic acid polyol (R3) was changed in the same manner as in Example 1 except that the polylactic acid was changed to 200 g of trade name 4032D (manufactured by Teijin Ltd.) and the amount of D-sorbitol used was changed to 10.0 g. Obtained.
- the obtained polylactic acid-based polyol has a number average molecular weight calculated from the concentration of OH groups measured by NMR of 3642, measured by a gel permeation chromatogram method, and converted by using standard polystyrene. The molecular weight was 4213.
- [Concentration of carboxylic acid in polylactic acid polyol] 1 g of the obtained polylactic acid-based polyol was dissolved in a mixed solution of chloroform (50 mL) / methanol (50 mL), and titrated with a 0.1N sodium aqueous solution using phenol red as an indicator.
- the carboxylic acid concentration in the polylactic acid-based polyol was 5.0 ⁇ mol / g.
- a polylactic acid-based polyol composition was prepared in the same manner as in Example 1 except that the polylactic acid-based polyol (R3) thus obtained was used and the amount of isocyanate (R2) used was changed to 3.0 g. And the molded body was evaluated. The results are shown in Table 1.
- Example 8 and 9 A polylactic acid-based polyol composition was prepared in the same manner as in Example 7 except that the raw materials shown in Table 1 were changed, and a molded body was produced, and the molded body was evaluated. The results are shown in Table 1.
- the obtained soft polyol has a number average molecular weight calculated from the concentration of OH groups measured by NMR of 1337, a number average molecular weight measured by gel permeation chromatogram method and converted by using standard polystyrene. 2300.
- Polylactic acid-based polyol (R3) 9 g, polybutylene succinate (R4) 0.5 g, silica compound (AZ-400) 0.5 g (5 parts by mass) were heated and mixed at 180 ° C. for 10 minutes to obtain a polylactic acid-based polyol composition. I got a thing.
- 3.0 g of an isocyanate compound (R2) was added, stirred at 180 ° C. for 1 minute, and then air-cooled to obtain a urethane resin composition.
- a polylactic acid-based polyol composition was prepared in the same manner as in Example 7 except that a silica compound was not used, and an attempt was made to produce a molded body. However, the gelation time of the urethane resin composition was short, and a molded body was formed. Was impossible. The results are shown in Table 1.
- AZ-400 Silica compound (manufactured by Tosoh Silica Corporation), BET specific surface area 300 m 2 / g, particle size 3.0 ⁇ m AEROSIL200: Silica compound (manufactured by Nippon Aerosil Co., Ltd.), BET specific surface area 200 m 2 / g, particle size 12 nm
- BY-601 Silica compound (manufactured by Tosoh Silica Corporation), BET specific surface area 450 m 2 / g, particle size 5.0 ⁇ m
- FB-3SDC silica compound (manufactured by Denki Kagaku Kogyo Co., Ltd.) BET specific surface area 3.4 m 2 / g, particle size 3.4 ⁇ m From the results of Examples 1 to 9, the polylactic acid polyol obtained by the transesterification reaction was purified by the reduced pressure method, and then a poly (polylactic acid) having a surface area of 40 m 2 or more
- the urethane resin composition has a gelation time during which it can be molded (90 s or more), and the resulting molded product exhibits shape memory properties.
- Example 10 shows that the adsorption effect of the polymerization catalyst contained in the polylactic acid-based polyol composition can be obtained even when the polylactic acid-based polyol composition to which the soft polyol is added is used.
- Comparative Examples 1 and 4 it can be seen from Comparative Examples 1 and 4 that even when a polylactic acid-based polyol purified by the reduced pressure method is used, the gelation time of the urethane resin composition is short and cannot be molded.
- Example 11 5.25 g of polylactic acid-based polyol (R3) was melted at 180 ° C., 0.016 g of dilaurate dibutyltin was added, stirred for 1 minute, air-cooled, and pulverized pulverized product was used as a master batch (R5).
- Example 12 The amount of polylactic acid polyol (R3) and master batch (R5) used was changed to 6.93 g of polylactic acid polyol (R3) and 1.07 g of master batch (R5), and dilaurate in the polylactic acid polyol composition.
- a polylactic acid-based polyol composition was obtained in the same manner as in Example 11 except that the dibutyltin content was 0.04% by mass, a urethane resin composition was prepared, and a molded body was produced.
- the gelation time of the urethane resin composition was 153 seconds, and the shape memory property of the molded product was good in both retention and restoration properties.
- the amount of silica compound used was 5 parts as in Example 1, but the gelation time of the urethane resin composition was shortened by adding the urethanization catalyst during the urethanization reaction, It shows that the gelation time of the urethane resin composition can be adjusted by the amount of the catalyst used.
- the amount of the silica compound used is 5 parts.
- the silica compound is added to the polylactic acid-based polyol simultaneously with the isocyanate, the gelation time of the urethane resin composition becomes extremely short and uncontrollable. It shows that the catalyst adsorption effect of the compound cannot be obtained.
- the polylactic acid-based polyol composition of the present invention is obtained only by mixing a specific silica compound with the polylactic acid-based polyol obtained by the transesterification reaction, and is used for the synthesis of the polylactic acid-based compound contained in the polylactic acid-based polyol.
- the produced polymerization catalyst can be deactivated, and the productivity is high.
- a silica compound does not decompose
- the molded object of the urethane resin composition obtained using the polylactic acid-type polyol composition of this invention is excellent in the physical property.
- molded using the urethane resin composition of this invention can be widely used in field
- areas such as an electronic material, a medical material, a packaging material, a fiber, a coating material, an adhesive agent, and an industrial material.
- this molded body also has shape memory, parts such as exterior materials for electronic devices such as personal computers and mobile phones, screws, fastening pins, switches, sensors, information recording devices, rollers for OA devices, belts, etc. It can be used for packing materials such as sockets and pallets, open / close valves for air conditioners and air conditioners, heat shrinkable tubes, and the like.
- it can be applied to various fields as automobile members such as bumpers, handles, rearview mirrors, household members such as casts, toys, glasses frames, hearing aids, orthodontic wires, bed slip prevention bedding, and the like.
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Abstract
Description
本発明のポリ乳酸系ポリオール組成物に含まれるポリ乳酸系ポリオールは、重合触媒を用いて合成されたポリ乳酸系化合物とポリオールとをエステル交換反応によって得られたものを挙げることができる。かかるポリ乳酸系化合物としては、L-乳酸やD-乳酸の重合体、これらの共重合体(ポリDL-乳酸)や、これらの乳酸とエステル形成能を有するその他のモノマーとの共重合体であってもよい。かかるモノマーとしては、例えば、グリコール酸、ヒドロキシ酪酸、ヒドロキシ吉草酸、ヒドロキシペンタン酸、ヒドロキシカプロン酸等のヒドロキシカルボン酸等を挙げることができる。また、ポリ乳酸系化合物は、ラクチド又はラクチドと上記ヒドロキシカルボン酸の環状物を、開環共重合しても製造できる。
本発明のポリ乳酸系ポリオール組成物中に含有されるシリカ化合物は、粗製ポリ乳酸系ポリオールには、原料のポリ乳酸系化合物中に残留するポリ乳酸系化合物の合成に使用された重合触媒、例えばスズ触媒が含有されることから、これらの触媒を吸着し、失活させるために用いられる。シリカ化合物としては、天然シリカ、合成シリカのいずれも使用可能である。具体的には、天然シリカとしては、珪藻土、酸性白土等の非晶質タイプ、石英、水晶、珪砂等の結晶質タイプを挙げることができ、これらは1種又は2種以上を組み合わせて使用することもできる。これらのうち結晶構造を持たない非晶質のシリカ化合物は人体に対しての安全性が高いため好ましい。合成シリカとしては、乾式シリカ、湿式シリカ、シリカゲル、アエロジル、ゼオライト等を挙げることができ、これらは1種又は2種以上を組み合わせて使用することもできる。これらの合成品シリカは湿式法、乾式法のいずれの製造方法により製造されたものでもよいが、凝集構造を得られやすい点で湿式法により製造されたシリカ化合物が好ましい。
本発明のウレタン樹脂組成物は、上記ポリ乳酸系ポリオール組成物と、ポリイソシアネート化合物とを含むウレタン原料を含むことを特徴とする。上記ポリ乳酸系ポリオール組成物と共にウレタン原料に含有され、ポリ乳酸系ポリオールをウレタン化するポリイソシアネート化合物は、少なくとも2つのイソシアネート基を有するものである。具体的には、カルボジイミド変性MDI、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、トリレンジイソシアネート、ナフチレンジイソシアネート、リジンジイソシアネート、リジントリイソシアネート等を挙げることができる。これらのうち、特に、アミノ酸誘導可能なリジンジイソシアネートやリジントリイソシアネートは、天然物由来のリンカーであり、好ましい。ポリイソシアネート化合物の使用量は、ポリ乳酸系ポリオールの水酸基とイソシアネート基のモル比が0.9~1.1:1の範囲になる範囲であることが、得られる成形体の強度が高くなり、好ましい。
本発明の成形体は、上記ウレタン樹脂組成物を用いて成形されたものであり、上記ポリ乳酸系ポリオール組成物と、ポリイソシアネート化合物と、触媒とを含有する未硬化のウレタン原料を成形し硬化して形成することができる。また、ウレタン原料中で反応を一部進行させ架橋してプレポリマーを調製し、これを成形し架橋・硬化して成形体を形成することができる。また、これらの未硬化のウレタン原料や、プレポリマーをクロロホルム等の溶媒に溶解し、キャストすることでポリウレタンフィルムを形成することができる。ウレタン原料の成形は、トランスファー成形、RIM成形、圧縮成形、発泡成形、光硬化成形等の方法を使用し、ポリ乳酸系ポリオールの分解温度未満で成形することができる。
[実施例1]
[ポリ乳酸系ポリオールの調製]
ポリ乳酸(テラマック:ユニチカ株式会社製)318gとD-ソルビトール11.0gを1Lのセパラブルフラスコに秤量し、窒素雰囲気下、210℃、5時間溶融混合しエステル交換反応を行った。さらに、セパラブルフラスコに蒸留装置を取り付け、減圧下(15mmHg以下)、210℃、3時間オリゴマーを留去した後、室温まで冷却し、ポリ乳酸系ポリオール(R1)を得た。
得られたポリ乳酸系ポリオールは、NMRにより測定したOH基の濃度から算出した数平均分子量が7098であり、ゲルパーミエーションクロマトグラム法により測定し、標準ポリスチレンを用いて換算して求めた数平均分子量が6413であった。
[ポリ乳酸系ポリオールのカルボン酸濃度]
得られたポリ乳酸系ポリオール1gをクロロホルム(50mL)/メタノール(50mL)混合溶液に溶解させ、指示薬にフェノールレッドを用いて、0.1Nナトリウム水溶液で滴定した。ポリ乳酸系ポリオール中のカルボン酸濃度は69.7μモル/gであった。
[ポリ乳酸系ポリオール組成物の調製]
得られたポリ乳酸系ポリオール10gと、シリカ化合物0.5g(5質量部)を180℃で10分間加熱混合し、ポリ乳酸系ポリオール組成物を得た。得られたポリ乳酸系ポリオール組成物に、イソシアネート(R2)を1.54g添加し180℃1分間撹拌後、空冷しウレタン樹脂組成物を得た。
得られたウレタン樹脂組成物について、表面温度計でホットプレートの表面温度を測定し、180±1℃の場所でゲル化時間を測定した。測定したゲル化時間を表1に示す。表中、Aはウレタン樹脂組成物が成形可能であることを示し、Bはウレタン樹脂組成物が成形不能であることを示す。
上記ウレタン樹脂組成物を180℃で30分間プレス成形し、2cm×3.5cm×1.6mmの成形体を作製した。
A 80°≦A1≦100°
B 70°≦A1<80°又は100°<A1≦110°
C 0°≦A1<70°又は110°<A1≦180°
この成形体を再度80℃で3分加熱した後、折り曲げた部分の角度(A2)により、成形体の形状復元性を評価した。結果を表1に示す。
A 170°≦A2≦180°
B 160°≦A2<170°
C 0°≦A2<160°
[実施例2~6]
表1に示す原料に変えた以外は実施例1と同様にしてポリ乳酸系ポリオール組成物を調製し、成形体を作製し、成形体の評価を行った。結果を表1に示す。
シリカ化合物を用いない以外は実施例1と同様にしてポリ乳酸系ポリオール組成物を調製し、成形体の作製を試みたが、ウレタン原料のゲル化時間が短く、成形体を形成することは不可能であった。結果を表1に示す。
表1に示す原料に変えた以外は実施例1と同様にしてポリ乳酸系ポリオール組成物を調製し、成形体の作製を試みた。比較例2のウレタン原料はゲル化時間が短く、成形体を形成することは不可能であった。結果を表1に示す。
[実施例7]
[ポリ乳酸系ポリオールの調製]
ポリ乳酸を、商品名4032D(帝人株式会社製)200gに変更し、D-ソルビトールの使用量を10.0gに変更した他は、実施例1と同様にして、ポリ乳酸系ポリオール(R3)を得た。
得られたポリ乳酸系ポリオールは、NMRにより測定したOH基の濃度から算出した数平均分子量が3642であり、ゲルパーミエーションクロマトグラム法により測定し、標準ポリスチレンを用いて換算して求めた数平均分子量が4213であった。
[ポリ乳酸系ポリオールのカルボン酸濃度]
得られたポリ乳酸系ポリオール1gをクロロホルム(50mL)/メタノール(50mL)混合溶液に溶解させ、指示薬にフェノールレッドを用いて、0.1Nナトリウム水溶液で滴定した。ポリ乳酸系ポリオール中のカルボン酸濃度は5.0μモル/gであった。
[ポリ乳酸系ポリオール組成物等の調製]
得られたポリ乳酸系ポリオール(R3)を用い、イソシアネート(R2)の使用量を3.0gに変更した他は、実施例1と同様にして、ポリ乳酸系ポリオール組成物を調製し、成形体を作製し、成形体の評価を行った。結果を表1に示す。
表1に示す原料に変えた以外は実施例7と同様にしてポリ乳酸系ポリオール組成物を調製し、成形体を作製し、成形体の評価を行った。結果を表1に示す。
[軟質ポリオール(ポリブチレンサクシネート(PBS))の合成]
無水コハク酸1170gと1,4-ブタンジオール1280gを190℃で4時間加熱後、さらに減圧下2時間加熱し、脱水縮合反応を行った。これをクロロホルム2Lに溶解し、過剰のメタノールに注ぎ再沈殿することで、末端に水酸基を有するポリブチレンサクシネート(R4)を得た。得られた軟質ポリオールは、NMRにより測定したOH基の濃度から算出した数平均分子量が1337であり、ゲルパーミエーションクロマトグラム法により測定し、標準ポリスチレンを用いて換算して求めた数平均分子量が2300であった。
[比較例4]
シリカ化合物を用いない以外は実施例7と同様にしてポリ乳酸系ポリオール組成物を調製し、成形体の作製を試みたが、ウレタン樹脂組成物のゲル化時間が短く、成形体を形成することは不可能であった。結果を表1に示す。
AZ-400:シリカ化合物(東ソーシリカ株式会社製)、BET比表面積 300m2/g、粒径 3.0μm
AEROSIL200:シリカ化合物(日本アエロジル株式会社製)、BET比表面積 200m2/g、粒径 12nm
BY-601:シリカ化合物(東ソーシリカ株式会社製)、BET比表面積 450m2/g、粒径 5.0μm
FB-3SDC:シリカ化合物(電気化学工業株式会社製)BET比表面積 3.4m2/g、粒径 3.4μm
実施例1~9の結果から、エステル交換反応で得たポリ乳酸ポリオールを減圧法で精製後、ポリ乳酸系ポリオール100gに対し40m2以上の表面積を有するシリカ化合物を70質量%以下で添加したポリ乳酸系ポリオール組成物を用いることにより、ウレタン樹脂組成物が成形可能なゲル化時間を有し(90s以上)、得られる成形体が形状記憶性を示すことが分かる。実施例10から、軟質ポリオールを添加したポリ乳酸系ポリオール組成物を用いた場合でも、ポリ乳酸系ポリオール組成物に含まれる重合触媒の吸着効果が得られることが分かる。一方、比較例1、4から、減圧法で精製したポリ乳酸系ポリオールを用いても、ウレタン樹脂組成物のゲル化時間が短く成形不可能であることが分かる。比較例2から、用いるシリカ化合物の表面積が小さいと、ポリ乳酸系ポリオール組成物に含まれる重合触媒を吸着しきれず、ウレタン樹脂組成物のゲル化時間が短くなり、成形体を成形することは不可能であることが分かる。比較例3から、用いるシリカ化合物の添加量が多いと、ポリ乳酸系ポリオールに含まれる重合触媒の吸着効果はあるが、得られる成形体の弾性率が高く、成形体を変形することが困難になり形状記憶性が不能となることが分かる。
ポリ乳酸系ポリオール(R3)5.25gを180℃で溶融し、ジラウレートジブチルスズを0.016g添加して1分間撹拌し、空冷後、粉砕した粉砕物をマスターバッチ(R5)とした。
ポリ乳酸系ポリオール(R3)とマスターバッチ(R5)の使用量を、ポリ乳酸系ポリオール(R3)6.93g、マスターバッチ(R5)1.07gに変更し、ポリ乳酸系ポリオール組成物中のジラウレートジブチルスズの含有量を0.04質量%とした他は、実施例11と同様にして、ポリ乳酸系ポリオール組成物を得て、ウレタン樹脂組成物を調製し、成形体を作製した。ウレタン樹脂組成物のゲル化時間は153秒であり、成形体の形状記憶性は保持性、復元性ともに良好であった。
ポリ乳酸系ポリオール(R1)10g(100部)を180°で溶融させて、シリカ化合物(AZ-400)0.5g(5部)とイソシアネート化合物(R2)を同時に添加し180℃で1分間撹拌後、空冷してプレポリマーを得た。プレポリマーの180℃のゲル化時間は10秒であり、成形不能であった。
Claims (13)
- エステル交換反応により得られたポリ乳酸系ポリオールと、シリカ化合物とを含み、該シリカ化合物が、前記ポリ乳酸系ポリオール100gに対し40m2以上の表面積を有し、前記シリカ化合物の含有量が70質量%以下であることを特徴とするポリ乳酸系ポリオール組成物。
- ガラス転移温度(Tg)が30℃未満のポリオールを含むことを特徴とする請求項1記載のポリ乳酸系ポリオール組成物。
- 前記シリカ化合物の平均一次粒子径が30μm以下であることを特徴とする請求項1又は2記載のポリ乳酸系ポリオール組成物。
- 前記シリカ化合物の表面が親水性であることを特徴とする請求項1から3のいずれか記載のポリ乳酸系ポリオール組成物。
- 前記シリカ化合物の平均二次粒子径が0.05μm以上、30μm以下であることを特徴とする請求項1から4のいずれか記載のポリ乳酸系ポリオール組成物。
- 請求項1から5のいずれか記載のポリ乳酸系ポリオール組成物と、ポリイソシアネート化合物とを含むウレタン原料を含むことを特徴とするウレタン樹脂組成物。
- スズ触媒を添加されたものであることを特徴とする請求項6記載のウレタン樹脂組成物。
- 前記スズ触媒が、ジラウリン酸ジブチルスズであることを特徴とする請求項7記載のウレタン樹脂組成物。
- 触媒を用いて得られたポリ乳酸系化合物とポリオールとをエステル交換して得られた粗製ポリ乳酸系ポリオールに、該粗製ポリ乳酸系ポリオール100gに対し40m2以上の表面積を有するシリカ化合物を含有量が70質量%以下の範囲となるように混合することを特徴とするポリ乳酸系ポリオール組成物の製造方法。
- 前記粗製ポリ乳酸系ポリオール組成物を減圧して揮発性オリゴマーを除去することを特徴とする請求項9記載のポリ乳酸系ポリオール組成物の製造方法。
- 前記シリカ化合物を混合する際、130℃以上230℃以下で1分~1時間加熱混合することを特徴とする請求項9又は10記載のポリ乳酸系ポリオール組成物の製造方法。
- 請求項1から5のいずれか記載のポリ乳酸系ポリオール組成物に、ポリイソシアネート化合物を添加する際に、触媒を添加することを特徴とするウレタン樹脂組成物の製造方法。
- 請求項6から8のいずれか記載のウレタン樹脂組成物を用いて成形されたことを特徴とする成形体。
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JP2021521283A (ja) * | 2018-04-06 | 2021-08-26 | ヘンケル アイピー アンド ホールディング ゲゼルシャフト ミット ベシュレンクテル ハフツング | 天然油によるポリ乳酸のエステル交換反応からのポリエステルを使用したラミネート接着剤 |
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CN105294970A (zh) * | 2015-11-24 | 2016-02-03 | 深圳光华伟业股份有限公司 | 一种生物基热塑性聚氨酯弹性体材料及其的制备方法 |
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US11891480B2 (en) | 2016-02-01 | 2024-02-06 | Henkel Ag & Co. Kgaa | Laminating adhesives using polyester from transesterification of polylactic acid with natural oils |
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