JP2004332166A - Polylactic acid fiber - Google Patents

Polylactic acid fiber Download PDF

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JP2004332166A
JP2004332166A JP2003131290A JP2003131290A JP2004332166A JP 2004332166 A JP2004332166 A JP 2004332166A JP 2003131290 A JP2003131290 A JP 2003131290A JP 2003131290 A JP2003131290 A JP 2003131290A JP 2004332166 A JP2004332166 A JP 2004332166A
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Prior art keywords
polylactic acid
example
fiber
spinning
obtained
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JP4423882B2 (en
Inventor
Yuhei Maeda
Katsuhiko Mochizuki
裕平 前田
克彦 望月
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Toray Ind Inc
東レ株式会社
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Abstract

An object of the present invention is to provide a polylactic acid fiber having improved heat resistance and hydrolysis resistance and good color tone, and a fiber product comprising the same.
A polylactic acid fiber is obtained by mixing a specific polycarbodiimide compound having two or more carbodiimide groups in a molecule and the terminal of which is sealed with a carboxylic acid. A polylactic acid fiber having a base terminal blocked and having a total carboxyl group terminal concentration of 10 equivalents / ton or less.
[Selection diagram] None

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a polylactic acid fiber having improved hydrolysis resistance and a good color tone, and, when processed into a fiber product, a pungent unpleasant odor due to a thermal decomposition product derived from a carbodiimide compound. The present invention relates to a polylactic acid fiber which does not generate and is excellent in handleability.
[0002]
[Prior art]
2. Description of the Related Art In recent years, with an increase in environmental awareness on a global scale, development of a fiber material that decomposes in a natural environment has been desired. For example, since conventional general-purpose plastics mainly use petroleum resources, depletion of petroleum resources in the future and global warming caused by mass consumption of petroleum resources have been taken up as major problems.
[0003]
Therefore, in recent years, research and development of various plastics and fibers such as aliphatic polyesters have been activated. Among them, attention has been focused on fibers made of plastics that are degraded by microorganisms, that is, biodegradable plastics.
[0004]
In addition, by using carbon dioxide as a raw material from plant resources that grow by taking in carbon dioxide from the atmosphere, it is expected that global warming can be suppressed by the circulation of carbon dioxide, and the problem of resource depletion may be solved. Therefore, plastics starting from plant resources, that is, plastics using biomass, are attracting attention.
[0005]
Heretofore, biodegradable plastics using biomass have problems such as low mechanical properties and heat resistance and high production costs, and have not been used as general-purpose plastics. On the other hand, in recent years, as a biodegradable plastic having relatively high mechanical properties and heat resistance and low production cost, polylactic acid made from lactic acid obtained by fermenting starch has been in the spotlight.
[0006]
Polylactic acid has long been used in the medical field, for example, as a surgical suture, but has recently been able to compete with other general-purpose plastics in price due to improvements in mass production technology. Therefore, the development of products as fibers has been activated.
[0007]
Agricultural materials and civil engineering materials that utilize biodegradability are ahead of the development of polylactic acid fibers. It is also expected to be applied to However, when it is applied to clothing and industrial materials, the high hydrolyzability of polylactic acid poses a major problem. In the clothing use of polylactic acid fiber, it is dyed in most cases, but it is difficult to dye it in a dark color. Therefore, a dyeing temperature of 110 ° C. or more is essential to increase the exhaustion rate. However, when dyeing at a temperature of 110 ° C. or higher, the hydrolysis of polylactic acid proceeds rapidly and the molecular weight decreases, and thus there is a problem that the tear strength of the fabric does not satisfy a practical level.
[0008]
In addition, since the hydrolysis proceeds even in the use environment, there is a problem that the product life is short especially in industrial material applications that require a high strength retention.
[0009]
In order to solve this problem, a polylactic acid fiber having improved hydrolysis resistance by adding a monocarbodiimide compound has been disclosed (see Patent Document 1). However, monocarbodiimide compounds are expensive and have a problem that bleed-out makes it difficult to obtain a high-concentration master. On the other hand, as relatively inexpensive carbodiimide compounds, resins and films in which polycarbodiimide is added to improve hydrolysis resistance have been disclosed (see Patent Documents 2 and 3). However, the polycarbodiimide compound has low dispersibility in polylactic acid, and is liable to gel, and the hydrolysis resistance is not sufficiently improved. It was hard. Furthermore, according to the study of the present inventors, due to poor heat resistance, when a polymer to which a polycarbodiimide compound is added is melt-spun, an irritating decomposition gas derived from the carbodiimide compound is generated, so that the working environment is reduced. It has been found that the same problem occurs when melt molding is carried out using the obtained polylactic acid fiber as a binder. Further, the polylactic acid fiber has a poor color tone, and is an index of the color tone.*Only those having a strong yellowish color with a value exceeding 10 were obtained.
[0010]
Due to the problems described above, polylactic acid fibers having excellent hydrolysis resistance have not been able to be stably produced, and there has been a great limitation on the development of applications. Therefore, a polylactic acid fiber having improved heat resistance and hydrolysis resistance and good color tone has been desired.
[0011]
[Patent Document 1]
JP 2001-261797 A (pages 2 to 4)
[0012]
[Patent Document 2]
JP-A-9-296097 (pages 5 to 6)
[0013]
[Patent Document 3]
JP-A-11-80522 (pages 2 to 4)
[0014]
[Problems to be solved by the invention]
An object of the present invention is to provide a polylactic acid fiber which is improved in heat resistance at the time of melt molding, does not generate an unpleasant pungent odor, has good hydrolysis resistance and color tone, and a fiber product comprising the same.
[0015]
[Means for Solving the Problems]
An object of the present invention is to provide a polylactic acid fiber in which at least a part of a carboxyl group terminal is blocked by a carbodiimide compound, wherein the carbodiimide compound has the formula 1
[0016]
Embedded image
[0017]
4,4'-dicyclohexylmethane diisocyanate represented by the formula:
[0018]
Embedded image
[0019]
An isophorone diisocyanate represented by the formula:
[0020]
Embedded image
[0021]
Is a polycarbodiimide compound derived from at least one kind of tetramethylxylylene diisocyanate represented by and having two or more carbodiimide groups in the molecule, and the isocyanate terminal of which is sealed with a carboxylic acid, This is achieved by a polylactic acid fiber characterized by having a carboxyl terminal concentration of 10 equivalents / ton or less.
[0022]
BEST MODE FOR CARRYING OUT THE INVENTION
The polylactic acid referred to in the present invention is-(O-CHCH3-CO) A polymer having a repeating unit of n-, which is obtained by polymerizing an oligomer of lactic acid such as lactic acid or lactide. Since two kinds of optical isomers of D-lactic acid and L-lactic acid exist in lactic acid, their polymers are also poly (D-lactic acid) composed of only D-form and poly (L-lactic acid) composed only of L-form and There is a polylactic acid consisting of both. As for the optical purity of D-lactic acid or L-lactic acid in polylactic acid, as they become lower, the crystallinity becomes lower and the melting point drop becomes larger. Therefore, in order to enhance heat resistance, the optical purity is preferably 90% or more.
[0023]
However, apart from a system in which two types of optical isomers are simply mixed as described above, after blending the two types of optical isomers to form a fiber, a high-temperature heat treatment of 140 ° C. or more is performed. It is more preferable to use a stereocomplex in which a racemic crystal is formed because the melting point can be dramatically increased.
[0024]
In addition, residual lactide exists as low-molecular-weight residues in polylactic acid, and these low-molecular-weight residues cause staining abnormalities such as heating heater stains in the stretching and false twisting steps and spotting in the dyeing step. It can be a trigger. In addition, it promotes hydrolysis of fibers and fiber molded products, and reduces durability. Therefore, the amount of residual lactide is preferably 3000 ppm or less, more preferably 1000 ppm or less, and still more preferably 300 ppm or less.
[0025]
Further, components other than lactic acid may be copolymerized as long as the properties of polylactic acid are not impaired. Components to be copolymerized include polyethers such as polyethylene glycol, aliphatic polyesters such as polybutylene succinate and polyglycolic acid, aromatic polyesters such as polyethylene isophthalate, and hydroxycarboxylic acids, lactones, dicarboxylic acids, and diols. Ester bond-forming monomers are exemplified. However, from the viewpoint of biomass utilization and biodegradability, the lactic acid monomer ratio in the polymer constituting the polylactic acid fiber must be 50% by weight or more. The ratio of the lactic acid monomer constituting the polymer is preferably at least 75% by weight, more preferably at least 96% by weight. Further, a thermoplastic polymer other than polylactic acid may be blended, or both components may be combined (core-sheath type, bimetal type, sea-island type). Further, additives such as particles, flame retardants, plasticizers, antistatic agents, antioxidants and ultraviolet absorbers may be contained as modifiers. When the molecular weight of the polylactic acid polymer is 50,000 to 350,000 in terms of weight average molecular weight, the balance between the mechanical properties of the fiber and the moldability is good, and the molecular weight is more preferably 100,000 to 250,000.
[0026]
The method for producing the polylactic acid of the present invention is not particularly limited. Specifically, a method disclosed in JP-A-6-65360 can be mentioned. That is, it is a direct dehydration condensation method in which lactic acid is directly dehydrated and condensed in the presence of an organic solvent and a catalyst. Also, this is a method disclosed in JP-A-7-173266, in which at least two kinds of homopolymers are copolymerized and transesterified in the presence of a polymerization catalyst. Further, there is a method disclosed in U.S. Pat. No. 2,703,316. That is, it is an indirect polymerization method in which lactic acid is once dehydrated to form a cyclic dimer, and then subjected to ring-opening polymerization.
[0027]
In the present invention, it is important to add and mix a specific polycarbodiimide compound as a hydrolysis-resistant stabilizer to polylactic acid to block the carboxyl group terminal contained in the polylactic acid.
[0028]
The present inventors have studied the behavior of the polycarbodiimide compound in polylactic acid in detail, and found that a so-called unreacted polycarbodiimide compound that has not reacted with a reactive active terminal is used as a melt spinning temperature or a binder of polylactic acid. It rapidly decomposed at a molding temperature of 200 to 250 ° C. at the time of use, which adversely affected the spinnability and color tone, and furthermore, caused the unpleasant irritating odor to occur, thereby deteriorating the working environment. . In order to solve these problems, it has been found that it is important to use a specific polycarbodiimide compound described later, and to control the addition amount of the compound and the melting temperature and residence time during kneading and spinning.
[0029]
The polycarbodiimide compound to be mixed with the polylactic acid fiber is 4,4′-dicyclohexylmethane diisocyanate (hereinafter abbreviated as HMDI) represented by the above formula 1, or isophorone diisocyanate (hereinafter, IPDI) represented by the above formula 2 Carbodiimide derived from any one of tetramethylxylylene diisocyanate (hereinafter abbreviated as TMXDI) represented by the above formula 3, or a mixture of two or three of the above compounds Of carbodiimides derived from the above-mentioned mixture and having two or more carbodiimide groups, preferably 5 or more carbodiimide groups in the molecule. In addition, the upper limit of the carbodiimide group in polycarbodiimide is 20. Such a carbodiimide can be produced by a carbodiimidization reaction involving HMDI, IPDI, or TMXDI or a mixture of two or a mixture of the above compounds, which is accompanied by a decarbonation reaction. Among these, carbodiimide using HMDI of 50% by weight or more is preferable, and carbodiimide using HMDI of 80% by weight or more is more preferable in that the obtained fibers have excellent mechanical properties.
[0030]
The carbodiimidization reaction is carried out in the presence of a suitable carbodiimidization catalyst. As a carbodiimidization catalyst that can be used, an organic phosphorus compound is preferable, and phosphorene oxides are particularly preferable in terms of activity. Specifically, 3-methyl-1-phenyl-2-phospholene-1-oxide, 3-methyl-1-ethyl-2-phospholene-1-oxide, 1,3-dimethyl-2-phospholene-1-oxide , 1-phenyl-2-phospholene-1-oxide, 1-methyl-2-phospholene-1-oxide and their double bond isomers, and among them, 3-methyl which is industrially easily available -1-Phenyl-2-phospholene-1-oxide is particularly preferred.
[0031]
The carbodiimidization reaction can be performed by a conventionally known method. For example, HMDI, or IPDI, or TMXDI or a mixture of two or three of the above compounds is dissolved in a solvent inert thereto. Alternatively, in the absence of a solvent, under a stream of an inert gas such as nitrogen or under bubbling, the above catalyst is added in an amount of 0.1 to 10% by weight, preferably 0.5 to 5% by weight based on all isocyanates, and the reaction temperature is 150 to 200 ° C. The carbodiimidization reaction accompanying the decarbonation reaction may be advanced by heating and stirring within the range.
[0032]
The reaction time of the above reaction varies depending on the reaction temperature, the type and amount of the catalyst, and the like. Usually, for example, HMDI is used as a raw material, and 3-methyl-1-phenyl-2-phospholene-1-oxide is added to the total isocyanate at a ratio of 1 to 1%. When the reaction temperature is set to 180 ° C. and the reaction temperature is set to 180 ° C., a carbodiimide compound derived from HMDI can be obtained in about 20 hours, and the same applies when IPDI or TMXDI is used as a raw material.
[0033]
The progress of the reaction was 2258 cm in the infrared absorption spectrum.-1The absorption of the isocyanate group observed in the above may be confirmed by a titration method.
[0034]
When HMDI, IPDI, TMXDI, or a mixture of any two of the above compounds is used in the above reaction, a carbodiimide represented by the following formula can be obtained.
[0035]
OCN- (R1-NCN) n-R2-NCO
In the above equation, R1And R2Is a residue other than the NCO group of HMDI, IPDI, or TMXDI used in the reaction. The mode of polymerization may be random or block.1And R2May be the same substance. n represents an integer of 2 or more.
[0036]
Further, as the polycarbodiimide compound to be mixed with the polylactic acid of the present invention, it is necessary that the carbodiimide of the terminal isocyanate obtained by the above-mentioned method is a compound whose terminal is blocked with a carboxylic acid. The carboxylic acids preferably used are monocarboxylic acids, for example, cyclohexanecarboxylic acid, benzoic acid, trimellitic anhydride, 2-naphthoic acid, nicotinic acid, isonicotinic acid, 2-furic acid, propionic acid, butyric acid, isobutyric acid, Examples include methacrylic acid, palmitic acid, stearic acid, oleic acid, cinnamic acid, glyceric acid, acetoacetic acid, benzylic acid, and anthranilic acid, among which cyclohexanecarboxylic acid is most preferred.
[0037]
By closing the isocyanate at the terminal of carbodiimide with these carboxylic acids, even if an unreacted polycarbodiimide compound is present in polylactic acid, the above-mentioned deterioration in thread formability and poor color tone due to excellent thermal stability, Furthermore, generation of irritating gas can be suppressed. When the carbodiimide having a terminal isocyanate is blocked with a carboxylic acid at the terminal, a carbodiimide represented by the following formula can be obtained by a decarbonation reaction.
[0038]
R3-CONH- (R1-NCN) n-R2-CONH-R4
In the above equation, R3And R4Is a residue of a carboxylic acid reacted with an isocyanate group, n is an integer of 2 or more,3And R4May be the same or different.
[0039]
As described above, when the terminal of the carbodiimide is capped with a carboxylic acid, the reaction between the isocyanate and these carboxylic acids may be performed before the carbodiimidation, or after the carbodiimidation to an appropriate degree of polymerization, to the remaining isocyanate. Alternatively, it may be performed by adding an equivalent amount of a sealing agent.
[0040]
The present invention is intended to deactivate the reactive terminal in the polymer by blocking the reactive terminal of the polylactic acid polymer and the oligomer contained therein with the above-mentioned polycarbodiimide compound, thereby suppressing the hydrolysis of polylactic acid. is there. The reactive end has a hydroxyl group and a carboxyl group, but the carbodiimide compound has an excellent carboxyl group-blocking property.
[0041]
It is more important to determine the amount of the polycarbodiimide compound to be added to the carboxyl group terminal than to the weight of polylactic acid. Furthermore, since the residual monomer and the residual oligomer also generate a carboxyl group terminal by hydrolysis, not only the carboxyl group terminal of the polymer but also the total amount of the terminal carboxyl group including those derived from the residual oligomer and the monomer is important. By adding a polycarbodiimide compound and making the total carboxyl group terminal concentration of the polylactic acid fiber 10 equivalents / ton or less based on the entire polylactic acid fiber, the desired heat resistance and hydrolysis resistance can be obtained. The total carboxyl group terminal concentration after the terminal is blocked with the polycarbodiimide compound is preferably 8 equivalents / ton or less, more preferably 5 equivalents / ton or less.
[0042]
In order to reduce the amount of pyrolysis gas generated due to thermal degradation of the unreacted polycarbodiimide compound, the amount of the polycarbodiimide compound to be added is not more than twice as much as the total carboxyl group terminal amount of polylactic acid as the carbodiimide group equivalent. Is preferred. The addition amount of the polycarbodiimide compound is more preferably 1.5 times equivalent or less, more preferably 1.2 times equivalent or less, of the total amount of carboxyl groups.
[0043]
The polylactic acid fiber of the present invention has an index of yellow tint b*Preferably the value is 7 or less. As a result, it can be used for applications where the color tone is important, such as clothing. b*The value is preferably 5 or less, more preferably 3.5 or less.
[0044]
Polylactic acid fiber b*For the improvement of the value, it is possible to use a bluing compound such as cobalt acetate or the like used in general-purpose polyesters, or a colorant, but if too much is used, the heat resistance decreases. In addition to impairing the yarn formability, the color becomes turbid at the time of dyeing, and the vivid color development characteristic of polylactic acid fibers is impaired. Therefore, even when used in combination, it is preferable that the amount added be 500 ppm or less based on the weight of polylactic acid.
[0045]
The hydrolysis resistance in the present invention can be evaluated by the fiber viscosity retention or strength retention. In the present invention, it is preferable that 30 g of a fiber sample and 300 g of water are placed in a pressure vessel and subjected to a hot water treatment at 120 ° C. for 60 minutes, and the viscosity retention ratio with respect to the viscosity before the heat treatment is 75% or more. The viscosity retention is more preferably at least 85%. The strength retention of the fibers before and after the above-mentioned hot water treatment is preferably 70% or more. The strength retention is more preferably at least 85%.
[0046]
The polylactic acid fiber of the present invention preferably has a strength of 2 cN / dtex or more in order to make the process passability and the mechanical strength of the product practical. More preferably, it is 3 cN / dtex or more. Further, it is preferable that the elongation of the fiber of the present invention is 15 to 70%, because the processability is improved. The elongation is more preferably 25 to 50%.
[0047]
The polylactic acid fiber of the present invention preferably has good dimensional stability of the fiber and the fiber product if the boiling water shrinkage is 0 to 20%. More preferably, it is 2 to 10%.
[0048]
The cross-sectional shape of the polylactic acid fiber of the present invention may be any of a round cross section, a triangular cross section, a multi-lobal cross section, a hollow cross section, a flat cross section, a W cross section, an X cross section, and other irregular cross sections. The form of the fibers is not particularly limited, such as long fibers and short fibers. In the case of long fibers, multifilaments or monofilaments may be used.
[0049]
The method for producing the polylactic acid fiber of the present invention is not particularly limited. For example, the following method can be employed.
[0050]
First, a polycarbodiimide compound and polylactic acid are produced by the above method. Specific methods for reducing the amount of residual lactide include, for example, using a metal deactivator, an antioxidant, or the like, lowering the polymerization temperature, and adding a catalyst, as described in Japanese Patent Application Publication No. 7-504939. It is preferable to control the rate. Also, the amount of residual lactide can be significantly reduced by subjecting the polymer to a vacuum treatment or extraction with chloroform or the like.
[0051]
Next, the total carboxyl group terminal concentration of the obtained polylactic acid is determined with reference to the method described in JP-A-2001-261797. That is, the weighed sample is dissolved in o-cresol, an appropriate amount of dichloromethane is added, and the sample is titrated with a 0.02 N KOH methanol solution. At this time, oligomers such as lactide, which is a cyclic dimer of lactic acid, are hydrolyzed to form carboxyl group terminals. Therefore, all of the polymer carboxyl group terminals, monomer-derived carboxyl group terminals, and oligomer-derived carboxyl group terminals are summed up. The calculated total carboxyl group terminal concentration is determined.
[0052]
Next, the polylactic acid and the polycarbodiimide compound are melt-kneaded and formed into fibers by melt spinning. At the time of kneading and melt spinning, it is important to promote a terminal blocking reaction between the polycarbodiimide compound and polylactic acid and to suppress the thermal decomposition of the unreacted polycarbodiimide compound. Therefore, the melt retention index T determined from the temperature T during kneading and melt spinning and the melt retention time pt*Is preferably controlled within the range of the following expression. Here, the melt residence time pt is a time that substantially passes through a portion heated to 190 to 250 ° C., which is a temperature setting of a kneader or a melting part, a pipe size, a dimension in a spinning pack, and the like. Can be estimated from the density of the polylactic acid in the molten state. When the step of kneading the polycarbodilite compound and the polylactic acid and the step of melt-spinning are separated, the melt retention index is calculated separately, and the sum is used as the melt retention index T*And
[0053]
Melt retention index T*= Pt x (T-100)1.5
190 ≦ T ≦ 250
(Unit T: ° C, pt: minute)
10,000 ≦ T*≤40,000
Melt retention index T*Is 10,000 or more, since the end-capping reaction between the polycarbodiimide compound and polylactic acid can be promoted, which is preferable. On the other hand, the melt retention index T*Is not more than 40,000, thermal decomposition of unreacted polycarbodiimide compound can be suppressed, which is preferable. In order to suppress the decomposition of the unreacted polycarbodiimide compound, the upper limit of the melt kneading temperature T is preferably 240 ° C., and more preferably 230 ° C.
[0054]
As described above, the mixing method of the polycarbodiimide compound is as described above. After separately drying the polylactic acid and the polycarbodiimide compound, a master chip is once prepared by a kneading machine, and the master chip and the polylactic acid are chip-blended and dried. And spinning may be performed, or a dried polycarbodiimide compound may be directly added during melt spinning. In the case of direct addition, there is a method in which a polycarbodiimide compound is added in a molten portion of polylactic acid, or a separately melted polycarbodiimide compound and polylactic acid are kneaded in a spinning pack using a static kneader or a sand filter layer. . In addition, at the time of kneading and melt spinning, in order to suppress the oxidative decomposition of polylactic acid, it is preferable to seal the part to be supplied to the chip pipe and the melting part with nitrogen.
[0055]
At this time, if the addition amount of the polycarbodiimide compound is not more than twice equivalent to the total terminal amount of the carboxyl group as described above, the unreacted polycarbodiimide is promoted while promoting the end-capping reaction between the polycarbodiimide compound and polylactic acid. Thermal decomposition of the compound can be suppressed. Here, it is important to determine the amount of polylactic acid to be added to the total amount of terminal carboxyl groups. For example, even if a small amount is added to the total weight of polylactic acid, the amount of polylactic acid before adding the polycarbodiimide compound is important. If the total carboxyl group terminal amount of lactic acid is small, the amount of unreacted polycarbodiimide compound increases, and the amount of pyrolysis gas generated by thermal deterioration increases. On the other hand, if the total carboxyl group terminal amount of the polylactic acid before the addition of the polycarbodiimide compound is large, the terminal capping will be insufficient and the effect of improving the hydrolysis resistance will be small. Further, it is preferable to set the melting residence time of the polycarbodiimide compound in the spinning machine in accordance with the kneading step as described above.
[0056]
After the yarn spun from the spinneret is cooled and solidified by chimney, a spinning oil agent is applied by an oil supply device, and is taken up using a godet roll or the like.
[0057]
In the case of long fibers, the drawn yarn may be once wound into a cheese-like package and then drawn and / or false-twisted, or drawn directly in one step using a spinning drawing apparatus. At this time, if the peripheral speed (hereinafter referred to as spinning speed) of the first godet roll (first hot roll in the case of direct spinning drawing) is 2500 to 7000 m / min, the drawability and false twisting workability due to the oriented crystallization of the fiber. Is preferred. Further, it is preferable that the stretching temperature at the time of stretching is 80 to 150 ° C., because the uniformity of the yarn is improved. Particularly when the film is stretched to a residual elongation of about 15 to 25% for high strength, the film is preferably stretched at 110 to 150 ° C. in order to suppress a discontinuous structure called a devitrification phenomenon. The heat treatment temperature may be changed according to the boiling water shrinkage of the polylactic acid fiber, but the heat treatment temperature is 110 to 150 ° C, more preferably 130 to 150 ° C, in order to increase the dimensional stability of the product. The stretching may be performed in one step or may be performed in multiple steps. Further, if necessary, false twisting, indentation, and mechanical crimping can be performed.
[0058]
In the case of short fibers, the drawn yarns are combined, temporarily received in a bunker, further combined into a tow, stretched and mechanically crimped, and an oil agent suitable for the next step is applied. And then cut to the desired length. At the time of stretching, it is preferable to adopt steam stretching or liquid bath stretching in consideration of the fact that the tow is thick and poor heat transfer, and the liquid bath temperature at this time is preferably 75 to 100 ° C.
[0059]
In the case of a non-woven fabric, the above-mentioned short fibers may be used, or a method in which spinning such as so-called spun bonding or melt blowing and a non-woven fabric forming step are continuous may be employed.
[0060]
The polylactic acid fiber of the present invention can take various fiber product forms, such as a woven fabric, a knitted fabric, a nonwoven fabric, and a molded product such as a fiber board.
[0061]
Further, the polylactic acid fiber of the present invention may be mixed with a raw material derived from a plant-derived material. For example, a fiber mixed with natural fibers such as silk, cotton, and hemp, and regenerated fibers such as rayon and acetate, or mixed and woven or knitted may be used.
[0062]
Further, the polylactic acid of the present invention is excellent in heat resistance at the time of melting and hardly generates irritating gas, which has been a problem in the past, and thus can be preferably used as a binder fiber. In particular, it is preferable to use the mixture with a biodegradable material such as pulp or natural fiber by utilizing the biodegradability of polylactic acid and use it for a nonwoven fabric or a molded article.
[0063]
The polylactic acid fiber of the present invention can be used not only for clothing such as shirts, blousons, and pants, but also for clothing materials such as cups and pads, curtains, carpets, mats, wallpapers, furniture and other interior uses, vehicle member uses, belts, and nets. , Ropes, heavy cloths, bags, sewing thread, industrial materials, felts, nonwoven fabrics, filters, artificial turf and the like.
[0064]
【Example】
Hereinafter, the polylactic acid fiber of the present invention will be described in detail using examples. The following methods were used for measuring and evaluating physical properties and the like in the examples.
A. Solution specific viscosity of polylactic acid (ηr)
3 g of the weighed sample was dissolved in 100 ml of o-chlorophenol to prepare a solution. Next, the specific viscosity was measured at 25 ° C. using an Ostwald viscometer.
B. Total carboxyl group terminal concentration
A precisely weighed sample was dissolved in o-cresol (5% water), an appropriate amount of dichloromethane was added to this solution, and the solution was titrated with a 0.02 N KOH methanol solution. At this time, an oligomer such as lactide, which is a cyclic dimer of lactic acid, is hydrolyzed to generate a carboxyl group terminal. Therefore, all of the polymer carboxyl group terminal, monomer-derived carboxyl group terminal, and oligomer-derived carboxyl group terminal are summed up. The obtained carboxyl group terminal concentration is determined.
C. Remaining lactide amount
1 g of a sample is dissolved in 20 ml of dichloromethane, and 5 ml of acetone is added to this solution. Further, the solution was precipitated with a fixed volume of cyclohexane, analyzed by liquid chromatography using GC17A manufactured by Shimadzu Corporation, and the amount of lactide was determined by an absolute calibration curve.
D. Weight loss rate of polycarbodiimide compound
TG-DTA2000S manufactured by Mac Science (MAC SCIENCE) Co., Ltd. Using a TG-DTA measuring device, the sample was heated at a rate of 20 ° C. under a nitrogen atmosphere with a sample weight of about 10 mg, and was kept at 240 ° C. for 60 minutes. The weight loss rate at that time was determined.
E. FIG. Ηr retention after hot water treatment (Rηr)
30 g of a sample and 300 g of water were placed in a pressure vessel and subjected to a hot water treatment at 120 ° C. for 60 minutes. Then, ηr was measured, and Rηr was obtained by the following equation. In addition, when the sample was a fiber, a thread flute was prepared and subjected to hot water treatment.
[0065]
Rηr (%) = (ηr of sample after hot water treatment / ηr before hot water treatment) × 100
F. Strength retention after hot water treatment (RT)
The sample was subjected to hot water treatment in the same manner as in D, and the RT was determined by the following equation. In addition, the strength of the polylactic acid fiber before the hot water treatment and the strength of the polylactic acid fiber after the hot water treatment were measured by the measuring method described in the section H.
[0066]
RT (%) = (strength of sample after hot water treatment / strength before hot water treatment) × 100
G. FIG. Color tone (b * value)
The scoured and knitted fabrics were laminated so that the underlying white plate was negligible, and the b * value was measured using Minolta “Spectrophotometer CM-3700d”. At this time, D65 (color temperature 6504K) was used as a light source, and measurement was performed in a 10 ° visual field.
H. Strength and elongation
The sample was measured with TENSILON UCT-100 manufactured by Orientec Co., Ltd. under constant-speed elongation conditions specified in JIS L1013 (Testing method for chemical fiber filament yarn). The elongation at break was determined from the elongation at the point showing the maximum strength in the SS curve.
I. Boiling water shrinkage
It was measured according to JIS L 1013 (test method for chemical fiber filament yarn). The scalpel was collected from the undrawn yarn package using a measuring machine, and 90 × 10-3The actual length measurement load of cN / dtex was applied to measure the length L1. Subsequently, the actual length measurement load was removed, put in boiling water for 15 minutes, taken out, air-dried, and again applied the actual length measurement load. L2 was measured, and the boiling water shrinkage was calculated by the following equation.
[0067]
Boiling water shrinkage (%) = [(L1−L2) / L1] × 100
Production of polylactic acid
Lactide prepared from L-lactic acid having an optical purity of 99.5% is polymerized in the presence of a bis (2-ethylhexanoate) tin catalyst (lactide to catalyst molar ratio = 10000: 1) at 180 ° C. for 220 minutes in a nitrogen atmosphere. Was done. Subsequently, delactide treatment was performed at 180 ° C. under reduced pressure. At the time of polymerization, "Ultranox 626" manufactured by GE was added as a stabilizer in an amount of 0.2% by weight relative to lactide. The obtained polylactic acid had ηr of 11.4, a total carboxyl group terminal concentration of 25 equivalents / ton, and a residual lactide amount of 240 ppm.
[0068]
Synthesis examples 1 to 3 of carbodiimide
To 2 kg of HMDI, 180 g of cyclohexanecarboxylic acid was added as a terminal blocking agent, and 10 g of 3-methyl-1-phenyl-2-phospholene-1-oxide was added as a carbodiimidation catalyst. The reaction was carried out for an hour to obtain a carbodiimide compound having a degree of polymerization of 8 (Synthesis Example 1). Further, a carbodiimide compound having a polymerization degree of 8 (Synthesis Example 2) was obtained in the same manner as in Synthesis Example 1 except that the terminal blocking agent was changed to benzoic acid. Further, a carbodiimide compound having a polymerization degree of 8 (Synthesis Example 3) was obtained in the same manner as in Synthesis Example 1 except that the terminal blocking agent was changed to trimellitic anhydride. Table 1 shows the heat resistance (weight loss rate) of Synthesis Examples 1 to 3.
[0069]
Synthesis Examples 4 to 6 of Carbodiimide
A carbodiimide compound having a polymerization degree of 8 (Synthesis Example 4) was obtained in the same manner as in Synthesis Example 1 except that the terminal blocking agent was changed to cyclohexylamine. Also, a carbodiimide compound having a polymerization degree of 8 (Synthesis Example 5) was obtained in the same manner as in Synthesis Example 1 except that the terminal blocking agent was changed to dibutylamine. Further, a carbodiimide compound having a polymerization degree of 8 (Synthesis Example 6) was obtained in the same manner as in Synthesis Example 1 except that the terminal blocking agent was changed to phthalic anhydride. Table 1 shows the heat resistance (weight loss rate) of Synthesis Examples 4 to 6.
[0070]
Synthesis Examples 7 and 8 of Carbodiimide
To 2 kg of IPDI, 180 g of cyclohexanecarboxylic acid as a terminal blocking agent, 18 g of 3-methyl-1-phenyl-2-phospholene-1-oxide as a carbodiimidation catalyst, and 16 g at 190 ° C. while bubbling nitrogen through. The reaction was carried out for an hour to obtain a carbodiimide compound derived from IPDI (polymerization degree 8).
[0071]
To 2 kg of TMXDI, 180 g of cyclohexanecarboxylic acid as a terminal blocking agent was added, 21 g of 3-methyl-1-phenyl-2-phospholene-1-oxide was added as a carbodiimidation catalyst, and the mixture was heated at 190 ° C. while bubbling nitrogen. For 21 hours to obtain carbodiimide derived from TMXDI (polymerization degree 8).
[0072]
Table 1 shows the heat resistance (weight loss rate) of Synthesis Examples 7 and 8.
[0073]
[Table 1]
[0074]
Example 1
The polylactic acid of ηr11.4 obtained in the production of polylactic acid and the polycarbodiimide compound derived from HMDI obtained in Synthesis Example 1 (1 equivalent of carbodiimide / 272 g of carbodiimide compound) in a weight ratio of 99.3: 0.7 (total). (Equivalent to 1.0 times the amount of the carboxyl group end), charged into a hopper 1, introduced into a twin screw extruder 2 and melt-kneaded at a melting temperature T1: 220 ° C., and subsequently heated to a spinning temperature T2: 220 ° C. The molten polymer was guided to the spinning pack 4 incorporated in the heated spin block 3 and spun out from a die 5 having a discharge hole diameter of 0.3 mm, a hole depth of 0.6 mm, and 36 holes (see FIG. 1). The melt residence time pt at this time was 5 minutes for the kneading step and 7 minutes for the melt spinning step, for a total of 12 minutes. At this time, the suction device 7 was installed at a position 10 cm below the base, and the subliming monomers and oligomers were removed at a suction speed of 25 m / min. The spun yarn was cooled and solidified at a wind speed of 25 m / min by a cooling chimney 6, and then refueled by an oiling device 8 installed 2 m below the base. In the spinning oil, a fatty acid ester is adjusted as a leveling agent at 70% by weight, and other additives (emulsifier, antistatic agent, antioxidant, rust inhibitor) are adjusted at a ratio of 30% by weight. The water emulsion was adjusted so as to have a weight percentage of 6% by weight and adhered to the fiber (0.9% by weight as pure oil).
[0075]
Next, entanglement is imparted by the entanglement nozzle 9 at 0.1 MPa, taken up by the first godet roll 10 at a peripheral speed of 3000 m / min, and subsequently taken up by the winding device 12 via the second godet roll 11, and 170 dtex, An undrawn yarn (cheese package 13) of 36 filaments was obtained. No irritating odor from the spun yarn immediately below the spinneret was felt at all, there was no yarn breakage or fluff during spinning, and the spinnability was good.
[0076]
The yarn is further preheated at a first hot roll temperature of 95 ° C., stretched 1.3 times, heat-set at a second hot roll temperature of 130 ° C., wound up through a non-heated cold roll, and extruded at 130 dtex, A 36 filament drawn yarn was obtained. There was no problem in the stretchability at this point, and five 1 kg windings were sampled, but the yarn breakage was zero.
[0077]
B of the obtained drawn yarn*The value was 3.2, indicating an excellent color tone that could be used without limitation for clothing. The total carboxyl group terminal concentration was 4.5 equivalents / ton, indicating excellent hydrolysis resistance.
[0078]
Example 2
Spinning and stretching were carried out in the same manner as in Example 1 except that the polycarbodiimide compound obtained in Synthesis Example 2 (1 equivalent of carbodiimide / 271 g of carbodiimide compound) was used as the polycarbodiimide compound to obtain a drawn yarn. The spinning of Example 2 produced some smoke, but hardly any pungent odor. In addition, both spinnability and stretchability were good, and the thread breakage was zero as in Example 1.
[0079]
B of the obtained drawn yarn*The value was 3.8, indicating an excellent color tone that could be used without limitation for clothing. The total carboxyl group terminal concentration was 4.8 eq / ton, indicating excellent hydrolysis resistance.
[0080]
Example 3
Spinning and stretching were carried out in the same manner as in Example 1 except that the polycarbodiimide compound (1 equivalent of carbodiimide / 289 g of carbodiimide compound) obtained in Synthesis Example 3 was used as the polycarbodiimide compound, to obtain a drawn yarn. In Example 3, as in Example 1, almost no pungent odor was felt. Further, both spinnability and stretchability were good. B of the obtained drawn yarn*The value was 3.5, indicating an excellent color tone that could be used without limitation for clothing. The total carboxyl group terminal concentration was 7.2 equivalents / ton, indicating excellent hydrolysis resistance.
[0081]
Comparative Example 1
Spinning and stretching were performed in the same manner as in Example 1 without adding the polycarbodiimide compound, to obtain a 130 dtex, 36 filament drawn yarn.
[0082]
B of the obtained drawn yarn*The value was 1.7, indicating an excellent color tone. However, the carboxyl group terminal concentration was 35 equivalents / ton, and the hydrolysis resistance was extremely poor.
[0083]
Comparative Example 2
Spinning and stretching were carried out in the same manner as in Example 1 except that the polycarbodiimide compound (1 equivalent of carbodiimide / 276 g of carbodiimide compound) obtained in Synthesis Example 4 was used as the polycarbodiimide compound, to obtain a drawn yarn. In Comparative Example 2, the generation of irritating gas in the melt spinning process was severe, and the working environment was extremely poor. In addition, b of the obtained drawn yarn*The value was 5.2, indicating a usable color tone if the application was limited for clothing.
[0084]
Comparative Example 3
Spinning and stretching were performed in the same manner as in Example 1 except that the polycarbodiimide compound (1 equivalent of carbodiimide / 284 g of carbodiimide compound) obtained in Synthesis Example 5 was used as the polycarbodiimide compound, to obtain a drawn yarn. In Comparative Example 3, as in Comparative Example 2, the generation of irritating gas in the melt spinning step was severe, and the working environment was extremely poor.
[0085]
Comparative Example 4
Spinning and stretching were carried out in the same manner as in Example 1 except that the polycarbodiimide compound (1 equivalent of carbodiimide / 277 g of carbodiimide compound) obtained in Synthesis Example 6 was used as the polycarbodiimide compound, to obtain a drawn yarn. In Comparative Example 4, although the generation of the irritating gas was smaller than that of Comparative Example 1, the obtained fiber had poor heat resistance, and*The value was 8.1, and the use for clothing was considerably limited.
[0086]
Example 4
Spinning and stretching were carried out in the same manner as in Example 1 except that the mixing ratio of the polylactic acid and the polycarbodiimide compound was 98.8: 1.2 (1.8 equivalents to the total amount of carboxyl groups), and the stretching was carried out. Yarn was obtained.
[0087]
B of the obtained drawn yarn*The value was 5.5, indicating a usable color tone if the application was limited for clothing. The carboxyl group terminal concentration was 3.8 equivalents / ton, indicating excellent hydrolysis resistance.
[0088]
Example 5
Spinning and stretching were performed in the same manner as in Example 1 except that the mixing ratio of the polylactic acid and the polycarbodiimide compound was 99.5: 0.5 (equivalent to 0.7 times the total amount of carboxyl groups), and the stretching was performed. Yarn was obtained.
[0089]
B of the obtained drawn yarn*The value was 2.6, which was an excellent color tone that could be used without limitation for clothing. Further, the carboxyl group terminal concentration was 8 equivalents / ton, indicating excellent hydrolysis resistance.
[0090]
Example 6
Spinning and stretching were performed in the same manner as in Example 1 except that the mixing ratio of the polylactic acid and the polycarbodiimide compound was 98: 2 (3.0 equivalents to the total amount of carboxyl group terminals), and a drawn yarn was obtained. .
[0091]
In the melt spinning of Comparative Example 5, yarn breakage occurred in both spinning and drawing due to thermal decomposition of the unreacted polycarbodiimide compound. In addition, b of the obtained drawn yarn*The value was 8.8, which meant that the use for clothing was considerably limited.
[0092]
[Table 2]
[0093]
Example 7 and Example 8
Spinning and stretching were performed in the same manner as in Example 1 except that the polycarbodiimide compound (1 equivalent of carbodiimide / 227 g of carbodiimide compound) obtained in Synthesis Example 7 was used as the polycarbodiimide compound, to obtain a drawn yarn (Example 7). . Further, spinning and stretching were performed in the same manner as in Example 1 except that the polycarbodiimide compound (1 equivalent of carbodiimide / 252 g of carbodiimide compound) obtained in Synthesis Example 8 was used as the polycarbodiimide compound, to obtain a drawn yarn (Example 8). ). The drawn yarns obtained in Example 7 and Example 8 each had lower strength than Example 1, but were excellent in color tone and hydrolysis resistance as in Example 1.
[0094]
Example 9
Spinning and drawing were performed in the same manner as in Example 1 except that the melting temperature T1 and the spinning temperature T2 were set to 245 ° C., to obtain a drawn yarn. In the melt spinning of Example 9, a slight irritating gas was generated due to the thermal decomposition of the unreacted polycarbodiimide compound. In addition, although the spinnability was good, a single yarn was wound on a hot roll by stretching.
[0095]
B of the obtained drawn yarn*The value was 6.1, and although the use was limited, it could be sufficiently used for clothing.
[0096]
Example 10
Spinning and drawing were performed in the same manner as in Example 1 except that the melting temperature T1 and the spinning temperature T2 were set to 200 ° C., to obtain a drawn yarn. In Example 10, no pungent odor was generated during melt spinning, and both spinnability and stretchability were good. In addition, b of the obtained drawn yarn*The value was 2.5, which was better than Example 1. Further, the hydrolysis resistance was also at a level that could sufficiently withstand practical use.
[0097]
Example 11
Spinning and stretching were performed in the same manner as in Example 1 except that the spinning temperature T2 was set to 255 ° C., to obtain a drawn yarn. A large amount of irritating gas was generated by thermal decomposition of unreacted polycarbodiimide compound. In addition, yarn breakage frequently occurred during spinning and drawing.
[0098]
Although the obtained drawn yarn is excellent in hydrolysis resistance, b*The value was 10.2, and the application was considerably limited as clothing.
[0099]
Example 12
Spinning was performed in the same manner as in Example 10 except that the filter layer of the spinning pack 4 was changed to a reduced one and the melt residence time in the melt spinning step was set to 4.5 minutes (total melt residence time pt: 9.5 minutes).・ Drawing was performed to obtain a drawn yarn. In Example 12, no pungent odor was generated in melt spinning, and both spinnability and stretchability were good. In addition, b of the obtained drawn yarn*The value was 2.3, which was better than that of Example 10.
[0100]
Example 13
Spinning and stretching were performed in the same manner as in Example 1 except that the filter layer of the spinning pack 4 was changed to an enlarged one and the total melt residence time pt was set to 32 minutes, to obtain a drawn yarn. Example 13 has excellent hydrolysis resistance, but b*The value was 7.3, and the use was considerably limited for clothing.
[0101]
Example 14
The polylactic acid having ηr11.4 obtained in the production of polylactic acid was subjected to solid-state polymerization, and ηr was set to 14. Furthermore, spinning was performed in the same manner as in Example 1 except that the spinning speed was 5000 m / min, and an undrawn yarn was obtained. Further, three unstretched yarns are combined, and the first hot roll temperature is 90 ° C., the second hot roll temperature is 120 ° C., and the third hot roll temperature is 150 ° C., and the temperature between the first hot roll and the second hot roll is 1. Stretched 3 times, further stretched 1.2 times between the second hot roll and the third hot roll, and performed a 3% relaxation treatment between the third hot roll and the unheated cold roll. Was wound at 800 m / min. B of the obtained 205 dtex, 108 filament drawn yarn*The value was 3.5. The carboxyl group terminal concentration was 4.6 equivalents / ton, indicating excellent hydrolysis resistance. Example 14 had an extremely high strength of 5.8 cN / dtex and was excellent in dimensional stability, and was therefore most suitable for clothing applications requiring high strength.
[0102]
Example 15
The polylactic acid having ηr11.4 obtained in the production of polylactic acid and the polycarbodiimide compound obtained in Synthesis Example 1 were mixed at a weight ratio of 80:20, and the mixture was led to a twin-screw extruder at a melting temperature of 210 ° C. A master chip of a carbodiimide compound was prepared. In addition, the melting residence time at this time was 5 minutes. Further, polylactic acid and this master chip were mixed at a ratio of 19: 1, guided to a single screw extruder, melt-kneaded at a melting temperature T1: 225 ° C., and subsequently spun at a spinning temperature T2: 225 ° C. The melting residence time at this time was 10 minutes. The undrawn yarn was taken up by a first take-up roll having a peripheral speed of 1500 m / min and the yarn was combined, and then received in a bunker. Then, the yarn received by the bunker was further combined into a 120,000 dtex tow. This was stretched 2.6 times in hot water at 90 ° C. And after passing through a crimper, it was refueled and cut into a fiber length of 52 mm.
[0103]
The obtained short fibers had a single fiber fineness of 5 dtex and a number of crimps of 22 / m. Also, b*The value was 4.0, which was an excellent color tone that could be used for clothing, and the carboxyl group terminal concentration was 5 equivalents / ton, showing excellent hydrolysis resistance.
[0104]
Note that b*Evaluation of fiber properties such as value and hydrolysis resistance was performed by partially sampling the yarn between the crimper and the oil supply.
[0105]
[Table 3]
[0106]
Example 16
Plain weave was produced using the yarn obtained in Example 1 for warp and weft. The resulting plain weave was scoured at 70 ° C according to a conventional method, and then subjected to an intermediate setting at 140 ° C. Further, staining was performed at 120 ° C. according to a conventional method. The obtained fabric had a squeaky feeling and a soft feeling, had an excellent texture for clothing, and exhibited a vivid coloration.
[0107]
Comparative Example 6
Using the yarn obtained in Comparative Example 1 as a warp and a weft, a plain weave was produced in the same manner as in Example 15, and dyed at 120 ° C. The resulting fabric had extremely low tear strength and was not practical. .
[0108]
Example 16
The short fiber obtained in Example 15 and a ramie cut to a fiber length of 58 mm were cotton-mixed at a weight ratio of 50:50, opened and sheeted, and laminated and compressed to obtain a laminate. Further, this laminate was heated and pressed at 235 ° C. and 3 MPa to obtain a 6 mm-thick fiber molded body composed of polylactic acid and ramie.
[0109]
This molded article had appropriate hardness, sound absorbing properties, and shock absorbing properties, and was optimal for a wall material or a floor material for a house.
[0110]
【The invention's effect】
The polylactic acid fiber of the present invention having excellent heat resistance, hydrolysis resistance and color tone allows the polylactic acid fiber to be expanded and developed for use in clothing.
[Brief description of the drawings]
FIG. 1 is a schematic view showing a spinning apparatus preferably used in the present invention.
[Explanation of symbols]
1: Hopper
2: Extruder
3: Spinning block
4: Spinning pack
5: Spinneret
6: suction device
7: Cooling chimney
8: Refueling device
9: Confounding nozzle
10: 1st godet roll
11: Second godet roll
12: Winding device
13: Cheese-like package

Claims (3)

  1. A polylactic acid fiber in which at least a part of a carboxyl group terminal is blocked by a carbodiimide compound, wherein the carbodiimide compound has the formula 1
    4,4′-dicyclohexylmethane diisocyanate represented by the formula:
    An isophorone diisocyanate represented by the formula:
    A polycarbodiimide compound derived from at least one of tetramethylxylylene diisocyanate represented by and having two or more carbodiimide groups in the molecule, and the isocyanate terminal of which is sealed with a carboxylic acid, A polylactic acid fiber having a carboxyl terminal concentration of 10 equivalents / ton or less.
  2. 2. The polylactic acid fiber according to claim 1, wherein the b * value as an index of color tone is 7 or less.
  3. A biodegradable fiber product using the polylactic acid fiber according to claim 1 or 2 at least in part.
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