JP2021147724A - Hot-bonding sheath-core composite fiber - Google Patents

Abstract

To provide a hot-bonding sheath-core composite fiber composed of a polyalkylene terephthalate resin as the core component and a polyolefin resin as the sheath component, involving a biomass resource-derived component as large parts of raw materials, and capable of suppressing decrease of fossil resources and increase of carbon dioxide.SOLUTION: A hot-bonding sheath-core composite fiber is composed of a phosphorus compound-involving polyalkylene terephthalate resin, obtained from a biomass resource-derived component as a raw material, as the core component, and a polyolefin resin, obtained from a biomass resource-derived component as a raw material, as the sheath component, wherein abundance of carbon derived from a biomass resource (bio-based content), determined based on a concentration of radioactive carbon (14C) in circulating carbon in the 1950s toward the total carbon atom in the whole hot-bonding sheath-core composite fiber, is 70% or over.SELECTED DRAWING: None

Description

The present invention relates to heat-adhesive core-sheath composite fibers. More specifically, the present invention relates to a heat-adhesive core-sheath composite fiber composed of a polyester resin and a polyolefin resin obtained from a component derived from a biomass resource, that is, a plant.

The heat-adhesive core-sheath composite fiber, which can be molded by heat fusion using the heat energy of hot air or a heating roll, is a paper diaper because it is easy to obtain a non-woven fabric having excellent bulkiness and flexibility. It is widely used for sanitary materials such as napkins and pads, and industrial materials such as daily necessities and filters.

In recent years, due to growing interest in various issues of the international community such as environmental issues, companies are required to make efforts toward a transition to a sustainable society. In particular, heat-adhesive core-sheath composites used for sanitary materials Since fibers come into direct contact with the human body and excrement and the like adhere to them, it is difficult to recycle them from the viewpoint of hygiene, and the current situation is that thermal recycling is preferable as a practical method. Therefore, various heat-adhesive core-sheath composite fibers made from carbon-neutral biomass resource-derived components have been proposed.

For example, Patent Document 1 proposes a heat-adhesive core-sheath composite fiber composed of a polyolefin resin made from a component derived from a biomass resource and an aromatic polyester resin. Regarding the aromatic polyester resin, although it is described that 1,3-propylene glycol derived from biomass resources can be used as a monomer component, there is no specific description in the examples. Raw materials composed of components derived from biomass resources may contain a large amount of impurities, and there are problems such as generation of foreign substances, change in color tone, and deterioration of thermal stability due to these impurities. Ingredients derived from fossil resources are partially used as raw materials.

On the other hand, in Patent Document 2, a heat-adhesive core-sheath composite fiber made of two types of polyolefin resins having different melting points using a component derived from a biomass resource as a raw material is used. Although heat-adhesive core-sheath composite fibers made of lactic acid resin have been proposed, heat-adhesive core-sheath composite fibers made of only polyolefin resin or using polylactic acid resin for the core lack rigidity, especially paper diapers and napkins. In applications such as those that come into direct contact with the human body, there is a problem that a non-woven fabric that is bulky and easily allows liquid to pass through and is easily ventilated cannot be obtained.

Under such circumstances, there is a demand for a heat-adhesive core-sheath composite fiber suitable for use as a sanitary material, which can obtain a non-woven fabric that is carbon-neutral, bulky, easily allows liquid to pass through, and is easily ventilated.

Japanese Unexamined Patent Publication No. 2011-38207 Japanese Unexamined Patent Publication No. 2013-76192 JP-A-2010-65342

The present invention is a heat-adhesive core-sheath composite composed of a polyalkylene terephthalate resin as a core component and a polyolefin resin as a sheath component, in which components derived from carbon-neutral biomass resources suitable for a sustainable society occupy most of the raw materials. It is intended to provide fiber.

As a result of diligent studies to solve the above problems, the present inventors have used glycol derived from a biomass resource and terephthalic acid derived from a biomass resource and / or an ester-forming derivative thereof as raw materials in a phosphorus compound. By using a polyalkylene terephthalate resin composition containing the above-mentioned material and using a polyolefin resin made from a component derived from a biomass resource in the sheath portion, a heat-adhesive core-sheath composite fiber suitable for use as a sanitary material can be obtained. Was found to be achieved.

That is, the present invention is a heat-adhesive core-sheath composite using a component derived from biomass resources as a raw material, a polyalkylene terephthalate resin containing a phosphorus compound as a core component, and a polyolefin resin using a component derived from biomass resources as a raw material as a sheath component. The abundance ratio of carbon derived from biomass resources (bio), which is a fiber and is obtained based on the concentration of radioactive carbon (carbon 14) in the circulating carbon in the 1950s with respect to all carbon atoms in the entire heat-adhesive core-sheath composite fiber. It is a heat-adhesive core-sheath composite fiber characterized by having a conversion rate of 70% or more.

According to the present invention, a heat-adhesive core-sheath composite fiber having a high biochemical rate can be obtained, and by substituting a product using a conventional fossil resource-derived raw material, the fossil resource is reduced and carbon dioxide due to incineration is reduced. The increase can be suppressed.

It is a schematic cross-sectional view of an example of the eccentric cross section of the heat-adhesive core-sheath composite fiber of this invention.

Hereinafter, embodiments of the heat-adhesive core-sheath composite fiber of the present invention will be specifically described.

As the core component of the heat-adhesive core-sheath composite fiber of the present invention, it is necessary to use a polyalkylene terephthalate resin made from a component derived from a biomass resource. Further, as the polyalkylene terephthalate resin in the present invention, polybutylene terephthalate (PBT) resin and polypropylene terephthalate (PPT) made of biomass resource-derived glycol, biomass resource-derived terephthalic acid and / or an ester-forming derivative thereof as raw materials. Examples thereof include at least one polyalkylene terephthalate resin selected from resins and polyethylene terephthalate (PET) resins having a melting point of 240 ° C. or higher, which basically have the same physical properties as those derived from conventional fossil resources. Is.

In the present invention, the glycol derived from the biomass resource is not particularly limited as long as it can be obtained from the biomass resource, but from the viewpoint of good physical properties of the obtained polyalkylene terephthalate resin, ethylene glycol, 1,3-propanediol and 1 , 4-Butanediol is preferably at least one selected. In particular, ethylene glycol is preferable because the melting point of the obtained resin is high.

The proportion of the glycol derived from the biomass resource in the glycol used in the present invention is preferably 50 to 100 mol%, more preferably 80 to 100 mol% with respect to the total glycol component.

The method for obtaining these glycols from the biomass resource is not particularly limited, and any method may be used, and examples thereof include the following methods.

As a method of obtaining ethylene glycol, there is a method of obtaining it from a biomass resource such as corn, sugar cane, wheat or a stem of a crop. These biomass resources are first converted to starch, which is then converted to glucose by water and enzymes, and then to sorbitol by a hydrogenation reaction, which continues to undergo a hydrogenation reaction in the presence of a catalyst at a constant temperature and pressure. There is a method of obtaining a mixture of various glycols and purifying the mixture to obtain ethylene sorbitol. Another method is to obtain bioethanol from carbohydrate-based crops such as sugar cane by a biological treatment method, convert it to ethylene, and further obtain ethylene glycol via ethylene oxide. As yet another method, there is a method of obtaining glycerin from a biomass resource and then obtaining ethylene glycol via ethylene oxide. The ethylene glycol thus obtained contains various impurities, and each of the impurities is 1,2-propanediol, 1,2-butanediol, 2,3-butanediol, and 1,4-butanediol. It is preferably 1% by weight or less, more preferably 0.5% by weight or less from the viewpoint of physical properties of the obtained polyester resin, and 0.1% by weight or less from the viewpoint of the color tone of the obtained polyester resin. More preferred.

The method for obtaining 1,3-propanediol from a biomass resource is not particularly limited, but it can be obtained by fermentation from a sugar such as glucose and subsequent purification.

The method for obtaining 1,4-butanediol from a biomass resource is not particularly limited, and for example, succinic acid, succinic anhydride, succinic acid ester, maleic acid, maleic anhydride, maleic anhydride obtained by a fermentation method, 1,4-Butanediol can be obtained by chemical synthesis such as reduction from tetrahydrofuran, γ-butyrolactone and the like.

On the other hand, the method for obtaining terephthalic acid derived from a biomass resource is not particularly limited, and any method may be used. For example, after obtaining isobutanol from corn, sugar, or wood, it is converted to isobutylene, and the second method. After obtaining isooctene by quantification, p-xylene was synthesized by a method known in the literature (Chemiste Technik, vol.38, No. 3, P116-119; 1986), that is, p-xylene was synthesized through radical cleavage, recombination, and cyclization. Examples include a method of oxidizing to obtain terephthalic acid. Alternatively, p-cymene is synthesized from cineole obtained from plants of the genus Eucalyptus (Journal of the Chemical Society of Japan, (2), P217-219; 1986), followed by p-methylbenzoic acid (Organic Syntheses, 27). 1947), a method of obtaining terephthalic acid can be mentioned. The biomass resource-derived terephthalic acid thus obtained may be further converted into an ester-forming derivative. The ester-forming derivative referred to here is a lower alkyl ester, an acid anhydride, an acyl chloride or the like.

Glycols and terephthalic acids derived from biomass resources and their ester-forming derivatives may contain various impurities, and colored substances are generated due to the influence of impurities due to heating during the polyester resin manufacturing process, which deteriorates the color tone of the product. May cause you to. Therefore, it is preferable to purify the product so that impurities are contained as little as possible. It is preferable to convert the above-mentioned biomass resource-derived terephthalic acid into a dimethyl ester or a diethyl ester because distillation purification can be performed and the purity can be improved.

The ratio of the biomass resource-derived terephthalic acid and / or its ester-forming derivative used in the present invention is preferably 50 to 100 mol%, more preferably 80 to 100 mol% with respect to the total dicarboxylic acid component. ..

Fragrances such as isophthalic acid, isophthalic acid-5-sulfonate, phthalic acid, naphthalene-2,6-dicarboxylic acid, and bisphenoldicarboxylic acid as copolymerization components within a range in which the effects of the present invention are not substantially impaired. Aliphatic dicarboxylic acids such as group dicarboxylic acids and ester-forming derivatives thereof, amber acid, adipic acid, pimeric acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonandicarboxylic acid, and 1,12-dodecanedicarboxylic acid. Dicarboxylic acid components such as acids and ester-forming derivatives thereof, propanediol, butanediol, pentanediol, hexanediol, polyethylene glycol having a molecular weight of 500 to 20,000, diethylene glycol, 2-methyl-1,3-propanediol, It may contain a diol component such as polyoxytetramethylene glycol, polyoxytrimethylene glycol, or bisphenol A-ethylene oxide adduct. These copolymerization components can be used alone or in combination of two or more.

The most preferable aspect of the polyalkylene terephthalate resin using a component derived from a biomass resource as a raw material in the present invention is that the glycol component of the raw material is only ethylene glycol derived from the biomass resource, and the dicarboxylic acid component is only terephthalic acid derived from the biomass resource. It is a polyethylene terephthalate derived from a biomass resource having a melting point of 240 ° C. or higher.

Regarding "the abundance ratio (bioversion rate) of carbon derived from biomass resources obtained based on the concentration of radioactive carbon (carbon-14) in the circulating carbon in the 1950s with respect to all carbon atoms in the resin" in the present invention. , Will be described below.

As the carbon derived from the biomass resource in the present invention, carbon that was present as carbon dioxide in the atmosphere is taken into the plant by carbon dioxide assimilation, and indicates carbon that is present in the resin synthesized from this as a raw material. It can be identified by measuring the concentration of radioactive carbon (ie, carbon-14).

The concentration of carbon-14 can be measured by the following radiocarbon concentration measuring method. The radiocarbon concentration measurement method uses the weight difference of atoms by the accelerator to the isotopes of carbon (carbon 12, carbon 13, carbon 14) contained in the sample to be analyzed by the accelerator mass spectrometry (AMS). This is a method of physically separating the atoms and measuring the abundance of each isotope atom. The carbon atom is usually carbon-12, and the isotope carbon-13 is present at about 1.1%. Carbon-14 is called a radioactive isotope, and its half-life is regularly decreasing at about 5370 years. It will take 226,000 years for all of these to collapse. Cosmic rays are continuously irradiated in the upper atmosphere of the earth, and although it is a trace amount, carbon-14 is constantly generated and balanced with radiation decay, and the concentration of carbon-14 in the atmosphere is almost constant (of carbon atoms). It is about one trillionth). This carbon-14 immediately undergoes an exchange reaction with carbon-12 of carbon dioxide, and carbon dioxide containing carbon-14 is produced. Since plants take in carbon dioxide from the atmosphere and grow by photosynthesis, carbon-14 is always contained in a constant concentration. On the other hand, carbon-14, which was originally contained in fossil resources such as petroleum, coal, and natural gas, has already collapsed over many years and is hardly contained. Therefore, by measuring the concentration of carbon-14, it is possible to determine how much carbon derived from biomass resources is contained and how much carbon derived from fossil resources is contained. In particular, it is common practice to use a standard that sets the carbon-14 concentration in circulating carbon in the natural world in the 1950s to 100%, and oxalic acid (National Institute of Standards and Science and Technology NIST supply) is used as a standard substance. The value expressed as is obtained. As a unit of this ratio, pMC (percent Modern Carbon) is used.
pMC = (14Csa / 14C50) x 100
14C50: Carbon-14 concentration of standard substance (carbon-14 concentration in circulating carbon in the natural world in the 1950s)
14Csa: Carbon-14 concentration of the measurement sample.

At present, the carbon-14 concentration in the atmosphere measured in this way is measured to be about 110 pMC (percent Modern Carbon), and if it is a substance derived from 100% biomass resources, the value is about 110 pMC, which is almost the same. It is known to show. The ratio (%) of pMC of the target substance obtained by using this value as a standard of 100% is defined as "the concentration of radioactive carbon (carbon-14) in the circulating carbon in the 1950s with respect to all carbon atoms in the resin" in the present invention. The abundance ratio of carbon derived from biomass resources (biocarbonization rate), which can be obtained as a standard, is called. On the other hand, it is known that the carbon-14 concentration (pMC) obtained by measuring a substance derived from a fossil resource is almost 0 pMC, and in this case, the biochemical rate is 0%.

The biomerization rate of the polyalkylene terephthalate resin using the component derived from the biomass resource of the present invention as a raw material is preferably 70% or more, more preferably 85% or more in order to further suppress the decrease in fossil resources and the increase in carbon dioxide. Especially, when there is no copolymerization component, 95% or more is preferable.

In addition, in the measurement of the concentration of radioactive carbon (carbon-14), the content ratio of carbon derived from biomass resources can be analyzed even for recycled resins, so that the recycling of biomass resource-derived components for recycling is promoted. It is also an effective method for planning. Therefore, the polyalkylene terephthalate resin used for the heat-adhesive core-sheath composite fiber of the present invention includes not only the polyalkylene terephthalate resin newly obtained by polymerizing the biomass resource-derived component, but also the biomass resource-derived polyalkylene terephthalate resin. It also contains a recycled polyalkylene terephthalate resin containing the above.

The polyalkylene terephthalate resin of the present invention is usually produced by one of the following processes.

That is, (a) a process in which terephthalic acid and alkylene glycol are used as raw materials, a low polymer is obtained by a direct esterification reaction, and then a high molecular weight polymer is obtained by a polycondensation reaction, and (b) dimethyl terephthalate and alkylene glycol are used as raw materials. , A low polymer is obtained by an ester exchange reaction, and a high polymer is obtained by a subsequent polycondensation reaction. Here, the esterification reaction proceeds even without a catalyst, but a compound such as magnesium, manganese, calcium, cobalt, zinc, lithium, or titanium may be used as a catalyst as in the transesterification catalyst. Further, as the catalyst used in the polycondensation, a titanium compound, an aluminum compound, a tin compound, an antimony compound, a germanium compound and the like are used. Biomass resource-derived raw materials contain a large amount of impurities, and deposits around the mouthpiece increase during spinning, which increases the number of times the mouthpiece is washed and thread breaks, reducing operability, but highly active titanium compounds and aluminum compounds as catalysts. Is preferable because the amount of the catalyst added can be reduced, and as a result, the deposits around the base can be reduced. On the other hand, in solid phase polymerization, the catalyst may be inactivated by impurities in the raw material derived from the biomass resource and the polymerization time may be extended. Therefore, it is preferable to use an antimony compound or a germanium compound that is difficult to inactivate.

Examples of the titanium compound include titanium alkoxides such as titanium complex, tetra-i-propyl titanate, tetra-n-butyl titanate, and tetra-n-butyl titanate tetramer, titanium oxide obtained by hydrolysis of titanium alkoxide, and titanium acetylacetonate. And so on. Of these, a titanium complex containing a polyvalent carboxylic acid and / or a hydroxycarboxylic acid and / or a polyhydric alcohol as a chelating agent is preferable from the viewpoint of the thermal stability of the polymer, the color tone, and the small amount of deposits around the mouthpiece. Examples of the titanium compound chelating agent include lactic acid, citric acid, mannitol, tripentaerythritol and the like.

Examples of the aluminum compound include aluminum carboxylate, aluminum alkoxide, aluminum chelate compound, and basic aluminum compound. Specific examples thereof include aluminum acetate, aluminum hydroxide, aluminum carbonate, aluminum ethoxydo, aluminum isopropoxide, and aluminum acetyl. Examples include acetonate and basic aluminum acetate.

Examples of the tin compound include monobutyltin oxide, and examples of the antimony compound include antimony alkoxide and antimony trioxide.

Since the glycol component derived from biomass resources and the terephthalic acid component derived from biomass resources may contain a large amount of impurities, the obtained polyalkylene terephthalate resin may generate foreign substances derived from impurities, or the color tone and thermal stability may deteriorate. However, biomass with a low bioversion rate such as a polyalkylene terephthalate resin composed of a glycol component derived from a biomass resource and a terephthalic acid component derived from a fossil resource, and a polyalkylene terephthalate resin composed of a glycol component derived from a fossil resource and a terephthalic acid component derived from a biomass resource. The resource-derived polyalkylene terephthalate resin did not pose a major problem.

However, in a completely biomass resource-derived polyalkylene terephthalate resin composed of a biomass resource-derived glycol component and a biomass resource-derived terephthalic acid component, the phenomenon is remarkable, and not only the color tone and thermal stability are deteriorated, but also a large amount of foreign matter particles are contained. It occurs and the moldability is significantly deteriorated. It is presumed that this is due to the reaction or formation of agglomerates between the impurities contained in the glycol resource-derived glycol component and the impurities contained in the terephthalic acid component derived from the biomass resource.

As a result of diligent studies on this issue, it is possible to obtain a polyalkylene terephthalate resin having good color tone and thermal stability by suppressing the generation of foreign particles by containing a phosphorus compound in the polyalkylene terephthalate resin. Do you get it. It is considered that this effect is due to the phosphorus compound in the polyalkylene terephthalate resin suppressing the reaction and aggregation due to impurities. Therefore, in the present invention, it is essential that the polyalkylene terephthalate resin contains a phosphorus compound. When a phosphorus compound is contained in the polyalkylene terephthalate resin, it can be easily processed into fibers or the like for the first time.

The phosphorus compound is not particularly limited, but is selected from one or more compounds selected from a phosphite compound, a phosphate compound, a phosphonite compound, a phosphonate compound, a phosphinite compound, and a phosphinate compound. Examples of the phosphite compound include phosphorous acid, phosphorous acid monoalkyl ester, phosphorous acid dialkyl ester, phosphorous acid trialkyl ester, and alkali metal salts thereof. Specifically, phosphorous acid, trimethyl phosphite, triethyl phosphite, triphenyl phosphite, etc., sodium phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol -Di-phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol-di-phosphite and the like can be mentioned. Examples of the phosphate compound include phosphoric acid, phosphoric acid monoalkyl ester, phosphoric acid dialkyl ester, phosphoric acid trialkyl ester, and alkali metal salts thereof. Specific examples thereof include phosphoric acid, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, sodium phosphate and the like. Examples of the phosphonite compound include phosphonic acid, phosphonic acid monoalkyl ester, phosphonic acid dialkyl ester, phosphonic acid trialkyl ester, and alkali metal salts thereof. Specifically, methyl phosphonic acid, ethyl phosphonic acid, propyl phosphonic acid, isopropyl phosphonic acid, butyl phosphonic acid, phenyl phosphonic acid, tetrakis (2,4-di-t-butylphenyl) [1 , 1-biphenyl] -4,4'-diylbisphosphonite, tetrakis (2,4-di-t-butyl-5-methylphenyl) [1,1-biphenyl] -4,4'-diylbisphosphonite And so on. Examples of the phosphonate compound include phosphonic acid, phosphonic acid monoalkyl ester, phosphonic acid dialkyl ester, phosphonic acid trialkyl ester, and alkali metal salts thereof. Specifically, sodium phosphonate, methylphosphonic acid, ethylphosphonic acid, propylphosphonic acid, isopropylphosphonic acid, butylphosphonic acid, phenylphosphonic acid, benzylphosphonic acid, trillphosphonic acid, xsilylphosphonic acid, biphenylphosphonic acid, naphthyl. Phosphonic acid, anthrylphosphonic acid, 2-carboxyphenylphosphonic acid, 3-carboxyphenylphosphonic acid, 4-carboxyphenylphosphonic acid, 2,3-dicarboxyphenylphosphonic acid, 2,4-dicarboxyphenylphosphonic acid, 2 , 5-Dicarboxyphenylphosphonic acid, 2,6-dicarboxyphenylphosphonic acid, 3,4-dicarboxyphenylphosphonic acid, 3,5-dicarboxyphenylphosphonic acid, 2,3,4-tricarboxyphenylphosphonic acid , 2,3,5-tricarboxyphenylphosphonic acid, 2,3,6-tricarboxyphenylphosphonic acid, 2,4,5-tricarboxyphenylphosphonic acid, 2,4,6-tricarboxyphenylphosphonic acid, methylphosphon Acid dimethyl ester, methylphosphonic acid diethyl ester, ethylphosphonic acid dimethyl ester, ethylphosphonic acid diethyl ester, phenylphosphonic acid dimethyl ester, phenylphosphonic acid diethyl ester, phenylphosphonic acid diphenyl ester, benzylphosphonic acid dimethyl ester, undylphosphonic acid diethyl ester, Diphenyl ester of benzylphosphonic acid, lithium (3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl), sodium (3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl), magnesium bis (Ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate), calcium bis (ethyl 3,5-di-tert-butyl-4-hydroxybenzylfophonate), diethylphosphonoacetic acid, diethylphospho Examples thereof include methyl noacetate and ethyl diethylphosphonoacetate. Examples of the phosphinite compound include phosphinic acid, phosphinic acid monoalkyl ester, phosphinic acid dialkyl ester, phosphinic acid trialkyl ester, and alkali metal salts thereof. Specifically, methyl phosphinic acid, ethyl phosphinic acid, propyl phosphinic acid, isopropyl phosphinic acid, butyl phosphinic acid, phenyl phosphinic acid, dimethyl phosphinic acid, diethyl phosphinic acid, dipropyl phosphinic acid, Examples thereof include diisopropyl subphosphinic acid, dibutyl subphosphinic acid and diphenyl subphosphinic acid. Examples of the phosphinate compound include hypophosphorous acid, hypophosphorous acid monoalkyl ester, hypophosphorous acid dialkyl ester, hypophosphorous acid trialkyl ester, and alkali metal salts thereof. Specifically, sodium hypophosphorous acid, methylphosphinic acid, ethylphosphinic acid, propylphosphinic acid, isopropylphosphinic acid, butylphosphinic acid, phenylphosphinic acid, tolylphosphinic acid, xsilylphosphinic acid, biphenylylphosphinic acid, diphenyl Phosphinic acid, dimethylphosphinic acid, diethylphosphinic acid, dipropylphosphinic acid, diisopropylphosphinic acid, dibutylphosphinic acid, ditrilphosphinic acid, dixysilylphosphinic acid, dibiphenylylphosphinic acid, naphthylphosphinic acid, anthrylphosphinic acid, 2 -Carboxyphenyl phosphinic acid, 3-carboxyphenyl phosphinic acid, 4-carboxyphenyl phosphinic acid, 2,3-dicarboxyphenyl phosphinic acid, 2,4-dicarboxyphenyl phosphinic acid, 2,5-dicarboxyphenyl phosphinic acid, 2,6-dicarboxyphenyl phosphinic acid, 3,4-dicarboxyphenyl phosphinic acid, 3,5-dicarboxyphenyl phosphinic acid, 2,3,4-tricarboxyphenyl phosphinic acid, 2,3,5-tricarboxy Phenylphosphinic acid, 2,3,6-tricarbokiphenylphosphinic acid, 2,4,5-tricarboxyphenylphosphinic acid, 2,4,6-tricarboxyphenylphosphinic acid, bis (2-carboxyphenyl) phosphinic acid, Bis (3-carboxyphenyl) phosphinic acid, bis (4-carboxyphenyl) phosphinic acid, bis (2,3-dicarboxyphenyl) phosphinic acid, bis (2,4-dicarboxyphenyl) phosphinic acid, bis (2) , 5-Dicarboxyphenyl) phosphinic acid, bis (2,6-dicarboxyphenyl) phosphinic acid, bis (3,4-dicarboxyphenyl) phosphinic acid, bis (3,5-dicarboxyphenyl) phosphinic acid, bis (2,3,4-tricarboxyphenyl) phosphinic acid, bis (2,3,5-tricarboxyphenyl) phosphinic acid, bis (2,3,6-tricarboxyphenyl) phosphinic acid, bis (2,4) 5-Tricarboxyphenyl) phosphinic acid, and bis (2,4,6-tricarboxyphenyl) phosphinic acid, methylphosphinic acid methyl ester, dimethylphosphinic acid methyl ester, methylphosphinic acid ethyl ester, dimethylphosphinic acid ethyl ester, ethyl Methyl phosphinate, diethyl phosphy Acid methyl ester, ethylphosphinic acid ethyl ester, diethylphosphinic acid ethyl ester, phenylphosphinic acid methyl ester, phenylphosphinic acid ethyl ester, phenylphosphinic acid phenyl ester, diphenylphosphinic acid methyl ester, diphenylphosphinic acid ethyl ester, diphenylphosphinic acid Examples thereof include phenyl ester, benzylphosphinic acid methyl ester, benzylphosphinic acid ethyl ester, benzylphosphinic acid phenyl ester, bisbenzylphosphinic acid methyl ester, bisbenzylphosphinic acid ethyl ester, and bisbenzylphosphinic acid phenyl ester. Among them, phosphoric acid, trimethyl phosphate, triethyl phosphate, ethyl diethylphosphonoacetate and the like are preferable because they have a high effect of suppressing the generation of foreign particles and thus have good molding processability. Further, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite (PEP-36: manufactured by Asahi Denka Co., Ltd.) and chemical formula (2) represented by the chemical formula (1). Tetrakiss (2,4-di-t-butyl-5-methylphenyl) [1,1-biphenyl] -4,4'-diylbisphosphonite (GSY-P101: manufactured by Osaki Kogyo Co., Ltd.), represented by. Bis (2,4-di-tert-butylphenyl) pentaerythritol-di-phosphite (PEP-24G: manufactured by Asahi Denka Co., Ltd. or IRGAFOS126: manufactured by Ciba Specialty Chemicals Co., Ltd.) represented by the chemical formula (3), Tetrakiss (2,4-di-t-butylphenyl) [1,1-biphenyl] -4,4'-diylsphosphonite (IRGAFOSP-EPQ: manufactured by Ciba Japan Chemicals) represented by the chemical formula (4). Alternatively, a trivalent phosphorus compound such as SandostabP-EPQ (manufactured by Clariant) is preferable from the viewpoint of improving color tone and thermal stability. These phosphorus compounds may be used alone or in combination of two or more.

The amount of the phosphorus compound contained in the polyalkylene terephthalate resin used in the present invention is not particularly limited, but the total amount of the phosphorus compound in terms of phosphorus atoms with respect to the obtained polyalkylene terephthalate resin is in the range of 0.1 to 1000 ppm. preferable. When the addition amount is within the above range, a polyalkylene terephthalate resin having good molding processability and excellent color tone and thermal stability can be obtained because the generation of foreign matter particles is suppressed. It is more preferably in the range of 1 to 300 ppm, and particularly preferably in the range of 5 to 100 ppm.

Further, the intrinsic viscosity of the polyalkylene terephthalate resin used in the present invention is preferably 0.4 to 1.0. Here, the intrinsic viscosity of the polyalkylene terephthalate resin is a value measured at 25 ° C. using orthochlorophenol as a solvent, and was measured using a polyalkylene terephthalate resin containing an additive such as a phosphorus compound added during polymerization. The value. When the polyalkylene terephthalate resin used in the present invention is polyethylene terephthalate (PET), the intrinsic viscosity is more preferably 0.5 to 0.8, and particularly preferably 0.6 to 0.7. If the intrinsic viscosity is less than 0.5, the crimp retention rate of the fiber is lowered, and a non-woven fabric having sufficient bulkiness may not be obtained. On the other hand, if the intrinsic viscosity exceeds 0.7, the melt viscosity may become high and it may be difficult to manufacture the fiber. When the polyalkylene terephthalate resin used in the present invention is polypropylene terephthalate (PPT), the intrinsic viscosity is more preferably 0.4 to 1.0, and particularly preferably 0.5 to 0.9. If the intrinsic viscosity is less than 0.4, the crimp retention rate of the fiber is lowered, and a non-woven fabric having sufficient bulkiness may not be obtained. On the other hand, if the intrinsic viscosity exceeds 1.0, the melt viscosity may become high and it may be difficult to manufacture the fiber. When the polyalkylene terephthalate resin used in the present invention is polybutylene terephthalate (PBT), the intrinsic viscosity IV is more preferably 0.6 to 1.0, and particularly preferably 0.7 to 0.9. preferable. If the intrinsic viscosity is less than 0.6, the crimp retention rate of the fiber is lowered, and a non-woven fabric having sufficient bulkiness may not be obtained. On the other hand, if the intrinsic viscosity exceeds 1.0, the melt viscosity may become high and it may be difficult to manufacture the fiber.

The polyalkylene terephthalate resin used in the present invention can reduce the number of operations such as foreign matter filter replacement and mouthpiece replacement when fiber production is performed for a long period of time, and improves operability. Therefore, the polyalkylene terephthalate resin is measured by a method described later. The filter pressure increase index is preferably 10 MPa or less, more preferably 8 MPa or less, further preferably 6 MPa or less, and particularly preferably 4 MPa or less.

The polyalkylene terephthalate resin used in the present invention preferably has 10 or less foreign particles having a maximum diameter of 10 μm or more as measured by a method described later in order to suppress thread breakage during fiber production. It is more preferably 8 pieces / g or less, further preferably 6 pieces / g or less, and particularly preferably 4 pieces / g or less.

The polyalkylene terephthalate resin used in the present invention preferably contains a color tone adjusting agent. When a raw material derived from a biomass resource is used, the resin may be colored. In that case, it is preferable to use a color tone adjusting agent because the color tone is equivalent to that of the resin derived from a fossil resource. As the color tone adjusting agent, it is preferable to use a dye used for a resin or the like. In particular, COLOR INDEX GENERIC NAME specifically mentions SOLVENT BLUE 104, SOLVENT BLUE 45, SOLVENT BLUE 11, SOLVENT BLUE 25, SOLVENT BLUE 35, SOLVENT BLUE 36, SOLVENT BLUE 83, SOLVENT BLUE 87, SOLVENT BLUE 94, SOLVENT BLUE 122 and other blue color adjusters, SOLVENT VIOLET 36, SOLVENT VIOLET 8, SOLVENT VIOLET 13, SOLVENT VIOLET 28, SOLVENT VIOLET 21 Purple color adjusters such as SOLVENT VIOLET 37, SOLVENT VIOLET 49, SOLVENT RED 24, SOLVENT RED 25, SOLVENT RED 27, SOLVENT RED 30, SOLVENT RED 49, SOLVENT RED 109, SOLVENT RED , SOLVENT RED 121, SOLVENT RED 135, SOLVENT RED 149, SOLVENT RED 168, SOLVENT RED 179, SOLVENT RED 195 and the like, and orange color adjusters such as SOLVENT ORANGE 60 and the like. Among them, blue color adjusters such as SOLVENT BLUE 104 and SOLVENT BLUE 45 and purple color adjusters such as SOLVENT VIOLET 36 do not contain halogens that easily cause device corrosion and have relatively high thermal stability at high temperatures. It is preferable because it has good color development and has a color tone equivalent to that of a resin derived from a fossil resource. These may be used alone or in combination of two or more.

The amount of the color tone adjusting agent contained in the polyalkylene terephthalate resin used in the present invention is not particularly limited, but the total amount is in the range of 0.1 to 100 ppm with respect to the polyalkylene terephthalate resin, and the brightness is high. It is preferable because it is a terephthalate resin. It is more preferably in the range of 0.5 to 20 ppm, and particularly preferably in the range of 1 to 5 ppm.

Further, the polyalkylene terephthalate resin used in the present invention may contain an antioxidant, an ultraviolet absorber, a flame retardant, a fluorescent whitening agent, a matting agent, a plasticizer or an antifoaming agent, or other additives, if necessary. It may be blended.

Further, the polyalkylene terephthalate resin used in the present invention may be a resin produced by chemical recycling. The method for obtaining a polyalkylene terephthalate resin produced by chemical recycling using a raw material derived from biomass resources is not particularly limited, and any method may be used. For example, waste of polyalkylene terephthalate resin derived from biomass resources. Is used as a raw material and a depolymerization reaction is carried out with a glycol component derived from a biomass resource or a fossil resource to first obtain bis (hydroxyalkyl) terephthalate, which may be polymerized again, but more preferably with methanol or ethanol. Transesterification is carried out to obtain dimethyl terephthalate or diethyl terephthalate, and these terephthalic acid dialkyl esters are preferable because they can be purified to high purity by distillation. It can be produced by repolymerizing with the terephthalic acid dialkyl ester derived from the biomass resource thus obtained.

The polyalkylene terephthalate resin used in the present invention can be produced by batch polymerization, semi-continuous polymerization, or continuous polymerization.

The heat-adhesive core-sheath composite fiber of the present invention needs to use a polyolefin resin made from a component derived from a biomass resource as a sheath component. Further, the polyolefin resin in the present invention is preferably a polyethylene (PE) resin, a polypropylene (PP) resin, or a copolymer thereof. Specifically, low density polyethylene resin (LDPE), linear low density polyethylene resin, medium density polyethylene resin, high density polyethylene resin (HDPE), polypropylene resin, binary copolymer of polypropylene resin and polyethylene resin, etc. Polyethylene resin can be mentioned, and basically, it has the same physical properties as those derived from conventional fossil resources.

The viscosity of the polyolefin resin using the component derived from the biomass resource used in the present invention as a raw material is a melt flow measured at a temperature of 190 ° C. and a load of 20.2 N (2160 gf) according to the method described in ASTM D1238-13. The rate (MFR) is preferably 8-80 g / 10 min, more preferably 10-40 g / 10 min. If the MFR is less than 8 g / 10 minutes, melt extrusion tends to be difficult, which is not preferable. On the other hand, if the MFR exceeds 80 g / 10 minutes, it becomes difficult to satisfactorily fiberize the fiber by melt extrusion, or the mechanical strength of the fiber tends to decrease, which is not preferable.

The method for producing the polyolefin resin using the component derived from the biomass resource used in the present invention as a raw material is not particularly limited, and any method may be used. For example, in the case of polyethylene resin, corn, sugar cane, sweet potato, etc. Bioethanol is produced by fermenting components derived from biomass resources such as starch and sugar obtained from the above with microorganisms, and ethylene is produced by dehydration reaction of this, and polyethylene resin can be obtained by further polymerizing. In the case of polypropylene resin, 1,3-propylene glycol is produced by changing the fermentation conditions for the above-mentioned components derived from biomass resources, and this is dehydrated to obtain propylene, which is further polymerized to produce polypropylene resin. Can be obtained. Further, the copolymer of polypropylene resin and polyethylene resin can be obtained by polymerizing a predetermined amount of a mixture of ethylene and propylene.

As the polyolefin resin using the component derived from the biomass resource used in the present invention as a raw material, the biomass resource obtained based on the concentration of radioactive carbon (carbon-14) in the circulating carbon in the 1950s with respect to all the carbon atoms constituting the polyolefin resin. The abundance ratio (that is, the biochemical rate) of the derived carbon is preferably 70% or more, and more preferably 85% or more in order to further suppress the decrease in fossil resources and the increase in carbon dioxide, and particularly co-existence. When there is no polymer component, 95% or more is preferable.

In addition, in the measurement of radioactive carbon (carbon-14), the content ratio of carbon derived from biomass resources can be analyzed even for recycled polyolefin resin, so promotion of recycling of biomass resource-derived components for recycling is promoted. It is also an effective method for planning. Therefore, as the polyolefin resin used for the heat-adhesive core-sheath composite fiber of the present invention, not only the polyolefin resin newly obtained by polymerizing the biomass resource-derived component but also the polyolefin resin derived from the biomass resource is contained and recycled. It also contains the obtained polyolefin resin.

The heat-adhesive core-sheath composite fiber of the present invention is a polyalkylene terephthalate resin (A) whose core component is a component derived from a biomass resource as a raw material, and a polyolefin resin (B) whose sheath component is a component derived from a biomass resource as a raw material. Yes, the composite ratio of the core component and the sheath component is in the range of (A) / (B) = 70/30 to 30/70 in terms of mass ratio. More preferably, the mass ratio is in the range of (A) / (B) = 55/45 to 45/55.

If the core component exceeds 70% by mass, the mass% of the sheath component, which is a heat-adhesive component, decreases, so that the adhesive strength of the non-woven fabric decreases. On the contrary, if the sheath component exceeds 70% by mass, the mass% of the core component is reduced, which causes a problem in the mechanical strength of the non-woven fabric.

Further, the core component and the sheath component of the heat-adhesive core-sheath composite fiber of the present invention may be eccentrically composited.

FIG. 1 is a schematic cross-sectional view for illustrating and explaining an eccentric cross section of the heat-adhesive core-sheath composite fiber of the present invention. In FIG. 1, the heat-adhesive core-sheath composite fiber of the present invention contains a polyalkylene terephthalate resin (A) made from a biomass resource-derived component constituting the core component and a biomass resource-derived component constituting the sheath component. It is made of a polyolefin resin (B) as a raw material. The eccentric core-sheath type composite fiber shown in FIG. 1 is arranged so that the position of the center of gravity of the entire eccentric core-sheath type composite fiber and the position of the center of gravity of the polyalkylene terephthalate resin (A) made from the biomass resource-derived component of the core component are deviated from each other. It is an eccentric core sheath type composite fiber. In particular, an eccentric core-sheath type fiber cross section is a preferred embodiment when a spiral three-dimensional crimp can be easily developed when heat-treated and a bulky non-woven fabric is desired.

The eccentricity of the polyalkylene terephthalate resin (A) made from the component derived from the biomass resource is obtained by magnifying the fiber cross section of the eccentric core-sheath type composite fiber with an electron microscope or the like and using the component derived from the biomass resource as the raw material. When the longest distance from the center of gravity of the terephthalate resin (A) to the outer circumference of the eccentric core sheath type composite fiber is R and the radius of the eccentric core sheath type composite fiber is r (see FIG. 1), the numerical value represented by the following formula is used. To tell.
Eccentricity (%) = (R-r) / r × 100
The eccentricity of the eccentric core-sheath type composite fiber is preferably 5 to 50%. A more preferable eccentricity is 10 to 40%. If the eccentricity is less than 5%, the eccentricity is small and the crimping property is insufficient, so that a sufficiently bulky non-woven fabric cannot be obtained. On the other hand, when the eccentricity exceeds 50%, the polyalkylene terephthalate resin (A) made from the biomass resource-derived component which is the core component is the raw material, and the polyolefin resin (B) is made from the biomass resource-derived component which is the sheath component. It may not be wrapped by the resin and may be exposed on the fiber surface, which causes a problem in the mechanical strength of the non-woven fabric.

The biochemical rate of the entire heat-adhesive core-sheath composite fiber of the present invention is preferably 70% or more, more preferably 85% or more, and particularly a copolymerization component, in order to further suppress the decrease in fossil resources and the increase in carbon dioxide. If there is no such thing, 95% or more is preferable. The biochemical rate of the entire fiber is the sum of the value obtained by multiplying the biochemical rate of the core component by the composite ratio of the sheath component and the value obtained by multiplying the biochemical rate of the sheath component by the composite ratio of the sheath component.

The single fiber fineness of the heat-adhesive core-sheath composite fiber of the present invention is preferably 0.9 to 10.0 dtex, more preferably 1.0 to 6.0 dtex. When the single fiber fineness is less than 0.9 dtex, the single fiber fineness is small, so that the processability with a card is lowered and the texture of the obtained non-woven fabric is deteriorated. If it exceeds 10.0 dtex, the fineness of the single fiber becomes high, so that the rigidity of the fiber becomes high and the texture of the obtained non-woven fabric becomes hard.

The number of crimps of the heat-adhesive core-sheath composite fiber of the present invention is preferably 10 to 20 ridges / 25 mm, more preferably 12 to 18 ridges / 25 mm. When the number of crimps is less than 10 threads / 25 mm, the entanglement of the fibers is lowered, so that the processability with the card is lowered and the texture of the obtained non-woven fabric is deteriorated. If it exceeds 20 threads / 25 mm, the entanglement of the fibers is strong, and the openness of the fibers is deteriorated, so that the processability with a card is lowered and the texture of the obtained non-woven fabric is deteriorated.

The degree of crimp of the heat-adhesive core-sheath composite fiber of the present invention is preferably 10 to 25%, more preferably 14 to 20%. When the degree of crimping is less than 10%, the entanglement of the fibers is lowered, so that the processability on the card is lowered and the texture of the obtained non-woven fabric is deteriorated. If it exceeds 25%, the entanglement of the fibers is strong and the openness of the fibers is deteriorated, so that the processability with the card is lowered and the texture of the obtained non-woven fabric is deteriorated.

The dry heat shrinkage rate of the heat-adhesive core-sheath composite fiber of the present invention at 120 ° C. is preferably 0.3 to 3.0%, more preferably 0.4 to 2.5%. In order to obtain a fiber having a dry heat shrinkage rate of less than 0.3%, the drying temperature condition is increased, and as a result, the polyethylene resin is easily melt-bonded, so that it is difficult to stably produce the fiber. If the fiber has a dry heat shrinkage rate of more than 3.0%, the dimensional stability of the non-woven fabric is inferior in the heat bonding process, and it becomes difficult to produce a stable product.

Next, a melt-spinning step in the method for producing a heat-adhesive core-sheath composite fiber of the present invention, and a preferable fiber manufacturing step thereafter will be described by exemplifying one embodiment.

In the method for producing a heat-adhesive core-sheath composite fiber of the present invention, the core component is a polyalkylene terephthalate resin made from a component derived from a biomass resource, and the sheath component is a polyolefin resin made from a component derived from a biomass resource. The components are melt-spun so as to have a core-sheath type cross-sectional shape, and then preferably undrawn yarn is obtained, heat-stretched, crimped with a push-in crimper, dried, and cut to a predetermined fiber length. To obtain a heat-adhesive core-sheath composite fiber. This will be described in more detail below.

First, a polyalkylene terephthalate resin made from a component derived from a biomass resource and a polyolefin resin made from a component derived from a biomass resource are melted, and the resin is discharged from a mouthpiece as a core sheath via a spinning pack. A spinneret having a discharge hole of preferably 150 to 2000 holes is spun at a spinning temperature that is about 10 to 30 ° C. higher than the melting point of a polyalkylene terephthalate resin made from a component derived from a biomass resource, and immediately after that, preferably 10 to 25. Air at a temperature of ° C. is preferably cooled at an air volume of 50 to 100 m / min, a spinning oil is applied, and the undrawn yarn tow is obtained by temporarily putting it in a can at a take-up speed of 1000 to 1500 m / min.

Next, the obtained undrawn yarn tow is stretched at a draw ratio of 2.0 to 4.0 times, preferably using a liquid bath having a temperature of 80 to 100 ° C., and crimped by a stuffer box type crimping machine or the like. The crimp is applied using a machine, and the heat treatment is performed by creating a hot air atmosphere at 100 to 115 ° C. If the temperature is lower than 100 ° C., a dry heat shrinkage rate of 3% or less cannot be obtained. When the temperature exceeds 115 ° C., when the polyolefin resin made from the biomass resource-derived component used as the sheath component is a polyethylene-based resin, it is difficult to stably obtain fibers because of melt-bonding.

The fibers heat-treated in a hot air atmosphere are cooled and the fibers are cut into short fibers. The fiber length can be selected according to the intended use and is not particularly limited, but is preferably 30 to 76 mm, more preferably 30 to 64 mm when the carding treatment is performed.

The oil agent can be applied in any process such as before and after applying crimping and after drying.

According to the present invention, most of the raw materials are carbon-neutral biomass resource-derived components having physical properties equivalent to those of conventional heat-adhesive core-sheath composite fibers derived from fossil resources and suitable for a sustainable society. , A heat-adhesive core-sheath composite fiber composed of a polyalkylene terephthalate resin as a core component and a polyolefin resin as a sheath component can be obtained. The non-woven fabric using the heat-adhesive core-sheath composite fiber obtained by the present invention is suitably used for sanitary materials such as diapers, napkins, and pads.

Hereinafter, the present invention will be described in more detail with reference to Examples. The measurement and evaluation of each physical property value in the examples were carried out by the following method.

A. Melting point (Tm)
Using a DSC device, first raise the temperature from 40 ° C. to 280 ° C. at a heating rate of 16 ° C./min, maintain the temperature for 3 minutes, remove the heat history, and then remove the heat history, and then remove the heat history at a temperature lowering rate of 16 ° C./min. The temperature was maintained for 3 minutes after the temperature was lowered. Finally, the temperature was raised to 280 ° C. at a heating rate of 16 ° C./min, and the melting temperature obtained during the second temperature raising process was defined as the melting point Tm.

B. Intrinsic viscosity (IV)
The measurement was carried out at 25 ° C. using orthochlorophenol as a solvent.

C. Biochemical rate measurement method After crushing the sample with sandpaper and a crusher, it is heated with copper oxide to completely oxidize it to carbon dioxide, which is then reduced to graphite with iron powder to convert it into a single carbon compound. do. The obtained graphite was introduced into an AMS apparatus and measured. The standard substance oxalic acid (supplied by the National Institute of Standards and Technology NIST) was measured at the same time, and the 14C concentration (pMC) was determined based on the 14C concentration of the standard substance. On the other hand, the 14C concentration (pMC) of 100% bio-derived polylactic acid was determined by the same method. The bioization rate of the sample was determined using the 14C concentration (pMC) of this polylactic acid as a standard of 100%. Rounded off to the first or lower minority. When it exceeded 100%, it was set to 100%.

D. Phosphorus content in resin After heating and melting a chip-shaped sample on an aluminum plate, a molded product having a flat surface is prepared with a compression press, and phosphorus is produced by a fluorescent X-ray elemental analyzer (System3270, manufactured by Rigaku Denki Kogyo Co., Ltd.). The content (ppm) was determined.

E. Filter pressure increase index The polyalkylene terephthalate resin was dried under reduced pressure at 150 ° C. for 12 hours, and then used with a 20 mm diameter uniaxial extruder using an X4 type 20 μm dynaloy filter (filter area 4.5 cm2) manufactured by Watanabe Seisakusho. Melt extrusion was performed at a temperature of 280 ° C. and a passing amount of 5 g / min, and the difference between the primary pressure and the secondary pressure of the filter was measured as a filter pressure. In the present invention, the difference in filter pressure between 120 minutes and 720 minutes after the start of melt extrusion of the polyalkylene terephthalate resin composition was measured as a filter pressure increase index.

F. Melt flow rate (MFR)
The measurement was carried out at a temperature of 190 ° C. and a load of 20.2 N (2160 gf) according to the method described in ASTM D1238-13.

G. Eccentricity When the longest distance from the position of the center of gravity of the core component resin in the cross section of the eccentric core sheath type composite fiber to the outer circumference of the eccentric core sheath type composite fiber is R, and the radius of the eccentric core sheath type composite fiber is r, the following formula is used. Eccentricity (%) = (R-r) / r × 100
The numerical value indicated by is taken as the eccentricity.

H. Biochemical rate of the entire fiber The value obtained by multiplying the biochemical rate a of the core component by the composite ratio A of the core component and the biochemical rate b of the sheath component multiplied by the composite ratio B of the sheath component are obtained. Bioversion rate (%) = a × (A / 100) + b × (B / 100)
As shown in, the total value of each of the obtained numerical values was taken as the biochemical rate of the entire fiber.

I. Single fiber fineness Measured by the method described in JIS L1015 (2010) 7.5.1 A method.

J. Number of crimps and crimp rate Measured by the method described in JIS L1015 (2010) 7.12.

K. Fiber length JIS L1015 (2010) 7.4.1 Measured by the method described in C method.

L. Spinning yarn breakage (spinning property)
In melt spinning, the judgment was made based on the number of times yarn breakage occurred per 20 packs (spinning packs) for 8 hours. In the thread breakage, the threads spun from one pack were bundled and passed through a slit guide having a length of 0.05 mm, and the thread breakage did not pass through the slit guide, and the number of times the thread bundle was broken was counted as the thread breakage.
・ Pass (good): 10 times or less / 20 packs ・ Fail: 11 times or more / 20 packs.

(Example 1)
Magnesium acetate equivalent to 10 ppm in terms of magnesium atom, 100 kg of dimethyl terephthalate derived from biomass resources, and 58 kg of ethylene glycol derived from biomass resources (manufactured by India Glycol) are melted with respect to the obtained polymer in a nitrogen atmosphere at 150 ° C. and then stirred. While the temperature was raised to 230 ° C. over 3 hours, methanol was distilled off and a transesterification reaction was carried out to obtain bis (hydroxyethyl) terephthalate. This was transferred to a polycondensation tank.

On the other hand, for the obtained polymer, antimon trioxide equivalent to 250 ppm in terms of antimony atom and trimethyl phosphate equivalent to 10 ppm in terms of phosphorus atom are previously mixed in a biomass resource-derived ethylene glycol (manufactured by India Glycol) in another mixing tank. After mixing and stirring at room temperature for 30 minutes, the mixture was added to a polycondensation tank to which bis (hydroxyethyl) terephthalate had been transferred. After another 5 minutes, ethylene glycol (derived from biomass resources, manufactured by India Glycol) slurry of titanium oxide particles was added in an amount of 0.3% by weight in terms of titanium oxide particles to the obtained polymer. Then, after another 5 minutes, the reaction system was depressurized and the reaction was started. The temperature inside the reactor was gradually raised from 250 ° C. to 290 ° C., and the pressure was lowered to 40 Pa. The time required to reach the final temperature and the final pressure was 60 minutes. When the stirring torque reaches a predetermined value, the reaction system is purged with nitrogen and returned to normal pressure to stop the polycondensation reaction. Pellets were obtained. The time from the start of depressurization to the arrival of the predetermined stirring torque was 2 hours and 20 minutes. The obtained polyethylene terephthalate resin had good color tone and thermal stability, and was used as a core component resin.

A high-density polyethylene resin having a biochemical rate of 100% (MFR; 18, melting point; 130 ° C., manufactured by Braskem) was used as the sheath component resin.

The resin of the core component and the sheath component was melted and spun through a concentric core sheath mouthpiece having 400 discharge holes so as to have a mass ratio of 50/50% via a spinning pack. Immediately after spinning by cooling with a uniflow type, the yarn was cooled at an air volume of 60 m / min, and then an undrawn yarn was obtained at a take-up speed of 1000 m / min.

Next, the obtained undrawn yarn tow is subjected to one-step stretching at a drawing ratio of 3.0 times using a liquid bath at a temperature of 85 ° C., and crimping is imparted using a stuffing box type crimping machine. , Dryed at 110 ° C. and cut. The obtained heat-adhesive core-sheath composite fiber had a single fiber fineness of 2.2 dtex, a number of crimps of 14 threads / 25 mm, a crimp degree of 20%, and a fiber length of 38 mm. The spinnability was good. The results are shown in Table 1.

(Example 2)
A heat-adhesive core-sheath composite fiber was obtained in the same manner as in Example 1 except that phosphoric acid was used as the phosphorus compound to be added. The obtained heat-adhesive core-sheath composite fiber had a single fiber fineness of 2.2 dtex, a number of crimps of 14 threads / 25 mm, a crimp degree of 20%, and a fiber length of 38 mm. The spinnability was good. The results are shown in Table 1.

(Example 3)
A heat-adhesive core-sheath composite fiber was obtained in the same manner as in Example 1 except that ethyl diethylphosphonoacetate was used as the phosphorus compound to be added. The obtained heat-adhesive core-sheath composite fiber had a single fiber fineness of 2.2 dtex, a number of crimps of 14 threads / 25 mm, a crimp degree of 20%, and a fiber length of 38 mm. The spinnability was good. The results are shown in Table 1.

(Example 4)
A heat-adhesive core-sheath composite fiber was obtained in the same manner as in Example 1 except that a polypropylene resin having a biochemical rate of 100% (MFR; 19, melting point; 160 ° C.) was used as the sheath component resin. The obtained heat-adhesive core-sheath composite fiber had a single fiber fineness of 2.2 dtex, a number of crimps of 14 threads / 25 mm, a crimp degree of 20%, and a fiber length of 38 mm. The spinnability was good. The results are shown in Table 1.

(Example 5)
A heat-adhesive core-sheath composite fiber was obtained in the same manner as in Example 1 except that the eccentric core-sheath cap was used for spinning. The obtained heat-adhesive core-sheath composite fiber had a single fiber fineness of 2.4 dtex, a number of crimps of 16 threads / 25 mm, a crimp degree of 21%, and a fiber length of 38 mm. The spinnability was good. The results are shown in Table 1.

(Example 6)
A heat-adhesive core-sheath composite fiber was obtained in the same manner as in Example 2 except that the eccentric core-sheath cap was used for spinning. The obtained heat-adhesive core-sheath composite fiber had a single fiber fineness of 2.4 dtex, a number of crimps of 18 threads / 25 mm, a crimp degree of 22%, and a fiber length of 38 mm. The spinnability was good. The results are shown in Table 1.

(Example 7)
A chelated titanium citrate complex equivalent to 10 ppm in terms of titanium atom, 82.5 kg of terephthalic acid derived from a biomass resource, and 89.5 kg of 1,4-butanediol derived from a biomass resource were added to the obtained polymer at a temperature of 220 ° C. and a pressure of 1. In the esterification reaction tank held at 2 × 105 Pa, the esterification reaction was carried out until the temperature of the distillate fell below 90 ° C. 135 kg of the obtained esterification reaction product was transferred to a polycondensation tank.

After transfer, 30 minutes before adding magnesium acetate equivalent to magnesium atom equivalent to 10 ppm to the obtained polymer and trimethyl phosphate equivalent to 10 ppm equivalent to phosphorus atom equivalent to the obtained polymer to the esterification reaction product. The mixture was premixed in 1,4-butanediol derived from biomass resources in another mixing tank, stirred at room temperature for 30 minutes, and then the mixture was added. After another 5 minutes, a 1,4-butanediol (derived from biomass resource) slurry of titanium oxide particles was added in an amount of 0.3% by weight in terms of titanium oxide particles to the obtained polymer. Then, after another 5 minutes, the reaction system was depressurized to start the reaction. The temperature inside the reactor was gradually raised from 220 ° C. to 250 ° C., and the pressure was lowered to 60 Pa. The time required to reach the final temperature and the final pressure was 60 minutes. When the stirring torque reached a predetermined value, the reaction system was purged with nitrogen and returned to normal pressure to stop the polycondensation reaction, discharged in a strand shape, cooled, and immediately cut to obtain polymer pellets. The time from the start of depressurization to the arrival of the predetermined stirring torque was 2 hours and 14 minutes. The obtained polybutylene terephthalate resin had good color tone and thermal stability, and was used as a core component resin.

A high-density polyethylene resin (MFR; 18, melting point; 130 ° C.) having a biochemical rate of 100% was used as the sheath component resin.

The resin of the core component and the sheath component was melted and spun through a concentric core sheath mouthpiece having 400 discharge holes so as to have a mass ratio of 50/50% via a spinning pack. Immediately after spinning by cooling with a uniflow type, the yarn was cooled at an air volume of 60 m / min, and then an undrawn yarn was obtained at a take-up speed of 1000 m / min.

Next, the obtained undrawn yarn tow is subjected to one-step stretching at a drawing ratio of 3.0 times using a liquid bath at a temperature of 85 ° C., and crimping is imparted using a stuffing box type crimping machine. , Dryed at 110 ° C. and cut. The obtained heat-adhesive core-sheath composite fiber had a single fiber fineness of 2.1 dtex, a number of crimps of 13 threads / 25 mm, a degree of crimp of 19%, and a fiber length of 38 mm. The spinnability was good. The results are shown in Table 1.

(Example 8)
A heat-adhesive core-sheath composite fiber was obtained in the same manner as in Example 5 except that a polypropylene resin having a biochemical rate of 100% (MFR; 19, melting point; 160 ° C.) was used as the sheath component resin. The obtained heat-adhesive core-sheath composite fiber had a single fiber fineness of 2.1 dtex, a number of crimps of 13 threads / 25 mm, a degree of crimp of 19%, and a fiber length of 38 mm. The spinnability was good. The results are shown in Table 1.

(Example 9)
A chelated titanium citrate complex equivalent to 10 ppm in terms of titanium atom, 82.5 kg of terephthalic acid derived from biomass resources, and 49.1 kg of 1,3-propanediol derived from biomass resources were added to the obtained polymer at a temperature of 240 ° C. and a pressure of 1.2. In the esterification reaction tank maintained at × 105 Pa, the esterification reaction was carried out until the temperature of the distillate fell below 90 ° C. 140 kg of the obtained esterification reaction product was transferred to a polycondensation tank.

After the transfer, 30 minutes before adding magnesium acetate equivalent to 10 ppm in terms of magnesium atom to the obtained polymer and trimethyl phosphate equivalent to 10 ppm in terms of phosphorus atom to the obtained polymer to the esterification reaction product. The mixture was premixed in 1,3-propanediol derived from biomass resources in another mixing tank, stirred at room temperature for 30 minutes, and then the mixture was added. After a further 5 minutes, a 1,3-propanediol (derived from biomass resource) slurry of titanium oxide particles was added in an amount of 0.3% by weight in terms of titanium oxide particles to the obtained polymer. Then, after another 5 minutes, the reaction system was depressurized to start the reaction. The temperature inside the reactor was gradually raised from 240 ° C. to 280 ° C., and the pressure was lowered to 40 Pa. The time required to reach the final temperature and the final pressure was 60 minutes. When the stirring torque reaches a predetermined value, the reaction system is purged with nitrogen and returned to normal pressure to stop the polycondensation reaction. rice field. The time from the start of depressurization to the arrival of the predetermined stirring torque was 2 hours and 9 minutes. The obtained polypropylene terephthalate resin had good color tone and thermal stability, and was used as a core component resin.

A high-density polyethylene resin (MFR; 18, melting point; 130 ° C.) having a biochemical rate of 100% was used as the sheath component resin.

The resin of the core component and the sheath component was melted and spun through a concentric core sheath mouthpiece having 400 discharge holes so as to have a mass ratio of 50/50% via a spinning pack. Immediately after spinning by cooling with a uniflow type, the yarn was cooled at an air volume of 60 m / min, and then an undrawn yarn was obtained at a take-up speed of 1000 m / min.

Next, the obtained undrawn yarn tow is subjected to one-step stretching at a drawing ratio of 3.0 times using a liquid bath at a temperature of 85 ° C., and crimping is imparted using a stuffing box type crimping machine. , Dryed at 110 ° C. and cut. The obtained heat-adhesive core-sheath composite fiber had a single fiber fineness of 2.4 dtex, a number of crimps of 14 threads / 25 mm, a crimp degree of 20%, and a fiber length of 38 mm. The spinnability was good. The results are shown in Table 1.

(Example 10)
A heat-adhesive core-sheath composite fiber was obtained in the same manner as in Example 7 except that a polypropylene resin having a biochemical rate of 100% (MFR; 19, melting point; 160 ° C.) was used as the sheath component resin. The obtained heat-adhesive core-sheath composite fiber had a single fiber fineness of 2.4 dtex, a number of crimps of 14 threads / 25 mm, a crimp degree of 20%, and a fiber length of 38 mm. The spinnability was good. The results are shown in Table 1.

(Comparative Examples 1 to 6)
Comparative Example 1 is the same as Example 1, Comparative Example 2 is the same as Example 4, and Comparative Example 3 is the same as Example 7, except that a phosphorus compound is not added to the core component polyalkylene terephthalate resin. Then, Comparative Example 4 was obtained in the same manner as in Example 8, Comparative Example 5 was obtained in the same manner as in Example 9, and Comparative Example 6 was obtained in the same manner as in Example 10 to obtain a heat-adhesive core-sheath composite fiber. The biochemical rate of the obtained heat-adhesive core-sheath composite fiber as a whole was 100%, but any of the polyalkylene terephthalate resins showed a value of more than 10 MPa in the elongation pressure increase index, and the spinning yarn breakage occurred frequently and the spinning property was spunability. Was bad. The results are shown in Table 2.

(Comparative Examples 7 to 8)
Comparative Example 7 was the same as in Example 1 and Comparative Example 8 was the same as in Example 4 except that ethylene glycol derived from the fossil resource and terephthalic acid derived from the fossil resource were used. A composite fiber was obtained. The biochemical rate of the obtained heat-adhesive core-sheath composite fiber as a whole was 0%, and the spinnability was good. The results are shown in Table 2.

(Comparative Examples 9 to 10)
Comparative Example 9 was the same as Example 7, and Comparative Example 10 was the same as Example 8 except that 1,4-butanediol derived from the fossil resource and terephthalic acid derived from the fossil resource were used. Adhesive core-sheath composite fibers were obtained. The biochemical rate of the obtained heat-adhesive core-sheath composite fiber as a whole was 0%, and the spinnability was good. The results are shown in Table 2.

(Comparative Examples 11-12)
Comparative Example 11 was the same as Example 9 and Comparative Example 12 was the same as Example 10 except that 1,3-propanediol derived from the fossil resource and terephthalic acid derived from the fossil resource were used. Adhesive core-sheath composite fibers were obtained. The biochemical rate of the obtained heat-adhesive core-sheath composite fiber as a whole was 0%, and the spinnability was good. The results are shown in Table 2.

(A): Core component (B): Sheath component R: Longest distance from the center of gravity position of the core component resin to the outer circumference of the eccentric core sheath type composite fiber r: Radius of the eccentric core sheath type composite fiber C: Center of gravity of the core component resin c: Center of eccentric core sheath type composite fiber

Claims (1)

A heat-adhesive core-sheath composite fiber using a component derived from a biomass resource as a raw material, a polyalkylene terephthalate resin containing a phosphorus compound as a core component, and a polyolefin resin using a component derived from a biomass resource as a raw material as a sheath component. The abundance ratio (bioversion rate) of carbon derived from biomass resources obtained based on the concentration of radioactive carbon (carbon 14) in the circulating carbon in the 1950s with respect to all carbon atoms in the entire heat-adhesive core-sheath composite fiber is 70. % Or more, a heat-adhesive core-sheath composite fiber.

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