JP5700515B2 - Nonwoven manufacturing method - Google Patents

Description

  The present invention relates to a method for producing a nonwoven fabric, and more particularly, to a method for producing a nonwoven fabric that can produce a nonwoven fabric that is less colored and has a small amount of additive elution with respect to a solvent and that is excellent in rigidity.

  Examples of the method for obtaining a nonwoven fabric include a spunbond method, a melt blown method, a spunlace method, a thermal bond method, a chemical bond method, an airlaid method, a needle punch method, flash spinning, and the like, and fibers having various fiber diameters are used. Nonwoven fabric is manufactured.

  Nonwoven fabric applications include seat covers for seats in cars, trains, aircraft, theaters, cushioning materials, non-woven fabrics for medical infection prevention, sanitary wipes, sanitary products, diapers, top sheets for sanitary products such as diaper covers, socks , Underwear, lab coat, cover, sheets, curtain, table cloth, mat, pillow cover, toiletries, wall coverings such as wallpaper, wiper, wipes, wipes such as wet tissue, tea bags such as coffee and tea There are various types such as food wrapping materials and filters for filtration.

  Among them, the filter used for liquid filtration is a filter made of polyolefin, which has good alkali resistance, oxidation resistance and chemical resistance, and is inexpensive and has excellent rigidity and antibacterial properties. ing.

  For example, Patent Document 1 discloses a filter cartridge using a nonwoven fabric obtained by molding a polypropylene homopolymer polymerized with a metallocene catalyst by a melt spinning method.

  Patent Document 2 discloses that the weight fractions of a low molecular weight product having a molecular weight of 2000 or less and a high molecular weight product having a molecular weight of 1 million or more in the weight molecular weight distribution curve are each less than 1% and a weight average molecular weight of 50,000 to A nonwoven fabric using 200,000 polyolefins is disclosed.

  In general, polyolefins have poor stability to heat and light, so that they are easily oxidized / degraded when exposed to a high temperature environment or strong light, and thus there is a problem that a required life as a product cannot be obtained. In order to prevent this oxidation / degradation, a stabilizer such as a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, a hydroxylamine compound, a hindered amine compound, an ultraviolet absorber, an acid scavenger, etc. should be added. Is generally done. In particular, phenolic antioxidants have a high stabilizing effect against thermal oxidation of polyolefins, and can impart resistance to oxidation and discoloration during storage to polyolefins, and thus have high utility as polyolefin stabilizers.

International Publication No. 2005/084777 JP-A-9-296347

  However, the phenolic antioxidant has a migratory property in the polyolefin, and when exposed to a solvent, the phenolic antioxidant in the polyolefin resin is eluted on the surface, which is undesirable in terms of hygiene.

  In Patent Documents 1 and 2, a nonwoven fabric using a polyolefin having a controlled weight average molecular weight is proposed in order to suppress elution of a low molecular weight product of polyolefin, but a polyolefin having a controlled weight average molecular weight may be used. The elution of phenolic antioxidants blended in polyolefins is not solved, and the hygienic problems such as stickiness of the non-woven fabric caused by the eluted additive and contamination of the non-woven fabric was there.

  Then, the objective of this invention is providing the manufacturing method of the nonwoven fabric which can manufacture the nonwoven fabric with little elution of the additive with respect to a solvent.

  As a result of intensive studies in view of the above situation, the present inventors use a polyolefin stabilized by adding a specific phenol-based antioxidant before or during the polymerization of the ethylenically unsaturated bond monomer. As a result, the present inventors have found that the above-described problems can be solved and have completed the present invention.

（式中、Ｒ_１及びＲ_２は、各々独立して、水素原子、分岐を有してもよい炭素原子数１〜５のアルキル基、又は炭素原子数７〜９のアリールアルキル基を表し、Ｒは分岐を有してもよい炭素原子数１〜３０のアルキル基、置換されていてもよい炭素原子数３〜１２のシクロアルキル基、置換基を有してもよい炭素原子数６〜１８のアリール基を表す。） That is, the manufacturing method of the nonwoven fabric of the present invention is a manufacturing method of a nonwoven fabric that manufactures a nonwoven fabric from at least one polyolefin,
Before or during the polymerization of the monomer having an ethylenically unsaturated bond, the phenol-based antioxidant represented by the following general formula (1) is added to organoaluminum with respect to 100 parts by mass of the monomer having the ethylenically unsaturated bond. Add 0.001 to 0.03 parts by mass and 0.001 to 0.04 parts by mass of a phosphorus-based antioxidant to the catalyst system, polymerization system or piping to polymerize the monomer. The polyolefin obtained by the above is used.

(In the formula, R ₁ and R ₂ each independently represent a hydrogen atom, an optionally branched alkyl group having 1 to 5 carbon atoms, or an arylalkyl group having 7 to 9 carbon atoms, R is an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted cycloalkyl group having 3 to 12 carbon atoms, and an optionally substituted carbon atom having 6 to 18 carbon atoms. Represents an aryl group of

  In the manufacturing method of the nonwoven fabric of this invention, it is preferable that the said organoaluminum compound is a trialkylaluminum.

  The nonwoven fabric of this invention is obtained by said manufacturing method of a nonwoven fabric, It is characterized by the above-mentioned.

  The sanitary cloth, filter cloth, or filter of the present invention is characterized by comprising the above-mentioned nonwoven fabric.

（式中、Ｒ_１及びＲ_２は、各々独立して、水素原子、分岐を有してもよい炭素原子数１〜５のアルキル基、又は炭素原子数７〜９のアリールアルキル基を表し、Ｒは分岐を有してもよい炭素原子数１〜３０のアルキル基、置換されていてもよい炭素原子数３〜１２のシクロアルキル基、置換基を有してもよい炭素原子数６〜１８のアリール基を表す。） Moreover, the manufacturing method of the nonwoven fabric of this invention is a manufacturing method of the nonwoven fabric which manufactures a nonwoven fabric from at least 1 sort (s) of polyolefin,
Before or during the polymerization of the monomer having an ethylenically unsaturated bond, the phenol-based antioxidant represented by the following general formula (1) is added to organoaluminum with respect to 100 parts by mass of the monomer having the ethylenically unsaturated bond. 0.001 to 0.03 parts by mass and 0.001 to 0.04 parts by mass of a phosphorus-based antioxidant added to the catalyst system, polymerization system or piping to polymerize the monomer Obtaining a polyolefin, and
A process for producing a nonwoven fabric using the obtained polyolefin,
It is characterized by providing.

(In the formula, R ₁ and R ₂ each independently represent a hydrogen atom, an optionally branched alkyl group having 1 to 5 carbon atoms, or an arylalkyl group having 7 to 9 carbon atoms, R is an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted cycloalkyl group having 3 to 12 carbon atoms, and an optionally substituted carbon atom having 6 to 18 carbon atoms. Represents an aryl group of

  According to the present invention, it is possible to provide a method for producing a nonwoven fabric that can produce a nonwoven fabric that is less colored and has a small amount of the additive eluted with respect to the solvent and that is excellent in rigidity.

（式中、Ｒ_１及びＲ_２は、各々独立して、水素原子、分岐を有してもよい炭素原子数１〜５のアルキル基、又は炭素原子数７〜９のアリールアルキル基を表し、Ｒは分岐を有してもよい炭素原子数１〜３０のアルキル基、置換されていてもよい炭素原子数３〜１２のシクロアルキル基、置換基を有してもよい炭素原子数６〜１８のアリール基を表す。） The phenolic antioxidant used in the present invention is a compound represented by the following general formula (1).

(In the formula, R ₁ and R ₂ each independently represent a hydrogen atom, an optionally branched alkyl group having 1 to 5 carbon atoms, or an arylalkyl group having 7 to 9 carbon atoms, R is an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted cycloalkyl group having 3 to 12 carbon atoms, and an optionally substituted carbon atom having 6 to 18 carbon atoms. Represents an aryl group of

Examples of the alkyl group having 1 to 5 carbon atoms which may have a branch represented by R ₁ and R ₂ in the general formula (1) include, for example, methyl, ethyl, propyl, isopropyl, butyl, second Examples include butyl, tertiary butyl, pentyl, secondary pentyl, tertiary pentyl, and the like. In particular, tertiary butyl group is preferable because the stabilizing effect of the phenolic antioxidant is improved.

Examples of the arylalkyl group having 7 to 9 carbon atoms represented by R ₁ and R ₂ in the general formula (1) include benzyl and 1-methyl-1-phenylethyl.

  Examples of the alkyl group having 1 to 30 carbon atoms which may have a branch and represented by R in the general formula (1) include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, sec-butyl group, t-butyl group, isobutyl group, pentyl group, isopentyl group, t-pentyl group, hexyl group, heptyl group, n-octyl group, isooctyl group, t-octyl group, nonyl group, isononyl group, decyl Group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, and the like, and those having 12 to 24 carbon atoms are particularly preferred in the present invention. Phenol antioxidants with fewer than 12 carbon atoms in the alkyl group may easily volatilize, and if the alkyl group has more than 24 carbon atoms, the ratio of phenol to the molecular weight of the phenolic antioxidant will decrease. Therefore, the stabilization effect may be reduced.

  The alkyl group may be interrupted by an oxygen atom, a sulfur atom, or the following aryl group, and the hydrogen atom in the alkyl group is a chain fatty acid such as a hydroxy group, a cyano group, an alkenyl group, or an alkenyloxy group. Group, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyrazole, isoxazole, isothiazole, pyridine, pyridazine, pyrimidine, pyrazine, piperidine, piperazine, morpholine, 2H-pyran, 4H-pyran, phenyl, biphenyl, tri It may be substituted with a cyclic aliphatic group such as phenyl, naphthalene, anthracene, pyrrolidine, pyridine, indolizine, indole, isoindole, indazole, purine, quinolidine, quinoline, isoquinoline, or a cycloalkyl group. These interruptions or substitutions may be combined.

  Examples of the optionally substituted cycloalkyl group represented by R in the general formula (1) having 3 to 12 carbon atoms include cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclohexane An octyl group, a cyclononyl group, a cyclodecyl group, and the like, and a hydrogen atom in the cycloalkyl group may be substituted with an alkyl group, an alkenyl group, an alkenyloxy group, a hydroxy group, or a cyano group, It may be interrupted by an oxygen atom or a sulfur atom.

  Examples of the aryl group which may have a substituent having 6 to 18 carbon atoms and represented by R in the general formula (1) include a phenyl group, a methylphenyl group, a butylphenyl group, and an octylphenyl group. 4-hydroxyphenyl group, 3,4,5-trimethoxyphenyl group, 4-t-butylphenyl group, biphenyl group, naphthyl group, methylnaphthyl group, anthracenyl group, phenanthryl group, benzyl, phenylethyl group, 1- A phenyl-1-methylethyl group etc. are mentioned. In addition, a hydrogen atom in the aryl group may be substituted with an alkyl group, an alkenyl group, an alkenyloxy group, a hydroxy group, or a cyano group, and the alkyl group may be interrupted with an oxygen atom or a sulfur atom. Good

As a specific structure of the phenolic antioxidant represented by the general formula (1), the following compound No. 1-No. 16 is mentioned. However, the present invention is not limited by the following compounds.

  In the case where the phenolic antioxidant represented by the general formula (1) is masked with organoaluminum, the phenolic antioxidant is 0.001 to 100 parts by mass of the monomer having an ethylenically unsaturated bond. 0.03 part by mass, preferably 0.005 to 0.02 part by mass is added.

  A method for adding the phenolic antioxidant represented by the general formula (1) masked with an organoaluminum compound is not particularly limited. As a preferred embodiment, the masked phenolic antioxidant is added to any one or more of a catalyst feed tank, a polymerization apparatus and a production line and mixed.

  The masking can be performed by mixing and stirring the organoaluminum compound and the phenolic antioxidant in an inert solvent. By mixing and stirring, the hydrogen of the phenolic hydroxyl group of the phenolic antioxidant is replaced with an organoaluminum compound. After mixing and stirring the phenolic antioxidant and the organoaluminum compound, they may be added to any one or more of the catalyst system, the polymerization system and the piping. The phenolic antioxidant and the organoaluminum compound are added to the catalyst system, respectively. Alternatively, it may be added and mixed in one or more of the polymerization system and the piping.

  In the masking reaction of the phenolic antioxidant, if the by-product compound does not affect the polymerization reaction or polymer of the monomer, it can be used as it is, but if the by-product compound inhibits the polymerization, the compound is reduced in pressure. It is preferable to add to any one or more of the catalyst system, the polymerization system and the piping after removing by distillation or the like.

  The masked phenolic antioxidant is preferably capable of regenerating phenol by reacting with a hydrogen-donating compound such as water, alcohol or acid added as a deactivation treatment of the polymerization catalyst after polymerization.

  As a mixing ratio of the organoaluminum compound and the phenolic antioxidant represented by the general formula (1), the mass ratio of the phenolic antioxidant represented by the organoaluminum compound / the general formula (1) = 1. / 5 to 100/1 is desirable. If the amount of organoaluminum compound is less than 1/5, there is a problem that excessive phenolic antioxidants adversely affect the catalytic activity. If the amount of organoaluminum compound is more than 100/1, organoaluminum compound remains in the polymer after polymerization. In some cases, however, the physical properties of the polymer are deteriorated or the desired polymerization cannot be performed due to the influence of the component ratio of the catalyst metal.

  Preferable examples of the organoaluminum compound include alkylaluminum or alkylaluminum hydride. Alkylaluminum is preferable, and trialkylaluminum is particularly preferable. The trialkylaluminum includes, for example, trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, etc. Mixtures can be used. Moreover, the aluminoxane obtained by reaction of alkylaluminum or alkylaluminum hydride and water can be used similarly.

  Examples of the inert solvent include aliphatic and aromatic hydrocarbon compounds. Examples of the aliphatic hydrocarbon compound include saturated hydrocarbon compounds such as n-pentane, n-hexane, n-heptane, n-octane, isooctane and purified kerosene, and cyclic saturated hydrocarbons such as cyclopentane, cyclohexane and cycloheptane. Examples of the aromatic hydrocarbon compound include compounds such as benzene, toluene, ethylbenzene, xylene, and gasoline fraction. Among these compounds, those which are n-hexane, n-heptane or gasoline fraction are preferably used. The concentration of the trialkylaluminum salt in the inert solvent is preferably in the range of 0.001 to 0.5 mol / L, particularly preferably 0.01 to 0.1 mol / L.

Examples of the phosphorus antioxidant used in the present invention include triphenyl phosphite, trisnonylphenyl phosphite, tris (2,4-ditertiarybutylphenyl) phosphite, tris (2,4-ditertiary). Butyl-5-methylphenyl) phosphite, tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl] phosphite, tridecyl phosphite , Octyl diphenyl phosphite, di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol Diphosphite, bis (2,6-ditert-butyl-4-methylphenol ) Pentaerythritol diphosphite, bis (2,4,6-tritert-butylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropyl Dendiphenol diphosphite, tetra (tridecyl) -4,4′-n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl- 4-hydroxy-5-tert-butylphenyl) butanetriphosphite, tetrakis (2,4-ditert-butylphenyl) biphenylene diphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene- 10-oxide, 2,2′-methylenebis (4,6-ditertiary butyrate Ruphenyl) -2-ethylhexyl phosphite, 2,2'-methylenebis (4,6-ditert-butylphenyl) -octadecyl phosphite, 2,2'-ethylidenebis (4,6-ditert-butylphenyl) fluoro Phosphite, tris (2-[(2,4,8,10-tetrakis tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl) oxy] ethyl) amine, Examples thereof include phosphites of 2-ethyl-2-butylpropylene glycol and 2,4,6-tritert-butylphenol. Of these, phosphorus-based antioxidants such as tris (2,4-ditertiarybutylphenyl) phosphite that do not adversely affect the polymerization even when added before polymerization are preferred.
The amount of the phosphorus antioxidant used is 0.001 to 0.04 parts by weight, preferably 0.005 to 0.03 parts by weight, based on 100 parts by weight of the monomer having an ethylenically unsaturated bond. .

  When the phosphorus antioxidant is added in the addition step, it is preferably mixed with the inert solvent, but inactive together with the phenol antioxidant represented by the general formula (1) in advance. In addition to the phenolic antioxidant represented by the general formula (1), it may be mixed with the inert solvent and added to the polymerization system, catalyst system or piping. Also good.

  Examples of the monomer having an ethylenically unsaturated bond used in the present invention include ethylene, propylene, 1-butene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl- Examples thereof include 1-pentene, vinylcycloalkane, styrene, and derivatives thereof.

  The monomer having an ethylenically unsaturated bond used in the present invention may be a single type or a combination of two or more types, preferably a combination of ethylene, propylene or α-olefin monomers. . For example, ethylene alone, propylene alone, a combination of ethylene-propylene, a combination of ethylene-propylene-butene and the like may be mentioned, and further a combination of an α-olefin monomer and a non-conjugated diene monomer may be used.

  The polymerization is performed in an inert gas atmosphere such as nitrogen in the presence of a polymerization catalyst, but may be performed in the inert solvent. In addition, an active hydrogen compound, a particulate carrier, an organoaluminum compound, an ion exchange layered compound, and an inorganic silicate may be added as long as polymerization is not inhibited.

  The polymerization catalyst is not particularly limited, and a known polymerization catalyst can be used. For example, transition metals belonging to Group 3 to 11 of the periodic table (for example, titanium, zirconium, hafnium, vanadium, iron, nickel, lead) , Platinum, yttrium, samarium, etc.), and typical examples include Ziegler catalysts, Ziegler-Natta catalysts composed of titanium-containing solid transition metal components and organometallic components, nitrogen, oxygen, sulfur, phosphorus, etc. Brookhart catalyst, which is a compound in which a hetero atom is bonded to a transition metal of Group 4 to Group 10 of the periodic table, Group 4 to Group 6 transition metal compound having at least one cyclopentadienyl skeleton, and a promoter The metallocene catalyst which consists of a component is mentioned, However, Since a high quality polymer is obtained when an electron donor compound is used, it is preferable.

  Examples of the electron donating compound include ether compounds, ester compounds, ketone compounds, and alkoxysilane compounds. A single compound may be added to the electron donor compound, or a plurality of compounds may be added as necessary.

  Examples of the ether compound include diethyl ether, dipropyl ether, diisopropyl ether, di-n-butyl ether, diethylene glycol dimethyl ether, propylene glycol dimethyl ether, ethylene oxide, tetrahydrofuran, 2,2,5,5-tetramethyltetrahydrofuran, dioxane and the like. Is mentioned.

  Examples of the ester compound include methyl acetate, ethyl acetate, acetic acid-n-propyl, isopropyl acetate, methyl propionate, ethyl propionate, propionate-n-propyl, methyl methacrylate, ethyl methacrylate, methacrylic acid- n-propyl, ethyl phenylacetate, methyl benzoate, ethyl benzoate, phenyl benzoate, methyl toluate, ethyl toluate, methyl anisate, ethyl anisate, methyl methoxybenzoate, ethyl methoxybenzoate, methyl methacrylate, Examples include ethyl methacrylate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, γ-butyrolactone, and ethyl cellosolve.

  Examples of the ketone compound include acetone, diethyl ketone, methyl ethyl ketone, acetophenone, and the like.

  Examples of the alkoxysilane compounds include tetramethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, t-butyltrimethoxysilane, i-butyltrimethoxysilane, phenyltrimethoxysilane, cyclohexyltri Methoxysilane, diethyldimethoxysilane, dipropyldimethoxysilane, diisopropyldimethoxysilane, diphenyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane, t-butyl-n-propyldimethoxysilane, t-butylisopropyldimethoxysilane , Cyclohexylmethyldimethoxysilane, tetraethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, isopropyl Reethoxysilane, t-butyltriethoxysilane, phenyltriethoxysilane, cyclohexyltriethoxysilane, diethyldiethoxysilane, dipropyldiethoxysilane, diisopropyldiethoxysilane, diphenyldiethoxysilane, t-butylmethyldiethoxysilane, Examples include cyclohexylmethyldiethoxysilane and dicyclopentyldimethoxylane.

  As a method for conducting the polymerization reaction, a method usually used in the polymerization reaction of monomers having an ethylenically unsaturated bond can be employed. For example, in the presence of a polymerization catalyst, aliphatic hydrocarbons such as butane, pentane, hexane, heptane and isooctane, alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane, and aromatic hydrocarbons such as toluene, xylene and ethylbenzene , A method of performing polymerization in the liquid phase in the presence of an inert solvent such as a gasoline fraction, a hydrogenated diesel fraction, a polymerization method using a monomer having a liquefied ethylenically unsaturated bond as a medium, and the liquid phase is substantially It is also possible to use a method in which polymerization is carried out in the gas phase under conditions not present in the above, or a polymerization method in which two or more of these are combined. The polymerization may be either a palindromic or continuous process, and may be a one-stage polymerization method or a multi-stage polymerization method.

  As a polymerization tank used in the polymerization reaction, a continuous reaction tank in an existing polymerization facility may be used as it is, and the present invention is not particularly limited to conventional polymerization facilities in terms of size, shape, material, and the like.

The polymerization of the monomer having an ethylenically unsaturated bond may contain a catalyst component other than the polymerization catalyst, for example, a carrier and the like as long as the polymerization is not inhibited. When the catalyst is supported on the support, the powder property of the polyolefin is improved and the granulation step can be omitted.
The type of the carrier is not limited, and examples thereof include inorganic carriers such as inorganic oxides and organic carriers such as porous polyolefin, and a plurality of them may be used in combination.
Examples of the inorganic carrier include silica, alumina, magnesium oxide, zirconium oxide, titanium oxide, iron oxide, calcium oxide, and zinc oxide. Other inorganic carriers include magnesium halides such as magnesium chloride and magnesium bromide, and magnesium alkoxides such as magnesium ethoxide.

Other inorganic carriers include ion exchange layered compounds. The ion-exchangeable layered compound has a crystal structure in which surfaces formed by ionic bonds or the like are stacked in parallel with a weak bonding force, and the ions contained therein can be exchanged. Specific examples thereof include kaolin, bentonite, talc, kaolinite, vermiculite, montmorillonite group, mica group, α-Zr (HAsO ₄ ) ₂ .H ₂ O, α-Zr (HPO ₄ ) ₂ .H ₂ O, α -Sn (HPO ₄ ) ₂ · H ₂ O, γ-Ti (NH ₄ PO ₄ ) ₂ · H ₂ O, and the like can be given.

  Examples of the organic carrier include polyethylene, polypropylene, polystyrene, ethylene-butene copolymer, ethylene-propylene copolymer, polymethacrylic acid ester, polyacrylic acid ester, polyacrylonitrile, polyamide, polycarbonate, and polyethylene terephthalate. Examples thereof include polyester, polyvinyl chloride, and the like, and these may be crosslinked, for example, as a styrene-divinylbenzene copolymer. In addition, a catalyst in which a catalyst is chemically bonded to these organic supports can be used.

  The particle size of these carriers is generally 0.1 to 300 μm, preferably 1 to 200 μm, more preferably 10 to 100 μm. When the particle size is small, the polymer is finely powdered, and when it is too large, coarse particles are produced, which facilitates handling of the powder.

The pore volume of these carriers is usually 0.1 to ⁵ cm ² / g, preferably 0.3 to ³ cm ² / g. The pore volume can be measured by, for example, the BET method or the mercury intrusion method.

  The polyolefin obtained by the above polymerization can be blended with other usual other additives as required. Other additives can be added during the polymerization of the monomer having an ethylenically unsaturated bond, as long as the polymerization is not inhibited. As other blending methods, there may be mentioned a method in which other additives are mixed with the polyolefin in a blending amount according to the purpose, and melt-kneaded by a molding processing machine such as an extruder, and granulated and molded.

  Other additives include, for example, phosphorus antioxidants, ultraviolet absorbers, hindered amine compounds, heavy metal deactivators, nucleating agents, flame retardants, metal soaps, hydrotalcite, fillers, lubricants, antistatic agents. , Pigments, dyes, plasticizers and the like.

Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone). 2-hydroxybenzophenones such as 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3, 5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5 -Dicumylphenyl) benzotriazole, 2,2'-methylenebis (4-tertiary Octyl-6-benzotriazolylphenol), 2- (2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzotriazole polyethylene glycol ester, 2- [2-hydroxy-3- (2-acryloyloxy) Ethyl) -5-methylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] benzotriazole, 2- [2-hydroxy-3- (2- Methacryloyloxyethyl) -5-tert-octylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] -5-chlorobenzotriazole, 2- [2 -Hydroxy-5- (2-methacryloyloxyethyl) phenyl] benzo Triazole, 2- [2-hydroxy-3-tert-butyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-amyl-5- (2-methacryloyloxyethyl) ) Phenyl] benzotriazole, 2- [2-hydroxy-3-tert-butyl-5- (3-methacryloyloxypropyl) phenyl] -5-chlorobenzotriazole, 2- [2-hydroxy-4- (2-methacryloyl) Oxymethyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxypropyl) phenyl ] 2- (2-hydroxyphenyl) such as benzotriazole Benzotriazoles; 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-hexyloxyphenyl) -4,6-diphenyl -1,3,5-triazine, 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2- Hydroxy-4- (3-C12-13 mixed alkoxy-2-hydroxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy- 4- (2-acryloyloxyethoxy) phenyl] -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxy-3-allylphenyl) 4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4,6-tris (2-hydroxy-3-methyl-4-hexyloxyphenyl) -1,3,5 2- (2-hydroxyphenyl) -4,6-diaryl-1,3,5-triazines such as triazine; phenyl salicylate, resorcinol monobenzoate, 2,4-ditert-butylphenyl-3,5-di Tert-butyl-4-hydroxybenzoate, octyl (3,5-ditert-butyl-4-hydroxy) benzoate, dodecyl (3,5-ditert-butyl-4-hydroxy) benzoate, tetradecyl (3,5-di Tert-butyl-4-hydroxy) benzoate, hexadecyl (3,5-ditert-butyl-4-hydroxy) benzoate, octadecyl (3,5-ditert-butyl) Benzoates such as til-4-hydroxy) benzoate and behenyl (3,5-ditert-butyl-4-hydroxy) benzoate; 2-ethyl-2′-ethoxyoxanilide, 2-ethoxy-4′-dodecyloxy Substituted oxanilides such as zanilides; cyanoacrylates such as ethyl-α-cyano-β, β-diphenyl acrylate and methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate; various metal salts Or metal chelates, especially nickel, chromium salts, or chelates.
The usage-amount of the said ultraviolet absorber is 0.001-5 mass parts with respect to 100 mass parts of said polyolefin, More preferably, it is 0.005-0.5 mass part.

Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2, 6,6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1 , 2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2, 6,6-tetramethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4 Piperidyl) .di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,4,4-pentamethyl-4-piperidyl) -2-butyl-2- (3,5 -Di-tert-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6- Bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6 -Tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,4-bis (N-butyl) -N- (2,2, , 6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis [2,4-bis ( N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8-12-tetraazadodecane, 1,6 , 11-tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] aminoundecane, 1,6 , 11-tris [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] aminoundecane, bis { 4- (1-octyloxy-2,2,6,6-tetra Methyl) piperidyl} decanedionate, bis {4- (2,2,6,6-tetramethyl-1-undecyloxy) piperidyl) carbonate, TINUVIN NOR 371 manufactured by Ciba Specialty Chemicals.
The usage-amount of the said hindered amine light stabilizer is 0.001-5 mass parts with respect to 100 mass parts of said polyolefin, More preferably, it is 0.005-0.5 mass part.

  Examples of the heavy metal deactivator include salicylamide-1,2,4-triazole-3-yl, bissalicylic acid hydrazide, dodecandioyl bis (2- (2-hydroxybenzoyl) hydrazide), bis (3- ( 3,5-di-t-butyl-4-hydroxyphenyl) propionic acid) hydrazide and the like, and is preferably 0.001 to 10 parts by mass, more preferably 0.05 to 100 parts by mass of the polyolefin. ~ 5 parts by weight are used.

Examples of the nucleating agent include carboxylic acids such as sodium benzoate, 4-tert-butylbenzoic acid aluminum salt, sodium adipate and disodium bicyclo [2.2.1] heptane-2,3-dicarboxylate. Metal salts, sodium bis (4-tert-butylphenyl) phosphate, sodium-2,2′-methylenebis (4,6-ditert-butylphenyl) phosphate and lithium-2,2′-methylenebis (4,6-di) Phosphate metal salts such as tert-butylphenyl) phosphate, polyhydric alcohol derivatives such as dibenzylidene sorbitol, bis (methylbenzylidene) sorbitol, bis (p-ethylbenzylidene) sorbitol, and bis (dimethylbenzylidene) sorbitol, N, N ′, N ″ -tris [2-methylcyclohexyl 1,2,3-propanetricarboxamide (RIKACLEAR PC1), N, N ′, N ″ -tricyclohexyl 1,3,5-benzenetricarboximide, N, N′-dicyclohexyl-naphthalenedicarboxamide, 1, Examples thereof include amide compounds such as 3,5-tri (dimethylisopropoylamino) benzene.
The usage-amount of the said nucleating agent is 0.001-10 mass parts with respect to 100 mass parts of said polyolefin, More preferably, it is 0.005-5 mass parts.

Examples of the flame retardant include aromatic phosphoric acid such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-xylenyl phosphate, and resorcinol bis (diphenyl phosphate). Phosphonates such as esters, divinyl phenylphosphonate, diallyl phenylphosphonate and phenylphosphonic acid (1-butenyl), phenyl diphenylphosphinate, methyl diphenylphosphinate, 9,10-dihydro-9-oxa-10-phospha Phosphonic acid esters such as phenanthrene-10-oxide derivatives, phosphazene compounds such as bis (2-allylphenoxy) phosphazene and dicresyl phosphazene, melamine phosphate, melamine pyrophosphate, Melamine phosphate, melam polyphosphate, ammonium polyphosphate, phosphorus-containing vinylbenzyl compounds and phosphorus-based flame retardants such as red phosphorus, metal hydroxides such as magnesium hydroxide and aluminum hydroxide, brominated bisphenol A type epoxy resin, bromine Phenol novolac epoxy resin, hexabromobenzene, pentabromotoluene, ethylenebis (pentabromophenyl), ethylenebistetrabromophthalimide, 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane, tetrabromocyclo Octane, hexabromocyclododecane, bis (tribromophenoxy) ethane, brominated polyphenylene ether, brominated polystyrene and 2,4,6-tris (tribromophenoxy) -1,3,5-triazine, tribromophenyl Reimido, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol A type dimethacrylate, pentabromobenzyl acrylate, and include brominated flame retardants such as brominated styrene and the like.
The usage-amount of the said flame retardant is 1-70 mass parts with respect to 100 mass parts of said polyolefin, More preferably, it is 10-30 mass parts.

Examples of the filler include talc, mica, calcium carbonate, calcium oxide, calcium hydroxide, magnesium carbonate, magnesium hydroxide, magnesium oxide, magnesium sulfate, aluminum hydroxide, barium sulfate, glass powder, glass fiber, clay, Dolomite, mica, silica, alumina, potassium titanate whisker, wollastonite, fibrous magnesium oxysulfate and the like are preferable. Among these fillers, those having an average particle diameter (spherical or flat) or an average fiber diameter (needle or fiber) of 5 μm or less are preferable.
The amount of the filler used can be appropriately used as long as the present invention is not impaired.

The above-mentioned lubricant is added for the purpose of imparting lubricity to the surface of the molded body and enhancing the effect of preventing damage. Examples of the lubricant include unsaturated fatty acid amides such as oleic acid amide and erucic acid amide; saturated fatty acid amides such as behenic acid amide and stearic acid amide. These may be used alone or in combination of two or more.
The addition amount of the lubricant is in the range of 0.03 to 2 parts by mass, more preferably 0.04 to 1 part by mass with respect to 100 parts by mass of the polyolefin. If the amount is less than 0.03 parts by mass, the desired lubricity may not be obtained. If the amount exceeds 2 parts by mass, the lubricant component may bleed on the surface of the polymer molded product or cause a decrease in physical properties.

  The antistatic agent is added for the purpose of reducing the chargeability of the molded product and preventing dust from adhering due to charging. There are various antistatic agents such as cationic, anionic and nonionic. Preferred examples include polyoxyethylene alkylamines, polyoxyethylene alkylamides or their fatty acid esters, glycerin fatty acid esters, and the like. These may be used alone or in combination of two or more. Moreover, the addition amount of the antistatic agent is preferably 0.03 to 2 parts by mass, more preferably 0.04 to 1 part by mass with respect to 100 parts by mass of the polyolefin. When the amount of the antistatic agent is too small, the antistatic effect is insufficient. On the other hand, when the amount is too large, bleeding to the surface and deterioration of physical properties of the polyolefin may be caused.

  As a method for obtaining a nonwoven fabric using the polyolefin, a known method can be employed. Examples thereof include a spun bond method, a melt blown method (melt blow method), a spun lace method, a thermal bond method, a chemical bond method, an airlaid method, a needle punch method, and flash spinning. Of these, the melt blown method or the spun bond method is preferable.

  The non-woven fabric obtained by the production method of the present invention may be a non-woven fabric composed of a composite fiber having other resin as a core component and polypropylene as the sheath component according to the present invention. Examples of other resins include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide, nylon, polyethylene different from the polyolefin according to the present invention, polypropylene, and the like.

  The use of the non-woven fabric obtained by the production method of the present invention is not particularly limited, and can be used for all uses where a non-woven fabric is conventionally used. For example, seat covers for seats in cars, trains, aircraft, theaters, cushioning materials, non-woven fabrics for infection prevention, sanitary wipes, sanitary products, diapers, diaper covers, top sheets for sanitary products, socks, underwear, lab coats , Covers, sheets, curtains, tablecloths, mats, pillow covers, toiletries, wall coverings such as wallpaper, wipes, cloths, wipes for wet tissues, etc., food bags in the form of tea bags such as coffee and tea, It can be used for applications such as filtration filters. Among these, it can use suitably as a filter for filtration.

  EXAMPLES Hereinafter, although this invention is demonstrated in more detail with an Example and a comparative example, this invention is not restrict | limited by these Examples. In addition, the physical-property value in an Example and a comparative example was measured with the following method.

(Dissolution test)
10 g of the nonwoven fabric obtained by the following method was cut out, put into a stainless steel container, sealed with 100 ml of ethanol, and allowed to stand in an oven at 70 ° C. for 6 hours. After 6 hours, the stainless steel container was taken out of the oven and cooled to room temperature, and then the additive and resin extracted into ethanol were quantitatively analyzed by the following method.

(Quantitative analysis)
Gas chromatography {Apparatus: Gas chromatography GC2010 manufactured by Shimadzu Corporation, Column: BPX5 manufactured by SGE (30 m × 0.25 mm D × 0.25 μm), Injection temperature: 330 ° C., Detector temperature: 330 ° C., Measurement conditions: A calibration curve was prepared by dissolving the blended additive in chloroform at a heating rate of 15 ° C./min}, and quantitative analysis of the additive extracted into ethanol was performed. The amount of the eluted resin was determined by taking the difference in the amount of the additive eluted from the total amount eluted to obtain the resin elution amount (mg).

(Tensile strength)
The tensile strength in the longitudinal direction (machine line direction) was measured in accordance with the general long fiber nonwoven fabric test method of JIS L1906. A 5 × 30 cm rectangle was cut out from the sheet-like non-woven fabric to obtain a test sample, the test piece was pulled at a pulling speed of 20 cm at a gripping interval of 10 cm / min, and the load when the test piece was cut was taken as the tensile strength.

(Thread breakage during spinning)
During spinning, light was illuminated from behind in the vicinity of the spinning nozzle, and the yarn breakage state (whether or not yarn breakage occurred) was visually observed.

(Seat pinhole)
From the back of the nonwoven fabric, the presence of pinholes was confirmed by illuminating the uniform light of a fluorescent lamp.

(Yellowness of nonwoven fabric; YI)
Based on JIS K7105, the yellowness (YI) of the nonwoven fabric was measured with a spectrocolorimeter (SC-P; manufactured by Suga Test Instruments Co., Ltd.).

[Examples 1 and 2 and Comparative Example 1]
(Masking of phenolic antioxidants)
Add 5.0 g of triisobutylaluminum and stabilizer (phenolic antioxidant) listed in Table 1 below to 50 ml of toluene so that the molar ratio of functional groups is 2: 1, and stir at room temperature for 30 minutes. Thus, a stabilizer solution inactivated with respect to the polymerization catalyst was obtained.

(polymerization)
300 ml of toluene was added to a 1000 ml autoclave purged with nitrogen. Methylaluminoxane (MMAO-3A manufactured by Tosoh Finechem Co., Ltd .: 9 mmol as aluminum), 2 ml of a toluene solution in which 1.28 mg of ethylenebis (tetrahydroindenyl) zirconium dichloride was dissolved, and a stabilizer solution described in Table 1 were sequentially added. The inside of the autoclave was replaced with a propylene atmosphere, a pressure of 6 kgf / cm ² G was applied with propylene, and a polymerization reaction was performed at 50 ° C. for 1 hour. After 10 ml of ethanol was added to the reaction solution to stop the polymerization reaction, the solvent was removed under reduced pressure, and then the polymer was dried at 60 ° C. in a vacuum for 24 hours to obtain polypropylene powder.

(Manufacture of non-woven fabric)
After adding and mixing 0.05 parts by mass of calcium stearate to 100 parts by mass of the above polypropylene powder, a single-screw extruder (apparatus: Laboplast Mill Micro manufactured by Toyo Seiki Seisakusho Co., Ltd., extrusion temperature 250 ° C., screw rotation speed) Kneading at 50 rpm), spinning by a melt blow method using a spinning machine (nozzle (0.45 mmΦ, nozzle 30 holes, discharge amount 1.0 g / min, air supply pressure: 0.7 kg / cm ² )), 30 g / m A nonwoven fabric with a fabric weight of ² was produced.

[Comparative Examples 2 to 4]
In the polymerization of Example 1, polypropylene powder was obtained in the same procedure as in Example 1 except that the stabilizer solution was not added at the time of polymerization but was added at the time of granulation.

１）ＡＯ−１：３−（３，５−ジ第三ブチル−４−ヒドロキシフェニル）−Ｎ−オクタデシルプロピオンアミド
２）ＡＯ−２：テトラキス〔メチレン−３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート〕メタン
３）Ｐ−１：トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト
４）重合時：オレフィン系モノマーの重合時に安定剤を添加
５）造粒時：オレフィン系モノマーの重合後、安定剤を添加・混合し、２５０℃で混練して造粒した。
６）添加剤の溶出量比とは、比較例１の酸化防止剤の溶出量を１としたときの、各配合における酸化防止剤の溶出量の比率を表す。

1) AO-1: 3- (3,5-Ditert-butyl-4-hydroxyphenyl) -N-octadecylpropionamide 2) AO-2: Tetrakis [methylene-3- (3,5-di-t- Butyl-4-hydroxyphenyl) propionate] methane 3) P-1: Tris (2,4-di-t-butylphenyl) phosphite 4) During polymerization: Add stabilizer during polymerization of olefinic monomer 5) Granulation Time: After polymerization of the olefin monomer, a stabilizer was added and mixed, and kneaded at 250 ° C. to granulate.
6) The elution amount ratio of the additive represents the ratio of the elution amount of the antioxidant in each formulation when the elution amount of the antioxidant of Comparative Example 1 is 1.

From Comparative Examples 1 and 2 above, those containing a total of 0.1 parts by weight of stabilizers were free of yarn breakage and sheet pinholes, and were able to produce a stabilized nonwoven fabric, but when the nonwoven fabric was exposed to ethanol The additive eluted. Moreover, in the compounding quantity of 0.1 mass part, the influence was not seen about the difference in the addition method at the time of superposition | polymerization and granulation.
Moreover, from Comparative Examples 3 and 4, when the total amount of the stabilizer was reduced to 0.12 parts by mass, elution of the additive by ethanol was suppressed, but the stabilization effect was impaired, and the yarn was broken. And sheet pinholes frequently occur, making it difficult to stably produce nonwoven fabrics. Also, in the dissolution test, it was confirmed that the amount of resin dissolution was large and the problem was great from the viewpoint of hygiene.

On the other hand, the nonwoven fabric produced by the present invention from Examples 1 and 2 is stable even when the nonwoven fabric is exposed to a solvent, and there is no elution of stabilizers and resins, and there is no occurrence of yarn breakage or sheet pinhole. The nonwoven fabric could be manufactured.
Since the nonwoven fabric obtained by the present invention is excellent in hygiene, it can be suitably used in a filter for filtration and the like.

Claims (6)

A method for producing a nonwoven fabric comprising producing a nonwoven fabric from at least one polyolefin,
Before or during the polymerization of the monomer having an ethylenically unsaturated bond, the phenol-based antioxidant represented by the following general formula (1) is added to organoaluminum with respect to 100 parts by mass of the monomer having the ethylenically unsaturated bond. Add 0.001 to 0.03 parts by mass and 0.001 to 0.04 parts by mass of a phosphorus-based antioxidant to the catalyst system, polymerization system or piping to polymerize the monomer. A method for producing a nonwoven fabric, comprising using a polyolefin obtained by

(In the formula, R ₁ and R ₂ each independently represent a hydrogen atom, an optionally branched alkyl group having 1 to 5 carbon atoms, or an arylalkyl group having 7 to 9 carbon atoms, R is an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted cycloalkyl group having 3 to 12 carbon atoms, and an optionally substituted carbon atom having 6 to 18 carbon atoms. Represents an aryl group of   The method for producing a nonwoven fabric according to claim 1, wherein the organoaluminum compound is trialkylaluminum.   A nonwoven fabric obtained by the method for producing a nonwoven fabric according to claim 1 or 2.   A sanitary cloth, a filter cloth, or a filter comprising the nonwoven fabric according to claim 3. A method for producing a nonwoven fabric comprising producing a nonwoven fabric from at least one polyolefin,
Before or during the polymerization of the monomer having an ethylenically unsaturated bond, the phenol-based antioxidant represented by the following general formula (1) is added to organoaluminum with respect to 100 parts by mass of the monomer having the ethylenically unsaturated bond. 0.001 to 0.03 parts by mass and 0.001 to 0.04 parts by mass of a phosphorus-based antioxidant added to the catalyst system, polymerization system or piping to polymerize the monomer Obtaining a polyolefin, and
A process for producing a nonwoven fabric using the obtained polyolefin,
A method for producing a nonwoven fabric, comprising:

(In the formula, R ₁ and R ₂ each independently represent a hydrogen atom, an optionally branched alkyl group having 1 to 5 carbon atoms, or an arylalkyl group having 7 to 9 carbon atoms, R is an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted cycloalkyl group having 3 to 12 carbon atoms, and an optionally substituted carbon atom having 6 to 18 carbon atoms. Represents an aryl group of   The method for producing a nonwoven fabric according to claim 5, wherein the organoaluminum compound is trialkylaluminum.