WO2017221455A1 - Procédé de production de coagulum - Google Patents

Procédé de production de coagulum Download PDF

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Publication number
WO2017221455A1
WO2017221455A1 PCT/JP2017/005661 JP2017005661W WO2017221455A1 WO 2017221455 A1 WO2017221455 A1 WO 2017221455A1 JP 2017005661 W JP2017005661 W JP 2017005661W WO 2017221455 A1 WO2017221455 A1 WO 2017221455A1
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WO
WIPO (PCT)
Prior art keywords
urethane resin
mass
aqueous
aqueous urethane
coagulum
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2017/005661
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English (en)
Japanese (ja)
Inventor
智博 鉄井
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DIC Corp
Original Assignee
DIC Corp
Dainippon Ink and Chemicals Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by DIC Corp, Dainippon Ink and Chemicals Co Ltd filed Critical DIC Corp
Priority to JP2017528602A priority Critical patent/JP6183577B1/ja
Publication of WO2017221455A1 publication Critical patent/WO2017221455A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/82—Post-polymerisation treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C08J3/16—Powdering or granulating by coagulating dispersions
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes

Definitions

  • the present invention relates to a method for producing a solidified material that can be used for producing, for example, a leather-like sheet.
  • the aqueous urethane resin composition in which the urethane resin is dispersed in an aqueous medium can reduce the burden on the environment as compared with conventional organic solvent-based urethane resin compositions, so that leather-like sheets such as artificial leather and synthetic leather, In recent years, it has been used favorably as a material for producing coating agents, adhesives and the like.
  • the liquid composition of the urethane resin once decreases in viscosity by heating, and the resin tends to adhere to the fiber intersection due to capillary phenomenon, and the resin restrains the fiber. It was pointed out that the resulting film was inferior in flexibility and flexibility and easily damaged.
  • the present invention provides a method for producing a coagulated product obtained by coagulating an aqueous urethane resin composition with a nonmetallic coagulant aqueous solution at 15 ° C. or higher.
  • a solidified product having excellent texture can be obtained.
  • the coagulation bath waste liquid can be easily treated, contributing to the reduction of manufacturing costs. it can.
  • a coagulant containing metal ions is not used, rusting or deterioration of the production apparatus when producing a coagulated product is not caused. Therefore, the solidified product obtained by the production method of the present invention can be suitably used for production of gloves, paints, leather-like sheets and the like.
  • the electron micrograph of sectional drawing of the fiber base material which has the solidified material obtained in Example 1 is shown (magnification 200 times).
  • the electron micrograph of the cross-sectional view of the fiber base material which has the solidified material obtained by the comparative example 1 is shown (magnification 200 times).
  • the method for producing a coagulated product according to the present invention is characterized in that an aqueous urethane resin composition is coagulated with a nonmetallic coagulant aqueous solution at 15 ° C. or higher.
  • the viscosity of the aqueous urethane resin composition and the coagulation speed are fast, and because of the ability to suppress resin fiber adhesion / restraint due to capillary phenomenon, an even better work cloth texture is obtained.
  • water used for the non-metal coagulant aqueous solution for example, ion exchange water, distilled water, tap water, or the like can be used. These waters may be used alone or in combination of two or more.
  • the solidified urethane resin is filled up to the inside of the fiber base material, and the state where the solidified material is entangled with the fiber base material is formed. It can be suitably used as an impregnated layer.
  • a urethane coagulated material layer is formed on the surface of the fiber substrate and in the vicinity of the surface, and therefore, it can be suitably used for manufacturing gloves.
  • the fiber base material having a solidified urethane resin can be immersed in running water for 10 minutes to 2 hours after the impregnation and solidification to wash away unnecessary coagulants.
  • the fibrous base material is used as the fibrous base material.
  • a method of directly impregnating the coagulation bath containing the mixture and squeezing excess with a mangle or the like can be mentioned.
  • the impregnation time is, for example, in the range of 1 to 30 minutes.
  • the impregnated base material is taken out and further immersed in the aqueous urethane resin composition, so that the urethane resin in the aqueous urethane resin composition is solidified, and the urethane solidified material is formed in the surface layer and the vicinity of the surface layer of the fiber base material.
  • a fiber substrate on which a layer is formed is obtained.
  • the impregnation / solidification time at this time is, for example, in the range of 1 to 30 minutes.
  • the fiber base material having a solidified urethane resin can be immersed in running water for 10 minutes to 2 hours after the impregnation and solidification to wash away unnecessary coagulants.
  • aqueous urethane resin composition that can be used in the present invention, for example, those containing an aqueous urethane resin (A) and an aqueous medium (B) can be used.
  • the aqueous urethane resin (A) can be dispersed in an aqueous medium (B) described later.
  • the aqueous urethane resin having a hydrophilic group such as an anionic group, a cationic group, or a nonionic group
  • An aqueous urethane resin or the like that is forcibly dispersed in the aqueous medium (B) with an emulsifier can be used.
  • These aqueous urethane resins (A) may be used alone or in combination of two or more.
  • a water-based urethane resin having a hydrophilic group it is preferable to use a water-based urethane resin having a hydrophilic group, the solidification property of the non-metal coagulant is further improved by the electric double layer compression effect, and the fiber group. It is more preferable to use an aqueous urethane resin having an anionic group from the viewpoint that the urethane resin is easily filled and entangled into the material and the texture is further improved.
  • Examples of a method for obtaining the aqueous urethane resin having an anionic group include a method using, as a raw material, one or more compounds selected from the group consisting of a compound having a carboxyl group and a compound having a sulfonyl group.
  • Examples of the compound having a carboxyl group include 2,2′-dimethylolpropionic acid, 2,2′-dimethylolbutanoic acid, 2,2′-dimethylolbutyric acid, 2,2′-dimethylolpropionic acid, , 2'-valeric acid and the like can be used. These compounds may be used alone or in combination of two or more.
  • Examples of the compound having a sulfonyl group include 3,4-diaminobutanesulfonic acid, 3,6-diamino-2-toluenesulfonic acid, 2,6-diaminobenzenesulfonic acid, N- (2-aminoethyl)- 2-Aminoethylsulfonic acid or the like can be used. These compounds may be used alone or in combination of two or more.
  • the carboxyl group and sulfonyl group may be partially or completely neutralized with a basic compound in the aqueous urethane resin composition.
  • a basic compound include organic amines such as ammonia, triethylamine, pyridine, and morpholine; alkanolamines such as monoethanolamine and dimethylethanolamine; metal base compounds including sodium, potassium, lithium, calcium, and the like. Can do.
  • Examples of the method for obtaining the aqueous urethane resin having a cationic group include a method using one or more compounds having an amino group as a raw material.
  • Examples of the compound having an amino group include compounds having primary and secondary amino groups such as triethylenetetramine and diethylenetriamine; N-alkyldialkanolamines such as N-methyldiethanolamine and N-ethyldiethanolamine, and N-methyl.
  • a compound having a tertiary amino group such as N-alkyldiaminoalkylamine such as diaminoethylamine and N-ethyldiaminoethylamine can be used. These compounds may be used alone or in combination of two or more.
  • Examples of the method for obtaining the aqueous urethane resin having a nonionic group include a method using one or more compounds having an oxyethylene structure as a raw material.
  • Examples of the compound having an oxyethylene structure include polyether polyols having an oxyethylene structure such as polyoxyethylene glycol, polyoxyethylene polyoxypropylene glycol, and polyoxyethylene polyoxytetramethylene glycol. These compounds may be used alone or in combination of two or more.
  • Examples of the emulsifier that can be used in obtaining the aqueous urethane resin that is forcibly dispersed in the aqueous medium (B) include polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styryl phenyl ether, Nonionic emulsifiers such as polyoxyethylene sorbitol tetraoleate and polyoxyethylene / polyoxypropylene copolymer; fatty acid salt such as sodium oleate, alkyl sulfate ester salt, alkylbenzene sulfonate, alkyl sulfosuccinate, naphthalene sulfonate Anionic emulsifiers such as salts, polyoxyethylene alkyl sulfates, alkane sulfonate sodium salts, sodium alkyl diphenyl ether sulfonates; alkyl amine salts, alkyl trimethyl Am
  • the content of the aromatic ring of the aqueous urethane resin (A) is preferably in the range of 0.8 to 8 mol / kg, more preferably in the range of 1 to 6 mol / kg.
  • aromatic polyisocyanate examples include phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, carbodiimidized diphenylmethane polyisocyanate, and the like. These polyisocyanates may be used alone or in combination of two or more. Among these, it is preferable to use diphenylmethane diisocyanate from the viewpoint of easy availability of raw materials and texture.
  • polyisocyanates examples include hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, and dimer acid diisocyanate.
  • An aliphatic or alicyclic polyisocyanate such as norbornene diisocyanate can be used.
  • These polyisocyanates may be used alone or in combination of two or more.
  • chain extender (a3) examples include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 1,2-cyclohexanediamine, 1, Amino groups such as 3-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4′-dicyclohexylmethanediamine, 3,3′-dimethyl-4,4′-dicyclohexylmethanediamine, 1,4-cyclohexanediamine, hydrazine, etc.
  • Chain extender having: ethylene glycol, diethylene recall, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, saccharo Scan, glycol, glycerine, sorbitol, bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, and the like can be used a chain extender having a hydroxyl group such as trimethylol propane. These chain extenders may be used alone or in combination of two or more. Among these, it is preferable to use a chain extender having a hydroxyl group from the viewpoint that oil grip properties and chemical resistance can be further improved.
  • the aqueous urethane resin (A) When the aqueous urethane resin (A) is produced, it is preferable to deactivate the isocyanate group remaining in the aqueous urethane resin (A). When the isocyanate group is deactivated, it is preferable to use an alcohol having one hydroxyl group such as methanol. The amount of the alcohol used is preferably in the range of 0.001 to 10 parts by mass with respect to 100 parts by mass of the aqueous urethane resin (A).
  • the mass ratio [(A) / (B)] between the aqueous urethane resin (A) and the aqueous medium (B) is preferably in the range of 10/80 to 70/30 from the viewpoint of workability.
  • the range of 20/80 to 60/40 is more preferable.
  • the amount used in the case of using the emulsifier is preferably in the range of 0.1 to 30 parts by mass with respect to 100 parts by mass of the aqueous urethane resin (A) from the viewpoint of water dispersion stability and texture. A range of 1 to 10 parts by mass is more preferable.
  • the aqueous urethane resin composition used in the present invention is more easily coagulated by the coagulant, more easily filled and entangled inside the fiber base material, further improved in texture, and water dispersion stability.
  • Water-based urethane resin containing an anionic group obtained by reacting an aromatic polyisocyanate, a polyol and a chain extender (A), an aqueous medium (B), and a nonionic emulsifier It is preferable to use a resin composition.
  • Synthesis Example 2 Preparation of Aqueous Urethane Resin Composition (X-2) Polyether polyol (“PTMG2000” Mitsubishi Kasei Co., Ltd.) in the presence of 3,281 parts by weight of methyl ethyl ketone and 0.1 part by weight of stannous octylate Manufactured, number average molecular weight: 2,000) 1,000 parts by mass, 17 parts by mass of 2,2′-dimethylolpropionic acid, 47 parts by mass of ethylene glycol, and 344 parts by mass of diphenylmethane diisocyanate have a solution viscosity of 20, After reacting at 70 ° C.
  • aqueous urethane resin composition (X-3) having a nonvolatile content of 40% by mass.
  • a methyl ethyl ketone solution of urethane prepolymer (X′-4) having an isocyanate group at the terminal was obtained.
  • phase inversion was performed.
  • a urethane resin composition (X-4) having a nonvolatile content of 40% by mass.
  • Example 1 100 parts by mass of the aqueous urethane resin composition (X-1) obtained in Synthesis Example 1, 5 parts by mass of a thickener (“Borch Gel L75N” manufactured by Borcher), a carbodiimide crosslinking agent (“Carbodilite SV manufactured by Nisshinbo Chemical Co., Ltd.) ⁇ 02 ”) 4 parts by mass and 200 parts by mass of ion-exchanged water were stirred with a mechanical mixer at 2,000 rpm for 2 minutes, and then deaerated with a vacuum deaerator to prepare a blended solution.
  • a thickener (“Borch Gel L75N” manufactured by Borcher)
  • Carbodiimide crosslinking agent (“Carbodilite SV manufactured by Nisshinbo Chemical Co., Ltd.) ⁇ 02 ”
  • the blended solution was solidified by immersing the non-woven fabric containing the blended solution in a coagulation bath of 5 mass% ammonium sulfate aqueous solution heated to 60 ° C. for 3 minutes. Finally, it was dried with a hot air dryer at 100 ° C. for 30 minutes to obtain a fiber base material having a coagulum.
  • Examples 2 to 4 A fiber base material having a coagulum was obtained in the same manner as in Example 1 except that the type of the aqueous urethane resin composition used was changed as shown in the table.
  • Example 5 A fiber base material having a coagulated product was obtained in the same manner as in Example 1 except that the temperature of the coagulation bath was changed to 22 ° C.
  • Example 2 In Example 1, a fiber base material was used in the same manner as in Example 1 except that a coagulation bath of 5 mass% ammonium sulfate aqueous solution heated to 60 ° C was used instead of a coagulation bath of 5 mass% ammonium sulfate aqueous solution at 10 ° C. However, the aqueous urethane resin composition (X-1) did not coagulate.
  • Examples 1 to 5 according to the present invention can provide a solidified product having an excellent texture. Further, as can be confirmed in FIG. 1, it was found that a solidified product of urethane resin was filled up to the inside of the fiber base material, and a state in which the solidified material was entangled with the fiber base material was formed.
  • Comparative Example 1 is a form in which coagulation was performed by thermal coagulation, but the texture was poor. Further, as can be confirmed in FIG. 2, the urethane resin was not filled up to the inside of the fiber base material, and entanglement of the fiber base material was not confirmed.
  • Comparative Example 2 was an embodiment in which the coagulation bath was not heated and was used at 10 ° C., but did not coagulate.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

Le but de la présente invention est de fournir un procédé de production d'un coagulum caractérisé en ce qu'il est obtenu par coagulation d'une composition aqueuse de résine d'uréthane à l'aide d'une solution aqueuse d'un agent coagulant non métallique, laquelle est chauffée à 40 °C ou plus. La présente invention traite le problème consistant à fournir un procédé de production qui permette d'obtenir un coagulum ayant une excellente texture sans utiliser de solvant organique. Le procédé de production selon la présente invention est capable de produire un coagulum d'une excellente texture. De plus, ledit procédé de production n'utilise pas de solvant organique dans un bain de coagulation, ce qui lui évite de poser un risque d'exposition à des substances volatiles nocives ou de diffusion de celles-ci dans l'environnement, et il permet à un liquide résiduaire du bain de coagulation d'être traité par un procédé simplifié, ce qui peut contribuer à réduire les coûts de production. En outre, étant donné que ce procédé de production n'utilise aucun agent coagulant qui contient du métal, il n'induit donc pas de rouille ni de détérioration de l'appareil de production utilisé pour produire le coagulum. Ainsi, le coagulum obtenu par le procédé de production selon la présente invention peut être utilisé de manière appropriée pour la production de gants, de matériaux de revêtement, de feuilles de type cuir, etc.
PCT/JP2017/005661 2016-06-20 2017-02-16 Procédé de production de coagulum Ceased WO2017221455A1 (fr)

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JP2017528602A JP6183577B1 (ja) 2016-06-20 2017-02-16 凝固物の製造方法

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JP2016-121665 2016-06-20
JP2016121665 2016-06-20

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021251053A1 (fr) * 2020-06-11 2021-12-16 Dic株式会社 Procédé de fabrication de produit coagulé
CN113825800A (zh) * 2019-02-25 2021-12-21 Dic株式会社 氨基甲酸酯树脂水分散体、皮革片及皮革片的制造方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4743176B1 (fr) * 1969-07-19 1972-10-31
JPS5035303A (fr) * 1973-07-30 1975-04-04
JPS5234661B1 (fr) * 1971-09-23 1977-09-05
JPS5360990A (en) * 1976-11-11 1978-05-31 Bayer Ag Preparation of water dispersable polyurethane
JPS55112312A (en) * 1979-02-20 1980-08-29 Kohjin Co Ltd Production of fibrous binder
JPH08120181A (ja) * 1994-10-24 1996-05-14 Nisshin Kogyo Kk 吹付け遮水用常温凝固性組成物
JP2004249564A (ja) * 2003-02-19 2004-09-09 Nippon Paper Industries Co Ltd インクジェット記録用キャストコート紙
JP2013217006A (ja) * 2012-03-15 2013-10-24 Nicca Chemical Co Ltd 皮革用材の製造方法及び皮革用材

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4743176B1 (fr) * 1969-07-19 1972-10-31
JPS5234661B1 (fr) * 1971-09-23 1977-09-05
JPS5035303A (fr) * 1973-07-30 1975-04-04
JPS5360990A (en) * 1976-11-11 1978-05-31 Bayer Ag Preparation of water dispersable polyurethane
JPS55112312A (en) * 1979-02-20 1980-08-29 Kohjin Co Ltd Production of fibrous binder
JPH08120181A (ja) * 1994-10-24 1996-05-14 Nisshin Kogyo Kk 吹付け遮水用常温凝固性組成物
JP2004249564A (ja) * 2003-02-19 2004-09-09 Nippon Paper Industries Co Ltd インクジェット記録用キャストコート紙
JP2013217006A (ja) * 2012-03-15 2013-10-24 Nicca Chemical Co Ltd 皮革用材の製造方法及び皮革用材

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113825800A (zh) * 2019-02-25 2021-12-21 Dic株式会社 氨基甲酸酯树脂水分散体、皮革片及皮革片的制造方法
WO2021251053A1 (fr) * 2020-06-11 2021-12-16 Dic株式会社 Procédé de fabrication de produit coagulé
JP7070805B1 (ja) * 2020-06-11 2022-05-18 Dic株式会社 凝固物の製造方法
CN115461507A (zh) * 2020-06-11 2022-12-09 Dic株式会社 凝固物的制造方法
CN115461507B (zh) * 2020-06-11 2024-03-19 Dic株式会社 凝固物的制造方法

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