WO2017104267A1 - Composition et feuille de polyuréthane - Google Patents

Composition et feuille de polyuréthane Download PDF

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Publication number
WO2017104267A1
WO2017104267A1 PCT/JP2016/081534 JP2016081534W WO2017104267A1 WO 2017104267 A1 WO2017104267 A1 WO 2017104267A1 JP 2016081534 W JP2016081534 W JP 2016081534W WO 2017104267 A1 WO2017104267 A1 WO 2017104267A1
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WIPO (PCT)
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mass
polyurethane
parts
sheet
polyurethane composition
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PCT/JP2016/081534
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English (en)
Japanese (ja)
Inventor
優紀 小松崎
友理 藤井
綱島　啓次
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DIC Corp
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DIC Corp
Dainippon Ink and Chemicals Co Ltd
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Priority to JP2017556398A priority Critical patent/JP6350764B2/ja
Publication of WO2017104267A1 publication Critical patent/WO2017104267A1/fr
Anticipated expiration legal-status Critical
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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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers

Definitions

  • the present invention relates to a polyurethane composition from which a sheet excellent in step following property, substrate adhesion, sheet holding property, and stain resistance can be obtained.
  • Silicon films having excellent heat resistance are widely used in heat conduction sheets, surface protection films, and the like used for electronic devices and electronic parts such as displays, LED lighting, transistors, and capacitors.
  • the sheet processing suitability required for the sheet for example, in the case of punching or slit processing, the cured product layer of the polyurethane composition is peeled off from the substrate by pressing of the processing blade, the paste powder of the cured product layer or Excellent base material adhesion that does not generate residue, and the cured product layer does not stick to the processing blade or the cured product layer protrudes from the end surface of the sheet, and the punched sheet and the sheet outer periphery remain bonded. It is required to have excellent sheet holding properties to prevent the above. Although improving the sheet processing suitability can reduce the number of cleanings of the processing blade and improve the yield and work efficiency, it is difficult to achieve both substrate adhesion and sheet retention. It was.
  • the problem to be solved by the present invention is to provide a polyurethane composition from which a sheet having excellent step following property, substrate adhesion, sheet retention, and stain resistance can be obtained.
  • the present invention provides a bifunctional polyol (a-1) and a compound (a-2) having three hydroxyl groups in an equivalent ratio [(a-1) / (a-2)] in the range of 0.7 to 100.
  • a polyurethane composition comprising a polyurethane (A) having a hydroxyl group, a crosslinking agent (B), and an organic solvent (C) using the contained polyol (a) as a raw material is provided.
  • this invention provides the sheet
  • the sheet formed from the polyurethane composition of the present invention is excellent in step followability, substrate adhesion, sheet retention, and stain resistance.
  • the polyurethane composition of the present invention comprises a bifunctional polyol (a-1) and a compound (a-2) having three hydroxyl groups in an equivalent ratio [(a-1) / (a-2)] of 0.7 to
  • a polyol (a) contained in a range of 100 is used as a raw material, and contains a polyurethane (A) having a hydroxyl group, a crosslinking agent (B), and an organic solvent (C).
  • a bifunctional polyol (a-1) and a compound (a-2) having three hydroxyl groups are used as raw materials, and their equivalent ratio [(a-1) / (a-2 )] Is in the range of 0.7 to 100.
  • the equivalent ratio is less than 0.7, the cohesive strength of the polyurethane itself is too high and / or the distance between crosslinks is too short, so that the flexibility and elongation of the sheet is insufficient, and the desired step following property is achieved. If the substrate adhesion is not obtained, and if it exceeds 100, the distance between crosslinks becomes too large, the sheet holding property cannot be obtained, or the adhesive residue or transfer due to the increase in adhesive force during the durability test And the desired stain resistance cannot be obtained.
  • the equivalence ratio is preferably in the range of 1 to 100, more preferably in the range of 1 to 80, since further excellent processability and stain resistance can be obtained.
  • the equivalent ratio is a normal equivalent ratio.
  • the bifunctional polyol (a-1) and the compound (a-2) having three hydroxyl groups are charged all at once, the polyurethane (A) is produced. Shows the equivalent ratio calculated from the functional group equivalent of the bifunctional polyol (a-1) / functional group equivalent of the compound (a-2) having three hydroxyl groups.
  • the bifunctional polyol (a-1) and the compound (a-2) having three hydroxyl groups are reacted stepwise, for example, first, the bifunctional polyol (a-1) and a polyisocyanate (a) described later are used.
  • the equivalent ratio calculated from each [NCO / OH] described later is shown.
  • polyurethane (A) examples include a polyol (a) containing the bifunctional polyol (a-1) and a compound (a-2) having three hydroxyl groups and a polyisocyanate (a-3). ) And the reaction product can be used.
  • bifunctional polyol (a-1) examples include polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxytetramethylene glycol, and polyoxypropylene.
  • Polyether diols such as polyoxytetramethylene glycol; polycarbonate diol, polyester diol, acrylic diol, polybutadiene diol, hydrogenated polybutadiene diol, and the like can be used. These bifunctional polyols may be used alone or in combination of two or more.
  • polyether diol in applications where transparency is required for the sheet, in order to suppress haze generation derived from the crystallinity of the polyol, it is relatively versatile, and from the viewpoint of easy selection of a low glass transition temperature product, polyether diol, It is preferable to use one or more polyols selected from the group consisting of polycarbonate diols and polyester diols.
  • the number average molecular weight of the bifunctional polyol (a-1) is preferably in the range of 100 to 20,000, more preferably in the range of 150 to 10,000, from the viewpoint of obtaining even better cohesion. preferable.
  • the number average molecular weight of the bifunctional polyol (a-1) is a value measured by the gel permeation chromatography (GPC) method under the following conditions.
  • Measuring device High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were connected in series. "TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000” (7.8 mm ID x 30 cm) x 1 "TSKgel G3000” (7.8 mm ID x 30 cm) x 1 “TSKgel G2000” (7.8 mm ID ⁇ 30 cm) ⁇ 1 detector: RI (differential refractometer) Column temperature: 40 ° C Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 mL / min Injection amount: 100 ⁇ L (tetrahydrofuran solution with a sample concentration of 0.4 mass%) Standard sample: A calibration curve was prepared using the following standard polystyrene.
  • Examples of the compound (a-2) having three hydroxyl groups include propylene oxide adducts such as an adduct of glycerin and propylene oxide, an adduct of trimethylolpropane and propylene oxide; propylene using glycerin as an initiator.
  • the number average molecular weight of the compound (a-2) having three hydroxyl groups is in the range of 1,500 to 10,000 from the viewpoint of obtaining good flexibility, substrate adhesion, and sheet retention. It is preferably in the range of 2,000 to 5,000.
  • the number average molecular weight of the compound (a-2) having three hydroxyl groups is a value obtained by measurement in the same manner as in the bifunctional polyol (a-1).
  • the polyol (a) may be a compound having four or more hydroxyl groups or a so-called chain extension, if necessary.
  • An agent or the like may be used in combination.
  • polyisocyanate (a-3) examples include aromatic polyisocyanates such as xylylene diisocyanate, phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate; hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, 4 Aliphatic or alicyclic polyisocyanates such as 4,4'-dicyclohexylmethane diisocyanate and tetramethylxylylene diisocyanate can be used. These polyisocyanates may be used alone or in combination of two or more.
  • both are reacted so that the molar ratio of the hydroxyl group of the polyol (a) is excessive with respect to the molar ratio of the isocyanate group of the polyisocyanate (a-3).
  • a method is mentioned.
  • the polyol (a) may be charged all at once or may be charged in two or more times while controlling the reaction.
  • the bifunctional polyol (a-1) and the polyisocyanate (a-3) are first added. And the like, and then a method of reacting the compound (a-2) having three hydroxyl groups may be used.
  • the molar ratio (NCO / OH) between the hydroxyl group of the polyol (a) and the isocyanate group of the polyisocyanate (a-3) is determined as follows. From the viewpoint of mechanical strength, the range is preferably from 0.3 to 0.99, and more preferably from 0.5 to 0.99.
  • the weight average molecular weight of the polyurethane (A) is preferably in the range of 10,000 to 700,000, and preferably in the range of 30,000 to 500,000 from the viewpoint that both flexibility and mechanical strength can be achieved at a high level. A range is more preferable.
  • the weight average molecular weight of the polyurethane (A) is a value measured in the same manner as the number average molecular weight of the bifunctional polyol (a-1).
  • the content of the hydroxyl group in the polyurethane (A) the crosslink density with the crosslinking agent (B) described later and the distance between crosslinks can be optimized, so that even better substrate adhesion and sheet retention can be obtained.
  • the range is preferably 0.005 to 0.3 mol / kg, more preferably 0.01 to 0.28 mol / kg, and particularly preferably 0.04 to 0.25 mol / kg.
  • content of the hydroxyl group in the said polyurethane (A) shows content of the hydroxyl group which occupies in the said raw material with respect to the total mass of each raw material which comprises the said polyurethane (A).
  • the content of the urethane bond in the polyurethane (A) the cohesive force can be controlled, and more excellent substrate adhesion, sheet retention, and stain resistance can be obtained.
  • the range is 0.2 to 10 mol / kg, more preferably 0.4 to 5 mol / kg, and particularly preferably 0.5 to 5 mol / kg.
  • content of the urethane bond in the said polyurethane (A) shows content of the urethane bond structure which occupies in the said raw material with respect to the total mass of each raw material which comprises the said polyurethane (A).
  • crosslinking agent (B) for example, a polyisocyanate crosslinking agent, an epoxy crosslinking agent, a melamine crosslinking agent, or the like can be used. These crosslinking agents may be used alone or in combination of two or more. Among these, by reacting with the hydroxyl group of the polyurethane (A) to form a three-dimensional crosslink, good mechanical strength, step following ability, substrate adhesion, sheet retention, and stain resistance can be obtained. From the viewpoint, it is preferable to use a polyisocyanate crosslinking agent.
  • polyisocyanate crosslinking agent examples include tolylene diisocyanate, chlorophenylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, and xylylene diisocyanate; hexamethylene diisocyanate trimethylolpropane Adduct, trimethylolpropane adduct of tolylene diisocyanate, trimethylolpropane adduct of isophorone diisocyanate, trimethylolpropane adduct of xylylene diisocyanate, isocyanurate of hexamethylene diisocyanate, nurate of tolylene diisocyanate, isophorone di Isocyanurate of isocyanate, and the like can be used isocyanurate of xylylene
  • the amount of the crosslinking agent (B) used is 0. 0 parts by mass with respect to 100 parts by mass of the polyurethane (A) (solid content) from the viewpoint that the step following ability, the substrate adhesion and the sheet retention can be achieved at a high level.
  • the range is preferably from 01 to 20 parts by mass, more preferably from 0.05 to 15 parts by mass, and still more preferably from 0.1 to 10 parts by mass.
  • the organic solvent (C) is used for improving the production stability of the polyurethane (A) and the coating property of the polyurethane composition, and examples thereof include esters such as ethyl acetate, methyl acetate, and butyl acetate.
  • Solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone; Aliphatic hydrocarbon solvent such as heptane, hexane, cyclohexane, methylcyclohexane; Aromatic hydrocarbon solvent such as toluene, o-xylene, m-xylene, p-xylene Alcohol solvents such as methanol, ethanol, isopropyl alcohol, isobutanol, sec-butanol, and tertiary butanol can be used. These organic solvents may be used alone or in combination of two or more.
  • the amount of the organic solvent (C) used is preferably in the range of 20 to 200 parts by weight, preferably in the range of 40 to 180 parts by weight, based on 100 parts by weight of the polyurethane (A), from the viewpoint of coating properties. Is more preferable.
  • the polyurethane composition of the present invention contains the polyurethane (A), the crosslinking agent (B), and the organic solvent (C) as essential components, and further contains other additives as necessary. Also good.
  • additives examples include carbodiimide compounds, antioxidants, plasticizers, rust inhibitors, thixotropic agents, dispersants, sensitizers, urethanization catalysts, polymerization inhibitors, leveling agents, tackifiers, A foam stabilizer or the like can be used. These additives may be used alone or in combination of two or more. Among these, it is preferable to contain a carbodiimide compound from the viewpoint that much more excellent stain resistance can be obtained.
  • carbodiimide compound examples include N, N′-dicyclohexylcarbodiimide, N, N′-diisopropylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide, and N- [3- (dimethylamino) propyl].
  • carbodiimide compounds may be used alone or in combination of two or more. Among these, it is preferable to use a carbodiimide compound having an isocyanate group because it reacts with the hydroxyl group of the polyurethane (A) to obtain further excellent stain resistance.
  • carbodiimide compound examples include “Carbodilite V-02”, “Carbodilite V-02-L2”, “Carbodilite V-04”, “Carbodilite V-05”, “Carbodilite V-07”, “Carbodilite V-09”. “Carbodilite E-01”, “Carbodilite E-02”, “Carbodilite E-03A”, “Carbodilite E-04” (manufactured by Nisshinbo Chemical Co., Ltd.) and the like are commercially available.
  • the amount used in the case of using the carbodiimide compound is preferably in the range of 0.1 to 7 parts by mass with respect to 100 parts by mass of the polyurethane (A) from the viewpoint of obtaining further excellent stain resistance.
  • the range of 0.5 to 5 parts by mass is more preferable.
  • the crosslinking agent (B) is added to the mixture in which the polyurethane (A) is dissolved in the organic solvent (C).
  • the method of adding an agent and mixing is mentioned.
  • Examples of the method of forming a sheet from the polyurethane composition of the present invention include a method of applying the polyurethane composition onto a plastic substrate, and drying and curing.
  • plastic substrate examples include polyester such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate, polyolefin, polyacrylate, polyvinyl chloride, polyethylene, polypropylene ethylene vinyl alcohol, polyurethane, polyamide, and polyimide. Sheet or film can be used.
  • the surface of these plastic substrates may be subjected to mold release treatment, antistatic treatment, corona treatment and the like. Further, the thickness of the plastic substrate is, for example, in the range of 10 to 200 ⁇ m.
  • Examples of the method of applying the polyurethane composition to the plastic substrate include a coating method using a roll coater, a gravure coater, a reverse coater, a spray coater, an air knife coater, a die coater, or the like.
  • the thickness of the sheet after drying with the organic solvent (C) is, for example, in the range of 5 to 100 ⁇ m.
  • Examples of the method of drying the polyurethane composition after coating the polyurethane composition on the plastic substrate include a method of drying at 50 to 120 ° C. for 30 seconds to 30 minutes. Further, after drying, aging may be performed at a temperature of, for example, 30 ° C. to 50 ° C. in order to accelerate the curing reaction.
  • the polyurethane composition of the present invention has excellent step following ability, substrate adhesion, sheet retention, and contamination resistance. Therefore, the sheet
  • Example 1 In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and a thermometer, polyoxypropylene glycol (number average molecular weight; 2,000, hereinafter abbreviated as “PPG2000”) 1,550 parts by mass, hexamethylene diisocyanate ( (Hereinafter abbreviated as “HDI”) is 165 parts by mass, dioctyltin dilaurate is 0.03 parts by mass, polyoxyethylene polyoxypropylene triol (number average molecular weight; 3,000, hereinafter abbreviated as “EOPO3000”).
  • PPG2000 polyoxypropylene glycol
  • HDI hexamethylene diisocyanate
  • EOPO3000 polyoxyethylene polyoxypropylene triol
  • Example 2 In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and a thermometer, 990 parts by mass of polyoxypropylene glycol (number average molecular weight; 2,000, hereinafter abbreviated as “PPG2000”), hexamethylene diisocyanate (hereinafter, , Abbreviated as “HDI”), 150 parts by mass of polyoxyethylene polyoxypropylene triol (number average molecular weight; 3,000, hereinafter abbreviated as “EOPO3000”), 1,460 parts by mass of dioctyltin dilaurate.
  • PPG2000 polyoxypropylene glycol
  • HDI hexamethylene diisocyanate
  • EOPO3000 polyoxyethylene polyoxypropylene triol
  • 1,460 parts by mass of dioctyltin dilaurate 1,460 parts by mass of dioctyltin dilaurate.
  • Nonvolatile content 60% by mass, viscosity: 4,100 mPa ⁇ s, hydroxyl group content 0.23 mol / kg, weight average molecular weight; 84,000, polyoxyalkylene content; 16.6 mol / kg, molar ratio of oxyethylene structure to oxypropylene structure; 15/85, content of urethane bond :
  • a polyurethane (A-2) solution of 0.69 mol / kg was obtained.
  • HDI nurate hexamethylene diisocyanate
  • Example 3 In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and a thermometer, 1760 parts by mass of polyoxypropylene glycol (number average molecular weight: 10,000, hereinafter abbreviated as “PPG10000”) and 40 parts by mass of HDI. Parts, 230 parts by mass of EOPO3000, 0.2 parts by mass of dioctyltin dilaurate and 1,095 parts by mass of ethyl acetate were charged into a separable flask and reacted by heating to 70 ° C.
  • PPG10000 polyoxypropylene glycol
  • the completion of the reaction was confirmed when the isocyanate group content was calculated from the charged amount by titration with dibutylamine and hydrochloric acid.
  • the nonvolatile content 65% by mass, viscosity: 12,000 mPa ⁇ s, hydroxyl group content
  • Amount 0.08 mol / kg, weight average molecular weight; 120,000, polyoxyalkylene content; 16.6 mol / kg, molar ratio of oxyethylene structure to oxypropylene structure; 5/95, content of urethane bond :
  • a polyurethane (A-3) solution of 0.23 mol / kg was obtained.
  • Example 4 In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and a thermometer, 1,560 parts by mass of PPG 3000, 110 parts by mass of isophorone diisocyanate (hereinafter abbreviated as “IPDI”), 680 parts by mass of EOPO 3000, 0.03 parts by mass of dioctyltin dilaurate and 995 parts by mass of ethyl acetate were charged into a separable flask and heated to 75 ° C.
  • IPDI isophorone diisocyanate
  • Example 5 In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and a thermometer, 200 parts by mass of polyoxypropylene glycol (number average molecular weight; 400, hereinafter abbreviated as “PPG400”), 85 parts by mass of HDI, and EOPO 3000 308 parts by mass, dioctyltin dilaurate 0.03 parts by mass and ethyl acetate in a separable flask and heated to 75 ° C.
  • PPG400 number average molecular weight
  • HDI high-dilaurate
  • EOPO 3000 3000
  • Example 6 1,015 mass parts of polyester diol (“MX2420” manufactured by DIC Corporation, number average molecular weight; 2000, hereinafter abbreviated as “PEs”) in a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and a thermometer.
  • PEs polyester diol
  • 105 parts by mass of HDI, 450 parts by mass of EOPO3000, 0.03 parts by mass of dioctyltin dilaurate, and ethyl acetate were charged into a separable flask and heated to 75 ° C.
  • Example 7 In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and a thermometer, 1,202 parts by mass of polyoxypropylene glycol (number average molecular weight; 200, hereinafter abbreviated as “PPG200”), and HDI of 1,017. Part by mass, 163 parts by mass of EOPO3000, 0.03 parts by mass of dioctyltin dilaurate, and ethyl acetate were charged into a separable flask and heated to 75 ° C.
  • PPG200 number average molecular weight
  • Example 8 In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and a thermometer, 1,002 parts by mass of PPG2000, 85 parts by mass of HDI, 18 parts by mass of EOPO3000, 0.03 parts by mass of dioctyltin dilaurate, ethyl acetate was charged into a separable flask and heated to 75 ° C. The completion of the reaction was confirmed when the isocyanate group content reached the content calculated from the charged amount by titration with dibutylamine and hydrochloric acid, and the reaction was cooled to a non-volatile content: 71% by mass; hydroxyl group content: 0.
  • a polyurethane (A-8) solution having a 007 mol / kg, a weight average molecular weight of 451,500, and a urethane bond content of 0.9 mol / kg was obtained.
  • a polyurethane (A-8) solution having a 007 mol / kg, a weight average molecular weight of 451,500, and a urethane bond content of 0.9 mol / kg was obtained.
  • 0.7 part by mass of HDI nurate as a crosslinking agent was added immediately before producing the sheet to obtain a polyurethane composition. Note that [(a-1) / (a-2)] is 55.7.
  • Example 9 In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and a thermometer, polycarbonate diol (“Duranate T5652” manufactured by Asahi Kasei Chemicals Corporation, number average molecular weight; 2000, hereinafter abbreviated as “PC”) is 1,015. Part by mass, 105 parts by mass of HDI, 450 parts by mass of EOPO3000, 0.03 parts by mass of dioctyltin dilaurate, and ethyl acetate were charged into a separable flask and heated to 75 ° C.
  • PC polycarbonate diol
  • Example 10 In Example 1, instead of 3.6 parts by mass of HDI nurate, the procedure was carried out except that the trimethylolpropane adduct of hexamethylene diisocyanate (hereinafter abbreviated as “HDI-TMP”) was changed to 4.7 parts by mass. A polyurethane composition was obtained in the same manner as in Example 1.
  • HDI-TMP trimethylolpropane adduct of hexamethylene diisocyanate
  • Example 11 In Example 6, instead of 3.6 parts by mass of HDI nurate, the trimethylolpropane adduct of toluene diisocyanate (hereinafter abbreviated as “TDI-TMP”) was changed to 4.7 parts by mass. 4 to obtain a polyurethane composition.
  • TDI-TMP trimethylolpropane adduct of toluene diisocyanate
  • Example 12 In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and a thermometer, polyoxymethylene glycol (number average molecular weight; 1000, hereinafter abbreviated as “PTMG1000”) is 1,032 parts by mass, and HDI is 260 parts by mass. Then, 1820 parts by mass of EOPO3000, 0.03 parts by mass of dioctyltin dilaurate, and ethyl acetate were charged into a separable flask and heated to 75 ° C.
  • PTMG1000 number average molecular weight
  • EOPO3000 0.03 parts by mass of dioctyltin dilaurate, and ethyl acetate were charged into a separable flask and heated to 75 ° C.
  • Example 13 In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and a thermometer, polyoxyethylene glycol (number average molecular weight; 200, hereinafter abbreviated as “PEG200”) is 1,025 parts by mass, and HDI is 194 parts by mass. Then, 449 parts by mass of EOPO3000, 0.03 parts by mass of dioctyltin dilaurate, and ethyl acetate were charged into a separable flask and heated to 75 ° C.
  • PEG200 number average molecular weight
  • HDI 194 parts by mass
  • Example 14 In Example 6, 1 part by mass of Nisshinbo Carbodiimide Compound “Carbodilite V-05” (hereinafter abbreviated as “V-05”) is added to 100 parts by mass of the nonvolatile content of polyurethane (A-6). A polyurethane composition was obtained in the same manner as in Example 6 except that.
  • a sheet obtained by cutting the sheet obtained in [Sheet Processing Method 1] into a size of 30 mm ⁇ 30 mm was used as a test piece.
  • the test piece was cut to a size of 20 mm ⁇ 20 mm and attached to a glass plate on which a polyethylene terephthalate (PET) film having a thickness of 25 ⁇ m was placed, and the gap between the PET film and the test piece was visually observed. Evaluation was performed as follows. “ ⁇ ”: No gap between the PET film and the test piece (complete tracking) “ ⁇ ”: A part of air enters between the PET film and the test piece, and the float is generated (partly following) "X”: Air exists around the PET film, and the test piece is floating (complete peeling)
  • [Contamination resistance evaluation method] A sheet obtained by cutting the sheet obtained in [Sheet Processing Method 2] into a size of 30 mm ⁇ 30 mm was used as a test piece, from which release PET was peeled off and attached to a glass plate. At that time, air bubbles were introduced between the sheet and the glass plate. The test piece was left for 72 hours at 60 ° C. and 90% humidity. Then, after leaving for 24 hours in an environment of 23 ° C., the sheet was peeled off from the glass plate by hand, irradiated with LED light from the lower part of the glass plate, and the contamination status was observed visually and with a microscope and evaluated as follows. did. “ ⁇ ”: There is no contamination on the glass plate.
  • the sheet formed from the polyurethane composition of the present invention has excellent step following ability, substrate adhesion, sheet retention, and stain resistance.
  • Comparative Example 1 is an embodiment in which the equivalent ratio of the bifunctional polyol (a-1) and the compound (a-2) having three hydroxyl groups is lower than the range defined in the present invention. The stain resistance was poor.
  • Comparative Example 2 is an embodiment in which the equivalent ratio of the bifunctional polyol (a-1) and the compound (a-2) having three hydroxyl groups exceeds the range specified in the present invention. Adhesion was poor.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

Le problème à résoudre par la présente invention est de fournir une composition de polyuréthane qui permet d'obtenir des feuilles qui sont excellentes en termes de conformabilité à des parties résistantes, d'adhérence à des substrats, de capacité de rétention des feuilles et de propriétés antitache. La présente invention concerne une composition de polyuréthane caractérisée en ce qu'elle comprend (A) un polyuréthane hydroxylé obtenu en utilisant, comme matières premières, (a) des polyols comprenant (a-1) un polyol bifonctionnel et (a-2) un composé comprenant trois groupes hydroxy selon un rapport équivalent, (a-1)/(a-2), de 0,7 à 100, (B) un agent de réticulation, et (C) un solvant organique. La présente invention concerne en outre une feuille caractérisée en ce qu'elle a été formée à partir de la composition de polyuréthane. La feuille formée à partir de la composition de polyuréthane de la présente invention est excellente en termes de conformabilité à des parties résistances, d'adhérence à des substrats, de capacité de rétention des feuilles et de propriétés antitache.
PCT/JP2016/081534 2015-12-17 2016-10-25 Composition et feuille de polyuréthane Ceased WO2017104267A1 (fr)

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EP3931232A4 (fr) 2019-02-25 2022-11-02 Henkel AG & Co. KGaA Matériaux d'interface thermique à base de polyuréthanes en deux parties

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JPH07126342A (ja) * 1993-10-21 1995-05-16 Saint Gobain Vitrage ポリウレタンの製造方法
JP2003221570A (ja) * 2002-01-31 2003-08-08 Nooteepu Kogyo Kk ポリウレタン粘着剤組成物及びこれを用いた粘着シート
JP2006124693A (ja) * 2004-09-30 2006-05-18 Asahi Glass Co Ltd ウレタン樹脂の製造方法および粘着剤
JP2007169376A (ja) * 2005-12-20 2007-07-05 Mitsubishi Chemicals Corp 帯電防止ポリウレタン接着剤及びその製造方法
JP2009275224A (ja) * 2008-05-13 2009-11-26 Tesa Se 化学的に架橋したポリウレタンフィルムを製造するためのホットメルト法
JP2012219128A (ja) * 2011-04-05 2012-11-12 Konishi Co Ltd 硬化性シリル化ウレタン系樹脂及びその製造方法
WO2013018478A1 (fr) * 2011-07-29 2013-02-07 Dic株式会社 Film de polyuréthane et film transformé produit à partir de celui-ci

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