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EP4081566A1 - Composition de résine de polyuréthane et produit moulé en résine de polyuréthane - Google Patents

Composition de résine de polyuréthane et produit moulé en résine de polyuréthane

Info

Publication number
EP4081566A1
EP4081566A1 EP20830163.0A EP20830163A EP4081566A1 EP 4081566 A1 EP4081566 A1 EP 4081566A1 EP 20830163 A EP20830163 A EP 20830163A EP 4081566 A1 EP4081566 A1 EP 4081566A1
Authority
EP
European Patent Office
Prior art keywords
compound
polyurethane resin
group
resin composition
polyol component
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.)
Withdrawn
Application number
EP20830163.0A
Other languages
German (de)
English (en)
Inventor
Tohru Matsumura
Shoko Aoki
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.)
Covestro Intellectual Property GmbH and Co KG
Original Assignee
Covestro Intellectual Property GmbH and Co KG
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.)
Filing date
Publication date
Priority claimed from JP2019232568A external-priority patent/JP2021100995A/ja
Application filed by Covestro Intellectual Property GmbH and Co KG filed Critical Covestro Intellectual Property GmbH and Co KG
Publication of EP4081566A1 publication Critical patent/EP4081566A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C08G18/16—Catalysts
    • C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
    • 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
    • C08G18/16—Catalysts
    • C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
    • C08G18/163—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22
    • 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
    • C08G18/16—Catalysts
    • C08G18/166—Catalysts not provided for in the groups C08G18/18 - C08G18/26
    • C08G18/168—Organic compounds
    • 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
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1808—Catalysts containing secondary or tertiary amines or salts thereof having alkylene polyamine groups
    • 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
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1816—Catalysts containing secondary or tertiary amines or salts thereof having carbocyclic groups
    • 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
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/225—Catalysts containing metal compounds of alkali or alkaline earth metals
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
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    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C08G18/3823—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
    • C08G18/3825—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing amide groups
    • 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
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4202—Two or more polyesters of different physical or chemical nature
    • 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
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4816—Two or more polyethers of different physical or chemical nature mixtures of two or more polyetherpolyols having at least three hydroxy groups
    • 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
    • C08G18/4829—Polyethers containing at least three hydroxy groups
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/141—Hydrocarbons
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143—Halogen containing compounds
    • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/005—< 50kg/m3
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/16—Unsaturated hydrocarbons
    • C08J2203/162—Halogenated unsaturated hydrocarbons, e.g. H2C=CF2
    • 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
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes

Definitions

  • the present invention relates to a polyurethane resin composition and a molded product of a polyurethane resin formed from the composition, and more particularly relates to a polyurethane resin composition capable of forming a polyurethane resin having excellent filling properties, surface properties, and strength.
  • Patent Literature 1 It has been known that the addition of a short-chain polyol is effective for increasing the strength of a polyurethane resin. However, when the addition amount is increased, a problem that filling properties are degraded and surface properties are also deteriorated has been caused (Patent Literature 1).
  • Patent Literature 2 it is described that the use of a reaction active compound having a relatively low molecular weight and a high OH value improves the resin strength, but it was not described for the filling properties of the resin (Patent Literature 2). Further, even if the reactivity was controlled by incorporating catalytic ability into a polyol skeleton to ensure filling properties, it was difficult to simultaneously improve strength (Patent Literature 3). Citation List
  • Patent Literature 1 JP H6-322099 A
  • Patent Literature 2 JP 2009-67995 A
  • Patent Literature 3 JP H5-97954 A
  • a polyurethane resin composition containing a polyol component and a polyisocyanate component contains a compound (also referred to as compound (A)) that has a molecular weight of 220 or less, has two or more reactive groups capable of reacting with an isocyanate in one molecule, and has one reactive group with a reaction activity with an isocyanate group that is higher than the reaction activity with an isocyanate group of the other reactive groups of compound (A), and the average hydroxyl value ratio of the compound (A) to the polyol component other than the compound (A) is set to 1.2 or more, whereby it is possible to obtain a polyurethane resin in which degradation of filling properties is suppressed or the filling properties are improved, and surface properties and strength are improved, thereby completing the present invention.
  • compound (A)) also referred to as compound (A)
  • the polyurethane resin composition of the present invention contains a polyol component and a polyisocyanate component, in which the composition contains a compound (A) as the polyol component or a component other than the polyol component, the compound (A) has a molecular weight of 220 or less, has two or more reactive groups capable of reacting with an isocyanate in one molecule, and has one reactive group with a reaction activity with an isocyanate group that is higher than the reaction activity with an isocyanate group of the other reactive groups of compound (A), and the ratio of the hydroxyl value of the compound (A) to the hydroxyl value of the polyol component is 1.2 or more, provided that when the compound (A) falls under the polyol component, the phrase “the hydroxyl value of the polyol component” refers to the hydroxyl value of the polyol component other than the compound (A).
  • a thermosetting polyurethane product preferably a thermosetting polyurethane product
  • the reactive group of the compound (A) is selected from the group consisting of hydroxyl groups including phenolic hydroxyl groups, secondary amines, carboxylic acid groups, epoxy groups, and amide groups.
  • one reactive group of the compound (A) is any of a primary hydroxyl group, a secondary hydroxyl group, a tertiary hydroxyl group, a phenolic hydroxyl group, a secondary amine, or a carboxylic acid group, and the other reactive group is selected from the group consisting of hydroxyl groups different therefrom, epoxy groups, and amide groups.
  • the polyurethane resin molded product of the present invention is formed from the polyurethane resin composition.
  • the polyurethane resin molded product of the present invention is a thermosetting polyurethane product, specifically a thermosetting polyurethane molded product.
  • the polyurethane foam of the present invention is formed from the polyurethane resin composition.
  • the polyurethane foam of the present invention is a thermosetting polyurethane product, specifically a thermosetting polyurethane foam.
  • a polyurethane resin composition capable of forming a polyurethane resin in which degradation of filling properties is suppressed or the filling properties are improved, and surface properties and strength are improved and a polyurethane resin molded product and polyurethane foam formed from the composition.
  • the composition of the present invention is a composition containing a polyol component and a polyisocyanate component, and is a composition used for forming a polyurethane resin.
  • the polyurethane resin composition of the present invention contains a compound (A) that has a molecular weight of 220 or less, has two or more reactive groups capable of reacting with an isocyanate in one molecule, and has one reactive group with a reaction activity with an isocyanate group that is higher than the reaction activity with an isocyanate group of the other reactive groups of compound (A).
  • the compound (A) may be used alone or in combination of two or more.
  • the reactive group of the compound (A) is selected from the group consisting of hydroxyl groups including phenolic hydroxyl groups, secondary amines, carboxylic acid groups, epoxy groups, urethane groups, and amide groups.
  • one reactive group of the compound (A) is any of a primary hydroxyl group, a secondary hydroxyl group, a tertiary hydroxyl group, a phenolic hydroxyl group, a secondary amine, or a carboxylic acid group, and the other reactive group is selected from the group consisting of hydroxyl groups different therefrom, epoxy groups, urethane groups, and amide groups.
  • the order of reactivity of the reactive groups is “amino group > hydroxyl group > phenolic hydroxyl group, urea, urethane, amide”, but the reactivity is affected by steric hindrance around the reactive group, electronegativity of a substituent, or the like.
  • examples of a suitable combination of the reactive groups of the compound (A) include one hydroxyl group and one or more amide groups, one hydroxyl group and one or more urethane, one primary hydroxyl group and one or more secondary hydroxyl groups, one primary hydroxyl group and one or more tertiary hydroxyl groups, and the like.
  • the compound (A) has reactive groups having different reactivity in the molecule, so that filling properties and surface properties are improved by the time difference until a reactive group having lower reactivity reacts with isocyanate after a reactive group having higher reactivity reacts.
  • the compound (A) preferably has a molecular weight of 70 to 220.
  • the compound (A) preferably has a hydroxyl value of more than 600.
  • the hydroxyl value is the number of mg of potassium hydroxide required to neutralize free hydroxyl groups in 1 g of a sample after complete acetylation with acetic anhydride (see JIS K 15572007).
  • the ratio of the hydroxyl value of the compound (A) to the hydroxyl value of the polyol component is 1.2 or more.
  • the hydroxyl value (OHV) thereof is expressed as the sum of the hydroxyl value of each compound (A) multiplied by weight ratio.
  • compounds (Al) and (A2) are contained as the compound (A), it is calculated by the following formula.
  • OHV (A) OHV (Al) x W (A1)/(W (Al) + W (A2))
  • the polyurethane resin composition of the present invention contains two or more polyol components (P)
  • the hydroxyl value (OHV) thereof is expressed as the sum of the hydroxyl value of each polyol component multiplied by weight ratio.
  • polyol components (PI), (P2) and (P3) are contained as the polyol component (P), it is calculated by the following equation.
  • OHV (P) OHV (PI) x W (P1)/(W (PI) + W (P2) + W (P3))
  • OHV (PI) hydroxyl value of the polyol component (PI);
  • OHV (P2) hydroxyl value of the polyol component (P2)
  • W (PI) parts by weight of the polyol component (PI); W (P2): parts by weight of the polyol component (P2);
  • the ratio of the hydroxyl value of the compound (A) to the hydroxyl value of the polyol component was calculated as OHV (A)/OHV (P) determined as described above.
  • the ratio of the compound (A) to the polyol composition is preferably 1 to 99% by mass, and more preferably 1 to 30% by mass.
  • the content of the compound (A) is preferably, for example, 0.5 to 20% by mass.
  • the compound (A) include propylene glycol, 1,3-butanediol, 3-methyl-l,3-butanediol (isoprene glycol), 2-ethyl- 1,3-hexanediol, 2-methylpentane-2,4-diol (hexylene glycol), diethanolamine, diisopropanolamine, 1,2-butanediol, 1,2-pentanediol, N-(2- hydroxyethyl)acrylamide, 2-acetamidoethanol, N-MAM (N-(hydroxymethyl)acrylamide, and N,N-bis(2-hydroxypropyl)-N-(hydroxyethyl)amine.
  • the compound (A) may be used as a polyol component or may be used as a component other than the polyol component.
  • the polyisocyanate component used in the composition of the present invention includes compounds having a plurality of isocyanate groups (polyisocyanates).
  • polyisocyanates include aliphatic, alicyclic, aromatic or araliphatic polyisocyanates, and modified products of these polyisocyanates are also included.
  • modified product of polyisocyanate include polyisocyanates having a structure such as uretdione, isocyanurate, urethane, urea, allophanate, biuret, carbodiimide, iminooxadiazinedione, oxadiazinetrione, or oxazolidone.
  • an isocyanate group-containing prepolymer obtained by reacting a polyol with a polyisocyanate may be used as the polyisocyanate.
  • examples of the aromatic polyisocyanate include phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, and the like.
  • Examples of the alicyclic polyisocyanate include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, dimethyldicyclohexylmethane diisocyanate, and the like.
  • Examples of the aliphatic polyisocyanate include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, and the like.
  • the polyisocyanate may be used alone or in combination of two or more.
  • the content of the polyisocyanate can be indicated by, for example, an isocyanate index, and is appropriately selected according to the type of the polyurethane resin composition.
  • the isocyanate index is preferably from 70 to 300, and further preferably from 100 to 250.
  • the isocyanate index refers to a value obtained by multiplying 100 by the ratio of the isocyanate group of the polyisocyanate to the total active hydrogen that reacts with isocyanate groups of a foaming agent and the like, in addition to the polyol component and the compound (A).
  • the polyol used in the composition of the present invention is a compound having a plurality of hydroxyl groups (polyol), and usually refers to a polymer polyol, and specific examples include polyether polyol, polyester polyol, polycarbonate polyol, polyester ether polyol, polyester polycarbonate polyol, polylactone polyol, polybutadiene polyol, polymer polyol, silicone polyol, and the like.
  • the polyols may be used alone or in combination of two or more.
  • the content of the polyol is appropriately adjusted depending on the amount of the polyisocyanate and desired performance, and is, for example, 15 to 50% by mass.
  • the compound (A) when the compound (A) has a plurality of hydroxyl groups, the compound (A) can be a polyol component.
  • the polyol component used in the composition of the present invention preferably has a number average molecular weight of 60 to 8000 g/mol, and further preferably 60 to 2000 g/mol.
  • the number average molecular weight is a polystyrene equivalent number average molecular weight measured by gel permeation chromatography.
  • the polyol component preferably has a hydroxyl value of 20 to 3000 mgKOH/g, and further preferably 100 to 1900 mgKOH/g.
  • the hydroxyl value is the number of mg of potassium hydroxide required to neutralize free hydroxyl groups in 1 g of a sample after complete acetylation with acetic anhydride (see JIS K 15572007).
  • the foaming agents that can be used in the composition of the present invention are generally classified into physical foaming agents and chemical foaming agents.
  • the physical foaming agent examples include fluorocarbons such as hydrochlorofluorocarbon (HCFC) and hydrofluorocarbon (HFC), hydrocarbons such as hydrofluoroolefm (HFO), hydrochlorofluoroolefm (HCFO), heptane, hexane, pentane and cyclopentane, carbon dioxide, and the like.
  • examples of the chemical foaming agent include water, carboxylic acids such as formic acid and acetic acid, and the like.
  • the foaming agents may be used alone or in combination of two or more. Further, a physical foaming agent and a chemical foaming agent may be used in combination.
  • the content of the foaming agent is, for example, 1 to 20% by mass.
  • the foaming agent of the present invention does not contain the combination of water and an adduct of a primary or secondary amine compound and carbon dioxide. More preferably, the foaming agent of the present invention does not contain any adduct of a primary or secondary amine compound and carbon dioxide. Most preferably, the foaming agent of the present invention does not contain any adduct of an amine compound and carbon dioxide.
  • the composition of the present invention preferably contains a catalyst component.
  • the catalysts that can be used in the catalyst component in the composition of the present invention include catalysts (foaming catalysts) that promote a reaction between water and isocyanate, catalysts (resinification catalysts) that promote a reaction between polyol and isocyanate, catalysts (trimerization catalysts) that promote a trimerization reaction of isocyanate (that is, formation of an isocyanurate ring), and the like.
  • foaming catalyst examples include dimorpholine-2, 2-diethyl ether, N,N,N',N",N"-pentamethyldiethylenetriamine, bis(dimethylaminoethyl)ether, 2-(2- dimethylaminoethoxy)ethanol, and the like.
  • the resinification catalyst examples include amine catalysts such as triethylenediamine, N,N-dimethylcyclohexylamine, N,N,N',N'- tetramethylethylenediamine, N,N,N',N",N"',N"'-hexamethyltriethylenetetramine, N- dimethylaminoethyl-N'-methylpiperazine, N,N,N',N'-tetramethylhexamethylenediamine, 1,2-dimethylimidazole, N,N-dimethylaminopropylamine and bis(dimethylaminopropyl)amine, alkanolamine catalysts such as N,N- dimethylaminoethanol, N,N,N'-trimethylaminoethylethanolamine, N,N,N' -trimethyl -N'- hydroxyethyl bisaminoethyl ether, N-(2-(dimethylamino)ethoxy)ethyl)
  • trimerization catalyst examples include aromatic compounds such as 2,4,6-tris(dialkylaminoalkyl)hexahydro-S-triazine, l,3,5-tris(N,N- dimethylaminopropyl)hexahydro-S-triazine, 2,4,6-tris(dimethylaminomethyl)phenol, 2,4- bis(dimethylaminomethyl)phenol and l-isobutyl-2-methylimidazole, alkali metal carboxylates such as potassium acetate, potassium 2-ethylhexanoate and potassium octylate, quaternary ammonium salts of carboxylic acid, or other onium salts, and the like. [0037]
  • the catalysts may be used alone or in combination of two or more.
  • the content of the catalyst component is appropriately adjusted depending on reactivity of a polyurethane foam stock solution, and is, for example, 0.1 to 8% by mass.
  • the catalyst component does not contain any catalyst with a cyclic phosphorous moiety or the catalyst component does not contain any catalyst that catalyzes the conversion of isocyanate groups to carbodiimide groups. More preferably, the catalyst component does not contain any catalyst with a cyclic phosphorous moiety that catalyzes the conversion of isocyanate groups to carbodiimide groups.
  • a surfactant As a foam stabilizer that can be used in the composition of the present invention, a surfactant is suitably used.
  • the surfactants include ionic surfactants such as anionic, cationic and amphoteric, and nonionic surfactants, but nonionic surfactants are preferred. Also, specific examples preferably include silicone-based surfactants.
  • the foam stabilizers may be used alone or in combination of two or more. In the polyurethane resin composition of the present invention, the content of the foam stabilizer is, for example, 0.1 to 5% by mass.
  • the composition of the present invention may include a flame retardant.
  • a phosphorus flame retardant is preferably used.
  • Specific examples preferably include tricresyl phosphate (TCP), triethyl phosphate (TEP), tris(P-chloroethyl) phosphate (TCEP), tris(P-chloropropyl) phosphate (TCPP), and the like.
  • solid (powder) flame retardants such as ammonium polyphosphate and red phosphorus are also used as necessary.
  • the flame retardants may be used alone or in combination of two or more.
  • the content of the flame retardant is, for example, 3 to 15% by mass.
  • a coloring agent for example, a coloring agent, a filler, an antioxidant, an ultraviolet absorber, a heat stabilizer, a light stabilizer, a plasticizer, a fungicide, an antibacterial agent, an industrial cashew nut shell liquid, a crosslinking agent, a solvent, a viscosity-reducing agent, a depressurizing agent, a separation inhibitor, and the like may be appropriately blended as necessary.
  • composition of the present invention can be prepared by mixing various components appropriately selected as necessary.
  • the composition of the present invention can be prepared by mixing a polyol composition containing a polyol component and the compound (A) with a polyisocyanate component.
  • the polyisocyanate component may be used alone or in a mixture with other components.
  • the polyurethane resin molded product and the polyurethane foam of the present invention are formed from the above-described polyurethane resin composition of the present invention. Since the composition of the present invention contains a polyol component and a polyisocyanate component, it is possible to proceed the reaction by mixing both to form a polyurethane resin.
  • the polyurethane resin may be a foam type or a non-foam type.
  • the foam type polyurethane resin is called a polyurethane foam.
  • examples of the shape of the polyurethane resin molded product include a sheet shape and the like.
  • the foaming method is not particularly limited, and known foaming means, for example, hand mixing foaming, simple foaming, injection method, floss injection method, spray method, and the like can be used.
  • the molding method is not particularly limited, and known molding means, for example, mold molding, slab molding, laminate molding, in-situ foam molding, and the like can be used.
  • the polyurethane resin molded product and polyurethane foam of the present invention can be used for various applications such as ships, vehicles, plants, heat insulation equipment, architecture, civil engineering, furniture, and interiors.
  • the polyurethane foam of the present invention preferably has a density of 10 to 800 kg/m 3 , and further preferably 20 to 100 kg/m 3 .
  • the density of the polyurethane foam is measured according to JIS K 7222: 2005. Examples
  • the raw materials used for producing the polyurethane foam are shown below.
  • Polyol A Polyether polyol [Sumiphen TM: manufactured by Sumika Covestro Urethane Co., Ltd.] functional group number: 3, hydroxyl value 380 mgKOH/g;
  • Polyol B Polyether polyol [SBU polyol Z450: manufactured by Sumika Covestro Urethane Co., Ltd.] functional group number: 4, hydroxyl value 350 mgKOH/g;
  • Polyol C Poly ether polyol [G400: manufactured by ADEKA Corporation] functional group number: 3, hydroxyl value 400 mgKOH/g;
  • Polyol D Polyester polyol [PHANTOL 6300: manufactured by Hitachi Chemical Co., Ltd.] functional group number: 2, hydroxyl value 225 mgKOH/g;
  • Polyol E Polyester polyol [RLK-085: manufactured by Kawasaki Kasei Chemicals Ltd.] functional group number: 2, hydroxyl value 200 mgKOH/g;
  • Polyol F Poly ether polyol [Sumiphen 0485: manufactured by Sumika Covestro Urethane Co., Ltd.] functional group number: 4, hydroxyl value 470 mgKOH/g.
  • Polyol K Tripropylene glycol monomethyl ether, functional group number: 1, hydroxyl value 272 mgKOH/g;
  • Polyol G Ethylene glycol, functional group number: 2, hydroxyl value 1807 mgKOH/g
  • Compound (A)-J Isoprene glycol, functional group number: 2, hydroxyl value 1077 mgKOH/g;
  • Polyisocyanate Polymeric MDI [Sumidur 44V20L: manufactured by Sumika Covestro Urethane Co., Ltd.] isocyanate group content: 31.5% by weight As foam stabilizer
  • Foam stabilizer Silicone nonionic surfactant [NIAX Silicone L6900: manufactured by Momentive Performance Materials Japan LLC]
  • Catalyst A N,N,N',N",N"-pentamethyldiethylenetriamine
  • Catalyst B N,N-dimethylcyclohexylamine
  • Catalyst C 25% Potassium acetate + 75% di ethylene glycol
  • Catalyst D 45% Onium salt catalyst + 55% ethylene glycol As foaming agents
  • Foaming agent A Water, hydroxyl value 6233 mgKOH/g
  • Foaming agent B Cyclopentane
  • Foaming agent C HFO-1233zd (trans-l-chloro-3,3,3-trifluoropropene)
  • reaction mixture of 4) was poured into an openable and closable vertical mold (internal length 400 mm (height: Z direction), width 300 mm (horizontal: Y direction), thickness 50 mm (vertical: X direction)) warmed to 40°C in advance.
  • a center part (200 mm (Z direction)*200 mm (Y direction)*25 mm (X direction)) is cut out from the polyurethane foam produced in the above mold, and further cut into small pieces (40 mm (Z direction)*40 mm (Y direction)*25 mm (X direction)), and the compressive strength of the obtained sample is measured using an autograph AGS- 10KNG (manufactured by Shimadzu Corporation) or TCM-1000 (manufactured by Minebea Co., Ltd.).
  • a sample cut out from the panel according to a predetermined rule is compressed using the autograph in the panel width direction (Y direction).
  • the measurement temperature is set to 23°C
  • the compression speed is set to 10 mm/min. Two samples are taken for each panel, and the average value thereof is taken as the compressive strength.
  • the compressive strength is calculated according to the following equation.
  • the surface of the panel formed by the vertical mold was found to have a dent due to large bubbles.
  • the dent part was visually marked and the total area was compared.
  • the evaluation criteria for panel surface properties are as follows.
  • the dent area is about 1.2 times or more than that of Comparative Example 1 or 4.
  • the dent area is about the same as that of Comparative Example 1 or 4.
  • the dent area is about 0.8 times that of Comparative Example 1 or 4.
  • the dent area is about 0.6 times or less than that of Comparative Example 1 or 4.
  • the evaluation criteria for filling properties are as follows.
  • the method is the same as that of Production Example 1, except that the strength of the cut sample (40 mm (Z directi on)*40 mm (Y direction)* 10 mm (X direction)) in the thickness direction (height: X direction) is measured.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

Le but de l'invention est de fournir une composition capable de former une mousse de polyuréthane présentant d'excellentes propriétés de remplissage, ainsi que de remarquables propriétés de surface et une très grande résistance. L'invention concerne une composition de résine de polyuréthane contenant un composant polyol et un composant polyisocyanate, la composition de résine de polyuréthane contenant un composé (A) en tant que composant polyol ou que composant autre que le composant polyol, le composé (A) présente un poids moléculaire égal ou inférieur à 220, comporte au moins deux groupes réactifs capables de réagir avec un isocyanate dans une molécule, ainsi qu'un groupe réactif présentant une activité réactionnelle avec un groupe isocyanate qui est supérieure à l'activité réactionnelle avec un groupe isocyanate des autres groupes réactifs du composé (A), et le rapport entre l'indice d'hydroxyle du composé (A) et l'indice d'hydroxyle du composant polyol est égal ou supérieur à 1,2, à condition que lorsque le composé (A) fait partie du composant polyol, la proposition « l'indice d'hydroxyle du composant polyol » se réfère à l'indice d'hydroxyle du composant polyol autre que le composé (A).
EP20830163.0A 2019-12-24 2020-12-17 Composition de résine de polyuréthane et produit moulé en résine de polyuréthane Withdrawn EP4081566A1 (fr)

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GB1584153A (en) * 1976-09-22 1981-02-04 Ici Ltd Carbodimides
JP3162138B2 (ja) 1991-05-10 2001-04-25 花王株式会社 硬質ポリウレタンフォームの製造方法
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US8481605B2 (en) * 2009-05-21 2013-07-09 Huntsman International Llc Rigid polyurethane foam and system and method for making the same
JP6921506B2 (ja) * 2016-11-25 2021-08-18 コベストロ、ドイチュラント、アクチエンゲゼルシャフトＣｏｖｅｓｔｒｏ Ｄｅｕｔｓｃｈｌａｎｄ Ａｇ 連続気泡性硬質ポリウレタンフォームの製造方法
WO2018155372A1 (fr) * 2017-02-22 2018-08-30 三井化学株式会社 Matière première d'élastomère de polyuréthane expansé, élastomère de polyuréthane expansé et procédé de production d'élastomère de polyuréthane expansé

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