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
  • C08G18/28—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
  • C08G18/4825—Polyethers containing two 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
  • C08G18/08—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
  • C08G18/08—Processes
  • C08G18/16—Catalysts
  • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
  • C08G18/20—Heterocyclic amines; Salts thereof
  • C08G18/2009—Heterocyclic amines; Salts thereof containing one heterocyclic ring
  • C08G18/2027—Heterocyclic amines; Salts thereof containing one heterocyclic ring having two nitrogen atoms in the ring
• • 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
  • 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
  • C08G18/4812—Mixtures of polyetherdiols with 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
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/4833—Polyethers containing oxyethylene units
  • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
• • 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
  • C08G18/50—Polyethers having heteroatoms other than oxygen
  • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
  • C08G18/5036—Polyethers having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
  • C08G18/5045—Polyethers having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing urethane 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
  • C08G18/6666—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
  • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
• • 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
  • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
  • C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group
  • C08G18/7642—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group containing at least two isocyanate or isothiocyanate groups linked to the aromatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate groups, e.g. xylylene diisocyanate or homologues substituted on the aromatic ring
• • 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
  • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
• • 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
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/78—Nitrogen
  • C08G18/7806—Nitrogen containing -N-C=0 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
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/78—Nitrogen
  • C08G18/7806—Nitrogen containing -N-C=0 groups
  • C08G18/7843—Nitrogen containing -N-C=0 groups containing urethane 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
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/78—Nitrogen
  • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
  • C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
  • C09J175/04—Polyurethanes
  • C09J175/08—Polyurethanes from polyethers
• • 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
  • C08G2170/00—Compositions for adhesives
  • C08G2170/40—Compositions for pressure-sensitive adhesives

Definitions

• the present invention relates to structural polyurethane adhesives.
• polyurethane adhesives have been widely used in various industrial fields.
• a polyurethane adhesive for example, a two-liquid curable polyurethane adhesive containing a polyisocyanate component and a polyol component is known.
• the following formulation has been proposed as a two-liquid curing type polyurethane adhesive. That is, the two-component coating agent comprises a urethane prepolymer composition and a polyisocyanate cross-linking agent, and the urethane prepolymer composition contains the reaction product of hexamethylene diisocyanate, copolycarbonate diol and ethylene glycol.
• the two-component coating agent is used in the production of synthetic imitation leather (see, for example, Patent Document 1 (Example 1 and Application Example 1)).
• the physical properties required for polyurethane adhesives differ depending on the field in which they are used.
• a polyurethane adhesive is used to bond members of a structure composed of a plurality of members, particularly excellent adhesive strength is required of the polyurethane adhesive.
• the polyurethane adhesive described above has a problem that it does not have sufficient adhesion properties.
• the present invention is a structural polyurethane adhesive with excellent adhesive properties.
• the present invention contains a polyisocyanate component and a polyol component, and the polyisocyanate component is a reaction product of a first raw material polyisocyanate containing an aromatic polyisocyanate and a first raw material polyol containing a macropolyol. and the polyol component is a hydroxyl group-terminated urethane prepolymer which is a reaction product of a second raw polyisocyanate containing an araliphatic polyisocyanate and a second raw polyol containing a macropolyol.
• a structural polyurethane adhesive containing a polymer and a low molecular weight polyol is included.
• the present invention provides the structural polyurethane adhesive according to [1] above, wherein the proportion of the hydroxyl group-terminated urethane prepolymer is 2% by mass or more and 30% by mass or less with respect to the total amount of the polyol component. , including
• the present invention includes the structural polyurethane adhesive according to [1] or [2] above, wherein the polyisocyanate component further contains a carbodiimide-modified aromatic polyisocyanate monomer.
• the present invention [4] provides the structural polyurethane adhesive according to any one of the above [1] to [3], wherein the polyol component further contains a polyether polyol having an average number of hydroxyl groups of 3 or more, contains.
• the present invention [5] includes the structural polyurethane adhesive according to any one of the above [1] to [4], wherein the aromatic polyisocyanate contains diphenylmethane diisocyanate.
• the present invention [6] includes the structural polyurethane adhesive according to any one of the above [1] to [5], wherein the araliphatic polyisocyanate contains xylylene diisocyanate.
• the present invention [7] includes the structural polyurethane adhesive according to any one of [1] to [6] above, wherein the hydroxyl group-terminated urethane prepolymer has a hydroxyl equivalent weight of 550 or less.
• the present invention [8] is a two-component curable adhesive comprising a main agent containing the polyisocyanate component and a curing agent containing the polyol component, according to any one of the above [1] to [7]. of structural polyurethane adhesives.
• the present invention [9] includes the structural polyurethane adhesive according to any one of [1] to [8] above, which is a solventless adhesive.
• the polyisocyanate component comprises an isocyanate group-terminated urethane prepolymer which is a reaction product of a first raw material polyisocyanate containing an aromatic polyisocyanate and a first raw material polyol containing a macropolyol. and the polyol component comprises a hydroxyl-terminated urethane prepolymer that is a reaction product of a second raw polyisocyanate containing an araliphatic polyisocyanate and a second raw polyol containing a macropolyol, and a low molecular weight polyol.
• the structural polyurethanes of the present invention have excellent adhesion properties.
• the structural polyurethane adhesive of the present invention is a structural adhesive defined in JIS K 6800 (1985). Specifically, structural polyurethane adhesives are "reliable adhesives that withstand heavy loads for extended periods of time.”
• the structural polyurethane adhesive contains a polyisocyanate component and a polyol component as essential components.
• a polyisocyanate component is a component containing free isocyanate groups.
• the polyol component is a component containing free hydroxyl groups.
• the structural polyurethane adhesive may be a one-liquid curable adhesive in which a polyisocyanate component and a polyol component are premixed.
• the adhesive may be a two-part curing adhesive comprising a main agent (A liquid) containing a polyisocyanate component and a curing agent (B liquid) containing a polyol component.
• a liquid a main agent
• B liquid curing agent
• the main agent and curing agent prepared separately are mixed at the time of use.
• the structural polyurethane adhesive is preferably a two-liquid curing adhesive from the viewpoint of workability, handleability, and the like.
• the polyisocyanate component contains a urethane prepolymer having two or more isocyanate groups at the molecular ends (hereinafter referred to as an isocyanate group-terminated urethane prepolymer).
• the isocyanate group-terminated urethane prepolymer is a reaction product of the first raw material polyisocyanate and the first raw material polyol.
• the first raw material polyisocyanate and the first raw material polyol react so that the isocyanate groups are excessive relative to the hydroxyl groups.
• the first raw material polyisocyanate contains an aromatic polyisocyanate, and preferably consists of an aromatic polyisocyanate.
• Aromatic polyisocyanates include, for example, aromatic polyisocyanate monomers and aromatic polyisocyanate derivatives.
• aromatic polyisocyanate monomers include aromatic diisocyanates.
• Aromatic diisocyanates include, for example, tolylene diisocyanate, phenylene diisocyanate, diphenyl diisocyanate, naphthalene diisocyanate, diphenylmethane diisocyanate, toluidine diisocyanate and diphenyl ether diisocyanate. These can be used alone or in combination of two or more.
• aromatic polyisocyanate derivatives include modified products obtained by modifying the above aromatic polyisocyanate monomers by a known method. More specifically, aromatic polyisocyanate derivatives include, for example, oligomers, isocyanurate modified products, allophanate modified products, polyol modified products, biuret modified products, urea modified products, oxadiazinetrione modified products and carbodiimide modified products. is mentioned. Moreover, polymethylene polyphenylene polyisocyanate is also mentioned as an aromatic polyisocyanate derivative. These can be used alone or in combination of two or more.
• aromatic polyisocyanates can be used alone or in combination of two or more.
• the aromatic polyisocyanate preferably includes an aromatic polyisocyanate monomer, more preferably an aromatic diisocyanate, and still more preferably a diphenylmethane diisocyanate.
• the first raw material polyisocyanate preferably contains diphenylmethane diisocyanate, and more preferably consists of diphenylmethane diisocyanate.
• the first raw material polyol contains macropolyol as an essential component.
• a macropolyol is a relatively high molecular weight organic compound having two or more hydroxyl groups.
• the number average molecular weight of the macropolyol (hereinafter referred to as the first macropolyol) in the first raw material polyol is 200 or more. Moreover, the number average molecular weight of the first macropolyol is usually 15,000 or less. In addition, a number average molecular weight is a polystyrene conversion molecular weight measured by a gel permeation chromatography (the same applies below).
• the first macropolyol examples include polyether polyols (described later), polyester polyols (described later) and polycarbonate polyols (described later), and more preferably polyether polyols (described later).
• the number average molecular weight of the first macropolyol is, for example, 200 or more, preferably 300 or more, more preferably 400 or more. Further, the number average molecular weight of the first macropolyol is, for example, 15000 or less, preferably 13000 or less, more preferably 12000 or less, even more preferably 10000 or less, still more preferably 8000 or less, particularly preferably 5000 or less. is.
• the hydroxyl group equivalent of the first macropolyol is, for example, 150 or more, preferably 200 or more. Moreover, the hydroxyl group equivalent of the first macropolyol is, for example, 10,000 or less, preferably 8,000 or less. Incidentally, the hydroxyl equivalent can be calculated from the hydroxyl value.
• the average number of hydroxyl groups of the first macropolyol is, for example, 1.8 or more, preferably 2 or more.
• the average number of hydroxyl groups of the first macropolyol is, for example, 6 or less, preferably 4 or less, more preferably 3 or less.
• the hydroxyl value and hydroxyl equivalent can be measured according to, for example, JIS K 1557-1 (2007) A method or B method. Also, the average number of hydroxyl groups can be calculated from the hydroxyl value, hydroxyl equivalent and molecular weight. Also, the hydroxyl value, hydroxyl equivalent and average number of hydroxyl groups can be calculated from the charging ratio of the raw material components (the same applies hereinafter).
• a first macropolyol having an average number of hydroxyl groups of 2 and a first macropolyol having an average number of hydroxyl groups of 3 are particularly preferably used together as the first raw material polyol.
• the first macropolyol having an average number of hydroxyl groups of 2 and the first macropolyol having an average number of hydroxyl groups of 3 are used together, the first macropolyol having an average number of hydroxyl groups of 3 is added to the total amount of 100 parts by mass, for example, More than 50 parts by mass, preferably 60 parts by mass or more. Also, the first macropolyol having an average number of hydroxyl groups of 3 is, for example, 90 parts by mass or less, preferably 80 parts by mass or less. Also, the first macropolyol having an average number of hydroxyl groups of 2 is, for example, 10 parts by mass or more, preferably 20 parts by mass or more. The first macropolyol having an average number of hydroxyl groups of 2 is, for example, less than 50 parts by mass, preferably 40 parts by mass or less.
• the first raw material polyol can contain a low-molecular-weight polyol as an optional component.
• Low molecular weight polyols are relatively low molecular weight organic compounds having two or more hydroxyl groups.
• the molecular weight of the low-molecular-weight polyol (hereinafter referred to as the first low-molecular-weight polyol) in the first raw material polyol is less than 200, preferably 180 or less.
• Examples of the first low-molecular-weight polyol include dihydric alcohols, trihydric alcohols, and tetrahydric or higher alcohols.
• dihydric alcohols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5- Pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol and dipropylene glycol are included.
• Trihydric alcohols include, for example, glycerin and trimethylolpropane.
• Examples of tetrahydric or higher alcohols include pentaerythritol and diglycerin. These can be used alone or in combination of two or more.
• the content of the first low-molecular-weight polyol is appropriately selected within a range that does not impair the excellent effects of the present invention. More specifically, the content of the first low-molecular-weight polyol is, for example, 30 parts by mass or less, preferably 20 parts by mass or less, more preferably 10 parts by mass, with respect to 100 parts by mass of the total amount of the first raw material polyol. part or less, and particularly preferably 0 part by mass. That is, from the viewpoint of adhesion properties, the first raw material polyol preferably does not contain the first low-molecular-weight polyol and consists of the first macropolyol.
• the isocyanate group-terminated urethane prepolymer is obtained by reacting the first raw material polyisocyanate and the first raw material polyol by a known method. More specifically, the first raw material polyisocyanate and the first raw material polyol are blended at a predetermined ratio and subjected to a urethanization reaction.
• the equivalent ratio (NCO/OH) of the isocyanate groups in the first raw polyisocyanate to the hydroxyl groups in the first raw polyol exceeds 1, preferably 1.1 or more, and more preferably is 1.3 or more, more preferably 1.5 or more, and most preferably 1.9 or more.
• the equivalent ratio (NCO/OH) is, for example, 50, preferably 15 or less, more preferably 10 or less, even more preferably 3 or less, and particularly preferably 2.5 or less.
• a known polymerization method is employed in the urethanization reaction.
• Polymerization methods include, for example, bulk polymerization and solution polymerization.
• bulk polymerization for example, the above components are blended and reacted under a nitrogen atmosphere.
• solution polymerization for example, the above components are added to a known organic solvent and reacted under a nitrogen atmosphere.
• the reaction temperature is, for example, 50° C. or higher and, for example, 120° C. or lower, preferably 100° C. or lower.
• the reaction time is, for example, 0.5 hours or longer, preferably 1 hour or longer, and for example, 24 hours or shorter, preferably 15 hours or shorter.
• the mixing ratio of the organic solvent is appropriately set according to the purpose and application.
• bulk polymerization reaction under no solvent
• a known urethanization catalyst is added as necessary. Also, if necessary, unreacted polyisocyanate is removed by a known method. Thereby, a first isocyanate component containing an isocyanate group-terminated urethane prepolymer is obtained.
• the isocyanate group-terminated urethane prepolymer preferably includes an isocyanate group-terminated urethane prepolymer that is a reaction product of an aromatic polyisocyanate and a polyether polyol, more preferably a reaction product of diphenylmethane diisocyanate and a polyether polyol. and an isocyanate group-terminated urethane prepolymer which is a product.
• the polyisocyanate component can contain free (unreacted) first raw material polyisocyanate, organic solvent and urethanization catalyst, if necessary.
• the free (unreacted) first raw material polyisocyanate, organic solvent and urethanization catalyst may be removed by known removal means. Removal means include, for example, extraction and distillation.
• the content of the free (unreacted) first raw material polyisocyanate is, from the viewpoint of adhesion properties, for example, 8.0% by mass or less, preferably 5.0% by mass or less, relative to the total amount of the polyisocyanate component. is.
• the average number of isocyanate groups in the isocyanate group-terminated urethane prepolymer is, for example, 1.2 or more, preferably 1.5 or more, and more preferably 2 or more.
• the average number of isocyanate groups in the first isocyanate component (solid content) is, for example, 4 or less, preferably 3 or less.
• the isocyanate group equivalent of the isocyanate group-terminated urethane prepolymer (solid content) is, for example, 84 or more, preferably 150 or more, and more preferably 168 or more.
• the isocyanate group equivalent of the isocyanate group-terminated urethane prepolymer (solid content) is, for example, 3500 or less, preferably 2800 or less, and more preferably 2335 or less.
• the isocyanate group equivalent has the same meaning as the amine equivalent, and can be obtained by Method A or Method B of JIS K 1603-1 (2007).
• the isocyanate group content (isocyanate group content, NCO %) of the isocyanate group-terminated urethane prepolymer (solid content) is, for example, 1.2% by mass or more, preferably 1.5% by mass or more, more preferably 1 8% by mass or more, more preferably 2.0% by mass or more, particularly preferably 2.1% by mass or more.
• the isocyanate group content of the isocyanate group-terminated urethane prepolymer (solid content) is, for example, 50% by mass or less, preferably 28% by mass or less, more preferably 25% by mass or less, and still more preferably 10% by mass. % or less, particularly preferably 6 mass % or less.
• the viscosity of the solid content of the isocyanate group-terminated urethane prepolymer at 25°C is, for example, 1000 mPa ⁇ s or more, preferably 5000 mPa ⁇ s or more. Further, the viscosity of the solid content of the isocyanate group-terminated urethane prepolymer at 25° C. is, for example, 200,000 mPa ⁇ s or less, preferably 100,000 mPa ⁇ s or less. The viscosity is measured using a Brookfield viscometer (same below).
• the polyisocyanate component can contain other polyisocyanates as optional components.
• Other polyisocyanates are isocyanate compounds other than the isocyanate group-terminated urethane prepolymers described above.
• polyisocyanates include, for example, polyisocyanate monomers and polyisocyanate derivatives.
• polyisocyanate monomers examples include aromatic polyisocyanate monomers, araliphatic polyisocyanate monomers, alicyclic polyisocyanate monomers and linear aliphatic polyisocyanate monomers.
• aromatic polyisocyanate monomers include the above aromatic polyisocyanate monomers.
• araliphatic polyisocyanate monomer include araliphatic polyisocyanate monomers described later.
• alicyclic polyisocyanate monomers include alicyclic polyisocyanate monomers described later.
• Chain aliphatic polyisocyanate monomers include, for example, ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate (PDI) and hexamethylene diisocyanate (HDI).
• polyisocyanate derivatives include modified products of the above polyisocyanate monomers. Modifications include, for example, oligomers, isocyanurate modifications, allophanate modifications, polyol modifications, biuret modifications, urea modifications, oxadiazinetrione modifications and carbodiimide modifications. These can be used alone or in combination of two or more.
• Polyisocyanate derivatives preferably include derivatives of aromatic polyisocyanate monomers (hereinafter referred to as aromatic polyisocyanate derivatives), and more preferably carbodiimide-modified aromatic polyisocyanate monomers.
• the polyisocyanate component preferably contains an aromatic polyisocyanate derivative, more preferably a carbodiimide-modified aromatic polyisocyanate monomer.
• the carbodiimide-modified aromatic polyisocyanate monomer is a reaction product of the carbodiimidation reaction of the aromatic polyisocyanate monomer.
• the aromatic polyisocyanate preferably includes aromatic diisocyanate, more preferably diphenylmethane diisocyanate.
• Carbodiimidation reactions include decarboxylation condensation reactions.
• decarboxylation condensation reaction for example, an aromatic polyisocyanate monomer is heated in the presence of a carbodiimidation catalyst.
• carbodiimidation catalysts include, but are not limited to, trialkyl phosphate compounds, phosphorene oxide compounds, phosphorene sulfide compounds, phosphine oxide compounds and phosphine compounds.
• the blending ratio of the carbodiimidation catalyst is appropriately set.
• the reaction conditions in the carbodiimidation reaction are appropriately set according to the type of aromatic polyisocyanate monomer and the type of catalyst.
• the aromatic polyisocyanate monomer may be subjected to a carbodiimidation reaction in the presence of the above-described organic solvent.
• the aromatic polyisocyanate monomer undergoes decarboxylation condensation to generate carbodiimide groups. As a result, a carbodiimide-modified aromatic polyisocyanate monomer is obtained.
• the carbodiimide-modified aromatic polyisocyanate monomer can contain free (unreacted) aromatic polyisocyanate monomer, organic solvent and carbodiimidation catalyst, if necessary.
• free (unreacted) aromatic polyisocyanate monomers, organic solvents and carbodiimidization catalysts may be removed by known removal means. Removal means include, for example, extraction and distillation.
• a commercially available product may also be used as a carbodiimide-modified aromatic polyisocyanate monomer.
• Commercially available products include, for example, Coronate MX (carbodiimide-modified diphenylmethane diisocyanate, NCO content of 29.0% by mass, manufactured by Tosoh Corporation).
• polyisocyanates as optional components also include other isocyanate group-terminated urethane prepolymers.
• Other isocyanate group-terminated urethane prepolymers are isocyanate group-terminated urethane prepolymers excluding the isocyanate group-terminated urethane prepolymer that is the reaction product of the first raw material polyisocyanate and the first raw material polyol.
• isocyanate group-terminated urethane prepolymers more specifically, isocyanate group-terminated urethane prepolymers obtained using araliphatic polyisocyanates (hereinafter, isocyanate group-terminated araliphatic urethane prepolymers), alicyclic poly Isocyanate group-terminated urethane prepolymer obtained using isocyanate (hereinafter referred to as isocyanate group-terminated alicyclic urethane prepolymer), and isocyanate group-terminated urethane prepolymer obtained using chain aliphatic polyisocyanate (hereinafter referred to as isocyanate group chain-terminated aliphatic urethane prepolymers). These can be used alone or in combination of two or more.
• isocyanate group-terminated urethane prepolymers obtained using araliphatic polyisocyanates
• isocyanate group-terminated urethane prepolymers preferably include isocyanate group-terminated araliphatic urethane prepolymers.
• the polyisocyanate component preferably contains other isocyanate group-terminated urethane prepolymers, and more preferably contains other isocyanate group-terminated araliphatic urethane prepolymers.
• the isocyanate group-terminated araliphatic urethane prepolymer is obtained, for example, by reacting an araliphatic polyisocyanate monomer and/or derivative with the first macropolyol.
• the araliphatic polyisocyanate monomer and/or derivative and the first macropolyol are reacted such that the isocyanate groups are in excess of the hydroxyl groups.
• a well-known method is employ
• polyisocyanates can be used alone or in combination of two or more.
• Other polyisocyanates preferably include polyisocyanate derivatives and other isocyanate group-terminated urethane prepolymers, more preferably polyisocyanate derivatives, and still more preferably aromatic polyisocyanate derivatives. Carbodiimide-modified aromatic polyisocyanate monomers are preferred.
• the ratio of the isocyanate group-terminated urethane prepolymer and other polyisocyanates is appropriately set according to the purpose and application.
• the ratio of the isocyanate group-terminated urethane prepolymer to the total amount of the isocyanate group-terminated urethane prepolymer and other polyisocyanate is, for example, 30% by mass or more, preferably 40% by mass or more, and more preferably, It is 50% by mass or more.
• the proportion of the isocyanate group-terminated urethane prepolymer is, for example, 100% by mass or less, preferably 90% by mass or less, and more preferably 80% by mass or less.
• the ratio of the other polyisocyanate to the total amount of the isocyanate group-terminated urethane prepolymer and the other polyisocyanate is, for example, 0% by mass or more, preferably 10% by mass or more, and more preferably 20% by mass. % or more.
• the ratio of other polyisocyanates is, for example, 70% by mass or less, preferably 60% by mass or less, and more preferably 50% by mass or less.
• the viscosity of the solid content of the polyisocyanate component at 25° C. is, for example, 1000 mPa ⁇ s or more, preferably 5000 mPa ⁇ s or more, and for example, 200,000 mPa ⁇ s or less, preferably 100,000 mPa ⁇ s or less. .
• the polyol component contains, as an essential component, a urethane prepolymer having two or more hydroxyl groups at the molecular ends (hereinafter referred to as a hydroxyl group-terminated urethane prepolymer).
• the hydroxyl group-terminated urethane prepolymer is a reaction product of the second raw material polyisocyanate and the second raw material polyol.
• the second raw material polyisocyanate and the second raw material polyol react so that the isocyanate groups are too small relative to the hydroxyl groups.
• the second raw material polyisocyanate contains an araliphatic polyisocyanate and/or an alicyclic polyisocyanate, and preferably consists of an araliphatic polyisocyanate and/or an alicyclic polyisocyanate.
• the araliphatic polyisocyanate includes, for example, araliphatic polyisocyanate monomers and araliphatic polyisocyanate derivatives.
• araliphatic polyisocyanate monomers include araliphatic diisocyanates.
• araliphatic diisocyanates include 1,3-xylylene diisocyanate (1,3-XDI), 1,4-xylylene diisocyanate (1,4-XDI), tetramethylxylylene diisocyanate, and ⁇ , ⁇ '-diisocyanate-1,4-diethylbenzene. These can be used alone or in combination of two or more.
• the araliphatic polyisocyanate derivative includes modified products similar to the aromatic polyisocyanate derivative described above. More specifically, araliphatic polyisocyanate derivatives include, for example, oligomers, isocyanurate-modified products, allophanate-modified products, polyol-modified products, biuret-modified products, urea-modified products, oxadiazinetrione-modified products and carbodiimide-modified products. body. These can be used alone or in combination of two or more.
• Alicyclic polyisocyanates include, for example, alicyclic polyisocyanate monomers and alicyclic polyisocyanate derivatives.
• Alicyclic polyisocyanate monomers include, for example, alicyclic diisocyanates.
• Alicyclic diisocyanates include, for example, isophorone diisocyanate (IPDI), norbornene diisocyanate ( NBDI ), methylenebis(cyclohexylisocyanate) ( H12MDI ), and bis(isocyanatomethyl)cyclohexane (H6XDI). These can be used alone or in combination of two or more.
• alicyclic polyisocyanate derivatives include modified products similar to the aromatic polyisocyanate derivative described above. More specifically, alicyclic polyisocyanate derivatives include, for example, multimers, isocyanurate modified products, allophanate modified products, polyol modified products, biuret modified products, urea modified products, oxadiazinetrione modified products and carbodiimide modified products. body. These can be used alone or in combination of two or more.
• the araliphatic polyisocyanate and/or alicyclic polyisocyanate preferably includes an araliphatic polyisocyanate monomer, more preferably an araliphatic diisocyanate, and still more preferably, from the viewpoint of adhesion properties.
• the araliphatic polyisocyanate preferably consists of xylylene diisocyanate, more preferably 1,3-xylylene diisocyanate.
• the second raw material polyol contains macropolyol as an essential component.
• the number average molecular weight of the macropolyol (hereinafter referred to as the second macropolyol) in the second raw material polyol is 100 or more. Also, the number average molecular weight of the second macropolyol is usually 15,000 or less.
• second macropolyols include polyether polyols, polyester polyols, polycarbonate polyols, polyurethane polyols, epoxy polyols, vegetable oil polyols, polyolefin polyols, acrylic polyols, and vinyl monomer-modified polyols.
• a 2nd macropolyol can be used individually or in combination of 2 or more types.
• second macropolyols preferably polyether polyols, polyester polyols and polycarbonate polyols are mentioned.
• polyether polyols examples include polyoxyalkylene (C2-3) polyols and polytetramethylene ether polyols, preferably polyoxyalkylene (C2-3) polyols.
• a polyoxy (C2-3) alkylene polyol is an addition polymer of an alkylene oxide having 2 to 3 carbon atoms with a known initiator.
• Initiators include, for example, known low molecular weight polyols and known polyamine compounds.
• Alkylene oxides include alkylene oxides having 2 to 3 carbon atoms. As alkylene oxides, more specifically, for example, ethylene oxide (IUPAC name: oxirane), propylene oxide (1,2-propylene oxide (IUPAC name: methyloxirane)), and triethylene oxide (1,3-propylene oxide). These alkylene oxides can be used alone or in combination of two or more. Alkylene oxides preferably include ethylene oxide and propylene oxide.
• Polyoxyalkylene (C2-3) polyols more specifically, for example, polyoxyethylene polyols, polyoxypropylene polyols, polyoxytriethylene polyols, and polyoxyethylene/polyoxypropylene polyols (random or block co-polyols) polymer).
• Polyoxyalkylene (C2-3) polyols can be used alone or in combination of two or more.
• the polyoxyalkylene (C2-3) polyol preferably includes polyoxypropylene polyol, more preferably polyoxypropylene glycol.
• polyether polyol is more preferable, and polyoxy(C2-3) alkylene polyol is more preferable.
• the number average molecular weight of the second macropolyol is, for example, 100 or more, preferably 150 or more, more preferably 180 or more, still more preferably 300 or more, still more preferably 350 or more, still more preferably 400 or more.
• the number average molecular weight of the second macropolyol is, for example, 15,000 or less, preferably 100,000, more preferably 8,000 or less, even more preferably 5,000 or less, still more preferably 2,000 or less, further preferably 1,000 or less, Especially preferably, it is 700 or less.
• the hydroxyl group equivalent of the second macropolyol is, for example, 90 or more, preferably 120 or more, more preferably 150 or more, still more preferably 200 or more.
• the hydroxyl group equivalent of the second macropolyol is, for example, 1000 or less, preferably 800 or less, more preferably 600 or less, still more preferably 550 or less.
• the average number of hydroxyl groups of the second macropolyol is, for example, 1.8 or more, preferably 2 or more.
• the average number of hydroxyl groups of the second macropolyol is, for example, 6 or less, preferably 4 or less, more preferably 3 or less.
• the second raw material polyol can contain a low-molecular-weight polyol as an optional component.
• the molecular weight of the low-molecular-weight polyol (hereinafter referred to as the second low-molecular-weight polyol) in the second raw material polyol is less than 100, preferably 90 or less.
• first low-molecular-weight polyols described above those having a molecular weight of less than 100 are used as the second low-molecular-weight polyol.
• the second low-molecular-weight polyol can be used alone or in combination of two or more.
• the content of the second low-molecular-weight polyol is appropriately selected within a range that does not impair the excellent effects of the present invention.
• the content of the second low-molecular-weight polyol is, for example, 30 parts by mass or less, preferably 20 parts by mass or less, more preferably 10 parts by mass, with respect to 100 parts by mass of the total amount of the second raw material polyol. part or less, and particularly preferably 0 part by mass. That is, from the viewpoint of adhesive strength, the second raw material polyol preferably consists of the second macropolyol.
• the hydroxyl group-terminated urethane prepolymer is obtained by reacting the second raw material polyisocyanate and the second raw material polyol by a known method. More specifically, the second raw material polyisocyanate and the second raw material polyol are blended at a predetermined ratio and urethanized.
• the equivalent ratio (OH/NCO) of the hydroxyl groups in the second raw polyol to the isocyanate groups in the second raw polyisocyanate is appropriately set according to the average number of functional groups of the second raw polyol. .
• the equivalent ratio (OH/NCO) of the hydroxyl groups in the second raw polyol to the isocyanate groups in the second raw polyisocyanate is, for example, 1. exceeding, preferably 1.1 or more, more preferably 1.3 or more, even more preferably 1.5 or more, and particularly preferably 1.9 or more.
• the equivalent ratio (OH/NCO) is, for example, 50, preferably 15 or less, more preferably 10 or less, still more preferably 3 or less, and most preferably 2.5 or less.
• the equivalent ratio (OH/NCO) of the hydroxyl groups in the second raw polyol to the isocyanate groups in the second raw polyisocyanate is, for example, 1. exceeding, preferably 1.1 or more, more preferably 1.3 or more, even more preferably 3 or more, and most preferably 3.5 or more.
• the equivalent ratio (OH/NCO) is, for example, 50, preferably 15 or less, more preferably 10 or less, even more preferably 5 or less, and most preferably 4.5 or less.
• a known polymerization method is employed in the urethanization reaction.
• Polymerization methods include, for example, bulk polymerization and solution polymerization.
• bulk polymerization for example, the above components are blended and reacted under a nitrogen atmosphere.
• solution polymerization for example, the above components are added to a known organic solvent and reacted under a nitrogen atmosphere.
• the reaction temperature is, for example, 50° C. or higher and, for example, 120° C. or lower, preferably 100° C. or lower.
• the reaction time is, for example, 0.5 hours or longer, preferably 1 hour or longer, and for example, 48 hours or shorter, preferably 24 hours or shorter.
• the mixing ratio of the organic solvent is appropriately set according to the purpose and application.
• bulk polymerization reaction under no solvent
• a known urethanization catalyst is added as necessary. Also, if necessary, unreacted polyisocyanate is removed by a known method. Thereby, a hydroxyl group-terminated urethane prepolymer is obtained.
• the hydroxyl-terminated urethane prepolymer preferably includes a hydroxyl-terminated urethane prepolymer that is a reaction product of an araliphatic polyisocyanate and a polyether polyol, more preferably a reaction product of xylylene diisocyanate and a polyether polyol. and a hydroxyl group-terminated urethane prepolymer that is a product.
• the number average molecular weight of the hydroxyl group-terminated urethane prepolymer is, for example, 300 or more, preferably 350 or more, more preferably 400 or more. Also, the number average molecular weight of the hydroxyl group-terminated urethane prepolymer is, for example, 10,000 or less, preferably 8,000 or less, and more preferably 5,000 or less.
• the hydroxyl group equivalent of the hydroxyl group-terminated urethane prepolymer is, for example, 150 or more, preferably 190 or more, more preferably 300 or more, and still more preferably 350 or more.
• the hydroxyl group equivalent of the hydroxyl group-terminated urethane prepolymer is, for example, 3100 or less, preferably 2100 or less, more preferably 1500, still more preferably 1100 or less, particularly preferably 1000 or less.
• the average number of hydroxyl groups in the hydroxyl group-terminated urethane prepolymer is, for example, 1.8 or more, preferably 2 or more.
• the average number of hydroxyl groups of the hydroxyl group-terminated urethane prepolymer is, for example, 6 or less, preferably 4 or less, more preferably 3 or less.
• the hydroxyl group-terminated urethane prepolymer can contain a free (unreacted) second raw material polyol, an organic solvent and a urethanization catalyst, if necessary.
• the free (unreacted) second raw material polyol, organic solvent and urethanization catalyst may be removed from the hydroxyl group-terminated urethane prepolymer by a known removing means. Removal means include, for example, extraction and distillation.
• the polyol component contains the hydroxyl group-terminated urethane prepolymer, excellent adhesive properties can be obtained. Furthermore, if the polyol component contains the hydroxyl group-terminated urethane prepolymer, excellent pot life and rapid curability are obtained, and workability is improved.
• the content of the hydroxyl group-terminated urethane prepolymer is, for example, 1% by mass or more, preferably 2% by mass or more, more preferably 5% by mass or more, more preferably 5% by mass or more, with respect to the total amount of the polyol component. is 8% by mass or more.
• the proportion of the hydroxyl group-terminated urethane prepolymer relative to the total amount of the polyol component is, for example, 100% by mass or less, preferably 80% by mass or less, more preferably 50% by mass or less, and still more preferably 30% by mass. Below, more preferably 20% by mass or less, particularly preferably 10% by mass or less.
• the polyol component contains a low-molecular-weight polyol (hereinafter referred to as a third low-molecular-weight polyol) as an essential component.
• the molecular weight of the third low molecular weight polyol is less than 200, preferably 180 or less.
• Examples of the third low-molecular-weight polyol include the above-described first low-molecular-weight polyol.
• the third low-molecular-weight polyol can be used alone or in combination of two or more.
• the content of the third low-molecular-weight polyol is, for example, 10 parts by mass or more, preferably 50 parts by mass or more, relative to 100 parts by mass of the hydroxyl group-terminated urethane prepolymer. Also, the content of the third low-molecular-weight polyol is, for example, 1000 parts by mass or less, preferably 300 parts by mass or less with respect to 100 parts by mass of the hydroxyl group-terminated urethane prepolymer.
• the polyol component can contain other macropolyols as optional components.
• Other macropolyols are macropolyols other than the hydroxyl-terminated urethane prepolymers described above.
• macropolyols examples include polyether polyols, polyester polyols, polycarbonate polyols, epoxy polyols, vegetable oil polyols, polyolefin polyols, acrylic polyols and vinyl monomer-modified polyols. These macropolyols can be used alone or in combination of two or more. Macropolyols preferably include polyether polyols.
• polyether polyols examples include the polyether polyols described above as the second raw material polyol. More specifically, polyether polyols include, for example, polyoxyalkylene (C2-3) polyols and polytetramethylene ether polyols, preferably polyoxyalkylene (C2-3) polyols. .
• Polyoxyalkylene (C2-3) polyols more specifically, for example, polyoxyethylene polyols, polyoxypropylene polyols, polyoxytriethylene polyols, and polyoxyethylene/polyoxypropylene polyols (random or block co-polyols) polymer).
• Polyoxyalkylene (C2-3) polyols can be used alone or in combination of two or more.
• the number average molecular weight of other macropolyols is, for example, 500 or more, preferably 1000 or more, more preferably 1500 or more, from the viewpoint of adhesive strength. Moreover, the number average molecular weight of the macropolyol is 10,000 or less, more preferably 7,500 or less, more preferably 5,000 or less, from the viewpoint of adhesive strength.
• the hydroxyl group equivalent of other macropolyols is, for example, 150 or more, preferably 200 or more. Moreover, the hydroxyl group equivalent of other macropolyols is, for example, 10,000 or less, preferably 8,000 or less.
• the average number of hydroxyl groups of other macropolyols is 1.9 or more, preferably 2 or more, more preferably 2.3 or more, still more preferably 2.5 or more, particularly preferably 2.5 or more, from the viewpoint of crosslink density and adhesive strength. is 3 or more.
• the average number of hydroxyl groups of other macropolyols is, for example, 4 or less, preferably 3.5 or less, from the viewpoint of adhesive strength.
• the polyol component preferably contains another macropolyol having an average number of hydroxyl groups of 3 or more, and more preferably contains a polyether polyol having an average number of hydroxyl groups of 3 or more.
• the content of the other macropolyols is, for example, 100 parts by mass or more, preferably 500 parts by mass or more, relative to 100 parts by mass of the hydroxyl-terminated urethane prepolymer.
• the content of other macropolyols is, for example, 5000 parts by mass or less, preferably 2000 parts by mass or less with respect to 100 parts by mass of the hydroxyl group-terminated urethane prepolymer.
• the structural polyurethane adhesive can contain additives as necessary.
• Additives include, for example, plasticizers, fillers, compatibilizers, urethanization catalysts, anti-aging agents, antioxidants, ultraviolet absorbers, heat stabilizers, polymeric light stabilizers, organic solvents, pigments, dyes, Foaming agents, dispersants, leveling agents, thixotropic agents, antiblocking agents, mold release agents, lubricants, interlayer control agents and viscosity control agents.
• the content of the additive is not particularly limited, and is appropriately set according to the purpose and application.
• the additive may be added, for example, to a mixture of a polyisocyanate component and a polyol component (for example, a one-liquid curing adhesive). Further, the additive may be contained, for example, in the main agent described later, may be contained in the curing agent described later, or may be contained in both of them.
• the structural polyurethane adhesive preferably does not contain an organic solvent.
• the structural polyurethane adhesive is preferably a solventless adhesive.
• the polyisocyanate component is, for example, prepared without using an organic solvent, or after being prepared using an organic solvent, the solvent is removed by a known method.
• the polyol component is prepared without using an organic solvent, or is prepared using an organic solvent and then is desolvated by a known method.
• the structural polyurethane adhesive is, as described above, preferably a two-component curing adhesive comprising a main agent containing a polyisocyanate component and a curing agent containing a polyol component.
• the two-component curable adhesive is a resin composition kit (two-component kit) for forming a cured product by blending (mixing) separately prepared main agent and curing agent at the time of use. That is, a resin mixture (polyurethane mixture) is obtained by mixing a main agent and a curing agent, and a cured product (polyurethane cured product) is obtained by a curing reaction of the resin mixture.
• the polyisocyanate component is a reaction product of the first raw polyisocyanate containing the aromatic polyisocyanate and the first raw polyol containing the macropolyol (first macropolyol). It contains an isocyanate group-terminated urethane prepolymer, and the polyol component is a hydroxyl group-terminated reaction product of a second raw polyisocyanate containing an araliphatic polyisocyanate and a second raw polyol containing a macropolyol (second macropolyol). It contains a urethane prepolymer and a low molecular weight polyol (third low molecular weight polyol). As such, the structural polyurethanes described above have excellent adhesive properties.
• the above-mentioned structural polyurethane adhesive is suitably used in structures (for example, automobiles and buildings) composed of a plurality of members for bonding the respective members.
• Structures include, for example, buildings, automobiles, transportation equipment and ships.
• a structural polyurethane adhesive for example, a mixture containing a polyisocyanate component and a polyol component is applied to a member by a known method, cured, and cured as necessary.
• the viscosity at 25°C of the mixture containing the polyisocyanate component and the polyol component is, for example, 100 mPa ⁇ s or more, preferably 300 mPa ⁇ s or more.
• the viscosity of the mixture at 25° C. is, for example, 500000 mPa ⁇ s or less, preferably 100000 mPa ⁇ s or less, more preferably 50000 mPa ⁇ s or less.
• the curing temperature is, for example, 10° C. or higher, preferably 20° C. or higher.
• the curing temperature is, for example, 80° C. or lower, preferably 60° C. or lower.
• the curing time is, for example, 0.5 hours or longer, preferably 1 hour or longer.
• the curing time is, for example, 10 hours or less, preferably 5 hours or less.
• the curing temperature is, for example, 10° C. or higher, preferably 20° C. or higher.
• the curing temperature is, for example, 80° C. or lower, preferably 70° C. or lower.
• the curing time is, for example, 1 hour or more, preferably 2 hours or more.
• the curing time is, for example, 2 weeks or less, preferably 1 week or less.
• the structural polyurethane adhesive can be cured and each member can be adhered well.
• Polyisocyanate component (Preparation example 1) isocyanate group-terminated urethane prepolymer Actcol DL4000 (trade name, polyether polyol having a number average molecular weight of 4000 and an average number of hydroxyl groups of 2, manufactured by Mitsui Chemicals) as the first raw material polyol 289 parts by mass, And Actcol T-5000 (trade name, polyether polyol having a number average molecular weight of 5000 and an average number of hydroxyl groups of 3, manufactured by Mitsui Chemicals) 578 parts by mass, and 4,4'-diphenylmethane diisocyanate (MDI) as the first raw material polyisocyanate ) and 133 parts by mass were mixed.
• Actcol DL4000 trade name, polyether polyol having a number average molecular weight of 4000 and an average number of hydroxyl groups of 2, manufactured by Mitsui Chemicals
• Actcol T-5000 trade name, polyether polyol having a number average molecular
• the equivalent ratio (NCO/OH) at this time was 2.16.
• an isocyanate group-terminated urethane prepolymer (MDI prepolymer) was obtained.
• the MDI prepolymer had a solid concentration of 100% and an isocyanate group content of 2.33% by mass.
• Coronate MX (carbodiimide-modified diphenylmethane diisocyanate, NCO content: 29.0% by mass, manufactured by Tosoh Corporation) was prepared.
• MDI carbodiimide the solid content in Coronate MX is referred to as MDI carbodiimide.
• reaction product is subjected to thin film distillation (wall temperature 145 to 155 ° C., vacuum degree 100 Pa or less, flow rate 3 to 5 g / min, cooling water temperature 10 ° C.), unreacted 1,3-xylylene diisocyanate (monomer ) was distilled off.
• XDI prepolymer an isocyanate group-terminated urethane prepolymer
• the XDI prepolymer had a solid content concentration of 100% and an isocyanate group content of 10.5% by mass.
• ⁇ Polyol component (Preparation example 4) Hydroxyl group-terminated urethane prepolymer (D-400/XDI) 813.01 parts by mass of Actcol D-400 (trade name, polyether polyol having a number average molecular weight of 400 and an average number of hydroxyl groups of 2, manufactured by Mitsui Chemicals) as the second raw material polyol, and 1,3 parts by mass as the second raw material polyisocyanate - 186.99 parts by mass of xylylene diisocyanate (XDI).
• the equivalent ratio (OH/NCO) at this time was 2.02. Then, the resulting mixture was stirred in a nitrogen stream at 60° C. for 1 hour, and further stirred at 70° C.
• the hydroxyl group-terminated urethane prepolymer had a hydroxyl value of 493, a solid content concentration of 100%, and a viscosity of 4500 mPa ⁇ s at 25°C.
• a hydroxyl group-terminated urethane prepolymer was obtained in the same manner as in Preparation Example 4.
• the hydroxyl group-terminated urethane prepolymer had a hydroxyl value of 380, a solid concentration of 100%, and a viscosity of 7400 mPa ⁇ s at 25°C.
• a hydroxyl group-terminated urethane prepolymer was obtained in the same manner as in Preparation Example 4.
• the hydroxyl group-terminated urethane prepolymer had a hydroxyl value of 1,093, a solid content concentration of 100%, and a viscosity of 1,900 mPa ⁇ s at 25°C.
• a hydroxyl group-terminated urethane prepolymer was obtained in the same manner as in Preparation Example 4.
• the hydroxyl group-terminated urethane prepolymer had a hydroxyl value of 524, a solid content concentration of 100%, and a viscosity of 73,600 mPa ⁇ s at 25°C.
• a hydroxyl group-terminated urethane prepolymer was obtained in the same manner as in Preparation Example 4.
• the hydroxyl group-terminated urethane prepolymer had a hydroxyl value of 484, a solid content concentration of 100%, and a viscosity of 2700 mPa ⁇ s at 25°C.
• each component was mixed according to the formulation (solid content) shown in Tables 1 to 3 to prepare a polyisocyanate component and a polyol component. 860 ppm of a catalyst (DABCO 33-LV) was added to the polyol component. This gave a structural polyurethane adhesive comprising a polyisocyanate component and a polyol component.
• a catalyst DABCO 33-LV
• Examples 2 and 3 are formulation examples in which the type of hydroxyl group-terminated urethane prepolymer is changed from Example 1.
• Examples 4 to 7 and Examples 11 to 12 are formulation examples in which the amount of the hydroxyl group-terminated urethane prepolymer is changed from that of Example 1.
• Example 8 is an example of formulation in which no macropolyol is blended with Examples 1 to 3.
• Example 9 is an example of formulation in which MDI carbodiimide is not blended with Example 1.
• Example 10 is an example of formulation in which MDI carbodiimide is not blended with Example 1 and another isocyanate group-terminated urethane prepolymer is blended.
• Comparative Example 1 is a comparative example in which a hydroxyl group-terminated urethane prepolymer is not blended with Example 1.
• Comparative Examples 2 and 3 are comparative examples in which the type of hydroxyl group-terminated urethane prepolymer was changed from that of Example 1.
• Comparative Example 4 is a comparative example in which the hydroxyl group-terminated urethane prepolymer was changed to a macropolyol with respect to Example 1.
• Comparative Example 5 is a comparative example in which a hydroxyl group-terminated urethane prepolymer is not blended with Example 9.
• Adhesion test (PP/SPCC) A test piece was prepared by cutting a polypropylene plate (J707G, made by Prime Polymer (PP)) into a width of 25 mm. This was subjected to a corona treatment immediately before the preparation of the adhesion test piece to adjust the wettability (JISK 6768 (1999)) to 40 dyn/cm or more, and an adherend 1 was obtained.
• an ED-SPCC plate JIS G 3141 (SPCC, SD), test piece
• SPCC cold-rolled steel plate
• ED cationic electrodeposition coating
• the polyisocyanate component and the polyol component were mixed at a ratio such that the equivalent ratio (NCO/OH) was 1.05.
• glass beads ASGB-60, manufactured by AS ONE, 0.250 to 0.355 mm
• the amount of glass beads added was adjusted to 1% by mass with respect to the total amount of the polyisocyanate component, polyol component and glass beads.
• the above mixture is applied to the adherend 1, and the adherend 1 and the adherend 2 are brought into close contact so that the adhesion area is 25 mm ⁇ 12.5 mm and the thickness of the adhesive layer is 0.3 mm. C. for 1 hour and cured at room temperature (18-28.degree. C., 45-55% RH) for 1 week.
• a test plate an adhered test piece (hereinafter referred to as a test plate) was obtained.
• the shear adhesive strength (hereinafter referred to as adhesive strength) [MPa] between the adherend 1 and the adherend 2 was measured with a tensile tester (U-4410, manufactured by Orientec Co., Ltd.) at a tensile speed of 50 mm / min. .
• Adhesion test (CFRP/SPCC) A CFRP (matte) 2.0 ⁇ 25 ⁇ 100 mm manufactured by Standard Test Piece Co., Ltd. was prepared. The CFPR surface was then degreased and cleaned with isopropyl alcohol and then dried. This was designated as adherend 1 . Other than that, the adhesive strength was measured for Examples 1 to 3 and Comparative Example 4 in the same manner as the above adhesive test (PP/SPCC).
• the solidification time indicates the time when the needle of the drying time recorder rides on the top surface of the coating film. Also, the pot life is the time for the coating film to be refilled after the needle has passed through. Then, the ratio of solidification to pot life (solidification time/pot life) was calculated. It should be noted that the smaller the ratio (solidification time/pot life), the longer the pot life and the shorter the solidification time, and thus the workability is excellent.
• the structural polyurethane adhesive of the present invention is suitably used for adhering each member in a structure composed of a plurality of members.

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