WO2020195982A1 - Objet durci de composition de prépolymère d'uréthane ainsi que procédé de fabrication de celui-ci, structure ainsi que procédé de fabrication de celle-ci, et dispositif d'affichage d'image - Google Patents

Objet durci de composition de prépolymère d'uréthane ainsi que procédé de fabrication de celui-ci, structure ainsi que procédé de fabrication de celle-ci, et dispositif d'affichage d'image Download PDF

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WO2020195982A1
WO2020195982A1 PCT/JP2020/011258 JP2020011258W WO2020195982A1 WO 2020195982 A1 WO2020195982 A1 WO 2020195982A1 JP 2020011258 W JP2020011258 W JP 2020011258W WO 2020195982 A1 WO2020195982 A1 WO 2020195982A1
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Prior art keywords
cured product
urethane prepolymer
prepolymer composition
elastic modulus
polyol
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PCT/JP2020/011258
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English (en)
Japanese (ja)
Inventor
翔大 石田
聡一郎 小宮
譲 高橋
和幸 馬籠
淳一 亀井
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日立化成株式会社
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Priority to CN202080024873.XA priority Critical patent/CN113631608A/zh
Priority to KR1020217033701A priority patent/KR20210146336A/ko
Priority to JP2021509064A priority patent/JPWO2020195982A1/ja
Publication of WO2020195982A1 publication Critical patent/WO2020195982A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/302—Water
    • C08G18/307—Atmospheric humidity
    • 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
    • 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
    • C09J175/06—Polyurethanes from polyesters
    • 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
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers

Definitions

  • the present invention relates to a cured product of a urethane prepolymer composition and a method for producing the same, a structure and a method for producing the same, and an image display device.
  • Hot melt adhesive is a solvent-free adhesive, it has less impact on the environment and the human body and can be adhered for a short time, so it is an adhesive suitable for improving productivity.
  • Hot melt adhesives can be broadly divided into two types: those containing a thermoplastic resin as a main component and those containing a reactive resin as a main component.
  • a reactive resin a urethane prepolymer having an isocyanate group at the end is mainly used.
  • the reactive hot melt adhesive containing urethane prepolymer as the main component develops a certain degree of adhesive strength in a short time by cooling and solidifying the adhesive itself after application. After that, the terminal isocyanate group of the urethane prepolymer reacts with moisture (moisture in the air or on the surface of the adherend) to increase the molecular weight, and crosslinks occur to exhibit good adhesive strength. Further, in order to improve adhesiveness, impact resistance and the like, a reactive hot melt adhesive composition containing a urethane prepolymer having a crystalline polyol as a constituent unit is also known (see, for example, Patent Document 1).
  • the present invention provides a cured product of a urethane prepolymer composition having a sufficiently reduced tensile modulus in a urethane prepolymer composition containing a urethane prepolymer having a structural unit derived from a crystalline polyol, and a method for producing the same.
  • the main purpose is to provide.
  • One aspect of the present invention relates to a method for producing a cured product of a urethane prepolymer composition containing a urethane prepolymer.
  • the urethane prepolymer has a structural unit derived from a polyol including a structural unit derived from a crystalline polyol.
  • One aspect of the method for producing a cured product of the urethane prepolymer composition is a step of moisture-curing the urethane prepolymer composition to obtain a first cured product of the urethane prepolymer composition, and a first cured product. It comprises a step of heating to obtain a second cured product of the urethane prepolymer composition.
  • the tensile elastic modulus of the second cured product is lower than the tensile elastic modulus of the first cured product, for example, it may be 50% or less of the tensile elastic modulus of the first cured product.
  • the crystalline polyol may contain a crystalline polyester polyol.
  • the content of the structural unit derived from the crystalline polyol may be 5% by mass or more based on the total amount of the structural unit derived from the polyol.
  • Another aspect of the method for producing a cured product of the urethane prepolymer composition is to heat the first cured product obtained by moisture-curing the urethane prepolymer composition to obtain a second cured product of the urethane prepolymer composition.
  • a step of obtaining a cured product is provided.
  • Another aspect of the present invention comprises a structure comprising a first adherend, a second adherend, and a cured product layer that adheres the first adherend and the second adherend to each other.
  • the method for producing the structure is a step of preparing a first adherend, a resin layer containing a urethane prepolymer composition containing a urethane prepolymer, and a laminate in which the second adherends are laminated in this order.
  • the present invention comprises a step of heating the cured product of No. 1 to form a second cured product layer containing the second cured product of the urethane prepolymer composition.
  • Urethane prepolymers have structural units derived from polyols, including structural units derived from crystalline polyols.
  • Another aspect of the present invention relates to a cured product of a urethane prepolymer composition containing a urethane prepolymer.
  • Urethane prepolymers have structural units derived from polyols, including structural units derived from crystalline polyols.
  • the cured product of the urethane prepolymer composition has a tensile elastic modulus of 15 MPa or less.
  • the structure includes a first adherend, a second adherend, and a cured product layer that adheres the first adherend and the second adherend to each other.
  • the cured product layer contains the cured product of the urethane prepolymer composition described above.
  • Another aspect of the present invention provides an image display device comprising the above structure.
  • a cured product of the urethane prepolymer composition having a sufficiently reduced tensile elastic modulus and a method for producing the cured product thereof.
  • an image display device using such a structure is provided.
  • FIG. 6 is a semi-logarithmic graph showing a change in tensile elastic modulus with respect to the heating time of the first cured product of Example 1. It is a semi-logarithmic graph which shows the change of the tensile elastic modulus with respect to the elapsed time at room temperature of the 2nd cured product of Example 1.
  • FIG. 6 is a semi-logarithmic graph showing a change in tensile elastic modulus with respect to the heating time of the first cured product of Example 1. It is a semi-logarithmic graph which shows the change of the tensile elastic modulus with respect to the elapsed time at room temperature of the 2nd cured product of Example 1.
  • polypoly means a compound having two or more hydroxyl groups in the molecule.
  • polyisocyanate means a compound having two or more isocyanate groups in the molecule.
  • the method for producing a cured product of the urethane prepolymer composition of one embodiment is a step of moisture-curing the urethane prepolymer composition to obtain a first cured product of the urethane prepolymer composition (hereinafter, “first step”). ”) And the step of heating the first cured product to obtain the second cured product of the urethane prepolymer composition (hereinafter, may be referred to as“ second step ”). Be prepared.
  • Urethane prepolymers have structural units derived from polyols, including structural units derived from crystalline polyols.
  • the urethane prepolymer contains a polymer chain containing a structural unit derived from a polyol containing a structural unit derived from a crystalline polyol and a structural unit derived from polyisocyanate, and has an isocyanate group as a terminal group of the polymer chain. You may.
  • the urethane prepolymer may be, for example, a reaction product of a polyol containing a crystalline polyol and a polyisocyanate, and having an isocyanate group as a terminal group of the reaction product.
  • a urethane prepolymer composition containing a urethane prepolymer has a property that the urethane prepolymer is mainly polymerized and cured by moisture by reacting with moisture in the air or moisture on the surface of an adherend. ing.
  • the polyol giving a structural unit derived from the polyol includes a crystalline polyol.
  • the urethane prepolymer is a polymerization containing a structural unit derived from a crystalline polyol, a structural unit derived from a polyol other than the crystalline polyol (that is, an amorphous polyol), and a structural unit derived from polyisocyanate. May include chains.
  • the crystallinity can be judged in the state at 25 ° C.
  • a crystalline polyol means a polyol that is crystalline at 25 ° C
  • a non-crystalline polyol (amorphous polyol) means a polyol that is non-crystalline at 25 ° C.
  • the crystallinity can also be judged by the presence or absence of the melting point (Tm) (endothermic peak associated with melting at DSC).
  • the crystalline polyol can be used without particular limitation as long as it is a compound having two or more hydroxyl groups and crystalline at 25 ° C.
  • Examples of the crystalline polyol include a crystalline polyester polyol, a crystalline polycarbonate polyol, a crystalline polycaprolactone polyol, and the like.
  • One of these crystalline polyols may be used alone, or two or more thereof may be used in combination.
  • the crystalline polyol may contain a crystalline polyester polyol.
  • a polyester polyol that is crystalline at 25 ° C. can be selected and used as the polyester polyol produced by the polycondensation reaction of the polyhydric alcohol and the polycarboxylic acid.
  • the polyester polyol has, for example, a polyhydric alcohol having 2 to 15 carbon atoms and 2 or 3 hydroxyl groups, and 2 to 14 carbon atoms (including carbon atoms in the carboxyl group), and 2 to 2 to It may be a polycondensate with a polycarboxylic acid having 6 carboxyl groups.
  • the polyester polyol may be a linear polyester diol formed from a diol and a dicarboxylic acid, or a branched polyester triol formed from a triol and a dicarboxylic acid.
  • the branched polyester triol can also be obtained by reacting a diol with a tricarboxylic acid.
  • polyhydric alcohol examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, butanediol isomers, pentanediol isomers, hexanediol isomers, and 2,2-.
  • Diols aliphatic or alicyclic diols such as 1,4-cyclohexanedimethanol; aromatic diols such as 4,4'-dihydroxydiphenylpropane, bisphenol A, bisphenol F, pyrocatechol, resorcinol, hydroquinone and the like can be mentioned.
  • One type of polyhydric alcohol may be used alone, or two or more types may be used in combination. Among these, an aliphatic diol is preferable, and an aliphatic diol having 2 to 6 carbon atoms is more preferable.
  • polycarboxylic acid examples include aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, 1,2,4-benzenetricarboxylic acid; maleic acid, fumaric acid, aconitic acid, 1,2,3-propane.
  • Polycarboxylic acids such as tricarboxylic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, cyclohexane-1,2-dicarboxylic acid, 1,4-cyclohexanediene-1,2-dicarboxylic acid
  • an alicyclic polycarboxylic acid and the like can be mentioned.
  • One type of polycarboxylic acid may be used alone, or two or more types may be used in combination.
  • a polycarboxylic acid derivative such as a carboxylic acid anhydride or a compound in which a part of the carboxyl group is esterified can also be used.
  • the polycarboxylic acid derivative include dodecylmaleic acid and octadecenylmaleic acid.
  • the number average molecular weight (Mn) of the crystalline polyester polyol is preferably in the range of 500 to 10000, more preferably in the range of 800 to 9000, and further preferably in the range of 1000 to 8000 from the viewpoint of improving waterproofness and adhesive strength. is there.
  • the number average molecular weight (Mn) is a value measured by gel permeation chromatography (GPC) and converted into standard polystyrene. The GPC measurement can be performed under the following conditions.
  • the content of the structural unit derived from the crystalline polyol may be 5% by mass or more, 8% by mass or more, or 10% by mass or more, based on the total amount of the structural unit derived from the polyol.
  • the content of structural units derived from crystalline polyol is 80% by mass or less, 60% by mass or less, 50% by mass or less, 45% by mass or less, 40% by mass or less, based on the total amount of structural units derived from polyol. , 35% by mass or less, or 30% by mass or less.
  • the amount is 80% by mass or less based on the total amount of structural units derived from the polyol, the workability tends to be excellent.
  • the crystalline polyol may contain a polyol other than the crystalline polyester polyol.
  • the polyol may contain an amorphous polyol.
  • the amorphous polyol include an amorphous polyester polyol and a polyether polyol.
  • a polyester polyol that is not crystalline at 25 ° C. can be selected and used as the polyester polyol produced by the polycondensation reaction of the polyhydric alcohol and the polycarboxylic acid.
  • Examples of the amorphous polyester polyol include an amorphous polyester polyol having a number average molecular weight (Mn) of 3000 or less and an amorphous polyester polyol having a number average molecular weight (Mn) of 5000 or more.
  • the Mn of the amorphous polyester polyol having Mn of 3000 or less is preferably in the range of 500 to 3000, more preferably in the range of 1000 to 3000, from the viewpoint of improving the adhesive strength of the urethane prepolymer composition.
  • the Mn of the amorphous polyester polyol having Mn of 5000 or more is preferably in the range of 5000 to 9000, more preferably in the range of 7000 to 8000, from the viewpoint of improving impact resistance.
  • polyether polyol examples include polyethylene glycol, polypropylene glycol, polybutylene glycol, polytetramethylene glycol, ethylene oxide-modified polypropylene glycol and the like.
  • the Mn of the polyether polyol is preferably in the range of 500 to 5000, more preferably in the range of 700 to 4500, and further preferably in the range of 1000 from the viewpoint of initial adhesive strength, adhesive strength after curing, and appropriate open time after coating. It is in the range of ⁇ 4000.
  • One type of polyether polyol may be used alone, or two or more types may be used in combination.
  • the amorphous polyol may contain a polyol other than the amorphous polyester polyol and the polyether polyol.
  • Polyisocyanate can be used without particular limitation as long as it is a compound having two or more isocyanate groups.
  • the polyisocyanate include aromatic isocyanates such as diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate and p-phenylenedi isocyanate; alicyclic isocyanates such as dicyclohexylmethane diisocyanate and isophorone diisocyanate; hexamethylene diisocyanate and the like.
  • aromatic isocyanates such as diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate and p-phenylenedi isocyanate
  • alicyclic isocyanates such as dicyclohexylmethane diisocyanate and is
  • the polyisocyanate preferably contains an aromatic diisocyanate, and more preferably contains a diphenylmethane diisocyanate.
  • One type of polyisocyanate may be used alone, or two or more types may be used in combination.
  • Urethane prepolymer can be synthesized by reacting polyol with polyisocyanate.
  • the urethane prepolymer preferably contains a polymer chain containing a structural unit derived from a polyol containing a structural unit derived from a crystalline polyol and a structural unit derived from polyisocyanate, and has an isocyanate group as a terminal group of the polymer chain.
  • the ratio of the isocyanate group (NCO) equivalent of polyisocyanate to the hydroxyl group (OH) of the polyol containing a crystalline polyol isocyanate group (NCO) equivalent of polyisocyanate / hydroxyl group (OH) of the polyol).
  • NCO / OH Equivalent, NCO / OH is greater than 1, preferably 1.5 to 3.0, more preferably 1.8 to 2.5.
  • NCO / OH ratio 1.5 or more, the viscosity of the obtained urethane prepolymer is suppressed from becoming too high, and the workability tends to be improved easily.
  • NCO / OH ratio 3.0 or less, foaming is less likely to occur during the moisture curing reaction of the urethane prepolymer composition, and a decrease in adhesive strength tends to be easily suppressed.
  • the urethane prepolymer composition may be composed of urethane prepolymer, but may contain other components if necessary.
  • the urethane prepolymer composition may further contain a catalyst from the viewpoint of accelerating the curing of the pretan prepolymer and developing higher adhesive strength.
  • a catalyst from the viewpoint of accelerating the curing of the pretan prepolymer and developing higher adhesive strength.
  • the catalyst include dibutyltin dilaurate, dibutylthioneoctate, dimethylcyclohexylamine, dimethylbenzylamine, trioctylamine and the like.
  • the content of the catalyst may be 0.01 to 1% by mass based on the total amount of the urethane prepolymer composition.
  • the urethane prepolymer composition may further contain a thermoplastic polymer from the viewpoint of increasing the rubber elasticity of the cured product to be formed and further improving the impact resistance.
  • a thermoplastic polymer examples include polyurethane, ethylene-based copolymer, propylene-based copolymer, vinyl chloride-based copolymer, acrylic copolymer, styrene-conjugated diene block copolymer and the like.
  • the content of the thermoplastic polymer may be 1 to 20% by mass based on the total amount of the urethane prepolymer composition.
  • the urethane prepolymer composition may further contain a tackifier resin from the viewpoint of imparting stronger adhesiveness to the formed cured product.
  • a tackifier resin examples include rosin resin, rosin ester resin, hydrogenated rosin ester resin, terpene resin, terpene phenol resin, hydrogenated terpene resin, petroleum resin, hydrogenated petroleum resin, kumaron resin, ketone resin, and styrene resin. Examples thereof include modified styrene resin, xylene resin, and epoxy resin.
  • the content of the tackifier resin may be 1 to 20% by mass based on the total amount of the urethane prepolymer composition.
  • the urethane prepolymer composition may contain an appropriate amount of an antioxidant, a pigment, an ultraviolet absorber, a surfactant, a flame retardant, a filler and the like, if necessary.
  • the urethane prepolymer composition is moisture-cured to obtain a first cured product.
  • the conditions for producing the first cured product may be the same as the conditions for moisture curing a normal reactive hot melt adhesive.
  • a urethane prepolymer composition is melted at 80 to 180 ° C. to prepare a film having a thickness of 10 to 500 ⁇ m by coating or the like, and the film is subjected to a temperature of 10 to 35 ° C., preferably a temperature. It can be obtained by moisture curing in an environment of 15 to 30 ° C., more preferably a temperature of 20 to 25 ° C., and a relative humidity of 30% or more, preferably 30 to 70% for 12 to 168 hours.
  • the tensile elastic modulus of the first cured product is not particularly limited, but may be more than 15 MPa and 100 MPa or less.
  • the tensile elastic modulus of the first cured product may be more than 15 MPa, 25 MPa or more, or 35 MPa or more, and may be 100 MPa or less, 80 MPa or less, or 60 MPa or less.
  • a tensile elastic modulus means a value measured by the method described in Example.
  • the first cured product is heated to obtain a second cured product.
  • the cured product of the urethane prepolymer composition means a second cured product.
  • the tensile elastic modulus of the first cured product generally tends to decrease by heating at a temperature exceeding the crystal melting point of the crystal component contained in the first cured product. That is, the change (reduction) in the tensile elastic modulus of the first cured product suggests the formation of the second cured product, and the second cured product exhibits a tensile elastic modulus lower than that of the first cured product.
  • the heating temperature of the first cured product can be appropriately set according to the crystal melting point of the crystal component, and may be, for example, 60 ° C. or higher, or 80 ° C. or higher.
  • the heating time of the first cured product can be appropriately set according to the decrease in tensile elastic modulus, and may be, for example, 2 minutes or more, 10 minutes or more, or 1 hour or more.
  • the second cured product may exhibit a tensile elastic modulus lower than that of the first cured product.
  • the tensile elastic modulus of the second cured product may be, for example, 50% or less of the tensile elastic modulus of the first cured product, and may be 45% or less, 40% or less, or 35% or less.
  • the impact resistance and stress relaxation property tend to be excellent.
  • the pretan prepolymer contained in the urethane prepolymer composition has a structural unit derived from a polyol whose polymer chain contains a structural unit derived from a crystalline polyol. Therefore, when the urethane prepolymer composition is melted and a film is formed by coating or the like, crystallization of the crystalline polyol proceeds as the temperature decreases, and a crystal portion is formed. After that, the first cured product obtained by moisture curing tends to have a higher tensile elastic modulus than that without the crystal portion because the crystal portion loses its flexibility.
  • the second cured product has a tensile modulus lower than that of the first cured product. It is considered to show elastic modulus. Further, since the molecular weight (number average molecular weight) of the second cured product is significantly increased with the polyurethane formation as compared with the case of melting the urethane prepolymer composition, the second cured product is left at room temperature (23 ° C.). However, it is expected that the progress of crystallization again will be suppressed.
  • the tensile elastic modulus is gradually restored by leaving it at room temperature (23 ° C.), it is considered that it takes an annual time to restore the tensile elastic modulus to 50% of the tensile elastic modulus of the first cured product. Be done.
  • a urethane prepolymer composition containing a urethane prepolymer having a structural unit derived from a crystalline polyol when the cured product of the urethane prepolymer composition obtained by moisture curing is heated, the tensile elastic modulus Is found in the phenomenon that is reduced. Therefore, another method for producing a cured product of the urethane prepolymer composition is to heat the first cured product obtained by moisture-curing the urethane prepolymer composition to obtain the first cured product of the urethane prepolymer composition. It may include a step of obtaining the cured product of 2.
  • the method for manufacturing a structure of one embodiment includes a first adherend, a second adherend, and a cured product layer that adheres the first adherend and the second adherend to each other.
  • the method for producing the structure is a step of preparing a first adherend, a resin layer containing a urethane prepolymer composition containing a urethane prepolymer, and a laminate in which the second adherends are laminated in this order.
  • step A the urethane prepolymer composition in the resin layer is moisture-cured to form a first cured product layer containing the first cured product of the urethane prepolymer composition.
  • step B A step of forming
  • step C a step of forming the cured product layer (2) (hereinafter, may be referred to as “C step”).
  • Urethane prepolymers have structural units derived from polyols, including structural units derived from crystalline polyols.
  • the cured product layer is synonymous with the second cured product layer.
  • a first adherend, a resin layer containing a urethane prepolymer composition containing a urethane prepolymer, and a laminate in which a second adherend is laminated in this order are prepared. Since the resin layer can exhibit adhesiveness by cooling and solidifying the urethane prepolymer composition, in the laminated body, the first adherend and the second adherend are adhered by the resin layer. Can be what you are doing.
  • the first adherend and the second adherend include metal base materials such as SUS and aluminum, and non-metal base materials such as polycarbonate, polyamide, glass, wood, cloth, and leather.
  • the first adherend and the second adherend may be the same or different from each other.
  • the laminate includes, for example, a step of forming a resin layer on at least one of a first adherend and a second adherend using the above-mentioned urethane prepolymer composition, and a first step via the resin layer. It can be obtained by a manufacturing method including a step of crimping the adherend and the second adherend.
  • the resin layer can be formed, for example, by melting the above-mentioned urethane prepolymer composition and applying it. Further, the resin layer can also be formed by, for example, melting the above-mentioned urethane prepolymer composition and then applying the film onto a support film such as polyethylene terephthalate to prepare a film and using the film.
  • the method for applying the urethane prepolymer composition is not particularly limited, and examples thereof include a method using a dispenser.
  • the melting temperature of the urethane prepolymer composition may be, for example, 80 to 180 ° C.
  • the thickness of the film may be, for example, 10 to 500 ⁇ m.
  • the method of crimping the first adherend and the second adherend via the resin layer is not particularly limited, and examples thereof include a method of crimping using a pressure roll or the like.
  • the urethane prepolymer composition in the resin layer of the laminate is moisture-cured to form a first cured product layer containing the first cured product of the urethane prepolymer composition.
  • the conditions for forming the first cured product layer may be the same as the conditions for obtaining the first cured product described above, for example. That is, the laminate is placed at a temperature of 10 to 35 ° C., preferably a temperature of 15 to 30 ° C., more preferably a temperature of 20 to 25 ° C., and a relative humidity of 30% or more, preferably 30 to 70% for 12 to 168 hours.
  • a first cured product layer containing the first cured product of the urethane prepolymer composition can be formed by moisture curing with.
  • the first cured product in the first cured product layer of the laminate is then heated to form a second cured product layer containing the second cured product of the urethane prepolymer composition.
  • the conditions for forming the second cured product layer may be the same as the conditions for obtaining the second cured product described above, for example. That is, the laminate including the first cured product layer containing the first cured product is heated at a heating temperature of 60 ° C. or higher or 80 ° C. or higher for 2 minutes or longer, 10 minutes or longer, or 1 hour or longer.
  • a second cured product layer containing a second cured product of the urethane prepolymer composition can be formed.
  • the second cured product may exhibit a tensile elastic modulus lower than the tensile elastic modulus of the first cured product.
  • the tensile elastic modulus of the second cured product may be, for example, 50% or less of the tensile elastic modulus of the first cured product, and may be 45% or less, 40% or less, or 35% or less.
  • the urethane prepolymer has a structural unit derived from a polyol including a structural unit derived from a crystalline polyol, and has a tensile elastic modulus of 15 MPa or less.
  • the cured product of the urethane prepolymer composition means a second cured product.
  • the tensile elastic modulus of the cured product (second cured product) of the urethane prepolymer composition is 15 MPa or less, and may be 13 MPa or less, 10 MPa or less, or 8 MPa or less.
  • the second cured product tends to be excellent in impact resistance and stress relaxation property.
  • the tensile elastic modulus of the second cured product may be 1 MPa or more, 3 MPa or more, or 5 MPa or more.
  • the crystalline polyol may contain a crystalline polyester polyol.
  • the content of the structural unit derived from the crystalline polyol may be 5% by mass or more based on the total amount of the structural unit derived from the polyol.
  • the cured product of the urethane prepolymer composition can adhere various adherends through it.
  • the cured product of the urethane prepolymer composition has excellent impact resistance because the tensile elastic modulus is sufficiently reduced.
  • the structure of one embodiment includes a first adherend, a second adherend, and a cured product layer that adheres the first adherend and the second adherend to each other, and is a cured product.
  • the layer contains a cured product of the urethane prepolymer composition described above.
  • the image display device of one embodiment includes the structure of this embodiment.
  • Examples of the image display device include a plasma display (PDP), a liquid crystal display (LCD), a cathode ray tube (CRT), a field emission display (FED), an organic EL display (OELD), a 3D display, and electronic paper (EP). Can be mentioned.
  • PDP plasma display
  • LCD liquid crystal display
  • CRT cathode ray tube
  • FED field emission display
  • OELD organic EL display
  • 3D display electronic paper
  • Example 1 ⁇ Preparation of urethane prepolymer>
  • the pre-dehydrated polyol (A) was added to the reaction vessel in the blending amount (part by mass) shown in Table 1 and mixed uniformly.
  • the polyisocyanate (B) is further added to the reaction vessel in the blending amount (part by mass) shown in Table 1, mixed uniformly, reacted at 110 ° C. for 1 hour, and further defoamed and stirred at 110 ° C. for 1 hour.
  • the obtained urethane prepolymer has an (NCO) equivalent / (OH) equivalent of greater than 1, suggesting that it has an isocyanate group as the terminal group of the polymerized chain.
  • the obtained urethane prepolymer was used as the urethane prepolymer composition of Example 1 in the preparation of the first cured product.
  • A1 Crystalline polyester polyol containing adipic acid and 1,6-hexanediol as main components (number of hydroxyl groups: 2, number average molecular weight: 5000)
  • A2 Crystalline polyester polyol containing adipic acid and 1,6-hexanediol as main components (number of hydroxyl groups: 2, number average molecular weight 3000)
  • A3 Amorphous polyester polyol containing adipic acid and ethylene glycol as main components (number of hydroxyl groups: 2, number average molecular weight 2000)
  • A4 Amorphous polyester polyol containing isophthalic acid and ethylene glycol as main components (number of hydroxyl groups: 2, number average molecular weight: 2000)
  • A5 Amorphous polyester polyol containing isophthalic acid and neopentyl glycol as main components (number of hydroxyl groups: 2, number average molecular weight: 2000)
  • A6 Polypropylene glycol
  • the urethane prepolymer composition was melted at 100 ° C. to form a film having a thickness of 100 ⁇ m, and then the film was moisture-cured by allowing it to stand in a constant temperature and humidity chamber at a temperature of 23 ° C. and a humidity of 50% for 24 hours.
  • the first cured product was obtained.
  • a test piece is prepared by punching the first cured product with a No. 1 dumbbell, and the tensile elastic modulus (MPa) of the test piece is based on JIS K-7127 using Autograph AGS-X (manufactured by Shimadzu Corporation). And measured.
  • the tensile elastic modulus of the first cured product was 26.4 MPa.
  • FIG. 1 is a semi-logarithmic graph showing the change in tensile elastic modulus with respect to the heating time of the first cured product of Example 1.
  • the tensile elastic modulus of the first cured product after 2 minutes of heating was 4.9 MPa
  • the tensile elastic modulus after 60 minutes of heating was 2.0 MPa.
  • FIG. 2 is a semi-logarithmic graph showing the change in tensile elastic modulus with respect to the elapsed time of the second cured product of Example 1 at room temperature. As shown in FIG.
  • the tensile elastic modulus of the second cured product tends to be restored (improved) with the passage of time, but the restoration time estimated from the approximate curve is the tensile elastic modulus of the first cured product. It was found that the time to restore to 50% (13.2 MPa) was about 1.5 years, and the time to restore to 100% (26.4 MPa) was about 50,000 years.
  • the obtained urethane prepolymer has an (NCO) equivalent / (OH) equivalent of greater than 1, suggesting that it has an isocyanate group as the terminal group of the polymerized chain.
  • the acrylic copolymer (C) was added to the obtained urethane prepolymer in the blending amount (parts by mass) shown in Table 2 to obtain the urethane prepolymer compositions of Examples 2-1 to 2-5.
  • the formation of the second cured product is suggested by heating the first cured product obtained by moisture-curing the urethane prepolymer composition containing the urethane prepolymer having a structural unit derived from the crystalline polyol. Was done. Further, it was confirmed that the tensile elastic modulus of the second cured product was sufficiently reduced with respect to the tensile elastic modulus of the first cured product.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention fournit un procédé de fabrication d'objet durci de composition de prépolymère d'uréthane qui contient un prépolymère d'uréthane. Ce procédé de fabrication comporte : une étape au cours de laquelle une composition de prépolymère d'uréthane est durcie à l'humidité, et un premier objet durci de cette composition de prépolymère d'uréthane est obtenu ; et une étape au cours de laquelle le premier objet durci est chauffé, et un second objet durci de cette composition de prépolymère d'uréthane est obtenu. Le prépolymère d'uréthane possède une unité structurale dérivée d'un polyol contenant une unité structurale dérivée d'un polyol cristallin.
PCT/JP2020/011258 2019-03-28 2020-03-13 Objet durci de composition de prépolymère d'uréthane ainsi que procédé de fabrication de celui-ci, structure ainsi que procédé de fabrication de celle-ci, et dispositif d'affichage d'image WO2020195982A1 (fr)

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CN202080024873.XA CN113631608A (zh) 2019-03-28 2020-03-13 氨基甲酸酯预聚物组合物的固化物及其制造方法、结构体及其制造方法、以及图像显示装置
KR1020217033701A KR20210146336A (ko) 2019-03-28 2020-03-13 유레테인 프리폴리머 조성물의 경화물 및 그 제조 방법, 구조체 및 그 제조 방법, 및 화상 표시 장치
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Citations (6)

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Publication number Priority date Publication date Assignee Title
JP2007091996A (ja) * 2005-09-30 2007-04-12 Dainippon Ink & Chem Inc 湿気硬化型ポリウレタンホットメルト接着剤
JP2016113552A (ja) * 2014-12-16 2016-06-23 Dic株式会社 湿気硬化型ホットメルトウレタン組成物及び接着剤
WO2017187968A1 (fr) * 2016-04-26 2017-11-02 日立化成株式会社 Composition adhésive thermofusible réactive durcissant à l'humidité et son procédé de production
JP2017222776A (ja) * 2016-06-15 2017-12-21 日立化成株式会社 耐衝撃性反応性ホットメルト接着剤組成物
JP2018177937A (ja) * 2017-04-11 2018-11-15 積水フーラー株式会社 湿気硬化型ホットメルト接着剤
JP2019165827A (ja) * 2018-03-22 2019-10-03 株式会社リブドゥコーポレーション 使い捨ておむつ

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007091996A (ja) * 2005-09-30 2007-04-12 Dainippon Ink & Chem Inc 湿気硬化型ポリウレタンホットメルト接着剤
JP2016113552A (ja) * 2014-12-16 2016-06-23 Dic株式会社 湿気硬化型ホットメルトウレタン組成物及び接着剤
WO2017187968A1 (fr) * 2016-04-26 2017-11-02 日立化成株式会社 Composition adhésive thermofusible réactive durcissant à l'humidité et son procédé de production
JP2017222776A (ja) * 2016-06-15 2017-12-21 日立化成株式会社 耐衝撃性反応性ホットメルト接着剤組成物
JP2018177937A (ja) * 2017-04-11 2018-11-15 積水フーラー株式会社 湿気硬化型ホットメルト接着剤
JP2019165827A (ja) * 2018-03-22 2019-10-03 株式会社リブドゥコーポレーション 使い捨ておむつ

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