Method for producing a polyurethane resin having vibration damping properties and polyurethane composition

Abstract

The present invention aims to provide a polyurethane resin that exhibits superior vibration damping characteristics compared to conventional materials, while simultaneously possessing sufficient physical properties such as tensile strength and elongation at break, and having sufficient adhesive performance. [Solution] A method for producing a polyurethane resin having vibration damping properties from a polyurethane composition comprising a first liquid L1 containing agent A and a second liquid L2 containing agent B, The method wherein agent A comprises an active hydrogen compound SO having an active hydrogen group-containing unit U1-1 and a nominal functional value of 0.5 or more and less than 1.5, and an active hydrogen compound MO having an active hydrogen group-containing unit U1-2 and a nominal functional value of 1.5 or more, and the polyurethane composition further satisfies predetermined conditions 1 and 2.

Description

Technical Field

[0001] The present invention relates to a method for producing a polyurethane resin having vibration damping properties and the field of polyurethane compositions. The present invention is suitable for industrial applications, particularly for uses in adhesion and sealing in the production and repair of automobiles.

Background Art

[0002] Polyurethane compositions have a long history in applications such as elastic adhesion and sealing in the manufacture and repair of vehicles such as automobiles, trucks, trains, boats, and the like.

[0003] Polyurethane compositions used for such elastic adhesion and sealing are required to have high vibration damping properties capable of sufficiently suppressing vibrations and noises from the viewpoint of vehicle comfort.

[0004] As such a polyurethane composition having vibration damping properties, for example, in Patent Document 1, in a two-component curing type composition, polymer fine particles having an average particle diameter within a predetermined range and a glass transition temperature within a predetermined range are blended at 5% by mass or more, so that a cured product thereof has a loss tangent of 0.15 or more under predetermined conditions. A two-component type polyurethane composition is disclosed.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] However, the present inventor considered that the polyurethane composition described in Patent Document 1 has room for further improvement in making the vibration damping properties even better.

[0007] Therefore, the object of the present invention is to provide a polyurethane composition suitable for industrial applications, particularly for bonding and sealing applications in the production and repair of automobiles, which exhibits superior vibration damping characteristics compared to conventional materials, and at the same time provides a polyurethane resin with sufficient physical properties such as tensile strength and elongation at break. [Means for solving the problem]

[0008] To achieve the above objective, the present invention has the following configuration in one embodiment. [1] A method for producing a polyurethane resin having vibration damping properties from a polyurethane composition comprising a first liquid L1 containing agent A and a second liquid L2 containing agent B, The aforementioned agent A comprises an active hydrogen compound SO having an active hydrogen group-containing unit U1-1 and a nominal functional value of 0.5 or more and less than 1.5, and an active hydrogen compound MO having an active hydrogen group-containing unit U1-2 and a nominal functional value of 1.5 or more. The aforementioned agent B contains an isocyanate compound IC having isocyanate group-containing units U1-3 and having a nominal functional value of 1.5 or more. The active hydrogen compound SO, the active hydrogen compound MO, and the isocyanate compound IC may further have a structure formed by the reaction of an active hydrogen group with an isocyanate group. The aforementioned structure has a nominal functional value. 0 Formed by reacting an active hydrogen compound having a nominal functional value of 0.5 or more and less than 1.5 and / or an active hydrogen compound having a nominal functional value of 1.5 or more with an isocyanate compound having a nominal functional value of 1.5 or more, wherein the nominal functional value is 0.5 or more, less than 1.5 It has a unit U2-1 derived from an active hydrogen compound, a unit U2-2 derived from an active hydrogen compound having a nominal functional value of 1.5 or more, and a unit U2-3 derived from an isocyanate compound having a nominal functional value of 1.5 or more. The polyurethane resin is obtained by mixing and reacting agent A and agent B, and in addition to the units U2-1 to U2-3 which may be optionally present, it has unit U3-1 derived from the active hydrogen compound SO, unit U3-2 derived from unit U1-2, and unit U3-3 derived from unit U1-3. The ratio (NCO / H) of the number of moles of NCO groups (NCO) contained in agent B to the number of moles of active hydrogen groups (H) contained in agent A is 0.7 (preferably 1.0) or more and less than 1.5. The polyurethane composition is provided by a method that satisfies the following conditions 1 and 2. Condition 1: 5 ≤ ([A_MU] / [A_HUI]) × 100 ≤ 28 (Of the above conditions 1, [A_MU] represents the sum of the number of moles of the active hydrogen compound SO having the unit U1-1 in a total weight of 100g of the first liquid L1 and the second liquid L2, and the number of moles of the unit U2-1 in a total weight of 100g of the first liquid L1 and the second liquid L2. [A_HUI] represents the sum of the number of moles of units U1-3 in the total weight of 100g of the first liquid L1 and the second liquid L2, where the molecular weight per isocyanate group is 200 or less, and the number of moles of units U2-3 in the total weight of 100g of the first liquid L1 and the second liquid L2, where the molecular weight per isocyanate group is 200 or less. Condition 2 20≦{([ARMU]+[ARHUMO]) / [ARHUI]}×100≦90 (Of the above condition 2, [ARMU] represents the number of moles of the active hydrogen compound SO having the unit U1-1 in the total weight of 100g of the first liquid L1 and the second liquid L2. [ARHUMO] represents the number of moles of units U1-2 in the total weight of 100g of the first liquid L1 and the second liquid L2, where the molecular weight per active hydrogen atom is 200 or less. [ARHUI] represents the number of moles of units U1-3 in the total weight of 100g of the first liquid L1 and the second liquid L2, where the molecular weight per isocyanate group is 200 or less. [2] A method relating to [1], which further satisfies the following condition 3. Condition 3: 25 ≤ ([A_HUMO] / [A_HUI]) × 100 ≤ 49 (Of the above condition 3, [A_HUMO] represents the sum of the number of moles of units U1-2 in which the molecular weight per active hydrogen atom is 200 or less, and the number of moles of units U2-2 in which the molecular weight per active hydrogen atom is 200 or less, in a total weight of 100g of the first liquid L1 and the second liquid L2. [A_HUI] represents the sum of the number of moles of units U1-3 in the total weight of 100g of the first liquid L1 and the second liquid L2, where the molecular weight per isocyanate group is 200 or less, and the number of moles of units U2-3 in the total weight of 100g of the first liquid L1 and the second liquid L2, where the molecular weight per isocyanate group is 200 or less. [3] The method according to [1] or [2], characterized in that the method is used in the manufacture of an adhesive. [4] A method for manufacturing an automotive component, comprising the step of manufacturing an automotive component using an adhesive obtained by the method described in [3]. [5] A polyurethane composition comprising a first liquid L1 containing agent A and a second liquid L2 containing agent B, used for producing a polyurethane resin having vibration damping properties, The aforementioned agent A comprises an active hydrogen compound SO having an active hydrogen group-containing unit U1-1 and a nominal functional value of 0.5 or more and less than 1.5, and an active hydrogen compound MO having an active hydrogen group-containing unit U1-2 and a nominal functional value of 1.5 or more. The aforementioned agent B contains an isocyanate compound IC having isocyanate group-containing units U1-3 and having a nominal functional value of 1.5 or more. The active hydrogen compound SO, the active hydrogen compound MO, and the isocyanate compound IC may further have a structure formed by the reaction of an active hydrogen group with an isocyanate group. The structure is formed by reacting an active hydrogen compound having a nominal functional value of 0.5 or more and less than 1.5 and / or an active hydrogen compound having a nominal functional value of 1.5 or more with an isocyanate compound having a nominal functional value of 1.5 or more, and has a unit U2-1 derived from the active hydrogen compound having a nominal functional value of 0.5 or more and less than 1.5, a unit U2-2 derived from the active hydrogen compound having a nominal functional value of 1.5 or more, and a unit U2-3 derived from the isocyanate compound having a nominal functional value of 1.5 or more. The polyurethane resin is obtained by mixing and reacting agent A and agent B, and in addition to the units U2-1 to U2-3 which may be optionally present, it has unit U3-1 derived from the active hydrogen compound SO, unit U3-2 derived from unit U1-2, and unit U3-3 derived from unit U1-3. The ratio (NCO / H) of the number of moles of NCO groups (NCO) contained in agent B to the number of moles of active hydrogen groups (H) contained in agent A is 0.7 (preferably 1.0) or more and less than 1.5. The polyurethane composition satisfies the following conditions 1 and 2. vinegar. Condition 1: 5 ≤ ([A_MU] / [A_HUI]) × 100 ≤ 28 (Of the above conditions 1, [A_MU] represents the sum of the number of moles of the active hydrogen compound SO having the unit U1-1 in a total weight of 100g of the first liquid L1 and the second liquid L2, and the number of moles of the unit U2-1 in a total weight of 100g of the first liquid L1 and the second liquid L2. [A_HUI] represents the sum of the number of moles of units U1-3 in the total weight of 100g of the first liquid L1 and the second liquid L2, where the molecular weight per isocyanate group is 200 or less, and the number of moles of units U2-3 in the total weight of 100g of the first liquid L1 and the second liquid L2, where the molecular weight per isocyanate group is 200 or less. Condition 2 20≦{([ARMU]+[ARHUMO]) / [ARHUI]}×100≦90 (Of the above condition 2, [ARMU] represents the number of moles of the active hydrogen compound SO in 100 g in total weight of the first liquid L1 and the second liquid L2, [ARHUMO] represents the number of moles of units among the unit U1-2 in 100 g in total weight of the first liquid L1 and the second liquid L2, where the molecular weight per active hydrogen is 200 or less, [ARHUI] represents the number of moles of units among the unit U1-3 in 100 g in total weight of the first liquid L1 and the second liquid L2, where the molecular weight per isocyanate group is 200 or less.)

Advantages of the Invention

[0009] The method of the present invention exhibits excellent vibration damping characteristics superior to the conventional ones, and at the same time, has physical properties such as sufficient tensile strength and elongation at break, and can provide a polyurethane resin having sufficient adhesion performance.

Brief Description of the Drawings

[0010] [Figure 1] It is a diagram showing E’ and tanδ of the polyurethane adhesive resin prepared in Example 2 and Comparative Example 4. [Figure 2] It is a diagram conceptually showing an example of the structure of a polymer obtained from the polyurethane composition of the present invention. [Figure 3] It is a diagram conceptually showing an example of the structure of a polymer obtained from the polyurethane composition of the present invention.

Embodiments for Carrying Out the Invention

[0011] In this text, the prefix "poly" in the names of substances such as "polyol," "polyisocyanate," "polyether," or "polyamine" formally indicates that each substance contains more than one of the functional groups appearing in its name per molecule. The term "polymer" as used herein includes, firstly, a collection of polymers that are chemically homogeneous but differ in degree of polymerization, molar mass, and chain length, and which are produced by "poly" reactions (polymerization, polyaddition, polycondensation). Secondly, the term also includes derivatives of such polymer collections derived from "poly" reactions, i.e., compounds obtained by reactions of functional groups on a particular polymer, e.g., addition or substitution, which may be chemically homogeneous or heterogeneous. The term further includes so-called prepolymers, i.e., reactive oligomeric initial adducts in which functional groups are involved in the formation of the polymer. The term "polyurethane polymer" includes all polymers produced by the so-called diisocyanate polyaddition method. This term also includes polymers in which urethane groups are substantially or completely absent. Examples of polyurethane polymers include polyether polyurethane, polyester polyurethane, polyether polyurea, polyurea, polyester polyurea, polyisocyanurate, and polycarbodiimide.

[0012] In this specification, "molecular weight" is understood to mean the molar mass (grams / mol) of one molecule or one molecular residue. "Average molecular weight" refers to the number-average Mn of a polydisperse mixture of oligomer molecules, polymer molecules, or molecular residues, and is usually determined by gel permeation chromatography (GPC) with polystyrene as the standard.

[0013] Weight percentage (abbreviated as weight%) refers to the proportion of a component's mass in a composition based on its overall composition, unless otherwise specified. The terms "mass" and "weight" are used synonymously in this document.

[0014] A "primary hydroxyl group" refers to an OH group bonded to a carbon atom that has two hydrogen atoms.

[0015] All industry standards and norms described in this document pertain to the version effective as of the initial filing date.

[0016] The "average OH functional value" is the average number of OH groups per polyol molecule across all polyol molecules. For example, if 50% of the polymer molecules contain two hydroxyl groups and the remaining 50% contain three hydroxyl groups, the average OH functional value is 2.5. This average OH functional value can be calculated specifically from the hydroxyl value and the molecular weight (Mn) measured by GPC.

[0017] Nominal functional value refers to the theoretical functional value based on the raw material components used to manufacture a compound, or the functional value according to catalog specifications. For example, polyetherol obtained by adding alkylene oxide to glycerin has a nominal functional value of 3. In this specification, a compound having a predetermined number (or more) of a certain functional group represents a compound whose nominal functional value is a predetermined number (or more). The average number of functional groups is preferably approximately equal to the nominal functional value.

[0018] The polyurethane composition of the present invention consists of a first liquid L1 containing agent A and a second liquid L2 containing agent B, which are stored in separate packages before application and mixed at the time of application of the polyurethane composition.

[0019] In this specification, a numerical range represented by "~" means a range that includes the numbers written before and after "~" as the lower and upper limits, respectively. In this specification, unless otherwise specified, each component may be composed of the substance corresponding to that component, either individually or in combination of two or more substances. If a component contains two or more substances, the content of the component means the total content of the two or more substances. In this specification, unless otherwise specified, there are no particular restrictions on the method of manufacture of each component. For example, conventionally known methods may be used. In addition, commercially available products may be used as each component. In this specification, the term "room temperature" refers to ambient temperature (0°C to 40°C). The term "room temperature curing type" means that the composition can be cured at ambient temperature (0°C to 40°C) without the need for external heat, and has a sufficiently long pot life. The term "room temperature" refers to a temperature of 23°C.

[0020] In this specification, a component that satisfies certain conditions is considered a "main component" if, with respect to 100% by weight of a given component, the component that satisfies the certain conditions accounts for 70% by weight or more of that component. In this case, it is more preferably 80% by weight or more, even more preferably 90% by weight or more, and even more preferably 95% by weight or more.

[0021] The polyurethane composition of the present invention, having the above-described structure, is expected to produce the desired effects. The reason for this is not clear, but it is presumed to be as follows. The polyurethane composition of the present invention contains an active hydrogen compound or a unit derived therefrom (U2-1) having only one active hydrogen group-containing unit (U1-1) (with a nominal functional value of 0.5 or more and less than 1.5), and an isocyanate compound or a hard segment unit derived therefrom having at least two isocyanate group-containing units (U1-3) (with a nominal functional value of 1.5 or more), of which the molecular weight per isocyanate group is less than or equal to a predetermined value (corresponding to a unit of unit U1-3 where the molecular weight per isocyanate group is 200 or less). An active hydrogen compound having an active hydrogen group-containing unit (U1-1) that is present in a predetermined proportion to (a unit in unit U2-3 where the molecular weight per isocyanate group is 200 or less) and has a nominal functional value of 0.5 or more and less than 1.5, and an active hydrogen compound having a unit (a unit in unit U1-2 where the molecular weight per active hydrogen group is 200 or less) that has multiple active hydrogen group-containing units and has a molecular weight per active hydrogen group of a predetermined proportion or less (a unit in unit U1-2 where the molecular weight per active hydrogen group is 200 or less) or a hard segment unit derived therefrom (a unit in unit U2-2 where the molecular weight per active hydrogen group is 200 or less) The above composition is formed when a unit having at least two isocyanate group-containing units (U1-3) (with a nominal functional value of 1.5 or more), and having a unit where the molecular weight per isocyanate group is less than or equal to a predetermined value (corresponding to a unit among units U1-3 where the molecular weight per isocyanate group is 200 or less), or a hard segment unit derived therefrom (corresponding to a unit among units U2-3 where the molecular weight per isocyanate group is 200 or less), is present in a predetermined proportion to the isocyanate compound or derived therefrom. The polyurethane resin obtained after curing will have a structure in which units with one end free (formation of U3-1 in addition to U2-1) and hard segment units (formation of units in U2-2 where the molecular weight per active hydrogen group is 200 or less, and units in U2-3 where the molecular weight per isocyanate group is 200 or less, as well as units in U3-2 where the molecular weight per active hydrogen group is 200 or less, and units in U3-3 where the molecular weight per isocyanate group is 200 or less) are suitably distributed within the cured molecule.As a result, the polyurethane resin obtained by curing the above composition has a three-dimensional structure with a deliberately broken crosslink network, while possessing diverse inter-crosslinking molecular weights including highly cohesive hard segment units. This is expected to result in sufficient vibration damping characteristics over a wider temperature range, while simultaneously exhibiting sufficient physical properties such as tensile strength and elongation at break, and thus providing excellent adhesive performance. Furthermore, the presence of a compound containing active hydrogen or hard segment units derived therefrom in a predetermined ratio with respect to the isocyanate compound or hard segment units derived therefrom further enhances the aforementioned effects. The mechanism described above is the inventor's speculation, and the mechanism of the present invention is not limited to that described above.

[0022] The present invention will be described in detail below. The present invention provides a production method for producing a polyurethane resin having vibration damping properties from a polyurethane composition comprising a first liquid L1 containing agent A and a second liquid L2 containing agent B.

[0023] [Solution 1 L1 containing Agent A] The first solution L1 contains agent A. Agent A contains an active hydrogen compound SO having a nominal functional value of 0.5 or more and less than 1.5, and an active hydrogen compound MO having a nominal functional value of 1.5 or more.

[0024] [Activated hydrogen compound SO] An active hydrogen compound SO having a nominal functional value of 0.5 or more and less than 1.5 theoretically has an active hydrogen group-containing unit U1-1 of 0.5 or more and less than 1.5. In other words, an active hydrogen compound SO is theoretically an active hydrogen compound having an active hydrogen group of 0.5 or more and less than 1.5 at the molecular terminal or side chain. The above active hydrogen compound SO preferably has a nominal functional value of 0.8 to 1.2, more preferably 0.9 to 1.1, even more preferably 0.95 to 1.05, and most preferably consists of an active hydrogen compound having a nominal functional value of 1 as its main component, and most preferably consists of an active hydrogen compound having a nominal functional value of 1. The above active hydrogen group may be a hydroxyl group, a thiol group, or an amine group, but is preferably a hydroxyl group.

[0025] The active hydrogen compound SO may be an aliphatic monool having a structure in which one hydroxyl group is bonded to an aliphatic compound, an alicyclic monool having a structure in which one hydroxyl group is bonded to an alicyclic compound, or a polyether monool having a structure in which one hydroxyl group is bonded to a polyether compound. The active hydrogen compound SO may be a single compound or a mixture of two or more compounds.

[0026] The above aliphatic monool may be, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, amyl alcohol, and alkanols such as 2-ethylhexanol.

[0027] The above-mentioned alicyclic monool is a compound having a carbon ring such as a benzene ring or a cycloalkyl group and only one hydroxyl group. When the active hydrogen compound SO has a benzene ring, it is preferable that the hydroxyl group is bonded to a part other than the benzene ring (for example, an optionally substituted hydrocarbon group).

[0028] The above-mentioned alicyclic monool may be a terpene phenol compound. The terpene phenol compound is a phenol derivative of a terpene, preferably an adduct of camphene and phenol, and more preferably an adduct of a monoterpene and phenol. As an adduct of camphene and phenol, for example, the compound described in Japanese Patent No. 7395090 can be used.

[0029] The above alicyclic monool may also be cardanol. Cardanol is a natural phenol compound extracted from cashew nut shells, a byproduct of the cashew nut industry, and has the following structure. [ka]

[0030] The above polyether monool may be, for example, a PO homopolymer, a blocked EO-PO copolymer, or a random EO / PO copolymer. The above polyether monool is preferably a PO homopolymer. As far as the copolymer is concerned, EO represents ethylene oxide and PO represents propylene oxide.

[0031] From the viewpoint of the effects of the present invention, the active hydrogen compound SO is preferably a monool having a cyclic structure, more preferably a monool having a cyclic structure and an ether bond, more preferably a monool having a benzene ring and an ether bond, even more preferably a monool having a phenoxy group, and most preferably 1-phenoxy-2-propanol (nominal functional value: 1.152.19 g / mol).

[0032] The active hydrogen compound SO preferably mainly comprises a compound in which the molecular weight per active hydrogen atom is 200 or less, more preferably mainly comprises a compound in which the molecular weight per active hydrogen atom is 100 to 200, more preferably mainly comprises a compound in which the molecular weight per active hydrogen atom is 110 to 190, even more preferably mainly comprises a compound in which the molecular weight per active hydrogen atom is 120 to 180, and even more preferably mainly comprises a compound in which the molecular weight per active hydrogen atom is 130 to 170.

[0033] The active hydrogen compound SO is present in the polyurethane composition of the present invention in an amount and ratio that satisfies conditions 1 and 2, and preferably in an amount and ratio that satisfies condition 3. Furthermore, in a preferred embodiment of the present invention, the active hydrogen compound SO is present in an amount of preferably 1.0 to 10.0% by weight, more preferably 2.0 to 9.0% by weight, even more preferably 3.0 to 8.0% by weight, even more preferably 3.5 to 6.5% by weight, and most preferably 4.0 to 5.6% by weight, based on 100% by weight of the total weight of the first liquid L1.

[0034] [Active hydrogen compound MO] An active hydrogen compound MO having a nominal functional value of 1.5 or higher theoretically has 1.5 or more active hydrogen group-containing units U1-2. In other words, an active hydrogen compound MO is theoretically an active hydrogen compound having 1.5 or more active hydrogen groups at its molecular termini or side chains (with a nominal functional value of 1.5 or higher). The nominal functional value of the above active hydrogen compound MO is preferably 1.6 or higher, more preferably 1.8 or higher, and particularly preferably 2.0 or higher. The above active hydrogen group may be a hydroxyl group, a thiol group, or an amine group, but is preferably a hydroxyl group.

[0035] The active hydrogen compound MO may be, for example, an aliphatic polyol having a structure in which at least two hydroxyl groups are bonded to an aliphatic compound, an alicyclic polyol having a structure in which at least two hydroxyl groups are bonded to an alicyclic compound, or a polyether polyol having a structure in which at least two hydroxyl groups are bonded to a polyether compound. The active hydrogen compound MO may be a single compound or a mixture of two or more compounds.

[0036] Active hydrogen compounds MO include active hydrogen compounds MOH, in which the molecular weight per active hydrogen atom is 200 or less, and active hydrogen compounds MOS, in which the molecular weight per active hydrogen atom is greater than 200. Here, the molecular weight per active hydrogen atom is determined by the average molecular weight and average number of functional groups (number of active hydrogen groups) of the active hydrogen compound. For example, the molecular weight per active hydrogen atom of a polyfunctional polyol with an average molecular weight of 600 and an average number of functional groups of 3 is 200.

[0037] [Active hydrogen compound MOH] The active hydrogen compound MOH has a structure in which the molecular weight per active hydrogen group is relatively small, and can form so-called hard segments in polyurethane resin. The active hydrogen compound MOH may be a single compound having such a structure, or a mixture of two or more compounds having such a structure, but a mixture of two or more compounds is more preferable.

[0038] The active hydrogen compound MOH preferably mainly comprises a compound in which the molecular weight per active hydrogen atom is 30 to 200, more preferably a compound in which the molecular weight per active hydrogen atom is 35 to 200, more preferably a compound in which the molecular weight per active hydrogen atom is 40 to 200, and even more preferably a compound in which the molecular weight per active hydrogen atom is 45 to 200.

[0039] The active hydrogen compound MOH may, for example, have an average of 2 to 20 active hydrogen groups per molecule. The number of active hydrogen groups per molecule is more preferably 2 to 15, even more preferably 2 to 12, particularly preferably 2 to 9, and most preferably 2 to 7.

[0040] The active hydrogen compound MOH may be, for example, an alkyl polyol, a polyether polyol, a polyester polyol, a poly(meth)acrylic polyol, or a castor oil-based polyol. Among these, the active hydrogen compound MOH preferably includes a mixture of alkyl polyol and polyether polyol.

[0041] The alkyl polyol described above is preferably a diol in which two primary hydroxyl groups are bonded to both ends of a hydrocarbon chain having 2 to 20 carbon atoms. The number of carbon atoms in the hydrocarbon chain is more preferably 2 to 11, even more preferably 3 to 10, and particularly preferably 4 to 9.

[0042] The alkyl polyols mentioned above include, for example, ethylene glycol (62.07 g / mol), 1,3-propanediol (76.09 g / mol), 1,4-butanediol (90.12 g / mol), 1,5-pentanediol (104.15 g / mol), 1,6-hexanediol (118.18 g / mol), 1,7-heptanediol (132.21 g / mol), 1,8-octanediol (146.24 g / mol), and 1,9-nonanediol (16 It may also be one or more selected from the group consisting of 0.27 g / mol, 1,10-decanediol (174.30 g / mol), 1,11-undecanediol (188.33 g / mol), 1,12-dodecanediol (202.36 g / mol), 1,13-tridecanediol (216.39 g / mol), 1,14-tetradecanediol (230.42 g / mol), and 2-ethyl-1,3-hexanediol (130.23 g / mol).

[0043] The alkyl polyol is preferably a combination of a diol in which two primary hydroxyl groups are bonded to both ends of a hydrocarbon chain having 2 to 7 carbon atoms, and a diol in which two primary hydroxyl groups are bonded to both ends of a hydrocarbon chain having 9 to 14 carbon atoms. It is even more preferable that it is a combination of 1,4-butanediol or 1,5-pentanediol and 1,9-nonanediol.

[0044] The above-mentioned polyether polyols, polyester polyols, poly(meth)acrylic polyols, and castor oil-based polyols have a polyether skeleton, polyester skeleton, poly(meth)acrylic skeleton, or castor oil skeleton, and have at least two active hydrogen groups at the molecular ends or side chains.

[0045] Polyether polyols are compounds having a polyether chain as the main chain and two or more hydroxyl groups. A polyether is a group having two or more ether bonds, and a specific example of this is a group having a total of two or more structural units -Ra-O-Rb-. Here, in the above structural units, Ra and Rb each independently represent a hydrocarbon group. The hydrocarbon group may be, for example, a linear alkylene group having 1 to 10 carbon atoms. Polyether polyols may be, for example, polyoxyethylenediol (polyethylene glycol), polyoxypropylenediol (polypropylene glycol: PPG), polyoxypropylenetriol, ethylene oxide / propylene oxide copolymer polyol, polybutadiene polyol (Poly BD), polytetramethylene ether glycol (PTMG), polytetraethylene glycol, or sorbitol-based polyols.

[0046] Polyester polyols may be compounds obtained by a polycondensation reaction between a dicarboxylic acid and a diol. Poly(meth)acrylic polyols may be, for example, homopolymers or copolymers of (meth)acrylic acid esters having hydroxyl groups.

[0047] Castor oil-based polyols are polymers derived from castor oil, and preferably have secondary hydroxyl groups. Castor oil-based polyols may be, for example, alkylene oxide adducts of castor oil, epoxidized castor oil, halogenated castor oil, or transesterified castor oil with polyhydric alcohols.

[0048] The castor oil-based polyol may be, for example, the URIC series (Ito Oil Co., Ltd.). The castor oil-based polyol may be one type only or a combination of two or more types.

[0049] Castor oil-based polyols preferably have an average of 2 to 3 hydroxyl groups per molecule. Castor oil-based polyols preferably have a hydroxyl value of 10 to 1000 mg KOH / g, more preferably 20 to 750 mg KOH / g, and even more preferably 30 to 500 mg KOH / g. The hydroxyl value can be determined by a neutralization titration method using an aqueous potassium hydroxide solution as described in JIS K 0070.

[0050] The plant-derived polyol may be certified using the so-called mass balance method. In that case, the plant-derived polyol A3 preferably has a biomass ratio of 20% or more. This biomass ratio is more preferably 50% or more, even more preferably 60% or more, even more preferably 70% or more, even more preferably 80% or more, and most preferably 90% or more.

[0051] The above-mentioned polyether polyols, polyester polyols, poly(meth)acrylic polyols, and castor oil-derived polyols preferably have an average molecular weight of 200 to 1500. The above average molecular weight is more preferably 220 to 1200, even more preferably 240 to 1000, and particularly preferably 250 to 900.

[0052] The active hydrogen compound MOH is present in the polyurethane composition of the present invention in an amount and ratio that satisfies conditions 1 and 2, and preferably in an amount and ratio that satisfies condition 3. Furthermore, in a preferred embodiment of the present invention, the active hydrogen compound MOH is present in an amount of preferably 0.5 to 15% by weight, more preferably 1.0 to 12.0% by weight, even more preferably 2.0 to 10.0% by weight, even more preferably 2.5 to 9.5% by weight, and most preferably 3.0 to 9.0% by weight, based on 100% by weight of the total weight of the first liquid L1.

[0053] [Molecular weight per active hydrogen group is over 200 in active hydrogen compounds (MOS)] The active hydrogen compound MOS has a structure in which the molecular weight per active hydrogen group is relatively large, and can form so-called soft segments in polyurethane resin. The active hydrogen compound MOS may be a single compound or a mixture of two or more compounds having such a structure, but it is preferably a mixture of two or more compounds.

[0054] The active hydrogen compound MOS preferably mainly comprises a compound with a molecular weight of 210 to 4000 per active hydrogen atom, more preferably mainly comprises a compound with a molecular weight of 220 to 3000 per active hydrogen atom, more preferably mainly comprises a compound with a molecular weight of 230 to 2500 per active hydrogen atom, even more preferably mainly comprises a compound with a molecular weight of 240 to 2400 per active hydrogen atom, even more preferably mainly comprises a compound with a molecular weight of 250 to 2200 per active hydrogen atom, and most preferably mainly comprises a compound with a molecular weight of 1000 to 2000 per active hydrogen atom.

[0055] The active hydrogen compound MOS may, for example, have an average of 2 to 20 active hydrogen groups per molecule. The number of active hydrogen groups is more preferably 2 to 15, even more preferably 2 to 12, particularly preferably 2 to 9, and most preferably 2 to 7.

[0056] The active hydrogen compound MOS may be, for example, a polyether polyol, a polyester polyol, a poly(meth)acrylic polyol, or a castor oil-derived polyol. Among these, the active hydrogen compound MOS preferably contains a polyether polyol.

[0057] Except for having a larger molecular weight per active hydrogen group, the active hydrogen compound MOS may have a structure similar to that of the active hydrogen compound MOH, such as an alkyl polyol, polyether polyol, polyester polyol, poly(meth)acrylic polyol, or castor oil-based polyol.

[0058] The active hydrogen compound MOS is present in the polyurethane composition of the present invention in an amount and ratio that satisfies conditions 1 and 2, and preferably in an amount and ratio that satisfies condition 3. Furthermore, in a preferred embodiment of the present invention, the active hydrogen compound MOS is present in an amount of preferably 20 to 70% by weight, more preferably 25 to 65% by weight, even more preferably 30 to 60% by weight, and particularly preferably 35 to 55% by weight, based on 100% by weight of the total weight of the first liquid L1.

[0059] [Second solution L2 containing agent B] The second liquid L2 of the above urethane composition contains agent B. Agent B contains the isocyanate compound IC.

[0060] [Isocyanate compound IC] The isocyanate compound IC is an isocyanate compound having a nominal functional value of 1.5 or higher. The isocyanate compound IC has an average of 1.5 or more isocyanate groups at the molecular ends or side chains. The nominal functional value of the isocyanate compound IC is preferably 1.8 to 5, more preferably 1.9 to 4, and even more preferably 2 to 3.

[0061] The isocyanate compound IC may preferably include a low molecular weight isocyanate compound ICL having a relatively low molecular weight and a high molecular weight isocyanate compound ICH having a relatively high molecular weight.

[0062] [Low molecular weight isocyanate compound ICL] Low molecular weight isocyanate compounds ICL are preferably compounds or oligomers thereof having multiple isocyanate groups in the molecule. Compounds having multiple isocyanate groups in the molecule include, for example, toluene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (unsubstituted MDI; also called pure MDI or monomeric MDI), 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 1,4-phenylenediisocyanate, polymethylene polyphenylene polyisocyanate, xylylene diisocyanate (XDI), tetramethyl xylylene diisocyanate (TMXDI), tolidine diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), triphenylmethane triisocyanate, polymeric MDI (diphenylmethane diisocyanate (pure Aromatic polyisocyanates such as compounds with high molecular weight (MDI), modified MDI (e.g., isocyanurate-modified MDI (a trimer of MDI), carbodiimide-modified MDI, urethane-modified MDI, etc.), pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate (NBDI), transcyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), bis(isocyanate-methyl)cyclohexane (H6XDI), dicyclohexylmethane diisocyanate (H6XDI) 12 These may be aliphatic and / or alicyclic polyisocyanates, such as MDIs, carbodiimide modifiers, and isocyanurate modifiers.

[0063] The low molecular weight isocyanate compound ICL preferably comprises a combination of an oligomer of an aromatic isocyanate and an isocyanurate allophanate modified aliphatic isocyanate, and more preferably comprises a combination of polymeric MDI and an isocyanurate allophanate modified PDI.

[0064] The low molecular weight isocyanate compound ICL may contain plant-derived components. When the low molecular weight isocyanate compound ICL contains plant-derived components, it preferably has a biomass content of 20% or more. This biomass content is more preferably 50% or more, even more preferably 60% or more, even more preferably 70% or more, even more preferably 80% or more, and most preferably 90% or more.

[0065] The low molecular weight isocyanate compound ICL may be certified using the so-called mass balance method. In this case, the isocyanate compound IC preferably has a biomass ratio of 20% or more. This biomass ratio is more preferably 50% or more, even more preferably 60% or more, even more preferably 70% or more, even more preferably 80% or more, and most preferably 90% or more.

[0066] The low molecular weight isocyanate compound ICL preferably mainly comprises a compound with a molecular weight of 80 to 200 per isocyanate group, more preferably a compound with a molecular weight of 90 to 190 per isocyanate group, even more preferably a compound with a molecular weight of 100 to 180 per isocyanate group, particularly preferably a compound with a molecular weight of 110 to 170 per isocyanate group, and most preferably a compound with a molecular weight of 120 to 160 per isocyanate group. Here, the molecular weight per isocyanate group is determined by the average molecular weight and average number of functional groups (number of isocyanate groups) of the isocyanate compound. For example, the molecular weight per isocyanate group of a polyfunctional isocyanate compound with an average molecular weight of 250 and an average number of functional groups of 2 is 125.

[0067] The low molecular weight isocyanate compound ICL is preferably present in an amount of 10 to 50% by weight, more preferably 15 to 45% by weight, even more preferably 20 to 40% by weight, even more preferably 22 to 37% by weight, and most preferably 25 to 35% by weight, relative to 100% by weight of agent B. Note that this low molecular weight isocyanate compound ICL includes residual isocyanate compounds resulting from the formation of the urethane prepolymer UPP, which will be described later.

[0068] [High molecular weight isocyanate compound ICH] The high molecular weight isocyanate compound ICH is preferably a urethane prepolymer UPP obtained by reacting a compound having multiple isocyanate groups in its molecule with a compound having an active hydrogen-containing group in its molecule, such that the isocyanate groups are in excess of the active hydrogen-containing groups (preferably, the ratio of isocyanate groups to active hydrogen-containing groups is about 2 to 6:1). The active hydrogen-containing group refers to a group containing active hydrogen, such as a hydroxyl group, an amino group, or an imino group, but preferably a hydroxyl group. The urethane prepolymer UPP is obtained by reacting a compound having multiple isocyanate groups in its molecule with a compound having an active hydrogen-containing group in its molecule under conditions such that the isocyanate groups are in excess of the active hydrogen-containing groups. Since various reaction patterns can be expected between the active hydrogen groups of the active hydrogen compound and the isocyanate groups of the isocyanate compound, the resulting urethane prepolymer UPP has a broad molecular weight distribution that is not uniform. In addition, after the formation of the urethane prepolymer UPP, the compound having multiple isocyanate groups in its molecule usually remains as well. Therefore, if a compound having multiple isocyanate groups in its molecule corresponds to the ICL, the composition produced by the reaction for the formation of the urethane prepolymer UPP consists of UPP and ICL with diverse molecular weight distributions.

[0069] Compounds having multiple isocyanate groups in their molecule that are used to prepare urethane prepolymer UPP may be those described as low molecular weight isocyanate compounds ICL.

[0070] The compound having an active hydrogen-containing group in its molecule used to prepare the urethane prepolymer UPP may be an active hydrogen compound MO (i.e., MOS) having an active hydrogen-containing unit with a molecular weight of more than 200 per active hydrogen group, and may also contain an active hydrogen compound SO. Preferably, it is a combination of an active hydrogen compound SO and an active hydrogen compound MO (MOS) having an active hydrogen-containing unit with a molecular weight of more than 200 per active hydrogen group. Alternatively, the urethane prepolymer UPP may be UPP-CE (UPP-Chain Extender) prepared by adding an active hydrogen compound MOH having an active hydrogen-containing unit with a molecular weight of 200 or less per active hydrogen group as a chain extender to the composition obtained by the urethane prepolymer UPP production reaction. In this case, the amount of MOH added as a chain extender is adjusted so that the amount of active hydrogen is less than 50% of the amount of isocyanate groups in the composition obtained by the urethane prepolymer UPP production reaction.

[0071] In a preferred embodiment of the present invention, the active hydrogen compound SO used to prepare the urethane prepolymer UPP may be a combination of a monool derived from propylene oxide and cardanol. In a preferred embodiment of the present invention, the active hydrogen compound MO used to prepare the urethane prepolymer UPP may be a combination of a polybutadiene polyol and polytetramethylene ether glycol.

[0072] The number of isocyanate groups in the high molecular weight isocyanate compound ICH may theoretically be 2 to 5, preferably 2 to 4, and more preferably 2 to 3. The above isocyanate groups are preferably located at the molecular ends or side chains of the high molecular weight isocyanate compound ICH.

[0073] In one preferred embodiment, the urethane prepolymer UPP is prepared by reacting an active hydrogen group-containing compound having a nominal functional value of 1.5 or more with an isocyanate compound having a nominal functional value of 1.5 or more, wherein the active hydrogen group-containing compound has a molecular weight greater than 200 per active hydrogen group. Furthermore, the active hydrogen group-containing compound and / or isocyanate compound used in the preparation of the urethane prepolymer UPP may have, for example, unit U2-2 (corresponding to the soft segment of U2-2) derived from the active hydrogen group-containing compound having a nominal functional value of 1.5 or more, unit U2-1 derived from the active hydrogen group-containing compound having a nominal functional value of 0.5 or more and less than 1.5, and / or unit U2-3 derived from the isocyanate group-containing compound having a nominal functional value of 1.5 or more. Furthermore, UPP-CE is a composition obtained by reacting the urethane prepolymer UPP with an active hydrogen compound MOH having an active hydrogen group-containing unit with a molecular weight of 200 or less per active hydrogen group as a chain extender, and in which U2-2, which corresponds to a hard segment, is intentionally introduced. The high molecular weight isocyanate compound ICH has an average molecular weight of about 400 to 200,000. The above average molecular weight is preferably 1,000 to 100,000.

[0074] Thus, the high molecular weight isocyanate compound ICH may contain the polyurethane prepolymer UPP and / or UPP-CE, and the isocyanate compound, including the low amount of isocyanate compound (ICL) remaining during the production process of the polyurethane prepolymer UPP and the low amount of isocyanate compound (ICL) added later, is preferably present in an amount of 5 to 70% by weight, more preferably 20 to 60% by weight, and even more preferably 25 to 50% by weight, based on 100% by weight of agent B.

[0075] The isocyanate compound IC, comprising a low molecular weight isocyanate compound ICL and a high molecular weight isocyanate compound ICH, may have an NCO% of 0.5 to 60% in a state free of fillers such as carbon black or calcium carbonate. The NCO% of the isocyanate compound IC is preferably 1 to 55%, more preferably 5 to 50%, even more preferably 7 to 25%, particularly preferably 10 to 20%, and most preferably 12 to 18%. The NCO% (isocyanate content) of the isocyanate compound IC is measured in accordance with Method A (toluene / dibutylamine, hydrochloric acid method) of JIS K1603-1:2007 "Test methods for aromatic isocyanates in plastics - polyurethane raw materials Part 1: Method for determining isocyanate group content".

[0076] [NCO / H] In the urethane composition of the present invention, the molar ratio (NCO / H) of the number of moles of NCO groups (NCO) contained in agent B to the number of moles of active hydrogen groups (H) contained in agent A is 0.5 or more and less than 1.5. This ratio is more preferably 0.6 or more and less than 1.4, even more preferably 0.7 or more and less than 1.4, even more preferably 0.8 or more and less than 1.4, particularly preferably 0.9 or more and less than 1.3, and most preferably 1.0 or more and less than 1.2. The molar ratio (NCO / OH) of the number of moles of NCO groups (NCO) contained in agent B to the number of moles of hydroxyl groups (OH) contained in agent A may be equivalent to the above molar ratio (NCO / H).

[0077] As described above, we will now discuss the expected reaction after mixing agents A and B when the ratio of moles of NCO groups (NCO) in agent B to moles of active hydrogen groups (H) in agent A is brought close to 1. As shown in Figure 2, for example, if the urethane prepolymer (UPP) contained in agent B is synthesized from a diol with a molecular weight of 1500 and a diisocyanate with a molecular weight of 250, then one end of the U2-2 unit starts with a molecular weight of 750 per active hydrogen group, followed by a U2-3 unit with a molecular weight of 125 per isocyanate group, and ends with a U1-3 unit with a molecular weight of 125 per isocyanate.

[0078] Agent B contains residual diisocyanate monomers from UPP synthesis and polyfunctional isocyanate monomers that are intentionally added after UPP synthesis. Many of the U1-3 units in these monomers have a molecular weight of 200 or less per isocyanate group. On the other hand, Agent A contains a variety of active hydrogen group-containing compounds whose molecular ends result in structures derived from U1-1 or U1-2. One of these, a diol compound with a molecular weight of 90, has a U1-2 at its molecular end, with a molecular weight of 45 per active hydrogen group. When this diol compound reacts with UPP in Agent B, where the molecular end results in a U1-3 with a molecular weight of 125 per isocyanate group, the U1-3 reacts with the U1-2 at one end of the diol compound with a molecular weight of 90 to form a urethane bond, so that U1-3 becomes U3-3 and U1-2 becomes U3-2. The molecular chain produced by this reaction begins with U3-3, which has a molecular weight of 125 per isocyanate group, derived from U1-3, which has a molecular weight of 125 per isocyanate group. This is followed by U3-2, which has a molecular weight of 45 per active hydrogen group, derived from U1-2, which has a molecular weight of 45 per active hydrogen group, and finally ends with U1-2, which has a molecular weight of 45 per active hydrogen group (Figure 3). It is thought that this molecular end then reacts with compounds containing isocyanate groups derived from agent B (compounds containing U1-3 units), and further reacts with various active hydrogen group-containing compounds that end with the molecular ends of U1-1 and U1-2 derived from agent A, and this process is repeated. When U1-3 is consumed due to the formation of this urethane bond, the growth of the molecular chain stops when U1-3 and U1-1 react. On the other hand, if U1-2, which reacts with U1-3, is derived from a polyol with more than two functional groups, a three-dimensional crosslinking network is generated by the formation of urethane bonds. Furthermore, the isocyanate group of a compound containing U1-3 units can react with moisture (humidity, H2O) present in the air or on the surface of the adherend. When reacting with moisture, it is thought that the primary amine terminus, which is generated from the decarboxylation of the carbamic acid ester converted from the isocyanate group, further reacts with another isocyanate group to form a urea bond.This reaction is essentially a side reaction for two-component polyurethane adhesives, which promote curing by mixing agent A containing an active hydrogen group compound and agent B containing an isocyanate group compound. However, it allows isocyanate group ends to be linked without the need for a polyol. Therefore, it is thought that U3-3, which is converted from U1-3, takes on a continuous molecular structure. Through the repetition of the various anticipated chemical reactions described above, ideally, the free isocyanate groups and free active hydrogen groups are expected to disappear in the end. The resulting crosslinked network derived from polyurethane is thought to have diverse molecular weights between urethane bonds as well as diverse levels of crosslinking. Nevertheless, some collapsed crosslinked structures are also formed. Such a structure can be said to be characteristic of the present invention.

[0079] [Condition 1] The polyurethane composition of the present invention satisfies condition 1. Condition 1: 5 ≤ ([A_MU] / [A_HUI]) × 100 ≤ 28 [A_MU] represents the sum of the number of moles of the active hydrogen compound SO in a total weight of 100g of the first liquid L1 and the second liquid L2 (same as [ARMU] above) and the number of moles of the unit U2-1 in a total weight of 100g of the first liquid L1 and the second liquid L2. [A_HUI] represents the sum of the number of moles of units U1-3 in a total weight of 100g of the first liquid L1 and the second liquid L2 in which the molecular weight per isocyanate group is 200 or less (same as [ARHUI] above) and the number of moles of units U2-3 in a total weight of 100g of the first liquid L1 and the second liquid L2 in which the molecular weight per isocyanate group is 200 or less.

[0080] Condition 1 is preferably 5 ≤ ([A_MU] / [A_HUI]) × 100 ≤ 28 from the viewpoint of vibration damping characteristics and adhesive performance, more preferably 7 ≤ ([A_MU] / [A_HUI]) × 100 ≤ 27, even more preferably 9.5 ([A_MU] / [A_HUI]) × 100 ≤ 26, and particularly preferably 11 ≤ ([A_MU] / [A_HUI]) × 100 ≤ 25.5.

[0081] The polyurethane composition of the present invention satisfies condition 2. Condition 2 20≦{([ARMU]+[ARHUMO]) / [ARHUI]}×100≦90 [ARMU] represents the number of moles of the active hydrogen compound SO having active hydrogen-containing units U1-1 in the total weight of 100g of the first liquid L1 and the second liquid L2. [ARHUMO] represents the number of moles of units U1-2 in the total weight of 100g of the first liquid L1 and the second liquid L2, where the molecular weight per active hydrogen atom is 200 or less. [ARHUI] represents the number of moles of units U1-3 in the total weight of 100g of the first liquid L1 and the second liquid L2, where the molecular weight per isocyanate group is 200 or less.

[0082] Condition 2 is preferably 30 ≤ {([ARMU] + [ARHUMO]) / [ARHUI]} × 100 ≤ 90 from the viewpoint of vibration damping characteristics and adhesive performance, more preferably 40 ≤ {([ARMU] + [ARHUMO]) / [ARHUI]} × 100 ≤ 90, even more preferably 50 ≤ {([ARMU] + [ARHUMO]) / [ARHUI]} × 100 ≤ 85, and particularly preferably 55 ≤ {([ARMU] + [ARHUMO]) / [ARHUI]} × 100 ≤ 80.

[0083] The polyurethane composition of the present invention preferably satisfies condition 3 in addition to conditions 1 and 2 above. Condition 3: 25 ≤ ([A_HUMO] / [A_HUI]) × 100 ≤ 49 [A_HUMO] represents the sum of the number of moles of units U1-2 in the total weight of 100g of the first liquid L1 and the second liquid L2, where the molecular weight per active hydrogen atom is 200 or less (same as ARHUMO above), and the number of moles of units U2-2 where the molecular weight per active hydrogen atom is 200 or less. [A_HUI] represents the sum of the number of moles of units U1-3 in the total weight of 100g of the first liquid L1 and the second liquid L2 in which the molecular weight per isocyanate group is 200 or less (same as [ARHUI] above), and the number of moles of units U2-3 in the total weight of 100g of the first liquid L1 and the second liquid L2 in which the molecular weight per isocyanate group is 200 or less.

[0084] Condition 3 is preferably 27≦([A_HUMO] / [A_HUI])×100≦48, more preferably 28≦([A_HUMO] / [A_HUI])×100≦47, even more preferably 29≦([A_HUMO] / [A_HUI])×100≦46, and particularly preferably 30≦([A_HUMO] / [A_HUI])×100≦45, from the viewpoint of vibration damping characteristics and adhesive performance.

[0085] [Urethane catalyst C] The first liquid L1 or agent A of the polyurethane composition used in the method of the present invention may contain a urethane catalyst C that promotes the reaction between the OH group of the compound contained in agent A and the NCO group of the compound contained in agent B. The urethane catalyst C may be, for example, an amino compound, a tin compound, a bismuth compound, or an acetylacetone metal salt.

[0086] The amino compound may be pentamethyldiethylenetriamine, triethylamine, N-methylmorpholine bis(2-dimethylaminoethyl) ether, bis(2-dimethylaminoethyl) ether, N,N,N',N”,N”-pentamethyldiethylenetriamine, N,N,N'-trimethylaminoethyl-ethanolamine, bis(2-dimethylaminoethyl) ether, N-methyl-N',N'-dimethylaminoethylpiperazine, imidazole compounds in which the secondary amine functional group in the imidazole ring is substituted with a cyanoethyl group, N,N-dimethylcyclohexylamine, diazabicycloundecene, triethylenediamine (DABCO), tetramethylethylenediamine, tetramethylhexamethylenediamine, 1-methylimidazole, trimethylaminoethylpiperazine, tripropylamine, etc. Among these, triethylenediamine (DABCO) is particularly preferred.

[0087] The tin compound may be, for example, stannous octylate, dibutyltin diacetate, or dibutyltin dilaurate.

[0088] The bismuth compound may be bismuth neodecanoate or bismuth octoate. The acetylacetone metal salt may be, for example, aluminum acetylacetone, iron acetylacetone, copper acetylacetone, zinc acetylacetone, beryllium acetylacetone, chromium acetylacetone, indium acetylacetone, manganese acetylacetone, molybdenum acetylacetone, titanium acetylacetone, cobalt acetylacetone, vanadium acetylacetone, or zirconium acetylacetone. The urethane catalyst C may be one of these types or a combination of two or more types.

[0089] The urethane catalyst C is preferably present in an amount of 0.001 to 5% by weight relative to 100% by weight of the polyurethane composition of the present invention. By keeping the amount of urethane catalyst C within the above range, the urethane reaction of the above composition can be promoted at an appropriate reaction rate.

[0090] [Filler F] The polyurethane composition used in the method of the present invention may optionally contain a filler F, as long as it does not impair the objective of the present invention. The filler may be contained in the first liquid L1 or the second liquid L2. Preferably, the filler is contained in both the first liquid L1 and the second liquid L2.

[0091] Filler F may be an inorganic filler. Inorganic fillers may include so-called inorganic fillers such as zeolite, alumina (aluminum oxide), magnesia (magnesium oxide), titanium oxide (titanium white), aluminum hydroxide, barium titanate, zinc oxide, silica particles, metal nanoparticles, and glass fibers; layered silicates such as talc, clay, mica, smectite, kaolin minerals, mica clay, and vermiculite; metal powders such as silver powder and copper powder; and aluminum nitride, boron nitride, silicon nitride, and gallium nitride. Filler may also be an organic filler such as silicon carbide, carbon black, graphite, carbon fiber, and carbon nanotubes.

[0092] The silica particles may be crystalline silica particles or amorphous silica particles, and these silica particles may be synthetic products. The silica may be synthesized by a dry method or a wet method. The silica particles may include at least one selected from the group consisting of fumed silica particles and sol-gel silica particles. The silica particles may be surface-treated silica particles from the viewpoint of excellent dispersibility in adhesive components. Surface-treated silica particles are obtained by hydrophobizing the hydroxyl groups on the surface of the silica particles with a silane compound or a silane coupling agent. Surface-treated silica particles may be silica particles surface-treated with a silane compound such as an alkoxysilane compound, a disilazane compound, or a siloxane compound, or silica particles surface-treated with a silane coupling agent.

[0093] Filler F is present in an amount of preferably 5 to 75% by weight, more preferably 10 to 70% by weight, even more preferably 15 to 65% by weight, and even more preferably 20 to 60% by weight, based on 100% by weight of the total mass of the polyurethane composition of the present invention, in order to ensure that the polyurethane resin obtained from the polyurethane composition of the present invention has a sufficient Tanδ value.

[0094] [Other additives] In one embodiment of the present invention, the polyurethane composition may further contain other additives as necessary, provided that the objectives of the present invention are not impaired. These other additives may include, for example, plasticizers such as diisononyl phthalate, antioxidants, anti-aging agents, and thixotropic agents. Each of these other additives may be present in an amount of 0 to 20% by weight relative to 100% by weight of the polyurethane composition of the present invention.

[0095] [Tanδ measurement] The polyurethane resin obtained by curing the polyurethane composition of the present invention preferably has a maximum Tanδ value at 10 Hz in the range of -20°C to 20°C. The maximum value of Tanδ is preferably 0.5 or higher, and more preferably 0.6 or higher.

[0096] The polyurethane resin obtained by curing the polyurethane composition of the present invention preferably has a first region in which the measured value of Tanδ decreases by a first rate (Tanδ / °C) as the temperature rises further from the temperature at which the measured value of Tanδ is at its maximum, and a second region in which the measured value of Tanδ decreases by a second rate (Tanδ / °C) smaller than the first rate as the temperature rises further from the temperature at the upper limit of the first region. Near the upper limit temperature of the first region (and therefore the lower limit temperature of the second region), the decrease in the measured value of Tanδ is preferably very small (e.g., 0 Tanδ / °C). The polyurethane resin obtained by curing the polyurethane composition of the present invention preferably has a plateau-like shape in the Tanδ curve due to the very small decrease in the measured value of Tanδ in the second region.

[0097] In the graph of Tanδ measurements for Example 2 shown in Figure 1, the Tanδ measurement is maximum around 0°C. In the first region from 0°C to around 20°C, the Tanδ measurement decreases at a first rate. Around 20°C, the decrease in the Tanδ measurement approaches 0 (Tanδ / °C). In the second region where the temperature rises further from around 20°C, the Tanδ measurement decreases at a second rate, which is much smaller than the first rate. As a result, the graph of Tanδ measurements for Example 2 has a plateau-like shape.

[0098] The first ratio is preferably 0.005 to 0.02 (Tanδ / °C), more preferably 0.0075 to 0.015 (Tanδ / °C). The second ratio is preferably 0.0001 to 0.004 (Tanδ / °C), more preferably 0.0001 to 0.003 (Tanδ / °C), and more preferably 0.0001 to 0.002 (Tanδ / °C). The ratio of the first ratio to the second ratio (first ratio / second ratio) is preferably 2.0 or more, more preferably 3.0 or more, even more preferably 4.0 or more, even more preferably 5.0 or more, and most preferably 7.0 or more. [Examples]

[0099] The present invention will be specifically described below with reference to examples.

[0100] [Manufacturing of polyurethane compositions] In each example and comparative example, Agent A was prepared to contain the components shown in Tables 1-1 to 1-3 below. Water was removed using a vacuum melting machine, and the mixture was kneaded until it became a homogeneous paste in the specified amount (weight %), then degassed under reduced pressure. The mixture was then sealed and filled into an aluminum cartridge and stored at room temperature. The powders used were dried at 120°C for at least one day beforehand. In each example and comparative example, first, as shown in the Urethane Prepolymer (UPP and UPP-CE) column of Tables 2-1 to 2-4 below (raw materials for the composition produced by the urethane prepolymer formation reaction), 4,4-MDI and a pre-dehydrated polyol were stirred under reduced pressure at 80°C for 5 hours to obtain each urethane prepolymer (UPP). Subsequently, some of the obtained urethane prepolymers were mixed with pre-dehydrated 1,4-butanediol or 1,9-nonanediol in the amount shown in Table 2-4, and stirred under reduced pressure at 80°C for 1 hour to obtain chain-extended urethane prepolymers (UPP-CE). To each of the obtained urethane prepolymers, UPP, or UPP-CE (compositions resulting from the formation reaction of urethane prepolymers), other materials shown in Tables 2-1 to 2-4 were added to prepare Agent B. Moisture was removed using a vacuum melting machine, and the mixture was kneaded until a homogeneous paste was formed in the specified amount (wt%). The mixture was then degassed under reduced pressure, sealed and filled into aluminum cartridges, and stored at room temperature. The powders used were pre-dried at 120°C for at least one day. This UPP or UPP-CE contains residual (unreacted) 4,4-MDI monomer. Subsequently, Agents A and B, sealed and filled into the aluminum cartridges, were sampled in the proportions shown in Tables 3-1 to 3-3, kneaded until homogeneous without introducing air, and applied to a substrate to create adhesion test specimens. Alternatively, the specimens were cast onto release paper with spacers, covered with more release paper, and pressed to create adhesive sheets. The adhesives were allowed to cure at room temperature for at least three days.

[0101] [Table 1-1]

[0102] [Table 1-2]

[0103] [Table 1-3]

[0104] [Table 2-1]

[0105] [Table 2-2]

[0106] [Table 2-3]

[0107] [Table 2-4]

[0108] [Table 3-1]

[0109] [Table 3-2]

[0110] [Table 3-3]

[0111] The details of the product names in the table of this specification are as follows: [Agent A] PREMINOL 5005: A polyol obtained by sequentially adding propylene oxide and ethylene oxide to a two-functional alcohol, with an average molecular weight of 4000, a molar ratio of PO / EO = 76 / 24, and an average number of functional groups of 2 (manufactured by AGC Inc.). PREMINOL 7001K: A polyol obtained by sequentially adding propylene oxide and ethylene oxide to a three-functional alcohol, with an average molecular weight of approximately 6000 and an average number of functional groups of 3 (manufactured by AGC Inc.). Polyol 3611: A polyol (primary hydroxyl group-terminated) formed by adding ethylene oxide to trimethylolpropane, with an average molecular weight of 275 and an average number of functional groups of 3 (manufactured by Perstorp Holding AB). EXCENOL 385SO: A polyfunctional polyether polyol initiated with sorbitol, with an average molecular weight of 500 and an average number of functional groups of 6 (manufactured by AGC Inc.). SC-1000: A polyfunctional polyether polyol initiated with sucrose, with an average molecular weight of approximately 850 and an average number of functional groups of 7 (manufactured by ADEKA Corporation). Polyol R6405: A polyol (primary hydroxyl group-terminated) obtained by adding ethylene oxide to dipentaerythritol, with an average molecular weight of 830 and an average number of functional groups of 6 (manufactured by Perstorp Holding AB). Polyol 4290: A polyol (primary hydroxyl group-terminated) obtained by adding ethylene oxide to pentamonoerythritol, with an average molecular weight of 800 and an average number of functional groups of 4 (manufactured by Perstorp Holding AB). Worlee Pol VP E-1800: Polyfunctional polyester polyol, average molecular weight 1800, average number of functional groups: 7 (manufactured by Worlee). Sovermol RC1005: A polyfunctional polyester polyol derived from castor oil, with an average molecular weight of approximately 1000 and an average number of functional groups of 2.2 (manufactured by BASF). PREMINOL S6075: Polyfunctional polyether polyol, average molecular weight 7500, average number of functional groups: 6 (manufactured by AGC Inc.) HS CM-075P: Castor oil-derived polyfunctional polyester polyol, average molecular weight approximately 800, average number of functional groups: 5 (manufactured by Toyokuni Oil Co., Ltd.) URIC H-102: A polyfunctional polyester polyol derived from castor oil, with an average molecular weight of approximately 900 and an average number of functional groups of 5 (manufactured by Ito Oil Co., Ltd.). Polycastor #10: CC-bonded castor oil polymer, average molecular weight approximately 2000, average number of functional groups: 5.5 (manufactured by Ito Oil Co., Ltd.) Polycastor #30: CC-bonded castor oil polymer, average molecular weight approximately 2000, average number of functional groups: 5.5 (manufactured by Ito Oil Co., Ltd.) 1,4-Butanediol: 1,4-butanediol, average molecular weight 90, average number of functional groups: 2 (manufactured by Kanto Chemical Co., Ltd.) 1,5-Pentandiol: 1,5-pentanediol, average molecular weight 104, average number of functional groups: 2 (manufactured by Kanto Chemical Co., Ltd.) Nonane Diol: 1,9-nonanediol, average molecular weight 160, average number of functional groups: 2 (manufactured by Kuraray Co., Ltd.) ENSOLINE PHP: 1-Phenoxy-2-propanol, average molecular weight 152, average number of functional groups: 1 (manufactured by Arkema Corporation) Zeolum A-4: Synthetic zeolite (manufactured by Tosoh Corporation) SUPER-S: Heavy calcium carbonate (manufactured by Maruo Calcium Co., Ltd.) Calfine 200: Colloidal light calcium carbonate (manufactured by Maruo Calcium Co., Ltd.) Monarch 570: Carbon Black (Cabot Co.) DABCO: 1,4-Diazabicyclo[2.2.2]octane (manufactured by Tosoh Corporation) [Agent B] 4,4-MDI: 4,4'-diphenylmethane diisocyanate, average molecular weight 250, average number of functional groups: 2, NCO%: 33.6 (manufactured by Tosoh Corporation) Bio PTMG 650: Polyoxytetramethylene glycol, average molecular weight 650, average number of functional groups: 2 (manufactured by Mitsubishi Chemical Corporation) PTMG 1500: Polyoxytetramethylene glycol, average molecular weight 1500, average number of functional groups: 2 (manufactured by Mitsubishi Chemical Corporation) POLYVEST EP HT LV: Polybutadienediol, average molecular weight 1900, average number of functional groups: 2.4 (manufactured by Evonik) POLYVEST eCO HT Bio: Mass-balanced plant-derived polybutadiene diol, average molecular weight 2900, average number of functional groups: 2.4 (manufactured by Evonik). Monarch 570: Carbon Black (Cabot Co.) SUPER-S: Calcium carbonate (manufactured by Maruo Calcium Co., Ltd.) RY 200S: Hydrophobic fumed silica (manufactured by Nippon Aerosil Co., Ltd.) MILIONATE MR-200: Polymeric MDI, average molecular weight approximately 270, average number of functional groups approximately 2.2, NCO%: 31.3 (manufactured by Tosoh Corporation) STABIO D-376N: Plant-derived PDI-based polyisocyanate, average molecular weight approximately 460, average number of functional groups: approximately 3, NCO%: 24, (manufactured by Mitsui Chemicals, Inc.) PREMINOL S-1004F: A monool obtained by adding propylene oxide to a monofunctional alcohol, with an average molecular weight of approximately 4000, an average number of functional groups of 1, and a hydroxyl value of 17 mg KOH / g (manufactured by AGC Inc.). NX-2026: High-purity cardanol, average molecular weight approximately 298, average number of functional groups: 1, plant-derived degree 98% (manufactured by Cardwright).

[0112] [Measurement of tensile strength and elongation at break] The A and B components obtained in each example and comparative example were mixed for 60 seconds using a SpeedMixer® (DAC150FV, Hauschild) until a homogeneous paste was formed, thereby obtaining each mixed polyurethane composition. Each mixed polyurethane composition was cast onto release paper, a 2 mm spacer was placed on top, and then another release paper was placed on top and pressed. The mixture was then cured at room temperature for at least 3 days, and each cured specimen was punched out with a JIS No. 3 dumbbell. The tensile strength and elongation at break of each cured specimen were measured at 20°C at a test speed of 500 mm / min using a Shimadzu Autograph in accordance with ISO 527.

[0113] [Evaluation Criteria for Tensile Strength] Tensile strength was evaluated according to the following criteria. 3.0 MPa or higher: Very high tensile strength 2.0 MPa or higher: High tensile strength Less than 2.0 MPa: Tensile strength is slightly inferior. Less than 1.5 MPa: Inferior tensile strength

[0114] [Evaluation Criteria for Elongation at Breaking] The elongation at break was evaluated according to the following criteria. 300% or more: Extremely high elongation at break. 150% or more: High elongation at break Less than 150%: Breaking elongation is slightly inferior. Less than 100%: Poor elongation at break.

[0115] [Measurement of tensile shear strength] Each polyurethane composition was obtained by mixing Agent A and Agent B obtained in each example and comparative example using a SpeedMixer® (DAC150FV, Hauschild) for 60 seconds until a homogeneous paste was formed. Each mixed polyurethane composition was applied to a 25 mm × 10 mm area with a layer thickness of 5.0 mm between an electrodeposited steel sheet degreased with isopropanol and coated with primer RC-50E (Sika Corporation) and a glass sheet degreased with isopropanol and coated with primer MS-90 (Sika Corporation), and cured at room temperature for at least 3 days. Before measuring the tensile shear strength, each sample was stored at 20°C or 90°C for 5 hours, and then the tensile shear strength and fracture state of each sample were measured and confirmed according to DIN EN 1465. (Tensile speed: 200 mm / min.)

[0116] [Evaluation criteria for tensile shear strength and fracture state at 20°C] The evaluation criteria for tensile shear strength and failure state are as follows: At pressures above 3.0 MPa, the failure state is cohesive failure (CF) of the adhesive layer: very high adhesive strength. At pressures above 2.0 MPa, the failure state is cohesive failure (CF) of the adhesive layer: high adhesive strength. Less than 2.0 MPa: Adhesion is slightly weaker. Less than 1.5 MPa: Poor adhesive strength [Evaluation criteria for tensile shear strength and fracture state at 90°C] The evaluation criteria for tensile shear strength and failure state are as follows: At pressures above 1.1 MPa, the failure state is cohesive failure (CF) of the adhesive layer: very high adhesive strength. At pressures above 0.7 MPa, the failure state is cohesive failure (CF) of the adhesive layer: high adhesive strength. Less than 0.7 MPa: Adhesion is slightly weaker. Less than 0.4 MPa: Poor adhesive strength

[0117] The following describes the state of adhesive failure: CF: Cohesive failure of adhesives TCF(G): Thin-layer cohesive fracture near the interface of the adhesive layer close to the glass substrate. PS(G): Delamination at the interface between the primer layer and the adhesive layer applied to the glass substrate. PS(ED): Delamination at the interface between the primer layer and adhesive layer applied to the electrodeposited plate. AF: Interfacial delamination of adhesives Additionally, if a number is listed to the right of the destruction status, it represents the percentage of that destruction status; if no number is listed, it represents 100% destruction.

[0118] [Measurement of elastic modulus and Tanδ] Polyurethane compositions were prepared in the same manner as for the measurement of tensile strength and elongation at break, and samples were obtained from 2 mm thick cured adhesive sheets after curing. Each sample was cut to a thickness of 2 mm, a width of 5 mm, and a length of 25 mm. The elastic modulus (E') and Tanδ (E'' / E') of each cut sample were measured using a viscoelasticity analyzer manufactured by UBM Co., Ltd., in tensile mode at a frequency of 10 Hz and a temperature range of -100°C to 200°C, and the elastic modulus (E') and Tanδ (E'' / E') of samples in the temperature range of -25°C to 80°C were confirmed.

[0119] [Evaluation criteria for elastic modulus (E')] Elastic modulus (MPa) at 20°C: 5-20: Excellent Elastic modulus (MPa) at 20°C: 1 or more and less than 5, or greater than 20 and less than or equal to 30: Excellent If the modulus of elasticity (MPa) at 20°C is 0.8 or more and less than 1, or greater than 30 and less than or equal to 80: Sufficient. Other than the above: Insufficient

[0120] [Evaluation criteria for Tanδ(E'' / E') at -25℃] 0.30 or higher: Very good 0.10 or higher: Good Less than 0.10: Somewhat insufficient Less than 0.08: Insufficient

[0121] [Evaluation criteria for Tanδ at 0°C] 0.30 or higher: Very good 0.20 or higher: Good Less than 0.20: Somewhat insufficient Less than 0.08: Insufficient

[0122] [Evaluation criteria for Tanδ at 20°C] 0.30 or higher: Very good 0.20 or higher: Good Less than 0.20: Somewhat insufficient Less than 0.08: Insufficient

[0123] [Evaluation criteria for Tanδ at 50°C] 0.30 or higher: Very good 0.15 or higher: Good Less than 0.15: Somewhat insufficient Less than 0.08: Insufficient

[0124] [Evaluation criteria for Tanδ at 80°C] 0.30 or higher: Very good 0.10 or higher: Good Less than 0.10: Somewhat insufficient Less than 0.08: Insufficient

[0125] The abbreviations in the tables of this specification represent the following: In Tables 1-2 and 1-3, "soft segment (derived from U1-2)" represents the number of moles (mol / 100g of Agent A) of units U1-2 derived from the active hydrogen compound in Agent A where the amount per active hydrogen group exceeds 200. In Tables 1-2 and 1-3, "A_HUMO" represents the sum of the number of moles of units U1-2 derived from the active hydrogen compound in Agent A, where the amount per active hydrogen group is 200 or less, and the number of moles of units U2-2 derived from the active hydrogen compound, where the amount per active hydrogen group is 200 or less (mol / 100g of Agent A). In Tables 1-2 and 1-3, "ARHUMO" represents the number of moles (mol / 100g of Agent A) of units U1-2 derived from the active hydrogen compound in Agent A, where the amount per active hydrogen group is 200 or less. In Tables 1-2 and 1-3, "A_HUI" represents the sum of the number of moles of units U1-3 derived from the isocyanate compound in Agent A, where the amount per isocyanate group is 200 or less, and the number of moles of units U2-3 derived from the isocyanate compound, where the amount per isocyanate group is 200 or less (mol / 100g of Agent A). In Tables 1-2 and 1-3, "ARHUI" represents the number of moles (mol / 100g of Agent A) of units U1-3 derived from the isocyanate compound in Agent A, where the amount per isocyanate group is 200 or less. In Tables 1-2 and 1-3, "A_MU" represents the sum of the number of moles of unit U1-1 derived from the active hydrogen compound SO, which has a nominal functional value of 0.5 or more and less than 1.5, and the number of moles of unit U2-1 derived from the active hydrogen compound SO, which has a nominal functional value of 0.5 or more and less than 1.5 (mol / 100g of agent A). In Tables 1-2 and 1-3, "ARMU" represents the number of moles (mol / 100g of Agent A) of unit U1-1 derived from the active hydrogen compound SO, which has a nominal functional value of 0.5 or more and less than 1.5 in Agent A.

[0126] In Tables 2-2 and 2-3, UPP represents the raw materials of the composition produced by the reaction of urethane prepolymer UPP. In Table 2-4, UPP-CE represents the raw material for the composition produced by the reaction of the urethane prepolymer UPP-CE. In Tables 2-2, 2-3, and 2-4, "Soft segment derived from UPP" represents the number of moles (mol / 100g of agent B) of units U2-2 derived from the active hydrogen compound in which the amount per active hydrogen group exceeds 200. In Tables 2-2, 2-3, and 2-4, "A_HUMO" represents the sum of the number of moles of units U1-2 derived from the active hydrogen compound in Agent B, where the amount per active hydrogen group is 200 or less, and the number of moles of units U2-2 derived from the active hydrogen compound, where the amount per active hydrogen group is 200 or less (mol / 100g of Agent B). In Tables 2-2, 2-3, and 2-4, "ARHUMO" represents the number of moles (mol / 100g of Agent B) of units U1-2 derived from the active hydrogen compound in Agent B, where the amount per active hydrogen group is 200 or less. In Tables 2-2, 2-3, and 2-4, "A_HUI" represents the sum of the number of moles of units U1-3 containing isocyanate groups of the isocyanate compound IC where the molecular weight per isocyanate group is 200 or less, and the number of moles of units U2-3 where the molecular weight per isocyanate group is 200 or less (mol / 100g of agent B). In Tables 2-2, 2-3, and 2-4, "ARHUI" represents the number of moles (mol / 100g of agent B) of units U1-3 containing isocyanate groups in the isocyanate compound IC where the molecular weight per isocyanate group is 200 or less. In Tables 2-2, 2-3, and 2-4, "A_MU" represents the sum of the number of moles of active hydrogen compound SO with a nominal functional value of 0.5 or more and less than 1.5, and the number of moles of unit U2-1 derived from active hydrogen compound with a nominal functional value of 0.5 or more and less than 1.5 (mol / 100g of agent B). In Tables 2-2, 2-3, and 2-4, "ARMU" represents the number of moles (mol / 100g of agent B) of active hydrogen compound SO with a nominal functional value of 0.5 or more and less than 1.5.

[0127] The soft segments in Tables 3-1, 3-2, and 3-3 represent the number of moles (mol / 100g of mixed Agent A and Agent B) of units U1-2 and U2-2 with a nominal functional value of 1.5 or higher derived from the active hydrogen compound, where the molecular weight per active hydrogen group exceeds 200, when Agent A and Agent B are mixed in the ratios shown in the tables. This is essentially equivalent to the number of moles (mol / 100g) of units U3-2 with a nominal functional value of 1.5 or higher, where the amount per active hydrogen group exceeds 200, which can be obtained by mixing and reacting Agent A and Agent B, or which may be arbitrarily present beforehand. In Tables 3-1, 3-2, and 3-3, "A_HUMO" represents the sum of the number of moles of units U1-2 derived from the active hydrogen compound where the amount per active hydrogen group is 200 or less, and the number of moles of units U2-2 derived from the active hydrogen compound where the amount per active hydrogen group is 200 or less (mol / 100g of A and B mixture). In Tables 3-1, 3-2, and 3-3, "ARHUMO" represents the number of moles (mol / 100g of mixed Agent A and Agent B) of units U1-2 derived from the active hydrogen compound, where the amount per active hydrogen group is 200 or less, when Agent A and Agent B are mixed in the ratios shown in the tables. In Tables 3-1, 3-2, and 3-3, "A_HUI" represents the sum of the number of moles of units U1-3 derived from the isocyanate compound where the amount per isocyanate group is 200 or less, and the number of moles of units U2-3 derived from the isocyanate compound where the amount per isocyanate group is 200 or less (mol / 100g of A and B mixture). In Tables 3-1, 3-2, and 3-3, "ARHUI" represents the number of moles (mol / 100g of mixed Agent A and Agent B) of units U1-3 derived from the isocyanate compound, where the amount per isocyanate group is 200 or less. In Tables 3-1, 3-2, and 3-3, "A_MU" represents the sum of the number of moles of unit U1-1 derived from the active hydrogen compound SO, which has a nominal functional value of 0.5 or more and less than 1.5, and the number of moles of unit U2-1 derived from the active hydrogen compound SO, which has a nominal functional value of 0.5 or more and less than 1.5, when agent A and agent B are mixed in the ratios shown in the tables (mol / 100g of mixed agent A and agent B). In Tables 3-1, 3-2, and 3-3, "ARMU" represents the number of moles (mol / 100g of mixed Agent A and Agent B) of Unit U1-1 derived from the active hydrogen compound SO, which has a nominal functional value of 0.5 or more and less than 1.5 when Agent A and Agent B are mixed in the ratios shown in the tables.

[0128] The resins obtained from the polyurethane compositions prepared in Examples 1-25 exhibited desirable vibration damping characteristics and adhesive performance, and were found to be superior to the cured products obtained in Comparative Examples 1-8.

[0129] Comparative Examples 1-4 satisfied Condition 2 but failed to satisfy Conditions 1 and 3. The adhesive resins obtained in Comparative Examples 1-4 were inferior to those of the Examples in terms of physical properties such as tensile strength and elongation at break, vibration damping characteristics, and adhesive performance.

[0130] Comparative Example 5 failed to meet Condition 1 due to an excessive amount of the active hydrogen compound SO (monool). The adhesive resin obtained in Comparative Example 5 was inferior to that of the Examples in terms of physical properties such as tensile strength and elongation at break.

[0131] Example 14 satisfied conditions 1, 2, and 3, but only satisfied condition 1 to the lower limit. This suggests that U3-1 and U2-1, generated from a single active hydrogen-containing unit U1-1 derived from the active hydrogen compound SO (monool), are present in smaller quantities compared to U3-3, which is generated from U2-3 and U1-3, and in units where the molecular weight per isocyanate group is 200 or less. As a result, the adhesive resin obtained in Example 14 exhibited the effects of the present invention in terms of physical properties such as tensile strength and adhesion, but was slightly inferior to the other examples in terms of vibration damping characteristics.

[0132] Example 15 satisfied the numerical range of Condition 1 and the numerical range of Condition 2 up to the upper limit, but did not satisfy Condition 3. This indicates that when agent A and agent B are mixed, the sum of the number of moles of U1-1 and the number of moles of U1-2 with a molecular weight of 200 or less per active hydrogen group is in equilibrium with the number of moles of U1-3 with a molecular weight of 200 or less per isocyanate group, and the sum of the number of moles of U3-2 from U1-2 with a molecular weight of 200 or less per active hydrogen group and the number of moles of U2-2 with a molecular weight of 200 or less per active hydrogen group is proportionally larger than the number of moles of U3-3 and U2-3 generated from U1-3 with a molecular weight of 200 or less per isocyanate group. In this case, the influence of the number of moles of U1-1 is thought to be strongly evident, and as a result, the adhesive resin obtained in Example 15 was slightly inferior to the other examples in terms of physical properties such as tensile strength and elongation at break.

[0133] Comparative Examples 6, 7, and 8 satisfied Condition 1 but not Conditions 2 and 3. The adhesive resins obtained in Comparative Examples 6, 7, and 8 had a higher proportion of hard segments derived from active hydrogen compounds than the compositional trend of Example 15, and as a result exceeded the upper limits of Conditions 2 and 3, but they were inferior to the example in terms of physical properties such as tensile strength and elongation at break.

[0134] Examples 16 and 17 satisfied the numerical range of Condition 1 and the upper limit of the numerical range of Condition 2, but did not satisfy Condition 3. This formulation system further increased the proportion of hard segments derived from active hydrogen compounds from the compositional trend of Example 15, and as a result exceeded the upper limit of Condition 3, but unlike Comparative Examples 6, 7, and 8, it satisfied Condition 2. As a result, the adhesive resin obtained in Example 16 was able to maintain physical properties such as tensile strength and elongation at break within acceptable limits, but its vibration damping characteristics were slightly inferior to those of the other examples.

[0135] Examples 19 and 20 were formulation systems in which the active hydrogen compound SO, having a nominal functional value of 0.5 or more and less than 1.5, was used together with the active hydrogen compound MOS, having a nominal functional value of 1.5 or more, during the production of the urethane prepolymer (UPP), resulting in a formulation system having U2-1 units in agent B. Examples 19 and 20 satisfied all of conditions 1, 2, and 3.

[0136] Examples 24 and 25 are formulation systems having U2-2 units in component B, obtained by adding the active hydrogen compound MOH, which has a nominal functional value of 1.5 or more, after the reaction of the active hydrogen compound MOS, which has a nominal functional value of 1.5 or more, with the isocyanate compound ICL (production of UPP) during the production of a chain-extended urethane prepolymer (UPP-CE), and allowing the reaction to proceed further. Examples 24 and 25 satisfied all of conditions 1, 2, and 3.

Claims

1. A method for producing a polyurethane resin having vibration damping properties from a polyurethane composition comprising a first liquid L1 containing agent A and a second liquid L2 containing agent B, The aforementioned agent A comprises an active hydrogen compound SO having an active hydrogen group-containing unit U1-1 and a nominal functional value of 0.5 or more and less than 1.5, and an active hydrogen compound MO having an active hydrogen group-containing unit U1-2 and a nominal functional value of 1.5 or more. The aforementioned agent B contains an isocyanate compound IC having isocyanate group-containing units U1-3 and having a nominal functional value of 1.5 or more. The active hydrogen compound SO, the active hydrogen compound MO, and the isocyanate compound IC may further have a structure formed by the reaction of an active hydrogen group with an isocyanate group. The structure is formed by reacting an active hydrogen compound having a nominal functional value of 0.5 or more and less than 1.5 and / or an active hydrogen compound having a nominal functional value of 1.5 or more with an isocyanate compound having a nominal functional value of 1.5 or more, and has a unit U2-1 derived from the active hydrogen compound having a nominal functional value of 0.5 or more and less than 1.5, a unit U2-2 derived from the active hydrogen compound having a nominal functional value of 1.5 or more, and a unit U2-3 derived from the isocyanate compound having a nominal functional value of 1.5 or more. The polyurethane resin is obtained by mixing and reacting agent A and agent B, and in addition to the units U2-1 to U2-3 which may be optionally present, it has unit U3-1 derived from the active hydrogen compound SO, unit U3-2 derived from unit U1-2, and unit U3-3 derived from unit U1-3. The ratio of the number of moles of NCO groups (NCO) contained in agent B to the number of moles of active hydrogen groups (H) contained in agent A (NCO / H) is 0.7 or more and less than 1.

5. The polyurethane composition is provided by a method that satisfies the following conditions 1, 2, and 3. Condition 1: 5 ≤ ([A_MU] / [A_HUI]) × 100 ≤ 28 (Of the above conditions 1, [A_MU] represents the sum of the number of moles of the active hydrogen compound SO having the unit U1-1 in a total weight of 100 g of the first liquid L1 and the second liquid L2, and the number of moles of the unit U2-1 in a total weight of 100 g of the first liquid L1 and the second liquid L2. [A_HUI] represents the sum of the number of moles of units U1-3 in the total weight of 100g of the first liquid L1 and the second liquid L2, where the molecular weight per isocyanate group is 200 or less, and the number of moles of units U2-3 in the total weight of 100g of the first liquid L1 and the second liquid L2, where the molecular weight per isocyanate group is 200 or less. Condition 2 20≦{([ARMU]+[ARHUMO]) / [ARHUI]}×100≦90 (Of the above condition 2, [ARMU] represents the number of moles of the active hydrogen compound SO having the unit U1-1 in the total weight of 100 g of the first liquid L1 and the second liquid L2. [ARHUMO] represents the number of moles of units U1-2 in the total weight of 100g of the first liquid L1 and the second liquid L2, where the molecular weight per active hydrogen atom is 200 or less. [ARHUI] represents the number of moles of units U1-3 in the total weight of 100 g of the first liquid L1 and the second liquid L2, where the molecular weight per isocyanate group is 200 or less. Condition 3: 25 ≤ ([A_HUMO] / [A_HUI]) × 100 ≤ 49 (Of the above condition 3, [A_HUMO] represents the sum of the number of moles of units U1-2 in which the molecular weight per active hydrogen atom is 200 or less, and the number of moles of units U2-2 in which the molecular weight per active hydrogen atom is 200 or less, in a total weight of 100 g of the first liquid L1 and the second liquid L2. [A_HUI] represents the sum of the number of moles of units U1-3 in the total weight of 100g of the first liquid L1 and the second liquid L2, where the molecular weight per isocyanate group is 200 or less, and the number of moles of units U2-3 in the total weight of 100g of the first liquid L1 and the second liquid L2, where the molecular weight per isocyanate group is 200 or less.

2. The method according to claim 1, characterized in that the method described above is used in the manufacture of an adhesive.

3. A method for manufacturing an automotive component, comprising the step of manufacturing an automotive component using an adhesive obtained by the method of claim 2.

4. A polyurethane composition comprising a first liquid L1 containing agent A and a second liquid L2 containing agent B, used for producing a polyurethane resin having vibration damping properties, The aforementioned agent A comprises an active hydrogen compound SO having an active hydrogen group-containing unit U1-1 and a nominal functional value of 0.5 or more and less than 1.5, and an active hydrogen compound MO having an active hydrogen group-containing unit U1-2 and a nominal functional value of 1.5 or more. The aforementioned agent B contains an isocyanate compound IC having isocyanate group-containing units U1-3 and having a nominal functional value of 1.5 or more. The active hydrogen compound SO, the active hydrogen compound MO, and the isocyanate compound IC may further have a structure formed by the reaction of an active hydrogen group with an isocyanate group. The structure is formed by reacting an active hydrogen compound having a nominal functional value of 0.5 or more and less than 1.5 and / or an active hydrogen compound having a nominal functional value of 1.5 or more with an isocyanate compound having a nominal functional value of 1.5 or more, and has a unit U2-1 derived from the active hydrogen compound having a nominal functional value of 0.5 or more and less than 1.5, a unit U2-2 derived from the active hydrogen compound having a nominal functional value of 1.5 or more, and a unit U2-3 derived from the isocyanate compound having a nominal functional value of 1.5 or more. The polyurethane resin is obtained by mixing and reacting agent A and agent B, and in addition to the units U2-1 to U2-3 which may be optionally present, it has unit U3-1 derived from the active hydrogen compound SO, unit U3-2 derived from unit U1-2, and unit U3-3 derived from unit U1-3. The ratio of the number of moles of NCO groups (NCO) contained in agent B to the number of moles of active hydrogen groups (H) contained in agent A (NCO / H) is 0.7 or more and less than 1.

5. The polyurethane composition satisfies the following conditions 1, 2, and 3. Condition 1: 5 ≤ ([A_MU] / [A_HUI]) × 100 ≤ 28 (Of the above conditions 1, [A_MU] represents the sum of the number of moles of the active hydrogen compound SO having the unit U1-1 in a total weight of 100 g of the first liquid L1 and the second liquid L2, and the number of moles of the unit U2-1 in a total weight of 100 g of the first liquid L1 and the second liquid L2. [A_HUI] represents the sum of the number of moles of units U1-3 in the total weight of 100g of the first liquid L1 and the second liquid L2, where the molecular weight per isocyanate group is 200 or less, and the number of moles of units U2-3 in the total weight of 100g of the first liquid L1 and the second liquid L2, where the molecular weight per isocyanate group is 200 or less. Condition 2 20≦{([ARMU]+[ARHUMO]) / [ARHUI]}×100≦90 (Of the above condition 2, [ARMU] represents the number of moles of the active hydrogen compound SO having the unit U1-1 in the total weight of 100 g of the first liquid L1 and the second liquid L2. [ARHUMO] represents the number of moles of units U1-2 in the total weight of 100g of the first liquid L1 and the second liquid L2, where the molecular weight per active hydrogen atom is 200 or less. [ARHUI] represents the number of moles of units U1-3 in the total weight of 100 g of the first liquid L1 and the second liquid L2, where the molecular weight per isocyanate group is 200 or less. Condition 3: 25 ≤ ([A_HUMO] / [A_HUI]) × 100 ≤ 49 (Of the above condition 3, [A_HUMO] represents the sum of the number of moles of units U1-2 in which the molecular weight per active hydrogen atom is 200 or less, and the number of moles of units U2-2 in which the molecular weight per active hydrogen atom is 200 or less, in a total weight of 100 g of the first liquid L1 and the second liquid L2. [A_HUI] represents the sum of the number of moles of units U1-3 in the total weight of 100g of the first liquid L1 and the second liquid L2, where the molecular weight per isocyanate group is 200 or less, and the number of moles of units U2-3 in the total weight of 100g of the first liquid L1 and the second liquid L2, where the molecular weight per isocyanate group is 200 or less.

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