Aqueous dispersion, adhesive composition, adhesive, attaching material, and adhesive tape

Abstract

An aqueous dispersion comprising a hydroxyl-terminated urethane prepolymer, wherein the hydroxyl-terminated urethane prepolymer is obtained by reacting an oxoalkylene polymer A having an average hydroxyl number per molecule of more than 2.0 and less than 3.0, an oxoalkylene polymer B having an average hydroxyl number per molecule of more than 1.2 and less than 2.0, and a diisocyanate compound, wherein the oxoethylene content of the aforementioned oxoalkylene polymer A is more than 15% by mass relative to the total amount of oxoalkylene, the oxoethylene content of the aforementioned oxoalkylene polymer B is more than 15% by mass relative to the total amount of oxoalkylene, and the oxoethylene content of the aforementioned hydroxyl-terminated urethane prepolymer is more than 20% by mass and less than 70% by mass relative to the total amount of oxoalkylene.

Description

Technical Field

[0001] This invention relates to aqueous dispersions, adhesive compositions, adhesives, bonding materials, and adhesive tapes. Background Technology

[0002] In the past, for example, in flat panel displays (liquid crystal displays, organic electroluminescent displays, etc.) widely used in electronic devices such as televisions, personal computers (PCs), mobile phones, and portable terminals, as well as in touch panel displays that combine flat panel displays and touch panels, surface protective films formed on substrates with adhesive layers have been widely used as protective films for their surfaces.

[0003] Typically, adhesive compositions known for manufacturing surface protective films contain polymer components consisting of acrylic polymers, prepolymer polymers (e.g., see Patent Document 1), and organic solvents.

[0004] The organic solvents contained in the adhesive composition may cause adverse environmental impacts such as carbon dioxide emissions, odor, and health hazards resulting from incineration. Therefore, the requirement to reduce the amount of organic solvents contained in the adhesive composition is gradually increasing.

[0005] Existing technology

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2018-131500 Summary of the Invention

[0008] The problem the invention aims to solve

[0009] However, as adhesive compositions for surface protective films of the prepolymer type, aqueous adhesive compositions free of organic solvents have not yet been obtained, and there is a strong demand for the long-term development of aqueous prepolymer type adhesive compositions for surface protective films. This is especially true for surface protective films intended for application where they are assumed to be adhered to an article and then peeled off as needed. Therefore, adhesives for surface protective films are unsuitable for use if the adhesive strength is either too strong or too weak; a suitable adhesive strength is required.

[0010] In view of the above-mentioned problems, the present invention aims to provide an adhesive composition that can be prepared with excellent water solubility and excellent coatability of solid components, an aqueous dispersion that can be prepared with adhesive with excellent adhesion and transparency, an adhesive composition containing the aqueous dispersion, an adhesive obtained by curing the adhesive composition, an adhesive material having an adhesive layer containing the adhesive, and an adhesive tape having the aforementioned adhesive layer containing the adhesive.

[0011] Solution for solving the problem

[0012] In order to solve the above-mentioned problems, the inventors conducted in-depth research and found that if a hydroxyl-terminated urethane prepolymer is included, and the hydroxyl-terminated urethane prepolymer is obtained by reacting an oxoalkylene polymer A with an average number of hydroxyl groups per molecule of more than 2.0 and less than 3.0, and an oxoalkylene polymer B with an average number of hydroxyl groups per molecule of more than 1.2 and less than 2.0, with a diisocyanate compound, and the oxoethylene content of oxoalkylene polymer A is 15% by mass or more relative to the total amount of oxoalkylene, the oxoethylene content of oxoalkylene polymer B is 15% by mass or more relative to the total amount of oxoalkylene, and the oxoethylene content of the hydroxyl-terminated urethane prepolymer is more than 20% by mass and less than 70% by mass, the aforementioned problems can be solved, and the present invention is thus completed.

[0013] That is, the present invention is as follows.

[0014] [1] An aqueous dispersion comprising a hydroxyl-terminated urethane prepolymer, wherein the hydroxyl-terminated urethane prepolymer is obtained by reacting an oxoalkylene polymer A having an average number of hydroxyl groups per molecule of more than 2.0 and less than 3.0, an oxoalkylene polymer B having an average number of hydroxyl groups per molecule of more than 1.2 and less than 2.0, with a diisocyanate compound, wherein the oxoethylene content of the aforementioned oxoalkylene polymer A is more than 15% by mass relative to the total amount of oxoalkylene, the oxoethylene content of the aforementioned oxoalkylene polymer B is more than 15% by mass relative to the total amount of oxoalkylene, and the oxoethylene content of the aforementioned hydroxyl-terminated urethane prepolymer is more than 20% by mass and less than 70% by mass relative to the total amount of oxoalkylene.

[0015] [2] According to the aqueous dispersion described in [1] above, wherein the aforementioned oxyalkylene polymer A comprises an oxyalkylene polymer with 3 hydroxyl groups, and the aforementioned oxyalkylene polymer B comprises an oxyalkylene polymer with 2 hydroxyl groups.

[0016] [3] According to the aqueous dispersion described in [1] or [2] above, the mass ratio of the aforementioned oxyalkylene polymer A to the aforementioned oxyalkylene polymer B is 20:80 to 60:40.

[0017] [4] The aqueous dispersion according to any one of [1] to [3] above, wherein the isocyanate index, which represents the molar ratio of the isocyanate group of the aforementioned diisocyanate compound to the hydroxyl groups of the aforementioned oxoalkylene polymer A and the aforementioned oxoalkylene polymer B, is 40 or more and 90 or less.

[0018] [5] The aqueous dispersion according to any one of [1] to [4] above, wherein the number average molecular weight of the aforementioned oxyalkylene polymer A and the aforementioned oxyalkylene polymer B is 1,000 to 50,000.

[0019] [6] The aqueous dispersion according to any one of [1] to [5] above, wherein the content of the oxyethylidene of the aforementioned hydroxyl-terminated urethane prepolymer relative to the total amount of oxyalkylene is 23% by mass or more and 65% by mass or less.

[0020] [7] The aqueous dispersion according to any one of [1] to [6] above, wherein the weight average molecular weight of the aforementioned hydroxyl-terminated urethane prepolymer is 10,000 or more and 250,000 or less.

[0021] [8] The aqueous dispersion according to any one of [1] to [7] above, wherein the average number of hydroxyl groups of the aforementioned hydroxyl-terminated urethane prepolymer is 1.7 or more and less than 3.0.

[0022] [9] An adhesive composition comprising: an aqueous dispersion as described in any one of [1] to [8] above, and a polyisocyanate compound having three or more isocyanate groups in one molecule.

[0023]

[10] According to the adhesive composition described above [9], wherein the polyisocyanate compound having three or more isocyanate groups in the aforementioned molecule is water-dispersible.

[0024]

[11] The adhesive composition according to [9] or

[10] above further comprises a catalyst, wherein the content of the catalyst is 0.001 parts by mass or more and 0.10 parts by mass or less, relative to a total of 100 parts by mass of the aforementioned hydroxyl-terminated urethane prepolymer and the aforementioned polyisocyanate compound having 3 or more isocyanate groups in 1 molecule.

[0025]

[12] An adhesive obtained by curing the adhesive composition described in

[10] or

[11] above.

[0026]

[13] According to the adhesive described in

[12] above, the content ratio of oxyethylidene to the total amount of oxyalkylene in the aforementioned adhesive is 10 to 70 by mass.

[0027]

[14] An adhesive material having a substrate and an adhesive layer, the adhesive layer being disposed on at least one surface of the aforementioned substrate and comprising the adhesive described in

[12] or

[13] .

[0028]

[15] An adhesive tape having a substrate and an adhesive layer disposed on at least one surface of the aforementioned substrate and comprising the adhesive described in

[12] or

[13] .

[0029] The effects of the invention

[0030] According to the present invention, it is possible to provide an adhesive composition that can be prepared with excellent water solubility and coating properties of solid components, an aqueous dispersion that can be prepared with adhesive with excellent adhesion and transparency, an adhesive composition containing the aqueous dispersion, an adhesive obtained by curing the adhesive composition, an adhesive material having an adhesive layer containing the adhesive, and an adhesive tape having the aforementioned adhesive layer containing the adhesive. Detailed Implementation

[0031] The definitions and meanings of the terms used in this specification are as follows.

[0032] In this specification, any expression described as "preferred" may be used, and it can be said that combinations of preferred options are even more preferred.

[0033] In addition, in this specification, the phrase "XX~YY" means "above XX and below YY".

[0034] Furthermore, in this specification, the lower and upper limits of the preferred numerical ranges (e.g., ranges of content, etc.) described in stages can be combined independently. For example, based on the description "preferably 10~90, more preferably 30~60", the "preferably lower limit (10)" and the "more preferably upper limit (60)" can be combined to obtain "10~60". In addition, the upper or lower limit of the numerical range described in this specification can also be replaced with the values ​​shown in the embodiments.

[0035] In addition, in this specification, the “unit” constituting the polymer refers to the atomic group formed by the polymerization of monomers.

[0036] In addition, in this specification, "oxyalkylene polymer" refers to a polymer having a polyoxyalkylene chain. Furthermore, repeating units based on alkylene oxides are referred to as "alkylene oxide units".

[0037] Furthermore, in this specification, "hydroxyl-terminated urethane prepolymer" refers to a compound obtained by reacting an organic compound having hydroxyl groups with a diisocyanate compound, wherein at least a portion of the end of the molecular chain has hydroxyl groups and the molecular chain contains urethane bonds. Additionally, in this specification, "isocyanate-terminated urethane prepolymer" refers to a compound obtained by reacting an organic compound having two or more hydroxyl groups in one molecule with a polyisocyanate compound, wherein at least a portion of the end of the molecular chain has isocyanate groups and the molecular chain contains urethane bonds.

[0038] Additionally, in this specification, for example, in the embodiments described later, a polyol (initiator A) that uses a KOH catalyst to perform an addition reaction between glycerol and propylene oxide up to a molecular weight of 3,000 is used to prepare the oxyalkylene polymer A1. However, in this case, the initiator of the oxyalkylene polymer A1 is not "polyol (initiator A)", but refers to glycerol as the starting material.

[0039] Additionally, in the case of purchasing a mixture of oxyalkylene polymers A and B as described in this specification, it can be achieved by using... 13 C-NMR is used to determine the type and molar ratio of initiators for oxyalkylene polymers A and B to calculate the average number of hydroxyl groups in oxyalkylene polymers A and B. On the other hand, when oxyalkylene polymers A and B are manufactured separately from initiators, the number of hydroxyl groups in the initiator used is itself the average number of hydroxyl groups in oxyalkylene polymers A and B, and the average number of hydroxyl groups in oxyalkylene polymers A and B can be identified based on the number of hydroxyl groups in the initiator used.

[0040] (Aqueous dispersion)

[0041] The aqueous dispersion of the present invention comprises a hydroxyl-terminated urethane prepolymer and water, and further comprises other components as needed.

[0042] The solid content of the aqueous dispersion of the present invention is preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 18% by mass or more, particularly preferably 20% by mass or more, and preferably 60% by mass or less, more preferably 56% by mass or less, particularly preferably 52% by mass or less.

[0043] When the content of the aforementioned solid components is within the above range, the water dispersibility of the solid components tends to become better.

[0044] <Hydroxy-terminated carbamate prepolymer>

[0045] Hydroxyl-terminated urethane prepolymers are obtained by reacting oxoalkylene polymer A, oxoalkylene polymer B, a diisocyanate compound, and other polyols (polyols other than oxoalkylene polymer A and oxoalkylene polymer B) as optional components. Through the reaction of the hydroxyl groups of oxoalkylene polymer A and oxoalkylene polymer B with the isocyanate groups of the diisocyanate compound, urethane bonds are formed between oxoalkylene polymer A and oxoalkylene polymer B and the diisocyanate compound. The hydroxyl groups of oxoalkylene polymer A and oxoalkylene polymer B that remain unreacted with the isocyanate groups of the diisocyanate compound become the terminal hydroxyl groups of the urethane prepolymer's molecular chain.

[0046] The proportion of other polyols is not particularly limited as long as it does not impede the function of the hydroxyl-terminated urethane prepolymer of the present invention. It is preferably 30% by mass or less, more preferably 10% by mass or less, relative to the total amount of oxyalkylene polymer A and oxyalkylene polymer B.

[0047] The content of hydroxyl-terminated urethane prepolymer in the aqueous dispersion of the present invention is preferably 10% by mass or more, more preferably 15% by mass or more, particularly preferably 20% by mass or more, and preferably 60% by mass or less, more preferably 56% by mass or less, particularly preferably 52% by mass or less.

[0048] When the aforementioned content is within the above range, the water dispersibility of the hydroxyl-terminated urethane prepolymer becomes better, and a more aesthetically pleasing film can be obtained during coating.

[0049] -Oxyalkylene polymer A-

[0050] Oxyalkylene polymer A (hereinafter also referred to as polymer A) is an oxyalkylene polymer with an average number of hydroxyl groups per molecule of more than 2.0 and less than 3.0.

[0051] There are no particular limitations on the average number of hydroxyl groups per molecule of the oxyalkylene polymer A, as long as it is greater than 2.0 and less than 3.0. It is preferred to be 2.2 or more, more preferably 2.5 or more, further preferably 2.8 or more, and particularly preferably 3.0.

[0052] When the average number of hydroxyl groups in oxyalkylene polymer A is within the above-mentioned range, the resulting adhesive can achieve a suitable level of adhesion to the substrate.

[0053] The average number of hydroxyl groups per molecule of oxyalkylene polymer A can be determined by using... 13 The type and molar ratio of the initiator are determined by C-NMR (nuclear magnetic resonance) to calculate the result. Based on 13 In C-NMR analysis, characteristic peaks can be seen at the initiator, so the type and molar ratio of the initiator can be determined based on the position and area of ​​the peak.

[0054] Typically, the number of hydroxyl groups per molecule of an oxoalkylene polymer is consistent with the number of hydroxyl groups per molecule of the initiator used in the synthesis of that oxoalkylene polymer. For example, when glycerol is used as an initiator to synthesize an oxoalkylene polymer, a polymer with 3 hydroxyl groups per molecule is usually obtained. Alternatively, for example, when pentaerythritol is used as an initiator to synthesize an oxoalkylene polymer, a polymer with 4 hydroxyl groups per molecule is usually obtained. Furthermore, for example, when dipropylene glycol is used as an initiator to synthesize an oxoalkylene polymer, a polymer with 2 hydroxyl groups per molecule is usually obtained.

[0055] Furthermore, the average number of hydroxyl groups per molecule of oxyalkylene polymer A can be calculated based on the number of hydroxyl groups per molecule and the molar fraction of the initiator, depending on the type of initiator. For example, if glycerol is 30 mol% and dipropylene glycol is 70 mol%, the average number of hydroxyl groups is 3 × 0.3 + 2 × 0.7 = 2.3.

[0056] When synthesizing alkylene oxide polymer A, there are no particular restrictions on the selection of the alkylene oxide as long as the content ratio of alkylene oxide to the total amount of alkylene oxide in alkylene oxide polymer A (ethylene oxide unit content) is 15% by mass or more. Ethylene oxide can be used alone, preferably in combination with alkylene oxide having 3 to 5 carbon atoms, and more preferably in combination with propylene oxide.

[0057] When two or more alkyl oxides undergo ring-opening addition, the arrangement of units derived from each alkyl oxide can be random, block, or conical. Here, when the arrangement of ethylene oxide and propylene oxide units is random, the alkylene oxide polymer A can typically have block forms of propylene oxide units and atactic forms of ethylene oxide and propylene oxide units. Alternatively, it can have block forms of ethylene oxide units and atactic forms of ethylene oxide and propylene oxide units. Furthermore, when the oxyalkylene polymer A has ethylene oxide and propylene oxide units arranged in a block configuration, it can sequentially have a block of propylene oxide units, a block of ethylene oxide units, and a block of propylene oxide units (a "PO block-EO block-PO block" structure), or it can sequentially have a block of ethylene oxide units, a block of propylene oxide units, and a block of ethylene oxide units (an "EO block-PO block-EO block" structure). Moreover, when the oxyalkylene polymer A has ethylene oxide and propylene oxide units arranged in a conical shape, it typically has a block of propylene oxide units, a random form of ethylene oxide and propylene oxide units, and a block of ethylene oxide units.

[0058] When using ethylene oxide and other ethylene oxides in combination as alkylene oxides, there are no particular restrictions on the molar ratio of ethylene oxide units to other alkylene oxide units in alkylene oxide polymer A, provided that the content of oxyethylidene relative to the total oxyalkylene oxide (ethylene oxide unit content) is 15% by mass or higher. A higher content of oxyethylidene (ethylene oxide unit content) tends to increase the hydrophilicity of alkylene oxide polymer A, while a lower content of oxyethylidene (ethylene oxide unit content) tends to decrease the crystallinity of alkylene oxide polymer A.

[0059] Furthermore, when the alkylene oxide polymer A is terminated with an ethylene oxide unit, it tends to have higher reactivity with diisocyanates compared to the case where the terminal unit is propylene oxide, because the terminal unit is a primary hydroxyl group.

[0060] The content ratio of oxyethylidene to the total amount of oxyalkylene in oxyalkylene polymer A (ethylene oxide unit content) is not particularly limited as long as it is 15% by mass or more, and can be 100% by mass, preferably 16% by mass or more, more preferably 18% by mass or more, particularly preferably 20% by mass or more, and preferably 95% by mass or less, more preferably 90% by mass or less, particularly preferably 85% by mass or less.

[0061] When the content ratio of oxyethylidene to the total amount of oxyalkylene in oxyalkylene polymer A (ethylene oxide unit content) is within the above-mentioned preferred range, oxyalkylene polymer A is prone to becoming non-crystalline, and therefore easy to handle. Even when the resulting adhesive is stored under high temperature and high humidity, it is easy to maintain peelability (hereinafter referred to as "damp heat resistance").

[0062] For the content ratio of oxyethylidene to the total amount of oxyalkylene in oxyalkylene polymer A (ethylene oxide unit content), use 13 The monomer composition of the alkylene chain is determined by C-NMR, and thus the content can be calculated. For example, if the alkylene polymer A is a polyol formed from propylene oxide and ethylene oxide units, the content ratio of ethylene to the total amount of alkylene (ethylene oxide unit content) can be determined based on the area ratio of the methyl signal in the propylene oxide unit to the area ratio of the methylene signal in the propylene oxide unit and the methylene signal in the ethylene oxide unit.

[0063] The number average molecular weight of the oxyalkylene polymer A is not particularly limited, but is preferably 1000 or more, more preferably 3000 or more, further preferably 5000 or more, particularly preferably 8000 or more, and preferably 50000 or less, more preferably 40000 or less, further preferably 30000 or less, and particularly preferably 25000 or less. When the number average molecular weight of the oxyalkylene polymer A is within the above-mentioned preferred range, the resulting adhesive exhibits better flexibility.

[0064] When two or more oxyalkylene polymers A are included, the number-average molecular weight of each oxyalkylene polymer A is preferably within the range described above.

[0065] There are no particular limitations on the molecular weight distribution of the oxyalkylene polymer A, but it is preferably less than 1.40, more preferably less than 1.20. By setting the molecular weight distribution of the oxyalkylene polymer A to less than 1.20, the reactivity becomes easier to improve, and the hydroxyl-terminated urethane prepolymer can be manufactured more efficiently, resulting in a more easily reduced viscosity.

[0066] When two or more oxyalkylene polymers A are included, the molecular weight distribution of each oxyalkylene polymer A is preferably within the range described above.

[0067] The number-average molecular weight (hereinafter referred to as "Mn") and molecular weight distribution (hereinafter referred to as "Mw / Mn") of the oxyalkylene polymer A are values ​​obtained by determination using the methods described below.

[0068] For multiple types of monodisperse polystyrene with different degrees of polymerization used as standard samples for molecular weight determination, measurements were performed using a commercially available GPC apparatus (HLC-8320GPC, manufactured by Tosoh Corporation). A standard curve was constructed based on the relationship between the molecular weight and retention time of polystyrene. The oxyalkylene polymer A used as the test sample was diluted to 0.5% by mass with tetrahydrofuran, passed through a 0.5 μm filter, and then measured using the aforementioned GPC apparatus. Using the standard curve, the GPC spectra of the test sample were analyzed by computer to determine the Mn and weight-average molecular weight (hereinafter referred to as Mw) of the test sample.

[0069] The molecular weight distribution is the value calculated based on Mw and Mn above, which is the ratio of Mw to Mn.

[0070] The degree of unsaturation of the oxyalkylene polymer A is not particularly limited, but is preferably 0.015 meq / g or less, more preferably 0.014 meq / g or less, and particularly preferably 0.013 meq / g or less. The degree of unsaturation of the oxyalkylene polymer A can be zero. When the degree of unsaturation of the oxyalkylene polymer A is below the above-mentioned upper limit, the resulting hydroxyl-terminated urethane prepolymer has better curability.

[0071] The degree of unsaturation of oxyalkylene polymer A was determined according to the method of JIS-K1557-6:2009.

[0072] The hydroxyl value of the alkylene polymer A is not particularly limited, but is preferably 2 mg KOH / g or more, more preferably 5 mg KOH / g or more, particularly preferably 8 mg KOH / g or more, and preferably 50 mg KOH / g or less, more preferably 45 mg KOH / g or less, particularly preferably 40 mg KOH / g or less. When the hydroxyl value of the alkylene polymer A is below the above-mentioned upper limit, the resulting adhesive has better flexibility.

[0073] The hydroxyl value of oxyalkylene polymer A was determined by titration according to JIS K 0070:1992.

[0074] As one aspect of the present invention, oxoalkylene polymer A comprises oxoalkylene polymer a (hereinafter referred to as "polymer a") having 3 hydroxyl groups per molecule. When oxoalkylene polymer A comprises polymer a, it is easier to set the adhesion to the substrate within a more moderate range.

[0075] The mass percentage of polymer a in oxyalkylene polymer A is not particularly limited, but is preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 100% by mass.

[0076] For the mass ratio of polymer a contained in oxyalkylene polymer A, for example, using 13 C-NMR (nuclear magnetic resonance) determines the types and molar ratios of initiators contained in oxyalkylene polymer A, which can be calculated in the form of the ratio of their peak areas.

[0077] To synthesize polymer a, an initiator having three hydroxyl groups per molecule is used. Glycerol is preferred as the initiator for synthesizing polymer a. Glycerol is readily available at low cost, which reduces the synthesis cost of oxyalkylene polymer a.

[0078] The alkylene oxide used in the synthesis of polymer a is the same alkylene oxide used in the synthesis of the aforementioned alkylene polymer A.

[0079] If the raw materials used in the synthesis of alkylene polymer A contain water, the epoxide is added to the polymer using water as an initiator, thereby generating a polymer with two hydroxyl groups per molecule (equivalent to polymer b described later) as a byproduct. The alkylene polymer A may also contain this byproduct if the average number of hydroxyl groups is greater than 2.0 and less than 3.0. This byproduct is preferably less than 2000 ppm, more preferably less than 1800 ppm, and even more preferably less than 1500 ppm relative to alkylene polymer A.

[0080] As a catalyst for the ring-opening addition polymerization of epoxides in an initiator, conventionally known catalysts can be used. Examples include base catalysts such as KOH, transition metal compound-porphyrin complex catalysts such as complexes obtained by reacting organoaluminum compounds with porphyrins, complex metal cyanide complex catalysts (DMC catalysts), and catalysts containing phosphazene compounds.

[0081] When using a complex metal cyanide catalyst (DMC catalyst) to obtain oxyalkylene polymer A, it is preferable to obtain oxyalkylene polymer A with a narrow molecular weight distribution, which makes it easier to obtain oxyalkylene polymer A with low viscosity.

[0082] The composite metal cyanide complex catalyst (DMC catalyst) can use conventionally known compounds, and the manufacturing method of the polymer using the composite metal cyanide complex catalyst (DMC catalyst) can also employ known methods. For example, compounds and manufacturing methods disclosed in International Publication No. 2003 / 062301, International Publication No. 2004 / 067633, Japanese Patent Application Publication No. 2004-269776, Japanese Patent Application Publication No. 2005-015786, International Publication No. 2013 / 065802, and Japanese Patent Application Publication No. 2015-010162 can be used.

[0083] As a method for obtaining oxyalkylene polymer A by ring-opening addition polymerization of an initiator with an alkyl oxide, conventionally known methods can be employed. For example, manufacturing methods disclosed in International Patent Publication No. 2011 / 125951, Japanese Patent No. 5648797, etc., can be used.

[0084] -Oxyalkylene polymers B-

[0085] Oxyalkylene polymer B (hereinafter also referred to as polymer B) is an oxyalkylene polymer with an average number of hydroxyl groups per molecule of 1.2 or more and 2.0 or less.

[0086] There are no particular limitations on the average number of hydroxyl groups per molecule of the oxyalkylene polymer B, as long as it is 1.2 or more and 2.0 or less, preferably 1.5 or more, more preferably 1.8 or more. The average number of hydroxyl groups per molecule of polymer B is particularly preferably 2.0.

[0087] When the average number of hydroxyl groups in the oxyalkylene polymer B is within the preferred range described above, the resulting adhesive can achieve a moderate level of adhesion to the substrate.

[0088] The average number of hydroxyl groups per molecule of oxyalkylene polymer B can be determined in the same way as in the case of oxyalkylene polymer A.

[0089] The average number of hydroxyl groups per molecule of oxyalkylene polymer B can be used as follows: 13 The measurements were performed using C-NMR. Specifically, based on... 13 The peaks obtained from C-NMR determine the type of initiator, indicating that the average number of hydroxyl groups is above 1.2 and below 2.0.

[0090] In addition, the average number of hydroxyl groups per molecule of oxyalkylene polymer B can also be calculated based on the number of hydroxyl groups per molecule based on the type of initiator and the molar fraction of the initiator. For example, if propanol (n-propyl alcohol) is 30 mol% and dipropylene glycol is 70 mol%, the average number of hydroxyl groups is 1 × 0.3 + 2 × 0.7 = 1.7.

[0091] The alkylene oxide polymer B is preferably obtained by ring-opening addition of an initiator having two hydroxyl groups in one molecule to an alkylene oxide.

[0092] The alkyl oxide used in the synthesis of alkylene oxide polymer B is selected in such a way that the content ratio of alkylene oxide to the total amount of alkylene oxide in alkylene oxide polymer B (ethylene oxide unit content) is 15% by mass or more. There are no particular restrictions. Ethylene oxide can be used alone, preferably in combination with alkyl oxides having 3 to 5 carbon atoms, and more preferably in combination with propylene oxide.

[0093] When two or more alkyl oxides undergo ring-opening addition, the arrangement of units derived from each alkyl oxide can be random, block, or conical. Here, when the arrangement of ethylene oxide and propylene oxide units is random, the alkylene oxide polymer B can typically have a block form of propylene oxide units, a random form of ethylene oxide and propylene oxide units, or alternatively, a block form of ethylene oxide units and a random form of ethylene oxide and propylene oxide units. Furthermore, when the alkylene oxide polymer B is arranged in a block configuration of ethylene oxide and propylene oxide units, it can sequentially have a block body of propylene oxide units, a block body of ethylene oxide units, and a block body of propylene oxide units (a "PO block-EO block-PO block" structure), or it can sequentially have a block body of ethylene oxide units, a block body of propylene oxide units, and a block body of ethylene oxide units (an "EO block-PO block-EO block" structure). Moreover, when the alkylene oxide polymer B is arranged in a conical configuration of ethylene oxide and propylene oxide units, it typically has a block body of propylene oxide units, a random form of ethylene oxide and propylene oxide units, and a block body of ethylene oxide units.

[0094] When using ethylene oxide and other ethylene oxides in combination as alkylene oxides, there are no particular limitations on the molar ratio of ethylene oxide units to other alkylene oxide units, as long as the content of oxyethylidene in the alkylene oxide polymer B relative to the total alkylene oxide (ethylene oxide unit content) is 15% by mass or more. A higher content of oxyethylidene (ethylene oxide unit content) tends to increase the hydrophilicity of the alkylene oxide polymer B, while a lower content of oxyethylidene (ethylene oxide unit content) tends to decrease the crystallinity of the alkylene oxide polymer B.

[0095] In addition, when the alkylene oxide polymer B is terminated with an ethylene oxide unit, the terminal is a primary hydroxyl group, and therefore tends to have higher reactivity with diisocyanates compared to the case where the terminal is a propylene oxide unit.

[0096] There is no particular limitation on the content ratio of oxyethylidene to the total amount of oxyalkylene in oxyalkylene polymer B (ethylene oxide unit content). As long as it is 15% by mass or more, there is no particular limitation. It can be 100% by mass, preferably 16% by mass or more, more preferably 17% by mass or more, particularly preferably 19% by mass or more, and preferably 95% by mass or less, more preferably 90% by mass or less, and particularly preferably 85% by mass or less.

[0097] When the content ratio of oxyethylidene to the total amount of oxyalkylene in oxyalkylene polymer B (ethylene oxide unit content) is within the above-mentioned preferred range, the resulting adhesive exhibits better resistance to damp heat.

[0098] The content ratio of oxyethylidene to the total amount of oxyalkylene in oxyalkylene polymer B (ethylene oxide unit content) can be calculated in the same way as in oxyalkylene polymer A.

[0099] For the content ratio of oxyethylidene relative to the total amount of oxyalkylene when containing two or more oxyalkylene polymers B (ethylene oxide unit content), the value calculated by their weighted average is preferably within the above-mentioned preferred range.

[0100] The Mn of the oxyalkylene polymer B is not particularly limited, but is preferably 1000 or more, more preferably 3000 or more, further preferably 5000 or more, particularly preferably 8000 or more. It is also preferably 50000 or less, more preferably 40000 or less, further preferably 30000 or less, and particularly preferably 25000 or less. When the Mn of the oxyalkylene polymer B is within the above-mentioned preferred range, the resulting adhesive exhibits better flexibility.

[0101] The Mw / Mn ratio of the alkylene polymer B is not particularly limited, but is preferably less than 1.40, more preferably less than 1.20, further preferably less than 1.13, and particularly preferably less than 1.10. By setting the molecular weight distribution of the alkylene polymer B within the above range, its reactivity is easily improved, enabling more efficient production of hydroxyl-terminated urethane prepolymers, and the viscosity of the resulting hydroxyl-terminated urethane prepolymer is more easily reduced. It should be noted that the Mn and Mw in the alkylene polymer B can be determined by GPC measurement using the same method as that used for the alkylene polymer A described above.

[0102] The degree of unsaturation of the oxyalkylene polymer B is preferably 0.015 meq / g or less, more preferably 0.013 meq / g or less, even more preferably 0.010 meq / g or less, and particularly preferably 0.008 meq / g or less. The degree of unsaturation of the oxyalkylene polymer B can be zero. When the degree of unsaturation of the oxyalkylene polymer B is below the above-mentioned upper limit, the resulting hydroxyl-terminated urethane prepolymer has better curability.

[0103] The hydroxyl value of the alkylene polymer B is not particularly limited, but is preferably 2 mg KOH / g or more, more preferably 5 mg KOH / g or more, particularly preferably 8 mg KOH / g or more, and preferably 80 mg KOH / g or less, more preferably 70 mg KOH / g or less, particularly preferably 60 mg KOH / g or less. When the hydroxyl value of the alkylene polymer B is within the above-mentioned preferred range, the resulting adhesive has better flexibility.

[0104] The degree of unsaturation and hydroxyl value of oxyalkylene polymer B can be determined in the same manner as those of oxyalkylene polymer A.

[0105] When the product contains two or more oxoalkylene polymers B, the Mn, Mw / Mn, degree of unsaturation, and hydroxyl value of each oxoalkylene polymer B are preferably within the ranges described above.

[0106] As with the case of oxyalkylene polymer A, a base catalyst such as KOH or a complex metal cyanide catalyst (DMC catalyst) is preferred as a catalyst.

[0107] As one aspect of the present invention, the oxyalkylene polymer B comprises an oxyalkylene polymer b (hereinafter referred to as "polymer b") having two hydroxyl groups per molecule. When the oxyalkylene polymer B comprises polymer b, it is easier to achieve a more moderate range of adhesion to the substrate.

[0108] There is no particular limitation on the mass ratio of polymer b in oxyalkylene polymer B, but it is preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 100% by mass.

[0109] The mass ratio of polymer b contained in oxyalkylene polymer B can be calculated in the same way as the mass ratio of polymer a contained in oxyalkylene polymer A.

[0110] To synthesize polymer b, water or an initiator having two hydroxyl groups per molecule is used. As the initiator having two hydroxyl groups per molecule for the synthesis of polymer b, one or more are preferably selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol, more preferably from one or more of propylene glycol and dipropylene glycol, and particularly preferably propylene glycol. Propylene glycol is readily available at low cost, thus reducing the synthesis cost of polymer b.

[0111] The alkylene oxide used in the synthesis of polymer b is the same as that used in the synthesis of the aforementioned alkylene polymer A, and preferably in the same manner. Polymer b can be synthesized by the same method as the aforementioned alkylene polymer A.

[0112] -Other oxoalkylene polymers-

[0113] The aqueous dispersion of the present invention may contain a reaction product obtained by reacting an oxoalkylene polymer other than the above-mentioned oxoalkylene polymers a and b with a diisocyanate compound. Examples of oxoalkylene polymers other than oxoalkylene polymers a and b include oxoalkylene polymer c (hereinafter referred to as "polymer c") having 4 or more hydroxyl groups per molecule and oxoalkylene polymer d (hereinafter referred to as "polymer d") having 1 hydroxyl group per molecule.

[0114] To synthesize polymer c, an initiator having four or more hydroxyl groups in one molecule is used. Examples of initiators having four or more hydroxyl groups in one molecule include polyols with four or more hydroxyl groups such as diglycerides, pentaerythritol, dipentaerythritol, and tripentaerythritol, as well as sugars or their derivatives such as glucose, sorbitol, dextrose, fructose, sucrose, and methyl glucoside.

[0115] To synthesize polymer d, an initiator having one hydroxyl group per molecule is used. As an initiator having one hydroxyl group per molecule, a monohydric alcohol having 2 to 4 carbon atoms is preferred from the perspective of being readily available at low cost; propanol (n-propanol), 2-propanol (isopropanol), 1-butanol (n-butanol), 2-butanol (sec-butanol), 2-methyl-1-propanol (isobutanol), and 2-methyl-2-propanol (tert-butanol) are more preferred; particularly preferred are 1-butanol (n-butanol), 2-butanol (sec-butanol), 2-methyl-1-propanol (isobutanol), and 2-methyl-2-propanol (tert-butanol).

[0116] The alkylene oxide used in the synthesis of polymer c or polymer d is the same as that used in the synthesis of the oxyalkylene polymer A described above, and preferably in the same manner. Polymer c or polymer d can be synthesized by the same method as the oxyalkylene polymer A described above.

[0117] The proportion of the total mass of polymers c and d relative to the total mass of oxyalkylene polymers A and B is preferably 20% by mass or less, more preferably 10% by mass or less, particularly preferably 3% by mass or less, or may be absent.

[0118] -Diisocyanate compounds-

[0119] The diisocyanate compound used to react the above-mentioned oxoalkylene polymer A and the above-mentioned oxoalkylene polymer B to obtain a hydroxyl-terminated urethane prepolymer is not particularly limited as long as it is an organic compound having two isocyanate groups in one molecule. Examples include aliphatic diisocyanate compounds, alicyclic diisocyanate compounds, aromatic diisocyanate compounds, and aromatic aliphatic diisocyanate compounds.

[0120] Examples of aliphatic diisocyanate compounds include, for instance, linear aliphatic diisocyanates such as tetramethylene diisocyanate, dodecamethylene diisocyanate, and hexamethylene diisocyanate (HDI); and branched aliphatic diisocyanates such as 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1,5-diisocyanate, and 3-methylpentane-1,5-diisocyanate. Aliphatic diisocyanate compounds can be used alone or in combination of two or more.

[0121] Among these, linear aliphatic diisocyanates are preferred, especially those with 4 to 8 carbon atoms, and more preferably linear aliphatic diisocyanates, based on the superior glass transition temperature, tensile strength, and elongation at break of the resulting adhesive. Hexamethylene diisocyanate (HDI) is particularly preferred.

[0122] Examples of alicyclic diisocyanate compounds include isophorone diisocyanate (IPDI), hydrogenated phenyl diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexene diisocyanate, and 1,3-bis(isocyanate methyl)cyclohexane. Alicyclic diisocyanate compounds can be used alone or in combination of two or more.

[0123] Among these, isophorone diisocyanate and 4,4'-dicyclohexylmethane diisocyanate are preferred, and isophorone diisocyanate is more preferred, considering that the resulting polyurethane (adhesive) has superior tensile strength and elongation at break.

[0124] Examples of aromatic diisocyanate compounds include, for example, toluene diisocyanate (TDI), 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-dibenzyl diisocyanate, 1,5-naphthalene diisocyanate, phenyl dimethyl diisocyanate, 1,3-phenylene diisocyanate, and 1,4-phenylene diisocyanate. Aromatic diisocyanate compounds can be used alone or in combination of two or more.

[0125] Among these, diphenylmethane diisocyanate is preferred, and 4,4'-diphenylmethane diisocyanate (MDI) is more preferred, considering that the resulting polyurethane has superior tensile strength and elongation at break.

[0126] Examples of aromatic aliphatic diisocyanate compounds include, for example, dialkyl diphenylmethane diisocyanate, tetraalkyl diphenylmethane diisocyanate, and α,α,α',α'-tetramethylphenyl diisocyanate. Aromatic aliphatic diisocyanate compounds can be used alone or in combination of two or more.

[0127] Among these, α,α,α',α'-tetramethylphenyldimethyl diisocyanate is preferred, considering its superior elongation at break.

[0128] For the diisocyanate compounds used in the manufacture of hydroxyl-terminated urethane prepolymers, from the perspective of obtaining polyurethanes with better tensile strength and elongation at break, aliphatic diisocyanate compounds and alicyclic diisocyanate compounds are preferred, aliphatic diisocyanate compounds are more preferred, aliphatic diisocyanate compounds with 4 to 6 carbon atoms are even more preferred, HDI and modified HDI are particularly preferred, and HDI and HDI isocyanurate modified HDI are most preferred.

[0129] As a diisocyanate compound for manufacturing hydroxyl-terminated urethane prepolymers, a difunctional isocyanate-terminated urethane prepolymer obtained by prepolymerizing the above-mentioned aliphatic diisocyanate compound, alicyclic diisocyanate compound, aromatic diisocyanate compound, or aromatic aliphatic diisocyanate compound with a diol can be used.

[0130] Examples of diols used in the manufacture of isocyanate-terminated urethane prepolymers include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, and 1,6-hexanediol. One diol may be used alone or in combination of two or more.

[0131] Among these, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, and 1,6-hexanediol are preferred, with propylene glycol being more preferred, based on the aspect that the glass transition temperature of the obtained polyurethane (adhesive) becomes higher.

[0132] The isocyanate index is set to be greater than 100 when manufacturing isocyanate-terminated urethane prepolymers. The isocyanate index is a value that sets the ratio of the molar number of isocyanate groups in the diisocyanate compound to the molar number of hydroxyl groups in the diol to 100.

[0133] Commercially available products that are difunctional isocyanate-terminated urethane prepolymers include, for example, DURANATE D101, DURANATE D201, and DURANATE A201H (all manufactured by Asahi Kasei Corporation).

[0134] The molar ratio (isocyanate index) of the isocyanate groups in the diisocyanate compound relative to the hydroxyl groups in oxoalkylene polymer A and oxoalkylene polymer B is not particularly limited, but is preferably 40 or more, more preferably 43 or more, particularly preferably 46 or more, and further preferably 90 or less, more preferably 80 or less, particularly preferably 75 or less. When the above molar ratio is within the above preferred range, hydroxyl-terminated urethane prepolymers with a suitable molecular chain length can be manufactured, thus further improving productivity. It should be noted that the isocyanate index is a value where the ratio of the molar number of isocyanate groups in the diisocyanate compound to the total molar number of hydroxyl groups in oxoalkylene polymer A and oxoalkylene polymer B is set to 100.

[0135] Method for manufacturing hydroxy-terminated carbamate prepolymers-

[0136] There are no particular limitations on the manufacturing method of hydroxyl-terminated urethane prepolymers; for example, a method can be used to react oxyalkylene polymer A and oxyalkylene polymer B with a diisocyanate compound.

[0137] The content ratio of oxyalkylene polymer A relative to the total mass of oxyalkylene polymer A and oxyalkylene polymer B is not particularly limited, but is preferably 20% by mass or more, more preferably 24% by mass or more, particularly preferably 28% by mass or more, and preferably 60% by mass or less, more preferably 55% by mass or less, particularly preferably 50% by mass or less. When the content ratio of oxyalkylene polymer A relative to the total mass of oxyalkylene polymer A and oxyalkylene polymer B is within the above-mentioned preferred range, gelation and high viscosity can be prevented during the manufacture of urethane prepolymer, and adhesion to the substrate can be maintained better.

[0138] The average number of hydroxyl-terminated urethane prepolymers is preferably 1.7 or more, more preferably 1.8 or more, particularly preferably 2.0 or more, and preferably less than 3.0, more preferably 2.9 or less, particularly preferably 2.5 or less. When the average number of hydroxyl-terminated urethane prepolymers is within the above-mentioned preferred range, the permeability and adhesion to the substrate of the resulting adhesive can be maintained better.

[0139] The "average number of hydroxyl groups f" of the hydroxyl-terminated urethane prepolymer is a value obtained by the following formula (I).

[0140] f = (Average number of hydroxyl groups in oxyalkylene polymer A) × (Number of moles of oxyalkylene polymer A relative to the total number of moles of oxyalkylene polymer A and oxyalkylene polymer B) + (Average number of hydroxyl groups in oxyalkylene polymer B) × (Number of moles of oxyalkylene polymer B relative to the total number of moles of oxyalkylene polymer A and oxyalkylene polymer B) (I)

[0141] In hydroxyl-terminated prepolymers, polyols other than oxyalkylene polymers can also be used as any component.

[0142] As polyols other than alkylene polymers, examples include polyester polyols, poly(meth)acrylate polyols, polycarbonate polyols, polyolefin polyols, and castor oil-based polyols. Substances described in Japanese Patent Application Publication No. 2020-37689

[0016] to

[0028] may be used without particular limitation. Polymer polyols formed by dispersing a polymer having units based on (meth)acrylate monomers in a polyether polyol may also be used. Polymer polyols may be commercially available products, such as the "ULTIFLOW (registered trademark)" series, the "SHARPFLOW (registered trademark)" series (all manufactured by Sanyo Chemical Industries, Ltd.), and the "EXCENOL (registered trademark)" series (manufactured by AGC Corporation).

[0143] Catalysts may be used as needed in the manufacture of hydroxyl-terminated urethane prepolymers.

[0144] Examples of catalysts include tertiary amine compounds, tin compounds, and non-tin compounds.

[0145] One type of catalyst can be used alone or in combination of two or more.

[0146] Examples of tertiary amine compounds include, for example, triethylamine, triethylenediamine, and 1,8-diazabicyclo(5,4,0)-7-undecene (DBU).

[0147] Examples of tin-based compounds include, for example, dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin disilicate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin acetate, triethylethoxytin, tributylethoxytin, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, and 2-ethylhexanoate.

[0148] Examples of non-tin compounds include, for instance, titanium compounds such as dibutyltitanium dichloride, tetrabutyl titanate, and butoxytitanium trichloride; lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate; iron compounds such as iron 2-ethylhexanoate and iron acetylacetone; cobalt compounds such as cobalt benzoate and cobalt 2-ethylhexanoate; zinc compounds such as zinc naphthenate and zinc 2-ethylhexanoate; zirconium compounds such as zirconium naphthenate; and so on.

[0149] There is no particular limitation on the amount of catalyst used when using the catalyst. It is preferably 0.001 parts by mass or more, more preferably 0.002 parts by mass or more, and particularly preferably 0.003 parts by mass or more, relative to a total of 100 parts by mass of oxyalkylene polymer A, oxyalkylene polymer B and diisocyanate compound. In addition, it is preferably 1.0 parts by mass or less, more preferably 0.2 parts by mass or less, and particularly preferably 0.05 parts by mass or less.

[0150] Solvents can be used as needed to manufacture hydroxyl-terminated urethane prepolymers.

[0151] Examples of solvents include ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate; and aromatic hydrocarbons such as toluene and xylene. A single solvent can be used alone, or two or more solvents can be used in combination.

[0152] There is no particular limitation on the amount of solvent used when using a solvent. It is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, and particularly preferably 50 parts by mass or more, relative to 100 parts by mass of the total alkylene polymer and diisocyanate compound. In addition, it is preferably 500 parts by mass or less, more preferably 450 parts by mass or less, and particularly preferably 400 parts by mass or less.

[0153] As a method for manufacturing hydroxyl-terminated urethane prepolymers, examples include the methods shown below.

[0154] Manufacturing Method 1: A method of simultaneously adding a diisocyanate compound, oxyalkylene polymer A and oxyalkylene polymer B, any catalyst, and any solvent.

[0155] Manufacturing Method 2: A method of adding oxyalkylene polymer A and oxyalkylene polymer B, any catalyst, and any solvent, followed by dropwise addition of a diisocyanate compound.

[0156] In the case of manufacturing method 2, the low molecular weight components in the raw materials can be preferentially reacted, resulting in a narrower molecular weight distribution and making the reaction easier to control.

[0157] The reaction temperature is preferably 50°C or higher, more preferably 60°C or higher, particularly preferably 65°C or higher, and further preferably below 100°C, more preferably below 95°C, particularly preferably below 80°C. When the reaction temperature is set within the above range, side reactions other than the urethane reaction are easily suppressed, thus making it easier to obtain the desired prepolymer.

[0158] After the reaction is complete, a reaction stopper can be added to deactivate the catalyst. Examples of reaction stoppers include acetylacetone. Two or more reaction stoppers can be used in combination.

[0159] The molecular weight (Mw) of the hydroxyl-terminated urethane prepolymer is not particularly limited, but is preferably 10,000 or more, more preferably 15,000 or more, particularly preferably 20,000 or more, and preferably 250,000 or less, more preferably 240,000 or less, particularly preferably 220,000 or less. When the weight-average molecular weight is within the above-mentioned preferred range, an adhesive composition with excellent coatability can be obtained, and the viscosity during synthesis can be adjusted.

[0160] The Mw of the hydroxyl-terminated urethane prepolymer can be determined by GPC determination using the same method as that used for the oxyalkylene polymer A described above.

[0161] The content ratio of oxyethylidene to the total amount of oxyalkylene groups in the hydroxy-terminated carbamate prepolymer (ethylene oxide unit content) is not particularly limited as long as it exceeds 20% by mass and is less than 70% by mass. Preferably, it is 23% by mass or more, more preferably 26% by mass or more, particularly preferably 29% by mass or more, and preferably 65% ​​by mass or less, more preferably 60% by mass or less, particularly preferably 55% by mass or less. When the content ratio of oxyethylidene to the total amount of oxyalkylene groups in the hydroxy-terminated carbamate prepolymer (ethylene oxide unit content) is at or above the lower limit, the water solubility of the hydroxy-terminated carbamate prepolymer is improved. Due to the presence of oxypropylidene (polar group) in the prepolymer, the affinity with the release agent (organosilicon) is improved, the coatability of the aqueous dispersion containing the hydroxy-terminated carbamate prepolymer is improved, and further, the transparency of the obtained adhesive is improved, and the resistance of the obtained adhesive to damp heat is better. When the content ratio of oxyethylidene to the total amount of oxyalkylene in the hydroxyl-terminated urethane prepolymer (ethylene oxide unit content) is below the upper limit, the haze of the resulting adhesive is easily suppressed and the transparency is easily improved.

[0162] It should be noted that the content ratio of oxyethylidene to the total amount of oxyalkylene in the urethane prepolymer (ethylene oxide unit content) is determined by using... 1 The monomer composition of the oxyalkylene chain is determined by H-NMR.

[0163] When the raw materials and amounts used in the synthesis are known, the content ratio of oxyethylidene to the total amount of oxyalkylene in the hydroxyl-terminated urethane prepolymer (ethylene oxide unit content) can be calculated in the form of (content ratio of oxyethylidene to the total amount of oxyalkylene in oxyalkylene polymer A) × (mass of oxyalkylene polymer A relative to the total mass of oxyalkylene polymer A and oxyalkylene polymer B) + (content ratio of oxyethylidene to the total amount of oxyalkylene in oxyalkylene polymer B) × (mass of oxyalkylene polymer B relative to the total mass of oxyalkylene polymer A and oxyalkylene polymer B).

[0164] <Water>

[0165] The water content in the aqueous dispersion of the present invention is preferably 40% by mass or more, more preferably 44% by mass or more, particularly preferably 48% by mass or more, and preferably 90% by mass or less, more preferably 85% by mass or less, particularly preferably 80% by mass or less.

[0166] When the aforementioned content is within the above-mentioned range, the coatability is further improved.

[0167] <Other Ingredients>

[0168] The aqueous dispersion of the present invention may contain antioxidants; organic solvents such as alcohols; and other components such as raw materials used in the preparation of hydroxyl-terminated carbamate prepolymers, such as epoxides, polyols (initiators), and diisocyanates.

[0169] The content of other components in the aqueous dispersion of the present invention is generally less than 20% by mass.

[0170] -Antioxidants-

[0171] Examples of antioxidants include free radical scavengers such as phenolic and amine compounds; peroxide decomposers such as sulfur and phosphorus compounds; and so on. Antioxidants can be used alone or in combination of two or more.

[0172] --Phenolic compounds--

[0173] Examples of phenolic compounds include: 2,6-di-tert-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, stearyl-β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4,4'-butylenebis(3-methyl-6-tert-butylphenol). tert-Butylphenol), 2,2'-dihydroxy-3,3'-di(α-methylcyclohexyl)-5,5'-dimethyldiphenylmethane (Seiko Chemical Co., Ltd. product name CBP), 3,9-bis[1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]2,4,8,10-tetraoxaspiro[5,5]undecane, phenylpropionic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-,C7-C9 side-chain alkyl ester (BASF product name Irganox) 1135), 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazine-2-ylamino)phenol (BASF product name Irganox 565), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tetra-[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane, bis[3,3'-bis-(4'-hydroxy-3'-tert-butylphenyl)butyrate]diol ester, 1,3,5-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)-triazine-2,4,6-(1H,3H,5H)trione, tocopherol, etc.

[0174] --Phosphorus compounds--

[0175] Examples of phosphorus compounds include, for instance, triphenyl phosphite, diphenylisodecyl phosphite, 4,4'-butylene-bis(3-methyl-6-tert-butylphenyl bis(tetrazyl) phosphite, cyclopentanetetramethylbis(octadecyl) phosphite, tris(nonylphenyl) phosphite, tris(mononylphenyl) phosphite, tris(dinonylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and 10-(3-... (5-di-tert-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decoxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene, tris(2,4-di-tert-butylphenyl) phosphite, cyclopentanetetramethylbis(2,4-di-tert-butylphenyl) phosphite, cyclopentanetetramethylbis(2,6-di-tert-butyl-4-methylphenyl) phosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl) octyl phosphite, etc.

[0176] By using antioxidants, the thermal degradation of hydroxyl-terminated urethane prepolymers can be prevented.

[0177] There is no particular limitation on the amount of antioxidant added. It is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and particularly preferably 0.2 parts by mass or more, relative to 100 parts by mass of hydroxyl-terminated urethane prepolymer. In addition, it is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and particularly preferably 2 parts by mass or less.

[0178] From the viewpoint of stability and antioxidant effect, it is preferable to use one or more phenolic compounds that act as free radical scavengers as antioxidants. It is also possible to use one or more phenolic compounds that act as free radical scavengers and one or more phosphorus compounds that act as peroxide decomposers in combination. Furthermore, as antioxidants, it is also possible to use phenolic compounds that act as free radical scavengers and phosphorus compounds that act as peroxide decomposers in combination, and to use these antioxidants in combination with hydrolysis inhibitors described later.

[0179] (Adhesive composition)

[0180] The adhesive composition of the present invention comprises the aqueous dispersion of the present invention and a polyisocyanate compound having three or more isocyanate groups in one molecule.

[0181] <Polyisocyanate compounds with three or more isocyanate groups in one molecule>

[0182] Examples of polyisocyanate compounds having three or more isocyanate groups in one molecule include, for example, isocyanurate modified forms of the above-mentioned diisocyanate compounds; biuret modified forms of the above-mentioned diisocyanate compounds; urethane modified forms of the above-mentioned diisocyanate compounds; trifunctional or higher isocyanate-terminated urethane prepolymers (addition modified forms) obtained by reacting the above-mentioned diisocyanate compounds with a polyol having three or more hydroxyl groups in one molecule; water-dispersible polyisocyanate compounds such as water-dispersible isocyanates and capped isocyanates; etc.

[0183] Commercially available isocyanurate modifiers include, for example, DURANATE TPA-100, DURANATETKA-100 (manufactured by Asahi Kasei Corporation), and CORONATE HX (manufactured by Tosoh Corporation).

[0184] Commercially available biuret modifiers include, for example, DURANATE 24A-100 and DURANATE 22A-75P (manufactured by Asahi Kasei Corporation).

[0185] Commercially available products that are trifunctional or higher isocyanate-terminated urethane prepolymers include, for example, CORONATE L, CORONATE L-55E, and CORONATE L-45E (all manufactured by Tosoh Corporation).

[0186] Commercially available water-dispersible isocyanates include, for example, DURANATE WB40-100, DURANATE WB40-80D, DURANATE WT20-100, DURANATE WL70-100, DURANATE WE50-100, DURANATE WR80-70P (manufactured by Asahi Kasei Corporation), Aquanate 105, Aquanate 130, Aquanate 140 (AQ-140), Aquanate200, and Aquanate 210 (manufactured by Tosoh Corporation).

[0187] Commercially available products containing terminal isocyanates include, for example, SU-268A, NBP-211, MEIKANATE CX, MEIKANATE TP-10, DM-6400 (all manufactured by Meisei Chemicals Co., Ltd.); WM44-L70G (manufactured by Asahi Kasei Corporation); Aqua BI200 and Aqua BI220 (both manufactured by Baxenden Chemicals); Takelac W and Takelac WPB (both manufactured by Mitsui Chemicals Co., Ltd.); BURNOCK (manufactured by DIC Corporation); Elastron (manufactured by Daiichi Kogyo Co., Ltd.); etc.

[0188] Among these, water-dispersible polyisocyanate compounds are preferred, and water-dispersible isocyanates are even more preferred.

[0189] The adhesive composition of the present invention can be a two-component adhesive composition comprising: a first agent comprising the aqueous dispersion of the present invention, and a second agent comprising a polyisocyanate compound having three or more isocyanate groups in one molecule.

[0190] By mixing the first agent and the second agent, urethane bonds are formed, resulting in an adhesive composition containing polyurethane.

[0191] The first or second agent may also contain a catalyst, a solvent, any components that can be mixed in the binder composition described later.

[0192] The first and second doses were stored in their respective containers. Various containers, such as tubes and bottles, could be used.

[0193] In addition to the form containing both the first agent and the second agent, the adhesive composition of the present invention can also be sold in a form containing the first agent but not the second agent (i.e., the aqueous dispersion of the present invention). For the form without the second agent, the user has greater freedom by using a separately prepared second agent.

[0194] <Method for manufacturing adhesive composition>

[0195] A method for manufacturing the adhesive composition of the present invention by reacting the aqueous dispersion of the present invention with a curing agent comprising a polyisocyanate compound having three or more isocyanate groups in one molecule will be described.

[0196] In addition to containing polyisocyanate compounds with three or more isocyanate groups in one molecule, the curing agent may also contain polyisocyanate compounds (diisocyanate compounds) with two isocyanate groups in one molecule.

[0197] Examples of the diisocyanate compounds mentioned above include the diisocyanate compounds described above and the difunctional isocyanate-terminated urethane prepolymers described above.

[0198] When the aqueous dispersion of the present invention is reacted with a curing agent comprising a polyisocyanate compound having three or more isocyanate groups per molecule to manufacture the adhesive composition of the present invention, the isocyanate index is preferably greater than 100, more preferably greater than 105, particularly preferably greater than 150, and further preferably less than 2000, more preferably less than 1750, and particularly preferably less than 1500. The isocyanate index is a value in which the ratio of the molar number of isocyanate groups in the curing agent to the molar number of hydroxyl groups in the hydroxyl-terminated urethane prepolymer is set to 100.

[0199] When manufacturing the adhesive composition of the present invention, a curing catalyst may be used as needed. The type of curing catalyst is preferably the catalyst described above. Furthermore, relative to 100 parts by weight of the total hydroxyl-terminated urethane prepolymer and curing agent, the amount of curing catalyst is preferably 0.001 parts by weight or more, more preferably 0.003 parts by weight or more, particularly preferably 0.005 parts by weight or more, and preferably 0.10 parts by weight or less, more preferably 0.05 parts by weight or less, particularly preferably 0.01 parts by weight or less. It is preferable to add a reaction stopper after the reaction is complete, thereby deactivating the catalyst.

[0200] The adhesive composition of the present invention may contain a solvent as needed. The solvents described above are preferred. Furthermore, relative to 100 parts by weight of the hydroxyl-terminated urethane prepolymer and the curing agent, the amount of solvent is preferably 30 parts by weight or more, more preferably 40 parts by weight or more, particularly preferably 50 parts by weight or more, and preferably 500 parts by weight or less, more preferably 450 parts by weight or less, particularly preferably 400 parts by weight or less.

[0201] The reaction temperature for the crosslinking reaction between the aqueous dispersion of the present invention and the curing agent is preferably 30°C or higher, more preferably 35°C or higher, particularly preferably 40°C or higher, and further preferably below 100°C, more preferably below 80°C, particularly preferably below 60°C. When the reaction temperature is set within the above range, side reactions other than the urethane reaction are easily suppressed, and thus the desired polymer is easily obtained.

[0202] <Any component that can be blended in the adhesive composition>

[0203] The adhesive composition of the present invention may, as needed and without impairing the effects of the present invention, contain hydrolysis inhibitors, antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, leveling agents, and other arbitrary components.

[0204] -Hydrolysis Inhibitor-

[0205] Examples of hydrolysis inhibitors include carbodiimide-based, isocyanate-based, oxazoline-based, and epoxy-based inhibitors. Hydrolysis inhibitors can be used alone or in combination of two or more.

[0206] Among these, from the perspective of hydrolysis inhibition effect, carbodiimide system is preferred.

[0207] --Carbodiimide series--

[0208] Carbodiimide hydrolysis inhibitors are compounds that have one or more carbodiimide groups in one molecule.

[0209] Examples of single-carbodiimide compounds include, for example, dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, diphenylcarbodiimide, and naphthylcarbodiimide.

[0210] Polycarbodiimide compounds can be generated by decarbonylation condensation of diisocyanates in the presence of a carbodiimide catalyst.

[0211] Examples of diisocyanates include, for example, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethoxy-4,4'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, 3,3'-dimethyl-4,4'-diphenyl ether diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1-methoxyphenyl-2,4-diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, tetramethylphenyl diisocyanate, etc.

[0212] Examples of carbodiimide catalysts include, for example, 1-phenyl-2-phospholene-1-oxide, 3-methyl-2-phospholene-1-oxide, 1-ethyl-3-methyl-2-phospholene-1-oxide, 1-ethyl-2-phospholene-1-oxide, and phospholene oxides such as these 3-phospholene isomers.

[0213] --Isocyanate series--

[0214] Examples of isocyanate-based hydrolysis inhibitors include, for example, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 3,3'-dichloro-4,4'-biphenylene diisocyanate, and 1,5-naphthalene diisocyanate. Cyanide esters, 1,5-tetrahydronaphthalene diisocyanate, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethyl diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclohexene diisocyanate, 1,4-cyclohexene diisocyanate, phenyl dimethyl diisocyanate, tetramethylphenyl dimethyl diisocyanate, hydrogenated phenyl dimethyl diisocyanate, lysine diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 3,3'-dimethyl-4,4'-dicyclohexylmethane diisocyanate, etc.

[0215] --Oxazoline series--

[0216] Examples of oxazoline hydrolysis inhibitors include, for example, 2,2'-o-phenylenebis(2-oxazoline), 2,2'-m-phenylenebis(2-oxazoline), 2,2'-p-phenylenebis(2-oxazoline), 2,2'-p-phenylenebis(4-methyl-2-oxazoline), 2,2'-m-phenylenebis(4-methyl-2-oxazoline), and 2,2'-p-phenylenebis(4,4'-dimethyl-2-oxazoline). (e.g., 2,2'-m-phenylenebis(4,4'-dimethyl-2-oxazoline), 2,2'-ethylenebis(2-oxazoline), 2,2'-tetramethylenebis(2-oxazoline), 2,2'-hexamethylenebis(2-oxazoline), 2,2'-octamethylenebis(2-oxazoline), 2,2'-ethylenebis(4-methyl-2-oxazoline), 2,2'-diphenylenebis(2-oxazoline), etc.)

[0217] --Epoxy System--

[0218] Examples of epoxy-based hydrolysants include, for instance, diglycidyl ethers of aliphatic diols such as 1,6-hexanediol, neopentyl glycol, and polyalkylene glycols; polyglycidyl ethers of aliphatic polyols such as sorbitol, sorbitan, polyglycerol, pentaerythritol, diglycerol, glycerol, and trimethylolpropane; polyglycidyl ethers of alicyclic polyols such as cyclohexanediol; diglycidyl esters or polyglycidyl esters of aliphatic or aromatic polycarboxylic acids such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, trimellitic acid, adipic acid, and sebacic acid; resorcinol, bis-(p-hydroxyphenyl)methane, and 2,2-bis-(p-hydroxyphenyl)methane. Diglycidyl ethers or polyglycidyl ethers of polyphenols such as N,N-diglycidyl aniline, N,N-diglycidyl toluidine, and N,N,N',N'-tetraglycidyl-bis-(p-aminophenyl)methane; N-glycidyl derivatives of amines such as aminophenol; triglycidyl tris(2-hydroxyethyl) isocyanurate; triglycidyl isocyanurate; o-cresol type epoxy resins, phenolic varnish type epoxy resins, etc.; etc.

[0219] There is no particular limitation on the amount of hydrolysis inhibitor added. It is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, and particularly preferably 0.5 parts by mass or more, relative to 100 parts by mass of hydroxyl-terminated urethane prepolymer. In addition, it is preferably 5 parts by mass or less, more preferably 4.5 parts by mass or less, and particularly preferably 3 parts by mass or less.

[0220] -Antioxidants-

[0221] As antioxidants, the aforementioned substances can be used, with preferred examples and addition amounts as described above.

[0222] -UV absorber-

[0223] Examples of UV absorbers include benzophenone compounds, benzotriazole compounds, salicylic acid compounds, oxaloyl aniline compounds, cyanoacrylate compounds, and triazine compounds. One type of UV absorber can be used alone, or two or more can be used in combination.

[0224] There is no particular limitation on the amount of ultraviolet absorber added. It is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and particularly preferably 0.2 parts by mass or more, relative to 100 parts by mass of hydroxyl-terminated urethane prepolymer. In addition, it is preferably 3 parts by mass or less, more preferably 2.5 parts by mass or less, and particularly preferably 2 parts by mass or less.

[0225] -Light stabilizers-

[0226] Examples of light stabilizers include hindered amine compounds and hindered piperidine compounds. Light stabilizers can be used alone or in combination of two or more.

[0227] There is no particular limitation on the amount of light stabilizer added. It is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and particularly preferably 0.2 parts by mass or more, relative to 100 parts by mass of hydroxyl-terminated urethane prepolymer. In addition, it is preferably 2 parts by mass or less, more preferably 1.5 parts by mass or less, and particularly preferably 1 part by mass or less.

[0228] -Antistatic agent-

[0229] Examples of antistatic agents include inorganic salts, polyol compounds, ionic liquids, and surfactants. Antistatic agents can be used alone or in combination of two or more.

[0230] Among these, ionic liquids are preferred. It should be noted that "ionic liquids" are also called room-temperature molten salts, which are salts that are fluid at 25°C.

[0231] --Inorganic salts--

[0232] Examples of inorganic salts include sodium chloride, potassium chloride, lithium chloride, lithium perchlorate, ammonium chloride, potassium chlorate, aluminum chloride, copper chloride, ferrous chloride, ferric chloride, ammonium sulfate, potassium nitrate, sodium nitrate, sodium carbonate, and sodium thiocyanate.

[0233] --Polyol compounds--

[0234] Examples of polyol compounds include propylene glycol, butanediol, hexanediol, polyethylene glycol, trimethylolpropane, and pentaerythritol.

[0235] --Ionic Liquids--

[0236] Examples of ionic liquids containing imidazolium ions include, for example, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide, and 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide; 1-methylpyridinium bis(trifluoromethanesulfonyl)imide, 1- Butylpyridinium bis(trifluoromethanesulfonyl)imide, 1-hexylpyridinium bis(trifluoromethanesulfonyl)imide, 1-octylpyridinium bis(trifluoromethanesulfonyl)imide, 1-hexyl-4-methylpyridinium bis(trifluoromethanesulfonyl)imide, 1-hexyl-4-methylpyridinium hexafluorophosphate, 1-octyl-4-methylpyridinium bis(trifluoromethanesulfonyl)imide Ionic liquids containing pyridinium ions, such as 1-octyl-4-methylpyridinium bis(fluorosulfonyl)imide, 1-methylpyridinium bis(perfluoroethylsulfonyl)imide, and 1-methylpyridinium bis(perfluorobutylsulfonyl)imide; ionic liquids containing ammonium ions, such as trimethylheptylammonium bis(trifluoromethanesulfonyl)imide, N,N-diethyl-N-methyl-N-propylammonium bis(trifluoromethanesulfonyl)imide, N,N-diethyl-N-methyl-N-pentylammonium bis(trifluoromethanesulfonyl)imide, N,N-diethyl-N-methyl-N-heptylammonium bis(trifluoromethanesulfonyl)imide, and tri-n-butylmethylammonium bis(trifluoromethanesulfonyl)imide; other ionic liquids such as pyrrolidineonium salts, phosphonium salts, and sulfonium salts; etc.

[0237] --surfactants--

[0238] Examples of surfactants include, for instance, nonionic low-molecular-weight surfactants such as glycerol fatty acid esters, polyoxyalkylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkylamines, polyoxyethylene alkylamine fatty acid esters, and fatty acid diethanolamides; anionic low-molecular-weight surfactants such as alkyl sulfonates, alkylbenzene sulfonates, and alkyl phosphates; cationic low-molecular-weight surfactants such as tetraalkylammonium salts and trialkylbenzylammonium salts; amphoteric low-molecular-weight surfactants such as alkyl betaine and alkyl imidazolium betaine; nonionic high-molecular-weight surfactants such as polyether ester amides, ethylene oxide-epimerol, and polyether esters; anionic high-molecular-weight surfactants such as polystyrene sulfonic acid; cationic high-molecular-weight surfactants such as acrylate polymers containing quaternary ammonium groups; and amphoteric high-molecular-weight surfactants such as amino acid-type amphoteric surfactants like higher alkylaminopropionates and betaine-type amphoteric surfactants like higher alkyl dimethyl betaine and higher alkyl dihydroxyethyl betaine.

[0239] There is no particular limitation on the amount of antistatic agent added. It is preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, and particularly preferably 0.05 parts by mass or more, relative to 100 parts by mass of hydroxyl-terminated urethane prepolymer. In addition, it is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and particularly preferably 3 parts by mass or less.

[0240] -Leveling agent-

[0241] Examples of leveling agents include acrylic leveling agents, fluorinated leveling agents, and silicone leveling agents. Leveling agents can be used alone or in combination of two or more.

[0242] Among these, acrylic leveling agents are preferred.

[0243] There is no particular limitation on the amount of leveling agent added. It is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and particularly preferably 0.1 parts by mass or more, relative to 100 parts by mass of hydroxyl-terminated urethane prepolymer. In addition, it is preferably 2 parts by mass or less, more preferably 1.5 parts by mass or less, and particularly preferably 1 part by mass or less.

[0244] -Any other ingredients-

[0245] Other arbitrary components include, for example, catalysts, resins other than urethane prepolymers, fillers (talc, calcium carbonate, and titanium dioxide, etc.), metal powders, colorants (pigments, etc.), foils, softeners, conductive agents, silane coupling agents, lubricants, corrosion inhibitors, heat stabilizers, weather stabilizers, polymerization inhibitors, defoamers, etc.

[0246] (Adhesive)

[0247] The adhesive of the present invention is obtained by curing the adhesive composition of the present invention.

[0248] The content ratio of oxyethylidene to oxyalkylene in the adhesive of the present invention is not particularly limited, but is preferably 10% by mass or more, more preferably 12% by mass or more, further preferably 15% by mass or more, even more preferably 20% by mass or more, particularly preferably 25% by mass or more, and preferably 70% by mass or less, more preferably 60% by mass or less, even more preferably 50% by mass or less, and even more preferably 40% by mass or less. If the content ratio of oxyethylidene to oxyalkylene in the adhesive of the present invention is at or above the lower limit, the adhesion to highly polar substrates is further improved, and the resistance to damp heat is easily improved. If the content ratio of oxyethylidene to oxyalkylene in the adhesive of the present invention is at or below the upper limit, haze is easily suppressed, and transparency is easily improved.

[0249] It should be noted that the content ratio of oxyethylidene to the total amount of oxyalkylene in the adhesive (ethylene oxide unit content) is determined by using... 1 The monomer composition of the oxyalkylene chain is determined by H-NMR.

[0250] (Attached materials)

[0251] The adhesive material of the present invention has a substrate and an adhesive layer comprising the adhesive of the present invention disposed on the surface of the substrate.

[0252] The preferred form of the adhesive material of the present invention is: an adhesive layer is provided on one side of a substrate film, and a release liner or load film is laminated in a peelable form with an adhesive surface covering the adhesive layer.

[0253] The adhesive material of the present invention is manufactured, for example, as follows: using a coating applicator, an aqueous adhesive solution (adhesive aqueous dispersion) in which the adhesive of the present invention is dissolved (dispersed) in water is applied to a load film, the applied aqueous adhesive solution (adhesive aqueous dispersion) is dried to form an adhesive layer, a substrate film is laminated on the surface of the formed adhesive layer opposite to the load film, and then cured.

[0254] Here, in the above-mentioned method for manufacturing the adhesive material, an adhesive layer can be formed on the substrate film, and a load film can be laminated on the surface of the formed adhesive layer opposite to the substrate film, instead of forming an adhesive layer on the load film and laminating the substrate film on the surface of the formed adhesive layer opposite to the load film.

[0255] The thickness of the aforementioned substrate film is not particularly limited, but is preferably 5 μm or more, more preferably 10 μm or more, particularly preferably 20 μm or more, and preferably 200 μm or less, more preferably 100 μm or less, particularly preferably 50 μm or less. When the thickness of the substrate film is within the aforementioned preferred range, the possibility of breakage of the adhesive material can be reduced. Examples of materials for the aforementioned substrate film include, for example, urethane polymers such as polyether urethane and polyester urethane; amide polymers such as polyether polyamide block polymers; acrylic polymers such as polyacrylates; olefin polymers such as polyethylene, polypropylene, and ethylene / vinyl acetate copolymers; ester polymers such as polyether polyesters; etc. Ester polymers are preferred as materials for the substrate film.

[0256] The substrate film can be made of one material alone or in combination of two or more materials. Furthermore, it can be a laminated film formed by stacking substrate films made of different materials. The substrate film can be laminated with fabrics such as woven fabrics, non-woven fabrics, knitted fabrics, or mesh.

[0257] The thickness of the adhesive layer is not particularly limited, but is preferably 5 μm or more, more preferably 10 μm or more, particularly preferably 20 μm or more, and preferably 100 μm or less, more preferably 50 μm or less, particularly preferably 30 μm or less. Better adhesion can be obtained when the thickness of the adhesive layer is within this range.

[0258] To prevent contamination of the adhesive layer surface, the adhesive material of the present invention is preferably pre-covered with a release liner or load film until use.

[0259] Specifically, as a release liner, it can be obtained by coating the surface of high-quality paper, cellophane, or parchment with a release agent having release properties such as silicone resin or fluororesin; or by coating the surface of high-quality paper with resin or high-quality paper laminated with polyethylene with a release agent having release properties such as silicone resin or fluororesin.

[0260] There are no particular limitations on the raw materials for the load film, but plastic films such as polyester film are preferred. The load film can be peelably laminated onto the side of the substrate film opposite to the side where the adhesive layer is formed. When peelably bonding the load film to the back of the substrate film, methods such as blow molding, extrusion lamination, lamination, or casting can be used. The thickness of the load film varies depending on the raw material, but is preferably 15 μm or more, more preferably 20 μm or more, particularly preferably 30 μm or more, and preferably 200 μm or less, more preferably 100 μm or less, and particularly preferably 50 μm or less.

[0261] (Adhesive tape)

[0262] The adhesive tape of the present invention has a substrate and an adhesive layer, the adhesive layer being disposed on at least one surface of the substrate and containing the adhesive of the present invention.

[0263] In the adhesive tape of the present invention, the adhesive layer may be disposed on only one surface of the substrate or on both surfaces of the substrate.

[0264] A preferred form of the adhesive tape of the present invention comprises an adhesive layer disposed on one side of a substrate film, and a release liner or load film having an adhesive surface covering the adhesive layer and being laminated in a peelable manner. This form is particularly referred to as a single-sided adhesive tape.

[0265] The substrate film, release liner, and load film are the same as those in the adhesive material of the present invention. Furthermore, the thickness of the adhesive layer is the same as that in the adhesive layer of the adhesive material of the present invention.

[0266] Furthermore, the adhesive tape of the present invention can be manufactured in the same manner as the adhesive material of the present invention.

[0267] Another preferred form of the adhesive tape of the invention comprises an adhesive layer disposed on both sides of a substrate film, and a release liner or load film laminated in a peelable manner, having an adhesive surface covering the adhesive layer. This form is specifically referred to as a double-sided adhesive tape.

[0268] The substrate film, release liner, and load film are the same as those in the adhesive material of the present invention. Furthermore, the thickness of the adhesive layer is the same as that in the adhesive layer of the adhesive material of the present invention.

[0269] Another preferred embodiment of the adhesive tape of the present invention comprises an adhesive layer disposed on one side of a peelable substrate film, and a release liner or load film having an adhesive surface covering the adhesive layer and being laminated in a peelable manner. This embodiment is specifically referred to as an adhesive transfer tape.

[0270] The peelable substrate film is preferably coated with a release agent with peeling properties, such as silicone resin or fluororesin, on the surface of the substrate film that can be used in the adhesive material of the present invention. The release liner and load film are the same as those in the adhesive material of the present invention. In addition, the thickness of the adhesive layer is the same as that of the adhesive layer in the adhesive material of the present invention.

[0271] Example

[0272] The present invention will now be described in detail with examples. However, the present invention is not limited to the examples described below.

[0273] Synthesis Examples 1-7, 9-13, 15, and 16 are implementation synthesis examples, while Synthesis Examples 8 and 14 are comparative synthesis examples.

[0274] Manufacturing Examples 1-9 and 15-22 are implementation manufacturing examples, while Manufacturing Examples 10 and 12-14 are comparative manufacturing examples.

[0275] Examples 1-9 and 13-20 are examples, and examples 10-12 are comparative examples.

[0276] <Methods for Determining Physical Properties>

[0277] [Hydroxy value]

[0278] The hydroxyl value of oxyalkylene polymer A was calculated according to the titration method of JIS K1557-1B:2007.

[0279] [Molecular weight Mn, Mw, Mw / Mn]

[0280] The number-average molecular weight Mn and molecular weight distribution Mw / Mn of the oxyalkylene polymers were obtained by methods described below.

[0281] For multiple types of monodisperse polystyrene with different degrees of polymerization used as standard samples for molecular weight determination, measurements were performed using a commercially available GPC apparatus (HLC-8320GPC, manufactured by Tosoh Corporation). A standard curve was constructed based on the relationship between the molecular weight and retention time of polystyrene. The oxyalkylene polymer used as the test sample was diluted to 0.5% by mass with tetrahydrofuran and passed through a 0.5 μm filter before being measured using the aforementioned GPC apparatus. Using the standard curve, the GPC spectra of the test sample were analyzed by computer to determine the Mn and weight-average molecular weight (hereinafter referred to as Mw).

[0282] The molecular weight distribution is the value calculated from Mw and Mn above, which is the ratio of Mw to Mn (hereinafter sometimes referred to as "Mw / Mn").

[0283] Furthermore, the Mw of the hydroxyl-terminated urethane prepolymer was determined using GPC in the same manner as described above.

[0284] [Unsaturation]

[0285] The degree of unsaturation of the oxyalkylene polymer was determined according to the method of JIS-K1557-6.

[0286] [Content of oxyethylidene (content of ethylene oxide units (EO units))]

[0287] Regarding the content ratio of oxyethylidene to the total amount of oxyalkylene in oxyalkylene polymers, urethane prepolymers, and adhesives (ethylene oxide unit content), use... 1 The monomer composition of the oxyalkylene chain was determined by H-NMR, and then the result was calculated.

[0288] For example, when the alkylene oxide polymer is a polyol formed from propylene oxide units and ethylene oxide units, the content of ethylene oxide units can be determined based on the area ratio of the signal of methyl groups in the propylene oxide units to the area ratio of the signal of methylene groups in the propylene oxide units and the area ratio of the signal of methylene groups in the propylene oxide units and the ethylene oxide units.

[0289] Synthesis of Oxyalkylene Polymers

[0290] [Synthesis Example 1: Synthesis of Polymer A1]

[0291] (Process a)

[0292] As an initiator, a polyol (initiator A) is used to perform an addition reaction between propylene oxide and glycerol using a KOH catalyst up to a molecular weight of 3,000.

[0293] First, in a pressure-resistant reaction vessel, 1243g of initiator A and a slurry of hexacyanocobaltate complex with tert-butanol as the ligand (hereinafter also referred to as TBA-DMC catalyst) are added as the reaction solution. The amount of TBA-DMC catalyst slurry is such that the concentration of the metal in the TBA-DMC catalyst in the reaction solution is 50ppm.

[0294] Next, after nitrogen replacement in the pressure-resistant reaction vessel, the reaction liquid was heated while being stirred. Heating was stopped after reaching 140°C, and 124g of propylene oxide (10.0 parts by mass relative to 100 parts by mass of initiator) was supplied into the pressure-resistant reaction vessel while stirring was continued to allow it to react.

[0295] (Process b)

[0296] After the temperature rise of the reaction solution stopped, it was cooled to 140°C. While stirring the reaction solution, a mixture of 1386g of propylene oxide and 1386g of ethylene oxide was fed into a pressure-resistant reaction vessel. After confirming that the internal pressure change had disappeared and the reaction was complete, the catalyst was neutralized and removed using a synthetic adsorbent (KYOWAAD 600S, manufactured by Kyowa Chemical Industry Co., Ltd.) to obtain polymer A1.

[0297] The number of hydroxyl groups, hydroxyl value, Mn, Mw / Mn, degree of unsaturation, and content of oxyethylidene units (hereinafter referred to as "EO units") of the polymer A1 thus obtained are shown in Table 1-1. It should be noted that these values ​​are determined by the method described above. Similarly, polymers A2-A8 and B1-B8 obtained in the following synthetic examples 2-14 are also shown in Table 1-1 and Table 1-2.

[0298] In addition, the “Hydroxy number” in Tables 1-1 and 1-2 records the number of hydroxyl groups (3 or 2) of the initiators (glycerol and propylene glycol) used in the synthesis of oxyalkylene polymers A and B, respectively. These values ​​are directly used as the average number of hydroxyl groups of oxyalkylene polymers A and B.

[0299] [Synthesis Example 2: Synthesis of Polymer A2]

[0300] Initiator A in (step a) was changed to 1232g, propylene oxide in (step b) was changed to 2043g, and ethylene oxide was changed to 703g. Otherwise, the same procedure as in Synthesis Example 1 was followed to synthesize polymer A2.

[0301] [Synthesis Example 3: Synthesis of Polymer A3]

[0302] Initiator A in (step a) was changed to 1970g, propylene oxide in (step b) was changed to 2924g, and ethylene oxide was changed to 2091g. Otherwise, the same procedure as in Synthesis Example 1 was followed to synthesize polymer A3.

[0303] [Synthesis Example 4: Synthesis of Polymer A4]

[0304] In step a, the initiator A was changed to a polyol (initiator B) that causes ethylene oxide to undergo an addition reaction with glycerol until the content of EO units is 80% by mass. The initiator B was 2100 g, the mass of propylene oxide in step b was changed to 759 g, and the mass of ethylene oxide was changed to 3036 g. Otherwise, the same procedure as in synthesis example 1 was followed to synthesize polymer A4.

[0305] [Synthesis Example 5: Synthesis of Polymer A5]

[0306] As an initiator, a polyol (initiator C) is used to perform an addition reaction between propylene oxide and glycerol using a KOH catalyst up to a molecular weight of 1,300.

[0307] Initiator C 1106g, KOH catalyst 12.6g, propylene oxide 1494g, and ethylene oxide 1400g were added to a pressure-resistant reaction vessel and stirred at 110°C for 1.5 hours to allow for ring-opening addition polymerization. The catalyst was then neutralized and removed using a synthetic adsorbent (KYOWAAD600S, manufactured by Kyowa Chemical Industry Co., Ltd.) to obtain polymer A5.

[0308] [Synthesis Example 6: Synthesis of Polymer A6]

[0309] Glycerin was used as an initiator.

[0310] 119g of glycerol, 25.3g of KOH catalyst, 1576g of propylene oxide, and 6305g of ethylene oxide were added to a pressure-resistant reaction vessel. The mixture was stirred at 110°C for 1.5 hours to induce ring-opening addition polymerization. The catalyst was then neutralized and removed using a synthetic adsorbent (KYOWAAD 600S, manufactured by Kyowa Chemical Industry Co., Ltd.) to obtain polymer A6.

[0311] [Synthesis Example 7: Synthesis of Polymer A7]

[0312] Initiator A in (step a) was changed to 743g, propylene oxide in (step b) was changed to 2291g, and ethylene oxide was changed to 966g. Otherwise, the same procedure as in Synthesis Example 1 was followed to synthesize polymer A7.

[0313] [Synthesis Example 8: Synthesis of Polymer A8]

[0314] (Process a)

[0315] As an initiator, a polyol (initiator D) is used to perform an addition reaction between propylene oxide and glycerol using a KOH catalyst up to a molecular weight of 1,500.

[0316] First, 1.4 g of zinc hexacyanocobaltate-ethylene glycol dimethyl ether complex (as a DMC catalyst) and 1050 g of initiator D were added to a pressure-resistant reactor as the reaction solution. After nitrogen purging of the pressure-resistant reactor, the reaction solution was heated to 140°C while stirring. Then, heating was stopped, and 105 g of propylene oxide (10.0 parts by mass relative to 100 parts by mass of initiator) was supplied to the pressure-resistant reactor to react with initiator D.

[0317] (Process b)

[0318] After the temperature rise of the reaction solution stopped, the pressure-resistant reaction vessel was filled with a nitrogen atmosphere at 130°C, and 5110g of propylene oxide was reacted for 5 hours to deactivate the catalyst. Subsequently, 22.1g of KOH catalyst was added, and dehydration was carried out at 120°C for 2 hours. After alkoxide formation, 840g of ethylene oxide was reacted, and the catalyst was neutralized and removed using a synthetic adsorbent (KYOWAAD 600S, manufactured by Kyowa Chemical Industry Co., Ltd.), yielding polymer A8 with ethylene oxide terminal addition.

[0319] [Synthesis Example 9: Synthesis of Polymer B1]

[0320] In step a, the initiator A was changed to a polyol (initiator E) that causes propylene oxide to undergo an addition reaction with propylene glycol up to a molecular weight of 2,000. The initiator E was set to 865g. In step b, the mass of propylene oxide and the mass of ethylene oxide were changed to 1689g. Otherwise, the same procedure as in synthesis example 1 was followed to synthesize polymer B1.

[0321] [Synthesis Example 10: Synthesis of Polymer B2]

[0322] The mass of initiator E in (step a) was changed to 800g, the mass of propylene oxide in (step b) was changed to 2494g, and the mass of ethylene oxide was changed to 800g. Otherwise, the same procedure as in synthesis example 9 was followed to synthesize polymer B2.

[0323] [Synthetic Example 11: Synthesis of Polymer B3]

[0324] The mass of initiator E in (step a) was changed to 1310 g, the mass of propylene oxide in (step b) was changed to 3684 g, and the mass of ethylene oxide was changed to 2079 g. Otherwise, the same procedure as in synthesis example 9 was followed to synthesize polymer B3.

[0325] [Synthesis Example 12: Synthesis of Polymer B4]

[0326] Dipropylene glycol was used as an initiator. 134 g of dipropylene glycol, 12.6 g of KOH catalyst, 660 g of propylene oxide, and 3200 g of ethylene oxide were added to a pressure-resistant reaction vessel. After ring-opening addition polymerization was carried out by stirring at 110°C for 1.5 hours, the catalyst was neutralized and removed using a synthetic adsorbent (KYOWAAD 600S, manufactured by Kyowa Chemical Industry Co., Ltd.) to obtain polymer B4.

[0327] [Synthetic Example 13: Synthesis of Polymer B5]

[0328] As an initiator, a polyol (initiator F) was used to initiate the addition reaction of propylene oxide and propylene glycol using a KOH catalyst up to a molecular weight of 400. 1200 g of initiator F and 18.9 g of KOH catalyst were added to a pressure-resistant reaction vessel, and the mixture was dehydrated at 120°C for 2 hours. After alkoxide formation, 2100 g of propylene oxide was reacted, followed by 2516 g of ethylene oxide. The catalyst was then neutralized and removed using a synthetic adsorbent (KYOWAAD 600S, manufactured by Kyowa Chemical Industry Co., Ltd.) to obtain polymer B5 with ethylene oxide at the end.

[0329] [Synthetic Example 14: Synthesis of Polymer B6]

[0330] In step a of Synthesis Example 8, the initiator D was replaced with 350g of a polyol (initiator G) used to perform an addition reaction between propylene oxide and propylene glycol up to a molecular weight of 700. The mass of the zinc hexacyanocobaltate-ethylene glycol dimethyl ether complex was replaced with 0.37g. The mass of the KOH catalyst was replaced with 6.3g. The mass of propylene oxide in step b was replaced with 1490g. The mass of ethylene oxide was replaced with 160g. Otherwise, the same procedure as in Synthesis Example 8 was followed to synthesize polymer B6.

[0331] [Synthetic Example 15: Synthesis of Polymer B7]

[0332] The mass of initiator E in (step a) was changed to 2800g, the mass of propylene oxide in (step b) was changed to 210g, and the mass of ethylene oxide was changed to 3990g. Otherwise, the same procedure as in synthesis example 9 was followed to synthesize polymer B7.

[0333] [Synthesis Example 16: Synthesis of Polymer B8]

[0334] In Synthesis Example 14, the mass of initiator G in step a was changed to 461 g, the mass of zinc hexacyanocobaltate-ethylene glycol dimethyl ether complex was changed to 0.40 g, the mass of propylene oxide in step b was changed to 1539 g, the mass of KOH catalyst was changed to 8.3 g, and the mass of ethylene oxide was changed to 632 g. Otherwise, the same procedure as in Synthesis Example 14 was followed to synthesize polymer B8.

[0335] <Manufacturing Example 1>

[0336] [Manufacturing of hydroxyl-terminated carbamate prepolymers]

[0337] In a reaction vessel equipped with a thermometer, stirrer, and condenser, as shown in Table 2-1, 20 parts by mass of polymer A1, 20 parts by mass of polymer A2, 30 parts by mass of polymer B1, and 30 parts by mass of polymer B2 were added. Next, 0.01 parts by mass of the carbamate catalyst (dibutyltin disilicate, manufactured by Tokyo Chemical Industry Co., Ltd.) and 1 part by mass of Irganox 1135 (manufactured by BASF) as an antioxidant were added. After mixing at 40°C, 1.05 parts by mass of hexamethylene diisocyanate (DURANATE 50M, manufactured by Asahi Kasei Corporation, designated as "HDI" in Table 2-1) as a diisocyanate compound were added, and the reaction was carried out at 70°C. The isocyanate index was 50. The reaction was exothermic, the internal temperature reached approximately 70°C, and the viscosity increased over time. After stirring at 70°C for 3 hours, and confirming the disappearance of isocyanate groups using FT-IR, the mixture was cooled to room temperature. After cooling, 335 parts by mass of water were added for dilution while stirring for 3 hours to prepare a homogeneous, transparent solution, resulting in an aqueous dispersion of a hydroxyl-terminated urethane prepolymer (also known as "urethane prepolymer U1") containing an average hydroxyl number of 2.4 and a solid content of 23% by mass. Table 2-1 shows the EO unit content (by mass%), average hydroxyl number, Mw, water solubility, and solid content (by mass%) of the obtained urethane prepolymer U1. The manufacturing examples below are also shown in Table 2-1.

[0338] It should be noted that in Tables 2-1 and 2-2, "index" is the value where the ratio of the molar number of isocyanate groups in the diisocyanate compound used in the manufacture of the hydroxyl-terminated urethane prepolymer to the total molar number of hydroxyl groups in the oxyalkylene polymer is set to 100 (isocyanate index); "EO unit content" is the proportion of oxyethylene in the hydroxyl-terminated urethane prepolymer to the total amount of oxyalkylene (ethylene oxide unit content) (unit: mass%); "average number of hydroxyl groups" is the average number of hydroxyl groups in one molecule of the hydroxyl-terminated urethane prepolymer calculated by the method described below; and "water solubility" is the water solubility of the hydroxyl-terminated urethane prepolymer (solid component) evaluated by the evaluation method described below. In Tables 2-1 and 2-2, "-" indicates that the component was not blended.

[0339] [Calculation of the average number of hydroxyl groups in urethane prepolymers]

[0340] The "average number of hydroxyl groups f" of the urethane prepolymer is calculated by the following formula (I).

[0341] f = (Average number of hydroxyl groups in oxyalkylene polymer A) × (Mass of oxyalkylene polymer A relative to the total mass of oxyalkylene polymer A and oxyalkylene polymer B) + (Average number of hydroxyl groups in oxyalkylene polymer B) × (Mass of oxyalkylene polymer B relative to the total mass of oxyalkylene polymer A and oxyalkylene polymer B) (I)

[0342] [Evaluation of the water solubility of urethane prepolymers]

[0343] The water solubility of the urethane prepolymer (solid component) obtained in Manufacturing Example 1 was evaluated.

[0344] The water solubility of urethane prepolymers (solid components) is evaluated based on the following benchmarks.

[0345] A It dissolves in water at 25°C and becomes transparent.

[0346] D It is insoluble in water at 25°C, producing haze, turbidity, or dissolved residue.

[0347] <Manufacturing Examples 2~10, 12~22>

[0348] The mixing amounts (parts by mass) were changed to those shown in Tables 2-1 and 2-2. Except for this, hydroxyl-terminated urethane prepolymers (also referred to as "urethane prepolymers U2~10, 12~22") were manufactured using the same procedures as in Manufacturing Example 1. The index, EO unit content (mass%), average hydroxyl number, Mw, water solubility, and solids content (mass%) of the resulting aqueous dispersions of the manufactured urethane prepolymers U2~10, 12~22 were measured, calculated, and evaluated in the same manner as in Manufacturing Example 1. The results are shown in Tables 2-1 and 2-2.

[0349] In Tables 2-1 and 2-2, “IPDI” represents “isophorone diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.)”, “D101” represents “difunctional isocyanate-terminated urethane prepolymer (manufactured by Asahi Kasei Corporation, DURANATE D101)”, “Irganox565” represents “2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol (manufactured by BASF, Irganox565)”, “BHT” represents “2,6-di-tert-butyl-4-methylphenol”, and “CBP-E” represents “2,2'-dihydroxy-3,3'-di(α-methylcyclohexyl)-5,5'-dimethyldiphenylmethane emulsion (manufactured by Seiko Chemical Co., Ltd., NONFLEX CBP-E)”.

[0350] <Example 1>

[0351] [Adhesive Manufacturing]

[0352] As shown in Table 3, 100 parts by weight of urethane prepolymer U1, 4.93 parts by weight of curing agent (water-dispersible isocyanate, WR80-70P, manufactured by Asahi Kasei Corporation), and 0.005 parts by weight of curing catalyst (Borchi Kat24, manufactured by Borchers Corporation) were uniformly mixed to obtain an adhesive composition. The obtained adhesive composition was then degassed and coated onto a polyester film (loaded film, thickness 38 μm) that had undergone release treatment using a blade coater to achieve a dry film thickness of 25 μm. The film was then cured and dried at 100°C for 3 minutes to form an adhesive layer.

[0353] After laminating a 38 μm thick polyester film (substrate film) onto the obtained adhesive layer, the adhesive layer was stored in a hot air dryer at 50°C for 3 days to complete the crosslinking reaction, thus producing an adhesive material (adhesive tape) having an adhesive layer formed by the adhesive. The coatability of the adhesive composition to the load film is evaluated below. In addition, the content of EO units (mass%), adhesion to glass (glass adhesion strength), and appearance (haze) of the adhesive in the adhesive layer of the obtained adhesive material (adhesive tape) are measured and evaluated by the following methods.

[0354] The obtained adhesive contained 26% by mass of oxyethylidene relative to the total amount of oxyalkylene in the unit solids component (ethylene oxide unit content). Table 3 shows the results of the determination and evaluation of the following: the proportion of oxyethylidene relative to the total amount of oxyalkylene in the unit solids component of the obtained adhesive (EO unit content) (mass%), the coatability of the obtained adhesive composition, the adhesion of the obtained adhesive to glass, and the appearance (haze) of the obtained adhesive.

[0355] In Table 3, “AQ-140” means “water-dispersible isocyanate (manufactured by Tosoh Corporation, Aquanate140)”.

[0356] [Copyability]

[0357] The coatability of the obtained adhesive composition, after degassing, was evaluated using a knife coater on a load film according to the following criteria, as described above.

[0358] A There is no shrinkage, resulting in an aesthetically pleasing coated film.

[0359] D Shrinkage occurred, resulting in an unattractive coating film.

[0360] [Adhesion to glass (adhesion to glass)]

[0361] The aforementioned adhesive material (adhesive tape) was cut into 25mm wide pieces to serve as test pieces. The adhesive layer obtained by peeling the load film from the test piece was then applied to float glass at 25°C.

[0362] Next, according to the adhesive tape of JIS Z 0237:2009 The test method described in "10 Adhesive Force" of the adhesive sheet test method involves pressing the adhesive layer of the test sheet onto float glass by reciprocating once at a speed of 300 mm / min with a 2 kg rubber roller. After 20 minutes, the peel force of the pressed test sheet is measured at a peel angle of 180 degrees and a peel speed of 300 mm / min.

[0363] The adhesion to glass was evaluated according to the following evaluation criteria. The evaluation results of the measured adhesion to glass are shown in the "Adhesion to Glass" column of Table 3.

[0364] A Amounts greater than 0.01 N / 25 mm but less than 0.1 N / 25 mm

[0365] D For values ​​greater than 0.1 N / 25 mm or less than 0.01 N / 25 mm

[0366] [The appearance (haze) of the adhesive]

[0367] Use of color A turbidity measuring instrument (manufactured by Nippon Denshoku Kogyo Co., Ltd., COH400) was used to measure the haze of the adhesive layer obtained by peeling a load film from the obtained adhesive material (adhesive tape). The haze was evaluated according to the following evaluation criteria. A haze value of less than 10% indicates good transparency. The evaluation results of the measured haze are shown in the "Haze" column of Table 3.

[0368] A Less than 10%

[0369] D More than 10%

[0370] <Example 2~Example 20>

[0371] Using the mixing amounts (parts by mass) shown in Table 3, the same procedure as in Example 1 was followed to manufacture the adhesive material (adhesive tape). The adhesive layer of the resulting adhesive material (adhesive tape) was measured and evaluated in the same manner as in Example 1, including the content ratio of oxyethylidene to the total amount of oxyalkylene (ethylene oxide unit content) (mass%), the coatability of the adhesive composition, the adhesion strength of the resulting adhesive to glass, and the haze of the resulting adhesive. The results are shown in Table 3. It should be noted that "-" in Table 3 indicates that the component was not mixed in.

[0372] [Table 1-1]

[0373]

[0374] [Table 1-2]

[0375]

[0376] [Table 2-1]

[0377]

[0378] [Table 2-2]

[0379]

[0380] [Table 3]

[0381]

[0382] As shown in Tables 2-1 and 2-2, in manufacturing examples 1-9 and 13-22, excellent water solubility of the solid components in the aqueous dispersions was obtained.

[0383] As shown in Table 3, in Examples 1-9 and 13-20, the adhesive compositions exhibited excellent coatability, as well as excellent adhesive strength and transparency.

[0384] In contrast, in Examples 10-12, excellent coatability of the adhesive composition was not obtained, nor were excellent adhesion and transparency of the adhesive obtained.

[0385] Industrial availability

[0386] The adhesive obtained by the present invention is suitable as a surface protective film for protecting the surfaces of flat panel displays (liquid crystal displays, organic electroluminescent displays, etc.) and touch panel displays widely used in electronic devices such as televisions, personal computers (PCs), mobile phones, and portable terminals, as well as substrates (glass substrates, ITO / glass substrates with an ITO (indium tin oxide) film formed on the glass substrate, etc.) manufactured or used in their manufacturing processes, and for protecting the surfaces of optical components, etc.

Claims

1. An aqueous dispersion comprising a hydroxyl-terminated urethane prepolymer, said hydroxyl-terminated urethane prepolymer being obtained by reacting an oxoalkylene polymer A having an average hydroxyl number per molecule of more than 2.0 and less than 3.0, an oxoalkylene polymer B having an average hydroxyl number per molecule of more than 1.2 and less than 2.0, and a diisocyanate compound. The oxyethylidene content of the oxyalkylene polymer A relative to the total amount of oxyalkylene is 15% or more by mass. The oxyethylidene content of the oxyalkylene polymer B relative to the total amount of oxyalkylene is 15% or more by mass. The hydroxyl-terminated carbamate prepolymer contains an oxyethylidene content of more than 20% by mass and less than 70% by mass relative to the total oxyalkylene content. The mass ratio of the oxyalkylene polymer A to the oxyalkylene polymer B is 20:80 to 60:

40. The water content in the aqueous dispersion is 40% by mass or more and 90% by mass or less. The oxoalkylene polymer A comprises an oxoalkylene polymer with 3 hydroxyl groups, and the oxoalkylene polymer B comprises an oxoalkylene polymer with 2 hydroxyl groups.

2. The aqueous dispersion according to claim 1, wherein, The isocyanate index, which indicates the molar ratio of the isocyanate groups in the diisocyanate compound to the hydroxyl groups in the oxoalkylene polymer A and the oxoalkylene polymer B, is 40 or more and 90 or less.

3. The aqueous dispersion according to claim 1 or 2, wherein, The number average molecular weights of the oxyalkylene polymer A and the oxyalkylene polymer B are 1,000 to 50,000.

4. The aqueous dispersion according to claim 1 or 2, wherein, The hydroxyl-terminated urethane prepolymer contains 23% by mass or more and 65% by mass or less of the total amount of oxyethylidene relative to oxyalkylene.

5. The aqueous dispersion according to claim 1 or 2, wherein, The weight-average molecular weight of the hydroxyl-terminated urethane prepolymer is above 10,000 and below 250,000.

6. The aqueous dispersion according to claim 1 or 2, wherein, The average number of hydroxyl-terminated urethane prepolymers is 1.7 or more and less than 3.

0.

7. An adhesive composition comprising: an aqueous dispersion according to any one of claims 1 to 6, and a polyisocyanate compound having three or more isocyanate groups in one molecule.

8. The adhesive composition according to claim 7, wherein, The polyisocyanate compound having three or more isocyanate groups in one molecule is water-dispersible.

9. The adhesive composition according to claim 7 or 8, further comprising a catalyst, The content of the catalyst is 0.001 parts by mass or more and 0.10 parts by mass or less, relative to a total of 100 parts by mass of the hydroxyl-terminated urethane prepolymer and the polyisocyanate compound having three or more isocyanate groups in one molecule.

10. An adhesive obtained by curing the adhesive composition of claim 8 or 9.

11. The adhesive according to claim 10, wherein, The adhesive contains 10 to 70% oxyethylidene relative to the total amount of oxyalkylene in its components.

12. An adhesive material having a substrate and an adhesive layer, the adhesive layer being disposed on at least one surface of the substrate and comprising the adhesive of claim 10 or 11.

13. An adhesive tape having a substrate and an adhesive layer, the adhesive layer being disposed on at least one surface of the substrate and comprising the adhesive of claim 10 or 11.

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