Aqueous dispersion, adhesive composition, adhesive, patch, and adhesive tape

Abstract

Provided is an aqueous dispersion liquid containing a hydroxyl-group-terminated urethane prepolymer obtained by reacting an oxyalkylene polymer A in which the average number of hydroxyl groups per molecule is greater than 2.0 and no greater than 3.0, an oxyalkylene polymer B in which the average number of hydroxyl groups per molecule is 1.2-2.0 (inclusive), and a diisocyanate compound, wherein the content ratio of oxyethylene groups to the total amount of oxyalkylene groups in the oxyalkylene polymer A is 15 mass% or greater, the content ratio of oxyethylene groups to the total amount of oxyalkylene groups in the oxyalkylene polymer B is 15 mass% or greater, and the content ratio of oxyethylene groups to the total amount of oxyalkylene groups in the hydroxyl-group-terminated urethane prepolymer is greater than 20 mass% and no greater than 70 mass%.

Description

[Technical Field]

[0001] The present invention relates to an aqueous dispersion, a pressure-sensitive adhesive composition, a pressure-sensitive adhesive, a patch, and a pressure-sensitive adhesive tape. [Background technology]

[0002] Conventionally, flat panel displays (liquid crystal displays, organic electroluminescence displays, etc.) widely used in electronic devices such as televisions, personal computers (PCs), mobile phones, and mobile terminals, as well as touch panel displays that combine a flat panel display with a touch panel, have widely used surface protection films that protect the surfaces of these devices, each of which has a pressure-sensitive adhesive layer formed on a substrate. It is known that pressure-sensitive adhesive compositions used to produce surface protection films generally contain a polymer component such as an acrylic polymer or a prepolymer (see, for example, Patent Document 1), and an organic solvent. The organic solvents contained in such PSA compositions may have adverse environmental effects such as carbon dioxide emissions when incinerated, as well as odors and health problems, and therefore there is a growing demand to reduce the amount of organic solvents used in PSA compositions. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2018-131500 A Summary of the Invention [Problem to be solved by the invention]

[0004] However, as a prepolymer type pressure-sensitive adhesive composition for a surface protection film, an aqueous pressure-sensitive adhesive composition containing no organic solvent has not yet been obtained, and the development of an aqueous prepolymer type pressure-sensitive adhesive composition for a surface protection film has been strongly desired for a long time. In particular, a surface protection film is expected to be applied to an article and then peeled off as needed. For this reason, a pressure-sensitive adhesive for a surface protection film is difficult to use if its adhesive strength is too strong or too weak, and it is necessary to achieve an adhesive strength suitable for use.

[0005] In view of the above problems, an object of the present invention is to provide an aqueous dispersion that can prepare a pressure-sensitive adhesive composition having excellent water solubility in solid matter and excellent coatability, and that can prepare a pressure-sensitive adhesive having excellent adhesive strength and transparency; a pressure-sensitive adhesive composition containing the aqueous dispersion; a pressure-sensitive adhesive obtained by curing the pressure-sensitive adhesive composition; an adhesive material having a pressure-sensitive adhesive layer containing the pressure-sensitive adhesive; and a pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer containing the pressure-sensitive adhesive. [Means for solving the problem]

[0006] As a result of intensive research into solving the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by a hydroxyl-terminated urethane prepolymer obtained by reacting an oxyalkylene polymer A having an average number of hydroxyl groups per molecule of more than 2.0 and not more than 3.0, an oxyalkylene polymer B having an average number of hydroxyl groups per molecule of 1.2 or more and not more than 2.0, and a diisocyanate compound, wherein the oxyalkylene polymer A has an oxyethylene group content of 15% by mass or more relative to the total number of oxyalkylene groups, the oxyalkylene polymer B has an oxyethylene group content of 15% by mass or more relative to the total number of oxyalkylene groups, and the hydroxyl-terminated urethane prepolymer has an oxyethylene group content of more than 20% by mass and not more than 70% by mass relative to the total number of oxyalkylene groups, and have completed the present invention. That is, the present invention is as follows. [1] An aqueous dispersion comprising a hydroxyl-terminated urethane prepolymer obtained by reacting an oxyalkylene polymer A having an average number of hydroxyl groups per molecule of more than 2.0 and not more than 3.0, an oxyalkylene polymer B having an average number of hydroxyl groups per molecule of 1.2 to 2.0, and a diisocyanate compound, wherein the oxyalkylene polymer A has an oxyethylene group content of 15% by mass or more relative to the total number of oxyalkylene groups, the oxyalkylene polymer B has an oxyethylene group content of 15% by mass or more relative to the total number of oxyalkylene groups, and the hydroxyl-terminated urethane prepolymer has an oxyethylene group content of more than 20% by mass and not more than 70% by mass relative to the total number of oxyalkylene groups. [2] The aqueous dispersion according to [1] above, wherein the oxyalkylene polymer A comprises an oxyalkylene polymer having three hydroxyl groups, and the oxyalkylene polymer B comprises an oxyalkylene polymer having two hydroxyl groups. [3] The aqueous dispersion according to the above [1] or [2], wherein the mass ratio of the oxyalkylene polymer A to the oxyalkylene polymer B is 20:80 to 60:40. [4] The aqueous dispersion according to any one of the above [1] to [3], wherein an isocyanate index, which represents the molar ratio of the isocyanate groups of the diisocyanate compound to the hydroxyl groups of the oxyalkylene polymer A and the oxyalkylene polymer B, is 40 or more and 90 or less. [5] The aqueous dispersion according to any one of the above [1] to [4], wherein the oxyalkylene polymer A and the oxyalkylene polymer B have number average molecular weights of 1,000 to 50,000. [6] The aqueous dispersion according to any one of the above [1] to [5], wherein the hydroxyl group-terminated urethane prepolymer has an oxyethylene group content of 23% by mass or more and 65% by mass or less relative to the total amount of oxyalkylene groups. [7] The aqueous dispersion according to any one of the above [1] to [6], wherein the weight average molecular weight of the hydroxyl group-terminated urethane prepolymer is 10,000 or more and 250,000 or less. [8] The aqueous dispersion according to any one of the above [1] to [7], wherein the average number of hydroxyl groups in the hydroxyl-terminated urethane prepolymer is 1.7 or more and less than 3.0. [9] A pressure-sensitive adhesive composition comprising the aqueous dispersion according to any one of the above [1] to [8] and a polyisocyanate compound having three or more isocyanate groups in one molecule.

[10] The pressure-sensitive adhesive composition according to the above [9], wherein the polyisocyanate compound having three or more isocyanate groups in one molecule is water-dispersible.

[11] The pressure-sensitive adhesive composition according to the above [9] or

[10] , further comprising a catalyst, the content of the catalyst being 0.001 parts by mass or more and 0.10 parts by mass or less per 100 parts by mass of the hydroxyl group-terminated urethane prepolymer and the polyisocyanate compound having three or more isocyanate groups per molecule.

[12] A pressure-sensitive adhesive obtained by curing the pressure-sensitive adhesive composition according to

[10] or

[11] above.

[13] The pressure-sensitive adhesive according to the above

[12] , wherein the content of oxyethylene groups relative to the total amount of oxyalkylene groups in the pressure-sensitive adhesive is 10 to 70 mass %.

[14] A patch comprising a substrate and an adhesive layer provided on at least one surface of the substrate, the adhesive layer comprising the adhesive according to

[12] or

[13] above.

[15] An adhesive tape comprising a substrate and an adhesive layer provided on at least one surface of the substrate, the adhesive layer comprising the adhesive according to

[12] or

[13] above. [Effects of the Invention]

[0007] According to the present invention, it is possible to provide an aqueous dispersion that can prepare a pressure-sensitive adhesive composition having excellent water solubility in the solid content and excellent coatability, and that can prepare a pressure-sensitive adhesive having excellent adhesive strength and transparency, a pressure-sensitive adhesive composition containing the aqueous dispersion, a pressure-sensitive adhesive obtained by curing the pressure-sensitive adhesive composition, a patch having a pressure-sensitive adhesive layer containing the pressure-sensitive adhesive, and a pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer containing the pressure-sensitive adhesive. DETAILED DESCRIPTION OF THE INVENTION

[0008] In this specification, the definitions and meanings of terms are as follows. In this specification, what is considered to be preferable can be adopted arbitrarily, and it can be said that a combination of preferable things is more preferable. In addition, in this specification, the expression "XX to YY" means "XX or more and YY or less." Furthermore, in this specification, for preferred numerical ranges (e.g., ranges of content, etc.), the lower and upper limits described in stages can be independently combined. For example, the description "preferably 10 to 90, more preferably 30 to 60" can be combined with the "preferable lower limit (10)" and the "more preferable upper limit (60)" to form "10 to 60." Furthermore, in the numerical ranges described in this specification, the upper or lower limit of the numerical range may be replaced with a value shown in the examples. In this specification, the term "unit" constituting a polymer means an atomic group formed by polymerization of a monomer. In this specification, the term "oxyalkylene polymer" refers to a polymer having a polyoxyalkylene chain, and a repeating unit based on alkylene oxide is referred to as an "alkylene oxide unit." In this specification, "hydroxyl-terminated urethane prepolymer" refers to a compound obtained by reacting an organic compound having hydroxyl groups with a diisocyanate compound, which has hydroxyl groups at at least some of the terminals of the molecular chain and urethane bonds in the molecular chain. In this specification, "isocyanate-terminated urethane prepolymer" refers to a compound obtained by reacting an organic compound having two or more hydroxyl groups per molecule with a polyisocyanate compound, which has isocyanate groups at at least some of the terminals of the molecular chain and urethane bonds in the molecular chain. Furthermore, in this specification, for example, in the examples described later, oxyalkylene polymer A1 is prepared using a polyol (initiator A) obtained by addition reaction of propylene oxide with glycerin using a KOH catalyst until the molecular weight reaches 3,000. In this case, the initiator for oxyalkylene polymer A1 is not "polyol (initiator A)" but the starting material glycerin. In addition, in the present specification, when a mixture of oxyalkylene polymers A and B is purchased, the types and molar ratios of the initiators of oxyalkylene polymers A and B are 13 By identifying them using C-NMR, it is possible to calculate the average number of hydroxyl groups of the oxyalkylene polymers A and B. On the other hand, when the oxyalkylene polymers A and B are produced from respective initiators, the number of hydroxyl groups of the initiator used is itself the average number of hydroxyl groups of the oxyalkylene polymers A and B, and the average number of hydroxyl groups of the oxyalkylene polymers A and B can be determined from the number of hydroxyl groups of the initiator used.

[0009] (aqueous dispersion) The aqueous dispersion of the present invention contains a hydroxyl group-terminated urethane prepolymer and water, and may further contain other components as required.

[0010] The solids content of the aqueous dispersion of the present invention is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 18% by mass or more, particularly preferably 20% by mass or more, and is preferably 60% by mass or less, more preferably 56% by mass or less, particularly preferably 52% by mass or less. When the solid content is within the above range, the water dispersibility of the solid content tends to be better.

[0011] <Hydroxyl-terminated urethane prepolymer> The hydroxyl-terminated urethane prepolymer is obtained by reacting an oxyalkylene polymer A, an oxyalkylene polymer B, a diisocyanate compound, and, as an optional component, another polyol (a polyol other than the oxyalkylene polymer A and the oxyalkylene polymer B). The reaction between the hydroxyl groups of the oxyalkylene polymer A and the oxyalkylene polymer B and the isocyanate groups of the diisocyanate compound forms urethane bonds between the oxyalkylene polymer A and the oxyalkylene polymer B and the diisocyanate compound. Of the hydroxyl groups of the oxyalkylene polymer A and the oxyalkylene polymer B, those that remain unreacted with the isocyanate groups of the diisocyanate compound become hydroxyl groups at the terminals of the molecular chains of the urethane prepolymer. The content of the other polyol is not particularly limited as long as it does not inhibit the function of the hydroxyl group-terminated urethane prepolymer of the present invention, and is preferably 30 mass% or less, more preferably 10 mass% or less, based on the total amount of oxyalkylene polymer A and oxyalkylene polymer B.

[0012] The content of the hydroxyl group-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, and particularly preferably 20% by mass or more, and is preferably 60% by mass or less, more preferably 56% by mass or less, and particularly preferably 52% by mass or less. When the content is within the above range, the water dispersibility of the hydroxyl group-terminated urethane prepolymer tends to be better, and a clearer coating film can be obtained during coating.

[0013] -Oxyalkylene polymer A- The oxyalkylene polymer A (hereinafter also referred to as polymer A) is an oxyalkylene polymer having an average number of hydroxyl groups per molecule of more than 2.0 and not more than 3.0. The average number of hydroxyl groups per molecule of the oxyalkylene polymer A is not particularly limited as long as it is more than 2.0 and not more than 3.0, but is preferably 2.2 or more, more preferably 2.5 or more, even more preferably 2.8 or more, and particularly preferably 3.0. When the average number of hydroxyl groups of the oxyalkylene polymer A is within the above range, the adhesive strength of the resulting pressure-sensitive adhesive to the substrate can be kept within an appropriate range.

[0014] The average number of hydroxyl groups per molecule of oxyalkylene polymer A is 13 It can be calculated by specifying the type and molar ratio of the initiator using C-NMR (nuclear magnetic resonance). 13 In C-NMR analysis, characteristic peaks of the initiator are observed, and the type and molar ratio of the initiator can be identified from the peak position and peak area. Usually, the number of hydroxyl groups per molecule of an oxyalkylene polymer is the same as the number of hydroxyl groups per molecule of the initiator used in synthesizing the oxyalkylene polymer. When an oxyalkylene polymer is synthesized using, for example, glycerin as an initiator, an oxyalkylene polymer having three hydroxyl groups per molecule is usually obtained. When an oxyalkylene polymer is synthesized using, for example, pentaerythritol as an initiator, an oxyalkylene polymer having four hydroxyl groups per molecule is usually obtained. When an oxyalkylene polymer is synthesized using, for example, dipropylene glycol as an initiator, an oxyalkylene polymer having two hydroxyl groups per molecule is usually obtained. The average number of hydroxyl groups per molecule of oxyalkylene polymer A can also be calculated from the number of hydroxyl groups per molecule based on the type of initiator and the molar fraction of the initiator. For example, when glycerin is 30 mol% and dipropylene glycol is 70 mol%, the average number of hydroxyl groups is 3 × 0.3 + 2 × 0.7 = 2.3.

[0015] The alkylene oxide used in synthesizing the oxyalkylene polymer A is not particularly limited, as long as it is selected so that the content ratio of oxyethylene groups relative to the total amount of oxyalkylene groups in the oxyalkylene polymer A (ethylene oxide unit content) is 15 mass% or more. Ethylene oxide alone may be used, but a combination of ethylene oxide and an alkylene oxide having 3 to 5 carbon atoms is preferred, and a combination of ethylene oxide and propylene oxide is more preferred. When two or more alkylene oxides are subjected to ring-opening addition, the arrangement of units derived from each alkylene oxide may be random, block, or tapered. Here, when the arrangement of ethylene oxide units and propylene oxide units is random, the oxyalkylene polymer A may usually have a block of propylene oxide units and a random unit of ethylene oxide units and propylene oxide units, or may have a block of ethylene oxide units and a random unit of ethylene oxide units and propylene oxide units. Furthermore, when the ethylene oxide units and propylene oxide units are arranged in a block form, the oxyalkylene polymer A may have a block of propylene oxide units, a block of ethylene oxide units, and a block of propylene oxide units in this order (a "PO block-EO block-PO block" structure), or a block of ethylene oxide units, a block of propylene oxide units, and a block of ethylene oxide units in this order (an "EO block-PO block-EO block" structure). Furthermore, when the ethylene oxide units and propylene oxide units are arranged in a tapered form, the oxyalkylene polymer A usually has a block of propylene oxide units, a random mixture of ethylene oxide units and propylene oxide units, and a block of ethylene oxide units. When ethylene oxide and an alkylene oxide other than ethylene oxide are used in combination as the alkylene oxide, the molar ratio of the ethylene oxide unit content to the alkylene oxide unit content other than ethylene oxide is not particularly limited as long as the content ratio of oxyethylene groups (ethylene oxide unit content) relative to the total amount of oxyalkylene groups in the oxyalkylene polymer A is 15 mass% or more. The higher the content ratio of oxyethylene groups (ethylene oxide unit content), the more improved the hydrophilicity of the oxyalkylene polymer A tends to be, while the lower the content ratio of oxyethylene groups (ethylene oxide unit content), the more reduced the crystallinity of the oxyalkylene polymer A tends to be. Furthermore, when the oxyalkylene polymer A has an ethylene oxide unit at the end, the end becomes a primary hydroxyl group, and therefore the reactivity with diisocyanate tends to be higher than when the end is a propylene oxide unit.

[0016] The content ratio of oxyethylene groups (ethylene oxide unit content) relative to the total amount of oxyalkylene groups in the oxyalkylene polymer A is not particularly limited as long as it is 15% by mass or more, and may be 100% by mass, but is preferably 16% by mass or more, more preferably 18% by mass or more, and particularly preferably 20% by mass or more, and is also preferably 95% by mass or less, more preferably 90% by mass or less, and particularly preferably 85% by mass or less. When the ratio of oxyethylene groups to the total amount of oxyalkylene groups in the oxyalkylene polymer A (ethylene oxide unit content) is within the above-mentioned preferred range, the oxyalkylene polymer A tends to become amorphous, making it easy to handle, and the resulting adhesive tends to maintain its peelability even when stored under high-temperature and high-humidity conditions (hereinafter referred to as "humid heat resistance").

[0017] The content ratio of oxyethylene groups to the total amount of oxyalkylene groups in the oxyalkylene polymer A (ethylene oxide unit content) is 13 It is calculated by determining the monomer composition of the oxyalkylene chain using C-NMR. For example, when the oxyalkylene polymer A is a polyol consisting of propylene oxide units and ethylene oxide units, the content ratio of oxyethylene groups to the total amount of oxyalkylene groups (ethylene oxide unit content) can be determined from the area ratio of the signal of the methyl group in the propylene oxide unit to the signal of the methylene group in the propylene oxide unit and the ethylene oxide unit.

[0018] The number average molecular weight of the oxyalkylene polymer A is not particularly limited, but is preferably at least 1000, more preferably at least 3000, even more preferably at least 5000, and particularly preferably at least 8000, and is preferably at most 50000, more preferably at most 40000, even more preferably at most 30000, and particularly preferably at most 25000. When the number average molecular weight of the oxyalkylene polymer A is within the above preferred range, the flexibility of the resulting pressure-sensitive adhesive becomes better. When two or more kinds of oxyalkylene polymers A are contained, it is preferable that the number average molecular weight of each of the oxyalkylene polymers A is within the above-mentioned preferable range.

[0019] The molecular weight distribution of the oxyalkylene polymer A is not particularly limited, but is preferably less than 1.40, more preferably less than 1.20. By making the molecular weight distribution of the oxyalkylene polymer A less than 1.20, the reactivity tends to be good, the hydroxyl-terminated urethane prepolymer can be produced more efficiently, and the viscosity of the obtained hydroxyl-terminated urethane prepolymer tends to be reduced. When two or more types of oxyalkylene polymers A are contained, it is preferable that the molecular weight distribution of each of the oxyalkylene polymers A is within the above-mentioned preferred range.

[0020] 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 measurement according to the methods described below. As standard samples for molecular weight measurement, several types of monodisperse polystyrenes with different degrees of polymerization are measured using a commercially available GPC measurement device (HLC-8320GPC, manufactured by Tosoh Corporation), and a calibration curve is created based on the relationship between the molecular weight of the polystyrene and retention time.The oxyalkylene polymer A, which is the measurement sample, is diluted to 0.5% by mass with tetrahydrofuran and passed through a filter with a pore size of 0.5 μm, and then the measurement sample is measured using the above GPC measurement device.Using the above calibration curve, the GPC spectrum of the measurement sample is analyzed by computer to determine the Mn and weight average molecular weight (hereinafter referred to as Mw) of the measurement sample. The molecular weight distribution is a value calculated from the above Mw and Mn, and is the ratio of Mw to Mn.

[0021] 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 may be zero. If the degree of unsaturation of the oxyalkylene polymer A is the above upper limit or less, the curability of the resulting hydroxyl-terminated urethane prepolymer is better. The degree of unsaturation of the oxyalkylene polymer A is a value measured according to the method of JIS-K1557-6:2009.

[0022] The hydroxyl value of the oxyalkylene polymer A is not particularly limited, but is preferably 2 mgKOH / g or more, more preferably 5 mgKOH / g or more, particularly preferably 8 mgKOH / g or more, and is preferably 50 mgKOH / g or less, more preferably 45 mgKOH / g or less, particularly preferably 40 mgKOH / g or less. If the hydroxyl value of the oxyalkylene polymer A is the above upper limit or less, the flexibility of the resulting pressure-sensitive adhesive is better. The hydroxyl value of the oxyalkylene polymer A is a value calculated by measurement according to the titration method of JIS K 0070:1992.

[0023] In one embodiment of the present invention, the oxyalkylene polymer A contains an oxyalkylene polymer a (hereinafter referred to as "polymer a") having three hydroxyl groups per molecule. When the oxyalkylene polymer A contains polymer a, the adhesive strength to the substrate is more likely to be within a more appropriate range.

[0024] The mass proportion of polymer a in oxyalkylene polymer A is not particularly limited, but is preferably 80 mass % or more, more preferably 90 mass % or more, and particularly preferably 100 mass %.

[0025] The mass ratio of the polymer a contained in the oxyalkylene polymer A is, for example, 13The type and molar ratio of the initiator contained in the oxyalkylene polymer A can be identified using C-NMR (nuclear magnetic resonance), and the ratio can be calculated as the ratio of the peak areas.

[0026] To synthesize polymer a, an initiator having three hydroxyl groups per molecule is used. Glycerin is preferred as the initiator for synthesizing polymer a. Glycerin is available at low cost, which can reduce the synthesis cost of oxyalkylene polymer a.

[0027] The alkylene oxide used in the synthesis of polymer a is the same as the alkylene oxide used in the synthesis of oxyalkylene polymer A described above. If the raw materials used in the synthesis of the oxyalkylene polymer A contain moisture, the alkylene oxide may undergo addition polymerization using water as an initiator to produce a polymer having two hydroxyl groups per molecule (corresponding to polymer b described below) as a by-product. As long as the average number of hydroxyl groups in the resulting oxyalkylene polymer A is more than 2.0 and not more than 3.0, the by-product may be contained in the oxyalkylene polymer A. The content of the by-product is preferably 2000 ppm or less, more preferably 1800 ppm or less, and even more preferably 1500 ppm or less, based on the oxyalkylene polymer A.

[0028] As a catalyst for ring-opening addition polymerization of alkylene oxide to an initiator, a conventionally known catalyst can be used, for example, an alkali catalyst such as KOH, a transition metal compound-porphyrin complex catalyst such as a complex obtained by reacting an organoaluminum compound with porphyrin, a double metal cyanide complex catalyst (DMC catalyst), or a catalyst made of a phosphazene compound. When the oxyalkylene polymer A is obtained using a composite metal cyanide complex catalyst (DMC catalyst), it is preferable because the molecular weight distribution of the obtained oxyalkylene polymer A can be narrowed and an oxyalkylene polymer A having a low viscosity can be easily obtained. The composite metal cyanide complex catalyst (DMC catalyst) may be a conventionally known compound, and a known method may be used for producing a polymer using the composite metal cyanide complex catalyst (DMC catalyst). For example, the compounds and production methods disclosed in International Publication No. 2003 / 062301, International Publication No. 2004 / 067633, Japanese Patent Application Laid-Open No. 2004-269776, Japanese Patent Application Laid-Open No. 2005-015786, International Publication No. 2013 / 065802, Japanese Patent Application Laid-Open No. 2015-010162, etc. may be used. A conventionally known method can be used to obtain the oxyalkylene polymer A by subjecting an alkylene oxide to ring-opening addition polymerization with an initiator, such as the production methods disclosed in International Publication No. 2011 / 125951 and Japanese Patent No. 5648797.

[0029] -Oxyalkylene polymer B- The oxyalkylene polymer B (hereinafter also referred to as polymer B) is an oxyalkylene polymer having an average number of hydroxyl groups per molecule of 1.2 or more and 2.0 or less. The average number of hydroxyl groups per molecule of oxyalkylene polymer B is not particularly limited as long as it is 1.2 or more and 2.0 or less, but is 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. When the average number of hydroxyl groups of the oxyalkylene polymer B is within the above preferred range, the adhesive strength of the resulting pressure-sensitive adhesive to the substrate can be kept within an appropriate range.

[0030] The average number of hydroxyl groups per molecule of the oxyalkylene polymer B can be specified in the same manner as in the case of the oxyalkylene polymer A. The average number of hydroxyl groups per molecule of oxyalkylene polymer B is 13 It can be measured using C-NMR. 13 By identifying the type of initiator from the peaks obtained by C-NMR, it can be seen that the average number of hydroxyl groups is 1.2 or more and 2.0 or less. The average number of hydroxyl groups per molecule of oxyalkylene polymer B can also be calculated from the number of hydroxyl groups per molecule based on the type of initiator and the molar fraction of the initiator. For example, when 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.

[0031] The oxyalkylene polymer B is preferably obtained by ring-opening addition of an alkylene oxide to an initiator having two hydroxyl groups in one molecule. The alkylene oxide used in synthesizing the oxyalkylene polymer B is selected so that the content ratio of oxyethylene groups (ethylene oxide unit content) relative to the total amount of oxyalkylene groups in the oxyalkylene polymer B is 15 mass% or more. There are no particular restrictions, and ethylene oxide alone may be used, but a combination of ethylene oxide and an alkylene oxide having 3 to 5 carbon atoms is preferred, and a combination of ethylene oxide and propylene oxide is more preferred. When two or more alkylene oxides are subjected to ring-opening addition, the arrangement of units derived from each alkylene oxide may be random, block, or tapered. Here, when the arrangement of ethylene oxide units and propylene oxide units is random, the oxyalkylene polymer B may usually have a block of propylene oxide units and a random unit of ethylene oxide units and propylene oxide units, or may have a block of ethylene oxide units and a random unit of ethylene oxide units and propylene oxide units. Furthermore, when the ethylene oxide units and propylene oxide units are arranged in a block form, the oxyalkylene polymer B may have a block of propylene oxide units, a block of ethylene oxide units, and a block of propylene oxide units in this order (a "PO block-EO block-PO block" structure), or a block of ethylene oxide units, a block of propylene oxide units, and a block of ethylene oxide units in this order (an "EO block-PO block-EO block" structure). Furthermore, when the ethylene oxide units and propylene oxide units are arranged in a tapered form, the oxyalkylene polymer B usually has a block of propylene oxide units, a random mixture of ethylene oxide units and propylene oxide units, and a block of ethylene oxide units. When ethylene oxide and an alkylene oxide other than ethylene oxide are used in combination as the alkylene oxide, the molar ratio of the ethylene oxide unit content to the alkylene oxide unit content other than ethylene oxide is not particularly limited as long as the content ratio of oxyethylene groups (ethylene oxide unit content) relative to the total amount of oxyalkylene groups in oxyalkylene polymer B is 15 mass% or more. The higher the content ratio of oxyethylene groups (ethylene oxide unit content), the more improved the hydrophilicity of oxyalkylene polymer B tends to be, and the lower the content ratio of oxyethylene groups (ethylene oxide unit content), the more reduced the crystallinity of oxyalkylene polymer B tends to be. Furthermore, when the oxyalkylene polymer B has an ethylene oxide unit at the end, the end becomes a primary hydroxyl group, and therefore the reactivity with diisocyanate tends to be higher than when the end is a propylene oxide unit.

[0032] The content ratio of oxyethylene groups (ethylene oxide unit content) relative to the total amount of oxyalkylene groups in oxyalkylene polymer B is not particularly limited, but is not particularly limited as long as it is 15% by mass or more, and may be 100% by mass, but is preferably 16% by mass or more, more preferably 17% by mass or more, and particularly preferably 19% by mass or more, and is also preferably 95% by mass or less, more preferably 90% by mass or less, and particularly preferably 85% by mass or less. When the content ratio of oxyethylene groups (ethylene oxide unit content) relative to the total amount of oxyalkylene groups in the oxyalkylene polymer B is within the above preferred range, the resulting pressure-sensitive adhesive has better moist heat resistance. The content ratio of oxyethylene groups to the total amount of oxyalkylene groups in oxyalkylene polymer B (ethylene oxide unit content) can be calculated in the same manner as for oxyalkylene polymer A. When two or more types of oxyalkylene polymers B are contained, the ratio of the oxyethylene group content (ethylene oxide unit content) to the total amount of oxyalkylene groups is preferably calculated as a weighted average within the above-mentioned preferred range.

[0033] The Mn of the oxyalkylene polymer B is not particularly limited, but is preferably at least 1000, more preferably at least 3000, even more preferably at least 5000, and particularly preferably at least 8000, and is preferably at most 50000, more preferably at most 40000, even more preferably at most 30000, and particularly preferably at most 25000. When the Mn of the oxyalkylene polymer B is within the above preferred range, the flexibility of the resulting pressure-sensitive adhesive becomes even better. The Mw / Mn of the oxyalkylene polymer B is not particularly limited, but is preferably less than 1.40, more preferably less than 1.20, even more preferably less than 1.13, and particularly preferably less than 1.10. By making the molecular weight distribution of the oxyalkylene polymer B within the above range, the reactivity tends to be good, the hydroxyl-terminated urethane prepolymer can be produced more efficiently, and the viscosity of the obtained hydroxyl-terminated urethane prepolymer tends to be lower. The Mn and Mw of the oxyalkylene polymer B can be determined by GPC measurement using the same method as for the oxyalkylene polymer A. 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 0.0010 meq / g or less, and particularly preferably 0.008 meq / g or less. The degree of unsaturation of the oxyalkylene polymer B may be zero. If the degree of unsaturation of the oxyalkylene polymer B is the above upper limit or less, the curability of the obtained hydroxyl group-terminated urethane prepolymer is better. The hydroxyl value of the oxyalkylene polymer B is not particularly limited, but is preferably 2 mgKOH / g or more, more preferably 5 mgKOH / g or more, particularly preferably 8 mgKOH / g or more, and is preferably 80 mgKOH / g or less, more preferably 70 mgKOH / g or less, particularly preferably 60 mgKOH / g or less. If the hydroxyl value of the oxyalkylene polymer B is within the above-mentioned preferred range, the flexibility of the resulting pressure-sensitive adhesive is better. The degree of unsaturation and hydroxyl value of the oxyalkylene polymer B can be measured in the same manner as for the oxyalkylene polymer A. When two or more kinds of oxyalkylene polymers B are contained, it is preferable that the Mn, Mw / Mn, degree of unsaturation and hydroxyl value of each of the oxyalkylene polymers B are within the above-mentioned preferred ranges.

[0034] As in the case of the oxyalkylene polymer A, it is preferable to use an alkali catalyst such as KOH or a composite metal cyanide complex catalyst (DMC catalyst) as the catalyst.

[0035] In one embodiment of the present invention, oxyalkylene polymer B contains oxyalkylene polymer b (hereinafter referred to as "polymer b") having two hydroxyl groups per molecule. When oxyalkylene polymer B contains polymer b, the adhesive strength to a substrate is more likely to fall within a more appropriate range.

[0036] The mass proportion of polymer b in oxyalkylene polymer B is not particularly limited, but is preferably 80 mass % or more, more preferably 90 mass % or more, and particularly preferably 100 mass %.

[0037] The mass proportion of polymer b contained in oxyalkylene polymer B can be calculated in the same manner as in the calculation of the mass proportion of polymer a contained in oxyalkylene polymer A described above.

[0038] 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 synthesizing polymer b, one or more selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol are preferred, one or more selected from propylene glycol and dipropylene glycol are more preferred, and propylene glycol is particularly preferred. Propylene glycol is available at low cost, and can reduce the synthesis cost of polymer b.

[0039] The alkylene oxide used in the synthesis of polymer b is the same as the alkylene oxide used in the synthesis of the above-mentioned oxyalkylene polymer A, and the preferred embodiments are also the same. Polymer b can be synthesized by the same method as the above-mentioned oxyalkylene polymer A.

[0040] -Other oxyalkylene polymers- The aqueous dispersion of the present invention may contain a reaction product obtained by reacting an oxyalkylene polymer other than the above-mentioned oxyalkylene polymers a and b with a diisocyanate compound. Examples of the oxyalkylene polymer other than the oxyalkylene polymer a and the oxyalkylene polymer b include oxyalkylene polymer c having four or more hydroxyl groups per molecule (hereinafter referred to as "polymer c") and oxyalkylene polymer d having one hydroxyl group per molecule (hereinafter referred to as "polymer d").

[0041] To synthesize polymer c, an initiator having four or more hydroxyl groups per molecule is used, including polyhydric alcohols with tetrahydric or higher alcohol content, such as diglycerin, pentaerythritol, dipentaerythritol, and tripentaerythritol, as well as sugars or derivatives thereof, such as glucose, sorbitol, dextrose, fructose, sucrose, and methyl glucoside.

[0042] To synthesize polymer d, an initiator having one hydroxyl group per molecule is used. As the initiator having one hydroxyl group per molecule, a monohydric alcohol having 2 to 4 carbon atoms is preferred because it is available at low cost, more preferred are propanol (n-propyl alcohol), 2-propanol (isopropyl alcohol), 1-butanol (n-butyl alcohol), 2-butanol (sec-butyl alcohol), 2-methyl-1-propanol (isobutyl alcohol), and 2-methyl-2-propanol (tert-butyl alcohol), and particularly preferred are 1-butanol (n-butyl alcohol), 2-butanol (sec-butyl alcohol), 2-methyl-1-propanol (isobutyl alcohol), and 2-methyl-2-propanol (tert-butyl alcohol).

[0043] The alkylene oxide used in the synthesis of polymer c or polymer d is the same as the alkylene oxide used in the synthesis of the above-mentioned oxyalkylene polymer A, and the preferred embodiments are also the same. Polymer c or polymer d can be synthesized by the same method as the above-mentioned oxyalkylene polymer A.

[0044] The ratio of the total mass of polymer c and polymer d to the total mass of oxyalkylene polymers A and B is preferably 20 mass% or less, more preferably 10 mass% or less, particularly preferably 3 mass% or less, and may not be included.

[0045] -Diisocyanate compounds- The diisocyanate compound used to react with the oxyalkylene polymer A and the oxyalkylene polymer B to obtain a hydroxyl group-terminated urethane prepolymer is not particularly limited as long as it is an organic compound having two isocyanate groups in one molecule, and examples thereof include an aliphatic diisocyanate compound, an alicyclic diisocyanate compound, an aromatic diisocyanate compound, and an araliphatic diisocyanate compound.

[0046] Examples of the aliphatic diisocyanate compound include 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. The aliphatic diisocyanate compounds may be used singly or in combination of two or more. Among these, linear aliphatic diisocyanates are preferred, linear aliphatic diisocyanates having 4 to 8 carbon atoms are more preferred, and hexamethylene diisocyanate (HDI) is particularly preferred, because the resulting pressure-sensitive adhesive has a higher glass transition temperature and is superior in tensile strength and elongation at break.

[0047] Examples of alicyclic diisocyanate compounds include isophorone diisocyanate (IPDI), hydrogenated xylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, etc. The alicyclic diisocyanate compounds may be used alone or in combination of two or more. Among these, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and hexamethylene diisocyanate are preferred, and isophorone diisocyanate and hexamethylene diisocyanate are more preferred, as the resulting polyurethane (adhesive) will have better tensile strength and elongation at break.

[0048] Examples of aromatic diisocyanate compounds include tolylene diisocyanate (TDI), 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-dibenzyl diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, etc. The aromatic diisocyanate compounds may be used alone or in combination of two or more. Among these, diphenylmethane diisocyanate is preferred, and 4,4'-diphenylmethane diisocyanate (MDI) is more preferred, in that the resulting polyurethane has better tensile strength and elongation at break.

[0049] Examples of the araliphatic diisocyanate compound include dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, α,α,α',α'-tetramethylxylylene diisocyanate, etc. The araliphatic diisocyanate compound may be used alone or in combination of two or more. Among these, α,α,α',α'-tetramethylxylylene diisocyanate is preferred because the resulting polyurethane has a better elongation at break.

[0050] The diisocyanate compound used in producing the hydroxyl group-terminated urethane prepolymer is preferably an aliphatic diisocyanate compound or an alicyclic diisocyanate compound, more preferably an aliphatic diisocyanate compound, even more preferably an aliphatic diisocyanate compound having 4 to 6 carbon atoms, particularly preferably HDI or a modified HDI, and most preferably HDI or an isocyanurate modified HDI, because the resulting polyurethane will have better tensile strength and elongation at break.

[0051] As the diisocyanate compound for producing the hydroxyl group-terminated urethane prepolymer, a bifunctional isocyanate group-terminated urethane prepolymer obtained by prepolymerizing the above-mentioned aliphatic diisocyanate compound, alicyclic diisocyanate compound, aromatic diisocyanate compound, or araliphatic diisocyanate compound with a diol may be used. Examples of diols for producing the isocyanate group-terminated urethane prepolymer include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, etc. The diols may be used alone or in combination of two or more. Among these, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, and 1,6-hexanediol are preferred, and propylene glycol is more preferred, since the resulting polyurethane (adhesive) has a higher glass transition temperature. The isocyanate index when producing an isocyanate group-terminated urethane prepolymer is greater than 100. The isocyanate index is the ratio of the number of moles of isocyanate groups in a diisocyanate compound to the number of moles of hydroxyl groups in a diol multiplied by 100. Commercially available difunctional isocyanate group-terminated urethane prepolymers include, for example, Duranate D101, Duranate D201, and Duranate A201H (all manufactured by Asahi Kasei Corporation).

[0052] The molar ratio (isocyanate index) of the isocyanate groups of the diisocyanate compound to the hydroxyl groups of the oxyalkylene polymer A and the oxyalkylene polymer B is not particularly limited, but is preferably 40 or more, more preferably 43 or more, and particularly preferably 46 or more, and is preferably 90 or less, more preferably 80 or less, and particularly preferably 75 or less. When the molar ratio is within the above preferred range, a hydroxyl-terminated urethane prepolymer having an appropriate molecular chain length can be produced, thereby further improving productivity. The isocyanate index is the ratio of the number of moles of isocyanate groups of the diisocyanate compound to the total number of moles of hydroxyl groups of the oxyalkylene polymer A and the oxyalkylene polymer B multiplied by 100.

[0053] -Method of manufacturing hydroxyl group-terminated urethane prepolymer- The method for producing the hydroxyl group-terminated urethane prepolymer is not particularly limited, but examples thereof include a method of reacting an oxyalkylene polymer A and an oxyalkylene polymer B with a diisocyanate compound. 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 is 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 increased viscosity during production of the urethane prepolymer can be prevented, and good adhesion to substrates can be maintained. The average number of hydroxyl groups in the hydroxyl-terminated urethane prepolymer is preferably 1.7 or more, more preferably 1.8 or more, and particularly preferably 2.0 or more, and is also preferably less than 3.0, more preferably 2.9 or less, and particularly preferably 2.5 or less. When the average number of hydroxyl groups in the hydroxyl-terminated urethane prepolymer is within the above preferred range, the resulting PSA can maintain better permeability and adhesion to substrates. The "average number of hydroxyl groups f" of the hydroxyl-terminated urethane prepolymer is a value obtained by the following formula (I). 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)

[0054] The hydroxyl-terminated prepolymer may also contain, as an optional component, a polyol other than the oxyalkylene polymer. Examples of polyols other than oxyalkylene polymers include polyester polyols, poly(meth)acrylic polyols, polycarbonate polyols, polyolefin polyols, and castor oil-based polyols, and those described in paragraphs

[0016] to

[0028] of JP 2020-37689 A can be used without particular limitation. Polymer polyols in which a polymer having units based on a (meth)acrylate monomer is dispersed in a polyether polyol can also be used. Polymer polyols may be commercially available products, such as the "Ultiflo (registered trademark)" series and the "Sharpflo (registered trademark)" series (both manufactured by Sanyo Chemical Industries, Ltd.), and the "Exenol (registered trademark)" series (manufactured by AGC Inc.). In the production of the hydroxyl group-terminated urethane prepolymer, a catalyst may be used as needed. Examples of the catalyst include tertiary amine compounds, tin compounds, and non-tin compounds. The catalysts can be used alone or in combination of two or more. Examples of tertiary amine compounds include triethylamine, triethylenediamine, and 1,8-diazabicyclo(5,4,0)-7-undecene (DBU). Examples of tin compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, and tin 2-ethylhexanoate. Examples of non-tin compounds include titanium compounds such as dibutyltitanium dichloride, tetrabutyltitanium, 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 acetylacetonate; cobalt compounds such as cobalt benzoate and cobalt 2-ethylhexanoate; zinc compounds such as zinc naphthenate and zinc 2-ethylhexanoate; and zirconium compounds such as zirconium naphthenate. When a catalyst is used, the amount of the catalyst used is not particularly limited, but is preferably 0.001 part by mass or more, more preferably 0.002 part by mass or more, and particularly preferably 0.003 part by mass or more, per 100 parts by mass of the total of the oxyalkylene polymer A, the oxyalkylene polymer B, and the diisocyanate compound, and is preferably 1.0 part by mass or less, more preferably 0.2 part by mass or less, and particularly preferably 0.05 part by mass or less.

[0055] In producing the hydroxyl group-terminated urethane prepolymer, a solvent may be used as needed. Examples of the solvent include ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, aromatic hydrocarbons such as toluene and xylene, etc. The solvents can be used alone or in combination of two or more. When a solvent is used, the amount of the solvent used is not particularly limited, but 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, per 100 parts by mass of the total of the oxyalkylene polymer and the diisocyanate compound, and 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.

[0056] Examples of methods for producing hydroxyl group-terminated urethane prepolymers include the following methods. Production method 1: A method in which a diisocyanate compound, an oxyalkylene polymer A, an oxyalkylene polymer B, an optional catalyst, and an optional solvent are charged all at once Production method 2: A method in which an oxyalkylene polymer A, an oxyalkylene polymer B, an optional catalyst, and an optional solvent are charged, and a diisocyanate compound is added dropwise thereto. In the case of production method 2, the low molecular weight components in the raw material are reacted preferentially, the molecular weight distribution can be narrowed, and the reaction can be easily controlled.

[0057] The reaction temperature is preferably 50° C. or higher, more preferably 60° C. or higher, and particularly preferably 65° C. or higher, and is less than 100° C., more preferably 95° C. or lower, and particularly preferably 80° C. or lower. When the reaction temperature is within the above range, side reactions other than the urethane reaction are easily suppressed, making it easier to obtain the desired prepolymer.

[0058] After the reaction is complete, a reaction terminator may be added to inactivate the catalyst. Examples of the reaction terminator include acetylacetone. Two or more reaction terminators may be used in combination.

[0059] The Mw of the hydroxyl group-terminated urethane prepolymer is not particularly limited, but is preferably at least 10,000, more preferably at least 15,000, and particularly preferably at least 20,000, and is preferably at most 250,000, more preferably at most 240,000, and particularly preferably at most 220,000. When the weight-average molecular weight is within the above preferred range, a pressure-sensitive adhesive composition with excellent coatability can be obtained, and the viscosity during synthesis can be adjusted. The Mw of the hydroxyl-terminated urethane prepolymer can be determined by GPC measurement in the same manner as for the oxyalkylene polymer A.

[0060] The ratio of oxyethylene groups to the total amount of oxyalkylene groups in the hydroxyl-terminated urethane prepolymer (ethylene oxide unit content) is not particularly limited as long as it is more than 20% by mass and not more than 70% by mass, but is preferably at least 23% by mass, more preferably at least 26% by mass, particularly preferably at least 29% by mass, and is preferably not more than 65% by mass, more preferably not more than 60% by mass, particularly preferably not more than 55% by mass. When the ratio of oxyethylene groups to the total amount of oxyalkylene groups in the hydroxyl-terminated urethane prepolymer (ethylene oxide unit content) is at or above the lower limit, the water solubility of the hydroxyl-terminated urethane prepolymer is improved, the presence of oxypropylene groups (polar groups) in the prepolymer increases affinity with release agents (silicones), the coatability of aqueous dispersions containing the hydroxyl-terminated urethane prepolymer is improved, and the transparency of the resulting pressure-sensitive adhesive is further improved, resulting in better moist heat resistance of the resulting pressure-sensitive adhesive. When the ratio of the oxyethylene group content (ethylene oxide unit content) to the total amount of oxyalkylene groups in the hydroxyl group-terminated urethane prepolymer is at most the upper limit, the haze of the resulting adhesive is easily suppressed and the transparency is easily improved. The ratio of oxyethylene groups to the total amount of oxyalkylene groups in the urethane prepolymer (ethylene oxide unit content) is: 1 It was calculated by determining the monomer composition of the oxyalkylene chain using H-NMR. When the raw materials and amounts used during synthesis are known, the ratio of oxyethylene groups to the total amount of oxyalkylene groups in the hydroxyl group-terminated urethane prepolymer (ethylene oxide unit content) can be calculated as follows: (ratio of oxyethylene groups to the total amount of oxyalkylene groups in oxyalkylene polymer A) × (mass of oxyalkylene polymer A to the total mass of oxyalkylene polymer A and oxyalkylene polymer B) + (ratio of oxyethylene groups to the total amount of oxyalkylene groups in oxyalkylene polymer B) × (mass of oxyalkylene polymer B to the total mass of oxyalkylene polymer A and oxyalkylene polymer B).

[0061] <Water> 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 is preferably 90% by mass or less, more preferably 85% by mass or less, particularly preferably 80% by mass or less. When the content is within the above range, the coating properties are further improved.

[0062] <Other ingredients> The aqueous dispersion of the present invention may contain, as other components, antioxidants; organic solvents such as alcohols; and raw materials used in preparing the hydroxyl group-terminated urethane prepolymer, such as alkylene oxides, polyols (initiators), and diisocyanates. The content of other components in the aqueous dispersion of the present invention is usually 20% by mass or less.

[0063] -Antioxidants- Examples of antioxidants include radical scavengers such as phenolic compounds and amine compounds; peroxide decomposers such as sulfur compounds and phosphorus compounds; etc. One antioxidant may be used alone, or two or more antioxidants may be used in combination.

[0064] --Phenol-based compounds-- Examples of phenolic compounds include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, stearin-β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-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-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]2,4,8,10-tetraoxaspiro[5,5]undecane, benzenepropanol Pantothenic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-, C7-C9 side chain alkyl ester (BASF product name Irganox 1135), 2,6-di-t-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol (BASF product name Irganox 565), 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di- t-butyl-4-hydroxybenzyl)benzene, tetrakis-[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane, bis[3,3'-bis-(4'-hydroxy-3'-t-butylphenyl)butyric acid]glycol ester, 1,3,5-tris(3',5'-di-t-butyl-4'-hydroxybenzyl)-S-triazine-2,4,6-(1H,3H,5H)trione, tocopherol, and the like.

[0065] --Phosphorus compounds-- Examples of phosphorus compounds include triphenyl phosphite, diphenyl isodecyl phosphite, 4,4'-butylidene-bis(3-methyl-6-tert-butylphenylditridecyl)phosphite, cyclic neopentanetetraylbis(octadecylphosphite), tris(nonylphenyl)phosphite, tris(mononylphenyl)phosphite, tris(dinonylphenyl)phosphite, diisodecyl pentaerythritol diphosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-tert-butylphenyl)phosphite, -4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene, tris(2,4-di-tert-butylphenyl)phosphite, cyclic neopentanetetraylbis(2,4-di-tert-butylphenyl)phosphite, cyclic neopentanetetraylbis(2,6-di-tert-butyl-4-methylphenyl)phosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octylphosphite, and the like.

[0066] The use of an antioxidant can prevent thermal degradation of the hydroxyl-terminated urethane prepolymer. The amount of antioxidant added is not particularly limited, but is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more, and particularly preferably 0.2 part by mass or more, per 100 parts by mass of the hydroxyl group-terminated urethane prepolymer, and 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.

[0067] As the antioxidant, from the viewpoint of stability and antioxidant effect, it is preferable to use one or more phenolic compounds as radical scavengers. One or more phenolic compounds as radical scavengers can also be used in combination with one or more phosphorus-based compounds as peroxide decomposers. Furthermore, as the antioxidant, a phenolic compound as a radical scavenger and a phosphorus-based compound as a peroxide decomposer can also be used in combination, and these antioxidants can also be used in combination with a hydrolysis inhibitor described below.

[0068] (Adhesive composition) The pressure-sensitive adhesive composition of the present invention contains the aqueous dispersion of the present invention and a polyisocyanate compound having three or more isocyanate groups in one molecule.

[0069] <Polyisocyanate compounds with three or more isocyanate groups per molecule> Examples of polyisocyanate compounds having three or more isocyanate groups in one molecule include isocyanurate-modified products of the above-mentioned diisocyanate compounds; biuret-modified products of the above-mentioned diisocyanate compounds; allophanate-modified products of the above-mentioned diisocyanate compounds; tri- or higher functional isocyanate-terminated urethane prepolymers (adduct modified products) obtained by reacting the above-mentioned diisocyanate compounds with polyols having three or more hydroxyl groups in one molecule; and water-dispersible polyisocyanate compounds such as water-dispersible isocyanates and blocked isocyanates. Commercially available isocyanurate-modified products include, for example, Duranate TPA-100 and Duranate TKA-100 (manufactured by Asahi Kasei Corporation), and Coronate HX (manufactured by Tosoh Corporation). Commercially available biuret-modified products include, for example, Duranate 24A-100 and Duranate 22A-75P (manufactured by Asahi Kasei Corporation). Commercially available tri- or higher functional isocyanate group-terminated urethane prepolymers include, for example, Coronate L, Coronate L-55E, and Coronate L-45E (all manufactured by Tosoh Corporation). Examples of commercially available water-dispersible isocyanates include Duranate WB40-100, Duranate WB40-80D, Duranate WT20-100, Duranate WL70-100, Duranate WE50-100, and Duranate WR80-70P (manufactured by Asahi Kasei Corporation), Aquanate 105, Aquanate 130, Aquanate 140 (AQ-140), Aquanate 200, and Aquanate 210 (manufactured by Tosoh Corporation). Commercially available blocked isocyanates include, for example, SU-268A, NBP-211, Meikanate CX, Meikanate TP-10, and DM-6400 (all manufactured by Meisei Chemical Industry 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, Inc.); Burnock (manufactured by DIC Corporation); and Elastron (manufactured by Daiichi Kogyo Co., Ltd.). Among these, water-dispersible polyisocyanate compounds are preferred, and water-dispersible isocyanates are more preferred.

[0070] The pressure-sensitive adhesive composition of the present invention may be a two-component pressure-sensitive adhesive composition comprising a first part containing the aqueous dispersion of the present invention and a second part containing a polyisocyanate compound having three or more isocyanate groups in one molecule. By mixing the first and second parts, the formation of urethane bonds progresses, and a pressure-sensitive adhesive composition containing polyurethane is obtained. The first or second agent may further contain a catalyst, a solvent, optional components that can be blended into the pressure-sensitive adhesive composition, which will be described later, and the like. The first and second agents are contained in separate containers, which may be various types such as tubes or bottles. The sales form of the pressure-sensitive adhesive composition of the present invention may be a form containing a first agent and a second agent, or a form containing a first agent but not a second agent (i.e., the aqueous dispersion of the present invention). In a sales form not containing a second agent, the user can use a second agent prepared separately, thereby increasing the user's flexibility.

[0071] <Method of manufacturing pressure-sensitive adhesive composition> A method for producing the pressure-sensitive adhesive composition of the present invention by reacting the aqueous dispersion of the present invention with a curing agent containing a polyisocyanate compound having three or more isocyanate groups in one molecule will be described.

[0072] The curing agent may contain a polyisocyanate compound having two isocyanate groups in one molecule (diisocyanate compound) in addition to a polyisocyanate compound having three or more isocyanate groups in one molecule. Examples of the diisocyanate compound include the above-mentioned diisocyanate compounds and the above-mentioned difunctional isocyanate group-terminated urethane prepolymers.

[0073] The isocyanate index when the pressure-sensitive adhesive composition of the present invention is produced by reacting the aqueous dispersion of the present invention with a curing agent containing a polyisocyanate compound having three or more isocyanate groups per molecule is preferably more than 100, more preferably 105 or more, particularly preferably 150 or more, and is preferably 2000 or less, more preferably 1750 or less, particularly preferably 1500 or less. The isocyanate index is the value obtained by multiplying the ratio of the number of moles of isocyanate groups in the curing agent to the number of moles of hydroxyl groups in the hydroxyl-terminated urethane prepolymer by 100.

[0074] When producing the pressure-sensitive 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. The amount of curing catalyst used is preferably 0.001 parts by mass or more, more preferably 0.003 parts by mass or more, and particularly preferably 0.005 parts by mass or more, per 100 parts by mass of the total of the hydroxyl-terminated urethane prepolymer and the curing agent, and is preferably 0.10 parts by mass or less, more preferably 0.05 parts by mass or less, and particularly preferably 0.01 parts by mass or less. After completion of the reaction, it is preferable to add a reaction terminator to inactivate the catalyst.

[0075] The pressure-sensitive adhesive composition of the present invention may contain a solvent, if necessary. The type of solvent is preferably the solvent described above. The amount of the solvent used is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, particularly preferably 50 parts by mass or more, and is preferably 500 parts by mass or less, more preferably 450 parts by mass or less, particularly preferably 400 parts by mass or less, per 100 parts by mass of the total of the hydroxyl group-terminated urethane prepolymer and the curing agent.

[0076] The reaction temperature when the aqueous dispersion of the present invention is crosslinked with a curing agent is preferably 30° C. or higher, more preferably 35° C. or higher, and particularly preferably 40° C. or higher, and is less than 100° C., more preferably 80° C. or lower, and particularly preferably 60° C. or lower. When the reaction temperature is within the above range, side reactions other than the urethane reaction are easily suppressed, and the desired polymer is easily obtained.

[0077] <Optional components that can be blended into the pressure-sensitive adhesive composition> The pressure-sensitive adhesive composition of the present invention may contain, as necessary, a hydrolysis inhibitor, an antioxidant, an ultraviolet absorber, a light stabilizer, an antistatic agent, a leveling agent, other optional components, and the like, within a range that does not impair the effects of the present invention.

[0078] -Hydrolysis inhibitor- Examples of the hydrolysis inhibitor include carbodiimide-based, isocyanate-based, oxazoline-based, epoxy-based, etc. One type of hydrolysis inhibitor may be used alone, or two or more types may be used in combination. Among these, carbodiimide-based compounds are preferred from the viewpoint of their hydrolysis suppression effect.

[0079] --Carbodiimide-based-- A carbodiimide hydrolysis inhibitor is a compound having one or more carbodiimide groups in one molecule. Examples of the monocarbodiimide compound include dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, diphenylcarbodiimide, and naphthylcarbodiimide. The polycarbodiimide compound can be produced by subjecting a diisocyanate to a decarboxylation condensation reaction in the presence of a carbodiimidization catalyst. Examples of diisocyanates include 4,4'-diphenylmethane diisocyanate, 3,3'-dimethoxy-4,4'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylether diisocyanate, 3,3'-dimethyl-4,4'-diphenylether diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1-methoxyphenyl-2,4-diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and tetramethylxylylene diisocyanate. Examples of the carbodiimidization catalyst include phospholene oxides such as 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 3-phospholene isomers thereof.

[0080] --Isocyanate-based-- Examples of isocyanate hydrolysis inhibitors include 2,4-tolylene diisocyanate, 2,6-tolylene 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, 1,5-naphthalene diisocyanate, and 1,5-tetrahydro- Examples of the diisocyanate include naphthalene diisocyanate, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and 3,3'-dimethyl-4,4'-dicyclohexylmethane diisocyanate.

[0081] --Oxazoline-- Examples of oxazoline-based hydrolysis inhibitors include 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). ), 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), and the like.

[0082] --Epoxy-based-- Examples of epoxy-based hydrolyzing agents include diglycidyl ethers of aliphatic diols such as 1,6-hexanediol, neopentyl glycol, and polyalkylene glycol; polyglycidyl ethers of aliphatic polyols such as sorbitol, sorbitan, polyglycerol, pentaerythritol, diglycerol, glycerol, and trimethylolpropane; polyglycidyl ethers of alicyclic polyols such as cyclohexanedimethanol; 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 diglycidyl ethers or polyglycidyl ethers of polyhydric phenols such as 2,2-bis-(p-hydroxyphenyl)propane, tris-(p-hydroxyphenyl)methane, and 1,1,2,2-tetrakis(p-hydroxyphenyl)ethane; N-glycidyl derivatives of amines such as N,N-diglycidylaniline, N,N-diglycidyltoluidine, and N,N,N',N'-tetraglycidyl-bis-(p-aminophenyl)methane; triglycidyl derivatives of aminophenols; triglycidyl tris(2-hydroxyethyl)isocyanurate; triglycidyl isocyanurate; and epoxy resins such as orthocresol epoxy resins and phenol novolac epoxy resins.

[0083] The amount of hydrolysis inhibitor added is not particularly limited, but is preferably at least 0.1 part by mass, more preferably at least 0.2 part by mass, and particularly preferably at least 0.5 part by mass, and is preferably at most 5 parts by mass, more preferably at most 4.5 parts by mass, and particularly preferably at most 3 parts by mass, per 100 parts by mass of the hydroxyl group-terminated urethane prepolymer.

[0084] -Antioxidants- As the antioxidant, those previously mentioned can be used, and the preferred examples and amounts added are also as previously mentioned.

[0085] -Ultraviolet absorber- Examples of ultraviolet absorbers include benzophenone compounds, benzotriazole compounds, salicylic acid compounds, oxalic acid anilide compounds, cyanoacrylate compounds, triazine compounds, etc. The ultraviolet absorbers may be used alone or in combination of two or more. The amount of ultraviolet absorber added is not particularly limited, but is preferably at least 0.01 part by mass, more preferably at least 0.1 part by mass, and particularly preferably at least 0.2 part by mass, relative to 100 parts by mass of the hydroxyl group-terminated urethane prepolymer, and is preferably at most 3 parts by mass, more preferably at most 2.5 parts by mass, and particularly preferably at most 2 parts by mass.

[0086] -Light stabilizer- Examples of the light stabilizer include hindered amine compounds, hindered piperidine compounds, etc. The light stabilizers may be used alone or in combination of two or more. The amount of the light stabilizer to be added is not particularly limited, but is preferably at least 0.01 part by mass, more preferably at least 0.1 part by mass, and particularly preferably at least 0.2 part by mass, relative to 100 parts by mass of the hydroxyl group-terminated urethane prepolymer, and is preferably at most 2 parts by mass, more preferably at most 1.5 parts by mass, and particularly preferably at most 1 part by mass.

[0087] -Antistatic agent- Examples of the antistatic agent include inorganic salts, polyhydric alcohol compounds, ionic liquids, surfactants, etc. The antistatic agents may be used alone or in combination of two or more. Among these, ionic liquids are preferred. Note that "ionic liquids" are also called room temperature molten salts, and are salts that are fluid at 25°C.

[0088] --Inorganic salts-- 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.

[0089] --Polyhydric alcohol compounds-- Examples of polyhydric alcohol compounds include propanediol, butanediol, hexanediol, polyethylene glycol, trimethylolpropane, and pentaerythritol.

[0090] --Ionic Liquids-- Examples of ionic liquids include ionic liquids containing imidazolium ions such as 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1,3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide, and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide; 1-methylpyridinium bis(trifluoromethylsulfonyl)imide, 1-butylpyridinium bis(trifluoromethylsulfonyl)imide, 1-hexylpyridinium bis(trifluoromethylsulfonyl)imide, 1-octylpyridinium bis(trifluoromethylsulfonyl)imide, 1-hexyl-4-methylpyridinium bis(trifluoromethylsulfonyl)imide, 1-hexyl-4-methylpyridinium hexafluorophosphate, 1-octyl-4-methylpyridinium bis(trifluoromethylsulfonyl)imide ... Examples of suitable ionic liquids include ionic liquids containing pyridinium ions, such as 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 bistrifluoromethanesulfonimide; and other ionic liquids, such as pyrrolidinium salts, phosphonium salts, and sulfonium salts.

[0091] --Surfactants-- Examples of surfactants include nonionic low-molecular-weight surfactants such as glycerin 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 betaines and alkyl imidazolium betaines; nonionic polymeric surfactants such as polyether ester amide types, ethylene oxide-epichlorohydrin types, and polyether ester types; anionic polymeric surfactants such as polystyrene sulfonate types; cationic polymeric surfactants such as quaternary ammonium base-containing acrylate polymer types; and amphoteric polymeric surfactants such as amino acid-type amphoteric surfactants such as higher alkylaminopropionates, and betaine-type amphoteric surfactants such as higher alkyl dimethyl betaines and higher alkyl dihydroxyethyl betaines.

[0092] The amount of antistatic agent added is not particularly limited, but is preferably 0.01 part by mass or more, more preferably 0.03 part by mass or more, and particularly preferably 0.05 part by mass or more, relative to 100 parts by mass of the hydroxyl group-terminated urethane prepolymer, and 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.

[0093] -Leveling agent- Examples of the leveling agent include acrylic leveling agents, fluorine-based leveling agents, silicone-based leveling agents, etc. The leveling agents may be used alone or in combination of two or more. Among these, acrylic leveling agents are preferred. The amount of the leveling agent added is not particularly limited, but is preferably at least 0.001 part by mass, more preferably at least 0.01 part by mass, and particularly preferably at least 0.1 part by mass, relative to 100 parts by mass of the hydroxyl group-terminated urethane prepolymer, and is preferably at most 2 parts by mass, more preferably at most 1.5 parts by mass, and particularly preferably at most 1 part by mass.

[0094] -Other optional ingredients- Other optional components include, for example, catalysts, resins other than urethane prepolymers, fillers (talc, calcium carbonate, titanium oxide, etc.), metal powders, colorants (pigments, etc.), foil-like materials, softeners, conductive agents, silane coupling agents, lubricants, corrosion inhibitors, heat stabilizers, weather stabilizers, polymerization inhibitors, and antifoaming agents.

[0095] (adhesive) The pressure-sensitive adhesive of the present invention is obtained by curing the pressure-sensitive adhesive composition of the present invention. The content ratio of oxyethylene groups relative to the total amount of oxyalkylene groups in the pressure-sensitive adhesive of the present invention is not particularly limited, but is preferably 10% by mass or more, more preferably 12% by mass or more, even more preferably 15% by mass or more, still more preferably 20% by mass or more, particularly preferably 25% by mass or more, and is 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. When the content ratio of oxyethylene groups relative to the total amount of oxyalkylene groups in the pressure-sensitive adhesive of the present invention is equal to or greater than the lower limit, adhesion to highly polar substrates is further improved, and moist heat resistance is likely to be improved. When the content ratio of oxyethylene groups relative to the total amount of oxyalkylene groups in the pressure-sensitive adhesive of the present invention is equal to or less than the upper limit, haze is likely to be suppressed and transparency is likely to be improved. The content ratio of oxyethylene groups to the total amount of oxyalkylene groups in the adhesive (ethylene oxide unit content) is: 1 It was calculated by determining the monomer composition of the oxyalkylene chain using H-NMR.

[0096] (adhesive material) The adhesive material of the present invention has a substrate and a pressure-sensitive adhesive layer provided on the surface of the substrate and containing the pressure-sensitive adhesive of the present invention. The adhesive patch of the present invention preferably has a pressure-sensitive adhesive layer provided on one surface of a base film, and a release liner or carrier film releasably laminated to cover the adhesive surface of the pressure-sensitive adhesive layer. The adhesive patch of the present invention is produced, for example, by applying an aqueous adhesive solution (aqueous adhesive dispersion) prepared by dissolving (dispersing) the adhesive of the present invention in water onto a support film using a coating applicator, drying the applied aqueous adhesive solution (aqueous adhesive dispersion) to form an adhesive layer, laminating a base film on the surface of the formed adhesive layer opposite the support film, and curing the layer. Here, in the above-mentioned method for producing an adhesive patch, instead of forming a pressure-sensitive adhesive layer on a carrier film and laminating a base film on the surface of the formed pressure-sensitive adhesive layer opposite the carrier film, a pressure-sensitive adhesive layer may be formed on a base film and a carrier film may be laminated on the surface of the formed pressure-sensitive adhesive layer opposite the base film.

[0097] The thickness of the 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 is 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 above-mentioned preferred range, the possibility of the patch breaking can be reduced. Examples of materials for the substrate film include urethane-based polymers such as polyether urethane and polyester urethane; amide-based polymers such as polyether polyamide block polymers; acrylic polymers such as polyacrylate; olefin-based polymers such as polyethylene, polypropylene, and ethylene / vinyl acetate copolymer; and ester-based polymers such as polyether polyester. Ester-based polymers are preferred as the material for the substrate film. The base film material may be one material alone or a combination of two or more materials. Furthermore, a laminated film may be formed by laminating base films made from different materials. The base film may be laminated with a fabric such as a woven fabric, a nonwoven fabric, a knitted fabric, or a net. The thickness of the adhesive layer is not particularly limited, but is preferably 5 μm or more, more preferably 10 μm or more, and particularly preferably 20 μm or more, and is preferably 100 μm or less, more preferably 50 μm or less, and particularly preferably 30 μm or less. When the thickness of the adhesive layer is within this range, better adhesiveness can be obtained.

[0098] In order to prevent contamination of the surface of the adhesive layer of the adhesive material of the present invention, it is preferable that the surface of the adhesive layer is covered with a release liner or a carrier film until use. Specifically, the release liner can be one in which the surface of high-quality paper, glassine paper, parchment paper, or the like is coated with a release agent having release properties such as silicone resin or fluororesin; or one in which the surface of high-quality paper anchor-coated with resin or high-quality paper laminated with polyethylene is coated with a release agent having release properties such as silicone resin or fluororesin. The material of the carrier film is not particularly limited, but a plastic film such as a polyester film is preferred. The carrier film can be releasably laminated on the surface of the base film opposite to the surface on which the pressure-sensitive adhesive layer is formed. The carrier film can be releasably attached to the back surface of the base film by methods such as inflation molding, extrusion lamination molding, lamination molding, or casting. The thickness of the carrier film varies depending on the material, but is preferably 15 μm or more, more preferably 20 μm or more, and particularly preferably 30 μm or more, and is preferably 200 μm or less, more preferably 100 μm or less, and particularly preferably 50 μm or less.

[0099] (adhesive tape) The pressure-sensitive adhesive tape of the present invention has a substrate and a pressure-sensitive adhesive layer provided on at least one surface of the substrate and containing the pressure-sensitive adhesive of the present invention. In the pressure-sensitive adhesive tape of the present invention, the pressure-sensitive adhesive layer may be provided on only one surface of the substrate, or on both surfaces of the substrate.

[0100] One embodiment of the pressure-sensitive adhesive tape of the present invention preferably comprises a base film having a pressure-sensitive adhesive layer on one side thereof and a release liner or carrier film releasably laminated to cover the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer. This embodiment is particularly referred to as a single-sided pressure-sensitive adhesive tape. The base film, release liner and carrier film are the same as those in the patch of the present invention, and the thickness of the adhesive layer is the same as that of the adhesive layer in the patch of the present invention. The pressure-sensitive adhesive tape of the present invention can be produced in the same manner as the adhesive patch of the present invention.

[0101] Another embodiment of the pressure-sensitive adhesive tape of the present invention preferably has a base film having pressure-sensitive adhesive layers on both sides thereof, and a release liner or carrier film releasably laminated to cover the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer. This embodiment is particularly called a double-sided pressure-sensitive adhesive tape. The base film, release liner and carrier film are the same as those in the patch of the present invention, and the thickness of the adhesive layer is the same as that of the adhesive layer in the patch of the present invention.

[0102] In still another embodiment of the pressure-sensitive adhesive tape of the present invention, a pressure-sensitive adhesive layer is provided on one surface of a releasable substrate film, and a release liner or carrier film is preferably provided releasably covering the adhesive surface of the pressure-sensitive adhesive layer. This embodiment is particularly referred to as a pressure-sensitive adhesive transfer tape. The releasable substrate film is preferably a substrate film usable for the adhesive patch of the present invention, the surface of which is coated with a release agent having releasability, such as a silicone resin or a fluororesin. The release liner and carrier film are the same as those in the adhesive patch of the present invention. The thickness of the adhesive layer is the same as that of the adhesive layer in the adhesive patch of the present invention. [Example]

[0103] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. Synthesis Examples 1 to 5, 7 to 13, 15, and 16 are Working Synthesis Examples, and Synthesis Examples 6 and 14 are Comparative Synthesis Examples. Production Examples 1 to 9 and 15 to 22 are working production examples, and Production Examples 10 and 12 to 14 are comparative production examples. Examples 1 to 9 and 13 to 20 are working examples, and Examples 10 to 12 are comparative examples.

[0104] <Methods for measuring physical properties> [Hydroxyl value] The hydroxyl value of the oxyalkylene polymer A was calculated according to the titration method of JIS K 1557-1B:2007.

[0105] [Molecular weight Mn, Mw, Mw / Mn] The number average molecular weight Mn and molecular weight distribution Mw / Mn of the oxyalkylene polymer are values ​​obtained by measurement according to the methods described below. As standard samples for molecular weight measurement, several types of monodisperse polystyrenes with different degrees of polymerization were measured using a commercially available GPC measurement device (HLC-8320GPC, manufactured by Tosoh Corporation), and a calibration curve was created based on the relationship between the molecular weight of polystyrene and retention time.The oxyalkylene polymer sample was diluted to 0.5% by mass with tetrahydrofuran and passed through a 0.5 μm filter, and then the sample was measured using the GPC measurement device.Using the calibration curve, the GPC spectrum of the sample was analyzed by computer to determine the Mn and weight average molecular weight (hereinafter referred to as Mw) of the sample. The molecular weight distribution is a value calculated from the above Mw and Mn, and is the ratio of Mw to Mn (hereinafter sometimes referred to as "Mw / Mn"). Furthermore, the Mw of the hydroxyl-terminated urethane prepolymer was measured by GPC in the same manner as above.

[0106] [Unsaturation degree] The degree of unsaturation of the oxyalkylene polymer is a value measured according to the method of JIS-K1557-6.

[0107] [Oxyethylene group content (ethylene oxide unit (EO unit) content)] The content ratio of oxyethylene groups to the total amount of oxyalkylene groups in the oxyalkylene polymer, urethane prepolymer, and adhesive (ethylene oxide unit content) is: 1 It was calculated by determining the monomer composition of the oxyalkylene chain using H-NMR. For example, when the oxyalkylene polymer is a polyol composed of propylene oxide units and ethylene oxide units, the ethylene oxide unit content can be determined from the area ratio of the signal of the methyl group in the propylene oxide unit to the signals of the methylene groups in the propylene oxide unit and the ethylene oxide unit.

[0108] <Synthesis of oxyalkylene polymer> [Synthesis Example 1: Synthesis of Polymer A1] (Step a) As an initiator, a polyol (initiator A) was used, which was prepared by addition reaction of propylene oxide with glycerin using a KOH catalyst until the molecular weight reached 3,000. First, 1243 g of initiator A and a slurry of a hexacyanocobaltate complex (hereinafter also referred to as TBA-DMC catalyst) whose ligand is t-butanol were added to a pressure-resistant reactor to prepare a reaction solution. The amount of TBA-DMC catalyst slurry was adjusted so that the metal concentration of the TBA-DMC catalyst in the reaction solution was 50 ppm. Next, the atmosphere inside the pressure-resistant reactor was replaced with nitrogen, and the reaction solution was heated while stirring. When the temperature reached 140°C, heating was stopped, and while continuing to stir, 124 g of propylene oxide (10.0 parts by mass relative to 100 parts by mass of the initiator) was supplied into the pressure-resistant reactor and reacted. (Step b) After the temperature rise of the reaction solution stopped, the reaction solution was cooled to 140°C, and while stirring the reaction solution, a mixture of 1386 g of propylene oxide and 1386 g of ethylene oxide was fed into the pressure-resistant reactor. After the internal pressure stopped changing and it was confirmed that the reaction was completed, the catalyst was neutralized and removed using a synthetic adsorbent (Kyowado 600S, manufactured by Kyowa Chemical Industry Co., Ltd.), and polymer A1 was obtained. The number of hydroxyl groups, hydroxyl value, Mn, Mw / Mn, degree of unsaturation, and content of oxyethylene units (hereinafter referred to as "EO units") of the polymer A1 thus obtained are shown in Table 1-1. These values ​​were measured by the above-mentioned method. The values ​​of polymers A2 to A8 and B1 to B8 obtained in the following synthesis examples 2 to 14 are also shown in Table 1-1 and Table 1-2. In addition, the "number of hydroxyl groups" in Tables 1-1 and 1-2 indicates the number of hydroxyl groups (3 or 2) of the initiators (glycerin, propylene glycol) used in the synthesis of oxyalkylene polymers A and B, respectively, and these values ​​are the average number of hydroxyl groups of oxyalkylene polymers A and B.

[0109] [Synthesis Example 2: Synthesis of Polymer A2] Polymer A2 was synthesized in the same manner as in Synthesis Example 1, except that the amount of initiator A in (step a) was changed to 1232 g, and the mass of propylene oxide in (step b) was changed to 2043 g and the mass of ethylene oxide was changed to 703 g.

[0110] [Synthesis Example 3: Synthesis of Polymer A3] Polymer A3 was synthesized in the same manner as in Synthesis Example 1, except that the amount of initiator A in (step a) was changed to 1970 g, and the mass of propylene oxide and the mass of ethylene oxide in (step b) were changed to 2924 g and 2091 g, respectively.

[0111] [Synthesis Example 4: Synthesis of Polymer A4] Polymer A4 was synthesized in the same manner as in Synthesis Example 1, except that initiator A in (step a) was changed to a polyol (initiator B) obtained by addition reaction of ethylene oxide to glycerin until the content of EO units reached 80% by mass, the amount of initiator B was changed to 2100 g, and the mass of propylene oxide in (step b) was changed to 759 g and the mass of ethylene oxide was changed to 3036 g.

[0112] [Synthesis Example 5: Synthesis of Polymer A5] As an initiator, a polyol (initiator C) was used, which was prepared by addition reaction of propylene oxide with glycerin using a KOH catalyst until the molecular weight reached 1,300. Into a pressure-resistant reactor, 1106 g of initiator C, 12.6 g of KOH catalyst, 1494 g of propylene oxide, and 1400 g of ethylene oxide were added, and the mixture was stirred at 110°C for 1.5 hours to carry out ring-opening addition polymerization. After that, the catalyst was neutralized and removed using a synthetic adsorbent (Kyowad 600S, manufactured by Kyowa Chemical Industry Co., Ltd.), and polymer A5 was obtained.

[0113] [Synthesis Example 6: Synthesis of Polymer A6] Glycerin was used as the initiator. Into a pressure-resistant reactor, 119 g of glycerin, 25.3 g of KOH catalyst, 1576 g of propylene oxide, and 6305 g of ethylene oxide were added, and the mixture was stirred at 110°C for 1.5 hours to carry out ring-opening addition polymerization. After that, the catalyst was neutralized and removed using a synthetic adsorbent (Kyowad 600S, manufactured by Kyowa Chemical Industry Co., Ltd.), thereby obtaining polymer A6.

[0114] [Synthesis Example 7: Synthesis of Polymer A7] Polymer A7 was synthesized in the same manner as in Synthesis Example 1, except that the amount of initiator A in (step a) was changed to 743 g, and the mass of propylene oxide in (step b) was changed to 2291 g and the mass of ethylene oxide was changed to 966 g.

[0115] [Synthesis Example 8: Synthesis of Polymer A8] (Step a) As an initiator, a polyol (initiator D) was used, which was prepared by addition reaction of propylene oxide with glycerin using a KOH catalyst until the molecular weight reached 1,500. First, 1.4 g of zinc hexacyanocobaltate-glyme complex, which is a DMC catalyst, and 1,050 g of initiator D were added to a pressure-resistant reactor to form a reaction solution. After the atmosphere inside the pressure-resistant reactor was replaced with nitrogen, the reaction solution was heated to 140°C with stirring. Next, heating was stopped, and 105 g of propylene oxide (10.0 parts by mass relative to 100 parts by mass of the initiator) was fed into the pressure-resistant reactor and reacted with initiator D. (Step b) After the temperature rise of the reaction solution stopped, the pressure-resistant reactor was heated to 130°C under a nitrogen atmosphere, and 5110 g of propylene oxide was reacted for 5 hours to deactivate the catalyst. 22.1 g of KOH catalyst was then added, and dehydration treatment was carried out at 120°C for 2 hours. After alcoholation, 840 g of ethylene oxide was reacted, and the catalyst was neutralized and removed using a synthetic adsorbent (Kyowado 600S, manufactured by Kyowa Chemical Industry Co., Ltd.), yielding polymer A8 with ethylene oxide added to the terminal.

[0116] [Synthesis Example 9: Synthesis of Polymer B1] Polymer B1 was synthesized in the same manner as in Synthesis Example 1, except that initiator A in (step a) was changed to a polyol (initiator E) obtained by addition reaction of propylene oxide to propylene glycol until the molecular weight reached 2,000, the amount of initiator E was changed to 865 g, and the mass of propylene oxide in (step b) was changed to 1689 g and the mass of ethylene oxide was changed to 1689 g.

[0117] [Synthesis Example 10: Synthesis of Polymer B2] Polymer B2 was synthesized in the same manner as in Synthesis Example 9, except that the mass of initiator E in (step a) was changed to 800 g, and the masses of propylene oxide and ethylene oxide in (step b) were changed to 2494 g and 800 g, respectively.

[0118] [Synthesis Example 11: Synthesis of Polymer B3] Polymer B3 was synthesized in the same manner as in Synthesis Example 9, except that the mass of initiator E in (step a) was changed to 1310 g, and the masses of propylene oxide and ethylene oxide in (step b) were changed to 3684 g and 2079 g, respectively.

[0119] [Synthesis Example 12: Synthesis of Polymer B4] 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 reactor and stirred at 110°C for 1.5 hours to carry out ring-opening addition polymerization. The catalyst was then neutralized and removed using a synthetic adsorbent (Kyowad 600S, manufactured by Kyowa Chemical Industry Co., Ltd.), yielding Polymer B4.

[0120] [Synthesis Example 13: Synthesis of Polymer B5] The initiator used was a polyol (initiator F) prepared by addition reaction of propylene oxide with propylene glycol using a KOH catalyst until the molecular weight reached 400. 1200 g of initiator F and 18.9 g of KOH catalyst were added to a pressure-resistant reactor, and dehydration treatment was carried out at 120°C for 2 hours. After alcoholation, 2100 g of propylene oxide was reacted, followed by reaction with 2516 g of ethylene oxide. The catalyst was then neutralized and removed using a synthetic adsorbent (Kyowado 600S, manufactured by Kyowa Chemical Industry Co., Ltd.), yielding polymer B5 having ethylene oxide added to the terminal.

[0121] [Synthesis Example 14: Synthesis of Polymer B6] Polymer B6 was synthesized in the same manner as in Synthesis Example 8, except that initiator D in (step a) of Synthesis Example 8 was changed to 350 g of a polyol (initiator G) obtained by addition reaction of propylene oxide to propylene glycol until the molecular weight reached 700, the mass of the zinc hexacyanocobaltate-glyme complex was changed to 0.37 g, the mass of the KOH catalyst was changed to 6.3 g, and the mass of propylene oxide in (step b) was changed to 1490 g, and the mass of ethylene oxide was changed to 160 g.

[0122] [Synthesis Example 15: Synthesis of Polymer B7] Polymer B7 was synthesized in the same manner as in Synthesis Example 9, except that the mass of initiator E in (step a) was changed to 2800 g, and the masses of propylene oxide and ethylene oxide in (step b) were changed to 210 g and 3990 g, respectively.

[0123] [Synthesis Example 16: Synthesis of Polymer B8] Polymer B8 was synthesized in the same manner as in Synthesis Example 14, except that the mass of initiator G in (step a) of Synthesis Example 14 was changed to 461 g, the mass of zinc hexacyanocobaltate-glyme complex was changed to 0.40 g, and 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.

[0124] <Production Example 1> [Production of hydroxyl-terminated urethane prepolymer] 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 to a reaction vessel equipped with a thermometer, a stirrer, and a condenser. Next, 0.01 parts by mass of a urethane catalyst (dibutyltin dilaurate, manufactured by Tokyo Chemical Industry Co., Ltd.) and 1 part by mass of Irganox 1135 (manufactured by BASF) as an antioxidant were added and mixed at 40°C. After that, 1.05 parts by mass of hexamethylene diisocyanate (Duranate 50M, manufactured by Asahi Kasei Corporation, referred to as "HDI" in Table 2-1) as a diisocyanate compound was added and reacted at 70°C. The isocyanate index was 50. The reaction generated heat, the internal temperature rose to approximately 70°C, and the viscosity also increased over time. The mixture was stirred at 70°C for 3 hours, and after confirming the disappearance of the isocyanate groups by FT-IR, it was cooled to room temperature. After cooling, 335 parts by mass of water was added and the mixture was stirred for 3 hours while diluting, yielding a uniform, transparent solution containing a hydroxyl-terminated urethane prepolymer-containing aqueous dispersion (also referred to as "urethane prepolymer U1") with an average hydroxyl group number of 2.4 and a solids content of 23% by mass. Table 2-1 shows the EO unit content (% by mass), average hydroxyl group number, Mw, water solubility, and solids content (% by mass) of the resulting aqueous dispersion of the resulting urethane prepolymer U1. Table 2-1 also shows the results of the following production examples. In Tables 2-1 and 2-2, "Index" refers to the ratio of the number of moles of isocyanate groups in the diisocyanate compound to the total number of moles of hydroxyl groups in the oxyalkylene polymer used to produce the hydroxyl-terminated urethane prepolymer multiplied by 100 (isocyanate index). "EO unit content" refers to the proportion of oxyethylene groups (ethylene oxide unit content) (unit: mass%) relative to the total number of oxyalkylene groups in the hydroxyl-terminated urethane prepolymer. "Average number of hydroxyl groups" refers to the average number of hydroxyl groups per molecule of the hydroxyl-terminated urethane prepolymer calculated using the calculation method described below. "Water solubility" refers to the water solubility of the hydroxyl-terminated urethane prepolymer (solid content) evaluated using the evaluation method described below. In Tables 2-1 and 2-2, "-" indicates that the component was not included.

[0125] [Calculation of the average number of hydroxyl groups in urethane prepolymer] The "average number of hydroxyl groups f" of the urethane prepolymer was calculated by the following formula (I). 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)

[0126] [Evaluation of water solubility of urethane prepolymer] The water solubility of the urethane prepolymer (solid content) obtained in Production Example 1 was evaluated. The water solubility of the urethane prepolymer (solid content) was evaluated according to the following criteria. A: Dissolves in water at 25°C and becomes transparent. D: Insoluble in water at 25°C, causing haze, cloudiness, or residual residue.

[0127] <Manufacturing Examples 2-10, 12-22> Hydroxyl-terminated urethane prepolymers (also referred to as "urethane prepolymers U2-10, 12-22") were produced in the same manner as in Production Example 1, except that the blending amounts (parts by mass) were changed as shown in Tables 2-1 and 2-2. The index, EO unit content (% by mass), average number of hydroxyl groups, Mw, water solubility, and solids content (% by mass) of the resulting aqueous dispersions of the produced urethane prepolymers U2-10, 12-22 were measured, calculated, and evaluated in the same manner as in Production Example 1. The obtained results are shown in Tables 2-1 and 2-2. However, in Tables 2-1 and 2-2, "IPDI" represents "isophorone diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.)," "D101" represents "bifunctional isocyanate-terminated urethane prepolymer (manufactured by Asahi Kasei Corporation, Duranate D101)," "Irganox565" represents "2,6-di-t-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol (manufactured by BASF, Irganox565)," "BHT" represents "2,6-di-t-butyl-4-methylphenol," and "CBP-E" represents "emulsion of 2,2'-dihydroxy-3,3'-di(α-methylcyclohexyl)-5,5'-dimethyldiphenylmethane (manufactured by Seiko Chemical Co., Ltd., Nonflex CBP-E)."

[0128] <Example 1> [Adhesive manufacturing] As shown in Table 3, a pressure-sensitive adhesive composition was obtained by uniformly mixing 100 parts by mass of urethane prepolymer U1, 4.93 parts by mass of a curing agent (water-dispersible isocyanate, WR80-70P, manufactured by Asahi Kasei Corporation), and 0.005 parts by mass of a curing catalyst (Borchi Kat24, manufactured by Borchers GmbH). The resulting pressure-sensitive adhesive composition was then degassed and applied to a release-treated polyester film (support film, thickness 38 μm) using a knife coater to a dry film thickness of 25 μm, and then cured and dried at 100°C for 3 minutes to form a pressure-sensitive adhesive layer. A 38 μm-thick polyester film (substrate film) was laminated onto the obtained adhesive layer, and then the adhesive was stored in a hot air dryer at 50°C for 3 days to complete the crosslinking reaction of the adhesive layer, thereby producing a patch (adhesive tape) having an adhesive layer made of the adhesive. The coatability of the adhesive composition onto the carrier film was evaluated as follows. Furthermore, the adhesive in the adhesive layer of the obtained patch (adhesive tape) was measured and evaluated for EO unit content (mass%), adhesion to glass (adhesion to glass), and appearance (haze) using the methods described below. The content ratio of oxyethylene groups (ethylene oxide unit content) relative to the total amount of oxyalkylene groups per solid content in the obtained pressure-sensitive adhesive was 26% by mass. Table 3 shows the measurement and evaluation results of the content ratio of oxyethylene groups (EO unit content) (% by mass) relative to the total amount of oxyalkylene groups per solid content in the obtained pressure-sensitive adhesive, the coatability of the obtained pressure-sensitive adhesive composition, the adhesive strength to glass of the obtained pressure-sensitive adhesive, and the appearance (haze) of the obtained pressure-sensitive adhesive. In Table 3, "AQ-140" refers to "water-dispersible isocyanate (manufactured by Tosoh Corporation, Aquanate 140)."

[0129] [Coatability] The pressure-sensitive adhesive composition obtained was degassed as described above, and then coated onto a support film using a knife coater, and the coatability was evaluated according to the following criteria. A: No repelling and a clean coating film can be obtained. D: Repelling occurs and a clean coating film cannot be obtained.

[0130] [Adhesion to glass (glass adhesion)] The adhesive material (adhesive tape) was cut into a 25 mm width to prepare a test piece. The support film was peeled off from this test piece, and the resulting adhesive layer was applied to a float glass in an atmosphere of 25°C. Next, in accordance with the test method described in "10. Adhesion Strength" of the JIS Z 0237:2009 Test Methods for Adhesive Tapes and Adhesive Sheets, a 2 kg rubber roll was moved back and forth once at a speed of 300 mm / min to press the adhesive layer of the test piece onto the float glass, and after leaving it for 20 minutes, the peel strength of the pressed test piece was measured at a peel angle of 180 degrees and a peel speed of 300 mm / min. The adhesive strength to glass was evaluated according to the following evaluation criteria. The column "Adhesion strength to glass" in Table 3 shows the evaluation results of the measured adhesive strength to glass. A: 0.01N / 25mm or more and less than 0.1N / 25mm D: 0.1N / 25mm or more or less than 0.01N / 25mm

[0131] [Appearance of adhesive (haze)] The haze of the adhesive in the adhesive layer obtained by peeling off the support film from the obtained adhesive tape was measured using a color and turbidity simultaneous measuring device (COH400, manufactured by Nippon Denshoku Industries Co., Ltd.). Haze was evaluated according to the following evaluation criteria. A haze value of less than 10% indicates good transparency. The "Haze" column in Table 3 shows the evaluation results of the measured haze. A: Less than 10% D...10% or more

[0132] <Example 2 to Example 20> Patches (adhesive tapes) were produced in the same manner as in Example 1, using the blending amounts (parts by mass) shown in Table 3. The adhesive in the adhesive layer of the obtained patch (adhesive tape) was measured and evaluated in the same manner as in Example 1 for the content ratio of oxyethylene groups (ethylene oxide unit content) (% by mass) relative to the total amount of oxyalkylene groups in the obtained adhesive, the coatability of the adhesive composition, the adhesive strength to glass of the obtained adhesive, and the haze of the obtained adhesive. The results obtained are shown in Table 3. In Table 3, "-" indicates that the component was not blended.

[0133] [Table 1-1]

[0134] [Table 1-2]

[0135] [Table 2-1]

[0136] [Table 2-2]

[0137] [Table 3]

[0138] As shown in Tables 2-1 and 2-2, in Production Examples 1 to 9 and 13 to 22, excellent results were obtained in the water solubility of the solid content of the aqueous dispersion. As shown in Table 3, in Examples 1 to 9 and 13 to 20, the adhesive compositions had excellent coatability, and the adhesive strength and transparency of the adhesives were also excellent. In contrast to this, in Examples 10 to 12, the adhesive composition did not have excellent coatability, and the adhesive strength and transparency of the adhesive were not excellent. [Industrial Applicability]

[0139] The pressure-sensitive adhesive obtained by the present invention is suitably used as a pressure-sensitive adhesive for surface protection films that protect the surfaces of flat panel displays (liquid crystal displays, organic electroluminescence displays, etc.) and touch panel displays that are widely used in electronic devices such as televisions, personal computers (PCs), mobile phones, and mobile terminals, as well as substrates (glass substrates, ITO / glass substrates in which an ITO (indium tin oxide) film is formed on a glass substrate, etc.) and optical components produced or used in the production process of these displays.

Claims

1. An aqueous dispersion comprising a hydroxyl-terminated urethane prepolymer obtained by reacting an oxyalkylene polymer A having an average number of hydroxyl groups per molecule of more than 2.0 and not more than 3.0, an oxyalkylene polymer B having an average number of hydroxyl groups per molecule of 1.2 or more and not more than 2.0, and a diisocyanate compound, the oxyalkylene polymer A has an oxyethylene group content of 22 to 77 mass% relative to the total amount of oxyalkylene groups; the content ratio of oxyethylene groups in the oxyalkylene polymer B is 15 to 95 mass% relative to the total amount of oxyalkylene groups; the hydroxyl group-terminated urethane prepolymer has an oxyethylene group content of more than 20% by mass and not more than 70% by mass relative to the total amount of oxyalkylene groups; the oxyalkylene polymer A contains an oxyalkylene polymer having three hydroxyl groups, and the oxyalkylene polymer B contains an oxyalkylene polymer having two hydroxyl groups, the oxyalkylene polymer A contains ethylene oxide units and propylene oxide units, the oxyalkylene polymer B contains ethylene oxide units and propylene oxide units, the mass ratio of the oxyalkylene polymer A to the oxyalkylene polymer B is 24:76 to 60:40; The aqueous dispersion has an oxyethylene group content of 30 to 51 mass % relative to the total amount of oxyalkylene groups in the hydroxyl group-terminated urethane prepolymer.

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

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

4. The aqueous dispersion according to any one of claims 1 to 3, wherein the weight average molecular weight of the hydroxyl group-terminated urethane prepolymer is 10,000 or more and 250,000 or less.

5. 5. The aqueous dispersion according to claim 1, wherein the average number of hydroxyl groups in the hydroxyl-terminated urethane prepolymer is 1.7 or more and less than 3.

0.

6. A pressure-sensitive adhesive composition comprising the aqueous dispersion according to any one of claims 1 to 5 and a polyisocyanate compound having three or more isocyanate groups in one molecule.

7. The pressure-sensitive adhesive composition according to claim 6 , wherein the polyisocyanate compound having three or more isocyanate groups in one molecule is water-dispersible.

8. further comprising a catalyst; 8. The pressure-sensitive adhesive composition according to claim 6, wherein the content of the catalyst is 0.001 parts by mass or more and 0.10 parts by mass or less relative to 100 parts by mass of the total of the hydroxyl group-terminated urethane prepolymer and the polyisocyanate compound having three or more isocyanate groups per molecule.

9. A pressure-sensitive adhesive obtained by curing the pressure-sensitive adhesive composition according to claim 7 or 8.

10. The pressure-sensitive adhesive according to claim 9, wherein the content of oxyethylene groups relative to the total amount of oxyalkylene groups in the pressure-sensitive adhesive is 30 to 51 mass %.

11. A patch comprising a substrate and a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive according to claim 9 or 10, provided on at least one surface of the substrate.

12. An adhesive tape comprising a substrate and an adhesive layer provided on at least one surface of the substrate, the adhesive layer comprising the adhesive according to claim 9 or 10.

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