Aqueous dispersion composition

Abstract

To provide an aqueous dispersion composition of a polyester block copolymer having relatively high viscosity.SOLUTION: There is provided an aqueous dispersion composition comprising: (A) a polyester block copolymer; (B) a polymer containing structural units derived from a (meth)acrylic acid; (C) a surfactant; and (D) an aqueous medium, wherein the polymer (B) is made from a polymer whose storage modulus (G') at an angular frequency of 0.1 rad / s, measured under the following conditions, is 10 to 1000 Pa. [Measurement condition: for a neutralized aqueous solution with a degree of neutralization of 70% containing 1.0 mass% of polymer (B), strain in subsequent frequency dispersion is determined to be 0.1% or 1% by measurement of the storage modulus in strain dispersion at a liquid temperature of 25°C and a frequency of a rheometer of 1 Hz, the storage modulus in the frequency dispersion obtained by changing the angular frequency from 0.1 to 300 rad / s is measured under the strain condition, and the storage modulus (G') at the angular frequency of 0.1 rad / s is determined.].SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to aqueous dispersion compositions of polymers, and more particularly to aqueous dispersion compositions containing polyester block copolymers. [Background technology]

[0002] Polyester block copolymers are used in a variety of applications, such as coating agents, adhesives, binders, heat-sealing agents, modifiers for emulsions and the like, and fiber sizing agents. When used in the applications listed here, it is particularly preferred that they be used as aqueous dispersion compositions. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 58-052366 [Patent Document 2] Japanese Patent Application Publication No. 09-227118 [Patent Document 3] Japanese Patent Application Publication No. 08-253570 [Patent Document 4] International Publication No. 2016 / 068206 [Patent Document 5] Japanese Patent Application Publication No. 2018-135417 [Patent Document 6] International Publication No. 2008 / 020520 Summary of the Invention [Problem to be solved by the invention]

[0004] However, since the aqueous dispersion composition of the polyester block copolymer has a relatively low viscosity, a suitable resin composition (molded article) may not be formed on a substrate. An object of one aspect of the present disclosure is to provide an aqueous dispersion composition of a polyester block copolymer having a relatively high viscosity. [Means for solving the problem]

[0005] Aspects of the present disclosure include, for example, the subject matter described in the following sections: Section 1. (A) a polyester block copolymer, (B) a polymer containing a structural unit derived from (meth)acrylic acid, (C) a surfactant, and (D) an aqueous medium; An aqueous dispersion composition comprising: The polymer (B) has a storage modulus (G') of 10 to 1000 Pa at an angular frequency of 0.1 rad / s measured under the following conditions: Aqueous dispersion composition. [Measurement conditions: (B) For a neutralized aqueous solution containing 1.0% by mass of polymer and having a degree of neutralization of 70%, the storage modulus is measured by strain dispersion at a liquid temperature of 25°C and a rheometer frequency of 1 Hz. The strain in the subsequent frequency dispersion is determined to be 0.1% or 1%. Under the strain conditions, the angular frequency is varied from 0.1 to 300 rad / s, and the storage modulus is measured by frequency dispersion to determine the storage modulus (G') at an angular frequency of 0.1 rad / s.] Section 2. (A) a polyester block copolymer, (B) a polymer containing a structural unit derived from (meth)acrylic acid, (C) a surfactant, and (D) an aqueous medium; An aqueous dispersion composition comprising: An aqueous dispersion composition (preferably the aqueous dispersion composition described in item 1) having a storage modulus (G') of 10 to 300 Pa at an angular frequency of 0.1 rad / s measured under the following conditions: [Measurement conditions: The storage modulus is measured under strain dispersion with the liquid temperature set to 25°C and the rheometer frequency set to 1 Hz. The strain under frequency dispersion is then determined to be 0.1% or 1%. Under the strain conditions, the angular frequency is varied from 0.1 to 300 rad / s, and the storage modulus is measured under frequency dispersion to determine the storage modulus (G') at an angular frequency of 0.1 rad / s.] Section 3. (A) The polyester block copolymer contains a hard segment (a1) and a soft segment (a2), the hard segment (a1) is a segment containing at least one selected from the group consisting of a polybutylene terephthalate structure containing a structural unit derived from terephthalic acid and / or dimethyl terephthalate and a structural unit derived from 1,4-butanediol, and a polybutylene isophthalate structure containing a structural unit derived from isophthalic acid and / or dimethyl isophthalate and a structural unit derived from 1,4-butanediol; Item 1 or 2. The aqueous dispersion composition according to item 1 or 2. Section 4. The soft segment (a2) is a segment containing an aliphatic polyether structure and / or an aliphatic polyester structure. Item 4. The aqueous dispersion composition according to item 3. Section 5. Item 5. The aqueous dispersion composition according to any one of Items 1 to 4, wherein the surfactant (C) contains an ethylene oxide / propylene oxide copolymer. [Effects of the Invention]

[0006] According to one aspect of the present disclosure, there is provided an aqueous dispersion composition of a polyester block copolymer having a relatively high viscosity, which, even when applied to a liquid-absorbent substrate (e.g., a base fabric), inhibits absorption of the liquid and allows the composition to remain on the substrate, thereby enabling the formation of a suitable resin composition (molded article). [Brief explanation of the drawings]

[0007] [Figure 1] This is a schematic diagram for determining whether to use a strain value of 0.1% or 1% as a condition for measuring the G' value (storage modulus) of a solution or dispersion with a frequency dispersion of 0.1 rad / s (this is a conceptual diagram unrelated to the measurement results of the samples used in the examples). It shows that if the linear region obtained in strain dispersion measurement at 1 Hz includes a strain of 1%, 1% is selected; if it includes a strain of 0.1% but not 1%, 0.1% is selected. DETAILED DESCRIPTION OF THE INVENTION

[0008] Each embodiment included in the present disclosure will be described in more detail below. The present disclosure preferably includes an aqueous dispersion composition including (A) a polyester block copolymer, (B) a polymer including structural units derived from (meth)acrylic acid, (C) a surfactant, and (D) an aqueous medium, but is not limited thereto. The present disclosure includes all of the disclosures herein that are recognizable to a person skilled in the art.

[0009] The aqueous dispersion composition encompassed by the present disclosure may be referred to as the aqueous dispersion composition of the present disclosure.

[0010] The (A) polyester block copolymer is not particularly limited, but may be, for example, a block copolymer having a hard segment (a1) and a soft segment (a2). The hard segment (a1) may be, for example, a segment having an aromatic polyester structure. The soft segment (a2) may be, for example, a segment having an aliphatic polyether structure and / or an aliphatic polyester structure. The (A) polyester block copolymer is preferably a polyester elastomer.

[0011] The hard segment (a1) of the polyester block copolymer (A) may be, for example, a segment having a polyester structure formed mainly from an aromatic dicarboxylic acid or its ester-forming derivative and a diol or its ester-forming derivative, in which case the polyester structure contains structural units derived from the aromatic dicarboxylic acid or its ester-forming derivative and structural units derived from the diol or its ester-forming derivative.

[0012] Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, anthracene dicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenoxyethane dicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, 5-sulfoisophthalic acid, and sodium 3-sulfoisophthalate.

[0013] Examples of ester-forming derivatives of aromatic dicarboxylic acids include lower alkyl esters, aryl esters, carbonate esters, and acid halides.

[0014] The hard segment (a1) of the polyester block copolymer (A) preferably contains two or more structural units derived from the aromatic dicarboxylic acid and / or its ester-forming derivative, such as a combination of terephthalic acid and isophthalic acid, terephthalic acid and dodecanedioic acid, or terephthalic acid and dimer acid. By containing two or more structural units derived from an aromatic dicarboxylic acid and / or its ester-forming derivative, the crystallinity and melting point of the hard segment can be reduced, flexibility can be imparted, and thermal adhesion to other thermoplastic resins can be improved.

[0015] Specific examples of the diol preferably include diols having a molecular weight of 400 or less, for example, aliphatic diols such as 1,4-butanediol, ethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, and decamethylene glycol; alicyclic diols such as 1,1-cyclohexanedimethanol, 1,4-dicyclohexanedimethanol, and tricyclodecane dimethanol; and aromatic diols such as xylylene glycol, bis(p-hydroxy)diphenyl, bis(p-hydroxy)diphenylpropane, 2,2'-bis[4-(2-hydroxyethoxy)phenyl]propane, bis[4-(2-hydroxyethoxy)phenyl]sulfone, 1,1-bis[4-(2-hydroxyethoxy)phenyl]cyclohexane, 4,4'-dihydroxy-p-terphenyl, and 4,4'-dihydroxy-p-quaterphenyl, with aliphatic glycols having 2 to 10 carbon atoms and alicyclic diols having a 5- to 10-membered ring being preferred. Such diols may also be used in the form of ester-forming derivatives, such as acetylated forms and alkali metal salts, etc. Two or more of these diols and their derivatives may be used in combination.

[0016] As the hard segment (a1), a segment having a polybutylene terephthalate structure (i) derived from terephthalic acid and / or dimethyl terephthalate and 1,4-butanediol, a segment having a polybutylene isophthalate structure (ii) derived from isophthalic acid and / or dimethyl isophthalate and 1,4-butanediol, or a segment consisting of both (i) and (ii)) is preferably used, with a segment having both (i) and (ii) being more preferred. A particularly preferred example of the hard segment (a1) is a segment having a polybutylene terephthalate structure.

[0017] (i) can also be described as a polybutylene terephthalate structure containing structural units derived from terephthalic acid and / or dimethyl terephthalate and structural units derived from 1,4-butanediol, and (ii) can also be described as a polybutylene isophthalate structure containing structural units derived from isophthalic acid and / or dimethyl isophthalate and structural units derived from 1,4-butanediol.

[0018] The soft segment (a2) of the polyester block copolymer (A) used in the aqueous dispersion composition of the present disclosure may be, for example, a segment having an aliphatic polyether structure and / or an aliphatic polyester structure.

[0019] Examples of the aliphatic polyether having the aliphatic polyether structure include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, a copolymer of ethylene oxide and propylene oxide, an ethylene oxide addition polymer of polytetramethylene glycol, an ethylene oxide addition polymer of polypropylene glycol, and a copolymer glycol of ethylene oxide and tetrahydrofuran.

[0020] Examples of the aliphatic polyester having the aliphatic polyester structure include poly(ε-caprolactone), polyenantholactone, polycaprylolactone, polybutylene adipate, and polyethylene adipate.

[0021] Among these aliphatic polyether structures and / or aliphatic polyester structures, in view of the elastic properties of the resulting polyester block copolymer, preferred aliphatic polyethers having the aliphatic polyether structure include ethylene oxide addition polymers of polytetramethylene glycol, ethylene oxide addition polymers of polypropylene glycol, and copolymer glycols of ethylene oxide and tetrahydrofuran, while preferred aliphatic polyesters having the aliphatic polyester structure include poly(ε-caprolactone), polybutylene adipate, polyethylene adipate, etc. In other words, preferred aliphatic polyether structures include structures derived from ethylene oxide addition polymers of polytetramethylene glycol, structures derived from ethylene oxide addition polymers of polypropylene glycol, and structures derived from copolymer glycols of ethylene oxide and tetrahydrofuran, while preferred aliphatic polyester structures include structures derived from poly(ε-caprolactone), structures derived from polybutylene adipate, and structures derived from polyethylene adipate.

[0022] Among these, the aliphatic polyether having the aliphatic polyether structure is preferably an ethylene oxide addition polymer of polytetramethylene glycol or an ethylene oxide addition polymer of polypropylene glycol, and the aliphatic polyester having the aliphatic polyester structure is preferably a copolymer glycol of ethylene oxide and tetrahydrofuran.

[0023] The number average molecular weight of the aliphatic polyether structure and / or the aliphatic polyester structure is preferably about 300 to 6,000.

[0024] Although not particularly limited, the (A) polyester block copolymer preferably has a hard segment (a1) containing at least one structure selected from the group consisting of a polybutylene terephthalate structure containing structural units derived from terephthalic acid and / or dimethyl terephthalate and structural units derived from 1,4-butanediol, and a polybutylene isophthalate structure containing structural units derived from isophthalic acid and / or dimethyl isophthalate and structural units derived from 1,4-butanediol, and a soft segment (a2) containing an aliphatic polyether structure and / or an aliphatic polyester structure. It is more preferred that the soft segment (a2) contains at least one structure selected from the group consisting of a structure derived from an ethylene oxide addition polymer of polytetramethylene glycol, a structure derived from an ethylene oxide addition polymer of poly(propylene oxide) glycol, and a structure derived from a copolymer glycol of ethylene oxide and tetrahydrofuran.

[0025] The amount of the soft segment (a2) in the polyester block copolymer (A) used in the aqueous dispersion composition of the present disclosure is, for example, 20 to 95% by mass, preferably 25 to 90% by mass, relative to 100% by mass of the polyester block copolymer (A). The copolymerization ratio of (a1) to (a2) can be set within this range. For example, when the amount of (a2) is 20 to 95% by mass, the amount of (a1) is 80 to 5% by mass.

[0026] The melting point of the (A) polyester block copolymer used in the aqueous dispersion composition of the present disclosure is preferably 105°C to 225°C, and more preferably 125°C to 205°C.

[0027] In the present disclosure, the melting point of the (A) polyester block copolymer is a value determined as follows.

[0028] That is, 5 mg of the polyester block copolymer to be measured is measured in a differential scanning calorimeter (DSC) by (i) heating it from 30°C to 200°C at a rate of 10°C / min, followed by cooling it to -50°C, (ii) heating it from -50°C to 200°C and then cooling it to -50°C, and (iii) again heating it from -50°C to 200°C and then cooling it to 30°C. The melting point is the average of the endothermic peak temperatures obtained during the heating processes of (ii) and (iii).

[0029] An example of a differential scanning calorimeter (DSC) is DSC7020 (Hitachi High-Tech Science Corporation).

[0030] The polyester block copolymer (A) used in the aqueous dispersion composition of the present disclosure can be produced by a known method or a method that can be easily derived from a known method, and the production method is not particularly limited. Specific examples of the production method include a method of polycondensing an ester of an aromatic dicarboxylic acid or its ester-forming derivative with a diol or its ester-forming derivative with a monomer constituting an aliphatic polyether and / or an aliphatic polyester, preferably in the presence of a catalyst.

[0031] The polyester block copolymer (A) used in the aqueous dispersion composition of the present disclosure may be a commercially available product. Examples of commercially available products include Hytrel (registered trademark) 3001 (melting point = 161°C) manufactured by Toray Celanese Co., Ltd., Hytrel (registered trademark) 3046 (melting point = 160°C) manufactured by Toray Celanese Co., Ltd., and Hytrel (registered trademark) 4057N (melting point = 150°C) manufactured by Toray Celanese Co., Ltd. Other examples include Vylon (registered trademark) GM-915 (melting point = 139°C) manufactured by Toyobo MC Co., Ltd.

[0032] In the aqueous dispersion composition of the present disclosure, the (A) polyester block copolymer may be used alone or in combination of two or more.

[0033] The polymer (B) containing a structural unit derived from (meth)acrylic acid contained in the aqueous dispersion composition of the present disclosure is, in other words, a polymer obtained by polymerizing (meth)acrylic acid as a monomer. Here, (meth)acrylic acid refers to acrylic acid and / or methacrylic acid. The (meth)acrylic acid may be either acrylic acid or methacrylic acid, or a combination of both.

[0034] The ratio of acrylic acid-derived structural units to methacrylic acid-derived structural units contained in a polymer containing (meth)acrylic acid-derived structural units is not particularly limited and can be selected appropriately. That is, the molar ratio of acrylic acid-derived structural units to methacrylic acid-derived structural units can be 100:0 to 0:100, for example, 10:90 to 90:10, or 20:80 to 80:20. Most preferably, the ratio of acrylic acid-derived structural units to methacrylic acid-derived structural units is 100:0.

[0035] A polymer containing a structural unit derived from (meth)acrylic acid may contain structural units other than the structural unit derived from (meth)acrylic acid, as long as the effects of the present invention are not impaired. Examples of such structural units include structural units derived from α,β-unsaturated carboxylic acids such as crotonic acid, maleic acid, fumaric acid, and itaconic acid, as well as propylene, butene, isobutene, butadiene, isoprene, and styrene. When these structural units are contained, one type may be contained alone, or two or more types may be contained.

[0036] Although there are no particular limitations as long as the effects of the invention according to the present disclosure are not impaired, it is preferred that 80 mol % or more of all structural units of the polymer containing structural units derived from (meth)acrylic acid are structural units derived from (meth)acrylic acid, and more preferably 85, 90, 95, 96, 97, 98, or 99 mol % or more of structural units derived from (meth)acrylic acid, and more preferably 100 mol % of structural units derived from (meth)acrylic acid.

[0037] (B) The polymer containing a structural unit derived from (meth)acrylic acid is preferably a polymer having a storage modulus (G') of 10 to 1000 Pa at an angular frequency of 0.1 rad / s measured under the following conditions. Measurement conditions: For a neutralized aqueous solution containing 1.0% by mass of a polymer containing a structural unit derived from (meth)acrylic acid and having a degree of neutralization of 70%, the storage modulus is measured by strain dispersion at a liquid temperature of 25°C and a rheometer frequency of 1 Hz, and the strain in the subsequent frequency dispersion is determined to be 0.1% or 1%. Under the strain conditions, the angular frequency is changed from 0.1 to 300 rad / s, and the storage modulus is measured by frequency dispersion, and the storage modulus (G') at an angular frequency of 0.1 rad / s is calculated.

[0038] The neutralized aqueous solution containing 1.0 mass% of a polymer containing structural units derived from (meth)acrylic acid and having a degree of neutralization of 70% is not particularly limited, but can be prepared, for example, by preparing an aqueous solution containing an appropriate amount of the polymer, adding an aqueous alkali (e.g., NaOH) solution of an appropriate concentration to neutralize 70% of the carboxyl groups in the polymer, and then adding water as necessary. As can be seen from this, the degree of neutralization is the proportion of neutralized carboxyl groups among the carboxyl groups in the polymer.

[0039] As described above, the G' value (storage modulus) at an angular frequency of 0.1 rad / s under the above measurement conditions is preferably 10 to 1000 Pa. The upper and lower limits of this range are, for example, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670, 680, 690, 700, 710, 720, 730, 740, 750, 760, 770, 780, 790, 800, 810, 820, 830, 840, 850, 860, 870, 880, 890, 900, 910, 920, 930 The pressure may be 10, 520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670, 680, 690, 700, 710, 720, 730, 740, 750, 760, 770, 780, 790, 800, 810, 820, 830, 840, 850, 860, 870, 880, 890, 900, 910, 920, 930, 940, 950, 960, 970, 980, or 990 Pa. Preferably, the range is 20 to 900 Pa, or 30 to 800 Pa.

[0040] The G' value (storage modulus) at an angular frequency of 0.1 rad / s was measured using a rheometer (e.g., TA Instruments (Model: AR 2000ex)) at a measurement temperature of 25°C, a frequency of 0.1 to 300 rad / s, and a strain of 0.1% or 1% (selected within the linear range obtained in strain dispersion measurement at 1 Hz). Measuring frequency dispersion by "selecting within the linear range obtained in strain dispersion measurement at 1 Hz" means that if the linear range of strain dispersion includes 1%, the frequency dispersion is measured using 1% strain, and if the linear range of strain dispersion includes 0.1% strain but does not include 1%, the frequency dispersion is measured using 0.1% strain. A schematic diagram of the selection of the strain value is shown in Figure 1.

[0041] Furthermore, the higher the degree of crosslinking in a polymer containing structural units derived from (meth)acrylic acid, the higher the G' value (storage modulus) tends to be. Therefore, when it is necessary to adjust the G' value (storage modulus), for example, by appropriately adjusting the amount of crosslinking agent, a polymer containing structural units derived from (meth)acrylic acid that satisfies the above-mentioned G' value (storage modulus) range can be produced. Note that the crosslinking agent is not particularly limited, but examples thereof include compounds having two or more ethylenically unsaturated groups, more specifically sucrose allyl ether, pentaerythritol allyl ether (among which pentaerythritol triallyl ether and pentaerythritol tetraallyl ether are preferred), and the like.

[0042] The surfactant (C) used in the aqueous dispersion composition of the present disclosure is preferably a nonionic surfactant. Examples of nonionic surfactants include polyvinyl alcohol, modified polyvinyl alcohol, polyethylene glycol, ethylene oxide / propylene oxide copolymer, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl thioether, polyoxyethylene sorbitan fatty acid monoester, polyoxyethylene alkylamide, and polyglycerin ester. Among these, polyvinyl alcohol and ethylene oxide / propylene oxide copolymer are preferred from the viewpoints of emulsion stabilization ability and excellent heat resistance. Preferred polyvinyl alcohols include, for example, vinyl alcohol / vinyl acetate copolymers, which are usually soluble in water and have emulsion stabilization ability.

[0043] Polyvinyl alcohol is, for example, a polymer represented by the following formula (I). H(CHCH(OH)) j (CH2CH(OCOCH3)) k H (I) However, in the polymer represented by formula (I), (CH2CH(OH)) and (CH2CH(OCOCH3)) are randomly arranged.

[0044] In formula (I), j and k each represent the number of moles added, j representing an integer of, for example, 1 to 3000, and k representing an integer of, for example, 0 to 1000. These may be the same as or different from each other.

[0045] The degree of polymerization of polyvinyl alcohol is not particularly limited, but the degree of polymerization (in other words, the value of i+k) is preferably 300 to 3,000, and more preferably 500 to 2,500.

[0046] The degree of saponification of polyvinyl alcohol is not particularly limited, but is preferably 70 to 99 mol %, more preferably 85 to 95 mol %.

[0047] The ethylene oxide / propylene oxide copolymer is not particularly limited as long as it is within a range in which the desired effect can be obtained, and is, for example, a block copolymer represented by the following formula (II). HO(CH2CH2O) p (CH2CH(CH3)O) q (CH2CH2O) r H (II) In formula (II), p, q, and r each represent the number of moles added, where p represents an integer of, for example, 2 to 300, q represents an integer of, for example, 10 to 150, and r represents an integer of, for example, 2 to 300. These may be the same as or different from each other.

[0048] The mass average molecular weight of the ethylene oxide / propylene oxide copolymer is not particularly limited, but is, for example, 3000 to 30000, preferably 6000 to 25000, and particularly preferably 8000 to 20000. The content of ethylene oxide-derived monomer units in the ethylene oxide / propylene oxide copolymer is not particularly limited, but is, for example, 40 to 95% by mass, preferably 45 to 90% by mass, and particularly preferably 50 to 85% by mass, relative to 100% by mass of the ethylene oxide / propylene oxide copolymer.

[0049] The surfactant (C) is preferably solid at room temperature, and more preferably has a melting point of 50° C. or higher. Such properties can more effectively prevent the surfactant (C) from bleeding onto the surface of the molded article.

[0050] The surfactant (C) can be used alone or in combination of two or more. By including the surfactant (C), the aqueous dispersion composition of the present disclosure can preferably be in the form of an emulsion.

[0051] The aqueous medium (D) used in the aqueous dispersion composition of the present disclosure is preferably water. The water is not particularly limited, and for example, ion-exchanged water, distilled water, etc. can be used appropriately.

[0052] The content of the (A) polyester block copolymer in the aqueous dispersion composition of the present disclosure is not particularly limited as long as it is within a range that does not impair the effects of the present disclosure, and may be, for example, approximately 1 to 60% by mass. The upper or lower limit of this range may be, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, or 55% by mass. For example, the range may be 2 to 55%, 10 to 50%, 20 to 45%, or 25 to 40% by mass.

[0053] The content of the (B) polymer containing structural units derived from (meth)acrylic acid in the aqueous dispersion composition of the present disclosure varies depending on the type of component (B) used, but is not particularly limited as long as it does not impair the effects of the present invention. It is preferably 0.1 to 10 parts by mass per 100 parts by mass of the polyester block copolymer (A). The upper or lower limit of this range may be, for example, 0.2, 0.3, 0.4, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9, or 10 parts by mass. For example, the range is more preferably 0.2 to 8 parts by mass, and even more preferably 0.3 to 5 parts by mass. Furthermore, depending on the amount of the (A) polyester block copolymer, the content of the (B) polymer containing structural units derived from (meth)acrylic acid in the aqueous dispersion composition is preferably about 0.05 to 2% by mass, more preferably about 0.1 to 1% by mass.

[0054] The content of the (C) surfactant in the aqueous dispersion composition of the present disclosure is preferably 1 to 20 parts by mass relative to 100 parts by mass of the (A) polyester block copolymer. The upper or lower limit of this range may be, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, or 19 parts by mass. For example, the range is more preferably 3 to 12 parts by mass, and even more preferably 4 to 10 parts by mass.

[0055] The amount of the (D) aqueous medium used is not particularly limited, but is set to, for example, 50 to 1000 parts by mass, preferably 50 to 250 parts by mass, per 100 parts by mass of the (A) polyester block copolymer. By using the aqueous medium in such a range, an aqueous dispersion composition with good dispersion stability can be obtained. Furthermore, an aqueous dispersion composition with excellent productivity and practicality can be obtained.

[0056] The aqueous dispersion composition of the present disclosure may contain other components as needed, as long as the effects of the present invention are not impaired. Examples of such other components include polymeric dispersion stabilizers. Examples of polymeric dispersion stabilizers include ethylene / ethylenically unsaturated carboxylic acid copolymers, oxidized polyethylene wax, hydroxyethyl cellulose, methyl cellulose, hydroxypropyl cellulose, and sodium alginate. The use of a polymeric dispersion stabilizer facilitates emulsification, allowing for the production of a stable aqueous dispersion composition with smaller particle sizes.

[0057] When a polymer dispersion stabilizer is used, the amount used is not particularly limited, but is, for example, 0.1 to 10 parts by mass, and preferably 0.2 to 5 parts by mass, per 100 parts by mass of the polyester block copolymer (A).

[0058] Examples of other components include known molding aids such as crystal nucleating agents and lubricants, antioxidants, neutralizing agents, hydrolysis resistance improvers, colorants such as pigments and dyes, antistatic agents, conductive agents, flame retardants, reinforcing agents, inorganic fillers, bulking agents, plasticizers, and mold release agents.

[0059] In the aqueous dispersion composition of the present disclosure, the average particle size of the polyester block copolymer (A) is, for example, 0.1 to 20 μm, preferably 0.2 to 15 μm, and more preferably 0.3 to 12 μm. Having an average particle size within this range improves the static stability of the aqueous dispersion composition and provides a viscosity that is more suitable for handling, particularly for producing molded articles, thereby providing molded articles with superior mechanical properties. The average particle size is the volume-average median particle size measured by a laser diffraction particle size distribution analyzer.

[0060] The particle shape is not particularly limited, but spherical particles are preferred. Examples include spherical particles, ellipsoidal particles, and rod-shaped particles. Of these, spherical particles are particularly preferred. Spherical particles reduce the number of irregularly shaped particles with protrusions, thereby reducing the surface area of ​​the particles, and thus more preferably suppressing a significant increase in the viscosity of the aqueous dispersion composition.

[0061] The viscosity of the aqueous dispersion composition of the present disclosure is preferably about 1,000 to 10,000 mPa·s. The upper or lower limit of this range may be, for example, 1,500, 2,000, 2,500, 3,000, 3,500, 4,000, 4,500, 5,000, 5,500, 6,000, 6,500, 7,000, 7,500, 8,000, 8,500, 9,000, or 9,500 mPa·s. The range may be, for example, 2,000 to 9,000 mPa·s or 3,000 to 8,000 mPa·s.

[0062] In this specification, viscosity is measured by placing 50 g of the composition to be measured in a 100 mL beaker, measuring the viscosity at 25°C using a BH-type rotational viscometer (product name: DV-II+ (manufactured by Brookfield)) with rotor No. 3 at a rotor rotation speed of 60 rpm, and reading the value one minute after the rotor starts rotating.

[0063] The aqueous dispersion composition of the present disclosure is preferably an aqueous dispersion composition having a storage modulus (G') of 10 to 300 Pa at an angular frequency of 0.1 rad / s measured under the following conditions. Measurement conditions: For the aqueous dispersion composition, the storage modulus is measured by strain dispersion with the liquid temperature set to 25°C and the rheometer frequency set to 1 Hz, and the strain in the subsequent frequency dispersion is determined to be 0.1% or 1%. Under the strain conditions, the angular frequency is changed from 0.1 to 300 rad / s, and the storage modulus is measured by frequency dispersion, and the storage modulus (G') at an angular frequency of 0.1 rad / s is calculated.

[0064] The upper or lower limit of the preferable range (10 to 300 Pa) of storage modulus (G') may be, for example, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, or 290 Pa. Preferably, the range may be 15 to 250 Pa, or 20 to 200 Pa. The aqueous dispersion composition of the present disclosure contains components (A) to (D), and by adjusting the component (B) contained therein so that it satisfies the above-mentioned specific storage modulus (G') range, the tendency to satisfy the storage modulus (G') range is enhanced. Therefore, for example, by appropriately adjusting these conditions in particular, an aqueous dispersion composition satisfying the storage modulus (G') value can be prepared.

[0065] The G' value (storage modulus) at an angular frequency of 0.1 rad / s was measured using a rheometer (e.g., TA Instruments (Model: AR 2000ex)) under the following conditions: measurement temperature: 25°C, frequency: 0.1 to 300 rad / s, strain: 0.1% or 1% (selected within the linear region obtained in strain dispersion measurement at 1 Hz). Measuring frequency dispersion by "selecting within the linear region obtained in strain dispersion measurement at 1 Hz" means measuring frequency dispersion using 1% strain if the linear region of strain dispersion includes 1% strain, or 0.1% strain if the linear region of strain dispersion includes 0.1% strain but does not include 1% strain. As mentioned above, Figure 1 shows an overview of the selection of the strain value.

[0066] The present disclosure further provides a method for producing the aqueous dispersion composition of the present disclosure. The aqueous dispersion composition of the present disclosure can be produced, for example, by emulsifying and dispersing (A) a polyester block copolymer in (D) an aqueous medium in the presence of (C) a surfactant, and then adding (B) component thereto and stirring the mixture. More specifically, the aqueous dispersion composition of the present disclosure can be produced, for example, by the following method.

[0067] First, (A) polyester block copolymer, (C) surfactant, and (D) aqueous medium are charged into a reactor and mixed to prepare an emulsion (aqueous dispersion composition), followed by adding and mixing component (B).

[0068] When component (B) is added, it is preferable to add a neutralizing agent at the same time. Alternatively, a neutralizing solution for component (B) may be prepared in advance and then added.

[0069] The neutralizing agent is preferably ammonia or an organic amine. Examples of organic amines include diisopropanolamine, 2-amino-2-methyl-1-propanol, and triethanolamine. Alkali metal hydroxides, organic acid salts, and inorganic acid salts can also be used as neutralizing agents. Examples of preferred alkali metal hydroxides include sodium hydroxide and potassium hydroxide. Examples of organic acid salts include known organic acid salts used in the field of topical compositions (particularly cosmetic compositions). Specific examples include citrates, lactates, and acetates. Examples of inorganic acid salts include known inorganic acid salts used in the field of topical compositions (particularly cosmetic compositions). Specific examples include phosphates. Examples of organic acid salts and inorganic acid salts include metal salts, more preferably alkali metal salts or alkaline earth metal salts. More specific examples include sodium salts, potassium salts, magnesium salts, and calcium salts. Examples of preferred organic acid salts and inorganic acid salts include sodium citrate, potassium citrate, sodium lactate, potassium lactate, sodium acetate, potassium acetate, sodium phosphate, and potassium phosphate. Such neutralizing agents can be used singly or in combination of two or more.

[0070] When a neutralizing agent is added when component (B) is added, the neutralizing agent preferably results in a degree of neutralization (%) of component (B) of about 5 to 95. The upper or lower limit of this range may be, for example, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90. For example, the range may be 10 to 85.

[0071] The apparatus used for emulsification is preferably an apparatus equipped with a heating means capable of heating to a temperature equal to or higher than the melting point of the (A) polyester block copolymer or lower than the melting point of the (A) polyester block copolymer, and a stirring means capable of applying shear force to the contents, such as a pressure-resistant autoclave equipped with a stirrer, a twin-screw extruder, or a kneader, with a twin-screw extruder being particularly preferred.

[0072] Next, each component is stirred (preferably heated) to emulsify. Then, component (B) is added and mixed to obtain the desired aqueous dispersion composition of polyester block copolymer (A). The method for applying heat to polyester block copolymer (A) is not particularly limited. Heat can be applied by heating using a heater or the like, or by applying strong mechanical shear force. The heating temperature is not particularly limited. However, in order to reduce the thermal history of polyester block copolymer (A), emulsification is performed, for example, at a temperature between 40°C lower and 100°C higher than the melting point of polyester block copolymer (A). Preferably, emulsification is performed at a temperature between 30°C lower and 60°C higher than the melting point of polyester block copolymer (A). Specifically, emulsification is performed, for example, in the range of 65°C to 325°C. In the present invention, emulsification at a temperature lower than the melting point can suppress decomposition of polyester block copolymer (A) due to thermal history.

[0073] By appropriately adjusting the rotation speed, stirring time, temperature, etc. during stirring, the average particle size of the polyester block copolymer (A) can be set to, for example, within the range of 0.1 to 20 μm. When preparing an aqueous dispersion composition that also contains the other components (e.g., polymer dispersion stabilizers), the method for adding the other components is not particularly limited. For example, the other components may be added when preparing a mixed solution of (A), (C), and (D), or may be added together with the addition of (B).

[0074] A molded article can be produced using the aqueous dispersion composition of the present disclosure. The method for producing a molded article is not particularly limited, but includes, for example, a step of applying the aqueous dispersion composition of the present disclosure to a substrate or pouring it into a mold, and a step of drying the applied or poured aqueous dispersion composition (i.e., removing the aqueous medium). A molded article in various forms, such as a coating, film, or sheet, containing (A) to (C) can be obtained by a molded article production method including such steps.

[0075] The substrate used to produce the molded article is not particularly limited, but may be made from, for example, metals such as aluminum and copper, glass, wood, rubber, thermoplastic resins, thermosetting resins, or resins reinforced with reinforcing fibers or fillers. The thickness and shape of the substrate are also not particularly limited. The method for applying the aqueous dispersion composition of the present disclosure to the substrate is not particularly limited, but examples include application methods using a brush, spatula, roller, or caulking gun, as well as application methods using an air spray, nozzle spray, roll coater, or bead. The amount of application to the substrate can be appropriately determined depending on the purpose. For example, the aqueous dispersion composition of the present disclosure is applied to a thickness of 0.001 mm to 5 mm. The method for pouring the aqueous dispersion composition into a mold is not particularly limited. The aqueous dispersion composition is applied to the substrate or poured into a mold, and then the water is removed. The drying temperature in the water removal step is not particularly limited, but is typically set to 40 to 300°C. The drying time is not particularly limited, and is, for example, 0.2 to 2 hours when drying at 100°C.

[0076] The molded article thus obtained (a molded article obtained by applying the composition to a substrate and drying it) can be combined with another substrate and heated, for example, using a hot press at 120 to 300°C, optionally under pressure of 0.1 to 100 MPa, for 1 to 500 seconds to produce a molded article in which the substrates are bonded in layers. The substrates to be bonded may be of different types or the same type.

[0077] As described in International Publication No. 2008 / 020520, aqueous polymer dispersion compositions can be used in a wide range of applications, including as materials for producing packaging films, automotive parts, sports-related products, medical devices, etc.; coating agents for nylon fibers and polyester fibers used in clothing materials, carpets, airbags, etc.; coating agents and gas barrier agents for paper and films; raw materials for foam rubber; sizing agents for fibrous materials such as synthetic fibers, natural fibers, and glass fibers; and raw materials for producing hoses, tubes, belts, gaskets, packing, etc. The aqueous dispersion composition of the present disclosure can also be used in a similar wide range of applications. The aqueous dispersion composition of the present disclosure can also be used as an adhesive.

[0078] It should be noted that in this specification, the term "comprising" includes "consisting essentially of" and "consisting of." Furthermore, the present disclosure encompasses all arbitrary combinations of the constituent elements described in this specification.

[0079] Furthermore, the various characteristics (properties, structures, functions, etc.) described in each embodiment of the present disclosure above may be combined in any way to specify the subject matter encompassed by the present disclosure, i.e., the present disclosure encompasses all subject matter consisting of any combination of the combinable characteristics described herein. [Example]

[0080] Hereinafter, the embodiments of the present disclosure will be described more specifically with reference to examples, but the embodiments of the present disclosure are not limited to the following examples. Preparation of aqueous dispersion composition [Manufacturing Example 1] A hopper was installed at the upstream end of a twin-screw extruder (model: MFU15 (manufactured by Technovel Co., Ltd.), shaft diameter: 15 mm, L / D: 90). A polyester block copolymer (product name: Hytrel 3001 (manufactured by Toray Celanese Co., Ltd.)) was added to the hopper at a rate of 3 kg / hr, an antioxidant (product name: Irganox 259 (manufactured by BASF Japan)) was added at a rate of 0.12 kg / hr, and an ethylene oxide-propylene oxide copolymer (product name: Newpol PE108 (manufactured by Sanyo Chemical Industries, Ltd.)) was added at a rate of 0.17 kg / hr. After melt-kneading at a cylinder temperature of 180 °C and a rotation speed of 750 rpm, a 14% by weight aqueous solution of ethylene oxide-propylene oxide copolymer (product name: Newpol PE108) was added at a rate of 0.96 kg / hr using a plunger pump from a second feed port located 315 mm from the upstream end of the twin-screw extruder. The twin-screw extruder was kneaded and emulsified from the upstream end to a third feed port located 1175 mm from the extruder's tip at a cylinder temperature of 150°C, a rotation speed of 750 rpm, and a solids concentration (total of polyester block copolymer, ethylene oxide-propylene oxide copolymer, and antioxidant) of 81% by mass. Pure water was fed into the third feed port at 3.89 kg / hr using a plunger pump. Mixing was continued from the third feed port to the twin-screw extruder outlet at a cylinder temperature of 90°C and a rotation speed of 750 rpm. The resulting mixture was then discharged from the twin-screw extruder to obtain an aqueous polyester block copolymer dispersion composition. Hereinafter, this aqueous polyester block copolymer dispersion is referred to as the aqueous dispersion composition of Production Example 1.

[0081] The concentration of the polyester block copolymer in the resulting aqueous dispersion composition can be calculated from the addition rates of each component. In this example, the addition rate of the polyester block copolymer was 3 kg / hr, the addition rate of the antioxidant was 0.12 kg / hr, the addition rate of the ethylene oxide-propylene oxide copolymer was 0.17 kg / hr, the addition rate of the ethylene oxide-propylene oxide copolymer (14% by mass aqueous solution) was 0.96 kg / hr, and the addition rate of the pure water was 3.89 kg / hr. Therefore, the total amount is 3 + 0.12 + 0.17 + 0.96 + 3.89 = 8.14 (kg / hr), and therefore the concentration of the polyester block copolymer is 3 / 8.14 ≒ 36.9% by mass. [Manufacturing Example 2] A polyester block copolymer aqueous dispersion composition was obtained by the same procedure as in Production Example 1, except that Hytrel 3046 (manufactured by Toray Celanese Co., Ltd.) was used as the polyester block copolymer and Newpol PE128 (manufactured by Sanyo Chemical Industries, Ltd.) was used as the ethylene oxide-propylene oxide copolymer. Hereinafter, this polyester block copolymer aqueous dispersion composition is referred to as Production Example 2 aqueous dispersion composition. [Manufacturing Example 3] A polyester block copolymer aqueous dispersion composition was obtained by the same procedure as in Production Example 1, except that Hytrel 4057N (manufactured by Toray Celanese Co., Ltd.) was used as the polyester block copolymer and Newpol PE128 (manufactured by Sanyo Chemical Industries, Ltd.) was used as the ethylene oxide-propylene oxide copolymer. Hereinafter, this polyester block copolymer aqueous dispersion composition is referred to as Production Example 3 aqueous dispersion composition. [Manufacturing Example 4] A polyester block copolymer aqueous dispersion composition was obtained by the same procedure as in Production Example 1, except that Vylon GM-915 (manufactured by Toyobo MC Co., Ltd.) was used as the polyester block copolymer. Hereinafter, this polyester block copolymer aqueous dispersion composition is referred to as Production Example 4 aqueous dispersion composition.

[0082] The polyester block copolymers used, namely Hytrel 3001, Hytrel 3046, Hytrel 4057N, and Vylon GM-915, all have hard and soft segments, with the hard segments having a polybutylene terephthalate structure and the soft segments having an aliphatic polyether structure and / or an aliphatic polyester structure. All of the polyester block copolymers used are polyester elastomers.

[0083] Examples and Comparative Examples Example 1 Preparation Example 1 25 g of the aqueous dispersion composition and 75 g of pure water were placed in a 200 mL beaker, and 7.5 g of a 2 mass % aqueous solution of polyacrylic acid (storage modulus (G') = 723 Pa s) and 0.1 g of a 28 mass % aqueous ammonia solution were added as the components to be investigated. The mixture was stirred at 500 rpm for 30 minutes using a stirrer with four 7 cm diameter paddle blades to obtain the final aqueous dispersion composition. Example 2 The same procedure as in Example 1 was carried out except that 25 g of the aqueous dispersion composition of Preparation Example 2 was used as the aqueous dispersion composition, to obtain a final aqueous dispersion composition. Example 3 The same procedure as in Example 1 was carried out except that 25 g of the aqueous dispersion composition of Production Example 3 was used as the aqueous dispersion composition, to obtain a final aqueous dispersion composition. Example 4 The same procedure as in Example 1 was carried out except that 25 g of the aqueous dispersion composition of Production Example 4 was used as the aqueous dispersion composition, to obtain a final aqueous dispersion composition. Example 5 The same procedure as in Example 1 was carried out except that 12.8 g of a 2 mass % aqueous solution of polyacrylic acid (storage modulus (G') = 52 Pa·s) was used as the component to be examined, to obtain a final aqueous dispersion composition. (Comparative Example 1) The aqueous dispersion composition of Production Example 1 was used as the final aqueous dispersion composition without adding any of the components to be investigated, and various evaluations were carried out. (Comparative Example 2) The same procedure as in Example 1 was carried out except that 7.5 g of a 2 mass % aqueous solution of polyacrylic acid (storage modulus (G') = 0.41 Pa·s) was used as the component to be examined, to obtain a final aqueous dispersion composition. (Comparative Example 3) Preparation Example 1: 25 g of the aqueous dispersion composition and 72.3 g of pure water were placed in a 200 mL beaker, and 2.7 g of a 4 mass % aqueous solution of hydroxyethyl cellulose (storage modulus (G') = 2.5 Pa s) as the component to be investigated was added. The mixture was stirred at 500 rpm for 30 minutes using a stirrer with four 7 cm diameter paddle blades to obtain the final aqueous dispersion composition. Comparative Example 4 Preparation Example 1: 25 g of the aqueous dispersion composition and 75 g of pure water were placed in a 200 mL beaker, and 0.11 g of polyethylene oxide (storage modulus (G') = 0.03 Pa s) was added as the component to be investigated. The mixture was stirred at 500 rpm for 30 minutes using a stirrer equipped with four paddle blades with a diameter of 7 cm to obtain the final aqueous dispersion composition. (Comparative Example 5) Preparation Example 1: 50 g of the aqueous dispersion composition and 50 g of pure water were placed in a 200 mL beaker, and 11.4 g of a 2 mass % aqueous solution of polyurethane (storage modulus (G') = 2.5 Pa s) as the component to be investigated was added. The mixture was stirred at 500 rpm for 30 minutes using a stirrer with four 7 cm diameter paddle blades to obtain the final aqueous dispersion composition.

[0084] [viscosity] The viscosity of the aqueous dispersion composition was measured in accordance with JIS Z 8803. Specifically, 50 g of the aqueous dispersion composition was placed in a 100 mL beaker and immersed in a constant temperature water bath maintained at 25°C. The viscosity was measured using a BH-type rotational viscometer (product name: DV-II+ (manufactured by Brookfield)) with rotor No. 3 at a spindle rotor rotation speed of 60 rpm, and the viscosity was read one minute after the rotor started rotating.

[0085] [Storage modulus of the component under consideration] 1)-1<Preparation of neutralized aqueous solution for measurement (in the case of polymers containing structural units derived from (meth)acrylic acid)> 99 g of pure water was placed in a 200 mL plastic beaker, and 1 g of each component under investigation was added while stirring at 500 rpm using a stirrer with four 5 cm diameter paddles. After 60 minutes of stirring, 0.05 g of a 28% by mass aqueous ammonia solution was added to achieve a degree of neutralization of 70%. Stirring was continued for 15 minutes at 500 rpm to prepare a 1.0% by mass neutralized aqueous solution of each component under investigation.

[0086] 1)-2<Preparation of aqueous solution for measurement (for components other than polymers containing structural units derived from (meth)acrylic acid)> 99 g of pure water was placed in a 200 mL plastic beaker, and while stirring at 500 rpm using a stirrer with four 5 cm diameter paddles, 1 g of each component was gradually added. Stirring was continued at 500 rpm for 3 hours to prepare a 1.0 mass % aqueous solution of each component.

[0087] 2) <Determination of strain by strain distribution> The temperature of the 1.0% by mass aqueous solutions of each component obtained in 1)-1 and 1)-2 above was brought to 25°C, and the frequency of a rheometer (TA Instruments, model number: AR-2000ex) was set to 1 Hz. The storage modulus (G') was measured while applying strain, and the measurement was terminated when a decrease in storage modulus (G') was observed. From the obtained strain dispersion graph, if the storage modulus (G') remained constant up to 1% strain but did not remain constant up to 10%, the strain in the measurement conditions in 3) below was determined to be 1%. If the storage modulus (G') remained constant up to 0.1% strain but did not remain constant up to 1%, the strain in the measurement conditions in 3) below was determined to be 0.1%.

[0088] 3) Determination of storage modulus (G') by frequency dispersion The 1.0 mass% aqueous solutions of each of the components obtained in 1)-1 and 1)-2 above were measured using a rheometer (TA Instruments, model number: AR-2000ex) at a measurement temperature of 25°C under the strain conditions determined in 2) above, with the angular frequency varied from 0.1 to 300 rad / s. From the measured values, the storage modulus (G') at an angular frequency of 0.1 rad / s was adopted.

[0089] [Storage modulus of final aqueous dispersion composition] 1) <Determination of strain by strain distribution> The liquid temperature of the final aqueous dispersion composition obtained in each Example and Comparative Example was adjusted to 25°C, and the frequency of a rheometer (TA Instruments, model number: AR-2000ex) was set to 1 Hz. The storage modulus (G') was measured while applying strain. The measurement was terminated when a decrease in the storage modulus (G') was observed. From the obtained strain distribution graph, if the storage modulus (G') maintained a constant value up to a strain of 1% but did not maintain a constant value up to 10%, the strain in the measurement conditions in 3) below was determined to be 1%. If the storage modulus (G') maintained a constant value up to a strain of 0.1% but did not maintain a constant value up to 1%, the strain in the measurement conditions in 3) below was determined to be 0.1%.

[0090] 2) Determination of storage modulus (G') by frequency dispersion The final aqueous dispersion compositions obtained in each Example and Comparative Example were measured using a rheometer (TA Instruments, model number: AR-2000ex) at a measurement temperature of 25°C under the strain conditions determined in 1) above, with the angular frequency varied from 0.1 to 300 rad / s. From the measured values, the storage modulus (G') at an angular frequency of 0.1 rad / s was adopted.

[0091] The results are summarized in Table 1.

[0092] [Table 1] [Industrial Applicability]

[0093] An aqueous dispersion composition containing a polyester block copolymer is provided, which is useful for environmental protection, for example, by enabling molded articles to be obtained without using organic solvents.

Claims

1. (A) a polyester block copolymer, (B) a polymer containing a structural unit derived from (meth)acrylic acid; (C) a surfactant, and (D) an aqueous medium; An aqueous dispersion composition comprising: The polymer (B) has a storage modulus (G') of 10 to 1000 Pa at an angular frequency of 0.1 rad / s measured under the following conditions: Aqueous dispersion composition. [Measurement conditions: For a neutralized aqueous solution containing 1.0% by mass of the (B) polymer and having a degree of neutralization of 70%, the storage modulus is measured by strain dispersion at a liquid temperature of 25°C and a rheometer frequency of 1 Hz, and the strain in the subsequent frequency dispersion is determined to be 0.1% or 1%. Under the strain conditions, the angular frequency is changed from 0.1 to 300 rad / s, and the storage modulus is measured by frequency dispersion to determine the storage modulus (G') at an angular frequency of 0.1 rad / s.]

2. (A) a polyester block copolymer, (B) a polymer containing a structural unit derived from (meth)acrylic acid; (C) a surfactant, and (D) an aqueous medium; An aqueous dispersion composition comprising: An aqueous dispersion composition having a storage modulus (G') of 10 to 300 Pa at an angular frequency of 0.1 rad / s measured under the following conditions: [Measurement conditions: The storage modulus is measured under strain dispersion with a liquid temperature of 25°C and a rheometer frequency of 1 Hz. The strain under frequency dispersion is then determined to be 0.1% or 1%. Under the strain conditions, the angular frequency is varied from 0.1 to 300 rad / s, and the storage modulus is measured under frequency dispersion to determine the storage modulus (G') at an angular frequency of 0.1 rad / s.]

3. (A) The polyester block copolymer contains a hard segment (a1) and a soft segment (a2), the hard segment (a1) is a segment containing at least one selected from the group consisting of a polybutylene terephthalate structure containing a structural unit derived from terephthalic acid and / or dimethyl terephthalate and a structural unit derived from 1,4-butanediol, and a polybutylene isophthalate structure containing a structural unit derived from isophthalic acid and / or dimethyl isophthalate and a structural unit derived from 1,4-butanediol; The aqueous dispersion composition according to claim 1 or 2.

4. The soft segment (a2) is a segment containing an aliphatic polyether structure and / or an aliphatic polyester structure. The aqueous dispersion composition according to claim 3.

5. 3. The aqueous dispersion composition according to claim 1, wherein the surfactant (C) comprises an ethylene oxide / propylene oxide copolymer.

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