Aqueous dispersion composition

Abstract

To provide a polyester block copolymer aqueous dispersion composition which hardly causes aggregation even when stored at a relatively low temperature.SOLUTION: The aqueous dispersion composition contains: (A) a polyester block copolymer; (B) at least one selected from the group consisting of a polyoxyalkylene ether, oleic acid and a salt thereof, a rosin acid and a salt thereof, a styrene-maleic acid half ester copolymer and a salt thereof, and a polyacrylic acid and a salt thereof; (C) a surfactant; and (D) an aqueous medium.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 Application Laid-Open No. 2008-208192 [Patent Document 2] Japanese Patent Application Laid-Open No. 2002-234904 [Patent Document 3] Japanese Patent Application Publication No. 07-292121 [Patent Document 4] Japanese Patent Application Laid-Open No. 2003-201378 [Patent Document 5] Japanese Patent Application Laid-Open No. 2005-206626 [Patent Document 6] International Publication No. 2008 / 020520 Summary of the Invention [Problem to be solved by the invention]

[0004] However, aqueous dispersion compositions of polyester block copolymers may aggregate when stored at relatively low temperatures (e.g., 3°C or lower), making them difficult to store in cold regions or during winter. Therefore, there is a demand for aqueous dispersion compositions of polyester block copolymers that are less likely to aggregate even when stored at relatively low temperatures.

[0005] An object of one aspect of the present disclosure is to provide an aqueous dispersion composition of a polyester block copolymer that is less likely to cause aggregation even when stored at a relatively low temperature. [Means for solving the problem]

[0006] Aspects of the present disclosure include, for example, the subject matter described in the following sections: Section 1. (A) a polyester block copolymer, (B) at least one selected from the group consisting of polyoxyalkylene ether, oleic acid and its salts, rosin acid and its salts, styrene-maleic acid half ester copolymer and its salts, and polyacrylic acid and its salts; (C) a surfactant, and (D) an aqueous medium; An aqueous dispersion composition comprising: Section 2. (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. The aqueous dispersion composition according to item 1. Section 3. The soft segment (a2) is a segment containing an aliphatic polyether structure and / or an aliphatic polyester structure. Item 3. The aqueous dispersion composition according to item 2. Section 4. Item 4. The aqueous dispersion composition according to any one of Items 1 to 3, wherein the surfactant (C) contains an ethylene oxide / propylene oxide copolymer. Section 5. 5. The aqueous dispersion composition according to claim 1, which does not undergo aggregation when left standing at 3° C. for 1 hour. Section 6. Item 6. The aqueous dispersion composition according to any one of Items 1 to 5, wherein the polyoxyalkylene ether is at least one selected from the group consisting of polyoxyalkylene alkyl ethers, polyoxyalkylene alkenyl ethers, polyoxyalkylene phenyl ethers, and polyoxyalkylene naphthyl ethers. Section 7. The polyoxyalkylene phenyl ether is The phenyl group in the phenyl ether structure is an alkyl group having 1 to 14 carbon atoms, and C6H5-CR i R ii - (R i and R ii are the same or different and represent a hydrogen atom or a methyl group, and C6H5- represents a phenyl group), Item 7. The aqueous dispersion composition according to item 6. [Effects of the Invention]

[0007] According to one aspect of the present disclosure, there is provided an aqueous dispersion composition of a polyester block copolymer (particularly a polyester elastomer) that is less likely to cause aggregation even when stored at a relatively low temperature. DETAILED DESCRIPTION OF THE INVENTION

[0008] Each embodiment of the present disclosure will be described in more detail below. The present disclosure preferably includes an aqueous dispersion composition containing (A) a polyester block copolymer, (B) a specific component, (C) a surfactant, and (D) an aqueous medium, but is not limited thereto. The present disclosure includes all of the disclosures herein that would be recognized by 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 component (B) in the aqueous dispersion composition of the present disclosure is at least one selected from the group consisting of polyoxyalkylene ether, oleic acid and its salts, rosin acid and its salts, styrene-maleic acid half ester copolymer and its salts, and polyacrylic acid and its salts. The component (B) can be used alone or in combination of two or more.

[0034] In the polyoxyalkylene ether, the alkylene of the polyoxyalkylene group is preferably a straight-chain or branched-chain alkylene having 2 to 6 (2, 3, 4, 5, or 6) carbon atoms, and more preferably ethylene, propylene, or butylene (particularly n-butylene). The polyoxyalkylene group may consist of one type of polyoxyalkylene, or may contain two or more (preferably 2, 3, or 4) types of polyoxyalkylenes with different carbon numbers. Examples of such polyoxyalkylenes include polyoxybutylene polyoxyethylene polyoxypropylene (which includes three different types of polyoxyalkylenes).

[0035] Furthermore, the number of moles of oxyalkylene added in the polyoxyalkylene ether is not particularly limited, but may be, for example, 3 to 20 (3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20).

[0036] More specific examples of polyoxyalkylene ethers include polyoxyalkylene alkyl ethers, polyoxyalkylene alkenyl ethers, polyoxyalkylene phenyl ethers, and polyoxyalkylene naphthyl ethers.

[0037] The alkyl in the polyoxyalkylene alkyl ether is preferably an alkyl having 1 to 24 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, or 24). The alkyl may be linear or branched, with linear being preferred. Of these, linear alkyl having 10 to 18 carbon atoms is preferred, and linear alkyl having 12 to 16 carbon atoms is more preferred.

[0038] The alkenyl in the polyoxyalkylene alkenyl ether is preferably an alkenyl having 2 to 24 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, or 24). It may be linear or branched, with linear being preferred. Of these, linear alkenyl having 10 to 18 carbon atoms is preferred, and linear alkenyl having 12 to 16 carbon atoms is more preferred.

[0039] The phenyl in the polyoxyalkylene phenyl ether is an alkyl group having 1 to 14 carbon atoms, and C6H5-CR i R ii - (R i and R iimay have at least one substituent selected from the group consisting of (the same or different groups represent a hydrogen atom or a methyl group, and C6H5- represents a phenyl group). When having a substituent, the number of substituents is preferably 1, 2, or 3, and more preferably 1. More specific examples of polyoxyalkylene phenyl ethers include polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene styrenated phenyl ether, polyoxyethylene phenyl ether, and polyoxyethylene benzyl ether. Among these, polyoxyethylene styrenated phenyl ether is preferred. Note that the styrenated phenyl in polyoxyethylene styrenated phenyl ether is preferably a phenyl having one or two (particularly two) C6H5-CH(CH3)- substituents. Structural examples of polyoxyethylene styrenated phenyl ethers in cases where the styrenated phenyl is a phenyl having 0 to 2 C6H5-CH(CH3)- as substituents are shown below (m represents 0, 1, or 2, and n represents the number of moles of ethylene oxide (EO) added):

[0040] [ka]

[0041] The naphthyl in the polyoxyalkylene naphthyl ether is an alkyl group having 1 to 14 carbon atoms, and C6H5-CR i R ii - (R i and R ii may have at least one substituent selected from the group consisting of (wherein CH- is the same or different and represents a hydrogen atom or a methyl group, and CH- is a phenyl group). When the polyoxyalkylene naphthyl ether has a substituent, the number of substituents is preferably 1, 2, or 3, and more preferably 1. More specific examples of polyoxyalkylene naphthyl ethers include polyoxyalkylene β-naphthyl ether.

[0042] The polyoxyalkylene ethers can be used singly or in combination of two or more.

[0043] The salt of oleic acid is preferably a metal salt, more preferably an alkali metal salt or an alkaline earth metal salt, further preferably a sodium salt, a potassium salt, a calcium salt, or a magnesium salt, and even more preferably a sodium salt or a potassium salt. Oleic acid or a salt thereof may be used alone or in combination of two or more.

[0044] Rosin acid is also known as abietic acid. The salt of rosin acid is preferably a metal salt, more preferably an alkali metal salt or an alkaline earth metal salt, even more preferably a sodium salt, a potassium salt, a calcium salt, or a magnesium salt, and even more preferably a sodium salt or a potassium salt. The rosin acid or its salt may be used singly or in combination of two or more.

[0045] As the salt of the styrene-maleic acid half ester copolymer, for example, an ammonium salt is preferred.

[0046] The salt of polyacrylic acid is preferably a metal salt, more preferably an alkali metal salt or an alkaline earth metal salt, further preferably a sodium salt, a potassium salt, a calcium salt, or a magnesium salt, and even more preferably a sodium salt or a potassium salt. The polyacrylic acid or a salt thereof may be used singly or in combination of two or more.

[0047] The surfactant (C) used in the aqueous dispersion composition of the present disclosure is preferably a nonionic surfactant. Examples of nonionic surfactants include polyethylene glycol, ethylene oxide / propylene oxide copolymer, polyoxyethylene sorbitan fatty acid monoester, polyoxyethylene alkylamide, and polyglycerin ester. Among these, ethylene oxide / propylene oxide copolymer is preferred from the viewpoint of emulsion stabilization ability and excellent heat resistance.

[0048] The ethylene oxide / propylene oxide copolymer is not particularly limited as long as it is within a range in which the effects of the invention according to the present disclosure can be obtained, and is, for example, a block copolymer represented by the following formula (I). HO(CH2CH2O) p (CH2CH(CH3)O) q (CH2CH2O) r H (I) In formula (I), 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.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] 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.

[0053] 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 invention, and may be, for example, approximately 1 to 60% by mass. The upper or lower limit of this range may be, for example, 2, 5, 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.

[0054] The content of component (B) in the aqueous dispersion composition of the present disclosure is not particularly limited as long as it does not impair the effects of the present invention, although it depends on the type of component (B) used. It is preferably 0.1 to 10 parts by mass relative to 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, 2, 3, 4, 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 6 parts by mass. Furthermore, although it depends on the amount of polyester block copolymer (A) and the type of component (B), the content of component (B) in the aqueous dispersion composition is preferably approximately 0.1 to 5% by mass. The upper or lower limit of this range may be, for example, 0.2, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, or 4.5% by mass. The range may be, for example, about 0.5 to 4 mass %.

[0055] 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, this range is more preferably 3 to 12 parts by mass, and even more preferably 4 to 10 parts by mass. Furthermore, although depending on the amount of the (A) polyester block copolymer, the content of the (C) surfactant in the aqueous dispersion composition is preferably about 0.5 to 5% by mass, and more preferably about 1 to 4% by mass.

[0056] 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.

[0057] 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, polyacrylic acid ester salts, 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 size.

[0058] 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).

[0059] Examples of other components include known molding aids such as crystal nucleating agents and lubricants, antioxidants, 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.

[0060] The aqueous dispersion composition of the present disclosure is highly stable and does not easily aggregate even when stored at relatively low temperatures. Of these, those that do not aggregate when left standing at 3°C ​​for 1 hour are particularly preferred.

[0061] 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.

[0062] 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.

[0063] 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.

[0064] 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).

[0065] 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.

[0066] Next, the components are stirred (preferably with heating) to emulsify. Then, component (B) is added and mixed to obtain the desired aqueous dispersion composition of the (A) polyester block copolymer. The method for applying heat to the (A) polyester block copolymer 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, but in order to reduce the thermal history of the (A) polyester block copolymer, the (A) polyester block copolymer is emulsified at a temperature between 40°C lower and 100°C higher than the melting point. Preferably, the (A) polyester block copolymer is emulsified at a temperature between 30°C lower and 60°C higher than the melting point. Specifically, the emulsification is carried out, 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 the (A) polyester block copolymer due to thermal history.

[0067] 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).

[0068] 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.

[0069] 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.

[0070] 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.

[0071] 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.

[0072] 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.

[0073] 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]

[0074] 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 3046 (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 PE128 (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 PE128) 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 using a plunger pump at a rate of 3.89 kg / hr. The mixture was kneaded 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 mixture was then discharged from the twin-screw extruder to obtain a polyester block copolymer aqueous dispersion composition. Hereinafter, this polyester block copolymer aqueous dispersion is referred to as the aqueous dispersion composition of Production Example 1.

[0075] 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 was obtained by the same procedure as in Production Example 1, except that Hytrel 3001 (manufactured by Toray Celanese Co., Ltd.) was used as the polyester block copolymer and Newpol PE108 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.

[0076] Furthermore, both of the polyester block copolymers used in Production Examples 1 and 2 are polyester elastomers.

[0077] Examples and Comparative Examples Example 1 Production Example 1: 100 g of the aqueous dispersion composition was placed in a 200 mL beaker and stirred at 300 rpm with a stirrer equipped with four 7 cm diameter paddle blades, while 0.4 g of polyoxyethylene styrenated phenyl ether (trade name: Noigen EA137 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)) was added as the component to be investigated. Stirring was continued for 10 minutes to obtain the final aqueous dispersion composition. Example 2 Preparation Example 2: 100 g of the aqueous dispersion composition was placed in a 200 mL beaker and stirred at 300 rpm with a stirrer equipped with four 7 cm diameter paddle blades, while 0.4 g of polyoxyethylene styrenated phenyl ether (trade name: Noigen EA197D (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)) was added as the component to be investigated. Stirring was continued for 10 minutes to obtain the final aqueous dispersion composition. Example 3 The same procedure as in Example 2 was carried out except that 0.2 g of potassium rosinate (trade name: Longis K25 (manufactured by Arakawa Chemical Industries, Ltd.)) was used as the component to be investigated, to obtain a final aqueous dispersion composition. Example 4 The same procedure as in Example 2 was carried out except that 0.2 g of potassium oleate (trade name: Nonsal OK-1 (manufactured by NOF Corporation)) was used as the component to be investigated, to obtain a final aqueous dispersion composition. Example 5 The same procedure as in Example 2 was carried out except that 0.8 g of styrene-maleic acid half ester copolymer ammonium salt (trade name: Discoat N14 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)) was used as the component to be examined, to obtain a final aqueous dispersion composition. Example 6 The same procedure as in Example 2 was carried out except that 2.0 g of sodium polyacrylate (trade name: Sharol AN103P (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)) was used as the component to be examined, to obtain a final aqueous dispersion composition. (Comparative Example 1) Various evaluations were carried out on the aqueous dispersion composition of Production Example 2 to which no component to be investigated was added. (Comparative Example 2) The same procedure as in Example 2 was carried out except that 2.0 g of dioctyl sodium sulfosuccinate (trade name: Rapisol B80 (manufactured by NOF Corporation)) was used as the component to be tested, to obtain a final aqueous dispersion composition. (Comparative Example 3) The same procedure as in Example 2 was carried out except that 2.0 g of sodium naphthalenesulfonate formalin condensate (trade name: Labelin FM45 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)) was used as the component to be investigated, to obtain a final aqueous dispersion composition. Comparative Example 4 The same procedure as in Example 2 was carried out except that 2.0 g of sodium polystyrene sulfonate (trade name: PS100 (manufactured by Tosoh Organic Chemical Industries)) was used as the component to be examined, to obtain a final aqueous dispersion composition. (Comparative Example 5) The same procedure as in Example 2 was carried out except that 1.2 g of polyvinyl alcohol (trade name: PVA (manufactured by Kuraray Co., Ltd.)) was used as the component to be examined, to obtain a final aqueous dispersion composition.

[0078] The polyoxyethylene styrenated phenyl ethers used in Examples 1 and 2 are both compounds represented by the following structural formula:

[0079] [ka]

[0080] [Low temperature stability] 100 g of the aqueous dispersion composition obtained in each Example and Comparative Example was placed in a 100 mL plastic container, immersed in a thermostatic water bath at 3°C ​​for 1 hour, and then stirred with a spatula, and the presence or absence of aggregation was visually confirmed. When no aggregation was observed, it was marked with ○, and when aggregation was observed, it was marked with ×.

[0081] The results are summarized in Table 1.

[0082] [Table 1] [Industrial Applicability]

[0083] 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) at least one selected from the group consisting of polyoxyalkylene ether, oleic acid and its salts, rosin acid and its salts, styrene-maleic acid half ester copolymer and its salts, and polyacrylic acid and its salts; (C) a surfactant, and (D) an aqueous medium; An aqueous dispersion composition comprising:

2. (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 of claim 1 .

3. 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 2.

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

5. 4. The aqueous dispersion composition according to claim 1, which does not undergo aggregation when left standing at 3° C. for 1 hour.

6. The aqueous dispersion composition according to any one of claims 1 to 3, wherein the polyoxyalkylene ether is at least one selected from the group consisting of polyoxyalkylene alkyl ethers, polyoxyalkylene alkenyl ethers, polyoxyalkylene phenyl ethers, and polyoxyalkylene naphthyl ethers.

7. The polyoxyalkylene phenyl ether is The phenyl group in the phenyl ether structure is an alkyl group having 1 to 14 carbon atoms, and ６ H ５ -CR ｉ R ｉｉ A group represented by - (R ｉ and R ｉｉ are the same or different and represent a hydrogen atom or a methyl group; C ６ H ５ (wherein "-" represents a phenyl group) The aqueous dispersion composition according to claim 6.

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