JP7102751B2 - Polycarbonate polyol and aqueous polyurethane resin dispersion - Google Patents

Description

The present invention relates to polycarbonate polyols.

Conventionally, polycarbonate polyols have been actively used as raw materials for various polyurethane resins. For example, a coating film obtained by applying an aqueous polyurethane resin dispersion made from a polycarbonate polyol having 1,6-hexanediol and a polyether polyol as a polyol monomer has flexibility, hydrolysis resistance, and chemical resistance. It is known to be excellent in property and toughness (that is, flexibility and mechanical durability) (see Patent Documents 1 and 2).

Japanese Unexamined Patent Publication No. 2005-8888 Japanese Patent No. 4528132

In Patent Documents 1 and 2, it is confirmed that a polyurethane elastomer having a high elastic modulus and excellent low temperature characteristics can be obtained from the polycarbonate diol. However, polycarbonate polyols that exhibit effective functions and properties such as flexibility and resilience in addition to the above-mentioned properties have been still desired.

An object of the present invention is to provide a polycarbonate polyol that solves the above problems and exhibits useful effects such as flexibility and resilience when induced in polyurethane.

（式中、Ｚ^１は、直鎖状、分岐状若しくは環状の、酸素原子で中断されていてもよく、置換基を有していても良い三価の炭化水素基、又は、置換基を有していても良い三価の芳香族炭化水素基を示す。Ｚ^２は、直鎖状、分岐状若しくは環状の、酸素原子で中断されていてもよく、置換基を有していても良い一価の炭化水素基、又は、置換基を有していても良い一価の芳香族炭化水素基を示す。ｎ１は、１から１００までの数字を示す。）
［４］ポリオール（Ｂ）が下記式（２）で示される、［１］～［３］のいずれかのポリカーボネートポリオール。

（式中、Ｚ^３は、直鎖状、分岐状若しくは環状の、酸素原子で中断されていてもよく、置換基を有していても良い二価の炭化水素基、又は、置換基を有していても良い二価の芳香族炭化水素基を示す。）
［５］［１］～［４］のいずれかのポリカーボネートポリオール（ａ）由来の構造と、ポリイソシアネート（ｂ）由来の構造とを有する、ポリウレタン樹脂。
［６］［５］のポリウレタン樹脂と水系媒体（ｃ）とを含有する、水性ポリウレタン樹脂分散体。
［７］［５］のポリウレタン樹脂を含有する、塗料組成物。
［８］［５］のポリウレタン樹脂を含有する、コーティング剤組成物。
［９］［５］のポリウレタン樹脂を含有する、インク組成物。
［１０］［５］のポリウレタン樹脂を乾燥及び硬化させて得られる、ポリウレタン樹脂フィルム。
［１１］［５］のポリウレタン樹脂を含有する、繊維処理剤組成物。 The problem of the present invention is solved by a polycarbonate polyol having a structure derived from the polyol (A) having a nonionic group in the side chain.
The present invention relates to the following.
[1] A polycarbonate polyol having a structure derived from the polyol (A) having a nonionic group in the side chain.
[2] Further, the polycarbonate polyol of [1] having a structure derived from the polyol (B) (excluding the polyol (A) having a nonionic group in the side chain).
[3] The polycarbonate polyol of [1] or [2], wherein the polyol (A) having a nonionic group in the side chain is represented by the following formula (1).

(In the formula, Z ¹ has a linear, branched or cyclic trivalent hydrocarbon group which may be interrupted by an oxygen atom and may have a substituent, or a substituent. It indicates a trivalent aromatic hydrocarbon group which may be used. Z ² may be linear, branched or cyclic, interrupted by an oxygen atom, or may have a substituent. Indicates a valent hydrocarbon group or a monovalent aromatic hydrocarbon group which may have a substituent. N1 indicates a number from 1 to 100.)
[4] The polycarbonate polyol according to any one of [1] to [3], wherein the polyol (B) is represented by the following formula (2).

(In the formula, Z ³ has a linear, branched or cyclic divalent hydrocarbon group which may be interrupted by an oxygen atom and may have a substituent, or a substituent. Indicates a divalent aromatic hydrocarbon group that may be used.)
[5] A polyurethane resin having a structure derived from the polycarbonate polyol (a) according to any one of [1] to [4] and a structure derived from the polyisocyanate (b).
[6] An aqueous polyurethane resin dispersion containing the polyurethane resin of [5] and the aqueous medium (c).
[7] A coating composition containing the polyurethane resin of [5].
[8] A coating agent composition containing the polyurethane resin of [5].
[9] An ink composition containing the polyurethane resin of [5].
[10] A polyurethane resin film obtained by drying and curing the polyurethane resin of [5].
[11] A fiber treatment agent composition containing the polyurethane resin of [5].

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a polycarbonate polyol that exhibits useful effects such as flexibility and resilience when induced in polyurethane.

[Polycarbonate polyol]
The polycarbonate polyol (hereinafter, also referred to as “polycarbonate polyol (a)”) has a structure derived from the polyol (A) having a nonionic group in the side chain. The polycarbonate polyol can further have a structure derived from the polyol (B) (excluding the polyol (A) having a nonionic group in the side chain).

(Polyol (A) having a nonionic group in the side chain)
Examples of the nonionic group in the polyol (A) having a nonionic group in the side chain (hereinafter, also referred to as “polyol (A)”) include a group having a (poly) alkyleneoxy group. The alkylene group in the (poly) alkyleneoxy group is preferably an alkylene group having 1 to 6 carbon atoms such as an ethylene group, a propylene group and a butylene group. The number of alkyleneoxy groups in the (poly) alkyleneoxy group is 1 or more, preferably 1 to 100. The number of carbon atoms in the main chain of the polyol (A) is not particularly limited, but is preferably 1 to 100, and particularly preferably 1 to 10. Here, the main chain of the polyol (A) refers to the carbon chain having the largest number of carbon atoms among the carbon chains connecting any two OH groups with the minimum number of carbon atoms. That is, the polyol (A) is a polyol in which a nonionic group is bonded to a carbon atom in the main chain of the polyol. In addition to the nonionic group, the polyol (A) may have a further side chain such as a linear or branched alkyl group described later.

（式中、Ｚ^１は、直鎖状、分岐状若しくは環状の、酸素原子で中断されていてもよく、置換基を有していても良い三価の炭化水素基、又は、置換基を有していても良い三価の芳香族炭化水素基を示す。Ｚ^２は、直鎖状、分岐状若しくは環状の、酸素原子で中断されていてもよく、置換基を有していても良い一価の炭化水素基、又は、置換基を有していても良い一価の芳香族炭化水素基を示す。ｎ１は、１～１００の数字を示す。） Examples of such a polyol (A) include compounds represented by the following formula (1).

(In the formula, Z ¹ has a linear, branched or cyclic trivalent hydrocarbon group which may be interrupted by an oxygen atom and may have a substituent, or a substituent. It indicates a trivalent aromatic hydrocarbon group which may be used. Z ² may be linear, branched or cyclic, interrupted by an oxygen atom, or may have a substituent. Indicates a valent hydrocarbon group or a monovalent aromatic hydrocarbon group which may have a substituent. N1 indicates a number from 1 to 100.)

Examples of the monovalent hydrocarbon group include an alkyl group.
Examples of the linear alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group and n-nonyl group. Examples thereof include an n-decyl group, an n-undecyl group and an n-dodecyl group.
Examples of the branched alkyl group include an i-propyl group, an i-butyl group, a sec-butyl group, and a tert-butyl group.
Examples of the cyclic alkyl group include a monocyclic or polycyclic cycloalkyl group having 3 to 20 carbon atoms, and a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclodecyl group. , Cyclododecyl group, adamantyl group and the like are preferable.

The alkyl group may be substituted with a substituent. The substituent of the alkyl group is not particularly limited, and examples thereof include a carboxyl group and a halogen atom.

The alkyl group may be interrupted by one or more oxygen atoms. When a linear or branched alkyl group is interrupted by one or more oxygen atoms, it becomes a (poly) alkyleneoxy-alkylene group. As such a (poly) alkyleneoxy-alkylene group, a methoxy (poly) ethyleneoxy group (CH ₃ O (CH ₂ CH ₂ O) _m1- (in the formula, m1 is 1 or more, and 1 to 100 is preferable. )) Or ethoxy (poly) ethyleneoxy group (CH ₃ CH ₂ O (CH ₂ CH ₂ O) _m2- (in the formula, m2 is 1 or more, preferably 1 to 100)), (poly) propyleneoxy. Groups, (poly) butyleneoxy groups and the like can be mentioned. Examples of the cyclic alkyl group interrupted by one or more oxygen atoms include a tetrahydrofuranyl group.

The linear or branched alkyl group may be interrupted by a cyclic alkylene group. Here, the cyclic alkylene group includes a group obtained by removing one hydrogen atom from the cyclic alkyl group. Examples of such a group include a group in which a linear or branched alkyl group having 2 to 20 carbon atoms is interrupted by a monocyclic or polycyclic cycloalkylene group having 3 to 20 carbon atoms. ..

When the monovalent hydrocarbon group is not interrupted by one or more oxygen atoms, the total number of carbon atoms is preferably 1 to 20, particularly preferably 1 to 4. When the monovalent hydrocarbon group is interrupted by one or more oxygen atoms, the total number of carbon atoms is preferably 2 to 200.

Examples of the monovalent aromatic hydrocarbon group include an aryl group and an aralkyl group. The aryl group preferably has 6 to 20 carbon atoms. Examples of the aryl group include a phenyl group, a biphenylyl group, a naphthyl group, an anthrasenyl group, a fluorenyl group and the like, and a phenyl group or a naphthyl group is preferable. The aryl group may be substituted with a substituent. The substituent of the aryl group is not particularly limited, and examples thereof include an alkyl group, a cycloalkyl group, and a halogen atom. The aralkyl group is an alkyl group substituted with an aryl group. Here, examples of the aryl group and the alkyl group include the above-mentioned groups. Examples of the aralkyl group include a methyl group substituted with a phenyl group or a naphthyl group (here, the phenyl group or the naphthyl group is substituted with a methyl group) and the like.

The trivalent hydrocarbon group or the trivalent aromatic hydrocarbon group is a group obtained by removing two hydrogen atoms from the monovalent hydrocarbon group or the monovalent aromatic hydrocarbon group. Can be mentioned.

Z ¹ is preferably a group obtained by removing two hydrogen atoms from a linear or branched alkyl group. Further, Z ² is preferably a linear or branched alkyl group.

n1 is preferably 1 to 70, more preferably 2 to 50, and particularly preferably 10 to 30. When n1 is in the above range, the flexibility and resilience of the polyurethane resin are increased, and the stability of the aqueous polyurethane resin dispersion is increased, which is preferable.

From the above, the polyol (A) is two or more selected from the group consisting of a polyalkylene oxide chain (for example, a polyethylene oxide chain, a polypropylene oxide chain, a polybutylene oxide chain, and a polyethylene oxide, a polypropylene oxide, and a polybutylene oxide). Polyol having a group having two hydroxyl groups at one end of the (chain of the copolymer) of the above is preferable, and a polyol in which one hydroxyl group of trimethylolpropane is replaced with a methoxy (poly) ethyleneoxy group or an ethoxy (poly) ethyleneoxy group. Is more preferable, and a polyol having a structure represented by the following formula (1a) is particularly preferable. Examples of commercially available products of the polyol (A) include Ymer N120 (manufactured by Perstoop) and Tegomer D-3403 (manufactured by Evonic).

（式（１ａ）中、ｎ２は、１９から２１までの数字を示す。）
ポリオール（Ａ）は、単独又は複数種の組合せであってもよい。

(In formula (1a), n2 represents a number from 19 to 21.)
The polyol (A) may be used alone or in combination of two or more.

（式中、Ｚ^３は、直鎖状、分岐状若しくは環状の、酸素原子で中断されていてもよく、置換基を有していても良い二価の炭化水素基、又は、置換基を有していても良い二価の芳香族炭化水素基を示す。） (Polyol (B) (excluding polyol (A) having a nonionic group in the side chain))
The polyol (B) (excluding the polyol (A) having a nonionic group in the side chain) (hereinafter, also referred to as “polyol (B)”) is not particularly limited as long as it is a polyol other than the polyol (A). Examples of the polyol (B) include compounds represented by the following formula (2).

(In the formula, Z ³ has a linear, branched or cyclic divalent hydrocarbon group which may be interrupted by an oxygen atom and may have a substituent, or a substituent. Indicates a divalent aromatic hydrocarbon group that may be used.)

The divalent hydrocarbon group or the divalent aromatic hydrocarbon group includes a monovalent hydrocarbon group or a group obtained by removing one hydrogen atom from the monovalent aromatic hydrocarbon group. Can be mentioned. However, Z ³ is not a group having a nonionic group in the side chain.

The divalent hydrocarbon group, which may be linear, branched or cyclic and may be interrupted by an oxygen atom and may have a substituent, is not interrupted by an oxygen atom and is cyclic. Examples thereof include an alkylene group which is not interrupted by an alkylene group, an alkylene group which is interrupted by one or more oxygen atoms, an alkylene group which is interrupted by a cyclic alkylene group, and the like. Examples of the divalent aromatic hydrocarbon group include an arylene group and an alkylene group interrupted by an arylene group. Here, the alkylene group includes a group obtained by removing one hydrogen atom from the alkyl group, and the arylene group includes a group obtained by removing one hydrogen atom from the aryl group.

Examples of the polyol (B) include ethylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, and 2-butyl-2-ethyl. -1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 2-methyl An aliphatic diol having 2 to 9 carbon atoms such as -1,8-octanediol, diethylene glycol, triethylene glycol, and tetraethylene glycol; 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexane Ring structure with 6 to 12 carbon atoms such as diol, 1,4-bis (hydroxyethyl) cyclohexane, 2,7-norbornandiol, tetrahydrofuran dimethanol, 2,5-bis (hydroxymethyl) -1,4-dioxane, etc. Diols with; polyhydric alcohols such as trimethylolpropane, pentaerythritol, sorbitol; 1,4-benzenedimethanol, 1,3-benzenedimethanol, 1,2-benzenedimethanol, 4,4'-naphthalenedimethanol , 3,4'-naphthalenediethanol and other aromatic diols.
The polyol (B) may be used alone or in combination of two or more.
The polyol (B) is preferably 1,6-hexanediol from the viewpoint of the flexibility and restorability of the obtained coating film when it is induced into polyurethane using the obtained polycarbonate polyol (a).

(Content)
When the polycarbonate polyol (a) contains both a structure derived from the polyol (A) and a structure derived from the polyol (B), the mass ratio of the structure derived from the polyol (A) to the structure derived from the polyol (B) (polyol). The structure derived from (A) / the structure derived from the polyol (B)) is preferably 10/90 to 90/10, more preferably 20/80 to 80/20. Within this range, higher flexibility and resilience can be exhibited when induced in polyurethane.

(Terminal olefination rate)
The end of the main chain of the polycarbonate polyol (a) may become an olefin as represented by the following formula in the manufacturing process thereof.

The terminal olefinization ratio (ratio of terminal olefins to all terminals) is preferably 1.0 mol% or less, and particularly preferably 0.5 mol% or less. Within this range, the urethanization reaction can be sufficiently advanced. In addition, the breaking point strength of the polyurethane film tends to increase.

(Terminal alkoxylation rate)
The end of the main chain of the polycarbonate polyol (a) may be an alkoxy group (showing a methoxy group as an example) as represented by the following formula in the manufacturing process thereof.

The terminal alkoxylation rate (ratio of terminal alkoxy groups to all terminals) is preferably 0.15 mol% or less, and particularly preferably 0.10 mol% or less. Within this range, the urethanization reaction can be sufficiently advanced. In addition, the breaking point strength of the polyurethane film tends to increase.

(Terminal alkoxy carbonateization rate)
The end of the main chain of the polycarbonate polyol (a) may be an alkoxy carbonate group (showing a methoxy carbonate group as an example) as represented by the following formula in the production process thereof.

The terminal alkoxycarbonation ratio (ratio of terminal alkoxycarbonate groups to all terminals) is preferably 0.15 mol% or less, and particularly preferably 0.10 mol% or less. Within this range, the urethanization reaction can be sufficiently advanced.

The polycarbonate polyol (a) may have an ester bond or an ether bond in the main chain to the extent that the function and properties are not impaired. By having an ester bond, it is expected that the compatibility with polyurethane will increase. In addition, having an ether bond is expected to increase the flexibility when induced in polyurethane.

(Hydroxy group value)
The hydroxyl value of the polycarbonate polyol (a) is preferably 20 to 600 mgKOH / g, more preferably 25 to 600 mgKOH / g, and particularly preferably 30 to 400 mgKOH / g. Within this range, higher flexibility and resilience can be exhibited when induced in polyurethane.

(Acid value)
The acid value of the polycarbonate polyol (a) is preferably 0.10 mgKOH / g or less, and particularly preferably 0.08 mgKOH / g or less. Within this range, the generation of by-products in the urethanization reaction can be suppressed. In addition, the breaking point strength of the polyurethane film tends to increase.

(Number average molecular weight)
The number average molecular weight of the polycarbonate polyol (a) can be appropriately adjusted depending on the intended purpose, but is preferably 200 to 5,000, more preferably 200 to 4,000, and more preferably 300 to 3,000. Is particularly preferred. Within this range, the handling of the polycarbonate polyol becomes easy, and the low temperature characteristics of the polyurethane derived from the polycarbonate polyol become good. The number average molecular weight shall be the number average molecular weight calculated based on the hydroxyl value measured in accordance with JIS K 1557. Specifically, the hydroxyl value is measured and calculated using (56.1 × 1,000 × valence) / hydroxyl value by the terminal group quantification method (in this formula, the unit of the hydroxyl value is [mgKOH /). g]). In the above formula, the valence is the number of hydroxyl groups in one molecule.

(Method for producing polycarbonate polyol (a))
The method for producing the polycarbonate polyol (a) (hereinafter, also referred to as “reaction of the present invention”) is not particularly limited, and for example, the following methods (1) and (2) can be applied.
(1) A method in which a polyol (A), a carbonic acid ester, a catalyst and, in some cases, a polyol (B) are mixed and reacted while distilling off low boiling point components (for example, by-produced alcohol) (hereinafter, "one-step method"). Also called).
(2) Polycarbonate is obtained by mixing one of the polyols (A) and the polyol (B), a carbonic acid ester, and a catalyst, and reacting them while distilling off low boiling point components (for example, by-produced alcohol). A method of producing oriole (synthesized from only one polyol) and further reacting one of the polyols (A) and the polyol (B) (however, not a polyol mixed with a carbonic acid ester and a catalyst) (hereinafter referred to as a method). , Also called "two-step method").
The reaction of the present invention may be carried out in a plurality of times, for example, once a prepolymer of a polycarbonate polyol (lower molecular weight than the target polycarbonate polyol) is obtained, and then the reaction is carried out in order to further increase the molecular weight. can.

The amount of the polyol (A) and the polyol (B) used is not particularly limited, but it is preferable that the structure derived from the polyol (A) and the structure derived from the polyol (B) satisfy the predetermined range.

(Carbonate ester)
Examples of the carbonic acid ester include dialkyl carbonate such as dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate; diaryl carbonate such as diphenyl carbonate; ethylene carbonate and propylene carbonate (4-methyl-1,3-dioxolan-2-one, trimethylene). Cyclic carbonates such as carbonate), butylene carbonate (4-ethyl-1,3-dioxolan-2-one, tetramethylene carbonate), 5-methyl-1,3-dioxane-2-one, dimethyl carbonate, diethyl Carbonic acid and ethylene carbonate are preferable.
The carbonic acid ester may be used alone or in combination of two or more.

The amount of the carbonic acid ester used is preferably 0.8 to 2.0 mol, particularly preferably 0.9 to 1.5 mol, based on 1 mol of the total amount of the polyol. Within this range, the desired polycarbonate polyol can be efficiently obtained at a sufficient reaction rate.

(catalyst)
The catalyst is not particularly limited as long as it is a known ester exchange catalyst, but for example, lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, zinc, aluminum, titanium, zirconium, cobalt, germanium, tin, etc. Examples of metals such as cerium and their hydroxides, alkoxides, carboxylates, carbonates, hydrogen carbonates, sulfates, phosphates, nitrates, organic metals, etc. include sodium hydride and titanium tetraisopropoxy. Do, titanium tetrabutoxide, zirconium tetrabutoxide, zirconium acetylacetonate, zirconium oxyacetate, dibutyltin dilaurate, dibutyltin dimethoxyde, dibutyltin oxide are preferred.
The catalyst may be used alone or in combination of two or more.

The amount of the catalyst used is preferably 0.001 to 0.1 mmol, more preferably 0.005 to 0.05 mmol, and 0.03 to 0, based on 1 mol of the total amount of polyol. It is particularly preferably 0.05 mmol. Within this range, the desired polycarbonate polyol can be efficiently obtained without complicating post-treatment. The catalyst may be used collectively at the start of the reaction, or may be divided and used (added) at the start of the reaction and after the start of the reaction.

(Reaction temperature and reaction pressure)
The reaction temperature can be appropriately adjusted depending on the type of carbonic acid ester, but is preferably 50 to 250 ° C, particularly preferably 70 to 230 ° C. The reaction temperature is the same regardless of whether the one-step method or the two-step method is adopted. The reaction pressure in the reaction of the present invention is not particularly limited as long as the pressure is such that the reaction is carried out while removing the low boiling point component, but it is preferably carried out under normal pressure or reduced pressure. Within this range, the desired polycarbonate polyol can be efficiently obtained without causing sequential reactions or side reactions.

[Polyurethane resin]
The polyurethane resin has a structure derived from the polycarbonate polyol (a) and a structure derived from the polyisocyanate (b). Since the polyurethane resin has a structure derived from the polycarbonate polyol (a), it is an extremely useful material having good flexibility such as low elastic modulus and high breaking point elongation.

(Polyisocyanate (b))
The polyisocyanate (b) can be appropriately selected depending on the purpose and application. For example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, naphthalene-1,5 -Aromatic aliphatic diisocyanis such as -diisocyanis, 3,3'-dimethyl-4,4'-biphenylenediisocyanis, polymethylene polyphenyl isocyanate, xylylene diisocyanate (XDI), phenylenediisocyanate; 4,4'-methylenebiscyclohexamethylene diisocyanate, Hexamethylene diisocyanis, isophoron diisocyanis, cyclohexane-1,3-diylbis (methylene) diisocyanate, and aliphatic diisocyanis such as trimethylhexamethylene diisocyanate can be mentioned. Part or all of the structure of the polyisocyanate (b) may be derivatized such as isocyanurate-forming, carbodiimide-forming, or biuret-forming.
The polyisocyanate (b) may be used alone or in combination of a plurality of types.

The amount of the polyisocyanate (b) used is such that the ratio of the isocyanate group of the polyisocyanate (b) to the hydroxyl group of the polycarbonate polyol (a) (isocyanate group / hydroxyl group (molar ratio)) is 0.8 to 10. It is preferably 0.9 to 5.0, and particularly preferably 0.9 to 5.0.

(Structure derived from other components)
The polyurethane resin is a structure derived from one or more other components selected from the group consisting of a structure derived from a chain extender, a structure derived from an acidic group-containing polyol, a structure derived from other polyols, and a structure derived from a terminal terminator. Can have. Further, when the polyurethane resin has a structure derived from an acidic group-containing polyol, a portion derived from the neutralizing agent may be further present as a counterion.

(Chain extender)
The polyurethane resin can include a structure derived from a chain extender for the purpose of increasing the molecular weight. The chain extender can be appropriately selected according to the purpose and application, for example,
water;
Ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,10-decanediol, 1,1-cyclohexanedimethanol, 1,4-Cyclohexanedimethanol, tricyclodecanedimethanol, xylylene glycol, bis (p-hydroxy) diphenyl, bis (p-hydroxyphenyl) propane, 2,2-bis [4- (2-hydroxyethoxy) phenyl ] Propane, low molecular weight polyols such as bis [4- (2-hydroxyethoxy) phenyl] sulfone, 1,1-bis [4- (2-hydroxyethoxy) phenyl] cyclohexane;
Polymer polyols such as polyester polyols, polyesteramide polyols, polyether polyols, polyether ester polyols, polycarbonate polyols, polyolefin polyols; and
Polyamines such as ethylenediamine, isophoronediamine, 2-methyl-1,5-pentanediamine, aminoethylethanolamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine;
Can be mentioned.

For the chain extender, for example, "Latest Polyurethane Applied Technology" (CMC Co., Ltd., published in 1985) can be referred to, and for the polymer polyol, for example, "Polyurethane Form" (Polyurethane Form). Publications, 1987) can be referred to.
The chain extender may be used alone or in combination of two or more.

(Acid group-containing polyol)
Examples of the acidic group-containing polyol include dimethylol alkanoic acids such as 2,2-dimethylol propionic acid and 2,2-dimethylol butanoic acid; N, N-bishydroxyethylglycine and N, N-bishydroxyethylalanine. , 3,4-Dihydroxybutanesulfonic acid, 3,6-dihydroxy-2-toluenesulfonic acid, 12-hydroxystearic acid and the like. From the viewpoint of dispersibility, the acidic group-containing polyol is preferably dimethylolalkanoic acid, and particularly preferably an alkanoic acid having 4 to 12 carbon atoms containing two methylol groups. The acidic group-containing polyol is preferably a hydroxyalkanoic acid containing one hydroxyl group such as 12-hydroxystearic acid and 1 to 3 carboxyl groups from the viewpoint of flexibility when induced in polyurethane. ..
The acidic group-containing polyol may be used alone or in combination of two or more.

(Neutralizer)
Examples of the neutralizing agent include trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-phenyldiethanolamine, dimethylethanolamine, diethylethanolamine, and N-methylmorpholine. , Organic amines such as pyridine; inorganic alkali salts such as sodium hydroxide and potassium hydroxide, and ammonia. The neutralizing agent is preferably organic amines, and particularly preferably tertiary amines (trimethylamine, triethylamine, triisopropylamine, tributylamine).
The neutralizing agent may be used alone or in combination of two or more.

(Other polyols)
The polyurethane resin has a structure derived from other polyols such as a low molecular weight polyol and a high molecular weight polyol (excluding a polycarbonate polyol having a structure derived from the polyol (A) and an acidic group-containing polyol) in order to adjust the molecular weight. Can have.
Other polyols may be used alone or in combination of two or more.

Examples of the low molecular weight polyol include ethylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, and 1, , 5-Pentanediol, 3-methyl-1,5-Pentanediol, 1,6-hexanediol and the like. The small molecule polyol is not particularly limited, but preferably has a number average molecular weight of less than 400.
The small molecule polyol may be alone or in combination of two or more.

The high molecular weight polyol is not particularly limited, but preferably has a number average molecular weight of 400 to 8,000. When the number average molecular weight is in this range, appropriate viscosity and good handleability can be obtained. Further, it is easy to secure the performance as a soft segment, and when a coating film is formed using the obtained aqueous resin dispersion containing a polyurethane resin, it is easy to suppress the occurrence of cracks. Further, the reactivity between the polyol and the polyisocyanate becomes sufficient, and the polyurethane prepolymer can be efficiently produced. The high molecular weight polyol preferably has a number average molecular weight of 400 to 4,000.

In the present specification, the number average molecular weight is the number average molecular weight calculated based on the hydroxyl value measured according to JIS K 1577. Specifically, the hydroxyl value is measured and calculated by the terminal group quantification method as (56.1 × 1,000 × valence) / hydroxyl value [mgKOH / g]. In the above formula, the valence is the number of hydroxyl groups in one molecule.

The high molecular weight polyol is not particularly limited, and examples thereof include a polycarbonate polyol (excluding the polycarbonate polyol (a)), a polyester polyol, and a polyether polyol. A polycarbonate polyol is preferable from the viewpoint of light resistance, weather resistance, heat resistance, hydrolysis resistance, and oil resistance of the aqueous resin dispersion containing the polyurethane resin and the coating film obtained from the aqueous resin dispersion.

Polycarbonate polyol (excluding polycarbonate polyol (a)) is obtained by reacting one or more kinds of polyol monomers with a carbonic acid ester or phosgene. A polycarbonate polyol obtained by reacting one or more kinds of polyol monomers with a carbonic acid ester is preferable because it is easy to produce and there is no by-production of terminal chlorinated products. The polycarbonate polyol may contain as many ether bonds and ester bonds as the average number of carbonate bonds in one molecule or less in the molecule.

The polyol monomer is not particularly limited, and examples thereof include an aliphatic polyol monomer, a polyol monomer having an alicyclic structure, an aromatic polyol monomer, a polyester polyol monomer, and a polyether polyol monomer.

The aliphatic polyol monomer is not particularly limited, but for example, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1 , 8-octanediol, 1,9-nonanediol and other linear aliphatic diols; 2-methyl-1,3-propanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5 Branched chain aliphatic diols such as -pentanediol and 2-methyl-1,9-nonanediol; trifunctional and higher functional alcohols such as trimethylolpropane and pentaerythritol can be mentioned.

The polyol monomer having an alicyclic structure is not particularly limited, and for example, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,3-cyclopentanediol, 1, Examples thereof include diols having an alicyclic structure in the main chain such as 4-cycloheptandiol, 2,7-norbornandiol, and 1,4-bis (hydroxyethoxy) cyclohexane.

The aromatic polyol monomer is not particularly limited, and is, for example, 1,4-benzenedimethanol, 1,3-benzenedimethanol, 1,2-benzenedimethanol, 4,4'-naphthalenemethanol, 3,4. '-Naphthalene methanol is mentioned.

The polyester polyol monomer is not particularly limited, but for example, a polyester polyol containing a hydroxycarboxylic acid and a diol such as a polyester polyol containing 6-hydroxycaproic acid and hexanediol, and a dicarboxylic acid such as a polyester polyol containing adipic acid and hexanediol. And polyester polyol with diol.

The carbonic acid ester is not particularly limited, and examples thereof include an aliphatic carbonic acid ester such as dimethyl carbonate and diethyl carbonate, an aromatic carbonic acid ester such as diphenyl carbonate, and a cyclic carbonic acid ester such as ethylene carbonate. In addition, phosgene or the like capable of producing a polycarbonate polyol can also be used. Of these, aliphatic carbonic acid esters are preferable, and dimethyl carbonate is particularly preferable, from the viewpoint of ease of production of polycarbonate polyol.

As a method for producing a polycarbonate polyol from a polyol monomer and a carbonic acid ester, for example, a carbonic acid ester and a polyol monomer having an excessive number of moles with respect to the number of moles of the carbonic acid ester are added to the reactor, and the temperature is 160 to 200 ° C. A method of reacting at a pressure of about 50 mmHg for 5 to 6 hours and then further reacting at a pressure of several mmHg or less at 200 to 220 ° C. for several hours can be mentioned. In the above reaction, it is preferable to carry out the reaction while extracting the alcohol produced as a by-product from the system. At that time, if the carbonic acid ester escapes from the system by azeotropically boiling with the alcohol produced as a by-product, an excessive amount of the carbonic acid ester may be added. Further, in the above reaction, a catalyst such as titanium tetrabutoxide may be used.

Examples of the polycarbonate polyol (excluding the polycarbonate polyol (a)) include a polycarbonate diol obtained by reacting 1,6-hexanediol with a carbonic acid ester, 1,6-hexanediol and 1,5-pentane. Polycarbonate diol obtained by reacting a mixture of diols with a carbonic acid ester, polycarbonate diol obtained by reacting a mixture of 1,6-hexanediol and 1,4-butanediol with a carbonic acid ester, 1,4- Polycarbonate diol obtained by reacting cyclohexanedimethanol with carbonic acid ester, polycarbonate diol obtained by reacting a mixture of 1,6-hexanediol and 1,4-cyclohexanedimethanol with carbonic acid ester, 1,6 Examples thereof include a polycarbonate diol obtained by reacting a mixture of -hexanediol and 2-methyl-1,5-pentanediol with a carbonic acid ester.

The polyester polyol is not particularly limited, and for example, polyethylene adipate diol, polybutylene adipate diol, polyethylene butylene adipate diol, polyhexamethylene isophthalate adipate diol, polyethylene succinate diol, polybutylene succinate diol, and polyethylene sebacate diol. , Polybutylene sebacate diol, poly-ε-caprolactone diol, poly (3-methyl-1,5-pentylene adipate) diol, polycondensate of 1,6-hexanediol and dimer acid and the like.

The polyether polyol is not particularly limited as long as it is a polyol having an ether bond in the molecule, and may contain a number of carbonate bonds and / or ester bonds less than the average number of ether bonds in one molecule. The polyether polyol is preferably one in which an alkylene group is ether-bonded, which is obtained by, for example, ring-opening polymerization of a cyclic ether or ring-opening polymerization of an epoxy compound.

The number of carbon atoms in the main chain of the polyether polyol is not particularly limited, but the number of carbon atoms in the main chain is preferably 2 to 4 from the viewpoint of availability. From the viewpoint of suppressing the decrease in water resistance of polyurethane due to water absorption, it is desirable that the content of oxygen atoms is small, the number of carbon atoms in the main chain is preferably 3 to 4, and the number of carbon atoms in the main chain is particularly high. preferable.

Polyether polyols include polytetramethylene ether glycol, polytetramethylene ether glycol having an alkyl side chain, polypyrropylene glycol, polyethylene glycol, and a copolymer of two or more of these; a random common weight of ethylene oxide and propylene oxide. Examples thereof include coalescing and block copolymers, random copolymers of ethylene oxide and butylene oxide, block copolymers, etc., such as polytetramethylene ether glycol, polytetramethylene ether glycol having an alkyl side chain, polypyrropylene glycol, and polyethylene. Glycols and copolymers of two or more of these are preferable. As the polyether polyol, a polyol having a nonionic group in the side chain, for example, Ymer N120 manufactured by Perstoop Co., Ltd. can also be used.
The high molecular weight polyol may be used alone or in combination of two or more.

(Terminal terminator)
The terminal terminator is a component capable of stopping the urethanization reaction and / or the chain extension reaction at the end of the polyurethane resin. Examples of the terminal terminator include compounds other than compounds having one acidic group and one hydroxyl group in one molecule and having one group that reacts with an isocyanato group. Specifically, glycolic acid (2-hydroxyacetic acid), hydroxypivalic acid (HPA), lactic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 10-hydroxydecanoic acid, hydroxypivalic acid (2,2-dimethyl). -3-Hydroxypropionic acid), 12-hydroxydodecanoic acid, 16-hydroxyhexadecanoic acid, lactic acid, trichlorolactic acid, salicylic acid, hydroxybenzoic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxypropionic acid, 2-hydroxyoctane Acids include 3-hydroxyundecanoic acid, 12-hydroxystearic acid (HSA), 12-hydroxyoleic acid and the like. Examples of the group that reacts with the isocyanato group include a compound having a total of one hydroxyl group, amino group, imino group, mercapto group and the like. Specific examples thereof include monoamines such as n-butylamine and di-n-butylamine; ethanol. , Monohydric alcohols such as isopropanol and butanol, and the like.
The terminal terminator may be used alone or in combination of two or more.

(Manufacturing method of polyurethane resin)
The polyurethane resin is one or more selected from the group consisting of polycarbonate polyol (a), polyisocyanate (b), and optional components such as chain extenders, acidic group-containing polyols, other polyols, and terminal terminators. It can be produced by reacting other components (hereinafter, also referred to as "polyurethaneization reaction").

(Urethane catalyst)
In the urethanization reaction, a known urethanization catalyst can be used to improve the reaction rate. Examples of the urethanization catalyst include organometallic salts such as tertiary amines, tin and titanium. For the urethanization catalyst, refer to pages 23 to 32 of "Polyurethane Resin" by Keiji Yoshida (published by Nikkan Kogyo Shimbun, 1969).

(solvent)
The polyurethaneization reaction can be carried out in the presence of a solvent. Examples of the solvent include esters such as ethyl acetate, butyl acetate, propyl acetate, γ-butyrolactone, γ-valerolactone, and δ-caprolactone; dimethylformamide, diethylformamide, dimethylacetamide, and "Equamid" manufactured by Idemitsu Kosan Co., Ltd. Amides such as β-alkoxypropionamide; sulfoxides such as dimethyl sulfoxide; ethers such as tetrahydrofuran, dioxane and 2-ethoxyethanol; ketones such as methylisobutylketone and cyclohexanone; aromatic carbides such as benzene and toluene Examples include hydrogens.

The polyurethaneization reaction can be carried out by adding a terminal terminator to adjust the molecular weight.

The polyurethane resin can be a flexible polyurethane foam, a rigid polyurethane foam, a thermoplastic polyurethane, a solvent-based polyurethane solution, an aqueous polyurethane resin dispersion, or the like. In addition, these can be used to process artificial leather, synthetic leather, heat insulating materials, cushioning materials, adhesives, paints, coating agents, molded products such as films, and the like.

[Polyurethane resin dispersion]
The polyurethane resin dispersion includes a polyurethane resin and a medium. Examples of the medium include an aqueous medium (c) and an organic medium. When the polyurethane resin dispersion contains a polyurethane resin and an aqueous medium (c), it becomes an aqueous polyurethane resin dispersion, and when the polyurethane resin dispersion contains a polyurethane resin and an organic medium, it becomes a solvent-based polyurethane resin dispersion.

(Aqueous medium (c))
Examples of the aqueous medium include water such as clean water, ion-exchanged water, distilled water, and ultrapure water, and a mixed medium of water and a hydrophilic organic solvent.

Examples of the hydrophilic organic solvent include ketones such as acetone and ethyl methyl ketone; pyrrolidones such as N-methylpyrrolidone and N-ethylpyrrolidone; ethers such as diethyl ether and dipropylene glycol dimethyl ether; methanol, ethanol and n. -Alcohols such as propanol, isopropanol, ethylene glycol and diethylene glycol; amides such as β-alkoxypropionamide represented by "KJCMPA (R) -100" manufactured by KJ Chemical Co., Ltd .; 2- (dimethylamino) -2-methyl Examples thereof include hydroxyl group-containing tertiary amines such as -1-propanol (DMAP).
The amount of the hydrophilic organic solvent in the aqueous medium is preferably 0 to 20% by mass.

(Organic medium)
The organic medium is not particularly limited as long as it can disperse the polyurethane resin, but the hydrophilic organic solvent is preferable.

(Additional ingredients)
Polyurethane resin dispersions can contain additional components such as heat stabilizers, light stabilizers, plasticizers, inorganic fillers, lubricants, colorants, silicone oils, foaming agents, flame retardants and the like. The additional components may be used alone or in combination of two or more, respectively.

(Manufacturing method of aqueous polyurethane resin dispersion)
The method for producing an aqueous polyurethane resin dispersion is, for example, a step of reacting a polycarbonate polyol (a), a polyisocyanate (b), and an acidic group-containing polyol in the presence or absence of a solvent to obtain a urethane prepolymer. , A step of neutralizing the acidic group in the prepolymer with a neutralizing agent, a step of dispersing the neutralized prepolymer in the aqueous medium (c), a prepolymer dispersed in the aqueous medium (c) and a chain extender. Examples thereof include a manufacturing method including a step of reacting with. In each step, a catalyst can be used as needed to accelerate the reaction and control by-products. In addition, the addition step of the other polyol and the terminal terminator can be appropriately selected. The aqueous polyurethane resin dispersion derived from the polycarbonate polyol (a) provides a film having excellent adhesion, flexibility, and tactile sensation, and is therefore particularly applicable to artificial leather and synthetic leather.

Examples of the polycarbonate polyol (a), polyisocyanate (b), aqueous medium (c), acidic group-containing polyol, other polyol, terminal terminator, solvent, and chain extender include the above-mentioned components.

When the aqueous polyurethane resin dispersion is produced using an acidic group-containing polyol, the amount of the polyisocyanate (b) used is the isocyanate group of the polyisocyanate (b) and the polyol (polypolypolyol (a), acidic group-containing polyol). , And all polyols such as low molecular weight polyols) to the total hydroxyl group (isocyanate group / hydroxyl group (molar ratio)) is preferably 0.8 to 2.0, preferably 0.9 to 1.8. It is particularly preferable to have.
The amount of the acidic group-containing polyol used is not particularly limited as long as the polyurethane resin can disperse the polyurethane resin in an aqueous medium. The amount of the neutralizing agent used is not particularly limited as long as it can neutralize the acidic groups in the polyurethane resin. The amount of other polyols, terminal terminators and chain extenders used can be appropriately selected.

(Manufacturing method of solvent-based polyurethane resin dispersion)
The method for producing the solvent-based polyurethane resin dispersion is not particularly limited as long as the desired solvent-based polyurethane resin dispersion can be obtained. For example, in the method for producing an aqueous polyurethane resin dispersion, a method in which an acidic group-containing polyol is not used and the aqueous medium (c) is replaced with an organic medium can be mentioned. Further, as a method for producing the solvent-based polyurethane resin dispersion, for example, the method described in JP2013-163792A can be mentioned.

[Use]
The polyurethane resin can be used in a coating composition, a coating agent composition, an ink composition, and a fiber treatment agent composition. Further, the polyurethane resin film can be produced by drying and curing the polyurethane resin.

(Paint composition, coating agent composition, ink composition and fiber treatment agent composition)
The coating composition, coating agent composition, ink composition and fiber treatment agent composition contain a polyurethane resin. The coating composition, the coating agent composition, the ink composition, and the fiber treatment agent composition contain a medium (that is, an aqueous medium (c) and an organic medium), other resins, a curing agent, and a coloring as components other than the polyurethane resin. It can contain pigments, extender pigments, glitter pigments and conventional additives. The components other than the polyurethane resin may be used alone or in combination of two or more.

(Other resins)
Examples of other resins include polyester resin, acrylic resin, polyether resin, polycarbonate resin, polyurethane resin, epoxy resin, alkyd resin, polyolefin resin, vinyl chloride resin and the like. These may be used alone or in combination of two or more. When the coating composition, the coating agent composition, the ink composition and the fiber treatment agent composition contain the aqueous medium (c), the other resin contains one or more hydrophilic groups from the viewpoint of dispersibility in water. It is preferable to have. Examples of the hydrophilic group include a hydroxyl group, a carboxy group, a sulfonic acid group, a polyethylene glycol group and the like.

The other resin is preferably at least one selected from the group consisting of polyester resin, acrylic resin, and polyolefin resin.

The polyester resin can be produced by an esterification reaction or a transesterification reaction between an acid component and an alcohol component. As the acid component, a compound usually used as an acid component in the production of the polyester resin can be used. As the acid component, for example, an aliphatic polybasic acid, an alicyclic polybasic acid, an aromatic polybasic acid and the like can be used.

The hydroxyl value of the polyester resin is preferably about 10 to 300 mgKOH / g, more preferably about 50 to 250 mgKOH / g, and particularly preferably about 80 to 180 mgKOH / g. The acid value of the polyester resin is preferably about 1 to 200 mgKOH / g, more preferably about 15 to 100 mgKOH / g, and particularly preferably about 25 to 60 mgKOH / g. The weight average molecular weight of the polyester resin is preferably 500 to 500,000, more preferably 1,000 to 300,000, and particularly preferably 1,500 to 200,000.

As the acrylic resin, a hydroxyl group-containing acrylic resin is preferable. The hydroxyl group-containing acrylic resin comprises a hydroxyl group-containing polymerizable unsaturated monomer and another polymerizable unsaturated monomer copolymerizable with the hydroxyl group-containing polymerizable unsaturated monomer, for example, by a solution polymerization method in an organic solvent, in water. It can be produced by copolymerizing by a known method such as the emulsion polymerization method of.

The hydroxyl group-containing polymerizable unsaturated monomer is a compound having one or more hydroxyl groups and one or more polymerizable unsaturated bonds in one molecule. For example, (meth) acrylic acids such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate and 2 to 8 carbon atoms. Monoesterates with dihydric alcohols; ε-caprolactone modified products of these monoesterates; N-hydroxymethyl (meth) acrylamide; allyl alcohols; (meth) acrylates having a polyoxyethylene chain having a hydroxyl group at the molecular end. And so on.

The hydroxyl group-containing acrylic resin preferably has an anionic functional group. As the hydroxyl group-containing acrylic resin having an anionic functional group, for example, as one kind of polymerizable unsaturated monomer, a polymerizable unsaturated monomer having an anionic functional group such as a carboxylic acid group, a sulfonic acid group, or a phosphoric acid group is used. It can be manufactured by using it.

The hydroxyl value of the hydroxyl group-containing acrylic resin is preferably 1 to 200 mgKOH / g, more preferably 2 to 100 mgKOH / g, and 3 to 60 mgKOH / g from the viewpoint of storage stability of the composition and water resistance of the obtained coating film. Is particularly preferable. When the hydroxyl group-containing acrylic resin has an acid group such as a carboxyl group, the acid value of the hydroxyl group-containing acrylic resin is preferably 1 to 200 mgKOH / g, preferably 2 to 150 mgKOH, from the viewpoint of water resistance of the obtained coating film. / G is more preferable, and 5 to 100 mgKOH / g is particularly preferable. The weight average molecular weight of the hydroxyl group-containing acrylic resin is preferably 1,000 to 200,000, more preferably 2,000 to 100,000, and particularly preferably 3,000 to 50,000.

Examples of the polyether resin include polymers or copolymers having an ether bond, and examples thereof include polyoxyethylene-based polyethers, polyoxypropylene-based polyethers, polyoxybutylene-based polyethers, bisphenol A, and bisphenol F. Examples thereof include polyethers derived from aromatic polyhydroxy compounds.

Examples of the polycarbonate resin include polymers produced from bisphenol compounds, and examples thereof include bisphenol A and polycarbonate.

Examples of the polyurethane resin include resins having a urethane bond obtained by reacting various polyol components such as acrylic, polyester, polyether, and polycarbonate with polyisocyanate.

Examples of the epoxy resin include a resin obtained by the reaction of a bisphenol compound and epichlorohydrin. Examples of bisphenol include bisphenol A and bisphenol F.

Examples of the alkyd resin include polybasic acids and polyhydric alcohols such as phthalic acid, terephthalic acid, and succinic acid, as well as fats and oils and fat fatty acids (soybean oil, linseed oil, coconut oil, stearic acid, etc.), and natural resins (for example, stearic acid). , Rosin, Kohaku, etc.), etc.), and alkyd resins obtained by reacting them.

As the polyolefin resin, a polyolefin resin obtained by appropriately polymerizing or copolymerizing an olefin-based monomer with another monomer according to a usual polymerization method is water-dispersed using an emulsifier, or an olefin-based monomer is appropriately used as another monomer. Examples thereof include a resin obtained by emulsifying and polymerizing together with the resin. Further, depending on the case, a so-called chlorinated polyolefin-modified resin in which the above-mentioned polyolefin resin is chlorinated may be used.

Examples of the olefin-based monomer include ethylene, propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-hexene and 1-. Α-olefins such as decene and 1-dodecene; conjugated diene and non-conjugated diene such as butadiene, etilidennorbornene, dicyclopentadiene, 1,5-hexadiene and styrenes can be mentioned. The olefin-based monomer may be used alone or in combination of two or more.

Examples of other monomers copolymerizable with the olefin-based monomer include vinyl acetate, vinyl alcohol, maleic acid, citraconic acid, itaconic acid, maleic anhydride, citraconic anhydride, itaconic anhydride and the like. The other monomers may be used alone or in combination of two or more.

(Hardener)
Examples of the curing agent include amino resins, polyisocyanates, blocked polyisocyanates, melamine resins, carbodiimides, polyols and the like. When the coating composition and the coating agent composition contain a curing agent, the water resistance of the coating film, the multilayer coating film, the coating film or the printed matter obtained by using the coating composition or the coating agent composition can be improved. .. The curing agent may be used alone or in combination of two or more.

Examples of the amino resin include a partially methylolated amino resin obtained by reacting an amino component with an aldehyde component. Examples of the amino component include melamine, urea, benzoguanamine, acetoguanamine, steloganamin, spiroganamin, dicyandiamide and the like. Examples of the aldehyde component include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde and the like.

Examples of the polyisocyanate include compounds having two or more isocyanato groups in one molecule, and examples thereof include hexamethylene diisocyanate and trimethylhexamethylene diisocyanate.

Examples of the blocked polyisocyanate include those obtained by adding a blocking agent to the isocyanato group of the above-mentioned polyisocyanate, and examples of the blocking agent include those obtained by adding a blocking agent.
Phenols such as phenol and cresol, aliphatic alcohols such as methanol and ethanol, active methylene such as dimethyl malonate and acetylacetone, mercaptans such as butyl mercaptan and dodecyl mercaptan, acid amides such as acetoanilide and acetate, ε -Caprolactam, δ-lactam such as valerolactam, acidimide such as imide succinate and imide maleate, oxime such as acetoaldoxime, acetoneoxime and methylethylketooxime, amine type such as diphenylaniline, aniline and ethyleneimine. And other blocking agents.

Examples of the melamine resin include methylol melamines such as dimethylol melamine and trimethylol melamine; alkyl ethers or condensates of these methylol melamines; and condensates of alkyl ethers of methylol melamine.

Examples of the polyol include polyrotaxane and compounds derived from the polyrotaxane.

(Coloring pigment)
Examples of the coloring pigment include titanium oxide, zinc flower, carbon black, molybdenum red, Prussian blue, cobalt blue, azo pigment, phthalocyanine pigment, quinacridone pigment, isoindoline pigment, slene pigment, perylene pigment and the like. Titanium and / or carbon black is preferred. The coloring pigment may be used alone or in combination of two or more.

(Constitution pigment)
Examples of the extender pigment include clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talc, silica, and alumina white, and barium sulfate and / or talc is preferable, and barium sulfate is more preferable. The extender pigment may be used alone or in combination of a plurality of types.

(Glowing pigment)
Examples of the glitter pigment include aluminum, copper, zinc, brass, nickel, aluminum oxide, mica, aluminum oxide coated with titanium oxide or iron oxide, and mica coated with titanium oxide or iron oxide. The glitter pigment may be used alone or in combination of two or more.

(Normal additive)
Examples of ordinary additives include thickeners, curing catalysts, ultraviolet absorbers, light stabilizers, defoamers, plasticizers, surface conditioners, anti-settling agents, and the like. It can be appropriately selected depending on the function, characteristics, application and the like of the coating composition and the coating agent composition. The usual additives may be used alone or in combination of a plurality of types, or commercially available products may be used as they are.

(Method for manufacturing paint composition, coating agent composition, ink composition and fiber treatment agent composition)
The method for producing the coating composition, the coating agent composition, the ink composition and the fiber treatment agent composition is not particularly limited, and a known production method can be adopted. The coating composition, the coating agent composition and the ink composition can be produced, for example, by mixing a polyurethane resin with the above-mentioned various additives and adjusting the viscosity according to the application method.

The coating composition, coating agent composition and ink composition can be applied to paper, plastics, films, metals, rubbers, elastomers, textile products and the like.

Examples of the fiber to be treated by the fiber treatment agent composition include fiber materials constituting fabrics, and specifically, natural fibers such as cotton, hemp, wool and silk; semi-synthetic fibers such as rayon and acetate. Fibers; synthetic fibers such as polyester, polyamide, polyacrylonitrile, and polyolefin; and blended and mixed knitted fabrics of these fibers can be mentioned.

(Polyurethane resin film)
The polyurethane resin film is formed from a polyurethane resin. The polyurethane resin film can be obtained by applying an aqueous polyurethane resin dispersion to a releasable base material, drying and curing it by means such as heating, and then peeling a cured product of the polyurethane resin from the releasable base material. Is preferable.

Examples of the heating method include a heating method using its own reaction heat and a heating method in which the reaction heat and the positive heating of the mold are used in combination. Examples of active heating of the mold include a method of heating the mold in a hot air oven, an electric furnace, or an infrared induction heating furnace. The heating temperature is preferably 40 to 200 ° C, particularly preferably 60 to 160 ° C. By heating at such a temperature, drying can be performed more efficiently. The heating time is preferably 0.0001 to 20 hours, and particularly preferably 1 to 10 hours. By setting such a heating time, a polyurethane resin film having higher hardness can be obtained.

The thickness of the polyurethane resin film is preferably 1 to 200 μm, and preferably 3 to 100 μm.

Next, the present invention will be specifically described with reference to examples, but the scope of the present invention is not limited thereto.

(Number average molecular weight)
The number average molecular weight was calculated based on the following formula.
Number average molecular weight = (56,100 × 2) / hydroxyl value The hydroxyl value of the polycarbonate polyol was determined by titration in accordance with JIS K 1557. Here, the unit of the hydroxyl value is mgKOH / g.
The acid value of the polycarbonate polyol was determined by titration in accordance with JIS K 1557. Here, the unit of acid value is mgKOH / g.

(Example 1; Synthesis of polycarbonate polyol (1))
Polycarbonate polyol (3) obtained by reacting 1,6-hexanediol with dimethyl carbonate in a glass round bottom flask equipped with a rectification tower, a stirrer, a thermometer and a nitrogen introduction tube (Ube Kosan Co., Ltd.) ) UH-300 (registered trademark) UH-300 (molecular weight 2900, hydroxyl value 38.6 mgKOH / g, 300 g) and a polyol having a nonionic group in the side chain (Perstop Co., Ltd., Ymer N120, hydroxyl value 38.6 mgKOH / g) , 95 g) was added and mixed. By heating and stirring at 150 ° C. for 5 hours, a polycarbonate polyol (1) having a nonionic group in the side chain was obtained.

The obtained polycarbonate polyol (1) had a number average molecular weight of 1,920, a hydroxyl value of 58.4 mgKOH / g, and an acid value of 0.1 mgKOH / g.

(Comparative Example 1; Preparation of Polycarbonate Polyol (2))
Polycarbonate polyol (2) obtained by reacting 1,6-hexanediol with dimethyl carbonate (manufactured by Ube Corporation, ETERNAL COLL® UH-200 (molecular weight 2,000, hydroxyl value 56.1 mgKOH /) g, acid value 0.03 mgKOH / g) was prepared.

(Example 2; Synthesis of aqueous polyurethane resin dispersion (1))
In a reactor equipped with a stirrer and a heater, 148.13 g of the polycarbonate polyol (1) of Example 1, a polycarbonate polyol (manufactured by Ube Kosan Co., Ltd., ETERNAL COLL (registered trademark) UH-200 (molecular weight 2,018, hydroxyl value) 55.6 mgKOH / g) 200 g, 2,2-dimethylol propionic acid 8.7 g, isophorone diisocyanate 76.9 g, dipropylene glycol dimethyl ether 143 g, and dibutyltin (IV) dilaurate 0.3 g were mixed and 80 in a nitrogen atmosphere. The reaction was carried out at ~ 90 ° C. for 5 hours (isocyanate group content at the end of the reaction; 1.33% by mass).
The obtained reaction solution was cooled to 80 ° C., 6.7 g of triethylamine was added thereto, and the mixture was stirred for 30 minutes. Of the reaction mixture, 549 g was withdrawn and added to 839 g of vigorously stirred water.
Further, 25.6 g of a 35 mass% 2-methyl-1.5-diaminopentane aqueous solution was added to obtain an aqueous polyurethane resin dispersion (1).

(Comparative Example 2; Synthesis of Aqueous Polyurethane Resin Dispersion (2))
In a reactor equipped with a stirrer and a heater, 328 g of the polycarbonate polyol (2) of Comparative Example 1, 9.4 g of 2,2-dimethylol propionic acid, and a polyol having a nonionic group in the side chain (Ymer N120, manufactured by Perstoop). , Hydroxyl value 111 mgKOH / g) 37.5 g, isophorone diisocyanate 90.1 g, dipropylene glycol dimethyl ether 154 g, and titanium (IV) tetrabutoxide 0.2 g are mixed and reacted at 80 to 90 ° C. for 6 hours under a nitrogen atmosphere. (Isocyanate group content at the end of the reaction; 1.54% by mass).
The obtained reaction solution was cooled to 80 ° C., 7.2 g of triethylamine was added thereto, and the mixture was stirred for 30 minutes. Of the reaction mixture, 578 g was withdrawn and added to 863 g of vigorously stirred water.
Further, 31.5 g of a 35 mass% 2-methyl-1,5-diaminopentane aqueous solution was added to obtain an aqueous polyurethane resin dispersion (2).

(Comparative Example 3; Synthesis of Aqueous Polyurethane Resin Dispersion (3))
In a reactor equipped with a stirrer and a heater, 300 g of the polycarbonate polyol (2) of Comparative Example 1, 15.8 g of 2,2-dimethylol propionic acid, 83.4 g of isophorone diisocyanate, 134 g of dipropylene glycol dimethyl ether, and dibutyltin (IV). ) Dilaurate (0.3 g) was mixed and reacted at 80 to 90 ° C. for 5 hours under a nitrogen atmosphere (isocyanate group content at the end of the reaction; 1.67% by mass).
The obtained reaction solution was cooled to 80 ° C., 11.9 g of triethylamine was added thereto, and the mixture was stirred for 30 minutes. Of the reaction mixture, 517 g was extracted and added to 746 g of strongly stirred water to obtain an aqueous polyurethane resin dispersion (3).

(Synthesis of polyurethane resin film)
The aqueous polyurethane resin dispersion was uniformly applied onto a polyethylene terephthalate (PET) film so that the film thickness after drying was about 80 μm. Then, after leaving it at room temperature for 15 hours, it was dried at 60 ° C. for 2 hours and at 120 ° C. for 2 hours to form a polyurethane resin. Next, the polyurethane resin was peeled off from the PET film and cured at room temperature for 10 hours to obtain a polyurethane resin film.

(Flexibility)
The elastic modulus and breaking point elongation of the polyurethane resin film were measured by a method according to JIS K 7113.

(Measurement of hysteresis loss)
The polyurethane resin film was stretched until the tensile elongation became 200% by a method according to JIS K 7113. After that, the change in elongation and the tensile stress when the test piece was tried to be returned to the original elongation were measured. The hysteresis loss was calculated by the method described in JP-A-2016-204595. The smaller the number, the smaller the hysteresis loss and the higher the stability.

From Table 1, the polyurethane resin film of Example 2 obtained by using the aqueous polyurethane resin dispersion derived from the polycarbonate polyol having a structure derived from the polyol having a nonionic group in the side chain has a low elastic modulus and has a low elastic modulus. It was found to show high resilience.
On the other hand, Comparative Example 1 obtained by using an aqueous polyurethane resin dispersion derived from a polyol having a nonionic group in the side chain and a polycarbonate polyol having no structure derived from the polyol having a nonionic group in the side chain. The polyurethane resin film of Comparative Example 2 obtained by using the polyurethane resin film and the aqueous polyurethane resin dispersion derived from the polycarbonate polyol having no structure derived from the polyol having a nonionic group in the side chain has an elastic coefficient. It was high and had low resilience.
Therefore, the polycarbonate polyol of Example 1 having a structure derived from a polyol having a nonionic group in the side chain was a polycarbonate polyol that exhibited useful effects such as flexibility and resilience when induced in polyurethane.

Polycarbonate polyol, which has a structure derived from a polyol having a nonionic group in the side chain, exhibits useful effects such as flexibility and resilience when induced in polyurethane, and is therefore a useful compound as a raw material for various polyurethane resins. be. Further, the aqueous polyurethane resin dispersion using the polycarbonate polyol having a structure derived from the polyol having a nonionic group in the side chain is specifically described in artificial leather, synthetic leather, paint, ink, coating material, elastic fiber, and adhesive. It can be used as a raw material for agents, adhesives and the like.

Claims (8)

An aqueous polyurethane resin dispersion containing a polyurethane resin and an aqueous medium (c).
The polyurethane resin has a structure derived from a polycarbonate polyol having a structure derived from a polyol (A) having a nonionic group in a side chain, a structure derived from a polyisocyanate (b), and a structure derived from an acidic group-containing polyol. ,
An aqueous polyurethane resin dispersion in which the polyol (A) having a nonionic group in the side chain is represented by the following formula (1).

(In the formula, Z ¹ has a linear, branched or cyclic trivalent hydrocarbon group which may be interrupted by an oxygen atom and may have a substituent, or a substituent. It indicates a trivalent aromatic hydrocarbon group which may be used. Z ² may be linear, branched or cyclic, interrupted by an oxygen atom, or may have a substituent. Indicates a valent hydrocarbon group or a monovalent aromatic hydrocarbon group which may have a substituent. N1 indicates a number from 1 to 100.) The aqueous polyurethane resin dispersion according to claim 1, wherein the polycarbonate polyol further has a structure derived from the polyol (B) (excluding the polyol (A) having a nonionic group in the side chain). The aqueous polyurethane resin dispersion according to claim 2, wherein the polyol (B) is represented by the following formula (2).

(In the formula, Z ³ has a linear, branched or cyclic divalent hydrocarbon group which may be interrupted by an oxygen atom and may have a substituent, or a substituent. Indicates a divalent aromatic hydrocarbon group that may be used.) A coating composition containing the aqueous polyurethane resin dispersion according to any one of claims 1 to 3. A coating agent composition containing the aqueous polyurethane resin dispersion according to any one of claims 1 to 3. An ink composition containing the aqueous polyurethane resin dispersion according to any one of claims 1 to 3. A polyurethane resin film obtained by drying and curing the aqueous polyurethane resin dispersion according to any one of claims 1 to 3. A fiber treatment agent composition containing the aqueous polyurethane resin dispersion according to any one of claims 1 to 3.