JP2019081887A - Emulsion composition - Google Patents

Abstract

To provide an emulsion composition whereby it is possible to obtain a coating that retains flexibility and tack-free properties, and yet prevents a coating face from cracking due to stretching, offering excellent primer followability.SOLUTION: An emulsion composition contains a polyurethane resin and an acrylic resin, wherein, (i) the polyurethane resin is a first polyurethane resin containing (a) a structure derived from a polyol having a polyethylene oxide chain; or, (ii) the polyurethane resin is a second polyurethane resin containing (b') a structure derived from a polyol (excluding (d) acidic group-containing polyol), (c) a polyisocyanate-derived structure, (d) an acidic group-containing polyol-derived structure, and (e) a chain extender-derived structure, wherein, the (b') polyol contains (b1) a polycarbonate polyol-derived structure, and (b2) a structure derived from a polyetherpolyol having an alkylene oxy skeleton with a C4 main chain.SELECTED DRAWING: None

Description

  The present invention relates to an emulsion composition comprising a polyurethane resin and an acrylic resin.

  A polyurethane resin emulsion is excellent in adhesion to a substrate, abrasion resistance, impact resistance, solvent resistance, and the like, and thus, paints, inks, adhesives, various coatings such as paper, plastics, films, metals Widely used in rubber, elastomers, textiles, etc. It is known that a coating film obtained by applying a polyurethane resin emulsion using polycarbonate polyol as a raw material is excellent in light resistance, weather resistance, heat resistance, hydrolysis resistance and oil resistance (Patent Document 1).

  In a polyurethane resin emulsion made of polycarbonate polyol as a raw material, in order to improve flexibility, a polyurethane prepolymer consisting of a raw material containing a compound having one acidic group and one hydroxyl group in one molecule is combined with an amino group and / or an imino group. There is known an aqueous polyurethane resin dispersion in which a polyurethane resin obtained by reacting with three or more chain extenders is dispersed in an aqueous medium (Patent Document 2). It is known that a coating film obtained by applying an aqueous polyurethane resin using a polyether polyol as a raw material is excellent in flexibility, hydrolysis resistance and moisture and heat resistance (Patent Document 3).

  As a binder for ink, there is disclosed a method using an aqueous urethane resin composition having an anionic group and a polyethylene oxide chain in a side chain in order to improve scratch resistance and chemical resistance (Patent Document 4) ). The textile product application of the polyurethane resin emulsion also includes the surface coating of fabric and the use as a binder for printing ink. Coatings and textiles for textile applications include the softness of coated surface not to inhibit the soft texture of the fabric, the fastness to rubbing, the wash resistance, the prevention of sticking when the product is folded, and the skin Tack-free property is required to provide a non-stick slippery texture. In addition, a smooth surface texture unique to polyurethane resin is one of the required characteristics.

  Disclosed is a method of blending a silicone emulsion with a polyurethane resin emulsion and using it as a binder to improve the rubbing fastness, washing resistance, dry cleaning resistance and stretch back properties of pigment printed matter, as a polyurethane resin emulsion for printing ink (Patent Document 5). Also, in order to provide an ink composition for ink jet printing that is excellent in both long-term stability of the ink and abrasion resistance and flexibility of the printing material, the composition contains a urethane resin emulsion, an emulsion silicone compound, and water. An ink composition for ink jet printing is disclosed (Patent Document 6).

Japanese Patent Application Laid-Open No. 10-120757 WO2014 / 103689 WO2015 / 194672 JP, 2011-140560, A Unexamined-Japanese-Patent No. 2-91280 JP, 2013-194222, A JP, 2007-332523, A JP, 2009-215506, A

Adhesion Handbook 4th Edition Editor: Japan Adhesiveness Society

  However, flexibility and tack freeness are contradictory issues (Non-patent Document 1), and an aqueous polyurethane resin emulsion which gives a coating excellent in both of these properties has not been proposed. Moreover, when using the ink composition for pigment printing which uses a polyurethane resin emulsion as a binder, a resin film insoluble in water is formed due to the dry fixation of the binder resin, causing problems such as clogging of the screen wrinkles. (Patent Document 7). In addition, the printed matter obtained by printing the ink composition for pigment printing on a cloth substrate may cause problems such as breakage or cracking of the coated film surface by tension (Patent Document 8).

  An object of the present invention is to provide an emulsion composition which gives a coating film excellent in substrate followability, in which the coating film surface is not broken by tension while being kept flexible and tack free.

  The present inventors are an emulsion composition comprising a polyurethane resin and an acrylic resin, wherein the polyurethane resin comprises (a) a first polyurethane resin comprising a structure derived from a polyol having a polyethylene oxide chain, or (b ') A structure derived from a polyol (but excluding (d) an acid group-containing polyol), (c) a structure derived from a polyisocyanate, (d) a structure derived from an acid group-containing polyol, and (e) a chain extender derived And the structure derived from the (b ′) polyol includes (b1) a structure derived from a polycarbonate polyol, and (b2) a structure derived from a polyether polyol having an alkylene oxy skeleton having 4 carbon atoms in the main chain. It has been found that the above-mentioned problems are solved by an emulsion composition which is a second polyurethane resin containing the same.

The present invention relates to the following.
[1] An emulsion composition comprising a polyurethane resin and an acrylic resin,
The emulsion composition in which the said polyurethane resin contains the structure derived from the polyol which has (a) polyethylene oxide chain.
[2] The polyurethane resin further comprises a structure derived from (b) a polyol (but excluding (a) a polyol having a polyethylene oxide chain and (d) an acidic group-containing polyol), and (c) a structure derived from a polyisocyanate The emulsion composition according to [1], which comprises (d) a structure derived from an acidic group-containing polyol and (e) a structure derived from a chain extender.
[3] (b) At least a structure derived from a polyol is selected from the group consisting of (b1) a structure derived from a polycarbonate polyol, and (b2) a structure derived from a polyether polyol having an alkylene oxy skeleton having 4 main chain carbon atoms The emulsion composition of [2], comprising a structure derived from one type of polyol.
[4] The emulsion composition of [2], wherein the structure derived from the polyol (b1) comprises a structure derived from the polycarbonate polyol.
[5] The emulsion composition according to any one of [1] to [4], wherein in the polyurethane urethane resin, the content of the (a) structure derived from a polyol having a polyethylene oxide chain is 0.5 to 20% by mass.
[6] An emulsion composition comprising a polyurethane resin and an acrylic resin,
The polyurethane resin has a structure derived from (b ′) polyol (however, except for (d) an acid group-containing polyol), (c) a structure derived from a polyisocyanate, and (d) a structure derived from an acid group-containing polyol, (E) containing a chain extender-derived structure,
An emulsion composition, wherein the structure derived from the (b ′) polyol includes (b1) a structure derived from a polycarbonate polyol and (b2) a structure derived from a polyether polyol having an alkylene oxy skeleton having 4 main chain carbon atoms.
[7] The emulsion composition according to any one of [1] to [6], wherein the proportion of the acrylic resin is 0.1 to 90% by mass with respect to the total solid content of the emulsion composition.
[8] The emulsion composition of any one of [1] to [7], wherein the glass transition temperature of the acrylic resin is 15 ° C. or less.
[9] The emulsion composition of any of [1] to [8], further comprising a silicone.
[10] The emulsion composition of [9], wherein the silicone is an acrylic silicone resin emulsion.
[11] The emulsion composition of [7] or [8], wherein the ratio of silicone is 0.5 to 30% by mass with respect to the total solid content of the emulsion composition.
The ink containing the emulsion composition in any one of [12] [1]-[11].
[13] A printing ink comprising the emulsion composition of any of [1] to [11].
[14] An ink for screen printing textile printing, comprising the emulsion composition of any of [1] to [11].

  According to the present invention, there is provided an emulsion composition which provides a coating excellent in substrate followability, in which the coating surface is not fractured by tension while maintaining flexibility and tack-free property.

[Emulsion composition]
The emulsion composition is an emulsion composition comprising a polyurethane resin and an acrylic resin, wherein the polyurethane resin is
(A) a first polyurethane resin comprising a structure derived from a polyol having a polyethylene oxide chain, or
(B ') a structure derived from a polyol (but excluding (d) an acidic group-containing polyol), (c) a structure derived from a polyisocyanate, (d) a structure derived from an acidic group-containing polyol, (e) chain extension And (b1) a polyol derived from (b1) a polycarbonate polyol, and (b2) a derived structure from a polyether polyol having an alkylene oxy skeleton having 4 carbon atoms in the main chain. A second polyurethane resin containing

  When the emulsion composition contains a polyurethane resin and an acrylic resin, when the printed matter is printed using the emulsion composition, the tackiness of the surface of the printed matter is reduced while maintaining the flexibility of the printed matter. Be done. In addition, since the coating film of the emulsion composition has flexibility, it does not inhibit the soft feel of the coated substrate. Since the coating film of the emulsion composition has a tack-free property, sticking of the coated surface is suppressed, or a suppressed feeling of sticking when touched with the skin is obtained. In addition, since the printing ink contains the emulsion composition, clogging of the screen wrinkles due to drying and fixing of the printing ink is suppressed. In addition, the emulsion composition is further excellent in water washability when used as a binder resin.

  The emulsion composition preferably comprises a polyurethane resin, an acrylic resin and an aqueous medium. In the emulsion composition, the polyurethane resin and the acrylic resin may be dispersed in the aqueous medium as separate particles respectively, or the polyurethane resin may be dispersed in a form in which the acrylic resin is contained, and a combination thereof It may be. Here, “the polyurethane resin and the acrylic resin are dispersed as separate particles in the aqueous medium” means that the polyurethane resin and the acrylic resin are completely separated and independently dispersed in the aqueous medium. Means state. The term "including" widely means other than the state in which the polyurethane resin and the acrylic resin are completely separated and independently dispersed in the aqueous medium. Specifically, it means that a part or all of the acrylic resin is included in the polyurethane resin, and more specifically, in the composite resin particles dispersed in the composite resin aqueous dispersion, the inside of the polyurethane resin Means that part or all of the acrylic resin is present. At this time, the presence position of the acrylic resin in the composite resin particle is not particularly limited, and may be separated into one or more at any position near the center or off from the center. In the emulsion composition, the polyurethane resin and the acrylic resin are preferably dispersed in the aqueous medium as separate particles. In this case, the emulsion composition comprises a polyurethane resin emulsion and an acrylic resin emulsion.

(Water based medium)
The aqueous medium includes water or a mixture of water and an organic solvent. Examples of water include, but are not limited to, fresh water, ion-exchanged water, distilled water, ultrapure water, etc., such as being easy to obtain and having little influence of salts causing particles to become unstable, etc. From the viewpoint of ion exchange water, it is preferable. Examples of the organic solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, dioxane, dimethylformamide, dimethyl sulfoxide, N-methyl pyrrolidone, N-ethyl pyrrolidone, β-alkoxypropionamide (KJ CMPA (R) -100 manufactured by KJ Chemicals KJCMBPA (R) -100), dipropylene glycol dimethyl ether, ethyl acetate and the like.

(Polyurethane resin)
The polyurethane resin is (a) a first polyurethane resin containing a structure derived from a polyol having a polyethylene oxide chain, or (b) a structure derived from a polyol (except (d) an acid group-containing polyol) c) A structure derived from a polyisocyanate, (d) a structure derived from an acidic group-containing polyol, and (e) a structure derived from a chain extender, and the (b ′) polyol is derived from a (b1) polycarbonate polyol And (b2) a structure derived from a polyether polyol having an alkyleneoxy skeleton having a main chain carbon number of 4 and a structure of (b2) having a main chain carbon number of 4).

<First polyurethane resin>
The first polyurethane resin comprises (a) a structure derived from a polyol having a polyethylene oxide chain. The first polyurethane resin further has, as an arbitrary structure, a structure derived from (b) a polyol (however, excluding (a) a polyol having a polyethylene oxide chain and (d) an acidic group-containing polyol), and (c) a poly It may include an isocyanate-derived structure, (d) a structure derived from an acid group-containing polyol, (e) a structure derived from a chain extender, and (f) a structure derived from an end terminator. When the first polyurethane resin has a structure derived from (d) an acidic group-containing polyol, a part of the (d ′) neutralizing agent may further be present as a counter ion. In the first polyurethane resin, the above-described structure may be a combination of a plurality of types.

  The structure derived from the polyol (a) having a polyethylene oxide chain means a partial structure other than the group involved in the polyurethane formation reaction among the molecular structures of the polyol (a) having a polyethylene oxide chain. The structures derived from (b) to (d) and the like are the same as (a). The (e) chain extender-derived structure means a partial structure other than the group involved in the chain extension reaction among the molecular structures of (e) chain extender. The structure derived from the (f) end terminator means a partial structure other than the group involved in the reaction for terminating the urethanation reaction and / or the chain extension reaction among the molecular structures of the (f) end terminator. The structures derived from (a) to (f) are introduced into the polyurethane resin by (a) to (f) respectively.

<< (a) Polyol having a polyethylene oxide chain >>
(A) A polyol having a polyethylene oxide chain (herein, “a polyol having a (a) polyethylene oxide chain” may be referred to as “(a)”) is not particularly limited, but polyethylene glycol, Random copolymer or block copolymer of ethylene oxide and propylene oxide, random copolymer or block copolymer of ethylene oxide and butylene oxide, or polyol having a group having two hydroxyl groups at one end of polyethylene oxide chain Among them, a polyol having a group having two hydroxyl groups at one end of a polyethylene oxide chain is preferable, and one hydroxyl group of trimethylolpropane is a methoxy (poly) ethylene oxy group (CH ₃ O (CH ₂ CH ₂ O) _m- (In the formula, m is 1 or more) More preferably substituted polyol is particularly preferably a polyol having a structure represented by the following formula (1). (A) As a commercial item of the polyol which has a polyethylene oxide chain | strand, Ymer N120 (made by Perstope), Tegomer D-3403 (made by Evonik) etc. are mentioned.

（式（１）中、ｎは、１９〜２１である。）
（ａ）ポリエチレンオキサイド鎖を有するポリオールは、複数種の組合せであってもよい。

(In the formula (1), n is 19 to 21.)
The polyol (a) having a polyethylene oxide chain may be a combination of plural kinds.

<< (b) Polyol (except for (a) and (d)) >>
(B) Polyol (In this specification, "(b) polyol" may be called "(b)") will not be specifically limited if it is a polyol which has a 2 or more hydroxyl group in 1 molecule. Examples of such (b) polyols include (b1) polycarbonate polyols, polyether polyols, polyester polyols, other polyols (eg, polyolefin polyols, acrylic polyols, polydiene polyols, low molecular weight diols, etc.), etc. .
The (b) polyol may be a combination of two or more. For example, the (b) polyol may contain one (b1) polycarbonate polyol and two or more polyether polyols.

<<< (b1) polycarbonate polyol >>>
(B1) The polycarbonate polyol is not particularly limited as long as it is a polyol having a carbonate bond in the molecule, and may contain ether bonds and / or ester bonds in number equal to or less than the average number of carbonate bonds in one molecule. . Examples of such (b1) polycarbonate polyols include those in which a polyol monomer such as a diol is carbonate-bonded.

  The polycarbonate polyol (b1) can be obtained, for example, by reacting one or more polyol monomers with a carbonic ester or phosgene. The polycarbonate polyol obtained by reacting one or more polyol monomers with a carbonate ester is preferable from the viewpoint of easy production and no occurrence of by-products of terminal chlorinated compounds.

  Examples of the raw material of the polycarbonate polyol (b1) include aliphatic polyol monomers, polyol monomers having an alicyclic structure, aromatic polyol monomers, polyester polyol monomers, and polyether polyol monomers.

  As an aliphatic polyol monomer, for example, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,5-hexanediol, 1,6-hexanediol, 1,7-heptanediol Straight-chain aliphatic diols such as 1, 8-octanediol and 1,9-nonanediol; 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-methyl Branched aliphatic diols such as 1,5-pentanediol, 3-methyl-1,5-pentanediol and 2-methyl-1,9-nonanediol; and trifunctional or higher such as trimethylolpropane and pentaerythritol A polyhydric alcohol is mentioned.

  As a polyol which has alicyclic structure in a principal chain, the polyol etc. which have a C5-C12 alicyclic group in a principal chain are mentioned, for example. Examples of polyols having an alicyclic structure in such a main chain include 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,3-cyclopentanediol, 1 Main chains of 2,4-cycloheptanediol, 2,5-bis (hydroxymethyl) -1,4-dioxane, 2,7-norbornanediol, tetrahydrofuran dimethanol, 1,4-bis (hydroxyethoxy) cyclohexane, isosorbide, etc. And diols having an alicyclic structure.

As an aromatic polyol monomer, for example, 1,4-benzenedimethanol, 1,3-benzenedimethanol, 1,2-benzenedimethanol, 4,4′-naphthalenedimethanol, 3,4′-naphthalenedimethanol Etc.
Examples of polyester polyol monomers include polyester polyols of hydroxycarboxylic acid and diol such as polyester polyol of 6-hydroxycaproic acid and hexanediol, and polyesters of dicarboxylic acid such as polyester polyol of adipic acid and hexanediol and diol Polyol etc. are mentioned.
Examples of polyether polyol monomers include polyethylene glycol, and polyalkylene glycols such as polypropylene glycol and polytetramethylene glycol.

  Examples of the carbonate include aliphatic carbonates such as dimethyl carbonate and diethyl carbonate, aromatic carbonates such as diphenyl carbonate and ditolyl carbonate, cyclic carbonates such as ethylene carbonate and propylene carbonate, and the like. In addition, phosgene etc. which can produce polycarbonate polyol can also be used. Among them, aliphatic carbonates and cyclic carbonates are preferable, and dimethyl carbonate, diethyl carbonate and ethylene carbonate are particularly preferable, from the viewpoint of ease of production of polycarbonate polyols.

  As a method for producing a polycarbonate polyol from a polyol monomer and a carbonate ester, for example, a carbonate ester and an excess number of moles of the polyol monomer with respect to the number of moles of the carbonate ester are added to a reactor, under normal pressure, temperature 160 After reacting at -200 ° C for 12 hours, a method of reacting at 200-220 ° C for several hours at a pressure of 6.7 kPa or less may be mentioned. In the above reaction, it is preferable to make the reaction take out the by-produced alcohol out of the system. At that time, when the carbonate ester is azeotropically formed with the by-produced alcohol and thus comes out of the system, an excess amount of the carbonate ester may be added. In the above reaction, a catalyst such as titanium tetrabutoxide may be used.

<<< Polyether Polyol >>>
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, for example, one obtained by ring-opening polymerization of cyclic ether or ring-opening polymerization of an epoxy compound, in which an alkylene group is ether-bonded. Examples of such polyether polyols include polytetramethylene ether glycol, polytetramethylene ether glycol having an alkyl side chain, polypropylene glycol, and copolymers of two or more of these.

  The carbon number of the main chain of the polyether polyol is not particularly limited, but the carbon number of the main chain is preferably 2 to 4 from the viewpoint of easy availability. From the viewpoint of suppressing a decrease in water resistance due to water absorption of the polyurethane resin, it is desirable that the content of oxygen atoms in the polyurethane resin be as small as possible. Therefore, the carbon number of the main chain of the polyether polyol is more preferably 3 to 4 and particularly preferably 4. Therefore, the polyether polyol is preferably a polyether polyol having the highest content of the alkyleneoxy skeleton having 4 carbon atoms in the main chain, and the polyether polyol is (b2) an alkylene oxy skeleton having 4 carbon atoms in the main chain Particularly preferred is a polyether polyol having

<<< polyester polyol>>>
As polyester polyol, for example, polyethylene adipate diol, polybutylene adipate diol, polyethylene butylene adipate diol, polyhexamethylene isophthalate adipate diol, polyethylene succinate diol, polybutylene succinate diol, polyethylene sebacate diol, polybutylene sebacate Polyester diols such as diol, poly-ε-caprolactone diol, poly (3-methyl-1,5-pentylene adipate) diol, polycondensate of 1,6-hexane diol and dimer acid, and the like can be mentioned.

<<< Other Polyols >>>
Other polyols are polyols other than polycarbonate polyols, polyether polyols, and polyester polyols. Examples of other polyols include, but are not particularly limited to, polyolefin polyols, acrylic polyols, polydiene polyols, low molecular weight polyols (preferably low molecular weight diols), and the like.

  The number average molecular weight of the low molecular weight polyol is not particularly limited, but is preferably 60 or more and less than 400. The low molecular weight polyol includes low molecular weight diols and low molecular weight polyols having three or more hydroxy groups in one molecule (also referred to as “low molecular weight polyhydric alcohol”). As low molecular weight diol, for example, ethylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 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- Aliphatic diols having 2 to 9 carbon atoms such as 1, 8-octanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, etc .; 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol 1,4-bis (hydroxyethyl) cyclohexane, 2,7-norbornane di Lumpur, tetrahydrofuran dimethanol, 2,5-bis diol having an alicyclic structure having 6 to 12 carbon atoms such as (hydroxymethyl) -1,4-dioxane. Examples of low molecular weight polyhydric alcohols include trimethylolpropane, pentaerythritol, and sorbitol.

<<< (b) Polyol Properties>
The number average molecular weight of the (b) polyol is preferably 400 to 8,000, and more preferably 400 to 4,000. When the number average molecular weight of the polyol (b) is in this range, a suitable viscosity and good handleability can be obtained, and (c) the reactivity with the polyisocyanate becomes sufficient, so that the polyurethane prepolymer can be obtained. Ease of manufacturing, efficiency improvement, etc. are improved. In addition, it is easy to ensure the performance of the obtained polyurethane resin as a soft segment, and it has an advantage that a tough coating can be obtained. Furthermore, when a coating film is formed using the emulsion composition containing the obtained polyurethane resin emulsion, it is easy to suppress generation | occurrence | production of a crack. In the present specification, the number average molecular weight is a number average molecular weight calculated based on the hydroxyl value measured in accordance with JIS K 1577. Specifically, the hydroxyl value is measured, and it is calculated by (56.1 × 1,000 × number of valence) / hydroxyl value [mg KOH / g] by an end group determination method. In the above formula, the valence is the number of hydroxyl groups in one molecule.

<<< preferred embodiment of (b) polyol>
From the viewpoint of obtaining an emulsion composition excellent in flexibility and hydrolysis resistance, the structure derived from (b) polyol has a structure derived from a polycarbonate polyol and / or a polyether polyol derived from an alkylene oxy skeleton having 4 main chain carbon atoms It is particularly preferred to include a structure derived from at least one polyol selected from the group consisting of Further, from the viewpoint of obtaining an emulsion composition which is more excellent in flexibility, the (b1) polycarbonate polyol is preferably a polycarbonate polyol having a branched aliphatic diol as a monomer component.

<< (c) Polyisocyanate >>
(C) As the polyisocyanate (herein, “(c) polyisocyanate” may be referred to as “(c)”), for example, aromatic polyisocyanate, aliphatic polyisocyanate, alicyclic poly And isocyanates.

<<< Aromatic Polyisocyanate >>>
As the aromatic polyisocyanate, for example, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate (TDI), 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate ( MDI), 2,4-diphenylmethane diisocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-di Isocyanato diphenylmethane, 1,5-naphthylene diisocyanate, 4,4 ′, 4 ′ ′-triphenylmethane triisocyanate, m-isocyanatophenylsulfonyl isocyanate, p-isocyanatophenylsulfonyl isocyanate and the like can be mentioned.

<<< Aliphatic Polyisocyanate >>>
Examples of aliphatic polyisocyanates include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecanetriisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate 2,6-diisocyanatomethyl caproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2, 6-diisocyanatohexanoate, etc. It can be mentioned.

<<< alicyclic type polyisocyanate >>>
As an alicyclic polyisocyanate, for example, isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2-isocyanato) Ethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate and the like.

(C) As the polyisocyanate, one having two isocyanato groups per one molecule can be used, but a polyisocyanate compound having three or more isocyanato groups per one molecule is also possible as long as the polyurethane prepolymer does not gel. It can be used. From the viewpoint that the durability of the coating film is improved, alicyclic polyisocyanate is preferable, and from the viewpoint of easy control of reaction, isophorone diisocyanate (IPDI) and 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI) are particularly preferable. .
(C) The polyisocyanate may be a combination of plural kinds, and may be modified to alphanate, nurate and the like.

<< (d) Acidic group-containing polyol >>
(D) Acid group-containing polyol (herein, “(d) acid group-containing polyol” may be referred to as “(d)”) is a polyol having at least one acid group in its molecule . As an acidic group, a carboxy group, a sulfonyl group, a phosphoric acid group, phenolic hydroxyl group etc. are mentioned, for example. (D) As the acidic group-containing polyol, for example, dimethylolalkanoic acid such as 2,2-dimethylol propionic acid, 2,2-dimethylol butanoic acid, N, N-bishydroxyethyl glycine, N, N-bis Hydroxyethylalanine, 3,4-dihydroxybutanesulfonic acid, 3,6-dihydroxy-2-toluenesulfonic acid and the like can be mentioned. From the viewpoint of easy availability, the (d) acidic group-containing polyol is preferably an alkanoic acid having 4 to 12 carbon atoms (dimethylol alkanoic acid) containing two methylol groups, and 2,2-dimethylol Particularly preferred is propionic acid.
The acidic group-containing polyol (d) may be a combination of plural kinds.

<< (d ') neutralizer >>
The (d ′) neutralizing agent (herein, “(d ′) neutralizing agent” may be referred to as “(d ′)”) is (d) an acid group of the acid group-containing polyol. It is not particularly limited as long as it can be added, and can be appropriately selected according to the type of acidic group and the like. (D ') As a neutralizing agent, for example, trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-phenyldiethanolamine, dimethylethanolamine, diethylethanolamine, Organic amines such as N-methylmorpholine, pyridine, and 2- (dimethylamino) -2-methyl-1-propanol (DMAP); inorganic alkali salts such as sodium hydroxide and potassium hydroxide; ammonia and the like. The (d ′) neutralizing agent is preferably an organic amine, more preferably a tertiary amine, and particularly preferably triethylamine.
The (d ′) neutralizing agent may be a combination of plural kinds.

<< (e) Chain extenders >>
(E) A chain extender (herein, "(e) chain extender" may be referred to as "(e)") is a component that contributes to the chain extension reaction of the polyurethane resin end. (E) The chain extender is not particularly limited as long as it is a compound having two or more groups which react with an isocyanato group. (E) As a chain extender, for example, ethylenediamine, 1,4-tetramethylenediamine, 2-methyl-1,5-pentanediamine, 1,4-butanediamine, 1,6-hexamethylenediamine, 1,4 Hexamethylenediamine, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, 1,3-bis (aminomethyl) cyclohexane, xylylenediamine, piperazine, adipoyl hydrazide, hydrazine, 2,5-dimethylpiperazine , Polyamine compounds such as diethylene triamine, triethylene tetramine; diol compounds such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol; polyalkylene glycols represented by polyethylene glycol; water etc. Be The (e) chain extender is preferably a polyamine compound, more preferably a diamine compound, and particularly preferably a primary diamine compound.
(E) The chain extender may be a combination of two or more.

<< (f) Terminator
(F) an end-stopping agent (herein, "(f) end-stopping agent" may be referred to as "(f)") stops the urethanization reaction and / or the chain extension reaction of the polyurethane resin end It is a possible ingredient. The (f) terminal stopper is not particularly limited as long as it is a compound having one group which reacts with an isocyanato group. Examples of the group that reacts with the isocyanato group include a hydroxyl group, an amino group, an imino group and a mercapto group. (F) Examples of the terminal stopper include monoamines such as n-butylamine and di-n-butylamine; and monohydric alcohols such as ethanol, isopropanol and butanol.
(F) The termination agent may be a combination of two or more.

<< Preferred Embodiment of First Polyurethane Resin >>
The first polyurethane resin has (a) a structure derived from a polyol having a polyethylene oxide chain, (b) a structure derived from a polyol, (c) a structure derived from a polyisocyanate, and (d) a structure derived from an acidic group-containing polyol It is preferable that it is a polyurethane resin which has and the structure derived from (e) chain extender.

<< Composition of First Polyurethane Resin >>
The content of the structure derived from the polyol (a) having a polyethylene oxide chain in the first polyurethane resin is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass, 1 It is particularly preferable that the content be 13% by mass. By setting it as this range, when it is set as a coating film, it can be set as an emulsion composition with a more favorable softness | flexibility, tack free property, and base | substrate followability.
The content of the structure derived from the (d) acidic group-containing polyol in the first polyurethane resin is preferably 0.5 to 10% by mass, and particularly preferably 1 to 5% by mass. By setting it as this range, it is possible to obtain an emulsion composition having better flexibility, tack freeness, and substrate followability when formed into a coating film.

In the first polyurethane resin, when (b) a structure derived from a polyol includes a structure derived from (b1) a polycarbonate polyol, (b) a content derived from (b1) a polycarbonate polyol with respect to 100% by mass of a structure derived from a polyol The content of the structure is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and particularly preferably 30 to 70% by mass. By setting it as this range, it is possible to obtain an emulsion composition having better flexibility, tack freeness, and substrate followability when formed into a coating film.
In the first polyurethane resin, (b) a polyol-derived structure is derived from (b2) at least one polyol selected from the group consisting of a structure derived from a polyether polyol having an alkylene oxy skeleton having 4 carbon atoms in the main chain. When it contains a structure, the content of the structure derived from the polyether polyol having an alkyleneoxy skeleton having 4 carbon atoms in the main chain (b2) with respect to 100% by mass of the content of the structure derived from the polyol (b) is 10 to 90 mass % Is preferable, 20 to 80% by mass is more preferable, and 30 to 70% by mass is particularly preferable. By setting it as this range, it is possible to obtain an emulsion composition having better flexibility, tack freeness, and substrate followability when formed into a coating film.
In the first polyurethane resin, from the group consisting of (b) a structure derived from a polyol, (b1) a structure derived from a polycarbonate polyol and (b2) a structure derived from a polyether polyol having an alkylene oxy skeleton having 4 main chain carbon atoms When it contains a structure derived from at least one selected polyol, it is selected from the group consisting of (b1) a structure derived from a polycarbonate polyol and (b2) a structure derived from a polyether polyol having an alkylene oxy skeleton having 4 main chain carbon atoms. The content ratio of the structure derived from the polyether polyol having an alkyleneoxy skeleton having an alkylene oxy skeleton of (b2) main chain carbon number 4 with respect to a total of 100% by mass of structures derived from at least one polyol is 10 to 90% by mass Preferably, 20 to 80% by mass is more preferable, and 30 to 7 And particularly preferably mass%. By setting it as this range, it is possible to obtain an emulsion composition having better flexibility, tack freeness, and substrate followability when formed into a coating film.

  (B) structure derived from a polyol, (c) structure derived from a polyisocyanate, (e) structure derived from a chain extender, (f) structure derived from an end terminator and (d ') neutralization in the first polyurethane resin The content of the part of the agent is not particularly limited. For example, the amount used as the usage-amount of each component in the manufacturing method of the polyurethane resin emulsion mentioned later is mentioned.

<Second polyurethane resin>
The second polyurethane resin has a structure derived from (b ') polyol (but excluding (d) an acidic group-containing polyol), (c) a structure derived from a polyisocyanate, and (d) a structure derived from an acidic group-containing polyol And (e) a structure derived from a chain extender, wherein the (b ′) polyol comprises (b1) a polycarbonate polyol and (b2) a polyether polyol having an alkyleneoxy skeleton with 4 main chain carbon atoms. Including. The second polyurethane resin can include (f) a structure derived from an end terminator as an arbitrary structure. In the second polyurethane resin, the (d ′) neutralizing agent may further be present as a counter ion of (d) an acidic group-containing polyol. In the second polyurethane resin, the structure described above may be a combination of a plurality of types.

  In the second polyurethane resin, (b1) polycarbonate polyol, (b2) polyether polyol having an alkylene oxy skeleton having 4 main chain carbon atoms, (c) polyisocyanate, (d) acidic group-containing polyol, (e) chain The extender and (d ′) neutralizing agent are as described above in the first polyurethane resin.

  In the second polyurethane resin, (b ′) polyol (in this specification, “(b ′) polyol may be referred to as“ (b ′) ”) is as described above for the first polyurethane resin (b Included are both polyols) and (a) polyols with polyethylene oxide chains. Therefore, in the second polyurethane resin, examples of (b ′) polyols other than (b1) polycarbonate polyols and (b2) polyether polyols having an alkylene oxy skeleton having a main chain carbon number of 4 include, for example, (a) polyethylene oxide Polyols having chains, polyether polyols other than (b2), polyester polyols, and other polyols (for example, polyolefin polyols, acrylic polyols, polydiene polyols, low molecular weight diols, etc.) and the like can be mentioned. These are as described above in the first invention. In the second polyurethane resin, the (b ') polyol may or may not contain the (a) polyol having a polyethylene oxide chain.

<< Composition of Second Polyurethane Resin >>
When the second polyurethane resin contains (a) a structure derived from a polyol having a polyethylene oxide chain, the content of the (a) structure derived from a polyol having a polyethylene oxide chain is more than 0% by mass and 20% by mass or less Is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass, and particularly preferably 1 to 13% by mass. By setting it as this range, when it is set as a coating film, it can be set as an emulsion composition with a more favorable softness | flexibility, tack free property, and base | substrate followability.
The content of the structure derived from the (d) acidic group-containing polyol in the second polyurethane resin is as described above in the first polyurethane resin.

In the second polyurethane resin, polyether polyol having a structure derived from (b1) polycarbonate polyol and (b2) an alkyleneoxy skeleton having 4 main chain carbon atoms with respect to 100% by mass of the content ratio of structure derived from (b ′) polyol The total content of the derived structure is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, and particularly preferably 70 to 100% by mass. By setting it as this range, it is possible to obtain an emulsion composition having better flexibility, tack freeness, and substrate followability when formed into a coating film.
In the second polyurethane resin, derived from at least one polyol selected from the group consisting of (b1) a structure derived from polycarbonate polyol and (b2) a structure derived from a polyether polyol having an alkylene oxy skeleton having 4 main chain carbon atoms (B2) The content of the structure derived from the polyether polyol having an alkyleneoxy skeleton with 4 main chain carbon atoms is preferably 10 to 90% by mass, and 20 to 80% by mass with respect to 100% by mass of the total structure. It is more preferable that it is, and it is especially preferable that it is 30-70 mass%. By setting it as this range, it is possible to obtain an emulsion composition having better flexibility, tack freeness, and substrate followability when formed into a coating film.

  (B ′) structure derived from a polyol, (c) structure derived from a polyisocyanate, (e) structure derived from a chain extender, (f) structure derived from an end terminator, and (d ′) in a second polyurethane resin There is no particular limitation on the content of the portion of the Japanese traditional medicine. For example, the amount used as the usage-amount of each component in the manufacturing method of the polyurethane resin emulsion mentioned later is mentioned.

<Characteristics of polyurethane resin>
The weight average molecular weight of the polyurethane resin is preferably 25,000 to 10,000,000, more preferably 50,000 to 5,000,000, and 100,000 to 1,000,000. Is particularly preferred. The weight average molecular weight is measured by gel permeation chromatography (GPC), and a conversion value obtained from a calibration curve of standard polystyrene prepared in advance can be used. By setting the weight average molecular weight to 25,000 or more, there is a tendency that a good coating film can be obtained by drying the emulsion composition containing the obtained polyurethane resin. By setting the weight average molecular weight to 10,000,000 or less, the drying property of the emulsion composition tends to be able to be enhanced.

<Polyurethane resin emulsion>
A polyurethane resin emulsion is an aqueous dispersion of a polyurethane resin in which a polyurethane resin is dispersed in an aqueous medium. The "polyurethane resin emulsion" is also referred to as "water-dispersible polyurethane resin" or "aqueous polyurethane resin dispersion".

<< Composition of polyurethane resin emulsion >>
In the polyurethane resin emulsion, the content of the polyurethane resin is preferably 5 to 60% by mass, and particularly preferably 15 to 50% by mass.

(Method of producing polyurethane resin)
The method for producing the polyurethane resin is not particularly limited as long as it is a method by which an emulsion composition containing the polyurethane resin can be obtained. For example, the polyurethane resin emulsion may be produced by a one-shot method in which all the raw materials are reacted at one time, or a prepolymer method in which a chain extender is reacted after producing an isocyanate-terminated polyurethane prepolymer. Hereinafter, an example of the manufacturing method of the polyurethane resin emulsion by a prepolymer method is demonstrated.

The method for producing a polyurethane resin emulsion by the prepolymer method is, for example,
Obtaining the polyurethane prepolymer (α),
Step (α1) of obtaining a polyurethane prepolymer by reacting (a) a polyol having a polyethylene oxide chain, (c) a polyisocyanate, optionally (b) a polyol, and (d) an acidic group-containing polyol ,
(B1) Polyol containing (b1) polycarbonate polyol and (b2) polyether polyol having an alkylene oxy skeleton having 4 main chain carbon atoms, (c) polyisocyanate, and (d) acid group-containing polyol To obtain a polyurethane prepolymer (α2),
Dispersing the polyurethane prepolymer in an aqueous medium (β),
Neutralizing the acidic groups of the polyurethane prepolymer with (d ′) a neutralizing agent (γ),
Reacting the polyurethane prepolymer with (e) a chain extender (δ)
including. Here, the step (α) may further include the step of adding (f) an end terminator to the obtained (A) polyurethane prepolymer.

<Step (α)>
The step (α) is the step (α1) or the step (α2). When the step (α) is the step (α1), an emulsion of the first polyurethane resin is obtained, and when the step (α) is the step (α2), an emulsion of the second polyurethane resin is obtained.

The step (α) may be performed under an inert gas atmosphere or may be performed under an air atmosphere.
Although the reaction temperature in a process ((alpha)) does not have a restriction | limiting in particular, 40-150 degreeC is preferable and 60-120 degreeC is especially preferable. By setting the reaction temperature to 40 ° C. or higher, the raw material is sufficiently dissolved or the raw material has sufficient fluidity, and the viscosity of the polyurethane prepolymer can be lowered to perform sufficient stirring, and the reaction temperature is 150 By setting the temperature to 0 ° C. or less, the reaction can be allowed to proceed without causing problems such as occurrence of side reactions.

  In the step (α), a catalyst can also be used to improve the reactivity. Examples of the catalyst include metal salts such as tin-based catalysts (such as trimethyltin laurate and dibutyltin dilaurate), lead-based catalysts (such as lead octylate), titanium-based catalysts (such as titanium tetrabutoxide), and organometallic derivatives. And amine-based catalysts (triethylamine, N-ethylmorpholine, triethylenediamine etc.) and diazabicycloundecene-based catalysts. Among them, dibutyltin dilaurate and titanium tetrabutoxide are preferable from the viewpoint of reactivity.

  The reaction in step (α) may be carried out without a solvent or with the addition of an organic solvent. When the reaction is carried out without a solvent, the mixture of the raw materials used in the step (α) is preferably liquid from the viewpoint of the stirring property. When adding an organic solvent and making it react, as an organic solvent to be used, the organic solvent mentioned above in an aqueous medium is mentioned. Acetone, methyl ethyl ketone and ethyl acetate are preferable because they can be removed by heating or depressurizing after dispersing the polyurethane prepolymer in water and performing chain extension reaction. Further, N-methyl pyrrolidone, N-ethyl pyrrolidone, β-alkoxypropionamide, and dipropylene glycol dimethyl ether are preferable because they function as a film forming aid when producing a coating film from the obtained polyurethane resin emulsion.

<< Polyurethane Prepolymer >>
The acid value (AV) of the polyurethane prepolymer obtained in step (α) is preferably 2 to 40 mg KOH / g, more preferably 3 to 30 mg KOH / g, and 4 to 20 mg KOH / g Particularly preferred. By setting the acid value of the polyurethane prepolymer to 4 mg KOH / g or more, the dispersibility in an aqueous medium and the storage stability tend to be able to be improved. Further, by setting the acid value of the polyurethane prepolymer to 20 mg KOH / g or less, the water resistance of the coating film of the emulsion composition containing the obtained polyurethane resin emulsion can be enhanced, and the flexibility of the coating film obtained can be enhanced. There is a tendency, and there is also a tendency that the drying property at the time of coating film preparation can be increased.

The term "acid value of polyurethane prepolymer" refers to the acid in the solid content excluding the solvent used for producing the polyurethane prepolymer and the neutralizing agent for dispersing the polyurethane prepolymer in an aqueous medium. Show the value. Specifically, the acid value of the polyurethane prepolymer can be derived by the following formula (3).
[Acid value of polyurethane prepolymer] = [((m) number of millimoles of acid group-containing polyol) × ((d) number of acid group in one molecule of acid group-containing polyol)] × 56.11 / [(a) Total weight of polyol having polyethylene oxide chain, (b) polyol, (d) acid group-containing polyol, and (c) polyisocyanate]] (3)

<< Amount of raw material used in process (α1) >>
In the step (α1), when a polyurethane prepolymer is obtained from (a) a polyol having a polyethylene oxide chain, (b) a polyol, (d) an acidic group-containing polyol, and (c) a polyisocyanate, , (B) and (d) may be reacted with (c) in random order, or may be reacted simultaneously.
In the step (α1), the use amount of (a) the polyol having a polyethylene oxide chain is (a) a polyol having a polyethylene oxide chain, (c) a polyisocyanate, (b) a polyol, and (d) an acidic group-containing The total amount of the polyol, (e) chain extender, and (f) end terminator 100 parts by weight (hereinafter referred to as “total 100 parts by weight of (a) to (f)”) 0.01 20 parts by mass is preferable, 0.1 to 15 parts by mass is more preferable, 0.5 to 10 parts by mass is further preferable, and 1.0 to 3.0 parts by mass Is particularly preferred. (A) By setting the amount of the polyol having a polyethylene oxide chain to 0.01 parts by mass or more, the flexibility of the coating film obtained by applying the polyurethane resin emulsion is increased, and the cleaning property of the ink is increased. When the content is 20 parts by mass or less, the tack-free property of the coating film obtained by applying the emulsion composition containing the obtained polyurethane resin emulsion tends to be higher. Moreover, the water resistance of the coating film obtained by apply | coating the emulsion composition containing the polyurethane resin emulsion obtained can be made high, and the softness | flexibility of the coating film obtained also tends to be able to be made favorable.
In addition, in the manufacturing method of a polyurethane resin emulsion, when (b) polyol, (d) acid group containing polyol, (e) chain extender and / or (f) terminal stopper is not used, content and content ratio The content of the non-existent component in the calculation of is 0 parts by mass.

  In the step (α1), the use amount of the (b) polyol is preferably 20 to 90 parts by mass, more preferably 30 to 80 parts by mass with respect to a total of 100 parts by mass of (a) to (f) Preferably, it is 50 to 80 parts by mass. When the amount of the polyol (b) used is 20 parts by mass or more, the drying property of the emulsion composition containing the resulting polyurethane resin emulsion tends to be able to be enhanced. There is a tendency for the storage stability of the emulsion composition containing the polyurethane resin emulsion to be improved.

When (b1) polycarbonate polyol is used in the step (α1), the amount of the (b1) polycarbonate polyol used is preferably 10 to 90 parts by mass, preferably 20 to 80 parts by mass with respect to 100 parts by mass of the (b) polyol. It is more preferably part, and particularly preferably 30 to 70 parts by mass. (B1) By setting the used amount of the polycarbonate polyol to 30 parts by mass or more, there is a tendency that the drying property of the emulsion composition containing the obtained polyurethane resin emulsion can be enhanced, and by setting it to 70 parts by mass or less The storage stability of the emulsion composition containing the resulting polyurethane resin emulsion tends to be improved.
In the step (α1), when (b2) a polyether polyol having an alkyleneoxy skeleton having 4 carbon atoms in the main chain is used, (b2) an alkyleneoxy having 4 carbon atoms in the main chain with respect to 100 parts by mass of the polyol. The amount of the polyether polyol having a skeleton is preferably 10 to 90 parts by mass, more preferably 20 to 80 parts by mass, and particularly preferably 30 to 70 parts by mass. (B2) The storage stability of the emulsion composition containing the resulting polyurethane resin emulsion tends to be improved by setting the amount of the polyether polyol having an alkylene oxy skeleton having 4 carbon atoms in the main chain to 30 parts by mass or more. If the amount is 90 parts by mass or less, the drying property of the resulting emulsion composition containing the polyurethane resin emulsion tends to be able to be enhanced.
In the step (α1), when (b1) polycarbonate polyol and (b2) a polyether polyol having an alkylene oxy skeleton having 4 main chain carbon atoms are used, (b1) polycarbonate polyol and (b2) main chain carbon number is 4 The amount of the polyether polyol having an alkyleneoxy skeleton having 4 carbon atoms in the main chain (b2) is 0.5 to 99.5 parts by mass with respect to 100 parts by mass of a polyether polyol having an alkyleneoxy skeleton of Preferably it is 80-20 mass parts, and it is especially preferable that it is 60-40 mass parts. With such an amount, the flexibility of the coating film obtained by applying the polyurethane resin emulsion tends to be higher.

  In the step (α1), the ratio of the number of moles of isocyanato groups of (c) polyisocyanate to the number of moles of all hydroxyl groups of (a) a polyol having a polyethylene oxide chain, (b) a polyol, and (d) an acidic group-containing polyol Hereinafter, the “first NCO / OH ratio” is also preferably 1.05 to 2.5, more preferably 1.1 to 2.0, and 1.2 to 1. 8 is particularly preferred.

By setting the first NCO / OH ratio to 1.05 or more, the amount of polyurethane prepolymer having no isocyanato group at the molecular terminal decreases, and the number of molecules that do not react with the chain extender decreases. This makes it easy to ensure the storage stability of the polyurethane resin emulsion.
By setting the first NCO / OH ratio to 2.5 or less, the amount of the unreacted polyisocyanate remaining in the reaction system decreases, and (c) the polyisocyanate and the chain extender react efficiently. The storage stability is improved because it is less likely to cause unwanted molecular elongation by reaction with water. Furthermore, when the first NCO / OH ratio is 2.5 or less, the drying property of the emulsion composition containing the resulting polyurethane resin emulsion tends to be high.

  In the step (α1), when the total amount of (a) to (f) is 100 parts by mass, the amount of the polyisocyanate (c) is in the range satisfying the condition of the above molar ratio, according to the type or amount It can be set appropriately.

  In the step (α1), the use amount of the (d) acidic group-containing polyol is preferably 0.5 to 10 parts by mass, and 1 to 5 parts by mass with respect to a total of 100 parts by mass of (a) to (f). Is particularly preferred. (D) By setting the used amount of the acidic group-containing polyol to 0.5 parts by mass or more, the dispersibility of the obtained aqueous polyurethane resin in the aqueous medium tends to be good, and 10 parts by mass or less The drying properties of the resulting emulsion composition containing the polyurethane resin emulsion tend to be high. Moreover, the water resistance of the coating film obtained by apply | coating an emulsion composition can be made high, and there exists a tendency which can also improve the softness | flexibility of the coating film obtained.

  In the step (α1), the proportion of the (f) end terminator can be appropriately determined in accordance with the molecular weight and the like of the desired polyurethane prepolymer.

  Further, in the step (α1), the total hydroxyl equivalent number of the (a) polyol having a polyethylene oxide chain, (b) the polyol, and (d) the acidic group-containing polyol (hereinafter also referred to as “total hydroxyl equivalent number 1”). Is preferably 100 to 1,000. If the total hydroxyl group equivalent number 1 is in this range, the drying property and the thickening property are easily increased, the polyurethane resin emulsion is easily manufactured, and a coating film excellent in hardness is easily obtained. Furthermore, the total hydroxyl group equivalent number 1 is more preferably 200 to 900, from the viewpoint of the storage stability of the obtained emulsion composition containing the polyurethane resin emulsion, the drying property, and the hardness of the coating film obtained by coating. It is more preferable that it is 300-800, and it is especially preferable that it is 500-800.

The number of hydroxyl group equivalents can be calculated by the following formulas (1) and (2).
Number of hydroxyl group equivalents of each polyol = molecular weight of each polyol / number of hydroxyl groups of each polyol (excluding phenolic hydroxyl groups) (1)
Total number of hydroxyl group equivalents of polyol = M / total number of moles of polyol (2)
In the case of a polyurethane resin, in the formula (2), M is [[number of hydroxyl group equivalents of polycarbonate polyol x number of moles of polycarbonate polyol] + [number of hydroxyl group equivalents of acidic group-containing polyol x number of moles of acid group-containing polyol] + [Number of hydroxyl equivalents of polyethylene oxide chain-containing polyol x number of moles of polyethylene oxide chain-containing polyol] is shown.

  In the step (α1), the amount used of the organic solvent is a mass with respect to the total amount of (b) polyol, (d) acid group-containing polyol, (a) polyethylene oxide chain-containing polyol, and (c) polyisocyanate It is preferably 0.1 to 2.0 times, particularly preferably 0.15 to 0.8 times, as a standard.

<< amount of raw material used in process (α2) >>
In the step (α2), (b ′) a polyol comprising (b1) a polycarbonate polyol and (b2) a polyether polyol having an alkylene oxy skeleton having a main chain carbon number of 4, (d) an acidic group-containing polyol, (c In the case of obtaining a polyurethane prepolymer from the polyisocyanate), (b ′) and (d) may be reacted with (c) in random order or may be reacted simultaneously.

  In the step (α2), the used amount of the (b1) polycarbonate polyol is 100 parts by mass with respect to a total of 100 parts by mass of the (b1) polycarbonate polyol and the (b2) polyether polyol having an alkylene oxy skeleton having 4 main chain carbon atoms. The amount is preferably 5 to 99.5 parts by mass, more preferably 80 to 20 parts by mass, and particularly preferably 60 to 40 parts by mass. With such an amount, the flexibility of the coating film obtained by applying the polyurethane resin emulsion tends to be higher.

  In the step (α2), the total use amount of (b1) polycarbonate polyol and (b2) polyether polyol having an alkylene oxy skeleton having 4 main chain carbon atoms with respect to 100 parts by mass in total of (b ′) polyol is The amount is preferably 50 to 100 parts by mass, more preferably 60 to 100 parts by mass, and particularly preferably 70 to 100 parts by mass.

  In the step (α2), the amount of the (b ′) polyol used is (b ′) a polyol, (c) a polyisocyanate, (d) an acidic group-containing polyol, (e) a chain extender, and (f) The amount is preferably 20 to 90 parts by mass, preferably 30 to 80 parts by mass, with respect to 100 parts by mass of the terminal stopper (hereinafter also referred to as "total 100 parts by mass of (b ') to (f)"). Is more preferable, and 50 to 80 parts by mass is particularly preferable. When the amount of the polyol (b ′) used is 20 parts by mass or more, the drying property of the obtained emulsion composition containing the polyurethane resin emulsion tends to be able to be enhanced, and by setting the amount to 90 parts by mass or less The storage stability of the emulsion composition containing the resulting polyurethane resin emulsion tends to be improved.

  In addition, in a process ((alpha) 2), when (f) terminal terminator is not used, content of (f) terminal terminator in calculation of content and content ratio will be 0 mass part.

  In the step (α2), the ratio of the number of moles of isocyanato groups of the polyisocyanate (c) to the number of moles of all hydroxyl groups of the (b ′) polyol and (d) acid group-containing polyol (hereinafter referred to as “second NCO / OH It is preferable that it is 1.05-2.5, it is more preferable that it is 1.1-2.0, and it is especially preferable that it is 1.2-1.8.

  By setting the second NCO / OH ratio to 1.05 or more, the amount of polyurethane prepolymer having no isocyanato group at the molecular terminal decreases, and the number of molecules that do not react with the chain extender decreases. This makes it easy to ensure the storage stability of the polyurethane resin emulsion.

  By setting the second NCO / OH ratio to 2.5 or less, the amount of the unreacted polyisocyanate remaining in the reaction system is reduced, and (c) the polyisocyanate and the chain extender react efficiently. The storage stability is improved because it is less likely to cause unwanted molecular elongation by reaction with water. Furthermore, by setting the second NCO / OH ratio to 2.5 or less, the drying property of the emulsion composition containing the resulting polyurethane resin emulsion tends to be high.

  In the step (α2), when the total amount of (b ′) to (f) is 100 parts by mass, the amount of (c) polyisocyanate is adjusted to the kind or amount within the range satisfying the above molar ratio. Can be set appropriately.

  In the step (α2), the use amount of the (d) acidic group-containing polyol is preferably 0.5 to 10 parts by mass, preferably 1 to 5 parts by mass, based on 100 parts by mass in total of (b ′) to (f). It is particularly preferred that it is a part. In the step (α2), when the amount of the (d) acidic group-containing polyol used is 0.5 parts by mass or more, the dispersibility of the obtained aqueous polyurethane resin in the aqueous medium tends to be good, 10 By setting the amount to less than the mass part, the drying property of the emulsion composition containing the obtained polyurethane resin emulsion tends to be high. Moreover, the water resistance of the coating film obtained by apply | coating an emulsion composition can be made high, and there exists a tendency which can also improve the softness | flexibility of the coating film obtained.

  In the step (α2), the total hydroxyl equivalent number of the (a) polyol having a polyethylene oxide chain, (b) the polyol, and (d) an acidic group-containing polyol (hereinafter, also referred to as “total hydroxyl equivalent number 2”) is And preferably 100 to 1,000. If the total hydroxyl group equivalent number 2 is in this range, the drying property and the thickening property are easily increased, the polyurethane resin emulsion is easily manufactured, and a coating film excellent in hardness is easily obtained. Furthermore, the total hydroxyl group equivalent number 2 is more preferably 200 to 900, from the viewpoint of the storage stability of the obtained emulsion composition containing the polyurethane resin emulsion, the drying property and the hardness of the coating film obtained by coating. It is more preferable that it is 300-800, and it is especially preferable that it is 500-800. The hydroxyl group equivalent number 2 can be determined in the same manner as the hydroxyl group equivalent number 1.

  In the step (α2), the amount of the organic solvent used is 0.1 to 2 on a mass basis with respect to the total amount of (b ′) polyol, (d) acidic group-containing polyol and (c) polyisocyanate. It is preferably 0 times and particularly preferably 0.15 to 0.8 times.

<Step (β)>
The method for dispersing the polyurethane prepolymer in the aqueous medium in the step (β) is not particularly limited, but, for example, a method of adding the polyurethane prepolymer to the aqueous medium stirred by a homomixer, a homogenizer or the like, A method of adding an aqueous medium to a polyurethane prepolymer stirred by a homomixer, a homogenizer or the like can be appropriately adopted.

<Step (γ)>
In the step (γ), the amount of the (d ′) neutralizing agent used is preferably 0.5 to 1.7 times the total number of moles of the (d) acidic group-containing polyol, and 0.6 to 1. It is more preferably 3 times, particularly preferably 0.7 to 1.2 times. Within this range, the dispersibility is improved. The number of moles of the acidic group of the polyurethane resin is basically a number obtained by multiplying the number of moles of the acidic group-containing polyol used in obtaining the polyurethane resin by the number of acidic groups in one minute of the acidic group-containing polyol. is there. Further, the number of moles of the neutralizing agent is the number of moles of the neutralizing agent added to the polyurethane resin emulsion.

<Step (δ)>
In the step (δ), the reaction between the polyurethane prepolymer and the (e) chain extender may be carried out slowly under cooling, if necessary, under an accelerated heating condition at 60 ° C. or less. It is also good. The reaction time under cooling can be, for example, 0.5 to 24 hours, and the reaction time under heating conditions of 60 ° C. or less can be, for example, 0.1 to 6 hours. In addition, since chain extension can also be performed by water, when the aqueous medium in the step (β) is water, water as a dispersion medium also serves as a chain extender (e).

  In the step (δ), the amount of the (e) chain extender used is preferably not more than the equivalent with respect to the isocyanato group as the chain extension starting point in the resulting polyurethane prepolymer, and is preferably 0.7 to 0.99. Particular preference is given to equivalents. Addition of a chain extender in an amount equal to or less than the equivalent weight of an isocyanato group does not reduce the molecular weight of a chain-extended urethane polymer, and a coated film obtained by applying an emulsion composition containing the obtained polyurethane resin emulsion There is a tendency to be able to increase the strength.

<Preferred embodiment>
Either of the step (β) and the step (γ) may be performed first. That is, after the polyurethane prepolymer obtained in step (α) is dispersed in an aqueous medium, a neutralizing agent may be added, and after adding the neutralizing agent to the polyurethane prepolymer obtained in step (α), an aqueous system It may be dispersed in a medium. A dispersion medium in which a neutralizing agent is dispersed in an aqueous medium is prepared in advance, and the polyurethane prepolymer obtained in the step (α) is put in the dispersion medium in the aqueous medium to obtain the process (β) and the process (γ). It can also be done at the same time.

  Either of the step (β) and the step (γ) may be performed first, or may be performed simultaneously. Further, the step (β) and the step (δ) may be performed simultaneously. That is, the chain extender may be added after the dispersion of the polyurethane prepolymer in the aqueous medium, or may be added during the dispersion. Furthermore, step (γ) and step (δ) may be performed simultaneously. From the viewpoint of improving the dispersion stability, it is preferable to perform the step (δ) after performing the step (β). Further, the step (β), the step (γ) and the step (δ) may be performed simultaneously.

  The method for producing the polyurethane resin emulsion is preferably a method for producing a polyurethane resin emulsion by the step (α); then the steps (β) and (γ); and then the step (δ).

  Also, the polyurethane resin emulsion can be produced by a method similar to the method described in, for example, WO2014 / 103689, WO2015 / 194671, WO2015 / 194672, WO2015 / 033939.

(acrylic resin)
An acrylic resin contains the polymer which consists of a repeating unit containing (meth) acrylic acid ester and / or (meth) acrylic acid. Here, (meth) acrylic acid means at least one of acrylic acid and methacrylic acid. In addition, acrylic resin shall not contain acrylic silicone resin.

  The glass transition temperature (Tg) of the acrylic resin is preferably 15 ° C. or less, more preferably −80 ° C. to 15 ° C., still more preferably −65 ° C. to −3 ° C., −55 ° C. It is particularly preferred that the temperature is -15 ° C. Further, the Tg of the acrylic resin may be −55 ° C. to −20 ° C. When the Tg of the acrylic resin is 15 ° C. or less, the flexibility is more excellent.

<Acrylic resin emulsion>
An acrylic resin emulsion is an aqueous dispersion of an acrylic resin in which an acrylic resin is dispersed in an aqueous medium. The "acrylic resin emulsion" is also referred to as "water-dispersible acrylic resin" or "aqueous acrylic resin dispersion".

As a commercial item of an acrylic resin emulsion, the following is mentioned, for example.
High pressure gas industry Ltd. make: Pegal 862 (Tg: -10 ° C), Pegal 751 (Tg: 25 ° C), LC6154 (Tg: 64 ° C), Showa Denko KK make: Polysol AP-3900 (Tg: 10 ° C) AP-1020 (Tg: 23 ° C.), AP-4735, TI-3052, SE-4210 E (Tg: -50 ° C.), Nippon Carbide Industries Co., Ltd .: Nicazole FX5697H (Tg: -60 ° C.), FX3750 (Tg) : -30 ° C, FX2138Y (Tg: -17 ° C), FX2555A (Tg: -17 ° C), FX2033 (Tg: 8 ° C), FX2018 (Tg: 29 ° C), FX672K (Tg: 50 ° C), Parachem Japan Ltd. make: Parabond LX-5 (Tg: -40 ° C), G-60 (Tg: -30 ° C), LX-2 (Tg: -30 ° C),亞 synthetic Co., Ltd.: NW-400 (Tg: -41 ℃)

<Composition of Acrylic Resin Emulsion>
In the acrylic resin emulsion, the proportion of the acrylic resin is preferably 0.1 to 90% by mass, more preferably 10 to 77% by mass, and particularly preferably 20 to 60% by mass.
The acrylic resin may be a combination of multiple types.

(silicone)
The emulsion composition can further comprise silicone. When the emulsion composition further contains silicone, the tack-free property is more excellent.

  When the emulsion composition contains silicone, the polyurethane resin, the acrylic resin and the silicone may be dispersed in the aqueous medium as separate particles respectively, and the polyurethane resin is dispersed in a form in which the acrylic resin and / or the silicone is contained. Or any combination thereof. In the emulsion composition, the polyurethane resin, the acrylic resin and the silicone are preferably dispersed in the aqueous medium as separate particles. In this case, the emulsion composition comprises a polyurethane resin emulsion, an acrylic resin emulsion, and an emulsion silicone.

  Silicone is a polymer having an organic functional group and having a siloxane unit as a repeating unit. Examples of the organic functional group include alkyl groups such as methyl and ethyl; aromatic ring groups such as phenyl, methylphenyl and diphenyl; hydroxyl, polyether, carboxyl, epoxy and amino. Be

  As silicone, for example, dimethyl silicone, methyl phenyl silicone, amino modified silicone, epoxy modified silicone, polyether modified silicone, alkyl modified silicone, higher fatty acid modified silicone, methyl hydrogen silicone, fluorine modified silicone, carboxy modified silicone, polyglycerol Modified silicone, carbinol modified silicone, epoxy polyether modified silicone, alkyl polyether modified silicone, reactive silicone, hydroxyl group modified silicone, acrylic silicone resin, etc. may be mentioned.

  The silicone is selected from dimethylsilicone, epoxy-modified silicone, amino-modified silicone, from the viewpoint of excellent compatibility with other components in the emulsion composition and better tack-free property, flexibility and / or texture. It is preferably at least one selected from the group consisting of reactive silicones and acrylic silicone resins. In addition, from the viewpoint of further improving the tack free property, silicone is particularly preferably an acrylic silicone resin.

  Examples of the acrylic silicone resin include (graft) copolymers of (meth) acrylic monomers and dialkylsiloxane monomers, acrylic silicone copolymers, acrylic modified organopolysiloxanes, acrylic acid-silicone copolymers, silicone modified (meta) And acrylic polymers, polyorganosiloxanes obtained by graft copolymerization of (meth) acrylic acid esters, and the like.

<Emulsion type silicone>
Emulsion type silicone is a water dispersion of silicone, and is also called "silicone water dispersible resin". The emulsion silicone is preferably an acrylic silicone resin emulsion. As a commercial item of acrylic silicone resin emulsion, the following is mentioned, for example.
Toagosei Co., Ltd .: Cymacs US-380, Cymacs US-450, Cymacs US-480, Nisshin Chemical Industry Co., Ltd .: Charyne FE-230N, FE-502, LC-190, R-170BX, E-370, Toray · Dow Corning Co., Ltd .: IE-7170, SE1980 CLEAR, BY 22-826 EX, POLON-MF-40, SABIC Innovative Plastics Japan GK Co., Ltd .: Lexan EXL, Idemitsu Kosan Co., Ltd .: Taflon Neo, Ciden Chemical Co., Ltd .: Bansta -S-806, manufactured by Nippon Gohsei Co., Ltd .: Movinir, Toray Co., Ltd .: Ko-Tax, Daito Kasei Kogyo Co., Ltd .: Daitozole 5000 SJ, Nippon SC Co., Ltd .: Yodosol GH41, Shin-Etsu Chemical Co., Ltd. : Acrylates / Ethyl hexyl acrylate / dimethic acid methacrylate copolymer (trade name: KP 578), DIC Corporation: Bon coat, ceranate, JSR: acrylic silicone emulsion “SIFCLEAR S101”, “SIFCLEAR S102”, etc.

<< Composition of emulsion-type silicone >>
In the emulsion silicone, the proportion of the silicone is preferably 0.1 to 99% by mass, more preferably 10 to 99% by mass, and particularly preferably 20 to 98% by mass.
The silicone may be a combination of two or more.

(Additive)
The emulsion composition is a thickener, a photosensitizer, a curing catalyst, an ultraviolet absorber, a light stabilizer, an antifoamer, a plasticizer, a surface conditioner, and an anti-settling agent depending on the required function, properties, applications and the like. Additives other than silicone can also be added, such as agents. The additive may be a combination of a plurality of types. Also, the types of these additives are known to those skilled in the art and can be used in amounts generally used.

(Composition of emulsion composition)
The content of the acrylic resin in the solid content of the emulsion composition is not particularly limited, but is preferably more than 0% by mass and 90% by mass or less, more preferably 0.1% by mass to 90% by mass, and 10 It is further more preferable that it is -77 mass%, and it is especially preferable that it is 20-60 mass%. When the content of the acrylic resin is 90% by mass or less, tack-free property and urethane-like texture are enhanced.

The content of silicone in the solid content of the emulsion composition is preferably 0.5 to 30% by mass, and more preferably 2 to 20% by mass, because tack-free property and / or flexibility is more excellent. More preferably, it is particularly preferably 2.5 to 15% by mass.
The content of the polyurethane resin in the solid content of the emulsion composition is not particularly limited, but is preferably an amount obtained by excluding the above-described content of the acrylic resin and the silicone resin from 100% by mass.

(Preferred embodiment of emulsion composition)
The emulsion composition is preferably an emulsion composition comprising a polyurethane resin emulsion and an acrylic resin emulsion.
The emulsion composition is preferably an emulsion composition comprising a polyurethane resin emulsion, an acrylic resin emulsion, and an emulsion silicone.

[Method of producing emulsion composition]
The method for producing the emulsion composition is not particularly limited as long as it can disperse the polyurethane resin, the acrylic resin, and the silicone which is an optional component in an aqueous solvent. The emulsion composition can be produced, for example, by mixing a polyurethane resin emulsion, an acrylic resin emulsion, and an optional emulsion silicone. Also, the emulsion composition may be prepared, for example, by dispersing a polyurethane prepolymer, an acrylic resin, and an optional silicone component in an aqueous solvent, and in the presence of an acrylic resin and an optional silicone component, a polyurethane prepolymer. It can be produced by reacting with a chain extender. Moreover, it can manufacture by the method of polymerizing the monomer of an acrylic resin in polyurethane resin emulsion in presence of a polyurethane resin.

[ink]
The ink comprises an emulsion composition. The ink contains, as components other than the emulsion composition, further components such as a white pigment for background shielding, a color pigment, an extender, an ultraviolet light absorber, an antioxidant, an organic solvent, a film forming aid, a rheology control agent, etc. Can. The additional components may be a combination of two or more.

  Examples of the base shielding white pigment include white pigments having high shielding properties such as titanium dioxide and zinc oxide, and titanium dioxide is preferable from the viewpoint of obtaining high light shielding properties.

  Examples of color pigments include titanium oxide, zinc flower, carbon black, molybdenum red, Prussian blue, cobalt blue, azo pigments, phthalocyanine pigments, quinacridone pigments, isoindoline pigments, styrene pigments, perylene pigments, etc. Titanium and / or carbon black are preferred. The color pigment may be a combination of multiple types.

  Examples of extender pigments include clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talc, silica and alumina white, with barium sulfate and / or talc being preferred, and barium sulfate is more preferred. The extender pigment may be a combination of multiple types.

  As a ultraviolet absorber, benzotriazoles and hindered amines can be mentioned. Examples of the antioxidant include hindered phenols and the like. As an organic solvent, the organic solvent mentioned above in the aqueous medium is mentioned. Types of coalescent and rheology control agents are known to those skilled in the art.

  The ink can be applied to paper, plastics, films, metals, rubbers, elastomers, textiles and the like. The inks are preferably used to print various objects. Examples of the textile printing materials include fiber materials constituting fabrics, and specifically, natural fibers such as cotton, hemp, wool and silk; semi-synthetic fibers such as rayon and acetate; polyester, polyamide, polyacrylonitrile, Synthetic fibers such as polyolefins; and blended yarns of those fibers, knitted and knitted articles.

  The ink is preferably a printing ink, and particularly preferably a screen printing printing ink.

  Printing inks are used to print fabrics. It does not specifically limit as a printing method to cloths, It can select suitably. The printed fabric is dried, heat-treated (usually 60 to 170 ° C., 1 to 10 minutes) or room temperature dried. Thereby, the printed matter printed with the printing ink is obtained.

  Screen printing printing inks are printed on fabrics by a screen printing method. As a method of printing on fabrics, the same method as in the case of ordinary pigment printing can be mentioned. Color paste (pigment finely dispersed in water uniformly), emulsion composition, thickener (sodium alginate, modified starch, sizing agent diluted with carboxymethyl cellulose water, terpene with nonionic surfactant) Sodium alginate, modified starch, carboxymethyl cellulose etc. in emulsion-thickened reducer-reducer with emulsion type emarcidin, taha half emulsion paste, acrylic resin based anionic type thickener etc etc., auxiliary agents (printing aptitude imparting agent, gum up Prepare printing paste (viscosity of 3,000 to 50,000 cP) with an inhibitor etc.). Thereafter, the screen printing printing ink is printed on the fabric using an auto screen printing machine, a rotary screen printing machine, a hand screen pasting frame, a squeegee and the like. The printed fabric is dried, heat-treated (usually 60 to 170 ° C., 1 to 10 minutes) or room temperature drying. Thereby, the printed matter printed with the screen printing printing ink is obtained.

  EXAMPLES The present invention will next be described by way of examples, which should not be construed as limiting the scope of the present invention.

Production Example 1 Synthesis of Polyurethane Resin Emulsion A
In a reaction vessel equipped with a stirrer, a thermometer, and a heater, ETERACOLL UH 200 (registered trademark; polycarbonate polyol manufactured by Ube Industries, Ltd .; number average molecular weight 2000; hydroxyl value 56.1 mg KOH / g; 1,6-hexanediol 760.3 g (0.380 mol) of polycarbonate polyol obtained by reacting with dimethyl carbonate, 36.3 g (0.271 mol) of 2,2-dimethylol propionic acid, 20.79 g (0.02 mol) of Ymer N120 221.6 g (0.997 mol) of isophorone diisocyanate, 341.4 g of dipropylene glycol dimethyl ether, and 0.37 g of titanium tetrabutoxide were mixed, and reacted at 80 to 90 ° C. for 4 hours while stirring under a nitrogen atmosphere. The obtained reaction solution is cooled to 80 ° C., and 27.5 g (0.272 mol) of triethylamine is added thereto for neutralization, and then 1,526 g of the reaction solution obtained by the above operation is vigorously stirred with 1,526 g of water Added to. Further, 70.7 g of a 35% by mass aqueous solution of 2-methyl-1,5-pentanediamine was added to obtain a polyurethane resin emulsion A. Here, Ymer N120 is a polyol having a (a) polyethylene oxide chain represented by the formula (1) (where n is 19.6).

Production Example 2 Synthesis of Polyurethane Resin Emulsion B
In a reaction vessel equipped with a stirrer, a thermometer, and a heater, ETERACOLL UH 200 (registered trademark; polycarbonate polyol manufactured by Ube Industries, Ltd .; number average molecular weight 2000; hydroxyl value 56.1 mg KOH / g; 1,6-hexanediol 760.9 g (0.381 mol) of polycarbonate polyol obtained by reacting with dimethyl carbonate, 40.9 g (0.301 mol) of 2,2-dimethylol propionic acid, 225.6 g (1.015 mol) of isophorone diisocyanate, 343.5 g of dipropylene glycol dimethyl ether and 0.37 g of titanium tetrabutoxide were mixed and reacted at 80 to 90 ° C. for 4 hours while stirring under a nitrogen atmosphere. The obtained reaction solution is cooled to 80 ° C., and 30.7 g (0.304 mol) of triethylamine is added thereto for neutralization, and then 1,250 g of water obtained by strongly stirring 1230 g of the reaction solution obtained by the above operation Added to. Furthermore, 72.1 g of a 35% by mass aqueous solution of 2-methyl-1,5-pentanediamine was added to obtain a polyurethane resin emulsion B.

Production Example 3 Synthesis of Polyurethane Resin Emulsion C
In a reaction vessel equipped with a stirrer, a thermometer, and a heater, ETERACOLL UH 200 (registered trademark; polycarbonate polyol manufactured by Ube Industries, Ltd .; number average molecular weight 2000; hydroxyl value 56.1 mg KOH / g; 1,6-hexanediol Polycarbonate polyol obtained by reacting with dimethyl carbonate 370.0 g (0.185 mol), 10.2 g (0.076 mol) of 2,2-dimethylol propionic acid, 42.18 g (0.042 mol) of Ymer N120 101.0 g (0.455 mol) of isophorone diisocyanate, 175.0 g of dipropylene glycol dimethyl ether, and 0.21 g of titanium tetrabutoxide were mixed and reacted at 80 to 90 ° C. for 4 hours with stirring under a nitrogen atmosphere. The resulting reaction solution is cooled to 80 ° C., and 7.6 g (0.076 mol) of triethylamine is added thereto for neutralization, and 880 g of water obtained by strongly stirring 588 g of the reaction solution obtained by the above operation Added to. Furthermore, 31.1 g of a 35% by mass aqueous solution of 2-methyl-1,5-pentanediamine was added to obtain a polyurethane resin emulsion C. Here, Ymer N120 is a polyol having a (a) polyethylene oxide chain represented by the formula (1) (where n is 19.6).

Preparation Example 4 Synthesis of Polyurethane Resin Emulsion D
In a reaction vessel equipped with a stirrer, a thermometer, and a heater, ETERACOLL UH 200 (registered trademark; polycarbonate polyol manufactured by Ube Industries, Ltd .; number average molecular weight 2003; hydroxyl value 56.0 mg KOH / g; 1, 6-hexanediol 379.6 g (0.190 mol) of polycarbonate polyol obtained by reacting with dimethyl carbonate, 12.5 g (0.093 mol) of 2,2-dimethylol propionic acid, 9.9 g (0.010 mol) of Ymer N120 101.4 g (0.456 mol) of isophorone diisocyanate, 166.5 g of dipropylene glycol dimethyl ether, and 0.25 g of titanium tetrabutoxide were mixed and reacted at 80 to 90 ° C. for 4 hours with stirring under a nitrogen atmosphere. The obtained reaction solution is cooled to 80 ° C., and after adding 9.4 g (0.093 mol) of triethylamine thereto for neutralization, 619 g of the reaction solution obtained by the above operation is added to 692 g of strongly stirred water added. Furthermore, 41.9 g of a 35% by mass aqueous solution of 2-methyl-1,5-pentanediamine was added to obtain a polyurethane resin emulsion D. Here, Ymer N120 is a polyol having a (a) polyethylene oxide chain represented by the formula (1) (where n is 19.6).

Preparation Example 5 Synthesis of Polyurethane Resin Emulsion E
In a reaction vessel equipped with a stirrer, a thermometer, and a heater, ETERACOLL UH 200 (registered trademark; polycarbonate polyol manufactured by Ube Industries, Ltd .; number average molecular weight 1948; hydroxyl value 57.6 mg KOH / g; 1,6-hexanediol Polycarbonate polyol obtained by reacting with dimethyl carbonate 171.3 g (0.088 mol), PTMG 2000 (manufactured by Mitsubishi Chemical Co., Ltd .; polytetramethylene ether glycol; number average molecular weight 1951; hydroxyl value 57.5 mg KOH / g) 170 .8 g (0.088 mol), 11.4 g (0.085 mol) of 2,2-dimethylol propionic acid, 8.8 g (0.0089 mol) of Ymer N120, 86.6 g (0.390 mol) of isophorone diisocyanate, dipropylene glycol Call dimethyl ether 149.4 g, and a mixture of titanium tetrabutoxide 0.22 g, in a nitrogen atmosphere, and reacted for 4 hours with stirring at 80-90 ° C.. The obtained reaction solution is cooled to 80 ° C., and 8.6 g (0.085 mol) of triethylamine is added thereto to neutralize it, and then 551 g of the reaction solution obtained by the above operation is added to 617 g of strongly stirred water added. Further, 30.8 g of a 35% by mass aqueous solution of 2-methyl-1,5-pentanediamine was added to obtain a polyurethane resin emulsion E. Here, Ymer N120 is a polyol having a (a) polyethylene oxide chain represented by the formula (1) (where n is 19.6).

Preparation Example 6 Synthesis of Polyurethane Resin Emulsion F
In a reaction vessel equipped with a stirrer, a thermometer, and a heater, ETERACOLL UH 200 (registered trademark; polycarbonate polyol manufactured by Ube Industries, Ltd .; number average molecular weight 1948; hydroxyl value 57.6 mg KOH / g; 1,6-hexanediol Polycarbonate polyol obtained by reacting with dimethyl carbonate 171.3 g (0.088 mol), PTMG 2000 (manufactured by Mitsubishi Chemical Co., Ltd .; polytetramethylene ether glycol; number average molecular weight 1951; hydroxyl value 57.5 mg KOH / g) 170 .8 g (0.088 mol), 11.4 g (0.085 mol) of 2,2-dimethylol propionic acid, 8.8 g (0.0089 mol) of Ymer N120, 86.6 g (0.390 mol) of isophorone diisocyanate, dipropylene glycol Call dimethyl ether 149.4 g, and a mixture of titanium tetrabutoxide 0.22 g, in a nitrogen atmosphere, and reacted for 4 hours with stirring at 80-90 ° C.. The obtained reaction solution is cooled to 80 ° C., and 8.6 g (0.085 mol) of triethylamine is added thereto to neutralize it, and then 551 g of the reaction solution obtained by the above operation is added to 617 g of strongly stirred water added. Furthermore, 30.8 g of a 35% by mass aqueous solution of 2-methyl-1,5-pentanediamine was added to obtain a polyurethane resin emulsion F. Here, Ymer N120 is a polyol having a (a) polyethylene oxide chain represented by the formula (1) (where n is 19.6).

Preparation Example 7 Synthesis of Polyurethane Resin Emulsion G
In a reaction vessel equipped with a stirrer, a thermometer and a heater, Kuraray Polyol C 2090 (Kuraray Polycarbonate Polyol; number average molecular weight 1993; hydroxyl number 56.3 mg KOH / g; 1,6-hexanediol and 3-methyl) 738.9 g (0.371 mol) of polycarbonate polyol obtained by reacting 1,5-pentanediol with dimethyl carbonate, 24.3 g (0.181 mol) of 2,2-dimethylol propionic acid, Ymer N120 19.2 g (0.019 mol), 194.9 g (0.877 mol) of isophorone diisocyanate, 325.3 g of dipropylene glycol dimethyl ether, and 0.48 g of titanium tetrabutoxide are mixed, and 80 to 90 with stirring in a nitrogen atmosphere. Let react for 4 hours at ° C . The obtained reaction solution is cooled to 80 ° C., and 18.3 g (0.181 mol) of triethylamine is added thereto for neutralization, and then 517 g of the reaction solution obtained in the above operation is added to 580 g of strongly stirred water added. Furthermore, 33.8 g of a 35% by mass aqueous solution of 2-methyl-1,5-pentanediamine was added to obtain a polyurethane resin emulsion G. Here, Ymer N120 is a polyol having a (a) polyethylene oxide chain represented by the formula (1) (where n is 19.6).

Production Example 8 Synthesis of Polyurethane Resin Emulsion H
In a reaction vessel equipped with a stirrer, a thermometer, and a heater, PTMG 2000 (manufactured by Mitsubishi Chemical Co., Ltd .; polytetramethylene ether glycol; number average molecular weight 1951; hydroxyl value 57.5 mg KOH / g) 760.0 g (0.390 mol) A mixture of 41.8 g (0.312 mol) of 2,2-dimethylol propionic acid, 225.9 g (1.017 mol) of isophorone diisocyanate, 341.4 g of dipropylene glycol dimethyl ether, and 0.37 g of titanium tetrabutoxide; The reaction was allowed to react at 80 to 90 ° C. for 4 hours while stirring under an atmosphere. The obtained reaction solution is cooled to 80 ° C., and 31.5 g (0.312 mol) of triethylamine is added thereto to neutralize it, and then 1737 g of water obtained by strongly stirring 1193 g of the reaction solution obtained in the above operation Added to. Further, 70.2 g of a 35% by mass aqueous solution of 2-methyl-1,5-pentanediamine was added to obtain a polyurethane resin emulsion H.

Preparation Example 9 Synthesis of Polyurethane Resin Emulsion I
In a reaction vessel equipped with a stirrer, a thermometer, and a heater, ETERACOLL UH 200 (registered trademark; polycarbonate polyol manufactured by Ube Industries, Ltd .; number average molecular weight 2000; hydroxyl value 56.1 mg KOH / g; 1,6-hexanediol Polycarbonate polyol obtained by reacting with dimethyl carbonate) 532.0 g (0.266 mol) PTMG 2000 (manufactured by Mitsubishi Chemical Corporation; polytetramethylene ether glycol; number average molecular weight 1951; hydroxyl value 57.5 mg KOH / g) 228. 0 g (0.117 mol), 28.9 g (0.215 mol) of 2,2-dimethylol propionic acid, 193.5 g (0.871 mol) of isophorone diisocyanate, 330.8 g of dipropylene glycol dimethyl ether, and titanium teto 0.37 g of rabutoxide was mixed and allowed to react at 80 to 90 ° C. for 4 hours while stirring under a nitrogen atmosphere. The obtained reaction solution is cooled to 80 ° C., and 21.8 g (0.215 mol) of triethylamine is added thereto for neutralization, and then 1156 g of the reaction solution obtained in the above operation is vigorously stirred 1276 g of water Added to. Further, 68.4 g of a 35% by mass aqueous solution of 2-methyl-1,5-pentanediamine was added to obtain a polyurethane resin emulsion I.

(Production Example 10; Synthesis of Polyurethane Resin Emulsion J)
In a reaction vessel equipped with a stirrer, a thermometer, and a heater, ETERACOLL UH 200 (registered trademark; polycarbonate polyol manufactured by Ube Industries, Ltd .; number average molecular weight 2000; hydroxyl value 56.1 mg KOH / g; 1,6-hexanediol Polycarbonate polyol obtained by reacting with dimethyl carbonate) 380.0 g (0.190 mol) PTMG 2000 (manufactured by Mitsubishi Chemical Corporation; polytetramethylene ether glycol; number average molecular weight 1951; hydroxyl value 57.5 mg KOH / g) 380. 0 g (0.195 mol), 29.0 g (0.217 mol) of 2,2-dimethylol propionic acid, 194.5 g (0.875 mol) of isophorone diisocyanate, 330.6 g of dipropylene glycol dimethyl ether, and titanium teto 0.37 g of rabutoxide was mixed and allowed to react at 80 to 90 ° C. for 4 hours while stirring under a nitrogen atmosphere. The obtained reaction solution is cooled to 80 ° C., and 21.9 g (0.216 mol) of triethylamine is added thereto for neutralization, and then 1155 g of the reaction solution obtained in the above operation is vigorously stirred 1276 g of water Added to. Further, 68.4 g of a 35% by mass aqueous solution of 2-methyl-1,5-pentanediamine was added to obtain a polyurethane resin emulsion J.

Production Example 11 Synthesis of Polyurethane Resin Emulsion K
In a reaction vessel equipped with a stirrer, a thermometer, and a heater, ETERNACOLL UH 200 (registered trademark; polycarbonate polyol manufactured by Ube Industries, Ltd .; number average molecular weight 1958; hydroxyl value 57.3 mg KOH / g; 1,6-hexanediol Polycarbonate polyol obtained by reacting with dimethyl carbonate 366.8 g (0.187 mol), PTMG 2000 (manufactured by Mitsubishi Chemical Co., Ltd .; polytetramethylene ether glycol; number average molecular weight 1972; hydroxyl value 56.9 mg KOH / g) 368 .5 g (0.187 mol), 28.6 g (0.213 mol) of 2,2-dimethylol propionic acid, 184.9 g (0.832 mol) of isophorone diisocyanate, 237.4 g of dipropylene glycol dimethyl ether, and 0.31 g of trabutoxide was mixed and allowed to react at 80 to 90 ° C. for 4 hours with stirring under a nitrogen atmosphere. The obtained reaction solution is cooled to 80 ° C., and 21.6 g (0.213 mol) of triethylamine is added thereto for neutralization, and then 539 g of water obtained by strongly stirring 500 g of the reaction solution obtained by the above operation Added to. Further, 29.8 g of a 35% by mass aqueous solution of 2-methyl-1,5-pentanediamine was added to obtain a polyurethane resin emulsion K.

Production Example 12 Synthesis of Polyurethane Resin Emulsion L
In a reaction vessel equipped with a stirrer, a thermometer, and a heater, ETERNACOLL UH 200 (registered trademark; polycarbonate polyol manufactured by Ube Industries, Ltd .; number average molecular weight 1958; hydroxyl value 57.3 mg KOH / g; 1,6-hexanediol Polycarbonate polyol obtained by reacting with dimethyl carbonate 366.8 g (0.187 mol), PTMG 2000 (manufactured by Mitsubishi Chemical Co., Ltd .; polytetramethylene ether glycol; number average molecular weight 1972; hydroxyl value 56.9 mg KOH / g) 368 .5 g (0.187 mol), 28.6 g (0.213 mol) of 2,2-dimethylol propionic acid, 184.9 g (0.832 mol) of isophorone diisocyanate, 237.4 g of dipropylene glycol dimethyl ether, and 0.31 g of trabutoxide was mixed and allowed to react at 80 to 90 ° C. for 4 hours with stirring under a nitrogen atmosphere. The obtained reaction solution is cooled to 80 ° C., and 21.6 g (0.213 mol) of triethylamine is added thereto for neutralization, and then 539 g of water obtained by strongly stirring 500 g of the reaction solution obtained by the above operation Added to. Further, 29.8 g of a 35% by mass aqueous solution of 2-methyl-1,5-pentanediamine was added to obtain a polyurethane resin emulsion L.

(Acrylic resin emulsion)
The acrylic resin emulsion used the following components.
FX-3750: manufactured by Nippon Carbide Industrial Co., Ltd .; acrylic emulsion; solid content concentration 60% by weight; Tg: -30 ° C
FX-2138Y: manufactured by Nippon Carbide Industries Co., Ltd .; acrylic emulsion; solid content concentration 60% by weight; Tg: -17 ° C
FX-2555A: Nippon Carbide Industrial Co., Ltd .; acrylic emulsion; solid content concentration: 59% by weight; Tg: -17 ° C

(Emulsion type silicone)
The following components were used for emulsion type silicone.
R-170BX: manufactured by Nisshin Chemical Co., Ltd .; acrylic silicone resin emulsion; solid content concentration 45% by weight
LC-190: Nisshin Chemical Industry Co., Ltd .; acrylic silicone resin emulsion; solid content concentration 45% by weight
KM-9787: Shin-Etsu Chemical Co., Ltd .; acrylic silicone resin emulsion; solid concentration 98% by weight

(Characteristics of polyurethane resin)
The physical properties of the polyurethane resin shown in Table 1 were measured as follows.
<Acid number of polyurethane resin>
The acid value of the polyurethane resin contained in the polyurethane resin emulsion was determined by applying the amount of the raw material to the following formula (3a).
[Acid value of polyurethane prepolymer] = [((m) number of millimoles of acid group-containing polyol) × ((d) number of acid group in one molecule of acid group-containing polyol)] × 56.11 / [(a) Total weight of polyol having polyethylene oxide chain, (b) polyol, (d) acid group-containing polyol, and (c) polyisocyanate]] (3a)
<NCO / OH ratio>
The NCO / OH ratio of the polyurethane resin was determined by applying the amount of the raw material to the following formula (3b).
[NCO / OH ratio] = (mmol of (c) polyisocyanate) / [mmol of total of (a) polyol having a polyethylene oxide chain, (b) polyol, and (d) polyol containing an acidic group] (3b)
<Content of Polyol Oxide-Derived Structure Having Polyethylene Oxide Chain>
The content rate of the structure derived from the polyol having a polyethylene oxide chain in the polyurethane resin was determined as the weight ratio of the structure derived from the polyol having a polyethylene oxide chain in the polyurethane resin, and was determined from the used amount of the raw material.

(Preparation of emulsion composition)
The polyurethane resin emulsion, the acrylic resin emulsion, and the emulsion silicone were stirred and mixed so as to have the proportions described in Tables 2 and 3 below in terms of mass of solid content, to obtain an emulsion composition.

(Manufacture of textile dye 1)
50 parts by weight of the emulsion composition, 40 parts by weight of titanium paste (aqueous paste of titanium oxide powder content 60%), 5 parts by weight of pigment water dispersion (manufactured by Toyo Color Co., Ltd .: EMF PINK 2B-1), 25% ammonia water ( One part by weight of Wako Pure Chemical Industries, Ltd. and 3.5 parts by weight of an alkaline thickener (manufactured by Parachem Japan Co., Ltd .: Parabond 10-N) were mixed to obtain a printing ink. Subsequently, the printing ink was printed twice on a white silk-colored cotton knit fabric using a 150-mesh screen and a urethane rubber squeegee. The printed matter was dried at 160 ° C. for 3 minutes to obtain a print 1.

(Evaluation of flexibility)
The flexibility was evaluated while pinching the textile 1 with a fingertip. Excellent flexibility is ◎, good flexibility is ○, acceptable flexibility is △, and flexibility is poor and hardness is x.

(Evaluation of tack freeness)
95 parts by weight of the emulsion composition, 1 part by weight of 25% ammonia water (manufactured by Wako Pure Chemical Industries, Ltd.), and 4 parts by weight of an alkaline thickener (manufactured by Parachem Japan Ltd .: Parabond 10-N) I obtained a printing ink. Subsequently, using a 150 mesh screen and a urethane rubber squeegee, the printing ink was printed five times on a white poma cotton knit fabric. The printed matter was dried at 60 ° C. for 1 minute to obtain a printed matter 2. The edge of the printed material 2 was folded so that the printed surfaces were inside, and a load of 10 kg was applied with a fingertip and pressed for 3 seconds. After removing the load, 捺 that the printed surfaces were spontaneously separated within 1 second, も の if the printed surfaces spontaneously separated within 5 seconds and 1 or more, within 5 seconds and 10 seconds The ones in which the printed surfaces were peeled off spontaneously were marked as Δ. There was no spontaneous peeling within 10 seconds, but the one peeled off lightly was rated as x.

(Evaluation of urethane feel)
A touch test of the printed matter 2 was carried out to determine the presence or absence of a smooth surface texture peculiar to the polyurethane resin.弾 Material that has elasticity and feels like silk 、, has elasticity, but something that feels a slight grip, ○, elasticity that is slightly low, that with a grip feeling △, elasticity It was low in sex and it was rated as a finger with a grip feeling.

(Evaluation of background tracking)
The printed material 1 was pulled to the limit, and the substrate followability was evaluated. Those with no cracks were ◎, those with slight cracks were ○, those with small cracks △, and those with large cracks were x.

(Evaluation of washability)
80 parts by weight of the emulsion composition, 17 parts by weight of titanium paste (aqueous paste with a titanium oxide powder content of 60% by weight), and 3 parts by weight of an alkaline thickener (Parachem Japan Ltd .: Parabond 10-N) I got an ink for textile printing. Subsequently, the printing ink was printed once on a white silk-colored cotton knit fabric using a 70-mesh screen and a urethane rubber squeegee. The screen used was dried at room temperature for 1 minute and then washed with a large amount of water.固 着 for adherents observed in excess of 0% and 3% or less with respect to the ink contact area on the surface of the screen ◎, and 10% or less for 3% and ○, and 10% or more What was observed below was made into (triangle | delta) and what was observed over 50% was made into x.

  The results are summarized in Tables 1 to 3.

From Table 2, the following can be seen.
The emulsion compositions of the examples provided a coating film excellent in substrate followability in which cracking of the coated film surface was reduced by tension while maintaining flexibility and tack-free property. In addition, the emulsion compositions of some examples were excellent in water washability when used as a binder resin.
In Comparative Examples 1 and 2, since the emulsion composition did not contain the acrylic resin emulsion, any of the softness, the base following property, and the cleaning property was inferior.
In Comparative Example 3, the polyurethane resin contained only the structure derived from the polycarbonate polyol, so the flexibility and the cleaning property were inferior.
In Comparative Examples 4 to 6, since the emulsion composition did not contain the polyurethane resin emulsion, the tack free property, the urethane feel and the cleaning property were inferior.

Comparing Example 1 with Comparative Example 1, when the emulsion composition contains a polyurethane resin emulsion containing a structure derived from a polyol having a polyethylene oxide chain and an acrylic resin emulsion, the flexibility, the base following property, and the cleaning property are obtained. Was excellent.
When Example 1 is compared with Examples 2 to 7, when the emulsion composition further contains an emulsion silicone, the tack-free property is more excellent.
Comparing Example 7 with Example 8, when the emulsion composition contained a polyurethane resin emulsion containing more structure derived from a polyol having a polyethylene oxide chain, the flexibility was more excellent.
Comparing Example 9 with Examples 10 to 11, when the emulsion composition contains a polyurethane resin emulsion containing a structure derived from a polyether polyol having an alkylene oxy skeleton having a main chain carbon number of 4, flexibility is obtained. It was better.
Comparing Example 9 with Example 12, when the emulsion composition contained a structure derived from a polycarbonate polyol having a branched aliphatic diol as a monomer component, the flexibility was more excellent.

From Table 3, the following can be seen.
In Comparative Example 7, the flexibility was inferior because the polyurethane resin contained only the structure derived from the polycarbonate polyol.
In Comparative Example 8, since the polyurethane resin contains only a structure derived from a polyether polyol having an alkylene oxy skeleton having a main chain carbon number of 4, the tack free property is inferior.

  Comparing Example 13 and Example 14, it is found that the emulsion composition contains a polyurethane resin emulsion containing more structures derived from a polyether polyol having an alkylene oxy skeleton having a main chain carbon number of 4 as compared with structures derived from a polycarbonate polyol. When it contains, the flexibility was better.

  The emulsion resin composition can be widely used as a raw material for paints, coatings, inks, binder resins and the like.

Claims (14)

An emulsion composition comprising a polyurethane resin and an acrylic resin, wherein
The emulsion composition in which the said polyurethane resin contains the structure derived from the polyol which has (a) polyethylene oxide chain.   The polyurethane resin further comprises a structure derived from (b) a polyol (but excluding (a) a polyol having a polyethylene oxide chain and (d) an acidic group-containing polyol), (c) a structure derived from a polyisocyanate, and (d The emulsion composition according to claim 1, comprising a structure derived from an acidic group-containing polyol and a structure derived from a (e) chain extender.   (B) At least one selected from the group consisting of (b1) a structure derived from a polycarbonate polyol, and (b2) a structure derived from a polyether polyol having an alkylene oxy skeleton having a main chain carbon number of 4 (b1) The emulsion composition of claim 2 comprising a polyol derived structure.   The emulsion composition according to claim 2, wherein the (b) polyol-derived structure comprises a (b1) polycarbonate polyol-derived structure.   The emulsion composition of any one of Claims 1-4 whose polyurethane resin WHEREIN: The content rate of the structure derived from the polyol which has (a) polyethylene oxide chain is 0.5-20 mass%. An emulsion composition comprising a polyurethane resin and an acrylic resin, wherein
The polyurethane resin has a structure derived from (b ′) polyol (however, except for (d) an acid group-containing polyol), (c) a structure derived from a polyisocyanate, and (d) a structure derived from an acid group-containing polyol, (E) containing a chain extender-derived structure,
An emulsion composition, wherein the structure derived from the (b ′) polyol includes (b1) a structure derived from a polycarbonate polyol and (b2) a structure derived from a polyether polyol having an alkylene oxy skeleton having 4 main chain carbon atoms.   The emulsion composition according to any one of claims 1 to 6, wherein the ratio of the acrylic resin is 0.1 to 90% by mass with respect to the total solid content of the emulsion composition.   The emulsion composition of any one of Claims 1-7 whose glass transition temperature of an acrylic resin is 15 degrees C or less.   The emulsion composition according to any one of claims 1 to 8, further comprising a silicone.   10. The emulsion composition of claim 9, wherein the silicone is an acrylic silicone resin.   The emulsion composition of Claim 9 or 10 whose ratio of a silicone is 0.5-30 mass% with respect to solid content whole quantity of an emulsion composition.   An ink comprising the emulsion composition of any one of claims 1-11.   A printing ink comprising the emulsion composition according to any one of claims 1 to 11.   An ink for screen printing textile printing, comprising the emulsion composition according to any one of claims 1 to 11.