JP2019210383A - Emulsion composition - Google Patents

Abstract

To provide an emulsion composition which gives a coating film excellent in scratch resistance.SOLUTION: The emulsion composition contains a polyurethane resin and an acrylic resin. The polyurethane resin has a structure derived from (a) a polycarbonate polyol, a structure derived from (b) an acidic group-containing polyol, and a structure derived from (c) a polyisocyanate. The total concentration of urethane groups and urea groups in the polyurethane resin is 5 mass% or more and 11 mass% or less.SELECTED DRAWING: None

Description

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

  Polyurethane resin emulsions are excellent in adhesion to substrates, abrasion resistance, impact resistance, solvent resistance, etc., so paper, plastics, films, metals as paints, inks, adhesives and various coating agents Widely used in rubber, elastomers, textile products, etc.

  It is known that a coating film obtained by applying a polyurethane resin emulsion made of polycarbonate polyol as a raw material is excellent in light resistance, weather resistance, heat resistance, hydrolysis resistance, and oil resistance (Patent Document 1).

  Among them, it is known that an aqueous polyurethane resin dispersion using a polycarbonate polyol having an alicyclic structure gives a coating film having high durability and hardness. (Patent Document 2).

  An aqueous polyurethane resin dispersion using a compound having one acidic group and one hydroxyl group in one molecule and a polyamine compound having three or more amino groups and / or imino groups in one molecule is flexible. It is known to give a coating film (Patent Document 3).

  It has been reported that a urethane emulsion composition comprising an aqueous resin emulsion obtained from an aqueous polyurethane emulsion and an unsaturated monomer is excellent in adhesion to a plastic substrate (Patent Document 4).

  An aqueous acrylic urethane resin having a reaction product of hexamethylene diisocyanate trimer and stearyl alcohol as a structural unit has been reported as a film coating material excellent in dust resistance, flexibility and water resistance (Patent Document 5).

  In addition, a laminated polyester film having a coating layer containing a urethane resin having a carbonate structure has been reported (Patent Document 6).

JP-A-10-120757 JP 2005-281544 A International Publication No. 2014/103689 Japanese Patent Laid-Open No. 10-273587 JP 2013-35895 A JP 2014-818 A

  However, the coating film obtained from the emulsion composition composed of the polyurethane resin and the acrylic resin described in Patent Documents 4, 5, and 6 has not had sufficient scratch resistance. In particular, an emulsion composition that gives a coating film excellent in scratch resistance on a polyester film has not been proposed.

  The subject of this invention is providing the emulsion composition which gives the coating film excellent in scratch resistance.

The present invention relates to the following [1] to [8].
[1] An emulsion composition comprising a polyurethane resin and an acrylic resin,
The polyurethane resin is
(A) a structure derived from a polycarbonate polyol, and (b) a structure derived from an acidic group-containing polyol,
(C) a polyisocyanate-derived structure;
Have
The emulsion composition, wherein the total concentration of urethane groups and urea groups in the polyurethane resin is 5% by mass or more and 11% by mass or less.
[2] The emulsion composition according to [1], further comprising a film-forming aid.
[3] The emulsion composition according to [1] or [2], wherein the film-forming aid is 3-methoxy-N, N-dimethylpropanamide.
[4] The polyurethane resin is (e-1) a structure derived from a terminal terminator having one acidic group and one hydroxyl group in one molecule, and (f-2) an amino group and / or an imino group in one molecule. The emulsion composition according to any one of [1] to [3], having a structure derived from a chain extender having 3 or more in total.
[5] The emulsion composition according to any one of [1] to [4], which contains the polyurethane resin in a proportion of 35 to 90% by mass when the total of the polyurethane resin and the acrylic resin is 100% by mass.
[6] A coating composition comprising the emulsion composition according to any one of [1] to [5].
[7] An ink composition comprising the emulsion composition according to any one of [1] to [5].
[8] A coating agent composition comprising the emulsion composition according to any one of [1] to [5].
[9] A laminate having a coating layer obtained by curing the coating agent composition according to [8] and a layer comprising a plastic substrate.
[10] The laminate according to [9], wherein the plastic substrate is a polyester resin.

  According to the present invention, an emulsion composition that provides a coating film excellent in scratch resistance is provided.

  Hereinafter, embodiments of the present invention will be described in detail. The polymer compound as in the present invention is a product having a number of structures obtained by reaction of a plurality of types of raw material compounds. Therefore, a polymer compound is not uniquely indicated by its structure even if a large number of structures included can be described by a general formula. In addition, it is difficult to directly measure and specify the physical properties by instrumental analysis or the like and to distinguish them from existing compounds. Therefore, in the present invention, a polymer compound such as “polyurethane resin” may be specified by a production method as necessary.

<Emulsion composition>
The emulsion composition includes a polyurethane resin and an acrylic resin, and an aqueous medium.

  When the emulsion composition contains a polyurethane resin and an acrylic resin, when the emulsion composition is used to form a laminate on a plastic film, the coating film formed from the plastic and the emulsion composition exhibits high scratch resistance. The

The polyurethane resin and the acrylic resin may be separately dispersed in the aqueous medium as the polyurethane resin emulsion and the acrylic resin emulsion, or the polyurethane resin may be dispersed in a form including the acrylic resin.
Here, “encapsulation” broadly means other than the state in which the polyurethane resin and the acrylic resin are completely separated and independently dispersed in the aqueous medium. At this time, the position of the acrylic resin in the polyurethane resin is not particularly limited, and the acrylic resin may be present in the vicinity of the center or at an arbitrary position shifted from the vicinity of the center in a single or plural separated position.

<< Polyurethane resin emulsion >>
The polyurethane resin emulsion contains a polyurethane resin and an aqueous medium. Specifically, the polyurethane resin emulsion is an aqueous dispersion of a polyurethane resin in which the polyurethane resin is dispersed in an aqueous medium. The “polyurethane resin emulsion” is also referred to as “water-dispersed polyurethane resin” or “aqueous polyurethane resin dispersion”.

<<< Polyurethane resin >>>
The polyurethane resin has (a) a structure derived from a polycarbonate polyol, (b) a structure derived from an acidic group-containing polyol, and (c) a structure derived from a polyisocyanate. The polyurethane resin is further optionally selected from the group consisting of (d) a structure derived from other polyols, (e) a structure derived from a terminal terminator, and (f) a structure derived from a chain extender. It can have the above further structure.
From the viewpoint of scratch resistance, it is preferable that (e) the structure derived from the terminal stopper has (e-1) a structure derived from a terminal stopper having one acidic group and one hydroxyl group in one molecule. Furthermore, it is preferable that the structure derived from the chain extender (f-2) has a structure derived from a chain extender having (f-2) 3 or more amino groups and / or imino groups in total in one molecule.

(A) The structure derived from polycarbonate polyol means a partial structure other than the group involved in the polyurethane-forming reaction in the molecular structure of (a) polycarbonate polyol. The structure derived from (a) polycarbonate polyol is introduced into the polyurethane by (a) polycarbonate polyol. The same applies to (b) to (d).
Further, (e) the structure derived from the terminal terminator means a partial structure other than the group involved in the reaction for terminating the urethanization reaction and / or chain extension reaction in the molecular structure of the (e) terminal terminator. . (E) The structure derived from the end terminator is introduced into the polyurethane by (e) the end terminator.
Moreover, the structure derived from (f) chain extender means a partial structure other than the group involved in the chain extension reaction in the molecular structure of (f) chain extender. The structure derived from (f) chain extender is introduced into the polyurethane by (f) chain extender.

<<<<< (a) Polycarbonate polyol >>>>
(A) A polycarbonate polyol will not be specifically limited if it is a polyol which has a carbonate bond in a molecule | numerator. (A) The polycarbonate polyol is preferably one in which a polyol monomer such as a diol is carbonate-bonded. Moreover, (a) polycarbonate polyol may contain the ether bond and ester bond of the number below the average number of the carbonate bond in a molecule | numerator.

  (A) Polycarbonate polyol is obtained, for example, by reacting a polyol monomer with a carbonate compound and / or phosgene.

  Although it does not specifically limit as a polyol monomer, For example, an aliphatic polyol monomer, a polyol monomer which has an alicyclic structure, an aromatic polyol monomer, a polyester polyol monomer, a polyether polyol monomer etc. are mentioned.

  Examples of the aliphatic polyol monomer include, but are not limited to, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptane. Linear aliphatic diols such as diol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol; isopropylene glycol, 1 , 3-butanediol, 2-methyl-1,3-propanediol, 1,4-pentanediol, 2-methyl-1,4-butanediol, neopentyl glycol, 1,5-hexanediol, 2-methyl- 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-o Branched chain aliphatic diols such as tandiol, 2-methyl-1,9-nonanediol, 2-methyl-1,3-propanediol, 1,1,1-trimethylolpropane, pentaerythritol; trimethylolpropane, penta Examples thereof include polyhydric alcohols having three or more functional groups such as erythritol.

  The polyol monomer having an alicyclic structure is not particularly limited. For example, 1,3-cyclopentanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,3-cyclohexanedimethanol, 1,4 -Cyclohexanedimethanol, 1,4-cycloheptanediol, 2,7-norbornanediol, 1,4-bis (hydroxyethoxy) cyclohexane, isosorbide, dimer diol and the like.

  The aromatic polyol monomer is not particularly limited, and examples thereof include catechol, hydroquinone, resorcinol, 1,3-benzenedimethanol, 1,4-benzenedimethanol, bisphenol A and the like.

  Although it does not specifically limit as a polyester polyol monomer, For example, dicarboxylic acid, such as polyester polyol of hydroxycarboxylic acid and diol, such as polyester polyol of 6-hydroxycaproic acid and hexanediol, polyester polyol of adipic acid and hexanediol And polyester polyol of diol.

  Although it does not specifically limit as a polyether polyol monomer, For example, polyalkylene glycol, such as polyethyleneglycol, polypropylene glycol, polytetramethylene glycol, these high polymers, etc. are mentioned.

  A plurality of polyol monomers may be used in combination.

The carbonate ester is not particularly limited, and examples thereof include aliphatic carbonate esters such as dimethyl carbonate and diethyl carbonate; aromatic carbonate esters such as diphenyl carbonate; cyclic carbonate esters such as ethylene carbonate. Aliphatic carbonic acid ester is preferable and dimethyl carbonate is particularly preferable because the production of polycarbonate polyol becomes easy.
A plurality of carbonate esters may be used in combination.

  The polycarbonate polyol is preferably a polycarbonate polyol obtained by reacting a polyol monomer and a carbonic acid ester compound from the viewpoints of low chlorine content and difficulty in coloring. Polycarbonate polyol is a polycarbonate polyol obtained by reacting a polyol monomer having no alicyclic structure in the main chain with a carbonate ester; a polycarbonate polyol obtained by reacting a polyol monomer having an alicyclic structure in the main chain with a carbonate ester A polycarbonate polyol obtained by reacting a polyol monomer having an alicyclic structure in the main chain, another polyol monomer (a polyol monomer having no alicyclic structure in the main chain), and a carbonic ester is more preferable.

  Here, as a polycarbonate polyol obtained by reacting a polyol monomer having no alicyclic structure in the main chain with a carbonate, a polycarbonate diol obtained by reacting one or more aliphatic diols with a carbonate; Aliphatic polycarbonate diols such as tetramethylene carbonate diol, polypentamethylene carbonate diol, polyhexamethylene carbonate diol; aromatic polycarbonate diols such as poly 1,4-xylylene carbonate diol; aliphatic diols, aromatic diols and carbonates Polycarbonate diol obtained by reacting with diol; copolymer polycarbonate diol such as polycarbonate diol obtained by reacting aliphatic diol, dimer diol and carbonate ester is preferred. .

  As described above, (a) as polycarbonate polyol, polycarbonate diol obtained by reacting 1,6-hexanediol and carbonate; a mixture of 1,6-hexanediol and 1,5-pentanediol and carbonate A polycarbonate diol obtained by reacting a mixture of 1,6-hexanediol and 1,4-butanediol with a carbonate ester; 1,4-cyclohexanedimethanol and a carbonate ester Particularly preferred are polycarbonate diols obtained by reacting a mixture of 1,6-hexanediol and 1,4-cyclohexanedimethanol with carbonates.

  Examples of a method for producing a polycarbonate polyol from a polyol monomer and a carbonic acid ester compound include the following methods. After adding carbonate ester and a polyol monomer in excess of the number of moles of this carbonate in the reactor and reacting at a temperature of 160 ° C. to 200 ° C. and a pressure of about 50 mmHg for 5 hours to 6 hours, further The method of making it react at 200 to 220 degreeC for several hours in the pressure of several mmHg or less is mentioned. In the above reaction, it is preferable to carry out the reaction while extracting by-produced alcohol out of the system. When the carbonate ester escapes from the system by azeotroping with the by-produced alcohol, an excessive amount of carbonate ester may be added. In the above reaction, a catalyst such as titanium tetrabutoxide may be used.

(Preferred embodiment)
(A) Although the number average molecular weight of polycarbonate polyol is not specifically limited, It is preferable that it is 400-8,000, and it is especially preferable that it is 400-4,000. (A) When the number average molecular weight of the polycarbonate polyol is 400 to 8,000, the viscosity of the polyurethane resin emulsion can be appropriately adjusted and the handleability of the polyurethane resin emulsion is improved. In addition, since the performance of the polycarbonate polyol as a soft segment is improved, when the coating film is formed using the emulsion composition, the coating film is hardly cracked, and the reactivity between the polycarbonate polyol and the isocyanate compound is further reduced. Therefore, the urethane resin can be produced efficiently.

  In this specification, the number average molecular weight is the number average molecular weight calculated based on the hydroxyl value measured according to JIS K 1577. Specifically, the number average molecular weight is calculated by measuring the hydroxyl value of the compound and using the formula (56.1 × 1,000 × valence) / hydroxyl value (mgKOH / g) by terminal group quantification. be able to. In the above formula, the valence is the number of hydroxyl groups in one molecule. When the polycarbonate polyol is polycarbonate diol, the valence is 2.

The polycarbonate polyol is preferably a polycarbonate diol having no alicyclic structure in the main chain from the viewpoint of adhesion, and from the viewpoint of chemical resistance, the polycarbonate diol obtained by reacting 1,6-hexanediol with a carbonate. Is more preferable.
(A) A plurality of polycarbonate polyols may be used in combination.

<<<<< (b) Acidic Group-Containing Polyol >>>>
(B) The acidic group-containing polyol is a polyol having two or more hydroxyl groups (not including a phenolic hydroxyl group) and one or more acidic groups in one molecule. Since the polyurethane resin has a structure derived from the (b) acidic group-containing polyol, even if the polyurethane resin emulsion does not contain a protective colloid, an emulsifier, and / or a surfactant, the aqueous resin dispersion composition can be added to water. Dispersion stability is improved.

  Here, examples of the acidic group of the acidic group-containing polyol include a carboxy group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group. From the viewpoint of dispersion stability in water, a carboxy group is preferable.

(B) Although it does not restrict | limit especially as an acidic group containing polyol, Specifically, dimethylol alkanoic acids, such as 2, 2- dimethylol propionic acid and 2, 2- dimethylol butanoic acid; N, N-bishydroxy Examples include ethyl glycine, N, N-bishydroxyethylalanine, 3,4-dihydroxybutanesulfonic acid, 3,6-dihydroxy-2-toluenesulfonic acid, and the like. From the viewpoint of easy availability, (b) the acidic group-containing polyol is preferably an alkanoic acid having 4 to 12 carbon atoms (dimethylolalkanoic acid) containing two methylol groups, and 2,2-dimethylolpropionic acid is Particularly preferred.
(B) A plurality of acidic group-containing polyols may be used in combination.

<<<<< (b ') Neutralizer >>>>
The (b ′) neutralizing agent is not particularly limited as long as it can neutralize the acidic group of the (b) acidic group-containing polyol, and can be appropriately selected according to the type of acidic group. (B ′) Specific examples of the neutralizer include trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-phenyldiethanolamine, dimethylethanolamine. , Diethylethanolamine, N-methylmorpholine, pyridine, organic amines such as 2- (dimethylamino) -2-methyl-1-propanol (DMAP); inorganic alkali salts such as sodium hydroxide and potassium hydroxide; ammonia and the like Is mentioned. (B ′) The neutralizing agent is preferably an organic amine, more preferably a tertiary amine, and particularly preferably triethylamine.
(B ') A neutralizing agent may use multiple types together.

<<<<< (c) Polyisocyanate Compound >>>>
(C) Polyisocyanate usually has 2 isocyanate groups per molecule, but polyisocyanate having 3 or more isocyanate groups such as triphenylmethane triisocyanate is also used as long as the polyurethane resin does not gel. can do.
(C) It does not specifically limit as polyisocyanate, Aromatic polyisocyanate, aliphatic polyisocyanate, alicyclic polyisocyanate, etc. are mentioned.

  The aromatic polyisocyanate is not particularly limited. Specifically, 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′-diisocyanate biphenyl, 3,3′-dimethyl-4,4′-diisocyanate biphenyl, 3,3′-dimethyl-4, 4′-diisocyanate diphenylmethane, 1,5-naphthylene diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, m-isocyanate phenylsulfonyl isocyanate, p-isocyanate phenylsulfonyl isocyanate 1,3-bis (2-isocyanatoethyl 2-propyl) benzene (TMXDI), and the like.

  Although it does not specifically limit as aliphatic polyisocyanate, Specifically, ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4 -Trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanate methylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanate hexanoate Etc.

  Although it does not specifically limit as alicyclic polyisocyanate, Specifically, isophorone diisocyanate (IPDI), 4,4'- dicyclohexylmethane diisocyanate (H12MDI, hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogen) Added TDI), bis (2-isocyanatoethyl) -4-dichlorohexene-1,2-dicarboxylate, 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate, hydrogenated xylylene diisocyanate (hydrogenated XDI), etc. Can be mentioned.

  From the viewpoint of suppressing yellowing of the cured coating film of the emulsion composition, (c) the polyisocyanate is preferably an aliphatic polyisocyanate or an alicyclic polyisocyanate, and from the viewpoint that the reaction can be easily controlled, isophorone diisocyanate and More preferably, it is 4,4′-dicyclohexylmethane diisocyanate.

From the viewpoint of increasing chemical resistance, 4,4′-dicyclohexylmethane diisocyanate is preferable. Isophorone diisocyanate is preferred from the viewpoint of improving adhesion to a plastic substrate.
(C) You may use multiple types of polyisocyanate together.

<<<<< (d) Other polyols >>>>
Other polyols are polyols other than (a) and (b). The polyol is not particularly limited as long as it has two or more hydroxyl groups in one molecule. Examples of such other polyols include polyester polyols, polyether polyols other than (a), polyolefin polyols, acrylic polyols, polydiene polyols, and the like.

(Polyester polyol)
Examples of the polyester polyol include, but are not limited to, polyethylene adipate diol, polybutylene adipate diol, polyethylene butylene adipate diol, polyhexamethylene isophthalate adipate diol, polyethylene succinate diol, polybutylene succinate diol, polyethylene sebacate diol Polyester diols such as polybutylene sebacate diol, poly-ε-caprolactone diol, poly (3-methyl-1,5-pentylene adipate) diol, polycondensate of 1,6-hexanediol and dimer acid It is done.

(Polyether polyol)
Examples of polyether polyols include polyethylene glycol, polypyrylene glycol, random copolymers and block copolymers of ethylene oxide and propylene oxide, random copolymers and block copolymers of ethylene oxide and butylene oxide, and polytetramethylene. And grille. Furthermore, a polyether polyester polyol having an ether bond and an ester bond may be used as the polyether diol.

(Low molecular weight diol)
The number average molecular weight of the low molecular weight diol is not particularly limited, but is preferably 60 or more and less than 400. Specific examples of the low molecular weight diol include, for example, ethylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, and 2-butyl-2. -Ethyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 2 -C2-C9 aliphatic diols such as methyl-1,8-octanediol, diethylene glycol, triethylene glycol, tetraethylene glycol; 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4 -Cyclohexanediol, 1,4-bis (hydroxyethyl) cyclohexane, 2,7-norvo Nanjioru, tetrahydrofuran dimethanol, 2,5-bis can be mentioned diols having an alicyclic structure having 6 to 12 carbon atoms such as (hydroxymethyl) -1,4-dioxane. Further, as the low molecular weight diol, a low molecular weight polyhydric alcohol such as trimethylolpropane, pentaerythritol, sorbitol or the like may be used as the low molecular weight diol.
(D) A plurality of other polyols may be used in combination.

<<<<< (e) End terminator >>>>
(E) A terminal terminator is a component capable of terminating the urethanization reaction and / or chain extension reaction at the end of the polyurethane resin. (E) As a terminal stopper, from the viewpoint of scratch resistance, (e-1) a compound having one acidic group and one hydroxyl group in one molecule is preferable. (F-2) may be used in combination with a chain extender and / or a film-forming aid having a structure derived from-, but from the viewpoint of obtaining a coating film having better scratch resistance, (e-1 The terminal terminator having a structure derived from () is preferably used in combination with a chain extender having a structure derived from (f-2).

  (E-1) As a compound having one acidic group and one hydroxyl group in one molecule, specifically, for example, glycolic acid (2-hydroxyacetic acid), hydroxypivalic acid (HPA), lactic acid, 3- Hydroxybutyric acid, 4-hydroxybutyric acid, 10-hydroxydecanoic acid, hydroxypivalic acid (2,2-dimethyl-3-hydroxypropionic acid), 12-hydroxydodecanoic acid, 16-hydroxyhexadecanoic acid, lactic acid, trichlorolactic acid, salicylic acid , Hydroxybenzoic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxypropionic acid, 2-hydroxyoctanoic acid, 3-hydroxyundecanoic acid, 12-hydroxystearic acid (HSA), 12-hydroxyoleic acid and the like. However, from the viewpoint of scratch resistance, 12-hydroxystearic acid (HSA It is particularly preferred.

(E-2) Examples of the terminal terminator other than the compound having one acidic group and one hydroxyl group in one molecule include compounds having one group that reacts with an isocyanato group. Examples of the group that reacts with the isocyanato group include compounds having a total of one hydroxyl group, amino group, imino group, mercapto group and the like. Specific examples include monoamines such as n-butylamine and di-n-butylamine; ethanol Monohydric alcohols such as isopropanol and butanol.
(E) Multiple types of terminal terminators may be used in combination.

<<<<< (f) Chain Extender >>>>
(F) Examples of the chain extender include a compound having two or more groups that react with an isocyanato group. For example, a polyamine, a polyol having a total of two or more amino groups and / or imino groups in one molecule, and Water is mentioned.

  As a polyamine compound having a total of two or more amino groups and / or imino groups in one molecule, (f-1) a polyamine having a total of two amino groups and / or imino groups in one molecule, and ( f-2) Polyamines having 3 or more amino groups and / or imino groups in total in one molecule.

  From the viewpoint of scratch resistance, it is preferable to use (f-2) a polyamine having 3 or more amino groups and / or imino groups in total in one molecule. (E-1) may be used in combination with a terminal terminator having a structure derived from and / or a film-forming aid, but from the viewpoint of obtaining a coating film having better scratch resistance, derived from (f-2) The chain extender having a structure is preferably used in combination with a terminal terminator having a structure derived from (e-1).

  (F-1) As a polyamine having a total of two amino groups and / or imino groups in one molecule, hydrazine, ethylenediamine, 1,4-tetramethylenediamine, 2-methyl-1,5-pentanediamine, 1, Primary diamines such as 6-hexamethylenediamine, 1,4-hexamethylenediamine, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, 1,3-bis (aminomethyl) cyclohexane, xylylenediamine; and Examples include diamines such as secondary diamine compounds such as piperazine and 2,5-dimethylpiperazine.

  (F-2) Examples of polyamines having a total of three or more amino groups and / or imino groups in one molecule are not particularly limited. For example, diethylenetriamine (DETA), bis (2-aminopropyl) amine, Triamines such as bis (3-aminopropyl) amine; triethylenetetramine, tripripyrenetetramine, N- (benzyl) triethylenetetramine, N, N ′ ″-(dibenzyl) triethylenetetramine, N- (benzyl)- Tetramines such as N ′ ″-(2-ethylhexyl) triethylenetetramine; pentamines such as tetraethylenepentamine and tetrapropylenepentamine; hexamines such as pentaethylenehexamine and pentapropylenehexamine; polyamines such as polyethyleneimine and polypropyleneimine Mentioned That is, from the viewpoint of scratch resistance, diethylenetriamine (DETA) is particularly preferred.

As the polyol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol and the like are preferable.
(F) Multiple types of chain extenders may be used in combination.

<<< Properties of polyurethane resin >>>
The content of urethane groups and urea groups in the polyurethane resin is 5% by mass or more and 11% by mass or less, and more preferably 8% by mass or more and 11% by mass or less. By setting it in this range, scratch resistance is improved.

Content of the urethane group in a polyurethane resin can be calculated | required with the following formula | equation.
(1) The number of moles of the total hydroxyl group of (a) polycarbonate polyol, (b) acidic group-containing polyol, (d) other polyol, (e) terminal terminator, and (f) chain extender. (C) When the number of moles of isocyanato groups of the polyisocyanate is less than (number of urethane groups in the polyurethane resin (mass%)) = {((a) polycarbonate polyol, (b) acidic group-containing polyol, ( d) The number of moles of the total hydroxyl group of other polyol, (e) terminal terminator, and (f) chain extender) × 59.02} / (polyurethane resin solid content (g)).

(2) The total number of moles of hydroxyl groups of (a) polycarbonate polyol, (b) acidic group-containing polyol, (d) other polyol, (e) terminal terminator, and (f) chain extender. , (C) when the number of moles of isocyanate groups of the polyisocyanate is greater than the number of moles of isocyanate groups (concentration of urethane groups in the polyurethane resin (mass%)) = {(c) moles of isocyanate groups of the polyisocyanate) × 59.02} / It is calculated | required by (urethane resin solid content (g)).

The content of urea groups in the polyurethane resin can be determined by the following formula.
(3) When the number of moles of isocyanato groups in the polyurethane prepolymer is less than the number of moles of amino groups in (f) chain extender, (the concentration of urea groups in the polyurethane resin (mass%)) = {(c) The number of moles of isocyanato groups of the polyisocyanate) × 58.04} / (polyurethane resin solid content (g)).

(4) When the number of moles of isocyanato groups in the polyurethane prepolymer is larger than the number of moles of amino groups in (f) chain extender, (the concentration of urea groups in the polyurethane resin (mass%)) = {(f) The number of moles of amino group of the chain extender) × 58.04} / (polyurethane resin solid content (g)).

  The weight average molecular weight of the polyurethane resin is not particularly limited, but is preferably, for example, 10,000 to 2,000,000, more preferably 10,000 to 1,000,000, and 20,000 to Particularly preferred is 500,000. In the present specification, the weight average molecular weight is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

  The alicyclic structure content ratio (hereinafter simply referred to as “alicyclic structure content ratio”) relative to the solid content of the polyurethane resin in the polyurethane resin emulsion (excluding the neutralizing agent for neutralizing the acidic group) is, for example, The content is preferably 1% by mass to 50% by mass, more preferably 3% by mass to 20% by mass, and still more preferably 5% by mass to 15% by mass. By setting it to 50% by mass or less, the adhesion to the plastic substrate tends to be high. There exists a tendency for chemical resistance to become high by setting it as 1 mass% or more.

  In the present specification, the alicyclic structure content ratio is the weight ratio of the alicyclic group in the polyurethane resin. For example, a cycloalkane residue such as a cyclohexane residue (in the case of 1,4-hexanedimethanol, a portion obtained by removing two hydrogen atoms from cyclohexane) or a dicyclohexylmethane residue (4,4′-dicyclohexylmethane diisocyanate). In the case of dicyclohexylmethane, 4 hydrogen atoms and 1 carbon atom are removed), isophorone residue (in the case of isophorone diisocyanate, 5 hydrogen atoms are removed from cyclohexane), tetrahydrofuran residue, etc. This is a value calculated based on an unsaturated heterocyclic residue (in the case of tetrahydrofuran dimethanol, the portion obtained by removing two hydrogen atoms from tetrahydrofuran).

<<< Polyurethane resin composition >>>
(A) a structure derived from a polycarbonate polyol in a polyurethane resin, (b) a structure derived from an acidic group-containing polyol, (c) a structure derived from a polyisocyanate, (d) a structure derived from another polyol, (e) derived from a terminal stopper The structure, (f) the structure derived from the chain extender, and (b ′) the content of the neutralizing agent part are not particularly limited. For example, the quantity used as the usage-amount of each component in the manufacturing method of the polyurethane resin emulsion mentioned later is mentioned.

<<< Aqueous medium >>>
In the polyurethane resin emulsion, the medium in which the polyurethane resin is dispersed includes water. Examples of water include clean water, ion-exchanged water, distilled water, and ultrapure water. However, it is easy to obtain and the influence of the salt that causes the particles to become unstable is small. From the viewpoint, ion-exchanged water is preferable.

<<< Film-forming aid >>>
From the viewpoint of scratch resistance, the aqueous medium preferably contains a film-forming aid. A terminal terminator having a structure derived from (e-1) and / or a chain extender having a structure derived from (f-2) may be used in combination, or a film-forming aid may be used alone.
The film-forming aid may be contained in the aqueous medium of the acrylic resin emulsion, or may be contained in the aqueous medium of the emulsion composition.
Examples of film forming aids include acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, dioxane, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, N-ethylpyrrolidone, β-alkoxypropionamide, dipropylene glycol dimethyl ether, ethyl acetate. Etc.
From the viewpoint of improving scratch resistance, β-alkoxypropionamide is particularly preferable.

<<< Method for producing polyurethane resin emulsion >>>
The method for producing the polyurethane resin emulsion is not particularly limited as long as the polyurethane resin is dispersed in an aqueous medium and an aqueous polyurethane resin dispersion is obtained. Examples of the method for producing a polyurethane resin emulsion include a one-shot method in which all raw materials are reacted at once, a prepolymer method in which an isocyanate-terminated polyurethane prepolymer is produced and then a chain extender is reacted. Hereinafter, an example of the manufacturing method of the polyurethane resin emulsion by a prepolymer method is demonstrated.

The production method of the polyurethane resin emulsion by the prepolymer method is as follows:
(A) Polycarbonate polyol, (b) acidic group-containing polyol, (c) polyisocyanate, and optionally (d) other polyol and (e) a terminal stopper are reacted to produce (A) polyurethane pre Obtaining a polymer (α);
(A) a step (β) of neutralizing acidic groups of the polyurethane prepolymer with (b ′) a neutralizing agent;
(A) Dispersing the polyurethane prepolymer in an aqueous solvent (γ),
A step (δ) of reacting (A) a polyurethane prepolymer with (f) a chain extender having reactivity to the isocyanate group of the (A) polyurethane prepolymer;
And the like. Here, the step (α) may further include a step of adding (e) a terminal terminator to the obtained (A) polyurethane prepolymer.

  Step (α) may be performed in an inert gas atmosphere or in an air atmosphere.

  In step (α), the amount of (a) polycarbonate polyol used is not particularly limited, but (a) polycarbonate polyol, (b) acidic group-containing polyol, (c) polyisocyanate, and optionally (d) For 100 parts by mass of the total amount of other polyols, (e) terminal terminator, and (f) chain extender (hereinafter also referred to as “total amount of 100 parts by mass of (a) to (f)”). Preferably it is 20-90 mass parts, Most preferably, it is 50-80 mass parts.

  In the step (α), the amount of the (c) polyisocyanate used is not particularly limited, but is (a) a polycarbonate polyol, (b) an acidic group-containing polyol, and (d) the number of moles of all hydroxyl groups of other polyols ( c) The ratio of the number of moles of isocyanato groups in the polyisocyanate is preferably 1.05 to 2.5, and particularly preferably 1.1 to 2.0. In the step (α), the amount of the (c) polyisocyanate compound with respect to 100 parts by mass of the total amount of (a) to (f) is within the range satisfying the above-described molar ratio, (a) polyol, (b) acidic It can be appropriately set according to the type or mass of the group-containing polyol and (d) other polyol.

  In the step (α), the amount of the (b) acidic group-containing polyol used is preferably 0.5 to 50 parts by mass, particularly preferably 1 to 30 parts per 100 parts by mass of the total amount of (a) to (g). Part by mass.

  In step (α), the amount of (d) other polyol used can be appropriately set.

  In the step (α), the amount of the (e) terminal terminator used is from (c) the number of moles of isocyanate groups of the polyisocyanate, from (a) polycarbonateol, (b) acidic group-containing polyol and (d) other polyols. It can be appropriately set within a range not exceeding the number of moles obtained by subtracting the number of moles of all hydroxyl groups.

  In the step (β), the amount of the (b ′) neutralizing agent used can be appropriately set within a range of 0.1 to 2 times the total number of moles of the (b) acidic group-containing polyol.

  In the step (γ), the method of dispersing the (A) polyurethane prepolymer in the aqueous solvent is not particularly limited. For example, the (A) polyurethane prepolymer is mixed in the aqueous solvent stirred by a homomixer or a homogenizer. Examples thereof include a method of adding a polymer, a method of adding an aqueous solvent to the polyurethane prepolymer (A) which is stirred by a homomixer, a homogenizer, or the like.

  The step (δ) may be performed slowly under cooling (for example, 0 to 40 ° C.), or in some cases, the reaction may be promoted under heating conditions of 60 ° C. or less. The reaction time under cooling is preferably 0.2 to 24 hours. The reaction time under heating conditions is preferably 0.1 to 6 hours.

  In the step (δ), the amount of the (f) chain extender used is preferably equal to or less than the isocyanate base that is the chain extension starting point in the (A) polyurethane prepolymer, more preferably the isocyanate group. It is 0.7-0.99 equivalent with respect to. It was obtained by applying the resulting polyurethane resin emulsion without reducing the molecular weight of the chain-extended urethane polymer (ie, polyurethane resin) by adding the chain extender (f) in an amount equal to or less than the equivalent of the isocyanato group. There exists a tendency which can make the intensity | strength of a coating film high. In addition, the ratio of the polyamine compound having three or more amino groups and / or imino groups in one molecule in the chain extender is preferably 10 to 100 mol%, and preferably 20 to 100 mol%. More preferably, it is more preferable that it is 40-100 mol%.

  In the method for producing a polyurethane resin emulsion including the steps (α) to (δ), either the step (β) or the step (δ) may be performed first or at the same time. Further, the step (β) may be performed simultaneously with the step (γ). Furthermore, the step (β), the step (γ), and the step (δ) may be performed simultaneously. Further, the step (δ) may be performed simultaneously with the step (γ), or may be performed after the step (γ).

  Moreover, a polyurethane resin emulsion can be manufactured by the method similar to the method described in WO2014 / 103687, WO2015 / 194671, WO2015 / 194672, WO2015 / 033939, for example.

<< Acrylic resin emulsion / Acrylic resin >>
An acrylic resin emulsion is an aqueous emulsion of an acrylic resin in which an acrylic resin is dispersed in an aqueous medium. Here, the aqueous medium may be the same as the aqueous medium described in the embodiment of the polyurethane resin emulsion.

  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.

As a commercial item of an acrylic resin emulsion, the following is mentioned, for example.
High pressure gas industry Co., Ltd .: Pegar 862 (Tg: -10 ° C), Pegar 751 (Tg: 25 ° C), LC6154 (Tg: 64 ° C), Showa Denko KK: Polysol AP-3900 (Tg: 10 ° C) AP-1020 (Tg: 23 ° C.), AP-4735, TI-3052, SE-4210E (Tg: −50 ° C.), manufactured by Nippon Carbide Industries, Ltd .: Nicazole FX5697H (Tg: −60 ° C.), FX3750 (Tg) : -30 ° C), FX2138 (Tg: -17 ° C), FX2555 (Tg: -17 ° C), FX2033 (Tg: 8 ° C), FX2018 (Tg: 27 ° C), FX672K (Tg: 53 ° C), parachem Made in Japan: Parabond LX-5 (Tg: -40 ° C), G-60 (Tg: -30 ° C), LX-2 (Tg: -30 ° C), Tojo Made formed Corporation: NW-400 (Tg: -41 ℃)

  The acrylic resin is not particularly limited, but the Tg (glass transition temperature) of the acrylic resin is preferably −80 ° C. to 60 ° C., more preferably −55 ° C. to 0 ° C., and −40 ° C. to − A temperature of 20 ° C. is particularly preferable. When the Tg of the acrylic resin is 60 ° C. or less, the adhesion of the coating film to plastic or the like is more excellent. When the Tg of the acrylic resin is −80 ° C. or higher, the chemical resistance of the coating film is more excellent.

  In addition, an acrylic resin and an acrylic resin emulsion may be used in combination, or a plurality of acrylic resins and acrylic resin emulsions may be used in combination.

<<< Method for Producing Acrylic Resin Emulsion >>>
The method for producing the acrylic resin emulsion is not particularly limited as long as the acrylic resin can be dispersed in an aqueous solvent. The acrylic resin emulsion can be produced, for example, by mixing an acrylic resin and water in the presence or absence of an emulsifier such as a surfactant.

<< Aqueous medium >>
The emulsion composition includes an aqueous medium. Water is mentioned as a medium which disperse | distributes a polyurethane resin and an acrylic resin. Examples of water include clean water, ion-exchanged water, distilled water, and ultrapure water. However, it is easy to obtain and the influence of the salt that causes the particles to become unstable is small. From the viewpoint, ion-exchanged water is preferable.

<<< Film-forming aid >>>
From the viewpoint of scratch resistance, the aqueous medium preferably contains a film-forming aid. A terminal terminator having a structure derived from (e-1) and / or a chain extender having a structure derived from (f-2) may be used in combination.
The film-forming aid may be contained in the aqueous medium of the polyurethane resin emulsion or may be contained as the aqueous medium of the acrylic resin emulsion.
Examples of film forming aids include acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, dioxane, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, N-ethylpyrrolidone, β-alkoxypropionamide, dipropylene glycol dimethyl ether, ethyl acetate. Etc.
From the viewpoint of improving scratch resistance, β-alkoxypropionamide is particularly preferable.

<< Emulsion composition >>
The content of the polyurethane resin in the solid content of the emulsion composition is 20 to 95% by weight, preferably 35 to 90%, particularly preferably 60 to 90%. When the content of the polyurethane resin is 20 to 95% by weight, scratch resistance is enhanced.

<Method for producing emulsion composition>
The method for producing the emulsion composition is not particularly limited as long as the polyurethane resin and the acrylic resin can be dispersed in an aqueous solvent. The emulsion composition can be produced, for example, by mixing a polyurethane resin emulsion and an acrylic resin emulsion. In addition, the emulsion composition includes, for example, (A) a polyurethane prepolymer, a silicone compound, and an acrylic resin dispersed in an aqueous solvent, and (A) a polyurethane prepolymer and a chain extender in the presence of the acrylic resin. It can manufacture by making these react.

Further, the emulsion composition of the present invention includes a thickener, a photosensitizer, a curing catalyst, an ultraviolet absorber, a light stabilizer, an antifoaming agent, a plasticizer, depending on the required function, characteristics, application, etc. Additives such as a surface conditioner, an anti-settling agent, and a colorant can also be added.
In addition, the said additive may use multiple types together. Moreover, the kind of these additives is well-known to those skilled in the art, and can be used in the amount of the range generally used.

<Coating composition, coating agent composition and ink composition>
The present invention also relates to a coating composition, a coating composition, and an ink composition containing the emulsion composition.

  In addition to the water-based polyurethane resin dispersion for water vapor gas barrier coating, other resins may be added to the coating composition, coating agent composition and ink composition of the present invention. Examples of other resins include polyester resins, polyether resins, polycarbonate resins, polyurethane resins, epoxy resins, alkyd resins, polyolefin resins, and vinyl chloride resins. These may use multiple types together. The other resin preferably has one or more hydrophilic groups from the viewpoint of dispersibility in water. Examples of the hydrophilic group include a hydroxyl group, a carboxy group, a sulfonic acid group, and a polyethylene glycol group.

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

  The polyester resin can be produced by an esterification reaction or an ester exchange reaction between an acid component and an alcohol component. As an acid component, the compound normally used as an acid component at the time of manufacture of a polyester resin can be used. As an acid component, an aliphatic polybasic acid, an alicyclic polybasic acid, an aromatic polybasic acid, etc. can be used, for example. The hydroxyl value of the polyester resin is preferably about 10 to 300 mgKOH / g, more preferably about 50 to 250 mgKOH / g, and still more preferably about 80 to 180 mgKOH / g.

  The acid value of the polyester resin is preferably about 1 to 200 mgKOH / g, more preferably about 15 to 100 mgKOH / g, and still more preferably about 25 to 60 mgKOH / g.

  The weight average molecular weight of the polyester resin is preferably 500 to 500,000, more preferably 1,000 to 300,000, and still more preferably 1,500 to 200,000.

  Examples of the polyether resin include a polymer or copolymer having an ether bond, such as polyoxyethylene-based polyether, polyoxypropylene-based polyether, polyoxybutylene-based polyether, bisphenol A or bisphenol F. Examples thereof include polyethers derived from aromatic polyhydroxy compounds.

  Examples of the polycarbonate resin include a polymer produced from a bisphenol compound, and examples thereof include bisphenol A / polycarbonate.

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

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

  Examples of the alkyd resin include polybasic acids such as phthalic acid, terephthalic acid, and succinic acid and polyhydric alcohols, and fats and oils and fatty acids (soybean oil, linseed oil, coconut oil, stearic acid, etc.), natural resins (for example, Alkyd resin obtained by reacting a modifying agent such as rosin, rosin, etc.).

  As the polyolefin resin, a polyolefin resin obtained by polymerizing or copolymerizing an olefin monomer with another monomer in accordance with a normal polymerization method is dispersed in water using an emulsifier, or the olefin monomer is appropriately replaced with another monomer. And a resin obtained by emulsion polymerization. In some cases, a so-called chlorinated polyolefin-modified resin in which the polyolefin resin is chlorinated may be used.

Examples of the olefin monomer include ethylene, propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-hexene, Α-olefins such as -decene and 1-dodecene; conjugated or non-conjugated dienes such as butadiene, ethylidene norbornene, dicyclopentadiene, 1,5-hexadiene, styrenes, and the like.
In addition, these monomers may use multiple types together.

Examples of other monomers copolymerizable with the olefinic monomer include vinyl acetate, vinyl alcohol, maleic acid, citraconic acid, itaconic acid, maleic anhydride, citraconic anhydride, and itaconic anhydride.
In addition, these monomers may use multiple types together.

  The coating composition and the coating composition of the present invention can further contain a curing agent. By including a curing agent, it is possible to improve the water resistance of a coating film or a multilayer coating film, a coating film or a printed matter obtained using the coating composition or the coating agent composition.

As the curing agent, for example, amino resins, polyisocyanates, blocked polyisocyanates, melamine resins, carbodiimides, polyols and the like can be used.
In addition, you may use multiple types of these hardening | curing agents together.

  Examples of the amino resin include a partial or completely methylolated amino resin obtained by a reaction between an amino component and an aldehyde component. Examples of the amino component include melamine, urea, benzoguanamine, acetoguanamine, steroguanamine, spiroguanamine, dicyandiamide and the like.

  Examples of the aldehyde component include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, and the like.

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

Examples of the blocked polyisocyanate include those obtained by adding a blocking agent to the isocyanate group of the aforementioned polyisocyanate.
Phenols such as phenol and cresol, aliphatic alcohols such as methanol and ethanol, active methylenes such as dimethyl malonate and acetylacetone, mercaptans such as butyl mercaptan and dodecyl mercaptan, acid amides such as acetanilide and acetate amide, ε -Lactams such as caprolactam and δ-valerolactam; acid imides such as succinimide and maleic imide; oximes such as acetoaldoxime, acetone oxime and methylethylketoxime; amines such as diphenylaniline, aniline and ethyleneimine And blocking agents such as

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

  Examples of the polyol include polyrotaxane and a compound derived therefrom.

  Coloring pigments, extender pigments, and glitter pigments can be added to the coating composition, coating agent composition, and ink composition of the present invention.

Examples of the color pigment include titanium oxide, zinc white, carbon black, molybdenum red, Prussian blue, cobalt blue, azo pigment, phthalocyanine pigment, quinacridone pigment, isoindoline pigment, selenium pigment, and perylene pigment. It is preferable to use titanium oxide and / or carbon black as the color pigment.
In addition, these may use multiple types together.

Examples of extender pigments include clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talc, silica, and alumina white. As extender pigments, barium sulfate and / or talc are preferably used, and barium sulfate is preferable. More preferably, is used.
In addition, these may use multiple types together.

  As the bright pigment, for example, aluminum, copper, zinc, brass, nickel, aluminum oxide, mica, aluminum oxide coated with titanium oxide or iron oxide, mica coated with titanium oxide or iron oxide can be used. .

The coating composition, coating composition, and ink composition of the present invention include a thickener, a curing catalyst, an ultraviolet absorber, a light stabilizer, an antifoaming agent, a plasticizer, and a surface depending on the function, specification, and use. Conventional additives such as a regulator and an anti-settling agent can be contained.
In addition, these may use multiple types together.

  Although the manufacturing method of the coating composition, coating agent composition, and ink composition of the present invention is not particularly limited, a known manufacturing method can be adopted, but preferably the coating composition, the coating agent composition, and The ink composition is produced by mixing the aqueous polyurethane resin dispersion for water vapor gas barrier coating and the various additives described above, adding an aqueous medium, and adjusting the viscosity according to the application method.

  Examples of the material to be coated of the paint composition and the material to be coated of the coating material of the coating agent composition include metals, plastics, inorganic materials, and wood. Among the base materials, a plastic is preferable and a polyester resin is particularly preferable from the viewpoint that adhesion can be secured.

  Examples of the coating method of the coating composition or the coating method of the coating agent composition include bell coating, spray coating, roll coating, shower coating, and immersion coating. Examples of the application method of the ink composition include an inkjet printing method, a flexographic printing method, a gravure printing method, a reverse offset printing method, a sheet-fed screen printing method, and a rotary screen printing method.

It is preferable to apply a coating composition, a coating agent composition, and an ink composition to a material to be applied, and then heat and cure to obtain a coating film and a coating.
Examples of the heating method include a heating method using its own reaction heat, and a heating method in which a coating composition, a coating agent composition, an ink composition, and an applied material are positively heated. The positive heating includes a method of heating the coating composition, the coating agent composition, the ink composition and the material to be applied in a hot air oven, an electric furnace, or an infrared induction heating furnace.

  The heating temperature is preferably 20 to 200 ° C, more preferably 60 to 160 ° C. By heating at such a temperature, drying can be performed more efficiently. The heating time is preferably 0.0001 to 20 hours, more preferably 1 to 10 hours. By setting it as such a heating time, a coating layer with higher hardness can be obtained. Examples of drying conditions for obtaining the coating layer include heating at 120 ° C. for 5 to 20 minutes.

  The thickness of the coating film after curing is not particularly limited, but a thickness of 0.1 to 100 μm is preferable, and it is particularly preferable to form a coating film having a thickness of 1 to 10 μm.

<Polyurethane resin film>
The present invention further relates to a polyurethane resin film obtained from the emulsion composition.

  A film can be obtained using the emulsion composition according to the present invention. Specifically, the emulsion composition is applied to the releasable substrate, dried and cured by means such as heating, and then the cured product of the emulsion composition is peeled off from the releasable substrate. A film is obtained from the object.

  Examples of the heating method include a heating method using its own reaction heat and a heating method using both the reaction heat and positive heating of the mold. Examples of the positive heating of the mold include a method of heating the mold in a hot air oven, an electric furnace, or an infrared induction heating furnace.

  The heating temperature is preferably 10 to 200 ° C, more preferably 60 to 160 ° C. By heating at such a temperature, drying can be performed more efficiently.

  The heating time is preferably 0.0001 to 20 hours, more preferably 1 to 10 hours. By setting it as such a heating time, a film with higher hardness can be obtained. As a drying condition for obtaining a film from the emulsion composition, a method of heating at room temperature to 200 ° C. is used. For example, a method of heating at 120 ° C. for 3 to 10 seconds is employed.

<Laminated body>
The present invention relates to a laminate having a coating layer obtained by curing the coating agent composition and a layer comprising a substrate.
Hereinafter, although embodiment of a laminated body is described, about what is not described in particular, it may be the same as embodiment of the said coating agent composition.

    The coating agent composition containing the emulsion composition according to the present invention is applied onto, for example, a plastic substrate, an elastomer substrate, a civil engineering substrate, a metal substrate and a glass substrate, and dried and cured. Thereby, it can be set as the laminated body which has a coating layer and the layer which consists of a base material.

Examples of the plastic substrate include substrates made of polyester, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, ABS resin, acrylic, polycarbonate, polyethylene terephthalate, nylon, and the like.
Examples of the elastomer base material include base materials made of natural rubber, styrene / butadiene rubber, isoprene rubber, butadiene rubber, chloroprene rubber, ethylene / propylene rubber, ethylene / propylene / diene rubber, urethane rubber, silicone rubber, fluorine rubber, and the like. .
Examples of the base material for civil engineering and construction include base materials made of concrete, mortar, tile and the like.
Examples of the metal substrate include substrates made of aluminum, iron, stainless steel, and the like, and substrates obtained by surface-treating these substrates.

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

<Polyurethane resin emulsion>
The polyurethane resin emulsion was produced by Production Examples 1-7.

[Production Example 1]
In a reactor equipped with a stirrer and a heater, ETERNACOLL UH-300 (registered trademark; polycarbonate diol manufactured by Ube Industries, Ltd .; number average molecular weight 2,907; hydroxyl value 38.6 mgKOH / g; 1,6-hexanediol and carbonic acid Polycarbonate diol obtained by reacting with dimethyl (300 g), 2,2-dimethylolpropionic acid (DMPA) 20.1 g, hydrogenated MDI (H12MDI) 112 g in diethyltin dilaurate 0 in 151 g of methyl ethyl ketone In the presence of .35 g, the mixture was heated at 80 to 90 ° C. for 6 hours under a nitrogen atmosphere. The reaction mixture was cooled to 64 ° C., and 16.7 g of triethylamine was added and mixed thereto. 563 g of the reaction mixture was added into 666.36 g of water under vigorous stirring. Next, 25.2 g of adipic acid dihydrazide (ADH) was added as a chain extender, and then methyl ethyl ketone was removed by heating under reduced pressure to obtain a polyurethane resin emulsion. The urethane group content was 6.5% by mass, and the urea group content was 4.0% by mass.

[Production Example 2]
In a reactor equipped with a stirrer and a heater, ETERNACOLL (registered trademark) UH200 (manufactured by Ube Industries; number average molecular weight 2,000; hydroxyl value 56 mgKOH / g; 1,6-hexanediol and carbonate ester were reacted. The obtained polycarbonate diol, 301 g), 2,2-dimethylolpropionic acid (16.3 g), and isophorone diisocyanate (90.0 g) were mixed in dipropylene glycol dimethyl ether (DMM, 132 g) with dibutyltin dilaurate ( 0.3 g) and heated at 80-95 ° C. for 5 hours under nitrogen atmosphere. The reaction mixture was cooled to 80 ° C., and 506 g was added to water (816 g) under vigorous stirring, among which triethylamine (12.0 g) was added and mixed. Subsequently, 35% by weight of 2-methyl-1,5-pentanediamine aqueous solution (31.3 g) was added to obtain an aqueous polyurethane resin dispersion. The urethane group content was 7.7% by mass, and the urea group content was 2.8% by mass.

[Production Example 3]
In a reaction apparatus equipped with a stirrer and a heater, ETERNACOLL UH-200 (registered trademark; polycarbonate diol manufactured by Ube Industries, Ltd .; number average molecular weight 2,000; hydroxyl value 57.30 mgKOH / g; 1,6-hexanediol and carbonic acid Polycarbonate diol obtained by reacting with dimethyl (1300 g), 2,2-dimethylolpropionic acid (DMPA) 39.1 g, isophorone diisocyanate 377 g, dipropylene glycol dimethyl ether (DMM) 627 g in dibutyltin The mixture was heated at 80 to 90 ° C. for 2 hours under a nitrogen atmosphere in the presence of 1.36 g of dilaurate. Thereafter, 173 g of 12-hydroxystearic acid (HSA) was added and heated at 90 ° C. for 2 hours. The reaction mixture was cooled to 80 ° C., and 86.8 g of triethylamine was added and mixed thereto. 2518.69 g of the reaction mixture was added into 3590 g of water under vigorous stirring. Subsequently, 72.0 g of 35% by weight diethylenetriamine (DETA) aqueous solution was added as a chain extender to obtain a polyurethane resin emulsion. The urethane group content was 5.9% by mass, and the urea group content was 2.5% by mass.

[Production Example 4]
In a reactor equipped with a stirrer and a heater, ETERNACOLL UH-200 (registered trademark; polycarbonate diol manufactured by Ube Industries, Ltd .; number average molecular weight 2,000; hydroxyl value 56.1 mgKOH / g; 1,6-hexanediol and carbonic acid 37.6 g) of polycarbonate diol obtained by reacting with dimethyl, 1.21 g of 2,2-dimethylolpropionic acid (DMPA), and 12.77 g of hydrogenated MDI (H12MDI). In 22.61 g of N, N-dimethylpropanamide (M-100), the mixture was heated at 80 to 90 ° C. for 2 hours in the presence of 0.05 g of dibutyltin dilaurate in a nitrogen atmosphere. Thereafter, 5.02 g of 12-hydroxystearic acid (HSA) was added and heated at 90 ° C. for 3 hours. The reaction mixture was cooled to 80 ° C., and 2.73 g of triethylamine was added and mixed thereto. 64.3 g of the reaction mixture was added into 101 g of water under vigorous stirring. Next, 2.31 g of a 35% by weight diethylenetriamine (DETA) aqueous solution was added as a chain extender to obtain a polyurethane resin emulsion. The urethane group content was 7.4% by mass, and the urea group content was 2.0% by mass.

[Production Example 5]
In a reaction apparatus equipped with a stirrer and a heater, ETERNACOLL UH-200 (registered trademark; polycarbonate diol manufactured by Ube Industries, Ltd .; number average molecular weight 2,000; hydroxyl value 57.3 mg KOH / g; 1,6-hexanediol and carbonic acid Polycarbonate diol obtained by reacting with dimethyl (1300 g), 2,2-dimethylolpropionic acid (DMPA) 39.1 g, and isophorone diisocyanate 377 g were mixed with 3-methoxy-N, N-dimethylpropanamide ( M-100) was heated at 80 to 90 ° C. for 2 hours in a nitrogen atmosphere in the presence of 1.36 g of dibutyltin dilaurate. Thereafter, 174 g of 12-hydroxystearic acid (HSA) was added and heated at 90 ° C. for 2 hours. The reaction mixture was cooled to 80 ° C., and 86.8 g of triethylamine was added and mixed thereto. 2519 g of the reaction mixture was added into 3590 g of water under vigorous stirring. Subsequently, 72.0 g of 35% by weight diethylenetriamine (DETA) aqueous solution was added as a chain extender to obtain a polyurethane resin emulsion. The urethane group content was 5.9% by mass, and the urea group content was 2.5% by mass.

[Production Example 6]
In a reactor equipped with a stirrer and a heater, ETERRNACOLL (registered trademark) UH200 (manufactured by Ube Industries; number average molecular weight 2,000; hydroxyl value 57 mgKOH / g; 1,6-hexanediol and carbonate ester are reacted. The resulting polycarbonate diol, 42.4 g), 2,2-dimethylolpropionic acid (2.79 g) and hydrogenated MDI (16.52 g) in dipropylene glycol dimethyl ether (DMM, 20.57 g). In the presence of dibutyltin dilaurate (0.05 g), the mixture was heated at 80 to 90 ° C. for 3 hours in a nitrogen atmosphere. The reaction mixture was cooled to 80 ° C., and triethylamine (2.1 g) was added to and mixed with it, and 79.1 g of this mixture was withdrawn and added to water (114.8 g) with vigorous stirring. . Subsequently, 35% by weight of 2-methyl-1,5-pentanediamine aqueous solution (6.20 g) was added to obtain an aqueous polyurethane resin dispersion. The urethane group content was 7.7% by mass, and the urea group content was 3.6% by mass.

[Production Example 7]
In a reaction vessel in which a stirrer, a reflux condenser and a thermometer are inserted, ETERNCOLL (registered trademark) UH100 (manufactured by Ube Industries; number average molecular weight 916; hydroxyl value 123 mgKOH / g; 1,6-hexanediol and carbonate ester are reacted. Polycarbonate diol, 150 g), 2,2-dimethylolpropionic acid (22.0 g), and hydrogenated MDI (145 g) in dibutyltin dilaurate in N-ethylpyrrolidone (NEP, 135 g). (0.3 g) was heated at 80-90 ° C. for 6 hours under nitrogen atmosphere. The reaction mixture was cooled to 80 ° C., and triethylamine (14.9 g) was added and mixed thereto. 436 g was extracted from the reaction mixture and added into water (690 g) under vigorous stirring. Subsequently, 35% by weight of an aqueous 2-methyl-1,5-pentanediamine solution (62.6 g) was added to obtain an aqueous polyurethane resin dispersion. The urethane group content was 11.4% by mass, and the urea group content was 6.9% by mass.

<Acrylic resin emulsion>
The following components were used for the acrylic resin emulsion.
LX-2: manufactured by Parachem Japan; acrylic emulsion; solid content 60%; Tg: -30 ° C

[Examples and Comparative Examples]
(Method for producing emulsion composition)
The polyurethane resin emulsion and the acrylic resin emulsion were stirred and mixed so that the mass described in Table 1 below had a solid mass, thereby obtaining an emulsion composition. To the obtained emulsion composition (10 g), BYK-345 (0.01 g) manufactured by Big Chemie as an antifoaming agent and EMF Pink 2B-1 (1 g) manufactured by Toyocolor as a coloring agent were added. (1) was obtained.
(Total concentration of urethane groups and urea groups in polyurethane resin)
For the total concentration of urethane groups and urea groups in the polyurethane resin, the calculation method for the content of urethane groups in the polyurethane resin and the calculation method for the content of urea groups in the polyurethane resin described in the embodiment of the polyurethane resin. Each concentration was calculated and calculated.

(Laminate manufacturing method)
The emulsion composition (1) was applied to a polyester film (Toray Lumirror T-60 manufactured by Toray Industries Inc.) with a bar coater # 3 (thickness: 6 μm). Next, it was dried and cured at room temperature for 2 minutes to obtain a laminate having a coating layer (coating film) and a layer made of a polyester film.

(Evaluation of scratch resistance)
After rubbing the coating layer (coating film) of the obtained laminate with a nylon brush, the state of the coating layer (coating film) was observed. It evaluated as follows by the peeling amount of a coating layer (coating film).
(The amount of peeled film is large: bad) × <△ <○ <◎ (The amount of peeled film is small: good)

The abbreviations in Table 1 are as follows.
HSA: 12-hydroxystearic acid (manufactured by Ogura Synthesis)
DETA: Diethylenetriamine (Wako Pure Chemical Industries)
LX-2: Acrylic emulsion (manufactured by Parachem Japan)
DMM: Dipropylene glycol dimethyl ether (Dow Chemical)
M-100: 3-methoxy-N, N-dimethylpropanamide (manufactured by KJ Chemicals)
NEP: N-ethylpyrrolidone (BASF)

  Table 1 shows the following. From a comparison between Example 1 and Comparative Example 1, it can be seen that Example 1 containing a polyurethane resin is excellent in scratch resistance. From a comparison between Example 1 and Comparative Example 2, it can be seen that Example 1 containing an acrylic resin is excellent in scratch resistance.

  From the comparison between Example 1 and Comparative Examples 3 and 4, it can be seen that Example 1 in which the total concentration of urethane groups and urea groups in the polyurethane resin is 5% by mass or more and 11% by mass or less is excellent in scratch resistance. .

  From the comparison between Example 2 and Example 3, as the structure of the polyurethane resin, (e-1) a structure derived from 12-hydroxystearic acid (HSA) having one acidic group and one hydroxyl group in one molecule, (F-2) It can be seen that Example 2 having a structure derived from diethylenetriamine (DETA) having a total of three or more amino groups and / or imino groups in one molecule is superior in scratch resistance.

  A comparison between Example 3 and Examples 4 and 5 shows that Examples 4 and 5 having 3-methoxy-N, N-dimethylpropanamide as a film-forming aid have better scratch resistance. .

  From comparison between Examples 3, 6 and 7, and Example 8, Examples 3, 6 and 7 in which the ratio of the polyurethane resin is 35 to 90% by mass with respect to the total mass of the polyurethane resin and the acrylic resin are as follows. It can be seen that higher scratch resistance is exhibited.

  The present invention relates to a novel emulsion composition. The emulsion composition is useful as a main component of various coating agents.

Claims (10)

An emulsion composition comprising a polyurethane resin and an acrylic resin,
The polyurethane resin is
(A) a structure derived from a polycarbonate polyol, and (b) a structure derived from an acidic group-containing polyol,
(C) a polyisocyanate-derived structure;
Have
The emulsion composition, wherein the total concentration of urethane groups and urea groups in the polyurethane resin is 5% by mass or more and 11% by mass or less.   The emulsion composition according to claim 1, further comprising a film-forming aid.   The emulsion composition according to claim 2, wherein the film-forming aid is 3-methoxy-N, N-dimethylpropanamide.   The polyurethane resin is (e-1) a structure derived from a terminal terminator having one acidic group and one hydroxyl group in one molecule, and (f-2) an amino group and / or an imino group in one molecule in total. The emulsion composition according to any one of claims 1 to 3, which has a structure derived from a chain extender having three or more.   The emulsion composition as described in any one of Claims 1-4 which contains a polyurethane resin in the ratio of 35-90 mass% when the sum total of a polyurethane resin and an acrylic resin is 100 mass%.   The coating composition containing the emulsion composition as described in any one of Claims 1-5.   An ink composition comprising the emulsion composition according to claim 1.   The coating agent composition containing the emulsion composition as described in any one of Claims 1-5.   A laminate comprising a coating layer obtained by curing the coating agent composition according to claim 8 and a layer comprising a plastic substrate. The laminate according to claim 9, wherein the plastic substrate is a polyester resin.