JP2019044073A - Emulsion composition - Google Patents

Abstract

To provide an emulsion composition giving a coating film excellent in adhesion to a plastic film.SOLUTION: The present invention relates to the emulsion composition for plastic film coating, which contains a polyurethane resin emulsion and an acrylic resin emulsion. 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 compound. The total concentration of urethane groups and urea groups in the polyurethane resin is 5 mass% or more and less than 15 mass%.SELECTED DRAWING: None

Description

  The present invention relates to an emulsion composition for plastic film coating comprising a polyurethane resin emulsion and an acrylic resin emulsion.

  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).

  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 3).

  A water-based 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 4).

  In addition, a laminated polyester film having a coating layer containing a urethane resin having a carbonate structure has been reported. (Patent Document 5).

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

  However, the emulsion composition comprising the polyurethane resin emulsions and the acrylic urethane resin emulsions described in Patent Documents 3, 4 and 5 did not have sufficient adhesion to the plastic film. In particular, the adhesion to the polyester film was insufficient.

  The subject of this invention is providing the emulsion composition which provides the coating film excellent in the adhesiveness to a plastic film.

The present invention relates to the following [1] to [8].
[1] A plastic film coating emulsion composition comprising a polyurethane resin emulsion and an acrylic resin emulsion,
The polyurethane resin is
(A) a structure derived from a polycarbonate polyol, (b) a structure derived from an acidic group-containing polyol, (c) a structure derived from a polyisocyanate compound,
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 less than 15% by mass.
[2] The emulsion composition according to [1], wherein the total concentration of urethane groups and urea groups in the polyurethane resin is 10% by mass or more and less than 15% by mass.
[3] The emulsion composition according to [1] or [2], wherein the (c) polyisocyanate compound contains hydrogenated MDI and / or isophorone diisocyanate.
[4] When the total solid content of the polyurethane resin and the acrylic resin is 100% by mass, the content of the solid content of the polyurethane resin is 60 to 90% by mass of [1] to [3] The emulsion composition as described in any one of Claims.
[5] A paint comprising the emulsion composition according to any one of [1] to [4].
[6] A cured product obtained by curing the emulsion composition according to any one of [1] to [4].
[7] A laminate in which a plastic film is coated with the emulsion composition according to any one of [1] to [4].
[8] The laminate according to [7], wherein the plastic is a polyester resin.

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

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

  The emulsion composition includes a polyurethane resin emulsion and an acrylic resin emulsion, and when the emulsion composition is used as a laminate to a plastic film, a coating film formed from the plastic film (particularly a polyester film) and the emulsion composition. High adhesion is expressed. In addition, the coating film obtained from the emulsion composition is provided with a coating film having the same or superior chemical resistance as compared with the coating film obtained from the conventional polyurethane resin emulsion while maintaining adhesion to the plastic film. It is an emulsion composition.

<< Polyurethane resin emulsion >>
The polyurethane resin emulsion contains a polyurethane resin and water. 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 compound. 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. In addition, when a polyurethane resin has the structure derived from (b) acidic group containing polyol, the part of (b ') neutralizer may exist as a counter ion further.

<<<<< (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.

  Each of the polyol monomers may be used alone or in combination of two or more.

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.
Carbonate ester may be individual and may use multiple types together.

  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) The number average molecular weight of the polycarbonate polyol is not particularly limited, but is preferably 400 to 8,000, and particularly preferably 400 to 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 polyurethane resin can be efficiently produced.

  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 that does not have an alicyclic structure in the main chain from the viewpoint of increasing adhesion to a plastic film, and from the viewpoint of chemical resistance, 1,6-hexanediol and a carbonate ester are reacted. More preferred is a polycarbonate diol obtained.
(A) Polycarbonate polyol may be used independently and may use multiple types together.

<<<<< (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, the aqueous resin dispersion is used even when the polyurethane resin emulsion does not contain a protective colloid, an emulsifier and / or a surfactant. The dispersion stability of the composition in water is improved.

  Here, examples of the acidic group include a carboxy group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group. (B) As an acidic group containing polyol, the compound which has two hydroxyl groups (however, a phenolic hydroxyl group is not included) and one carboxy group in 1 molecule 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) The acidic group-containing polyol may be used alone or in combination of two or more.

<<<<< (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 be used independently and may use multiple types together.

<<<<< (c) Polyisocyanate Compound >>>>
(C) It does not specifically limit as a polyisocyanate compound, 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.

  (C) Polyisocyanate compounds having 3 or more isocyanate groups such as triphenylmethane triisocyanate as long as the number of isocyanate groups per molecule of the polyisocyanate compound is usually 2 but the polyurethane resin does not gel. Can be used.

  From the viewpoint of suppressing yellowing of the cured coating film of the emulsion composition, (c) the polyisocyanate compound is preferably an aliphatic polyisocyanate or an alicyclic polyisocyanate compound, and from the viewpoint that the reaction can be easily controlled, isophorone. More preferred is diisocyanate and / or 4,4′-dicyclohexylmethane diisocyanate. From the viewpoint of increasing chemical resistance, 4,4'-dicyclohexylmethane diisocyanate is preferable. Isophorone diisocyanate is preferable from the viewpoint of further improving the adhesion to a plastic film.

  (C) A polyisocyanate compound may be used independently and may use multiple types 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 Polyester polyol is not particularly limited, but for example, polyethylene adipate diol, polybutylene adipate diol, polyethylene butylene adipate diol, polyhexamethylene isophthalate adipate diol, polyethylene succinate diol, polybutylene succinate diol, polyethylene Polyesters such as sebacate diol, polybutylene sebacate diol, poly-ε-caprolactone diol, poly (3-methyl-1,5-pentylene adipate) diol, polycondensate of 1,6-hexanediol and dimer acid Diols are mentioned.

・ Polyether polyol Polyether polyol includes polyethylene glycol, polypyrylene glycol, random copolymer or block copolymer of ethylene oxide and propylene oxide, or random copolymer or block copolymer of ethylene oxide and butylene oxide. And polytetramethylene glycol. 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) Another polyol may be individual and may use multiple types together.

<<<<< (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) Examples of the terminal terminator include compounds other than a compound having one acidic group and one hydroxyl group in one molecule and having one group that reacts with an isocyanato group. Specifically, glycolic acid (2-hydroxyacetic acid), hydroxypivalic acid (HPA), lactic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 10-hydroxydecanoic acid, hydroxypivalic acid (2,2-dimethyl) -3-hydroxypropionic acid), 12-hydroxydodecanoic acid, 16-hydroxyhexadecanoic acid, lactic acid, trichlorolactic acid, salicylic acid, hydroxybenzoic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxypropionic acid, 2-hydroxyoctane Examples include acid, 3-hydroxyundecanoic acid, 12-hydroxystearic acid (HSA), and 12-hydroxyoleic acid. 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) A terminal terminator may be used independently and may use multiple types together.

<<<<< (f) Chain Extender >>>>
(F) Examples of chain extenders include compounds having two or more groups that react with isocyanato groups. For example, polyamine compounds and polyol compounds having a total of two or more amino groups and / or imino groups in one molecule. As well as water.

  As a polyamine compound having two or more amino groups and / or imino groups in total in one molecule, a polyamine compound having two amino groups and / or imino groups in total in one molecule, and amino in one molecule And a polyamine compound having a total of 3 or more groups and / or imino groups.

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

  Examples of polyamine compounds having a total of 3 or more amino groups and / or imino groups in one molecule are not particularly limited. For example, diethylenetriamine (DETA), bis (2-aminopropyl) amine, bis (3- Triamine compounds such as aminopropyl) amine; triethylenetetramine, tripripylenetetramine, N- (benzyl) triethylenetetramine, N, N ′ ″-(dibenzyl) triethylenetetramine, N- (benzyl) -N ″ Tetramine compounds such as'-(2-ethylhexyl) triethylenetetramine; pentamine compounds such as tetraethylenepentamine and tetrapropylenepentamine; hexamine compounds such as pentaethylenehexamine and pentapropylenehexamine; polyethyleneimine and polypropyleneimine Riamin, and the like.

  As the polyol compound, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol and the like are preferable.

(F) The chain extender is preferably a polyamine compound having two or more amino groups and / or imino groups in total in one molecule.
(F) A chain extender may be used independently and may use multiple types together.

<<< Properties of polyurethane resin >>>
The total concentration of urethane groups and urea groups in the polyurethane resin is 5% by mass or more and less than 15% by mass. By setting it as this range, it is excellent in the adhesiveness to a plastic film. The total concentration of urethane groups and urea groups in the polyurethane resin is preferably 10% by mass or more and 15% by mass from the viewpoint of further improving the adhesion to the plastic film and improving the chemical resistance and the storage stability of the emulsion composition. More preferably, it is 10 mass% or more and 14 mass% or less, Most preferably, it is 11 mass% or more and 14 mass% or less. The polyurethane resin has a structure derived from at least (a) to (c). In the emulsion composition, the polyurethane resin exists in the form of an emulsion dispersed in an aqueous medium. It has both a bond and a urea bond.

  The concentration of the urethane group in the polyurethane resin is arbitrary as long as the total concentration of the urethane group and the urea group in the polyurethane resin described above is satisfied, but is preferably 4.5% by mass or more and less than 14.5% by mass. Especially preferably, it is 5 mass% or more and less than 10 mass%. The concentration of urea groups in the polyurethane resin is a concentration obtained by subtracting the concentration of urethane groups in the polyurethane resin from the total concentration of urethane groups and urea groups in the polyurethane resin.

The density | concentration 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 less than the number of moles of isocyanato groups of the polyisocyanate compound, (concentration (mass%) of urethane groups in the polyurethane resin) = {((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 isocyanate groups in the polyisocyanate compound is larger than the number of moles, the concentration of urethane groups in the polyurethane resin (mass%) = {(c) the number of moles of isocyanate groups in the polyisocyanate compound) × 59.02. } / (Polyurethane resin solid content (g)).

The concentration of urea groups in the polyurethane resin can be determined by the following equation.
(3) When the number of moles of isocyanato groups in the urethane 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 compound) × 58.04} / (polyurethane resin solid content (g)).

  (4) When the number of moles of isocyanato groups in the urethane prepolymer is greater 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 emulsion (excluding the neutralizing agent for neutralizing acidic groups) 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. There exists a tendency for the adhesiveness to a plastic film to increase more by setting it as 50 mass% or less. 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. The calculated value is 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) structure derived from polycarbonate polyol in polyurethane resin, (b) structure derived from acidic group-containing polyol, (c) structure derived from polyisocyanate compound, (d) structure derived from other polyol, (e) derived from terminal stopper The structure of (f), the structure derived from the chain extender, and the content of the (b ′) neutralizer are not particularly limited. For example, the quantity used as the usage-amount of each component in the manufacturing method of the polyurethane resin dispersion 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 exchange water is preferable. The aqueous medium may contain an organic solvent. Examples of the organic solvent 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 and the like. Can be mentioned.

<<< 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) a polycarbonate polyol, (b) an acidic group-containing polyol compound, (c) a polyisocyanate compound, and optionally (d) another polyol and (e) a terminal terminator are reacted (A) Obtaining a polyurethane prepolymer (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 compound, (c) polyisocyanate compound, and ( d) 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)”). The amount is preferably 20 to 90 parts by mass, particularly preferably 50 to 80 parts by mass.

  In the step (α), the amount of the (c) polyisocyanate compound used is not particularly limited, but (a) the polycarbonate polyol, (b) the acidic group-containing polyol, and (d) the number of moles of all hydroxyl groups of the other polyol, (C) An amount in which the ratio of the number of isocyanato groups in the polyisocyanate compound is 1.05 to 2.5 is preferable, and an amount in which 1.1 to 2.0 is particularly preferable. 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 step (α), the amount of (e) terminal terminator used is determined from (c) the number of moles of isocyanate groups in the polyisocyanate compound, (a) polycarbonateol, (b) acidic group-containing polyol, and (d) other polyols. The number of moles of all hydroxyl groups can be appropriately set within a range not exceeding the number of moles.

  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 >>
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 is a polyurethane resin emulsion as described above. 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: Pegar 862 (Tg: -10 ° C), Pegar 751 (Tg: 25 ° C), LC6154 (Tg: 64 ° C), Showa Denko: 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: 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), manufactured by Parachem Japan: Parabond LX- 5 (Tg: -40 ° C), G-60 (Tg: -30 ° C), LX-2 (Tg: -30 ° C), Toagosei Co., Ltd .: NW-400 (Tg: -4) ℃)

  The Tg (glass transition temperature) of the acrylic resin is preferably -80 ° C to 60 ° C, more preferably -55 ° C to 50 ° C, and particularly preferably -30 ° C to 20 ° C. When the Tg of the acrylic resin is 60 ° C. or lower, the adhesion to the plastic film is further increased. When the Tg of the acrylic resin is −80 ° C. or higher, chemical resistance is excellent.

  An acrylic resin emulsion may be used independently and may use multiple types together.

<< Emulsion composition >>
In the solid content of the emulsion composition, when the total of the polyurethane resin and the acrylic resin is 100% by mass, the solid content of the polyurethane resin is preferably 20 to 95% by mass, more preferably 50%. It is -92 mass%, More preferably, it is 60-90 mass%, Most preferably, it is 75-85 mass%. If content of a polyurethane resin emulsion is 20 mass% or more, chemical resistance will increase. If content of a polyurethane resin emulsion is 95 mass% or less, the adhesiveness to a plastic film will increase more.

<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 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.

In addition, the emulsion composition has a thickener, a photosensitizer, a curing catalyst, an ultraviolet absorber, a light stabilizer, an antifoaming agent, a plasticizer, and a surface conditioner depending on the required function, characteristics, application, etc. Additives such as anti-settling agents can also be added.
In addition, the said additive may be used individually by 1 type, and may use 2 or more 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.

<Plastic film>
The emulsion composition is used to coat a plastic film. The material of the plastic in the plastic film is not particularly limited. From the viewpoint of further improving the adhesion, the plastic is preferably a polyester resin. In addition, the plastic may be subjected to pretreatment for improving adhesion.

  Although the thickness of a plastic film is not specifically limited, 1-5,000 micrometers is preferable and 10-500 micrometers is especially preferable.

<Usage method of emulsion composition>
The emulsion composition for coating a plastic film can be used for coating a plastic film alone or in the form of a paint containing the emulsion composition described later.

<< Paint >>
The paint contains an emulsion composition for plastic film coating.

  In addition to the emulsion composition, other resins can be added to the paint. 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 be used alone or in combination of two or more. 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 be individual and 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 be individual and may use multiple types together.

  The paint can further include a curing agent. By including a curing agent, it is possible to improve the water resistance of a coating film or multilayer coating film obtained by using a paint, a coating film or a printed material.

As the curing agent, for example, amino resins, polyisocyanates, blocked polyisocyanates, melamine resins, carbodiimides, polyols and the like can be used.
In addition, these hardening | curing agents may be individual and may use multiple types 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 methyl ethyl ketoxime; 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.

  The paint can further contain a color pigment, an extender pigment, a glitter pigment, and the like.

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 be individual and 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 be individual and 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 paint contains normal additives such as thickeners, curing catalysts, UV absorbers, light stabilizers, antifoaming agents, plasticizers, surface conditioners, anti-settling agents, depending on the function, specifics, and applications. be able to.
In addition, these may be used independently, may use multiple types together, and may use a commercial item as it is.

  The production method of the paint is not particularly limited, but a known production method can be adopted. Preferably, the paint is prepared by mixing the polyurethane resin emulsion and the various additives described above, and further adding an aqueous medium. It is manufactured by adjusting the viscosity according to the application method.

  The material to be coated of the paint is plastic, and polyester resin is particularly preferable from the viewpoint of better adhesion.

  Examples of the paint coating method include bell coating, spray coating, roll coating, shower coating, and immersion coating.

  The coating film can be dried and cured by means such as heating. Examples of the heating method include a heating method using its own reaction heat and a heating method in which the reaction heat and the positive heating of the mold are used in combination. Examples of 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 40 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 film with higher hardness can be obtained. As drying conditions for obtaining a coating film from the emulsion composition, for example, a method of heating at 120 ° C. for 3 to 10 seconds is employed.

  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.

<Hardened product>
The cured product is formed by curing the emulsion composition. Although the shape of hardened | cured material is not specifically limited, A film (film | membrane) is preferable. Examples of the method for curing the emulsion composition include those described above for the paint. The thickness of the cured product includes the thickness of the coating film after curing described above in the paint.

<Laminate>
The laminate is a laminate obtained by coating a plastic film with an emulsion composition. That is, the laminate has a cured film of the emulsion composition on a plastic film. From the viewpoint of further improving the adhesion, the plastic is preferably a polyester resin. The plastic may be subjected to a pretreatment for improving adhesion. As for the thickness of the coating layer of an emulsion composition, the thickness of the coating film after hardening mentioned above in a coating material is mentioned.

  Although the manufacturing method of a laminated body is not specifically limited, The method of applying an emulsion composition to a plastic film and hardening is mentioned. Examples of the curing method include those described above for the paint.

  The use of the laminate is not particularly limited. For example, a liquid crystal panel, a protective film for interior and exterior of an automobile, an electronic device, a decorative film for an automobile, a backlight unit of a liquid crystal display, a prism layer, a microlens layer, and a hard coat layer. And a laminated film having a curable resin layer such as an anti-sticking layer and a light diffusion layer.

  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 1-5.

[Production Example 1]
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 Polycarbonate diol obtained by reacting with dimethyl, 37.6 g), 1.21 g of 2,2-dimethylolpropionic acid (DMPA), and 12.77 g of hydrogenated MDI (H12MDI), and N-methylpyrrolidone In 22.61 g, the mixture was heated at 80 to 90 ° C. for 2 hours in the presence of 0.05 g of dibutyltin dilaurate under 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 concentration was 7.4% by mass, and the urea group concentration was 2.0% 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 with dibutyltin dilaurate (0. 0. g) in N-ethylpyrrolidone (132 g). 3g) Heated at 80-95 ° C. for 5 hours under nitrogen atmosphere in the presence. 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 concentration was 7.7% by mass, and the urea group concentration was 2.8% by mass.

[Production Example 3]
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 obtained polycarbonate diol, 42.4 g), 2,2-dimethylolpropionic acid (2.79 g), and hydrogenated MDI (16.52 g) were mixed with dibutyl in N-methylpyrrolidone (20.57 g). The mixture was heated at 80 to 90 ° C. for 3 hours in the presence of tin dilaurate (0.05 g) under 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 concentration was 7.7% by mass, and the urea group concentration was 3.6% by mass.

[Production Example 4]
In a reaction vessel into which a stirrer, a reflux condenser, and a thermometer were inserted, ETERNCOLLUM UM90 (1/3) (manufactured by Ube Industries; number average molecular weight 916; hydroxyl value 123 mgKOH / g; polyol component 1,4-cyclohexanedimethanol: 1 , 6-hexanediol = 1: 3 molar ratio of a polycarbonate diol obtained by reacting with a carbonate ester, 150 g), 2,2-dimethylolpropionic acid (22.0 g), and hydrogenation MDI (145 g) was heated in N-methylpyrrolidone (135 g) in the presence of dibutyltin dilaurate (0.3 g) at 80-90 ° C. for 6 hours in a 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 concentration was 11.4% by mass, and the urea group concentration was 6.9% by mass.

[Production Example 5]
In a reaction vessel in which a stirrer, a reflux condenser and a thermometer were inserted, ETERNCOLLUM UM90 (3/1) (manufactured by Ube Industries; number average molecular weight 916; hydroxyl value 123 mgKOH / g; polyol component 1,4-cyclohexanedimethanol: 1 , 6-hexanediol = 3: 1 polycarbonate diol obtained by reacting a polyol mixture with a carbonate ester (1,500 g), 2,2-dimethylolpropionic acid (220 g), hydrogenated MDI ( 1450 g) in N-methylpyrrolidone (1350 g) in the presence of dibutyltin dilaurate (2.6 g) at 80-90 ° C. for 6 hours in a nitrogen atmosphere. The reaction mixture was cooled to 80 ° C., and triethylamine (149 g) was added and mixed thereto. 4360 g was extracted from the reaction mixture and added to water (6900 g) under vigorous stirring. Subsequently, 35% by weight of 2-methyl-1,5-pentanediamine aqueous solution (626 g) was added to obtain an aqueous polyurethane resin dispersion. The urethane group concentration was 11.4% by mass, and the urea group concentration was 6.9% by mass.

<Acrylic resin emulsion>
The following components were used for the acrylic resin emulsion.
FX2555: manufactured by Nippon Carbide Industries; acrylic emulsion; solid content concentration 60%; Tg: -17 ° C
FX2033: manufactured by Nippon Carbide Industries; acrylic emulsion; solid content concentration 60%; Tg: 8 ° C
FX2018: manufactured by Nippon Carbide Industries; acrylic emulsion; solid content concentration 45%; Tg: 27 ° C
FX672K: manufactured by Nippon Carbide Industries; acrylic emulsion; solid content concentration 50%; Tg: 53 ° C.

[Examples and Comparative Examples]
(Preparation of emulsion composition)
The polyurethane resin emulsion and the acrylic resin emulsion were stirred and mixed so as to have the ratios shown in Tables 1 to 3 below in terms of the weight of the solid content to obtain an emulsion composition.
(Preparation of coating solution)
Ethanol was added to the emulsion composition so that the solid content of the obtained emulsion composition was 21% by mass to obtain a coating solution.

(Manufacture of laminates)
About Examples 1-12 and Comparative Examples 1-4, a coating liquid is apply | coated to a polyester film (adhesive PET: Toray Lumirror T11) with bar coater # 3, it is made to dry at 180 degreeC for 10 minutes, and polyester is used. A film laminate was obtained. For Examples 13 to 20, an untreated polyester film (untreated PET: Lumirror S10 manufactured by Toray Industries, Inc.), which is a condition that makes it more difficult to adhere, is 140 ° C., 10 The polyester film laminate was obtained by drying in minutes.

(Evaluation of adhesion)
The polyester film laminate was evaluated by a cross-cut peeling method. That is, 100 squares of 1 mm ² were prepared on a test piece with a cutter, and peelability was examined with a cellophane tape. The test result shows “(number of sheets not peeled) / (total number of hooks) (number of times the test was repeated)”, and “100/100 (4)” showed no peeling at all in the four repeated tests. It shows that. Further, “82/100 (4)” indicates that no peeling was observed in the three repeated tests, and 82 sheets were not peeled in the four repeated tests.

(Evaluation of stability)
The coating solution was stored at room temperature (25 ° C.) for 3 days and the state was observed. ○: No change. X: Gelation and thickening were observed, making application difficult.

(chemical resistance)
The following chemicals were placed on the polyester film laminate, and the state of the laminate after 24 hours was observed. Water resistance: pure water, ethanol resistance: 80% by weight ethanol aqueous solution, acid resistance: 5% by weight sulfuric acid aqueous solution, alkali resistance: 5% by weight sodium hydroxide aqueous solution A: No change.
○: Scratches, tears, and whitening are observed in a very small part.
Δ: Some scratches, tears, and whitening are observed.
X: Scratches, tears, and whitening are observed on the entire surface.

  The results are shown in Tables 1 to 3.

Table 1 shows the following.
It turned out that Examples 1-8 containing the polyurethane resin and acrylic resin whose total density | concentration of a urethane group and a urea group are 5 mass% or more and less than 15 mass% have high adhesiveness. When Examples 1 to 8 were compared, Examples 2 to 8 in which the total concentration of urethane groups and urea groups was 10% by mass or more and less than 15% by mass showed high storage stability.
On the other hand, Comparative Examples 1 and 2 had poor adhesion because the total concentration of urethane groups and urea groups in the polyurethane resin emulsion was 15% by mass or more.

Table 2 shows the following.
Comparing Examples 9 to 12, it was found that Examples 10 and 12 using hydrogenated MDI as isocyanate showed high chemical resistance. Moreover, Example 9 and 10 whose polyurethane resin is 60-90 mass% can be compatible with adhesiveness and high chemical resistance with respect to the solid content of a polyurethane resin, and the total solid content of an acrylic resin 100 mass%. I understood.
On the other hand, Comparative Examples 3 and 4 had poor adhesion because the emulsion composition did not contain an acrylic resin emulsion.

  From Table 3, in Examples 13 to 20, even though the plastic film was an untreated polyester film, a coating film having excellent adhesion was obtained.

Claims (8)

An emulsion composition for plastic film coating comprising a polyurethane resin emulsion and an acrylic resin emulsion,
The polyurethane resin is
(A) a structure derived from a polycarbonate polyol, (b) a structure derived from an acidic group-containing polyol, (c) a structure derived from a polyisocyanate compound,
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 less than 15% by mass.   The emulsion composition according to claim 1, wherein the total concentration of urethane groups and urea groups in the polyurethane resin is 10% by mass or more and less than 15% by mass.   (C) The emulsion composition of Claim 1 or 2 in which a polyisocyanate compound contains hydrogenated MDI and / or isophorone diisocyanate.   The solid content of the polyurethane resin is 60 to 90% by mass when the total solid content of the polyurethane resin and the acrylic resin is 100% by mass. An emulsion composition as described.   The coating material containing the emulsion composition as described in any one of Claims 1-4.   Hardened | cured material formed by hardening | curing the emulsion composition as described in any one of Claims 1-4.   The laminated body which coat | covered the emulsion composition as described in any one of Claims 1-4 on the plastic film.   The laminate according to claim 7, wherein the plastic is a polyester resin.