WO2019131414A1

WO2019131414A1 - Aqueous resin composition and laminated body and article employing same

Info

Publication number: WO2019131414A1
Application number: PCT/JP2018/046942
Authority: WO
Inventors: 達史小柳; 武志岩尾
Original assignee: Dic株式会社
Priority date: 2017-12-26
Filing date: 2018-12-20
Publication date: 2019-07-04
Also published as: TW201930498A; JPWO2019131414A1; KR20200085905A; CN111511836A

Abstract

The present invention addresses the problem of providing an aqueous resin composition that is capable of forming a coating layer having good substrate adhesion and ink adhesion with respect to two types of substrates, namely, a polyester resin and a polyolefin resin. The present invention employs an aqueous resin composition containing: a urethane resin (A) having a carboxy group; a basic compound (B); a cross-linking agent (C); and an aqueous medium (D), and is characterized in that the urethane resin (A) is a reaction product of raw materials containing a polyol (a1) and a polyisocyanate (a2), the polyol (a1) contains at least one type of substance selected from a group consisting of a polyol (a1-1) having a carboxy group, a polyester polyol (a1-2), and a polyether polyol (a1-3), and the cross-linking agent (C) contains a carbodiimide compound.

Description

Aqueous resin composition, laminate using the same, and article

The present invention relates to an aqueous resin composition, a laminate using the same, and an article.

A biaxially stretched thermoplastic film (biaxially stretched film) is excellent in electrical and physical properties such as electrical insulation, transparency, dimensional stability and toughness, so it is an insulating material, drawing, photographic film, It is used in a wide range of fields such as magnetic tapes, metallized films, and various packaging materials. However, as a result of the molecular chains of the resin constituting the film being highly oriented by biaxial stretching, there is a problem that the adhesiveness between the biaxially stretched film surface and the printing ink, magnetic paint, vapor deposited metal, adhesive agent, etc. is inferior. is there.

In order to cope with these problems, an aqueous resin composition called a primer coating agent or an anchor coating agent is applied to the surface of the biaxially stretched film, and a coating layer (primer layer, anchor) different from the substrate on the biaxial stretched film in advance. There has been proposed a method of forming a layer or undercoat layer to improve the affinity to printing ink, magnetic paint, vapor deposited metal, adhesive and the like. In Patent Document 1, a coating applied to a polyester film substrate is prepared using a melamine cross-linking component and a polyurethane component that can be derived from at least one diisocyanate and at least one high molecular weight polyol, as a care coating composition. The formation is described (see, for example, Patent Document 1).

JP-A-2017-523254

However, according to the study of the present inventors, in the case of using a polyolefin resin as the base, the primer coat agent conventionally known adheres to both the coating layer (primer layer) and both the base and the printing ink. It became clear that the sex decreased.
An object of the present invention is to provide an aqueous resin composition capable of forming a coating layer having good substrate adhesion and ink adhesion to both polyester resin and polyolefin resin substrates.

The present invention is a resin composition comprising a urethane resin (A) having a carboxy group, a basic compound (B), a crosslinking agent (C) and an aqueous medium (D), wherein the urethane resin (A) is a polyol (A1) and a reactant of a raw material containing polyisocyanate (a2), wherein the polyol (a1) is a polyol (a1-1) having a carboxy group, a polyester polyol (a1-2), and a polyether polyol (a1) An aqueous resin composition is used which contains at least one selected from the group consisting of -3), and the crosslinking agent (C) contains a carbodiimide compound.

The aqueous resin composition of the present invention can form a coating layer having good substrate adhesion and ink adhesion to both polyester resin and polyolefin resin substrates.

The resin composition of the present invention comprises a urethane resin (A) having a carboxy group, a basic compound (B), a crosslinking agent (C) and an aqueous medium (D).

The urethane resin (A) having a carboxy group is a reactant of a raw material containing a polyol (a1) and a polyisocyanate (a2).

The polyol (a1) contains a polyol (a1-1) having a carboxy group, and at least one selected from the group consisting of a polyester polyol (a1-2) and a polyether polyol (a1-3).

The polyol (a1-1) having a carboxy group is a compound having a carboxy group and two or more hydroxy groups, and has, for example, 3 to 10 carbon atoms (preferably 3 to 8 and more preferably 3 or more). Compounds obtained by substituting two or more of hydrogen atoms (provided that they are bonded to carbon atoms) contained in the aliphatic carboxylic acid of 6 or less with a hydroxy group; reacting the compound with a polyvalent carboxylic acid The polyester polyol etc. which are obtained are mentioned. As a compound in which a hydrogen atom contained in the aliphatic carboxylic acid is substituted with a hydroxy group, specifically, one or two or more can be used. For example, 2,2′-dimethylol propionic acid, 2 2,2'-dimethylolbutanoic acid, 2, '-dimethylolpentanoic acid, 2,2'-dimethylolhexanoic acid, 2,2'-dimethylolheptanoic acid, 2,2'-dimethyloloctanoic acid etc. Be

The molecular weight of the carboxyl group-containing polyol (a1-1) is preferably 80 or more, more preferably 100 or more, still more preferably 120 or more, preferably 3000 or less, more preferably 2000 or less, still more preferably 1000 or less. It is.

The content of the carboxyl group-containing polyol (a1-1) is preferably 0.5 parts by mass with respect to 100 parts by mass in total of the polyester polyol (a1-2) and the polyether polyol (a1-3) described later. The content is more preferably 1 part by mass or more, further preferably 3 parts by mass or more, preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and still more preferably 8 parts by mass or less.

The polyester polyol (a1-2) is a polyester having two or more hydroxy groups, and, for example, a reaction product of a low molecular weight polyol (for example, a polyol having a molecular weight of 50 or more and 300 or less) and a polycarboxylic acid; Ring-opened polymers of cyclic ester compounds; copolymers of the low molecular weight polyols, polycarboxylic acids, cyclic ester compounds and the like, and the like.

As the low molecular weight polyol, one or more kinds can be used, and examples thereof include ethylene glycol, diethylene glycol, 1,2-propylene glycol, dipropylene glycol, neopentyl glycol, 2-butyl-2-ethyl-1 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanediol, 1,6-hexanediol, carbon of cyclohexanedimethanol Examples thereof include polyols having 2 to 10 atoms (preferably 2 to 8 carbon atoms, more preferably 2 to 5 carbon atoms).
The low molecular weight polyol is preferably an alkane diol.

Aliphatic polycarboxylic acids having 4 to 14 (preferably 6 to 10) carbon atoms such as succinic acid, adipic acid, sebacic acid and dodecanedicarboxylic acid as the polycarboxylic acids; terephthalic acid, isophthalic acid, phthalic acid, And aromatic polycarboxylic acids such as naphthalene dicarboxylic acid; and anhydrides or ester-forming derivatives of the above aliphatic polycarboxylic acids and aromatic polycarboxylic acids, and the like, including aromatic polycarboxylic acids and aliphatic polycarboxylic acids Is preferred.

The content rate of the aromatic polycarboxylic acid is preferably 30% by mass or more, more preferably 50% by mass or more, preferably 80% by mass or less, more preferably 70% by mass or less in the polycarboxylic acid.

The polycarboxylic acid is preferably a dicarboxylic acid, an anhydride of a dicarboxylic acid or an ester-forming derivative.

As the cyclic ester compound, one or more species can be used, and examples include butyrolactone, ε-caprolactone, σ-valerolactone, β-methyl-σ-valerolactone and the like.

The number average molecular weight of the polyester polyol (a1-2) is preferably more than 300, more preferably 400 or more, still more preferably 500 or more, preferably 5000 or less, more preferably 4000 or less, still more preferably 3000 or less. is there.
In the present invention, the number average molecular weight and the weight average molecular weight represent polystyrene equivalent values obtained by measurement by gel permeation chromatography.

The acid value of the polyester polyol (a1-2) is preferably 0.1 mg KOH / g or more, more preferably 0.2 mg KOH / g or more, still more preferably 0.3 mg KOH / g or more, and preferably 10 mg KOH / g or less More preferably, it is 5 mg KOH / g or less, still more preferably 2 mg KOH / g or less.
In the present invention, the acid value is a value measured as the amount (unit: mg) of potassium hydroxide necessary to neutralize 1 g of a polymer (nonvolatile matter only), and titration with potassium hydroxide aqueous solution It can be determined by

The hydroxyl value of the polyester polyol (a1-2) is preferably 5 mg KOH / g or more, more preferably 10 mg KOH / g or more, still more preferably 20 mg KOH / g or more, preferably 500 mg KOH / g or less, more preferably 400 mg KOH / g. It is at most g, more preferably at most 300 mg KOH / g.
In the present invention, the hydroxyl value can be measured in accordance with JIS K 0070.

The aromatic ring concentration of the polyester polyol (a1-2) is preferably 0.1 mol / kg or more, more preferably 0.3 mol / kg or more, still more preferably 0.5 mol / kg or more, and preferably 25 mol / kg. The following amount is more preferably 15 mol / kg or less, still more preferably 7 mol / kg or less.

The content of the polyester polyol (a1-2) is preferably 10% by mass or more, more preferably 20% by mass or more, and still more preferably 30% by mass or more, based on the total amount of the polyol (a1), preferably 99% by mass. % Or less, more preferably 95% by mass or less, still more preferably 80% by mass or less.

The polyether polyol (a1-3) is a polyether having two or more hydroxy groups, and for example, one or two or more compounds having two or more groups (—NH— or —OH) having active hydrogen atoms. The thing which carried out addition polymerization of the alkylene oxide is mentioned by making species or more into an initiator.

As the initiator, one or more species can be used, and examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, and 1,4-butanediol. Compounds having two hydroxyl groups such as 1,6-hexanediol and bisphenol A; compounds having three hydroxyl groups such as glycerin, trimethylolethane and trimethylolpropane may be mentioned.

As the alkylene oxide, one or more kinds can be used. For example, epoxide compounds such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, etc .; 4 or more carbon atoms such as tetrahydrofuran (preferably Are, for example, cyclic ethers having 4 to 6 carbon atoms, particularly preferably 4 carbon atoms.

The number average molecular weight of the polyether polyol is preferably more than 300, more preferably 400 or more, still more preferably 500 or more, preferably 4,000 or less, more preferably 3,000 or less.

The content of the polyether polyol (a1-3) is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 5% by mass or more, based on the total amount of the polyol (a1). Is 99.5% by mass or less, more preferably 97.5% by mass or less, and still more preferably 95% by mass or less.

The total content of the polyester polyol (a1-2) and the polyether polyol (a1-3) is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably, based on the total amount of the polyol (a1). It is 30% by mass or more, preferably 99.5% by mass or less, more preferably 97.5% by mass or less, and still more preferably 95% by mass or less.

The polyol (a1) preferably further contains a low molecular weight polyol (a1-4). The molecular weight of the low molecular weight polyol is, for example, 50 or more, preferably 100 or more, and for example, 300 or less, more preferably 250 or less.

As the low molecular weight polyol (a1-4), one or more kinds can be used. For example, ethylene glycol, diethylene glycol, 1,2-propylene glycol, dipropylene glycol, neopentyl glycol, 2-butyl- 2-ethyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanediol, 1,6-hexanediol, Cyclohexane dimethanol etc. are mentioned.

The content of the low molecular weight polyol (a1-4) is preferably 0.1 parts by mass or more, more preferably 100 parts by mass in total of the polyester polyol (a1-2) and the polyether polyol (a1-3). Is 1 part by mass or more, more preferably 2 parts by mass or more, preferably 10 parts by mass or less, more preferably 5 parts by mass or less.

The polyol (a1) further contains a polyol (a1-1) having a carboxy group, a polyester polyol (a1-2), and another polyol (a1-4) other than the polyether polyol (a1-3). It is also good. Examples of the other polyols (a1-5) include polycarbonate polyols and polyolefin polyols.

Examples of the polycarbonate polyol include a reaction product of a carbonate ester and a polyol; a reaction product of phosgene and a polyol and the like.

Examples of the carbonic ester include methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate and the like.

Examples of polyols that can react with the above-mentioned carbonate and phosgene include polyols exemplified as the above-mentioned low molecular weight polyols; high molecular weight polyols such as polyether polyols (polyethylene glycol, polypropylene glycol etc.), polyester polyols (polyhexamethylene adipate etc.) (Number average molecular weight is 300 or more and 5,000 or less) and the like.

The content of the other polyol (a1-5) in the polyol (a1) is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, still more preferably 20% by mass The content is particularly preferably 10% by mass or less.
In particular, the content of the polycarbonate polyol in the polyol (a1) is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, particularly preferably 1% by mass or less, most preferably It is 0 mass%.

The polyisocyanate (a2) which reacts with the polyol (a1) to form a urethane resin (A) is a compound having two or more isocyanate groups in the molecule. As said polyisocyanate (a2), 1 type, or 2 or more types can be used, For example, 4, 4'- diphenylmethane diisocyanate, 2, 4'- diphenylmethane diisocyanate, carbodiimide modified | denatured diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate Aromatic polyisocyanates such as triene diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate; Aliphatic polyisocyanates such as hexamethylene diisocyanate and lysine diisocyanate; cyclohexane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane Alicyclic such as diisocyanate Such polyisocyanates having concrete and the like.
In the present specification, "having an alicyclic structure" may be simply referred to as "alicyclic".

The equivalent ratio [isocyanate group / hydroxyl group] of the isocyanate group of the polyisocyanate (a2) to the hydroxyl group contained in the polyol (a1) is preferably 0.8 or more, more preferably 0.9 or more on a molar basis. Preferably it is 2.5 or less, More preferably, it is 2.0 or less, More preferably, it is 1.5 or less.

As a raw material of the said urethane resin (A) which has a carboxy group, you may contain the terminator (a3) as needed. Examples of the terminal stopper (a3) include compounds having one group (—NH— or —OH) having an active hydrogen atom. As the terminal stopper (a3), one or more kinds can be used. For example, the number of carbon atoms of methanol, ethanol, propanol, butanol, pentanol, hexanol and the like (preferably 1 to 6 carbon atoms) Alcohols of 1 to 4) can be mentioned.

The content of the terminal stopper (a3) is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, still more preferably 0. 1 part by mass, with respect to 100 parts by mass in total of the polyol (a1). It is 1 part by mass or more, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and still more preferably 3 parts by mass or less.

As a raw material of the urethane resin (A) having a carboxy group, if necessary, a chain extender (a4) may be further contained. The chain extender (a4) is a compound having two or more groups (—NH— or —OH) having active hydrogen atoms, and includes polyol compounds, polyamine compounds, hydrazine compounds and the like, with preference given to polyol compounds.

As the polyol compound, one or more kinds can be used. For example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4 -Glycols such as butanediol, hexamethylene glycol, sucrose, methylene glycol, glycerin and sorbitol; bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, hydrogenated Examples thereof include bisphenol A, phenol such as hydroquinone, water and the like.

As the polyamine compound, one or more kinds can be used. For example, ethylene diamine, 1,2-propane diamine, 1,6-hexamethylene diamine, piperazine, 2,5-dimethyl piperazine, isophorone diamine, 4 Diamines such as 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,4-cyclohexanediamine, N-ethylaminoethylamine, N-methylaminopropylamine and the like; N-hydroxy Diamines having a hydroxy group such as methylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine; triamines such as diethylenetriamine, dipropylenetriamine; triethylenetetramine etc. Min and the like.

As the hydrazine compound, one or more kinds can be used. For example, hydrazine, N, N'-dimethylhydrazine, 1,6-hexamethylenebishydrazine, succinic acid dihydrazide, adipic acid dihydrazide, glutaric acid dihydrazide Sebacic acid dihydrazide, isophthalic acid dihydrazide, β-semicarbazide propionic acid hydrazide, 3-semicarbazide-propyl-carbazic acid ester, semicarbazide-3-semicarbazide methyl-3,5,5-trimethylcyclohexane and the like.

The molecular weight of the chain extender (a4) is preferably 300 or less, more preferably 200 or less, and for example, 10 or more, preferably 50 or more.

The content of the chain extender (a4) is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, still more preferably 0.1 parts by mass, with respect to 100 parts by mass in total of the polyol (a1). It is 5 parts by mass or more, preferably 10 parts by mass or less, more preferably 7 parts by mass or less, and further preferably 3 parts by mass or less.

The reaction sequence of the polyol (a1) and the polyisocyanate (a2) and the optional terminator (a3) and the chain extender (a4) is not particularly limited, and examples include polyols (a1) and polyisocyanates (a) After reacting a2) and, if necessary, a chain extender (a4), it may be reacted with an optional terminator (a3).

The acid value of the carboxyl group-containing urethane resin (A) is preferably 1 mg KOH / g or more, more preferably 5 mg KOH / g or more, still more preferably 10 mg KOH / g or more, preferably 100 mg KOH / g or less, more preferably It is 75 mg KOH / g or less, more preferably 40 mg KOH / g or less.

The content of the carboxyl group-containing urethane resin (A) is preferably 10% by mass or more, more preferably 20% by mass or more, and still more preferably 30% by mass or more in the nonvolatile component of the resin composition. It is 100% by mass.

The basic compound (B) neutralizes the carboxy group contained in the urethane resin (A) to ensure electrical neutrality, thereby stably dispersing the urethane resin (A) in the aqueous medium (D) It can be done. As the basic compound (B), an organic amine compound is preferable, and as the organic amine compound, ammonia; primary amines such as monoethanolamine; tertiary amines such as triethylamine and diethylethanolamine; morpholine etc. Cyclic amines and the like can be mentioned.

The content of the basic compound (B) is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, still more preferably 2 parts by mass with respect to 100 parts by mass of the carboxyl group-containing urethane resin (A). It is not less than 30 parts by mass, preferably not more than 20 parts by mass, and more preferably not more than 10 parts by mass.

The crosslinking agent (C) is a compound capable of reacting with a carboxyl group to form a crosslinked structure, and includes a carbodiimide compound. By including a carbodiimide compound as the crosslinking agent (C), it is possible to form a coating layer having good substrate adhesion and ink adhesion to both polyester resin and polyolefin resin substrates. As said carbodiimide compound, a monocarbodiimide compound and a polycarbodiimide compound are mentioned, It is preferable that a polycarbodiimide compound is included.

As the monocarbodiimide compound, one or more species can be used. For example, N, N-dicyclohexylcarbodiimide, N, N-diisopropylcarbodiimide, N, N-dimethylcarbodiimide, N, N-diisobutylcarbodiimide, N, N-dioctyl carbodiimide, N, N-t-butyl isopropyl carbodiimide, N, N-diphenyl carbodiimide, N, N-di-t-butyl carbodiimide, N, N-di-β-naphthyl carbodiimide and the like can be mentioned.

Examples of the polycarbodiimide compound include diisocyanate and a monoisocyanate used as needed, or a decarboxylative condensation product of the end terminator.

As said diisocyanate, 1 type, or 2 or more types can be used, For example, 4,4'- diphenylmethane diisocyanate, 2,4'- diphenylmethane diisocyanate, carbodiimide modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, triene diisocyanate, Aromatic polyisocyanates such as naphthalene diisocyanate, xylylene diisocyanate and tetramethyl xylylene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate and lysine diisocyanate; and oils such as cyclohexane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate and dicyclohexylmethane diisocyanate Ring structure Such as isocyanate, and the like.

As said monoisocyanate, 1 type (s) or 2 or more types can be used, For example, phenyl isocyanate, toluylene isocyanate, dimethylphenyl isocyanate, cyclohexyl isocyanate, butyl isocyanate, a naphthyl isocyanate etc. are mentioned.

In forming the decarboxylated condensate, 1-phenyl-2-phospholene-1-oxide, 3-methyl-2-phospholene-1-oxide, 1-ethyl-2-phospholene-1-oxide, 3-methyl- A catalyst such as 1-phenyl-2-phospholene-1-oxide or a phosphorene oxide such as these 3-phospholene isomers may be coexistent.

The polycarbodiimide compound preferably has a hydrophilic segment. Examples of the hydrophilic segment include quaternary ammonium salts of dialkylaminoalcohols and quaternary ammonium salts of dialkylaminoalkylamines; alkyl sulfonates having at least one hydroxy group; polyoxyalkylene diols having an alkoxy group at the end (preferably And polyethylene glycol, polyoxypropylene diol and mixtures thereof). The repeating unit of the polyoxyalkylene diol is preferably 3 or more, more preferably 5 or more, preferably 50 or less, more preferably 35 or less.

The polycarbodiimide compound may be cationic, anionic or nonionic, and is preferably nonionic.

The polymerization degree of the polycarbodiimide compound is preferably 2 or more, more preferably 3 or more, preferably 10 or less, more preferably 7 or less.

The isocyanate group equivalent (chemical formula weight per 1 mol of carbodiimide group) of the polycarbodiimide compound is preferably 300 or more, more preferably 350 or more, still more preferably 400 or more, preferably 600 or less, more preferably 550 or less More preferably, it is 500 or less.

The pH of a 40% by mass aqueous solution of the polycarbodiimide compound is preferably 12 or less, more preferably 11 or less, preferably 7 or more, more preferably 8 or more.

The content of the polycarbodiimide compound in the carbodiimide compound is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and the upper limit is 100% by mass.

The content of the carbodiimide compound in the crosslinking agent (C) is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and the upper limit is 100% by mass.

As said crosslinking agent (C), other crosslinking agents other than a carbodiimide compound may be included. The other crosslinking agent may be used alone or in combination of two or more, and examples thereof include aldehyde compounds such as formaldehyde, glyoxal and glutaraldehyde; ketone compounds such as diacetyl and cyclopentanedione; Active halogen compounds such as chloroethyl urea) -2-hydroxy-4,6-dichloro-1,3,5-triazine and 2,4-dichloro-6-S-triazine sodium salt; divinyl sulfonic acid, 1,3- Active vinyl compounds such as vinylsulfonyl-2-propanol, N, N′-ethylenebis (vinylsulfonylacetamide), 1,3,5-triacryloyl-hexahydro-S-triazine; dimethylol urea, methylol dimethyl hydantoin N-methylol compounds such as; melamine resins (eg methylolmera And alkylated methylolmelamines); epoxy resins; isocyanate compounds such as 1,6-hexamethylene diisocyanate; aziridine compounds described in U.S. Pat. Nos. 3,017,280 and 2,983,611; Carboxyimide compounds described in the following; epoxy compounds such as glycerol triglycidyl ether; ethyleneimino compounds such as 1,6-hexamethylene-N, N'-bisethyleneurea; halogens such as mucochloric acid and mucophenoxychloric acid Carboxaldehyde compounds; Dioxane compounds such as 2,3-dihydroxydioxane; Metals containing compounds such as titanium lactate, aluminum sulfate, chromium alum, potassium alum, zirconyl acetate, chromium acetate, etc., polyamines such as tetraethylenepentamine Examples thereof include compounds, hydrazide compounds such as adipic acid dihydrazide and the like, low molecules or polymers containing two or more oxazoline groups, and the like.

The content of the crosslinking agent (C) is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and still more preferably 1. parts by mass with respect to 100 parts by mass of the carboxyl group-containing urethane resin (A). It is 5 parts by mass or more, preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and still more preferably 12 parts by mass or less.

Examples of the aqueous medium (D) include water; hydrophilic organic solvents; mixtures of water and hydrophilic organic solvents and the like, and from the viewpoint of safety and load on the environment, water or a mixture of water and hydrophilic organic solvents is preferable.
The hydrophilic organic solvent may be used alone or in combination of two or more, and is preferably miscible with water. For example, alcohol solvents such as methanol, ethanol, n-propanol and 2-propanol; acetone Ketone solvents such as methyl ethyl ketone; polyhydric alcohol solvents such as ethylene glycol, diethylene glycol, propylene glycol, polyalkylene glycol, and glycerin; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, ethyl carbitol And ether solvents such as N-methyl-2-pyrrolidone.

When the aqueous medium (D) contains water and a hydrophilic organic solvent, the content of water in the aqueous medium (D) is preferably 80% by mass or more, more preferably 85% by mass or more, still more preferably 90% by mass. % Or more, for example, 100% by mass or less, or even 95% by mass or less is acceptable.

The content of the aqueous medium (D) in the resin composition is preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, preferably 99% by mass or less, more preferably Is 95 mass% or less, more preferably 92 mass% or less.

The resin composition is, if necessary, colorants such as pigments and dyes, plasticizers, softeners, antioxidants, fillers such as fibers made of glass or plastic, balloons, beads, metal powders, film formation assistance You may contain additives, such as an agent, a leveling agent, a wetting agent, a thickener (viscosity modifier), a water repellent, and an antifoamer. When the said resin composition contains the said additive, the content is preferably more than 0 mass part and 1 mass part or less with respect to 100 mass parts of urethane resin (A) which has a carboxy group.

The pH of the resin composition is preferably 9 or less, more preferably 8.5 or less, still more preferably 8 or less, preferably 6 or more, more preferably 6.5 or more.

The resin composition can be a coating agent.

The laminate of the present invention has a base material layer and a coating layer which is a cured product of the resin composition. As a base material used for a layered product of the present invention, a metal base material, a plastic base material, a glass base material, a paper base material, a wood base material, a fibrous base material etc. are mentioned, for example. Among these base materials, the resin composition of the present invention contains the specific urethane resin (A) and the specific crosslinker (C), so that the plastic base material, particularly polyester resin and polyolefin resin base material, is used. The adhesion to a substrate and the adhesion to an ink are good.

As a material of the plastic base material, polyester resin (polyethylene terephthalate (PET), polybutylene terephthalate (PBT)), polyolefin resin (polyethylene, polypropylene, polycycloolefin (COP), etc.), acrylic resin (polymethyl methacrylate, etc.) Polycarbonate resin, acrylonitrile-butadiene-styrene copolymer (ABS resin), composite resin of ABS resin and polycarbonate, polystyrene resin, polyurethane resin, epoxy resin, polyvinyl chloride resin, polyamide resin, triacetyl cellulose (TAC), etc. Can be mentioned.

The resin composition of the present invention can form a coating film on the surface of the substrate by, for example, directly applying to the surface of the substrate, and then drying and curing. A method of drying the coating agent of the present invention and promoting curing may be a method of curing for about 1 to 10 days under normal temperature, but since curing can be rapidly progressed, the temperature is 100 ° C. to 150 ° C. It is preferable to heat at a temperature of about 1 to 600 seconds. In addition, when using a plastic base material that is easily deformed or discolored at a relatively high temperature, it is preferable to heat at a relatively low temperature of about 70 ° C. to 100 ° C.

As a method for applying the coating agent of the present invention to the surface of the substrate, for example, a gravure coater, roll coater, comma coater, knife coater, air knife coater, curtain coater, kiss coater, shower coater, flow coater, spin coater, An application method using dipping, screen printing, spraying, brushing, an applicator, a bar coater or the like can be mentioned.

The film thickness of the coating film formed using the coating agent of the present invention can be appropriately adjusted depending on the application to be used, but usually, it is preferably in the range of 0.01 to 20 μm.

The laminate of the present invention is, for example, plastic molded articles such as mobile phones, home appliances, automobile interior and exterior materials, OA equipment, etc., film base materials made of plastic (such as antireflective film, retardation film, prism lens sheet etc.) It can be used for highly functional films such as packaging films (particularly, food packaging films) such as optical films) and aluminum vapor deposition films, and is particularly useful as a food packaging film.

Hereinafter, the present invention will be more specifically described by way of examples.

Synthesis Example 1: Synthesis of Polyester Polyol (1)
35.4 parts of isophthalic acid, 17.8 parts of sebacic acid, 7.8 parts of adipic acid, 6.2 parts of ethylene glycol while introducing nitrogen gas in a reaction vessel equipped with a thermometer, a nitrogen gas introduction pipe, and a stirrer , 22.9 parts of neopentyl glycol, 11.7 parts of 1,6-hexanediol and 0.03 parts of dibutyl tin oxide are charged, and the polycondensation reaction is carried out at 180 ° C to 230 ° C for 24 hours until the acid value becomes 1 or less. The polyester polyol (1) [number average molecular weight 2100, acid value 0.6 mg KOH / g, hydroxyl value 42.5 mg KOH / g, aromatic ring concentration 2.51 mol / kg] was obtained.

Production Example 1: Synthesis of Carboxy Group-Containing Polyurethane Resin (I) Composition
In a reaction vessel, 69.0 parts by mass of the polyester polyol (1) of Synthesis Example 1 was dehydrated at 100 ° C. under reduced pressure, then cooled to 80 ° C., 93.30 parts by mass of methyl ethyl ketone was added, and stirred and uniformly mixed. Next, 3.0 parts by mass of 1,4-butanediol and 6.1 parts by mass of 2,2'-dimethylol propionic acid are added, and then 19.4 parts by mass of tolylene diisocyanate is added, and the reaction is carried out at 80 ° C for 12 hours. It was made to react and the urethanization process was implemented. After confirming that the isocyanate value has become 0.1% or less, 0.3 part by mass of n-butanol is added, reacted for 2 hours, cooled to 50 ° C., acid value 25 mg KOH / g, nonvolatile content = 51.0 mass% of carboxy group-containing polyurethane resin (I) compositions were obtained.

Production Example 2 Preparation of Aqueous Resin Composition (II)
To 163.5 parts by mass of the carboxy group-containing urethane resin (I) composition obtained in Production Example 1, 4.6 parts by mass of triethylamine was added, and 548 parts by mass of ion exchanged water was slowly added to carry out water solubilization. Subsequently, methyl ethyl ketone was removed under reduced pressure at 30 to 50 ° C. to prepare an aqueous resin composition (II) having a nonvolatile content of 23.5% by mass.

Example 1-1 Preparation of Primer (P-1a)
100 parts by mass of the aqueous resin composition (II) obtained in Production Example 2 and 6 parts by mass of a carbodiimide crosslinking agent (Carbodilite SV-02: Nisshinbo Co., non-volatile content = 40.0%) and 153 parts by mass of ion exchanged water By mixing, nonvolatile content = 10.0% primer (P-1b) was obtained.

Comparative Example 1-1: Preparation of Primer (P-1b)
By mixing 100 parts by mass of the aqueous resin composition (II) obtained in Production Example 2 with 135 parts by mass of ion exchanged water, a primer (P-1) having a nonvolatile content of 10.0% by mass was obtained.

Comparative Example 1-2: Preparation of Primer (P-1c)
100 parts by mass of the aqueous resin composition (II) obtained in Production Example 2 and 6 parts by mass of a melamine crosslinking agent (Beckamine M-3: manufactured by DIC, non volatile matter = 78.0%) and 175.8 parts by mass of ion exchanged water And a non-volatile content = 10.0% by mass of a primer (P-1c).

Example 2-1 Production of Laminate (1)
Dry on the surface of a film substrate (thickness 125 μm) made of polyethylene terephthalate (abbreviated as "PET" below) or a film substrate (thickness 30 μm) made of polypropylene (hereinafter abbreviated as "PP") The primer (P-1a) obtained in Example 1-1 was applied so as to give a film thickness of about 1 μm, and the coating layer was applied to the surface of the substrate by heating at 150 ° C. for 5 minutes. It formed. Next, the surface of the coating layer is coated with a photocurable ink (UV-1) at a coating thickness of 15 μm, and irradiated with ultraviolet light at an irradiation intensity of 400 mJ / cm ² using a high pressure mercury lamp as a light source. A PET laminate (1) or PP laminate (1) having a coating layer on the surface of the material and a photocured layer on the surface of the coating layer was obtained.

(Comparative Example 2-1: Preparation of Laminated Body (1 '))
It carried out like Example 2-1 except having not used the primer (P-1a) used in Example 2-1, and obtained PET layered product (1 ') or PP layered product (1'). .

(Comparative Example 2-2: Preparation of Laminate (2 '))
The procedure of Example 2-1 is repeated except that the primer (P-1b) obtained in Comparative Example 1-1 is used instead of the primer (P-1a) used in Example 2-1. A laminate (2 ') or a PP laminate (2') was obtained.

(Comparative Example 2-3: Preparation of Laminated Body (3 '))
The procedure of Example 2-1 is repeated except that the primer (P-1c) obtained in Comparative Example 1-2 is used instead of the primer (P-1a) used in Example 2-1. A laminate (3 ') or PP laminate (3') was obtained.

A test plate was prepared according to the following procedure, and the adhesion between the substrate and the coating layer and the adhesion between the coating layer and the ink layer were evaluated. The results are shown in Table 1.

[Preparation of test plate]
A primer is applied to the surface of a 125 μm-thick polyethylene terephthalate substrate to a dry thickness of about 1 μm, and heated at 150 ° C. for 5 minutes to form a coating layer on the surface of the substrate. A test plate consisting of laminated members was produced.
A primer is applied on the surface of a 30 μm-thick polypropylene substrate to a dry thickness of about 1 μm, and the coating layer is laminated on the surface of the substrate by heating at 90 ° C. for 5 minutes. The test plate which consists of the member which produced is produced.

[Adhesiveness between substrate and coating layer <cellophane adhesive tape peeling test>]
A 24 mm wide adhesive tape manufactured by Nichiban Co., Ltd. was attached to the surface of the coating layer constituting the test plate prepared by the above method.
Then, the pressure-sensitive adhesive tape was pulled in a direction perpendicular to the coating layer, and the state of the surface of the coating layer when the pressure-sensitive adhesive tape was peeled off from the surface of the coating layer was visually evaluated according to the following evaluation criteria.
◎: The coating layer did not peel at all from the surface of the substrate constituting the test plate.
○: A very small part of the coating layer was peeled from the surface of the substrate constituting the test plate, but the peeled range was less than 10% of the total area of the film constituting the test plate.
Fair: The coating layer in the range of 10% to less than 50% of the area of the coating layer constituting the test plate was peeled off from the surface of the substrate constituting the test plate.
X: The coating layer of 50% or more of the whole area of the coating layer which comprises a test plate peeled from the base-material surface which comprises a test plate.

[Adhesiveness between Coating Layer and Ink Layer <Cellophane Adhesive Tape Peeling Test>]
The adhesive tape of 24 mm width made by Nichiban Co., Ltd. was stuck on the surface of the ink layer which constitutes the layered product obtained by the example and the comparative example.
Then, the pressure-sensitive adhesive tape was pulled in a direction perpendicular to the ink layer, and the state of the surface of the ink layer was visually evaluated according to the following evaluation criteria when the pressure-sensitive adhesive tape was peeled from the surface of the ink layer.
◎: The ink layer did not peel at all from the surface of the substrate constituting the laminate.
Good: A part of the ink layer peeled off from the surface of the substrate constituting the laminate, but the peeled range was less than 10% of the total area of the ink layers constituting the laminate.
Fair: The ink layer in the range of 10% to less than 50% with respect to the total area of the ink layer constituting the laminate peeled off from the surface of the substrate constituting the laminate.
X: The ink layer in the range of 50% or more with respect to the total area of the ink layer constituting the laminate peeled off from the surface of the substrate constituting the laminate.

The laminate (1) of Example 2-1 is formed using the aqueous resin composition of the present invention, and the substrate adhesion and the ink adhesion to the substrate of both the polyester resin and the polyolefin resin Was good. The laminate (1 ') of Comparative Example 2-1 was one in which the coating layer was not formed, and the ink adhesion to the PET laminate was poor. The laminate (2 ′) of Comparative Example 2-2 is formed using an aqueous resin composition not containing the crosslinking agent (C), and the substrate adhesion and the ink adhesion to the polyolefin resin substrate Was bad. The laminate (3 ′) of Comparative Example 2-3 is formed using an aqueous resin composition containing only a melamine crosslinking agent as the crosslinking agent (C), and the substrate adhesion to the polyolefin resin substrate is And the ink adhesion was poor.

Claims

A resin composition comprising a urethane resin (A) having a carboxy group, a basic compound (B), a crosslinking agent (C) and an aqueous medium (D),
The urethane resin (A) is a reactant of a raw material containing a polyol (a1) and a polyisocyanate (a2),
The polyol (a1) contains a polyol (a1-1) having a carboxy group, and at least one selected from the group consisting of a polyester polyol (a1-2) and a polyether polyol (a1-3). ,
An aqueous resin composition characterized in that the crosslinking agent (C) contains a carbodiimide compound.
The aqueous resin composition according to claim 1, wherein the content of the crosslinking agent (C) is 0.1 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing urethane resin (A).
The aqueous resin composition according to claim 1 or 2, wherein the acid value of the carboxyl group-containing urethane resin (A) is 1 mg KOH / g or more and 100 mg KOH / g or less.
The aqueous resin composition according to any one of claims 1 to 3, wherein the polyol (a1) further comprises a chain extender (a1-4).
The aqueous resin composition according to any one of claims 1 to 4, wherein the raw material of the urethane resin (A) further contains a termination agent (a3).
The aqueous resin composition according to any one of claims 1 to 5, wherein the basic compound (B) is an organic amine compound.
A laminate comprising a substrate layer and a coating layer which is a cured product of the resin composition according to any one of claims 1 to 6,
The laminated body whose said base material is comprised by at least 1 sort (s) chosen from the group which consists of polyester resin and polyolefin resin.
A packaging film comprising the laminate according to claim 7.