JP2017186411A - Composite resin aqueous dispersion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composite resin aqueous dispersion capable of being applied as a coating agent to a substrate to be coated.SOLUTION: There is provided a composite resin aqueous dispersion where a polyurethane resin (A) obtained by reacting polycarbonate polyol, polyisocyanate and acidic group-containing polyol and an acrylic polymer (B) are dispersed in an aqueous medium, which at least consists of a vinyl polymer (B) included in the polyurethane resin (A) and has mass of the polyurethane resin (A) of 5 to 95 mass%.SELECTED DRAWING: None

Description

  The present invention relates to a novel composite resin aqueous dispersion.

Conventionally, composite resin aqueous dispersions are excellent in adhesion to various base materials, abrasion resistance, impact resistance, solvent resistance, etc., for example, paper as paints, inks, adhesives, and various coating agents. Widely used in plastics, films, metals, rubber, elastomers, textile products, etc.
As such a composite resin aqueous dispersion, for example, the vinyl polymer in the composite resin aqueous dispersion has a specific glass transition temperature, and the content of the vinyl polymer per polyurethane resin is 20 parts by weight or more, A composite resin aqueous dispersion of 400 parts by weight or less is disclosed (for example, see Patent Document 1).

JP 2005-281544 A

Patent Document 1 discloses a composite resin aqueous dispersion having a vinyl polymer having a specific glass transition temperature (Tg), a laminate (coating film) produced by coating it on an aluminum foil, and an aluminum foil. The evaluation results of the adhesion of are described.
However, when the glass transition temperature of the vinyl polymer is below room temperature, a highly flexible coating film can be obtained. Therefore, in the above method, it is required as a coating film as a paint, ink, adhesive, and various coating agents. There was a probability that the effect could not be demonstrated. Moreover, only the aluminum foil was examined about the adhesiveness of the obtained coating film (laminated body).

  Therefore, a composite resin aqueous dispersion that can be applied as paints, inks, adhesives and various coating agents to various substrates has been demanded.

  The object of the present invention is to solve the above problems and provide an aqueous composite resin dispersion that can be applied as a paint, ink, adhesive, and various coating agents.

The subject of the present invention is
In the composite resin aqueous dispersion in which the polyurethane resin (A) and the acrylic polymer (B) are dispersed in an aqueous medium, at least from the vinyl polymer (B) encapsulated in the polyurethane resin (A). Become
The polyurethane resin (A) includes at least a repeating unit represented by the following formula (1), formula (2), and formula (3),
The composite resin aqueous dispersion, wherein a mass of the polyurethane resin (A) is 5 to 95% by mass with respect to a total mass of the polyurethane resin (A) and the acrylic polymer (B). Solved by.

(In the formula, Z is a linear divalent aliphatic hydrocarbon group having 2 to 12 carbon atoms, a divalent branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, or 6 to 6 carbon atoms. 18 represents a divalent cycloaliphatic hydrocarbon group, and n represents a repeating unit of the formula (1).
R is a divalent linear aliphatic hydrocarbon group having 2 to 12 carbon atoms, a divalent branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, or a divalent cyclic group having 6 to 18 carbon atoms. An aliphatic hydrocarbon group or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms is shown.
AG represents an acidic group, and X represents a linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms. )

  According to the present invention, an aqueous composite resin dispersion exhibiting sufficient adhesion and adhesion to a substrate to be coated can be provided.

[Composite resin aqueous dispersion]
“Aqueous composite resin dispersion” of the present invention is an aqueous composite resin dispersion in which “polyurethane resin (A)” and “acrylic polymer (B)” are dispersed in an aqueous medium, It consists of an acrylic polymer (B) encapsulated in the polyurethane resin (A).
Here, “encapsulation” of “acrylic polymer (B) encapsulated in polyurethane resin (A)” means that polyurethane resin (A) and acrylic polymer (B) are completely separated and independent. Broadly means other than dispersed in an aqueous medium. Specifically, it means a state in which part or most of the acrylic polymer is included in the polyurethane resin, and more specifically, in the composite resin particles (particles dispersed in the composite resin aqueous dispersion). Means that an acrylic polymer is present.
In addition, a part of the acrylic polymer may be partially outside the composite resin particles (particles dispersed in the composite resin aqueous dispersion) as long as the function and characteristics of the composite resin aqueous dispersion are not impaired. In addition, the position where the acrylic polymer is present in the composite resin particles is not particularly limited, and the acrylic polymer may be present separately or separately in the vicinity of the center or at an arbitrary position shifted from the vicinity of the center.

[Polyurethane resin (A)]
The polyurethane resin (A) is obtained by reacting a polycarbonate polyol, a polyisocyanate, and an acidic group-containing polyol, and is at least a repetition represented by the following formula (1), formula (2), and formula (3). Includes units.
The acidic group in the polyurethane resin (A) is preferably neutralized with a neutralizing agent from the viewpoint of dispersibility in an aqueous medium.

(In the formula, Z is a linear divalent aliphatic hydrocarbon group having 2 to 12 carbon atoms, a divalent branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, or 6 to 6 carbon atoms. 18 represents a divalent cycloaliphatic hydrocarbon group, and n represents a repeating unit of the formula (1).
R is a divalent linear aliphatic hydrocarbon group having 2 to 12 carbon atoms, a divalent branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, or a divalent cyclic group having 6 to 18 carbon atoms. An aliphatic hydrocarbon group or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms is shown.
AG represents an acidic group, and X represents a linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms. )

(Repeating unit represented by formula (1))
The repeating unit represented by the formula (1) is a constituent derived from the polycarbonate polyol used when synthesizing the polyurethane resin.
In formula (1), Z is a linear divalent aliphatic hydrocarbon group having 2 to 12 carbon atoms, a divalent branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, or the number of carbon atoms. 6-18 represents a bivalent cycloaliphatic hydrocarbon group, and n represents a repeating unit.

The “linear divalent aliphatic hydrocarbon group having 2 to 12 carbon atoms” is a group obtained by removing two hydrogens from the “linear aliphatic hydrocarbon group having 2 to 12 carbon atoms”. For example, ethylene group, trimethylene group (propylene group), tetramethylene group (butylene group), pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, A dodecamethylene group is exemplified, and a tetramethylene group, a pentamethylene group, and a hexamethylene group are preferred.
A plurality of different repeating units may be included.

The “divalent branched aliphatic hydrocarbon group having 3 to 12 carbon atoms” refers to a group obtained by removing two hydrogen atoms from the “branched aliphatic hydrocarbon having 3 to 12 carbon atoms”, For example, 2-methyl-1,3-trimethyl group, 2- or 3-methyl-1,5-pentyl group, 2,2,4- or 2,4,4-trimethylhexamethylene group, 1,5-hexylene Group and the like.
A plurality of different repeating units may be included.

The “divalent cycloaliphatic hydrocarbon group having 6 to 18 carbon atoms” refers to a group obtained by removing two hydrogens from the “cycloaliphatic hydrocarbon having 6 to 18 carbon atoms”. , 3-cyclohexylene group, 1,4-cyclohexylene group, 1,4-dimethylenecyclohexylene group (methylene-cyclohexylene-methylene group) and the like.
A plurality of different repeating units may be included.

  In addition, n is the number of repeating units of the formula (1) and depends on the number average molecular weight of the polycarbonate polyol, but is preferably 1 to 40, more preferably 2 to 30, and more preferably 3 to 25.

  The polycarbonate polyol may have an ester bond or an ether bond as long as the function and characteristics are not impaired. By having an ester bond, it is expected that the compatibility with polyurethane is increased. Moreover, by having an ether bond, it is expected that the flexibility of polyurethane is further increased.

(Number average molecular weight of polycarbonate polyol)
The number average molecular weight of the polycarbonate polyol of the present invention is appropriately adjusted according to the purpose, but is preferably 500 to 10000, more preferably 500 to 8000, and more preferably 500 to 6000.
In addition, let a number average molecular weight be the number average molecular weight computed based on the hydroxyl value measured based on JISK1557. Specifically, the hydroxyl value is measured and calculated by (56.1 × 1000 × valence) / hydroxyl value by terminal group quantification method (in this formula, the unit of hydroxyl value is [mgKOH / g]. Is). In the above formula, the valence is the number of hydroxyl groups in one molecule.

(Repeating unit represented by formula (2))
The repeating unit represented by the formula (2) is a constituent component derived from polyisocyanate used when a polyurethane resin is synthesized.
In the formula (2), R is a divalent linear aliphatic hydrocarbon group having 2 to 12 carbon atoms, a divalent branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, and 6 to 6 carbon atoms. 18 is a divalent cyclic aliphatic hydrocarbon group or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms.

  The “divalent linear aliphatic hydrocarbon group having 2 to 12 carbon atoms” means “a divalent branched aliphatic hydrocarbon group having 3 to 12 carbon atoms” and “6 carbon atoms”. The ˜18 divalent cycloaliphatic hydrocarbon group ”is the same as that represented by the formula (1).

The “divalent aromatic hydrocarbon group having 6 to 18 carbon atoms” refers to a group obtained by removing two hydrogen atoms from the “aromatic hydrocarbon having 6 to 18 carbon atoms”. , Tolylene group, xylylene group, tetramethylxylylene group, 4,4′-diphenylenemethylene group, 4,4′-methylenebiscyclohexyl group, isophorone group and the like.
A plurality of different repeating units may be included.

(Repeating unit represented by formula (3))
The repeating unit represented by the formula (3) is a constituent component derived from an acidic group-containing polyol used when a polyurethane resin is synthesized.
In formula (3), AG represents an acidic group, and X represents a linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms.

The “acidic group” is not particularly limited as long as it is a group that can impart hydrophilicity by releasing protons (H ⁺ ) in an aqueous medium. For example, a carboxyl group, a sulfonic acid group, a phosphorus group, and the like can be used. An acid group, a phenolic hydroxyl group and the like can be mentioned, and a carboxyl group is preferable.

Examples of the “linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms” include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, and a hexyl group. And preferably a methyl group, an ethyl group or a propyl group.
These groups include various isomers and may include a plurality of different repeating units.

(Neutralizer)
The “neutralizing agent” is not particularly limited as long as it can neutralize acidic groups in the polyurethane resin. For example, ammonia; primary amines such as monomethylamine, monoethylamine, monoisopropylamine, monobutylamine; dimethylamine Secondary amines such as diethylamine, diisopropylamine, dibutylamine and morpholine; tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine, triisopropylamine, tributylamine, N-methylmorpholine and pyridine; sodium hydroxide, potassium hydroxide and the like Alkali metal hydroxides; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, polyurethane resins While suppressing the reaction between the terminal isocyanate groups, from the viewpoint of ease of coating with the polyurethane resin, preferably a tertiary amine, more preferably used are trialkylamine.
These neutralizing agents may be used in combination of two or more.

(Synthesis of polyurethane resin (A))
“Polyurethane resin (A)” is a polycarbonate polyol having a repeating unit represented by formula (1), a polyisocyanate having a repeating unit represented by formula (2), and an acid having a repeating unit represented by formula (3). After reacting the group-containing polyol, it can be produced by neutralizing the acidic group with a neutralizing agent (hereinafter sometimes referred to as “urethanization reaction”).
The reaction form is not particularly limited, and a known one-shot method or prepolymer method can be appropriately selected.

Specifically, for example,
A step of reacting polycarbonate polyol, polyisocyanate, and acidic group-containing polyol in the presence or absence of a solvent to form a urethane prepolymer;
Neutralizing acidic groups in the prepolymer with a neutralizing agent;
Dispersing the neutralized prepolymer in an aqueous medium;
Reacting a prepolymer dispersed in an aqueous medium with a chain extender;
It can manufacture by performing sequentially.
In each step, by using a catalyst as necessary, the reaction can be promoted and the by-products can be controlled.
By adopting this production method, an aqueous polyurethane that can sufficiently neutralize the acidic group of the polyurethane resin containing an acidic group with a base without damaging the terminal isocyanate group of the polyurethane resin and has good dispersibility. A resin dispersion can be obtained.

(Polycarbonate polyol)
The polycarbonate polyol used in the urethanization reaction of the present invention has a skeleton represented by the formula (1). Such a polycarbonate polyol includes, for example, one or more aliphatic polyols and a carbonate ester. Is obtained in the presence of a catalyst (hereinafter also referred to as “carbonation reaction”).

(Aliphatic polyol)
Examples of the aliphatic polyol include those having 2 to 12 carbon atoms such as ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, undecanediol, and dodecanediol. A linear aliphatic polyol;
Such as 2-methyl-1,3-propanediol, 2- or 3-methyl-1,5-pentanediol, 2,2,4- or 2,4,4-trimethylhexanediol, 1,5-hexanediol, etc. A branched aliphatic polyol having 3 to 18 carbon atoms;
Cycloaliphatic polyols having 6 to 18 carbon atoms such as 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like are preferable, but preferably pentanediol, hexanediol, 1,4 -Cyclohexanedimethanol is used.
In addition, the said aliphatic polyol may use 2 or more types together.

(Carbonate ester)
Examples of the carbonate ester include dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate; diaryl carbonates such as diphenyl carbonate; ethylene carbonate, propylene carbonate (4-methyl-1,3-dioxolan-2-one, trimethylene Carbonate), butylene carbonate (4-ethyl-1,3-dioxolan-2-one, tetramethylene carbonate), cyclic carbonates such as 5-methyl-1,3-dioxan-2-one, and the like, preferably dimethyl Carbonate, diethyl carbonate and ethylene carbonate are used.
These carbonate esters may be used in combination of two or more.

The amount of the carbonate ester used is preferably 0.8 to 2.0 mol, more preferably 0.9 to 1.5 mol, with respect to 1 mol of the aliphatic polyol.
By setting the amount within this range, the target polycarbonate polyol can be efficiently obtained at a sufficient reaction rate.

(Reaction temperature and reaction pressure)
The reaction temperature in the carbonation reaction of the present invention is appropriately adjusted according to the type of carbonate, but is preferably 50 to 250 ° C, more preferably 70 to 230 ° C.
The reaction pressure is not particularly limited as long as it is a pressure that causes the reaction while removing low-boiling components, and it is preferably performed under normal pressure or reduced pressure.
By setting it as this range, the target polycarbonate polyol can be obtained efficiently without causing sequential reaction or side reaction.

(catalyst)
In the carbonation reaction of the present invention, a known transesterification catalyst can be used. For example, lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, zinc, aluminum, titanium, zirconium, cobalt , Metals such as germanium, tin, cerium, and their hydroxides, alkoxides, carboxylates, carbonates, bicarbonates, sulfates, phosphates, nitrates, organic metals, etc., preferably hydrogen Sodium fluoride, titanium tetraisopropoxide, titanium tetrabutoxide, zirconium tetrabutoxide, zirconium acetylacetonate, zirconium oxyacetate, dibutyltin dilaurate, dibutyltin dimethoxide, dibutyltin oxide are used .
Two or more of these catalysts may be used in combination.

The amount of the catalyst used is preferably 0.001 to 0.1 mmol, more preferably 0.005 to 0.05 mmol, more preferably 0.01 to 0.03 mmol, with respect to 1 mol of the aliphatic polyol. It is.
By setting it as this range, the target polycarbonate polyol can be obtained efficiently without complicating the post-treatment.
The catalyst may be used in a lump at the start of the reaction, or may be used (added) separately at the start of the reaction and after the start of the reaction.

(Polyisocyanate)
The polyisocyanate used in the urethanization reaction of the present invention has a skeleton represented by the formula (2).
The polyisocyanate to be used is appropriately selected according to the purpose and application.
A linear aliphatic polyisocyanate having 2 to 12 carbon atoms such as ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate;
1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanate) Branched aliphatic polyisocyanates having 3 to 12 carbon atoms, such as natoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate;
Cycloaliphatic polyisocyanates having 6 to 18 carbon atoms such as 4,4′-methylenebiscyclohexyl diisocyanate (H12MDI), hexamethylene diisocyanate, isophorone diisocyanate, cyclohexane-1,3-diylbis (methylene) diisocyanate, trimethylhexamethylene diisocyanate ;
2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate (MDI), naphthalene-1,5-diisocyanate, 3,3′-dimethyl-4,4′-biphenylene diisocyanate Aromatic polyisocyanates having 6 to 18 carbon atoms such as polymethylene polyphenyl isocyanate, xylylene diisocyanate (XDI), phenylene diisocyanate, tetramethylene xylylene diisocyanate (TMXDI) are used.
In addition, these polyisocyanates may use 2 or more types together, and a part or all of the structure may be derivatized, such as isocyanurate formation, carbodiimidization, or biuretization.

  The amount of the polyisocyanate used is the ratio (isocyanate group / hydroxyl group (molar ratio)) between the isocyanate group of the polyisocyanate and the hydroxyl group of the polycarbonate polyol (including the hydroxyl group if an aliphatic polyol is contained). , Preferably 1.5 to 8.0, more preferably 2.0 to 5.0.

(Acid group-containing polyol)
The acidic group-containing polyol used in the urethanization reaction of the present invention has a skeleton represented by the formula (3).
The acidic group-containing polyol to be used is appropriately selected according to the purpose and application.
2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 3,4-dihydroxybutanesulfonic acid and the like are used.
These acidic group-containing polyols may be used alone or in admixture of two or more. N, N-bishydroxyethylglycine, N, N-bishydroxyethylalanine, 3,6-dihydroxy-2 -Toluenesulfonic acid can be used as well.
In addition, the usage-amount will not be restrict | limited especially if a polyurethane resin can disperse | distribute a polyurethane resin in an aqueous medium, Moreover, you may use 2 or more types together.

(Chain extender)
In the urethanization reaction of the present invention, a chain extender can be used for the purpose of increasing the molecular weight. The chain extender to be used can be appropriately selected according to the purpose and use, for example,
water;
Ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,10-decanediol, 1,1-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, xylylene glycol, bis (p-hydroxy) diphenyl, bis (p-hydroxyphenyl) propane, 2,2-bis [4- (2-hydroxyethoxy) phenyl Low molecular polyols such as propane, bis [4- (2-hydroxyethoxy) phenyl] sulfone, 1,1-bis [4- (2-hydroxyethoxy) phenyl] cyclohexane;
Polymer polyols such as polyester polyols, polyester amide polyols, polyether polyols, polyether ester polyols, polycarbonate polyols, polyolefin polyols;
Polyamines such as ethylenediamine, isophoronediamine, 2-methyl-1,5-pentanediamine, aminoethylethanolamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine are used.
As for the chain extender, for example, “Latest Polyurethane Application Technology” (CMC Co., Ltd., issued in 1985) can be referred to. For the polymer polyol, for example, “Polyurethane Form” (polymer) Publications, 1987).
Moreover, these chain extenders may use 2 or more types together.

(Urethane catalyst)
In the urethanization reaction of the present invention, a known polymerization catalyst can be used in order to improve the reaction rate. For example, an organic metal salt such as tertiary amine, tin or titanium is used.
As for the polymerization catalyst, pages 23 to 32 of “Polyurethane resin” written by Keiji Yoshida (published by Nihon Kogyo Shimbun, 1969) may be used, and two or more kinds may be used in combination.

(solvent)
The urethanization reaction of the present invention can be carried out in the presence of a solvent, for example, esters such as ethyl acetate, butyl acetate, propyl acetate, γ-butyrolactone, γ-valerolactone, δ-caprolactone; N-methylpyrrolidone, Pyrrolidones such as N-ethylpyrrolidone; Amides such as dimethylformamide, diethylformamide and dimethylacetamide; Sulphoxides such as dimethyl sulfoxide; Ethers such as tetrahydrofuran, dioxane and 2-ethoxyethanol; Ketones such as methyl isobutyl ketone and cyclohexanone Aromatic hydrocarbons such as benzene and toluene; Amides such as β-alkoxypropionamide represented by “Examide” manufactured by Idemitsu Kosan Co., Ltd. are used.
Two or more of these solvents may be used in combination.

  The urethanization reaction of the present invention can be performed by adding a terminal terminator in order to adjust the molecular weight.

[Acrylic polymer (B)]
The acrylic polymer (B) indicates a polymer obtained by polymerizing “(meth) acrylic monomers” having one or more “(meth) acrylic groups”.
Here, the (meth) acryl group means a (meth) acryloyl group (an atomic group obtained by removing a hydroxyl group from (meth) acrylic acid, and the “(meth) acryl group” means “acryl group” and “methacryl group”. (Methacryl group) "is a general term.
The acrylic polymer (B) may contain a polymer composed of “a polymerizable monomer having no (meth) acryloyl group” (hereinafter referred to as a polymerizable monomer). The monomer and the polymerizable monomer may be copolymerized.

((Meth) acrylic monomer)
Examples of the (meth) acrylic monomer include:
2-ethylhexyl (meth) acrylate, methyl (meth) acrylate, butyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclo Pentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol-polypropylene glycol mono (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) Mono (meth) acrylate, poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate, metho (Meth) acrylic acid alkyl esters such as polyethylene glycol mono (meth) acrylate, octoxypolyethylene glycol-polypropylene glycol mono (meth) acrylate, lauroxy polyethylene glycol mono (meth) acrylate, stearoxy polyethylene glycol mono (meth) acrylate ;
Phenoxyethyl (meth) acrylate, nonylphenoxy polyethylene glycol mono (meth) acrylate, nonylphenoxy polypropylene glycol polyethylene glycol mono (meth) acrylate, phenoxypolyethylene glycol mono (meth) acrylate, phenoxypolypropylene glycol polyethylene glycol mono (meth) acrylate, etc. (Meth) acrylic acid aryl ester;
Ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) ) Acrylate, 1,6-hexanediol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol-polypropylene glycol di (meth) ) Acrylate, poly (ethylene glycol-tetramethylene glycol) di (meth) acrylate, poly (propylene glycol-tetramethylene glycol) Di (meth) acrylate, methoxy polyethylene glycol di (meth) acrylate, octoxy polyethylene glycol-polypropylene glycol di (meth) acrylate, lauroxy polyethylene glycol di (meth) acrylate, stearoxy polyethylene glycol di (meth) acrylate, nonylphenoxy Polyethylene glycol di (meth) acrylate, nonylphenoxy polypropylene glycol polyethylene glycol di (meth) acrylate, reaction product of 2 molecules of (meth) acrylic acid and 1 molecule of 1,6-hexanediol diglycidyl (eg, Nagase Chemtech) “DA-212”), a reaction product of two molecules of epoxy (meth) acrylic acid and one molecule of neopentyl glycol diglycidyl, two molecules of (meta Reaction product of acrylic acid and 1 molecule of bisphenol A diglycidyl (eg, “DA-250” manufactured by Nagase ChemteX Corp.) Reaction of 2 molecules of (meth) acrylic acid and diglycidyl derivative of propylene oxide adduct of bisphenol A Product: Reaction product of 2 molecules of (meth) acrylic acid and 1 molecule of diglycidyl phthalate (eg “DA-721” manufactured by Nagase Chemtech) 2 molecules of (meth) acrylic acid and 1 molecule of polyethylene Reaction product with glycol diglycidyl (eg, “DM-811”, “DM-832”, “DM-851” manufactured by Nagase Chemtech) 2 molecules (meth) acrylic acid and 1 molecule polypropylene glycol diglycidyl Reaction product of (meth) acrylic acid and polyol diglycidyl such as reaction product with glycidyl (meth) a Di (meth) acrylate esters such as adducts of acrylate and (meth) acrylic acid;
Trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene oxide (6 mol) modified trimethylolpropane tri Tri (meth) acrylic acid esters such as alkylene oxide-modified trimethylolpropane tri (meth) acrylate (Laromer (registered trademark) PO33F manufactured by BASF) such as (meth) acrylate (Laromar (registered trademark) LR8863 manufactured by BASF); penta Erythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethylene oxide (4 mol) Ritorutetora (meth) acrylate (Daicel Cytec, Ebecryl 40) tetra (meth) acrylic acid esters such as alkylene oxide modified pentaerythritol tetra (meth) acrylate and the like;
Penta (meth) acrylic acid esters such as dipentaerythritol penta (meth) acrylate;
Hexa (meth) acrylic esters such as dipentaerythritol hexa (meth) acrylate are used.
These (meth) acrylic monomers may be used in combination of two or more.

Examples of the “polymerizable monomer” include unsaturated hydrocarbon compounds such as propylene, butadiene, pentadiene, hexadiene and cyclopentadiene; aromatic compounds having an unsaturated group such as styrene and α-methylstyrene; vinylidene chloride, fluorine. Halogenated unsaturated hydrocarbon compounds such as vinylidene fluoride; carboxylic acid unsaturated esters such as vinyl acetate, allyl acetate and vinyl benzoate; amides having an unsaturated group such as N-vinylpyrrolidone.
In addition, these polymerizable monomers may use 2 or more types together.

  The acrylic polymer (B) of the present invention is preferably a polymer formed from at least one methacrylic ester monomer. Specifically, the “methacrylic ester polymer” or “methacrylic” “A copolymer of an acid ester and an acrylate ester” is more preferably used.

(Glass transition temperature of acrylic polymer (B))
The “glass transition temperature (Tg)” of the acrylic polymer (B) can be calculated from the weight ratio of the (meth) acrylic monomer of the acrylic polymer according to the following Fox formula.
[Fox equation]
1 / Tg = Σ (W _m / Tg _m )
(Wherein, W _m is the weight ratio of the (meth) acrylic monomer, Tg _m is the glass transition temperature of each (meth) acrylic monomer, m denotes the number of kinds of (meth) acrylic monomer.)

(Synthesis of acrylic polymer (B))
The acrylic polymer (B) comprises one or a plurality of (meth) acrylic monomers (in the presence of other polymerizable vinyl monomers if necessary), a (meth) acrylic monomer by a polymerization initiator, light, heat or the like. Can be produced by polymerizing.
In the aqueous composite resin dispersion of the present invention, since the polyurethane resin (A) contains the acrylic polymer (B), it is desirable to polymerize the (meth) acrylic monomer in the presence of the polyurethane resin (A). .

[Aqueous medium]
Examples of the aqueous medium include water such as clean water, ion exchange water, distilled water, and ultrapure water, and a mixed medium of water and a hydrophilic organic solvent.

Examples of the hydrophilic organic solvent include ketones such as acetone and ethyl methyl ketone; pyrrolidones such as N-methylpyrrolidone and N-ethylpyrrolidone; ethers such as diethyl ether and dipropylene glycol dimethyl ether; methanol, ethanol, Examples include alcohols such as n-propanol, isopropanol, ethylene glycol, and diethylene glycol; amides such as β-alkoxypropionamide represented by “Ecamide” manufactured by Idemitsu Kosan Co., Ltd.
The amount of the hydrophilic organic solvent in the aqueous medium is preferably 0 to 20% by mass.

[Synthesis of aqueous composite resin dispersion]
In the composite resin aqueous dispersion of the present invention, the polyurethane resin (A), the (meth) acrylic monomer, and the aqueous medium are mixed, and then the (meth) acrylic monomer is polymerized by a polymerization initiator, light, or a combination thereof. Can be produced by producing an acrylic polymer (B).
The reaction temperature in that case becomes like this. Preferably it is 30-100 degreeC.

(Polymerization initiator)
Examples of the polymerization initiator include persulfates such as ammonium persulfate, potassium persulfate, and sodium persulfate; 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvalero). Azo compounds such as nitrile); peroxides such as hydrogen peroxide, t-butyl hydroperoxide, benzoyl peroxide, lauroyl peroxide, and the like.
In addition, these polymerization initiators can use 2 or more types together, and can also be used as aqueous solution or an organic-solvent solution.

Moreover, it can also be used as a redox type | system | group initiator by using the said polymerization initiator and a reducing agent together, As a reducing agent, for example, sodium sulfite, sodium bisulfite, sodium thiosulfate, tartaric acid, L or D -Ascorbic acid etc. can be used.
In addition, these reducing agents can use 2 or more types together, and can also be used as aqueous solution or an organic-solvent solution.

  The amount of the polymerization initiator and the reducing agent used may be appropriately adjusted according to the required reaction rate (polymerization rate) and the state of heat generation during the polymerization, and does not impair the function and characteristics of the composite resin aqueous dispersion. , A polymerization initiator, a reducing agent, or a decomposition product thereof may be present.

  In order to suppress a rapid polymerization reaction, an emulsifier may be appropriately present.

In the composite resin aqueous dispersion of the present invention, the mass of the polyurethane resin (A) is 5 to 95% by mass with respect to the total mass of the polyurethane resin (A) and the acrylic polymer (B), more preferably. 10 to 90% by mass.
By setting it as this range, the adhesiveness to a to-be-coated base material improves.

  By the above, the composite resin aqueous dispersion of the present invention can be obtained. Depending on the purpose, a thickener, a photosensitizer, a curing catalyst, an ultraviolet absorber, a light stabilizer, an antifoaming agent, a plasticizer, and a surface conditioner. Agents, anti-settling agents, heat stabilizers, inorganic fillers, lubricants, colorants, silicone oils, foaming agents, flame retardants, and the like can be present.

  The aqueous composite resin dispersion of the present invention can be processed into molded articles such as artificial leather, synthetic leather, heat insulating material, cushioning material, adhesive, paint, coating agent, and film.

[Composition containing composite resin aqueous dispersion]
For example, a coating composition or a coating composition can be produced using the aqueous composite resin dispersion of the present invention.
Specifically, it can be produced by mixing the aqueous dispersion of the composite resin of the present invention, various additives, and, if necessary, the aqueous medium and other resins.

(Additive)
As the additive,
For example, colored pigments such as titanium oxide, zinc white, carbon black, molybdenum red, Prussian blue, cobalt blue, azo pigment, phthalocyanine pigment, quinacridone pigment, isoindoline pigment, selenium pigment, perylene pigment;
Extenders such as clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talc, silica, alumina white;
Luminous pigments such as aluminum, copper, zinc, brass, nickel, aluminum oxide, mica, aluminum oxide coated with titanium oxide or iron oxide, and mica coated with titanium oxide or iron oxide can be used.
Further, usual paint additives such as a thickener, a curing catalyst, an ultraviolet absorber, a light stabilizer, an antifoaming agent, a plasticizer, a surface conditioner, and an anti-settling agent can also be used.
In addition, these additives can use 2 or more types together.

Furthermore, the presence of a curing agent as an additive can improve the water resistance of the coating film, multilayer coating film, and coating film obtained from the composition.
As such a curing agent, for example, amino resins, polyisocyanates, blocked polyisocyanates, melamine resins, carbodiimides and the like can be used.
In addition, these hardening | curing agents can use 2 or more types together.

(Other resins)
Examples of the other resins include polyester resins, acrylic resins, polyether resins, polycarbonate resins, polyurethane resins, epoxy resins, alkyd resins, and polyolefin resins. From the viewpoint of dispersibility in aqueous media, It is desirable to have a hydrophilic group (for example, an acidic group).

(Coating substrate)
The aqueous composite resin dispersion of the present invention and the coating composition or coating composition containing the same are applied to an appropriate “substrate to be coated” (hereinafter sometimes simply referred to as a substrate) and dried. As a result, the base material can be coated (to form a coating film). At that time, the viscosity of the aqueous composite resin dispersion and the composition thereof can be appropriately adjusted.

As the substrate to be coated, for example,
Polymethyl methacrylate resin (PMMA), acrylonitrile-butadiene-styrene terpolymer (ABS), polycarbonate resin, polyamide resin, polyimide resin, polyurethane resin, polyurea resin, polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride Thermoplastic resins such as resins, polyvinyl acetate resins, phenol resins, epoxy resins, polyester resins, synthetic rubbers, natural rubbers and elastomers, thermosetting resins, synthetic resins and molded articles thereof;
Metal base materials such as iron, nickel, aluminum, copper, and lead, alloys containing these metals, various surface-treated metal base materials that have been subjected to plating and chemical conversion treatment, and molded articles thereof;
Building materials such as concrete, slate, tile, tile, glass, wooden building materials and molded articles thereof;
Synthetic fibers, glass fibers, carbon fibers, plant fibers, animal fibers, dietary fibers, and the like, and molded articles thereof may be mentioned. From the viewpoint of adhesion, polymethyl methacrylate resin (PMMA), acrylonitrile-butadiene-styrene An original copolymer (ABS) is preferably used.
In addition, these resins can use 2 or more types together.

As the coating law, a known method can be appropriately selected. For example, bell painting, spray painting, roll painting, shower painting, immersion painting, or the like is employed.
Moreover, although the thickness of a coating film is suitably selected according to a use, Preferably it is 1-100 micrometers, More preferably, it is 3-50 micrometers.

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

Synthesis Example 1 (Synthesis of polyurethane resin)
In a reaction vessel equipped with a stirrer, a reflux condenser and a thermometer, polycarbonate diol (ETERRNACOLL (registered trademark) UH-200, manufactured by Ube Industries, Ltd .; number average molecular weight 2000, hydroxyl value 57 mgKOH / g, 1,6-hexane (Polycarbonate diol obtained by reacting diol with dimethyl carbonate) 300 g, 2,2-dimethylolpropionic acid 16.3 g, and N-methylpyrrolidone 135 g were mixed in a nitrogen atmosphere. Next, 85.6 g of isophorone diisocyanate and 0.6 g of dibutyltin dilaurate were added and heated to 90 ° C. and reacted for 5 hours while stirring.
After completion of the reaction, 12.3 g of methylethylamine was added for neutralization, and the mixture was added to 816 g of water under strong stirring. Furthermore, an aqueous polyurethane resin dispersion (solid content: 30% by weight) was obtained by adding 34.7 g of a 35% by weight 2-methyl-1,5-pentanediamine aqueous solution.

Example 1 (Synthesis of aqueous composite resin dispersion)
In a reactor equipped with a stirrer and a heater, 500 g of the aqueous polyurethane resin dispersion obtained in Synthesis Example 1, 150 g of 2-ethylhexyl methacrylate, and 331 g of water were mixed and heated to 50 ° C. Subsequently, 15.0 g of a 1% by mass L-ascorbic acid aqueous solution and 4.2 g of a 7% by mass t-butyl hydroperoxide aqueous solution were added and reacted at 50 ° C. for 1 hour with stirring to obtain an aqueous composite resin dispersion 1. It was.
The glass transition temperature (Tg) of the acrylic polymer was −10 ° C.

Example 2 (Synthesis of aqueous composite resin dispersion)
In a reaction apparatus equipped with a stirrer and a heater, 700 g of the aqueous polyurethane resin dispersion obtained in Synthesis Example 1, 90 g of 2-ethylhexyl methacrylate, and 199 g of water were mixed and heated to 50 ° C. Next, 9.0 g of a 1% by mass L-ascorbic acid aqueous solution and 2.5 g of a 7% by mass t-butyl hydroperoxide aqueous solution were added and reacted at 50 ° C. for 1 hour with stirring to obtain an aqueous composite resin dispersion 2. It was.
The glass transition temperature (Tg) of the acrylic polymer was −10 ° C.

Example 3 (Synthesis of composite resin aqueous dispersion)
In a reactor equipped with a stirrer and a heater, 300 g of the aqueous polyurethane resin dispersion obtained in Synthesis Example 1, 210 g of 2-ethylhexyl methacrylate, and 463.7 g of water were mixed and heated to 50 ° C. Subsequently, 21.0 g of a 1% by mass L-ascorbic acid aqueous solution and 6.0 g of a 7% by mass t-butyl hydroperoxide aqueous solution were added and reacted at 50 ° C. for 1 hour with stirring to obtain an aqueous composite resin dispersion 3. It was.
The glass transition temperature (Tg) of the acrylic polymer was −10 ° C.

Example 4 (Synthesis of composite resin aqueous dispersion)
A reactor equipped with a stirrer and a heater was charged with 500 g of the aqueous polyurethane resin dispersion obtained in Synthesis Example 1, 150 g of a mixture of 2-ethylhexyl methacrylate and methyl methacrylate (88/12 (mass ratio)), and 331 g of water. Mix and warm to 50 ° C. Next, 15.0 g of a 1% by mass L-ascorbic acid aqueous solution and 4.2 g of a 7% by mass t-butyl hydroperoxide aqueous solution were added, and the mixture was reacted at 50 ° C. for 1 hour with stirring to obtain an aqueous composite resin dispersion 4. It was.
The glass transition temperature (Tg) of the acrylic polymer was 0 ° C.

Example 5 (Synthesis of aqueous composite resin dispersion)
In a reaction apparatus equipped with a stirrer and a heater, 500 g of the aqueous polyurethane resin dispersion obtained in Synthesis Example 1, 150 g of isobornyl methacrylate, and 331 g of water were mixed and heated to 50 ° C. Subsequently, 15.0 g of a 1% by mass ascorbic acid aqueous solution and 4.2 g of a 7% by mass t-butyl hydroperoxide aqueous solution were added and reacted at 50 ° C. for 1 hour with stirring to obtain an aqueous composite resin dispersion 5.
The glass transition temperature (Tg) of the acrylic polymer was 180 ° C.

(Synthesis and evaluation of laminates)
After the composite resin aqueous dispersions obtained in Synthesis Example 1 and Examples 1 to 5 were dried on polymethyl methacrylate resin (manufactured by Engineering Test Service Co., Ltd.), the film thickness after drying was 10 μm (bar coater # 20 ) And dried by heating at 80 ° C. for 30 minutes.
Subsequently, a cross-cut peel test was performed using the obtained coating film. The coating was cut at an interval of 20 mm × 20 mm at intervals of 2 mm in length and width, and after the adhesive tape was applied, the state when peeled was evaluated according to the following criteria.
5: No peeling of coating film 4: Part of coating film (less than 10%) peeled 3: Part of coating film (less than 30%) peeled 2: Part of coating film (30% or more) peeled 1 : The entire surface of the coating film was peeled. The results are shown in Table 1.

  From the above results, it was found that the aqueous composite resin dispersion of the present invention showed excellent adhesion to the substrate to be coated.

  The present invention relates to a novel composite resin aqueous dispersion. Since the aqueous composite resin dispersion of the present invention is excellent in adhesion to a substrate to be coated, it can be used as a material for coating various substrates.

Claims (7)

In the composite resin aqueous dispersion in which the polyurethane resin (A) and the acrylic polymer (B) are dispersed in an aqueous medium, at least from the vinyl polymer (B) encapsulated in the polyurethane resin (A). Become
The polyurethane resin (A) includes at least a repeating unit represented by the following formula (1), formula (2), and formula (3),
The composite resin aqueous dispersion, wherein a mass of the polyurethane resin (A) is 5 to 95% by mass with respect to a total mass of the polyurethane resin (A) and the acrylic polymer (B). .

(In the formula, Z represents a linear divalent aliphatic hydrocarbon group having 2 to 12 carbon atoms or a divalent branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, and n represents a formula The repeating unit of (1) is shown.
R is a divalent linear aliphatic hydrocarbon group having 2 to 12 carbon atoms, a divalent branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, or a divalent cyclic group having 6 to 18 carbon atoms. An aliphatic hydrocarbon group or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms is shown.
AG represents an acidic group, and X represents a linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms. )   The aqueous composite resin dispersion according to claim 1, wherein the acrylic polymer (B) is a polymer formed from at least one methacrylic acid ester monomer.   The aqueous composite resin dispersion according to claim 2, wherein the polymer formed from at least one methacrylic acid ester monomer is a methacrylic acid ester polymer or a copolymer of a methacrylic acid ester and an acrylate ester.   In a cross-cut peel test of a coating film obtained by coating on a polymethyl methacrylate resin so that the film thickness after drying is 10 μm and heating and drying at 80 ° C. for 30 minutes, there is no peeling of the coating film The composite resin aqueous dispersion according to any one of claims 1 to 3.   The coating composition containing the composite resin aqueous dispersion of any one of Claims 1-4.   The coating composition containing the composite resin aqueous dispersion of any one of Claims 1-4.   A laminate obtained by curing a composite resin aqueous dispersion or a composition containing the composite resin aqueous dispersion on a substrate to be coated.