JP6565337B2 - Composite resin aqueous dispersion and use thereof - Google Patents

Description

  The present invention relates to an aqueous composite resin dispersion in which a composite resin containing polyurethane and a vinyl polymer is dispersed in an aqueous medium, and use thereof.

  Polycarbonate polyol is a useful compound that can be used as a raw material for polyurethane resins, and can react with isocyanate compounds to produce polyurethane resins used in hard foams, flexible foams, paints, adhesives, synthetic leather, ink binders, and the like. it can. A coating film obtained by applying an aqueous polyurethane resin dispersion using polycarbonate polyol as a raw material is known to have excellent light resistance, weather resistance, heat resistance, hydrolysis resistance, and oil resistance (Patent Documents). 1).

  Among them, a coating film obtained by applying an aqueous urethane resin dispersion using an aliphatic polycarbonate polyol is known to be used as an undercoat agent because of improved adhesion to a substrate and blocking resistance. (See Patent Document 2). However, when only the aliphatic polycarbonate polyol is used as a raw material, the hardness and chemical resistance of the coating film obtained from the aqueous polyurethane resin dispersion are, for example, automotive interior / exterior materials, mobile phone casings, home appliance casings. , The problem that it is not sufficient in the field of paints and coatings for synthetic resin moldings such as personal computer casings, decorative films, optical films, synthetic leather, genuine leather, flooring, etc. was there.

  In order to improve the hardness and durability of the coating film, an aqueous polyurethane resin dispersion using a polycarbonate polyol having an alicyclic structure has also been generally proposed (see Patent Documents 3, 4 and 5). There was a problem that the sex was not enough.

  Water-based polyurethane resin and vinyl polymer using polycarbonate polyol having an alicyclic structure for the purpose of increasing adhesion to resin base materials such as ABS (acrylonitrile-butadiene-styrene copolymer) resin and tensile strength and hardness of the coating film An aqueous dispersion of a polyurethane- (meth) acrylic polymer composite resin in which is combined is reported (see Patent Document 6). Compounding is performed so that polyurethane is 50% by mass and vinyl polymer is 50% by mass with respect to the total mass of polyurethane and vinyl polymer, but there is a problem that the alcohol resistance is not sufficient.

JP-A-10-120757 JP 2005-281544 A JP-A-6-248046 International Publication No. 2009/145242 International Publication No. 2009/004951 JP 2010-150519 A

  An object of this invention is to provide the composite resin aqueous dispersion which gives the coating film excellent in alcohol resistance.

  As a result of various studies to overcome the problems of the prior art, the present inventors have found that the composite resin is an aqueous dispersion in which at least the composite resin is dispersed in an aqueous medium. Comprises at least a polyurethane resin (A) and a vinyl polymer (B) encapsulated in the polyurethane resin (A), and the polyurethane resin (A) comprises at least a polycarbonate polyol (a ), An acidic group-containing polyol (b), and a polyisocyanate (c), which are obtained by reacting the polyurethane resin (A) and the vinyl polymer (B) with respect to the total mass. The present invention has obtained the knowledge that the problem can be solved by using a composite resin aqueous dispersion characterized in that the mass of the polyurethane resin (A) is 70 to 90% by mass. Led was.

  The present invention (1) is a composite resin aqueous dispersion in which at least a composite resin is dispersed in an aqueous medium, and the composite resin includes at least a polyurethane resin (A) and the polyurethane resin (A). The polyurethane resin (A) comprises at least a polycarbonate polyol (a) having an alicyclic structure, an acidic group-containing polyol (b), and a polyisocyanate (c). The polyurethane resin (A) has a mass of 70 to 90% by mass with respect to the total mass of the polyurethane resin (A) and the vinyl polymer (B). The present invention relates to an aqueous composite resin dispersion.

  In the present invention (2), the polyurethane resin (A) comprises a polycarbonate polyol (a) having an alicyclic structure, an acidic group-containing polyol (b), a polyisocyanate (c), and a chain extender (d). It is related with the composite resin aqueous dispersion of this invention (1) which is a polyurethane resin obtained by making it react.

  The present invention (3) relates to a coating composition containing the aqueous composite resin dispersion of the present invention (1) or (2).

  This invention (4) relates to the coating agent composition containing the composite resin aqueous dispersion of this invention (1) or (2).

  ADVANTAGE OF THE INVENTION According to this invention, the composite resin aqueous dispersion which provides the coating film excellent in the alcohol-resistant characteristic can be provided.

The present invention is an aqueous composite resin dispersion in which at least a composite resin is dispersed in an aqueous medium,
The composite resin comprises at least a polyurethane resin (A) and a vinyl polymer (B) encapsulated in the polyurethane resin (A),
The polyurethane resin (A) is obtained by reacting at least a polycarbonate polyol (a) having an alicyclic structure, an acidic group-containing polyol (b), and a polyisocyanate (c),
The present invention relates to an aqueous composite resin dispersion in which the mass of the polyurethane resin (A) is 70 to 90% by mass with respect to the total mass of the polyurethane resin (A) and the vinyl polymer (B). .

<Polyurethane resin (A)>
The polyurethane resin (A) used in the present invention comprises at least a polycarbonate polyol (a) having an alicyclic structure, an acidic group-containing polyol (b), a polyisocyanate (

obtained by reacting with c).

  Furthermore, it may be a polyurethane resin (A) obtained by reacting a polyol other than the polycarbonate polyol (a) having an alicyclic structure and the acidic group-containing polyol (b), or a chain extender (d).

<< Polycarbonate polyol (a) having an alicyclic structure >>
As the polycarbonate polyol used in the present invention, it is preferable to use a polycarbonate polyol having an alicyclic structure in the main chain from the viewpoint of obtaining a coating film having excellent storage stability of the composite resin aqueous dispersion and excellent adhesion. The polycarbonate polyol (a) having an alicyclic structure in the main chain (hereinafter sometimes referred to as “polycarbonate polyol (a)” or “(a)”) is, for example, a polyol having an alicyclic structure in the main chain. And a polycarbonate polyol obtained by reacting a carbonic acid ester with a carbonate ester, and a copolymer polycarbonate polyol obtained by reacting a polyol having an alicyclic structure in the main chain with another polyol and a carbonate ester.

  The number average molecular weight of the polycarbonate polyol (a) is preferably 400 to 3000, more preferably 400 to 1500, and particularly preferably 500 to 1300.

  If the number average molecular weight of the polycarbonate polyol (a) is too small, the performance as a soft segment is inferior, and cracks tend to occur when a coating film is formed using the obtained composite resin aqueous dispersion. If the number average molecular weight of the polycarbonate polyol (a) is too large, the reactivity between the polycarbonate polyol (a) and the isocyanate compound is reduced, and the production process of the urethane prepolymer takes time, or the reaction does not proceed sufficiently. The viscosity of the polycarbonate polyol (a) may be increased and handling may be difficult.

In the present invention, the number average molecular weight was calculated by the following formula by measuring the hydroxyl value based on JIS K 1557 and measuring the end group.
[Equation 1]
Number average molecular weight = (56.1 × 1000 × 2) / hydroxyl value In the above formula, the unit of the hydroxyl value is [mgKOH / g].

The polyol having an alicyclic structure in the main chain is not particularly limited. For example, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,3-cyclopentanediol 1,4-cycloheptanediol, 2,5-bis (hydroxymethyl) -1,4-dioxane, 2,7-norbornanediol, tetrahydrofuran dimethanol, 1,4-bis (hydroxyethoxy) cyclohexane, tricyclo [5 .2.1.0 ^2,6 ] diols having an alicyclic structure in the main chain such as structural isomers of tricyclodecane dimethanol represented by decanedimethanol or a mixture thereof, among others. 1,4-cyclohexanedimethanol is preferred because of its ease.

  The other polyol is not particularly limited, and examples thereof include an aliphatic polyol, a polyol having an alicyclic structure in a side chain, an aromatic polyol, a polyester polyol, and a polyether polyol. In the present specification, the alicyclic structure includes those having a hetero atom such as an oxygen atom or a nitrogen atom in the ring.

  The aliphatic polyol is not particularly limited, and examples thereof include an aliphatic polyol having 3 to 12 carbon atoms. Specifically, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9 -Linear aliphatic diol such as nonanediol; 2-methyl-1,3-propanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-1 Branched aliphatic diols such as 1,9-nonanediol; polyfunctional alcohols having 3 or more functional groups such as 1,1,1-trimethylolpropane and pentaerythritol.

  The aromatic polyol is not particularly limited, and examples thereof include 1,4-benzenedimethanol, 1,3-benzenedimethanol, 1,2-benzenedimethanol, 1,8-naphthalenediethanol, and 2,3-naphthalene. Examples include dimethanol and 2,7-naphthalenediethanol.

  The polyester polyol is not particularly limited. For example, a polyester polyol of hydroxycarboxylic acid and diol such as a polyester polyol of 6-hydroxycaproic acid and hexanediol, a dicarboxylic acid such as polyester polyol of adipic acid and hexanediol, and the like. Examples thereof include polyester polyols with diols.

  The polyether polyol is not particularly limited, and examples thereof include polyethylene glycol (for example, diethylene glycol, triethylene glycol, tetraethylene glycol and the like), polyalkylene glycol such as polypropylene glycol and polytetramethylene glycol, and the like.

  The carbonate is not particularly limited, and examples thereof include aliphatic carbonates such as dimethyl carbonate and diethyl carbonate, aromatic carbonates such as diphenyl carbonate, and cyclic carbonates such as ethylene carbonate. In addition, phosgene or the like capable of producing a polycarbonate polyol can be used. Of these, aliphatic carbonates are preferred and dimethyl carbonate is particularly preferred because of the ease of production of the polycarbonate polyol.

  As a method for producing a polycarbonate polyol from the polyol and the carbonate ester, for example, a carbonate ester and a polyol having an excess number of moles relative to the number of moles of the carbonate ester are added in a reactor, and the temperature is 160 to 200 ° C. Examples include a method of reacting at a pressure of about 50 mmHg for 5 to 6 hours and further reacting at 200 to 220 ° C. for several hours at a pressure of several mmHg or less. In the reaction, it is preferable to carry out the reaction while extracting by-produced alcohol out of the system. At that time, if 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 reaction, a catalyst such as titanium tetrabutoxide may be used.

  The alicyclic structure content in the polycarbonate polyol (a) is preferably 20 to 65% by mass, and more preferably 30 to 55% by mass. When the alicyclic structure content is smaller than this range, the alcohol resistance of the coating film may be lowered. On the other hand, when the content of the alicyclic structure is large, the viscosity of the urethane prepolymer at the time of producing the composite resin aqueous dispersion becomes high and handling becomes difficult, or the storage stability of the composite resin aqueous dispersion decreases. There is.

  Here, the alicyclic structure content in the polycarbonate polyol (a) refers to the mass ratio of the alicyclic structure group in the polycarbonate polyol (a). The alicyclic structure group is a portion obtained by removing two hydrogen atoms from cycloalkane.

  For example, in the case of 1,4-cyclohexanedimethanol, the alicyclic structure group is a portion obtained by removing two hydrogen atoms from cyclohexane.

<< Acid group-containing polyol (b) >>
The acidic group-containing polyol (b) contains two or more hydroxyl groups and one or more acidic groups in one molecule. Examples of the acidic group include a carboxy group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group. The acidic group-containing polyol (b) preferably contains a compound having two hydroxyl groups and one carboxy group in one molecule. An acidic group containing polyol (b) may be used independently and may use multiple types together.

  Specific examples of the acidic group-containing polyol (b) include dimethylol alkanoic acids such as 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid, N, N-bis (hydroxyethyl) glycine, N, N-bis (hydroxyethyl) alanine, 3,4-dihydroxybutanesulfonic acid, 3,6-dihydroxy-2-toluenesulfonic acid and the like can be mentioned. Among these, from the viewpoint of easy availability, dimethylol alkanoic acid having 4 to 12 carbon atoms containing two methylol groups is preferable. Among dimethylolalkanoic acids, 2,2-dimethylolpropionic acid and / or 2,2 -Dimethylolbutanoic acid is more preferred, and 2,2-dimethylolpropionic acid is particularly preferred.

  In the present invention, the total number of hydroxyl equivalents of the polyol (a) and the acidic group-containing polyol (b) is preferably 120 to 600. If the number of hydroxyl equivalents is within this range, it is easy to produce an aqueous composite resin dispersion containing the obtained polyurethane resin, and a coating film excellent in hardness is easily obtained. From the viewpoint of the storage stability of the resulting aqueous composite resin dispersion and the hardness of the coating film obtained by coating, the hydroxyl equivalent number is preferably 130 to 600, more preferably 150 to 500, and particularly preferably 170 to 400. is there.

The number of hydroxyl equivalents can be calculated by the following formulas (1) and (2).
Number of hydroxyl equivalents of each polyol = molecular weight of each polyol / number of hydroxyl groups of each polyol (1)
Total number of hydroxyl equivalents of polyol = M / total number of moles of polyol (2)
In the case of the polyurethane resin (A), in the formula (2), M is [[number of hydroxyl equivalents of polyol (a) × number of moles of polyol (a)] + [number of hydroxyl equivalents of acidic group-containing polyol (b) × The number of moles of the acidic group-containing polyol (b)]].

<< Other polyols >>
In addition to the polycarbonate polyol (a) and the acidic group-containing polyol (b), other polyols can be used. Examples of other polyols include polymer polyols such as polymer polyols and low molecular polyols. Examples of the polymer polyol include those having a number average molecular weight of 400 to 6000. The polyol may be a diol or a trihydric or higher polyhydric alcohol. Other polyols may be used alone or in combination of two or more. From the viewpoint that the hardness of the coating film becomes high, a low molecular polyol is preferable, and a low molecular diol is particularly preferable.

  The polymer polyol is not particularly limited, and polyester polyol, polyether polyol, (meth) acryl polyol, polydiene polyol, and polycarbonate polyol having no alicyclic structure in the main chain can be suitably used.

  The polyester polyol, not particularly limited, for example, polyethylene adipate polyol, polybutylene adipate polyol, polyethylene butylene adipate polyol, polyhexamethylene isophthalate adipate polyol, polyethylene succinate polyol, polybutylene succinate polyol, polyethylene sebacate polyol, Examples thereof include polybutylene sebacate polyol, poly-ε-caprolactone polyol, poly (3-methyl-1,5-pentylene adipate) polyol, polycondensate of 1,6-hexanediol and dimer acid.

  The polyether polyol is not particularly limited, and examples thereof include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, a random copolymer of ethylene oxide and butylene oxide, a block copolymer, and the like. Furthermore, a polyether polyester polyol having an ether bond and an ester bond can also be used.

  The polydiene polyol is not particularly limited, and examples thereof include polydiene polyols containing units derived from butadiene, isoprene, 1,3-pentadiene, chloroprene, cyclopentadiene, and the like. Specific examples of the polydiene polyol include, for example, hydroxyl-terminated liquid polybutadiene (“Poly bd” manufactured by Idemitsu Kosan Co., Ltd.), bifunctional hydroxyl-terminated liquid polybutadiene (“KRASOL” manufactured by Idemitsu Kosan Co., Ltd.), and hydroxyl-terminated liquid polyisoprene. (“Poly ip” manufactured by Idemitsu Kosan Co., Ltd.), hydroxyl-terminated liquid polyolefin (“Ebol” manufactured by Idemitsu Kosan Co., Ltd.), and the like.

The poly (meth) acrylic polyol is not particularly limited. For example, a polymer of a (meth) acrylic monomer having a hydroxyl group or a copolymer of a (meth) acrylic monomer having a hydroxyl group and a (meth) acrylic monomer having no hydroxyl group. A polymer etc. are mentioned.
In addition, about description of "(meth) acryl monomer" in this specification, "(meth) acrylic acid", "(meth) acrylate" etc., all have the compound which has acryloyl group, and the compound which has methacryloyl group. It is a concept to be included and may have either an acryloyl group, a methacryloyl group, or both.

  As the (meth) acrylic monomer having a hydroxyl group and the (meth) acrylic monomer having no hydroxyl group, one type of monomer may be used alone, or a plurality of types of monomers may be used in combination.

  Examples of the monomer polymerization method include emulsion polymerization, suspension polymerization, dispersion polymerization, solution polymerization and the like. In emulsion polymerization, it can also be polymerized stepwise.

  Examples of the (meth) acrylic monomer having a hydroxyl group include (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid-2-hydroxybutyl, and glycerin ( (Meth) acrylic acid monoester, (meth) acrylic acid diester of glycerol, (meth) acrylic acid monoester of trimethylolpropane, (meth) acrylic acid ester having a hydroxyl group such as (meth) acrylic acid diester of trimethylolpropane; Examples include (meth) acrylamide having a hydroxyl group such as N-methylolacrylamide, vinyl alcohol and the like.

  Examples of the (meth) acrylic monomer having no hydroxyl group include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylate-n-butyl, (meth) Acrylic acid esters such as 2-ethylhexyl acrylate; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, and itaconic acid; unsaturated amides such as (meth) acrylamide and diacetone acrylamide; glycidyl methacrylate, styrene, Examples include vinyl toluene, vinyl acetate, acrylonitrile, dibutyl fumarate and the like.

  The polycarbonate polyol having no alicyclic structure in the main chain is not particularly limited, and examples thereof include aliphatic polycarbonate diols such as polytetramethylene carbonate diol, polypentamethylene carbonate diol, and polyhexamethylene carbonate diol; -Aromatic polycarbonate diol such as xylylene carbonate diol; copolymer polycarbonate diol which is a reaction product of multiple types of aliphatic diol and carbonate; reaction product of aliphatic diol, aromatic diol and carbonate A copolymer polycarbonate diol such as a copolymer polycarbonate diol or a copolymer polycarbonate diol which is a reaction product of an aliphatic diol, a dimer diol and a carbonate can be used.

  Examples of the copolymer polycarbonate diol include copolymer polycarbonate diol which is a reaction product of 1,3-propanediol, 1,4-butanediol and carbonate, 1,4-butanediol and 1,5-pentane. Copolymer polycarbonate diol which is a reaction product of diol and carbonate ester, Copolymer polycarbonate diol which is a reaction product of 1,5-pentanediol, 1,6-hexanediol and carbonate ester, 1,4-butanediol Copolymer polycarbonate diol which is a reaction product of 1,6-hexanediol and carbonate, copolymer polycarbonate diol which is a reaction product of 1,3-propanediol, 1,6-hexanediol and carbonate, etc. Is mentioned.

  The low molecular polyol is not particularly limited, and examples thereof include those having a number average molecular weight of 60 or more and less than 400. For example, ethylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol Aliphatic diol having 2 to 9 carbon atoms such as diethylene glycol, triethylene glycol and tetraethylene glycol; 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,4-bis (Hydroxyethyl) cyclohexane, 2,7-norbornanediol, tetrahydrofuran Diols having an alicyclic structure having 6 to 12 carbon atoms such as methanol and 2,5-bis (hydroxymethyl) -1,4-dioxane; 1,4-benzenedimethanol, 1,3-benzenedimethanol, 1, And aromatic diols such as 4-dihydroxybenzene. Further, as the low molecular weight polyol, a trifunctional or higher functional low molecular weight polyhydric alcohol such as trimethylolpropane, pentaerythritol, sorbitol and the like may be used.

  It is preferable that the ratio of the other polyol with respect to a polycarbonate polyol (a) is 40 mass% or less with respect to the polycarbonate polyol which has an alicyclic structure. If it is this range, it will be easy to avoid that the alcohol resistance of the coating film obtained falls or manufacture of a composite resin aqueous dispersion becomes difficult. The ratio of the other polyol is more preferably 20% by mass or less based on the polycarbonate polyol having an alicyclic structure.

<< Polyisocyanate (c) >>
Although it does not restrict | limit especially as polyisocyanate (c), For example, aromatic polyisocyanate, aliphatic polyisocyanate, alicyclic polyisocyanate etc. are mentioned.

  Specific examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate (TDI), 2,6-tolylene diisocyanate, 4,4′-. Diphenylmethane diisocyanate (MDI), 2,4′-diphenylmethane diisocyanate, 4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4, 4'-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4 ', 4' '-triphenylmethane triisocyanate, m-isocyanatophenylsulfonyl isocyanate, p-isocyanatophenylsulfonyl isocyanate and the like. .

  Specific examples of the aliphatic polyisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate. Lysine diisocyanate, 2,6-diisocyanatomethyl caproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexano Eate.

  Specific examples of the alicyclic polyisocyanate include isophorone diisocyanate (IPDI), 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2 -Isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate and the like.

  The number of isocyanato groups per molecule of the polyisocyanate is usually two, but a polyisocyanate having three or more isocyanato groups such as triphenylmethane triisocyanate is also used as long as the polyurethane resin in the present invention does not gel. be able to.

  Among the polyisocyanates, alicyclic polyisocyanates having an alicyclic structure are preferable from the viewpoint of increasing the hardness after curing with active energy rays (for example, ultraviolet rays), and isophorone diisocyanate is preferable because the reaction can be easily controlled. (IPDI), 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI) is particularly preferred.

  Polyisocyanate may be used independently and may use multiple types together.

<< Chain extender (d) >>
In some cases, the polyurethane resin (A) in the present invention can be a polyurethane resin further reacted with a chain extender (d). Examples of the chain extender (d) include ethylenediamine, 1,4-tetramethylenediamine, 2-methyl-1,5-pentanediamine, 1,4-butanediamine, 1,6-hexamethylenediamine, 1, 4-hexamethylenediamine, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, 1,3-bis (aminomethyl) cyclohexane, xylylenediamine, piperazine, 2,5-dimethylpiperazine, hydrazine, adipoyl Amine compounds such as dihydrazide, diethylenetriamine, triethylenetetramine, diol compounds such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, and polyethylene glycol Polyalkyl In view of the hardness and alcohol resistance of the resulting coating film, the chain extender (d) is preferably an organic compound, more preferably a polyamine compound, A polyamine compound having a group is particularly preferred. These may be used alone or in combination of two or more.

<Vinyl polymer (B)>
The composite resin aqueous dispersion of the present invention contains a vinyl polymer (B). The vinyl polymer (B) is not particularly limited as long as it is a product obtained by addition polymerization of a polymerizable vinyl monomer having one or more kinds of vinyl groups.

  As the polymerizable vinyl monomer, one or more kinds of polymerizable vinyl monomers can be used. As said polymerizable vinyl monomer, it is preferable that 50 mass% or more is (meth) acrylic acid or / and (meth) acrylic acid ester.

  Examples of the (meth) acrylic acid ester include mono (meth) acrylic acid alkyl ester, mono (meth) acrylic acid aryl ester, poly (meth) acrylic acid alkyl ester, poly (meth) acrylic acid aryl ester, and the like.

  Examples of the mono (meth) acrylic acid alkyl ester include 2-ethylhexyl (meth) acrylate, methyl (meth) acrylate, butyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl ( (Meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (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, methoxy polyethylene glycol mono (meth) acrylate, octoxy polyethylene glycol-polypropylene glycol mono (meth) acrylate, lauroxy polyethylene glycol mono (meth) acrylate, stearoxy polyethylene glycol mono (meta) ) Acrylate and the like.

Examples of the mono (meth) acrylic acid aryl ester include phenoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol mono (meth) acrylate, nonylphenoxypolypropylene glycol polyethylene glycol mono (meth) acrylate, phenoxypolyethylene glycol mono (meth) acrylate, Mention may be made of phenoxy polypropylene glycol polyethylene glycol mono (meth) acrylate and the like.

  Examples of the poly (meth) acrylic acid alkyl ester and poly (meth) acrylic acid aryl ester include di (meth) acrylate, tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (meth) acrylate. Etc.

  Examples of the di (meth) acrylate include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and 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, methoxypolyethyleneglycol di (meth) acrylate, octoxypolyethyleneglycol-polypropyleneglycoldi (meth) acrylate, lauroxypolyethyleneglycoldi (meth) acrylate, stearoxypolyethyleneglycoldi Reaction of (meth) acrylate, nonylphenoxypolyethylene glycol di (meth) acrylate, nonylphenoxypolypropylene glycol polyethylene glycol di (meth) acrylate, 2 molecules of (meth) acrylic acid and 1 molecule of 1,6-hexanediol diglycidyl Product (for example, “DA-212” manufactured by Nagase ChemteX Corporation), 2 molecules of epoxy (meth) acrylic acid and 1 molecule of neopentyl glycol di Reaction product with ricidyl, reaction product of 2 molecules of (meth) acrylic acid and 1 molecule of bisphenol A diglycidyl (eg “DA-250” manufactured by Nagase Chemtech), 2 molecules of (meth) acrylic acid and A reaction product of a propylene oxide adduct of bisphenol A with a diglycidyl compound, a reaction product of two molecules of (meth) acrylic acid and one molecule of diglycidyl phthalate (for example, “DA-721” manufactured by Nagase Chemtech) Reaction product of two molecules of (meth) acrylic acid and one molecule of polyethylene glycol diglycidyl (for example, “DM-811”, “DM-832”, “DM-851” manufactured by Nagase Chemtech) (Meth) acrylic acid and polyol diglycy such as reaction product of (meth) acrylic acid and 1 molecule of polypropylene glycol diglycidyl Reaction products with jill, adducts of glycidyl (meth) acrylate and (meth) acrylic acid, and the like.

  Examples of the tri (meth) acrylate include trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Alkylene oxide-modified trimethylolpropane tri (meth) acrylate (BASF's Laromer (registered trademark) PO33F) such as ethylene oxide (6 mol) modified trimethylolpropane tri (meth) acrylate (BASF's Laromer (registered trademark) LR8863) Is mentioned.

  Examples of the tetra (meth) acrylate include pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethylene oxide (4 mol) modified pentaerythritol tetra (meth) acrylate (Daicel Cytec, Ebecryl 40), and the like. And alkylene oxide-modified pentaerythritol tetra (meth) acrylate.

  Examples of penta (meth) acrylate include dipentaerythritol penta (meth) acrylate.

  Examples of hexa (meth) acrylate include dipentaerythritol hexa (meth) acrylate.

  A well-known thing can be used as a (meth) acrylate compound of polymers. Examples of the (meth) acrylate compounds of the polymers include poly (meth) acrylates such as di (meth) acrylate, tri (meth) acrylate, and tetra (meth) acrylate in addition to mono (meth) acrylate.

  Other polymerizable vinyl monomers include methacrylamide derivatives, acrylonitrile, vinylidene chloride, vinylidene fluoride, vinyl esters such as vinyl acetate, N-vinylamides such as N-vinylpyrrolidone, styrene such as styrene and α-methylstyrene. Derivatives, 1,3-diene derivatives such as 1,3-butadiene and the like can be mentioned.

  Only one kind of these polymerizable vinyl monomers may be used, or a plurality of kinds may be used in combination.

  The vinyl polymer (B) can be appropriately selected according to the intended use of the composite resin aqueous dispersion. The glass transition temperature (Tg) of such a vinyl polymer (B) is not particularly limited, but in addition to being excellent in alcohol resistance, it is improved in adhesion to the electrodeposition plate, for example, 20 ° C. The following can be used suitably. Furthermore, what is -10 degrees C or less, -20 degrees C or less, and -50 degrees C or less can be used more suitably. Moreover, in addition to the point which is excellent in alcohol resistance, that whose glass transition temperature (Tg) is -10 degreeC or more can be used suitably from the point etc. which a coating film of high hardness is obtained. Furthermore, the thing of 20 degreeC or more, 50 degreeC or more, 70 degreeC or more, and 100 degreeC or more can be used more suitably.

The glass transition temperature (Tg) of the vinyl polymer (B) can be calculated from the following formula (3).
1 / Tg = Σ (mi / Tgi) (3)
Tg: Glass transition temperature of polymer mi: Weight fraction of polymerizable vinyl monomer i component Tgi: Glass transition temperature of homopolymer of polymerizable vinyl monomer i component (K)

  The ratio of the polyurethane resin (A) to the total mass of the polyurethane resin (A) and the vinyl polymer (B) is 70 to 90% by mass. If the proportion of the polyurethane resin (A) is too small or too large, the alcohol resistance of the resulting coating film is lowered.

  In the aqueous composite resin dispersion of the present invention, the polyurethane resin (A) and the vinyl polymer (B) are dispersed in an aqueous medium, and the vinyl polymer (B) is included in the polyurethane resin (A). Has been. Examples of the aqueous medium include water and a mixed medium of water and a hydrophilic organic solvent.

  Examples of the water include clean water, ion exchange water, distilled water, and ultrapure water. Among them, it is preferable to use ion-exchanged water in consideration of the availability and the fact that the particles become unstable due to the influence of salt.

  Examples of the hydrophilic organic solvent include lower monohydric alcohols such as methanol, ethanol, and propanol; polyhydric alcohols such as ethylene glycol and glycerol; N-methylmorpholine, dimethyl sulfoxide, dimethylformamide, N-methylpyrrolidone, and the like. Aprotic hydrophilic organic solvents and the like. The amount of the hydrophilic organic solvent in the aqueous medium is preferably 0 to 20% by mass.

  In the present invention, the acid value of the aqueous composite resin dispersion is preferably 80 mgKOH / g or less, more preferably 8 to 70 mgKOH / g, and still more preferably 10 to 60 mgKOH / g. If it is this range, it will be easy to ensure the dispersibility to an aqueous medium and the water resistance of a coating film.

Specifically, the acid value can be derived from the following formula (4).
[Acid value of aqueous composite resin dispersion] = [number of moles of acidic groups in acidic group-containing polyol (b)] × 56.11 / [mass of total resin in aqueous composite resin dispersion (g)] (4)
The “mass of the total resin content of the composite resin aqueous dispersion” is the mass of the resin containing the polyurethane resin (A) and the vinyl polymer (B). When the composite resin aqueous dispersion contains a resin other than the polyurethane resin (A) and the vinyl polymer (B), the mass of the resin is also “the mass of the total resin of the composite resin aqueous dispersion”. include.

<Composite resin aqueous dispersion>
In the aqueous composite resin dispersion of the present invention, the solid content is preferably 1 to 70% by mass, and more preferably 5 to 50% by mass of the entire aqueous composite resin dispersion.

  In the present invention, the solid content of the aqueous composite resin dispersion is a component remaining as a coating film after the aqueous composite resin dispersion is applied to a substrate, dried, and crosslinked by light irradiation or / and heating. Aqueous media and neutralizing agents are not included in the solid content.

  Moreover, the composite resin aqueous dispersion of this invention may contain the polymerization initiator mentioned later.

<Method for producing composite resin aqueous dispersion>
Next, the manufacturing method of the composite resin aqueous dispersion will be described.

  The method for producing the aqueous composite resin dispersion of the present invention is slightly different between the case where the above-described chain extender (d) is used and the case where no chain extender is used.

The method for producing the aqueous composite resin dispersion of the present invention when using the chain extender (d) includes, for example, a polycarbonate polyol (a) having an alicyclic structure, an acidic group-containing polyol (b), and a polyisocyanate (c). (Α) to obtain a polyurethane prepolymer (A1) by reacting with
A step (β) of neutralizing acidic groups of the polyurethane prepolymer (A1);
A step (γ) of dispersing the polyurethane prepolymer (A1) in an aqueous medium;
A step (δ) of obtaining a polyurethane resin (A) by reacting an isocyanate group of the polyurethane prepolymer (A1) with a reactive chain extender (d);
Adding the polymerizable vinyl monomer (B1) to the aqueous medium and stirring to encapsulate the polymerizable vinyl monomer (B1) in the polyurethane resin (A);
A step (ζ) of polymerizing the polymerizable vinyl monomer (B1) to obtain a vinyl polymer (B).

Moreover, the manufacturing method of the composite resin aqueous dispersion of this invention when not using a chain extension agent (d) is, for example, polycarbonate polyol (a) having an alicyclic structure, acidic group-containing polyol (b), and polyisocyanate ( c) to obtain a polyurethane resin (A) (α ′);
Neutralizing acidic groups of the polyurethane resin (A) (β ′);
A step of dispersing the polyurethane resin (A) in an aqueous medium (γ ′);
Adding a polymerizable vinyl monomer (B1) to an aqueous medium and stirring to encapsulate the polymerizable vinyl monomer (B1) in the polyurethane resin (A) (ε ′);
A step (ζ ′) of polymerizing the polymerizable vinyl monomer (B1) to obtain vinyl polymerization resistance (B).

  The step (α) for obtaining the polyurethane prepolymer (A1) is preferably carried out in the presence of nitrogen in order to avoid unnecessary consumption of isocyanato groups. Moreover, the temperature of the process ((alpha)) which obtains the said polyurethane prepolymer (A1) can be performed at 40-120 degreeC. Preferably it is performed at 60-100 degreeC.

  In addition, as an acidic group neutralizing agent that can be used in the step of neutralizing acidic groups of the polyurethane prepolymer (A1) (β) and the step of neutralizing acidic groups of the polyurethane resin (A) (β ′), Organic amines such as trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, N-phenyldiethanolamine, dimethylethanolamine, diethylethanolamine, N-methylmorpholine, pyridine; sodium hydroxide, water Inorganic alkalis such as potassium oxide, ammonia and the like can be mentioned. Among these, organic amines can be preferably used, more preferably tertiary amines can be used, and most preferably triethylamine can be used.

  The amount of the acidic group neutralizing agent used is 0. 1 mol per mol of the polyurethane prepolymer (A1) or polyurethane resin (A) with respect to the acidic group of the polyurethane prepolymer (A1) or acidic group of the polyurethane resin (A). It is preferable to use it so that it may become 8-1.5 mol. If the amount of the acidic group neutralizing agent used is less than this amount, the dispersibility of the polyurethane prepolymer (A1) in water may decrease, or the storage stability of the aqueous composite resin dispersion may decrease. is there. If the amount of the acidic group neutralizing agent used is greater than this amount, the odor of the aqueous composite resin dispersion may become strong.

  The steps (β) and (β ′) of neutralizing the acidic groups of the polyurethane prepolymer (A1) and polyurethane resin (A), and the polyurethane prepolymer (A1) and polyurethane resin (A) are dispersed in an aqueous medium. A step (δ) in which an aqueous polyurethane resin is obtained by reacting the step (γ) and the step (γ ′) with the chain extender (d) having reactivity with the isocyanate group of the polyurethane prepolymer (A1); Steps (ε) and (ε ′) in which the vinyl monomer (B1) is added to an aqueous medium and stirred to encapsulate the polymerizable vinyl monomer (B1) in the polyurethane resin (A), and the polymerizable vinyl monomer ( The step (ζ) and the step (ζ ′) for polymerizing B1) to obtain a vinyl polymer (B) are the same as the method and the operation sequence thereof. The polyurethane (A) and the vinyl polymer (B) are separated into an aqueous medium. If possible, not particularly limited. For example, (A1) and (B1) are dispersed in an aqueous medium, (B1) is polymerized and then (A1) is chain-extended, or (A1) and (B1) are dispersed in an aqueous medium. (A1) after chain extension, (B1) polymerization method, (A1) mixed and dispersed in an aqueous medium, (A1) chain extension, Examples thereof include dispersion of (B1) in an aqueous medium and polymerization.

  For the mixing, stirring, and dispersion, a known stirring device such as a homomixer or a homogenizer can be used. In addition, in order to adjust viscosity, improve workability, and improve dispersibility, the hydrophilic organic solvent and water are added to the polyurethane prepolymer (A1) and the polymerizable vinyl monomer (B1) in advance before mixing. You can also.

  In the step (γ) and the step (γ ′) of mixing the polyurethane prepolymer (A1) and the polyurethane resin (A), when the polymerizable vinyl monomer (B1) is present, a polymerizable unsaturated bond is present. In order to avoid unnecessary consumption of oxygen, it is preferably carried out in the presence of oxygen. Moreover, you may add a polymerization inhibitor as needed. The temperature at which the polyurethane prepolymer (A1) and the polymerizable vinyl monomer (B1) are mixed is preferably 0 to 100 ° C. in order to avoid unnecessary consumption of the polymerizable unsaturated bond. More preferably, it is performed at 80 ° C, more preferably 0-70 ° C, and particularly preferably 50-70 ° C.

  In the production method of the present invention, the step of neutralizing acidic groups of the polyurethane prepolymer (A1) (β), the step of neutralizing acidic groups of the polyurethane resin (A) (β ′), and the polyurethane prepolymer Step (γ) of dispersing (A1) in an aqueous medium (γ) The step (γ ′) of dispersing the polyurethane resin (A) in an aqueous medium may be performed first or simultaneously. . In this case, (A1) or (A), the aqueous medium and the acidic group neutralizing agent may be mixed at once, or the acidic group neutralizing agent is previously mixed in the aqueous medium, and (A1) ) And (A) may be mixed.

  A step (γ) of dispersing the polyurethane prepolymer (A1) in an aqueous medium, and a step (δ) of obtaining an aqueous polyurethane resin by reacting the polyurethane prepolymer (A1) with the chain extender (d). Can be done at the same time.

  In this case, (A1), (d), and the aqueous medium may be mixed at once, or (d) may be mixed in advance with the aqueous medium, and (A1) may be mixed with these.

  A step (β) of neutralizing acidic groups of the polyurethane prepolymer (A1), a step (γ) of dispersing the polyurethane prepolymer (A1) in an aqueous medium, the polyurethane prepolymer (A1) and the chain. The step (δ) of obtaining an aqueous polyurethane resin by reacting with the extender (d) can be performed simultaneously. In this case, (A1) and (d), the acidic group neutralizing agent and the aqueous medium may be mixed at once, or (d) and the acidic group neutralizing agent are previously mixed in the aqueous medium, These and (A1) may be mixed.

  In the step (δ) of obtaining an aqueous polyurethane resin by reacting the polyurethane prepolymer (A1) with the chain extender (d) having reactivity with the isocyanate group of the polyurethane prepolymer (A1), the reaction is carried out under cooling. The reaction may be carried out slowly, and in some cases, the reaction may be promoted under heating conditions of 60 ° C. or lower. The reaction time under cooling can be about 0.5 to 24 hours, and the reaction time under heating conditions of 60 ° C. or less is about 0.1 to 6 hours.

  The addition amount of the chain extender (d) is preferably equal to or less than the equivalent of the isocyanato group serving as the chain extension starting point in the polyurethane prepolymer (A1) to be obtained, and more preferably 0.7 to 0.99 of the isocyanato group. Is equivalent. When the chain extender (d) is added exceeding the equivalent of the isocyanato group, the molecular weight of the chain-extended polyurethane polymer (A) becomes small, and the obtained composite resin aqueous dispersion is applied. The strength of the coated film decreases. The chain extender (d) may be added after the polyurethane prepolymer (A1) is dispersed in the aqueous medium, or may be added during the dispersion. Chain extension can also be carried out with water. In this case, water as a dispersion medium also serves as a chain extender.

  The step (ζ) and the step (ζ ′) of obtaining the vinyl polymer (B) by polymerizing the polymerizable vinyl monomer (B1) are performed by adding a polymerization initiator. As the polymerization initiator, it is possible to use a polymerization initiator which is made abnormal in normal emulsion polymerization. For example, persulfates such as ammonium persulfate, potassium persulfate, sodium persulfate, azo compounds such as 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), Examples include radical polymerization initiators such as hydrogen peroxide, hydroperoxides such as t-butyl hydroperoxide, and organic peroxides such as benzoyl peroxide and lauroyl peroxide. These may be used alone or in combination of two or more. Can be used in combination. In addition, these radical polymerization initiators and reducing agents such as sodium sulfite, sodium hydrogen sulfite, sodium thiosulfate, tartaric acid and L-ascorbic acid can be used in combination as a redox polymerization initiator. The polymerization temperature of the polymerizable vinyl monomer (B1) is preferably 30 ° C to 100 ° C.

  The number average molecular weight of the polyurethane resin (A) in the aqueous composite resin dispersion is preferably 1,000 to 1,000,000.

  The number average molecular weight of the vinyl polymer (B) in the aqueous composite resin dispersion is preferably 1,000 to 1,000,000.

  In the composite resin aqueous dispersion of the present invention, a thickener, a photosensitizer, a curing catalyst, an ultraviolet absorber, a light stabilizer, an antifoaming agent, a plasticizer, a surface conditioner, and an anti-settling agent are added as necessary. Additives such as can also be added. An additive may be individual and may use multiple types together. The aqueous composite resin dispersion of the present invention preferably contains substantially no protective colloid, emulsifier, or surfactant from the viewpoint of the hardness and chemical resistance of the resulting coating film.

<Coating composition and coating agent composition>
The present invention also relates to a coating composition and a coating agent composition containing the aqueous composite resin dispersion.

  In addition to the composite resin aqueous dispersion, other resins may be added to the coating composition and the coating composition of the present invention. Examples of other resins include polyester resins, acrylic resins, polyether resins, polycarbonate resins, polyurethane resins, epoxy resins, alkyd resins, and polyolefin resins. These may be single and may use multiple types together. The other resin preferably has one or more hydrophilic groups. 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, an acrylic resin, and a polyolefin resin.

The polyester resin can be usually 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.

  As the acrylic resin, a hydroxyl group-containing acrylic resin is preferable. Hydroxyl group-containing acrylic resin is a hydroxyl group-containing polymerizable unsaturated monomer and other polymerizable unsaturated monomer copolymerizable with the hydroxyl group-containing polymerizable unsaturated monomer, for example, in a solution polymerization method in an organic solvent, in water It can manufacture by making it copolymerize by known methods, such as an emulsion polymerization method.

  The hydroxyl group-containing polymerizable unsaturated monomer is a compound having at least one hydroxyl group and one polymerizable unsaturated bond in one molecule. For example, (meth) acrylic acid such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like and 2 to 8 carbon atoms. Monoesterified products of dihydric alcohols with these compounds; ε-caprolactone modified products of these monoesterified products; N-hydroxymethyl (meth) acrylamide; allyl alcohol; (meth) acrylates having a polyoxyethylene chain whose molecular ends are hydroxyl groups Etc.

  The hydroxyl group-containing acrylic resin preferably has an anionic functional group. For the hydroxyl group-containing acrylic resin having an anionic functional group, for example, a polymerizable unsaturated monomer having an anionic functional group such as a carboxylic acid group, a sulfonic acid group, or a phosphoric acid group is used as one kind of the polymerizable unsaturated monomer. It can be manufactured by using.

  The hydroxyl value of the hydroxyl group-containing acrylic resin is preferably about 1 to 200 mgKOH / g, more preferably about 2 to 100 mgKOH / g, and more preferably 3 to 60 mgKOH from the viewpoints of storage stability of the composition and water resistance of the resulting coating film. / G is more preferable.

  When the hydroxyl group-containing acrylic resin has an acid group such as a carboxyl group, the acid value of the hydroxyl group-containing acrylic resin is preferably about 1 to 200 mgKOH / g from the viewpoint of water resistance of the resulting coating film, About 150 mgKOH / g is more preferable, and about 5 to 100 mgKOH / g is still more preferable.

  The weight average molecular weight of the hydroxyl group-containing acrylic resin is preferably 1,000 to 200,000, more preferably 2,000 to 100,000, and still more preferably in the range of 3,000 to 50,000. is there.

  Examples of the polyether resin include polymers or copolymers having an ether bond, and examples include aromatics such as polyoxyethylene-based polyether, polyoxypropylene-based polyether, polyoxybutylene-based polyether, bisphenol A or bisphenol F. And polyethers derived from group polyhydroxy compounds.

  Examples of the polycarbonate resin include a polymer produced from a bisphenol compound, such as bisphenol A / polycarbonate.

  Examples of the polyurethane resin include resins having a urethane bond obtained by reacting 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 bisphenol include bisphenol A and bisphenol F.

  Alkyd resins include polybasic acids such as phthalic acid, terephthalic acid and succinic acid and polyhydric alcohols, as well as fats and oils and fats (soybean oil, linseed oil, coconut oil, stearic acid, etc.) Alkyd resin obtained by reacting a modifier such as

  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, 1-hexene, Examples include α-olefins such as decene and 1-dodecene; conjugated dienes such as butadiene, ethylidene norbornene, dicyclopentadiene, 1,5-hexadiene, styrenes, and the like. These monomers are used alone. It may also be used in combination.

  Examples of other monomers copolymerizable with olefinic monomers include vinyl acetate, vinyl alcohol, maleic acid, citraconic acid, itaconic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, and the like. May be used alone or in combination.

  The coating composition and the coating composition of the present invention may contain a curing agent, whereby the coating film or multilayer coating film obtained by using the coating composition or the coating composition, the water resistance of the coating film Etc. can be improved.

  As the curing agent, for example, amino resin, polyisocyanate, blocked polyisocyanate, melamine resin, carbodiimide and the like can be used. A hardening | curing agent 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 polyisocyanate group of the aforementioned polyisocyanate. Examples of the blocking agent include 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, acetanilide, and acetic acid amide. Acid amides such as ε-caprolactam and δ-valerolactam, acid imides such as succinimide and maleic imide, oximes such as acetoaldoxime, acetone oxime and methyl ethyl ketoxime, diphenylaniline and aniline And amine-based blocking agents such as ethyleneimine.

  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, and the like.

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

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

  Examples of extender pigments include clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talc, silica, and alumina white. These may be single and may use multiple types together. In particular, barium sulfate and / or talc are preferably used as extender pigments, and barium sulfate is more preferably used.

  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, or the like may be used. it can.

  The coating composition and coating composition of the present invention include a thickener, a curing catalyst, an ultraviolet absorber, a light stabilizer, an antifoaming agent, a plasticizer, a surface conditioner, an anti-settling agent, etc., if necessary. Usual paint additives can be contained. These may be single and may use multiple types together.

  Although the manufacturing method in particular of the coating composition and coating agent composition of this invention is not restrict | limited, A well-known manufacturing method can be used. In general, the coating composition and the coating composition are produced by mixing the aqueous composite resin dispersion and the various additives described above, adding an aqueous medium, and adjusting the viscosity according to the coating method. The

  Examples of the coating material of the coating composition or the coating material of the coating agent composition include metals, plastics, inorganic materials, and wood.

  The coating composition and the coating agent composition of the present invention have high adhesion to plastic, and particularly high adhesion to poly (meth) acrylic resin and ABS resin. For this reason, as the material to be coated and the material to be coated, poly (meth) acrylate resin and / or ABS resin are preferable.

  Examples of the coating method of the coating composition or the coating method of the coating agent composition include bell coating, spray coating, roll coating, shower coating, and dip coating.

  The thickness of the coating film is not particularly limited, but a thickness of 1 to 100 μm is preferable. More preferably, it is preferable to form a coating film having a thickness of 3 to 50 μm.

  EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated further in detail, this invention is not limited to these.

[Synthesis Example 1]
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 NMP (1350 g) in the presence of dibutyltin dilaurate (2.6 g) under nitrogen atmosphere at 80-90 ° C. for 6 hours. The NCO group content in the prepolymer at the end of the urethanization reaction was 3.97% by mass. 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 mass% of 2-methyl-1,5-pentanediamine aqueous solution (626 g) was added to obtain a polyurethane resin (aqueous dispersion).

[Example 1]
In a reactor equipped with a stirrer and a heater, n-butyl acrylate (glass transition temperature (calculated value): −54 ° C., 33.4 g) was added to the polyurethane resin (aqueous dispersion (500 g)) obtained in Synthesis Example 1. ) And water (85.8 g) were added and heated to 50 ° C. Next, 1 mass% ascorbic acid aqueous solution (9.3 g) and 7 mass% butyl peroxide aqueous solution (2.7 g) were added. After the heat generation had subsided, heating at 50 ° C. for 1 hour gave a composite resin aqueous dispersion in which the polyurethane resin containing the vinyl polymer was dispersed in the aqueous medium.

[Example 2]
In a reaction apparatus equipped with a stirrer and a heater, 2-ethylhexyl acrylate (glass transition temperature (calculated value): −85 ° C., 33.4 g) was added to the polyurethane resin (aqueous dispersion (500 g)) obtained in Synthesis Example 1. ) And water (85.8 g) were added and heated to 50 ° C. Next, 1 mass% ascorbic acid aqueous solution (9.3 g) and 7 mass% butyl peroxide aqueous solution (2.7 g) were added. After the heat generation had subsided, heating at 50 ° C. for 1 hour gave a composite resin aqueous dispersion 2 in which polyurethane resin particles encapsulating the vinyl polymer were dispersed in an aqueous medium.

[Example 3]
In a reaction apparatus equipped with a stirrer and a heater, 2-ethylhexyl methacrylate (glass transition temperature (calculated value): −10 ° C., 33.4 g) was added to the polyurethane resin (aqueous dispersion (500 g)) obtained in Synthesis Example 1. ) And water (85.8 g) were added and heated to 50 ° C. Next, 1 mass% ascorbic acid aqueous solution (9.3 g) and 7 mass% butyl peroxide aqueous solution (2.7 g) were added. After the exotherm had subsided, the mixture was heated at 50 ° C. for 1 hour to obtain a composite resin aqueous dispersion 3 in which the polyurethane resin encapsulating the vinyl polymer was dispersed in the aqueous medium.

[Example 4]
In a reactor equipped with a stirrer and a heater, n-butyl methacrylate (glass transition temperature (calculated value): 20 ° C., 33.4 g) was added to the polyurethane resin (aqueous dispersion (500 g)) obtained in Synthesis Example 1. And water (85.8 g) were added and heated to 50 ° C. Next, 1 mass% ascorbic acid aqueous solution (9.3 g) and 7 mass% butyl peroxide aqueous solution (2.7 g) were added. After the heat generation had subsided, heating at 50 ° C. for 1 hour gave a composite resin aqueous dispersion 4 in which the polyurethane resin containing the vinyl polymer was dispersed in the aqueous medium.

[Example 5]
In a reactor equipped with a stirrer and a heater, the polyurethane resin obtained in Synthesis Example 1 (aqueous dispersion (500 g)) was added to methyl methacrylate (glass transition temperature (calculated value): 105 ° C., 33.4 g), Water (85.8 g) was added and warmed to 50 ° C. Next, 1 mass% ascorbic acid aqueous solution (9.3 g) and 7 mass% butyl peroxide aqueous solution (2.7 g) were added. After the heat generation had subsided, heating at 50 ° C. for 1 hour gave a composite resin aqueous dispersion in which the polyurethane resin containing the vinyl polymer was dispersed in the aqueous medium.

[Comparative Example 1]
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 NMP (1350 g) in the presence of dibutyltin dilaurate (2.6 g) under nitrogen atmosphere at 80-90 ° C. for 6 hours. The NCO group content in the prepolymer at the end of the urethanization reaction was 3.97% by mass. 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 mass% of 2-methyl-1,5-pentanediamine aqueous solution (626 g) was added to obtain a polyurethane resin (aqueous dispersion).

[Comparative Example 2]
In a reactor equipped with a stirrer and a heater, the aqueous polyurethane resin dispersion (500 g) obtained in Synthesis Example 1 was added to n-butyl acrylate (glass transition temperature (calculated value): −54 ° C., 89.2 g). , Water (236 g) was added, and the mixture was heated to 50 ° C. Next, 1 mass% ascorbic acid aqueous solution (12.4 g) and 7 mass% butyl peroxide aqueous solution (3.5 g) were added. After the heat generation had subsided, heating at 50 ° C. for 1 hour gave a composite resin aqueous dispersion in which the polyurethane resin containing the vinyl polymer was dispersed in the aqueous medium.

[Evaluation]
(Alcohol resistance)
The composite resin aqueous dispersions obtained in Examples 1 to 5 and Comparative Examples 1 and 2 were applied to glass plates. In addition, it apply | coated so that the final film thickness after drying might be set to 10 microns. Then, the dried coating film was formed by heating and drying at 120 ° C. for 120 minutes to obtain a glass substrate laminate.

  Absorbent cotton impregnated with alcohol for disinfection was placed on the dried coating film of the obtained glass substrate laminate, and allowed to stand for 5 minutes. Thereafter, the absorbent cotton was removed, the place where the absorbent cotton was placed was scratched with a needle, and the appearance of the coating film was visually evaluated. The results are shown in Table 1.

The evaluation criteria are as follows.
○: No tearing of the coating film or peeling of the coating film was observed.
X: The tear of the coating film and peeling of the coating film were observed.

(Pencil hardness)
The composite resin aqueous dispersions of Examples 1 to 5 and Comparative Examples 1 and 2 were applied to a glass plate. In addition, it apply | coated uniformly so that the final film thickness after drying might be set to about 20 microns. Then, the glass base material laminated body was obtained by drying at 80 degreeC for 30 minutes. The cured coating film (resin film) was peeled off from the glass plate from the obtained glass substrate laminate, and the pencil hardness was measured by a method according to JIS K 5600-5-4.

(Adhesion)
The composite resin aqueous dispersions obtained in Examples 1 to 5 and Comparative Examples 1 and 2 were applied to a thickness of 40 μm (bar coater # 20) on an automobile steel plate cationic electrodeposition coating plate (manufactured by Nippon Test Panel Co., Ltd.). Then, it was heated and dried at 140 ° C. for 30 minutes, and a cross-cut peel test was performed using the obtained coating film. The coating was scored at intervals of 1 mm vertically and horizontally in an area of 10 mm × 10 mm, and after applying an adhesive tape, the state when it was peeled off was evaluated according to the following criteria.
○: state in which the coating film is not peeled △: state in which a part of the coating film is peeled ×: state in which the entire surface of the coating film is peeled

  The aqueous composite resin dispersion of the present invention can be widely used as a raw material for paints, coating agents, primers, adhesives, and the like. In particular, it can be suitably used as a glass coating agent and its raw material.

Claims (6)

  A composite resin aqueous dispersion in which at least a composite resin is dispersed in an aqueous medium, wherein the composite resin includes at least a polyurethane resin (A) and a vinyl polymer encapsulated in the polyurethane resin (A) ( B), and the polyurethane resin (A) is obtained by reacting at least a polycarbonate polyol (a) having an alicyclic structure, an acidic group-containing polyol (b), and a polyisocyanate (c). The composite resin, wherein the polyurethane resin (A) has a mass of 70 to 90% by mass with respect to the total mass of the polyurethane resin (A) and the vinyl polymer (B). Aqueous dispersion.   Polyurethane resin (A) is a polyurethane resin obtained by reacting polycarbonate polyol (a) having an alicyclic structure, acidic group-containing polyol (b), polyisocyanate (c), and chain extender (d). The aqueous composite resin dispersion according to claim 1. The vinyl polymer (B) is (meth) acrylic acid, (meth) acrylic acid ester, methacrylamide derivative, acrylonitrile, vinylidene chloride, vinylidene fluoride, vinyl esters, N-vinylamides, styrene derivatives, or 1,3. The aqueous composite resin dispersion according to claim 1 or 2, comprising one or more addition-polymerized products of a diene derivative. The aqueous composite resin dispersion according to claim 1 or 2, wherein the vinyl polymer (B) includes a product obtained by addition polymerization of a (meth) acrylic acid ester. The coating composition containing the composite resin aqueous dispersion of any one of Claims 1-4 . The coating agent composition containing the composite resin aqueous dispersion of any one of Claims 1-4 .