JPH11263928A - Coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition capable of a coating film excellent in water-repellency, appearances and adhesive property to a base material by including a binder resin, coloring agent and wax comprising a long side chain-containing specific polymer. SOLUTION: This composition is obtained by including (A) a binder resin (e.g., alkyd resin), (B) a coloring agent (e.g. organic or inorganic dye or pigment) and (C) a polymer wax comprising; a long side chain-containing polymer having 50 to 100 wt.% of any of the repeating units of formula I (R<1> is H or CH3 ; R<2> is a 15-30C aliphatic hydrocarbon; and D is e.g. OCO) or formula H (R<4> and R<5> are each H or 1-30C aliphatic hydrocarbon); and/or the modified long side chain-containing polymer. The composition pref. comprises 45 to 98 wt.% of component A, 2 to 55 wt.% of component B and 0.1 to 30 wt.% of component C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating composition for forming a coating film having excellent water repellency and excellent appearance and adhesion to a substrate.

[0002]

2. Description of the Related Art As is well known, coating compositions containing a polyester resin, an epoxy resin, an acrylic resin or the like as a binder and a coloring agent are widely used for various coatings. In these coating compositions, in order to improve the water repellency and water resistance of the coating film, a water repellent is added to the coating, and wax is widely used. As the wax, for example, a natural wax such as carnauba wax or beeswax, or a synthetic wax such as polyethylene wax, polypropylene wax, or polytetrafluoroethylene wax is used.

However, since these conventional waxes have low affinity for the binder resin, there is a problem that the bleeding occurs at the interface between the coating film and the base material and the adhesion is reduced. In addition, since the compatibility between the wax and the binder resin is poor, when the coating film is formed, there may be a problem that the surface is mottled or the surface is inferior due to unevenness.

[0004]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the conventional coating compositions. That is, an object of the present invention is to provide a coating composition which forms a coating film having excellent water repellency and excellent appearance and adhesion to a substrate.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above problems can be solved by adding a specific polymer to a coating composition. That is, the present invention has the following configuration. In the coating composition containing a binder resin, a colorant and a wax, the wax is represented by the following general formula (1)
And a long side chain-containing polymer having at least one selected from the repeating units represented by the following general formula (2) in the range of 50 to 100% by weight, and a modified product of the long side chain-containing polymer. A coating composition containing at least one polymeric wax.

[0006]

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[0007]

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[0008] The coating composition as described above, wherein the wax comprises a polyolefin wax, alone and / or in the form of a reactant.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The coating composition of the present invention contains 50 to 100% by weight, preferably 80 to 100% by weight of at least one selected from the repeating units represented by the above general formulas (1) and (2) as a wax. It contains at least one polymer wax (I) selected from a long side chain-containing polymer having a weight percent range and a modified product of the long side chain-containing polymer.

In the polymer having a long side chain, the repeating unit represented by the general formulas (1) and (2) is 50% by weight.
If it is lower than the above, there is a problem that crystallinity is reduced and water repellency is reduced. When the amount of the repeating units represented by the general formulas (1) and (2) is 50% by weight or more and less than 100% by weight, the balance has other repeating units than the above. General formula (1)
Is derived from the long side chain-containing vinyl monomer (A-1) described later, and the repeating unit represented by the general formula (2) is a long side chain containing vinyl monomer described later. It is derived from (A-2).

The weight average molecular weight of the polymer wax (I) is preferably from 1,000 to 100,000. If the weight average molecular weight is lower than 1,000, the water repellency may decrease. If it is higher than 100,000, the appearance may be impaired. The melting point or softening temperature of the polymer wax (I) is preferably 40 ° C. or higher. When the temperature is lower than 40 ° C., the coating film may be easily contaminated.

The modified products of the long side chain-containing polymer include:
For example, those modified using a polyolefin-based wax, for example, a product obtained by polymerizing a monomer component for a long side chain-containing polymer in the presence of a polyolefin-based wax, a polyolefin-based wax and a long side A product obtained by mixing a chain-containing polymer with heating, and a monomer component for a long side chain-containing polymer in the presence of a polymerizable group (such as a double bond) previously introduced into a polyolefin wax. The reactive group (for example, carboxyl group and epoxy group, isocyanate group and amino group, carboxylic anhydride and hydroxyl group, etc.) of each of the product obtained by polymerization, the long side chain-containing polymer and the polyolefin wax is used. Products obtained by reacting with each other are included. In the above-mentioned products, it is considered that at least a part of the polyolefin-based wax is contained in a form of a reactant, but a part of the polyolefin-based wax is not reacted and may be contained in a single form.

[0013] By modifying with a polyolefin-based wax, the scratch resistance of the coating film is improved. Examples of the polyolefin-based wax include polyethylene wax, polypropylene wax, and polytetrafluoroethylene wax. Among them, polyethylene wax is preferred from the viewpoint of compatibility.

The proportion of the polyolefin wax in the modified product is, for example, in the range of 1 to 95% by weight, preferably 1 to 70% by weight, more preferably 1 to 50% by weight, based on the total amount of the modified product. . When the proportion of the polyolefin-based wax is large, the affinity for the solvent or the binder resin is reduced, and the storage stability of the paint may be reduced.

The polymer wax (I) used in the present invention
Next, a method of manufacturing the device will be described. The polymer wax (I) has the following general formula (3)

[0016]

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The long side chain-containing vinyl monomer (A)
-1) and the following general formula (4)

[0018]

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A long side chain-containing vinyl monomer represented by the formula (A)
-2) Monomer comprising at least one long side chain-containing monomer (A) selected from 50 to 100% by weight, preferably 80 to 100% by weight, and another polymerizable monomer (B) Obtained by polymerizing the components. When the total amount of the long side chain-containing monomer (A) represented by the general formulas (3) and (4) in the monomer components is 50% by weight or more and less than 100% by weight, the remainder is described later. Long side chain containing monomer (A-
1) and a polymerizable monomer (B) other than the long side chain-containing monomer (A-2).

The polymerization is carried out by radical polymerization, ionic polymerization or the like, and the polymerization can be carried out by any polymerization method such as bulk polymerization, solution polymerization, emulsion polymerization or suspension polymerization. The polymer wax (I) may be a solution in which the polymer wax (I) is dissolved, a suspension in which solid particles of the polymer wax (I) are dispersed in a medium, or a solution particle of the polymer wax (I). Obtained as an emulsion dispersed in a medium. By removing volatile components such as unreacted monomers and solvents from the reaction mixture, a solid polymer wax (I) can be obtained. Further, the polymer wax (I) can be prepared in any polymerization form such as block, graft, random and the like.

The long side chain-containing vinyl monomer (A-1)
Is represented by the above general formula (3), and R ² is bonded to the right side of the divalent group exemplified as D above. R
³ is typically an aliphatic, alicyclic or aromatic hydrocarbon group having 2 to 30 carbon atoms. The long side chain-containing vinyl monomer (A-1), for example, (meth) acrylate, stearyl (meth) behenyl acrylate (meth) of higher alcohols of acrylic acid and C ₁₅ -C ₃₀ (Meth) acrylic acid higher alkyl esters which are esters; of a monobasic linear fatty acid such as stearic acid and a polymerizable monomer capable of undergoing an addition reaction with a carboxyl group such as glycidyl (meth) acrylate or isopropenyloxazoline Additives; fatty acids of vegetable oils such as coconut oil (mixed fatty acids)
And an adduct of a polymerizable monomer capable of undergoing an addition reaction with a carboxyl group as described above; a higher alcohol such as stearyl alcohol and oleyl alcohol, a polyvalent isocyanate compound, and a polymerization having a hydroxyl group such as hydroxyethyl (meth) acrylate. Adducts of hydrophilic monomers; higher fatty acid vinyl esters such as vinyl stearate; higher alcohols such as stearyl alcohol and oleyl alcohol or higher fatty acids such as stearic acid and isocyanate groups such as methacryloyl isocyanate and methacryloyloxyethyl isocyanate Adducts with polymerizable monomers; adducts of monovalent isocyanates having a higher alkyl group such as octadecyl isocyanate with polymerizable monomers having a hydroxyl group such as hydroxyethyl (meth) acrylate. It can be.

The long side chain-containing maleic acid monomer (A-
The 2), for example, stearyl maleate, behenyl maleate, higher alkyl malate such C ₁₅ -C _30, such as distearyl maleate; stearyl fumarate, behenyl fumarate, C _15, such as distearyl fumarate - _C30 higher alkyl fumarate and the like can be mentioned.

As the polymerizable monomer (B) other than the above-mentioned long side chain-containing monomer (A-1) and long side chain-containing monomer (A-2) used in the synthesis of the polymer wax (I). Is not particularly limited, for example, styrene derivatives such as styrene, vinyltoluene, α-methylstyrene, and chloromethylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and (meth) ) (Meth) acrylic esters synthesized by esterification of (meth) acrylic acid such as dodecyl acrylate, 2-ethylhexyl (meth) acrylate and C ₁ -C ₁₄ monoalcohol; (meth) acrylic acid , Crotonic acid, maleic acid,
Unsaturated carboxylic acids such as fumaric acid, itaconic acid or their half esters and their salts; (meth) acrylamide, N-monomethyl (meth) acrylamide, N-
(Meth) such as monoethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, salts thereof, and quaternary compounds thereof
Acrylamide derivatives; unsaturated monomers containing hydroxyl groups such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and monoesters of (meth) acrylic acid with polypropylene glycol or polyethylene glycol Sulfonic acid group-containing unsaturated monomers such as ethyl (meth) acrylate-2-sulfonate, vinyl sulfonic acid, styrene sulfonic acid, and salts thereof; dimethylaminoethyl (meth) acrylate, dimethylamino Basic unsaturated monomers such as ethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, vinylpyridine, vinylimidazole and vinylpyrrolidone; (meth) acrylic acid and ethylene glycol, 1,3-butylene glycol, diethylene Guri A polymerizable unsaturated group in the molecule such as an ester with a polyhydric alcohol such as alcohol, 1,6-hexane glycol, neopentyl glycol, polyethylene glycol, polypropylene glycol, trimethylolpropane, pentaerythritol and dipentaerythritol. Or more polyfunctional (meth) acrylic acid esters; unsaturated monomers containing an organic silicon group such as vinyltrimethoxysilane, γ- (meth) acryloylpropyltrimethoxysilane, allyltriethoxysilane, and trimethoxysilylpropylallylamine Oxazoline group-containing polymerizable monomers such as 2-isopropenyl-2-oxazoline and 2-vinyloxazoline; epoxy group-containing polymerizable monomers such as glycidyl (meth) acrylate and allyl glycidyl ether; Vinyl chloride Halogenated unsaturated monomers such as vinylidene fluoride, vinyl chloride, and vinylidene chloride; unsaturated monomers containing halohydrin groups such as 2-hydroxy-3-chloropropylene (meth) acrylate; (meth) acrylic acid- Aziridinyl group-containing polymerizable monomers such as 2-aziridinylethyl; blocked isocyanate group-containing unsaturated monomers such as reaction adducts of (meth) acrylate-2-isocyanatoethyl with ethyl alcohol; Unsaturated monomers having two ethylenically unsaturated groups such as divinylbenzene and diallyl phthalate; vinyl esters of saturated carboxylic acids such as vinyl acetate;
(Meth) acrylonitrile; and acrolein, and the like. Any one of them can be used alone, or two or more can be used in combination.

When a water-soluble monomer such as an unsaturated carboxylic acid or a hydroxyl group-containing unsaturated monomer is used, the content thereof is preferably 10 mol% or less in the polymer wax (I) from the viewpoint of water repellency. It is preferred to use By using an epoxy group-containing polymerizable monomer or an unsaturated carboxylic acid as these other monomers (B), the adhesion to a base material or a lower layer such as a primer can be increased.

The method for synthesizing the polymer wax (I) is preferably a radical polymerization method using a radical polymerization initiator. Any conventionally known radical polymerization initiator can be used, and any of oil-soluble and water-soluble radical initiators can be used. Examples of the oil-soluble initiator include, for example, azobisisobutyronitrile, azobisvaleronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), 1,1′-azobis- (cyclohexane-
1-carbonitrile), 2,2'-azobis- (2-aminopropane) dihydrochloride, 4,4'-azobis- (4-
Azo compounds such as cyanopentanoic acid); benzoyl peroxide, cumene hydroperoxide, di-t
Organic peracids such as -butyl peroxide, t-butyl hydroperoxide, and t-butyl peroxy-2-ethylhexanoate. Examples of the water-soluble initiator include potassium persulfate, ammonium persulfate, hydrogen peroxide and the like. In order to increase the polymerization rate, an oxidizing agent type polymerization initiator can be used as a redox initiator in combination with a reducing agent, if necessary. The amount of the polymerization initiator used is in the range of 0.01 to 5 parts by weight based on 100 parts by weight of the polymerizable monomer component. The addition of the radical polymerization initiator can be carried out at an appropriate time, similarly to ordinary radical polymerization. As the polymerization apparatus used for the radical polymerization of the polymerizable monomer component, a conventionally known apparatus can be applied. The polymerization temperature is 0 to 200 ° C, preferably 50 to 150 ° C, and the polymerization time is 1 to 15 hours.

The production method when the polymer wax (I) is a modified product of the long side chain-containing polymer will be described. Among those modified using the polyolefin wax,
In the case of, for example, a polyolefin wax containing no or containing a polymerizable group is dissolved in an appropriate solvent (for example, a solvent used in a coating composition), and the long side chain-containing polymer is added to the wax solution. The radical polymerization may be performed by adding a monomer component for use and a polymerization initiator by dropping or the like.

In the above case, for example, a polyolefin wax containing no or containing a reactive group and a long side chain containing no or containing a reactive group which reacts with the reactive group to form a covalent bond. The contained polymer and the polymerization initiator may be dissolved in an appropriate solvent (for example, a solvent used for a coating composition) and the reaction may be performed under heating and stirring at 50 to 180 ° C.
The coating composition of the present invention contains a binder resin, a colorant, and a wax as essential components, and contains a solvent and other additives as necessary. A hot-melt type coating composition containing no solvent may be used, or a solvent-based coating composition containing a solvent may be used. The solvent may be an organic solvent such as toluene, xylene, cyclohexanone, methyl ethyl ketone, or ethyl acetate, or may be an aqueous solvent. The aqueous solvent contains 50% by weight or more of water and, if necessary, isopropyl alcohol, butyl cellosolve,
It contains a water-miscible solvent such as ethylene glycol in a range of less than 50% by weight.

As the binder resin, the colorant, the solvent and the additive, those used in conventional coating compositions may be contained in the same proportions as in the conventional range. Typically, 45 to 98% by weight of a binder resin and 2 to 2
55% by weight and 0.1 to 30% by weight of wax. If the amount of the wax is less than 0.1 part by weight, the water repellency may decrease. If the amount of the wax is more than 30 parts by weight, the adhesion to the base material or the lower layer such as the primer may decrease. More preferably, the wax is in the range of 0.5 to 15% by weight of the solid content.

In the present invention, it is important to contain the polymer wax (I) as the wax component, and it is preferably at least 10% by weight of the wax component, more preferably 40% by weight.
More preferably, it is the above. Polymer wax (I)
Other than the wax that can be included, conventionally known waxes, for example, carnauba wax, candelilla wax, sugar wax, rice wax, wood wax,
Plant-based natural waxes such as bayberry wax, ocully wax, and esparto wax; animal-based natural waxes such as beeswax, insect wax, whale wax, shellac wax, lanolin wax; petroleum-based natural waxes such as paraffin wax and microcrystalline wax; Mineral natural waxes such as montan wax, ozokerite wax, and ceresin; Hoechst wax, polyethylene wax,
Synthetic waxes such as polypropylene wax, carbowax, caster wax, and Fischer-Tropsch wax (also referred to as Sasol wax (manufactured by Sasol, South Africa)); higher fatty acids; higher alcohols; Among these,
Polyolefin waxes are preferred, and polyethylene waxes are particularly preferred. The reason is as described in the case where the polymer wax (I) of the present invention is used as a raw material for a modified product of a polymer having a long side chain.

Examples of the binder resin include alkyd resin, acrylic resin, urethane resin, epoxy resin, polyester resin, phenol resin, amino resin,
There are a vinyl chloride resin, a vinylidene fluoride resin and the like, and they can be used alone or in combination of two or more. As the colorant, an organic or inorganic pigment or dye can be used. Examples of the additive include a curing agent, a dispersant, a spreading agent, and an antifoaming agent.

The coating composition of the present invention can be produced by using a wax containing the polymer wax (I), a pigment, a binder, and an additive in the same manner as a conventional method for producing a coating composition. Examples of the form of the paint composition include water-based paint,
Solvent-based paints, powder paints, and solventless paints are exemplified.

The method for adding the polymer wax (I) is not particularly limited, and the polymer wax (I) may be added as a solution in which the polymer wax (I) is dissolved in a solvent or a dispersion in which the polymer wax (I) is dispersed or semi-solubilized. Alternatively, it may be added as a solid. The polymer wax (I) may be added after being uniformly mixed with other waxes by, for example, melt-kneading, or may be added separately.

The coating composition of the present invention can be used in the same applications as those in which conventional coating compositions are used,
For example, it can be used for buildings, automobiles, plastics, woodwork, and the like. As a substrate on which the coating composition of the present invention is applied, wood, plastic, glass, cloth,
Examples include paper, cement, concrete, and the like.

The coating using the coating composition of the present invention can be performed by a conventionally known coating method such as brush coating, roller coating, roll coating, flow coating, spray coating, electrostatic coating, and electrodeposition coating. Usually, it is applied so that the coating thickness after drying is 0.5 to 30 μm. Drying of the coating film is performed by heating at room temperature to 400 ° C. by a conventionally known method.

[0035]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. In the examples, "parts" means "parts by weight" unless otherwise specified.
Shall be expressed. Reference Example 1 100 parts of toluene was charged into a stainless steel flask equipped with a stirrer, a dropping funnel, a nitrogen inlet tube, a thermometer, and a reflux condenser, and heated to 80 ° C. while gently blowing nitrogen gas under stirring. Next, a previously prepared polymerizable monomer solution consisting of 10 parts of stearyl methacrylate, 90 parts of stearyl acrylate, 50 parts of toluene and 1 part of 2,2′-azobisisobutylylonitrile was dropped from the dropping funnel. It was added dropwise over 2 hours and polymerized at 80 ° C. After completion of the dropwise addition, aging was carried out at the same temperature for 1 hour and then at reflux for 2 hours. Then, this toluene solution was added to 250 parts of a mixed solvent (xylene / cyclohexanone = 1/1 weight ratio, the same applies hereinafter) to obtain a polymer wax solution (solid content: 20%). When this solution was analyzed by gas chromatography, no residual monomer was detected, and the conversion was 100%. When the solvent was distilled off from this solution under reduced pressure heating, a white solid compound having a weight average molecular weight of 50,000 was obtained.

Reference Example 2 The same flask as in Reference Example 1 was charged with 100 parts of toluene and heated to 80 ° C. while gently blowing nitrogen gas under stirring. Next, a previously prepared polymerizable monomer comprising 70 parts of behenyl methacrylate, 20 parts of stearyl maleate, 10 parts of styrene, 50 parts of toluene and 0.4 part of 2,2'-azobisisobutyronitrile. The body solution was dropped from the dropping funnel over 2 hours and polymerized at 80 ° C. After completion of the dropwise addition, aging was carried out at the same temperature for 1 hour and then at reflux for 2 hours. Then, 250 parts of a mixed solvent was added to the toluene solution to obtain a polymer wax solution (solid content: 20%). When this solution was analyzed, the polymerization rate was 99.2%. When the solvent was distilled off from this solution under reduced pressure heating, the weight average molecular weight was 5.3.
10,000 white solid compounds were obtained.

Reference Example 3 The same flask as in Reference Example 1 was charged with 100 parts of toluene and heated to 80 ° C. while gently blowing nitrogen gas under stirring. Next, a polymerizable polymer consisting of 80 parts of stearyl acrylate, 15 parts of methyl methacrylate, 5 parts of glycidyl methacrylate, 50 parts of toluene and 0.5 part of 2,2′-azobisisobutyronitrile prepared in advance. Add monomer solution from dropping funnel 2
It was added dropwise over time and polymerized at 80 ° C. After completion of the dropwise addition, aging was carried out at the same temperature for 1 hour and then at reflux for 2 hours.
Then, 250 parts of a mixed solvent was added to the toluene solution,
A polymer wax solution (20% solids) was obtained. When this solution was analyzed, the polymerization rate was 100%. Also,
The solvent was distilled off from this solution while heating under reduced pressure to obtain a white solid compound having a weight average molecular weight of 50000.

Reference Example 4 The same flask as in Reference Example 1 was charged with 100 parts of toluene and heated to a reflux state.
Next, prepared in advance, stearyl acrylate 100
, 50 parts of toluene and 0.5 parts of 2,2'-azobisisobutyronitrile were added dropwise from a dropping funnel over 2 hours, and polymerization was carried out under a nitrogen atmosphere under reflux. Then, 100 parts of polyethylene wax (Sunwax E-250-P, manufactured by Sanyo Chemical Industries, Ltd., molecular weight: 2,000, acid value: 20) and 50 parts of toluene were added, and the mixture was heated to a reflux state and completely dissolved. Then, this solution was added to 600 parts of the mixed solvent cooled to 10 ° C. while stirring with a homogenizer to obtain a polymer wax paste having a solid content of 20%. When this paste was analyzed, the conversion was 100%. When the solvent was distilled off from the paste under reduced pressure and heating, a white solid compound was obtained.

(Reference Example 5) Into the same flask as in Reference Example 1, 30 parts of polypropylene wax (Viscol 550-P manufactured by Sanyo Chemical Industries) and 50 parts of toluene were charged.
Heated to reflux under a nitrogen atmosphere. Next, a previously prepared polymerizable monomer solution consisting of 65 parts of stearyl acrylate, 5 parts of methyl acrylate, 20 parts of toluene and 0.5 part of t-butyl hydroperoxide was added from the dropping funnel over 2 hours. It was added dropwise and polymerized under reflux. Then
This solution was added to 330 parts of the mixed solvent cooled to 10 ° C. while stirring with a homogenizer to obtain a polymer wax paste having a solid content of 20%. When this paste was analyzed, the conversion was 100%. When the solvent was distilled off from the paste under reduced pressure and heating, a white solid compound was obtained.

Reference Example 6 In the same flask as in Reference Example 1, polyethylene wax (Sunwax E-250-P, Sanyo Chemical Industries, Ltd., molecular weight 2000, acid value 20) 1
Then, 00 parts, 5 parts of glycidyl methacrylate, 0.01 part of t-butylhydroxytoluene and 150 parts of toluene were charged and refluxed for 1 hour with stirring to dissolve the wax. Next, 80 parts of stearyl acrylate, 15 parts of lauryl methacrylate, 50 parts of toluene and 2,
A polymerizable monomer solution comprising 0.5 part of 2'-azobisisobutyronitrile was dropped from the dropping funnel over 2 hours, and polymerization was carried out under a nitrogen atmosphere under reflux. After completion of the dropwise addition, aging was performed for 2 hours under reflux. Then, this solution was added to 600 parts of the mixed solvent cooled to 10 ° C. while stirring with a homogenizer to obtain a polymer wax paste having a solid content of 20%. When this paste was analyzed, the polymerization rate was 100%.
Met. When the solvent was distilled off from the paste under reduced pressure and heating, a white solid compound was obtained.

(Reference Example 7) In the same flask as in Reference Example 1, polyethylene wax (Mitsui Petrochemical Industry Co., Ltd.)
Manufactured by Mitsui High Wax 2203A, molecular weight 2700, acid value 30) 120 parts, glycidyl methacrylate 4 parts, t-
0.01 parts of butylhydroxytoluene and 15 parts of toluene
0 parts were charged and refluxed for 1 hour with stirring to dissolve the wax. Next, a previously prepared polymerizable monomer solution consisting of 70 parts of stearyl acrylate, behenyl methacrylate, 50 parts of toluene and 0.5 part of 2,2′-azobisisobutyronitrile was dropped from the dropping funnel. The solution was added dropwise over 2 hours and polymerized under reflux in a nitrogen atmosphere. After completion of the dropwise addition, aging was performed for 2 hours under reflux. Then, this solution was added to 600 parts of the mixed solvent cooled to 10 ° C. while stirring with a homogenizer to obtain a polymer wax paste having a solid content of 20%. When this paste was analyzed, the polymerization rate was 10
It was 0%. When the solvent was distilled off from the paste under reduced pressure and heating, a white solid compound was obtained.

Reference Example 8 The same flask as in Reference Example 1 was charged with 100 parts of toluene and heated to a reflux state.
Next, glycidyl methacrylate 5 prepared in advance
, 90 parts of stearyl acrylate, 5 parts of styrene, 50 parts of toluene, and 0.5 part of 2,2'-azobisisobutyronitrile were added dropwise from a dropping funnel to a polymerizable monomer solution.
The mixture was added dropwise over a period of time and polymerized under reflux in a nitrogen atmosphere. Then, polyethylene wax (Sunwax E-250-P manufactured by Sanyo Chemical Industries, Ltd., molecular weight 2000, acid value 20)
100 parts and 50 parts of toluene were added, and the mixture was aged for 2 hours under reflux. Then, the mixed solvent 6 cooled to 10 ° C.
This solution was added to 00 parts while stirring with a homogenizer to obtain a polymer wax paste having a solid content of 20%. When this paste was analyzed, the conversion was 100%. When the solvent was distilled off from the paste under reduced pressure and heating, a white solid compound was obtained.

REFERENCE EXAMPLE 9 In the same flask as in Reference Example 1, 1 part of acrylic acid and hydroxyethyl methacrylate 3
0 parts, 0.01 part of t-butylhydroxytoluene and 66 parts of toluene were charged and heated to 80 ° C. with stirring. Next, octadecyl isocyanate 69 prepared in advance
, 0.01 parts of dibutyltin dilaurate and 34 parts of toluene were added dropwise from a dropping funnel over 2 hours and reacted at 80 ° C. After the completion of the dropwise addition, the reaction was carried out at the same temperature for 2 hours. After cooling, the resulting polymerizable monomer solution
0.4 part of 2'-azobisisobutyronitrile was added, and the mixture was transferred to a dropping funnel. Toluene 100 in another flask
The mixture was heated to 80 ° C. while gently blowing nitrogen gas under stirring. Next, the polymerizable monomer solution was dropped from the dropping funnel over 2 hours and polymerized at 80 ° C. After completion of the dropwise addition, aging was carried out at the same temperature for 1 hour and then at reflux for 2 hours. Then, the mixed solvent 20 was added to the toluene solution.
0 parts were added to obtain a polymer wax solution (solid content: 20%). When this solution was analyzed, the polymerization rate was 100%. When the solvent was distilled off from this solution under reduced pressure heating, a white solid compound having a weight average molecular weight of 21,000 was obtained.

Comparative Reference Example 1 The same flask as in Reference Example 1 was charged with 50 parts of toluene, and heated to 80 ° C. while gently blowing nitrogen gas under stirring. Next, prepared in advance are 40 parts of stearyl acrylate and 5 parts of styrene.
A polymerizable monomer solution consisting of 5 parts, 5 parts of glycidyl methacrylate, 20 parts of toluene and 0.4 part of 2,2′-azobisisobutyronitrile was dropped from a dropping funnel over 2 hours, and polymerized at 80 ° C. did. After the completion of the dropwise addition, the mixture was aged at the same temperature for 1 hour to give 2,2′-azobisisobutyronitrile 0.2%.
Parts of an initiator solution consisting of 4 parts of toluene. Then, aging was performed for 2 hours under reflux. Then, 330 parts of a mixed solvent was added to this solution, and a polymer solution (solid content: 20%) was added.
I got Analysis of this solution showed that styrene was 0.4%.
% Was detected, and the polymerization rate was 100.0%. The solvent and the remaining styrene were distilled off from this solution under heating under reduced pressure to obtain a transparent viscous substance having a weight average molecular weight of 68,000.

(Comparative Reference Example 2) In the same flask as in Reference Example 1, polyethylene wax (Mitsui Petrochemical Co., Ltd.)
100 parts of Mitsui High Wax 4052E) and 100 parts of toluene were charged, and the temperature was raised to the reflux temperature while gently blowing nitrogen gas with stirring to complete dissolution. Then, this solution was added to 300 parts of the mixed solvent cooled to 10 ° C. while stirring with a homogenizer to obtain a polyethylene wax paste having a solid content of 20%.

Comparative Reference Example 3 Carnauba wax paste was obtained by repeating the same operation except that carnauba wax (purified carnauba wax No. 1 manufactured by Noda Wax Co., Ltd.) was used instead of the polyethylene wax of Comparative Reference Example 2. (Solid content 20%) was obtained. (Examples 1 to 11 and Comparative Examples 1 to 5) <Preparation of paint> 100 parts of acrylic resin (Alloset 2551, Nippon Shokubai Co., Ltd., nonvolatile content 45%), titanium white (CR
95, manufactured by Ishihara Sangyo Co., Ltd.) 30 parts, diluting solvent (cyclohexanone / butanol / ethyl acetate = 6/2/2 weight ratio, the same applies hereinafter) 20 parts, and Reference Examples 1 to 9 and Comparative Reference Examples 1 to 1
The wax obtained in the step 3 or the solution was added and dispersed in a sand mill to obtain paints (AP). Table 1 shows the types and amounts of the waxes. 50 ° C for each paint
For one month and examined for changes in appearance and viscosity. The results are shown in Table 1. ○ indicates no change, Δ indicates a slight change, and × indicates a remarkable change. <Method of manufacturing test plate> After diluting the test paint to an appropriate viscosity, a slate plate (75 mm x 150 mm, thickness 5 m
m) was spray-coated so that the dry film thickness was 30 μm. After drying at room temperature for 7 days, a coated plate was prepared. Table 2 shows the types of paints used. <Evaluation method of test plate> Performance evaluation was performed as follows using the obtained test plate. The results are shown in Table 2. Appearance of coating film: The uniformity of the color of the coating film was visually judged, and a good one was evaluated as ○, a slightly mottled pattern as Δ, and a markedly mottled pattern as X. Water repellency: After the test plate was immersed in water at 25 ° C. for 7 days, the coating film was inclined at 45 ° to drop water drops, and the flow of the water drops was visually observed. Good water repellency was evaluated as ○, slightly poor one as Δ, and poor one as ×. Adhesion: After drying the coated board subjected to the above-described evaluation of water resistance at room temperature for one day, cut 100 squares of 1 mm square on the coating film with a cutter knife, paste a cellophane tape, and peel off the cellophane tape. The coating film adhesion was examined. The number of squares where the coating film remained was indicated (100 is no peeling, 0 is all peeled).

[0047]

[Table 1]

[0048]

[Table 2]

[0049]

As described above, the coating composition of the present invention comprises:
Since it contains the specific polymer wax (I), it has good compatibility between the polymer wax (I) and the binder resin, has a smooth and uniform coating appearance, and is excellent in water repellency and adhesion. A coated film is formed. Further, since the polymer wax (I) has a high affinity for a solvent or a resin, the coating composition can be stably stored for a long period of time.

Claims (2)

[Claims] 1. A coating composition comprising a binder resin, a colorant and a wax, wherein the wax comprises at least one selected from repeating units represented by the following general formulas (1) and (2): A coating composition containing at least one polymer wax selected from a long side chain-containing polymer having a content of 100% by weight and a modified product of the long side chain-containing polymer. Embedded image Embedded image 2. The coating composition according to claim 1, wherein the wax comprises a polyolefin wax, alone and / or in the form of a reactant.