JP2018193529A - Coating Composition - Google Patents

Abstract

To provide a coating composition capable of forming a coating film having excellent adhesiveness to a substrate and high strength even when a coating surface of the substrate has a complicated shape.SOLUTION: There is provided a coating composition which comprises: a urethane (meth)acrylate (A) having two or more (meth)acryloyl groups in one molecule and a weight average molecular weight of 550 or more and less than 10000; a compound (B) having at least one group selected from the group consisting of a carboxyl group, a phosphate group and a phosphonic acid group and a weight average molecular weight of 50 or more and less than 550; a polymerizable unsaturated compound (C) having two or more polymerizable unsaturated groups in one molecule and no carboxyl group, phosphate group and phosphonic acid group and a weight average molecular weight of 200 or more and less than 550; and a polymerization initiator (D).SELECTED DRAWING: None

Description

  The present invention relates to a coating composition.

  Conventionally, for the purpose of imparting excellent appearance and performance to the substrate surface, a coating composition is applied on the substrate surface, and the formed wet coating film is cured to form a coating film. Has been done. Moreover, as the coating composition, a solvent-type coating composition and an active energy ray-curable coating composition in which the wet coating film is cured with active energy rays have been proposed (see, for example, Patent Document 1). In particular, the latter has been studied a lot from the viewpoint of energy saving and productivity improvement.

  Furthermore, in recent years, in various technical fields, high adhesion between a coating film and a substrate is required in addition to high strength on the painted surface of the substrate. However, generally, when the coating film strength is increased, the adhesion between the coating film and the substrate tends to decrease. This tendency becomes remarkable when the active energy ray-curable coating composition is used.

  Moreover, the opportunity to apply the said coating composition to the base material in which the coating surfaces, such as the outer-board part of a motor vehicle body, the interior / exterior components for motor vehicles, household appliances, furniture, and a building material, form a complicated shape is increasing.

International Publication No. 2009/050957

However, when the painted surface of the base material is a complicated shape, for example, a shape formed by combining a plurality of flat surfaces and / or curved surfaces, a portion having insufficient adhesion between the coating film made of the coating composition and the base material Are likely to occur, and problems such as peeling and swelling may occur.
On the other hand, the coating composition that forms a coating film having high strength and excellent adhesion to the base material is still not known in the prior art, including the technique disclosed in Patent Document 1. Absent.

  Accordingly, an object of the present invention is to provide a new coating composition that can form a coating film having high strength and excellent adhesion to the substrate even when the coated surface of the substrate has a complicated shape. It is in.

  As a result of intensive studies to achieve the above object, the present inventors have at least one group selected from the group consisting of a specific urethane (meth) acrylate, carboxyl group, phosphoric acid group and phosphonic acid group. It has been found that the above object can be achieved by using a coating composition containing a specific compound, a specific polymerizable unsaturated compound having no carboxyl group, phosphoric acid group and phosphonic acid group and a polymerization initiator.

That is, the present invention is as follows.
<1> Urethane (meth) acrylate (A) having a weight average molecular weight in the range of 550 or more and less than 10,000 and having two or more (meth) acryloyl groups in one molecule, and a weight average molecular weight of 50 A compound (B) having at least one group selected from the group consisting of a carboxyl group, a phosphoric acid group and a phosphonic acid group, and having a weight average molecular weight of 200 or more and less than 550. A polymerizable unsaturated compound (C) having two or more polymerizable unsaturated groups in one molecule and having no carboxyl group, phosphoric acid group and phosphonic acid group, and a polymerization initiator (D) A coating composition containing
<2> As at least one of the urethane (meth) acrylate (A), the weight average molecular weight is in the range of 550 or more and less than 10,000, and two or more (meth) acryloyl groups in one molecule. The coating composition as described in <1> above, which contains urethane (meth) acrylate (A11) having a polyoxyalkylene chain and one or more polyoxyalkylene chains.
<3> At least one of the urethane (meth) acrylates (A) has a weight average molecular weight in the range of 550 or more and less than 10,000, and two or more (meth) acryloyl groups in one molecule. And <1> or <2>, wherein the coating composition contains urethane (meth) acrylate (A12) having at least one cyclohexane ring.
<4> At least one of the urethane (meth) acrylates (A) has a weight average molecular weight in the range of 550 or more and less than 10,000, and two or more (meth) acryloyl groups in one molecule. <1>-<3> The coating composition of any one of said <1> containing the urethane (meth) acrylate (A13) which has 1 and one or more isocyanurate rings.
<5> As at least one of the compounds (B), the weight average molecular weight is in the range of 50 or more and less than 550, and at least one selected from the group consisting of a carboxyl group, a phosphate group and a phosphonate group. The coating composition according to any one of <1> to <4>, which contains a polymerizable unsaturated compound (B ′) having a group.
<6> Any one of the above <1> to <5>, which contains a polymerizable unsaturated compound (C ′) having a polyoxyalkylene chain as at least one of the polymerizable unsaturated compounds (C). The coating composition as described.
<7> When the nonvolatile content in the coating composition is 100 parts by mass in total, the nonvolatile content of the urethane (meth) acrylate (A) is 10 to 70 parts by mass, and the nonvolatile content of the compound (B) is 1 to 20 parts by mass, the nonvolatile content of the polymerizable unsaturated compound (C) is 10 to 80 parts by mass, and the nonvolatile content of the polymerization initiator (D) is 0.1 to 20 parts by mass. The coating composition according to any one of <1> to <6>.
<8> The coating composition according to any one of <1> to <7>, further containing a pigment.
<9> The amount of the pigment according to <8>, wherein the amount of the pigment is in the range of 0.1 to 40 parts by mass when the total amount of the polymerizable unsaturated compound in the coating composition is 100 parts by mass. Paint composition.
<10> The coating composition according to any one of <1> to <9>, wherein a non-volatile component accounts for 90 to 100% by mass in the coating composition.

  The coating composition according to the present invention includes a specific compound having at least one group selected from the group consisting of a specific urethane (meth) acrylate, a carboxyl group, a phosphate group, and a phosphonate group, a carboxyl group, a phosphate group, and It contains a specific polymerizable unsaturated compound having no phosphonic acid group and a polymerization initiator, has high strength, and even when the coated surface of the substrate has a complicated shape, A coating film having excellent adhesion can be formed.

Hereinafter, the coating composition of the present invention will be described in more detail.
In the present specification, “to” indicating a numerical range is used in a sense including numerical values described before and after the numerical value as a lower limit value and an upper limit value. In addition, “(meth) acryloyl” means at least one of acryloyl and methacryloyl, “(meth) acrylate” means at least one of acrylate and methacrylate, and “(meth) acrylic acid” At least one of acrylic acid and methacrylic acid, and “(meth) acrylamide” mean at least one of acrylamide and methacrylamide, respectively.

  The coating composition according to the present invention has a urethane (meth) acrylate (A) having a weight average molecular weight in the range of 550 or more and less than 10,000 and having two or more (meth) acryloyl groups in one molecule. The compound (B) having a weight average molecular weight in the range of 50 or more and less than 550 and having at least one group selected from the group consisting of a carboxyl group, a phosphoric acid group and a phosphonic acid group, and a weight average molecular weight of 200 or more A polymerizable unsaturated compound (C) within a range of less than 550, having two or more polymerizable unsaturated groups in one molecule, and having no carboxyl group, phosphoric acid group and phosphonic acid group; Contains a polymerization initiator (D).

[Urethane (meth) acrylate (A)]
The urethane (meth) acrylate (A) in the present invention has a weight average molecular weight in the range of 550 or more and less than 10,000, and has at least one of two or more acryloyl groups and methacryloyl groups in one molecule. A compound.

  Among these, the urethane (meth) acrylate (A) preferably has an average of 2 to 4 (meta) in one molecule from the viewpoint of adhesion between the coating film to be formed and the substrate and coating film strength. ) An acryloyl group, more preferably an average of 2 to 3 (meth) acryloyl groups in one molecule, and particularly preferably an average of 2 to 3 acryloyl groups in one molecule. In the present specification, the average number of (meth) acryloyl groups in one molecule of a compound is a theoretical value calculated from the equivalent ratio of raw materials used in the synthesis of the compound.

  Moreover, the weight average molecular weight of urethane (meth) acrylate (A) exists in the range of 550 or more and less than 10,000 as mentioned above. When the weight average molecular weight is 550 or more, the adhesion between the coating film and the substrate becomes good when the coating film is formed. Moreover, the coating-film external appearance and coating-film intensity | strength become it favorable that it is less than 10,000. From the viewpoint of coating film appearance, adhesion between the formed coating film and the substrate, and coating film strength, the weight average molecular weight is preferably in the range of 750 to 5,000, more preferably in the range of 1,000 to 3,500. is there.

  In this specification, the weight average molecular weight is the retention time (retention capacity) of a standard polystyrene having a known molecular weight measured under the same conditions as the retention time (retention capacity) measured using a gel permeation chromatograph (GPC). Is a value obtained by converting to a molecular weight of polystyrene. Specifically, “HLC-8120GPC” (trade name, manufactured by Tosoh Corporation) is used as a gel permeation chromatograph apparatus, and “TSKgel G4000HXL”, “TSKgel G3000HXL”, “TSKgel G2500HXL” and “TSKgel” are used as columns. G2000HXL "(trade name, all manufactured by Tosoh Corporation), using a differential refractometer as the detector, mobile phase: tetrahydrofuran, measurement temperature: 40 ° C, flow rate: 1 mL / min Can be measured below.

  Further, the glass transition temperature (Tg) of the urethane (meth) acrylate (A) is preferably 10 ° C. to 80 ° C., more preferably 30 from the viewpoints of adhesion between the formed coating film and the substrate and coating film strength. It is in the range of -50C.

  In addition, in this specification, the glass transition temperature (Tg) of urethane (meth) acrylate (A) is a static glass transition temperature. The static glass transition temperature is obtained, for example, by taking a sample in a measuring cup and completely removing the solvent by vacuum suction, and then using a differential scanning calorimeter “DSC-50Q type” (manufactured by Shimadzu Corporation, trade name) It can be measured by measuring the change in calorie in the range of −100 ° C. to 150 ° C. at a rate of temperature increase of 3 ° C./min and setting the first baseline change point on the low temperature side as the static glass transition temperature. .

  Examples of the urethane (meth) acrylate (A) include a polyisocyanate compound (a1) and a hydroxyl group-containing (meth) acrylate (a2) having one or more hydroxyl groups and one or more (meth) acryloyl groups in one molecule. ) And, if necessary, the polyol compound (a3) and / or the chain extension component (a4) of the hydroxyl group-containing compound, the urethane (meth) acrylate (A1); the polyol compound (a3); Isocyanate group-containing (meth) acrylate (a5) having one or more isocyanate groups and one or more (meth) acryloyl groups in one molecule, and if necessary, the polyisocyanate compound (a1) and / or hydroxyl group Urethane (meth) acrylate obtained by reacting with the chain extension component (a4) of the compound It is possible to use the door (A2) and the like.

(Polyisocyanate compound (a1))
The polyisocyanate compound (a1) is a compound having two or more isocyanate groups in one molecule. Examples of the polyisocyanate compound (a1) include aliphatic diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate and lysine diisocyanate, and uretdione type adducts, adduct type adducts and burettes of these diisocyanates. Type adduct, isocyanurate ring adduct; isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2,6-diisocyanate, 1,3-di (isocyanato) Methyl) cyclohexane, 1,4-di (isocyanatomethyl) cyclohexane, 1,4-cyclohexane diisocyanate, 1,3-cyclo Alicyclic diisocyanate compounds such as pentane diisocyanate and 1,2-cyclohexane diisocyanate and uretdione type adducts, adduct type adducts, burette type adducts, isocyanurate ring adducts of these diisocyanates; xylylene diisocyanate, metaxylylene diene Isocyanate, tetramethylxylylene diisocyanate, tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 1,4-naphthalene diisocyanate, 4,4′-toluidine diisocyanate, 4,4′-diphenyl ether diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethyl Aromatic diisocyanate compounds such as -4,4'-biphenylene diisocyanate, bis (4-isocyanatophenyl) sulfone, isopropylidenebis (4-phenylisocyanate), and uretdione type adducts, adduct type adducts of these diisocyanates, views Let type adduct, isocyanurate ring adduct; triphenylmethane-4,4 ′, 4 ″ -triisocyanate, 1,3,5-triisocyanatobenzene, 2,4,6-triisocyanatotoluene, 4, Polyisocyanate compounds having 3 or more isocyanate groups in one molecule such as 4'-dimethyldiphenylmethane-2,2 ', 5,5'-tetraisocyanate, and uretdione type adducts and adduct type adducts of these polyisocyanates , Buret tie Adducts, isocyanurate cycloadducts; ethylene glycol, propylene glycol, 1,4-butylene glycol, dimethylolpropionic acid, polyalkylene glycol, trimethylolpropane, hexanetriol and other isocyanate groups in excess of hydroxyl groups Examples thereof include urethanated adducts obtained by reacting polyisocyanate compounds in proportions, burette type adducts of these polyisocyanates, and isocyanurate ring adducts.

(Hydroxyl group-containing (meth) acrylate (a2))
The hydroxyl group-containing (meth) acrylate (a2) is a compound having one or more hydroxyl groups and one or more (meth) acryloyl groups in one molecule.

  Examples of the hydroxyl group-containing (meth) acrylate (a2) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. A monoesterified product of (meth) acrylic acid and a dihydric alcohol having 2 to 8 carbon atoms, such as a monoesterified product of the (meth) acrylic acid and a dihydric alcohol having 2 to 8 carbon atoms, N-hydroxymethyl (meth) acrylamide; allyl alcohol; (meth) acrylate having a polyoxyalkylene chain whose molecular end is a hydroxyl group; glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol Di (meta) acrelay Di (meth) acrylate compounds and the like; and tri (meth) acrylate compounds such as pentaerythritol tri (meth) acrylate.

(Polyol compound (a3))
The polyol compound (a3) is a compound having two or more hydroxyl groups in one molecule other than the hydroxyl group-containing (meth) acrylate (a2).

  Examples of the polyol compound (a3) include ethylene glycol, propylene glycol, diethylene glycol, trimethylene glycol, tetraethylene glycol, triethylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 2 , 3-butanediol, 1,2-butanediol, 2-methyl-1,3-propanediol, 3-methyl-1,2-butanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,2-pentanediol, 1,5-pentanediol, 1,4-pentanediol, 2,4-pentanediol, 2,3-dimethyltrimethylene glycol, tetramethylene glycol, 3-methyl-4,3-pentane Diol, 3-methyl-1,5-pentane 2,2,4-trimethyl-1,3-pentanediol, 1,6-hexanediol, 1,5-hexanediol, 1,4-hexanediol, 2,5-hexanediol, neopentyl glycol, Dihydric alcohols such as 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, hydroxypivalic acid neopentyl glycol ester, hydrogenated bisphenol A, hydrogenated bisphenol F, and dimethylolpropionic acid; ε- Polylactone diol added with a lactone compound such as caprolactone; Ester diol compound such as bis (hydroxyethyl) terephthalate; Alkylene oxide adduct of bisphenol A, polyethylene glycol, polypropylene glycol, polybutylene glycol Polyol compounds having a polyoxyalkylene chain such as: glycerin, trimethylolethane, trimethylolpropane, diglycerin, triglycerin, 1,2,6-hexanetriol, pentaerythritol, dipentaerythritol, tris (2-hydroxyethyl) Examples include trihydric or higher alcohols such as isocyanuric acid, sorbitol, and mannitol; polylactone polyol compounds obtained by adding lactone compounds such as ε-caprolactone to these trihydric or higher alcohols; fatty acid esterified products of glycerin, and the like.

(Chain Elongation Component of Hydroxyl-Containing Compound (a4))
The chain extension component (a4) of the hydroxyl group-containing compound is a compound capable of extending a molecular chain by reacting with a hydroxyl group-containing compound such as the hydroxyl group-containing (meth) acrylate (a2) and the polyol compound (a3).

  Examples of the chain extension component (a4) of the hydroxyl group-containing compound include lactone compounds such as ε-caprolactone and γ-valerolactone; and alkylene oxide compounds such as ethylene oxide and propylene oxide.

(Isocyanate group-containing (meth) acrylate (a5))
The isocyanate group-containing (meth) acrylate (a5) is a compound having one or more isocyanate groups and one or more (meth) acryloyl groups in one molecule.

  Examples of the isocyanate group-containing (meth) acrylate (a5) include isocyanate methyl (meth) acrylate, isocyanate ethyl (meth) acrylate, isocyanate propyl (meth) acrylate, isocyanate butyl (meth) acrylate, and isocyanate octyl (meth) acrylate. P-methacryloxy-α, α′-dimethylbenzyl isocyanate, m-acryloxy-α, α′-dimethylbenzyl isocyanate, m- or p-isopropenyl-α, α′-dimethylbenzyl isocyanate, 1,1-bis ( (Meth) acryloyloxymethyl) ethyl isocyanate, reaction product of 1 mole of hydroxyalkyl (meth) acrylate and 1 mole of diisocyanate compound, specifically, for example, isophorone diiso Equimolar addition of a compound having two isocyanate groups (different in reactivity) such as anate and a hydroxyl group-containing polymerizable unsaturated monomer such as 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate Examples include compounds obtained by the reaction.

(Method for synthesizing urethane (meth) acrylate (A))
The urethane (meth) acrylate (A) can be synthesized by subjecting a hydroxyl group-containing component and an isocyanate group-containing component to a known urethanization reaction. The above reaction can usually be carried out in an organic solvent. Examples of organic solvents include aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, and ester solvents such as ethyl acetate, propyl acetate, isobutyl acetate, and butyl acetate. Can be mentioned. These can be used as one or a mixture of two or more. The reaction temperature is preferably from room temperature to 100 ° C., and the reaction time is preferably from 1 to 10 hours.

  In the urethanization reaction, the progress of the reaction can be confirmed by tracking the isocyanate equivalent of the reaction solution. The isocyanate equivalent can be determined by back titration using dibutylamine. Specifically, the back titration can be carried out by adding an excess of dibutylamine to a sample and reacting, and titrating the remaining dibutylamine with an aqueous hydrochloric acid solution using bromophenol blue as a titration indicator.

  In the above reaction, an organic tin catalyst such as dibutyltin dilaurate, dibutyltin diethylhexoate or dibutyltin sulfite may be used as necessary. The amount of the catalyst is preferably 0.01 to 1.0 part by mass, and more preferably 0.1 to 0.5 part by mass with respect to 100 parts by mass of the total amount of reaction raw materials. A polymerization inhibitor such as hydroquinone monomethyl ether may be used. When using a polymerization inhibitor, it is preferable that the addition amount is 0.01-1.0 mass part with respect to 100 mass parts of total amounts of a reaction raw material.

The urethane (meth) acrylate (A) is preferably a urethane (meth) acrylate (A11) having one or more polyoxyalkylene chains from the viewpoint of adhesion between the coating film to be formed and the substrate. From the viewpoint of further improving the adhesion between the coating film to be formed and the substrate and the strength of the coating film, urethane (meth) acrylate (A11 ′) having a polyoxyalkylene chain and a cyclohexane ring is more preferable.
Among these, the urethane (meth) acrylate (A11) having a polyoxyalkylene chain preferably has an average of 1 in one molecule from the viewpoint of adhesion between the coating film to be formed and the substrate and coating film strength. ~ 100 polyoxyalkylene chains, more preferably 2 to 80 polyoxyalkylene chains on average per molecule, particularly preferably 10 to 60 polyoxyalkylene chains on average per molecule It is good. In the present specification, the average number of polyoxyalkylene chains in one molecule of a compound is a theoretical value calculated from the equivalent ratio of raw materials used in the synthesis of the compound.

  The urethane (meth) acrylate (A11) having a polyoxyalkylene chain is, for example, a hydroxyl group-containing (meth) acrylate having a polyoxyalkylene chain as at least one of the hydroxyl group-containing (meth) acrylate (a2). Method used: It can be produced by a method using a polyol compound having the polyoxyalkylene chain as at least one of the polyol compounds (a3).

Moreover, as said urethane (meth) acrylate (A), the urethane (meth) acrylate (A12) which has a 1 or more cyclohexane ring from a viewpoint of the intensity | strength of the coating film formed is also preferable. The urethane (meth) acrylate (A12) having a cyclohexane ring can be produced, for example, by a method using the polyisocyanate compound having a cyclohexane ring as at least one of the polyisocyanate compounds (a1).
Among these, the urethane (meth) acrylate (A12) having a cyclohexane ring is preferably 1 to 60 on average in one molecule from the viewpoints of adhesion between the coating film to be formed and the substrate and coating film strength. It is preferable to have one cyclohexane ring, more preferably 4 to 50 cyclohexane rings on average in one molecule, and particularly preferably 8 to 40 cyclohexane rings on average in one molecule. In this specification, the average number of cyclohexane rings in one molecule of a compound is a theoretical value calculated from the equivalent ratio of raw materials used during the synthesis of the compound.

  Moreover, as said urethane (meth) acrylate (A), the urethane (meth) acrylate (A13) which has a 1 or more isocyanurate ring from a viewpoint of the intensity | strength of the coating film formed is also preferable, and it forms especially. From the viewpoint of further improving the adhesion between the coating film and the substrate and the strength of the coating film, urethane (meth) acrylate (A13 ′) having a polyoxyalkylene chain and an isocyanurate ring is more preferable.

  Among these, the urethane (meth) acrylate (A13) having an isocyanurate ring is preferably 1 to 1 on average in one molecule from the viewpoint of adhesion between the coating film to be formed and the substrate and coating film strength. It is preferable to have 10 isocyanurate rings, more preferably 1 to 8 isocyanurate rings on average per molecule, and particularly preferably 1 to 6 isocyanurate rings on average per molecule. In the present specification, the average number of isocyanurate rings in one molecule of a compound is a theoretical value calculated from the equivalent ratio of raw materials used in the synthesis of the compound.

  The urethane (meth) acrylate (A13) having an isocyanurate ring is produced by, for example, a method using the polyisocyanate compound having an isocyanurate ring as at least one of the polyisocyanate compound (a1). Can do.

  Urethane (meth) acrylate (A) can be used individually or in combination of 2 or more types.

[Compound (B) having at least one group selected from the group consisting of carboxyl group, phosphoric acid group and phosphonic acid group]
The compound (B) in the present invention is a compound having a weight average molecular weight in the range of 50 or more and less than 550, and having at least one group selected from the group consisting of a carboxyl group, a phosphate group and a phosphonate group. .
Among these, from the viewpoint of adhesion between the coating film to be formed and the substrate, the weight average molecular weight of the compound (B) is preferably in the range of 100 to 400, more preferably 120 to 350. .

  Further, the total number of carboxyl groups, phosphoric acid groups and / or phosphonic acid groups in one molecule of the compound (B) is the viewpoint of the adhesion between the formed coating film and the substrate and the water resistance of the formed coating film. Therefore, it is preferably 1 to 3 on average, and more preferably 1 to 2 on average.

  The acid value of the compound (B) is preferably 100 to 950 mgKOH / g from the viewpoint of coating film appearance, adhesion between the formed coating film and the substrate, and water resistance of the formed coating film. -800 mgKOH / g is more preferable, and 120-650 mgKOH / g is more particularly preferable.

  In the present specification, the acid value (mgKOH / g) is expressed in mg of potassium hydroxide when the amount of acid groups contained in 1 g (solid content) of the sample is converted into potassium hydroxide. The molecular weight of potassium hydroxide is 56.1.

  Examples of the compound having a carboxyl group in the compound (B) include acetic acid (ethanoic acid), propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, Saturated fatty acids such as tetradecanoic acid; hydroxy acids such as lactic acid (2-hydroxypropanoic acid), malic acid (2-hydroxybutanedioic acid), citric acid (2-hydroxypropanetricarboxylic acid), benzoic acid (benzenecarboxylic acid), Aromatic carboxylic acids such as phthalic acid (benzene-1,2-dicarboxylic acid), isophthalic acid (benzene-1,3-dicarboxylic acid), terephthalic acid (benzene-1,4-dicarboxylic acid); Acid), malonic acid (propanedioic acid), succinic acid (butanedioic acid), glutaric acid (pentanedioic acid), adipic acid (hexanoic acid) Dicarboxylic acids such as dicarboxylic acid; tricarboxylic acids such as aconitic acid (1-propene-1,2,3-tricarboxylic acid); polymerizable unsaturated compounds having a carboxyl group among the polymerizable unsaturated compounds (B ′) described later And saturated compounds.

  Among the compounds (B), examples of the compound having a phosphate group include phosphoric acid; mono-n-propyl phosphoric acid, monoisopropyl phosphoric acid, mono-n-butyl phosphoric acid, monoisobutyl phosphoric acid, mono-tert- Monoalkyl phosphoric acid such as butyl phosphoric acid, monooctyl phosphoric acid, monodecyl phosphoric acid; di-n-propyl phosphoric acid, diisopropyl phosphoric acid, di-n-butyl phosphoric acid, diisobutyl phosphoric acid, di-tert-butyl phosphoric acid, dioctyl phosphoric acid Dialkyl phosphoric acid such as didecyl phosphoric acid; mono-n-propyl phosphorous acid, monoisopropyl phosphorous acid, mono-n-butyl phosphorous acid, monoisobutyl phosphorous acid, mono-tert-butyl phosphorous acid, monooctyl Monoalkyl phosphorous acid such as phosphorous acid and monodecyl phosphorous acid; di-n-propyl phosphorous acid, diisopropyl Phosphorous acid, di-n-butyl phosphorous acid, diisobutyl phosphorous acid, di-tert-butyl phosphorous acid, dialkyl phosphorous acid such as dioctyl phosphorous acid, didecyl phosphorous acid and the like; Among the compounds (B ′), a polymerizable unsaturated compound having a phosphate group can be mentioned.

  Examples of the compound having a phosphonic acid group in the compound (B) include phosphonic acid; a polymerizable unsaturated compound having a phosphonic acid group in the polymerizable unsaturated compound (B ′) described later.

  As said compound (B), it is preferable to use the compound which has the said carboxyl group, and / or the compound which has a phosphate group from a viewpoint of the adhesiveness of the coating film formed and a base material.

Moreover, as said compound (B), the polymeric property which has at least 1 group chosen from the group which consists of a carboxyl group, a phosphoric acid group, and a phosphonic acid group from a viewpoint of the adhesiveness of the coating film formed and a base material. An unsaturated compound (B ′) is preferred.
The polymerizable unsaturated compound (B ′) is a compound having a polymerizable unsaturated group in one molecule and having a weight average molecular weight in the range of 50 or more and less than 550.

The number of polymerizable unsaturated groups in one molecule of the polymerizable unsaturated compound (B ′) is preferably 1 to 6 on average from the viewpoint of adhesion between the coating film to be formed and the substrate. More preferably, the number is 1 to 4, more preferably 1 to 3.
In addition, the unsaturated group equivalent of the polymerizable unsaturated compound (B ′) is preferably 50 to 550 g / mol, more preferably 60 to 500 g / mol from the viewpoint of adhesion between the coating film to be formed and the substrate. 70 to 450 g / mol is more preferable.

  In addition, in this specification, an unsaturated group equivalent is the mass of the compound per mol of polymerizable unsaturated groups, and is a value obtained by dividing the mass of the compound by the amount of polymerizable unsaturated groups present in the compound ( g / mol). In the present specification, the unsaturated group equivalent is a theoretical value calculated from the mass of the raw material used during the synthesis of the compound.

  Among the polymerizable unsaturated compounds (B ′), examples of the polymerizable unsaturated compound having a carboxyl group include acrylic acid, acrylic acid dimer, acrylic trimer, methacrylic acid, crotonic acid, isocrotonic acid, itaconic acid, maleic acid. Acid, fumaric acid, cinnamic acid, citraconic acid, 2-acryloyloxyethyl succinic acid, monomethyl itaconate, 2-acryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl trimellitic acid, 2-methacryloyloxyethyl pyromellitic Acid, 2-carboxyethyl (meth) acrylate (for example, β-carboxyethyl acrylate), 2-carboxypropyl (meth) acrylate, 3-carboxypropyl (meth) acrylate, 5-carboxypentyl (meth) acrylate, itaconic anhydride , Maleic anhydride, fumaric anhydride, ω-carboxy-polycaprolactone (n≈2) monoacrylate (trade name “Aronix M5300”, manufactured by Toagosei Co., Ltd.), phthalic acid monohydroxyethyl acrylate (trade name “Aronix M5400”) , Manufactured by Toagosei Co., Ltd.).

  As the polymerizable unsaturated compound having a phosphate group in the polymerizable unsaturated compound (B ′), for example, a phosphate ester-based (meth) acrylate (for example, 2- (methacryloyloxy) ethyl phosphate (trade name “Sartomer SR9050”) is used. ”, Manufactured by Sartomer), tris [2- (methacryloyloxy) ethyl] phosphate (trade name“ Sartomer SR9051 ”, manufactured by Sartomer), tris [2- (acryloyloxy) ethyl phosphate] (trade name“ Sartomer SR9053 ”) ", Manufactured by Sartomer), trifunctional acrylic acid ester (trade name" EM2305 ", manufactured by Changxing Chemical Co., Ltd.), and the like.

  Examples of the polymerizable unsaturated compound having a phosphonic acid group in the polymerizable unsaturated compound (B ′) include 2-phosphonoethyl acrylate and 2-phosphonoethyl methacrylate.

  Among the polymerizable unsaturated compounds (B ′), it is possible to form a coating film having excellent adhesion to the substrate and having high strength, and therefore, the polymerizable unsaturated compound having at least one of a carboxyl group and a phosphate group. Saturated compounds are preferred, from 2-carboxyethyl (meth) acrylate (eg β-carboxyethyl acrylate), ω-carboxy-polycaprolactone (n≈2) monoacrylate (trade name “Aronix M5300”) and “Sartomer SR9050” It is more preferable to use at least one selected.

  A compound (B) can be used individually or in combination of 2 or more types.

[Polymerizable unsaturated compound having no carboxyl group, phosphoric acid group and phosphonic acid group (C)]
The polymerizable unsaturated compound (C) in the present invention has a weight average molecular weight in the range of 200 or more and less than 550, has two or more polymerizable unsaturated groups in one molecule, and has a carboxyl group, phosphorus It is a polymerizable unsaturated compound having neither an acid group nor a phosphonic acid group.

  Among these, 2 to 4 polymerizable unsaturated compounds (C) are averaged in one molecule, preferably 2 to 2 from the viewpoints of adhesion between the coating film to be formed and the substrate and coating film strength. It preferably has 3 polymerizable unsaturated groups.

The weight average molecular weight of the polymerizable unsaturated compound (C) is 200 or more and less than 550 as described above. When the weight average molecular weight is 200 or more, the adhesion between the formed coating film and the substrate is improved. Moreover, by being less than 550, the coating film appearance, the adhesion between the formed coating film and the substrate, and the coating film strength are improved.
The weight average molecular weight of the polymerizable unsaturated compound (C) is preferably 200 to 400, more preferably from the viewpoints of coating film appearance, adhesion between the formed coating film and the substrate, and coating film strength. 200-300.

  In addition, the unsaturated group equivalent of the polymerizable unsaturated compound (C) is preferably 100 to 250 g / mol from the viewpoint of coating film appearance, adhesion between the formed coating film and the substrate, and coating film strength. 100 to 200 g / mol is more preferable, and 100 to 150 g / mol is particularly preferable.

Examples of the polymerizable unsaturated compound (C) include an esterified product of a polyhydric alcohol and (meth) acrylic acid. Specifically, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol Di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,3-butanediol di (meth) ) Acrylate, 1,4-butanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, , 6-hexanediol di (meth) acrylate, bisphenol A ethylene oxide modified di (meth) acrylate, isocyanuric acid ethylene oxide modified di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, isosorbide di (meth) acrylate, etc. Di (meth) acrylate compound: glycerin tri (meth) acrylate, glycerin ethylene oxide modified tri (meth) acrylate, glycerin propylene oxide modified tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide modified Tri (meth) acrylate, trimethylolpropane propylene oxide modified tri (meth) acrylate, isocyanuric acid ethylene oxide Tri (meth) acrylate compounds such as modified tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ε-caprolactone modified tris (acryloxyethyl) isocyanurate; pentaerythritol tetra (meth) acrylate, pentaerythritol ethylene oxide modified tetra (Meth) acrylate, pentaerythritol propylene oxide modified tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ditrimethylolpropane ethylene oxide modified tetra (meth) acrylate, ditrimethylolpropane propylene oxide modified tetra (meth) acrylate, di Glycerin tetra (meth) acrylate, diglycerin ethylene oxide modified tetra (meth) acrylate DOO, tetra (meth) acrylate compounds such as diglycerin propylene oxide-modified tetra (meth) acrylate and the like; dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate.
A polymerizable unsaturated compound (C) can be used individually or in combination of 2 or more types.

  In the present invention, from the viewpoint of adhesion between the coating film to be formed and the substrate, the polymerizable unsaturated compound (C) is preferably a polymerizable unsaturated compound (C ′) having a polyoxyalkylene chain.

[Polymerization initiator (D)]
The polymerization initiator (D) is a polymerization initiator selected from the photopolymerization initiator (D1) and the thermal polymerization initiator (D2). Among these, the polymerization initiator is excellent because it can form a coating film having excellent coating storage stability, excellent thermal adhesion of the base material, excellent adhesion to the base material, and high strength. It is preferable to use a photopolymerization initiator (D1) as at least one of (D).

  Moreover, as a polymerization initiator (D), the said photoinitiator (D1) and thermal-polymerization initiator (D2) can be used in combination. In addition, when performing active energy ray irradiation when forming a coating film using a coating composition, a photoinitiator (D1) is used as at least 1 type of the said polymerization initiator (D), and it heats. In this case, a thermal polymerization initiator (D2) is used as at least one kind of the polymerization initiator (D).

  When forming a coating film using the coating composition according to the present invention, when the substrate is a substrate that is easily thermally deformed, such as an organic material, a photopolymerization initiator (D) is used as the polymerization initiator (D). It is preferable to perform active energy ray irradiation using D1) because it is possible to form a coating film having excellent adhesion to the substrate and high strength while suppressing thermal deformation of the substrate. .

[Photopolymerization initiator (D1)]
The photopolymerization initiator (D1) is a compound that absorbs active energy rays and generates free radicals (even in the form of an intermediate), and may be a mixture of two or more compounds. Photoinitiators (D1) include photochemically activatable compounds (for example, benzoin), combinations of chromophores and coinitiators (for example, benzophenone and tertiary amines), mixtures thereof, sensitizers, Redox systems such as combinations of coinitiators (eg thioxanthone and tertiary amine) or chromophores (eg thioxanthone and aminoketone), combinations of H ₂ O ₂ and iron (II) salts, dyes and boron Examples thereof include electron transport pairs such as acid salts and / or amines.

  Specific examples of the photopolymerization initiator (D1) include, for example, α-diketone compounds such as benzyl and diacetyl; acyloin compounds such as benzoin; acyloin ether compounds such as benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; Thioxanthone compounds such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, thioxanthone-4-sulfonic acid; benzophenone, o-methylbenzoylbenzoate, 4-methylbenzophenone, 4-phenylbenzophenone, 4,4′-bis (dimethyl) Benzophenone compounds such as amino) benzophenone and 4,4′-bis (diethylamino) benzophenone; Michler's ketone compound; acetophenone, 2- (4-toluenesulfonyloxy) 2-phenylacetophenone, p-dimethylaminoacetophenone, α, α′-dimethoxyacetoxybenzophenone, 2,2′-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl [4- (methylthio) phenyl]- 2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, α-isohydroxyisobutylphenone, α, α′-dichloro-4-phenoxy Acetophenone compounds such as acetophenone and 1-hydroxy-cyclohexyl-phenyl-ketone; acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (acyl) phosphine oxide; anthraquinone; , 4-quinone of naphthoquinone; can be exemplified peroxides such as di -t- butyl peroxide or the like; phenacyl chloride, trihalomethyl phenyl sulfone, tris (trihalomethyl) -s-halogen compounds such as triazines.

  Examples of commercially available photopolymerization initiators (D1) include IRGACURE-127, IRGACURE-184, IRGACURE-261, IRGACURE-369, IRGACURE-500, IRGACURE-651, IRGACURE-754, IRGACURE-819, Irgacure-907, Irgacure-CGI-1700, Irgacure-2959, Irgacure-TPO, Darocur-1173 (above, product name manufactured by BASF); Kayacure-DETX-S, Kayacure-EPA (above, Nippon Kayaku) ESACURE KIP 150, ESACURE ONE (LAMBERTI, trade name); SB-PI701, SB-PI703, SB-PI704, SB-PI705, SB-PI707 SB-PI710, SB-PI711, SB-PI712, SB-PI714, SB-PI716, SB-PI718, SB-PI719, SB-PI751, SB-PI759, SB-PI769, SB-PI777, SB-PI799, SB- PI818, SB-PI850, SB-PI865, SB-PI8100 (above, trade name, manufactured by SHOKUYO INDUSTRY CO., LTD.) And the like.

  The said photoinitiator (D1) can be used individually or in combination of 2 or more types, respectively.

[Thermal polymerization initiator (D2)]
The thermal polymerization initiator (D2) is a compound that generates free radicals (even in the form of an intermediate) or a mixture of these compounds when heated. Examples of the thermal polymerization initiator (D2) include benzoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, cumene hydroperoxide, tert-butyl peroxide, tert-butyl peroxylaurate, and tert- Organic peroxides such as butyl peroxyisopropyl carbonate, tert-butyl peroxyacetate, diisopropylbenzene hydroperoxide; azobisisobutyronitrile, azobis (2,4-dimethylvaleronitrile), azobis (2-methylpropiononitrile) ), Azobis (2-methylbutyronitrile), 4,4′-azobis (4-cyanobutanoic acid), dimethylazobis (2-methylpropionate), azobis [2-methyl-N- (2-H Azo compounds such as droxyethyl) -propionamide] and azobis {2-methyl-N- [2- (1-hydroxybutyl)]-propionamide}; persulfates such as potassium persulfate, ammonium persulfate and sodium persulfate Can be mentioned.

  Commercially available products of the thermal polymerization initiator (D2) include, for example, VA-044, VA-046B, V-50, VA-057, VA-061, VA-067, VA-086, V-60, V-70. , V-65, V-601, V-59, V-40, VF-096, VAm-110 (above, Wako Pure Chemical Industries, Ltd., trade name), Perbutyl H, Perocta O (above, NOF Corporation) , Trade name) and the like.

  The thermal polymerization initiator (D2) may be used as a redox initiator in combination with a reducing agent such as sugar, sodium formaldehyde sulfoxylate, or iron complex, if necessary. The said thermal-polymerization initiator (D2) can be used individually or in combination of 2 or more types.

[Coating composition]
The coating composition according to the present invention is a coating composition containing the urethane (meth) acrylate (A), the compound (B), the polymerizable unsaturated compound (C) and the polymerization initiator (D) described above. .

The blending ratio of the nonvolatile content of urethane (meth) acrylate (A), compound (B), polymerizable unsaturated compound (C), and polymerization initiator (D) in the coating composition is the coating film and substrate to be formed. From the viewpoints of adhesiveness and coating film strength, when the nonvolatile content of the coating composition is 100 parts by mass in total, it is preferably within the following range.
Urethane (meth) acrylate (A): Preferably it is 10-70 mass parts, More preferably, it is 25-65 mass parts, More preferably, it is 30-60 mass parts.
Compound (B): Preferably 1-20 mass parts, More preferably, it is 1-15 mass parts, More preferably, it is 1-10 mass parts.
Polymerizable unsaturated compound (C): Preferably it is 10-80 mass parts, More preferably, it is 15-70 mass parts, More preferably, it is 20-60 mass parts.
Polymerization initiator (D): Preferably it is 0.1-20 mass parts, More preferably, it is 0.5-15 mass parts, More preferably, it is 1.0-10 mass parts.
When the polymerizable unsaturated compound (C ′) having a polyoxyalkylene chain is used as at least one kind of the polymerizable unsaturated compound (C), the polymerizable unsaturated compound having a polyoxyalkylene chain is used. The blending ratio of the non-volatile content of (C ′) is determined when the non-volatile content of the coating composition (1) is 100 parts by mass in total from the viewpoint of the adhesion between the coating film to be formed and the base material and the coating film strength. Preferably, it is 5-75 mass parts, More preferably, it is 8-65 mass parts, More preferably, it is 10-55 mass parts.

The non-volatile content in the coating composition according to the present invention preferably occupies 90 to 100% by mass, more preferably 95 to 100% by mass, and even more preferably 98 to 100% by mass, so-called solventless coating. A composition is preferable, and an active energy ray-curable coating composition is more preferable.
In addition, in this specification, a non-volatile component means all the components except a solvent among the components which comprise a coating composition.

[Other polymerizable unsaturated compounds]
The coating composition of the present invention may further contain other polymerizable unsaturated compounds other than the components (A), (B) and (C).
As other polymerizable unsaturated compounds other than the components (A), (B), and (C), one polymerizable unsaturated group is contained in one molecule, and a carboxyl group, a phosphate group, and A compound having no phosphonic acid group can be preferably used.

  Examples of other polymerizable unsaturated compounds other than the above components (A), (B) and (C) include, for example, esterified products of monohydric alcohol and (meth) acrylic acid, hydroxyl group-containing (meth) acrylate, glycidyl group. Examples thereof include a containing (meth) acrylate, a vinyl aromatic compound, a nitrogen-containing alkyl (meth) acrylate, a polymerizable amide compound, and a hydrolyzable silane compound having a polymerizable unsaturated group. Among these, esterified products of monohydric alcohol and (meth) acrylic acid, hydroxyl group-containing (meth) acrylate, and nitrogen-containing alkyl (meth) acrylate are preferable.

  Examples of esterified products of monohydric alcohol and (meth) acrylic acid include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth). Acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, neopentyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl ( And (meth) acrylate, N-acryloyloxyethyl hexahydrophthalimide and the like.

  Examples of the hydroxyl group-containing (meth) acrylate include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and the like.

  Examples of the glycidyl group-containing (meth) acrylate include glycidyl (meth) acrylate and allyl glycidyl ether.

  Examples of the vinyl aromatic compound include styrene, α-methylstyrene, vinyltoluene, α-chlorostyrene, and the like.

  Examples of the nitrogen-containing alkyl (meth) acrylate include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, Nt-butylaminoethyl (meth) acrylate, 4- ( And (meth) acryloylmorpholine.

  Examples of the polymerizable amide compound include acrylamide, methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N- (2-hydroxyethyl) ( And (meth) acrylamide.

  Examples of the hydrolyzable silane compound having a polymerizable unsaturated group include 3- (meth) acryloyloxypropyltrimethoxysilane, 2- (meth) acryloyloxyethyltrimethoxysilane, and 3- (meth) acryloyloxypropyltri Examples include ethoxysilane, 2- (meth) acryloyloxyethyltriethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, trimethoxyvinylsilane, and triethoxyvinylsilane.

  When the coating composition according to the present invention contains other polymerizable unsaturated compounds, the blending ratio of the other polymerizable unsaturated compounds in the coating composition is such that the nonvolatile content of the coating composition is 100 parts by mass in total. 1 to 50 parts by mass is preferable, 3 parts by mass or more is more preferable, and 45 parts by mass or less is more preferable.

[Additive]
In addition to the above, the coating composition according to the present invention may further contain an ultraviolet absorber and / or a light stabilizer. If necessary, cross-linking agent, solvent (organic solvent, water), pigment, catalyst, antioxidant, surface conditioner, antifoaming agent, emulsifier, surfactant, antifouling agent, wetting agent, thickener. In addition, other additive components ordinarily used in the field of coating, such as dyes, scratch resistance improvers, and gloss modifiers, can be appropriately contained.

(UV absorber)
As the ultraviolet absorber, conventionally known ones can be used. For example, a benzotriazole-based absorbent, a triazine-based absorbent, a salicylic acid derivative-based absorbent, a benzophenone-based absorbent, or the like can be used. Moreover, the said ultraviolet absorber may have a polymerizable unsaturated group.

  Specific examples of the benzotriazole-based absorbent include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- ( 2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2 -(2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-t-amylphenyl) benzotriazole 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole, 2- {2′-hydroxy-3 ′-(3 ″, 4 ″, 5 ″, 6 ″ -teto Hydro) -5'-methylphenyl} benzotriazole, 2- [2-hydroxy-5- [2- (methacryloyloxy) ethyl] phenyl] -2H- benzotriazole.

  Specific examples of the triazine-based absorbent include 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-isooctyloxyphenyl) -1,3,5-triazine, 2- [4 ((2-hydroxy-3-dodecyloxypropyl) -oxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [ 4-((2-hydroxy-3-tridecyloxypropyl) -oxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and the like.

  Specific examples of the salicylic acid derivative-based absorbent include phenyl salicylate, p-octylphenyl salicylate, 4-tert-butylphenyl salicylate, and the like.

  Specific examples of the benzophenone-based absorbent include 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-octadecyloxy Benzophenone, sodium 2,2′-dihydroxy-4,4′-dimethoxy-5-sulfobenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 5-chloro-2 -Hydroxy Nzophenone, resorcinol monobenzoate, 2,4-dibenzoylresorcinol, 4,6-dibenzoylresorcinol, hydroxydodecylbenzophenone, 2,2′-dihydroxy-4 (3-methacryloxy-2-hydroxypropoxy) benzophenone, etc. .

  Moreover, as a commercial item of the said ultraviolet absorber, for example, TINUVIN 900, TINUVIN 928, TINUVIN 348-2, TINUVIN 479, TINUVIN 405, TINUVIN 400, (manufactured by BASF, trade name, TINUVIN \ Tinuvin is a registered trademark), And RUVA 93 (trade name, manufactured by Otsuka Chemical Co., Ltd.).

  When the coating composition of this invention contains the said ultraviolet absorber, the compounding quantity of this ultraviolet absorber exists in the range of 0.5-10 mass% with respect to the non volatile matter total amount of this coating composition. More preferably, it is 0.8-9 mass%, More preferably, it is 1.0-8 mass%.

(Light stabilizer)
The light stabilizer is used as a radical chain inhibitor that traps active radical species generated during the deterioration process of the coating film, and examples thereof include a light stabilizer of a hindered amine compound.

  Among the light stabilizers, a hindered piperidine compound may be mentioned as a light stabilizer exhibiting an excellent light stabilizing action. Examples of the hindered piperidine compound include bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis ( N-methyl-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 4-benzoyloxy-2,2 ′, 6,6′-tetramethylpiperidine, bis (1,2,2,6, Monomer type such as 6-pentamethyl-4-piperidyl) {[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl} butyl malonate; poly {[6- (1,1 , 3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene Oligomer type such as (2,2,6,6-tetramethyl-4-piperidyl) iminol]}; 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and succinic acid Examples include polyester-bonded types such as polyesters, but are not limited thereto. A known polymerizable light stabilizer can also be used as the light stabilizer.

  Commercially available products of the light stabilizer include, for example, TINUVIN 123, TINUVIN 152, TINUVIN 292 (trade name, TINUVIN \ Tinuvin is a registered trademark), HOSTAVIN 3058 (trade name, Hostavin is a registered trademark, manufactured by Clariant). ), ADK STAB LA-82 (manufactured by ADEKA Corporation, trade name, ADK STAB \ ADKSTAB and ADK STAB are registered trademarks), and the like.

  When the coating composition of this invention contains the said light stabilizer, the compounding quantity of this light stabilizer is in the range of 0.5-10 mass% with respect to the non volatile matter total amount of this coating composition. More preferably, it is 0.8-9 mass%, More preferably, it is 1.0-8 mass%.

(Crosslinking agent)
As the crosslinking agent, for example, a carbodiimide compound or the like can be used. When at least one of the components (A), (B), and (C) has a hydroxyl group, the polyisocyanate compound, blocked poly Isocyanate compounds, melamine resins, and the like can also be used.

(solvent)
As said solvent, an organic solvent, water, etc. can be used, for example. Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate, butyl acetate, methyl benzoate, ethyl ethoxypropionate, ethyl propionate, and methyl propionate; tetrahydrofuran, dioxane Ethers such as dimethoxyethane; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate; aromatic hydrocarbons, aliphatic hydrocarbons And the like.

(Pigment)
Examples of the pigment include a luster pigment, a color pigment, and an extender pigment. The pigments can be used alone or in combination of two or more.

  Examples of the bright pigment include aluminum (including vapor-deposited aluminum), copper, zinc, brass, nickel, glass flake, aluminum oxide, mica, titanium oxide and / or iron oxide coated with iron oxide, titanium oxide, and the like. Examples thereof include mica coated with iron oxide.

  Examples of the color pigment include titanium oxide, zinc oxide, carbon black, molybdenum red, Prussian blue, cobalt blue, azo pigment, phthalocyanine pigment, quinacridone pigment, isoindoline pigment, selenium pigment, and perylene pigment. , Dioxazine pigments, diketopyrrolopyrrole pigments, thermal barrier pigments and the like.

  Examples of the extender pigment include clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talc, silica, and alumina white.

  When the coating composition (1) contains the pigment, the amount of the pigment is determined in the coating composition (1) from the viewpoints of adhesion between the coating film to be formed and the substrate and coating film strength. When the total amount of the polymerizable unsaturated compounds is 100 parts by mass, it is preferably within the range of 0.1 to 40 parts by mass, more preferably 3 to 30 parts by mass, and even more preferably 5 to 20 parts by mass. It is.

[Method for forming coating film by coating composition]
After forming a wet coating film (uncured coating film) by coating the coating composition of the present invention on a substrate, the target coating film can be formed by curing the wet coating film. .

  There is no restriction | limiting in particular as a material of a base material, Any of an inorganic material or an organic material, or the hybrid material of an organic material and an inorganic material may be sufficient.

  Examples of the inorganic material include metal materials such as iron, aluminum, brass, copper, tinplate, stainless steel, galvanized steel, and zinc alloy (eg, Zn—Al, Zn—Ni, Zn—Fe, etc.) plated steel; Glass; cement; concrete and the like.

  Examples of the organic material include acrylic resins such as polymethyl methacrylate, polyethylene terephthalate, polyethylene naphthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4, 4′-diene. Polyester resins such as carboxylate and polybutylene terephthalate, epoxy resins represented by commercial products such as Epicoat (trade name: manufactured by Yuka Shell Epoxy Co., Ltd.), polycarbonate resins, polyimide resins, novolac resins, phenol resins, Acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-ethylene-styrene (AES) resin, acrylonitrile-styrene-acrylate (ASA) resin, vinyl chloride resin, vinylidene chloride resin, Urethane resin, cellulose ester (eg, triacetylcellulose, diacetylcellulose, propionylcellulose, butyrylcellulose, acetylpropionylcellulose, nitrocellulose), polyamide, polystyrene (eg, syndiotactic polystyrene), polyolefin (eg, polypropylene, polyethylene, Polymethylpentene), polysulfone, polyethersulfone, polyarylate, polyetherimide, polyetherketone, various fiber reinforced plastic materials (hereinafter referred to as FRP material or simply FRP), and the like.

  Among them, the materials of the base material include vinyl chloride (PVC) resin, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-ethylene-styrene (AES) resin, acrylonitrile-styrene-acrylate (ASA) resin, and polycarbonate (PC). Resins are preferred, and vinyl chloride resins are particularly preferred.

  In general, since vinyl chloride resin is excellent in processability, it is relatively often used as a base material for articles having complex shapes, and the effect is further enhanced when the coating composition of the present invention is applied. Further, the base material can have a complicated shape formed by combining, for example, a plurality of planes and / or curved surfaces in addition to a simple shape including only a plane. In particular, in the case of a complicated shape, a portion having insufficient adhesion to a coating film made of a coating composition is likely to be generated, and the effect is further enhanced when the coating composition of the present invention is applied.

  In addition, the base material is coated with a primer paint, a cationic electrodeposition paint, an intermediate paint or a top paint, on a material such as the inorganic material or the organic material, or a hybrid material of an organic material and an inorganic material, A primer layer, an electrodeposition coating layer, an intermediate coating layer, a top coating layer, or the like may be formed in advance.

  The substrate has been subjected to treatment (physical treatment) by at least one physical method selected from plasma treatment, corona discharge treatment, active energy ray treatment, flame treatment, blast treatment, polishing treatment, and the like. Also good.

  In addition, the application of the object to be coated with the coating composition according to the present invention is not particularly limited, and examples thereof include an outer plate portion of an automobile body such as a passenger car, a truck, a motorcycle, and a bus; a bumper, a center pillar, and a mirror. Automotive interior and exterior parts such as door handles, instrument panels, door trims, center consoles, etc .; furniture and building materials related parts such as chairs, makeup mirrors, window frames, and gates; outer panels of household electrical products such as mobile phones and audio equipment And the like.

The method for applying the coating composition on the substrate is not particularly limited. For example, it can be applied by air spray, airless spray, rotary atomizing coater, dip coating, applicator, brush, roller or the like. You may apply electrostatic at the time of application | coating. The coating film thickness is usually 10 to 100 μm, preferably 10 to 70 μm, and more preferably 10 to 40 μm as a cured film thickness.
The coating composition is preferably applied directly on the substrate.

  The coating composition of the present invention comprises a specific urethane (meth) acrylate (A), a compound (B) having at least one group selected from the group consisting of a carboxyl group, a phosphoric acid group and a phosphonic acid group, a carboxyl group, phosphorus It contains a polymerizable unsaturated compound (C) having no acid group and phosphonic acid group, and a polymerization initiator (D). The presence of the compound (B) makes it easier for the polymerizable unsaturated compound (C) to penetrate into the interior of the substrate surface, and the penetrated polymerizable unsaturated compound (C) when the coating film is cured. And the urethane (meth) acrylate (A) and polymerizable unsaturated compound (C) on the surface of the base material are polymerized to form a cured coating film, so that the adhesion between the base material and the coating film is excellent. It is assumed that

  When the polymerization initiator (D) is a photopolymerization initiator (D1), the coating composition of the present invention irradiates the coating composition with an active energy ray and applies the coating composition on the coated substrate. It can be cured.

(Active energy ray irradiation)
A well-known thing can be used as an active energy ray irradiated. Specific examples include ultraviolet light, visible light, laser light (near infrared laser, visible light laser, ultraviolet laser, etc.), microwave, electron beam, electromagnetic wave, and the like. Of these active energy rays, ultraviolet rays are preferable from the viewpoint of economy.

  Irradiation of active energy rays can be performed using any light source that emits electromagnetic waves having a wavelength that can be absorbed by the photopolymerization initiator (D1) present in the coating composition applied onto the substrate. Such a light source usually emits an electromagnetic wave having a wavelength in the range of 200 nm to 2,000 nm.

  A well-known thing can be used as an irradiation source of an active energy ray. Specifically, for example, ultra high pressure, high pressure, medium pressure, low pressure mercury lamp, electrodeless lamp, chemical lamp, carbon arc lamp, xenon lamp, metal halide lamp, fluorescent lamp, tungsten lamp, LED (Light Emitting Diode), light emitting diode ), Sunlight, etc. can be used. In addition, a pulsed emission type active energy ray irradiation apparatus can also be used.

  In addition, the irradiation with active energy rays may be performed on the entire region and / or part of the region through, for example, a mask or a laser beam. It is also possible to cure the coating only in a specific area by the means.

The dose of the active energy ray, usually, for example, in the case of a high-pressure mercury lamp, 50~3,000mJ / cm ^2, in the case of a metal halide lamp, 100~5,000mJ / cm ^2, especially for a high-pressure mercury lamp, 100 In the case of ˜1,000 mJ / cm ² and a metal halide lamp, it is preferably in the range of 500 to 2,000 mJ / cm ² . Irradiation of active energy rays can be performed in air or under an inert gas. As the inert gas, nitrogen gas, carbon dioxide, argon, helium, or a mixture thereof can be used.

  Moreover, you may heat together with hardening by an active energy ray. As the heating means, for example, hot air, hot gas, infrared heater, IR radiator, oven, hot roller, microwave and the like can be used. When heating is performed, the heating conditions are determined from the viewpoints of productivity, workability, and thermal stability of the substrate, but the heating temperature is within a range of 30 to 120 ° C, particularly 50 to 90 ° C. The heating time is preferably in the range of 1 to 60 minutes, particularly 1 to 20 minutes.

  When heating, the order of active energy ray irradiation and heating is not particularly limited, heating may be performed after active energy ray irradiation, active energy ray irradiation may be performed after heating, and active energy ray irradiation. Heating may be performed simultaneously.

  When performing active energy ray irradiation and heating at the same time, heat from an active energy ray irradiation source (for example, heat generated by a lamp) may be used as a heat source. Furthermore, when the active energy ray irradiation is performed after the heating, the active energy ray irradiation may be performed in a state where the substrate on which the coating composition is applied is heated (a state having a residual heat).

  Moreover, when a polymerization initiator (D) is a thermal polymerization initiator (D2), the coating composition on the apply | coated base material can be hardened by heating a coating composition.

(heating)
For the heating, a method known in this field can be appropriately used. Specifically, for example, hot air, hot gas, an infrared heater, an IR radiator, an oven, a heat roller, and a microwave can be used. In the present invention, it is preferable to perform heating with hot air, an infrared heater or the like from the viewpoints of ease of work and ability to perform at a low temperature.

  The heating temperature is preferably in the range of 30 to 150 ° C, more preferably 40 to 140 ° C, and still more preferably 50 to 130, from the viewpoints of productivity, workability, thermal stability of the base material, and the like. ° C. The heating time is preferably in the range of 1 to 60 minutes, more preferably 1 to 40 minutes.

  Hereinafter, the present invention will be described more specifically with reference to production examples, examples and comparative examples. However, the present invention is not limited to these. In each example, “parts” and “%” are based on mass unless otherwise specified. Moreover, the film thickness of a coating film is based on a cured coating film.

  Each component used in the following examples is as follows.

[Urethane (meth) acrylate (A)]
Urethane (meth) acrylate (A-1): a weight average molecular weight of 3,000, Tg of 40 ° C., obtained by appropriately selecting and reacting the above components (a1) to (a5) A compound having an average of 2 acryloyl groups in the molecule and 20 polyoxyethylene chains and 12 cyclohexane rings in one molecule.
Urethane (meth) acrylate (A-2): a weight-average molecular weight of 2,400, Tg of 26 ° C., obtained by appropriately selecting and reacting the components (a1) to (a5) A compound having an average of 2 acryloyl groups in the molecule and 20 polyoxyethylene chains in one molecule.
Urethane (meth) acrylate (A-3): a weight average molecular weight of 3,200, Tg of 45 ° C., obtained by appropriately selecting and reacting the above components (a1) to (a5), 1 A compound having an average of 2 acryloyl groups in the molecule and 12 cyclohexane rings in one molecule.
Urethane (meth) acrylate (A-4): a weight average molecular weight of 2,600, Tg of 23 ° C., obtained by appropriately selecting and reacting the above components (a1) to (a5), 1 A compound having an average of two acryloyl groups in the molecule but no polyoxyethylene chain and cyclohexane ring in one molecule.
Urethane (meth) acrylate (A-5): a weight average molecular weight of 1,500, Tg of 37 ° C., obtained by appropriately selecting and reacting the components (a1) to (a5) above A compound having an average of 3 acryloyl groups in the molecule and two polyoxyethylene chains and two isocyanurate rings in one molecule.
Urethane (meth) acrylate (A-6): a weight average molecular weight of 1,400, Tg of 48 ° C., obtained by appropriately selecting and reacting the above components (a1) to (a5) A compound having an average of 3 acryloyl groups in the molecule and two isocyanurate rings in one molecule.
Urethane (meth) acrylate (A-7): 1 molecular weight obtained by appropriately selecting and reacting the above components (a1) to (a5) having a weight average molecular weight of 850 and a Tg of 44 ° C. A compound having an average of 2 acryloyl groups and 2 polyoxyethylene chains and 4 cyclohexane rings in one molecule.
Urethane (meth) acrylate (A-8): a weight-average molecular weight of 9,800, Tg of 38 ° C., obtained by appropriately selecting and reacting the above components (a1) to (a5) A compound having an average of 2 acryloyl groups in the molecule and 80 polyoxyethylene chains and 42 cyclohexane rings in one molecule.
Urethane (meth) acrylate (A-9): “EBECRYL 8402” (trade name, manufactured by Daicel Ornex Co., Ltd., weight average molecular weight 1,000, polymerizable unsaturated group number 2)

[Comparison components (a-1) to (a-3)]
Comparative components (a-1) to (a-3) were used as comparative components in place of urethane (meth) acrylate (A).
Comparative component (a-1): Urethane (meth) acrylate: weight average molecular weight is 2,900, Tg is 40 ° C., obtained by appropriately selecting and reacting the above components (a1) to (a5) Further, a compound having an average of one acryloyl group in one molecule and 20 polyoxyethylene chains and 12 cyclohexane rings in one molecule.
Comparative component (a-2): Urethane (meth) acrylate: weight average molecular weight is 490, Tg is 42 ° C., obtained by appropriately selecting and reacting the above components (a1) to (a5), A compound having an average of two acryloyl groups in one molecule and two cyclohexane rings in one molecule.
Comparative component (a-3): urethane (meth) acrylate: weight average molecular weight of 11,000, Tg of 29 ° C., obtained by appropriately selecting and reacting the above components (a1) to (a5) Further, a compound having an average of 2 acryloyl groups in one molecule and 128 polyoxyethylene chains and 32 cyclohexane rings in one molecule.

[Compound (B) having a weight average molecular weight of 50 or more and less than 550 and having at least one group selected from the group consisting of a carboxyl group, a phosphoric acid group and a phosphonic acid group]
Compound (B-1): Acrylic acid (weight average molecular weight is 72, corresponding to the polymerizable unsaturated compound (B ′))
Compound (B-2): “β-CEA” (trade name, manufactured by Daicel Ornex Co., Ltd., β-carboxyethyl acrylate, weight average molecular weight 144, polymerizable unsaturated group number 1, polymerizable unsaturated compound (B ′) Equivalent.)
Compound (B-3): “Aronix M5300” (trade name, manufactured by Toagosei Co., Ltd., ω-carboxy-polycaprolactone (n≈2) monoacrylate, weight average molecular weight 300, polymerizable unsaturated group number 1, polymerizable non-polymerizable Corresponds to saturated compound (B ′).)
Compound (B-4): “Sartomer SR9050” (trade name, manufactured by Sartomer, 2- (methacryloyloxy) ethyl phosphate, weight average molecular weight 210, equivalent to polymerizable unsaturated compound (B ′))
Compound (B-5): Acetic acid (weight average molecular weight 60)

[Comparison component (b-1)]
As a comparative component replacing the compound (B) having a weight average molecular weight of 50 or more and less than 550 and having at least one group selected from the group consisting of a carboxyl group, a phosphoric acid group and a phosphonic acid group, a comparative component (b-1) is used. Using.
Comparative component (b-1): A carboxyl group-containing polyester resin having a hydroxyl value of 105 and a weight average molecular weight of 850. The synthesis method is as follows.
In a reaction vessel equipped with a thermometer, thermostat, stirrer, reflux condenser and water separator, 58.4 parts (0.3 mol) of adipic acid (molecular weight 146), 1,6-hexanediol (molecular weight 118) 70. 8 parts (0.60 mol) and 42 parts (0.40 mol) of neopentyl glycol (molecular weight 104) were charged and the temperature was raised to 230 ° C. over 3 hours, and then condensed water was distilled off with a water separator. The reaction was continued at 0 ° C. until the acid value reached 10 mg KOH / g. Subsequently, after cooling to 170 ° C., 38.4 parts (0.2 mol) of trimellitic anhydride (molecular weight 192) was charged and reacted until the acid value became 105 mgKOH / g to obtain a carboxyl group-containing polyester resin.

[Polymerizable unsaturated compound (C) having a weight average molecular weight of 200 or more and less than 550 and having two or more polymerizable unsaturated groups in one molecule and having no carboxyl group, phosphoric acid group and phosphonic acid group ]
Polymerizable unsaturated compound (C-1): “Light acrylate 3EG-A” (trade name, manufactured by Kyoeisha Chemical Co., Ltd., triethylene glycol diacrylate, weight average molecular weight 258, polymerizable unsaturated group number 2, polyoxyalkylene chain Equivalent to a polymerizable unsaturated compound (C ′) having
Polymerizable unsaturated compound (C-2): “Sartomer SR230” (trade name, manufactured by Sartomer, diethylene glycol diacrylate, weight average molecular weight 212, polymerizable unsaturated group number 2, polymerizable unsaturated compound having a polyoxyalkylene chain (Equivalent to (C '))
Polymerizable unsaturated compound (C-3): “NK ester A-400” (trade name, Shin-Nakamura Chemical Co., Ltd., polyethylene glycol # 400 diacrylate, weight average molecular weight 508, polymerizable unsaturated group number 2, poly Equivalent to polymerizable unsaturated compound (C ′) having an oxyalkylene chain)
Polymerizable unsaturated compound (C-4): “HDDA” (trade name, manufactured by Daicel Ornex, 1,6-hexanediol diacrylate (1,6-HDDA), weight average molecular weight 226, number of polymerizable unsaturated groups 2)
Polymerizable unsaturated compound (C-5): “Irr214K” (trade name, manufactured by Daicel Ornex Co., Ltd., tricyclodecane dimethanol diacrylate, weight average molecular weight 300, polymerizable unsaturated group number 2)
Polymerizable unsaturated compound (C-6): “New Frontier HPN” (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., hydroxypivalic acid neopentyl glycol diacrylate, weight average molecular weight 312 and number of polymerizable unsaturated groups 2)
Polymerizable unsaturated compound (C-7): “Aronix M315” (trade name, manufactured by Toagosei Co., Ltd., isocyanuric acid ethylene oxide modified di- and triacrylate, weight average molecular weight 387, polymerizable unsaturated group number 2)

[Comparison components (c-1) to (c-3)]
The weight average molecular weight is in the range of 200 or more and less than 550, has two or more polymerizable unsaturated groups in one molecule, and does not have a carboxyl group, a phosphate group or a phosphonic acid group. Comparative components (c-1) to (c-3) were used as comparative components in place of the saturated compound (C).
Comparative component (c-1): “EBECRYL110” (trade name, manufactured by Daicel Ornex Co., Ltd., ethoxylated phenyl acrylate, weight average molecular weight 236, number of polymerizable unsaturated groups 1)
Comparative component (c-2): “Sartomer SR213” (trade name, manufactured by Sartomer, 1,4-butanediol diacrylate, weight average molecular weight 198, polymerizable unsaturated group number 2)
Comparative component (c-3): “NK ester A-DPH” (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., dipentaerythritol hexaacrylate, weight average molecular weight of 578, polymerizable unsaturated group number 6)

[Polymerization initiator (D)]
Polymerization initiator (D-1): “IRGACURE 907” (trade name, manufactured by BASF, photopolymerization initiator, nonvolatile content: 100%)
Polymerization initiator (D-2): “IRGACURE TPO” (trade name, manufactured by BASF, photopolymerization initiator, nonvolatile content: 100%)
Polymerization initiator (D-3): “DETX-S” (trade name, manufactured by Nippon Kayaku Co., Ltd., 2,4-diethylthioxanthone, photopolymerization initiator, nonvolatile content 100%)
Polymerization initiator (D-4): “Perocta O” (trade name, manufactured by NOF Corporation, thermal polymerization initiator, nonvolatile content: 100%)

[Other polymerizable unsaturated compounds]
“ACMO”: trade name, manufactured by KJ Chemicals, 4-acryloylmorpholine “HEAA”: trade name, manufactured by KJ Chemicals, hydroxyethyl acrylamide “IBOA-B”: trade name, manufactured by Daicel Ornex, isobornyl acrylate “Light acrylate EC-A”: trade name, manufactured by Kyoeisha Chemical Co., Ltd., ethoxydiethylene glycol acrylate

[Other additives]
"TINUVIN 400": trade name, manufactured by BASF, UV absorber "TINUVIN 292": trade name, manufactured by BASF, light stabilizer "BYK-333": trade name, manufactured by BYK Chemie, surface conditioner Butyl acetate: Organic Solvent “TAROX LL-50”: trade name, manufactured by Titanium Industry Co., Ltd., iron oxide pigment “Todacolor KN-O”: trade name, manufactured by Toda Kogyo Co., Ltd., iron oxide pigment “JR-806”: trade name, manufactured by Teika, Titanium oxide pigment “Carbon MA-100”: trade name, manufactured by Mitsubishi Chemical Corporation, carbon black pigment “BYK-168”: trade name, manufactured by BYK, pigment dispersant

[Example 1]
In the blending ratio (parts by mass) shown in Table 1 below, various components were mixed to obtain a coating composition. Ie;
Urethane (meth) acrylate (A-1) 40 parts (nonvolatile content 40 parts), carboxyl group-containing compound (B-2) (β-CEA) 2 parts (nonvolatile content 2 parts), polymerizable unsaturated compound (C -1) 20 parts (light acrylate 3EG-A) (nonvolatile content 20 parts), polymerizable unsaturated compound (C-4) (1,6-HDDA) 10 parts (nonvolatile content 10 parts), polymerizable unsaturated compound (C-5) (Irr214K) 20 parts (nonvolatile content 20 parts), polymerization initiator (D-1) (IRGACURE 907 (Irg907)) 1 part (nonvolatile content 1 part), polymerization initiator (D-2) ( IRGACURE TPO (IrgTPO)) 4 parts (nonvolatile content 4 parts), polymerization initiator (D-3) (DETX-S) 1 part (nonvolatile content 1 part), other polymerizable unsaturated compound (ACMO) 8 parts ( Nonvolatile content 8 parts), UV absorption Example 1 paint by uniformly mixing 2 parts of agent (2 parts of non-volatile content), 2 parts of light stabilizer (2 parts of non-volatile content) and 0.1 part of surface conditioner (0.1 part of non-volatile content) A composition was obtained.

[Examples 2-45 and Comparative Examples 1-12]
In the same manner as in Example 1, various components were mixed in the blending ratios (parts by mass) described in Tables 1 to 12 to obtain coating compositions of Examples 2 to 45 and Comparative Examples 1 to 12, respectively.

In Examples 1 to 9, the type of urethane (meth) acrylate (A) was changed, or no other polymerizable unsaturated compound was added (Table 1).
Examples 10-14 changed the kind of compound (B) which has at least 1 group chosen from the group which consists of a carboxyl group, a phosphoric acid group, and a phosphonic acid group (Table 2).
Examples 15-21 changed the kind of polymerizable unsaturated compound (C) which does not have a carboxyl group, a phosphoric acid group, and a phosphonic acid group (Table 3).
In Examples 22 to 24, the type of photoinitiator was changed, or other polymerizable unsaturated compounds were added (Table 4).
In Examples 25 to 29, the types and addition amounts of other polymerizable unsaturated compounds were changed (Table 5).
Examples 30-33 changed content of the polymerizable unsaturated compound (C) which does not have a urethane (meth) acrylate (A) and a carboxyl group, a phosphoric acid group, and a phosphonic acid group (Table 6).
In Examples 34 to 39, the content of the compound (B) having at least one group selected from the group consisting of a carboxyl group, a phosphoric acid group and a phosphonic acid group was changed, or the nonvolatile content of the coating composition was changed. The thermal polymerization initiator was added (Table 7).
Examples 40-43 changed the kind of base material (Table 8).
In Examples 44 and 45, the film thickness of the formed coating film (cured coating film) was changed (Table 9).
Comparative Examples 1 to 4 do not contain urethane (meth) acrylate (A) or contain comparative components (a-1) to (a-3) instead of urethane (meth) acrylate (A) (Table 10). ).
Comparative Examples 5 to 8 did not contain the compound (B) or contained the comparative component (b-1) instead of the compound (B) (Table 11).
Comparative Examples 9-12 do not contain the polymerizable unsaturated compound (C) which does not have a carboxyl group, a phosphoric acid group, and a phosphonic acid group, or it replaces with a polymerizable unsaturated compound (C), and is a comparison component (c-1). ) To (c-3) (Table 12).

[Coating film formation method (test plate preparation)]
The coating composition obtained in Examples or Comparative Examples was applied on a 100 mm × 150 mm × 3.0 mm vinyl chloride substrate (PVC) using a bar coater so as to have a desired cured coating film thickness. . Subsequently, setting was performed at 23 ° C. for 1 minute, and then UV irradiation at 400 mW / cm ² and 1,000 mJ / cm ² was performed using a metal halide lamp to prepare a test plate.
Acrylonitrile-butadiene-styrene (ABS) substrate (Example 40), acrylonitrile-ethylene-styrene (AES) substrate (Example 41), acrylonitrile-styrene-acrylate (ASA) substrate (Example 42) When using a polycarbonate (PC) base material (Example 43), a test plate was prepared in the same manner as described above.
For Example 39, instead of performing UV irradiation using a metal halide lamp, heating was performed at 80 ° C. for 30 minutes.

[Evaluation of formed coating film]
About each obtained test board, adhesiveness and pencil hardness were evaluated.
(Adhesion)
100 pieces of 2 mm x 2 mm goby eyes are made on the coated surface of each test plate according to JIS K 5600-5-6 (1990), adhesive tape is stuck on the surface, and the gobang eye coating after abruptly peeling off The remaining state of the film was examined, and the adhesion was evaluated according to the following criteria. The evaluation results are shown in Tables 1 to 12. In the table, ◎, ○, ○-, Δ, and x mean the following, respectively, and ◎, ○, and ○-mean pass.
A: Remaining number / total number = 100/100, no chipping ○: Remaining number / total number = 100/100, less than 10 remaining coatings ○ −: Remaining number / total number = 10 or more remaining coatings with 100/100 missing edges Δ: remaining number / total number = 90-99 / 100 ×: remaining number / total number = 0-89 / 100

(Pencil hardness)
Based on JIS K 5600-5-4 (1999) "Scratch hardness (pencil method)", the pencil hardness of the coated surface of each test plate was measured. The pencil hardness is in the order of 3B <2B <B <HB <F <H. If the pencil hardness is HB or higher, the hardness is good, but even if the pencil hardness is B, if the adhesion is ○ or higher It can be said that the result is generally good as a coating film. The evaluation results are shown in Tables 1 to 12.

[Production of pigment dispersion]
(Production Example 1)
“Light acrylate 3EG-A” (trade name, manufactured by Kyoeisha Chemical Co., Ltd., triethylene glycol diacrylate) (C-1) 5 parts (nonvolatile content 5 parts), “ACMO” (trade name, manufactured by KJ Chemicals Co., Ltd., 4 -Acryloylmorpholine) 5 parts (nonvolatile content 5 parts), "BYK-168" (trade name, manufactured by BYK, pigment dispersant, nonvolatile content 30%) 3 parts (nonvolatile content 0.9 parts), "TAROX LL- 50 "(trade name, manufactured by Titanium Industry Co., Ltd., iron oxide pigment) 4.6 parts," Toda Color KN-O "(trade name, manufactured by Toda Industries Co., Ltd., iron oxide pigment) 1.7 parts," JR-806 "( Place 2.6 parts of trade name, manufactured by Teica, titanium oxide pigment) and 0.2 part of “Carbon MA-100” (trade name, manufactured by Mitsubishi Chemical Corporation, carbon black pigment) in a wide-mouth glass bottle, and add glass beads. Sealed and pane After dispersing for 30 minutes on a shaker, to remove the glass beads to give a pigment dispersion liquid (P-1).

(Production Example 2)
“Light acrylate 3EG-A” (trade name, manufactured by Kyoeisha Chemical Co., Ltd., triethylene glycol diacrylate) (C-1) 5 parts (nonvolatile content 5 parts), “ACMO” (trade name, manufactured by KJ Chemicals Co., Ltd., 4 -Acryloylmorpholine) 5 parts (nonvolatile content 5 parts), "BYK-168" (trade name, manufactured by BYK, pigment dispersant, nonvolatile content 30%) 3 parts (nonvolatile content 0.9 parts), "TAROX LL- 50 "(trade name, manufactured by Titanium Industry Co., Ltd., iron oxide pigment) 0.1 part," Todacolor KN-O "(trade name, manufactured by Toda Kogyo Co., Ltd., iron oxide pigment) 0.1 part," JR-806 "( Place 15 parts of the trade name, manufactured by Teica, titanium oxide pigment) and 0.2 part of “Carbon MA-100” (trade name, manufactured by Mitsubishi Chemical Corporation, carbon black pigment) in a wide-mouth glass bottle, and add glass beads to seal. And paint After dispersing for 30 minutes at Eka, by removing the glass beads to give a pigment dispersion liquid (P-2).

(Production Example 3)
“EBECRYL 8402” (trade name, manufactured by Daicel Ornex Co., Ltd., weight average molecular weight 1,000, number of polymerizable unsaturated groups 2) (A-9) 2.5 parts (nonvolatile content 2.5 parts), “light acrylate 3EG -A "(trade name, manufactured by Kyoeisha Chemical Co., Ltd., triethylene glycol diacrylate) (C-1) 5 parts (nonvolatile content 5 parts)," light acrylate EC-A "(trade name, manufactured by Kyoeisha Chemical Co., Ltd., ethoxydiethylene glycol) Acrylate) 2.5 parts (nonvolatile content 2.5 parts), “BYK-168” (trade name, manufactured by BYK, pigment dispersant, nonvolatile content 30%) 3 parts (nonvolatile content 0.9 parts), “TAROX LL-50 "(trade name, manufactured by Titanium Industry Co., Ltd., iron oxide pigment) 4.6 parts," Todacolor KN-O "(trade name, manufactured by Toda Kogyo Co., Ltd., iron oxide pigment) 1.7 parts," JR-806 ""(Product name, 2.6 parts of squid (titanium oxide pigment) and 0.2 parts of “Carbon MA-100” (trade name, manufactured by Mitsubishi Chemical Corporation, carbon black pigment) are placed in a wide-mouth glass bottle and sealed with glass beads. After dispersing for 30 minutes with a paint shaker, the glass beads were removed to obtain a pigment dispersion (P-3).

(Production Example 4)
“EBECRYL 8402” (trade name, manufactured by Daicel Ornex Co., Ltd., weight average molecular weight 1,000, number of polymerizable unsaturated groups 2) (A-9) 2.5 parts (nonvolatile content 2.5 parts), “light acrylate 3EG -A "(trade name, manufactured by Kyoeisha Chemical Co., Ltd., triethylene glycol diacrylate) (C-1) 5 parts (nonvolatile content 5 parts)," light acrylate EC-A "(trade name, manufactured by Kyoeisha Chemical Co., Ltd., ethoxydiethylene glycol) Acrylate) 2.5 parts (nonvolatile content 2.5 parts), “BYK-168” (trade name, manufactured by BYK, pigment dispersant, nonvolatile content 30%) 3 parts (nonvolatile content 0.9 parts), “TAROX LL-50 "(trade name, manufactured by Titanium Industry Co., Ltd., iron oxide pigment) 0.1 part," Todacolor KN-O "(trade name, manufactured by Toda Kogyo Co., Ltd., iron oxide pigment) 0.1 part," JR-806 "(Product name, Place 15 parts of squid oxide (titanium oxide pigment) and 0.2 parts of “Carbon MA-100” (trade name, Mitsubishi Chemical Corporation, carbon black pigment) in a wide-mouth glass bottle, add glass beads, seal and paint After dispersing for 30 minutes with a shaker, the glass beads were removed to obtain a pigment dispersion (P-4).

[Example 46]
[Production of coating composition (1)]
In the blending ratio (parts by mass) shown in Table 13 below, various components were mixed to prepare a coating composition (1). Ie:
40 parts of urethane (meth) acrylate (A-1) (nonvolatile content 40 parts),
Compound (B-2) having a carboxyl group (B-CEA) 5 parts (nonvolatile content 5 parts),
Polymerizable unsaturated compound (C-1): “Light acrylate 3EG-A” (manufactured by Kyoeisha Chemical Co., Ltd., triethylene glycol diacrylate, weight average molecular weight 258, polymerizable unsaturated group number 2) 12 parts (nonvolatile content 12 parts) ,
Polymerizable unsaturated compound (C-5): “Irr214K” (trade name, manufactured by Daicel Ornex Co., Ltd., tricyclodecane dimethanol diacrylate, weight average molecular weight 300, polymerizable unsaturated group number 2) 10 parts (nonvolatile content 10) Part),
Polymerization initiator (D-1) “IRGACURE 907” (trade name, manufactured by BASF, photopolymerization initiator, nonvolatile content 100%) 1 part (nonvolatile content 1 part),
Polymerization initiator (D-2) “IRGACURE TPO” (trade name, manufactured by BASF, photopolymerization initiator, nonvolatile content 100%) 4 parts (nonvolatile content 4 parts),
Polymerization initiator (D-3): “KAYACURE DETX-S” (trade name, manufactured by Nippon Kayaku Co., Ltd., photopolymerization initiator, nonvolatile content 100%) 1 part (nonvolatile content 1 part),
“ACMO” (trade name, manufactured by KJ Chemicals, 4-acryloylmorpholine, weight average molecular weight 141, number of polymerizable unsaturated groups 1) 7 parts (nonvolatile content 7 parts),
"IBOA-B" (trade name, manufactured by Daicel Ornex Co., Ltd., isobornyl acrylate, weight average molecular weight 208, number of polymerizable unsaturated groups 1) 10 parts (nonvolatile content 10 parts),
"Light acrylate EC-A" (trade name, manufactured by Kyoeisha Chemical Co., Ltd., ethoxydiethylene glycol acrylate, weight average molecular weight 188, polymerizable unsaturated group number 1) 10 parts (nonvolatile content 10 parts),
13.3 parts of pigment dispersion (P-1) obtained in Production Example 1 (12 parts of nonvolatile content),
2 parts of “TINUVIN 400” (trade name, manufactured by BASF, triazine-based ultraviolet absorber, nonvolatile content: 100%),
“TINUVIN 292” (trade name, manufactured by BASF, hindered amine light stabilizer, nonvolatile content 100%) 2 parts, and “BYK-333” (trade name, manufactured by BYK Chemie, silicon-based surface conditioner, nonvolatile content The coating composition (1) was obtained by uniformly mixing 0.1 part).

[Preparation of test plate]
A 100 mm × 150 mm × 3.0 mm vinyl chloride substrate (PVC) is heated to 50 ° C. and then allowed to stand at 23 ° C., and a non-contact type thermometer “THERMO-HUNTER PT-80” (manufactured by OPTEX, product) Name, long-distance narrow-field measurement type portable non-contact thermometer), the surface temperature of the vinyl chloride substrate was continuously measured. When the surface temperature of the vinyl chloride substrate reached 30 ° C., the coating composition (1) obtained in Example 46, which was kept at a coating temperature of 23 ° C. on the vinyl chloride substrate, was Was applied so that the film thickness of the cured coating film was 10 μm. Subsequently, setting was performed at 23 ° C. for 1 minute, and then UV irradiation at 400 mW / cm ² and 1,000 mJ / cm ² was performed using a metal halide lamp to prepare a test plate.

[Examples 47 to 52]
Example 46 was repeated except that the type of each component in the coating composition (1) was changed as shown in Table 13. The results are shown in Table 13.

[Example 53]
Example 46 was repeated except that the type of each component in the coating composition (1) was changed as shown in Table 13 and a test plate was prepared as follows. The results are shown in Table 13.
[Preparation of test plate]
A 100 mm × 150 mm × 3.0 mm vinyl chloride substrate (PVC) is heated to 50 ° C. and then allowed to stand at 23 ° C., and a non-contact type thermometer “THERMO-HUNTER PT-80” (manufactured by OPTEX, product) Name, long-distance narrow-field measurement type portable non-contact thermometer), the surface temperature of the vinyl chloride substrate was continuously measured. When the surface temperature of the vinyl chloride substrate reached 30 ° C., the coating composition (1) obtained in Example 46, which was kept at a coating temperature of 23 ° C. on the vinyl chloride substrate, was Was applied so that the film thickness of the cured coating film was 10 μm. Subsequently, setting was performed at 23 ° C. for 1 minute, and then UV irradiation at 400 mW / cm ² and 1,000 mJ / cm ² was performed using a metal halide lamp. Subsequently, the coating composition (1) obtained in Example 46 kept at a coating temperature of 23 ° C. on the cured coating film was cured using a bar coater so that the thickness of the cured coating film became 10 μm. Painted on. Subsequently, setting was performed at 23 ° C. for 1 minute, and then UV irradiation at 400 mW / cm ² and 1,000 mJ / cm ² was performed using a metal halide lamp to prepare a test plate.

[Example 54]
Example 53 was repeated except that the coating composition (1) obtained in Example 47 was used twice instead of the coating composition (1) obtained in Example 46 as the coating composition (1). It was. The results are shown in Table 13.

[Comparative Example 13]
Example 46 was repeated except that the type of each component in the coating composition (1) was changed as shown in Table 13. The results are shown in Table 13.

From the above results, by using the coating composition according to the present invention, it was possible to form a coating film having excellent adhesion to the substrate and high strength. On the other hand, the coating film using the coating composition as a comparative example could not exhibit the above effect.

Claims (10)

  Urethane (meth) acrylate (A) having a weight average molecular weight of 550 or more and less than 10,000 and having two or more (meth) acryloyl groups in one molecule, and a weight average molecular weight of 50 or more and less than 550 And a compound (B) having at least one group selected from the group consisting of a carboxyl group, a phosphoric acid group and a phosphonic acid group, a weight average molecular weight of 200 or more and less than 550, Contains a polymerizable unsaturated compound (C) and a polymerization initiator (D) having two or more polymerizable unsaturated groups in the molecule and having no carboxyl group, phosphoric acid group and phosphonic acid group Paint composition.   At least one of the urethane (meth) acrylates (A) has a weight average molecular weight in the range of 550 or more and less than 10,000, and two or more (meth) acryloyl groups and one in one molecule. The coating composition of Claim 1 containing the urethane (meth) acrylate (A11) which has the above polyoxyalkylene chain.   At least one of the urethane (meth) acrylates (A) has a weight average molecular weight in the range of 550 or more and less than 10,000, and two or more (meth) acryloyl groups and one in one molecule. The coating composition of Claim 1 or 2 containing the urethane (meth) acrylate (A12) which has the above cyclohexane ring.   At least one of the urethane (meth) acrylates (A) has a weight average molecular weight in the range of 550 or more and less than 10,000, and two or more (meth) acryloyl groups and one in one molecule. The coating composition of any one of Claims 1-3 containing the urethane (meth) acrylate (A13) which has the said isocyanurate ring.   At least one of the compounds (B) has a weight average molecular weight in the range of 50 or more and less than 550, and has at least one group selected from the group consisting of a carboxyl group, a phosphate group, and a phosphonate group. The coating composition of any one of Claims 1-4 containing a polymerizable unsaturated compound (B ').   The coating composition according to any one of claims 1 to 5, comprising a polymerizable unsaturated compound (C ') having a polyoxyalkylene chain as at least one of the polymerizable unsaturated compounds (C). .   When the nonvolatile content in the coating composition is 100 parts by mass in total, the urethane (meth) acrylate (A) has a nonvolatile content of 10-70 parts by mass, and the compound (B) has a nonvolatile content of 1-20. The non-volatile content of the polymerizable unsaturated compound (C) is 10 to 80 parts by mass, and the non-volatile content of the polymerization initiator (D) is 0.1 to 20 parts by mass. The coating composition according to any one of -6.   Furthermore, the coating composition of any one of Claims 1-7 containing a pigment.   The coating composition according to claim 8, wherein the blending amount of the pigment is in the range of 0.1 to 40 parts by mass when the total amount of the polymerizable unsaturated compounds in the coating composition is 100 parts by mass.   The coating composition according to any one of claims 1 to 9, wherein a non-volatile content accounts for 90 to 100% by mass in the coating composition.