JP6207232B2 - Block polyisocyanate composition and crosslinkable composition - Google Patents

Description

  The present invention relates to a blocked polyisocyanate composition and a crosslinkable composition comprising the composition.

  Polyurethane coatings have chemical resistance, weather resistance, etc., and the market is expanding. The polyurethane coating is usually formed from a polyol and a polyisocyanate. The isocyanate group of polyisocyanate is highly reactive and reacts with the hydroxyl group of polyol at room temperature. Therefore, when the product is shipped, the polyol and the polyisocyanate are put in a container, and the polyol and the polyisocyanate are mixed and coated before coating.

  The blocked polyisocyanate is a compound in which the isocyanate group of the polyisocyanate is blocked with a blocking agent. By blocking with the blocking agent, the blocked isocyanate group does not react with the hydroxyl group of the polyol at room temperature, for example. Therefore, polyol and block polyisocyanate can be mixed before product shipment. This paint reacts with the blocked isocyanate group and the hydroxyl group by heating after coating. If the heating temperature at this time is high, the heat resistance of the substrate to be coated is required, and the energy used is also increased. Therefore, a block polyisocyanate composition having low temperature curability is required. In order to solve this problem, for example, Patent Document 1 describes an active methylene-based block polyisocyanate composition having low-temperature curability.

  Moreover, since such block polyisocyanate has high viscosity, it is usually diluted with an organic solvent and used. However, organic solvents may be released to the atmosphere during painting. Therefore, in order to reduce environmental burden, reduction of organic solvents is required.

Japanese Patent Laid-Open No. 9-278865

  However, when the organic solvent is reduced and the concentration of the block polyisocyanate is increased, turbidity is generated, which may induce coating defects such as repellency, and improvement of turbidity has been desired.

  This invention is made | formed in view of the said problem, Comprising: Even if block polyisocyanate is high concentration, the block polyisocyanate composition which does not produce turbidity, and the crosslinkable composition containing this composition are provided. For the purpose.

  As a result of intensive investigations to solve the above problems, the present inventors have found that the above-mentioned problem can be solved if it is a block polyisocyanate composition containing a predetermined amount of a salt of an alkyl acid phosphate and a basic compound in a predetermined ratio. The inventors have found that this can be solved, and have completed the present invention.

That is, the present invention is as follows.
[1]
Block polyisocyanate;
A salt of an alkyl acid phosphate having an alkyl group with 6 or more carbon atoms and a basic compound,
And the salt contains a dialkyl acid phosphate salt in a molar concentration of 70 mol% or more,
Block polyisocyanate composition.
[2]
The blocked polyisocyanate composition according to item [1], wherein the blocked polyisocyanate is obtained by blocking an isocyanate group of polyisocyanate with an active methylene compound.
[3]
The block polyisocyanate composition according to item [1] or [2], wherein the block polyisocyanate contains an aliphatic diisocyanate monomer unit.
[4]
The block polyisocyanate composition according to any one of [1] to [3] above, which contains 65% by mass or more of the block polyisocyanate.
[5]
A crosslinkable composition comprising the block polyisocyanate composition according to any one of [1] to [4].

  ADVANTAGE OF THE INVENTION According to this invention, even if block polyisocyanate is high concentration, the block polyisocyanate composition which does not produce turbidity, and the crosslinkable composition containing this composition can be provided.

DESCRIPTION OF EMBODIMENTS Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. However, the present invention is not limited to this, and various modifications can be made without departing from the gist thereof. Is possible.

[Block polyisocyanate composition]
The block polyisocyanate composition according to this embodiment is
Block polyisocyanate;
A salt of an alkyl acid phosphate having an alkyl group with 6 or more carbon atoms and a basic compound,
The salt contains a dialkyl acid phosphate salt in a molar concentration of 70 mol% or more.

[Block polyisocyanate]
The blocked polyisocyanate used in the present embodiment is a compound in which the isocyanate group of the polyisocyanate is blocked with a blocking agent.

(Polyisocyanate)
Although it does not specifically limit as said polyisocyanate, For example, it is preferable that it is a polymer containing the at least 1 sort (s) of monomer unit chosen from an aliphatic diisocyanate monomer. That is, the block polyisocyanate preferably contains an aliphatic diisocyanate monomer unit. When the block polyisocyanate contains an aliphatic diisocyanate monomer unit, the weather resistance and the toughness of the cured coating film tend to be superior. Here, “aliphatic diisocyanate monomer” refers to a compound that does not contain a benzene ring structure or an alicyclic structure in its structure. Hereinafter, the isocyanate group of the aliphatic diisocyanate monomer is referred to as “aliphatic isocyanate group”.

  Although it does not specifically limit as said aliphatic diisocyanate monomer, For example, a C4-C30 thing is preferable. Such an aliphatic diisocyanate monomer is not particularly limited. For example, tetramethylene-1,4-diisocyanate, pentamethylene-1,5-diisocyanate, hexamethylene diisocyanate (hereinafter also referred to as “HDI”), 2 2,4-trimethyl-hexamethylene-1,6-diisocyanate, lysine diisocyanate. An aliphatic diisocyanate monomer may be used individually by 1 type, or may use 2 or more types together. Among these, HDI is preferable. By using the block polyisocyanate in which the isocyanate group of the polyisocyanate containing HDI is blocked with a blocking agent, a block polyisocyanate composition capable of forming a film that can more follow the deformation of the substrate to be coated tends to be obtained. is there.

  Moreover, as a diisocyanate monomer, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, etc. which are alicyclic diisocyanate monomers which have a cyclohexane ring etc. in a molecule | numerator can also be used together as needed.

  A polyisocyanate that is a precursor of a block polyisocyanate used in the present embodiment can be obtained from the diisocyanate monomer. The polyisocyanate can include, for example, a biuret bond, a urea bond, an isocyanurate bond, a uretdione bond, a urethane bond, an allophanate bond, an iminooxadiazine dione bond, and the like. Moreover, two or more bonds such as isocyanurate bond and allophanate bond, isocyanurate bond and uretdione bond may be included. Among these, it is preferable that an isocyanurate bond is included. By using a polyisocyanate containing an isocyanurate bond, a coating film having better heat resistance tends to be obtained.

  The polyisocyanate having a biuret bond is not particularly limited, but, for example, a so-called biuret agent such as water, t-butanol and urea and a diisocyanate monomer are mixed in a molar ratio of (biuret agent) / (isocyanate group of diisocyanate monomer). Can be obtained by removing the diisocyanate monomer after the reaction under the condition of about 1/2 to about 1/100. A method for producing a polyisocyanate having a biuret bond is not particularly limited, but is disclosed in, for example, JP-A-53-106797, JP-A-55-11452, JP-A-59-95259, and the like. Yes.

  The polyisocyanate having a urea bond is not particularly limited, and can be formed, for example, from a compound having an isocyanate group and a compound having water or an amine group. The content of urea bonds in the polyisocyanate is preferably small. When the urea bond content is small, the solubility of the resulting block polyisocyanate tends to be improved.

  The polyisocyanate having an isocyanurate bond is not particularly limited. For example, the isocyanurate conversion reaction of the diisocyanate monomer is performed with a catalyst or the like, and the reaction is stopped when the conversion becomes about 5 to about 80% by mass. It can be obtained by removing the reactive diisocyanate monomer. In this case, an alcohol compound can be used in combination as a raw material. Although it does not specifically limit as an alcohol compound which can be used together, For example, the compound which has a hydroxyl group which can be used as a raw material of the polyisocyanate which has a urethane bond mentioned later is mentioned. When these alcohol compounds are used together as a raw material, the polyisocyanate obtained may contain a polyisocyanate having an allophanate bond together with a polyisocyanate having an isocyanurate bond. The method for producing the polyisocyanate having an isocyanurate bond is not particularly limited. For example, JP-A 55-38380, JP-A 57-78460, JP 57-47321, JP JP-A-61-111371, JP-A-64-33115, JP-A-2-250872, JP-A-6-312969, and the like.

  The polyisocyanate having a uretdione bond is not particularly limited, and can be obtained, for example, by using a uretdione-forming catalyst. Although it does not specifically limit about the manufacturing method of polyisocyanate which has a uretdione bond, For example, it is disclosed by Unexamined-Japanese-Patent No. 2007-332133, Unexamined-Japanese-Patent No. 2008-273788, Unexamined-Japanese-Patent No. 2009-137961, etc.

  The polyisocyanate having a urethane bond is not particularly limited, and can be obtained, for example, from a compound having a hydroxyl group and a diisocyanate monomer. The compound having a hydroxyl group is not particularly limited, and examples thereof include a compound having no polymerization history and a compound having a polymerization history. Although it does not specifically limit as a compound which has a hydroxyl group and there is no superposition | polymerization history, For example, 1-6 valent alcohol is mentioned. More specifically, after reacting the equivalent ratio of the hydroxyl group of the following 1-6 valent alcohol and the isocyanate group of the diisocyanate monomer at about 1/2 to about 1/100, the diisocyanate monomer is removed to form a urethane bond. The polyisocyanate possessed can be obtained.

  Although it does not specifically limit as said monohydric alcohol, For example, ethanol, isobutanol, n-butanol, 2-ethylhexanol etc. are mentioned.

  The dihydric alcohol is not particularly limited. For example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-propanediol, 1,3-propanediol, 1, 2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,2-propanediol, 1,5-pentanediol, 2-methyl-2, 3-butanediol, 1,6-hexanediol, 1,2-hexanediol, 2,5-hexanediol, 2-methyl-2,4-pentanediol, 2,3-dimethyl-2,3-butanediol, 2-ethyl-hexanediol, 1,2-octanediol, 1,2-de Njioru, 2,2,4-trimethylpentane diol, 2-butyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol.

  Although it does not specifically limit as said trihydric alcohol, For example, glycerol, a trimethylol propane, etc. are mentioned.

  Although it does not specifically limit as said tetrahydric alcohol, For example, a pentaerythritol etc. are mentioned.

  Although it does not specifically limit as said pentahydric alcohol, For example, glucose etc. are mentioned.

  Although it does not specifically limit as said hexavalent alcohol, For example, sorbitol etc. are mentioned.

  The compound having a hydroxyl group and having a polymerization history is not particularly limited, and examples thereof include polyester polyol, polyether polyol, acrylic polyol, polyolefin polyol, and polycarbonate polyol.

  The polyester polyol is not particularly limited. For example, a polyester polyol obtained by a condensation reaction of a dibasic acid alone or a mixture with a polyhydric alcohol alone or a mixture, or a polyhydric alcohol compound is used to open ε-caprolactone. Examples thereof include ring-opening polymers such as polycaprolactones obtained by ring polymerization. Among these, a ring-opening polymer is preferable. The dibasic acid alone or as a mixture thereof is not particularly limited, and examples thereof include a group consisting of carboxylic acids such as succinic acid, adipic acid, sebacic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid and the like. One type selected from a single type or a mixture of two or more types may be mentioned. In addition, the polyhydric alcohol alone or as a mixture is not particularly limited. For example, one or two kinds selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, trimethylolpropane, glycerin and the like. The above mixture is mentioned.

  The polyether polyol is not particularly limited. For example, a polyhydric alcohol compound is used alone or as a mixture, and a hydroxide, a strongly basic catalyst, a complex metal cyanide complex, or the like is used. Polyether polyols obtained by random or block addition; polyether polyols obtained by reacting an alkylene oxide with a polyamine compound such as ethylenediamine; and obtained by polymerizing acrylamide or the like using these polyether polyols as a medium. And so-called polymer polyols.

  Although it does not specifically limit as said polyhydric alcohol compound individually or in mixture, In addition to the alcohol compound illustrated above, a non-saccharide, a sugar alcohol type compound, a monosaccharide, a disaccharide, a trisaccharide, and a tetrasaccharide are mentioned.

  The non-saccharide is not particularly limited, and examples thereof include diglycerin, ditrimethylolpropane, pentaerythritol, and dipentaerythritol.

  The sugar alcohol compound is not particularly limited, and examples thereof include erythritol, D-threitol, L-arabinitol, ribitol, xylitol, sorbitol, mannitol, galactitol, and rhamnitol.

  Although it does not specifically limit as said monosaccharide, For example, arabinose, ribose, xylose, glucose, mannose, galactose, fructose, sorbose, rhamnose, fucose, a ribose source etc. are mentioned.

  The disaccharide is not particularly limited, and examples thereof include trehalose, sucrose, maltose, cellobiose, gentiobiose, lactose, melibiose, and the like.

  Although it does not specifically limit as said trisaccharide, For example, raffinose, a gentianose, meretitol, etc. are mentioned.

  Although it does not specifically limit as said tetrasaccharide, For example, stachyose etc. are mentioned.

  Although it does not specifically limit as said hydroxide, For example, hydroxides, such as lithium, sodium, and potassium, are mentioned.

  Although it does not specifically limit as said strong basic catalyst, For example, an alcoholate, an alkylamine, etc. are mentioned.

  Although it does not specifically limit as said composite metal cyanide complex, For example, a metal porphyrin, a hexacyanocobaltic acid zinc complex, etc. are mentioned.

  Although it does not specifically limit as said alkylene oxide individually or in mixture, For example, a propylene oxide, a butylene oxide, a cyclohexene oxide, a styrene oxide etc. are mentioned.

  The acrylic polyol is not particularly limited. For example, an active hydrogen-containing acrylic acid ester such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, and the like, and active hydrogen are used. Examples include acrylic polyols obtained by copolymerizing non-containing methyl acrylate, ethyl methacrylate, and the like.

  The polyolefin polyol is not particularly limited, and examples thereof include polybutadiene having two or more hydroxyl groups, hydrogenated polybutadiene, polyisoprene, and hydrogenated polyisoprene.

  Although it does not specifically limit as a polycarbonate polyol, For example, the polymer which polymerized carbonate ester, such as alkylene carbonate, such as ethylene carbonate, and dialkyl carbonate, such as diethyl carbonate, is mentioned.

  The polyisocyanate having an allophanate bond is not particularly limited, and can be produced from, for example, an alcohol compound similar to a compound having a hydroxyl group that can be used as a raw material for a polyisocyanate having a urethane bond, and a diisocyanate monomer. The allophanate bond is a bond in which an isocyanate group is added to a urethane bond, and this bond is formed by using a catalyst, heat, or the like. Allophanate bonds and urethane bonds may coexist.

  The polyisocyanate having an iminooxadiazinedione bond is not particularly limited, and for example, a catalyst or the like can be used. Although it does not specifically limit about the manufacturing method of the polyisocyanate which has an iminooxadiazine dione bond, For example, it is disclosed by Unexamined-Japanese-Patent No. 2004-534870 etc.

  The diisocyanate monomer concentration in the polyisocyanate containing biuret bond, urea bond, isocyanurate bond, uretdione bond, urethane bond, allophanate bond, iminooxadiazine dione bond, etc. obtained as described above is not particularly limited. 3 mass% or less is preferable, 1 mass% or less is more preferable, and 0.5 mass% or less is further more preferable. When the concentration is in the above range, the curability tends to be further improved. These polyisocyanates may be used alone or in combination of two or more.

(Viscosity of polyisocyanate at 25 ° C.)
The viscosity of polyisocyanate at 25 ° C. is not particularly limited, but is preferably 50 to 2,000,000 mPa · s, more preferably 3,000 to 50,000 mPa · s, and 3,000 to 30,000 mPa · s. Is more preferable. When the viscosity is 50 mPa · s or more, as a result, the statistical average number of isocyanate groups contained in one molecule of polyisocyanate (hereinafter referred to as “average number of isocyanate groups”) tends to increase. Further, when the viscosity is 2,000,000 mPa · s or less, the appearance of the formed film tends to be better when this is used. The viscosity can be measured by the method described in the examples.

(Average number of isocyanate groups in polyisocyanate)
The average number of isocyanate groups in the polyisocyanate is not particularly limited, but is preferably 3.0 or more and 20 or less, more preferably 3.5 or more and 15 or less, further preferably 4.0 or more and 15 or less, and 4.5 or more and 15 or less. Even more preferred. When the average number of isocyanate groups is 3.0 or more, the crosslinking property tends to be more excellent. Further, when the average number of isocyanate groups is 20 or less, the reactivity between the blocked isocyanate group and the hydroxyl group which is a reaction partner tends to be excellent.

(Block agent)
Although it does not specifically limit as a blocking agent which comprises the block polyisocyanate used by this embodiment, For example, it is preferable to use an active methylene type compound. Although it does not specifically limit as said active methylene type compound, For example, there exist a malonic acid diester compound and an acetoacetate compound. By using an active methylene-based compound, the low-temperature curability tends to be superior. A blocking agent may be used individually by 1 type, or may use 2 or more types together.

  Although it does not specifically limit as said malonic acid diester compound, Specifically, dimethyl malonate, diethyl malonate, diisopropyl malonate, di-n-propyl malonate, di-n-butyl malonate, ethyl n-butyl malonate Methyl n-butyl malonate, ethyl t-butyl malonate, methyl t-butyl malonate, diethyl methyl malonate, dibenzyl malonate, diphenyl malonate, benzyl methyl malonate, ethyl phenyl malonate, t-butyl malonate Examples thereof include phenyl and isopropylidene malonate. A malonic acid diester compound may be used individually by 1 type, or may use 2 or more types together. Among these, diethyl malonate is preferable. By using diethyl malonate, the low temperature curability tends to be superior.

  The acetoacetate compound is not particularly limited, and specifically, methyl acetoacetate, ethyl acetoacetate, isopropyl acetoacetate, n-propyl acetoacetate, t-butyl acetoacetate, n-butyl acetoacetate, acetoacetic acid Examples include benzyl and phenyl acetoacetate. The acetoacetate compound may be used alone or in combination of two or more. Of these, ethyl acetoacetate is preferable. By using ethyl acetoacetate, the storage stability tends to be superior.

  As other blocking agents, alcohols, phenols, acid amides, imidazoles, pyridines, mercaptans, oximes, amines in combination with the above active methylene compounds or in place of the active methylene compounds , Pyrazoles and the like can be used. Among these, oximes such as methyl ethyl ketoxime; amines such as isopropylamine; pyrazoles such as 3,5-dimethylpyrazole are preferable. Among these, 3,5-dimethylpyrazole is more preferable. The amount of the other blocking agent used in combination with the active methylene compound is preferably 40 equivalent% or less based on the isocyanate group of the polyisocyanate.

  For the reaction between the polyisocyanate and a blocking agent such as an active methylene compound, a catalyst is usually used. Although it does not specifically limit as a catalyst, For example, a basic compound (henceforth "basic compound catalyst") is preferable. The basic compound is not particularly limited, but examples thereof include alkali metal alcoholates such as sodium methylate, sodium ethylate, sodium phenolate and potassium methylate; tetraalkylammonium such as tetramethylammonium, tetraethylammonium and tetrabutylammonium. Hydroxides; acetates such as tetraalkylammonium, organic weak acid salts such as octylate, myristic acid, and benzoate; alkali metal salts of alkylcarboxylic acids such as acetic acid, caproic acid, octylic acid, and myristic acid; Metal salts such as tin, zinc and lead of carboxylic acids; aminosilyl group-containing compounds such as hexamethylene disilazane; hydroxides of alkali metals such as lithium, sodium and potassium. Alkali metal alcoholates are preferred.

  The addition amount of the catalyst is 0.01 to 5% by mass with respect to the polyisocyanate, preferably 0.05 to 3% by mass, and particularly preferably 0.1 to 2% by mass. The reaction of the polyisocyanate with a blocking agent such as an active methylene compound can be performed regardless of the presence or absence of a solvent. The reaction between a polyisocyanate and a blocking agent such as an active methylene compound can be generally carried out at -20 to 150 ° C, preferably 0 to 100 ° C. By being 150 degreeC or less, it exists in the tendency for the possibility of a side reaction to become lower. Moreover, it exists in the tendency for reaction rate to become faster because it is -20 degreeC or more.

  When a polyisocyanate and a blocking agent such as an active methylene compound are dissolved and reacted in an organic solvent, the organic solvent that can be used is not particularly limited. For example, a compound that does not have active hydrogen that reacts with an isocyanate group may be used. preferable.

  The organic solvent having no active hydrogen is not particularly limited. For example, hydrocarbons such as toluene, xylene, cyclohexane, etc .; esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, etc .; Examples include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; for example, ethers such as diethylene glycol dimethyl ether and dipropylene glycol dimethyl ether.

  65 mass% or more is preferable with respect to the whole block polyisocyanate composition, 70 mass% or more is more preferable, and, as for content of block polyisocyanate, 75 mass% or more is further more preferable. Although the upper limit of content is not specifically limited, 90 mass% or less is preferable. When the content is 65% by mass or more, the amount of the organic solvent to be used is small, the resin concentration is high, and it tends to be more excellent for high solid paints. Further, when the content is 90% by mass or less, a block polyisocyanate composition having a lower viscosity and better workability tends to be obtained.

[Salt of alkyl acid phosphate and basic compound]
The block polyisocyanate composition according to this embodiment includes a salt of an alkyl acid phosphate and a basic compound. The method for forming the salt is not particularly limited. For example, after the reaction of the isocyanate group of the polyisocyanate with the blocking agent, the basic compound catalyst used in the reaction is neutralized by addition of alkyl acid phosphate and deactivated. And a method of forming a salt in the block polyisocyanate composition. In this case, the addition amount of the alkyl acid phosphate is 0.3 to 3 mol, preferably 0.5 to 2 mol, and more preferably 0.7 to 1.2 mol with respect to the basic compound catalyst. Basic compound catalysts are basic and are neutralized with alkyl acid phosphates. In other words, the basic compound catalyst forms a salt with the alkyl acid phosphate and deactivates. By deactivating the basic compound catalyst, thermal stability such as color tone of the resulting block polyisocyanate composition is improved.

  The carbon number of the alkyl group of the alkyl acid phosphate of this embodiment is 6 or more, and 8 or more is more preferable. Moreover, 12 or less are preferable and, as for carbon number of the alkyl group of a dialkyl acid phosphate, 10 or less are more preferable. When the alkyl group has 6 or more carbon atoms, the solubility of the salt with the basic compound is superior. Further, when the alkyl group has 12 or less carbon atoms, it tends to be liquid and tends to be superior in solubility and workability. The alkyl group may have a linear structure or a branched structure. Among these, a branched structure is preferable.

  Usually, the alkyl acid phosphate is a mixture of dialkyl acid phosphate and monoalkyl acid phosphate. Therefore, the salt formed by the alkyl acid phosphate and the basic compound catalyst includes a salt of a dialkyl acid phosphate and a basic compound catalyst (hereinafter, also referred to as “dialkyl acid phosphate salt”), and a monoalkyl acid phosphate and a basic compound. And a salt with a catalyst (hereinafter, also referred to as “monoalkyl acid phosphate salt”).

The concentration of the dialkyl acid phosphate salt contained in the salt of the alkyl acid phosphate and the basic compound of the present embodiment can be obtained by the following formula [1].
Dialkyl acid phosphate salt concentration (mol%) = number of moles of dialkyl acid phosphate salt / (number of moles of dialkyl acid phosphate salt + number of moles of monoalkyl acid phosphate salt) × 100 (1)

  The concentration of the dialkyl acid phosphate salt of this embodiment is 70 mol% or more, preferably 80 mol% or more, and more preferably 95 mol% or more. The upper limit of the concentration is not particularly limited, but is preferably 100 mol% or less. When the concentration is 70 mol% or more, turbidity does not occur even in a block polyisocyanate composition having a high block polyisocyanate mass concentration. Thus, it was surprising that the concentration of dialkyl acid phosphate salt affects the turbidity of the blocked polyisocyanate composition. This turbidity may affect the repelling of the coating film, the transparency of the paint and the coating film, and the like. In addition, although the present inventors disclosed the manufacturing method of an active methylene type block polyisocyanate composition in patent document 1, the di2 ethyl alkyl acid phosphate density | concentration in the 2-ethylhexyl acid phosphate used here was 66 mol%. It was.

  Although it does not specifically limit as a specific compound of the alkyl acid phosphate used for this embodiment, For example, dihexyl acid phosphate, di n-octyl acid phosphate, di2 ethyl acid phosphate etc. are mentioned.

  Although it does not specifically limit as active hydrogen, For example, a hydroxyl group, a phenol group, an oxime group, an amino group etc. are mentioned. Among these, a hydroxyl group, a phenol group, and an oxime group are preferable, and a hydroxyl group is more preferable. The number of active hydrogen groups (the number of active hydrogens that one molecule has) is preferably 1. When the number of active hydrogen groups is 1, since the molecular weight is not increased, an increase in the viscosity of the block polyisocyanate composition tends to be suppressed.

  Although it does not specifically limit as an organic solvent which has the said active hydrogen group, For example, the organic solvent which has a hydroxyl group, a phenol group, an oxime group, an amino group, and a thiol group is mentioned. The organic solvent having an active hydrogen group is preferably contained together with a blocked polyisocyanate in which 70% or more of all isocyanate groups of the polyisocyanate are blocked isocyanate groups, and more than 80% is contained with a blocked polyisocyanate which is a blocked isocyanate group. It is more preferable that 90% or more be included together with the blocked polyisocyanate which is a blocked isocyanate group. By being contained together with such a block polyisocyanate, it tends to be more excellent in storage stability.

  Examples of the organic solvent having a hydroxyl group include monoalcohols and are not particularly limited. For example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, pentanol, hexanol, Examples include heptanol, octanol, 2-ethyl-1-hexanol, n-butyl cellosolve, propylene glycol monomethyl ether, cyclohexanol, and benzyl alcohol.

  The organic solvent having a phenol group is not particularly limited, and examples thereof include phenol, cresol, xylenol, carvacrol, thymol, and catechol.

  The organic solvent having an oxime group is not particularly limited, and examples thereof include acetooxime, methyl ethyl ketoxime, and cyclohexanone oxime.

  Although it does not specifically limit as an organic solvent which has an amino group, For example, 2 aminoethanol etc. are mentioned. Among the above, alcohols having 4 or more carbon atoms are preferable.

  The organic solvent having no active hydrogen and the organic solvent having active hydrogen can be used in combination. The block polyisocyanate composition according to the present embodiment preferably contains the organic solvent having active hydrogen. By including an organic solvent having active hydrogen, there is a tendency to obtain a block polyisocyanate composition that can further suppress an increase in viscosity when stored for a long period of time.

  Although content of the organic solvent which has active hydrogen can be selected arbitrarily, 10-500 equivalent% is preferable with respect to the blocked isocyanate group by which the isocyanate group was blocked with the blocking agent, and 20-400 equivalent% is more. Preferably, 30 to 300 equivalent% is more preferable. In this case, 1 mol of the organic solvent is defined as 1 equivalent.

(Crosslinkable composition)
The crosslinkable composition according to this embodiment includes the block polyisocyanate composition. Although a crosslinkable composition is not specifically limited, For example, you may further contain the compound which has 2 or more of active hydrogens in a molecule | numerator. When the crosslinkable composition of this embodiment is heated, the blocked isocyanate group of the blocked polyisocyanate and the hydroxyl group of the polyol react to form a crosslinked resin.

  The compound having two or more active hydrogens is not particularly limited, and examples thereof include polyols and polyamines. Of these, polyol is preferable. Although it does not specifically limit as a polyol, For example, an acrylic polyol, polyester polyol, polyether polyol, a fluorine polyol etc. are mentioned. Among these, acrylic polyol, polyester polyol, and fluorine polyol are preferable. These polyols are preferably selected from a hydroxyl value of 30 to 200 mg KOH / g and an acid value of 0 to 30 mg KOH / g.

  Although it does not specifically limit as a polyamine, For example, a polyacrylamine etc. are mentioned.

<Hydroxyl value and acid value of polyol>
The polyol has a hydroxyl group (hydroxyl value) and an acid group (acid value) or a hydroxyl group (hydroxyl value), which can be measured by a known method.

  The equivalent ratio of blocked isocyanate group of blocked polyisocyanate / hydroxyl group of polyol is preferably 0.5 to 1.5, more preferably 0.8 to 1.2. This ratio is appropriately selected according to the required physical properties. By setting the equivalent ratio within the above range and combining the number of blocked isocyanate groups and the number of hydroxyl groups, a high crosslinking density tends to be obtained in a coating film or the like.

  The crosslinkable composition can be added with a melamine curing agent such as a complete alkyl type curing agent, a methylol group type alkyl, an imino group type alkyl or the like, if necessary.

  Moreover, various solvents and additives can be used according to the application and purpose. Examples of the solvent include, but are not limited to, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate, n-butyl acetate, and cellosolve acetate; alcohols such as butanol and isopropyl alcohol; It can be appropriately selected from the group according to the purpose and application. These solvents may be used alone or in combination of two or more.

  In addition, the crosslinkable composition may contain an antioxidant such as hindered phenol; an ultraviolet absorber such as benzotriazole or benzophenone; a pigment such as titanium oxide, carbon black, indigo, quinacridone, or pearl mica; Metal powder pigments; rheology control agents such as hydroxyethyl cellulose, urea compounds, and microgels; and hardening accelerators such as tin compounds, zinc compounds, and amine compounds.

  The crosslinkable composition prepared in this way can be applied to rolls, curtain flow coating, spray coating, electrostatic coating, bell coating, electrodeposition coating, etc. Useful as a primer or overcoat for materials such as molecules, inorganic materials, etc. to impart cosmetics, weather resistance, acid resistance, rust resistance, chipping resistance, etc. It is. It is also useful as a urethane raw material for adhesives, pressure-sensitive adhesives, elastomers, foams, surface treatment agents and the like.

  Hereinafter, the present embodiment will be described more specifically using examples and comparative examples. This embodiment is not limited at all by the following examples.

(Method for measuring the molar concentration of dialkyl acid phosphate and basic compound salt in alkyl acid phosphate and basic compound salt)
After dissolving the block polyisocyanate composition of Example or Comparative Example in methanol, water having the same mass as methanol was added to extract the salt of alkyl acid phosphate and basic compound. A calibration curve was prepared in advance using liquid chromatography and mass spectrum using salts of monoalkyl acid phosphates and dialkyl acid phosphates with known concentrations with basic compounds. Thereafter, the concentration of the salt of each monoalkyl acid phosphate and dialkyl acid phosphate with the base compound in the extract was determined using liquid chromatography and mass spectrum. The models used for this were as follows.
Liquid chromatography: ACQUITY UPLC I-Class (Water
Product name) column; Imtakt, Presto FF-C18 (2 mm ID × 30 mm) silica particles 2 μm
Mass spectrum: Synapt G2 (trade name of Waters), ionization; electrospray ionization.

(Measurement method of number average molecular weight)
The number average molecular weight of the polyisocyanate produced in the production example was determined as a polystyrene-based number average molecular weight using gel permeation chromatography (hereinafter referred to as “GPC”) using the following apparatus.
Equipment: Tosoh Corporation HLC-802A
Column: Tosoh Corporation G1000HXL x 1
G2000HXL x 1
G3000HXL x 1 Carrier: Tetrahydrofuran Detection method: Differential refractometer

(Measurement method of unreacted diisocyanate monomer concentration)
The unreacted diisocyanate monomer concentration is based on the following formula from the peak area of the polyisocyanate obtained by measurement of the number average molecular weight and the peak area of the molecular weight corresponding to the unreacted diisocyanate monomer (for example, 168 for HDI). Calculated.
(Unreacted diisocyanate monomer concentration) = (Area of peak corresponding to unreacted diisocyanate monomer) / {(Area of peak of polyisocyanate) + (Area of peak corresponding to unreacted diisocyanate monomer)} × 100

(Measurement method of isocyanate group concentration of polyisocyanate)
In an Erlenmeyer flask, 1 to 3 g of the polyisocyanate produced in the production example was precisely weighed (Wg), and then 20 mL of toluene was added to completely dissolve the polyisocyanate. Thereafter, 10 mL of a 2N di-n-butylamine toluene solution was added, thoroughly mixed, and allowed to stand at room temperature for 15 minutes. Furthermore, 70 mL of isopropyl alcohol was added to this solution and mixed thoroughly. This solution was titrated with a 1 N hydrochloric acid solution (factor F) using an indicator to obtain a titration value V ₂ mL. The same titration operation was performed without using polyisocyanate, and a titration value V ₁ mL was obtained. From the obtained titration value V ₂ mL and titration value V ₁ mL, the isocyanate group concentration of the polyisocyanate was calculated based on the following formula.
Isocyanate group concentration% = (V ₁ −V ₂ ) × F × 42 / (W × 1000) × 100

(Method for measuring the average number of isocyanate groups in polyisocyanate)
The average number of isocyanate groups in the polyisocyanate produced in Production Example was determined from the following formula from the isocyanate group concentration and the number average molecular weight of the polyisocyanate.
Isocyanate group average number = number average molecular weight × isocyanate group concentration / 100/42

(Method for measuring viscosity of polyisocyanate)
The viscosity of the polyisocyanate was measured at 25 ° C. using an E-type viscometer (VISCONIC ED type manufactured by Tokimec).

(Measurement method of block polyisocyanate concentration)
After precisely weighing an aluminum dish having a bottom diameter of 38 mm, about 1 g of the block polyisocyanate composition of the example or comparative example was placed on the aluminum dish and precisely weighed (W1), and the block polyisocyanate composition had a uniform thickness. After being adjusted to 1 hour, it was kept in an oven at 105 ° C. for 1 hour. After the aluminum dish reached room temperature, the block polyisocyanate remaining on the aluminum dish was precisely weighed (W2).
Block polyisocyanate concentration (mass%) = W2 / W1 × 100

(Measurement method of turbidity of block polyisocyanate composition)
About 30 mL of the block polyisocyanate composition of the example or the comparative example was put in a 50 mL transparent sample bottle and allowed to stand at 23 ° C. for 1 week, and then visually checked for turbidity. The case where it was not turbid was marked with ◯ (good), and the case where it was not indicated with x (bad).

[Production Example 1: Production of polyisocyanate]
A four-necked flask equipped with a stirrer, thermometer, reflux condenser, nitrogen blowing tube, and dropping funnel is placed in a nitrogen atmosphere, 600 g of HDI, polycaprolactone-based polyester triol “Placcel 303” (Co., Ltd.) Daicel Chemical Co., Ltd. product name molecular weight 300) 30 g was charged, and the temperature in the reactor was kept at 90 ° C. for 1 hour with stirring. Thereafter, the reactor internal temperature was maintained at 80 ° C., tetramethylammonium capryate as an isocyanuration reaction catalyst was added, and phosphoric acid was added when the yield reached 54% to stop the reaction. After filtering the reaction solution, unreacted HDI was removed using a thin film evaporator to obtain the polyisocyanate of Production Example 1. The resulting polyisocyanate had a viscosity of 9,500 mPa · s at 25 ° C., an isocyanate group concentration of 19.2% by mass, a number average molecular weight of 1,100, an average number of isocyanate groups of 5.1, and a residual HDI concentration of 0.8. It was 2 mass%. In addition, the said yield can be calculated | required by the measurement of the refractive index of a reaction liquid.

[Production Example 2: Production of polyisocyanate]
Using the same apparatus as in Production Example 1, the inside of the four-necked flask was put into a nitrogen atmosphere, 600 g of HDI was charged, and the temperature in the reactor was kept at 70 ° C. with stirring. Isocyanuration catalyst tetramethylammonium capriate was added, and when the yield reached 40%, phosphoric acid was added to stop the reaction. After filtering the reaction solution, unreacted HDI was removed using a thin film evaporator to obtain the polyisocyanate of Production Example 2. The resulting polyisocyanate has a viscosity at 25 ° C. of 2,700 mPa · s, an isocyanate group concentration of 21.7 mass%, a number average molecular weight of 660, an isocyanate group average number of 3.4, and a residual HDI concentration of 0.2 mass. %Met.

[Example 1: Production of block polyisocyanate composition]
A four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen blowing tube was placed in a nitrogen atmosphere. Production Example 1 Polyisocyanate 100 g, diethyl malonate 51 g, ethyl acetoacetate 21 g, butyl acetate 25 g were charged. 0.7 g of 28% sodium methylate solution was added at room temperature and reacted at 60 ° C. for 6 hours. Thereafter, 29 g of 1-butanol was added and stirring was continued at that temperature for 1 hour. Thereafter, 1.1 g of a di-isomer molar ratio (di2ethylhexyl acid phosphate / (di2ethylhexyl acid phosphate + mono2ethylhexyl acid phosphate) 80 mol% di2ethylhexyl acid phosphate was added. Block polyisocyanate mass concentration 75% A block polyisocyanate composition was obtained, and the turbidity evaluation was ○, and the value (including sodium salt) of the di-isomer ratio measured by the above method was the same as the addition (molar ratio). It is shown in 1.

[Examples 2 to 6, Comparative Examples 1 and 2, Reference Example]
The procedure was the same as in Example 1 except that it was shown in Table 1. The results are shown in Table 1.

１．Ｄ２ＥＨＰ；リン酸ジ２エチルヘキシル（アルキル基炭素数８）
２．ＤＢＰ；リン酸ジブチル（アルキル基炭素数４）
３．２８％ナトリウムメチラート；ナトリウムメチラートの２８％メタノール溶液。
４．ジ体／（モノ体＋ジ体）モル比率；ジアルキルアシッドホスフェートをジ体、モノアルキルアシッドホスフェートをモノ体と表記し、そのモル比率。

1. D2EHP; di2-ethylhexyl phosphate (alkyl group having 8 carbon atoms)
2. DBP; dibutyl phosphate (alkyl group having 4 carbon atoms)
3. 28% sodium methylate; sodium methylate in 28% methanol.
4). Di-isomer / (mono-isomer + di-isomer) molar ratio; dialkyl acid phosphate is expressed as di-isomer and monoalkyl acid phosphate is expressed as mono-isomer, and the molar ratio.

  The block polyisocyanate composition of the present invention has industrial applicability in a high solid paint having a reduced amount of organic solvent.

Claims (4)

Block polyisocyanate;
Alkyl acid phosphate carbon atoms of 6 or more alkyl groups and a salt with a basic compound, only including,
The block polyisocyanate contains an aliphatic diisocyanate monomer unit that does not contain a benzene ring structure or an alicyclic structure in its structure,
And the salt contains a dialkyl acid phosphate salt in a molar concentration of 70 mol% or more,
Block polyisocyanate composition.   The blocked polyisocyanate composition according to claim 1, wherein the blocked polyisocyanate is obtained by blocking an isocyanate group of a polyisocyanate with an active methylene compound. The block polyisocyanate composition according to claim 1 or 2 , comprising 65% by mass or more of the block polyisocyanate. The crosslinkable composition containing the block polyisocyanate composition of any one of Claims 1-3 .