JP2016210944A - Polyisocyanate composition, method for producing the same, curable composition, cured product, and cured resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyisocyanate composition which is excellent in transparency and exhibits low water absorption when formed into a cured film.SOLUTION: The polyisocyanate composition contains a polyisocyanate obtained by reacting a polyisocyanate precursor obtained from at least one diisocyanate selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates with a polybutadiene polyol. The molar ratio of isocyanurate groups to allophanate groups in the polyisocyanate is 1/99 to 80/20 inclusive.SELECTED DRAWING: None

Description

  The present invention relates to a polyisocyanate composition and a method for producing the same, a curable composition, a cured product, and a cured resin.

  Polyisocyanates composed of aliphatic diisocyanates or alicyclic diisocyanates are non-yellowing. A polyurethane resin obtained using this polyisocyanate as a curing agent is known to have excellent weather resistance, chemical resistance, and flexibility. Polyurethane resins make use of these excellent performances, and are used in applications such as paints, adhesives, elastomers, and thermoplastic resins.

  Further, as a method for further improving the performance of the polyurethane resin such as adhesion to the base material, extensibility, and water resistance, there is a method in which the polyisocyanate is reacted with a polyol as an auxiliary material in advance for modification. Polyols to be reacted include polyester polyols, polyether polyols, polybutadiene polyols, acrylic polyols, and the like. In particular, polybutadiene polyols are excellent in terms of water resistance, insulation, adhesion, chemical resistance, and extensibility.

  For example, in Patent Document 1, a urethane prepolymer comprising a hydroxyl group-containing polybutadiene-based polymer in which 1,4-trans and / or cis-isomers of butadiene units are 70 to 90 mol% and excess organic polyisocyanate is disclosed in Patent Document 2 has, as an essential component of a one-component moisture-curable primer, a urethane prepolymer obtained by reacting polybutadiene glycol with an excess of a polyisocyanate compound, and in Patent Document 3, 1,2-vinyl body has 85% or more. A reactive urethane prepolymer obtained by reacting a polybutadiene polyol with an isocyanate is proposed.

Japanese Patent Laid-Open No. 11-286673 Japanese Patent Laid-Open No. 11-50004 JP 2005-306951 A

  However, the conventional urethane prepolymers described in Patent Documents 1 to 3 are difficult to handle depending on the application due to their high viscosity. Further, this urethane prepolymer is liable to become cloudy due to insufficient compatibility with the polybutadiene polyol. Therefore, in an application that is used alone such as a moisture-curing paint, turbidity may occur in the appearance of the coating film. Further, even in a two-component type used by mixing with a main agent such as polyol or polyamine, there is a concern that compatibility with the main agent is deteriorated. Furthermore, this urethane polymer also has the disadvantage that it takes a long time to cure and the tackiness of the coating film is lost.

  Then, an object of this invention is to provide the polyisocyanate composition which is excellent in transparency and has a low water absorption when it is set as a cured film.

  As a result of intensive studies in order to solve the above-described problems of the prior art, the inventors of the present invention include a polyisocyanate having a specific structure, and the molar ratio of the isocyanurate group to the allophanate group of the polyisocyanate is within a predetermined range. It has been found that a certain polyisocyanate composition achieves both transparency and low water absorption when used as a cured film, and the present invention has been completed.

That is, the present invention is as follows.
[1]
A polyisocyanate obtained by a reaction of a polyisocyanate precursor obtained from at least one diisocyanate selected from the group consisting of an aliphatic diisocyanate and an alicyclic diisocyanate, and a polybutadiene polyol,
The polyisocyanate composition, wherein the polyisocyanate has a molar ratio of isocyanurate groups to allophanate groups of 1/99 or more and 80/20 or less.
[2]
The polyisocyanate composition according to [1], wherein the polyisocyanate has a molar ratio of isocyanurate groups to allophanate groups of 2/98 or more and 70/30 or less.
[3]
The polybutadiene polyol has a total amount of the structural unit having a 1,2-vinyl bond and the structural unit obtained by hydrogenating the structural unit of 85% or more based on the total amount of the structural unit [1] or [2 ]. Polyisocyanate composition as described in any one of.
[4]
The polyisocyanate composition according to any one of [1] to [3], wherein the diisocyanate is hexamethylene diisocyanate.
[5]
The polyisocyanate composition according to any one of [1] to [4], wherein a molar ratio of an isocyanate group of the polyisocyanate precursor to a hydroxyl group of the polybutadiene polyol is 2.0 or more and 40 or less.
[6]
Polyisocyanate precursor obtained from at least one diisocyanate selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates, and having a molar ratio of isocyanurate groups to allophanate groups of 1/99 or more and 80/20 or less Body,
The manufacturing method of a polyisocyanate composition which has the process of making a polybutadiene polyol react and obtaining a polyisocyanate composition.
[7]
The polybutadiene polyol has 85% or more of the total amount of the structural unit having a 1,2-vinyl bond and the structural unit obtained by hydrogenating the structural unit, based on the total amount of the structural unit. A method for producing a polyisocyanate composition.
[8]
A curable composition containing the polyisocyanate composition according to any one of [1] to [5].
[9]
Hardened | cured material obtained by hardening | curing the curable composition as described in [8].
[10]
A cured resin obtained from the polyisocyanate composition according to any one of [1] to [5].

  According to the polyisocyanate composition according to the present invention, both excellent transparency and low water absorption when used as a cured film can be achieved.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. The following embodiment is an exemplification for explaining the present invention, and the present invention is not limited to the following embodiment. The present invention can be appropriately modified within the scope of the gist. In this specification, the quantity of the specific functional group or structural unit which a composition or a compound has can be represented by "molar ratio." That is, the dimension of the value obtained by dividing the number of specific functional groups or structural units of the composition or compound by the Avogadro number is defined as mole. Thereby, the amount of the specific functional group or structural unit is expressed as a “molar ratio” with respect to the amount of the other specific functional group or structural unit. In addition, the specific functional group or structural unit which a composition has means the specific functional group or structural unit which the compound contained in a composition has.

[Polyisocyanate composition]
The polyisocyanate composition of the present embodiment comprises a polyisocyanate obtained by reacting a polyisocyanate precursor obtained from at least one diisocyanate selected from the group consisting of an aliphatic diisocyanate and an alicyclic diisocyanate and a polybutadiene polyol. Including. Moreover, the molar ratio with respect to the allophanate group of the isocyanurate group which the said polyisocyanate has is 1/99 or more and 80/20 or less. The polyisocyanate composition of the present embodiment may contain the unreacted polyisocyanate precursor in addition to the polyisocyanate.

  The polyisocyanate of this embodiment is obtained by reaction of a polyisocyanate precursor obtained from at least one diisocyanate selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates and polybutadiene polyol.

  The molar ratio of the isocyanurate group to the allophanate group of the polyisocyanate in the polyisocyanate composition is 1/99 or more and 80/20 or less from the viewpoint of compatibility with the polybutadiene polyol and transparency of the polyisocyanate composition. Preferably, it is 2/98 or more and 75/25 or less, More preferably, it is 2/98 or more and 70/30 or less, More preferably, it is 20/80 or more and 65/35 or less. In order to obtain a polyisocyanate having the above molar ratio in such a range, the molar ratio of the isocyanurate group to the allophanate group of the polyisocyanate precursor described later is adjusted, or the molar ratio of the isocyanate group to the hydroxyl group described later. And the ratio of allophanate groups may be controlled.

<Polyisocyanate precursor>
The polyisocyanate precursor of this embodiment is obtained from at least one diisocyanate selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates, and is preferably a dimer or more of the diisocyanate.

  Although it does not specifically limit as a raw material of a polyisocyanate precursor, In addition to the at least 1 sort (s) of diisocyanate selected from aliphatic diisocyanate and alicyclic diisocyanate, C1-C20 monoalcohol is also mentioned.

  Examples of the aliphatic diisocyanate include, but are not limited to, butane diisocyanate, pentane diisocyanate, hexamethylene diisocyanate (hereinafter also simply referred to as “HDI”), trimethylhexamethylene diisocyanate, and lysine diisocyanate. Aliphatic diisocyanate may be used individually by 1 type, and may use 2 or more types together.

  Examples of the alicyclic diisocyanate include, but are not limited to, isophorone diisocyanate (hereinafter also simply referred to as “IPDI”), hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and 1,4-cyclohexane diisocyanate. It is done. An alicyclic diisocyanate may be used individually by 1 type, and may use 2 or more types together.

  Either an aliphatic diisocyanate or an alicyclic diisocyanate may be used alone, or two kinds of an aliphatic diisocyanate and an alicyclic diisocyanate may be used in combination. Among the diisocyanates, HDI and IPDI are preferable from the viewpoint of industrial availability and compatibility, and HDI is more preferable from the viewpoint of extensibility.

  In the monoalcohol having 1 to 20 carbon atoms, the lower limit of the carbon number of the monoalcohol is preferably 2, more preferably 3, still more preferably 4, and still more from the viewpoint of further preventing turbidity of the polyisocyanate composition. Preferably it is 6. Further, the upper limit of the carbon number is preferably 16, more preferably 12, and still more preferably 9 from the viewpoint of making the curability better. Monoalcohol may be used individually by 1 type and may use 2 or more types together.

  The monoalcohol having 1 to 20 carbon atoms may contain an ether group, an ester group, a carbonyl group or the like in the molecule, but a monoalcohol consisting only of a saturated hydrocarbon group is preferred. Moreover, the monoalcohol which has a branch is more preferable from a viewpoint of viscosity reduction and compatibility with an active hydrogen compound.

  Examples of the monoalcohol having 1 to 20 carbon atoms include, but are not limited to, for example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, 1-pentanol, 2-pentanol, isoamyl alcohol, 1-hexanol, 2-hexanol, 1-heptanol, 1-octanol, 2-ethyl-1-hexanol, 3,5,5-trimethyl-1-hexanol, tridecanol, pentadecanol, Examples include palmityl alcohol, stearyl alcohol, cyclopentanol, cyclohexanol, methylcyclohexanol, and trimethylcyclohexanol. Among these, isobutanol, 1-butanol, isoamyl alcohol, 1-hexanol, 1-heptanol, 1-octanol, 2-ethyl-1-hexanol, tridecanol, pentadecanol, palmityl alcohol, stearyl alcohol, 3, 5,5-trimethyl-1-cyclohexanol is preferred, and isobutanol, isoamyl alcohol, and 2-ethyl-1-hexanol are more preferred.

The polyisocyanate precursor of this embodiment preferably has an isocyanurate group and an allophanate group in its molecule. The isocyanurate group is a structure formed from three isocyanate groups, and specifically has a structure represented by the following formula.

The allophanate group is a structure formed from a hydroxyl group and an isocyanate group of a monoalcohol, and specifically has a structure represented by the following formula.

  The molar ratio of the isocyanurate group to the allophanate group of the polyisocyanate precursor is preferably 1/99 or more and 80/20 or less from the viewpoint of compatibility with the polybutadiene polyol and the transparency of the polyisocyanate composition. More preferably, it is 2/98 or more and 75/25 or less, More preferably, it is 2/98 or more and 70/30 or less, More preferably, it is 20/80 or more and 65/35 or less. In order to obtain a polyisocyanate precursor having the above molar ratio in such a range, the type and amount of raw materials in the polyisocyanate precursor production method described later may be adjusted by the methods (I) to (III). .

  The polyisocyanate precursor may further contain a polyisocyanate having a bonding group different from the isocyanurate group and the allophanate group. Examples of other linking groups include, but are not limited to, biuret groups, uretdione groups, urethane groups, urea groups, oxadiazinetrione groups, and iminooxadiazinedione groups. The content of another linking group is preferably 0.5 mol or less, more preferably 0.4 mol or less, and still more preferably 0.3 mol or less with respect to 1 mol in total of the isocyanurate group and the allophanate group. In the case where the other linking group is a uretdione group, an oxadiazinetrione group, and an iminooxadiazinedione group, the above content is determined by 13C-NMR, and the other linking group is a biuret group, a urethane group, and a urea group. In this case, it can be calculated by determining the amount of each linking group by 1H-NMR.

<Method for producing polyisocyanate precursor>
Examples of a method for producing a polyisocyanate precursor having an isocyanurate group and an allophanate group include the following three methods.
(I) A method of obtaining a polyisocyanate precursor by performing a urethanization reaction of a monoalcohol and a diisocyanate, and thereafter or simultaneously performing an allophanatization reaction and an isocyanurate reaction (hereinafter, simply referred to as “method (I)”).
(II) A urethanation reaction of monoalcohol and diisocyanate is performed, and then or simultaneously, an allophanatization reaction is performed to obtain a polyisocyanate having an allophanate group, a diisocyanate isocyanurate reaction is performed, and a polyisocyanate having an isocyanurate group is obtained. A method of obtaining a polyisocyanate precursor by mixing the obtained polyisocyanate having an allophanate group and the obtained polyisocyanate having an isocyanurate group (hereinafter simply referred to as “method (II)”).
(III) A urethanization reaction of monoalcohol and diisocyanate is performed, and thereafter or allophanation reaction is performed to obtain polyisocyanate having an allophanate group, and urethanization reaction of monoalcohol and diisocyanate is performed, and thereafter or simultaneously, allophanate formation and An isocyanurate-forming reaction is performed to obtain a polyisocyanate having an allophanate group and an isocyanurate group, and the resulting polyisocyanate having an allophanate group and the obtained polyisocyanate having an allophanate group and an isocyanurate group are mixed, A method for obtaining a precursor (hereinafter, simply referred to as “method (III)”).

  The method (I) tends to be excellent in production efficiency because a polyisocyanate precursor can be produced by a one-step process. In the method (II) and the method (III), a polyisocyanate having an isocyanurate structure or a polyisocyanate having an isocyanurate structure and an allophanate structure and a polyisocyanate having an allophanate group may be mixed in an arbitrary ratio. Since it is possible, it tends to be easy to adjust the physical properties of the resulting polyisocyanate precursor.

  Among the methods (I) to (III), the method (I) and the method (III) are preferable from the viewpoint of compatibility and curability, and the method (I) is more preferable from the viewpoint of production efficiency.

  In the above method, the molar ratio of the isocyanurate group to the allophanate group of the polyisocyanate precursor is preferably 1/99 or more and 80/20 or less, more preferably 2/98 or more and 75/25 or less, and still more preferably 2 / Any method may be used as long as the polyisocyanate precursor is produced in a range of 98 to 70/30, more preferably 20/80 to 65/35.

  The reaction temperature of the urethanization reaction is preferably 20 ° C. or higher and 200 ° C. or lower, more preferably 40 ° C. or higher and 150 ° C. or lower, and further preferably 60 ° C. or higher and 120 ° C. or lower. When the reaction temperature is 20 ° C. or higher, the reaction tends to be faster, and when the reaction temperature is 200 ° C. or lower, side reactions such as uretdione formation are suppressed, and coloration also tends to be suppressed. .

  The reaction time of the urethanization reaction is preferably from 10 minutes to 24 hours, more preferably from 15 minutes to 15 hours, and even more preferably from 20 minutes to 10 hours. When the reaction time is 10 minutes or more, the reaction tends to be completed, and when the reaction time is 24 hours or less, there is no problem in production efficiency, and side reactions are also suppressed. There is a tendency. The urethanization reaction can be carried out without a catalyst or in the presence of a tin-based or amine-based catalyst.

  The reaction temperature of the allophanatization reaction is preferably 20 ° C. or higher and 200 ° C. or lower, more preferably 40 ° C. or higher and 180 ° C. or lower, more preferably 60 ° C. or higher and 160 ° C. or lower, even more preferably 90 ° C. or higher and 150 ° C. or lower, More preferably, it is 110 degreeC or more and 150 degrees C or less. When the reaction temperature is 20 ° C. or higher, the amount of the allophanatization catalyst can be reduced, and the time required to complete the reaction tends to be shortened. The reaction temperature is 200 ° C. or lower. As a result, side reactions such as uretdione formation are suppressed, and coloring of the reaction product tends to be suppressed.

  The reaction time of the allophanatization reaction is preferably 10 minutes to 24 hours, more preferably 15 minutes to 12 hours, further preferably 20 minutes to 8 hours, and even more preferably 20 minutes to 6 hours. When the reaction time is 10 minutes or more, the reaction tends to be controlled, and when the reaction time is within 24 hours, the production efficiency tends to be sufficient. In addition, when reaction temperature exceeds 130 degreeC, since uretdione may produce | generate as a side reaction, Preferably reaction time is less than 8 hours, More preferably, it is less than 6 hours, More preferably, it is less than 4 hours.

  The reaction temperature of the isocyanuration reaction or the reaction temperature of the allophanation and isocyanuration reactions is preferably a temperature of 20 ° C. or higher and 180 ° C. or lower, more preferably 30 ° C. or higher and 160 ° C. or lower, and even more preferably 40 ° C. or higher and 140 ° C. Hereinafter, it is more preferably 60 ° C. or higher and 130 ° C. or lower, and still more preferably 80 ° C. or higher and 110 ° C. or lower. When the reaction temperature is 20 ° C. or higher, the amount of the catalyst can be reduced, and side reactions such as nylon reaction tend to occur less easily. When the reaction temperature is 180 ° C. or lower, uretdione conversion is achieved. Side reactions such as the above are suppressed, and coloring of the reaction product tends to be suppressed.

  The reaction time for the isocyanuration reaction, or the reaction time for the allophanation and isocyanuration reaction is preferably 10 minutes to 24 hours, more preferably 15 minutes to 12 hours, and even more preferably 20 minutes to 8 hours, More preferably, it is 20 minutes or more and 6 hours or less. When the reaction time is 10 minutes or longer, the control of the reaction tends to be easy, and when the reaction time is within 24 hours, the production efficiency tends to be sufficient.

  When employing the method (I), it is preferable to use a catalyst for the allophanate reaction and isocyanurate reaction, and the molar ratio of the isocyanurate group to the allophanate group of the polyisocyanate precursor to be produced is 1/99 or more. More preferably, a catalyst that can be 80/20 or less is used. Examples of such catalysts include tetraalkylammonium, hydroxyalkylammonium carboxylates, hydroxides, aminosilyl group-containing compounds; lead, zinc, bismuth, tin, zirconium, zirconyl carboxylates; zinc, zirconium, tin Alkoxides of these; and a mixture thereof, more specifically, tetramethylammonium caprate and zirconium 2-ethylhexanoate.

  When employing the method (II) or the method (III), it is preferable to use a catalyst for the allophanate reaction, and the catalyst capable of increasing the selectivity of the allophanate group, that is, the polyisocyanate precursor to be formed has. Catalyst in which the molar ratio of isocyanurate groups to allophanate groups is preferably 0/100 or more and 30/70 or less, more preferably 0/100 or more and 20/80 or less, and further preferably 0/100 or more and 10/90 or less. It is more preferable to select. Examples of such a catalyst include lead, zinc, bismuth, tin, zirconium, zirconyl carboxylates; zinc, zirconium, tin alkoxides; and mixtures thereof.

  When employing the method (II), it is preferable to use a catalyst for the isocyanuration reaction. Examples of such catalysts include tetraalkylammonium, hydroxyalkylammonium, alkali metal salts of carboxylic acids, hydroxides, aminosilyl group-containing compounds; and mixtures thereof.

  When employing the method (III), it is preferable to use a catalyst for the allophanatization reaction and the isocyanurate reaction. Examples of such catalysts include tetraalkylammonium, hydroxyalkylammonium, carboxylic acid alkali metal salts, hydroxides, aminosilyl group-containing compounds, and the like, lead, zinc, bismuth, tin, zirconium, zirconyl carboxylates; Zinc, zirconium, tin alkoxides; and mixtures thereof.

  The amount of the catalyst used is preferably 0.001% by mass or more and 2.0% by mass or less, more preferably 0.01% by mass or more, based on the total mass of the reaction solution, from the viewpoint of the efficiency of the catalytic reaction and the catalytic reaction control. 0.5 mass% or less is more preferable.

  The method for adding the catalyst is not particularly limited. For example, the catalyst may be added before the production of the compound having a urethane group, that is, prior to the urethanization reaction between the diisocyanate and the organic compound having a hydroxyl group, or the diisocyanate and the hydroxyl group may be added. It may be added during the urethanization reaction with the organic compound having, or may be added after producing the compound having a urethane group. In addition, as a method of addition, a required amount of catalyst may be added all at once, or may be added in several portions, or may be added continuously at a constant addition rate.

  The urethanization reaction and the allophanatization reaction can proceed in the absence of a solvent. In addition, in these reactions, ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as methyl ethyl ketone; aromatic solvents such as toluene, xylene, and diethylbenzene; dialkyl polyalkylene glycol ether Organic solvents that are not reactive with isocyanate groups; mixtures thereof can also be used as solvents.

  The process of urethanization reaction, allophanate reaction, isocyanurate reaction, allophanate reaction and isocyanurate reaction in the production of the polyisocyanate precursor can be traced by measuring the isocyanate group content or refractive index of the reaction solution. .

  The allophanate reaction, isocyanurate reaction, allophanate reaction, and isocyanurate reaction can be stopped, for example, by cooling to room temperature or using a reaction terminator. When a catalyst is used for the reaction, it is preferable to use a reaction terminator because it tends to suppress side reactions. The amount of addition of the reaction terminator is preferably 0.25 times or more and 20 times or less, more preferably 0.5 times or more and 16 times or less, more preferably 1. The molar amount is 0 to 12 times. When the molar amount is 0.25 times or more, it tends to be completely deactivated, and when it is 20 times or less, the storage stability tends to be good.

  The reaction terminator is not particularly limited as long as it deactivates the catalyst. For example, phosphoric acid, pyrophosphoric acid and other phosphoric acid compounds; phosphoric acid and pyrophosphoric acid monoalkyl or dialkyl esters; monochloro Halogenated acetic acid such as acetic acid; benzoyl chloride, sulfonic acid ester, sulfuric acid, sulfuric acid ester, ion exchange resin, and chelating agent. Among these, phosphoric acid, pyrophosphoric acid, metaphosphoric acid, polyphosphoric acid, phosphoric acid monoalkyl ester, and phosphoric acid dialkyl ester are preferable because they tend to hardly corrode stainless steel. Specific examples of phosphoric acid monoester and phosphoric acid diester include, for example, phosphoric acid monoethyl ester and phosphoric acid diethyl ester, phosphoric acid monobutyl ester and phosphoric acid dibutyl ester, phosphoric acid mono (2-ethylhexyl) ester and phosphoric acid. Di (2-ethylhexyl) ester, phosphoric acid monodecyl ester, phosphoric acid didecyl ester, phosphoric acid monolauryl ester, phosphoric acid dilauryl ester, phosphoric acid monotridecyl ester, phosphoric acid ditridecyl ester, phosphoric acid monooleyl ester Dioleyl phosphate, monotetradecyl phosphate, ditetradecyl phosphate, monohexadecyl phosphate, dihexadecyl phosphate, monooctadecyl phosphate, dioctadecyl phosphate, and these Compounds, and the like.

  Moreover, it is also possible to use adsorption agents, such as a silica gel and activated carbon, as a terminator. In this case, an addition amount of 0.05% by mass or more and 10% by mass or less is preferable with respect to the mass of the diisocyanate used in the reaction.

  After completion of the reaction, unreacted diisocyanate and solvent may be separated from the polyisocyanate or polyisocyanate precursor. From the viewpoint of safety, it is preferable to separate unreacted diisocyanate. Examples of the method for separating unreacted diisocyanate and the solvent include a thin film distillation method and a solvent extraction method.

  In the polyisocyanate composition or the polyisocyanate precursor, the molar ratio ((a) / (b)) of the isocyanurate group (a) to the allophanate group (b) of the polyisocyanate can be determined by 1H-NMR. . An example of a method for measuring a polyisocyanate composition using HDI as a raw material by 1H-NMR is shown below.

  Measurement method example of 1H-NMR: A polyisocyanate composition or a polyisocyanate precursor is dissolved in deuterium chloroform at a concentration of 10% by mass (0.03% by mass of tetramethylsilane is added to polyisocyanate). As a chemical shift standard, a hydrogen signal of tetramethylsilane was set to 0 ppm. Measured by 1H-NMR, signal of hydrogen atom bonded to nitrogen atom of allophanate group near 8.5 ppm (1 mol hydrogen atom per 1 mol of allophanate group) and isocyanurate of isocyanurate group around 3.8 ppm The signal area ratio of the hydrogen atom of the methylene group adjacent to the nitrogen atom of the ring (6 mol of hydrogen atom per mol of isocyanurate group) is measured. The molar ratio ((a) / (b)) of the isocyanurate group (a) to the allophanate group (b) of the polyisocyanate is about a predetermined formula ((a) / (b) = (3.8 ppm). Signal area / 6) / (signal area around 8.5 ppm)). More specifically, it can be measured by the method described in Examples described later.

  The isocyanate group content of the polyisocyanate composition or the polyisocyanate precursor (hereinafter also referred to as “NCO group content”) is 10% by mass or more and 25% in a state that does not substantially contain a solvent and unreacted diisocyanate. % By mass or less is preferable, and 13% by mass to 22% by mass is more preferable. The NCO group content can be determined, for example, by reacting the isocyanate group of the polyisocyanate with an excess of amine (such as dibutylamine) and back titrating the remaining amine with an acid such as hydrochloric acid. More specifically, it can be measured by the method described in Examples described later.

The viscosity at 25 ° C. of the polyisocyanate precursor is preferably 150 mPa · s or more and 800 mPa · s or less, in a state that does not substantially contain a solvent and unreacted diisocyanate. The viscosity is measured with an E-type viscometer (manufactured by Tokimec Co., Ltd.), and a standard rotor (1 ° 34 ′ × R24) can be used as the rotor. Further, the rotational speed at that time is as follows. More specifically, it can be measured by the method described in Examples described later.
100r. p. m. (If less than 128 mPa · s)
50r. p. m. (In the case of 128 mPa · s or more and less than 256 mPa · s)
20r. p. m. (In the case of 256 mPa · s or more and less than 640 mPa · s)
10r. p. m. (In the case of 640 mPa · s or more and less than 1280 mPa · s)
5.0 r. p. m. (In the case of 1280 mPa · s or more and less than 2560 mPa · s)

The number average molecular weight (Mn) of the polyisocyanate in the polyisocyanate composition or the polyisocyanate precursor is not particularly limited, but is preferably 450 or more and 1200 or less, more preferably 500 or more and 1000 or less. Mn is calculated by gel permeation chromatograph (hereinafter referred to as “GPC”) measurement, and the area ratio of each peak of GPC is defined as mass%.
Apparatus: Product name “HLC-802A” manufactured by Tosoh Corporation
Column: Trade name “G1000HXL” × 1, “G2000HXL” × 1, “G3000HXL” × 1 manufactured by Tosoh Corporation Carrier: Tetrahydrofuran Detection method: differential refractometer

The number average functional group number (fn) of the polyisocyanate is not particularly limited, but is preferably 2.00 or more and 4.00 or less, more preferably 2.00 or more and 3.50, from the viewpoint of curability and low viscosity. It is as follows. fn can be obtained by the following equation.
fn = Mn × NCO group content / 4200

<Polybutadiene polyol>
The polybutadiene polyol of this embodiment is a polymer having polybutadiene units and hydroxyl groups in the molecule. Polybutadiene polyol obtains polybutadiene units by polymerization of 1,3-butadiene. Examples of the structural unit formed by the polymerization include structural units having a trans 1,4-vinyl bond, a cis 1,4-vinyl bond, and a 1,2-vinyl bond, and any of them is included. Just do it. The proportions of structural units having a trans 1,4-vinyl bond, structural units having a cis 1,4-vinyl bond, and structural units having a 1,2-vinyl bond may be arbitrarily mixed. Furthermore, the structural unit having a trans 1,4-vinyl bond, a cis 1,4-vinyl bond, or a 1,2-vinyl bond may be a structural unit in which all or part of the structural unit is hydrogenated. From the viewpoint of compatibility and transparency, the polybutadiene polyol preferably has a total amount of the structural unit having a 1,2-vinyl bond and the structural unit in which the structural unit is hydrogenated, based on the total amount of the structural unit. 50% or more, more preferably 80% or more, and still more preferably 85% or more. The proportion of this structural unit can be determined from a 1H-NMR spectrum.

  The number average molecular weight of the polybutadiene polyol is preferably 500 or more and 4000 or less, and more preferably 800 or more and 3500 or less, from the viewpoint of reducing the viscosity of the modified product and the water resistance of the cured resin. The number average molecular weight of the polybutadiene polyol can be measured by the same method as the number average molecular weight of the polyisocyanate described above.

  The average hydroxyl value of the polybutadiene polyol is preferably 20 mgKOH / g or more and 200 mgKOH / g or less, more preferably 25 mgKOH / g or more and 150 mgKOH / g or less, from the viewpoint of reducing the viscosity of the modified product. The average hydroxyl value can be measured by a method of “neutralization titration method (JIS K0070-1992)”.

The number average functional group number of the hydroxyl group possessed by the polybutadiene polyol is preferably 2.0 or more and 4.0 or less, and more preferably 2.0 or more and 3.0 or less, from the viewpoint of reducing the viscosity of the modified product and the isocyanate group content. . The number average functional group number of the hydroxyl group can be calculated from the following formula. In addition, the number average molecular weight by GPC is measured on the measurement conditions similar to the measurement conditions used for the measurement of the viscosity at 25 degreeC mentioned above.
Number average functional group number = (number average molecular weight by GPC × average hydroxyl value) / 56100

  Polybutadiene polyol can be produced by various methods such as living anionic polymerization and radical polymerization.

  Examples of commercially available products of polybutadiene polyol include “Nisso-PB” (trade name manufactured by Nippon Soda Co., Ltd.) and “Poly bd” (trade name manufactured by Idemitsu Kosan Co., Ltd.).

(Method for producing polyisocyanate composition)
The production method of the polyisocyanate composition of this embodiment is obtained from at least one diisocyanate selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates, and the molar ratio of isocyanurate groups to allophanate groups is 1 / A method of obtaining a polyisocyanate composition by reacting a polyisocyanate precursor having a molecular weight of 99 or more and 80/20 or less with a polybutadiene polyol (hereinafter, also simply referred to as “method (i)”), (ii) polybutadiene polyol. And at least one diisocyanate selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates, followed by isocyanuration and allophanate reaction (hereinafter also simply referred to as “method (ii)”) But) And efficiency of the granulation, from the viewpoint of obtaining a polyisocyanate composition having a desired molar ratio (isocyanurate groups / allophanate group), preferably the method of (i).

  In the method for producing a polyisocyanate composition of the present embodiment, from the viewpoint of compatibility and transparency, the polybutadiene polyol is preferably a structural unit having a 1,2-vinyl bond and a structural unit in which the structural unit is hydrogenated. Is 50% or more, more preferably 80% or more, and still more preferably 85% or more based on the total amount of structural units.

  In the method (i), in the reaction between the polyisocyanate precursor and the polybutadiene polyol, from the viewpoint of viscosity, compatibility, transparency, and extensibility, the mole of the isocyanate group that the polyisocyanate precursor has relative to the hydroxyl group that the polybutadiene polyol has. The ratio (isocyanate group / hydroxyl group, NCO / OH) is preferably 2.0 or more and 80 or less, more preferably 3.0 or more and 70 or less, further preferably 4.0 or more and 60 or less, and more preferably 4.0 or more and 40 or less. Further preferred. The molar ratio is more preferably 2.0 or more and 40 or less.

  In the reaction between the polyisocyanate precursor and the polybutadiene polyol, a new urethane bond tends to be formed, and allophanate groups and isocyanurate groups tend not to be formed. Therefore, the isocyanurate group allophanate molar ratio of the polyisocyanate precursor and the isocyanurate group allophanate molar ratio of the polyisocyanate obtained by the above reaction tend to be almost the same value.

  In the reaction between the polyisocyanate precursor and the polybutadiene polyol, the reaction temperature is preferably −20 ° C. or higher and 150 ° C. or lower, more preferably 30 ° C. or higher and 130 ° C. or lower, from the viewpoint of reaction rate control and side reaction suppression.

  In the reaction of the polyisocyanate precursor and the polybutadiene polyol, an organic solvent may be used to reduce the viscosity. The organic solvent is not particularly limited as long as the reaction with an isocyanate group does not proceed. For example, an aliphatic hydrocarbon solvent such as hexane, heptane, and octane; an alicyclic hydrocarbon solvent such as cyclohexane and methylcyclohexane Solvents; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, methyl lactate, ethyl lactate; toluene, xylene, diethylbenzene, mesitylene, anisole, Aromatic solvents such as benzyl alcohol, phenyl glycol, chlorobenzene; ethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate, dipropylene glycol monomethyl ether, propylene glycol Glycol solvents such as coal monomethyl ether; ether solvents such as diethyl ether, tetrahydrofuran and dioxane; halogenated hydrocarbon solvents such as dichloromethane, 1,2-dichloroethane and chloroform; pyrrolidones such as N-methyl-2-pyrrolidone Solvents; Amide solvents such as N, N-dimethylacetamide and N, N-dimethylformamide; Sulfoxide solvents such as dimethyl sulfoxide; Lactone solvents such as γ-butyrolactone; Amine solvents such as morpholine; Can be mentioned.

  Moreover, according to the objective and use, a hardening acceleration | stimulation catalyst, antioxidant, a ultraviolet absorber, a light stabilizer, a pigment, a leveling agent, a plasticizer, surfactant, and various activators can be used.

  Examples of the curing accelerating catalyst include, but are not limited to, tin compounds such as dibutyltin dilaurate, dibutyltin diacetate, dioctyltin dilaurate, dimethyltin dineodecanoate, and bis (2-ethylhexanoic acid) tin; Zinc compounds such as zinc 2-ethylhexanoate and zinc naphthenate; titanium compounds such as titanium 2-ethylhexanoate and titanium diisopropoxybis (ethylacetonate); cobalt such as cobalt 2-ethylhexanoate and cobalt naphthenate Compounds; Bismuth compounds such as bismuth 2-ethylhexanoate and bismuth naphthenate; Zirconium compounds such as zirconium tetraacetylacetonate, zirconyl 2-ethylhexanoate, zirconyl naphthenate; and amine compounds. Antioxidants are not limited to the following, but include, for example, hindered phenol compounds, phosphorus compounds, and sulfur compounds. Although not limited to the following as an ultraviolet absorber, For example, a benzotriazole type, a triazine type, and a benzophenone type compound are mentioned. Examples of the light stabilizer include, but are not limited to, hindered amines, benzotriazoles, triazines, benzophenones, and benzoates. Examples of the pigment include, but are not limited to, titanium oxide, carbon black, indigo, pearl mica, and aluminum. The leveling agent is not limited to the following, and examples thereof include silicone oil. Examples of the plasticizer include, but are not limited to, phthalates, phosphoric acid esters, and polyester resins. The surfactant is not limited to the following, and examples thereof include known anionic surfactants, cationic surfactants, and amphoteric surfactants.

  The viscosity at 25 ° C. of the polyisocyanate composition obtained by reacting as described above is preferably from 300 mPa · s to 50,000 mPa · s, more preferably from 500 mPa · s to 40,000 mPa · s from the viewpoint of handleability. Is more preferably 800 mPa · s or more and 30,000 mPa · s or less. For the measurement of viscosity, a rheometer (RS-1 manufactured by HAAKE) is used in addition to the E-type viscometer. Moreover, a rotor can be selected according to a viscosity. More specifically, it can be measured by the method described in Examples described later.

(Block polyisocyanate composition)
The polyisocyanate composition of this embodiment can make the isocyanate group of the said polyisocyanate react with a heat dissociable blocking agent, and can be set as the block polyisocyanate composition containing block polyisocyanate. The “thermal dissociation” of the thermally dissociable blocking agent herein means that the thermally dissociable blocking agent bonded to the isocyanate group is dissociated by heating to become a reactive isocyanate group. The temperature necessary for this dissociation varies depending on the structure of the thermally dissociable blocking agent, but is, for example, 40 ° C. or more and 300 ° C. or less.

  Examples of the heat dissociable blocking agent include, but are not limited to, for example, oxime-based, alcohol-based, acid amide-based, acid imide-based, phenol-based, amine-based, active methylene-based, imidazole-based, and pyrazole-based compounds. Can be mentioned.

  Examples of oxime compounds include, but are not limited to, formal oxime, acetoald oxime, acetoxime, methyl ethyl ketoxime, and cyclohexanone oxime. Examples of alcohol compounds include, but are not limited to, methanol, ethanol, 2-propanol, n-butanol, sec-butanol, 2-ethyl-1-hexanol, 2-methoxyethanol, 2-ethoxyethanol. 2-butoxyethanol. Examples of acid amide compounds include, but are not limited to, acetanilide, acetic acid amide, ε-caprolactam, δ-valeroactam, and γ-butyrolactam. The acid imide-based compound is not limited to the following compounds, and examples thereof include succinimide and maleic imide. Examples of phenolic compounds include, but are not limited to, phenol, cresol, ethylphenol, butylphenol, nonylphenol, dinonylphenol, styrenated phenol, and hydroxybenzoic acid ester. Examples of amine compounds include, but are not limited to, diphenylamine, aniline, carbazole, di-n-propylamine, diisopropylamine, and isopropylethylamine. The active methylene-based compound is not limited to the following compounds, and examples thereof include dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone. Examples of the imidazole compound include, but are not limited to, imidazole and 2-methylimidazole. Examples of the pyrazole-based compound include, but are not limited to, pyrazole, 3-methylpyrazole, and 3,5-dimethylpyrazole. Among these, oxime-based, acid amide-based, amine-based, active methylene-based, and pyrazole-based compounds are preferable from the viewpoints of availability, viscosity of the produced block polyisocyanate composition, reaction temperature, and reaction time, and methyl ethyl ketoxime. , Ε-caprolactam, diethyl malonate, ethyl acetoacetate, and 3,5-dimethylpyrazole are more preferable.

  A heat dissociable blocking agent may be used individually by 1 type, and may use 2 or more types together. Moreover, although it may block completely or partially by a well-known method, it is preferable to block all. When all the isocyanate groups are blocked, the molar ratio of the heat dissociable blocking agent to the isocyanate groups in the polyisocyanate composition (thermal dissociable blocking agent) / (isocyanate group) is 1.0 or more and 1.5 or less. Preferably there is. In that case, excess and / or unreacted thermally dissociable blocking agent remains in the blocked polyisocyanate composition. The blocking reaction may be carried out in the absence of a solvent as in the method for producing a polyisocyanate precursor, or may be carried out using an organic solvent that does not have reactivity with an isocyanate group, if necessary. In addition, when using an organic solvent, you may isolate | separate the organic solvent after reaction.

  The reaction temperature with the heat dissociable blocking agent is preferably −20 ° C. or higher and 150 ° C. or lower, and more preferably 0 ° C. or higher and 100 ° C. or lower from the viewpoint of reaction rate and side reaction.

(Curable composition)
The curable composition of this embodiment contains the polyisocyanate composition of this embodiment. A curable composition is prepared by mixing the polyisocyanate composition mentioned above and an active hydrogen compound (polyvalent active hydrogen compound) as a main ingredient, for example.

[Cured product]
The cured product of the present embodiment is obtained by curing the curable composition. In particular, when the curable composition contains a block polyisocyanate composition, the curable composition is bonded to the isocyanate group of the polyisocyanate in the block polyisocyanate composition by being heated. The thermally dissociable blocking agent is dissociated, and the dissociated isocyanate group reacts with active hydrogen in the active hydrogen compound to form a cured product.

  The active hydrogen compound is a compound in which two or more active hydrogens are bonded in the molecule. Examples of the active hydrogen compound include polyols, polyamines, and polythiols, and polyols are preferable.

  Examples of the polyol include, but are not particularly limited to, polyester polyol, acrylic polyol, polyether polyol, polyolefin polyol, fluorine polyol, polycarbonate polyol, and epoxy resin.

  Examples of the polyester polyol include, but are not limited to, for example, at least one selected from the group consisting of succinic acid, adipic acid, sebacic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, and terephthalic acid. A polyester polyol obtained by a condensation reaction between a dibasic acid of carboxylic acid and at least one polyhydric alcohol selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, trimethylolpropane, and glycerin; and Examples include polycaprolactones obtained by ring-opening polymerization of ε-caprolactone using a polyhydric alcohol.

  As the acrylic polyol, for example, an ethylenically unsaturated bond-containing monomer having a hydroxyl group alone or a mixture thereof and another ethylenically unsaturated bond-containing monomer copolymerizable therewith can be used. An acrylic polyol obtained by polymerizing is mentioned.

  Examples of the monomer having an ethylenically unsaturated bond having a hydroxyl group include, but are not limited to, for example, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate And hydroxybutyl methacrylate. Of these, hydroxyethyl acrylate and hydroxyethyl methacrylate are preferred.

  Examples of other ethylenically unsaturated bond-containing monomers copolymerizable with the ethylenically unsaturated bond-containing monomer having a hydroxyl group include, but are not limited to, for example, methyl acrylate, ethyl acrylate, Propyl acrylate, isopropyl acrylate, acrylate-n-butyl, acrylate isobutyl, acrylate-n-hexyl, cyclohexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, benzyl acrylate, phenyl acrylate, etc. Acrylic acid ester; methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, -n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, Methacrylic acid esters such as lauryl tacrylate, benzyl methacrylate and phenyl methacrylate, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid and itaconic acid; acrylamide, methacrylamide, N, N-methylenebisacrylamide, diacetone Unsaturated amides such as acrylamide, diacetone methacrylamide, maleic acid amide, maleimide; vinyl monomers such as glycidyl methacrylate, styrene, vinyl toluene, vinyl acetate, acrylonitrile, dibutyl fumarate; vinyltrimethoxysilane, vinylmethyl Examples thereof include vinyl monomers having a hydrolyzable silyl group such as dimethoxysilane and γ- (meth) acryloxypropyltrimethoxysilane.

  The polyether polyol is not particularly limited. For example, a hydroxide such as lithium, sodium or potassium; a strongly basic catalyst such as alcoholate or alkylamine is used, and a polyvalent hydroxy compound is used alone or in a mixture. Polyether polyols obtained by adding a single or mixture of alkylene oxides such as oxide, propylene oxide, butylene oxide, cyclohexene oxide, and styrene oxide; polyhydric compounds obtained by reacting an alkylene oxide with a polyfunctional compound such as ethylenediamine Ether polyols; so-called polymer polyols obtained by polymerizing acrylamide or the like using these polyether polyols as media.

The polyvalent hydroxy compound is not particularly limited.
(1) diglycerin, ditrimethylolpropane, pentaerythritol, dipentaerythritol;
(2) Sugar alcohol compounds such as erythritol, D-threitol, L-arabinitol, ribitol, xylitol, sorbitol, mannitol, galactitol, and rhamnitol;
(3) monosaccharides such as arabinose, ribose, xylose, glucose, mannose, galactose, fructose, sorbose, rhamnose, fucose, ribosese;
(4) Disaccharides such as trehalose, sucrose, maltose, cellobiose, gentiobiose, lactose, melibiose;
(5) Trisaccharides such as raffinose, gentianose, meletitose;
(6) tetrasaccharides such as stachyose;
Is mentioned.

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

  The fluorine polyol is not particularly limited as long as it is a polyol containing fluorine in the molecule. For example, fluoroolefins, cyclovinyl ethers disclosed in JP-A-57-34107 and JP-A-61-275111, Examples thereof include copolymers such as hydroxyalkyl vinyl ether and monocarboxylic acid vinyl ester.

  Although it does not specifically limit as polycarbonate polyol, For example, low molecular polyols used for low molecular carbonate compounds, such as dialkyl carbonates, such as dimethyl carbonate, alkylene carbonates, such as ethylene carbonate, diaryl carbonates, such as diphenyl carbonate, and the above-mentioned polyester polyol And polycarbonate polyol obtained by condensation polymerization.

  The epoxy resin is not particularly limited. For example, novolak type, glycidyl ether type, glycol ether type, epoxy type of aliphatic unsaturated compound, epoxy type fatty acid ester, polyvalent carboxylic acid ester type, aminoglycidyl type, β- Examples include methyl epichrome type, cyclic oxirane type, halogen type, and resorcin type epoxy resin.

  The hydroxyl value of the polyol is preferably 10 mgKOH / g or more and 300 mgKOH / g or less per resin from the viewpoint of crosslink density and mechanical properties of the cured resin.

  In the curable composition of the present embodiment, the equivalent ratio of isocyanate groups to active hydrogen groups is preferably adjusted to 10/1 or more and 1/10 or less.

  The curable composition may be used in combination with a curing agent such as a melamine curing agent or an epoxy curing agent. Typical examples of the melamine curing agent include fully alkyl etherified melamine resins, methylol group type melamine resins, and imino group type melamine resins having an imino group in part. When a melamine curing agent is used in combination, addition of an acidic compound is more effective. Specific examples of the acidic compound include carboxylic acid, sulfonic acid, acidic phosphate ester, and phosphite ester. Typical examples of the carboxylic acid include acetic acid, lactic acid, succinic acid, oxalic acid, maleic acid, and decanedicarboxylic acid. Examples of the sulfonic acid include p-toluenesulfonic acid, dodecylbenzenesulfonic acid, and dinonylnaphthalenedisulfonic acid. Examples of the acidic phosphate ester include dimethyl phosphate, diethyl phosphate, dibutyl phosphate, dioctyl phosphate, dilauryl phosphate, monomethyl phosphate, monoethyl phosphate, monobutyl phosphate, and monooctyl phosphate. Examples of the phosphite include diethyl phosphite, dibutyl phosphite, dioctyl phosphite, dilauryl phosphite, monoethyl phosphite, monobutyl phosphite, monooctyl phosphite and monolauryl phosphite. Although it does not specifically limit as an epoxy-type hardening | curing agent, For example, an aliphatic polyamine, an alicyclic polyamine, an aromatic polyamine, an acid anhydride, a phenol novolak, a polymercaptan, an aliphatic tertiary amine, an aromatic tertiary amine, imidazole Examples thereof include a Lewis acid complex.

  Various additives such as curing accelerators, antioxidants, UV absorbers, light stabilizers, pigments, leveling agents, plasticizers, surfactants, etc. are mixed into the polyisocyanate composition or polyol according to the purpose and application. Can be used.

  Although it does not specifically limit as a hardening acceleration | stimulation catalyst, For example, tin-type compounds, such as dibutyltin dilaurate, dibutyltin diacetate, dioctyltin dilaurate, dimethyltin dineodecanoate, bis (2-ethylhexanoic acid) tin; 2-ethyl Zinc compounds such as zinc hexanoate and zinc naphthenate; titanium compounds such as titanium 2-ethylhexanoate and titanium diisopropoxybis (ethylacetonate); cobalt compounds such as cobalt 2-ethylhexanoate and cobalt naphthenate; 2 -Bismuth compounds such as bismuth ethylhexanoate and bismuth naphthenate; zirconium compounds such as zirconium tetraacetylacetonate, zirconyl 2-ethylhexanoate and zirconyl naphthenate; and amine compounds. Although it does not specifically limit as antioxidant, For example, a hindered phenol type, phosphorus type, and a sulfur type compound are mentioned. Although it does not specifically limit as a ultraviolet absorber, For example, a benzotriazole type, a triazine type | system | group, a benzophenone type compound is mentioned. The light stabilizer is not particularly limited, and examples thereof include hindered amines, benzotriazoles, triazines, benzophenones, and benzoates. Although it does not specifically limit as a pigment, For example, a titanium oxide, carbon black, indigo, pearl mica, and aluminum are mentioned. Although it does not specifically limit as a leveling agent, For example, a silicone oil is mentioned. Although it does not specifically limit as a plasticizer, For example, phthalic acid ester, phosphoric acid type, and polyester type are mentioned. Although it does not specifically limit as surfactant, For example, a well-known anionic surfactant, a cationic surfactant, and an amphoteric surfactant are mentioned.

[Curing resin]
The cured resin of this embodiment is obtained from the polyisocyanate composition of this embodiment. For example, a one-component moisture-curing polyisocyanate composition is used, and the isocyanate group of the polyisocyanate composition is reacted with moisture in the air to obtain a cured resin. This cured resin can achieve all of dryness, extensibility, and low water absorption, as well as a cured product crosslinked with an active hydrogen compound.

[Use]
The polyisocyanate composition of the present embodiment includes a curable composition such as a coating composition, a pressure-sensitive adhesive composition, an adhesive composition, and a casting composition; various surface treatment compositions such as a fiber treatment agent; various elastomers It can be used as a composition; a crosslinking agent such as a foam composition; a modifier; an additive.

  The coating composition containing the polyisocyanate composition of the present embodiment can be suitably used as a primer, intermediate coating or top coating on various materials by roll coating, curtain flow coating, spray coating, electrostatic coating, bell coating, etc. . In addition, this coating composition imparts cosmetics, weather resistance, acid resistance, rust resistance, chipping resistance, insulation, adhesion, etc. to pre-coated metal, automobiles, plastics, electronic boards, etc. It is suitably used for this purpose.

  The pressure-sensitive adhesive composition and adhesive composition containing the polyisocyanate composition of the present embodiment can be used in fields such as automobiles, building materials, home appliances, woodworking, and solar cell laminates. For example, home appliances such as a television, a personal computer, a digital camera, and a mobile phone need to be laminated with films and plates of various adherends in order to develop various functions in optical members for liquid crystal displays and the like. Therefore, since sufficient tackiness or adhesiveness is required between the films and plates of various adherends, home appliances including the optical member are used for the pressure-sensitive adhesive composition and adhesive composition of the present embodiment. Preferred as an example.

  The adherend to which the curable composition containing the polyisocyanate composition of the present embodiment can be used is not particularly limited. For example, glass; various metals such as aluminum, iron, galvanized steel, copper, stainless steel; wood Porous members such as paper, mortar, stones; members coated with fluorine, urethane, acrylic urethane, etc .; cured sealants such as silicone-based cured products, modified silicone-based cured products, urethane-based cured products; Rubbers such as vinyl chloride, natural rubber and synthetic rubber; leathers such as natural leather and artificial leather; fibers such as plant fibers, animal fibers, carbon fibers and glass fibers; non-woven fabrics, polyester, acrylic, polycarbonate, tri Films and plates of resins such as acetylcellulose and polyolefin; UV curable acrylic resin layer, printing ink, UV Ink such as Nki and the like.

  The polyisocyanate composition of this embodiment is excellent in transparency and low viscosity although it contains substantially no organic solvent. Moreover, when it is set as a curable composition, hardened | cured material, or cured resin, it is excellent in extensibility, drying property, curability, water absorption, and compatibility with active hydrogen compounds, such as a polyol.

  Hereinafter, the present embodiment will be described in more detail by showing specific synthesis examples, examples, and comparative examples. The present embodiment is not limited by these synthesis examples, examples, and comparative examples as long as the gist thereof is not exceeded. In the following, “part” and “%” indicating the amount or ratio of a product mean values based on mass unless otherwise specified. Various physical properties in Synthesis Examples, Examples and Comparative Examples were measured as follows.

(Physical property 1) molar ratio ((a) / (b))
Using the polyisocyanate composition as a sample, the molar ratio ((a) / (b)) of the isocyanurate group (a) of the polyisocyanate to the allophanate group (b) is 1H-NMR (trade name “FT” manufactured by Bruker). -NMR DPX-400 ") and measured as follows. A polyisocyanate precursor or polyisocyanate composition is dissolved in deuterium chloroform at a concentration of 10% by mass (0.03% by mass of tetramethylsilane is added to polyisocyanate), and the chemical shift standard is hydrogen of tetramethylsilane. Measured by 1H-NMR, the signal of the hydrogen atom bound to the nitrogen atom of the allophanate group near 8.5 ppm (1 mol hydrogen atom per 1 mol of the allophanate group) and the signal around 3.8 ppm The signal area ratio of the hydrogen atom of the methylene group adjacent to the nitrogen atom of the isocyanurate ring of the isocyanurate group (6 mol of hydrogen atom per mol of isocyanurate group) was determined, and isocyanurate group / allophanate group = (3. Signal area around 8 ppm / 6) / (around 8.5 ppm) The Gunaru area) was calculated isocyanurate groups of the polyisocyanate (a) and the molar ratio of allophanate groups and (b) (a) / (b).

(Physical property 2) NCO group content rate After using the polyisocyanate precursor or polyisocyanate composition as a sample, the isocyanate group content rate (NCO group content rate, mass%) was neutralized with an excess of 2N amine, It was determined by back titration with 1N hydrochloric acid. Moreover, the isocyanate group content rate of the reaction liquid in the synthesis example 3 was calculated | required similarly.

(Physical property 3) Viscosity The viscosity of the polyisocyanate precursor was measured with an E-type viscometer (manufactured by Tokimec Co., Ltd.). The rotor used for the measurement was a standard rotor (1 ° 34 ′ × R24), and the rotational speed was set as follows.
100r. p. m. (If less than 128 mPa · s)
50r. p. m. (In the case of 128 mPa · s or more and less than 256 mPa · s)
20r. p. m. (In the case of 256 mPa · s or more and less than 640 mPa · s)
10r. p. m. (In the case of 640 mPa · s or more and less than 1280 mPa · s)
5.0 r. p. m. (In the case of 1280 mPa · s or more and less than 2560 mPa · s)
The viscosity of the polyisocyanate composition was measured at 25 ° C. using a rheometer (RS-1 manufactured by HAAKE). The rotor used for the measurement was 2 ° × R10. The number of revolutions was set as described above.

[Synthesis Example 1] Polyisocyanate precursor A-1
The inside of a four-necked flask equipped with a stirrer, a thermometer, and a cooling tube was purged with nitrogen. To this four-necked flask, 1000 g of HDI and 30 g of 2-ethylhexanol were charged, and a urethanization reaction was performed at 90 ° C. for 1 hour with stirring. At 90 ° C., 0.6 g of a solid content 5% isobutanol solution of tetramethylammonium caprate was added as a catalyst for the allophanate reaction and isocyanurate reaction. After further stirring for 2 hours, 0.06 g of 85% aqueous phosphoric acid solution was added to stop the reaction. After filtering the reaction solution, unreacted HDI was removed using a thin film distillation apparatus to obtain a polyisocyanate precursor A-1. The obtained polyisocyanate precursor A-1 was a transparent liquid, the yield was 210 g, the viscosity at 25 ° C. was 340 mPa · s, and the NCO group content was 20.3%. When 1H-NMR was measured, the isocyanurate group / allophanate group molar ratio was 50/50.

[Synthesis Example 2] Polyisocyanate precursor A-2
In the same apparatus as in Synthesis Example 1, 1000 g of HDI and 50 g of 2-ethylhexanol were charged and a urethanization reaction was performed by stirring at 90 ° C. for 1 hour. As a catalyst for the allophanatization reaction and isocyanuration reaction, 0.53 g of a 10% solid content n-butanol solution of tetramethylammonium caprate was added. After further stirring for 3 hours, 0.10 g of a 85% solid solution of phosphoric acid was added to stop the reaction. After filtration of the reaction solution, unreacted HDI was removed by the same method as in Synthesis Example 1 to obtain polyisocyanate precursor A-2. The obtained polyisocyanate precursor A-2 was a pale yellow transparent liquid, the yield was 440 g, the viscosity at 25 ° C. was 450 mPa · s, and the NCO group content was 19.6%. When 1H-NMR was measured, the isocyanurate group / allophanate group molar ratio was 40/60.

[Synthesis Example 3] Polyisocyanate precursor A-3
In the same apparatus as in Synthesis Example 1, 500 g of HDI was charged, and 0.08 g of tetramethylammonium capryate was added with stirring at 60 ° C. After allowing the reaction to proceed for 4 hours, 0.2 g of phosphoric acid was added to stop the reaction. After filtering the reaction solution, unreacted HDI was removed in the same manner as in Synthesis Example 1 to obtain polyisocyanate precursor A-3. The obtained polyisocyanate precursor A-3 was a pale yellow transparent liquid, the yield was 102 g, the viscosity at 25 ° C. was 1400 mPa · s, and the NCO group content was 23.4%. When 1H-NMR was measured, the isocyanurate group / allophanate group molar ratio was 100/0.

[Synthesis Example 4] Polyisocyanate precursor A-4
In the same apparatus as in Synthesis Example 1, 561.9 g of HDI and 38.1 g of isobutanol were charged, and a urethanization reaction was performed at 90 ° C. for 60 minutes with stirring. After raising the temperature to 120 ° C., 0.28 g of 20% mineral spirit solution of zirconyl 2-ethylhexanoate in solid content was added as a catalyst for the allophanatization reaction and isocyanurate reaction. Further, after stirring for 60 minutes, 0.097 g of 85% solid solution of phosphoric acid was added to stop the reaction. After filtering the reaction solution, unreacted HDI was removed in the same manner as in Synthesis Example 1 to obtain polyisocyanate precursor A-4. The obtained polyisocyanate precursor A-4 was a pale yellow transparent liquid, the yield was 203 g, the viscosity at 25 ° C. was 130 mPa · s, and the NCO group content was 18.8%. When 1H-NMR was measured, the molar ratio of isocyanurate group / allophanate group was 3/97.

[Examples 1 to 10, Comparative Examples 1 to 3] Polyisocyanate Composition Polyisocyanate precursors A-1 to A-4 obtained in Synthesis Examples 1 to 4 and polyol B shown below in the same apparatus as Synthesis Example 1 -1 to B-3 are selected from the types shown in Table 1, and the amounts are adjusted so that the molar ratio of the isocyanate groups to the hydroxyl groups (NCO / OH ratio) shown in Tables 1 and 2 is adjusted. The mixture was stirred at 100 ° C. for 4 hours under a nitrogen atmosphere to obtain a polyisocyanate composition.
Polyol B-1 (trade name “NISSO-PB G-1000” manufactured by Nippon Soda Co., Ltd., polybutadiene polyol, 1,2 bond is 85% or more)
Polyol B-2 (Nippon Soda Co., Ltd., trade name “NISSO-PB G-2000”, polybutadiene polyol, 1,2 bond is 85% or more)
Polyol B-3 (trade name “Excenol 2020” manufactured by Asahi Glass Co., polyether polyol).

  The molar ratio ((a) / (b)), NCO group content, and viscosity of the obtained polyisocyanate composition were measured, and the transparency was evaluated by visually observing the presence or absence of turbidity or separation. . The results are shown in Table 1. In addition, since the polyisocyanate composition of Comparative Example 2 was visually observed and separated, the moisture cured film and the two-component cured film described later were not evaluated.

[Moisture-cured film]
(Evaluation 2-1) Extensibility The polyisocyanate compositions obtained in Examples and Comparative Examples were diluted with methyl ethyl ketone so as to have a solid content of 80%, and “Neostan U-810” (Nitto Kasei Co., Ltd. product) Name, dioctyltin dilaurate) was added to a concentration of 5000 ppm / solid to obtain a coating composition.

  The obtained coating composition was applied to an PP applicator so as to have a resin film thickness of 40 μm. After curing for 7 days at a temperature of 23 ° C. and a humidity of 50%, a cured resin film was obtained by peeling from the plate.

The breaking elongation of the obtained cured resin film was measured using a trade name “TENSILON RTE-1210” manufactured by A & D (A & D). Based on the measured elongation at break, the extensibility of the moisture cured film was evaluated according to the following evaluation criteria. The obtained results are shown in Tables 1 and 2. Moreover, the measurement conditions which measured the breaking elongation are as follows.
Tensile speed: 20mm / min
Sample dimensions: 20 mm long x 10 mm wide x 40 μm thick
Measurement environment: temperature 23 ° C, humidity 50%
(Evaluation criteria)
○: Breaking elongation of the coating film is 50% or more ×: Breaking elongation of the coating film is less than 50%

(Evaluation 2-2) Dryability Using the polyisocyanate compositions obtained in Examples and Comparative Examples, a coating composition was prepared under the same conditions as in the above (Evaluation 2-1) extensibility. The applicator was coated to a thickness of 40 μm. After curing for 7 hours at a temperature of 23 ° C. and a humidity of 50%, spherical cotton was placed on the coating film, and 100 g of weight was placed on it for 60 seconds. Thereafter, the weight and the cotton were removed, the traces of the cotton remaining on the coating film were observed, and the drying property of the moisture cured film was evaluated according to the following evaluation criteria. The obtained results are shown in Tables 1 and 2.
(Evaluation criteria)
○: Slightly no cotton left △: Not much cotton left, slightly left ×: Many cotton left

(Evaluation 2-3) Curability A coating composition was prepared from the polyisocyanate compositions obtained in Examples and Comparative Examples under the same conditions as the above (Evaluation 2-1) Extensibility, and the above [Extensibility] and The applicator was painted under the same conditions. After curing at a temperature of 23 ° C. and a humidity of 50% for 24 hours, the coating film was peeled off from the plate, and the remaining film ratio (gel fraction) when immersed in acetone at 23 ° C. for 24 hours was measured. Thus, the curability of the moisture cured film was evaluated. The obtained results are shown in Tables 1 and 2.
(Evaluation criteria)
○: Gel fraction is 90% or more Δ: Gel fraction is 80% or more and less than 90% ×: Gel fraction is less than 80%

(Evaluation 2-4) Water absorption The polyisocyanate compositions obtained in Examples and Comparative Examples were prepared as coating compositions under the same conditions as the above (Evaluation 2-1) extensibility, and the above [Extensibility] and The applicator was painted under the same conditions. After curing for 6 days at a temperature of 23 ° C. and a humidity of 50%, the coating film was peeled off from the plate. It was immersed in distilled water at a temperature of 23 ° C. and a humidity of 50% for 7 days, and the weight change rate (%) before and after immersion was taken as the water absorption rate, and the water absorption of the moisture cured film was evaluated according to the following evaluation criteria. The obtained results are shown in Tables 1 and 2.
(Evaluation criteria)
○: Water absorption is 1% or more ×: Water absorption is less than 1%

[Two-component cured film]
(Evaluation 3-1) Extensibility Polyisocyanate compositions obtained in Examples and Comparative Examples and “Setalux 1767” (acrylic polyol, trade name, manufactured by Nuplex, hydroxyl value 97.5 mg KOH / g (solid), solid 65% by mass), so that the molar ratio of isocyanate groups to hydroxyl groups (NCO / OH) is 1.0, diluted with butyl acetate to a solid content of 50%, and on a PP plate, the resin film thickness is 40 μm. The applicator was painted so that After curing for 7 days at a temperature of 23 ° C. and a humidity of 50%, a cured resin film was obtained by peeling from the plate. The breaking elongation of the obtained cured resin film was evaluated as extensibility under the same conditions as in (Evaluation 2-1).
(Evaluation criteria)
○: Breaking elongation of the coating film is 50% or more ×: Breaking elongation of the coating film is less than 50%

(Evaluation 3-2) Curability The polyisocyanate compositions obtained in Examples and Comparative Examples were blended in the same manner as the above (Evaluation 3-1) compatibility so that the resin film thickness was 40 μm on the PP plate. Applicator painted. After curing at a temperature of 23 ° C. and a humidity of 50% for 24 hours, the coating film was peeled off from the plate, and the remaining film ratio (gel fraction) when immersed in acetone at 23 ° C. for 24 hours was measured. Was used to evaluate the curability of the two-component cured film. The obtained results are shown in Tables 1 and 2.
(Evaluation criteria)
○: Gel fraction is 90% or more Δ: Gel fraction is 80% or more and less than 90% ×: Gel fraction is less than 80%

(Evaluation 3-3) Water Absorption Using the polyisocyanate compositions obtained in Examples and Comparative Examples, a coating composition was prepared under the same conditions as in the above (Evaluation 3-1) extensibility. ) Applicator was coated under the same conditions as extensibility. After curing for 6 days at a temperature of 23 ° C. and a humidity of 50%, the water absorption of the two-component cured film was evaluated under the same conditions as the above (Evaluation 2-4) Water absorption. The obtained results are shown in Tables 1 and 2.
(Evaluation criteria)
○: Water absorption is 2% or more ×: Water absorption is less than 2%

  The polyisocyanate composition according to the present invention exhibits excellent performance as a paint, an adhesive, a pressure-sensitive adhesive, an ink, a sealing agent, a casting agent, a sealant, a surface modifier, a coating agent, and the like.

Claims (10)

A polyisocyanate obtained by a reaction of a polyisocyanate precursor obtained from at least one diisocyanate selected from the group consisting of an aliphatic diisocyanate and an alicyclic diisocyanate, and a polybutadiene polyol,
The polyisocyanate composition, wherein the polyisocyanate has a molar ratio of isocyanurate groups to allophanate groups of 1/99 or more and 80/20 or less.   The polyisocyanate composition according to claim 1, wherein the polyisocyanate has a molar ratio of isocyanurate groups to allophanate groups of 2/98 or more and 70/30 or less.   The said polybutadiene polyol has 85% or more of the total amount of the structural unit which has a 1, 2- vinyl bond, and the structural unit by which this structural unit was hydrogenated with respect to the total amount of a structural unit. The polyisocyanate composition described.   The polyisocyanate composition according to any one of claims 1 to 3, wherein the diisocyanate is hexamethylene diisocyanate.   The polyisocyanate composition according to any one of claims 1 to 4, wherein a molar ratio of an isocyanate group of the polyisocyanate precursor to a hydroxyl group of the polybutadiene polyol is 2.0 or more and 40 or less. Polyisocyanate precursor obtained from at least one diisocyanate selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates, and having a molar ratio of isocyanurate groups to allophanate groups of 1/99 or more and 80/20 or less Body,
The manufacturing method of a polyisocyanate composition which has the process of making a polybutadiene polyol react and obtaining a polyisocyanate composition.   The said polybutadiene polyol has 85% or more of the total amount of the structural unit which has a 1, 2- vinyl bond, and the structural unit by which this structural unit was hydrogenated with respect to the total amount of a structural unit. A method for producing a polyisocyanate composition.   The curable composition containing the polyisocyanate composition of any one of Claims 1-5.   A cured product obtained by curing the curable composition according to claim 8.   A cured resin obtained from the polyisocyanate composition according to any one of claims 1 to 5.