JP6595234B2 - Polyisocyanate composition, block polyisocyanate composition and method for producing them - Google Patents

Description

  The present invention includes a polyisocyanate composition, a block polyisocyanate composition and a production method thereof, a resin composition containing the polyisocyanate composition, a resin obtained from the polyisocyanate composition, and the block polyisocyanate composition. The present invention relates to a curable composition and a cured product obtained from the curable composition.

  A polyurethane resin using a polyisocyanate composed of an aliphatic diisocyanate or an alicyclic diisocyanate as a curing agent is excellent in terms of chemical resistance, flexibility, weather resistance, and the like. When this polyisocyanate is used as a curing agent for polyurethane coatings, a wide variety of substrates are applied. When polyisocyanate is applied to a deformable substrate such as thin plate, plastic film, cloth, leather, rubber, or intentionally after applying polyisocyanate to a hard substrate such as an aluminum plate, iron plate, copper plate, or stainless steel plate In order to follow this deformation, the coating film needs to be extensible. As a method for imparting this extensibility, there is a method in which a polyol is used as an auxiliary material and polyisocyanate is modified in advance.

  For example, in Patent Document 1, an isocyanate composition using a polyester polyol is used as Patent Document 1, an isocyanate composition using a polyether polyol is used in Patent Document 2, and a homopolymerized polycarbonate diol such as polyhexamethylene carbonate diol is used in Patent Document 3. Coating compositions have been proposed.

  On the other hand, these polyurethane resins include a room temperature curable two-component type or a thermosetting one-component type depending on use conditions. In the one-pack type, a blocked polyisocyanate in which the isocyanate group of the polyisocyanate is protected with a heat dissociable blocking agent is used. Even if it mixes with active hydrogen compounds, such as a polyol and polyamine which are main ingredients, block polyisocyanate does not react at normal temperature. By heating the mixture of the block polyisocyanate and the active hydrogen compound, the thermally dissociable blocking agent is dissociated to regenerate the isocyanate group, and the reaction between the block polyisocyanate and the active hydrogen compound proceeds. For this reason, it becomes possible to store in the state which mixed the main ingredient and the hardening | curing agent (block polyisocyanate) previously. As an example of the block polyisocyanate, a block polyisocyanate composition using a specific thermally dissociable blocking agent as described in Patent Document 4 has been proposed.

Japanese Patent Laid-Open No. 10-7757 JP-A-10-168155 JP2012-107101A European Patent Application No. 0159117

  However, the isocyanate composition described in Patent Document 1 may not have sufficient water resistance. Moreover, the isocyanate composition described in Patent Document 2 may not have sufficient heat resistance. Furthermore, the coating composition described in Patent Document 3 has a problem that moisture stability and adhesion are not sufficient.

  The same problem occurs when the isocyanate composition described in Patent Documents 1 to 3 is changed to block polyisocyanate by a heat dissociable blocking agent and used as a curing agent for the coating composition.

  Since the block polyisocyanate composition described in Patent Document 4 has low extensibility, it is liable to be cracked or cracked during deformation, and the adhesion is insufficient.

  One embodiment of the present invention has been made in view of the above problems, and in addition to extensibility, water resistance, and heat resistance, a polyisocyanate composition excellent in moisture stability, a method for producing the same, and the polyisocyanate composition It aims at providing the resin composition obtained from this, and the resin obtained from this polyisocyanate composition. One embodiment of the present invention also provides a block polyisocyanate composition excellent in adhesion in addition to extensibility, water resistance, and heat resistance, a method for producing the same, and a curable composition containing the block polyisocyanate composition. The purpose is to do.

As a result of diligent studies to solve the above problems, the present inventors have found that a PCD-containing polyisocyanate formed from a raw material containing a specific polyisocyanate precursor and a specific polycarbonate diol, and a polyuret having a biuret group. The present inventors have found that a polyisocyanate composition containing an isocyanate and a block polyisocyanate composition formed from a raw material containing the polyisocyanate composition and a heat dissociable blocking agent can solve the above-mentioned problems, and have completed the present invention. It was.
That is, the present invention is as follows.

[1]
A polyisocyanate composition comprising a PCD-containing polyisocyanate formed from a raw material containing the following polyisocyanate precursor and the following polycarbonate diol; and a polyisocyanate having a biuret group;
Polyisocyanate precursor: a polyisocyanate precursor selected from polyisocyanates consisting of dimers or more of at least one diisocyanate selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates,
Polycarbonate diol: A polycarbonate diol obtained by copolymerizing at least one diol selected from the group consisting of diols having 2 to 20 carbon atoms and a carbonate compound.

[2]
The polyisocyanate composition according to [1], wherein the polycarbonate diol is a polycarbonate diol obtained by copolymerizing at least two diols selected from the group consisting of diols having 2 to 20 carbon atoms and a carbonate compound.

[3]
The polyisocyanate composition according to [1] or [2], wherein the polyisocyanate composition further includes a polyisocyanate having a uretdione group.

[4]
The polyisocyanate composition according to [3], wherein a molar ratio of biuret groups to uretdione groups (biuret groups: uretodione groups) in the polyisocyanate composition is 100: 0 to 60:40.

[5]
The polyisocyanate composition according to any one of [1] to [4], wherein the polyisocyanate precursor forming the PCD-containing polyisocyanate includes a polyisocyanate precursor having a biuret group.

[6]
The polyisocyanate composition according to any one of [3] to [5], wherein the polyisocyanate precursor forming the PCD-containing polyisocyanate includes a polyisocyanate precursor having a uretdione group.

[7]
The polyisocyanate composition according to [6], wherein the polyisocyanate precursor forming the PCD-containing polyisocyanate includes a polyisocyanate precursor having a biuret group and a polyisocyanate precursor having a uretdione group.

[8]
The polyisocyanate composition according to [7], wherein a molar ratio (biuret group: uretodione group) of biuret groups and uretdione groups in the polyisocyanate precursor forming the PCD-containing polyisocyanate is 100: 0 to 60:40. object.

[9]
Any one of [1] to [8], wherein the polycarbonate diol is a polycarbonate diol obtained by copolymerizing at least one diol selected from the group consisting of diols having 3 to 6 carbon atoms and a carbonate compound. Polyisocyanate composition.

[10]
Any one of [1] to [9], wherein the polycarbonate diol is a polycarbonate diol obtained by copolymerizing at least two diols selected from the group consisting of diols having 3 to 6 carbon atoms and a carbonate compound. Polyisocyanate composition.

[11]
The polyisocyanate composition according to [10], wherein the polycarbonate diol is a polycarbonate diol obtained by copolymerizing a diol having 5 carbon atoms, a diol having 6 carbon atoms, and a carbonate compound.

[12]
The polyisocyanate composition according to [10], wherein the polycarbonate diol is a polycarbonate diol obtained by copolymerizing two or more isomers of a diol having 4 carbon atoms and a carbonate compound.

[13]
The polyisocyanate composition according to [10], wherein the polycarbonate diol is a polycarbonate diol obtained by copolymerizing a diol having 4 carbon atoms, a diol having 6 carbon atoms, and a carbonate compound.

[14]
The block polyisocyanate composition containing the block polyisocyanate formed from the raw material containing the polyisocyanate composition in any one of [1]-[13], and a heat dissociable blocking agent.

[15]
The block polyisocyanate according to [14], wherein the thermally dissociable blocking agent is at least one selected from the group consisting of oxime compounds, acid amide compounds, amine compounds, active methylene compounds, and pyrazole compounds. Composition.

[16]
A process for producing a polyisocyanate composition, comprising a step of obtaining a PCD-containing polyisocyanate from a raw material containing the following polyisocyanate precursor and the following polycarbonate diol;
Polyisocyanate precursor: a polyisocyanate precursor comprising a dimer or more of at least one diisocyanate selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates, selected from polyisocyanates having a biuret group,
Polycarbonate diol: A polycarbonate diol obtained by copolymerizing at least one diol selected from the group consisting of diols having 2 to 20 carbon atoms and a carbonate compound.

[17]
The method for producing a polyisocyanate composition according to [16], further comprising a step of obtaining the polyisocyanate precursor by performing a biuretization reaction and a uretdioneation reaction.

[18]
A step of obtaining a PCD-containing block polyisocyanate from a raw material containing the following polyisocyanate precursor, the following polycarbonate diol and a heat dissociable blocking agent, and a raw material containing a polyisocyanate precursor having a biuret group and a heat dissociable blocking agent A process for producing a block polyisocyanate composition comprising a step of obtaining a biuret group-containing block polyisocyanate from
Polyisocyanate precursor: a polyisocyanate precursor selected from polyisocyanates consisting of dimers or more of at least one diisocyanate selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates,
Polycarbonate diol: A polycarbonate diol obtained by copolymerizing at least one diol selected from the group consisting of diols having 2 to 20 carbon atoms and a carbonate compound.

[19]
After reacting a polyisocyanate precursor having a biuret group and a polycarbonate diol at a ratio of isocyanate group / hydroxyl group (NCO / OH) = 2.5 to 40.0, the reaction product obtained (unreacted) The polyisocyanate precursor having a biuret group) is reacted with a heat dissociable blocking agent to simultaneously obtain the PCD-containing block polyisocyanate and the biuret group-containing block polyisocyanate. [18] Manufacturing method.

[20]
[18] or [19], comprising a step of obtaining a polyisocyanate precursor by subjecting at least one diisocyanate selected from the group consisting of an aliphatic diisocyanate and an alicyclic diisocyanate to a biuretization reaction and a uretdiionization reaction. The manufacturing method of block polyisocyanate composition of description.

[21]
The resin composition containing the polyisocyanate composition in any one of [1]-[13].

[22]
A resin obtained from the polyisocyanate composition according to any one of [1] to [13].

[23]
A curable composition containing an active hydrogen compound and the block polyisocyanate composition according to [14].

[24]
Hardened | cured material obtained by heat-hardening the curable composition as described in [23].

  According to the present invention, in addition to extensibility, water resistance and heat resistance, a polyisocyanate composition excellent in moisture stability and a production method thereof, a resin composition containing the polyisocyanate composition, and a polyisocyanate composition The resulting resin can be provided. The present invention also provides a block polyisocyanate composition excellent in adhesion in addition to extensibility, water resistance and heat resistance, a method for producing the same, a curable composition containing the block polyisocyanate composition, and the curable composition. A cured product obtained from the product 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.

[Polyisocyanate composition]
The polyisocyanate composition according to this embodiment has a polyisocyanate formed from a raw material containing the following polyisocyanate precursor and the following polycarbonate diol (hereinafter also referred to as “PCD-containing polyisocyanate”), and a biuret group. Polyisocyanate (hereinafter also referred to as “biuret group-containing polyisocyanate”).
Polyisocyanate precursor: A polyisocyanate precursor selected from polyisocyanates composed of dimers or more of at least one diisocyanate selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates.
Polycarbonate diol: A polycarbonate diol obtained by copolymerizing at least one diol selected from the group consisting of diols having 2 to 20 carbon atoms and a carbonate compound.

  In the polyisocyanate composition according to this embodiment, the PCD-containing polyisocyanate and the biuret group-containing polyisocyanate may be the same. In the present specification, when simply described as “polyisocyanate composition”, it differs from the composition corresponding to “block polyisocyanate composition” and does not include a thermally dissociable blocking agent described later.

  The polycarbonate diol is preferably a polycarbonate diol obtained by copolymerizing at least two diols selected from the group consisting of diols having 2 to 20 carbon atoms and a carbonate compound. When such a polycarbonate diol is used, the polyisocyanate composition tends to have good extensibility.

  The polyisocyanate composition according to this embodiment preferably contains a polyisocyanate having a biuret group represented by the following formula (1). Further, the polyisocyanate having a biuret group may be the same as or different from the PCD-containing polyisocyanate in the present embodiment.

  The polyisocyanate composition according to this embodiment is selected from the group consisting of isocyanurate groups, uretdione groups, allophanate groups, oxadiazinetrione groups, iminooxadiazinedione groups, and the like in addition to polyisocyanates having biuret groups. A polyisocyanate having at least one linking group can be contained at the same time. A plurality of these linking groups may be present in one compound, or may be separately present in two or more compounds. When a plurality of compounds are present in one compound, they may be the same as or different from each other. In the polyisocyanate composition according to this embodiment, the compound containing these bonding groups may be the same as the PCD-containing polyisocyanate and / or the biuret group-containing polyisocyanate.

  In the polyisocyanate composition according to the present embodiment, the molar fraction of biuret groups is the biuret group, isocyanurate group, uretdione group, allophanate group, oxadiazinetrione group and iminooxadiazinedione group in the composition. It is preferable that it is 40-100 mol% with respect to a total of 100 mol%, It is more preferable that it is 50-100 mol%, It is further more preferable that it is 60-100 mol%.

  The polyisocyanate composition according to the present embodiment preferably contains a uretdione group-containing polyisocyanate that is a polyisocyanate having a uretdione group. When such a uretdione group-containing polyisocyanate is included, the polyisocyanate composition tends to achieve both low viscosity and extensibility.

  The polyisocyanate composition according to this embodiment preferably contains a polyisocyanate having a uretdione group represented by the following formula (2) from the viewpoint of obtaining a low-viscosity composition.

  Furthermore, in terms of heat resistance and adhesion, in the polyisocyanate composition of the present embodiment, the molar ratio of biuret group to uretdione group (biuret group: uretodione group) is preferably 100: 0 to 60:40. More preferably, it is 100: 0 to 70:30, More preferably, it is 100: 0 to 80:20. The molar ratio between the biuret group and the uretdione group can be determined by the method described in the examples below. When the molar ratio between the biuret group and the uretdione group is within the above range, the adhesiveness of the polyisocyanate composition tends to be more excellent.

  In addition to the biuret group and the uretdione group, the polyisocyanate composition of the present embodiment is at least one selected from the group consisting of the isocyanurate group, allophanate group, oxadiazinetrione group, and iminooxadiazinedione group. A linking group may be included. The content of the linking group is preferably 60 mol% or less with respect to 100 mol% in total of biuret group, uretdione group, isocyanurate group, allophanate group, oxadiazinetrione group and iminooxadiazinedione group, The mol% or less is more preferable, and 40 mol% or less is more preferable. The content of the binding group of the biuret group, uretdione group, isocyanurate group, allophanate group, oxadiazinetrione group and iminooxadiazinedione group can be determined by 13C-NMR or 1H-NMR, and will be described in detail later. It can obtain | require by the method as described in an Example.

[PCD-containing polyisocyanate]
The PCD-containing polyisocyanate used in the present embodiment is a diisocyanate or higher polyisocyanate precursor composed of at least one diisocyanate selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates; and a diol having 2 to 20 carbon atoms. A polycarbonate diol obtained by copolymerizing at least one diol selected from the group consisting of and a carbonate compound.

[Polyisocyanate precursor]
The polyisocyanate precursor that forms the PCD-containing polyisocyanate will be described. The polyisocyanate precursor is a multimer composed of a dimer or more of at least one diisocyanate selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates.

(Aliphatic diisocyanate)
In the present embodiment, the “aliphatic diisocyanate” refers to a compound having a chain aliphatic hydrocarbon and no aromatic hydrocarbon when an isocyanate group is excluded from the molecule. The aliphatic diisocyanate is not particularly limited, and examples thereof include butane diisocyanate, pentane diisocyanate, hexamethylene diisocyanate (hereinafter also referred to as “HDI”), trimethylhexamethylene diisocyanate, and lysine diisocyanate. Use of such an aliphatic diisocyanate is more preferable because the resulting polyisocyanate precursor has a low viscosity.

(Alicyclic diisocyanate)
In the present embodiment, “alicyclic diisocyanate” refers to a compound having a cyclic aliphatic hydrocarbon having no aromaticity in the molecule. Although it does not specifically limit as said alicyclic diisocyanate, For example, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, 1, 4- cyclohexane diisocyanate etc. are mentioned.

  Among the aliphatic diisocyanates and alicyclic diisocyanates, HDI, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate are preferable because they are easily available industrially, and HDI is more preferable. By using HDI, the weather resistance and flexibility of the coating film obtained from the polyisocyanate composition tend to be more excellent.

  Aliphatic diisocyanate and alicyclic diisocyanate may be used alone or in combination of two or more.

  The polyisocyanate precursor may have a specific bonding group, and is not particularly limited. For example, a biuret group, an isocyanurate group, a uretdione group, an allophanate group, an oxadiazinetrione group, and an iminooxadiazinedione group. And a polyisocyanate precursor having at least one group selected from the group consisting of:

  Among them, the polyisocyanate precursor that forms the PCD-containing polyisocyanate preferably includes a polyisocyanate precursor having a biuret group from the viewpoint of heat resistance and adhesion. Moreover, it is preferable that the polyisocyanate precursor which forms PCD containing polyisocyanate contains the polyisocyanate precursor which has a uretdione group from a viewpoint of viscosity reduction. Furthermore, it is more preferable that the polyisocyanate precursor forming the PCD-containing polyisocyanate contains a polyisocyanate precursor having a biuret group and a polyisocyanate precursor having a uretdione group from the viewpoint of lowering the viscosity. The polyisocyanate precursor having a biuret group and the polyisocyanate precursor having a uretdione group may be the same. That is, it may be a polyisocyanate precursor having a biuret group and a uretdione group at the same time.

  The molar ratio (biuret group: uretodione group) of biuret groups and uretdione groups in the polyisocyanate precursor forming the PCD-containing polyisocyanate is preferably 100: 0 to 60:40, more preferably 100: 0. 70:30, more preferably 100: 0 to 80:20. The molar ratio between the biuret group and the uretdione group can be determined by the method described in the examples below. When the molar ratio between the biuret group and the uretdione group in the polyisocyanate precursor forming the PCD-containing polyisocyanate is within the above range, the heat resistance and adhesion of the polyisocyanate composition tend to be more excellent.

[Method for producing polyisocyanate precursor]
Although it does not specifically limit as a method to manufacture the said polyisocyanate precursor, For example, the following method is mentioned.

  (I) A biuretization reaction of at least one diisocyanate selected from the group consisting of an aliphatic diisocyanate and an alicyclic diisocyanate is performed, or after or simultaneously with the biuretization reaction, a uretdioneation reaction, an isocyanurate reaction, or an allophanate formation A method of obtaining a polyisocyanate precursor by performing a reaction or the like.

  (Ii) A biuretization reaction of at least one diisocyanate selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates, and the resulting polyisocyanate multimer having a biuret group and a dimer or more consisting of diisocyanate. A method of obtaining a polyisocyanate precursor by mixing a polyisocyanate multimer.

(Iii) A method for obtaining a polyisocyanate precursor by carrying out an isocyanuration reaction, uretdioneation reaction, allophanation reaction or the like of at least one diisocyanate selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates.
Among these, the method (i) is more preferable from the viewpoint of the simplicity of the production process.

(Biuretization reaction and uretdioneization reaction)
The polyisocyanate precursor having a biuret group can be obtained by a biuretization reaction in which at least one diisocyanate selected from the group consisting of an aliphatic diisocyanate and an alicyclic diisocyanate is reacted with a biuretizing agent. Although it does not specifically limit as a biuret agent, For example, water, monovalent | monohydric tertiary alcohol, formic acid, hydrogen sulfide, an organic primary monoamine, an organic primary diamine etc. can be mentioned, Preferably it is water.

  The raw material ratio in the biuretization reaction is preferably 0.1 mol or more and 150 mol or less, more preferably 0.2 mol or more and 60 mol or less, and still more preferably 0 with respect to 1 mol of the biuret agent. .3 mol or more and 20 mol or less. By making the raw material ratio in the biuretization reaction within this range, it is possible to achieve both high production efficiency and adhesion of the resulting polyisocyanate precursor.

  A solvent can be used in the biuretization reaction. The solvent dissolves the diisocyanate and a biuretizing agent such as water and forms a homogeneous phase under the reaction conditions. That is, it is preferable to add an amount of a solvent necessary for forming a homogeneous phase. Thereby, production of by-products such as polyurea can be suppressed. A solvent having a low solubility of the biuretizing agent such as water is not preferable because the amount of addition increases accordingly, and the solvent is separated and recovered after completion of the reaction. This solvent preferably has a solubility of a biuretizing agent such as water of 0.5% by weight or more. In addition, the boiling point of the solvent is preferably lower than the boiling point of the raw diisocyanate monomer in consideration of recovery and separation of unreacted diisocyanate and the like. A solvent represented by the following formula (3) is preferable because it does not react with an isocyanate group and is hydrophilic.

(In the formula (3), R ₁ and R ₂ are alkyl groups or acyl groups having 1 to 4 carbon atoms, which may be the same or different, R ₃ is a methyl group or hydrogen, and n is 1 It is an integer of ~ 2.)

  Specific examples of the solvent are not particularly limited, and examples thereof include ethylene glycol-based ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, and ethylene glycol monoisopropyl ether acetate. , Ethylene glycol mono-n-butyl ether acetate, ethylene glycol diacetate, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol di-n-propyl ether, ethylene glycol diisopropyl ether, ethylene glycol di-n-butyl ether, ethylene glycol Methyl ethyl ether, ethylene glycol methyl isopropyl ether, ethylene glycol Coalmethyl-n-butyl ether, ethylene glycol ethyl-n-propyl ether, ethylene glycol ethyl isopropyl ether, ethylene glycol ethyl n-butyl ether, ethylene glycol-n-propyl-n-butyl ether, ethylene glycol isopropyl-n-butyl ether, diethylene glycol Monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-propyl ether acetate, diethylene glycol monoisopropyl ether acetate, diethylene glycol mono-n-butyl ether acetate, diethylene glycol diacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, die Lenglycol di-n-propyl ether, diethylene glycol diisopropyl ether, diethylene glycol di-n-butyl ether, diethylene glycol methyl ethyl ether, diethylene glycol methyl isopropyl ether, diethylene glycol methyl n-propyl ether, diethylene glycol methyl n-butyl ether, diethylene glycol ethyl isopropyl ether, Examples include diethylene glycol ethyl-n-propyl ether, diethylene glycol ethyl-n-butyl ether, diethylene glycol-n-propyl-n-butyl ether, and diethylene glycol isopropyl-n-butyl ether.

  In addition, for example, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol monoisopropyl ether acetate, propylene glycol mono-n-butyl ether acetate, Propylene glycol diacetate, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol di-n-propyl ether, propylene glycol diisopropyl ether, propylene glycol di-n-butyl ether, propylene glycol methyl ethyl ether, propylene glycol methyl isopropyl ether, Propylene glycol Methyl-n-butyl ether, propylene glycol ethyl-n-propyl ether, propylene glycol ethyl isopropyl ether, propylene glycol ethyl n-butyl ether, propylene glycol-n-propyl-n-butyl ether, propylene glycol isopropyl-n-butyl ether, dipropylene Glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol mono-n-propyl ether acetate, dipropylene glycol monoisopropyl ether acetate, dipropylene glycol mono-n-butyl ether acetate, dipropylene glycol diacetate, dipropylene Glycol dimethyl ether, dipropylene glycol di Chill ether, dipropylene glycol di-n-propyl ether, dipropylene glycol diisopropyl ether, dipropylene glycol di-n-butyl ether, dipropylene glycol methyl ethyl ether, dipropylene glycol methyl isopropyl ether, dipropylene glycol methyl-n-propyl ether , Dipropylene glycol methyl-n-butyl ether, dipropylene glycol ethyl isopropyl ether, dipropylene glycol ethyl-n-propyl ether, dipropylene glycol ethyl-n-butyl ether, dipropylene glycol-n-propyl-n-butyl ether, dipropylene And glycol isopropyl-n-butyl ether.

  Preferred ethylene glycol solvents include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol diacetate, diethylene glycol dimethyl ether, etc. Preferred propylene glycol solvents include propylene glycol monomethyl ether acetate, propylene glycol monoester. Examples include ethyl ether acetate, propylene glycol diacetate, and dipropylene glycol dimethyl ether.

  Alkyl phosphate solvents are preferred because they do not react with isocyanate groups and have hydrophilicity. The alkyl phosphate solvent is not particularly limited, and examples thereof include trimethyl phosphate, triethyl phosphate, tripropyl phosphate, and tributyl phosphate, and trimethyl phosphate and triethyl phosphate are preferable.

  These may be used alone or in admixture of two or more. A preferable mixing weight ratio of the solvent is 3/7 to 9/1 in the ethylene glycol solvent / phosphoric acid solvent.

  In some cases, an OH acidic compound such as di (2-ethylhexyl) phosphate exemplified in JP-A-8-225511 can be added.

  The biuretization reaction temperature is preferably 70 ° C. or higher and 200 ° C. or lower, and more preferably 90 ° C. or higher and 180 ° C. or lower.

  After completion of the reaction, unreacted diisocyanate and solvent may be separated from the polyisocyanate precursor. From the viewpoint of safety, it is preferable to separate the unreacted diisocyanate. Although it does not specifically limit as a method of isolate | separating an unreacted diisocyanate and a solvent, For example, a thin film distillation method and a solvent extraction method are mentioned.

  The polyisocyanate precursor having an uretdione group can be obtained by using a uretdione reaction catalyst. Although it does not specifically limit as a uretdione-ized reaction catalyst, Specifically, Tris phosphines, such as trialkyl phosphine, such as tri-n-butylphosphine and tri-n-octylphosphine, and tris- (dimethylamino) -phosphine ( And tertiary phosphine such as cycloalkylphosphine such as dialkylamino) phosphine and cyclohexyl-di-n-hexylphosphine. These compounds can also serve as allophanatization reaction catalysts. In addition, many of these compounds simultaneously promote an isocyanuration reaction, and in addition to a uretdione group-containing polyisocyanate such as a uretdione dimer, an isocyanurate group-containing polyisocyanate such as an isocyanurate trimer is produced. The polyisocyanate precursor having a uretdione group can also be obtained by heating without using a uretdione reaction catalyst. The uretdione group-containing polyisocyanate such as a uretdione dimer used in the present embodiment is preferably produced by heating from the viewpoint of storage stability.

[Polycarbonate diol]
The polycarbonate diol used in the present embodiment includes at least one diol selected from the group consisting of diols having 2 to 20 carbon atoms (hereinafter also simply referred to as “at least one diol”) and a carbonate compound. It is a polymerized one. Hereinafter, polycarbonate diol will be described.

  300-4000 are preferable, as for the number average molecular weight of the polycarbonate diol used by this embodiment, 400-2500 are more preferable, and 500-2000 are more preferable. When the number average molecular weight of the polycarbonate diol is within the above range, the extensibility of the polyisocyanate composition tends to be more excellent. The number average molecular weight can be calculated from a hydroxyl value determined by a titration method.

[Production method of polycarbonate diol]
Although it does not specifically limit as a manufacturing method of polycarbonate diol, For example, it can obtain by carrying out dealcoholization reaction, dephenol reaction, etc. with at least 1 sort (s) of diol, and a carbonate compound. Alternatively, a high molecular weight polycarbonate polyol can be obtained by transesterification using at least one diol.

  In addition, there is no limitation in particular in the method of performing a polymerization reaction with diol and a carbonate compound, for example, a well-known method, for example, H.H. Various methods described in pages 9 to 20 of “Polymer Reviews Volume 9” by Schnell (published by Interscience Publishers, USA in 1964) can be used.

  Although it does not specifically limit as said at least 1 sort (s) of diol, For example, the diol chosen from the group which consists of aliphatic diol and aromatic diol is mentioned. Among these, alkylene glycol having 2 to 20 carbon atoms and having 2 hydroxyl groups is preferable. By using such a diol, the coating film obtained using the polyisocyanate composition tends to have better weather resistance and chemical resistance. Here, the “alkylene group” may have a branch and may contain an alicyclic structure. These bifunctional alcohols may be used alone or in combination of two or more. However, when two or more types are used in combination, the resulting polycarbonate diol has a lower viscosity, which is more preferable.

  Examples of the diol include, but are not limited to, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 2-ethyl-1,6-hexanediol, 2-methyl- 1,3-propanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 2,2′-bis (4-hydroxycyclohexyl) -propane, p-xylylenediol, p-tetrachloroxylylenediol, 1,4-dimethylolcyclo Xanthine, bishydroxymethyltetrahydrofuran, di (2-hydroxyethyl) dimethylhydantoin, diethylene glycol, dipropylene glycol, polypropylene glycol, polytetramethylene glycol, 2,6′-dihydroxyethylhexyl ether, 2,4′-dihydroxyethyl butyl ether, 2 , 5'-dihydroxyethylpentyl ether, 2,3'-dihydroxy-2 ', 2'-dimethylethylpropyl ether, thioglycol and the like.

  Among these, a C2-C11 diol is preferable and a C3-C6 diol is more preferable. The diol may be one kind or two or more kinds. However, it is preferable to include at least two kinds of diols because crystallization of the produced polyisocyanate composition is suppressed and the viscosity is lowered. The number of carbon atoms of the diol is preferably 3 to 6, but the combination of at least two types is a combination of a diol having 5 carbon atoms and a diol having 6 carbon atoms, or a combination of two or more isomers of a diol having 4 carbon atoms. Or a combination of a diol having 4 carbon atoms and a diol having 6 carbon atoms is more preferable. By using such two kinds of diols, the stretchability, heat resistance and water resistance of the coating film obtained using the polyisocyanate composition tend to be more excellent. Such a diol is not particularly limited, and specifically, from 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 2-methyl-1,3-propanediol. A combination of one or two or more selected from the group consisting of 1,6-hexanediol and 1,5-pentanediol, a combination of 1,6-hexanediol and 1,4-butanediol, A combination of 1,4-butanediol and 2-methyl-1,3-propanediol is more preferred.

  Although it does not specifically limit as a carbonate compound used for manufacture of polycarbonate diol, For example, the compound chosen from alkylene carbonate, a dialkyl carbonate, a diaryl carbonate, and phosgene is mentioned. Such a carbonate compound is not particularly limited, and specific examples include ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, diphenyl carbonate, and the like. Among these, ethylene carbonate and diethyl carbonate are preferable in terms of ease of production. A carbonate compound may be used individually by 1 type, and may use 2 or more types together.

[Biuret group-containing polyisocyanate]
The biuret group-containing polyisocyanate used in the present embodiment is preferably obtained from at least one diisocyanate selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates. As aliphatic diisocyanate and alicyclic diisocyanate, the same diisocyanate as the polyisocyanate precursor forming the PCD-containing polyisocyanate can be used.

  As the polyisocyanate having a biuret group, the above-described polyisocyanate precursor having a biuret group, which can be included in the polyisocyanate precursor forming the PCD-containing polyisocyanate, can be used. The polyisocyanate composition of this embodiment preferably contains a polyisocyanate having a biuret group represented by the above formula (1).

The biuret group-containing polyisocyanate and the polyisocyanate precursor forming the PCD-containing polyisocyanate may be the same or different, but are preferably the same from the viewpoint of the simplicity of the production process.
In the polyisocyanate composition according to this embodiment, the PCD-containing polyisocyanate and the biuret group-containing polyisocyanate may be the same.

  Furthermore, in the polyisocyanate composition according to the present embodiment, the mass ratio of the polycarbonate diol is preferably 3.0 to 80.0% by mass, and 5.0 to 70.0% by mass with respect to the entire composition. Is more preferable, and it is still more preferable that it is 7.0-60.0 mass%.

[Block polyisocyanate composition]
The block polyisocyanate composition according to the present embodiment includes a block polyisocyanate formed from a raw material containing the polyisocyanate composition and a heat dissociable blocking agent.

  The block polyisocyanate composition according to this embodiment is also referred to as a block polyisocyanate (hereinafter referred to as “PCD-containing block polyisocyanate”) formed from a raw material containing the PCD-containing polyisocyanate and the heat dissociable blocking agent. ) And a block polyisocyanate formed from a raw material containing a polyisocyanate having a biuret group and a thermally dissociable blocking agent (hereinafter also referred to as “biuret group-containing block polyisocyanate”).

  The PCD-containing block polyisocyanate and the biuret group-containing block polyisocyanate used in this embodiment are produced by reacting the isocyanate groups of the PCD-containing polyisocyanate and the biuret group-containing polyisocyanate with a heat dissociable blocking agent to form a block. can do. Here, “thermal dissociation” means that the blocking agent bonded to the isocyanate group is dissociated by heating. The temperature required for dissociation varies depending on the structure of the blocking agent, but is, for example, 40 ° C to 300 ° C.

[Thermal dissociable blocking agent]
Examples of the heat dissociable blocking agent are not particularly limited. For example, oxime compounds, alcohol compounds, acid amide compounds, acid imide compounds, phenol compounds, amine compounds, active methylene compounds, imidazole compounds Compounds, pyrazole compounds and the like.

  Although it does not specifically limit as an oxime type compound, For example, formal oxime, aceto ald oxime, aceto oxime, methyl ethyl ketoxime, cyclohexanone oxime etc. are mentioned. Examples of alcohol compounds include methanol, ethanol, 2-propanol, n-butanol, sec-butanol, 2-ethyl-1-hexanol, 2-methoxyethanol, 2-ethoxyethanol, and 2-butoxyethanol. The acid amide compound is not particularly limited, and examples thereof include acetanilide, acetic acid amide, ε-caprolactam, δ-valerolactam, and γ-butyrolactam. Although it does not specifically limit as an acid imide type compound, For example, a succinic acid imide, a maleic acid imide, etc. are mentioned. Although it does not specifically limit as a phenol type compound, For example, phenol, cresol, ethylphenol, butylphenol, nonylphenol, dinonylphenol, styrenated phenol, hydroxybenzoic acid ester etc. are mentioned. The amine compound is not particularly limited, and examples thereof include diphenylamine, aniline, carbazole, di-n-propylamine, diisopropylamine, and isopropylethylamine. The active methylene compound is not particularly limited, and examples thereof include dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone. The imidazole compound is not particularly limited, and examples thereof include imidazole and 2-methylimidazole. Although it does not specifically limit as a pyrazole type compound, For example, a pyrazole, 3-methyl pyrazole, 3, 5- dimethyl pyrazole, etc. are mentioned.

Among these, from the viewpoint of availability, viscosity of the produced block polyisocyanate composition, reaction temperature, reaction time, oxime compounds, acid amide compounds, amine compounds, active methylene compounds, and pyrazole compounds are preferable. Methyl ethyl ketoxime, ε-caprolactam, diethyl malonate, ethyl acetoacetate, diisopropylamine, and 3,5-dimethylpyrazole are more preferable, and methylethyl ketoxime and 3,5-dimethylpyrazole are more preferable. In particular, 3,5-dimethylpyrazole is extremely preferable because both low-temperature curability and compatibility with the active hydrogen compound as the main component are compatible.
One kind of the heat dissociable blocking agent may be used, or two or more kinds may be used in a desired ratio.

[Method for producing polyisocyanate composition]
The manufacturing method of the polyisocyanate composition which concerns on this embodiment is demonstrated.
The production method of the polyisocyanate composition according to this embodiment is as follows:
A step of obtaining a PCD-containing polyisocyanate from a raw material containing the following polyisocyanate precursor and the following polycarbonate diol;
Polyisocyanate precursor: a polyisocyanate precursor selected from polyisocyanates consisting of dimers or more of at least one diisocyanate selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates,
Polycarbonate diol: A polycarbonate diol obtained by copolymerizing at least one diol selected from the group consisting of diols having 2 to 20 carbon atoms and a carbonate compound.

Moreover, it is preferable that the manufacturing method of the polyisocyanate composition of this embodiment has the process of performing a biuretization reaction and obtaining a polyisocyanate precursor,
Furthermore, it is more preferable to have a step of obtaining a polyisocyanate precursor by performing a biuretization reaction and a uretdioneization reaction.

  Although it does not specifically limit as a method to manufacture the polyisocyanate composition of this embodiment, For example, the following five methods are mentioned.

1. A method of reacting an excess of a polyisocyanate precursor having a biuret group with a polycarbonate diol.

2. A method of mixing a polyisocyanate precursor having a biuret group with a polycarbonate diol, and then mixing the reaction product with another polyisocyanate having a bonding group other than the biuret group.

3. A method in which a polyisocyanate having a biuret group and another polyisocyanate having a bonding group other than a biuret group are mixed to form a polyisocyanate precursor, and an excess polyisocyanate precursor is reacted with the polycarbonate diol.

4). A method of reacting a polyisocyanate precursor having a bonding group other than a biuret group with a polycarbonate diol, and then mixing the reaction product with another polyisocyanate having a biuret group.

5). A reaction product (including PCD-containing polyisocyanate and a polyisocyanate precursor having an unreacted biuret group) obtained by reacting an excess of a polyisocyanate precursor having a biuret group with a polycarbonate diol, and other than the biuret group Another reaction product obtained by reacting an excess of a polyisocyanate precursor having a linking group with polycarbonate diol (including a PCD-containing polyisocyanate and a polyisocyanate precursor having a linking group other than an unreacted biuret group) ).

  Among these, the method 1 is particularly preferable from the viewpoint of the simplicity of the production process.

  The reaction ratio between the excess polyisocyanate precursor and the polycarbonate diol is not particularly limited, but in terms of viscosity and extensibility, the excess polyisocyanate precursor isocyanate group / polycarbonate diol hydroxyl group (NCO / OH) = 2. 5-40 are preferable, 2.5-20 are more preferable, and 3-10 are more preferable. When NCO / OH is within the above range, the water stability of the polyisocyanate composition tends to be more excellent.

  The reaction temperature between the polyisocyanate precursor and the polycarbonate diol is preferably -20 to 150 ° C, more preferably 30 to 100 ° C.

  In addition, the method for producing the polyisocyanate composition of the present embodiment includes a polyisocyanate precursor by performing biuretization reaction and uretdiionization reaction on at least one diisocyanate selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates. It is preferable to have the process of obtaining a body.

[Method for producing block polyisocyanate composition]
The manufacturing method of the block polyisocyanate composition which concerns on this embodiment is demonstrated.

The production method of the block polyisocyanate composition according to this embodiment is preferably,
A step of obtaining a PCD-containing block polyisocyanate from a raw material containing the following polyisocyanate precursor, the following polycarbonate diol and a heat dissociable blocking agent, and a raw material containing a polyisocyanate precursor having a biuret group and a heat dissociable blocking agent Obtaining a biuret group-containing blocked polyisocyanate from
Polyisocyanate precursor: a polyisocyanate precursor selected from polyisocyanates consisting of dimers or more of at least one diisocyanate selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates,
Polycarbonate diol: A polycarbonate diol obtained by copolymerizing at least one diol selected from the group consisting of diols having 2 to 20 carbon atoms and a carbonate compound.

  In the manufacturing method of the block polyisocyanate composition which concerns on this embodiment, you may perform simultaneously the process of obtaining PCD containing block polyisocyanate, and the process of obtaining biuret group containing block polyisocyanate.

  In the manufacturing method of the block polyisocyanate composition according to the present embodiment, specific examples of the method for simultaneously obtaining the PCD-containing block polyisocyanate and the biuret group-containing block polyisocyanate are not particularly limited. For example, the following five types may be mentioned: It is done.

1. After reacting excess polyisocyanate precursor having biuret group with polycarbonate diol, the reaction product (including polyisocyanate precursor having unreacted biuret group) is reacted with thermally dissociable blocking agent. How to make.

2. After reacting a polyisocyanate precursor having a biuret group with a polycarbonate diol, the reaction product and another polyisocyanate having a bonding group other than the biuret group are mixed, and the mixture is reacted with a thermally dissociable blocking agent. How to make.

3. A polyisocyanate having a biuret group and another polyisocyanate having a linking group other than a biuret group are mixed to form a polyisocyanate precursor, and after the excess polyisocyanate precursor and polycarbonate diol are reacted, the reaction product is produced. A method of reacting a product (including a polyisocyanate precursor having an unreacted biuret group) with a thermally dissociable blocking agent.

4). After reacting a polyisocyanate precursor having a bonding group other than a biuret group and a polycarbonate diol, the reaction product and another polyisocyanate having a biuret group are mixed, and the mixture is reacted with a heat dissociable blocking agent. How to make.

5). A reaction product (including PCD-containing polyisocyanate and a polyisocyanate precursor having an unreacted biuret group) obtained by reacting an excess of a polyisocyanate precursor having a biuret group with a polycarbonate diol, and other than the biuret group Another reaction product obtained by reacting an excess of a polyisocyanate precursor having a linking group with polycarbonate diol (including a PCD-containing polyisocyanate and a polyisocyanate precursor having a linking group other than an unreacted biuret group) ) And reacting the mixture with a thermally dissociable blocking agent.
Among these, the method 1 is particularly preferable from the viewpoint of simplicity of the production process.

  In the above methods 1, 3 and 5, the reaction ratio (isocyanate group / hydroxyl group (NCO / OH)) when reacting the polyisocyanate precursor and the polycarbonate diol is preferably 2.5 to 40.0. 0.5 to 20.0 is more preferable, and 3.0 to 10.0 is more preferable. When the reaction ratio (NCO / OH) is within the above range, the resulting block polyisocyanate composition tends to be more excellent in extensibility, water resistance and heat resistance.

  In the production method of the block polyisocyanate composition of this embodiment, a polyisocyanate precursor having a biuret group and a polycarbonate diol are reacted at a ratio of isocyanate group / hydroxyl group (NCO / OH) = 2.5 to 40.0. Then, the obtained reaction product (including a polyisocyanate precursor having an unreacted biuret group) is reacted with a thermally dissociable blocking agent to obtain a PCD-containing block polyisocyanate and a biuret group-containing block polyisocyanate. It is preferable to obtain them simultaneously. Here, the term “simultaneously” is sufficient if both the PCD-containing block polyisocyanate and the biuret group-containing block polyisocyanate are obtained, and do not need to be strictly strictly in time.

  In general, the reaction between the polyisocyanate precursor and the polycarbonate diol is preferably performed at -20 to 150 ° C, and more preferably at 30 to 120 ° C. If the reaction temperature is 150 ° C. or lower, the possibility of causing a side reaction is reduced. On the other hand, if the reaction temperature is −20 ° C. or higher, the reaction rate does not become too low.

  Moreover, although the reaction which blocks using the said heat dissociable blocking agent and obtains a block polyisocyanate composition may be made into all or a partial block, it is preferable that all make it block. When all the isocyanate groups are blocked, (number of moles of thermally dissociable blocking agent) / (number of moles of isocyanate groups contained in the reaction product of polyisocyanate precursor and polycarbonate diol) is 1.0 to 1. 5 is preferable. In that case, excess or unreacted thermally dissociable blocking agent remains in the block polyisocyanate composition. The heat dissociable blocking agent may be added after the reaction between the polyisocyanate precursor and the polycarbonate diol, or may be added during the reaction or simultaneously with the polycarbonate diol.

  The reaction temperature for blocking with the heat dissociable blocking agent is preferably -20 to 150 ° C, more preferably 30 to 120 ° C, in terms of suppression of side reactions and production efficiency. In the reaction for blocking, an organic metal salt such as tin, zinc or lead; a tertiary amine compound; an alcoholate of an alkali metal such as sodium may be used as a catalyst.

  Reaction of the said polyisocyanate precursor, the said polycarbonate diol, and the said heat dissociable block agent may be performed without a solvent, or you may use an organic solvent as needed.

  Such an organic solvent is not particularly limited. Specifically, for example, an aliphatic hydrocarbon solvent such as hexane, heptane, and octane; an alicyclic hydrocarbon solvent such as cyclohexane and methylcyclohexane; acetone, Ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate and isobutyl acetate; aromatic solvents such as toluene, xylene, diethylbenzene, mesitylene, anisole and chlorobenzene; ethylene glycol Glycol solvents such as monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate and propylene glycol monomethyl ether acetate; ether solvents such as diethyl ether, tetrahydrofuran and dioxane; Halogenated hydrocarbon solvents such as chloromethane, 1,2-dichloroethane and chloroform; pyrrolidone solvents such as N-methyl-2-pyrrolidone; amide solvents such as N, N-dimethylacetamide and N, N-dimethylformamide; A sulfoxide solvent such as dimethyl sulfoxide; a lactone solvent such as γ-butyrolactone; an organic solvent not reactive with an isocyanate group such as an amine solvent such as morpholine; and a mixture thereof can be used. . This organic solvent can be removed after the reaction.

  Moreover, the manufacturing method of the block polyisocyanate composition of this embodiment performs polyuretization reaction and uretdioneization reaction with respect to at least 1 sort (s) of diisocyanate chosen from the group which consists of aliphatic diisocyanate and alicyclic diisocyanate. It is preferable to have a step of obtaining a precursor.

[Other additives]
The polyisocyanate composition and the block polyisocyanate composition of this embodiment may contain various organic solvents as additives depending on the purpose and application. The organic solvent to be added is not particularly limited. For example, aliphatic hydrocarbon solvents such as hexane, heptane, and octane; alicyclic hydrocarbon solvents such as cyclohexane and methylcyclohexane; acetone, methyl ethyl ketone, methyl isobutyl ketone, Ketone solvents such as cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, methyl lactate, and ethyl lactate; aromatics such as toluene, xylene, diethylbenzene, mesitylene, anisole, benzyl alcohol, phenyl glycol, chlorobenzene Family solvents: glycosyl such as ethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether Ether solvents such as diethyl ether, tetrahydrofuran and dioxane; halogenated hydrocarbon solvents such as dichloromethane, 1,2-dichloroethane and chloroform; pyrrolidone solvents such as N-methyl-2-pyrrolidone; N, N An amide solvent such as dimethylacetamide and N, N-dimethylformamide; a sulfoxide solvent such as dimethyl sulfoxide; a lactone solvent such as γ-butyrolactone; an amine solvent such as morpholine; and a mixture thereof.

  In the polyisocyanate composition of the present embodiment, another polyisocyanate composed of a diisocyanate of diisocyanate is added to the reaction product of the polyisocyanate precursor and the polycarbonate diol at an arbitrary ratio. May be. The bonding group constituting the other polyisocyanate is not particularly limited as long as the final polyisocyanate composition contains a biuret group. Further, in the block polyisocyanate composition according to the present embodiment, the reaction product of the polyisocyanate precursor, the polycarbonate diol, and the heat dissociable blocking agent is another block composed of a diisocyanate or more of diisocyanate. You may add polyisocyanate in arbitrary ratios. At that time, the bonded thermally dissociable blocking agent may be the same as or different from the reaction product.

  In addition, the polyisocyanate composition and the block polyisocyanate composition of the present embodiment include a curing accelerating catalyst, an antioxidant, an ultraviolet absorber, a light stabilizer, a pigment, a leveling agent, and a plasticizer depending on purposes and applications Various additives such as a rheology control agent and a surfactant can be contained.

Although it does not specifically limit as said hardening acceleration | stimulation catalyst, For example, tin-type compounds, such as dibutyltin dilaurate, dibutyltin diacetate, dioctyltin dilaurate, dimethyltin dineodecanoate, bis (2-ethylhexanoic acid) tin; Zinc compounds such as zinc ethylhexanoate and zinc naphthenate; titanium compounds such as titanium 2-ethylhexanoate and titanium diisopropoxybis (ethylacetonate); cobalt compounds such as cobalt 2-ethylhexanoate and cobalt naphthenate; Bismuth compounds such as bismuth 2-ethylhexanoate and bismuth naphthenate; zirconium compounds such as zirconium tetraacetylacetonate, zirconyl 2-ethylhexanoate and zirconyl naphthenate; amine compounds and the like.
Although it does not specifically limit as said antioxidant, For example, a hindered phenol type compound, a phosphorus compound, a sulfur type compound, etc. are mentioned.
Although it does not specifically limit as said ultraviolet absorber, For example, a benzotriazole type compound, a triazine type compound, a benzophenone type compound etc. are mentioned.

The light stabilizer is not particularly limited, and examples thereof include hindered amine compounds, benzotriazole compounds, triazine compounds, benzophenone compounds, and benzoate compounds.
The pigment is not particularly limited, and examples thereof include titanium oxide, carbon black, indigo, quinacridone, pearl mica, and aluminum.
Although it does not specifically limit as said leveling agent, For example, silicone oil etc. are mentioned.
The plasticizer is not particularly limited, and examples thereof include phthalic acid esters, phosphoric acid compounds, and polyester compounds.
Although it does not specifically limit as said rheology control agent, For example, a hydroxyethyl cellulose, a urea compound, a microgel, etc. are mentioned.
Although it does not specifically limit as said surfactant, For example, a well-known anionic surfactant, a cationic surfactant, an amphoteric surfactant etc. are mentioned.

  Moreover, in the polyisocyanate composition and the block polyisocyanate composition according to this embodiment, the content of the other additives described above is preferably 0 to 80% by mass, and preferably 0 to 70% by mass. Preferably, it is 0 to 60% by mass.

When the polyisocyanate composition and the block polyisocyanate composition according to the present embodiment contain a biuret group and a polycarbonate diol residue in the specific range, the curing includes the block polyisocyanate composition and an active hydrogen compound described later. The cured product obtained by heating the adhesive composition has both extensibility and adhesion, and is excellent in water resistance and heat resistance.
In the present embodiment, the polycarbonate diol residue means a polycarbonate diol bonded to the polyisocyanate precursor.

[Resin composition, resin]
The resin composition according to this embodiment includes the polyisocyanate composition. Although it does not specifically limit as a manufacturing method of the resin composition which concerns on this embodiment, For example, it can obtain by mixing the said polyisocyanate composition and an active hydrogen compound (polyvalent active hydrogen compound).

  The resin according to this embodiment can be obtained from the polyisocyanate composition. Although it does not specifically limit as a manufacturing method of resin which concerns on this embodiment, For example, polyisocyanate is mixed with the said polyisocyanate composition by mixing an active hydrogen compound (polyvalent active hydrogen compound) or contacting water. A method of obtaining a resin by reacting an isocyanate group therein with active hydrogen or water in an active hydrogen compound can be mentioned.

[Curable composition, cured product]
It is preferable that the curable composition of this embodiment contains an active hydrogen compound and the above-mentioned block polyisocyanate composition.
Moreover, it is preferable that the hardened | cured material of this embodiment is obtained by heat-hardening the said curable composition.

  The curable composition of this embodiment is formed by mixing the block polyisocyanate composition described above with an active hydrogen compound (polyvalent active hydrogen compound) as a main agent. In the curable composition of this embodiment, when heated, the thermally dissociable blocking agent bonded to the isocyanate group is dissociated, and the isocyanate group and the active hydrogen in the active hydrogen compound react to form a cured product. be able to.

  Hereinafter, the active hydrogen compound (polyvalent active hydrogen compound) and the like that can be used in the resin composition and resin, the curable composition, and the cured product according to the present embodiment will be described.

  The active hydrogen compound is a compound in which two or more active hydrogens are bonded in the molecule. Although it does not specifically limit as an example of an active hydrogen compound, For example, although a polyol, a polyamine, an alkanolamine, a polythiol etc. are mentioned, a polyol is used in many cases.

  Although it does not specifically limit as said polyamine, For example, diamines, such as ethylenediamine, propylenediamine, butylenediamine, triethylenediamine, hexamethylenediamine, 4,4'-diaminodicyclohexylmethane, piperazine, 2-methylpiperazine, isophoronediamine; Chain polyamines having three or more amino groups such as bishexamethylenetriamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentamethylenehexamine, tetrapropylenepentamine; 1,4,7,10,13,16 -Hexaazacyclooctadecane, 1,4,7,10-tetraazacyclodecane, 1,4,8,12-tetraazacyclopentadecane, 1,4,8,11-tetraazacyclotetradecane, etc. Jo polyamines and the like. The alkanolamine is not particularly limited, and examples thereof include monoethanolamine, diethanolamine, triethanolamine, aminoethylethanolamine, N- (2-hydroxypropyl) ethylenediamine, mono-, di- (n- or iso-). ) Propanolamine, ethylene glycol-bis-propylamine, neopentanolamine, methylethanolamine and the like.

  The polythiol is not particularly limited, and examples thereof include bis- (2-hydrothioethyloxy) methane, dithioethylene glycol, dithioerythritol, and dithiothreitol.

  Although it does not specifically limit as said polyol, For example, polyester polyol, acrylic polyol, polyether polyol, polyolefin polyol, fluorine polyol, polycarbonate polyol, an epoxy resin etc. are mentioned.

  Although it does not specifically limit as said polyester polyol, For example, polyester polyol, polycaprolactone, etc. are mentioned. The polyester polyol is not particularly limited, and can be obtained, for example, by a condensation reaction between a dibasic acid alone or a mixture and a polyhydric alcohol alone or a mixture. The dibasic acid is not particularly limited. For example, a dibasic acid selected from the group consisting of carboxylic acids such as succinic acid, adipic acid, sebacic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, etc. Examples include acids. The polyhydric alcohol is not particularly limited, and specific examples include polyhydric alcohols selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, trimethylolpropane, glycerin and the like. Polycaprolactones are not particularly limited, and can be obtained, for example, by ring-opening polymerization of ε-caprolactone using a polyhydric alcohol.

  The acrylic polyol is not particularly limited. 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. Those obtained by copolymerization alone or with a mixture may be mentioned.

  The ethylenically unsaturated bond-containing monomer having a hydroxyl group is not particularly limited. For example, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, methacrylic acid, Examples include hydroxybutyl acid. Of these, hydroxyethyl acrylate and hydroxyethyl methacrylate are preferred.

  The other ethylenically unsaturated bond-containing monomer copolymerizable with the ethylenically unsaturated bond-containing monomer having a hydroxyl group is not particularly limited, and examples thereof include methyl acrylate, ethyl acrylate, and acrylic acid. Acrylic acid such as propyl, isopropyl acrylate, acrylate-n-butyl, acrylate isobutyl, acrylate-n-hexyl, cyclohexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, benzyl acrylate, and phenyl acrylate Esters; methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, -n-butyl methacrylate, isobutyl methacrylate, methacrylic acid -n-hexyl, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, Methacrylic acid esters such as lauryl crylate, benzyl methacrylate, phenyl methacrylate; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, 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 And vinyl monomers having hydrolyzable silyl groups such as dimethoxysilane and γ- (meth) acryloxypropyltrimethoxysilane.

  Although it does not specifically limit as said polyether polyol, For example, the use of hydroxides, such as lithium, sodium, potassium, or strong basic catalysts, such as alcoholate and alkylamine, is individual or a mixture of a polyhydric hydroxy compound. Polyether polyols obtained by adding a single or mixture of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, styrene oxide, and the like; obtained by reacting alkylene oxide with a polyfunctional compound such as ethylenediamine Examples of polyether polyols include so-called polymer polyols obtained by polymerizing acrylamide or the like using the above polyethers as a medium.

  The polyvalent hydroxy compound is not particularly limited, and examples thereof include diglycerin, ditrimethylolpropane, pentaerythritol, dipentaerythritol and the like; erythritol, D-threitol, L-arabinitol, ribitol, xylitol, sorbitol, mannitol, gatrito Sugar alcohol compounds such as lactitol and rhamnitol; monosaccharides such as arabinose, ribose, xylose, glucose, mannose, galactose, fructose, sorbose, rhamnose, fucose, ribodesource; trehalose, sucrose, maltose, cellobiose, gentiobiose, lactose, melibiose And the like; disaccharides such as raffinose, gentianose, and meletitose; and tetrasaccharides such as stachyose.

  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, and is, for example, a polyol containing fluorine in the molecule. For example, fluoroolefins and cycloolefins disclosed in JP-A-57-34107 and JP-A-61-275111 are disclosed. Examples thereof include copolymers such as vinyl ether, hydroxyalkyl vinyl ether, and monocarboxylic acid vinyl ester.

  Although it does not specifically limit as said polycarbonate polyol, For example, 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 low molecule used for the above-mentioned polyester polyol Examples thereof include those obtained by condensation polymerization of polyols.

  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 -Methyl epichrome type, cyclic oxirane type, halogen type, resorcin type and the like.

  The hydroxyl value of the polyol is preferably 10 to 300 mgKOH / g per resin from the viewpoint of crosslinking density and mechanical properties of the cured product. The hydroxyl value can be determined by a titration method.

  In the curable composition of this embodiment, it is preferable that the molar ratio of the isocyanate group to the active hydrogen group (isocyanate group: active hydrogen group) is usually set to 10: 1 to 1:10.

  The curable composition of this embodiment can contain other hardening | curing agents, such as a melamine type hardening | curing agent and an epoxy-type hardening | curing agent. Although it does not specifically limit as a melamine type hardening | curing agent, For example, a complete alkyl etherified melamine resin, a methylol group type melamine resin, and the imino group type melamine resin which has an imino group in part are illustrated as a typical thing.

When a melamine curing agent is used in combination, the addition of an acidic compound is effective. Although it does not specifically limit as a specific example of an acidic compound, For example, carboxylic acid, a sulfonic acid, acidic phosphoric acid ester, phosphorous acid ester is mentioned.
The carboxylic acid is not particularly limited, and examples thereof include acetic acid, lactic acid, succinic acid, oxalic acid, maleic acid, decanedicarboxylic acid, and the like.

  Although it does not specifically limit as sulfonic acid, For example, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonyl naphthalene disulfonic acid etc. are mentioned.

  The acidic phosphate ester is not particularly limited, and examples thereof include dimethyl phosphate, diethyl phosphate, dibutyl phosphate, dioctyl phosphate, dilauryl phosphate, monomethyl phosphate, monoethyl phosphate, monobutyl phosphate, monooctyl phosphate and the like.

  Although it does not specifically limit as phosphite, For example, diethyl phosphite, dibutyl phosphite, dioctyl phosphite, dilauryl phosphite, monoethyl phosphite, monobutyl phosphite, monooctyl phosphite, monolauryl phosphite Etc.

  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 compound and a Lewis acid complex.

[Use]
The polyisocyanate composition and the block polyisocyanate composition according to the present embodiment are a curable composition such as a coating composition, a pressure-sensitive adhesive composition, an adhesive composition, or a casting composition; various surfaces such as a fiber treatment agent. It can be used as a treating agent composition; various elastomer compositions; a crosslinking agent such as a foam composition; a modifier;

  The coating composition containing the polyisocyanate composition and the block polyisocyanate composition according to the present embodiment is a primer or intermediate coating on various materials by roll coating, curtain flow coating, spray coating, electrostatic coating, bell coating, It is suitably used as a top coat. In addition, this coating composition further imparts cosmetic properties, weather resistance, acid resistance, rust resistance, chipping resistance, adhesion, etc. to pre-coated metal, automobile coating, plastic coating, etc. that contain a rust-proof steel plate. Preferably used.

  Fields of use of the pressure-sensitive adhesive composition and the adhesive composition including the polyisocyanate composition and the block polyisocyanate composition according to this embodiment include automobiles, building materials, home appliances, woodworking, solar cell laminates, and the like. Among them, optical members for liquid crystal displays of home appliances such as televisions, personal computers, digital cameras, and mobile phones exhibit various functions. Therefore, it is necessary to laminate films and plates of various adherends. Since the material used between the films and plates of various adherends requires sufficient tackiness or adhesiveness, use of the pressure-sensitive adhesive composition and adhesive composition containing the block polyisocyanate composition of the present embodiment Preferred as an example.

  Although it does not specifically limit as an adherend which can use the curable composition etc. which contain the polyisocyanate composition and block polyisocyanate composition which concern on this embodiment, For example, glass; Aluminum, iron, zinc steel plate, copper, Various metals such as stainless steel; porous members such as wood, paper, mortar and stone; members coated with fluorine coating, urethane coating, acrylic urethane coating, etc .; silicone-based cured products, modified silicone-based cured products, urethane-based cured products Hardened materials such as vinyl chloride, natural rubber and synthetic rubber; leather such as natural leather and artificial leather; fibers such as plant fiber, animal fiber, carbon fiber and glass fiber; non-woven fabric Films and plates of resins such as polyester, acrylic, polycarbonate, triacetylcellulose, and polyolefin; purple Line-curable acrylic resin layer, printing inks, include inks such as UV inks.

  Hereinafter, the present embodiment will be described in more detail with reference to examples and comparative examples. This embodiment is not limited at all by the following examples.

Each measurement method and evaluation method in the present examples and comparative examples will be described.
<Viscosity of polyisocyanate precursor>
The viscosity at 25 ° C. of the polyisocyanate precursors obtained in Synthesis Examples 1 to 7 was measured using an E-type viscometer RE-85R (manufactured by Toki Sangyo Co., Ltd.), and the rotor was a standard rotor (1 ° 34 ′ × R24) was used. The number of rotations was 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 1,280 mPa · s)
5r. p. m. (In the case of 1,280 mPa · s or more and less than 2,560 mPa · s)
2.5r. p. m. (In the case of 2,560 mPa · s or more and less than 5,120 mPa · s)
1.0r. p. m. (In the case of 5,120 mPa · s or more and less than 12,800 mPa · s)
0.5r. p. m. (In the case of 12,800 mPa · s or more and less than 25,600 mPa · s)

<NCO group content of polyisocyanate precursor and polyisocyanate composition>
2 to 3 g of the polyisocyanate precursor or polyisocyanate composition is dissolved in 20 mL of toluene, and 20 mL of 2N di-n-butylamine toluene solution is added and mixed, and left for 15 minutes. 70 mL of isopropanol was added and back titrated with 1N hydrochloric acid. The NCO group content (mass%) of the polyisocyanate precursor was determined from the result of this back titration.

<Molar ratio of biuret group, uretdione group, and isocyanurate group>
The molar ratio of biuret group, uretdione group, and isocyanurate group in the polyisocyanate precursor obtained in the synthesis example and in the polyisocyanate composition and block polyisocyanate composition obtained in the examples was 13C-NMR ( It was determined by Bruker, FT-NMR DPX-400). An example of a method for measuring a polyisocyanate precursor using HDI as a raw material by 13 C-NMR is shown below.

  Measurement method example of 13C-NMR: The polyisocyanate precursor prepared in Synthesis Examples 1 to 7, the polyisocyanate composition prepared in Examples 14 and 15, and the block polyisocyanate composition prepared in Examples 31 to 33. Each was dissolved in deuterium chloroform at a concentration of 10% by mass.

As a chemical shift standard, the carbon atom signal of deuterium chloroform was 77.0 ppm. The area of the carbon atom signal of the biuret group near 156.4 ppm and the area of the carbon atom signal of the uretdione group near 157.8 ppm were measured. Based on the obtained area, the molar ratio of biuret groups and uretdione groups in the polyisocyanate precursor and in the blocked isocyanate composition was determined.
Biuret group / uretdione group = (signal area around 156.4 ppm / 2) / (signal area around 157.8 ppm / 2)

  Furthermore, the area of the signal of the carbon atom of the isocyanurate group around 149.0 ppm was measured. Based on the obtained area, the molar ratio of biuret group, uretdione group and isocyanurate group in the polyisocyanate precursor was determined by the following formula.

  Biuret group / uretdione group / isocyanurate group = (signal area around 156.4 ppm / 2) / (signal area around 157.8 ppm / 2) / (signal area around 149.0 ppm / 3)

<OH value of polycarbonate diol>
The OH value of the polycarbonate diol was determined according to JIS K 0070: 1992. Acetic anhydride (12.5 g) was diluted with 50 mL of pyridine to prepare an acetylating reagent. Next, 2.5 to 5.0 g of the polycarbonate diol produced in the synthesis example was precisely weighed into a 100 mL eggplant flask. To the eggplant flask, 5 mL of an acetylating reagent and 10 mL of toluene were added with a whole pipette, a condenser tube was attached, and the mixture was stirred and heated at 100 ° C. for 1 hour. Distilled water (2.5 mL) was added with a whole pipette, and the mixture was further heated and stirred for 10 min. After cooling for 2 to 3 minutes, 12.5 mL of ethanol was added, and after adding 2-3 drops of phenolphthalein as an indicator, titration was performed with 0.5 mol / L ethanolic potassium hydroxide.

<Number average molecular weight of polycarbonate diol>
The number average molecular weight of the polycarbonate diol was calculated by the following formula.
Number average molecular weight = 2 / (OH number of polycarbonate diol × 10−3 / 56.11)
On the other hand, as a blank test, 5 mL of an acetylating reagent, 10 mL of toluene, and 2.5 mL of distilled water were put into a 100 mL eggplant flask and stirred for 10 minutes, and then titrated in the same manner. Based on this result, the OH value was calculated by the following formula.
OH value (mg-KOH / g) = {(ba) × 28.05 × f} / e
a: Titration volume of sample (mL)
b: Titrate of blank test (mL)
e: Sample weight (g)
f: Factor of titrant

<Copolymerization composition of polycarbonate diol>
The copolymer composition of polycarbonate diol was measured as follows.
1 g of a sample was taken into a 100 mL eggplant flask, 30 g of ethanol and 4 g of potassium hydroxide were added, and reacted at 100 ° C. for 1 hour. After cooling to room temperature, 2-3 drops of phenolphthalein was added to the indicator and neutralized with hydrochloric acid. After cooling in the refrigerator for 1 hour, the precipitated salt was removed by filtration and analyzed by gas chromatography. The analysis was performed by using gas chromatography GC-14B (manufactured by Shimadzu Corporation) with DB-WAX (manufactured by J & W) as a column, diethylene glycol diethyl ester as an internal standard, and a detector as FID. The temperature rising profile of the column was a profile in which the temperature was raised to 250 ° C. at 10 ° C./min after holding at 60 ° C. for 5 minutes.

<Viscosity of block polyisocyanate composition>
The viscosity of the block polyisocyanate composition was measured at 25 ° C. using an E-type viscometer RE-85R or RE-80U (manufactured by Toki Sangyo Co., Ltd.). As the latter rotor, a high viscosity rotor (3 ° × R14) was used, and the rotational speed was as follows.
100r. p. m. (If less than 5 Pa · s)
50r. p. m. (In case of 5 Pa · s or more and less than 10 Pa · s)
20r. p. m. (10 Pa · s or more and less than 25 Pa · s)
10r. p. m. (In the case of 25 Pa · s or more and less than 50 Pa · s)
5r. p. m. (In case of 50 Pa · s or more and less than 100 Pa · s)
2.5r. p. m. (In the case of 100 Pa · s or more and less than 200 Pa · s)
1.0r. p. m. (In case of 200 Pa · s or more and less than 500 Pa · s)
0.5r. p. m. (In the case of 500 Pa · s or more and less than 1,000 Pa · s)

<Effective NCO group content of block polyisocyanate composition>
The effective NCO group content was calculated based on the following formula from the charged amount of the polyisocyanate precursor and the polycarbonate diol, the NCO group content, the charged amount of the heat dissociable blocking agent, and the solid content.
Effective NCO group content (mass%)
= ((A * (d / 100)) * (e / (e + 1))) / (a + b + c / 1.03)) * f
a: Charge amount of polyisocyanate precursor (g)
b: Charge amount of polycarbonate diol (g)
c: Charge of thermally dissociable blocking agent (g)
d: NCO group content of polyisocyanate precursor (mass%)
e: Reaction ratio NCO / OH
f: Solid content (mass%)

<Evaluation method>
[Production method of resin film (polyisocyanate composition)]
For the polyisocyanate compositions obtained in Examples 1 to 15 and Comparative Examples 1 to 4, Setalux 1767 (acrylic polyol, manufactured by Nuplex Resins, hydroxyl value 97.5 mg KOH / g (solid), solid content 65% by mass) Was blended so that NCO / OH = 1, and diluted with butyl acetate to a solid content of 50% to obtain a resin composition. At that time, dibutyltin dilaurate was added to a resin concentration of 0.05% by mass. The obtained resin composition was applied to a polypropylene (PP) plate so as to have a resin film thickness of 40 μm, the coating film was cured at 60 ° C., and then peeled from the plate to obtain a polyurethane resin film.

[Production Method of Resin Film (Block Polyisocyanate Composition)]
For the block polyisocyanate compositions obtained in Examples 16 to 41 and Comparative Examples 5 to 8, Setalux 1767 (acrylic polyol, manufactured by Nuplex Resins, hydroxyl value 97.5 mg KOH / g (solid), solid content 65% by mass ) Was formulated so that NCO / OH = 1.0 and diluted to 50% solids with butyl acetate. At that time, dibutyltin dilaurate was added to a resin concentration of 0.5% by mass to obtain a coating composition. The obtained coating composition was applied to an applicator on a polypropylene (PP) plate so as to have a resin film thickness of 40 μm. When the heat dissociable blocking agent is 3,5-dimethylpyrazole (Examples 16 to 33 and Comparative Examples 5 to 8), 140 ° C., 30 minutes, and when methylethylketoxime (Examples 34 to 41) is 160 ° C., 30 After baking for minutes, the polyurethane resin film was obtained by peeling a coating film from PP board.

[Method of evaluating extensibility]
The breaking elongation of the polyurethane resin film obtained by the resin film production method was measured using a trade name TENSILON RTE-1210 manufactured by A & D (A & D). Based on the measured elongation at break, extensibility was evaluated according to the following evaluation criteria.
Measurement conditions: Tensile speed: 20 mm / min, sample dimensions: 20 mm long × 10 mm wide × 40 μm thickness, temperature 23 ° C./humidity 50%
(Evaluation criteria)
A: Breaking elongation of the coating film (film) is 50% or more B: Breaking elongation of the coating film (film) is 20% or more and less than 50% X: Breaking elongation of the coating film (film) is less than 20%

[Evaluation method of water resistance]
The polyurethane resin film obtained by the resin film production method was immersed in warm water at 80 ° C. for 1 week, and the strength retention was measured. The strength retention in this test is the rate of change in maximum breaking stress before and after immersion {(maximum breaking stress after immersion / maximum breaking stress before immersion) × 100} (%), and A & D (A Measurement was performed using a trade name TENSILON (TESILON) RTE-1210 manufactured by And Day. Based on the measured strength retention, the water resistance of the polyisocyanate composition was evaluated according to the following evaluation criteria.
Measurement conditions: Tensile speed: 20 mm / min, sample dimensions: 20 mm long × 10 mm wide × 40 μm thickness, temperature 23 ° C./humidity 50%
(Evaluation criteria)
○: Strength retention is 70% or more ×: Strength retention is less than 70%

[Evaluation method of heat resistance]
The polyurethane resin film obtained by the resin film production method was placed in an atmosphere of 120 ° C. for 1 week, and the strength retention was measured. The strength retention in this test is the rate of change of the maximum breaking stress before and after placing at 120 ° C. {(the maximum breaking stress of the film after placing at 120 ° C.) / (The maximum breaking of the film before placing at 120 ° C. Stress) × 100} (%), and was measured using a trade name TENSILON (TESILON) RTE-1210 manufactured by A & D (A & D). Based on the measured strength retention, the heat resistance of the polyisocyanate composition was evaluated according to the following evaluation criteria.
Measurement conditions: Tensile speed: 20 mm / min, sample dimensions: 20 mm long × 10 mm wide × 40 μm thickness, temperature 23 ° C./humidity 50%
(Evaluation criteria)
◎: Strength retention is 70% or more ○: Strength retention is 50% or more and less than 70% ×: Strength retention is less than 50%

[Evaluation method of moisture stability]
Mixing of 30 parts by mass of n-butyl acetate and 30 parts by mass of xylene containing 0.2 parts by mass of water with respect to 40 parts by mass of the polyisocyanate compositions obtained in Examples 1 to 15 and Comparative Examples 1 to 4 described later. The solvent was mixed. The obtained mixture was placed in an atmosphere of 20 ° C., and the number of days until the appearance became cloudy was visually observed.
(Evaluation criteria)
◎: No cloudiness for 10 days or more ○: Cloudiness for 5 days or more and less than 10 days ×: Cloudiness for less than 5 days

[Adhesion evaluation method]
Using a polyurethane resin film produced on a mild steel plate by a method for producing a resin film using the block polyisocyanate composition described in Examples 16 to 41 and Comparative Examples 5 to 8 below, JIS K5600-5-6 (coating film The adhesion test was carried out according to the cross-cut method). At this time, the case where the number of remaining cells was 100 was evaluated as ◯, the case of 60 or more and 99 or less as Δ, and the case of 59 or less as ×.

<Synthesis example of polyisocyanate precursor>
(Synthesis Example 1)
(Synthesis of polyisocyanate precursor A-1)
After making the inside of the flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen blowing tube into a nitrogen atmosphere, HDI: 700 parts by mass, trimethyl phosphoric acid: 150 parts by mass, methyl cellosolve acetate: 150 parts by mass, and water: 12 .5 parts by mass (HDI / water molar ratio = 6) was charged, and the liquid temperature was maintained at 160 ° C. for 1 hour. The resulting reaction liquid was fed to a thin film distiller to obtain polyisocyanate precursor A-1. The resulting polyisocyanate precursor A-1 had a viscosity at 25 ° C. of 9700 mPa · s and an isocyanate group (NCO group) content of 21.5%. Moreover, when polyisocyanate precursor A-1 measured 13C-NMR, biuret group / uretdione group (molar ratio) was 95/5.

(Synthesis Example 2)
(Synthesis of polyisocyanate precursor A-2)
Synthesis was performed in the same manner as in Synthesis Example 1 except that the amount of water charged was 4.2 parts by mass (HDI / water molar ratio = 18) to obtain a polyisocyanate precursor A-2. The resulting polyisocyanate precursor A-2 had a viscosity at 25 ° C. of 2300 mPa · s and an isocyanate group (NCO group) content of 23.3%. Moreover, when polyisocyanate precursor A-2 measured 13C-NMR, biuret group / uretdione group (molar ratio) was 90/10.

(Synthesis Example 3)
(Synthesis of polyisocyanate precursor A-3)
In the synthesis example 1, it synthesize | combined by the same method except having made the water preparation amount into 2.5 mass parts (HDI / water molar ratio = 30), and obtained polyisocyanate precursor A-3. The resulting polyisocyanate precursor A-3 had a viscosity at 25 ° C. of 1060 mPa · s and an isocyanate group (NCO group) content of 23.7%. Moreover, when 13C-NMR was measured for polyisocyanate precursor A-3, biuret group / uretdione group (molar ratio) was 85/15.

(Synthesis Example 4)
(Synthesis of polyisocyanate precursor A-4)
Synthesis was performed in the same manner as in Synthesis Example 1 except that the amount of water charged was 1.5 parts by mass (HDI / water molar ratio = 50) to obtain a polyisocyanate precursor A-4. The obtained polyisocyanate precursor A-4 had a viscosity at 25 ° C. of 360 mPa · s and an isocyanate group (NCO group) content of 23.9%. Moreover, when the polyisocyanate precursor A-4 was measured for 13C-NMR, the biuret group / uretodione group (molar ratio) was 75/25.

(Synthesis Example 5)
(Synthesis of polyisocyanate precursor A-5)
Synthesis was performed in the same manner as in Synthesis Example 1 except that the amount of water charged was 0.9 parts by mass (HDI / water molar ratio = 83) to obtain a polyisocyanate precursor A-5. The obtained polyisocyanate precursor A-5 had a viscosity at 25 ° C. of 120 mPa · s and an isocyanate group (NCO group) content of 24.1%. Moreover, when polyisocyanate precursor A-5 measured 13 C-NMR, biuret group / uretdione group (molar ratio) was 60/40.

(Synthesis Example 6)
(Synthesis of polyisocyanate precursor A-6)
In the same apparatus as in Synthesis Example 1, 1000 g of HDI was charged, and the temperature in the reactor was kept at 60 ° C. with stirring. Then, 2.1 g of tetramethylammonium acetate (2-butanol 5.0% by mass solution) was added as an isocyanuration reaction catalyst to carry out the reaction. After 4 hours, the reaction end point was confirmed by measuring the refractive index of the reaction solution, and 0.2 g of phosphoric acid (85 mass% aqueous 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-6 having an isocyanurate group. The obtained polyisocyanate precursor A-6 had a viscosity at 25 ° C. of 2500 mPa · s and an isocyanate group (NCO group) content of 22.2% by mass. Moreover, when the polyisocyanate precursor A-6 was measured by 13C-NMR, the biuret group / uretdione group / isocyanurate group (molar ratio) was 0/0/100.

(Synthesis Example 7)
(Synthesis of polyisocyanate precursor A-7)
The inside of a four-necked flask equipped with a stirrer, thermometer and condenser was replaced with nitrogen, charged with 1000 g of HDI, and stirred at 60 ° C., 0.1 g of tetramethylammonium capriate and 1.0 g of isobutanol were used as catalysts The reaction was carried out by adding simultaneously. After 4 hours, the reaction end point set by measuring the refractive index of the reaction solution was confirmed, and 0.2 g of phosphoric acid was added to stop the reaction. Then, after filtering a reaction liquid, the isocyanurate type polyisocyanate A-7 was obtained by removing an unreacted HDI monomer with a thin film distillation apparatus. The obtained polyisocyanate A-7 had a viscosity at 25 ° C. of 1300 mPa · s and an isocyanate group (NCO group) content of 23.2%. Moreover, when the polyisocyanate precursor A-7 was measured by 13C-NMR, the biuret group / uretdione group / isocyanurate group (molar ratio) was 0/0/100.

<Synthesis example of polycarbonate diol>
(Synthesis Example 8)
(Synthesis of polycarbonate diol B-1)
A 2 L separable flask equipped with a stirrer, a thermometer, and a vacuum jacketed Oldershaw with a reflux head at the top was charged with 382 g of 1,5-pentanediol, 433 g of 1,6-hexanediol, and 650 g of ethylene carbonate at 70 ° C. After stirring and dissolving, 0.015 g of lead acetate trihydrate was added as a catalyst. The flask was heated in an oil bath set at 175 ° C., the flask was heated at an internal temperature of 140 ° C., and the degree of vacuum was 1.0 to 1.5 kPa. Reacted for hours. Then, the Oldershaw was replaced with a simple distillation apparatus, and the flask was heated in an oil bath set at 180 ° C., and the flask was cooled to an internal temperature of 140 to 150 ° C. and the vacuum level was reduced to 0.5 kPa. The diol and ethylene carbonate were removed. Then, the setting of the oil bath was raised to 185 ° C., and the reaction was further performed for 4 hours while removing the produced diol at an internal temperature of the flask of 160 to 165 ° C. By this reaction, a viscous liquid was obtained at room temperature. The obtained polycarbonate diol B-1 had an OH value of 56.1 mgKOH / g (molecular weight 2000) and a copolymer composition of 1,5-pentanediol / 1,6-hexanediol = 50/50 (molar ratio). It was.

(Synthesis Example 9)
(Synthesis of polycarbonate diol B-2)
In Synthesis Example 8, after replacing the Oldershaw with a simple distillation apparatus, the setting of the oil bath was raised to 185 ° C., the internal temperature of the flask was changed to 160 to 165 ° C., and the time for removing the diol produced was 1.5 hours. Except that, polycarbonate diol B-2 was synthesized in the same manner. The obtained polycarbonate diol B-2 had an OH value of 224.4 mgKOH / g (molecular weight 500) and a copolymer composition of 1,5-pentanediol / 1,6-hexanediol = 50/50 (molar ratio). It was.

(Synthesis Example 10)
(Synthesis of polycarbonate diol B-3)
In Synthesis Example 8, instead of 1,5-pentanediol and 1,6-hexanediol, 330 g of 2-methyl-1,3-propanediol and 330 g of 1,4-butanediol were used, and Oldershaw was used as a simple distillation apparatus. After the replacement, the setting of the oil bath was raised to 185 ° C., the internal temperature of the flask was changed to 160 to 165 ° C., and the time for removing the produced diol was changed to 2.0 hours. -3 was synthesized. The obtained polycarbonate diol B-3 has an OH value of 141.1 mgKOH / g (molecular weight 800) and a copolymer composition of 2-methyl-1,3-propanediol / 1,4-butanediol = 50/50 (moles). Ratio).

(Synthesis Example 11)
(Synthesis of polycarbonate diol B-4)
In Synthesis Example 8, the same method except that 330 g of 2-methyl-1,3-propanediol and 330 g of 1,4-butanediol were used instead of 1,5-pentanediol and 1,6-hexanediol. To synthesize polycarbonate diol B-4. The obtained polycarbonate diol B-4 has an OH value of 56.1 mgKOH / g (molecular weight 2000) and a copolymer composition of 2-methyl-1,3-propanediol / 1,4-butanediol = 50/50 (moles). Ratio).

(Synthesis Example 12)
(Synthesis of polycarbonate diol B-5)
In Synthesis Example 8, polycarbonate diol B was prepared in the same manner except that 462 g of 1,4-butanediol and 260 g of 1,6-hexanediol were used instead of 1,5-pentanediol and 1,6-hexanediol. -5 was synthesized. The obtained polycarbonate diol B-5 had an OH value of 56.1 mgKOH / g (molecular weight 2000) and a copolymer composition of 1,4-butanediol / 1,6-hexanediol = 70/30 (molar ratio). It was.

(Synthesis Example 13)
(Synthesis of polycarbonate diol B-6)
A 2 L reactor equipped with a stirrer was charged with 520 g of 1,6-hexanediol and 410 g of ethylene carbonate, and then 0.009 g of lead acetate trihydrate was added as a catalyst to a rectification column packed with regular packing. Connected. The reactor was immersed in an oil bath at 210 ° C. and reacted at a reaction temperature of 170 ° C. for 20 hours while extracting a part of the distillate. Thereafter, the reactor was directly connected to a condenser, the temperature of the oil bath was lowered to 190 ° C., and the pressure was gradually lowered to carry out the reaction for another 8 hours. By this reaction, 517 g of polycarbonate diol B-6 which was a white solid at room temperature was obtained. The obtained polycarbonate diol B-6 had an OH value of 56.1 mgKOH / g (molecular weight 2000).

<Synthesis example and evaluation of polyisocyanate composition>
[Example 1]
A 4-necked flask equipped with a stirrer, thermometer, reflux condenser, nitrogen blowing tube, and dropping funnel was placed in a nitrogen atmosphere, and 100 parts by mass of the polyisocyanate precursor A-1 obtained in Synthesis Example 1 was synthesized. 104 parts by mass of the polycarbonate diol B-1 obtained in Example 8 was charged so that the molar ratio (NCO / OH) between the isocyanate group in the polyisocyanate precursor and the hydroxyl group in the polycarbonate diol was 5. The mixture was stirred at 100 ° C. for 3 hours under a nitrogen atmosphere to obtain a reaction product (including unreacted polyisocyanate precursor A-1) of a polyisocyanate precursor and a polycarbonate diol. The isocyanate group content in the obtained polyisocyanate composition was 8.5%. Moreover, each characteristic of the obtained polyisocyanate composition was evaluated by the said method. The evaluation results are shown in Table 1.

[Examples 2 to 12]
In Example 1, the polyisocyanate composition was synthesize | combined by the same method except having changed the raw material and reaction ratio NCO / OH which are used for a polyisocyanate composition as described in Table 1. Moreover, each characteristic of the obtained polyisocyanate composition was evaluated by the said method. The evaluation results are shown in Table 1.

Example 13
In Example 1, the polyisocyanate composition was changed in the same manner except that the polyisocyanate precursor was changed to a mixture of 80 parts by mass of polyisocyanate precursor A-2 and 20 parts by mass of polyisocyanate precursor A-7. Synthesized. Moreover, each characteristic of the obtained polyisocyanate composition was evaluated by the said method. The evaluation results are shown in Table 1.

Example 14
The polyisocyanate A-2 of Synthesis Example 2 was used as the polyisocyanate precursor, and the polycarbonate diol B-1 of Synthesis Example 8 was used as the copolymerized polycarbonate diol. These were mixed so that the active hydrogen in the polycarbonate diol was 1 equivalent (reaction ratio NCO / OH = 5) with respect to 5 equivalents of the isocyanate group in the polyisocyanate precursor, and the PCD was reacted at 100 ° C. for 4 hours. A containing polyisocyanate was obtained. Furthermore, the polyisocyanate composition is prepared by mixing the polyisocyanate A-7 of Synthesis Example 7 with the PCD-containing polyisocyanate so that the molar ratio of biuret group / uretodione group / isocyanurate group is 72/8/20. Got.
The resulting polyisocyanate composition had an NCO group content of 10.3% by mass. Moreover, each characteristic of the obtained polyisocyanate composition was evaluated by the said method. The evaluation results are shown in Table 1.

Example 15
Polyisocyanate A-7 of Synthesis Example 7 was used as a polyisocyanate precursor, and Polycarbonate Diol B-1 of Synthesis Example 8 was used as a copolymerized polycarbonate diol. These were mixed so that the active hydrogen in the polycarbonate diol was 1 equivalent (reaction ratio NCO / OH = 5) with respect to 5 equivalents of the isocyanate group in the polyisocyanate precursor, and the PCD was reacted at 100 ° C. for 4 hours. A containing polyisocyanate was obtained. Further, a polyisocyanate composition is obtained by mixing the polyisocyanate precursor A-2 with the PCD-containing polyisocyanate so that the molar ratio of biuret group / uretdione group / isocyanurate group is 72/8/20. It was.
The isocyanate group content of the obtained polyisocyanate composition was 17.8% by mass. Moreover, each characteristic of the obtained polyisocyanate composition was evaluated by the said method. The evaluation results are shown in Table 1.

[Comparative Example 1]
Polyisocyanate A-7 of Synthesis Example 7 was used as a polyisocyanate precursor, and Polycarbonate Diol B-1 of Synthesis Example 8 was used as a copolymerized polycarbonate diol. By mixing these so that the active hydrogen in the polycarbonate diol becomes 1 equivalent (reaction ratio NCO / OH = 5) with respect to 5 equivalents of isocyanate groups in the polyisocyanate precursor, and reacting at 100 ° C. for 4 hours, A polyisocyanate composition was obtained. The isocyanate group content of the obtained polyisocyanate composition was 8.4% by mass. Moreover, each characteristic of the obtained polyisocyanate composition was evaluated by the said method. The evaluation results are shown in Table 2.

[Comparative Example 2]
Polyisocyanate A-2 of Synthesis Example 2 was used as the polyisocyanate precursor, and OD-X-2722 (manufactured by DIC, molecular weight 2000) was used as the polyester diol. By mixing these so that the active hydrogen in the polyester diol becomes 1 equivalent (reaction ratio NCO / OH = 5) with respect to 5 equivalents of the isocyanate group in the polyisocyanate precursor, and reacting at 100 ° C. for 4 hours, A polyisocyanate composition was obtained. The isocyanate group content of the obtained polyisocyanate composition was 9.0% by mass. Moreover, each characteristic of the obtained polyisocyanate composition was evaluated by the said method. The evaluation results are shown in Table 2.

[Comparative Example 3]
The polyisocyanate A-2 of Synthesis Example 2 was used as the polyisocyanate precursor, and EXCENOL 2020 (manufactured by Asahi Glass Co., Ltd., molecular weight 2000) was used as the polyether diol. By mixing these so that the active hydrogen in the polyether diol is 1 equivalent (reaction ratio NCO / OH = 5) with respect to 5 equivalents of the isocyanate group in the polyisocyanate precursor, the mixture is reacted at 100 ° C. for 4 hours. A polyisocyanate composition was obtained. The isocyanate group content of the obtained polyisocyanate composition was 9.0% by mass. Moreover, each characteristic of the obtained polyisocyanate composition was evaluated by the said method. The evaluation results are shown in Table 2.

[Comparative Example 4]
Polyisocyanate A-2 of Synthesis Example 2 was used as the polyisocyanate composition. Each characteristic of this polyisocyanate composition was evaluated by the said method. The evaluation results are shown in Table 2.

<Synthesis example and evaluation of block polyisocyanate composition>
(Example 16)
A 4-necked flask equipped with a stirrer, thermometer, reflux condenser, nitrogen blowing tube, and dropping funnel was placed in a nitrogen atmosphere, and 100 parts by mass of the polyisocyanate precursor A-1 obtained in Synthesis Example 1 was synthesized. 52 parts by mass of the polycarbonate diol B-1 obtained in Example 8 was charged so that the molar ratio (NCO / OH) between the isocyanate group in the polyisocyanate precursor and the hydroxyl group in the polycarbonate diol was 10. Into the flask, butyl acetate as a solvent is charged so that the concentration of the blocked polyisocyanate component becomes 70% by mass, and stirred at 100 ° C. for 3 hours in a nitrogen atmosphere to obtain a reaction product (unreacted product) of the polyisocyanate precursor and polycarbonate diol. Reaction polyisocyanate precursor A-1 was obtained). After the inside of the flask was cooled to 80 ° C., 47.5 parts by mass of 3,5-dimethylpyrazole (hereinafter also referred to as “DMP”) as a heat dissociable blocking agent was added to the reaction product (polyisocyanate precursor and The amount of the isocyanate group present in the reaction product with the polycarbonate diol was 1.05 times the molar amount) and stirred, and it was confirmed that the characteristic absorption of the isocyanate group disappeared in the infrared spectrum. The obtained block polyisocyanate composition had an effective isocyanate group content (effective NCO group content) of 6.9% by mass.

(Examples 17 to 30)
In Example 1, the block polyisocyanate composition was synthesized in the same manner except that the raw materials and NCO / OH used in the block polyisocyanate composition were changed as shown in Table 3. The effective NCO group content and viscosity of each block polyisocyanate composition obtained were as shown in Table 1.

  In Examples 17 to 30, the mole fraction of biuret groups in the obtained block polyisocyanate composition was equivalent to the mole fraction of biuret groups in the polyisocyanate precursor used as a raw material.

(Example 31)
100 parts by mass of a reaction product (including unreacted polyisocyanate precursor A-2) of polyisocyanate precursor A-2 and polycarbonate diol B-2 produced by the method described in Synthesis Example 2, and Synthesis Example 6 was mixed with 21.6 parts by mass of the polyisocyanate precursor A-6 produced in No. 6. To the obtained mixture, 52.4 parts by mass of 3,5-dimethylpyrazole (1.05 times the molar amount with respect to the isocyanate group present in the mixture) was added, and the mixture was stirred at 80 ° C. It was confirmed that the absorption of the characteristic was lost. According to 13C-NMR of the obtained block polyisocyanate composition, the mole fraction of biuret groups was 72 mol%. The effective NCO group content and viscosity of the resulting block polyisocyanate composition were as shown in Table 3.

(Example 32)
In the same apparatus as in Example 1, 100 parts by mass of polyisocyanate precursor A-2, 32.7 parts by mass of polyisocyanate precursor A-6, 36.4 parts by mass of polycarbonate diol B-2 (NCO in all polyisocyanates) / OH = 5), and butyl acetate as a solvent is added so that the concentration of the blocked polyisocyanate component is 70% by mass, and the reaction product (unreacted polyisocyanate precursor) is stirred at 100 ° C. for 3 hours in a nitrogen atmosphere. A-2) was obtained. After cooling the inside of the flask to 80 ° C., 59.1 parts by mass of 3,5-dimethylpyrazole as a heat dissociable blocking agent (1.05 times the isocyanate group present in the reaction product) was added to the reaction product. Molar amount) was added and stirred, and it was confirmed by infrared spectrum that the characteristic absorption of isocyanate groups was lost. According to 13C-NMR of the obtained block polyisocyanate composition, the mole fraction of biuret groups was 72 mol%. The effective NCO group content and viscosity of the resulting block polyisocyanate composition were as shown in Table 3.

(Example 33)
In the same apparatus as in Example 1, 30 parts by mass of polyisocyanate precursor A-6, 8.0 parts by mass of polycarbonate diol B-2 (NCO / OH = 5 in all polyisocyanates), and butyl acetate as a solvent, The block polyisocyanate component concentration was adjusted to 70% by mass, and the mixture was stirred at 100 ° C. for 3 hours under a nitrogen atmosphere to obtain a reaction product. After cooling the inside of the flask to 80 ° C., 111 parts by mass of the polyisocyanate precursor A-2 and 74.7 parts by mass of 3,5-dimethylpyrazole as a heat dissociable blocking agent are present in the reaction product. It was confirmed that the characteristic absorption of the isocyanate group disappeared by infrared spectrum. According to 13C-NMR of the obtained block polyisocyanate composition, the mole fraction of biuret groups was 72 mol%. The effective NCO group content and viscosity of the resulting block polyisocyanate composition were as shown in Table 3.

(Example 34)
In the same apparatus as in Example 1, 100 parts by mass of the polyisocyanate precursor A-2 obtained in Synthesis Example 2 and 28 parts by mass of the polycarbonate diol B-1 obtained in Synthesis Example 8 as a polycarbonate diol were prepared. NCO / OH was set to 20. Into the flask, butyl acetate as a solvent is charged so that the final block polyisocyanate component concentration is 70% by mass, and the reaction product (unreacted polyisocyanate precursor A-2 is stirred under a nitrogen atmosphere at 100 ° C. for 3 hours. Obtained). After the inside of the flask was cooled to 60 ° C., 47.5 parts by mass of methylethylketoxime (hereinafter also referred to as “MEKO”) as a heat dissociable blocking agent was added to the reaction product (reaction of polyisocyanate precursor and polycarbonate diol). 1.05 times the molar amount of the isocyanate group present in the product) was added and stirred, and it was confirmed by infrared spectrum that the characteristic absorption of the isocyanate group disappeared. The effective NCO group content and viscosity of the resulting block polyisocyanate composition were as shown in Table 4.

(Examples 35-41)
In Example 34, a block polyisocyanate composition was synthesized in the same manner except that the raw materials and NCO / OH used in the block polyisocyanate composition were changed as described in Table 4. The effective NCO group content and viscosity of each block polyisocyanate composition obtained were as shown in Table 4.

(Each evaluation)
The block polyisocyanate composition synthesized in Examples 16 to 41 was evaluated by the evaluation method. The results are as shown in Tables 3 and 4.

(Comparative Example 5)
In Example 22, the polyisocyanate precursor A-6 of Synthesis Example 6 was used instead of the polyisocyanate precursor A-2, and the polycarbonate diol B-1 of Synthesis Example 8 was used instead of the polycarbonate diol B-2. Synthesized a block polyisocyanate composition in the same manner. The effective NCO group content and viscosity of the obtained block polyisocyanate composition were as shown in Table 5.

(Comparative Example 6)
In the same apparatus as in Example 1, 100 parts by mass of the polyisocyanate precursor A-2 of Synthesis Example 2, 62.1 parts by mass of butyl acetate, and 53.3 parts by mass of 3,5-dimethylpyrazole (isocyanate of the polyisocyanate precursor) It was confirmed that the characteristic absorption of the isocyanate group disappeared in the infrared spectrum by stirring at 80 ° C. The effective NCO group content and viscosity of the obtained block polyisocyanate composition were as shown in Table 5.

(Comparative Example 7)
In Example 16, the polyisocyanate precursor A-2 of Synthesis Example 2 was used instead of the polyisocyanate precursor A-1, and OD-X-2722 (manufactured by DIC, as a polyester diol instead of the polycarbonate diol B-1). A block polyisocyanate composition was synthesized in the same manner except that these were mixed so that NCO / OH in the polyisocyanate was 5 and reacted at 100 ° C. for 4 hours. The effective NCO group content and viscosity of the obtained block polyisocyanate composition were as shown in Table 5.

(Comparative Example 8)
In Example 16, the polyisocyanate precursor A-2 of Synthesis Example 2 was used instead of the polyisocyanate precursor A-1, and EXCENOL 2020 (manufactured by Asahi Glass Co., Ltd., molecular weight 2000) as a polyether diol instead of the polycarbonate diol B-1. These were mixed so that the NCO / OH in the polyisocyanate was 5 and reacted at 100 ° C. for 5 hours to obtain a block polyisocyanate composition by the same method. The effective NCO group content and viscosity of the obtained block polyisocyanate composition were as shown in Table 5.

(Each evaluation)
The block polyisocyanate composition synthesized in Comparative Examples 1 to 4 was evaluated by the evaluation method. The results were as shown in Table 5.

  The polyisocyanate composition and the block polyisocyanate composition of the present invention have industrial applicability as additives such as curable compositions, various surface treatment agent compositions, various elastomer compositions, cross-linking agents, and modifiers. Have.

Claims (23)

PCD-containing polyisocyanate formed from a raw material containing the following polyisocyanate precursor and the following polycarbonate diol, and
Including a polyisocyanate having a biuret group other than the PCD-containing polyisocyanate ,
A polyisocyanate composition, wherein the polyisocyanate precursor forming the PCD-containing polyisocyanate comprises a polyisocyanate precursor having a biuret group;
Polyisocyanate precursor: a polyisocyanate precursor selected from polyisocyanates consisting of dimers or more of at least one diisocyanate selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates,
Polycarbonate diol: A polycarbonate diol obtained by copolymerizing at least one diol selected from the group consisting of diols having 2 to 20 carbon atoms and a carbonate compound.   The polyisocyanate composition according to claim 1, wherein the polycarbonate diol is a polycarbonate diol obtained by copolymerizing at least two diols selected from the group consisting of diols having 2 to 20 carbon atoms and a carbonate compound.   The polyisocyanate composition according to claim 1 or 2, wherein the polyisocyanate composition further comprises a polyisocyanate having a uretdione group.   The polyisocyanate composition according to claim 3, wherein a molar ratio of biuret group to uretdione group (biuret group: uretodione group) in the polyisocyanate composition is 100: 0 to 60:40.   The polyisocyanate composition of Claim 3 or 4 in which the polyisocyanate precursor which forms the said PCD containing polyisocyanate contains the polyisocyanate precursor which has a uretdione group.   The polyisocyanate composition according to claim 5, wherein the polyisocyanate precursor forming the PCD-containing polyisocyanate includes a polyisocyanate precursor having a biuret group and a polyisocyanate precursor having a uretdione group.   The polyisocyanate composition according to claim 6, wherein a molar ratio (biuret group: uretodione group) of biuret groups and uretdione groups in the polyisocyanate precursor forming the PCD-containing polyisocyanate is 100: 0 to 60:40. object.   The polycarbonate diol is a polycarbonate diol obtained by copolymerizing at least one diol selected from the group consisting of diols having 3 to 6 carbon atoms and a carbonate compound. Polyisocyanate composition.   The polycarbonate diol is a polycarbonate diol obtained by copolymerizing at least two diols selected from the group consisting of diols having 3 to 6 carbon atoms and a carbonate compound. Polyisocyanate composition.   The polyisocyanate composition according to claim 9, wherein the polycarbonate diol is a polycarbonate diol obtained by copolymerizing a diol having 5 carbon atoms, a diol having 6 carbon atoms, and a carbonate compound.   The polyisocyanate composition according to claim 9, wherein the polycarbonate diol is a polycarbonate diol obtained by copolymerizing two or more isomers of a diol having 4 carbon atoms and a carbonate compound.   The polyisocyanate composition according to claim 9, wherein the polycarbonate diol is a polycarbonate diol obtained by copolymerizing a diol having 4 carbon atoms, a diol having 6 carbon atoms, and a carbonate compound.   The block polyisocyanate composition containing the block polyisocyanate formed from the raw material containing the polyisocyanate composition in any one of Claims 1-12, and a heat dissociable blocking agent.   The block polyisocyanate according to claim 13, wherein the thermally dissociable blocking agent is at least one selected from the group consisting of oxime compounds, acid amide compounds, amine compounds, active methylene compounds and pyrazole compounds. Composition. The manufacturing method of the polyisocyanate composition in any one of Claims 1-12 which has the process of obtaining PCD containing polyisocyanate from the raw material containing the following polyisocyanate precursor and the following polycarbonate diol;
Polyisocyanate precursor: a polyisocyanate precursor comprising a dimer or more of at least one diisocyanate selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates, selected from polyisocyanates having a biuret group,
Polycarbonate diol: A polycarbonate diol obtained by copolymerizing at least one diol selected from the group consisting of diols having 2 to 20 carbon atoms and a carbonate compound.   The method for producing a polyisocyanate composition according to claim 15, further comprising a step of obtaining the polyisocyanate precursor by performing a biuretization reaction and a uretdioneation reaction. A step of obtaining a PCD-containing block polyisocyanate from a raw material containing the following polyisocyanate precursor, the following polycarbonate diol and a heat dissociable blocking agent, and a raw material containing a polyisocyanate precursor having a biuret group and a heat dissociable blocking agent The manufacturing method of the block polyisocyanate composition of Claim 13 or 14 which has the process of obtaining biuret group containing block polyisocyanate from 1 ;
Polyisocyanate precursor: a polyisocyanate precursor selected from polyisocyanates consisting of dimers or more of at least one diisocyanate selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates,
Polycarbonate diol: A polycarbonate diol obtained by copolymerizing at least one diol selected from the group consisting of diols having 2 to 20 carbon atoms and a carbonate compound.   After reacting a polyisocyanate precursor having a biuret group and a polycarbonate diol at a ratio of isocyanate group / hydroxyl group (NCO / OH) = 2.5 to 40.0, the reaction product obtained (unreacted) The block polyisocyanate composition according to claim 17, wherein the PCD-containing block polyisocyanate and the biuret group-containing block polyisocyanate are obtained at the same time by reacting a polyisocyanate precursor having a biuret group) with a thermally dissociable blocking agent. Manufacturing method.   19. The method according to claim 17, comprising a step of obtaining a polyisocyanate precursor by subjecting at least one diisocyanate selected from the group consisting of an aliphatic diisocyanate and an alicyclic diisocyanate to a biuretization reaction and a uretdiionization reaction. A method for producing a block polyisocyanate composition.   The resin composition containing the polyisocyanate composition as described in any one of Claims 1-12.   Resin obtained from the polyisocyanate composition as described in any one of Claims 1-12.   A curable composition containing an active hydrogen compound and the block polyisocyanate composition according to claim 13.   A cured product obtained by heat-curing the curable composition according to claim 22.