WO2025033431A1 - Blocked isocyanate composition, resin composition, resin layer, and method for producing resin layer - Google Patents

Abstract

The present disclosure provides: a blocked isocyanate composition which is characterized by containing a compound represented by formula (1) and a blocked isocyanate; and a resin composition which contains a compound represented by formula (1), a blocked isocyanate, and a thermoplastic resin. (In the formula, each of R¹, R², R³, and R⁴ independently represents an organic group having 1 to 20 carbon atoms, the organic group is a substituted or unsubstituted hydrocarbon group, a group containing a substituted or unsubstituted heterocyclic ring, or a group that is obtained by substituting one or more methylene groups in the hydrocarbon group or the group containing a heterocyclic ring with a divalent group that is selected from the <Group A> described below, X^b- represents a b-valent anion, a represents an integer of 1 to 3 inclusive, and b represents an integer of 1 to 3 inclusive. <Group A> consists of -O-, -CO-, -COO-, -OCO-, -NR¹¹-, -NR¹¹CO-, and -S-, and R¹¹ represents a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms.)

Description

Blocked isocyanate composition, resin composition, resin layer, and method for producing resin layer

The present invention relates to a composition containing a blocked isocyanate.

Blocked isocyanates are compounds in which the isocyanate group is reacted with a compound containing an active hydrogen group (blocking agent) to inactivate (block) the reactivity of the isocyanate group; when this compound is heated, a deblocking reaction occurs, the blocking agent dissociates, and the isocyanate group is regenerated.

Applications of blocked isocyanates include use as an adhesive for films formed from plastisol compositions (e.g., Patent Document 1) and as an adhesive for thermoplastic resin compositions (e.g., Patent Document 2).

Furthermore, Patent Document 3 describes that in a curable composition containing an epoxy resin, it is preferable to add a blocked isocyanate prepolymer formed by blocking polyurethane with a blocking agent, from the viewpoint of better storage stability.

JP 2021-011525 A JP 2014-210900 A JP 2021-084936 A

However, when dissociating the blocking agent from the blocked isocyanate, there is a problem in that the heating temperature required for the deblocking reaction is high (for example, 170°C or higher in Patent Document 3, etc.). In addition, if the dissociation temperature of the blocking agent is lowered, there is a problem in that the blocking agent dissociates over time during storage of the blocked isocyanate composition, causing an increase in viscosity and a decrease in storage stability.

The present invention was made in consideration of the above problems, and aims to provide a blocked isocyanate composition that has excellent low-temperature reactivity, making it possible to deblock blocked isocyanates at lower temperatures, and also has excellent storage stability.

The inventors conducted extensive research to solve the above problems, and discovered that the combined use of a blocked isocyanate and a phosphorus compound with a specific structure facilitates the deblocking reaction of the blocked isocyanate at lower temperatures (hereinafter, this may be referred to as "excellent low-temperature reactivity") and improves the storage stability of the blocked isocyanate composition, leading to the present invention.

In other words, the present disclosure provides a blocked isocyanate composition that contains a phosphorus compound represented by the following formula (1) and a blocked isocyanate.

(In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represent an organic group having 1 to 20 carbon atoms,
The organic group is a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted heterocyclic ring-containing group, or a group in which one or more methylene groups in the hydrocarbon group or the heterocyclic ring-containing group are substituted with a divalent group selected from the following <Group A>:
X ^b− represents an anion having a valence of b, a represents an integer of 1 or more and 3 or less, and b represents an integer of 1 or more and 3 or less.
<Group A> is —O—, —CO—, —COO—, —OCO—, —NR ¹¹ —, —NR ¹¹ CO— and —S—;
R ¹¹ represents a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms.

The present disclosure also provides a resin composition that contains a phosphorus compound represented by the above formula (1), a blocked isocyanate, and a thermoplastic resin.

The present disclosure further provides a resin layer that is characterized by including a phosphorus compound represented by the above formula (1), a polyisocyanate compound or a urethane polyisocyanate compound, and a thermoplastic resin.

The present disclosure also provides a method for producing a resin layer, which is characterized by having a coating step of coating the above-mentioned resin composition, and a heating step of heating the coating film formed by the coating step.

According to the present disclosure, by containing a blocked isocyanate and a specific phosphorus compound, it is possible to provide a blocked isocyanate composition and a resin composition that have excellent low-temperature reactivity and storage stability. Furthermore, according to the resin layer and the method for producing a resin layer of the present disclosure, by using the blocked isocyanate composition or resin composition, it is possible to dissociate the blocking agent from the blocked isocyanate at a lower temperature and regenerate the isocyanate group, making it possible to form a resin layer that has excellent adhesion at a lower temperature.

1A is a schematic diagram of the evaluation test piece, and FIG. 1B is a cross-sectional view of the evaluation test piece along the line A-A'.

The present disclosure relates to a blocked isocyanate composition, a resin composition, a resin layer, and a method for producing a resin layer.
The present disclosure will be described in detail below.

A. Blocked Isocyanate Composition First, the blocked isocyanate composition of the present disclosure will be described.
The blocked isocyanate composition of the present disclosure is characterized by containing a phosphorus compound represented by the following formula (1) and a blocked isocyanate.

(In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represent an organic group having 1 to 20 carbon atoms,
The organic group is a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted heterocyclic ring-containing group, or a group in which one or more methylene groups in the hydrocarbon group or the heterocyclic ring-containing group are substituted with a divalent group selected from the following <Group A>:
X ^b− represents an anion having a valence of b, a represents an integer of 1 or more and 3 or less, and b represents an integer of 1 or more and 3 or less.
<Group A> is —O—, —CO—, —COO—, —OCO—, —NR ¹¹ —, —NR ¹¹ CO— and —S—;
R ¹¹ represents a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms.

The blocked isocyanate composition disclosed herein has excellent low-temperature reactivity and storage stability due to the combined use of a blocked isocyanate and a phosphorus compound represented by the above formula (1) (hereinafter, sometimes referred to as phosphorus compound 1).

The reason why the combined use of blocked isocyanate and phosphorus compound 1 results in excellent low-temperature reactivity and storage stability is not clear, but is presumed to be as follows.
Phosphorus Compound 1 has a structure in which an organic group is bonded to a phosphorus (P) atom as a cationic component, and thus has excellent nucleophilicity, which allows Phosphorus Compound 1 to exert excellent nucleophilic attack on the carbonyl group in the urethane bond formed by the reaction of the isocyanate group of the blocked isocyanate with the blocking agent.
In addition, the cationic component containing a phosphorus atom represented by the phosphorus compound 1 and the anionic component are a combination of weak Lewis acidity and weak Lewis basicity, and are highly ionic and easily dissociated into the two components. For this reason, the above-mentioned nucleophilic attack is easily exhibited.
As a result, compared to the case where the blocked isocyanate is used alone, the deblocking reaction can occur at a lower temperature, and the blocked isocyanate composition of the present disclosure has excellent low-temperature reactivity.
In addition, since the blocked isocyanate composition has excellent low-temperature reactivity, isocyanate groups are regenerated at a lower temperature. Therefore, when a resin layer or an adhesive layer to be used as a protective layer is formed using the blocked isocyanate composition or resin composition of the present disclosure, the layer can be formed at a lower temperature.
In addition, since the phosphorus compound 1 has a structure in which an organic group is bonded to a phosphorus (P) atom, the presence of the organic group makes it possible to adjust the van der Waals interaction between the cationic component and the anionic component, and the above-mentioned adjustment of ionicity becomes easy. This makes it easy to make the phosphorus compound 1 have a low melting point and high thermal stability. As a result, low-temperature dissociation of the blocking agent in the blocked isocyanate composition containing the phosphorus compound 1 is facilitated, and it is possible to suppress the deblocking reaction in the temperature range up to the desired reaction temperature, resulting in excellent storage stability.
For the above reasons, the blocked isocyanate composition of the present disclosure has excellent low-temperature reactivity and storage stability.

The components of the blocked isocyanate composition disclosed herein are described in detail below.

1. Phosphorus Compound 1
The phosphorus compound 1 is a phosphorus compound represented by the following formula (1).

(In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represent an organic group having 1 to 20 carbon atoms,
The organic group is a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted heterocyclic ring-containing group, or a group in which one or more methylene groups in the hydrocarbon group or the heterocyclic ring-containing group are substituted with a divalent group selected from the following <Group A>:
X ^b− represents an anion having a valence of b, a represents an integer of 1 or more and 3 or less, and b represents an integer of 1 or more and 3 or less.
<Group A> is —O—, —CO—, —COO—, —OCO—, —NR ¹¹ —, —NR ¹¹ CO— and —S—;
R ¹¹ represents a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms.

The organic groups used for the above R ¹ , R ² , R ³ and R ⁴ (hereinafter sometimes collectively referred to as R ¹ etc.) are groups having 1 to 20 carbon atoms.

Examples of the hydrocarbon group used as the organic group include an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and an aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms.

The aliphatic hydrocarbon group having 1 to 20 carbon atoms may be a hydrocarbon group that does not contain an aromatic hydrocarbon ring or a heterocycle, and examples of such groups include linear aliphatic hydrocarbon groups having 1 to 20 carbon atoms and aliphatic ring-containing groups having 3 to 20 carbon atoms.
Examples of the chain aliphatic hydrocarbon group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms and an alkenyl group having 2 to 20 carbon atoms.
Examples of the aliphatic ring-containing group having 3 to 20 carbon atoms include a cycloalkyl group having 3 to 20 carbon atoms and a cycloalkylalkyl group having 4 to 20 carbon atoms.

The alkyl group having 1 to 20 carbon atoms may be linear or branched. Examples of linear alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, and n-octadecyl. Examples of branched alkyl groups include iso-propyl, 2-butyl, tert-butyl, iso-butyl, iso-pentyl, tert-pentyl, 2-hexyl, 3-hexyl, 2-heptyl, 3-heptyl, iso-heptyl, tert-heptyl, iso-octyl, tert-octyl, and 2-ethylhexyl groups.

The alkenyl group having 2 to 20 carbon atoms may be linear or branched. It may also be a terminal alkenyl group having an unsaturated bond at the end, or an internal alkenyl group having an unsaturated bond inside. Examples of terminal alkenyl groups include vinyl groups, allyl groups, 2-methyl-2-propenyl groups, 3-butenyl groups, 4-pentenyl groups, and 5-hexenyl groups. Examples of internal alkenyl groups include 2-butenyl groups, 3-pentenyl groups, 2-hexenyl groups, 3-hexenyl groups, 2-heptenyl groups, 3-heptenyl groups, 4-heptenyl groups, 3-octenyl groups, 3-nonenyl groups, 4-decenyl groups, 3-undecenyl groups, 4-dodecenyl groups, and 4,8,12-tetradecatrienyl allyl groups.

The above-mentioned cycloalkyl group having 3 to 20 carbon atoms includes a saturated monocyclic alkyl group having 3 to 20 carbon atoms, a saturated polycyclic alkyl group having 3 to 20 carbon atoms, and a group having 4 to 20 carbon atoms in which one or more hydrogen atoms in the ring of these groups are replaced with an alkyl group. Examples of the saturated monocyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, and a cyclodecyl group. Examples of the saturated polycyclic alkyl group include an adamantyl group, a decahydronaphthyl group, an octahydropentalene group, and a bicyclo[1.1.1]pentanyl group. Examples of the alkyl group replacing a hydrogen atom in the ring of a saturated monocyclic or saturated polycyclic alkyl group include the groups exemplified above as the alkyl group having 1 to 20 carbon atoms. Examples of the group in which one or more hydrogen atoms in the ring of a saturated polycyclic alkyl group are replaced with an alkyl group include a bornyl group.

The cycloalkylalkyl group having 4 to 20 carbon atoms means a group having 4 to 20 carbon atoms in which a hydrogen atom of an alkyl group is replaced with a cycloalkyl group. The cycloalkyl group in the cycloalkylalkyl group may be monocyclic or polycyclic. Examples of cycloalkylalkyl groups having 4 to 20 carbon atoms and a monocyclic cycloalkyl group include cyclopropylmethyl group, 2-cyclobutylethyl group, 3-cyclopentylpropyl group, 4-cyclohexylbutyl group, cycloheptylmethyl group, cyclooctylmethyl group, 2-cyclononylethyl group, and 2-cyclodecylethyl group. Examples of cycloalkylalkyl groups having 4 to 20 carbon atoms and a polycyclic cycloalkyl group include 3-3-adamantylpropyl group, and decahydronaphthylpropyl group.

The aromatic hydrocarbon ring-containing group having from 6 to 20 carbon atoms is a hydrocarbon group that contains an aromatic hydrocarbon ring and does not contain a heterocycle, and may contain an aliphatic hydrocarbon group.
Examples of such aromatic hydrocarbon ring-containing groups include aryl groups having 6 to 20 carbon atoms, and arylalkyl groups having 7 to 20 carbon atoms.

The aryl group having 6 to 20 carbon atoms may have a monocyclic structure, a condensed ring structure, or a structure in which two aromatic hydrocarbon rings are linked together.
The aryl group in which two aromatic hydrocarbon rings are linked may be one in which two aromatic hydrocarbon rings of a monocyclic structure are linked, one in which an aromatic hydrocarbon ring of a monocyclic structure is linked to an aromatic hydrocarbon ring of a fused ring structure, or one in which an aromatic hydrocarbon ring of a fused ring structure is linked to an aromatic hydrocarbon ring of a fused ring structure.
The linking group linking two aromatic hydrocarbon rings may be any group capable of making the aryl group as a whole aromatic, and examples thereof include a single bond. Examples of aryl groups having a single ring structure include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, and a 2,4,6-trimethylphenyl group. Examples of aryl groups having a condensed ring structure include a naphthyl group, an anthracenyl group, a phenanthryl group, and a pyrenyl group. Examples of aryl groups in which two aromatic hydrocarbon rings having a single ring structure are linked include a biphenyl group, a diphenyl sulfide group, and a benzoylphenyl group.

The above arylalkyl group having 7 to 20 carbon atoms means a group in which one or more hydrogen atoms in an alkyl group are substituted with an aryl group. Examples of arylalkyl groups having 7 to 20 carbon atoms include benzyl, fluorenyl, indenyl, 9-fluorenylmethyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl, and naphthylpropyl groups.

The heterocyclic ring-containing group used as the organic group includes a heterocyclic group having 2 to 20 carbon atoms, and a hydrocarbon group having 3 to 20 carbon atoms in which one or more hydrogen atoms are substituted with the heterocyclic group.

Heterocyclic groups include pyridyl, quinolyl, thiazolyl, tetrahydrofuran, dioxolanyl, tetrahydropyranyl, morpholylfuran, methylthiophene, hexylthiophene, benzothiophene, pyrrole, pyrrolidine, imidazole, imidazolidine, imidazoline, pyrazole, pyrazolidine, piperidine, piperazine, pyrimidyl, furyl, thienyl, benzoxazol-2-yl, thiazole, isothiazole, oxazole, isoxazole, and morpholinyl groups.

The group containing a heterocycle may be one in which a heterocycle is linked to an aromatic hydrocarbon ring of a monocyclic structure, or one in which a heterocycle is linked to an aromatic hydrocarbon ring of a condensed ring structure. Examples of the linking group linking two aromatic hydrocarbon rings include a single bond and a carbonyl group. Examples of the group containing a heterocycle in which a heterocycle is linked to an aromatic hydrocarbon ring of a monocyclic structure include a benzothiophene group.

In the present disclosure, a substituted hydrocarbon group refers to a group in which a hydrogen atom in a hydrocarbon group is substituted with a substituent, and a substituted heterocycle-containing group refers to a group in which a hydrogen atom in a heterocycle-containing group is substituted with a substituent.
Examples of the substituent that substitutes a hydrogen atom in such a hydrocarbon group or a group containing a heterocycle include a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, and a carboxyl group.

A group in which one or more methylene groups in a hydrocarbon group or a group containing a heterocycle are substituted with a divalent group selected from group A above does not have a structure in which multiple divalent groups are adjacent to each other. The multiple divalent groups may be the same or different.

In the present disclosure, the number of carbon atoms in a group specifies the number of carbon atoms in the group after the substitution when a hydrogen atom in the group is substituted with a substituent. For example, in the case of "a group in which a hydrogen atom of an alkyl group having 1 to 20 carbon atoms is substituted with a substituent", the number of carbon atoms in the group is 1 to 20, and does not refer to the number of carbon atoms in the alkyl group before the hydrogen atom is substituted.
In the present disclosure, the number of carbon atoms in a group in which a methylene group in a group having a certain number of carbon atoms is replaced with a divalent group refers to the number of carbon atoms in the group after the replacement. For example, in the case of "a group in which a methylene group in an alkyl group having 1 to 20 carbon atoms is replaced with a divalent group", the number of carbon atoms in the alkyl group after the methylene group is replaced with the divalent group, and does not refer to the number of carbon atoms in the alkyl group before the replacement.

In the present disclosure, the type of organic group represented by R ¹ , R ² , R ³ and R ⁴ is preferably a substituted or unsubstituted hydrocarbon group or a group in which one or more methylene groups in the hydrocarbon group are substituted with a divalent group selected from the following <Group A>, more preferably a substituted or unsubstituted hydrocarbon group, and even more preferably an unsubstituted hydrocarbon group, because the blocked isocyanate composition is superior in low-temperature dissociation property of the blocking agent and storage stability.
In the present disclosure, the hydrocarbon group used as the organic group in R ¹ , R ² , R ³ and R ⁴ is preferably an aliphatic hydrocarbon group, more preferably a chain aliphatic hydrocarbon group, and even more preferably an alkyl group, because the blocked isocyanate composition has better low-temperature reactivity and storage stability.

In the present disclosure, the number of carbon atoms in the organic groups represented by R ¹ , R ² , R ³ , and R ⁴ is preferably independently from 1 to 18, more preferably from 2 to 16, and even more preferably from 3 to 13. This is because the blocked isocyanate composition has better low-temperature reactivity and storage stability.
However, since the preferred range of the number of carbon atoms in the organic group varies depending on the type of X ^b- described below, the preferred range of the number of carbon atoms in the organic group depending on the type of X ^b- will be explained below.

When the X ^b- is a phosphate anion having a phosphate ester structure, a thioether anion, an azolate anion, or the like, the number of carbon atoms in the organic groups used in the R ¹ , R ² , R ³ and R ⁴ is preferably 1 to 12, more preferably 1 to 6. This is because the blocked isocyanate composition has better low-temperature reactivity and storage stability. In particular, the number of carbon atoms in the organic group used in the R ¹ is preferably 1 to 5, more preferably 2 to 4, and even more preferably 3 to 4. This is because the blocked isocyanate composition has better low-temperature reactivity and storage stability when the number of carbon atoms is within the above range.

In the present disclosure, when X ^b- described later is a halogen-based anion, a phosphate-based anion not having a phosphate ester structure, a borate-based anion, a carbonate-based anion, or the like, the number of carbon atoms in the organic group used in R ¹ is preferably 6 or more and 13 or less, more preferably 7 or more and 13 or less, and even more preferably 8 or more and 12 or less. When the number of carbon atoms is within the above range, the blocked isocyanate composition has better low-temperature reactivity and storage stability.

In the present disclosure, when the X ^b- is a phosphate anion, a thioether anion, an azolate anion, a halogen anion, a borate anion, a carbonate anion, or the like, the number of carbon atoms in the organic groups used in the R ² , R ^{3 ,} and R ⁴ is preferably 1 to 5, more preferably 2 to 4, and even more preferably 3 to 4. It is also preferable that R ² , R ^{3 ,} and R ⁴ are all the same group. This is because the blocked isocyanate composition has better low-temperature reactivity and storage stability.

In the present disclosure, the a is an integer of 1 or more and 3 or less, more preferably an integer of 1 or more and 2 or less, and most preferably 1. This is because the blocked isocyanate composition has excellent low-temperature reactivity and storage stability.

In the present disclosure, the above X ^b− represents an anion having a valence of b.
The above b is an integer of 1 or more and 3 or less, more preferably an integer of 1 or more and 2 or less, and most preferably 1. This is because the blocked isocyanate composition has better low-temperature reactivity and storage stability.
Examples of such anions include hydroxide anions; alkoxide anions; halogen anions such as halide anions, perhalide anions, and pseudohalide anions; sulfate anions such as sulfate anion, sulfite anion, sulfonate anion, and sulfonimide anion; phosphate anions such as phosphate anion, phosphite anion, phosphonate anion, and phosphinate anion; borate anions such as tetrafluoroborate anion; carbonate anions; thiophosphate anion, thiocarboxylate anion, and thio Examples of anions include thioether anions such as carbamate anion, thiocarbonate anion, xanthate anion, thiosulfonate anion, and thiosulfate anion; azolate anions such as imidazolate anion, triazolate anion, and tetrazolate anion; methide anion, carboxylate anion, carbamate anion, nitrate anion, nitrite anion, hexafluorophosphate anion, perchlorate anion, halometallates, amino acids, and polyfluoroalkoxyaluminates.

In the present disclosure, the above X ^b- is preferably a halogen-based anion, a phosphate-based anion, a borate-based anion, a carbonate-based anion, a thioether-based anion, an azolate-based anion, or the like, more preferably a halogen-based anion, a phosphate-based anion, a thioether-based anion, or an azolate-based anion, even more preferably a phosphate-based anion, a thioether-based anion, or an azolate-based anion, and most preferably a phosphate-based anion or a thioether-based anion, because the blocked isocyanate composition has superior low-temperature reactivity and storage stability.

In the present disclosure, the halogen-based anion used for X ^b- is preferably a halide anion or a perhalide anion, and more preferably a halide anion, because the blocked isocyanate composition is superior in low-temperature dissociation property of the blocking agent and storage stability.
In the present disclosure, the phosphate anion used for X ^b- is preferably a phosphate anion or a phosphite anion, and more preferably a phosphate anion, because the blocked isocyanate composition has better low-temperature reactivity and storage stability.
In the present disclosure, the thioether anion used for X ^b- is preferably a thiophosphate anion, a thiocarboxylate anion, a thiocarbamate anion, or a thiocarbonate anion, and more preferably a thiophosphate anion, because the blocked isocyanate composition has better low-temperature reactivity and storage stability.
In the present disclosure, the azolate anion used for X ^b- is preferably an imidazolate anion or a triazolate anion, and more preferably a triazolate anion, because the blocked isocyanate composition has better low-temperature reactivity and storage stability.

Specific examples of the above-mentioned anions include those described in JP-A-2021-528490.
For example, the alkoxide anion may be an alkoxide anion, an aryloxide anion, or the like, which is represented by R ^a O ^- .
Examples of halide anions include F ⁻ , Cl ⁻ , Br ⁻ , and I ⁻ .
Examples of perhalide anions include I ₃ ^- , I ₂ Br ^- , IBr ₂ ^- , Br ₃ ^- , Br ₂ Cl ^- , BrCl ₂ ^- , ICl ₂ ^- , I ₂ Cl ^- , Cl ₃ ^{- ,} and the like.
Examples of pseudohalide anions include N ₃ --, NCS ^-- , NCSe ^-- , NCO ^-- , and CN ^-- .
Examples of sulfate anions include HSO ₄ ⁻ , SO ₄ ²⁻ , and R ^a OSO ₂ O ⁻ .
Examples of sulfite anions include HSO ₃ ⁻ , SO ₃ ²⁻ , and R ^a OSO ²⁻ .
The sulfonate anion includes, for example, R ^a SO ₂ O ^— .
The sulfonimide anion may, for example, be (R ^a SO ₂ ) ₂ N ^— .
Examples of phosphate anions include H ₂ PO ₄ ^-- , HPO ₄ ^2- , PO ₄ ^3- , (R ^a O)PO ₃ ^2- , (R ^a O) ₂ PO ₂ ^-- , and the like.
Examples of the phosphite anion include H ₂ PO ₃ ⁻ , HPO ₃ ²⁻ , R ^a OPO ₂ ²⁻ , (R ^a O) ₂ PO ⁻ , and the like.
Examples of the phosphonate anion include R ^a PO ₃ ^2- , R ^a P(O)(OR ^b )O ^- , and the like.
The phosphinate anion includes R ^a R ^b P(O)O 2 ^- and the like.
Examples of borate anions include _BO33- , ^{HBO32- ,} _{H2BO3- , RaBO3-} ^, _RaHBO3- ^, _RaBO32- , ^B ( ^{ORa ) 4-} , _B ( _HSO4 ) ^- , B( _RaSO4 ) ^{- , and} _the ^{like .}
Examples of carbonate anions include CO ₃ ^2- , HCO ₃ ^- , and R ^a CO ₃ ^- (more specifically, MeCO ₃ ^- ).
The thiocarbonate anion includes, for example, R ^a OCS ^2- .
An example of the thiocarbamate anion is R ^a 2NCS ²⁻ .
An example of the thiocarboxylate anion is R ^a CS ^2- .
Examples of thiophosphate anions include HPSO ³⁻ , HPSO ₃ ²⁻ , PSO ₃ ³⁻ , (R ^a O)PSO ₂ ²⁻ , (R ^a O) ₂ PSO ⁻ , (R ^a O) PS ₂ O ²⁻ , (R ^a O) ₂ PS ₂₋ ^, and the like.
An example of the thiosulfonate anion is R ^a S(O)2S ⁻ .
The thiosulfate anion includes, for example, R ^a OS(O)2S ⁻ .
Examples of the azolate anion include 3,5-dinitro-1,2,4-triazolate, 4-nitro-1,2,3-triazolate, and a benzotriazole anion represented by the following general formula (10).
Imidazolate anions include, for example, 2,4-dinitroimidazolate, 4,5-dinitroimidazolate, 4,5-dicyano-imidazolate, 4-nitroimidazolate, and the like.
In the above formula, R ^a and R ^b can each independently be the same groups as those exemplified as the organic groups having 1 to 20 carbon atoms used for R ¹ and the like.

In the present disclosure, the phosphate anion used in X ^b- is preferably H ₂ PO ₄ ^- , HPO ₄ ^2- , or PO ₄ ^3- , and more preferably H ₂ PO ₄ ^- , because the composition has better low-temperature reactivity and stability.
The phosphate anion used in X ^b- preferably contains a phosphate ester structure ((P═O)—(OR ^a )), more preferably (R ^a O)PO ₃ ²⁻ or (R ^a O) ₂ PO ₂ ^— , and even more preferably (R ^a O) ₂ PO ₂ ^— . This is because the composition has better low-temperature reactivity and storage stability, and in particular has better storage stability.
In the present disclosure, the phosphite anion used in X ^b- is preferably H ₂ PO ₃ ^- or HPO ₃ ^2- , and more preferably H ₂ PO ₃ ^{- ,} because the blocked isocyanate composition has better low-temperature reactivity and storage stability.
In the present disclosure, the halide anion used for X ^b- is preferably F ^- , Cl ^- , Br ^- , or I ^-, and more preferably Br ^- or I ^- , because the blocked isocyanate composition has better low-temperature reactivity and storage stability.
In the present disclosure, the boric acid anion used for X ^b- is preferably BO ₃ ^3- , HBO ₃ ^2- , or H ₂ BO ₃ ^- , and more preferably H ₂ BO ₃ ^- , because the blocked isocyanate composition has better low-temperature reactivity and storage stability.
In the present disclosure, the carbonate anion used for X ^b- is preferably R ^a CO ₃ ^— , and R ^a is more preferably an alkyl group having 1 to 5 carbon atoms, because the blocked isocyanate composition has better low-temperature reactivity and storage stability.
In the present disclosure, the thiophosphate anion used in X ^b- is preferably a thiophosphate anion having a phosphate ester structure ((P═O)—(OR ^a )), more preferably (R ^a O)PSO ₂ ²⁻ , (R ^a O) _2PSO ⁻ , (R ^a O)PS _{2 O} ²⁻ or (R ^a O) _2PS ²⁻ , even more preferably (R ^a _O ) _2PSO ⁻ or (R ^a O) 2PS ₂₋ , still more preferably (R ^a O ^{) 2PS 2−} _, ^and most preferably R ^a is _an alkyl group having from 1 to 5 carbon atoms. This is because the blocked isocyanate composition has superior low-temperature reactivity and storage stability.
In the present disclosure, the azolate anion used for X ^b- is preferably a benzotriazole anion represented by the following general formula (10), R ^c is more preferably a hydrogen atom or a hydrocarbon group having from 1 to 20 carbon atoms, R ^c is even more preferably a hydrogen atom or an alkyl group having from 1 to 10 carbon atoms, and R ^c is most preferably a hydrogen atom, because the blocked isocyanate composition has better low-temperature reactivity and storage stability.

(In the formula, R ^c can be independently a hydrogen atom or the same groups as those exemplified as the organic groups having 1 to 20 carbon atoms used for R ¹ etc.)

Specific examples of such phosphorus compounds 1 include tetraethyl phosphonium hydroxide, tetrabutyl phosphonium chloride, hexadecyl tributyl phosphonium chloride, dodecyl tributyl phosphonium chloride, tributyl tetradecyl phosphonium chloride, trihexyl tetradecyl phosphonium chloride, tetraethyl phosphonium bromide, tetrabutyl phosphonium bromide, tributyl hexadecyl phosphonium bromide, triethyl pentyl phosphonium bromide, triethyl octyl phosphonium bromide, ethyl trioctyl phosphonium bromide, trihexyl tetradecyl phosphonium bromide, tributyl-n-octyl phosphonium bromide, tetra-n-octyl phosphonium bromide, tributyl ethyl phosphonium bromide, tributyl hexyl phosphonium bromide, tributyl octyl phosphonium bromide, tributyl decyl phosphonium bromide, tributyl dodecyl phosphonium bromide, tributyl methyl ... iodide, ethyl triphenylphosphonium iodide, tributyl ethyl phosphonium diethyl phosphate, tributyl (methyl) phosphonium dimethyl phosphate, trihexyl tetradecyl phosphonium bis (2-ethylhexyl) phosphate, tetrabutyl phosphonium hexafluorophosphate, tributyl hexyl phosphonium hexafluorophosphate, tributyl ethyl phosphonium hexafluorophosphate, trihexyl tetradecyl phosphonium hexafluorophosphate, trihexyl tetradecyl phosphonium bis (2,4,4-trimethylpentyl) phosphate, tetrabutyl phosphonium o,o-diethyl phosphorodithioate, tetrabutyl phosphonium tetrafluoroborate, tributyl ethyl phosphonium tetrafluoroborate, tributyl hexyl phosphonium tetrafluoroborate, tetrabutyl phosphonium tetraphenylborate, triisobutyl methyl phosphonium tosylate, tributyl tetradecyl phosphonium nium dodecylbenzenesulfonate, tributylmethylphosphonium methylsulfonate, tributyltetradecylphosphonium methanesulfonate, trihexyltetradecylphosphonium decanoate, tributylmethoxyethylphosphonium bis(fluoromethanesulfonyl)imide, triethylmethoxymethylphosphonium bis(fluoromethanesulfonyl)imide, tributylmethylphosphonium bis(fluoromethanesulfonyl)imide, trihexyl(tetradecyl)phosphonium bis(fluoromethanesulfonyl)imide, triethyloctylphosphonium bis(fluoromethanesulfonyl)imide, triethylpentylphosphonium bis(fluoromethanesulfonyl)imide, tributylhexylphosphonium bis(fluoromethanesulfonyl)imide, tetrabutylphosphonium bis(fluoromethanesulfonyl)imide, tributylethylphosphonium bis(fluoromethanesulfonyl)imide, tributylmethoxyethylphosphonium bis(trifluoromethanesulfonyl)imide tansulfonyl)imide, triethylmethoxymethylphosphonium bis(trifluoromethanesulfonyl)imide, tributylmethylphosphonium bis(trifluoromethanesulfonyl)imide, trihexyl(tetradecyl)phosphonium bis(trifluoromethanesulfonyl)imide, triethyloctylphosphonium bis(trifluoromethanesulfonyl)imide, triethylpentylphosphonium bis(trifluoromethanesulfonyl)imide, tributylhexylphosphonium bis(trifluoromethanesulfonyl)imide, tetrabutylphosphonium bis(trifluoromethanesulfonyl)imide, tributylethylphosphonium bis(trifluoromethanesulfonyl)imide, trihexyltetradecylphosphonium dicyanamide, tributylmethylphosphonium methylcarbonate, trioctylmethylphosphonium methylcarbonate, trihexyltetradecylphosphonium tricyanomethanide, tetrabutylphosphonium benzotriazolate, etc.

The content of the phosphorus compound 1 is preferably 0.05 parts by mass or more and 10 parts by mass or less, more preferably 0.2 parts by mass or more and 5 parts by mass or less, and even more preferably 0.5 parts by mass or more and 3 parts by mass or less, per 100 parts by mass of the blocked isocyanate composition. This is because the blocked isocyanate composition has superior low-temperature reactivity and storage stability.

The content of the phosphorus compound 1 is preferably 0.1 parts by mass or more and 15 parts by mass or less, more preferably 1 part by mass or more and 10 parts by mass or less, and even more preferably 2 parts by mass or more and 5 parts by mass or less, per 100 parts by mass of the total of the phosphorus compound 1 and the blocked isocyanate. This is because the blocked isocyanate composition has superior low-temperature reactivity and storage stability.

2. Blocked Isocyanate As the blocked isocyanate used in the present disclosure, a compound having a structure in which an isocyanate group has reacted with a blocking agent can be used.
Examples of such blocked isocyanates include blocked polyisocyanate compounds, which are compounds obtained by reacting an isocyanate group contained in a polyisocyanate compound with a blocking agent, and blocked urethane polyisocyanate compounds, which are compounds obtained by reacting an isocyanate group contained in a urethane polyisocyanate compound obtained by reacting a polyisocyanate compound with a polyol compound with a blocking agent.
In the present disclosure, the blocked isocyanate preferably contains a blocked polyisocyanate compound, because the blocked isocyanate composition has superior low-temperature reactivity and storage stability.

The polyisocyanate compounds mentioned above do not contain urethane bonds formed by the reaction of an isocyanate group with a hydroxyl group, and examples of such compounds include aromatic diisocyanate compounds such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate; linear aliphatic diisocyanate compounds such as hexamethylene diisocyanate and lysine diisocyanate; and alicyclic structure-containing diisocyanate compounds such as cyclohexane diisocyanate, isophorone diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate. In addition, isocyanurate compounds obtained by trimerizing diisocyanate compounds such as the aromatic diisocyanate compounds, linear aliphatic diisocyanate compounds, and alicyclic structure-containing diisocyanate compounds can also be used.

In the present disclosure, the polyisocyanate compound preferably contains the isocyanurate compound, because the blocked isocyanate composition has better low-temperature reactivity and storage stability.
In the present disclosure, the polyisocyanate compound preferably contains an aromatic diisocyanate compound or an alicyclic structure-containing diisocyanate compound or an isocyanurate compound thereof, more preferably contains an aromatic diisocyanate compound or an isocyanurate compound thereof, even more preferably contains an isocyanurate compound of an aromatic diisocyanate compound, and most preferably contains an isocyanurate compound of tolylene diisocyanate, because the blocked isocyanate composition has superior low-temperature reactivity and storage stability.

In the present disclosure, a known method can be used as a method for synthesizing an isocyanurate compound by trimerizing a diisocyanate compound. For example, the method described in WO 2021/106963 can be mentioned as such a method.

As the polyol compound, a compound having two or more hydroxyl groups in the molecule can be used, and examples thereof include polyether polyol, polyester polyol, polycarbonate polyol, polyester amide polyol, acrylic polyol, polyurethane polyol, and the like.
The polyol compound may contain only one type of compound, or may contain two or more types of compounds.
Such polyol compounds can be similar to those described in, for example, Japanese Patent Publication No. 5322912, International Publication No. 2021/106963, and the like.

Examples of the blocking agent include active methylene compounds such as malonic acid diesters (diethyl malonate, etc.), acetylacetone, and acetoacetate esters (ethyl acetoacetate, etc.); oxime compounds such as acetoxime, methyl ethyl ketoxime (MEK oxime), and methyl isobutyl ketoxime (MIBK oxime); monohydric alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, heptyl alcohol, hexyl alcohol, octyl alcohol, 2-ethylhexyl alcohol, isononyl alcohol, and stearyl alcohol, and isomers thereof; methyl glycol, ethyl glycol glycol derivatives such as chol, ethyl diglycol, ethyl triglycol, butyl glycol, and butyl diglycol; amine compounds such as dicyclohexylamine; monophenols such as phenol, cresol, ethylphenol, n-propylphenol, isopropylphenol, butylphenol, tertiary butylphenol, octylphenol, nonylphenol, dodecylphenol, cyclohexylphenol, chlorophenol, and bromophenol; phenols such as resorcinol, catechol, hydroquinone, bisphenol A, bisphenol S, bisphenol F, and naphthol;
Examples include ε-caprolactone and ε-caprolactam.
In the present disclosure, the blocking agent is preferably a phenol, more preferably a monophenol, even more preferably phenol, cresol, ethylphenol, n-propylphenol, isopropylphenol, butylphenol, or tertiary butylphenol, and most preferably phenol or cresol, because the blocked isocyanate composition has superior low-temperature reactivity and storage stability.

As a method of reacting an isocyanate group contained in the polyisocyanate with a blocking agent, and a method of reacting an isocyanate group contained in the polyurethane polyisocyanate with a blocking agent, known reaction methods can be used.
In the above reaction, the amount of blocking agent added, the reaction temperature, etc. can be the same as those described in Japanese Patent Publication No. 5322912, International Publication No. 2021/106963, etc.

The content of the blocked isocyanate in 100 parts by mass of the blocked isocyanate composition is preferably 60 parts by mass or more, more preferably 80 parts by mass or more and 99.9 parts by mass or less, even more preferably 90 parts by mass or more and 99.8 parts by mass or less, even more preferably 95 parts by mass or more and 99.5 parts by mass or less, and most preferably 96 parts by mass or more and 99.3 parts by mass or less, because the blocked isocyanate composition has superior low-temperature dissociation properties and storage stability of the blocking agent.
When the blocked isocyanate composition contains a plasticizer, the content of the blocked isocyanate is preferably 5 parts by mass or more, more preferably 10 parts by mass or more and 70 parts by mass or less, even more preferably 15 parts by mass or more and 50 parts by mass or less, still more preferably 20 parts by mass or more and 40 parts by mass or less, and most preferably 25 parts by mass or more and 30 parts by mass or less, per 100 parts by mass of the blocked isocyanate composition, because the blocked isocyanate composition has superior low-temperature reactivity and storage stability.

The total content of the phosphorus compound 1 and the blocked isocyanate is preferably 60 parts by mass or more, more preferably 80 parts by mass or more, even more preferably 90 parts by mass or more, and most preferably 95 parts by mass or more, per 100 parts by mass of the blocked isocyanate composition, because the blocked isocyanate composition has superior low-temperature reactivity and storage stability.
When the blocked isocyanate composition contains a plasticizer, the total content of the phosphorus compound 1 and the blocked isocyanate is preferably 5 parts by mass or more, more preferably 10 parts by mass or more and 70 parts by mass or less, even more preferably 15 parts by mass or more and 50 parts by mass or less, still more preferably 20 parts by mass or more and 40 parts by mass or less, and most preferably 25 parts by mass or more and 35 parts by mass or less, per 100 parts by mass of the blocked isocyanate composition, because the blocked isocyanate composition has superior low-temperature reactivity and storage stability.

3. Plasticizer The blocked isocyanate composition of the present disclosure contains the above-mentioned blocked isocyanate and phosphorus compound 1, but preferably contains a plasticizer. This is because, when the blocked isocyanate composition is used by blending with a thermoplastic resin, for example, blending with the thermoplastic resin becomes easier.
Here, the plasticizer may be any that can plasticize a thermoplastic resin when the composition of the present disclosure is used in combination with the thermoplastic resin.
The thermoplastic resin may be the same as that described in the section "B. Resin composition" below, and therefore a detailed description thereof will be omitted here.

Examples of such plasticizers include benzoate esters such as diethylene glycol dibenzoate; phthalate esters such as dibutyl phthalate (DBP), di-2-ethylhexyl phthalate (DOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), diundecyl phthalate (DUP), and ditridecyl phthalate (DTDP); terephthalate esters such as bis(2-ethylhexyl) terephthalate (DOTP); isophthalate esters such as bis(2-ethylhexyl) isophthalate (DOIP); pyromellitic acid esters such as tetra-2-ethylhexyl pyromellitic acid (TOPM); di-2-ethylhexyl adipate (DOA), diisononyl adipate (DINA), diisodecyl adipate (DIDA), di-2-ethylhexyl sebacate (DOS), and sebacic acid esters such as tetra-2-ethylhexyl pyromellitic acid (TOPM). Examples of such fatty acid esters include aliphatic dibasic acid esters such as diisononyl phosphate (DINS); phosphate esters such as tri-2-ethylhexyl phosphate (TOP) and tricresyl phosphate (TCP); alkyl esters of polyhydric alcohols such as pentaerythritol; polyesters having a molecular weight of 800 to 4,000 synthesized by polyesterification of a dibasic acid such as adipic acid with a glycol; epoxidized esters such as epoxidized soybean oil and epoxidized linseed oil; alicyclic dibasic acids such as diisononyl hexahydrophthalate; fatty acid glycol esters such as 1,4-butanediol dicaprate; acetyl tributyl citrate (ATBC); chlorinated paraffin obtained by chlorinating paraffin wax or n-paraffin; chlorinated fatty acid esters such as chlorinated stearic acid ester; and higher fatty acid esters such as butyl oleate.
In the present disclosure, the plasticizer preferably contains a phthalate ester, and more preferably contains diisononyl phthalate (DINP) or diisodecyl phthalate (DIDP). This is because the blocked isocyanate composition has excellent compatibility with thermoplastic resins. As a result, when mixed with the thermoplastic resin, each component of the blocked isocyanate composition can be uniformly dispersed in the thermoplastic resin, and the reactivity of the isocyanate group after the blocking agent is dissociated is excellent.

The content of the plasticizer is preferably within a range of 20 parts by mass or more and 90 parts by mass or less, more preferably 35 parts by mass or more and 85 parts by mass or less, and even more preferably 50 parts by mass or more and 80 parts by mass or less, per 100 parts by mass of the blocked isocyanate composition. This is because the blocked isocyanate composition has superior low-temperature reactivity and storage stability. In addition, the blocked isocyanate composition has superior compatibility with thermoplastic resins.

4. Isocyanate Curing Catalyst The blocked isocyanate composition of the present disclosure contains the above-mentioned blocked isocyanate and phosphorus compound 1, but preferably contains an isocyanate curing catalyst that promotes the reaction between an isocyanate group generated by dissociation of a blocking agent from the blocked isocyanate and an active hydrogen group. This is because the blocked isocyanate composition has excellent reactivity of the isocyanate group after dissociation of the blocking agent.

Examples of active hydrogen groups include hydroxyl groups, phenol groups, amino groups, imino groups, carboxyl groups, urethane groups, thiol groups, and sulfonic acid groups.

The isocyanate curing catalyst includes an amine catalyst, an organometallic catalyst, and the like.
In the present disclosure, the isocyanate curing catalyst preferably contains an organometallic catalyst, because the blocked isocyanate composition has excellent reactivity of the isocyanate group after the blocking agent is dissociated.
The isocyanate curing catalyst may contain only one type, or may contain two or more types in combination.

Examples of the organometallic catalyst include stannous diacetate, stannous dioctoate, stannous dioleate, stannous dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dioctyltin dilaurate, lead octoate, lead naphthenate, nickel naphthenate, and cobalt naphthenate.
In the present disclosure, the organometallic catalyst preferably contains a tin-containing compound such as dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dioctyltin dilaurate, etc., and more preferably contains dibutyltin dilaurate, dioctyltin dilaurate, etc. This is because the blocked isocyanate composition has excellent reactivity of the isocyanate group after the blocking agent is dissociated.

As the amine catalyst, for example, those described as catalysts used in synthesizing polyurethane resins in Japanese Patent No. 6,806,488 can be used.

The content of the isocyanate curing catalyst is preferably 0.01 parts by mass or more and 5 parts by mass or less, and more preferably 0.05 parts by mass or more and 2 parts by mass or less, per 100 parts by mass of the blocked isocyanate composition. This is because the blocked isocyanate composition has excellent reactivity of the isocyanate group after the blocking agent is dissociated.

The content of the isocyanate curing catalyst is preferably 0.0001 parts by mass or more and 10 parts by mass or less, more preferably 0.01 parts by mass or more and 6 parts by mass or less, even more preferably 0.10 parts by mass or more and 5 parts by mass or less, and even more preferably 0.20 parts by mass or more and 4 parts by mass or less, relative to 100 parts by mass of the blocked isocyanate. This is because the blocked isocyanate composition has excellent reactivity of the isocyanate group after deblocking.

5. Epoxy Compound The blocked isocyanate composition may contain an epoxy compound.
As such an epoxy compound, for example, the epoxy resin described in WO 2021/106963 can be used.
Specifically, polyglycidyl ether compounds of mononuclear polyhydric phenol compounds, polyglycidyl ether compounds of polynuclear polyhydric phenol compounds, polyglycidyl ether compounds of polyhydric alcohol compounds, glycidyl ester compounds of aliphatic polybasic acids, glycidyl ester compounds of aromatic polybasic acids, glycidyl ester compounds of alicyclic polybasic acids, homopolymers or copolymers of glycidyl methacrylate, epoxy compounds having glycidyl amino groups, epoxidized products of cyclic olefin compounds, epoxidized conjugated diene polymers, and heterocyclic epoxy compounds can be mentioned. These epoxy compounds may be internally crosslinked with a prepolymer of terminal isocyanate, or may be polymerized with a polyvalent active hydrogen compound (polyhydric phenol, polyamine, carbonyl group-containing compound, polyphosphate ester, etc.).

In the present disclosure, the content of the epoxy compound is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 25 parts by mass or less, in 100 parts by mass of the blocked isocyanate composition. In addition, the content of the epoxy compound is preferably 10 parts by mass or more, and more preferably 15 parts by mass or more, in 100 parts by mass of the blocked isocyanate composition. This is because the blocked isocyanate composition has superior low-temperature reactivity and storage stability.

6. Other Components The blocked isocyanate composition of the present disclosure may contain other components as necessary in addition to the above-mentioned phosphorus compound 1, blocked isocyanate, isocyanate curing catalyst, plasticizer, and epoxy compound.
Such other components include fillers, colorants, antioxidants, foaming agents, diluents, ultraviolet absorbing agents, and the like.

As the filler, either an inorganic filler or an organic filler can be used.
Examples of the inorganic filler include silicas such as fused silica, fused spherical silica, crystalline silica, colloidal silica, fumed silica, and silica gel; metal oxides such as alumina, iron oxide, and antimony trioxide; ceramics such as silicon nitride, aluminum nitride, boron nitride, and silicon carbide; minerals such as mica and montmorillonite; metal hydroxides such as aluminum hydroxide and magnesium hydroxide, or those modified by organic modification treatment or the like; metal carbonates such as calcium carbonate, calcium silicate, magnesium carbonate, and barium carbonate, or those modified by organic modification treatment or the like; metal borates, pigments such as carbon black, and the like; carbon fiber, graphite, whiskers, kaolin, talc, glass fiber, glass beads, glass microspheres, silica glass, layered clay minerals, clay, silicon carbide, quartz, aluminum, and zinc.
Examples of the organic filler include acrylic beads, polymer fine particles, transparent resin beads, wood flour, pulp, and cotton chips.

As the colorant, for example, inorganic pigments such as titanium dioxide and carbon black, and organic pigments such as azo pigments and phthalocyanine pigments can be used.
As the antioxidant, for example, a phenol-based or amine-based antioxidant can be used.
As the foaming agent, for example, an azo-based foaming agent that generates gas when heated, such as azodicarbonamide and azobisformamide, can be used.
As the diluent, for example, a solvent such as xylene or mineral turpentine can be used.
As the ultraviolet absorbing agent, a benzotriazole-based compound or the like can be used.

In the present disclosure, the total content of the other components may be within a range in which the effects of the present disclosure can be satisfactorily exhibited, but for example, it is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less, per 100 parts by mass of the composition. This is because the blocked isocyanate composition has superior low-temperature reactivity and storage stability.

7. Method for Producing Blocked Isocyanate Composition The method for producing the blocked isocyanate composition of the present disclosure may be any method that can produce a composition containing each component in the desired amount, and any known mixing method can be used.

8. Uses of the blocked isocyanate composition The uses of the blocked isocyanate composition of the present disclosure are preferably uses that utilize a reaction of an isocyanate group after dissociation of a blocking agent from the blocked isocyanate, and more preferably uses that require low-temperature reactivity.
Such applications include, for example, paints, adhesives, etc., and more specifically, paints and adhesives for molded products such as miscellaneous goods, toys, industrial parts, and electrical parts.
In the present disclosure, the above-mentioned applications are preferably paints and adhesives, more preferably paints and adhesives other than electrodeposition paints, intermediate coat paints, and clear paints for automobiles, even more preferably adhesives, still more preferably adhesives for automobiles, electrical materials, and building materials, and most preferably adhesives for automobiles, electrical materials, and building materials (excluding electrodeposition paints, intermediate coat paints, and clear paints for automobiles).

Automotive components for which adhesives are used are preferably components made of metal materials, and more preferably components made of metal materials on whose surfaces paint is formed.
Such members include, for example, the lower structural parts of an automobile body, that is, the underside of the floor, the wheel house (tire house), the rocker panel, the side sill, the front apron, the front and rear fenders, the lower parts of the doors, and the like.
A protective layer may be formed on the above-mentioned components to prevent paint peeling due to collision with pebbles, gravel, etc. while driving. The composition of the present disclosure can stably form an adhesive layer (resin layer) that can be used as the above-mentioned protective layer at low temperatures. Therefore, it is possible to achieve effects such as reduction in carbon dioxide emissions and energy saving, which are required in automobile factories and the like.
Examples of automotive components that use metal materials include those in which the metal material, electrodeposition coating, adhesive layer (protective layer), and surface coating (undercoat paint, topcoat paint (clear paint), etc.) are formed in this order.

In the present disclosure, the adhesive layer (resin layer) is formed between the electrodeposition coating and the surface coating, so that a protective layer with excellent adhesion can be formed at a low temperature, and the effects of the present disclosure can be effectively achieved. In addition, the blocked isocyanate composition can stably dissociate the blocking agent from the blocked isocyanate contained as a component of the composition at a low temperature, so that the regenerated isocyanate group has excellent reactivity with the hydroxyl group and the like present on the electrodeposition coating surface. Therefore, by using the blocked isocyanate composition, excellent adhesion can be achieved even when treated at a low temperature.
When the composition is used for adhesive applications, the blocked isocyanate composition itself may be used as an adhesive, but it is preferably used as an adhesion imparting agent for a resin composition containing a thermoplastic resin, because this allows the effect of excellent low-temperature reactivity of the present disclosure to be more effectively exhibited.
In addition, the preferred types of thermoplastic resins, the preferred ranges of the contents of each component contained in the above composition per 100 parts by mass of the thermoplastic resin, etc. can be the same as those described in the section "B. Resin composition" below, so description thereof will be omitted here.

B. Resin Composition Next, the resin composition of the present disclosure will be described.
The resin composition of the present disclosure is characterized by containing a phosphorus compound represented by the above formula (1), a blocked isocyanate, and a thermoplastic resin.

According to the present disclosure, by containing the phosphorus compound 1, the blocked isocyanate, and the thermoplastic resin, the blocking agent in the resin composition is more dissociated from the blocked isocyanate, and the resin composition has excellent low-temperature reactivity. As a result, when the resin composition is used as a resin layer-forming composition, a resin layer that is adhered to an adherend can be formed at a low temperature.
Moreover, the resin composition has excellent storage stability.
For the above reasons, the resin composition of the present disclosure has excellent low-temperature reactivity and storage stability.

The components of the resin composition disclosed herein are described in detail below.

1. Phosphorus Compound 1
The phosphorus compound 1 is a phosphorus compound represented by the general formula (1).
The types of such phosphorus compounds 1 can be similar to those described in the above section "A. Blocked isocyanate composition," and therefore will not be described here.

The content of the phosphorus compound 1 is preferably 0.01 parts by mass or more and 1.0 parts by mass or less, more preferably 0.03 parts by mass or more and 0.5 parts by mass or less, and even more preferably 0.05 parts by mass or more and 0.3 parts by mass or less, per 100 parts by mass of the resin composition. This is because the resin composition has better low-temperature reactivity and storage stability.

The content of the phosphorus compound 1 is preferably 0.01 parts by mass or more and 1.0 parts by mass or less, more preferably 0.03 parts by mass or more and 0.5 parts by mass or less, and even more preferably 0.05 parts by mass or more and 0.3 parts by mass or less, relative to 100 parts by mass of the thermoplastic resin. This is because the resin composition has better low-temperature reactivity and storage stability.

2. Blocked Isocyanate As the blocked isocyanate, a compound having a structure in which an isocyanate group has reacted with a blocking agent can be used.
The details of such blocked isocyanates can be the same as those described in the above section "A. Blocked isocyanate composition," and therefore a detailed description thereof will be omitted here.

The content of the blocked isocyanate is preferably 0.1 parts by mass or more and 25 parts by mass or less, more preferably 0.5 parts by mass or more and 15 parts by mass or less, even more preferably 1.0 parts by mass or more and 10 parts by mass or less, and most preferably 1.5 parts by mass or more and 5 parts by mass or less, per 100 parts by mass of the resin composition. This is because the resin composition has superior low-temperature reactivity and storage stability.

The content of the blocked isocyanate is preferably 0.1 parts by mass or more and 25 parts by mass or less, more preferably 1 part by mass or more and 20 parts by mass or less, even more preferably 2 parts by mass or more and 15 parts by mass or less, and most preferably 5 parts by mass or more and 12 parts by mass or less, relative to 100 parts by mass of the thermoplastic resin. This is because the resin composition has better low-temperature reactivity and storage stability.

3. Thermoplastic resin Examples of the thermoplastic resin include vinyl chloride resin, acrylic resin, ionomer resin, AAS resin (acrylonitrile/styrene/special rubber), AES resin (acrylonitrile/EPDM/styrene), AS resin (acrylonitrile/styrene), ABS resin (acrylonitrile/butadiene/styrene), thermoplastic polyurethane resin, and polyester resin.
In the present disclosure, the thermoplastic resin preferably contains a vinyl chloride resin, an acrylic resin, or the like, and more preferably contains an acrylic resin, because the resin composition has better low-temperature reactivity and storage stability.

The vinyl chloride resin may be any resin containing vinyl chloride as a raw material, and may be, for example, a homopolymer of vinyl chloride, or a copolymer with other acrylic monomers such as methacrylic acid, acrylic acid, itaconic acid, etc.; diene monomers such as isoprene, butadiene, etc.; styrene monomers such as styrene, α-methylstyrene, etc.; acrylonitrile, etc.
More specifically, examples of vinyl chloride resins include polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride-various vinyl ether copolymer, and the like.

As the acrylic resin, for example, a resin containing an acrylic ester monomer such as an alkyl ester of acrylic acid or an alkyl ester of methacrylic acid as a raw material can be used.
The acrylic resin may be a homopolymer of an acrylic acid ester monomer, or a copolymer with other acrylic monomers such as methacrylic acid, acrylic acid, and itaconic acid; diene monomers such as isoprene and butadiene; and styrene monomers such as styrene and α-methylstyrene.
Specific examples of the acrylic acid monomer include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, benzyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, and benzyl methacrylate.

The content of the thermoplastic resin may be any amount that provides the desired low-temperature reactivity, etc., and for example, it is preferable that the content be 50 parts by mass or more and 99 parts by mass or less, more preferably 75 parts by mass or more and 98 parts by mass or less, even more preferably 80 parts by mass or more and 96 parts by mass or less, and most preferably 85 parts by mass or more and 94 parts by mass or less, per 100 parts by mass of the resin composition.
Furthermore, the content of the thermoplastic resin, for example, when the resin composition contains a plasticizer, is preferably 5 parts by mass or more and 99 parts by mass or less, more preferably 10 parts by mass or more and 50 parts by mass or less, even more preferably 15 parts by mass or more and 40 parts by mass or less, and most preferably 20 parts by mass or more and 35 parts by mass or less, per 100 parts by mass of the resin composition.
This is because the resin composition has better low-temperature reactivity and storage stability.

4. Plasticizer The resin composition preferably contains a plasticizer, because this provides the resin composition with excellent moldability and the like.
The type of the plasticizer can be the same as that described in the above section "A. Blocked isocyanate composition," and therefore a description thereof will be omitted here.

The content of the plasticizer is preferably 1 part by mass or more and 60 parts by mass or less, more preferably 10 parts by mass or more and 50 parts by mass or less, even more preferably 20 parts by mass or more and 45 parts by mass or less, and most preferably 30 parts by mass or more and 40 parts by mass or less, per 100 parts by mass of the resin composition. This is because the resin composition has superior low-temperature reactivity and storage stability.

The content of the plasticizer is preferably 10 parts by mass or more and 300 parts by mass or less, more preferably 50 parts by mass or more and 200 parts by mass or less, even more preferably 100 parts by mass or more and 200 parts by mass or less, and most preferably 110 parts by mass or more and 150 parts by mass or less, relative to 100 parts by mass of the thermoplastic resin. This is because the resin composition has superior low-temperature reactivity and storage stability.

5. Isocyanate Curing Catalyst The resin composition of the present disclosure preferably contains an isocyanate curing catalyst that promotes the reaction between an isocyanate group and an active hydrogen group, because the resin composition has excellent reactivity of the isocyanate group after deblocking.

Such an isocyanate curing catalyst can be, for example, the same as that described in the above section "A. Blocked isocyanate composition," so a detailed description is omitted here.

The content of the isocyanate curing catalyst is preferably 0.01 parts by mass or more and 1.0 parts by mass or less, more preferably 0.03 parts by mass or more and 0.5 parts by mass or less, and even more preferably 0.05 parts by mass or more and 0.3 parts by mass or less, per 100 parts by mass of the resin composition. This is because the resin composition has better low-temperature reactivity and storage stability.

The amount of the isocyanate curing catalyst relative to the blocked isocyanate and the amount of the filler can be the same as those described in the "A. Blocked isocyanate composition" section above, so the explanation here is omitted.

6. Filler The resin composition of the present disclosure preferably contains a filler, because this provides the resin composition with excellent mechanical strength.

As such a filler, for example, those exemplified as the filler in the above section "A. Blocked isocyanate composition" can be used.
In the present disclosure, the filler preferably contains an inorganic filler, and more preferably contains a metal carbonate, because this provides the resin composition with excellent mechanical strength.

The content of the filler is preferably 1 part by mass or more and 60 parts by mass or less, more preferably 10 parts by mass or more and 50 parts by mass or less, even more preferably 20 parts by mass or more and 40 parts by mass or less, and most preferably 25 parts by mass or more and 35 parts by mass or less, per 100 parts by mass of the resin composition. This is because the resin composition has superior low-temperature reactivity and storage stability.

The content of the filler is preferably 10 parts by mass or more and 300 parts by mass or less, more preferably 50 parts by mass or more and 200 parts by mass or less, and more preferably 100 parts by mass or more and 150 parts by mass or less, per 100 parts by mass of the thermoplastic resin. This is because the resin composition has better low-temperature reactivity and storage stability.

7. Epoxy Compound The resin composition of the present disclosure may contain an epoxy compound.
As such an epoxy compound, for example, the epoxy compounds described in the above section "A. Composition" can be used.
In the present disclosure, the content of the epoxy compound is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 1 part by mass or less in 100 parts by mass of the resin composition, because the resin composition has better low-temperature reactivity and storage stability.

8. Other Components The resin composition may contain other components as necessary in addition to the above-mentioned phosphorus compound 1, blocked isocyanate, thermoplastic resin, isocyanate curing catalyst, plasticizer, filler, and epoxy compound.
Such other components may be the same as the other components described in the section "A. Blocked isocyanate composition" above, except for the filler.

In the present disclosure, the total content of the other components may be within a range in which the effects of the present disclosure can be satisfactorily exhibited. For example, the total content is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less, per 100 parts by mass of the resin composition. This is because the resin composition has superior low-temperature reactivity and storage stability.

The resin composition of the present disclosure is preferably used in a reaction of an isocyanate group after deblocking from a blocked isocyanate, and may be used in the same manner as described above for the composition in the section "A. Blocked isocyanate composition."

C. Method for Producing Resin Layer Next, a method for producing the resin layer according to the present disclosure will be described.
The method for producing a resin composition according to the present disclosure is characterized by comprising a coating step of coating the above-mentioned resin composition, and a heating step of heating the coating film formed by the coating step to form a resin layer.

According to the present disclosure, by using the above-mentioned resin composition, a resin layer with excellent adhesion can be easily formed at a lower temperature. In addition, since the above-mentioned resin composition has excellent storage stability, it is possible to easily control the position, thickness, etc. of the above-mentioned resin layer.

The method for producing a resin composition according to the present disclosure includes a coating step and a heating step.
Hereinafter, each step of the method for producing the resin composition of the present disclosure will be described in detail.

1. Coating Step This step is a step of coating the above-mentioned resin composition.
The coating method in this step may be any method that can obtain a coating film capable of forming a desired resin layer, and any known coating method may be used.
Examples of such coating methods include known coating methods such as brush coating, roller coating, air spray coating, and airless spray coating.

The thickness of the coating film formed in this process is preferably 100 μm or more and 10,000 μm or less, more preferably 200 μm or more and 5,000 μm or less, and even more preferably 300 μm or more and 4,000 μm or less. This is because the effects of the present disclosure can be more effectively exhibited.

2. Heating Step This is a step of heating the coating film formed in the above coating step to form a resin layer.
The heating temperature in this step is preferably 70° C. or higher and 150° C. or lower, more preferably 80° C. or higher and 140° C. or lower, even more preferably 90° C. or higher and 120° C. or lower, and most preferably 95° C. or higher and 110° C. or lower, because the effects of the present disclosure can be more effectively exhibited at such a temperature.

The heating time in this process is preferably from 1 minute to 60 minutes, more preferably from 5 minutes to 45 minutes, and even more preferably from 10 minutes to 30 minutes. This is because the effects of the present disclosure can be more effectively exerted in this manner.

The thickness of the resin layer formed in this process is preferably 100 μm or more and 10,000 μm or less, more preferably 500 μm or more and 5,000 μm or less, and even more preferably 1,000 μm or more and 3,000 μm or less. This is because the effects of the present disclosure can be more effectively exhibited.

3. Others The manufacturing method of the present disclosure includes a coating step and a heating step, but may include other steps as necessary.
The use of the resin layer produced by the production method of the present disclosure can be, for example, similar to the use of the composition described in the above section "A. Composition."

D. Resin Layer Next, the resin layer of the present disclosure will be described.
The resin layer of the present disclosure is characterized in that it is formed using the above-mentioned resin composition.

According to the present disclosure, the resin layer is easy to form.

The resin layer of the present disclosure uses the above-mentioned resin composition.
Such a resin layer can be formed in the same manner as described in the above section "C. Method for producing resin layer."
The uses of such a resin layer may be the same as those of the composition described in the above section "A. Blocked isocyanate composition."

The resin layer of the present disclosure is characterized by containing a polyisocyanate compound or a urethane polyisocyanate compound, a compound represented by the following formula (1), and a thermoplastic resin.

(In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represent an organic group having 1 to 20 carbon atoms,
The organic group is a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted heterocyclic ring-containing group, or a group in which one or more methylene groups in the hydrocarbon group or the heterocyclic ring-containing group are substituted with a divalent group selected from the following <Group A>:
X ^b− represents an anion having a valence of b, a represents an integer of 1 or more and 3 or less, and b represents an integer of 1 or more and 3 or less.
<Group A> is —O—, —CO—, —COO—, —OCO—, —NR ¹¹ —, —NR ¹¹ CO— and —S—;
R ¹¹ represents a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms.

According to the present disclosure, for example, it can be easily formed by using the above-mentioned "B. Resin composition."

The resin layer of the present disclosure contains a polyisocyanate compound or a urethane polyisocyanate compound, a phosphorus compound 1, and a thermoplastic resin.

The types of phosphorus compound 1 and thermoplastic resin contained in the resin layer may be the same as those described in the section "B. Resin composition" above.
The content of phosphorus compound 1 and thermoplastic resin in 100 parts by mass of the resin layer can be the same as that described above in the section "B. Resin composition" as the content in 100 parts by mass of the resin composition.

The type of polyisocyanate compound or urethane polyisocyanate compound (hereinafter, collectively referred to as isocyanate compound) contained in the resin layer may be the same as that described in the above section "A. Blocked isocyanate composition."
The content of the isocyanate compound per 100 parts by mass of the thermoplastic resin and the content in 100 parts by mass of the resin layer can be the same as the content of the blocked isocyanate per 100 parts by mass of the thermoplastic resin and the content of the blocked isocyanate in 100 parts by mass of the resin composition described in the above section “B. Resin composition”.

The resin layer may contain, in addition to the isocyanate compound, the phosphorus compound 1, and the thermoplastic resin, an isocyanate curing catalyst, a plasticizer, a filler, and other components.
The contents of each of these components can be the same as those described in the section "B. Resin composition" above, so a detailed description thereof will be omitted here.

The method for forming the resin layer may be any method capable of forming a resin layer of the desired shape, and examples of such methods include those described in the above section "C. Method for manufacturing the resin layer."

The uses of the resin layer can be the same as those described above for the compositions described in the section "A. Blocked isocyanate composition."

F. Others The present disclosure includes the following aspects.

[1]
A phosphorus compound represented by the following formula (1),
Blocked isocyanate,
A blocked isocyanate composition comprising:

(In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represent an organic group having 1 to 20 carbon atoms,
The organic group is a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted heterocyclic ring-containing group, or a group in which one or more methylene groups in the hydrocarbon group or the heterocyclic ring-containing group are substituted with a divalent group selected from the following <Group A>:
X ^b− represents an anion having a valence of b, a represents an integer of 1 or more and 3 or less, and b represents an integer of 1 or more and 3 or less.
<Group A> is —O—, —CO—, —COO—, —OCO—, —NR ¹¹ —, —NR ¹¹ CO— and —S—;
R ¹¹ represents a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms.

[2]
The blocked isocyanate composition according to [1], characterized in that R ¹ , R ² , R ³ , and R ⁴ are each independently a substituted or unsubstituted hydrocarbon group having from 1 to 20 carbon atoms, and the hydrocarbon group used for R ¹ , R ² , R ^3, and R ⁴ is an aliphatic hydrocarbon group.

[3]
The blocked isocyanate composition according to [1] or [2], wherein X ^b- is a halogen anion, a phosphate anion, a borate anion, a carbonate anion, a thioether anion, or an azolate anion.

[4]
The blocked isocyanate composition according to any one of [1] to [3], characterized in that the organic group used for R ¹ has 6 to 13 carbon atoms.

[5]
The number of carbon atoms in the organic group used for R ¹ is 6 or more and 13 or less, and X ^b- is a halogen-based anion, a phosphate-based anion not having a phosphate ester structure, a borate-based anion, or a carbonate-based anion,
The blocked isocyanate composition according to any one of [1] to [4], characterized in that the number of carbon atoms in the organic group used for ^R1 is 1 or more and 5 or less, and ^Xb- is a phosphate anion having a phosphate ester structure, a thioether anion, or an azolate anion.

[6]
The blocked isocyanate composition according to any one of [1] to [5], wherein the number of carbon atoms in the organic groups used for R ² , R ³ and R ⁴ is each independently 1 or more and 5 or less.

[7]
The blocked isocyanate composition according to any one of [1] to [6], characterized in that the content of the phosphorus compound represented by the formula (1) is 0.1 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the blocked isocyanate.

[8]
The blocked isocyanate composition according to any one of [1] to [7], characterized in that the blocked isocyanate comprises a blocked polyisocyanate compound, and the polyisocyanate compound comprises an aromatic diisocyanate compound, an alicyclic structure-containing diisocyanate compound, or an isocyanurate compound of an aromatic diisocyanate compound or an alicyclic structure-containing diisocyanate compound.

[9]
The blocked isocyanate composition according to any one of [1] to [8], further comprising a plasticizer.

[10]
The blocked isocyanate composition according to any one of [1] to [9], further comprising an isocyanate curing catalyst.

[11]
The blocked isocyanate composition according to any one of [1] to [10], comprising an epoxy compound.

[12]
A resin composition comprising a phosphorus compound represented by the following formula (1), a blocked isocyanate, and a thermoplastic resin:

(In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represent an organic group having 1 to 20 carbon atoms,
The organic group is a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted heterocyclic ring-containing group, or a group in which one or more methylene groups in the hydrocarbon group or the heterocyclic ring-containing group are substituted with a divalent group selected from the following <Group A>:
X ^b− represents an anion having a valence of b, a represents an integer of 1 or more and 3 or less, and b represents an integer of 1 or more and 3 or less.
<Group A> is —O—, —CO—, —COO—, —OCO—, —NR ¹¹ —, —NR ¹¹ CO— and —S—;
R ¹¹ represents a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms.

[13]
The resin composition according to [12], further comprising a filler.

[14]
The resin composition according to [12] or [13], comprising a plasticizer.

[15]
The resin composition according to any one of [12] to [14], further comprising an isocyanate curing catalyst.

[16]
The resin composition according to any one of [12] to [15], comprising an epoxy compound.

[17]
A resin layer formed using the resin composition according to any one of [12] to [16].

[18]
A resin layer comprising a compound represented by the following formula (1), a polyisocyanate compound or a urethane polyisocyanate compound, and a thermoplastic resin:

(In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represent an organic group having 1 to 20 carbon atoms,
The organic group is a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted heterocyclic ring-containing group, or a group in which one or more methylene groups in the hydrocarbon group or the heterocyclic ring-containing group are substituted with a divalent group selected from the following <Group A>:
X ^b− represents an anion having a valence of b, a represents an integer of 1 or more and 3 or less, and b represents an integer of 1 or more and 3 or less.
<Group A> is —O—, —CO—, —COO—, —OCO—, —NR ¹¹ —, —NR ¹¹ CO— and —S—;
R ¹¹ represents a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms.

[19]
The resin layer according to [18], comprising a filler.

[20]
The resin layer according to [18] or [19], comprising a plasticizer.

[21]
The resin layer according to any one of [18] to [20], further comprising an isocyanate curing catalyst.

[22]
The resin layer according to any one of [18] to [21], characterized in that it contains an epoxy compound.

[23]
A method for producing a resin layer, comprising: a coating step of coating the resin composition according to any one of [12] to [16]; and a heating step of heating the coating film formed by the coating step.

The present invention is not limited to the above-described embodiments. The above-described embodiments are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits similar effects is included within the technical scope of this disclosure.

The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples.

<Synthesis of phosphorus compounds>
(Synthesis Example 1)
Tetrabutylphosphonium bromide (Bu ₄ P ⁺ Br ^- ) as an alkylphosphonium halogen salt was anion-exchanged using a strongly basic ion exchange resin to obtain tetrabutylphosphonium hydroxide (Bu ₄ P ⁺ OH ^- ) as an alkylphosphonium hydroxide salt. Next, the tetrabutylphosphonium hydroxide was reacted with boric acid in ethanol under heating conditions at 40° C., and the solvent ethanol was then removed to obtain a phosphorus compound A1 represented by the following formula (A1).

(Synthesis Example 2)
Tributylphosphine (Bu ₃ P) and dimethyl carbonate were reacted in methanol under heating conditions at 40° C., and the solvent, methanol, was then removed to obtain a phosphorus compound A2 represented by the following formula (A2).

(Synthesis Example 3)
A phosphorus compound A3 represented by the following formula (A3) was obtained in the same manner as in Synthesis Example 1, except that phosphorous acid was used in place of boric acid in Synthesis Example 1.

(Synthesis Example 4)
A phosphorus compound A4 represented by the following formula (A4) was obtained in the same manner as in Synthesis Example 1, except that (C ₈ H ₁₇ )Bu ₃ P ⁺ Br ⁻ was used as the alkylphosphonium halogen salt instead of tetrabutylphosphonium bromide, and reacted with phosphoric acid instead of boric acid.

(Synthesis Example 5)
Phosphorus compound A5 represented by the following formula (A5) was obtained in the same manner as in Synthesis Example 1, except that (C ₈ H ₁₇ )Bu ₃ P ⁺ Br ⁻ was used as the alkylphosphonium halogen salt instead of tetrabutylphosphonium bromide, and reacted with phosphorous acid instead of boric acid.

(Synthesis Example 6)
A phosphorus compound A6 represented by the following formula (A6) was obtained in the same manner as in Synthesis Example 1, except that (C ₈ H ₁₇ )Bu ₃ P ⁺ Br ⁻ was used as the alkylphosphonium halogen salt instead of tetrabutylphosphonium bromide.

(Synthesis Example 7)
A phosphorus compound A7 represented by the following formula (A7) was obtained in the same manner as in Synthesis Example 1, except that ( _C12H25 ) _Bu3P ^{+ Br-} was used as the alkylphosphonium halogen salt instead of _{tetrabutylphosphonium} bromide and reacted with phosphoric acid instead of boric acid.

(Synthesis Example 8)
A phosphorus compound A8 represented by the following formula ( _A8 ) was obtained in the same manner as in Synthesis Example 1, except that ( _C12H25 ) _Bu3P ^{+ Br-} was used as the alkylphosphonium halogen salt instead of tetrabutylphosphonium bromide, and reacted with phosphorous acid instead of boric acid.

(Synthesis Example 9)
Compound A9 represented by the following formula (A9) was obtained in the same manner as in Synthesis Example 1, except that (C ₁₂ H ₂₅ )Bu ₃ P ⁺ Br ⁻ was used as the alkylphosphonium halogen salt.

(Synthesis Example 10)
A phosphorus compound A10 represented by the following formula (A10) was obtained in the same manner as in Synthesis Example 1, except that (C ₁₄ H ₂₉ )Bu ₃ P ⁺ Br ⁻ was used as the alkylphosphonium halogen salt and reacted with phosphoric acid instead of boric acid.

(Synthesis Example 11)
The phosphorus compound A11 represented by the following formula ( _A11 ) was obtained in the same manner as in Synthesis Example 1, except that ( _C14H29 ) _Bu3P ^{+ Br-} was used as the alkylphosphonium halogen salt and reacted with phosphoric acid instead of boric acid (so that the amount of the cation was 3 equivalents relative to the phosphoric acid).

<Synthesis of blocked isocyanate>
(Synthesis Example 12)
In a three-neck flask, 305 g of diisononyl phthalate (DNIP, plasticizer) and 62 g of nonylphenol (blocking agent) were charged, and dehydration was carried out under reduced pressure for 1 hour at 100 to 110 ° C. and a pressure of less than 30 mmHg. This was cooled to 80 ° C., tolylene diisocyanate (TDI) nurate (containing 50% butyl acetate) (polyisocyanate compound, Tosoh Corporation's Coronate 2037) 120 g and dibutyltin dilaurate (isocyanate curing catalyst) 0.36 g were added, and the reaction was carried out for 4 hours at 130 ° C. to 140 ° C. while carrying out desolvation under a pressure of less than 30 mmHg, and then cooled, and aged for 1 hour at 80 ° C. to 90 ° C. and a pressure of less than 30 mmHg while degassing, to obtain a blocked isocyanate pre-composition 1 containing a blocked isocyanate (compound B1).
It was confirmed by infrared absorption spectroscopy that the absorption of isocyanate (NCO) at 2260 cm ^-1 had completely disappeared.
The blocked isocyanate pre-composition 1 was a mixture containing 100 parts by mass of the blocked isocyanate (compound B1), 250 parts by mass of the plasticizer (C1), and 0.3 parts by mass of the isocyanate curing catalyst (E1).
The viscosity of the obtained blocked isocyanate pre-composition 1 at 25°C was 20,000 mPa.s, and the blocked NCO% of the blocked isocyanate (compound B1) was 2.0% by mass (the theoretical value of the blocked NCO% when all NCOs are blocked is 2.25% by mass).
The viscosity was measured using an E-type viscometer manufactured by Toki Sangyo (rotation speed: 10 rpm).
Block NCO % was measured in accordance with JIS K 7301-1995.

(Synthesis Example 13)
In a three-neck flask, 305 g of diisononyl phthalate (DNIP, plasticizer) and 62.0 g of nonylphenol (blocking agent) were charged, and dehydration was carried out under reduced pressure at 100 to 110 ° C. and a pressure of less than 30 mmHg for 1 hour. This was cooled to 80 ° C., and 120 g of tolylene diisocyanate (TDI) nurate (containing 50% butyl acetate) (polyisocyanate compound) and 0.12 g of dibutyltin dilaurate (isocyanate curing catalyst) were added, and the mixture was reacted for 4 hours at 130 to 140 ° C. while performing desolvation under reduced pressure at a pressure of less than 30 mmHg. The mixture was then cooled to 80 ° C., and 85 g of EP-4100E (manufactured by ADEKA Corporation; bisphenol A type epoxy resin) was added, and the mixture was aged for 1 hour. Except for this, a blocked isocyanate pre-composition 2 containing a blocked isocyanate (compound B1) was obtained in the same manner as in Synthesis Example 12.
The viscosity of the resulting blocked isocyanate pre-composition 2 at 25° C. was 14,500 mPa.s.
The blocked isocyanate pre-composition 2 was a mixture containing 100 parts by mass of the blocked isocyanate (compound B1), 250 parts by mass of the plasticizer (C1), 70 parts by mass of the epoxy compound (D1), and 0.1 parts by mass of the isocyanate curing catalyst (E1).

Synthesis Example 14
In a three-neck flask, 207 g of diisononyl phthalate (DNIP, plasticizer) and 62.0 g of nonylphenol (blocking agent) were charged, and dehydration was carried out under reduced pressure at 100 to 110 ° C. and a pressure of less than 30 mmHg for 1 hour. This was cooled to 80 ° C., and 120 g of tolylene diisocyanate (TDI) nurate (containing 50% butyl acetate) (polyisocyanate compound) and 0.12 g of dibutyltin dilaurate (isocyanate curing catalyst) were added, and the reaction was carried out for 4 hours at 130 to 140 ° C. while carrying out desolvation under reduced pressure at a pressure of less than 30 mmHg. After that, the mixture was cooled to 80 ° C., and 85 g of EP-4100E (manufactured by ADEKA Corporation; bisphenol A type epoxy resin) was added, and the mixture was aged for 1 hour. Except for this, a blocked isocyanate pre-composition 3 containing a blocked isocyanate (compound B1) was obtained in the same manner as in Synthesis Example 12.
The viscosity of the resulting blocked isocyanate pre-composition 3 at 25° C. was 175,000 mPa.s.
Blocked isocyanate pre-composition 3 was a mixture containing 100 parts by mass of blocked isocyanate (compound B1), 170 parts by mass of plasticizer (C1), 70 parts by mass of epoxy compound (D1), and 0.1 part by mass of isocyanate curing catalyst (E1).

[Examples 1 to 21 and Comparative Examples 1 to 3]
Blocked isocyanate compositions were obtained by blending the components according to the formulations shown in Tables 1 and 2 below. Specifically, phosphorus compounds A1 to 11 and commercially available phosphorus compounds A12 to 18 obtained in Synthesis Examples 1 to 11 below and blocked isocyanate pre-compositions 1 to 3 obtained in Synthesis Examples 12 to 14 below were blended according to the formulations shown in Tables 1 and 2 to prepare blocked isocyanate compositions of Examples 1 to 21, respectively. Furthermore, commercially available compounds A'1 and 2 shown below and blocked isocyanate pre-composition 1 shown below were blended according to the formulations shown in Tables 1 and 2 to prepare blocked isocyanate compositions of Comparative Examples 2 and 3, respectively.
The following materials were used for each component.
The blend amounts in Tables 1 and 2 indicate parts by mass of each component.
The amounts of blocked isocyanate B1, plasticizer C1, epoxy compound D1, and isocyanate curing catalyst E1 blended are those shown in the blocked isocyanate pre-compositions 1 to 3 obtained in Synthesis Examples 12 to 14.

(Compound 1)
A1: Phosphorus compound A1 obtained in Synthesis Example 1 (compound represented by the following formula (A1))
A2: Phosphorus compound A2 obtained in Synthesis Example 2 (compound represented by the following formula (A2))
A3: Phosphorus compound A3 obtained in Synthesis Example 3 (compound represented by the following formula (A3))
A4: Phosphorus compound A4 obtained in Synthesis Example 4 (compound represented by the following formula (A4))
A5: Phosphorus compound A5 obtained in Synthesis Example 5 (compound represented by the following formula (A5))
A6: Phosphorus compound A6 obtained in Synthesis Example 6 (compound represented by the following formula (A6))
A7: Phosphorus compound A7 obtained in Synthesis Example 7 (compound represented by the following formula (A7))
A8: Phosphorus compound A8 obtained in Synthesis Example 8 (compound represented by the following formula (A8))
A9: Phosphorus compound A9 obtained in Synthesis Example 9 (compound represented by the following formula (A9))
A10: Phosphorus compound A10 obtained in Synthesis Example 10 (compound represented by the following formula (A10))
A11: Phosphorus compound A11 obtained in Synthesis Example 11 (compound represented by the following formula (A11))
A12: Phosphorus compound A12 represented by the following formula (A12) (manufactured by Nippon Chemical Industry Co., Ltd., Hishicoline PX-4ET)
A13: Phosphorus compound A13 represented by the following formula (A13) (manufactured by Nippon Chemical Industry Co., Ltd., Hishicolin PX-4MP)
A14: Phosphorus compound A14 represented by the following formula (A14) (manufactured by Nippon Chemical Industry Co., Ltd., Hishicolin PX-4MI)
A15: Phosphorus compound A15 represented by the following formula (A15) (manufactured by Nippon Chemical Industry Co., Ltd., Hishicoline PX-4BT)
A16: Phosphorus compound A16 represented by the following formula (A16) (manufactured by Nippon Chemical Industry Co., Ltd., Hishicoline PX-82B)
A17: Phosphorus compound A17 represented by the following formula (A17) (manufactured by Nippon Chemical Industry Co., Ltd., Hishicoline PX-28B)
A18: Phosphorus compound A18 represented by the following formula (A18) (Sigma Aldrich, ethyltriphenylphosphonium iodide (ETPPI))
A'1: Compound A'1 represented by the following formula (A'1) (U-CAT SA1 (phenol salt of 1,8-diazabicyclo[5.4.0]undecene-7 (DBU) manufactured by San-Apro Co., Ltd.)
A'2: Compound A'2 represented by the following formula (A'2) (1,8-diazabicyclo[5.4.0]undecene-7 (DBU))

(Blocked isocyanate)
B1: Compound B1 obtained in Synthesis Examples 12 to 14

(Plasticizer)
C1: DINP

(Epoxy Compound)
D1: EP-4100E (manufactured by ADEKA Corporation; bisphenol A type epoxy compound)

(Isocyanate curing catalyst)
E2: Dibutyltin dilaurate (DBTDL)

[evaluation]
The storage stability and adhesion (low-temperature reactivity) of each of the resulting blocked isocyanate compositions when a resin layer was formed were evaluated according to the following procedures. The results are shown in Tables 1 and 2.

1. Storage Stability The blocked isocyanate compositions obtained in Examples 1 to 21 and Comparative Examples 1 to 3 were evaluated using an E-type rotational viscometer (manufactured by Toki Sangyo Co., Ltd.) in terms of the rate of thickening (rate of change in viscosity) from the initial state when stored (left to stand) in a container at 40° C. for 7 days.
Specifically, the initial viscosity of each blocked isocyanate composition immediately after preparation at 25° C. was measured for 3 minutes using an E-type rotational viscometer at a rotation speed of 2 rpm.
In addition, each of the blocked isocyanate compositions was placed in a sealed container and stored at 40° C. for 7 days, and then cooled to 25° C., and the viscosity after 7 days was measured at 2 rpm for 3 minutes using an E-type rotational viscometer in the same manner as for the initial viscosity.
The viscosity increase rate was calculated using the initial viscosity and the viscosity after 7 days according to the following formula (A) and evaluated according to the following evaluation criteria. The results are shown in Tables 1 and 2 below.
Viscosity increase rate (%) = [(viscosity after 7 days - initial viscosity) ÷ initial viscosity] x 100 (A)

<Evaluation criteria>
⊚: The viscosity increase rate is within 50%.
Good: The viscosity increase rate is more than 50% and not more than 100%.
Δ: The viscosity increase rate is more than 100% and not more than 200%.
×: The viscosity increase rate is more than 200%.
In addition, the smaller the viscosity increase rate, the more the dissociation of the blocking agent from the blocked isocyanate is suppressed, and it can be determined that the blocked isocyanate composition has excellent storage stability.
2. Low-temperature reactivity The blocked isocyanate compositions obtained in Examples 1 to 21 and Comparative Examples 1 to 3 were mixed with the respective components according to the formulation described below to obtain resin compositions (hereinafter referred to as evaluation resin compositions).

(Resin composition for evaluation)
Blocked isocyanate composition: 8 parts by weight Thermoplastic resin: 30 parts by weight Plasticizer: 35 parts by weight Filler: 35 parts by weight Isocyanate curing catalyst: 0.1 parts by weight

The following materials were used as the components of the resin composition for evaluation.
Thermoplastic resin: Acrylic resin (Dianal LP-3121 manufactured by Mitsubishi Chemical Corporation)
Plasticizer: Diisononyl phthalate (DINP, manufactured by C.G. Ester Corporation)
Filler: Calcium carbonate Isocyanate Curing catalyst: Dibutyltin dilaurate (DBTDL)

(Preparation of test specimens for evaluation)
As shown in Fig. 1 (a) and (b), a test panel 3 (width 25 mm x length 100 mm x thickness 1.0 mm) made of a cationic electrodeposition-coated steel plate was prepared, and the resin composition for evaluation was applied at an angle to the electrodeposition-coated surface of the test panel 3 to form a coating film. Specifically, the resin composition for evaluation was applied using a spatula to the electrodeposition-coated surface on which a ruler having an inclination was installed at both ends, and then the unnecessary resin composition for evaluation was scraped off while pressing the spatula against the inclined part of the ruler, thereby forming a coating film with an inclination. Thereafter, the resin layer 4 (hereinafter sometimes referred to as the 100 ° C. resin layer) was formed by heating at 100 ° C. for 30 minutes, and a test piece for evaluation 1 was obtained. Similarly, the coating film formed by the inclined application was heated at 120 ° C. for 30 minutes to form a resin layer 4 (hereinafter sometimes referred to as the 120 ° C. resin layer), and a test piece for evaluation 2 was obtained.
As shown in FIG. 1(b), the resin layer 4 had a wedge shape with a thickness of 0 mm at one end in the width direction and 3 mm at the other end in the width direction, gradually decreasing in thickness from 3 mm to 0 mm.

(Evaluation Method)
Each of the obtained evaluation specimens (evaluation specimen 1 and evaluation specimen 2) was scratched with a fingernail from the thick film side of the resin layer 4 (100° C. resin layer and 120° C. resin layer) as shown in Figure 1 (a) and (b) (scratch direction 5), and the peeling state of the resin layer 4 from the test panel 3 was visually observed and evaluated according to the following evaluation criteria. The results are shown in Tables 1 and 2 below.

<Evaluation criteria>
⊚: The entire peeled surface of the 100° C. resin layer was in a state of cohesive failure.
◯: The peeled surface of the 100° C. resin layer was in a state in which cohesive failure and interfacial failure were mixed.
Δ: The entire peeled surface of the 100° C. resin layer was in a state of interfacial failure, and the peeled surface of the 120° C. resin layer was in a state of a mixture of cohesive failure and interfacial failure.
x: The entire peeled surface of the 100° C. resin layer was in a state of interfacial destruction, and the entire peeled surface of the 120° C. resin layer was in a state of interfacial destruction.
It can be determined that the lower the temperature under which the resin layer is formed and the higher the rate of cohesive failure, the higher the adhesion of the resin layer and the more excellent the low-temperature reactivity.

[summary]
From Tables 1 and 2, it was confirmed that the use of the blocked isocyanate compositions of the Examples enabled the formation of resin layers having excellent storage stability and excellent adhesion even when formed at low temperatures (100° C. and 120° C.) compared with the blocked isocyanate compositions of the Comparative Examples. In particular, it was confirmed that the blocked isocyanate compositions of Examples 4, 7, 12, and 21 exhibited excellent low-temperature reactivity and storage stability.

1, 2: Test piece for evaluation, 3: Test panel, 4: Resin layer, 5: Scratch direction

Claims (11)

A phosphorus compound represented by the following formula (1),
Blocked isocyanate,
1. A blocked isocyanate composition comprising:

(In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represent an organic group having 1 to 20 carbon atoms,
The organic group is a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted heterocyclic ring-containing group, or a group in which one or more methylene groups in the hydrocarbon group or the heterocyclic ring-containing group are substituted with a divalent group selected from the following <Group A>:
X ^b− represents an anion having a valence of b, a represents an integer of 1 or more and 3 or less, and b represents an integer of 1 or more and 3 or less.
<Group A> is —O—, —CO—, —COO—, —OCO—, —NR ¹¹ —, —NR ¹¹ CO— and —S—;
R ¹¹ represents a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms. 2. The blocked isocyanate composition according to claim 1, wherein the organic groups represented by ^R1 , ^R2 , ^R3 , and ^R4 are each independently a substituted or unsubstituted hydrocarbon group. 2. The blocked isocyanate composition according to claim 1, wherein X ^b- is selected from a halogen-based anion, a phosphate-based anion, a borate-based anion, a carbonate-based anion, a thioether-based anion, or an azolate-based anion. 2. The blocked isocyanate composition according to claim 1, wherein the organic group represented by R ¹ has 6 or more and 13 or less carbon atoms. The number of carbon atoms in the organic group used for R ¹ is 6 or more and 13 or less, and X ^b- is a halogen-based anion, a phosphate-based anion not having a phosphate ester structure, a borate-based anion, or a carbonate-based anion, or
2. The blocked isocyanate composition according to claim 1, wherein the number of carbon atoms in the organic group used for R ¹ is 1 or more and 5 or less, and X ^b- is a phosphate anion having a phosphate ester structure, a thioether anion, or an azolate anion. The blocked isocyanate composition according to claim 1, wherein the content of the phosphorus compound represented by formula (1) is 0.1 parts by mass or more and 15 parts by mass or less per 100 parts by mass of the phosphorus compound represented by formula (1) and the blocked isocyanate combined. The blocked isocyanate includes a blocked polyisocyanate compound,
The blocked isocyanate composition according to claim 1, wherein the polyisocyanate compound comprises an aromatic diisocyanate compound, an alicyclic structure-containing diisocyanate compound, or an isocyanurate compound of the aromatic diisocyanate compound or the alicyclic structure-containing diisocyanate compound. A phosphorus compound represented by the following formula (1),
Blocked isocyanate,
A thermoplastic resin;
A resin composition comprising:

(In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represent an organic group having 1 to 20 carbon atoms,
The organic group is a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted heterocyclic ring-containing group, or a group in which one or more methylene groups in the hydrocarbon group or the heterocyclic ring-containing group are substituted with a divalent group selected from the following <Group A>:
X ^b− represents an anion having a valence of b, a represents an integer of 1 or more and 3 or less, and b represents an integer of 1 or more and 3 or less.
<Group A> is —O—, —CO—, —COO—, —OCO—, —NR ¹¹ —, —NR ¹¹ CO— and —S—;
R ¹¹ represents a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms. A resin layer formed using the resin composition according to claim 8. A phosphorus compound represented by the following formula (1),
A polyisocyanate compound or a urethane polyisocyanate compound,
A thermoplastic resin;
A resin layer comprising:

(In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represent an organic group having 1 to 20 carbon atoms,
The organic group is a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted heterocyclic ring-containing group, or a group in which one or more methylene groups in the hydrocarbon group or the heterocyclic ring-containing group are substituted with a divalent group selected from the following <Group A>:
X ^b− represents an anion having a valence of b, a represents an integer of 1 or more and 3 or less, and b represents an integer of 1 or more and 3 or less.
<Group A> is —O—, —CO—, —COO—, —OCO—, —NR ¹¹ —, —NR ¹¹ CO— and —S—;
R ¹¹ represents a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms. A coating step of coating the resin composition according to claim 8;
a heating step of heating the coating film formed by the coating step;
The method for producing a resin layer comprising the steps of:

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