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

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, Xb- 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

[0001] The present invention relates to compositions containing blocked isocyanates.

[0002] Blocked isocyanates are compounds in which the reactivity of an isocyanate group is inactivated (blocked) by reacting the isocyanate group with an active hydrogen group-containing compound (blocking agent). When this compound is heated, a deblocking reaction occurs, the blocking agent dissociates, and the isocyanate group is regenerated.

[0003] Examples of uses of blocked isocyanates include an adhesive agent for a film formed from a plastisol composition (see, for example, Patent Document 1) and an agent for imparting adhesion to a thermoplastic resin composition (see, for example, Patent Document 2).

[0004] 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 achieving better storage stability.

[0005] JP 2021-011525 A JP 2014-210900 A JP 2021-084936 A

[0006] However, there has been a problem in that the heating temperature required for the deblocking reaction when dissociating the blocking agent from the blocked isocyanate is high (for example, 170°C or higher in Patent Document 3, etc.). Furthermore, when the dissociation temperature of the blocking agent is lowered, there has been 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.

[0007] The present invention has been made in view of the above problems, and an object of the present invention is to provide a blocked isocyanate composition that has excellent low-temperature reactivity, enabling the unblocking reaction of a blocked isocyanate at a lower temperature, and also has excellent storage stability.

[0008] The present inventors have conducted extensive research to solve the above-mentioned problems, and as a result have found that using a blocked isocyanate in combination with a phosphorus compound having a specific structure facilitates the unblocking reaction of the blocked isocyanate at lower temperatures (hereinafter, this may also be referred to as "excellent low-temperature reactivity") and also improves the storage stability of the blocked isocyanate composition, thereby completing the present invention.

[0009] That is, the present disclosure provides a blocked isocyanate composition comprising a phosphorus compound represented by the following formula (1) and a blocked isocyanate:

[0010]

[0011] (In the formula, R 1 , R 2 , R 3 and R 4 are each independently an organic group having from 1 to 20 carbon atoms, the organic group being a substituted or unsubstituted hydrocarbon group, a group containing a substituted or unsubstituted heterocycle, or a group in which one or more methylene groups in the hydrocarbon group or the group containing a heterocycle are substituted with a divalent group selected from the following <Group A>, b- represents a b-valent anion, 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> represents —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.

[0012] The present disclosure also provides a resin composition comprising a phosphorus compound represented by the above formula (1), a blocked isocyanate, and a thermoplastic resin.

[0013] Furthermore, the present disclosure provides a resin layer comprising a phosphorus compound represented by the above formula (1), a polyisocyanate compound or a urethane polyisocyanate compound, and a thermoplastic resin.

[0014] The present disclosure also provides a method for producing a resin layer, 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.

[0015] According to the present disclosure, a blocked isocyanate composition and a resin composition that contain a blocked isocyanate and a specific phosphorus compound and therefore have excellent low-temperature reactivity and storage stability can be provided. 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, thereby enabling the formation of a resin layer that has excellent adhesion at a lower temperature.

[0016] 1A is a schematic diagram of the evaluation test piece, and FIG. 1B is a cross-sectional view of the evaluation test piece taken along the line AA'.

[0017] 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 is described in detail below.

[0018] 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.

[0019]

[0020] (In the formula, R 1 , R 2 , R 3 and R 4 are each independently an organic group having from 1 to 20 carbon atoms, the organic group being a substituted or unsubstituted hydrocarbon group, a group containing a substituted or unsubstituted heterocycle, or a group in which one or more methylene groups in the hydrocarbon group or the group containing a heterocycle are substituted with a divalent group selected from the following <Group A>, b- represents a b-valent anion, 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> represents —O—, —CO—, —COO—, —OCO—, —NR11 -, -NR 11 CO- and -S-, R 11 represents a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms.

[0021] According to the blocked isocyanate composition of the present disclosure, by using a blocked isocyanate in combination with the phosphorus compound represented by the above formula (1) (hereinafter, may be referred to as phosphorus compound 1), the composition has excellent low-temperature reactivity and storage stability.

[0022] Here, 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 therefore has excellent nucleophilicity. As a result, phosphorus compound 1 exhibits excellent nucleophilic attack on the carbonyl group in the urethane bond formed by the reaction of the isocyanate group of the blocked isocyanate with a blocking agent. Furthermore, the cationic component containing the phosphorus atom represented by the phosphorus compound 1 and the anionic component are a combination that is weakly Lewis acidic and Lewis basic, has high ionicity, and easily dissociates into the two components. For these reasons, the above-mentioned nucleophilic attack is easily exhibited. As a result, the deblocking reaction can occur at a lower temperature than when the blocked isocyanate is used alone, and the blocked isocyanate composition of the present disclosure exhibits excellent low-temperature reactivity. Furthermore, because the blocked isocyanate composition has excellent low-temperature reactivity, isocyanate groups are regenerated at lower temperatures. Therefore, when a resin layer or adhesive layer used as a protective layer is formed using the blocked isocyanate composition or resin composition of the present disclosure, it can be formed at lower temperatures. Furthermore, because the phosphorus compound 1 has a structure in which an organic group is bonded to the 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, facilitating the adjustment of the ionicity described above. This facilitates the attainment of a low melting point for the phosphorus compound 1, while also providing 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 the deblocking reaction can be suppressed in the temperature range up to the desired reaction temperature, resulting in excellent storage stability. For these reasons, the blocked isocyanate composition of the present disclosure has excellent low-temperature reactivity and storage stability.

[0023] Each component of the blocked isocyanate composition of the present disclosure will be described in detail below.

[0024] 1. Phosphorus Compound 1 The phosphorus compound 1 is a phosphorus compound represented by the following formula (1).

[0025]

[0026] (In the formula, R 1 , R 2 , R 3 and R 4 are each independently an organic group having from 1 to 20 carbon atoms, the organic group being a substituted or unsubstituted hydrocarbon group, a group containing a substituted or unsubstituted heterocycle, or a group in which one or more methylene groups in the hydrocarbon group or the group containing a heterocycle are substituted with a divalent group selected from the following <Group A>, b- represents a b-valent anion, 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> represents —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.

[0027] The above R 1 , R 2 , R 3 and R 4 (Hereafter, these are collectively referred to as R 1 The organic group used in the above (sometimes referred to as "aromatic group") is a group having 1 to 20 carbon atoms.

[0028] 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.

[0029] The aliphatic hydrocarbon group having from 1 to 20 carbon atoms may be a hydrocarbon group that does not contain an aromatic hydrocarbon ring or a heterocycle, and examples thereof include a chain aliphatic hydrocarbon group having from 1 to 20 carbon atoms and an aliphatic ring-containing group having from 3 to 20 carbon atoms. Examples of the chain aliphatic hydrocarbon group having from 1 to 20 carbon atoms include an alkyl group having from 1 to 20 carbon atoms and an alkenyl group having from 2 to 20 carbon atoms. Examples of the aliphatic ring-containing group having from 3 to 20 carbon atoms include a cycloalkyl group having from 3 to 20 carbon atoms and a cycloalkylalkyl group having from 4 to 20 carbon atoms.

[0030] The alkyl group having 1 to 20 carbon atoms may be linear or branched. Examples of linear alkyl groups include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, and an n-octadecyl group. Examples of the branched alkyl group include an isopropyl group, a 2-butyl group, a tert-butyl group, an isobutyl group, an isopentyl group, a tert-pentyl group, a 2-hexyl group, a 3-hexyl group, a 2-heptyl group, a 3-heptyl group, an isoheptyl group, a tert-heptyl group, an isooctyl group, a tert-octyl group, and a 2-ethylhexyl group.

[0031] 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 terminal, or an internal alkenyl group having an internal unsaturated bond. Examples of terminal alkenyl groups include vinyl, allyl, 2-methyl-2-propenyl, 3-butenyl, 4-pentenyl, and 5-hexenyl. Examples of internal alkenyl groups include 2-butenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 2-heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl, 3-undecenyl, 4-dodecenyl, and 4,8,12-tetradecatrienylallyl.

[0032] Examples of the cycloalkyl group having from 3 to 20 carbon atoms include saturated monocyclic alkyl groups having from 3 to 20 carbon atoms, saturated polycyclic alkyl groups having from 3 to 20 carbon atoms, and groups having from 4 to 20 carbon atoms in which one or more hydrogen atoms in the ring of these groups are substituted 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 substituting 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 from 1 to 20 carbon atoms. Examples of groups in which one or more hydrogen atoms in the ring of a saturated polycyclic alkyl group are substituted with an alkyl group include a bornyl group.

[0033] The cycloalkylalkyl group having from 4 to 20 carbon atoms refers to a group having from 4 to 20 carbon atoms in which a hydrogen atom of an alkyl group is substituted with a cycloalkyl group. The cycloalkyl group in the cycloalkylalkyl group may be monocyclic or polycyclic. Examples of cycloalkylalkyl groups having from 4 to 20 carbon atoms in which the cycloalkyl group is monocyclic include a cyclopropylmethyl group, a 2-cyclobutylethyl group, a 3-cyclopentylpropyl group, a 4-cyclohexylbutyl group, a cycloheptylmethyl group, a cyclooctylmethyl group, a 2-cyclononylethyl group, and a 2-cyclodecylethyl group. Examples of cycloalkylalkyl groups having from 4 to 20 carbon atoms in which the cycloalkyl group is polycyclic include a 3-3-adamantylpropyl group and a decahydronaphthylpropyl group.

[0034] The aromatic hydrocarbon ring-containing group having from 6 to 20 carbon atoms is a hydrocarbon group that contains an aromatic hydrocarbon ring but does not contain a heterocycle, and may have an aliphatic hydrocarbon group. Examples of such aromatic hydrocarbon ring-containing groups include aryl groups having from 6 to 20 carbon atoms and arylalkyl groups having from 7 to 20 carbon atoms.

[0035] The aryl group having 6 to 20 carbon atoms may have a monocyclic structure, a fused ring structure, or may further comprise two linked aromatic hydrocarbon rings. The aryl group having two linked aromatic hydrocarbon rings may comprise two linked aromatic hydrocarbon rings having a monocyclic structure, a linked aromatic hydrocarbon ring having a monocyclic structure and a linked aromatic hydrocarbon ring having a fused ring structure, or a linked aromatic hydrocarbon ring having a fused ring structure and an linked aromatic hydrocarbon ring having a fused ring structure. The linking group connecting the two aromatic hydrocarbon rings may be any group that can impart aromaticity to the aryl group as a whole, such as a single bond. Examples of aryl groups having a monocyclic 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 fused ring structure include a naphthyl group, an anthracenyl group, a phenanthryl group, and a pyrenyl group. Examples of the aryl group in which two monocyclic aromatic hydrocarbon rings are linked together include a biphenyl group, a diphenyl sulfide group, and a benzoylphenyl group.

[0036] The arylalkyl group having from 7 to 20 carbon atoms refers to a group in which one or more hydrogen atoms in an alkyl group are substituted with an aryl group. Examples of the arylalkyl group having from 7 to 20 carbon atoms include a benzyl group, a fluorenyl group, an indenyl group, a 9-fluorenylmethyl group, an α-methylbenzyl group, an α,α-dimethylbenzyl group, a phenylethyl group, and a naphthylpropyl group.

[0037] Examples of the heterocyclic ring-containing group used as the organic group include a heterocyclic group having from 2 to 20 carbon atoms, and a hydrocarbon group having from 3 to 20 carbon atoms in which one or more hydrogen atoms have been substituted with the heterocyclic group.

[0038] Examples of the heterocyclic group include a pyridyl group, a quinolyl group, a thiazolyl group, a tetrahydrofuran group, a dioxolanyl group, a tetrahydropyranyl group, a morpholylfuran group, a methylthiophene group, a hexylthiophene group, a benzothiophene group, a pyrrole group, a pyrrolidine group, an imidazole group, an imidazolidine group, an imidazoline group, a pyrazole group, a pyrazolidine group, a piperidine group, a piperazine group, a pyrimidyl group, a furyl group, a thienyl group, a benzoxazol-2-yl group, a thiazole group, an isothiazole group, an oxazole group, an isoxazole group, and a morpholyl group.

[0039] The group containing a heterocycle may be one in which a heterocycle and an aromatic hydrocarbon ring of a monocyclic structure are linked together, or one in which a heterocycle and an aromatic hydrocarbon ring of a fused ring structure are linked together. 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 and an aromatic hydrocarbon ring of a monocyclic structure are linked together include a benzothiophene group.

[0040] 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 heterocyclic group refers to a group in which a hydrogen atom in a heterocyclic group is substituted with a substituent. Examples of the substituent substituting the hydrogen atom in such a hydrocarbon group or heterocyclic group include a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, and a carboxyl group.

[0041] A hydrocarbon group or a heterocyclic group in which one or more methylene groups have been substituted with a divalent group selected from Group A 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.

[0042] In the present disclosure, the number of carbon atoms in a group refers to the number of carbon atoms in the group after the substitution of a hydrogen atom with a substituent. For example, in the case of a "group in which the hydrogen atom of an alkyl group having 1 to 20 carbon atoms is substituted with a substituent," the term "1 to 20 carbon atoms" refers to the number of carbon atoms in the alkyl group after the hydrogen atom is substituted with a substituent, not the number of carbon atoms in the alkyl group before the hydrogen atom is substituted. Also, in the present disclosure, the number of carbon atoms in a group in which a methylene group in a group having a specified number of carbon atoms is replaced with a divalent group refers to the number of carbon atoms in the group after the substitution. For example, in the case of a "group in which the methylene group in an alkyl group having 1 to 20 carbon atoms is replaced with a divalent group," the term "1 to 20 carbon atoms" refers to the number of carbon atoms in the alkyl group after the methylene group is replaced with a divalent group, not the number of carbon atoms in the alkyl group before the substitution.

[0043] In the present disclosure, the above R 1 , R 2 , R 3 and R 4 The type of organic group represented by the formula (I) 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. This is because the blocked isocyanate composition has better low-temperature dissociation properties of the blocking agent and better storage stability. In the present disclosure, 1 , R 2 , R 3 and R 4 The hydrocarbon group used as the organic group is preferably an aliphatic hydrocarbon group, more preferably a chain aliphatic hydrocarbon group, and even more preferably an alkyl group, because this provides the blocked isocyanate composition with superior low-temperature reactivity and storage stability.

[0044] In the present disclosure, the above R 1 , R 2 , R 3 and R 4The number of carbon atoms in the organic groups represented by the formula (I) is preferably 1 or more and 18 or less, more preferably 2 or more and 16 or less, and even more preferably 3 or more and 13 or less, independently of one another. This is because the blocked isocyanate composition has better low-temperature reactivity and storage stability. However, the preferred range of the number of carbon atoms in the organic groups is determined by the formula (I) described later. b- Since it also varies depending on the type of X b- The preferred range of the number of carbon atoms in the organic group depending on the type will be explained below.

[0045] Above X b- is a phosphate anion having a phosphate ester structure, a thioether anion, an azolate anion, or the like, 1 , R 2 , R 3 and R 4 The number of carbon atoms in the organic groups used in R is preferably 1 or more and 12 or less, and more preferably 1 or more and 6 or less. This is because the blocked isocyanate composition has better low-temperature reactivity and storage stability. 1 The number of carbon atoms in the organic group used is preferably from 1 to 5, more preferably from 2 to 4, and even more preferably from 3 to 4. When the number of carbon atoms is within the above range, the blocked isocyanate composition has better low-temperature reactivity and storage stability.

[0046] In this disclosure, X b- 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, 1 The number of carbon atoms in the organic group used 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.

[0047] In the present disclosure, the above X b-is a phosphate anion, a thioether anion, an azolate anion, a halogen anion, a borate anion, a carbonate anion, or the like, 2 , R 3 and R 4 The number of carbon atoms in the organic groups used in R is preferably 1 or more and 5 or less, more preferably 2 or more and 4 or less, and even more preferably 3 or more and 4 or less. 2 , R 3 and R 4 are preferably all the same group, because the blocked isocyanate composition has better low-temperature reactivity and storage stability.

[0048] In the present disclosure, the above 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 better low-temperature reactivity and storage stability.

[0049] In the present disclosure, the above X b-represents a b-valent anion. The 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 anions, sulfite anions, sulfonate anions, and sulfonimide anions; phosphate anions such as phosphate anions, phosphite anions, phosphonate anions, and phosphinate anions; borate anions such as tetrafluoroborate anions; carbonate anions; thiophosphate anions, thiocarboxylate anions, and thio Examples of the 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.

[0050] 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 better low-temperature reactivity and storage stability.

[0051] In the present disclosure, X b-The halogen-based anion used in X is preferably a halide anion or a perhalide anion, and more preferably a halide anion, because the blocked isocyanate composition has excellent low-temperature dissociation properties of the blocking agent and excellent storage stability. b- The phosphate anion used in X 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. b- The thioether anion used in X 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. b- The azolate anion used in the above is preferably an imidazolate anion or a triazolate anion, and more preferably a triazolate anion, because this provides the blocked isocyanate composition with superior low-temperature reactivity and storage stability.

[0052] Specific examples of the anions include those described in JP-A-2021-528490. For example, alkoxide-based anions include R anions such as alkoxide anions and aryloxide anions. a O - Examples of the halide anion include F - , Cl - ,Br - , I - Examples of perhalide anions include I3 - , IBr - , IBr2 - , Br3 - , Br2Cl - , BrCl - , IC12 - , I2Cl- , Cl3 - Examples of pseudohalide anions include N3- and NCS. - , NCSe - , NCO - , C.N. - Examples of sulfate anions include HSO4 - , SO4 2- , R a OSO2O - Examples of sulfite anions include HSO3 - , SO3 2- , R a OSO 2- Examples of sulfonate anions include R a SO2O - Examples of sulfonimide anions include (R a SO2)2N - Examples of phosphate anions include H2PO4 - , HPO4 2- , PO4 3- , (R a O) PO3 2- , (R a O)2PO2 - The phosphite anion includes H2PO3 - , HPO3 2- , R a OPO2 2- , (R a O) 2PO - The phosphonate anion includes R a PO3 2- , R a P(O)(OR b ) O - The phosphinate anion includes R a R b P(O)O - Examples of boric acid anions include BO3 3- , HBO3 2- , H2BO3 - , R a BO3 - , R aHBO3 - , R a BO3 2- , B(OR a ) 4 - , B(HSO4) - , B(R a SO4) - Carbonate anions include CO3 2- , HCO3 - , R a CO3 - (More specifically, MeCO3 - Examples of the thiocarbonate anion include R a OCS 2- Examples of the thiocarbamate anion include R a 2NCS 2- Examples of the thiocarboxylic acid anion include R a CS 2- Examples of the thiophosphate anion include HPSO 3- , HPSO3 2- , PSO3 3- , (R a O) PSO2 2- , (R a O) 2PSO - , (R a O) PS2O 2- , (R a O) 2PS2 - Examples of the thiosulfonate anion include R a S(O)2S - Examples of the thiosulfate anion include R a OS(O)2S - Examples of azolate anions 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). Examples of imidazolate anions include 2,4-dinitroimidazolate, 4,5-dinitroimidazolate, 4,5-dicyano-imidazolate, and 4-nitroimidazolate. In the above formula, R a and R bare each independently the above R 1 The same groups as those exemplified as the organic groups having 1 to 20 carbon atoms used in the above and other examples can be used.

[0053] In the present disclosure, X b- The phosphate anion used in - , HPO4 2- , PO4 3- , and H2PO4 - It is more preferable that the composition is X because the composition has better low-temperature reactivity and stability. b- The phosphate anion used in the present invention has a phosphate ester structure ((P=O)-(OR a )) and (R a O) PO3 2- , (R a O)2PO2 - It is more preferable that (R a O)2PO2 - It is even more preferable that the composition is one of the above-mentioned compounds, because the composition has excellent low-temperature reactivity and storage stability, and particularly excellent storage stability. b- The phosphite anion used in - , HPO3 2- , and H2PO3 - It is more preferable that the blocked isocyanate composition is one of the above, because the blocked isocyanate composition has excellent low-temperature reactivity and storage stability. b- The halide anions used in - , Cl - ,Br - , I - Preferably, Br - , I - It is more preferable that the blocked isocyanate composition is one of the above, because the blocked isocyanate composition has excellent low-temperature reactivity and storage stability. b- The boric acid anion used in 3- , HBO3 2- , H2BO3- Preferably, H2BO3 - It is more preferable that the blocked isocyanate composition is one of the above, because the blocked isocyanate composition has excellent low-temperature reactivity and storage stability. b- The carbonate anions used in a CO3 - Preferably, 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. b- The thiophosphate anion used in the present invention has a phosphate ester structure ((P═O)—(OR a )), and preferably a thiophosphate anion having (R a O) PSO2 2- , (R a O) 2PSO - , (R a O) PS2O 2- , (R a O) 2PS2 - It is more preferable that (R a O) 2PSO - , (R a O) 2PS2 - It is even more preferable that (R a O) 2PS2 - Even more preferably, R a However, it is most preferable that X is an alkyl group having 1 to 5 carbon atoms. This is because the blocked isocyanate composition has better low-temperature reactivity and storage stability. b- The azolate anion used in R is preferably a benzotriazole anion represented by the following general formula (10): c is more preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R c is even more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R cis most preferably a hydrogen atom, because the blocked isocyanate composition has better low-temperature reactivity and storage stability.

[0054]

[0055] (In the formula, R c are each independently a hydrogen atom or the above R 1 The same groups as those exemplified as the organic groups having 1 to 20 carbon atoms used in the above can be used.)

[0056] Specific examples of such phosphorus compounds 1 include tetraethylphosphonium hydroxide, tetrabutylphosphonium chloride, hexadecyltributylphosphonium chloride, dodecyltributylphosphonium chloride, tributyltetradecylphosphonium chloride, trihexyltetradecylphosphonium chloride, tetraethylphosphonium bromide, tetrabutylphosphonium bromide, tributylhexadecylphosphonium bromide, triethylpentylphosphonium bromide, triethyloctylphosphonium bromide, ethylenediamine, ethylenediaminetetradecyl ... Tributyltrioctylphosphonium bromide, trihexyltetradecylphosphonium bromide, tributyl-n-octylphosphonium bromide, tetra-n-octylphosphonium bromide, tributylethylphosphonium bromide, tributylhexylphosphonium bromide, tributyloctylphosphonium bromide, tributyldecylphosphonium bromide, tributyldodecylphosphonium bromide, tributylmethylphosphonium iodide, ethyltriphenylphosphonium iodide, tributylethylphosphonium diethylphosphenide phosphate, tributyl(methyl)phosphonium dimethyl phosphate, trihexyltetradecylphosphonium bis(2-ethylhexyl)phosphate, tetrabutyl phosphonium hexafluorophosphate, tributylhexylphosphonium hexafluorophosphate, tributylethylphosphonium hexafluorophosphate, trihexyltetradecylphosphonium hexafluorophosphate, trihexyltetradecylphosphonium bis(2,4,4-trimethylpentyl)phosphate, tetrabutylphosphonium o,o-diethylphosphorodithioate, tetrabutylphosphonium tetrafluoroborate, tributylethylphosphonium tetrafluoroborate, tributylhexylphosphonium tetrafluoroborate, tetrabutylphosphonium tetraphenylborate, triisobutylmethylphosphonium tosylate, tributyltetradecylphosphonium dodecylbenzenesulfonate, tributylmethylphosphonium methylsulfonate, tributyltetradecylphosphonium methanesulfonate, trihexyltetradecylphosphonium decanoate,Tributyl methoxyethyl phosphonium bis(fluoromethanesulfonyl)imide, triethyl methoxymethyl phosphonium bis(fluoromethanesulfonyl)imide, tributyl methyl phosphonium bis(fluoromethanesulfonyl)imide, trihexyl(tetradecyl) phosphonium bis(fluoromethanesulfonyl)imide, triethyl octyl phosphonium bis(fluoromethanesulfonyl)imide, triethyl pentyl phosphonium bis(fluoromethanesulfonyl)imide, tributyl hexyl phosphonium bis(fluoromethanesulfonyl)imide, tetrabutyl phosphonium bis(fluoromethanesulfonyl)imide, tributyl ethyl phosphonium bis(fluoromethanesulfonyl)imide, tributyl methoxyethyl phosphonium bis(trifluoromethanesulfonyl)imide, triethyl methoxymethyl phosphonium 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 methyl carbonate, trioctylmethylphosphonium methyl carbonate, trihexyltetradecylphosphonium tricyanomethanide, tetrabutylphosphonium benzotriazolate, and the like.

[0057] The content of the phosphorus compound 1 is preferably from 0.05 to 10 parts by mass, more preferably from 0.2 to 5 parts by mass, and even more preferably from 0.5 to 3 parts by mass, per 100 parts by mass of the blocked isocyanate composition, because this provides the blocked isocyanate composition with superior low-temperature reactivity and storage stability.

[0058] The content of the phosphorus compound 1 is preferably from 0.1 to 15 parts by mass, more preferably from 1 to 10 parts by mass, and even more preferably from 2 to 5 parts by mass, per 100 parts by mass of the total of the phosphorus compound 1 and the blocked isocyanate, because this provides the blocked isocyanate composition with superior low-temperature reactivity and storage stability.

[0059] 2. Blocked Isocyanate The blocked isocyanate used in the present disclosure can be a compound having a structure in which an isocyanate group has reacted with a blocking agent. Examples of such blocked isocyanates include blocked polyisocyanate compounds, which are compounds in which an isocyanate group contained in a polyisocyanate compound has reacted with a blocking agent, and blocked urethane polyisocyanate compounds, which are compounds in which an isocyanate group contained in a urethane polyisocyanate compound obtained by reacting a polyisocyanate compound with a polyol compound has reacted with a blocking agent. In the present disclosure, the blocked isocyanate preferably includes a blocked polyisocyanate compound. This is because the blocked isocyanate composition has superior low-temperature reactivity and storage stability.

[0060] The polyisocyanate compound may be one that does not contain a urethane bond formed by the reaction of an isocyanate group with a hydroxyl group, and examples thereof include aromatic diisocyanate compounds such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate; chain 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. Furthermore, isocyanurate compounds obtained by trimerizing diisocyanate compounds such as the aromatic diisocyanate compounds, the chain aliphatic diisocyanate compounds, and alicyclic structure-containing diisocyanate compounds may also be used.

[0061] In the present disclosure, the polyisocyanate compound preferably contains the isocyanurate compound. This is because the blocked isocyanate composition has superior 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 an aromatic diisocyanate compound or an isocyanurate compound thereof, even more preferably an isocyanurate compound of an aromatic diisocyanate compound, and most preferably an isocyanurate compound of tolylene diisocyanate. This is because the blocked isocyanate composition has superior low-temperature reactivity and storage stability.

[0062] In the present disclosure, a known method can be used as a method for synthesizing an isocyanurate compound by trimerizing a diisocyanate compound. Examples of such methods include the method described in WO 2021 / 106963.

[0063] As the polyol compound, a compound having two or more hydroxyl groups in the molecule can be used, for example, polyether polyol, polyester polyol, polycarbonate polyol, polyesteramide polyol, acrylic polyol, polyurethane polyol, etc. 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 and International Publication No. 2021 / 106963.

[0064] Examples of the blocking agent include active methylene compounds such as malonic acid diesters (diethyl malonate, etc.), acetylacetone, and acetoacetic acid 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, or isomers thereof; methyl glycol, ethyl glycol Examples of suitable blocking agents include glycol derivatives such as ethanol, ethyl diglycol, ethyl triglycol, butyl glycol, and butyl diglycol; amine compounds such as dicyclohexylamine; monophenols such as phenol, cresol, ethylphenol, n-propylphenol, isopropylphenol, butylphenol, tert-butylphenol, octylphenol, nonylphenol, dodecylphenol, cyclohexylphenol, chlorophenol, and bromophenol; and phenols such as resorcinol, catechol, hydroquinone, bisphenol A, bisphenol S, bisphenol F, and naphthol; ε-caprolactone, ε-caprolactam, and the like. 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 tert-butylphenol, and most preferably phenol or cresol. This is because the blocked isocyanate composition exhibits superior low-temperature reactivity and storage stability.

[0065] Known reaction methods can be used as a method of reacting an isocyanate group contained in the polyisocyanate with a blocking agent, a method of reacting an isocyanate group contained in the polyurethane polyisocyanate with a blocking agent, etc. 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.

[0066] The content of the blocked isocyanate 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, per 100 parts by mass of the blocked isocyanate composition. This is because the blocked isocyanate composition exhibits 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, 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 30 parts by mass or less, per 100 parts by mass of the blocked isocyanate composition. This is because the blocked isocyanate composition has excellent low-temperature reactivity and storage stability.

[0067] 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. This is 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, 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 blocked isocyanate composition. This is because the blocked isocyanate composition has superior low-temperature reactivity and storage stability.

[0068] 3. Plasticizer The blocked isocyanate composition of the present disclosure contains the above-described blocked isocyanate and phosphorus compound 1, but preferably contains a plasticizer. This is because, for example, when the blocked isocyanate composition is used in combination with a thermoplastic resin, blending with the thermoplastic resin becomes easier. Here, the plasticizer may be any plasticizer that can plasticize the 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 further description here is omitted.

[0069] 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 pyromellitate (TOPM); di-2-ethylhexyl adipate (DOA), diisononyl adipate (DINA), diisodecyl adipate (DIDA), di-2-ethylhexyl sebacate (DOS), and sebacic acid esters. Examples of suitable plasticizers include aliphatic dibasic acid esters such as diisononyl phthalate (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 paraffins obtained by chlorinating paraffin wax or n-paraffin; chlorinated fatty acid esters such as chlorinated stearic acid esters; 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, and as a result, when mixed with the thermoplastic resin, each component of the blocked isocyanate composition can be uniformly dispersed in the thermoplastic resin, resulting in excellent reactivity of the isocyanate group after the blocking agent is dissociated.

[0070] The content of the plasticizer is preferably in the range of 20 to 90 parts by mass, more preferably 35 to 85 parts by mass, and even more preferably 50 to 80 parts by mass, per 100 parts by mass of the blocked isocyanate composition, because the blocked isocyanate composition has superior low-temperature reactivity and storage stability, and also because the blocked isocyanate composition has excellent compatibility with thermoplastic resins.

[0071] The blocked isocyanate composition of the present disclosure contains the above-described blocked isocyanate and phosphorus compound 1, and preferably contains an isocyanate curing catalyst that promotes the reaction between an isocyanate group generated upon dissociation of the blocking agent from the blocked isocyanate and an active hydrogen group. This is because the blocked isocyanate composition exhibits excellent reactivity of the isocyanate group after dissociation of the blocking agent.

[0072] Examples of the active hydrogen group include a hydroxyl group, a phenol group, an amino group, an imino group, a carboxyl group, a urethane group, a thiol group, and a sulfonic acid group.

[0073] Examples of the isocyanate curing catalyst include an amine catalyst and an organometallic catalyst. In the present disclosure, the isocyanate curing catalyst preferably contains an organometallic catalyst. This is because the blocked isocyanate composition has excellent reactivity of the isocyanate group after the blocking agent dissociates. The isocyanate curing catalyst may contain only one type, or may contain a combination of two or more types.

[0074] Examples of organometallic catalysts 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, or dioctyltin dilaurate, and more preferably contains dibutyltin dilaurate, dioctyltin dilaurate, or the like. This is because the blocked isocyanate composition exhibits excellent reactivity of the isocyanate group after the blocking agent dissociates.

[0075] As the amine catalyst, for example, those described as catalysts used in synthesizing polyurethane resins as described in Japanese Patent No. 6,806,488 can be used.

[0076] The content of the isocyanate curing catalyst is preferably from 0.01 to 5 parts by mass, and more preferably from 0.05 to 2 parts by mass, per 100 parts by mass of the blocked isocyanate composition, because the blocked isocyanate composition has excellent reactivity of the isocyanate group after the blocking agent dissociates.

[0077] The content of the isocyanate curing catalyst is preferably from 0.0001 to 10 parts by mass, more preferably from 0.01 to 6 parts by mass, even more preferably from 0.10 to 5 parts by mass, and even more preferably from 0.20 to 4 parts by mass, relative to 100 parts by mass of the blocked isocyanate, because the blocked isocyanate composition has excellent reactivity of the isocyanate groups after deblocking.

[0078] 5. Epoxy Compound The blocked isocyanate composition can contain an epoxy compound. Examples of such epoxy compounds include the epoxy resins described in International Publication No. WO 2021 / 106963. Specific examples include 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 glycidylamino groups, epoxidized products of cyclic olefin compounds, epoxidized conjugated diene polymers, and heterocyclic epoxy compounds. These epoxy compounds may be internally crosslinked with a prepolymer of a terminal isocyanate, or may be polymerized with a polyvalent active hydrogen compound (such as a polyhydric phenol, a polyamine, a carbonyl group-containing compound, or a polyphosphate ester).

[0079] 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, per 100 parts by mass of the blocked isocyanate composition. Furthermore, the content of the epoxy compound is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, 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.

[0080] 6. Other Components The blocked isocyanate composition of the present disclosure may contain other components as needed in addition to the above-described phosphorus compound 1, blocked isocyanate, isocyanate curing catalyst, plasticizer, and epoxy compound. Such other components include fillers, colorants, antioxidants, foaming agents, diluents, and ultraviolet absorbers.

[0081] The filler can be either an inorganic filler or an organic filler. 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; metal carbonates such as calcium carbonate, calcium silicate, magnesium carbonate, and barium carbonate, or those modified by organic modification treatment; pigments such as metal borates and carbon black; 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 microparticles, transparent resin beads, wood flour, pulp, and cotton chips.

[0082] Examples of colorants that can be used include inorganic pigments such as titanium dioxide and carbon black, and organic pigments such as azo pigments and phthalocyanine pigments. Examples of antioxidants that can be used include phenolic and amine antioxidants. Examples of foaming agents that can be used include azo foaming agents that generate gas when heated, such as azodicarbonamide and azobisformamide. Examples of diluents that can be used include solvents such as xylene and mineral turpentine. Examples of ultraviolet absorbers that can be used include benzotriazole compounds.

[0083] 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 is, for example, 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, because this provides the blocked isocyanate composition with superior low-temperature reactivity and storage stability.

[0084] 7. Method for Producing Blocked Isocyanate Composition Any method can be used to produce the blocked isocyanate composition of the present disclosure as long as it can produce a composition containing the desired amounts of each component, and any known mixing method can be used.

[0085] 8. Uses of Blocked Isocyanate Composition The use of the blocked isocyanate composition of the present disclosure is preferably an application that utilizes a reaction of an isocyanate group after dissociation of a blocking agent from the blocked isocyanate, and more preferably an application that requires low-temperature reactivity. Examples of such applications include paints and adhesives, and specifically include paints and adhesives for molded products such as miscellaneous goods, toys, industrial parts, and electrical parts. In the present disclosure, the above application is preferably a paint or adhesive, more preferably a paint or adhesive other than an electrodeposition paint, primer paint, and clear paint for automobiles, even more preferably an adhesive, still more preferably an adhesive for automobiles, electrical materials, and building materials, and most preferably an adhesive for automobiles, electrical materials, and building materials (excluding electrodeposition paint, primer paint, and clear paint for automobiles).

[0086] Automotive components using adhesives are preferably components using metal materials, and more preferably components on which a paint is formed on the surface of a metal material. Examples of such components include the underbody of an automobile, i.e., the underside of the floor, wheel wells (tire wells), rocker panels, side sills, front aprons, front and rear fenders, and lower door sections. A protective layer may be formed on the above components to prevent paint peeling due to collisions 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 protective layer at low temperatures. Therefore, it can achieve effects such as reducing carbon dioxide emissions and saving energy, which are required in automobile factories, etc. Automotive components using metal materials include those in which the metal material, electrodeposition coating, adhesive layer (protective layer), and surface coating (primary coating, top coating (clear coating), etc.) are formed in this order.

[0087] In the present disclosure, the adhesive layer (resin layer) is formed between the electrodeposition coating and the surface coating, thereby enabling the formation of a protective layer with excellent adhesion at low temperatures and effectively achieving the effects of the present disclosure. Furthermore, the blocked isocyanate composition can stably dissociate the blocking agent from the blocked isocyanate contained as a component of the composition at low temperatures, resulting in excellent reactivity between the regenerated isocyanate group and hydroxyl groups, etc., present on the electrodeposition coating surface. Therefore, use of the blocked isocyanate composition can provide excellent adhesion even when processed at low temperatures. When used in 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. This is because the effect of excellent low-temperature reactivity of the present disclosure can be more effectively achieved. Note that the preferred types of thermoplastic resins, the preferred ranges of the contents of each component contained in the composition per 100 parts by mass of thermoplastic resin, and the like are the same as those described in the section "B. Resin Composition" below, and therefore will not be described here.

[0088] 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.

[0089] According to the present disclosure, by including the phosphorus compound 1, the blocked isocyanate, and the thermoplastic resin, the resin composition is able to dissociate the blocking agent from the blocked isocyanate to a greater extent, resulting in excellent low-temperature reactivity. Furthermore, as a result, when the resin composition is used as a resin layer-forming composition, it is possible to form a resin layer that adheres to an adherend at low temperatures. Furthermore, the resin composition has excellent storage stability. For these reasons, the resin composition of the present disclosure has excellent low-temperature reactivity and storage stability.

[0090] Each component of the resin composition of the present disclosure will be described in detail below.

[0091] 1. Phosphorus Compound 1 The phosphorus compound 1 is a phosphorus compound represented by the general formula (1). The types of such phosphorus compound 1 can be the same as those described in the section "A. Blocked Isocyanate Composition" above, and therefore further description here will be omitted.

[0092] The content of the phosphorus compound 1 is preferably 0.01 part by mass or more and 1.0 part by mass or less, more preferably 0.03 part by mass or more and 0.5 part by mass or less, and even more preferably 0.05 part by mass or more and 0.3 part by mass or less, per 100 parts by mass of the resin composition, because the resin composition has better low-temperature reactivity and storage stability.

[0093] The content of the phosphorus compound 1 is preferably 0.01 part by mass or more and 1.0 part by mass or less, more preferably 0.03 part by mass or more and 0.5 part by mass or less, and even more preferably 0.05 part by mass or more and 0.3 part by mass or less, relative to 100 parts by mass of the thermoplastic resin, because the resin composition has better low-temperature reactivity and storage stability.

[0094] 2. Blocked Isocyanate The blocked isocyanate may be a compound having a structure in which an isocyanate group has reacted with a blocking agent. The details of such blocked isocyanates may be the same as those described in the above section "A. Blocked Isocyanate Composition," and therefore, further explanation will be omitted here.

[0095] The content of the blocked isocyanate is preferably from 0.1 to 25 parts by mass, more preferably from 0.5 to 15 parts by mass, even more preferably from 1.0 to 10 parts by mass, and most preferably from 1.5 to 5 parts by mass, per 100 parts by mass of the resin composition, because this provides the resin composition with superior low-temperature reactivity and storage stability.

[0096] The content of the blocked isocyanate is preferably from 0.1 to 25 parts by mass, more preferably from 1 to 20 parts by mass, even more preferably from 2 to 15 parts by mass, and most preferably from 5 to 12 parts by mass, relative to 100 parts by mass of the thermoplastic resin, because this provides the resin composition with superior low-temperature reactivity and storage stability.

[0097] 3. Thermoplastic Resin Examples of the thermoplastic resin include vinyl chloride resin, acrylic resin, ionomer resin, AAS resin (acrylonitrile / styrene / specialty 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 includes a vinyl chloride resin, an acrylic resin, or the like, and more preferably includes an acrylic resin. This is because the resin composition has better low-temperature reactivity and storage stability.

[0098] 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, and itaconic acid; diene monomers such as isoprene and butadiene; styrene monomers such as styrene and α-methylstyrene; or acrylonitrile. More specific 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, and vinyl chloride-various vinyl ether copolymers.

[0099] Examples of acrylic resins that can be used include those containing acrylic acid ester monomers such as alkyl acrylates and alkyl methacrylates as raw materials. The acrylic resins may be homopolymers of acrylic acid ester monomers, or copolymers 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 monomers include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, ter-butyl acrylate, cyclohexyl acrylate, benzyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, ter-butyl methacrylate, cyclohexyl methacrylate, and benzyl methacrylate.

[0100] The content of the thermoplastic resin may be any content that provides the desired low-temperature reactivity, etc., but is preferably 50 to 99 parts by mass, more preferably 75 to 98 parts by mass, even more preferably 80 to 96 parts by mass, and most preferably 85 to 94 parts by mass, per 100 parts by mass of the resin composition. Furthermore, when the resin composition contains a plasticizer, the content of the thermoplastic resin is preferably 5 to 99 parts by mass, more preferably 10 to 50 parts by mass, even more preferably 15 to 40 parts by mass, and most preferably 20 to 35 parts by mass. This is because the resin composition has better low-temperature reactivity and storage stability.

[0101] 4. Plasticizer The resin composition preferably contains a plasticizer. This is because the resin composition has excellent moldability and the like. The type of plasticizer can be the same as that described in the section "A. Blocked Isocyanate Composition" above, and therefore a description thereof will be omitted here.

[0102] 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, because the resin composition has better low-temperature reactivity and storage stability.

[0103] 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, because the resin composition has better low-temperature reactivity and storage stability.

[0104] 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.

[0105] Such an isocyanate curing catalyst may be, for example, the same as that described in the above section "A. Blocked isocyanate composition," and therefore a description thereof will be omitted here.

[0106] The content of the isocyanate curing catalyst is preferably from 0.01 to 1.0 part by mass, more preferably from 0.03 to 0.5 parts by mass, and even more preferably from 0.05 to 0.3 parts by mass, per 100 parts by mass of the resin composition, because this provides the resin composition with better low-temperature reactivity and storage stability.

[0107] The content of the isocyanate curing catalyst relative to the blocked isocyanate and the content of the filler can be the same as those described in the section "A. Blocked Isocyanate Composition" above, and therefore further explanation will be omitted here.

[0108] 6. Filler The resin composition of the present disclosure preferably contains a filler, because this provides the resin composition with excellent mechanical strength.

[0109] As such a filler, for example, those listed as fillers described 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. This is because the resin composition has excellent mechanical strength.

[0110] 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, because the resin composition has better low-temperature reactivity and storage stability.

[0111] 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, relative to 100 parts by mass of the thermoplastic resin, because the resin composition has better low-temperature reactivity and storage stability.

[0112] 7. Epoxy Compound The resin composition of the present disclosure may contain an epoxy compound. Examples of such epoxy compounds that can be used include those listed as epoxy compounds in the above section "A. Composition." 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, per 100 parts by mass of the resin composition. This is because the resin composition has better low-temperature reactivity and storage stability.

[0113] 8. Other Components The resin composition may contain other components as needed in addition to the phosphorus compound 1, blocked isocyanate, thermoplastic resin, isocyanate curing catalyst, plasticizer, filler, and epoxy compound. Such other components may be the same as the components other than the filler among the other components described in the section "A. Blocked Isocyanate Composition" above.

[0114] 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, and is, for example, 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, because the resin composition has better low-temperature reactivity and storage stability.

[0115] The resin composition of the present disclosure is preferably used in a reaction of an isocyanate group after deblocking from a blocked isocyanate, and can be used in the same manner as the use of the composition described in the above section "A. Blocked isocyanate composition," for example.

[0116] C. Manufacturing Method of Resin Layer Next, a manufacturing method of the resin layer of the present disclosure will be described. The manufacturing method of the resin composition of the present disclosure is characterized by having a coating step of applying the above-mentioned resin composition and a heating step of heating the coating film formed by the above-mentioned coating step to form a resin layer.

[0117] According to the present disclosure, since the resin composition described above is used, a resin layer having excellent adhesion can be easily formed at a lower temperature. Furthermore, since the resin composition has excellent storage stability, it is possible to easily control the position, thickness, etc. of the resin layer.

[0118] The method for producing a resin composition according to the present disclosure includes a coating step and a heating step. Each step of the method for producing a resin composition according to the present disclosure will be described in detail below.

[0119] 1. Coating Step This step is a step of coating the resin composition described above. 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 can be used. Examples of such coating methods include known coating methods such as brush coating, roller coating, air spray coating, and airless spray coating.

[0120] The thickness of the coating film formed in this step 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, because the effects of the present disclosure can be more effectively exhibited in this manner.

[0121] 2. Heating Step This step is a step of heating the coating film formed in the 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. This is because the effects of the present disclosure can be more effectively exhibited.

[0122] The heating time in this step 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, because this allows the effects of the present disclosure to be exerted more effectively.

[0123] The thickness of the resin layer formed in this step 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, because the effects of the present disclosure can be more effectively exhibited in this manner.

[0124] 3. Others The manufacturing method of the present disclosure includes a coating step and a heating step, but may include other steps as necessary. Uses of the resin layer manufactured by the manufacturing method of the present disclosure can be, for example, the same as those described as uses of the composition described in the above section "A. Composition."

[0125] D. Resin Layer Next, the resin layer of the present disclosure will be described. The resin layer of the present disclosure is characterized by being formed using the resin composition described above.

[0126] According to the present disclosure, the resin layer is easy to form.

[0127] The resin layer of the present disclosure uses the above-mentioned resin composition. The method for forming such a resin layer may be the same as that described in the above section "C. Method for producing a resin layer." Furthermore, the use of such a resin layer may be the same as that of the composition described in the above section "A. Blocked isocyanate composition."

[0128] 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.

[0129]

[0130] (In the formula, R 1 , R 2 , R 3 and R 4are each independently an organic group having from 1 to 20 carbon atoms, the organic group being a substituted or unsubstituted hydrocarbon group, a group containing a substituted or unsubstituted heterocycle, or a group in which one or more methylene groups in the hydrocarbon group or the group containing a heterocycle are substituted with a divalent group selected from the following <Group A>, b- represents a b-valent anion, 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> represents —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.

[0131] According to the present disclosure, for example, it can be easily formed by using the above-mentioned "B. Resin composition."

[0132] The resin layer of the present disclosure contains a polyisocyanate compound or a urethane polyisocyanate compound, a phosphorus compound 1, and a thermoplastic resin.

[0133] 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 contents of phosphorus compound 1 and thermoplastic resin in 100 parts by mass of the resin layer may be the same as those described as the contents in 100 parts by mass of the resin composition in the section "B. Resin composition" above.

[0134] The type of polyisocyanate compound or urethane polyisocyanate compound (hereinafter sometimes 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 may be the same as that described in the above section "B. Resin Composition" 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.

[0135] The resin layer may contain an isocyanate curing catalyst, a plasticizer, a filler, and other components in addition to the isocyanate compound, the phosphorus compound 1, and the thermoplastic resin. The contents of each of these components may be the same as those described in the section "B. Resin composition" above, and therefore, a description thereof will be omitted here.

[0136] The method for forming the resin layer may be any method that can form a resin layer in a desired shape, and examples thereof include the methods described in the above section "C. Method for producing resin layer."

[0137] The use of the resin layer can be the same as that described above for the use of the composition described in the section "A. Blocked isocyanate composition."

[0138] F. Others The present disclosure includes the following aspects.

[0139] [1] A blocked isocyanate composition comprising: a phosphorus compound represented by the following formula (1); and a blocked isocyanate:

[0140]

[0141] (In the formula, R 1 , R 2 , R 3 and R 4 are each independently an organic group having from 1 to 20 carbon atoms, the organic group being a substituted or unsubstituted hydrocarbon group, a group containing a substituted or unsubstituted heterocycle, or a group in which one or more methylene groups in the hydrocarbon group or the group containing a heterocycle are substituted with a divalent group selected from the following <Group A>, b- represents a b-valent anion, 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> represents —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.

[0142] [2] R 1 , R 2 , R3 and R 4 are each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, R 1 , R 2 , R 3 and R 4 The blocked isocyanate composition according to [1], wherein the hydrocarbon group used is an aliphatic hydrocarbon group.

[0143] [3] X b- is 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.

[0144] [4] R 1 The blocked isocyanate composition according to any one of [1] to [3], wherein the number of carbon atoms in the organic group used is 6 or more and 13 or less.

[0145] [5] R 1 The number of carbon atoms in the organic group used in X is 6 or more and 13 or less, 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 1 The number of carbon atoms in the organic group used in X is 1 or more and 5 or less, b- is a phosphate anion having a phosphate ester structure, a thioether anion, or an azolate anion.

[0146] [6] R 2 , R 3 and R 4 The blocked isocyanate composition according to any one of [1] to [5], wherein the number of carbon atoms in the organic groups used is independently 1 or more and 5 or less.

[0147] [7] The blocked isocyanate composition according to any one of [1] to [6], wherein the content of the phosphorus compound represented by 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.

[0148] [8] The blocked isocyanate composition according to any one of [1] to [7], wherein 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.

[0149] [9] The blocked isocyanate composition according to any one of [1] to [8], further comprising a plasticizer.

[0150]

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

[0151]

[11] The blocked isocyanate composition according to any one of [1] to

[10] , which contains an epoxy compound.

[0152]

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

[0153]

[0154] (In the formula, R 1 , R 2 , R 3 and R 4 each independently represents an organic group having from 1 to 20 carbon atoms, the organic group being a substituted or unsubstituted hydrocarbon group, a group containing a substituted or unsubstituted heterocycle, or a group in which one or more methylene groups in the hydrocarbon group or the group containing a heterocycle are substituted with a divalent group selected from the following <Group A>, b-represents a b-valent anion, 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> represents —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.

[0155]

[13] The resin composition according to

[12] , characterized in that it contains a filler.

[0156]

[14] The resin composition according to

[12] or

[13] , characterized in that it contains a plasticizer.

[0157]

[15] The resin composition according to any one of

[12] to

[14] , characterized by containing an isocyanate curing catalyst.

[0158]

[16] The resin composition according to any one of

[12] to

[15] , characterized by containing an epoxy compound.

[0159]

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

[12] to

[16] .

[0160]

[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:

[0161]

[0162] (In the formula, R 1 , R 2 , R 3 and R 4 are each independently an organic group having from 1 to 20 carbon atoms, the organic group being a substituted or unsubstituted hydrocarbon group, a group containing a substituted or unsubstituted heterocycle, or a group in which one or more methylene groups in the hydrocarbon group or the group containing a heterocycle are substituted with a divalent group selected from the following <Group A>, b- represents a b-valent anion, 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> represents —O—, —CO—, —COO—, —OCO—, —NR11 -, -NR 11 CO- and -S-, R 11 represents a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms.

[0163]

[19] The resin layer according to

[18] , characterized in that it contains a filler.

[0164]

[20] The resin layer according to

[18] or

[19] , characterized by containing a plasticizer.

[0165]

[21] The resin layer according to any one of

[18] to

[20] , characterized by containing an isocyanate curing catalyst.

[0166]

[22] The resin layer according to any one of

[18] to

[21] , characterized by containing an epoxy compound.

[0167]

[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.

[0168] The present invention is not limited to the above-described embodiments. The above-described embodiments are merely examples, and any embodiment 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 the present disclosure.

[0169] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0170] <Synthesis of phosphorus compounds> (Synthesis Example 1) Tetrabutylphosphonium bromide (BuP + Br - ) was anion-exchanged using a strongly basic ion exchange resin to give tetrabutylphosphonium hydroxide (BuP), an alkylphosphonium hydroxide salt. + OH -Next, tetrabutylphosphonium hydroxide and boric acid were reacted 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).

[0171] Synthesis Example 2 Tributylphosphine (Bu3P) and dimethyl carbonate were reacted in methanol under heating conditions at 40°C, and then the solvent methanol was removed to obtain a phosphorus compound A2 represented by the following formula (A2).

[0172] 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.

[0173] (Synthesis Example 4) As the alkylphosphonium halogen salt, (CH 17 ) Bu3P + Br - The procedure of Synthesis Example 1 was repeated except that the compound was reacted with phosphoric acid instead of boric acid, to obtain a phosphorus compound A4 represented by the following formula (A4).

[0174] (Synthesis Example 5) As the alkylphosphonium halogen salt, (CH 17 ) Bu3P + Br - The procedure of Synthesis Example 1 was repeated except that the compound was reacted with phosphorous acid instead of boric acid, to obtain a phosphorus compound A5 represented by the following formula (A5).

[0175] (Synthesis Example 6) As the alkylphosphonium halogen salt, (CH 17 ) Bu3P + Br - A phosphorus compound A6 represented by the following formula (A6) was obtained in the same manner as in Synthesis Example 1, except that the following compound A6 was used.

[0176] (Synthesis Example 7) As the alkylphosphonium halogen salt, (C 12 H 25 ) Bu3P + Br -The procedure of Synthesis Example 1 was repeated except that the compound was reacted with phosphoric acid instead of boric acid, to obtain a phosphorus compound A7 represented by the following formula (A7).

[0177] (Synthesis Example 8) As the alkylphosphonium halogen salt, (C 12 H 25 ) Bu3P + Br - A phosphorus compound A8 represented by the following formula (A8) was obtained in the same manner as in Synthesis Example 1, except that the compound was reacted with phosphorous acid instead of boric acid.

[0178] (Synthesis Example 9) As an alkylphosphonium halogen salt, (C 12 H 25 ) Bu3P + Br - Compound A9 represented by the following formula (A9) was obtained in the same manner as in Synthesis Example 1, except that

[0179] (Synthesis Example 10) As an alkylphosphonium halogen salt, (C 14 H 29 ) Bu3P + Br - A phosphorus compound A10 represented by the following formula (A10) was obtained in the same manner as in Synthesis Example 1, except that the compound was reacted with phosphoric acid instead of boric acid.

[0180] Synthesis Example 11 As an alkylphosphonium halogen salt, (C 14 H 29 ) Bu3P + Br - A phosphorus compound A11 represented by the following formula (A11) was obtained in the same manner as in Synthesis Example 1, except that the above compound was reacted with phosphoric acid instead of boric acid (so that the amount of cation was 3 equivalents relative to phosphoric acid).

[0181] Synthesis of Blocked Isocyanate (Synthesis Example 12) A three-neck flask was charged with 305 g of diisononyl phthalate (DNIP, plasticizer) and 62 g of nonylphenol (blocking agent), and the mixture was subjected to vacuum dehydration at 100 to 110°C and a pressure of less than 30 mmHg for 1 hour. The mixture was cooled to 80°C, and 120 g of tolylene diisocyanate (TDI) nurate (containing 50% butyl acetate) (polyisocyanate compound, Tosoh Corporation, Coronate 2037) and 0.36 g of dibutyltin dilaurate (isocyanate curing catalyst) were added. The mixture was reacted at 130 to 140°C for 4 hours while removing the solvent under reduced pressure at less than 30 mmHg. The mixture was then cooled and aged at 80 to 90°C for 1 hour while degassing at a pressure of less than 30 mmHg to obtain a blocked isocyanate pre-composition 1 containing a blocked isocyanate (compound B1). In the infrared absorption spectrum, the absorption of isocyanate (NCO) is 2260 cm -1 It was confirmed that the color had completely disappeared. Blocked isocyanate pre-composition 1 was a mixture containing 100 parts by mass of blocked isocyanate (compound B1), 250 parts by mass of plasticizer (C1), and 0.3 parts by mass of 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 blocked NCO% when all NCOs are blocked is 2.25% by mass). The viscosity was measured using a TOKI SANGYO E-type viscometer (rotation speed: 10 rpm). The blocked NCO% was measured in accordance with JIS K 7301-1995.

[0182] Synthesis Example 13: A three-neck flask was charged with 305 g of diisononyl phthalate (DNIP, plasticizer) and 62.0 g of nonylphenol (blocking agent), and the mixture was subjected to vacuum dehydration at 100 to 110°C and a pressure of less than 30 mmHg for 1 hour. The mixture was cooled to 80°C, and 120 g of tolylene diisocyanate (TDI) nurate (containing 50% butyl acetate) (a polyisocyanate compound) and 0.12 g of dibutyltin dilaurate (an isocyanate curing catalyst) were added. The mixture was reacted at 130 to 140°C for 4 hours while removing the solvent 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 epoxy resin) was added. The mixture was then aged for 1 hour. A blocked isocyanate precomposition 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. Blocked isocyanate pre-composition 2 was a mixture containing 100 parts by mass of blocked isocyanate (compound B1), 250 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).

[0183] Synthesis Example 14: A three-neck flask was charged with 207 g of diisononyl phthalate (DNIP, plasticizer) and 62.0 g of nonylphenol (blocking agent), and the mixture was subjected to vacuum dehydration at 100 to 110°C and a pressure of less than 30 mmHg for 1 hour. The mixture was cooled to 80°C, and 120 g of tolylene diisocyanate (TDI) nurate (containing 50% butyl acetate) (a polyisocyanate compound) and 0.12 g of dibutyltin dilaurate (an isocyanate curing catalyst) were added. The mixture was reacted at 130 to 140°C for 4 hours while removing the solvent 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 epoxy resin) was added. The mixture was then aged for 1 hour. A blocked isocyanate precomposition 3 containing a blocked isocyanate (compound B1) was obtained in the same manner as in Synthesis Example 12. The viscosity of the obtained 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).

[0184] Examples 1 to 21 and Comparative Examples 1 to 3 Blocked isocyanate compositions were prepared by blending the components according to the formulations shown in Tables 1 and 2 below. Specifically, the blocked isocyanate compositions of Examples 1 to 21 were prepared by blending the phosphorus compounds A1 to 11 and commercially available phosphorus compounds A12 to 18 obtained in Synthesis Examples 1 to 11 and the blocked isocyanate pre-compositions 1 to 3 obtained in Synthesis Examples 12 to 14 according to the formulations shown in Tables 1 and 2. The blocked isocyanate compositions of Comparative Examples 2 and 3 were prepared by blending the commercially available compounds A'1 and A'2 shown below and the blocked isocyanate pre-composition 1 according to the formulations shown in Tables 1 and 2. The following materials were used for each component. The blend amounts in Tables 1 and 2 represent parts by mass of each component. The amounts of blocked isocyanate B1, plasticizer C1, epoxy compound D1, and isocyanate curing catalyst E1 shown are those in blocked isocyanate pre-compositions 1 to 3 obtained in Synthesis Examples 12 to 14.

[0185] (Compound 1) A1: Phosphorus compound A1 obtained in Synthesis Example 1 (compound represented by formula (A1) below) A2: Phosphorus compound A2 obtained in Synthesis Example 2 (compound represented by formula (A2) below) A3: Phosphorus compound A3 obtained in Synthesis Example 3 (compound represented by formula (A3) below) A4: Phosphorus compound A4 obtained in Synthesis Example 4 (compound represented by formula (A4) below) A5: Phosphorus compound A5 obtained in Synthesis Example 5 (compound represented by formula (A5) below) A6: Phosphorus compound A6 obtained in Synthesis Example 6 (compound represented by formula (A6) below) A7: Phosphorus compound A7 obtained in Synthesis Example 7 (compound represented by formula (A7) below) A8: Phosphorus compound A8 obtained in Synthesis Example 8 (compound represented by formula (A8) below) A9: Phosphorus compound A9 obtained in Synthesis Example 9 (compound represented by formula (A9) below) A10: Phosphorus compound A10 obtained in Synthesis Example 10 (compound represented by formula (A10) below) 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) (Hishicolin PX-4ET, manufactured by Nippon Chemical Industry Co., Ltd.) A13: Phosphorus compound A13 represented by the following formula (A13) (Hishicolin PX-4MP, manufactured by Nippon Chemical Industry Co., Ltd.) A14: Phosphorus compound A14 represented by the following formula (A14) (Hishicolin PX-4MI, manufactured by Nippon Chemical Industry Co., Ltd.) A15: Phosphorus compound A15 represented by the following formula (A15) (Hishicolin PX-4BT, manufactured by Nippon Chemical Industry Co., Ltd.) A16: Phosphorus compound A16 represented by the following formula (A16) (Hishicolin PX-82B, manufactured by Nippon Chemical Industry Co., Ltd.) A17: Phosphorus compound A17 represented by the following formula (A17) (Hishicolin PX-28B, manufactured by Nippon Chemical Industry Co., Ltd.) A18: Phosphorus compound A18 represented by the following formula (A18) (ethyltriphenylphosphonium iodide (ETPPI) manufactured by Sigma-Aldrich) 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) A'2: Compound A'2 represented by the following formula (A'2) (1,8-diazabicyclo[5.4.0]undecene-7(DBU))

[0186]

[0187]

[0188]

[0189]

[0190]

[0191]

[0192]

[0193]

[0194]

[0195]

[0196]

[0197]

[0198]

[0199]

[0200]

[0201]

[0202]

[0203]

[0204]

[0205]

[0206] (Blocked isocyanate) B1: Compound B1 obtained in Synthesis Examples 12 to 14

[0207] (Plasticizer) C1: DINP

[0208] (Epoxy compound) D1: EP-4100E (manufactured by ADEKA Corporation; bisphenol A type epoxy compound)

[0209] (Isocyanate curing catalyst) E2: Dibutyltin dilaurate (DBTDL)

[0210] [Evaluation] Each of the obtained blocked isocyanate compositions was evaluated for storage stability and adhesion (low-temperature reactivity) when a resin layer was formed, according to the following procedures. The results are shown in Tables 1 and 2.

[0211] 1. Storage Stability The blocked isocyanate compositions obtained in Examples 1 to 21 and Comparative Examples 1 to 3 were evaluated for their viscosity increase rate (rate of viscosity change) from the initial value when stored (left stationary) in a container at 40°C for 7 days using an E-type rotational viscometer (manufactured by Toki Sangyo Co., Ltd.). Specifically, for each blocked isocyanate composition immediately after preparation, the initial viscosity at 25°C was measured for 3 minutes at 2 rpm using an E-type rotational viscometer. Furthermore, each of the blocked isocyanate compositions was placed in a sealed container and stored at 40°C for 7 days, then cooled to 25°C. Similarly to the initial viscosity, the viscosity after 7 days was measured for 3 minutes at 2 rpm using an E-type rotational viscometer. Using the obtained initial viscosity and viscosity after 7 days, the viscosity increase rate was calculated 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)

[0212] <Evaluation criteria> ◎: The viscosity increase rate is 50% or less. ◯: The viscosity increase rate is more than 50% but not more than 100%. △: The viscosity increase rate is more than 100% but not more than 200%. ×: The viscosity increase rate is more than 200%. Note that 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 storage stability of the blocked isocyanate composition is excellent. 2. Low-temperature reactivity The blocked isocyanate compositions obtained in Examples 1 to 21 and Comparative Examples 1 to 3 were blended with the respective components according to the blending ratio described below to obtain resin compositions (hereinafter referred to as resin compositions for evaluation).

[0213] (Resin composition for evaluation) Blocked isocyanate composition: 8 parts by mass Thermoplastic resin: 30 parts by mass Plasticizer: 35 parts by mass Filler: 35 parts by mass Isocyanate curing catalyst: 0.1 parts by mass

[0214] 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)

[0215] (Preparation of Evaluation Test Pieces) As shown in Figures 1(a) and (b), a test panel 3 (25 mm wide x 100 mm long x 1.0 mm thick) made of a cationic electrodeposition-coated steel plate was prepared. 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 with a sloped ruler attached to both ends, and then the spatula was pressed against the sloped portion of the ruler to scrape off any unnecessary resin composition for evaluation, thereby forming a sloped coating film. The test piece was then heated at 100°C for 30 minutes to form a resin layer 4 (hereinafter sometimes referred to as the 100°C resin layer), thereby obtaining an evaluation test piece 1. Similarly, the coating film formed by sloped 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), thereby obtaining an evaluation test piece 2. 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 from 3 mm to 0 mm.

[0216] (Evaluation Method) Each of the obtained evaluation specimens (evaluation specimen 1 and evaluation specimen 2) was scratched with a fingernail (scratch direction 5) from the thick film side of the resin layer 4 (100°C resin layer and 120°C resin layer) as shown in Figures 1(a) and 1(b), 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.

[0217] <Evaluation criteria> ⊚: The entire peeled surface of the 100°C resin layer is in a state of cohesive failure. ◯: The peeled surface of the 100°C resin layer is in a state of a mixture of cohesive failure and interfacial failure. Δ: The entire peeled surface of the 100°C resin layer is in a state of interfacial failure, and the peeled surface of the 120°C resin layer is in a state of a mixture of cohesive failure and interfacial failure. ×: The entire peeled surface of the 100°C resin layer is in a state of interfacial failure, and the entire peeled surface of the 120°C resin layer is in a state of interfacial failure. It can be determined that the lower the forming conditions of the resin layer and the higher the proportion of cohesive failure, the higher the adhesion of the resin layer and the better the low-temperature reactivity.

[0218]

[0219]

[0220] [Summary] Tables 1 and 2 confirm that the use of the blocked isocyanate compositions of the Examples provides superior storage stability compared to the blocked isocyanate compositions of the Comparative Examples, and enables the formation of resin layers with excellent adhesion even when formed at low temperatures (100°C and 120°C). In particular, the blocked isocyanate compositions of Examples 4, 7, 12, and 21 were confirmed to exhibit excellent low-temperature reactivity and storage stability.

[0221] 1, 2: Evaluation test piece, 3: Test panel, 4: Resin layer, 5: Scratch direction

Claims

1. A blocked isocyanate composition comprising: 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 represents an organic group having from 1 to 20 carbon atoms, the organic group being a substituted or unsubstituted hydrocarbon group, a group containing a substituted or unsubstituted heterocycle, or a group in which one or more methylene groups in the hydrocarbon group or the group containing a heterocycle are substituted with a divalent group selected from the following <Group A>, b- represents a b-valent anion, 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> represents -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. R 1 , R 2 , R 3 and R 4 The blocked isocyanate composition according to claim 1 , wherein each of the organic groups represented by the following formula (I) is independently a substituted or unsubstituted hydrocarbon group.

3. X b- The blocked isocyanate composition according to claim 1, wherein 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.

4. R 1 The blocked isocyanate composition according to claim 1, wherein the organic group represented by the formula (I) has 6 or more and 13 or less carbon atoms.

5. R 1 The organic group used in X has 6 to 13 carbon atoms. 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 1 The number of carbon atoms in the organic group used in X is 1 or more and 5 or less, b- The blocked isocyanate composition according to claim 1 , wherein is a phosphate anion having a phosphate ester structure, a thioether anion, or an azolate anion.

6. 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.

7. The blocked isocyanate composition according to claim 1, wherein 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 the aromatic diisocyanate compound or the alicyclic structure-containing diisocyanate compound.

8. 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 represents an organic group having from 1 to 20 carbon atoms, the organic group being a substituted or unsubstituted hydrocarbon group, a group containing a substituted or unsubstituted heterocycle, or a group in which one or more methylene groups in the hydrocarbon group or the group containing a heterocycle are substituted with a divalent group selected from the following <Group A>, b- represents a b-valent anion, 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> represents -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.

9. A resin layer formed using the resin composition according to claim 8.

10. A resin layer comprising: a phosphorus 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 represents an organic group having from 1 to 20 carbon atoms, the organic group being a substituted or unsubstituted hydrocarbon group, a group containing a substituted or unsubstituted heterocycle, or a group in which one or more methylene groups in the hydrocarbon group or the group containing a heterocycle are substituted with a divalent group selected from the following <Group A>, b- represents a b-valent anion, 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> represents -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.

11. A method for producing a resin layer, comprising: a coating step of coating the resin composition according to claim 8; and a heating step of heating the coating film formed by the coating step.

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