Blocked isocyanate compounds

Abstract

The present invention provides a novel blocked isocyanate compound that can be produced at a high yield, a compound having a double bond that can be crosslinked at a low temperature (100°C or less) using the blocked isocyanate compound, and a resin obtained by curing the compound having a double bond. The present invention includes a compound having an isocyanate group (a1), a blocked isocyanate compound (A) obtained by urethane bonding of a compound having a hydroxyl group (a2) represented by the following formula (1) via the above isocyanate group and the above hydroxyl group. (In formula (1), R 1 and R 2 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. R 3 and R 4 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.)

Description

TECHNICAL FIELD

[0001] The present application relates to a blocked isocyanate compound as a blocking body of a compound having an isocyanate group. BACKGROUND

[0002] The blocked isocyanate compound is a compound in which the isocyanate group of a compound having an isocyanate group is reacted with a blocking agent to deactivate the reactivity of the isocyanate group (blocking). For example, in the case where the blocked isocyanate compound is used as a curing agent, by blocking the isocyanate group, it is not necessary to separately prepare, for example, a 1 liquid containing a main agent having a reactive hydrogen group, and a 2 liquid containing a compound having an isocyanate group for reacting with the reactive hydrogen group, and it is possible to preliminarily mix the main agent having a reactive hydrogen group and the blocked isocyanate compound in the 1 liquid. Therefore, the blocked isocyanate compound is widely used in adhesives, coating agents, molding materials, resins, and the like.

[0003] Crosslinking formation at the time of resin production is an important means for improving the properties of the resin. On the other hand, in order to resinize the substrate and save energy, it is required to lower the heating temperature at the time of crosslinking formation, for example, to 100°C or lower. As one of the methods in which crosslinking formation can be performed under low temperature conditions, it is known to introduce a double bond to a (co)polymer that becomes the main chain of the resin.

[0004] In the cited document 1, an aqueous resin composition is disclosed, which is characterized by containing a polymer obtained by polymerizing a vinyl monomer (A) containing an isocyanate group, in which the isocyanate group is blocked by forming an adduct with sulfurous acid or hydrosulfite, and an olefinically unsaturated compound (B) containing a reactive hydrogen group that has reactivity with the isocyanate group. In addition, the aqueous resin composition is a self-crosslinking type resin composition, and as a method of self-crosslinking, it is disclosed that heating at normal temperature to 200°C can be performed after molding or coating of the aqueous resin composition, and the like.

[0005] In Citation 2, a monomer-poor 1:1 monoadduct formed from a diisocyanate and a hydroxy (meth) acrylate having a free diisocyanate content of less than 0.7 mass% and a free NCO content of 10.4 to 16.4 mass% is disclosed, which is prepared by reacting 5 to 20 moles of a diisocyanate with 1 mole of a hydroxy (meth) acrylate in the presence of an inhibitor at a temperature ranging from 40 to 120°C, at which time the reaction is carried out until the acrylate component is completely reacted, and then unreacted diisocyanate is separated from the reaction product by flashing at 80 to 220°C / 0.1 to 10 mbar, and a mixture of air, nitric oxide, oxygen, or a mixture containing 1 to 90% by volume of carbon dioxide, nitrogen, or a rare gas in addition to air, oxygen, and nitric oxide, or a mixture of these gases is introduced as an inhibitor gas to the apparatus.

[0006] Prior Art Documents

[0007] Patent Documents

[0008] Patent Document 1: Japanese Patent Laid-Open No. 11-116658

[0009] Patent Document 2: Japanese Patent Laid-Open No. 2002-138112 SUMMARY

[0010] Problems to be Solved by the Invention

[0011] The water-based resin composition containing a blocked isocyanate compound disclosed in Patent Document 1, although described as being capable of being crosslinked at 200°C or lower, has a limited number of blocked isocyanate compounds that can be used to crosslink the resin composition at low temperature conditions of 100°C or lower. Therefore, in order to crosslink the resin at low temperature conditions of 100°C or lower, there is still room for improvement in the blocked isocyanate compound that introduces a double bond into a (co)polymer that becomes the main chain of the resin.

[0012] Further, in Patent Document 2, although a compound having a double bond obtained by reacting a diisocyanate and a hydroxy (meth) acrylate is disclosed, an operation of removing excess isocyanate monomers remaining in the reaction system by flashing is required, leaving room for improvement in the yield of the reaction product.

[0013] The present invention has been made in order to solve the above-described problems, and aims to provide a novel blocked isocyanate compound that can be produced at a high yield, a compound having a double bond that can be crosslinked at low temperature (100°C or lower) using the blocked isocyanate compound, and a resin obtained by curing the compound having a double bond.

[0014] Method for Solving the Problems

[0015] As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by a blocked isocyanate compound and a compound having a double bond formed from the blocked isocyanate compound and a specific base, and thus completed the present application. That is, the present application includes the following [1] to

[13] .

[0016] [1] A blocked isocyanate compound (A) which is a compound (al) having an isocyanate group, and a compound (a2) having a hydroxyl group represented by the following formula (1) are urethane-bonded via the above isocyanate group and the above hydroxyl group.

[0017]

[0018] In formula (1), R 1 and R 2 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. R 3 and R 4 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

[0019] [2] The blocked isocyanate compound (A) according to [1], wherein the compound (al) having an isocyanate group is 2,2'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, m-xylylene diisocyanate, 2,4-toluene diisocyanate, or 2,6-toluene diisocyanate.

[0020] [3] The blocked isocyanate compound (A) according to [1], wherein the compound (al) having an isocyanate group has an olefinic double bond (dl).

[0021] [4] The blocked isocyanate compound (A) according to [3], wherein the compound (al) having an isocyanate group having an olefinic double bond (dl) is 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 2-(isocyanateethyloxy)ethyl acrylate, 2-(isocyanateethyloxy)ethyl methacrylate, or 1,1-bis(acryloyloxymethyl)ethyl isocyanate.

[0022] [5] The blocked isocyanate compound (A) according to any one of [1] to [4], wherein R 3 and R 4 of the compound (a2) having a hydroxyl group are hydrogen atoms.

[0023] [6] The blocked isocyanate compound (A) according to any one of [1] to [5], wherein R 1 and R2 It is an alkyl group having 1 to 3 carbon atoms.

[0024] [7] The blocked isocyanate compound (A) according to any one of [1] to [6], wherein the compound (a2) having a hydroxyl group is diethyl malate.

[0025] [8] A blocked isocyanate polymer (H) comprising, as any one of [3] to [7], a blocked isocyanate compound (A) as a monomer unit.

[0026] [9] A blocked isocyanate polymer (I) having an olefinic double bond (d2) is formed from the blocked isocyanate polymer (H) described in [8] and a base (B).

[0027]

[10] According to the blocked isocyanate polymer (I) having an olefinic double bond (d2) as described in [9], the base (B) is 1,8-diazabicyclo[5.4.0]-undecene-7, 1,5-diazabicyclo[4.3.0]-5-nonene or 1,1,3,3-tetramethylguanidine.

[0028]

[11] A blocked isocyanate resin (K) is formed by curing a blocked isocyanate polymer (I) having an olefinic double bond (d2) as described in [9] or

[10] .

[0029]

[12] Compounds containing olefinic double bonds as shown in formula (2-1) or formula (2-2) (C).

[0030]

[0031] In equation (2-1), R 2 It consists of a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. R 3 and R 4 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. R 5 It is a hydrocarbon group with a valence of m and a carbon number of 1 to 20. m is an integer from 1 to 3.

[0032]

[0033] In equation (2-2), R 1 It consists of a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. R 3 and R 4 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. R 5 It is a hydrocarbon group with a valence of m and a carbon number of 1 to 20. m is an integer from 1 to 3.

[0034]

[13] The blocked isocyanate compound (A) shown in formula (3) below.

[0035]

[0036] In equation (3), R 1 and R 2 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. R 3 and R 4 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. R 5 It is a hydrocarbon group with a valence of m and a carbon number of 1 to 20. m is an integer from 1 to 3.

[0037] The effects of the invention

[0038] According to the present invention, a novel blocked isocyanate compound that can be manufactured in high yield, a compound having double bonds that can be crosslinked at low temperature (below 100°C) using the blocked isocyanate compound, and a resin obtained by curing the compound having double bonds. Attached Figure Description

[0039] Figure 1 For the compound obtained in Example 1 1 H-NMR spectrum.

[0040] Figure 2 For the compound obtained in Example 2 1 H-NMR spectrum.

[0041] Figure 3 For the compound obtained in Example 3 1 H-NMR spectrum.

[0042] Figure 4 For the compound obtained in Example 4 1 H-NMR spectrum.

[0043] Figure 5 For the compound obtained in Example 5 1 H-NMR spectrum.

[0044] Figure 6 For the compound obtained in Example 6 1 H-NMR spectrum.

[0045] Figure 7 For the compound obtained in Example 7 1 H-NMR spectrum.

[0046] Figure 8 For the compound obtained in Example 1 13 C-NMR spectrum.

[0047] Figure 9For the compound obtained in Example 2 13 C-NMR spectrum.

[0048] Figure 10 For the compound obtained in Example 3 13 C-NMR spectrum.

[0049] Figure 11 For the compound obtained in Example 4 13 C-NMR spectrum.

[0050] Figure 12 For the compound obtained in Example 5 13 C-NMR spectrum.

[0051] Figure 13 For the compound obtained in Example 6 13 C-NMR spectrum.

[0052] Figure 14 For the compound obtained in Example 7 13 C-NMR spectrum.

[0053] Figure 15 The image shows the LC chromatogram of the compound obtained in Example 14.

[0054] Figure 16 The LC-MS chromatogram of the compound of formula (16) obtained in Example 14 with an elution time of 13.76 minutes is shown.

[0055] Figure 17 For the compound of formula (16) obtained in Example 14 1 H-NMR spectrum.

[0056] Figure 18 For the compound of formula (17) obtained in Example 14 1 H-NMR spectrum. Detailed Implementation

[0057] The embodiments of the present invention will now be described in detail. However, the present invention is not limited to the embodiments shown below.

[0058] In this invention, (meth)acrylic acid refers to acrylic acid or methacrylic acid. For example, (meth)acrylate compounds refer to acrylate compounds or methacrylate compounds.

[0059] <Blocked Isocyanate Compound (A)>

[0060] As one embodiment of the present invention, the blocked isocyanate compound (A) is a compound (a1) having an isocyanate group and a compound (a2) having a hydroxyl group as shown in the following formula (1) having an urethane bond via the isocyanate group and the hydroxyl group.

[0061]

[0062] In equation (1), R 1 and R 2 Each group is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrocarbon group having 1 to 5 carbon atoms, more preferably a hydrocarbon group having 1 to 3 carbon atoms. The hydrocarbon group is preferably an alkyl group. R 3 and R 4 Each of the components is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and more preferably a hydrogen atom.

[0063] The blocked isocyanate compound (A) is preferably the compound shown in the following formula (3).

[0064]

[0065] In equation (3), R 1 R 2 R 3 and R 4 The symbols have the same meaning as in equation (1).

[0066] R 5 It is a linear or branched aliphatic chain hydrocarbon group or aliphatic cyclic hydrocarbon group with a valence number of m and 1 to 20 carbon atoms, preferably 2 to 13, more preferably 6 to 10, and even more preferably 6 or 7, or an aromatic hydrocarbon group with 6 to 20 carbon atoms, preferably 6 to 13, which may have substituents. Furthermore, R 5 It can contain ether bonds or ester bonds.

[0067] R 5 If the olefinic double bond (d1) is present, a crosslinking structure can be further introduced into the blocked isocyanate resin (K) described later, which is therefore preferred. More preferably, the group having the olefinic double bond (d1) is -CH2CH2OC(=O)C(-CH3)=CH2 or -CH2CH2OC(=O)CH2=CH2, and even more preferably -CH2CH2OC(=O)CH2=CH2.

[0068] m is an integer from 1 to 3, and is preferably 1 or 2 from the perspective of ease of manufacture, and more preferably 1.

[0069] (Compounds with isocyanate groups (a1))

[0070] The compound (a1) having an isocyanate group is a compound having at least one isocyanate group, preferably a compound shown in the following formula (4).

[0071] R 5 (NCO) m ···(4)

[0072] In equation (4), R 5 The meanings of the symbols in equation (3) above are the same as those of the symbols in equation (3).

[0073] Examples of compounds (a1) having an isocyanate group as shown in formula (4) include, for example, aliphatic isocyanate compounds, alicyclic isocyanate compounds and aromatic isocyanate compounds.

[0074] Examples of aliphatic isocyanate compounds include, for example, an aliphatic isocyanate compound (a1-1) having an olefinic double bond (d1) and an aliphatic isocyanate compound (a1-2) not having an olefinic double bond (d1).

[0075] Examples of aliphatic isocyanate compounds (a1-1) having an olefinic double bond (d1) include, for example, 2-methacryloyloxyethyl isocyanate, 3-methacryloyloxy-n-propyl isocyanate, 2-methacryloyloxyisopropyl isocyanate, 4-methacryloyloxy-n-butyl isocyanate, 2-methacryloyloxy-tert-butyl isocyanate, 2-methacryloyloxybutyl-4-isocyanate, 2-methacryloyloxybutyl-3-isocyanate, 2-methacryloyloxybutyl-2-isocyanate, 2-methacryloyloxybutyl-1-isocyanate, 5-methacryloyloxy-n-pentyl isocyanate, 6-methacryloyloxy-n-hexyl isocyanate, 7-methacryloyloxy-n-heptyl isocyanate, 2-(isocyanatoethyloxy)ethyl methacrylate, 3-methacryloyloxyphenyl isocyanate, 4-methacryloyloxyphenyl isocyanate, and 2-acryloyloxyethyl isocyanate. Acrylates, 3-acryloyloxy-n-propyl isocyanate, 2-acryloyloxy-isopropyl isocyanate, 4-acryloyloxy-n-butyl isocyanate, 2-acryloyloxy-tert-butyl isocyanate, 2-acryloyloxy-butyl-4-isocyanate, 2-acryloyloxy-butyl-3-isocyanate, 2-acryloyloxy-butyl-2-isocyanate, 2-acryloyloxy-butyl-1-isocyanate, 5-acryloyloxy-n-pentyl isocyanate, 6-acryloyloxy-n- Hexyl isocyanate, 7-acryloyloxy-n-heptyl isocyanate, 2-(isocyanate-ethyloxy)ethyl acrylate, 3-acryloyloxyphenyl isocyanate, 4-acryloyloxyphenyl isocyanate, 1,1-bis(methacryloyloxymethyl)methyl isocyanate, 1,1-bis(methacryloyloxymethyl)ethyl isocyanate, 1,1-bis(acryloyloxymethyl)methyl isocyanate and 1,1-bis(acryloyloxymethyl)ethyl isocyanate.

[0076] Examples of aliphatic isocyanate compounds (a1-2) that do not have an olefinic double bond (d1) include, for example, heptyl isocyanate, octyl isocyanate, nonyl isocyanate, dodecyl isocyanate, 2-ethylhexyl isocyanate, leucine methyl ester isocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, 1,6-diisocyanate-2,2,4-trimethylhexane, butyl isocyanate, tert-butyl isocyanate, and hexyl isocyanate.

[0077] Examples of alicyclic isocyanate compounds include cyclohexyl isocyanate, isophorone diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane 4,4'-diisocyanate, and adamantyl isocyanate.

[0078] Examples of aromatic isocyanate compounds include, for example, phenyl isocyanate, benzyl isocyanate, 2,6-dimethylphenyl isocyanate, 3,5-dimethylphenyl isocyanate, 2,6-diisopropylphenyl isocyanate, 4-fluorophenyl isocyanate, 2,4-difluorophenyl isocyanate, 2,4,6-trifluorophenyl isocyanate, 3-(trifluoromethyl)phenyl isocyanate, toluenesulfonyl isocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, and isophthalimide diisocyanate. Cyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, toluene-2,4-diisocyanate, trimethylhexamethylene diisocyanate, 4,4-bis(phenylisocyanate) oxide, 2,5-phenylene diisocyanate, 4,4'-diisocyanate-3,3'-dimethylbiphenyl, 1,3-bis(1-isocyanate-1-methylethyl)benzene and 2,2-bis[[4-(isocyanate-methyl)phenyl]methyl]carbamate.

[0079] Among these, considering ease of manufacture and / or ease of obtaining raw materials, the compound (a1) having an isocyanate group is preferably 2,2'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, isophthalimethylene diisocyanate, 2,4-toluene diisocyanate or 2,6-toluene diisocyanate.

[0080] Furthermore, from the perspective of introducing the crosslinking structure of the blocked isocyanate resin (K) resin described later, the compound (a1) having an isocyanate group preferably has an olefinic double bond (d1), more preferably 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 2-(isocyanate-ethyloxy)ethyl acrylate, 2-(isocyanate-ethyloxy)ethyl methacrylate and 1,1-bis(acryloyloxymethyl)ethyl isocyanate, further preferably 2-acryloyloxyethyl isocyanate and 2-methacryloyloxyethyl isocyanate, and most preferably 2-acryloyloxyethyl isocyanate.

[0081] (Compounds containing hydroxyl groups (a2))

[0082] The compound (a2) having a hydroxyl group is used as a blocking agent for the compound (a1) having an isocyanate group, and is represented by the following formula (1).

[0083]

[0084] In equation (1), R 1 and R 2Each group is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, preferably having 1 to 5 carbon atoms, and more preferably having 1 to 3 carbon atoms. The hydrocarbon group is preferably an alkyl group. R 3 and R 4 Each of the components is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and more preferably a hydrogen atom.

[0085] Of the compounds shown in formula (1), considering the ease of manufacture when using a blocked isocyanate compound (A) as a starting material to manufacture the blocked isocyanate polymer (H), blocked isocyanate polymer (I), and compound (C) containing an olefinic double bond (described later), the compound (a2) having a hydroxyl group is preferably malate, tartrate, or citrate, with malate being the most preferred. The number of carbon atoms in the ester site is not particularly limited, but is preferably 1 to 5, more preferably 1 to 2. Specifically, diethyl malate is preferred.

[0086] (Method for manufacturing blocked isocyanate compound (A))

[0087] The blocked isocyanate compound (A) can be manufactured by conventionally known methods as long as the isocyanate group of the compound (a1) having an isocyanate group is urethane-bonded to the hydroxyl group of the compound (a2) having a hydroxyl group. For example, it can be manufactured by reacting the compound (a1) having an isocyanate group and the compound (a2) having a hydroxyl group in a reaction vessel as follows.

[0088] There are no particular restrictions on the order in which these compounds are added to the reaction vessel. As a method for producing the closed isocyanate compound (A), the following methods (1) to (3) can be used, for example: (1) adding a compound having a hydroxyl group (a2) to the reaction vessel and adding a compound having an isocyanate group (a1) under stirring to allow it to react; (2) adding a compound having an isocyanate group (a1) to the reaction vessel and adding a compound having a hydroxyl group (a2) under stirring to allow it to react; (3) adding both a compound having a hydroxyl group (a2) and a compound having an isocyanate group (a1) to the reaction vessel and stirring to allow them to react.

[0089] The reaction temperature of the compound having an isocyanate group (a1) and the compound having a hydroxyl group (a2) is generally preferably -10°C or higher and 90°C or lower, more preferably 5°C or higher and 70°C or lower, and even more preferably 10°C or higher and 40°C or lower. If the reaction temperature is -10°C or higher, the reaction rate can be increased, and the blocked isocyanate compound (A) can be obtained productively, which is therefore preferred. Furthermore, if the reaction temperature is 90°C or lower, the reverse reaction is less likely to occur, and the blocked isocyanate compound (A) can be obtained with high purity, which is also preferred.

[0090] The reaction typically proceeds until either the isocyanate-containing compound (a1) or the hydroxyl-containing compound (a2) disappears. The reaction time is not particularly limited, but is generally preferred to be 30 minutes or more and 168 hours or less. Regarding the hydroxyl-containing compound (a2), for example, based on high-performance liquid chromatography analysis, the disappearance of the hydroxyl-containing compound (a2) is defined as reducing its mass to less than 2 parts by mass based on 100 parts by mass of the blocked isocyanate compound (A). On the other hand, regarding the isocyanate-containing compound (a1), for example, based on IR determination, the disappearance of the isocyanate-containing compound (a1) is defined as reducing its mass to less than 2% by mass based on the absorption of the isocyanate group. Furthermore, this reaction time also includes the time for adding the isocyanate-containing compound (a1) and the hydroxyl-containing compound (a2) by dropwise addition, etc.

[0091] In the above-described manufacturing process, when the compound (a1) having an isocyanate group is as shown in formula (4) above, and when m = 1 in formula (4), it is preferable to contact the compound (a2) having a hydroxyl group with the compound (a1) at a molar ratio of 0.1 to 4.0 times, more preferably at a molar ratio of 0.5 to 3.0 times, even more preferably at a molar ratio of 0.75 to 1.25 times, and particularly preferably at a molar ratio of 1.00 times. Theoretically, the reaction ratio of these compounds is 1:1 (molar ratio), but by contacting them at the above-described range, the reaction can proceed smoothly. Furthermore, in the above formula (4), when m=2, the amount of the hydroxyl-containing compound (a2) that contacts the isocyanate-containing compound (a1) only needs to be twice the amount in the case of m=1, and when m=3, the amount of the hydroxyl-containing compound (a2) that contacts the isocyanate-containing compound (a1) only needs to be three times the amount in the case of m=1.

[0092] Furthermore, it is preferable to pre-add the polymerization inhibitor to the reaction system for manufacturing the blocked isocyanate compound (A). The polymerization inhibitor can be used after the manufacture of the blocked isocyanate compound (A), but it is more preferable to use it during the manufacture of the blocked isocyanate compound (A). Regarding the polymerization inhibitor, for example, in the case where the blocked isocyanate compound (A) contains a (meth)acryloyl group, the blocked isocyanate compound (A) can be stabilized in such a way that the polymerization reaction caused by the (meth)acryloyl group does not proceed.

[0093] As polymerization inhibitors, commonly used substances such as phenothiazine, p-methoxyphenol, and 2,6-di-tert-butyl-4-methylphenol (hereinafter also referred to as "BHT") can be used.

[0094] The amount of polymerization inhibitor used varies depending on the type of compound (a2) with hydroxyl groups and the type of compound (a1) with isocyanate groups. However, as the total amount used during and after the manufacture of the blocked isocyanate compound (A), it is preferably 10 ppm by mass or more and 2.00 × 10⁻⁶ ppm relative to the blocked isocyanate compound (A). 4 Less than ppm by mass, more preferably 50 ppm by mass and 1.00 × 10⁻⁶ 4 Below ppm by mass, more preferably above 100 ppm by mass and 1.00 × 10⁻⁶ 3 Mass below ppm.

[0095] There are no particular restrictions on the method of adding the polymerization inhibitor. Examples include adding it to the reaction vessel together with a compound having hydroxyl groups (a2); adding it to the reaction vessel in combination with a compound having isocyanate groups (a1); adding it to both the compound having hydroxyl groups (a2) and the compound having isocyanate groups (a1) in separate reaction vessels; and adding it to the resulting blocked isocyanate compound (A) after the reaction is complete.

[0096] In the above-described method for manufacturing the blocked isocyanate compound (A), the blocked isocyanate compound (A) may also be used as a solvent or dispersion medium, the reaction may be carried out under solvent-free conditions, or a known organic solvent may be used as a solvent or dispersion medium. The solvent is not particularly limited, and examples include alcohol solvents such as cellosolve, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, octanol, nonanol, decanol, benzyl alcohol, and hexanediol; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, and propylene glycol monobutyl ether acetate; ether solvents such as ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, and diethylene glycol dimethyl ether; aromatic hydrocarbon solvents such as benzene, toluene, and xylene; and amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. Furthermore, halogen-substituted compounds may also be used. Among these, ester solvents such as propylene glycol monomethyl ether acetate and ketone solvents such as acetone are preferred, and propylene glycol monomethyl ether acetate is more preferred. They can be used individually or in combination with two or more.

[0097] In the reaction system for producing the blocked isocyanate compound (A), catalysts, additives, etc., can be added. Examples of catalysts include dibutyltin dilaurate.

[0098] <Blocked Isocyanate Polymer (H)>

[0099] In one embodiment of the present invention, the blocked isocyanate polymer (H) is a polymer comprising a blocked isocyanate compound (A) as a monomer unit. The blocked isocyanate polymer (H) can be obtained by polymerizing a compound (a1-1) having an olefinic double bond (d1) as a monomer. The polymerization also includes copolymerization with a monomer (G) having an olefinic double bond, described later.

[0100] To polymerize the blocked isocyanate compound (A), a free radical polymerization initiator is preferably used. There are no particular limitations on the free radical polymerization initiator, but examples include organic peroxides such as benzoyl peroxide, lauroyl peroxide, hexanoyl peroxide, tert-butyl peroxyoctanoate, and diacetyl peroxide; azobisisobutyronitrile, azobis-α,γ-dimethylpentanonitrile, 2,2'-azobis(isobutyric acid) dimethyl ester, azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carboxynitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylpentanonitrile), 2,2'-azobis(2,4-dimethylpentanonitrile), 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile), and 2,2'-azobis[2-(2-imidazolin-2-yl)propane] disalt. Salts, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] disulfate dihydrate, 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis(2-methylpropanediamine) dihydrochloride, 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropanediamine] n-hydrate, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide], 2,2'-azobis(N-butyl-2-methylpropionamide), 4,4'-azobis(4-cyanopentanoic acid) and other azo compounds; dialkyl peroxide dicarbonates such as diisopropyl peroxide carbonate, and redox initiators, etc.

[0101] The free radical polymerization initiator is preferably used in the range of 0.01 to 15 parts by mass relative to a total of 100 parts by mass of the blocked isocyanate compound (A) and the monomer (G) having an olefinic double bond, more preferably in the range of 0.1 to 10 parts by mass.

[0102] Polymerization can be carried out using known methods, but if the reaction is carried out at excessively high temperatures, the blocking agent (compound (a2) with hydroxyl groups) of the isocyanate-containing compound (a1) may partially dissociate from the blocked isocyanate compound (A). The dissociated blocking agent acts as a chain transfer agent, causing a broadening of the molecular weight distribution, and the resin gels due to crosslinking of the isocyanate groups derived from the free isocyanate groups of the compound (a1) and the amino groups generated by the decomposition of the isocyanate groups. Therefore, polymerization is preferably carried out at a temperature below 120°C.

[0103] From the perspective of suppressing the increase in polymer viscosity, the weight-average molecular weight of the blocked isocyanate polymer (H) is preferably 100,000 or less, more preferably 50,000 or less, and particularly preferably 30,000 or less. The weight-average molecular weight of the blocked isocyanate polymer (H) is preferably 1,000 or more. The weight-average molecular weight can be determined by gel permeation chromatography (GPC).

[0104] (Monomers with olefinic double bonds (G))

[0105] In one embodiment of the invention, the blocked isocyanate polymer (H) may comprise a copolymer of a blocked isocyanate compound (A) and a monomer (G) having an olefinic double bond as a monomer component.

[0106] There are no particular limitations on the monomer (G) that has an olefinic double bond and can copolymerize with a blocked isocyanate compound (A). The monomer (G) with an olefinic double bond does not include compounds with isocyanate groups (a1).

[0107] Examples of monomers (G) having olefinic double bonds include, for example, (meth)acrylates and their derivatives, styrene and its derivatives, (meth)acrylonitrile and its derivatives, vinyl esters of organic carboxylic acids and their derivatives, allyl esters of organic carboxylic acids and their derivatives, dialkyl esters of fumaric acid and their derivatives, dialkyl esters of itaconic acid and their derivatives, N-vinylamide derivatives of organic carboxylic acids, maleimide and its derivatives, terminal unsaturated hydrocarbons and their derivatives, etc.

[0108] Examples of (meth)acrylates and their derivatives include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, and 2-hydroxyethyl methacrylate. Monofunctional (meth)acrylates include methyl methacrylate, 2-hydroxyphenyl ethyl methacrylate, 4-hydroxybutyl methacrylate, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, and N-acryloylmorpholine; and polyfunctional (meth)acrylates include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol pentamethacrylate, and pentaerythritol hexamethacrylate.

[0109] Examples of styrene and its derivatives include styrene, 2,4-dimethyl-α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, 2,4,6-trimethylstyrene, o-chlorostyrene, 2-vinylbiphenyl, 1-vinylanthracene, p-isopropenyltoluene, divinylbenzene, and divinylbiphenyl.

[0110] Examples of (meth)acrylonitrile and its derivatives include acrylonitrile and methacrylonitrile.

[0111] Vinyl esters and their derivatives, which are organic carboxylic acids, include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, and vinyl adipate.

[0112] Examples of allyl esters and their derivatives that are organic carboxylic acids include allyl acetate, allyl benzoate, diallyl adipate, diallyl terephthalate, diallyl isophthalate, and diallyl phthalate.

[0113] Examples of dialkyl esters and derivatives of fumaric acid include dimethyl fumarate, diethyl fumarate, di-2-ethylhexyl fumarate, and dibenzyl fumarate.

[0114] Examples of dialkyl esters and derivatives of maleic acid include dimethyl maleate, diethyl maleate, di-2-ethylhexyl maleate, and dibenzyl maleate.

[0115] Examples of dialkyl esters and derivatives of itaconic acid include dimethyl itaconic acid, diethyl itaconic acid, 2-ethylhexyl itaconic acid, and dibenzyl itaconic acid.

[0116] Examples of N-vinylamide derivatives of organic carboxylic acids include N-methyl-N-vinylacetamide.

[0117] Examples of maleimides and their derivatives include N-phenylmaleimide and N-cyclohexylmaleimide.

[0118] Examples of terminal unsaturated hydrocarbons and their derivatives include 1-butene, 1-pentene, 1-hexene, vinylcyclohexane, vinyl chloride, and allyl alcohol.

[0119] Preferably, (meth)acrylates and their derivatives are used, and more preferably, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, and sec-butyl (meth)acrylate.

[0120] Monomers (G) with olefinic double bonds can be used alone or in combination with two or more.

[0121] The amount of monomer (G) having an olefinic double bond relative to the blocked isocyanate compound (A) is preferably 0 mol% or more and 5.0 × 10⁻⁶. 4 Below mol%, more preferably 50 mol% or more and 1×10 4 Below 100 mol%, more preferably above 100 mol% and 2 × 10⁻⁶ 3 Below mol%.

[0122] <Blocked isocyanate polymers with olefinic double bonds (d2) (I)>

[0123] One embodiment of the present invention comprises a blocked isocyanate polymer (I) having an olefinic double bond (d2) in a structure derived from a hydroxyl-containing compound (a2) in a blocked isocyanate polymer (H) by means of a base (B), wherein the substituent R 3 The combined carbon atom and R 4 A blocked isocyanate polymer with olefinic double bonds (d2) is obtained by forming double bonds between the bound carbon atoms. Regarding the olefinic double bonds (d2), it can be considered that the blocked isocyanate polymer (H) undergoes decarboxylation via a base (B) reaction after a dealcoholization reaction, for example, after becoming the compound shown in formula (5-1) below, in R... 3and R 4 Each carbon-carbon bond forms an inter-carbon bond, thereby obtaining a blocked isocyanate polymer (I). R in formula (5-1) 2 R 3 and R 4 The symbols have the same meaning as those in equation (1).

[0124]

[0125] Furthermore, regarding the alkene double bond (d2), for example, it can be considered that after conversion to the compound shown in formula (5-2), decarboxylation occurs via a reaction with a base (B), in R 3 and R 4 Each carbon-carbon bond forms an inter-carbon bond, thereby obtaining a blocked isocyanate polymer (I). R in formula (5-2) 1 R 3 and R 4 The symbols have the same meaning as those in equation (1).

[0126]

[0127] (Base(B))

[0128] In one embodiment of the invention, the base (B) used is only required to be in the structure of the isocyanate compound (A) derived from the compound (a2) containing a hydroxyl group, at the substituent R. 3 The combined carbon atom and R 4 There are no particular restrictions on the formation of double bonds between the carbon atoms in the bond.

[0129] The base (B) is preferably represented by the following formula (6).

[0130] R 6 N=CR 7 -NR 8 R 9 ···(6)

[0131] In the formula, R 6 It consists of hydrogen atoms, hydrocarbon groups with 1 to 20 carbon atoms, or -NR. 10 The group shown in 2. R 7 R 8 R 9 and R 10 It consists of a hydrocarbon group with 1 to 20 hydrogen atoms or carbon atoms, and has 2 R atoms. 10 They can be the same or different. 6 R 7 R 8 R 9 and 2 Rs 10 Any two or more groups can combine to form a ring structure.

[0132] The base (B) can be a compound represented by formula (6-2).

[0133] R 6a N=CR 7a -NR 8a R 9a ···(6-2)

[0134] In the formula, R 6a R 7a R 8a and R 4a It is a hydrocarbon group, R 6a With R 9a and R 7a With R 3a They combine to form a ring structure, R 6a With R 9a The sum of the number of carbon atoms is 3 to 20, preferably 5 to 10, R 7a With R 8a The sum of the number of carbon atoms is 3 to 20, preferably 5 to 10.

[0135] Among the bases (B) shown in formula (6), 1,8-diazabicyclo[5.4.0]-undecene-7, 1,5-diazabicyclo[4.3.0]-5-nonene, and 1,1,3,3-tetramethylguanidine are preferred, and 1,8-diazabicyclo[5.4.0]-undecene-7 is more preferred.

[0136] The base (B) preferably has a pKa of 12.5 or higher at 25°C. Furthermore, the base (B) that meets the requirement of having a pKa of 12.5 or higher at 25°C includes substances with a pKa of 12.5 or higher in aqueous solution, and substances that are too acidic to be measured in aqueous solution but have a pKa of 12.5 or higher in aqueous solution calculated from the measurement results in an organic solvent.

[0137] The amount of alkali (B) relative to the blocked isocyanate polymer (H) is preferably 100 ppm by mass or more and 1.00 × 10⁻⁶. 5 Below ppm by mass, more preferably 1.00 × 10⁻⁶. 3 Mass above ppm and 1.00 × 10 4 The mass concentration is below ppm. If the base (B) is 100 ppm or more relative to the blocked isocyanate polymer (H), a sufficient reaction rate can be obtained when the alkali double bond is introduced from the blocked isocyanate polymer (H) into the hydroxyl-containing compound (a2) acting as a blocking agent, which is preferred. If the amount of base (B) relative to the blocked isocyanate polymer (H) is 1.00 × 10⁻⁶, a suitable mass concentration is obtained. 5 If the mass concentration is below ppm, then there is no excess alkali, which is the preferred option.

[0138] The reaction between the blocked isocyanate polymer (H) and the base (B) is not particularly limited, but it is preferred to be carried out in the presence of a solvent. Examples of solvents that can be used include: cellosolvers, methyl cellosolvers, butyl cellosolvers, propylene glycol monomethyl ether, methanol, ethanol, propanol, isopropanol, butanol, benzyl alcohol, hexanediol, and other alcohol-based solvents; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and other ketone-based solvents; ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monobutyl ether acetate, and other ester-based solvents; ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, and other ether-based solvents; aromatic hydrocarbon solvents such as benzene, toluene, and xylene; and amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone, with propylene glycol monomethyl ether acetate being the most preferred. One or more of these solvents may be used alone or in combination.

[0139] The amount of solvent relative to the blocked isocyanate polymer (H) having olefinic double bonds is preferably 0.1 to 100 times by mass, more preferably 1 to 50 times by mass, and even more preferably 5 to 30 times by mass. Within this range, the exothermic reaction can be suppressed, which is preferable.

[0140] The reaction temperature is preferably 0–150°C, more preferably 50–120°C, and even more preferably 80–110°C.

[0141] The reaction time is preferably 0.1 to 10 hours, more preferably 0.3 to 5 hours, and even more preferably 0.5 to 3 hours.

[0142] The gas inside the reaction vessel is not particularly limited; air, dry air, nitrogen, helium, etc., can be used, with dry air or nitrogen being preferred. The pressure inside the reaction vessel is not particularly limited, but atmospheric pressure is preferred.

[0143] <Blocked Isocyanate Curable Compositions (J)>

[0144] One example of an embodiment of the present invention is a blocked isocyanate curable composition (J) comprising a blocked isocyanate polymer (I) having olefinic double bonds (d2) and a polymerization initiator. The composition is cured by polymerization and crosslinking reactions occurring between the olefinic double bonds (d2) in the blocked isocyanate polymer (I) having olefinic double bonds (d2) via the polymerization initiator. The blocked isocyanate curable composition (J) may further, as needed, comprise a water-soluble polyester resin, a polyurethane dispersion, a reactive diluent, pigments, surface conditioners, fillers, degradation inhibitors, and crosslinking agents (e.g., melamine resins, various polyols, polyamines, polythiols, epoxy crosslinking agents, acid crosslinking agents, and alkoxy crosslinking agents).

[0145] Examples of polymerization initiators include photopolymerization initiators and thermal polymerization initiators, with photopolymerization initiators being preferred.

[0146] Examples of photopolymerization initiators include, for instance, 1-hydroxycyclohexylphenyl ketone, 2,2'-dimethoxy-2-phenylacetophenone, dibenzo-4-pyranone (xanthone), diphenyl ketone (fluorene), diphenylene ketone (fluorene ketone), benzaldehyde, anthraquinone (anthraquinone), triphenylamine, diphenylimine (carbazole), 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, 4,4'-bis(dimethylamino)benzophenone (michalcone), benzoylpropyl ether, benzoin ethyl ether, and benzoyldimethyl ether. The photopolymerization initiators include ketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one, and 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methylpropane-1-one. Among these, 2,4,6-trimethylbenzoyl diphenylphosphine oxide and 1-hydroxycyclohexylphenyl ketone are preferred. One of the above photopolymerization initiators can be used alone, or two or more can be used in combination.

[0147] As a thermal polymerization initiator, the compounds exemplified as free radical polymerization initiators in the [Blocked Isocyanate Polymers (H)] section can be used.

[0148] The amount of polymerization initiator relative to the blocked isocyanate compound (A) is preferably 100 ppm by mass or more and 1.00 × 10⁻⁶. 5 Below ppm by mass, more preferably 1.00 × 10⁻⁶. 3 Mass above ppm and 1.00 × 10 4 Mass below ppm.

[0149] <Blocked Isocyanate Resin (K)>

[0150] The blocked isocyanate resin (K) in one embodiment of the present invention is a substance obtained by curing a blocked isocyanate polymer (I) having olefinic double bonds (d2). The blocked isocyanate curable composition (J) can also be cured to obtain the blocked isocyanate resin (K). It is conceivable that by irradiating the blocked isocyanate polymer (I) having olefinic double bonds (d2) with active energy rays such as ultraviolet or visible light, or by heating, a three-dimensional network structure crosslinking is formed through the polymerization reaction of the olefinic double bonds (d2).

[0151] The heating temperature is preferably 50–100°C, more preferably 70–90°C. By blocking the olefinic double bonds (d2) in the isocyanate polymer (I), a cross-linked structure can be formed within this temperature range.

[0152] The active energy rays used for curing are preferably electron beams or light in the wavelength range from ultraviolet to infrared. For example, ultraviolet light can be used with an ultra-high pressure mercury light source or a metal halide light source; visible light can be used with a metal halide light source or a halogen light source; and infrared light can be used with a halogen light source. Lasers, LEDs, and other light sources can also be used. The irradiation dose of the active energy rays is appropriately set according to the type of light source and the thickness of the coating.

[0153] The blocked isocyanate resin (K) obtained by this operation is suitable for use in automotive coatings, industrial coatings, marine coatings, film coatings, adhesives, bonding agents, photoresists, etc.

[0154] <Compounds containing alkene double bonds (C)>

[0155] One embodiment of the present invention is a compound (C) containing an olefinic double bond, as shown in formula (2-1) or formula (2-2) below.

[0156]

[0157] In equation (2-1), R 2 It is a hydrocarbon group having 1 to 20 hydrogen atoms or carbon atoms, preferably a hydrocarbon group having 1 to 5 carbon atoms, more preferably a hydrocarbon group having 1 to 3 carbon atoms. The hydrocarbon group is preferably an alkyl group. R 3 and R 4 Each of the components is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and more preferably a hydrogen atom.

[0158] R 5 It is a linear or branched aliphatic chain hydrocarbon group or aliphatic cyclic hydrocarbon group with a valence number of m and 1 to 20 carbon atoms, preferably 2 to 13, more preferably 6 to 10, and even more preferably 6 or 7, or an aromatic hydrocarbon group with 6 to 20 carbon atoms, preferably 6 to 13, which may have substituents. Furthermore, R 5 It can contain ether bonds or ester bonds.

[0159] R 5 Preferably, it has an olefinic double bond (d1). As a group having an olefinic double bond (d1), it is more preferably -CH2CH2OC(=O)C(-CH3)=CH2 or -CH2CH2OC(=O)CH2=CH2, and even more preferably -CH2CH2OC(=O)CH2=CH2.

[0160] m is an integer from 1 to 3, and is preferably 1 or 2 from the perspective of ease of manufacture, and more preferably 1.

[0161]

[0162] In equation (2-2), R 1 The hydrocarbon group is a hydrocarbon group with 1 to 20 carbon atoms, preferably with 1 to 5 carbon atoms, and more preferably with 1 to 3 carbon atoms. The hydrocarbon group is preferably an alkyl group. R in formula (2-2) 3 ~R 5 The meanings of m and the symbols in equation (2-1) are the same.

[0163] The compound (C) containing an olefinic double bond is derived from the structure of the hydroxyl-containing compound (a2) in the isocyanate compound (A) through the base (B), with the substituent R... 3 The combined carbon atom and R 4 Compounds containing olefinic double bonds (d2) are formed by the formation of double bonds between the carbon atoms. It can be considered that in the compound (C) containing olefinic double bonds, the blocked isocyanate compound (A) undergoes a dealcolytic reaction to become the compound shown in formula (7-1), and then undergoes decarboxylation through a reaction with a base (B), resulting in R in formula (7-1). 3 and R 4 It is obtained by forming alkene double bonds between the carbon-carbon bonds of each bond. R in formula (7-1) 2 ~R 5 The symbols have the same meaning as those in equation (2-1).

[0164]

[0165] Furthermore, it can be considered that in the compound (C) containing an olefinic double bond, after the blocked isocyanate compound (A) is converted to the compound shown in formula (7-2) via a dealcoholization reaction, it undergoes decarboxylation via a reaction with a base (B), and in formula (7-2) R 3 and R 4 It is obtained by forming alkene double bonds between carbon-carbon bonds.

[0166] R in equation (7-2) 1 R 3 ~R 5 The symbols have the same meaning as those in equation (2-2).

[0167]

[0168] The blocked isocyanate compound (A) is assumed to reach formula (2-1) via formula (7-1) and formula (2-2) via formula (7-2).

[0169] In density functional theory (DFT), wB97XD was used as the density functional and 6-31+g(d) was used as the basis function to calculate the transition states in the formation pathways of each product. The results suggest that the pathway from equation (7-1) to equation (2-1) has a smaller activation barrier than the pathway from equation (7-2) to equation (2-2), and thus becomes the dominant transformation pathway. Therefore, it can be assumed that the products exist in a mixture where the number of constituent units with the group shown in equation (2-1) is greater than the number of constituent units with the group shown in equation (2-2).

[0170] The base (B) can be used in the substances exemplified in the above section [blocked isocyanate polymers (I) having olefinic double bonds (d2)].

[0171] The amount of base (B) relative to the blocked isocyanate compound (A) is preferably 100 ppm by mass or more and 1.00 × 10⁻⁶. 5 Below ppm by mass, more preferably 1.00 × 10⁻⁶. 3 Mass above ppm and 1.00 × 10 4 The mass concentration is below ppm. A sufficient reaction rate is obtained when the base (B) is 100 ppm or more relative to the blocked isocyanate compound (A), which is preferred. If the amount of base (B) relative to the blocked isocyanate compound (A) is 1.00 × 10⁻⁶, the reaction rate is also preferred. 5 If the mass concentration is below ppm, then there is no excess alkali, which is the preferred option.

[0172] The reaction of the blocked isocyanate compound (A) with the base (B) is not particularly limited and can be carried out in the presence of a solvent, or using a separately prepared compound (C) containing an olefinic double bond as a solvent. The solvent can be any of the solvents exemplified in the section on [Blocked Isocyanate Polymers with Oleic Double Bonds (d2)]

[0173] The amount of solvent relative to the blocked isocyanate compound (A) is preferably 0.1 to 100 times by mass, more preferably 1 to 50 times by mass, and even more preferably 5 to 30 times by mass. Within this range, the exothermic reaction can be suppressed, which is preferable.

[0174] The reaction temperature is preferably 0–150℃, more preferably 50–120℃, and even more preferably 80–110℃.

[0175] The reaction time is preferably 0.1 to 10 hours, more preferably 0.3 to 5 hours, and even more preferably 0.5 to 3 hours.

[0176] The gas inside the reaction vessel is not particularly limited; air, dry air, nitrogen, helium, etc., can be used, with dry air or nitrogen being preferred. The pressure inside the reaction vessel is not particularly limited, but atmospheric pressure is preferred.

[0177] Example

[0178] The present invention will be further described in detail below through examples and comparative examples, but the present invention is not limited to the following examples. In addition, measurements and tests were performed in the examples, etc., by the following methods.

[0179] [Quantification of compound amount]

[0180] The quantitative determination of blocked isocyanate compounds was performed by HPLC under the following conditions.

[0181] Device: Agilent 1200 Series

[0182] Pillar: Shodex (registered trademark) KF-801 manufactured by Showa Denko Co., Ltd.

[0183] Eluent: Tetrahydrofuran

[0184] Flow rate: 0.8 mL / min

[0185] Injection volume: 0.01 mL

[0186] Column temperature: 40℃

[0187] Detector: RI (Differential Refractive Index)

[0188] Optical system temperature: 40℃

[0189] [Weight-average molecular weight (Mw)]

[0190] GPC measurements were performed using a GPC system manufactured by Shimadzu Corporation, with a differential refractive index detector RID-10A as the detector and three Shodex LF804 (registered trademark) columns and one KF-801 column manufactured by Showa Denko Corporation as columns. The measurements were conducted at a column temperature of 40°C and a flow rate of 1.5 mL / min.

[0191] [IR]

[0192] IR measurements were performed using a NICOLETis10 instrument from Servo Science & Technology Co., Ltd., with a SMART iTR as an accessory. The peak wavelength of the isocyanate group was set to 2200 cm⁻¹ using the ATR method. -1 Set the peak wavelength of C=C to 690cm. -1 The measurements were then performed.

[0193] [Gel fraction]

[0194] While spreading approximately 0.2 g of sample solution onto a glass plate of known mass, accurately weigh the sample and heat it at 100°C for 20 minutes. After cooling, immerse the sample and glass plate together in a container with added acetone overnight. Filter / wash the acetone solution containing the glass plate and sample using filter paper of known weight, dry it at 40°C overnight, and weigh it. Calculate the acetone-insoluble component by removing the weight of the glass plate and filter paper, and divide it by the initial weight of the composition to obtain the gel fraction.

[0195] Nuclear magnetic resonance (NMR) 1 H- and 13 [C-NMR analysis]

[0196] Nuclear magnetic resonance (NMR) of each compound obtained in Examples 1-7 1 H- and 13 C-NMR analysis was performed by dissolving 102 mg of each compound in approximately 0.5 mL of CDCl3 and adding the solution to an NMR sample tube with an outer diameter of 5 mm. The analysis was conducted at 25 °C using either an AVANCENEO 400 or an AVANCE 500 manufactured by Blu-ray Corporation.

[0197] [Analysis and Interpretation of Liquid Chromatography (LC) and Liquid Chromatography-Mass Spectrometry (LC-MS)]

[0198] The liquid chromatography (LC) and liquid chromatography-mass spectrometry (LC-MS) analyses of the compounds in Example 1 were performed under the following conditions.

[0199] Device LC: Ultimate3000 (manufactured by Dionex)

[0200] LC-MS: OrbitrapElite (manufactured by ThermoFisher Scientific)

[0201] Ionization method: Electrospray ionization (ESI) method (Posi-Nega)

[0202] Separator column: SHODEX GS-220HQ (registered trademark), manufactured by Showa Denko Co., Ltd.

[0203] Volume introduced: 2μL

[0204] Mass spectrometry measurement range: m / z = 80-1000

[0205] Mobile phase: 10 mM ammonium acetate aqueous solution: acetonitrile = 1:1 (mass ratio)

[0206] Flow rate: 0.5 mL / min

[0207] Column temperature: 40℃

[0208] LC detector: photodiode array detector

[0209] LC-MS detector: FT

[0210] Spray Voltage (kV): (Posi)³ / (Nega)².5

[0211] Evaporator temperature (°C): 500

[0212] Sheath Gas Flow Rate (arb): 50

[0213] Aux Gas Flow Rate (arb): 15

[0214] Sweep Gas Flow Rate (arb): 3

[0215] Capillary temperature (°C): 250

[0216] [Example 1]

[0217] <AOI-MDE Synthesis>

[0218] In a 500 mL four-necked flask equipped with a stirrer, thermometer, dropping funnel, and reflux cooler, 190.2 g of diethyl malate (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.17 g of 2,6-di-tert-butyl-4-methylphenol (manufactured by Okusaris Kemica Co., Ltd.), and 0.33 g of dibutyltin dilaurate (hereinafter also referred to as "DBTDL") (manufactured by Nitto Chemical Co., Ltd.) were added, and the mixture was cooled to 15–20 °C. After cooling, 141.1 g of 2-acryloyloxyethyl isocyanate (manufactured by Showa Denko Co., Ltd., CARENZ AOI-VM (registered trademark): compounds having isocyanate groups (a1)) was added dropwise over 1 hour while maintaining the internal temperature at 15–20 °C. After the addition was completed, cooling was stopped, and the mixture was allowed to react at room temperature (25 °C) for 13 hours. The reaction was confirmed to be complete by the disappearance of the isocyanate group peak by IR, yielding 331 g of the target compound (blocked isocyanate compound (A), hereinafter also referred to as "AOI-MDE") as shown in formula (8). The yield was over 99% by mass, and the appearance was a colorless and transparent liquid with a purity (area percentage) of 97.7% as determined by HPLC. The obtained compound was then subjected to... 1 H- and 13The C-NMR diagram is shown in Figure 1 and Figure 8 middle.

[0219]

[0220] <MOI-MDE Synthesis>

[0221] 28.5 g of diethyl malate, 0.01 g of BHT, and 0.05 g of DBTDL were added to a 100 mL four-necked flask equipped with a stirrer, thermometer, dropping funnel, and reflux cooler, and the mixture was cooled to 15–20 °C. After cooling, 23.3 g of 2-methacryloyloxyethyl isocyanate (manufactured by Showa Denko Co., Ltd., CARENZ MOI (registered trademark): compound having an isocyanate group (a1)) was added dropwise over 1 hour while maintaining the internal temperature at 15–20 °C. After the addition was completed, cooling was stopped, and the mixture was allowed to react at room temperature (25 °C) for 13 hours. The reaction was confirmed to be complete by the disappearance of the isocyanate group peak by IR, and 51 g of the target compound (blocked isocyanate compound (A), hereinafter also referred to as "MOI-MDE") as shown in the following formula (9) was obtained. The yield was ≥99% by mass, the appearance was a colorless and transparent liquid, and the purity (area percentage) determined by HPLC was 99.4%. The resulting compound 1 H- and 13 The C-NMR diagram is shown in Figure 2 and Figure 9 middle.

[0222]

[0223] <MOI-EG-MDE Synthesis>

[0224] 28.5 g of diethyl malate, 0.01 g of BHT, and 0.05 g of DBTDL were added to a 100 mL four-necked flask equipped with a stirrer, thermometer, dropping funnel, and reflux cooler, and the mixture was cooled to 15–20 °C. After cooling, 29.9 g of 2-(isocyanate-ethyloxy)ethyl methacrylate (manufactured by Showa Denko Co., Ltd., CARENZ MOI-EG (registered trademark): compound having an isocyanate group (a1)) was added dropwise over 1 hour while maintaining the internal temperature at 15–20 °C. After the addition was completed, cooling was stopped, and the mixture was allowed to react at room temperature (25 °C) for 13 hours. The reaction was confirmed to be complete by the disappearance of the isocyanate group peak by IR, and 58 g of the target compound (blocked isocyanate compound (A), hereinafter also referred to as "MOI-EG-MDE") as shown in the following formula (10) was obtained. The yield was over 99% by mass, and the product was a pale yellow, transparent liquid with a purity (area percentage) of 96.4% determined by HPLC. The obtained compound... 1 H- and 13The C-NMR diagram is shown in Figure 3 and Figure 10 middle.

[0225]

[0226] [Example 4]

[0227] <BEI-MDE Synthesis>

[0228] In a 100 mL four-necked flask equipped with a stirrer, thermometer, dropping funnel, and reflux cooler, 20.9 g of diethyl malate, 50 mL of toluene (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.01 g of BHT, and 0.05 g of DBTDL were added, and the mixture was cooled to 15–20 °C. After cooling, 29.9 g of 1,1-bis(acryloyloxymethyl)ethyl isocyanate (manufactured by Showa Denko Co., Ltd., CLENZ BEI (registered trademark): compound having an isocyanate group (a1)) was added dropwise over 1 hour while maintaining the internal temperature at 15–20 °C. After the addition was completed, cooling was stopped, and the mixture was allowed to react at room temperature (25 °C) for 10 days. The reaction was confirmed to be complete by the disappearance of the isocyanate group peak by IR spectroscopy. The toluene was removed by vacuum distillation using an evaporator to obtain 50 g of the target compound shown in formula (11) below (blocked isocyanate compound (A), hereinafter also referred to as "BEI-MDE"). The yield was over 99% by mass, and the product was a pale yellow, transparent liquid with a purity (area percentage) of 93.1% determined by HPLC. The obtained compound... 1 H- and 13 The C-NMR diagram is shown in Figure 4 and Figure 11 middle.

[0229]

[0230] [Example 5]

[0231] <HDI-MDE Synthesis>

[0232] 38.4 g of diethyl malate and 0.06 g of DBTDL were added to a 100 mL four-necked flask equipped with a stirrer, thermometer, dropping funnel, and reflux cooler, and the mixture was cooled to 15–20 °C. After cooling, 16.8 g of hexamethylene diisocyanate (Kanto Chemical Reagent: Compounds with Isocyanate Groups (a1)) was added dropwise over 1 hour while maintaining the internal temperature at 15–20 °C. After the addition was completed, cooling was stopped, and the mixture was allowed to react at room temperature (25 °C) for 13 hours. The reaction was confirmed to be complete by the disappearance of the isocyanate group peak by IR. Toluene was removed by vacuum distillation using an evaporator to obtain 55 g of the target compound (blocked isocyanate compound (A), hereinafter also referred to as "HDI-MDE") as shown in formula (12). The yield was ≥99% by mass, the appearance was a light yellow transparent liquid, and the purity (area percentage) determined by HPLC was ≥99%. The obtained compound was... 1 H- and 13 The C-NMR diagram is shown in Figure 5 and Figure 12 middle.

[0233]

[0234] [Example 6]

[0235] <MDI-MDE Synthesis>

[0236] 38.4 g of diethyl malate and 0.06 g of DBTDL were added to a 100 mL four-necked flask equipped with a stirrer, thermometer, dropping funnel, and reflux cooler, and the mixture was cooled to 15–20 °C. After cooling, 25.3 g of 4,4'-diphenylmethane diisocyanate (manufactured by Nippon Chemicals, Inc.: a compound with an isocyanate group (a1)) dissolved in 25 g of toluene was added dropwise over 1 hour while maintaining an internal temperature of 15–20 °C. After the addition was completed, cooling was stopped, and the mixture was allowed to react at room temperature (25 °C) for 13 hours. The reaction was confirmed to be complete by the disappearance of the isocyanate group peak by IR spectroscopy. The toluene was removed by vacuum distillation using an evaporator to obtain 63 g of the target compound (blocked isocyanate compound (A), hereinafter also referred to as "MDI-MDE") as shown in formula (13). The yield was over 99% by mass, and the liquid was a light yellow transparent liquid with a purity (area percentage) of 93.8% as determined by HPLC.

[0237] The resulting compound 1 H- and 13 The C-NMR diagram is shown in Figure 6 and Figure 13 middle.

[0238]

[0239] [Example 7]

[0240] <IPDI-MDE Synthesis>

[0241] 38.4 g of diethyl malate, 0.05 g of DBTDL, and 50 mL of toluene were added to a 100 mL four-necked flask equipped with a stirrer, thermometer, dropping funnel, and reflux cooler, and the mixture was cooled to 15–20 °C. After cooling, 22.3 g of isophorone diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.: a compound with an isocyanate group (a1)) was added dropwise over 1 hour while maintaining the internal temperature at 15–20 °C. After the addition was completed, cooling was stopped, and the mixture was allowed to react at room temperature (25 °C) for 10 days. The reaction was confirmed to be complete by the disappearance of the isocyanate group peak by IR. The toluene was removed by vacuum distillation using an evaporator, yielding 60 g of the target compound (blocked isocyanate compound (A), hereinafter also referred to as "IPDI-MDE") as shown in formula (14). The yield was over 99% by mass, and the appearance was a light yellow transparent liquid with a purity (area percentage) of 88.6% as determined by HPLC. The obtained compound was subjected to... 1 H- and 13 The C-NMR diagram is shown in Figure 7 and Figure 14 middle.

[0242]

[0243] [Example 8]

[0244] <Preparation of Blocked Isocyanate Polymer (H)>

[0245] 224 g of propylene glycol monomethyl ether acetate (manufactured by Kanto Chemical Co., Ltd.) was added to a 1 L detachable flask equipped with a stirrer, thermometer, dropping funnel, and reflux cooler, and the temperature was raised to 90°C. The mixture of 40 g of AOI-MDE prepared in Example 1, 86 g of n-butyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.: monomer (G) with olefinic double bonds), 76 g of methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.: monomer (G) with olefinic double bonds), and 24 g of dimethyl 2,2'-azobis(isobutyrate) (manufactured by Fujifilm and Wako Pure Pharmaceutical Co., Ltd., hereinafter also referred to as "V-601") was added dropwise over 2 hours. After the addition was completed, the temperature inside the container was maintained at 90°C for 30 minutes. Then, liquid containing 4 g of V-601 dissolved in 16 g of propylene glycol monomethyl ether acetate was added, and the reaction was carried out for another 3 hours to obtain 448 g of blocked isocyanate polymer (H) with a weight average molecular weight of 9000. IR analysis confirmed the absence of a peak originating from the olefinic double bond (d2) of the compound containing the hydroxyl group (a2).

[0246] [Example 9]

[0247] <Preparation of Blocked Isocyanate Polymers (I) with Alkenyl Double Bonds (d2)>

[0248] 100 g of the blocked isocyanate polymer prepared in Example 8 and 0.1 g of 1,8-diazabicyclo[5.4.0]-undecene-7 were added to a 200 mL four-necked flask equipped with a stirrer, thermometer, dropping funnel, and reflux cooler. The mixture was heated to an internal temperature of 80 °C, and foaming was confirmed after 5 minutes. The mixture was then maintained at 80 °C for 30 minutes to obtain 99 g of the compound shown in Formula (15) below (a blocked isocyanate polymer (I) having an olefinic double bond (d2)). The presence of a peak of the olefinic double bond (d2) derived from the compound (a2) having a hydroxyl group was confirmed by IR.

[0249]

[0250] [Example 10]

[0251] <Manufacturing of Blocked Isocyanate Resin (K) by Thermopolymerization>

[0252] 100 g of the compound prepared in Example 9 was heated to 90°C, and 2 g of V-601 was added, allowing the reaction to proceed for 1 hour, yielding 100 g of blocked isocyanate resin. The weight-average molecular weight was 55,400, an increase compared to the weight-average molecular weight of 9,000 of the compound prepared in Example 9. Furthermore, in IR spectroscopy, the peak originating from the olefinic double bond (d2) identified in the compound prepared in Example 9 disappeared.

[0253] [Example 11]

[0254] (Manufacturing using photopolymerized blocked isocyanate resin (K))

[0255] The sample solution prepared using 5g of the compound manufactured in Example 9 was coated with a 6cm long and 2cm wide strip using a rod coater No. 34 (wet film thickness approximately 77.86μm). The presence or absence of C=C double bonds was confirmed by IR. The film was prepared by drying at ambient pressure and 40°C for 15 hours using a dryer. The film was then exposed to light using an exposure machine (manufactured by Sen Special Light Source Co., Ltd., (UV irradiator: HB100A-1(5), lamp: HLR100T-2)) at 20J / cm. 2 The membrane was irradiated with 254 nm light for 1 minute. Changes in IR and gel fraction were measured. The results are shown in Table 1.

[0256]

[0257] [Examples 12, 13, and Reference Examples 1-3]

[0258] The polymers and photopolymerization initiators listed in Table 1 were used, and the photopolymerization of the resin was carried out in the same manner as in Example 11. Additionally, IRGACURE (registered trademark) 184 is 1-hydroxycyclohexylphenyl ketone (manufactured by Chivas Petroleum Technology Co., Ltd.), and IRGACURE (registered trademark) 651 is 2,2'-dimethoxy-2-phenylacetophenone (manufactured by IGM Resins BV Co., Ltd.).

[0259] [Example 14]

[0260] <Structural confirmation of the compound after decarboxylation>

[0261] 10 g of the blocked isocyanate compound (A) obtained in Example 1 and 10 g of toluene (manufactured by Kanto Chemical) were added to a 100 mL three-necked flask equipped with a stirrer, thermometer, dropping funnel, and reflux cooler. After heating to 80 °C, 0.02 g of 1,8-diazabicyclo[5.4.0]-undecene-7 was added. The mixture was heated at 80 °C for 30 minutes until the foaming subsided, and then cooled to 23 °C. The decarboxylation reaction was confirmed by HPLC. As a result, the peak of AOI-MDE contained in the blocked isocyanate compound (A) disappeared, and two peaks were confirmed as new products.

[0262] To determine the structure of the compound resulting from the decarboxylation reaction, two components were separated from the liquid obtained by silica gel column chromatography. 1 The structures were confirmed by H-NMR, and the two products were identified as compounds of formula (16) and formula (17) respectively, generated by decarboxylation via AOI-MDE. Furthermore, LC and LC-MS plots were presented... Figure 15 and 16 middle.

[0263]

[0264] The olefinic double bonds (d2) present in the blocked isocyanate polymer (I) with olefinic double bonds (d2) produced in Example 9 disappeared after light irradiation in the blocked isocyanate polymer (I) produced in Example 9. On the other hand, the olefinic double bonds (d2) were not observed in the resins (Reference Examples 1 to 3) produced by the blocked isocyanate polymer obtained in Example 8 before and after light irradiation.

[0265] Regarding the gel fraction, the gel fraction was 25% to 41% in Examples 11-13, but 0% in Reference Examples 1-3. These results show that cross-linking was formed in Examples 11-13.

Claims

1. A blocked isocyanate compound (A) which is a compound (al) having an isocyanate group, a compound (a2) having a hydroxyl group represented by the following formula (1) which is urethane-bonded via the isocyanate group and the hydroxyl group, ###0001### (1) In formula (1), R 1 and R 2 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R 3 and R 4 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, the compound (al) having an isocyanate group has an olefinic double bond (dl).

2. The blocked isocyanate compound (A) according to claim 1, wherein the compound (al) having an isocyanate group having an olefinic double bond (dl) is 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 2- (isocyanateethyloxy)ethyl acrylate, 2-(isocyanateethyloxy)ethyl methacrylate, or 1,1- bis(acryloyloxymethyl)ethyl isocyanate.

3. The blocked isocyanate compound (A) according to claim 1 or 2, wherein R of the compound (a2) having a hydroxyl group 3 and R 4 is a hydrogen atom.

4. The blocked isocyanate compound (A) according to claim 1 or 2, wherein R of the compound (a2) having a hydroxyl group 1 and R 2 is an alkyl group having 1 to 3 carbon atoms.

5. The blocked isocyanate compound (A) according to claim 1 or 2, wherein the compound (a2) having a hydroxyl group is diethyl malonate.

6. A blocked isocyanate polymer (H) comprising the blocked isocyanate compound (A) according to any one of claims 1 to 5 as a monomer unit.

7. A blocked isocyanate polymer (I) having an olefinic double bond (d2) which is formed from the blocked isocyanate polymer (H) according to claim 6 and a base (B), ###0002### (6) the base (B) is represented by the following formula (6), 8. The blocked isocyanate polymer (I) having an olefinic double bond (d2) according to claim 7, wherein the base (B) is 1,8-diazabicyclo[5.4.0]-undec-7-ene, 1,5- diazabicyclo[4.3.0]-5-nonene, or 1,1,3,3-tetramethylguanidine. R 6 N = CR 7 -NR 8 R 9 ···(6) wherein R 6 is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group represented by -NR 10 7 R 8 , R 9 , and R 10 are a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and two R 10 may be the same as or different from each other; R 6 , R 7 , R 8 , R 9 , and two R 10 may combine to form a ring structure.​ 9. A blocked isocyanate resin (K) which is cured from the blocked isocyanate polymer (I) having an olefinic double bond (d2) according to claim 7 or 8.

10. A compound (C) having an olefinic double bond represented by the following formula (2-1) or the following formula (2-2), ###0003### 11. A blocked isocyanate compound (A) represented by the following formula (3), ###0004### (3) In formula (2-1), R 2 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R 3 and R 4 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R 5 is a hydrocarbon group having 1 to 20 carbon atoms and a valence number of m; m is an integer of 1 to 3; R 5 has an olefinic double bond (d1); In formula (2-2), R 1 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R 3 and R 4 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R 5 is a hydrocarbon group having 1 to 20 carbon atoms and a valence number of m; m is an integer of 1 to 3; and R 5 has an olefinic double bond (d1). ​ In formula (3), R 1 and R 2 each independently is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R 3 and R 4 each independently is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R 5 is a hydrocarbon group having 1 to 20 carbon atoms and a valence number of m; m is an integer of 1 to 3; R 5 has an olefinic double bond (d1).

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