JP2011236388A - Blocked isocyanate composition and resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a blocked isocyanate composition which can dissociate a blocking agent at a low temperature and improve close adhesion with a substrate while the composition can be efficiently prepared; and a resin composition obtained by using the blocked isocyanate composition.SOLUTION: This blocked isocyanate composition includes a blocked isocyanate, blocked of the isocyanate group of an isocyanate compound containing an aliphatic isocyanate and/or alicyclic isocyanate, by a blocking agent, in which 95 mol% or more of the total isocyanate groups in the total isocyanate compounds are blocked by 30-70 mol% oxime-based blocking agent and 30-70 mol% pyrazole-based blocking agent, and in which at least a blocked isocyanate having both an isocyanate group blocked by the oxime-based blocking agent and an isocyanate group blocked by the pyrazole-based blocking agent in one molecule is contained.

Description

  The present invention relates to a blocked isocyanate composition and a resin composition, and more specifically to a blocked isocyanate composition used as a curing agent, and a resin composition obtained using the blocked isocyanate composition.

  Block isocyanate is isocyanate that dissociates upon heating and the isocyanate group is regenerated, and has a long pot life and excellent processability. Therefore, polyol components (main agent) and isocyanate components (curing agents) such as paints and adhesives are used. Is used as a curing agent for a two-component curable polyurethane resin that is blended at the time of use.

  In recent years, as such a blocked isocyanate, a low-temperature dissociation type blocked isocyanate capable of dissociating a blocking agent at a lower temperature has been studied in order to reduce carbon dioxide emission. As a low-temperature dissociation type blocked isocyanate, a pyrazole-based blocked isocyanate using a pyrazole compound as a blocking agent has been studied.

  On the other hand, in the case of pyrazole-based blocked isocyanate, the adhesion to a substrate to an electrodeposition plate or the like may be inferior.

  Therefore, in order to improve the adhesion to the substrate, for example, a polymer having a functional group capable of reacting with an isocyanate group, a blocked isocyanate compound blocked with a methyl ethyl ketone oxime blocking agent, pyrazole, 3-methylpyrazole, 3 An adhesive containing a blocked isocyanate compound blocked with a blocking agent selected from the group consisting of 1,5-dimethylpyrazole and 1,2,4-triazole has been proposed (for example, see Patent Document 1).

  In addition, for example, an isocyanate group (aliphatic and / or alicyclic) is produced by a blocking agent mixture containing 1,2,4-triazole, 3,5-dimethylpyrazole, and other blocking agents in a specific blending amount. A blocked isocyanate in which a formula-bonded isocyanate group) is blocked has been proposed (for example, see Patent Document 2).

JP 2004-107409 A JP-A-7-304843

  However, the adhesive described in Patent Document 1 has a problem that the work is complicated because the polymer and at least two types of blocked isocyanate compounds are mixed at the time of use. Moreover, the adhesiveness with respect to the base material in low temperature and storage stability are inadequate.

  In addition, the blocked isocyanate described in Patent Document 2 has insufficient adhesion to the substrate at low temperatures.

  Accordingly, an object of the present invention is to provide a blocked isocyanate composition that can be efficiently prepared, can dissociate the blocking agent at a low temperature, and can improve adhesion to a substrate, and the blocked isocyanate composition It is providing the resin composition obtained using a thing.

  In order to achieve the above object, the blocked isocyanate composition of the present invention is a blocked isocyanate composition containing a blocked isocyanate in which an isocyanate group of an isocyanate compound is blocked by a blocking agent, and the isocyanate compound is aliphatic. In all the blocking agents containing isocyanate and / or alicyclic isocyanate, 95 mol% or more of all isocyanate groups in all the isocyanate compounds are blocked by the blocking agent, and blocking all the isocyanate groups, 30 to 70 mol% of the system block agent and 30 to 70 mol% of the pyrazole block agent are contained, and are blocked by the isocyanate group blocked by the oxime block agent and the pyrazole block agent. And an isocyanate group, a blocked isocyanate having both in one molecule, is characterized by containing at least.

  Moreover, in the blocked isocyanate composition of this invention, it is suitable that the isocyanate group blocked with the said blocking agent contains 1-20 mass%.

  In the blocked isocyanate composition of the present invention, it is preferable that 70% by mass or more of the isocyanate compound is a trimer.

  In the blocked isocyanate composition of the present invention, it is preferable that the pyrazole-based blocking agent is 3,5-dimethylpyrazole.

  In the blocked isocyanate composition of the present invention, it is preferable that the oxime blocking agent is methyl ethyl ketone oxime.

  Moreover, it is preferable that the blocked isocyanate composition of the present invention further contains a plasticizer.

  The resin composition of the present invention is characterized by containing plastisol, an active hydrogen compound having an active hydrogen group, and the above-mentioned blocked isocyanate composition.

  While the blocked isocyanate composition of the present invention can be efficiently prepared, the blocking agent can be dissociated at a low temperature, and the adhesion to the substrate can be improved.

  The blocked isocyanate composition of the present invention contains a blocked isocyanate in which an isocyanate group of an isocyanate compound is blocked with a blocking agent.

  The isocyanate compound contains aliphatic isocyanate and / or alicyclic isocyanate as an essential component.

  Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), penta Examples include aliphatic diisocyanates such as methylene diisocyanate, hexamethylene diisocyanate (hereinafter abbreviated as HDI), 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, and 2,6-diisocyanate methyl capate. .

Examples of the alicyclic polyisocyanate include 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), and 3-isocyanatomethyl-3. , 5,5-trimethylcyclohexyl isocyanate (isophorodiisocyanate, hereinafter abbreviated as IPDI), methylene bis (cyclohexyl isocyanate) (4,4'-, 2,4'- or 2,2'-methylene bis (cyclohexyl isocyanate, these of Trans, Trans- body, Trans, Cis body, Cis, Cis body, or mixtures thereof)) _(hereinafter abbreviated as H 12 MDI), methylcyclohexane diisocyanate ( Til-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate), norbornane diisocyanate (various isomers or mixtures thereof) (hereinafter abbreviated as NBDI), bis (isocyanatomethyl) cyclohexane (1,3- Or alicyclic diisocyanates such as 1,4-bis (isocyanatomethyl) cyclohexane or a mixture thereof (hereinafter abbreviated as H ₆ XDI).

  Moreover, as an isocyanate compound, the derivative | guide_body of the above-mentioned essential component isocyanate compound (aliphatic polyisocyanate, alicyclic polyisocyanate) is mentioned, for example.

  Examples of the derivatives include multimers of the above-described isocyanate compounds (for example, dimers such as uretdione modified products, trimers such as isocyanurate modified products or iminooxadiazine dione modified products), allophanate modified products (for example, , Allophanate-modified products produced from the reaction of the above polyisocyanates and alcohols), urethane-modified products (for example, urethane-modified products produced from the reaction of polyisocyanate and polyol), biuret-modified products (for example, the above) Modified polyisocyanates with water and amines, etc., modified biurets), urea-modified products (for example, urea-modified products generated by reaction of the above polyisocyanates with diamines), oxadiazine trione modified Body (e.g. Oxadiazinetrione, etc.) produced by reaction of the Aneto and carbon dioxide, carbodiimide modified product (carbodiimide modified product produced by decarboxylation condensation reaction of the polyisocyanate described above, etc.), and the like uretonimine modified product.

  The derivative of the essential component isocyanate compound is preferably a trimer of an isocyanate compound, more preferably an isocyanurate-modified product.

  Moreover, as an isocyanate compound, aromatic polyisocyanate, araliphatic polyisocyanate, etc. are mentioned as an arbitrary component, for example.

  Examples of the aromatic polyisocyanate include tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or a mixture thereof) (hereinafter, abbreviated as TDI), phenylene diisocyanate (m-, p-phenylene diisocyanate or a mixture thereof). Mixture), 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate (hereinafter abbreviated as NDI), diphenylmethane diisocyanate (4,4'-, 2,4'- or 2,2'-diphenylmethane dii Succinate or a mixture thereof (hereinafter abbreviated as MDI), 4,4'-toluidine diisocyanate (hereinafter abbreviated as TODI), aromatic diisocyanates such as 4,4'-diphenyl ether diisocyanate, and the like.

  Examples of the araliphatic polyisocyanate include xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or a mixture thereof) (hereinafter abbreviated as XDI), tetramethylxylylene diisocyanate (1,3- or 1,4-tetramethylxylylene diisocyanate or a mixture thereof (hereinafter abbreviated as TMXDI), and araliphatic diisocyanates such as ω, ω′-diisocyanate-1,4-diethylbenzene.

  Examples of the isocyanate compound include derivatives of the above-described optional isocyanate compounds (aromatic polyisocyanates and araliphatic polyisocyanates).

  Examples of the derivative of the optional isocyanate compound include, for example, the isocyanate compound multimer, allophanate-modified product, urethane-modified product, biuret-modified product, urea-modified product, and oxadiazinetrione-modified as in the case of the essential component isocyanate compound described above. Body, carbodiimide modified body, uretonimine modified body and the like.

  These isocyanate compounds can be used alone or in combination of two or more.

  Moreover, when using 2 or more types of isocyanate compounds together, Preferably, the trimer is contained 70 mass% or more, Furthermore, 80 mass% or more is contained.

  When the trimer of the isocyanate compound is in the above-described ratio, the adhesion to the substrate can be improved.

  The blocking agent is an organic compound that is dissociated from the isocyanate compound by heat treatment, and contains a pyrazole-based blocking agent and an oxime-based blocking agent as essential components.

  Examples of the pyrazole blocking agent include pyrazole, 3,5-dimethylpyrazole, 3-methylpyrazole, 4-benzyl-3,5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole, and 4-bromo-3. , 5-dimethylpyrazole, 3-methyl-5-phenylpyrazole and the like.

  The pyrazole block agent can be used alone or in combination of two or more kinds, and preferably 3,5-dimethylpyrazole is used.

  Examples of the oxime blocking agent include formaldehyde oxime, acetoald oxime, acetone oxime, methyl ethyl ketone oxime, cyclohexanone oxime, diacetyl monooxime, benzophenoxime, 2,2,6,6-tetramethylcyclohexanone oxime, diisopropyl ketone. Oxime, methyl t-butyl ketone oxime, diisobutyl ketone oxime, methyl isobutyl ketone oxime, methyl isopropyl ketone oxime, methyl 2,4-dimethylpentyl ketone oxime, methyl 3-ethyl heptyl ketone oxime, methyl isoamyl ketone oxime, n-amyl Ketone oxime, 2,2,4,4-tetramethyl-1,3-cyclobutanedione monooxime, 4,4′-dimethoxybenzophenone oxime Such as 2-cycloheptanone oxime and the like.

  The oxime blocking agent can be used alone or in combination of two or more kinds, and preferably methyl ethyl ketone oxime.

  In addition, as a blocking agent, as an optional component, for example, an alcohol blocking agent, a phenol blocking agent, an active methylene blocking agent, an amine blocking agent, an imine blocking agent, a carbamic acid blocking agent, a urea blocking agent, Examples include acid amide (lactam) compounds, acid imide blocking agents, triazole blocking agents, imidazole blocking agents, imidazoline blocking agents, mercaptan blocking agents, and bisulfites.

  Examples of the alcohol blocking agent include methanol, ethanol, 2-propanol, n-butanol, s-butanol, 2-ethylhexyl alcohol, 1- or 2-octanol, cyclohexyl alcohol, ethylene glycol, benzyl alcohol, 2, 2,2-trifluoroethanol, 2,2,2-trichloroethanol, 2- (hydroxymethyl) furan, 2-methoxyethanol, methoxypropanol, 2-ethoxyethanol, n-propoxyethanol, 2-butoxyethanol, 2- Ethoxyethoxyethanol, 2-ethoxybutoxyethanol, butoxyethoxyethanol, 2-ethylhexyloxyethanol, 2-butoxyethylethanol, 2-butoxyethoxyethanol, N, N-dibutyl 2-hydroxyacetamide, N-hydroxysuccinimide, N-morpholine ethanol, 2,2-dimethyl-1,3-dioxolane-4-methanol, 3-oxazolidineethanol, 2-hydroxymethylpyridine, furfuryl alcohol, 12-hydroxystearin Acid, triphenylsilanol, 2-hydroxyethyl methacrylate and the like can be mentioned.

  Examples of the phenol blocking agent include phenol, cresol, ethylphenol, n-propylphenol, isopropylphenol, n-butylphenol, s-butylphenol, t-butylphenol, n-hexylphenol, 2-ethylhexylphenol, n-octylphenol, n-nonylphenol, di-n-propylphenol, diisopropylphenol, isopropylcresol, di-n-butylphenol, di-s-butylphenol, di-t-butylphenol, di-n-octylphenol, di-2-ethylhexylphenol, di- n-nonylphenol, nitrophenol, bromophenol, chlorophenol, fluorophenol, dimethylphenol, styrenated phenol, methylsali Rato, methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, 2-ethylhexyl hydroxybenzoate, 4-[(dimethylamino) methyl] phenol, 4-[(dimethylamino) methyl] nonylphenol, bis (4-hydroxy Phenyl) acetic acid, pyridinol, 2- or 8-hydroxyquinoline, 2-chloro-3-pyridinol, pyridine-2-thiol and the like.

  Examples of the active methylene blocking agent include Meldrum's acid, dialkyl malonate (for example, dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-t-butyl malonate, di-2-ethylhexyl malonate, malon Methyl n-butyl acid, ethyl n-butyl malonate, methyl s-butyl malonate, ethyl s-butyl malonate, methyl t-butyl malonate, ethyl t-butyl malonate, diethyl methylmalonate, dibenzyl malonate, Diphenyl malonate, benzyl methyl malonate, ethyl phenyl malonate, t-butylphenyl malonate, isopropylidene malonate, etc.), alkyl acetoacetate (eg, methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, acetoacetate) Isopropyl, n-butyl acetoacetate, aceto Acid t- butyl, acetoacetate benzyl, acetoacetic acid phenyl), 2-acetoacetoxyethyl methacrylate, acetylacetone, and the like such as ethyl cyanoacetate.

  Examples of the amine blocking agent include dibutylamine, diphenylamine, aniline, N-methylaniline, carbazole, bis (2,2,6,6-tetramethylpiperidinyl) amine, di-n-propylamine, diisopropylamine. , Isopropylethylamine, 2,2,4-, or 2,2,5-trimethylhexamethyleneamine, N-isopropylcyclohexylamine, dicyclohexylamine, bis (3,5,5-trimethylcyclohexyl) amine, piperidine, 2, 6-dimethylpiperidine, 2,2,6,6-tetramethylpiperidine, (dimethylamino) -2,2,6,6-tetramethylpiperidine, 2,2,6,6-tetramethyl-4-piperidine, 6 -Methyl-2-piperidine, 6-aminocaproic acid, etc. It is below.

  Examples of the imine blocking agent include ethyleneimine, polyethyleneimine, 1,4,5,6-tetrahydropyrimidine, guanidine and the like.

  Examples of the carbamic acid blocking agent include phenyl N-phenylcarbamate.

  Examples of the urea blocking agent include urea, thiourea, and ethylene urea.

  Examples of acid amide (lactam) compounds include acetanilide, N-methylacetamide, acetic acid amide, ε-caprolactam, δ-valerolactam, γ-butyrolactam, pyrrolidone, 2,5-piperazinedione, laurolactam, and the like. It is done.

  Examples of the acid imide blocking agent include succinimide, maleic imide, phthalimide, and the like.

  Examples of the triazole-based blocking agent include 1,2,4-triazole, 4-amino-1,2,4-triazole, benzotriazole, and the like.

  Examples of the imidazole blocking agent include imidazole, benzimidazole, 2-methylimidazole, 4-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, Examples include 2-phenylimidazole and 4-methyl-2-phenylimidazole.

  Examples of the imidazoline-based blocking agent include 2-methylimidazoline and 2-phenylimidazoline.

  Examples of the mercaptan-based blocking agent include butyl mercaptan, dodecyl mercaptan, hexyl mercaptan, and the like.

  Examples of the bisulfite include sodium bisulfite.

  Examples of the optional blocking agent include other blocking agents such as benzoxazolone, isatoic anhydride, and tetrabutylphosphonium acetate.

  The blocked isocyanate can be obtained, for example, by reacting an isocyanate compound and a blocking agent in a solvent.

  Examples of the solvent include a low boiling point solvent and a plasticizer.

  The low boiling point solvent is an organic solvent that is inert to the isocyanate group and can be easily removed by a method such as distillation. For example, esters such as ethyl acetate and butyl acetate, ketones such as acetone and methyl ethyl ketone, For example, ethers such as tetrahydrofuran, and nitriles such as acetonitrile are exemplified.

  Examples of the plasticizer include phthalic acid plasticizers, fatty acid plasticizers, aromatic polycarboxylic acid plasticizers, phosphoric acid plasticizers, polyol plasticizers, epoxy plasticizers, and polyester plasticizers. It is done.

  Examples of the phthalic acid plasticizer include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, diheptyl phthalate, di- (2-ethylhexyl) phthalate, di-n-octyl phthalate, dinonyl. Phthalate, diisononyl phthalate, didecyl phthalate, diisodecyl phthalate, ditridecyl phthalate, diundecyl phthalate, dilauryl phthalate, distearyl phthalate, diphenyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, dicyclohexyl phthalate, octyl decyl phthalate, dimethyl isophthalate, Phthalate plasticizers such as di- (2-ethylhexyl) isophthalate and diisooctylisophthalate, such as Di - (2-ethylhexyl) tetrahydrophthalate, di -n- octyl tetrahydrophthalate include tetrahydrophthalic acid ester plasticizers such as diisodecyl tetrahydrophthalate.

  Examples of the fatty acid plasticizer include adipic acid such as di-n-butyl adipate, di- (2-ethylhexyl) adipate, diisodecyl adipate, diisononyl adipate, di (C6-C10 alkyl) adipate, dibutyl diglycol adipate Plasticizers, for example, azelaic acid plasticizers such as di-n-hexylazelate, di- (2-ethylhexyl) azelate, diisooctylazelate, such as di-n-butyl sebacate, di- (2- Sebacic acid plasticizers such as ethylhexyl) sebacate and diisononyl sebacate, for example maleic plasticizers such as dimethyl malate, diethyl maleate, di-n-butyl maleate, di- (2-ethylhexyl) maleate, Di-n-butyl fumarate, di- (2-ethylhexyl) F) Fumarate plasticizers such as fumarate, for example, itaconic acid plasticizers such as monomethyl itaconate, monobutyl itaconate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, di- (2-ethylhexyl) itaconate, For example, stearic acid plasticizers such as n-butyl stearate, glycerin monostearate, diethylene glycol distearate, for example, oleic acid plasticizers such as butyl oleate, glyceryl monooleate, diethylene glycol monooleate, such as triethyl citrate Citric acid plasticizers such as methyl acetyl acrylate, tri-n-butyl citrate, acetyl triethyl citrate, acetyl tributyl citrate, acetyl tri- (2-ethylhexyl) citrate Ricinoleic acid plasticizers such as norate, butylacetylricinoleate, glyceryl monoricinoleate, diethylene glycol monoricinoleate, and other fatty acid plasticizers such as diethylene glycol monolaurate, diethylene glycol dipelargonate, pentaerythritol fatty acid ester, etc. Can be mentioned.

  Examples of the aromatic polycarboxylic acid plasticizer include tri-n-hexyl trimellitate, tri- (2-ethylhexyl) trimellitate, tri-n-octyl trimellitate, triisooctyl trimellitate, triisononyl. Trimellitic acid plasticizers such as trimellitate, tridecyl trimellitate and triisodecyl trimellitate, for example, pyromellitic acid type such as tetra- (2-ethylhexyl) pyromellitate and tetra-n-octylpyromellitate Examples include plasticizers.

  Examples of the phosphoric acid plasticizer include triethyl phosphate, tributyl phosphate, tri- (2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, octyl diphenyl phosphate, cresyl diphenyl phosphate, cresyl phenyl phosphate, tricres Examples include zircyl phosphate, trixylenyl phosphate, tris (chloroethyl) phosphate, tris (chloropropyl) phosphate, tris (dichloropropyl) phosphate, tris (isopropylphenyl) phosphate, and the like.

  Examples of the polyol plasticizer include diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethylene glycol dibenzoate, triethylene glycol di- (2-ethylbutyrate), and triethylene glycol di- (2-ethylhexoate). ), Glycol plasticizers such as dibutylmethylenebisthioglycolate, and glycerin plasticizers such as glycerol monoacetate, glycerol triacetate, and glycerol tributyrate.

  Examples of the epoxy plasticizer include epoxidized soybean oil, epoxybutyl stearate, di-2-ethylhexyl epoxyhexahydrophthalate, diisodecyl epoxyhexahydrophthalate, epoxy triglyceride, octyl epoxidized oleate, decyl epoxidized oleate Etc.

  Examples of the polyester plasticizer include adipic acid-based polyester, sebacic acid-based polyester, and phthalic acid-based polyester.

  Other examples of the plasticizer include partially hydrogenated terphenyl, adhesive plasticizer, and polymerizable plasticizers such as diallyl phthalate, acrylic monomers and oligomers. These plasticizers can be used alone or in combination of two or more.

  The solvent is preferably a plasticizer, more preferably a phthalic acid plasticizer, and still more preferably di (2-ethylhexyl) phthalate, di-n-octyl phthalate, diisononyl phthalate. It is done.

  If a plasticizer is used as the solvent, it can be used as it is without removing the solvent when used as a plastisol curing agent, which will be described later, and furthermore, good compatibility with plastisol can be ensured.

  And in order to make an isocyanate compound and a blocking agent react, a blocking agent is mix | blended with the solution which dissolved the isocyanate compound in the solvent, for example.

  Also, for example, first, the isocyanate compound and the polyol described below are reacted so that the equivalent ratio of the hydroxyl group of the polyol to the isocyanate group of the isocyanate compound (hydroxyl group / isocyanate group) is less than 1.0, and then the block An agent can also be blended.

  As a method of blending the blocking agent, for example, a pyrazole block agent is first blended in a solution in which an isocyanate compound is dissolved in a solvent, and then the pyrazole block agent and the isocyanate compound are reacted, and then the oxime. A system block agent is mix | blended and an oxime system block agent and an isocyanate compound are made to react.

  If the pyrazole-based blocking agent is blended first and then the oxime-based blocking agent is blended, more blocked isocyanate in which both the pyrazole-based blocking agent and the oxime-based blocking agent have reacted with each molecule of the isocyanate compound is obtained. be able to.

  The method of blending the blocking agent is not limited to the method of sequentially blending the pyrazole block agent and the oxime block agent as described above. For example, first, the oxime block agent is blended, A pyrazole block agent can also be blended, for example, a pyrazole block agent and an oxime block agent can be blended together.

  Also, when blending an optional blocking agent, the blending method is not limited as described above, and the blending is performed sequentially or in a batch.

  The pyrazole type blocking agent has a molar ratio (active group / isocyanate group) of the active group that reacts with the isocyanate group in the pyrazole type blocking agent to the isocyanate group of the isocyanate compound, for example, 0.3 to 0.7, preferably , 0.4 to 0.6.

  In the oxime blocking agent, the molar ratio of the active group that reacts with the isocyanate group in the oxime blocking agent to the isocyanate group of the isocyanate compound (active group / isocyanate group) is, for example, 0.3 to 0.7, preferably , 0.4 to 0.6.

  The reaction conditions between the blocking agent and the isocyanate compound can be appropriately selected depending on the type of the blocking agent. For example, the atmospheric pressure is an inert gas (eg, nitrogen gas, argon gas, etc.) atmosphere. The reaction is carried out at 150 ° C., preferably 20 to 120 ° C., for example, for 5 minutes to 12 hours, preferably for 5 minutes to 8 hours.

  In this reaction, in the obtained blocked isocyanate, the reaction is completed so that 95 mol% or more, preferably 97 mol% or more of all isocyanate groups in all isocyanate compounds are blocked by the blocking agent.

  In addition, completion | finish of reaction can be judged by employ | adopting infrared spectroscopy etc. and confirming the loss | disappearance of an isocyanate group, for example.

  Thereby, the blocked isocyanate in which the isocyanate group of the isocyanate compound is blocked by the blocking agent can be synthesized.

  In the obtained blocked isocyanate, the content of an isocyanate group blocked by a blocking agent (hereinafter referred to as a latent isocyanate group) is, for example, 1 to 20% by mass, preferably 5 to 16% by mass.

  Further, in all blocking agents blocking isocyanate groups, the oxime blocking agent is 30 to 70 mol%, preferably 40 to 60 mol%, and the pyrazole blocking agent is 30 to 70 mol%, preferably 40 ~ 60 mol%.

  Further, the obtained all blocked isocyanate contains at least a blocked isocyanate having both an isocyanate group blocked with an oxime blocking agent and an isocyanate group blocked with a pyrazole blocking agent in one molecule. Yes.

  That is, the blocked isocyanate composition obtained by mixing the blocked isocyanate blocked only with the oxime blocking agent and the blocked isocyanate blocked only with the pyrazole blocking agent is an isocyanate group blocked with the oxime blocking agent. And a blocked isocyanate composition having an isocyanate group blocked with a pyrazole-based blocking agent in a molecule is substantially absent, and the blocked isocyanate composition of the present invention is distinguished from such an isocyanate composition. .

  When a low boiling point solvent is used as the solvent, the low boiling point solvent is removed by a method such as distillation after synthesizing a blocked isocyanate, if necessary.

  Further, when the blocked isocyanate composition is used as a plastisol curing agent, when a plasticizer is used as a solvent, the total content of the plasticizer is 100 parts by mass of the blocked isocyanate composition without removing the plasticizer. On the other hand, for example, a plasticizer can be further added so as to be 25 to 400 parts by mass, preferably 33.3 to 300 parts by mass.

  Thereby, a blocked isocyanate composition is prepared. Solid content of a block isocyanate composition is 20-80 mass%, for example, Preferably, it is 25-75 mass%.

  Known additives such as catalysts and stabilizers can be added to the thus obtained blocked isocyanate composition.

  Examples of the catalyst include known urethanization catalysts such as amines and organometallic compounds.

  Examples of the amines include tertiary amines such as triethylamine, triethylenediamine, bis- (2-dimethylaminoethyl) ether, N-methylmorpholine, and quaternary ammonium salts such as tetraethylhydroxylammonium, such as imidazole, Examples thereof include imidazoles such as 2-ethyl-4-methylimidazole.

  Examples of organometallic compounds include tin acetate, tin octylate, tin oleate, tin laurate, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin dimercaptide, dibutyltin maleate, dibutyltin dineodecano Organic tin compounds such as lead, dioctyltin dimercaptide, dioctyltin dilaurate, dibutyltin dichloride, for example, organic lead compounds such as lead octoate and lead naphthenate, for example, organic nickel compounds such as nickel naphthenate, for example, naphthenic acid Examples include organic cobalt compounds such as cobalt, organic copper compounds such as copper octenoate, and organic bismuth compounds such as bismuth octylate and bismuth neodecanoate. Preferably, an organometallic compound is mentioned, More preferably, an organotin type compound is mentioned.

  Furthermore, examples of the catalyst include potassium salts such as potassium carbonate, potassium acetate, and potassium octylate.

  These catalysts can be used alone or in combination of two or more.

  A catalyst is mix | blended with the compounding ratio of 0.01-0.3 mass part with respect to 100 mass parts of block isocyanate compositions, for example, Preferably, 0.03-0.15 mass part.

  Examples of the stabilizer include orthotoluenesulfonamide (OTS) and tetraphenyldipropylene glycol diphosphite.

  A stabilizer is mix | blended with the compounding ratio of 0.3 mass part or less with respect to 100 mass parts of blocked isocyanate compositions, for example, Preferably it is 0.15 mass part or less.

  The use of the blocked isocyanate composition is not particularly limited, and can be used as a curing agent for various resins. For example, various known resins such as plastisol, polyurethane resin, polyolefin resin, polyester resin, and polyacrylic resin can be used. It can be used as a curing agent. Preferably, it is used as a plastisol curing agent.

  If the block isocyanate composition is used as a plastisol curing agent, the adhesion to the object to be coated can be improved.

  The plastisol contains, for example, a resin, a plasticizer, and a filler.

  Examples of the resin include vinyl chloride resin, vinyl acetate copolymerized vinyl chloride resin, and acrylic resin.

  The resin is blended, for example, in an amount of 14 to 45 parts by mass, preferably 20 to 39 parts by mass with respect to 100 parts by mass of the plastisol.

  Examples of the plasticizer include the above-described plasticizers. Preferred plasticizers are also the same as those described above.

  A plasticizer is mix | blended, for example in 30-300 mass parts with respect to 100 mass parts of resin, Preferably, it is 50-200 mass parts.

  Examples of the filler include, but are not limited to, known fillers, such as calcium carbonate, hydrous basic magnesium carbonate, kaolinite, halloysite, allophane, pyrophyllite, talc, sericite, illite, mica, montmorillonite. , Piderite, amesite, chamosite, calcined clay, asbestos, mica, bentonite, calcium silicate, zeolite, pumice powder, slate powder, diatomaceous earth, quartz sand, quartzite powder, dibsite, boehmite, barium sulfate, calcium sulfate, Examples thereof include metal powder, wet and dry silica, and organically treated fillers thereof.

  These may be used alone or in combination of two or more, preferably calcium carbonate.

  The filler is blended, for example, in the range of 42 to 420 parts by mass, preferably 70 to 280 parts by mass with respect to 100 parts by mass of the resin.

  In addition, the plastisol can be blended with a colorant or the like, if necessary.

  Examples of the colorant include, but are not limited to, known colorants such as inorganic pigments such as titanium dioxide (titanium white), zinc oxide, carbon black, ferric oxide, titanium yellow, chrome green, and cobalt blue. Examples thereof include organic pigments such as permanent red, pyrazolone red, first yellow, phthalocyanine green, and dioxazine violet, such as basic dyes, direct dyes, acid dyes, metal-containing complex dyes, and oil-soluble dyes.

  The colorant is blended in an amount of, for example, 210 parts by mass or less, preferably 140 parts by mass or less, with respect to 100 parts by mass of the resin.

  In order to cure the plastisol, first, a resin composition containing a plastisol, a blocked isocyanate composition, and an active hydrogen compound is prepared.

  The active hydrogen compound has an active hydrogen group that reacts with an isocyanate group, such as a hydroxyl group or an amino group, and examples thereof include polyols and polyamines.

  The polyol has two or more hydroxyl groups, and examples thereof include a low molecular weight polyol and a macropolyol (high molecular weight polyol).

  Examples of the low molecular weight polyol include aliphatic diols such as ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, 1,6-hexanediol, and ether diols such as diethylene glycol, triethylene glycol, and dipropylene glycol. Can be mentioned.

  Examples of the macropolyol include known macropolyols used in the production of polyurethane resins, and examples thereof include polyether polyols, polyester polyols, polycarbonate polyols, polyurethane polyols, polyacrylic polyols, and the like.

  The polyamine has two or more amino groups, and examples thereof include a low molecular weight polyamine, a high molecular weight polyamine, and a polyamide polyamine.

  Low molecular weight polyamines include, for example, aromatic amines such as 4,4′-diphenylmethanediamine, araliphatic amines such as 1,3- or 1,4-xylylenediamine or mixtures thereof, such as 3-amino Alicyclic amines such as methyl-3,5,5-trimethylcyclohexylamine (common name: isophoronediamine), 1,3-bis (aminomethyl) cyclohexane, 1,4-cyclohexanediamine, such as ethylenediamine, 1,3 -Aliphatic amines such as propanediamine, 1,4-butanediamine, 1,6-hexamethylenediamine, hydrazine (including hydrate), diethylenetriamine, triethylenetetramine, and tetraethylenepentamine.

  Examples of the high molecular weight polyamine include polyoxyalkylene diamine (weight average molecular weight 400 to 4000), polyoxyalkylene triamine (weight average molecular weight 400 to 5000), and the like.

  Polyamide polyamines include, for example, tomide series such as tomide 210, tomide 215-X, tomide 225-X, tomide 245, and tomide 275 (manufactured by Fuji Kasei Kogyo Co., Ltd.) as compounds having both an amide bond and an amino group in the molecule. ), For example, sunmides such as sunmide 305, sunmide 315, sunmide 328A, sunmide 330, sunmide 336 as compounds obtained by reaction of aliphatic amines with dimer acid obtained by polymerizing unsaturated natural fatty acids Series (manufactured by Air Products Japan).

  These active hydrogen compounds can be used alone or in combination of two or more, preferably polyamines, more preferably polyamide polyamines.

  The resin composition is, for example, 0.5 to 10 parts by mass, preferably 1 to 8 parts by mass, and active hydrogen compound, for example 0.5 to 5 parts, based on 100 parts by mass of plastisol. It is prepared by mixing 1 part by mass, preferably 1 to 3 parts by mass and mixing.

  In addition, the resin composition includes, for example, an epoxy resin, an acrylic resin, a urethane resin, a coating property improving agent, a leveling agent, an antifoaming agent, a stabilizer such as an antioxidant or an ultraviolet absorber, and a surfactant. Well-known additives such as antifungal agents can be appropriately blended. The compounding amount of the additive is appropriately determined depending on the purpose and application.

  Next, the resin composition is applied to the application target and heated.

  The heating temperature is not particularly limited as long as the blocking agent is dissociated, but is, for example, 100 to 160 ° C, preferably 110 to 130 ° C.

  As a result, the blocking agent is dissociated to regenerate the isocyanate group of the isocyanate compound, the isocyanate group and the active hydrogen group of the active hydrogen compound can be reacted, the resin composition is cured, and a coating film is obtained. Can do.

  According to this blocked isocyanate composition, while the resin composition can be efficiently prepared, the blocking agent can be dissociated at a low temperature, and the adhesion to the substrate can be improved.

Next, although this invention is demonstrated based on an Example and a comparative example, this invention is not limited by the following Example.
(Components of blocked isocyanate composition)
1. Isocyanate compound (1) Takenate D-170N (hexamethylene diisocyanate trimer, isocyanate group content 21.0%, manufactured by Mitsui Chemicals)
(2) Takenate D-165N (hexuremethylene diisocyanate modified biuret, isocyanate group content 23.5%, manufactured by Mitsui Chemicals)
2. Blocking agent (1) Methyl ethyl ketone oxime (MEK-O)
(2) 3,5-dimethylpyrazole (DMP)
3. Polyol (1) Actol D-1000 (polypropylene glycol, weight average molecular weight: 1000, hydroxyl value: 112.2 mg KOH / g, manufactured by Mitsui Chemicals)
(2) Actol D-400 (polypropylene glycol, weight average molecular weight: 400, hydroxyl value: 280.5 mg KOH / g, manufactured by Mitsui Chemicals)
4). Plasticizer diisononyl phthalate (DINP, manufactured by Daihachi Chemical Industry)
5). Catalyst Dibutyltin dilaurate (DBTDL)
(Components of resin composition)
1. Resin Kane Vinyl Paste PCH-843 (Vinyl acetate copolymerized vinyl chloride resin, Kaneka)
2. 2. Filler calcium carbonate Active hydrogen group-containing compound Polyamide polyamine (Tomide 215-X, manufactured by Fuji Kasei Kogyo)
(Preparation of blocked isocyanate composition)
Examples 1-5
A five-necked flask equipped with a stirrer, a Dimroth cooler, a nitrogen inlet tube, a silica gel drying tube and a thermometer, was charged with 200 parts by mass of diisononyl phthalate and Takenate D-170N in a blending amount shown in Table 1, The mixture was uniformly mixed under a nitrogen atmosphere.

  Next, 3,5-dimethylpyrazole was blended in the blending amounts shown in Table 1. After confirming heat generation, the internal temperature was raised to 80 ° C., and the mixture was stirred for 2 hours at an internal temperature of 80 ° C. After confirming that the predetermined isocyanate group content was reached, the mixture was cooled to 60 ° C.

  Next, methyl ethyl ketone oxime was blended in the blending amounts shown in Table 1. After confirming heat generation, the internal temperature was raised to 80 ° C., and the internal temperature was maintained at 80 ° C. until there were no remaining isocyanate groups.

  After confirming that there were no remaining isocyanate groups, 300 parts by mass of diisononyl phthalate and 0.5 parts by mass of dibutyltin dilaurate were added, stirred at an internal temperature of 80 ° C. for 30 minutes, and then cooled to an internal temperature of 40 ° C.

  Thereby, the blocked isocyanate composition was obtained. Table 1 shows the content of latent isocyanate groups (B-NCO%) in the obtained blocked isocyanate composition.

Example 6
A five-necked flask equipped with a stirrer, a Dimroth cooler, a nitrogen inlet tube, a silica gel drying tube and a thermometer, was charged with 200 parts by mass of diisononyl phthalate and Takenate D-170N in a blending amount shown in Table 1, The mixture was uniformly mixed under a nitrogen atmosphere.

  Next, Actol D-1000 was blended in the blending amounts shown in Table 1, 0.025 parts by mass of dibutyltin dilaurate was added, the internal temperature was raised to 80 ° C, and the mixture was stirred at an internal temperature of 80 ° C for 2 hours. After confirming that the predetermined isocyanate group content was reached, the mixture was cooled to 60 ° C.

  Next, 3,5-dimethylpyrazole was blended in the blending amounts shown in Table 1. After confirming heat generation, the internal temperature was raised to 80 ° C., and the mixture was stirred for 2 hours at an internal temperature of 80 ° C. After confirming that the predetermined isocyanate group content was reached, the mixture was cooled to 60 ° C.

  Next, methyl ethyl ketone oxime was blended in the blending amounts shown in Table 1. After confirming heat generation, the internal temperature was raised to 80 ° C., and the internal temperature was maintained at 80 ° C. until there were no remaining isocyanate groups.

  After confirming that there were no remaining isocyanate groups, 300 parts by mass of diisononyl phthalate and 0.475 parts by mass of dibutyltin dilaurate were added, stirred at an internal temperature of 80 ° C. for 30 minutes, and then cooled to an internal temperature of 40 ° C.

  Thereby, the blocked isocyanate composition was obtained. Table 1 shows the content of latent isocyanate groups in the obtained blocked isocyanate composition.

Example 7
A five-necked flask equipped with a stirrer, a Dimroth cooler, a nitrogen inlet tube, a silica gel drying tube and a thermometer, was charged with 200 parts by mass of diisononyl phthalate and Takenate D-170N in a blending amount shown in Table 1, The mixture was uniformly mixed under a nitrogen atmosphere.

  Next, Actol D-400 was blended in the blending amounts shown in Table 1, 0.035 parts by mass of dibutyltin dilaurate was added, the internal temperature was raised to 80 ° C., and the mixture was stirred at 80 ° C. for 2 hours. After confirming that the predetermined isocyanate group content was reached, the mixture was cooled to 60 ° C.

  Next, 3,5-dimethylpyrazole was blended in the blending amounts shown in Table 1. After confirming heat generation, the internal temperature was raised to 80 ° C., and the mixture was stirred for 2 hours at an internal temperature of 80 ° C. After confirming that the predetermined isocyanate group content was reached, the mixture was cooled to 60 ° C.

  Next, methyl ethyl ketone oxime was blended in the blending amounts shown in Table 1. After confirming heat generation, the internal temperature was raised to 80 ° C., and the internal temperature was maintained at 80 ° C. until there were no remaining isocyanate groups.

  After confirming that there were no remaining isocyanate groups, 100 parts by mass of diisononyl phthalate and 0.665 parts by mass of dibutyltin dilaurate were added, stirred at an internal temperature of 80 ° C. for 30 minutes, and then cooled to an internal temperature of 40 ° C.

  Thereby, the blocked isocyanate composition was obtained. Table 1 shows the content of latent isocyanate groups in the obtained blocked isocyanate composition.

Examples 8-11
In a five-necked flask equipped with a stirrer, a Dimroth cooler, a nitrogen inlet tube, a silica gel drying tube, and a thermometer, 200 parts by mass of diisononyl phthalate and the amount of Takenate D-170N and Takenate D-165N in the amounts shown in Table 1 Was mixed uniformly at room temperature under a nitrogen atmosphere, and 0.025 parts by mass of dibutyltin dilaurate was added.

  Next, 3,5-dimethylpyrazole was blended in the blending amounts shown in Table 1. After confirming heat generation, the internal temperature was raised to 80 ° C., and the mixture was stirred for 2 hours at an internal temperature of 80 ° C. After confirming that the predetermined isocyanate group content was reached, the mixture was cooled to 60 ° C.

  Next, methyl ethyl ketone oxime was blended in the blending amounts shown in Table 1. After confirming heat generation, the internal temperature was raised to 80 ° C., and the internal temperature was maintained at 80 ° C. until there were no remaining isocyanate groups.

  After confirming that there were no remaining isocyanate groups, 300 parts by mass of diisononyl phthalate and 0.475 parts by mass of dibutyltin dilaurate were added, stirred at an internal temperature of 80 ° C. for 30 minutes, and then cooled to an internal temperature of 40 ° C.

  Thereby, the blocked isocyanate composition was obtained. Table 1 shows the content of latent isocyanate groups in the obtained blocked isocyanate composition.

Comparative Examples 1 and 2
A blocked isocyanate composition was obtained in the same manner as in Production Example 1 except that the amount of each component was changed to the amount shown in Table 1. Table 1 shows the content of latent isocyanate groups in the obtained blocked isocyanate composition.
(Preparation of resin composition)
In a polypropylene container, Kane vinyl paste PCH-843, calcium carbonate and diisononyl phthalate are blended in a ratio of Kane vinyl paste PCH-843 / calcium carbonate / diisononyl phthalate = 100/140/100, mixed uniformly, and vinyl chloride. A paste (plastisol) was prepared.

Next, in a polypropylene container, 93 parts by mass of vinyl chloride paste, 2 parts by mass of polyamide polyamine, and the blended amounts shown in Table 2, the block isocyanate compositions obtained in each Example and each Comparative Example were uniformly mixed, Resin compositions of each application example and each application comparison example were prepared.
(Evaluation)
(1) Preparation of test piece The resin composition of each example and each comparative example was applied to a cationic electrodeposition coating plate (manufactured by Test Piece: JIS G3141 (SPCC, SD), and heated under the conditions shown in Table 2 respectively. Then, a cationic electrodeposition coated plate having a coating film with a thickness of 2 mm was prepared as a test piece.
(2) Adhesion test The coating film surface of the obtained test piece was scratched with a nail to confirm peeling of the coating film from the cationic electrodeposition coating plate. The results are shown in Table 2.
○: No peeling of the coating film from the cationic electrodeposition coated plate.
(Triangle | delta): A coating film peels partially from a cation electrodeposition coating board.
X: Almost all of the coating film peels off from the cationic electrodeposition coated plate.
(3) Storage stability test The blocked isocyanate composition obtained by each manufacture example and each comparative manufacture example was stored at 25 degreeC for 2 weeks, and the change of the block isocyanate composition was confirmed visually. The results are shown in Table 2.
○: No particular change is observed.
(Triangle | delta): Cloudiness is seen.
X: It becomes cloudy and causes phase separation. Or, crystallization occurs and the fluidity is lost.

Claims (7)

A blocked isocyanate composition containing a blocked isocyanate in which an isocyanate group of an isocyanate compound is blocked by a blocking agent,
The isocyanate compound contains an aliphatic isocyanate and / or an alicyclic isocyanate,
95 mol% or more of all isocyanate groups in all the isocyanate compounds are blocked by the blocking agent,
In all blocking agents blocking all the isocyanate groups, oxime blocking agent is contained in 30 to 70 mol%, pyrazole blocking agent is contained in 30 to 70 mol%,
A blocked isocyanate composition comprising at least a blocked isocyanate having both an isocyanate group blocked with an oxime blocking agent and an isocyanate group blocked with a pyrazole blocking agent in one molecule. .   The blocked isocyanate composition according to claim 1, wherein the isocyanate group blocked by the blocking agent is contained in an amount of 1 to 20% by mass.   The blocked isocyanate composition according to claim 1 or 2, wherein 70 mass% or more of the isocyanate compound is a trimer.   The blocked isocyanate composition according to claim 1, wherein the pyrazole-based blocking agent is 3,5-dimethylpyrazole.   The blocked isocyanate composition according to claim 1, wherein the oxime blocking agent is methyl ethyl ketone oxime.   The blocked isocyanate composition according to claim 1, further comprising a plasticizer.   A resin composition comprising a plastisol, an active hydrogen compound having an active hydrogen group, and the blocked isocyanate composition according to claim 6.