JP2020138962A - Phosphazene compound - Google Patents

Abstract

To provide a catalyst substance which can be applied to an NCO-OH crosslinking reaction type thermosetting resin composition, has validity and resin composition stability as a catalyst, and is alternative to a metal catalyst.SOLUTION: A phosphazene compound has one or more organic groups represented by the following formula in the molecule. In the formula, ** is a bond or a hydrogen atom. X is a divalent organic group having 1 to 18 carbon atoms, and the organic group may contain an oxygen atom and/or a nitrogen atom. R1 represents a hydrogen atom or an organic group having 1 to 18 carbon atoms, and the organic group may contain at least one selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom and a halogen atom. A1, A2 and A3 represent a monovalent organic group, the organic group may contain at least one selected from the group consisting of a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom, a phosphorus atom, a sulfur atom and a halogen atom, may be each independent and the same, and the two or more kinds thereof may be connected to each other to form a cyclic structure.SELECTED DRAWING: None

Description

The present invention relates to a phosphazene compound, a method for producing the same, and a thermosetting resin composition containing the above phosphazene compound.

The isocyanate curing agent is a kind of curing agent for paints and the like, and polyisocyanates that are active at room temperature, blocked polyisocyanates that are inactivated at room temperature, and the like are widely used.
As a catalyst for accelerating the curing reaction of the isocyanate curing agent, organic tin compounds such as dibutyltin oxide, dioctyltin oxide, dibutyltin dilaurate, and dioctyltin dilaurate have been generally used (Patent Documents 1 and 2).

However, although the catalytic performance of an organic tin compound is very high, its toxicity has become a problem in recent years, so that a catalyst that replaces the organic tin compound has been sought. As an alternative to this, bismuth-based or zinc-based catalysts have been developed (Patent Documents 3 and 4).

Japanese Unexamined Patent Publication No. 2004-307800 Japanese Unexamined Patent Publication No. 2005-139273 Japanese Unexamined Patent Publication No. 2000-290542 Japanese Unexamined Patent Publication No. 2012-152725

Since all the conventional thermosetting coating compositions contain an organic tin catalyst, there is an environmental problem. Further, the bismuth-based catalyst and the zinc-based catalyst have problems that they are expensive, the catalytic effect is insufficient, and the paint stability is low.

The problem to be solved by the present invention is applicable to an NCO-OH cross-linking reaction type thermosetting resin composition containing isocyanate and / or blocked isocyanate, and has effectiveness as a catalyst and coating stability. , To provide a catalytic material that replaces a metal catalyst.

As a result of diligent studies to solve the above-mentioned problems, the inventors have found that the above-mentioned problems can be solved by using a phosphazene compound having a specific structure as a catalyst, and have completed the present invention. That is, the present invention provides the following phosphazene compound, a method for producing the same, and a thermosetting resin composition containing the above phosphazene compound.
Item 1. A phosphazene compound having at least one organic group represented by the following general formula (1) in the molecule.

[In equation (1), ★★ is a bond or a hydrogen atom. X is a divalent organic group having 1 to 18 carbon atoms, and the organic group may contain an oxygen atom and / or a nitrogen atom. R ¹ represents a hydrogen atom or an organic group having 1 to 18 carbon atoms, and the organic group may contain at least one selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom and a halogen atom. A ¹ , A ² and A ³ represent a monovalent organic group, and the organic group is at least one selected from the group consisting of a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom, a phosphorus atom, a sulfur atom and a halogen atom. May be included, each may be independent or the same, and two or more kinds may be connected to form an annular structure. ]
Item 2. Item 2. The phosphazene compound according to Item 1, wherein the ★★ of the general formula (1) is a bond.
Item 3. Item 2. The phosphazene compound according to Item 1 or 2, wherein A ¹ , A ² , and / or A ³ of the general formula (1) are organic groups represented by the following general formula (2).

[In equation (2), ★ is a joiner. R ^{2 to} R ⁷ represent an organic group having 1 to 12 carbon atoms, and the organic group may contain an oxygen atom and / or a nitrogen atom, and each of them may be independent or the same. The above may be connected to form an annular structure. n represents an integer of 0 or more and 10 or less. ]
Item 4. Item 3. The item 1 to 3 above, wherein A ¹ , A ² , and / or A ³ of the general formula (1) are organic groups represented by the following general formula (3). The phosphazene compound described.

[In equation (3), R ² and R ³ have the same meanings as described above. ]
Item 5. A ¹ , A ² , and / or A ³ of the general formula (1) are N, N-dimethylamino group, N, N-diethylamino group, N, N-dipropylamino group, N, N-diisopropylamino. Group, N, N-dibutylamino group, N, N-dioctylamino group, N-methyl-N-propylamino group, N-methyl-N-butylamino group, N, N-di (2-ethylhexyl) amino group The phosphazene compound according to any one of Items 1 to 4, which is at least one selected from the group consisting of a pyrrolyl group, a morpholino group, a piperidino group, a pyrrolidino group, and an N-alkylpiperazino group.
Item 6. The phosphazene compound according to any one of the above items 1 to 5, which has one or more organic groups represented by the general formula (1) in the molecule and has a number average molecular weight of 400 to 1,000,000. ..
Item 7. Any one of the above items 1 to 6, wherein the molecule may have one or more organic groups having the structure of the following general formula (4), and a part or all of the organic groups may be ionized. The phosphazene compound according to.

[In equation (4), ★, X, R ¹ , A ¹ , A ² and A ³ have the same meanings as described above. ]
Item 8. Any one of the above items 1 to 7, wherein the molecule may have one or more organic groups having the structure of the following general formula (5), and a part or all of the organic groups may be ionized. The phosphazene compound according to.

[In equation (5), ★, X, R ¹ , A ¹ , A ² and A ³ have the same meanings as described above. ]
Item 9. Item 2. The method for producing a phosphazene compound according to Item 2, wherein the compound having one or more reactive functional groups in the molecule is reacted with the phosphazene compound represented by the following general formula (1)'.

[In equation (1)', X, R ¹ , A ¹ , A ² and A ³ have the same meanings as described above. ]
Item 10. A thermosetting resin composition containing the phosphazene compound according to any one of Items 1 to 8, the hydroxyl group-containing resin (A), and the curing agent (B), wherein the curing agent (B) is poly. A thermosetting resin composition, which is an isocyanate curing agent and / or a blocked polyisocyanate curing agent.

By applying the phosphazene compound of the present invention to an isocyanate and / or blocked isocyanate-based thermosetting resin composition, good paint stability is maintained and excellent coating curability can be achieved without using a metal catalyst. A thermosetting resin composition having is obtained. Further, according to the thermosetting resin composition to which the phosphazene compound of the present invention is applied, it is possible to form a coating film having good finish and excellent water resistance.

In the present invention, the "compound" means a generic term including a monomer, an oligomer, a polymer (resin) and the like.

The present invention relates to a phosphazene compound, a method for producing the same, and a thermosetting resin composition containing the above phosphazene compound. The details will be described below.

<1. Phosphazene compound (C)>
The phosphazene compound of the present invention is a phosphazene compound (C) having one or more organic groups represented by the following general formula (1) in its molecule.

In the above formula (1), ★★ is a bond or a hydrogen atom. X is a divalent organic group having 1 to 18 carbon atoms, and the organic group may contain an oxygen atom and / or a nitrogen atom. R ¹ represents a hydrogen atom or an organic group having 1 to 18 carbon atoms, and the organic group may contain at least one selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom and a halogen atom. A ¹ , A ² and A ³ represent a monovalent organic group, and the organic group is at least one selected from the group consisting of a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom, a phosphorus atom, a sulfur atom and a halogen atom. May be included, each may be independent or the same, and two or more kinds may be connected to form an annular structure.

In the present invention, the phosphazene compound is a compound having a phosphazene unit, and the phosphazene unit represents a binding unit of N = P. It is possible to connect a plurality of phosphazene units, and it is generally known that the more phosphazene units there are, the higher the basicity of the compound.

The phosphazene compound (C) of the present invention is very effective as a curing catalyst for the NCO-OH cross-linking reaction. In the blocked polyisocyanate curing agent, the blocking agent is dissociated by heat. As a result, the free isocyanate group is regenerated, and the hydroxyl group-containing resin reacts with the isocyanate group to proceed with the cross-linking reaction. Phosphazene is a strong base and is considered to function as a dissociation catalyst for a blocked polyisocyanate curing agent and a reaction catalyst for a hydroxyl group-containing resin and an isocyanate group. Therefore, by applying the phosphazene compound (C) of the present invention to a hydroxyl group-containing resin and a resin composition containing a polyisocyanate curing agent and / or a blocked polyisocyanate curing agent, a conventional organic tin catalyst can be used. The NCO-OH cross-linking reaction can proceed without this.

In the phosphazene compound (C) of the present invention, A ¹ , A ² and A ³ in the above formula (1) are at least one, respectively, from the viewpoint of compound stability, catalytic performance, and coating performance (water resistance, etc.). It is an organic group containing one or more nitrogen atoms, and it is preferable that a phosphorus atom adjacent to the organic group and a nitrogen atom in the organic group are single-bonded.

In the phosphazene compound (C) of the present invention, it is preferable that A ¹ , A ² and / or A ³ are organic groups represented by the following formula (2).

In the above equation (2), ★ is a connecting hand. R ^{2 to} R ⁷ represent an organic group having 1 to 12 carbon atoms, and the organic group may contain an oxygen atom and / or a nitrogen atom, and each of them may be independent or the same. The above may be connected to form an annular structure. n represents an integer of 0 or more and 10 or less.

The phosphazene compound (C) of the present invention becomes more basic as the number of phosphazene units increases, and the catalytic effect when applied to the resin composition is improved, but on the other hand, the stability and coating film performance (water resistance) of the resin composition are improved. Etc.) will decrease. Therefore, from the viewpoint of stability of the resin composition and coating film performance (water resistance, etc.), the phosphazene compound (C) of the present invention preferably has n in the formula (2) of 0 or more and 7 or less. It is more preferably 0 or more and 4 or less, further preferably 0 or 1, and particularly preferably 0. When n is 0, the formula (2) is represented by the following formula (3).

In the above formula (3), ★, R ² and R ³ are synonymous with the above formula (2).

Specific examples of the organic group represented by the above formula (3) include N, N-dimethylamino group, N, N-diethylamino group, N, N-dipropylamino group and N, N-diisopropyl. Amino group, N, N-dibutylamino group, N, N-dioctylamino group, N-methyl-N-propylamino group, N-methyl-N-butylamino group, N, N-di (2-ethylhexyl) amino Dialkylamino groups such as groups; cyclic amino groups such as pyrrolyl group, morpholino group, piperidino group, pyrrolidino group, N-alkylpiperadino group and the like can be mentioned. The phosphazene compound (C) of the present invention has A ¹ , A ² and A ^{3 of the} above formula (1) from the viewpoint of the stability of the compound itself, the stability of the resin composition and the coating film performance (water resistance, etc.). It is particularly preferably a cyclic amino group.

The number average molecular weight of the phosphazene compound (C) of the present invention is preferably 400 to 1,000,000 from the viewpoint of coating film performance (water resistance, etc.). It is more preferably 600 to 500,000, still more preferably 1,000 to 100,000, and in the present specification, the number average molecular weight is a gel permeation chromatograph ( It is a value obtained by converting the holding time (holding capacity) measured using GPC) into the molecular weight of polystyrene by the holding time (holding capacity) of standard polystyrene having a known molecular weight measured under the same conditions. Specifically, "HLC8120GPC" (trade name, manufactured by Tosoh Corporation) is used as a gel permeation chromatograph, and "TSKgel G-4000HXL", "TSKgel G-3000HXL", and "TSKgel G-2500HXL" are used as columns. And "TSKgel G-2000HXL" (trade name, both manufactured by Tosoh Corporation) can be used for measurement under the conditions of a measurement temperature of 40 ° C., a flow velocity of 1 mL / min, and a detector RI. The mobile phase was measured using tetrahydrofuran added with 0.5% by mass of triethanolamine for the phosphazene compound and tetrahydrofuran for the other compounds.

The phosphazene compound (C) of the present invention may contain a hydroxyl group. When a hydroxyl group is contained, the hydroxyl group undergoes a cross-linking reaction with the isocyanate curing agent, so that the water resistance of the coating film is improved.

Examples of the phosphazene compound (C) of the present invention include a phosphazene compound (C1) in which ★★ in the formula (1) is a hydrogen atom and a phosphazene compound (C2) in which ★★ in the formula (1) is a bond. Be done. The method for producing each phosphazene compound is described below.

<2-1. Method for producing phosphazene compound (C1)>
The phosphazene compound (C1) is a compound in which ★★ of the above formula (1) is a hydrogen atom, and is represented by the following formula (1)'.

In the above formula (1)', X, R ¹ , A ¹ , A ² and A ³ are synonymous with the above formula (1).

The phosphazene compound (C1) is a diamine compound represented by the following formula (6) after reacting phosphorus pentachloride with an arbitrary organic compound (A') having one or more reactive functional groups in the molecule. It is produced by reacting with D) and deprotonating with a strong base.

In the above formula (6), X and R ¹ are synonymous with the above formula (1).

By reacting phosphorus pentachloride with any organic compound (A') having one or more reactive functional groups in the molecule in the presence of dichloromethane, the intermediate (α) represented by the following formula (7) Can be manufactured.

In the above formula (7), A ¹ , A ² and A ³ are synonymous with the above formula (1).

Any organic compound (A') having one or more reactive functional groups in the molecule becomes the organic groups of A ¹ , A ² and A ³ in the above formula (7) by reacting with phosphorus pentachloride. .. The organic compound (A') contains at least one selected from the group consisting of carbon atom, hydrogen atom, oxygen atom, nitrogen atom, phosphorus atom, sulfur atom and halogen atom, and has one or more reactive functional elements in the molecule. Any organic compound having a group can be used without particular limitation, but an organic compound having an amine as a reactive functional group is preferable. Specifically, for example, N, N-dimethylamine, N, N-diethylamine, N, N-dipropylamine, N, N-diisopropylamine, N, N-dibutylamine, N, N-dioctylamine, N. Dialkylamines such as -methyl-N-propylamine, N-methyl-N-butylamine, N, N-di (2-ethylhexyl) amines; cyclic amines such as pyrrole, morpholine, piperidine, pyrrolidine, N-alkylpiperazine, etc. These can be used alone or in combination of two or more. The organic compound (A') is particularly preferably a cyclic amine from the viewpoint of the stability of the phosphazene compound (C1), the stability of the resin composition, and the coating film performance (water resistance, etc.).

When the diamine compound (D) represented by the formula (6) is added to the intermediate (α), the amino group of the diamine compound (D) reacts with the intermediate (α), whereby the following formula (8) The intermediate (β) represented by is produced.

In the above formula (8), X, R ¹ , A ¹ , A ² and A ³ are synonymous with the above formula (1).

When R ¹ is a hydrogen atom in the diamine compound (D) of the above formula (6), that is, when both of the two amino groups of the diamine compound (D) are primary amines, an intermediate (α) and two It is highly possible that the amino group reacts to form a diamine. Therefore, the diamine compound (D) preferably has one primary amino group and one secondary amino group. Specifically, in the diamine compound (D) of the above formula (6), R ¹ is preferably a monovalent organic group having 1 to 18 carbon atoms, and more preferably a monovalent organic group having 1 to 10 carbon atoms. It is preferably an organic group. When the diamine compound (D) contains both a primary amino group and a secondary amino group, the intermediate (α) preferentially reacts with the more reactive primary amino group, and thus the intermediate (β). ) Is improved.

The phosphazene compound (C1) of the formula (1)'can be produced by adding a strong base to the intermediate (β) and deprotonating it.

The phosphazene compound (C1) of the general formula (1)'can be used by itself as a dissociation catalyst for a blocked polyisocyanate curing agent and a reaction catalyst between a hydroxyl group-containing resin and an isocyanate group. From the viewpoint of performance (water resistance, etc.), it is preferable to react the phosphazene compound (C1) with a compound having at least one reactive functional group in the molecule to obtain a phosphazene compound (C2).

<2-2. Method for producing phosphazene compound (C2)>
The phosphazene compound (C2) is a compound in which ★★ of the above formula (1) is a binder, and has one or more amino groups and reactive functional groups in the molecule of the above-mentioned phosphazene compound (C1) (E). ) Is reacted with.

The compound (E) having one or more reactive functional groups in the molecule is not particularly limited in the type of the compound as long as it has one or more reactive functional groups that react with the active hydrogen group. For example, acrylic. Resins, polyester resins, urethane resins, epoxy resins, polyisocyanate compounds and the like can be used.

The compound (E) having one or more reactive functional groups in the molecule preferably has a number average molecular weight of 150 or more, preferably 150 to 1,000,000, from the viewpoint of coating film performance (water resistance, etc.). More preferably, 400 to 500,000 is further preferable, and 800 to 100,000 is particularly preferable.

Specific examples of the reactive functional group in the compound (E) having one or more reactive functional groups in the molecule include a glycidyl group, an isocyanate group, a blocked isocyanate group, a carbonyl group, a carboxyl group and the like. However, at least one selected from the group consisting of a glycidyl group, an isocyanate group, and a blocked isocyanate group is preferable, and a glycidyl group having a structure represented by the following formula (9) or formula (10) is particularly preferable.

In the above equations (9) and (10), ★ is a bond.

By reacting a compound containing a glycidyl group with a phosphazene compound (C1), a phosphazene compound (C2-1) having an organic group represented by the following formula (4) can be produced. The organic group of the following formula (4) may be partially or completely ionized.

In the above equation (4), ★ is a connecting hand. X, R ¹ , A ¹ , A ² and A ³ are synonymous with the above formula (1).

When the compound having a glycidyl group having the structure represented by the formula (9) or the formula (10) is reacted with the phosphazene compound (C1), the phosphazene compound (C2) having an organic group represented by the following formula (11), respectively A phosphazene compound (C2-1-2) having an organic group represented by 1-1) or the following formula (12) can be produced. The organic groups of the following formulas (11) and (12) may be partially or completely ionized.

In the above equations (11) and (12), ★ is a bond. X, R ¹ , A ¹ , A ² and A ³ are synonymous with the above formula (1).

By reacting a compound containing an isocyanate group or a blocked isocyanate group with a phosphazene compound (C1), a phosphazene compound (C2-2) having an organic group represented by the following formula (5) can be produced. The organic group of the following formula (5) may be partially or completely ionized.

In the above equation (5), ★ is a connecting hand. X, R ¹ , A ¹ , A ² and A ³ are synonymous with the above formula (1).

<3. Thermosetting resin composition>
The phosphazene compound (C) of the present invention can be applied as a catalyst for a thermosetting resin composition containing a hydroxyl group-containing resin (A) and a polyisocyanate curing agent and / or a blocked polyisocyanate curing agent.

As the hydroxyl group-containing resin (A), any known resin that has a hydroxyl group and can be crosslinked with the curing agent (B) can be used without particular limitation.

Reactive functional groups other than hydroxyl groups that can be crosslinked with polyisocyanate curing agents and blocked polyisocyanate curing agents include reactive functional groups having active hydrogen such as amino groups, carboxyl groups, and active methylene groups, as well as epoxy groups and carboxylic acids. Examples thereof include an acid anhydride group, and these can be used in combination with a hydroxyl group.

Examples of the type of the hydroxyl group-containing resin (A) include acrylic resin, polyester resin, epoxy resin, alkyd resin, polyether resin, polyurethane resin, and polyamide resin, and these may be used alone or in combination of two or more. Can be used in combination. Among them, at least one selected from acrylic resin, polyester resin, and epoxy resin is preferable.

The hydroxyl group-containing resin (A) is preferably in a dispersed state (for example, an emulsion state in an aqueous solvent) or a dissolved state in the thermosetting resin composition. Further, in the case of a dispersed state, it may be crosslinked resin particles.

The curing agent (B) that can be used in the thermosetting resin composition of the present invention is a polyisocyanate curing agent (B1) and / or a blocked polyisocyanate curing agent (B2). As the polyisocyanate curing agent (B1), known ones can be used without particular limitation, for example, tolylene diisocyanate, xylylene diisocyanate, phenylenedi isocyanate, diphenylmethane-2,2'-diisocyanate, diphenylmethane-2,4'. Aromatic, aliphatic or such as −diisocyanate, diphenylmethane-4,4'-diisocyanate, crude MDI [polymethylenepolyphenylisocyanate], bis (isocyanatemethyl) cyclohexane, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, isophorone diisocyanate. Alicyclic polyisocyanate compounds; cyclized polymers or billets of these polyisocyanate compounds; or combinations thereof can be mentioned.

The blocked polyisocyanate curing agent (B2) is an addition reaction product of the polyisocyanate compound and the isocyanate blocking agent in a substantially chemical theoretical amount.

As the polyisocyanate compound used in the blocked polyisocyanate curing agent, known compounds can be used without particular limitation, and for example, the compounds listed in (B1) above can be used.

The isocyanate blocking agent is a compound added to the isocyanate group of the polyisocyanate compound. The blocked polyisocyanate compound produced by the addition of the isocyanate blocking agent is stable at room temperature, but when heated to the baking temperature of the coating film (usually about 80 to about 200 ° C.), the blocking agent is dissociated and released. It is desirable to regenerate the isocyanate group of.

Examples of the isocyanate blocking agent used in the blocked polyisocyanate curing agent (B2) include oxime compounds such as methyl ethyl ketooxime and cyclohexanone oxime; phenolic compounds such as phenol, parat-butylphenol and cresol; n-butanol. , 2-Ethylhexanol, phenylcarbinol, methylphenylcarbinol, ethyleneglycol monobutyl ether, diethylene glycol monoethyl ether, ethylene glycol, propylene glycol and other alcohol compounds; ε-caprolactam, γ-butyrolactam and other lactam compounds; malon Active methylene compounds such as dimethyl acid, diethyl malonate, diisopropyl malate, ethyl acetoacetate, methyl acetoacetate, and acetylacetone; pyrazole compounds such as dimethylpyrazole, etc., may be used alone or in combination of two or more. Can be used in combination. Among them, from the viewpoint of dissociation temperature and stability of the resin composition, it is preferable to use at least one selected from alcohol-based compounds, pyrazole-based compounds, oxime-based compounds, and lactam-based compounds, and alcohol-based compounds are particularly preferable. ..

As the blending ratio of the hydroxyl group-containing resin (A) and the curing agent (B) in the thermosetting resin composition of the present invention, the component (A) is usually 10 to 10 based on the total solid mass of the resin composition. A coated article excellent in finishability and curability, in which 90% by mass, preferably 20 to 80% by mass, and the component (B) is usually in the range of 10 to 60% by mass, preferably 15 to 55% by mass. It is preferable to obtain.

The content of the phosphazene compound (C) of the present invention is usually 0.01 to 30% by mass based on the total solid content mass of the resin composition when converted by the mass of the organic group moiety of the above formula (1). It is preferably in the range of 0.1 to 15% by mass from the viewpoint of curability and water resistance.

The thermosetting resin composition of the present invention is not particularly limited, but for example, in addition to a phosphazene compound, a hydroxyl group-containing resin (A), and a curing agent (B), a hydroxyl group-free resin is required. , Solvents, neutralizers, surfactants, surface conditioners, thickeners, antisettling agents, UV absorbers, light stabilizers, defoamers, dissociation catalysts, plasticizers and the like.

As the solvent, known solvents such as water and organic solvents can be used without limitation. Examples of the organic solvent include hydrocarbon systems such as toluene, xylene, cyclohexane and n-hexane; ester systems such as methyl acetate, ethyl acetate and butyl acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone and isobutyl methyl ketone. Ketones such as; dimethylformamide, amides such as dimethylacetamide; alcohols such as methanol, ethanol, n-propanol and iso-propanol, ether alcohols such as ethylene glycol monobutyl ether, diethylene glycol monoethyl ether and propylene glycol monomethyl ether. Compounds; or mixtures thereof, etc. may be mentioned.

In addition to the phosphazene compound used in the present application, a bismuth-based compound, a zinc-based compound, a titanium-based compound, an amidine-based compound, a quaternary salt-based compound, a proazaphosphatran-based compound, and the like are preferable as the dissociation catalyst of the isocyanate blocking agent. Can be used for. However, it is preferable that organic tin compounds such as dibutyltin dibenzoate, dioctyltin oxide, and dibutyltin oxide are substantially not used in consideration of the environment.

Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples.
Conventionally known methods in the art are used for polymerization methods of various resins, methods for producing resin compositions and paints, evaluation test methods, and the like. However, the present invention is not limited to this, and various modifications and modifications can be made within the same range of the technical idea of the present invention and the claims.
In each example, "part" indicates a mass part and "%" indicates a mass%.

Production Example 1 (acrylic resin)
31 parts of propylene glycol monomethyl ether was placed in a four-necked flask equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen gas inlet, and the temperature was raised to 110 ° C. under ventilation of nitrogen gas. After reaching 110 ° C., the aeration of nitrogen gas was stopped, and 22 parts of 2-hydroxyethyl acrylate, 30 parts of methyl methacrylate, 22 parts of 2-ethylhexyl acrylate, 25 parts of styrene, 1 part of acrylic acid, and 2,2' -A mixture consisting of 4 parts of azobis (isobutyronitrile) was added dropwise over 4 hours. Then, it was aged at 110 ° C. with nitrogen gas for 2 hours, cooled to 100 ° C., and diluted with propylene glycol monomethyl ether to obtain an acrylic resin (A-1) solution having a solid content of 60%. .. The acrylic resin (A-1) had a number average molecular weight of 7,000 and a hydroxyl value of 106 mgKOH / g.

Production Example 2 (epoxy resin)
950 parts of jER1001 (trade name, manufactured by Mitsubishi Chemical Corporation, epoxy resin, epoxy equivalent 475, number average molecular weight 900), 1,6-hexanediol 236 in a flask equipped with a stirrer, thermometer, nitrogen introduction tube and reflux condenser. A part, 0.2 g of dimethylbenzylamine was added and reacted at 200 ° C. until the epoxy equivalent became 30,000 or more, and ethylene glycol monobutyl ether was further added to obtain an epoxy resin (A-2) solution having a solid content of 60%. It was. The number average molecular weight of the epoxy resin (A-2) was 2,500.

<Manufacturing of hardener>
Production Example 3 (blocked polyisocyanate curing agent)
272 parts of hexamethylene diisocyanate (B-1) and 214 parts of methyl ethyl ketone were charged into a four-necked flask equipped with a stirrer, a heating device, a cooling device, and a depressurizing device, and heated to 60 ° C. Then, 169 parts of methyl ethyl ketooxime was gradually added over 1 hour with stirring. Then, after reacting at 60 ° C. for 2 hours, 59 parts of trimethylolpropane was gradually added so that the temperature did not exceed 70 ° C. Under stirring, the reaction mixture was reacted at 60 ° C. by infrared spectroscopy until no free isocyanate groups were detected. After completion of the reaction, a blocked polyisocyanate curing agent (B-2) having a solid content of 70% was obtained. The amount of NCO of the obtained blocked polyisocyanate curing agent (B-2) was 16.4%.

<Manufacturing of pigment dispersion paste>
Production Example 4 (Pigment dispersion paste)
In a flask equipped with a stirrer, thermometer, dropping funnel and reflux cooler, jER828 (trade name, manufactured by Mitsubishi Chemical Corporation, epoxy resin, epoxy equivalent 190, number average molecular weight 370) 1010 parts, bisphenol A 390 parts, praxel 212 (Product name, polycaprolactone diol, Daicel Chemical Industry Co., Ltd., weight average molecular weight of about 1,250) Add 240 parts and 0.2 part of dimethylbenzylamine, and react at 130 ° C. until the epoxy equivalent reaches about 1,090. It was. Next, 134 parts of dimethylethanolamine and 150 parts of lactic acid were added, and the mixture was reacted at 120 ° C. for 4 hours. Next, methyl isobutyl ketone was added to adjust the solid content, and a resin solution for dispersing a quaternary ammonium salt-type pigment having a solid content of 60% was obtained.

Subsequently, 8.3 parts of the resin solution for pigment dispersion (5 parts of solid content), 14.5 parts of titanium oxide, 8.0 parts of purified clay, 0.3 part of carbon black and 24.5 parts of propylene glycol monomethyl ether were added. In addition, it was dispersed in a ball mill for 20 hours to obtain a pigment-dispersed paste having a solid content of 50%.

<Production of phosphazene compound (C)>
Example 1 Phosphazene compound (C-1)
A suspension of 101.5 g of dichloromethane and 20.8 g (0.1 mol) of phosphorus pentachloride was held at around −30 ° C. in a flask equipped with a thermometer and a dropping funnel under a nitrogen atmosphere and stirred. 21.3 g (0.3 mol) of pyrrolidine and 40.5 g (0.4 mol) of triethylamine were added dropwise thereto. This was returned to room temperature. The obtained reaction product was kept at around 0 ° C., and 26.5 g (0.3 mol) of N-ethylethylenediamine was added dropwise. Then, the reaction product was kept at room temperature of 20 ° C. to 35 ° C. The resulting insoluble material was filtered, and the obtained filtrate was washed with dichloromethane and deionized water, and the obtained organic phase was concentrated. A potassium methoxyde / methanol solution (containing 6.3 g (0.09 mol) of potassium methoxyde) was added to the obtained reaction product, and the mixture was stirred at room temperature. The produced insoluble material was filtered and concentrated to obtain a phosphazene compound (C-1) having a molecular weight of 327. The yield after purification was about 80%.
1H-NMR (DMSO) δ (ppm): 0.99 (dd, J = 7.0 Hz, 3H), 1.73 (m, 13H), 2.42 (t, J = 5.6 Hz, 2H) ), 2.51 (dd, J1 = 14.4 Hz, J2 = 7.2 Hz, 2H), 3.06 (m, 14H).

Example 2 Phosphazene compound (C-2)
In a flask equipped with a stirrer, a thermometer, a nitrogen introduction tube and a reflux condenser, 327 parts of the phosphazene compound (C-1) obtained in Example 1, jER1001 (trade name, manufactured by Mitsubishi Chemical Corporation, epoxy resin, epoxy equivalent). 475 parts, number average molecular weight 900) 475 parts and 537 parts of methyl isobutyl ketone were added, and the reaction was carried out to react 99% or more of the epoxy group amount.
Ethylene glycol monobutyl ether was added to adjust the solid content to obtain a phosphazene compound (C-2) solution having a solid content of 50%. The number average molecular weight of the phosphazene compound (C-2) was 1,500.

Example 3 Phosphazene compound (C-3)
In a flask equipped with a stirrer, a thermometer, a nitrogen introduction tube and a reflux condenser, 327 parts of the phosphazene compound (C-1) obtained in Example 1, jER1004 (trade name, manufactured by Mitsubishi Chemical Corporation, epoxy resin, epoxy equivalent). 925, number average molecular weight 1650) 925 parts and 537 parts of methylisobutylketone were added, and the reaction was carried out to react 99% or more of the epoxy group amount.
Ethylene glycol monobutyl ether was added to adjust the solid content to obtain a phosphazene compound (C-3) solution having a solid content of 50%. The number average molecular weight of the phosphazene compound (C-3) was 2,300.

Example 4 Phosphazene compound (C-4)
31 parts of methoxypropyl acetate was placed in a four-necked flask equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen gas inlet, and the temperature was raised to 110 ° C. under ventilation of nitrogen gas. After reaching 110 ° C., the aeration of nitrogen gas was stopped, 28 parts of 2-isocyanatoethyl methacrylate, 30 parts of methyl methacrylate, 22 parts of 2-ethylhexyl acrylate, 20 parts of styrene, and 2,2'-azobis (iso). A mixture consisting of 4 parts of butyronitrile) was added dropwise over 4 hours. Then, the mixture was aged at 110 ° C. with nitrogen gas for 2 hours and then diluted with methyl isobutyl ketone to obtain an isocyanate group-containing acrylic resin solution (NCO-Ac) having a solid content of 50%. The acrylic resin had a number average molecular weight of 7,000.
In a flask equipped with a stirrer, a thermometer, a nitrogen introduction tube and a reflux condenser, 327 parts 147.7 parts of the phosphazene compound (C-1) obtained in Example 1 and the above-mentioned isocyanate group-containing acrylic resin solution (NCO-Ac). ) 502.5 parts and 537 parts of methyl isobutyl ketone were added, and the reaction was carried out.
Ethylene glycol monobutyl ether was added to adjust the solid content to obtain a phosphazene compound (C-4) solution having a solid content of 50%. The number average molecular weight of the phosphazene compound (C-4) was 10,200.

Example 5 Phosphazene compound (C-5)
236 parts of 1.6-hexanediol and 438 parts of adipic acid were charged in a reaction device having a heating device, a stirrer, a nitrogen introduction tube and a fractional distillation column, heating was started under dry nitrogen, and the temperature was gradually raised to 230 ° C. The esterification reaction was carried out. The temperature is maintained at 230 ° C., the esterification reaction is carried out until the resin acid value reaches 186 mgKOH / g, the mixture is cooled to 170 ° C., ethylene glycol monobutyl ether is added, and a polyester resin (COOH-PE) having a resin solid content of 50% by mass is added. ) A solution was obtained. The obtained polyester resin (COOH-PE) had an acid value of 186 mgKOH / g as a resin solid content and a number average molecular weight of 680.
327 parts of the phosphazene compound (C-1) obtained in Example 1, 340 parts of the polyester resin (COOH-PE), and 537 parts of methyl isobutyl ketone were placed in a flask equipped with a stirrer, a thermometer, a nitrogen introduction tube, and a reflux condenser. Part was added and the reaction was carried out.
Ethylene glycol monobutyl ether was added to adjust the solid content to obtain a phosphazene compound (C-5) solution having a solid content of 50%. The number average molecular weight of the phosphazene compound (C-5) was 1,300.

Example 6 Phosphazene compound (C-6)
A suspension of 114.0 g of dichloromethane and 3.1 g (0.015 mol) of phosphorus pentachloride was held at around −30 ° C. in a flask equipped with a thermometer and a dropping funnel under a nitrogen atmosphere and stirred. Here, 3.2 g (0.045 mol) of pyrrolidine and 6.1 g (0.060 mol) of triethylamine were added dropwise. This was returned to room temperature. The obtained reaction product was kept at around 0 ° C., and 2.7 g (0.045 mol) of ethylenediamine was added dropwise. Then, the reaction product was kept at room temperature of 20 ° C. to 35 ° C. When the produced insoluble matter was filtered and the obtained filtrate was then washed with dichloromethane and deionized water, the organic phase and the aqueous phase did not separate and washing could not be performed. A potassium methoxyde / methanol solution (containing 1.0 g (0.0014 mol) of potassium methoxyde) was added to the obtained reaction product, and the mixture was stirred at room temperature. The insoluble material produced was filtered and concentrated to obtain a phosphazene compound (C-6) having a molecular weight of 299.

Example 7 Phosphazene compound (C-7)
A suspension of 101.5 g of dichloromethane and 20.8 g (0.1 mol) of phosphorus pentachloride was held at around −30 ° C. in a flask equipped with a thermometer and a dropping funnel under a nitrogen atmosphere and stirred. Here, 13.5 g (0.3 mol) of dimethylamine was aerated, and 40.5 g (0.4 mol) of triethylamine was added dropwise. This was returned to room temperature. The obtained reaction product was kept at around 0 ° C., and 26.5 g (0.3 mol) of N-ethylethylenediamine was added dropwise. Then, the reaction product was kept at room temperature of 20 ° C. to 35 ° C. The resulting insoluble material was filtered, and the obtained filtrate was washed with dichloromethane and deionized water, and the obtained organic phase was concentrated. A potassium methoxyde / methanol solution (containing 6.3 g (0.09 mol) of potassium methoxyde) was added to the obtained reaction product, and the mixture was stirred at room temperature. The insoluble material produced was filtered and concentrated to obtain a phosphazene compound (C-7) having a molecular weight of 249.

Example 8 Phosphazene compound (C-8)
In a flask equipped with a stirrer, a thermometer, a nitrogen introduction tube and a reflux condenser, 249 parts of the phosphazene compound (C-7) obtained in Example 7, jER1001 (trade name, manufactured by Mitsubishi Chemical Corporation, epoxy resin, epoxy equivalent). 475 parts, number average molecular weight 900) 475 parts and 537 parts of methyl isobutyl ketone were added, and the reaction was carried out to react 99% or more of the epoxy group amount.
Ethylene glycol monobutyl ether was added to adjust the solid content to obtain a phosphazene compound (C-8) solution having a solid content of 50%. The number average molecular weight of the phosphazene compound (C-8) was 1,400.

Table 1 below shows a list of phosphazene compounds used in producing the thermosetting resin composition described below. Regarding the phosphazene compounds produced in Examples 1 to 8, in addition to the compounds in Table 1, by-products and unreacted products may be present.

(Note 1) C-9: 79408-5ML (product number, manufactured by Aldrich),
(Note 2) C-12: 79421-5ML (product number, manufactured by Aldrich),
(Note 3) EP1: jER1001 (trade name, manufactured by Mitsubishi Chemical Corporation, epoxy resin, epoxy equivalent 475, number average molecular weight 900),
(Note 4) EP2: jER1004 (trade name, manufactured by Mitsubishi Chemical Corporation, epoxy resin, epoxy equivalent 925, number average molecular weight 1650),
(Note 5) NCO-AC: Isocyanate group-containing acrylic resin (see Example 4 above),
(Note 6) COOH-PE: Polyester resin having a terminal carboxyl group (see Example 5 above).

<Manufacturing of thermosetting resin composition>
Example 9 Thermosetting resin composition (X-1)
The acrylic resin (A-1) solution obtained in Production Example 1 was 58.3 parts (solid content 35 parts), and the epoxy resin (A-2) solution obtained in Production Example 2 was 58.3 parts (solid content). 35 parts), 42.9 parts (solid content 30 parts) of the blocked polyisocyanate curing agent (B-2) obtained in Production Example 3, and the phosphazene compound (C-1) obtained in Example 1. Five parts were mixed and stirred uniformly, and 46.0 parts of propylene glycol monomethyl ether was further added to prepare a thermosetting resin composition (X-1) having a solid content of 50%.

Examples 10 to 17, Comparative Examples 1 to 4
Thermosetting resin compositions (X-2) to (X-13) having a solid content of 50% were produced in the same manner as in Example 1 except that they are shown in Tables 2 and 3 below.

<Manufacturing of thermosetting paint>
A thermosetting paint was produced for use in the water resistance evaluation test described later.

Example 18 Thermosetting paint (Y-1)
50 parts (30 parts solid content) of the acrylic resin (A-1) solution obtained in Production Example 1 and 58.3 parts (35 parts solid content) of the epoxy resin (A-2) solution obtained in Production Example 2. ), 42.9 parts (solid content 30 parts) of the blocked polyisocyanate curing agent (B-2) obtained in Production Example 3, and 55.6 parts (solid content) of the pigment dispersion paste obtained in Production Example 4. 27.8 parts, resin solid content 5 parts) and 5.5 parts of the phosphazene compound (C-1) obtained in Example 1 were mixed and stirred uniformly, and 49.8 parts of propylene glycol monomethyl ether was further added. A thermosetting paint (Y-1) having a solid content of 50% was produced.

Examples 19-26, Comparative Examples 5-8
Thermosetting paints (Y-2) to (Y-13) having a solid content of 50% were produced in the same manner as in Example 18 except as shown in Tables 4 and 5 below.

<Evaluation method>
Thermosetting resin compositions (X-1) to (X-13) using a phosphazene compound and thermosetting paints (Y-1) to (Y-13) to which a pigment was added for water resistance evaluation. Was produced, and the curability and water resistance were evaluated, respectively. In the present invention, it is preferable that both curability and water resistance are excellent.

Regarding the evaluation test of curability and water resistance conducted by the method described later, the results of curability (gel fraction) are shown in Tables 2 and 3, and the results of water resistance (gloss retention) are shown in Tables 4 and 5. Shown in.

Evaluation test <curability (gel fraction)>
The thermosetting resin compositions (X-1) to (X-13) obtained in Examples and Comparative Examples were coated on a glass plate using an applicator so as to have a cured film thickness of about 30 μm. The coating film was peeled off from the glass plate by heat curing at a temperature of 140 ° C. for 30 minutes. Next, the coating film placed in the wire mesh was placed in a separate round-bottom flask, 100 g of acetone was added to 1 g of the coating film, and the mixture was refluxed for 5 hours. The removed coating film was dried at 105 ° C. for 30 minutes, the weight of the coating film was measured, and the gel fraction was calculated by the following formula.

Gel fraction (%) = coating film weight after reflux / coating film weight before reflux x 100
The evaluation was performed according to the following criteria. S to C pass and D fails.
S: The gel fraction is 70% or more.
A: The gel fraction is 60% or more and less than 70%.
B: The gel fraction is 50% or more and less than 60%.
C: The gel fraction is 40% or more and less than 50%.
D: The gel fraction is less than 40%.

<Water resistance (gloss retention)>
Cold-rolled steel plate (size 400 x 300 x 0.8 mm) treated with "Palbond # 3020" (manufactured by Nippon Parkering Co., Ltd., treated with zinc phosphate) and "Epoxy GT-10" (manufactured by Kansai Paint Co., Ltd., thermosetting) Epoxy resin-based cationic electrodeposition paint) is electrodeposited to a thickness of 20 μm, heated at 170 ° C for 30 minutes to cure, and “TP-65” (manufactured by Kansai Paint Co., Ltd., trade name) is applied onto the coating film. , Polyester / melamine resin-based automobile intermediate coating paint) was air-spray coated so as to have a dry film thickness of 35 μm, and cured by heating at 140 ° C. for 30 minutes.
Next, the thermosetting paints (Y-1) to (Y-13) obtained in Examples and Comparative Examples were coated on it using an applicator so as to have a cured coating film of about 20 μm, and the temperature was 140 ° C. Was heat-cured for 30 minutes.
The obtained test plate was immersed in pure water and left at 40 ° C. for 720 hours, and the glossiness after immersion was measured to calculate the gloss retention rate.

The gloss retention is calculated by the following formula based on the value obtained by measuring the surface (test surface) of the surface (test surface) based on JIS Z 8741-1997 and measuring the mirror gloss at an incident angle of 60 degrees. is there.

Gloss retention rate (%) = (gloss after water resistance test / initial gloss) x 100
The evaluation was performed according to the following criteria. S to C pass and D fails.
S: The gloss retention rate is 95% or more, and the water resistance is very excellent.
A: The gloss retention rate is 90% or more and less than 95%, and the water resistance is slightly excellent.
B: The gloss retention rate is 80% or more and less than 90%, and the water resistance is excellent.
C: The gloss retention rate is 70% or more and less than 80%, and the water resistance is normal.
D: The gloss retention rate is less than 70%, and the water resistance is inferior.

Claims (10)

A phosphazene compound having at least one organic group represented by the following general formula (1) in the molecule.

[In equation (1), ★★ is a bond or a hydrogen atom. X is a divalent organic group having 1 to 18 carbon atoms, and the organic group may contain an oxygen atom and / or a nitrogen atom. R ¹ represents a hydrogen atom or an organic group having 1 to 18 carbon atoms, and the organic group may contain at least one selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom and a halogen atom. A ¹ , A ² and A ³ represent a monovalent organic group, and the organic group is at least one selected from the group consisting of a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom, a phosphorus atom, a sulfur atom and a halogen atom. May be included, each may be independent or the same, and two or more kinds may be connected to form an annular structure. ] The phosphazene compound according to claim 1, wherein the ★★ of the general formula (1) is a bond. The phosphazene compound according to claim 1 or 2, wherein A ¹ , A ² , and / or A ³ of the general formula (1) are organic groups represented by the following general formula (2).

[In equation (2), ★ is a joiner. R ^{2 to} R ⁷ represent an organic group having 1 to 12 carbon atoms, and the organic group may contain an oxygen atom and / or a nitrogen atom, and each of them may be independent or the same. The above may be connected to form an annular structure. n represents an integer of 0 or more and 10 or less. ] The item according to any one of claims 1 to 3, wherein A ¹ , A ² , and / or A ³ of the general formula (1) are organic groups represented by the following general formula (3). The phosphazene compound described.

[In equation (3), R ² and R ³ have the same meanings as described above. ] A ¹ , A ² , and / or A ³ of the general formula (1) are N, N-dimethylamino group, N, N-diethylamino group, N, N-dipropylamino group, N, N-diisopropylamino. Group, N, N-dibutylamino group, N, N-dioctylamino group, N-methyl-N-propylamino group, N-methyl-N-butylamino group, N, N-di (2-ethylhexyl) amino group The phosphazene compound according to any one of claims 1 to 4, which is at least one selected from the group consisting of a pyrrolyl group, a morpholino group, a piperidino group, a pyrrolidino group, and an N-alkylpiperadino group. The phosphazene compound according to any one of claims 1 to 5, which has one or more organic groups represented by the general formula (1) in the molecule and has a number average molecular weight of 400 to 1,000,000. .. Any one of claims 1 to 6, wherein the molecule may have one or more organic groups having the structure of the following general formula (4), and a part or all of the organic groups may be ionized. The phosphazene compound according to.

[In equation (4), ★, X, R ¹ , A ¹ , A ² and A ³ have the same meanings as described above. ] Any one of claims 1 to 7, wherein the molecule may have one or more organic groups having the structure of the following general formula (5), and a part or all of the organic groups may be ionized. The phosphazene compound according to.

[In equation (5), ★, X, R ¹ , A ¹ , A ² and A ³ have the same meanings as described above. ] The method for producing a phosphazene compound according to claim 2, wherein a compound having one or more reactive functional groups in the molecule is reacted with a phosphazene compound represented by the following general formula (1)'.

[In equation (1)', X, R ¹ , A ¹ , A ² and A ³ have the same meanings as described above. ] A thermosetting resin composition containing the phosphazene compound according to any one of claims 1 to 8, the hydroxyl group-containing resin (A), and the curing agent (B), wherein the curing agent (B) is poly. A thermosetting resin composition, which is an isocyanate curing agent and / or a blocked polyisocyanate curing agent.