KR20210113313A - Polyisocyanurate raw material composition, and method for producing polyisocyanurate - Google Patents

Abstract

식 (I) 중, R¹ 및 R²는 수소 원자를 나타낸다. R³ 내지 R⁵는 각각 독립적으로, 수소 원자, 탄소수 1 내지 10의 알콕시기, 아미노기, 탄소수 1 내지 10의 모노알킬아미노기, 또는 탄소수 2 내지 20의 디알킬아미노기를 나타낸다. 각각 3개의 R³ 내지 R⁵는 각각 동일해도 되고, 달라도 된다. 단, 각각 3개의 R³ 내지 R⁵ 중, 적어도 하나는 아미노기, 탄소수 1 내지 10의 모노알킬아미노기, 또는 탄소수 2 내지 20의 디알킬아미노기이다.A polyisocyanurate raw material composition comprising a polyfunctional isocyanate, a compound (I) represented by the following formula (I), and an epoxy compound.

In formula (I), R<^1> and R<^2> represent a hydrogen atom. R ³ to R ⁵ each independently represent a hydrogen atom, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms. Each of the three R ³ to R ⁵ may be the same as or different from each other. However, ^{among the three R 3} to R ⁵ , at least one is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.

Description

Polyisocyanurate raw material composition, and method for producing polyisocyanurate

The present invention relates to a polyisocyanurate raw material composition and a method for producing polyisocyanurate. Further, the present invention relates to a polyisocyanurate production kit, a cured polyisocyanurate raw material, and a catalyst for polyisocyanurate production reaction. This application claims priority on the basis of Japanese Patent Application No. 2019-024875, filed in Japan on February 14, 2019, and Application No. 201911106849.6, filed in China on November 13, 2019, the content of which It is incorporated herein by reference.

Polyisocyanurate is a resin in which isocyanurate rings are arbitrarily linked. Although it is said that heat resistance and a flame retardance improve by introduce|transducing an isocyanurate ring structure into a polyurethane foam, industrial use of polyisocyanurate itself has not progressed.

Polyisocyanurates are synthesized by trimerization of polyfunctional isocyanates. Conventionally, as a catalyst for the trimerization reaction of isocyanate, a tertiary amine, a quaternary ammonium salt, a metal salt, etc. are used (for example, patent document 1).

Japanese Patent Laid-Open No. 3-95213

However, since catalysts, such as a tertiary amine, a quaternary ammonium salt, and a metal salt, have high hygroscopicity, they become a cause of foaming at the time of thermosetting.

On the other hand, a phosphorus catalyst is mentioned as a catalyst with low hygroscopicity. However, in a phosphorus catalyst, the reaction efficiency of polyfunctional isocyanate trimerization reaction is low, and it cannot produce|generate the isocyanurate ring of sufficient quantity for thermosetting.

The present invention has been made in view of the above circumstances, a method for producing polyisocyanurate having low foaming during thermal curing and good curability, a polyisocyanurate raw material composition usable in the production method, and a polyisocyanurate production kit , and an object of the present invention is to provide a catalyst for the polyisocyanurate production reaction. Another object of the present invention is to provide a polyisocyanurate with little foaming, that is, a cured polyisocyanurate raw material produced by the above production method.

The present invention includes the following aspects.

[1] A polyisocyanurate raw material composition comprising a polyfunctional isocyanate, a compound (I) represented by the following general formula (I), and an epoxy compound.

[In general formula (I), R ¹ and R ² represent a hydrogen atom. R ³ to R ⁵ each independently represent a hydrogen atom, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms. Each of the three R ³ to R ⁵ may be the same as or different from each other. However, ^{among the three R 3} to R ⁵ , at least one is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.]

[2] The polyisocyanurate raw material composition according to [1], wherein the ratio (molar ratio) of the compound (I) to the polyfunctional isocyanate is polyfunctional isocyanate/compound (I) = 100/0.001 to 100/5.

[3] The polyfunctional isocyanate is at least one selected from the group consisting of diphenylmethane diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, bis(isocyanatomethyl)cyclohexane, and modified polyisocyanates thereof. , The polyisocyanurate raw material composition according to [1] or [2].

[4] A kit for preparing polyisocyanurate comprising (a) a polyfunctional isocyanate, (b) a compound represented by the following general formula (I), and (c) an epoxy compound, wherein (a) to (c) are Kits, each housed in a separate container.

[In general formula (I), R ¹ and R ² represent a hydrogen atom. R ³ to R ⁵ each independently represent a hydrogen atom, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms. Each of the three R ³ to R ⁵ may be the same as or different from each other. However, ^{at least one of the three R 3} to R ⁵ is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.]

[5] (d) a composition comprising a polyfunctional isocyanate and a compound (I) represented by the following general formula (I), and (c) a kit for preparing polyisocyanurate comprising an epoxy compound, wherein (d) and (c) is a kit, each housed in a different container.

[In general formula (I), R ¹ and R ² represent a hydrogen atom. R ³ to R ⁵ each independently represent a hydrogen atom, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms. Each of the three R ³ to R ⁵ may be the same as or different from each other. However, ^{at least one of the three R 3} to R ⁵ is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.]

[6] (d) a composition comprising a polyfunctional isocyanate and a compound (I) represented by the following general formula (I), and (e) a polyisocyanurate comprising a composition comprising a polyfunctional isocyanate and an epoxy compound A kit, wherein (d) and (e) are accommodated in different containers, respectively.

[In general formula (I), R ¹ and R ² represent a hydrogen atom. R ³ to R ⁵ each independently represent a hydrogen atom, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms. Each of the three R ³ to R ⁵ may be the same as or different from each other. However, ^{at least one of the three R 3} to R ⁵ is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.]

[7] (e) a composition comprising a polyfunctional isocyanate and an epoxy compound, and (b) a kit for preparing polyisocyanurate comprising a compound (I) represented by the following general formula (I), wherein (e) and (b) is a kit, each housed in a different container.

[In general formula (I), R ¹ and R ² represent a hydrogen atom. R ³ to R ⁵ each independently represent a hydrogen atom, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms. Each of the three R ³ to R ⁵ may be the same as or different from each other. However, ^{at least one of the three R 3} to R ⁵ is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.]

[8] A cured polyisocyanurate raw material obtained by heating the polyisocyanurate raw material composition according to any one of [1] to [3].

[9] a polyisocyanurate produced from a polyfunctional isocyanate;

Compound (I) represented by the following general formula (I), or a compound (I) represented by the following general formula (I) and a compound (I') represented by the following general formula (I');

epoxy compound

Containing, polyisocyanurate raw material cured product.

[In general formula (I) or (I'), R ¹ and R ² represent a hydrogen atom. R ³ to R ⁵ each independently represent a hydrogen atom, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms. Each of the three R ³ to R ⁵ may be the same as or different from each other. However, ^{at least one of the three R 3} to R ⁵ is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.]

[10] Polyisocyanu comprising a mixing step of mixing a polyfunctional isocyanate, a compound (I) represented by the following general formula (I), and an epoxy compound, and a heating step of heating the mixture obtained in the mixing step A method of making a lattice.

[In general formula (I), R ¹ and R ² represent a hydrogen atom. R ³ to R ⁵ each independently represent a hydrogen atom, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms. Each of the three R ³ to R ⁵ may be the same as or different from each other. However, ^{among the three R 3} to R ⁵ , at least one is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.]

[11] The method for producing polyisocyanurate according to [10], wherein the mixing step is a step of mixing the epoxy compound with the mixture (d) of the polyfunctional isocyanate and the compound (I).

[12] The method for producing polyisocyanurate according to [10], wherein the mixing step is a step of mixing the compound (I) with the mixture (e) of the polyfunctional isocyanate and the epoxy compound.

[13] The method for producing polyisocyanurate according to any one of [10] to [12], wherein the heating step is performed at a temperature of 40 to 240°C.

[14] The method for producing polyisocyanurate according to [13], wherein the heating step is a step of heating at 60 to 120° C. for 1 to 180 minutes, and then further heating at 120 to 240° C. for 1 to 180 minutes.

[15] A catalyst for a production reaction for producing polyisocyanurate from polyfunctional isocyanate, comprising a combination of a compound (I) represented by the following general formula (I) and an epoxy compound.

[In general formula (I), R ¹ and R ² represent a hydrogen atom. R ³ to R ⁵ each independently represent a hydrogen atom, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms. Each of the three R ³ to R ⁵ may be the same as or different from each other. However, ^{among the three R 3} to R ⁵ , at least one is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.]

[16] A kit for producing polyisocyanurate, comprising a combination of compound (I) represented by the following general formula (I) and an epoxy compound as a catalyst for a reaction for producing polyisocyanurate from polyfunctional isocyanate.

[In general formula (I), R ¹ and R ² represent a hydrogen atom. R ³ to R ⁵ each independently represent a hydrogen atom, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms. Each of the three R ³ to R ⁵ may be the same as or different from each other. However, ^{at least one of the three R 3} to R ⁵ is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.]

According to the present invention, a method for producing polyisocyanurate having low foaming and good curability during thermosetting, a polyisocyanurate raw material composition usable in the production method, a kit for producing polyisocyanurate, and polyisocyanurate A catalyst for the production reaction is provided. In addition, there is provided a cured polyisocyanurate or polyisocyanurate raw material with low foaming produced by the above production method.

BRIEF DESCRIPTION OF THE DRAWINGS It is a scatter diagram which shows the relationship between the HOMO level of the compound shown in Table 14, and the average charge of an ortho position.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail. However, this invention is not limited to embodiment shown below.

As used herein, the term "polyisocyanurate" refers to a compound having a structure in which a plurality of isocyanurate rings are arbitrarily linked through a divalent organic group.

As used herein, the term "polyisocyanurate raw material composition" is a composition containing either or both of a raw material of polyisocyanurate (a reaction product of a polyisocyanurate formation reaction) and a catalyst of a polyisocyanurate formation reaction, It refers to a polyisocyanurate or polyisocyanurate raw material used in the production of a cured product.

As used herein, the "kit for polyisocyanurate production" is a kit containing a polyisocyanurate raw material and a catalyst for a polyisocyanurate production reaction, and is used for the production of a polyisocyanurate or polyisocyanurate raw material cured product will become

As used herein, the term "cured polyisocyanurate raw material" refers to a cured product containing polyisocyanurate obtained by heating a polyisocyanurate raw material composition.

In this specification, when referring to carbon number of an alkyl group, an alkoxy group, a fluorinated alkyl group, and an aryl group, the carbon number in a substituent shall not be included in the said carbon number.

[Polyisocyanurate Raw Material Composition]

«First embodiment»

In one embodiment, the present invention provides a polyisocyanurate raw material composition comprising a polyfunctional isocyanate, a compound represented by the following general formula (I) (hereinafter also referred to as “compound (I)”), and an epoxy compound. provides

[In general formula (I), R ¹ and R ² represent a hydrogen atom. R ³ to R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, 2 to carbon atoms A dialkylamino group of 20, a carboxy group, a cyano group, a fluorinated alkyl group of 1 to 10 carbon atoms, or a halogen atom is represented. Each of the three R ³ to R ⁵ may be the same as or different from each other. However, ^{among the three R 3} to R ⁵ , at least one is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.]

(polyfunctional isocyanate)

"Polyfunctional isocyanate" means a compound containing two or more isocyanato groups (-N=C=O). As the polyfunctional isocyanate, those generally used for the production of polyisocyanurate may be used without particular limitation. Although it will not specifically limit if the number of the isocyanato groups which polyfunctional isocyanate contains is two or more, 2-5 pieces are preferable, 2 or 3 pieces are more preferable, and 2 pieces are still more preferable. As polyfunctional isocyanate, an aliphatic isocyanate, aromatic isocyanate, etc. are mentioned, for example.

The aliphatic isocyanate is a polyfunctional isocyanate containing an aliphatic hydrocarbon group and two or more isocyanato groups. The aliphatic hydrocarbon group may be a linear or branched aliphatic hydrocarbon group, or an aliphatic hydrocarbon group containing a ring in its structure. Examples of the aliphatic hydrocarbon group containing a ring in its structure include an alicyclic group, a group in which an alicyclic group is bonded to the terminal of a straight or branched aliphatic hydrocarbon group, a group in which the alicyclic group is interposed in the middle of a straight or branched aliphatic hydrocarbon group, etc. can be heard The aliphatic hydrocarbon group preferably has 1 to 15 carbon atoms, more preferably 3 to 10 carbon atoms, still more preferably 5 to 10 carbon atoms.

Aromatic isocyanate is polyfunctional isocyanate containing at least 1 aromatic ring and 2 or more isocyanato groups. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having (4n+2) π electrons, and may be monocyclic or polycyclic. An aromatic hydrocarbon ring may be sufficient as an aromatic ring, and an aromatic heterocyclic ring may be sufficient as it. 6-15 are preferable and, as for carbon number of an aromatic ring, 6-12 are more preferable. 1-5 are preferable, as for the number of the aromatic rings which aromatic isocyanate has, 1-3 are more preferable, and 1 or 2 is especially preferable. The aromatic isocyanate may contain an aliphatic hydrocarbon group in addition to an aromatic ring and an isocyanato group. As said aliphatic hydrocarbon group, the thing similar to what was mentioned as an aliphatic hydrocarbon group in aliphatic isocyanate is mentioned.

Specific examples of the aliphatic isocyanate include tetramethylene-1,4-diisocyanate, pentamethylene-1,5-diisocyanate, hexamethylene-1,6-diisocyanate, octamethylene-1,8-diisocyanate, dodecamethylene- 1,12-diisocyanate, 2,2,4-trimethylhexamethylene-1,6-diisocyanate, 2,4,4-trimethylhexamethylene-1,6-diisocyanate, 1-isocyanato-3,3 ,5-trimethyl-5-isocyanatomethylcyclohexanecis-cyclohexane-1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane trans-cyclohexane Hexane-1,4-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, ω,ω'-diisocyanatomethyl-1,4-cyclohexane, ω,ω'-diisocyanatomethyl-1 ,3-cyclohexane, 3,10-diisocyanatotricyclo[5,2,1,0 ^2.6 ]decane, 2,2-bis(4-isocyanatocyclohexyl)propane, 6,8-diisocyana Tobicyclo[3,3,0]octene, undecane-1,6,10-triisocyanate, lysine diisocyanate methyl ester, N,N'-bis(ω-isocyanatopropyl)oxadiazinetrione, etc. can, but is not limited to these.

Specific examples of the aromatic isocyanate include tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate, diphenylmethane-2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, Naphthylene-1,5-diisocyanate, tolylene diisocyanate, bitolylene diisocyanate, anisidine diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate, diphenyl ether-4,4'-di Isocyanate, triphenylmethane-4,4',4"-triisocyanate, tris(4-isocyanatophenyl)thiophosphate, xylylene-1,3-diisocyanate, xylylene-1,4-diisocyanate etc. are mentioned, but it is not limited to these.

In addition, polyfunctional isocyanate is a type of polyphenylpolymethylene polyisocyanate obtained by condensing aniline with formalin and then phosgenation, and is liquid at room temperature containing a carbodiimide group or a uretonimine group described in German Patent No. 1092007. Diphenylmethane diisocyanate, or modified polyisocyanate containing a urethane bond, an allophanate bond, an isocyanurate ring structure, a urea bond, a biuret bond, or a uretdione ring structure, etc. may be sufficient.

The polyfunctional isocyanate may be an isocyanate base prepolymer obtained by excessively reacting the above isocyanate with a polyol used in the urethane industry.

Among them, as the polyfunctional isocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, bis(isocyanatomethyl)cyclohexane, and modified polyisocyanates thereof are preferable.

As the polyfunctional isocyanate, commercially available ones may be used. As a commercial item of polyfunctional isocyanate, For example, Milionate (trademark) MT (Toso), Coronate (trademark) T-65 (Toso), Coronate (trademark) T-80 (Toso), Coronate (registered trademark) T-100 (Toso), HDI (Toso), Duranate (registered trademark) 50M (Asahi Kasei Chemicals), Takenate (registered trademark) 600 (Mitsui Chemical), Coronate (registered trademark) HX (Toso), Duranate (registered trademark) TPA-100 (Asahi Kasei Chemicals), Duranate (registered trademark) 24A-100 (Asahi Kasei Chemicals), Duranate (registered trademark) D201 (Asahi Kasei Chemicals), etc. can be heard

Moreover, as for polyfunctional isocyanate, the thing in which the isocyanato group was blocked may be sufficient as it. "The isocyanato group was blocked" means that the isocyanato group is protected by the protecting group. The blocked isocyanato group can be represented by the general formula "-N-C(=O)-B (B is a protecting group)". As the protecting group, those generally used as the protecting group of the isocyanato group can be used without particular limitation. By using the polyfunctional isocyanate (Hereinafter, it may be called "blocked polyfunctional isocyanate") in which the isocyanato group was blocked, advancing of the trimerization reaction unintentionally can be prevented.

Polyfunctional isocyanate may be used individually by 1 type, and may use 2 or more types together.

As a ratio of polyfunctional isocyanate in the polyisocyanurate raw material composition of this embodiment, 80 mol% or more and less than 100 mol% are illustrated, for example. The ratio of polyfunctional isocyanate in the polyisocyanurate raw material composition is preferably 85 mol% or more and 99.99 mol% or less, more preferably 90 mol% or more and 98 mol% or less, and furthermore, 93 mol% or more and 97 mol% or less. desirable. If the ratio of polyfunctional isocyanate is more than the lower limit of the said range, favorable heat resistance can be implement|achieved. Moreover, it will become easy to take balance with another component that the ratio of polyfunctional isocyanate is below the upper limit of the said range.

(Compound (I))

Compound (I) is a compound represented by the following general formula (I).

[In general formula (I), R ¹ and R ² represent a hydrogen atom. R ³ to R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, 2 to carbon atoms A dialkylamino group of 20, a carboxy group, a cyano group, a fluorinated alkyl group of 1 to 10 carbon atoms, or a halogen atom is represented. Each of the three R ³ to R ⁵ may be the same as or different from each other. However, ^{at least one of the three R 3} to R ⁵ is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.]

In the general formula (I), R ¹ and R ² represent a hydrogen atom.

In the general formula (I), R ³ to R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, and 1 to 10 carbon atoms. represents a monoalkylamino group, a dialkylamino group having 2 to 20 carbon atoms, a carboxy group, a cyano group, a fluorinated alkyl group having 1 to 10 carbon atoms, or a halogen atom.

The alkyl group having 1 to 10 carbon atoms in R ³ to R ⁵ may be linear or branched, and may have a ring in its structure. The alkyl group having 1 to 10 carbon atoms in R ³ to R ⁵ preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, still more preferably 1 or 2 carbon atoms.

Examples of the linear or branched alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, n-pentyl group, neopentyl group , an isopentyl group, and a sec-pentyl group.

The linear or branched alkyl group in ^{R 3} to R ^{5 may have a substituent.}

In this specification, "you may have a substituent" means that the hydrogen atom (-H) of a hydrocarbon group may be substituted by the monovalent group. As a substituent, an amino group, a carboxy group, a cyano group, a halogen atom etc. are illustrated, for example. Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

As a ^{linear or branched alkyl group in R<3>} -R<^5> , it is more preferable that it does not have a substituent.

Examples of the alkyl group containing a ring in the structure include a cycloalkyl group, a group in which a cycloalkane ring is bonded to the terminal of a linear or branched alkyl group, and a group in which a cycloalkane ring is interposed in the middle of a linear or branched alkyl group. In the above, although monocyclic or polycyclic may be sufficient as a cycloalkane ring, it is preferable that it is monocyclic. Examples of the alkyl group containing a ring in the structure include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a group in which a linear or branched alkyl group is bonded to the cycloalkyl group.

The alkyl group including a ring in the structure for ^{R 3} to R ^{5 may have a substituent.} As a substituent, an amino group, a carboxy group, a cyano group, a halogen atom etc. are illustrated, for example.

The alkoxy group having 1 to 10 carbon atoms in R ³ to R ⁵ preferably has 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms, still more preferably 1 or 2 carbon atoms.

The alkoxy group is a group represented by -OR (R is an alkyl group). The alkyl group for R may be linear or branched, and may contain a ring in the structure, but a linear or branched alkyl group is preferable. As said alkyl group, the thing similar to what was mentioned for the said C1-C10 alkyl group is mentioned.

Specific examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group. Among them, ^{the alkoxy group having 1 to 10 carbon atoms in R 3} to R ⁵ is preferably a methoxy group or an ethoxy group, and more preferably a methoxy group.

The aryl group having 6 to 12 carbon atoms in R ³ to R ^{5 has preferably 6 to 10 carbon atoms.} Specific examples of the aryl group include a phenyl group, a tolyl group, an o-xylyl group, a naphthyl group, and a biphenyl group.

The aryl group having 6 to 12 carbon atoms in R ³ to R ^{5 may have a substituent.} As a substituent, a C1-C5 alkyl group, an amino group, a carboxy group, a cyano group, a halogen atom etc. are illustrated, for example.

The fluorinated alkyl group having 1 to 10 carbon atoms in R ³ to R ⁵ preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, still more preferably 1 or 2 carbon atoms. Specific examples of the fluorinated alkyl group having 1 to 10 carbon atoms in R ³ to R ⁵ include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, and a part of hydrogen atoms in the alkyl group exemplified as the alkyl group having 1 to 10 carbon atoms. Or the group etc. which were all substituted by the fluorine atom are mentioned.

Examples ^{of the halogen atom in R 3} to R ⁵ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among them, as ^{the halogen atom in R 3} to R ⁵ , a fluorine atom is preferable.

Each alkyl group which the monoalkylamino group having 1 to 10 carbon atoms or the dialkylamino group having 2 to 20 carbon atoms in R ³ to R ^{5 has is preferably 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and 1 to 3 carbon atoms.} This is more preferable, and C1 or C2 is still more preferable. The said alkyl group may be linear or branched may be sufficient as it, and the thing containing a ring in structure may be sufficient as it. Specific examples of the monoalkylamino group having 1 to 10 carbon atoms or the dialkylamino group having 2 to 20 carbon atoms in R ¹ and R ² include a methylamino group, a dimethylamino group, and one or two hydrogen atoms of the amino group having 1 to 2 carbon atoms. The group etc. substituted with the alkyl group illustrated as the alkyl group of 10 are mentioned.

Among them, as R ³ to R ⁵ , a hydrogen atom or an electron-donating group is preferable from the viewpoint of reactivity. More specifically, R ³ to R ⁵ are preferably a hydrogen atom, an alkoxy group, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms, a hydrogen atom, an alkoxy group, or a carbon number 1 to A 10 monoalkylamino group or a C2-C20 dialkylamino group is more preferable. Preferred examples of R ³ to R ⁵ include a hydrogen atom, an alkoxy group having 1 to 4 carbon atoms, an alkylamino group having 1 to 4 carbon atoms, or a dialkylamino group having 2 to 8 carbon atoms, a hydrogen atom, a methoxy group, monomethyl An amino group or a dimethylamino group is particularly preferred.

In the general formula (I), each of three R ³ to R ⁵ may be the same as or different from each other. Three R ³ may be different from each other, two of three may be the same and one may be different, and all ^three may be the same, but it is preferable that all three R 3 are the same. Three R ⁴ may be different from each other, two of three may be the same and one may be different, and all three may be the same, but it is preferable that all ^{three R 4 are the same.} Three R ⁵ may be different from each other, two out of three may be the same and one may be different, and all three may be the same, but it is preferable that all ^{three R 5 are the same.} However, ^{among the three R 3} to R ⁵ , at least one is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.

Specific examples of the compound (I) include compounds of phosphorus catalysts No. 13 to 59 described in Tables 15 to 16 described later, and DMAPDPP (phosphorus catalyst No. 12) described later.

The compounds of the phosphorus catalysts Nos. 12 to 59 are compounds satisfying the following formula (1). The average charge of the level of HOMO and the ortho position can be calculated by the method described in Examples. Among them, a phosphorus catalyst having an activation energy of 32.17 kcal/mol or less is preferable because it can be expected to exhibit catalytic activity equivalent to or higher than that of phosphorus catalyst No. 11 (TOAP: see Tables 1 to 3). The activation energy can be calculated by the method described in Examples.

y<28.5x+5.644 … (One)

x: level of HOMO/a.u.

y: average charge at ortho positions

Compound (I) may be used individually by 1 type, and may use 2 or more types together.

As a ratio of compound (I) in the polyisocyanurate raw material composition of this embodiment, more than 0 mol% and 10 mol% or less are illustrated, for example. The ratio of compound (I) in the polyisocyanurate raw material composition is preferably 0.001 mol% or more and 5 mol% or less, more preferably 0.01 mol% or more and 2 mol% or less, and 0.05 mol% or more and 2 mol% or less. more preferably. When the ratio of compound (I) is equal to or more than the lower limit of the above range, good reaction efficiency can be realized. Moreover, it will become easy to take balance with another component that the ratio of compound (I) is below the upper limit of the said range.

Polyfunctional isocyanate/compound (I)=100/0.001-100/5 are preferable, as for the ratio (molar ratio) of compound (I) with respect to polyfunctional isocyanate, 100/0.01-100/2 are more preferable, 100/0.05 to 100/2 are more preferable.

(epoxy compound)

The epoxy compound in this embodiment is a compound containing one or more epoxy groups. The epoxy compound may be used without particular limitation, which is generally used for the trimerization reaction of isocyanate. Although the epoxy equivalent of an epoxy compound is not specifically limited, 50 g/mol - 1000 g/mol are preferable, 100 g/mol - 500 g/mol are more preferable, 100 g/mol - 300 g/mol are still more preferable.

Specific examples of the epoxy compound include, for example, allyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, butylene oxide, propylene oxide, octylene oxide, styrene oxide, glycidol, versatic acid. monoepoxides such as glycidyl ester;

1,2-cyclohexanedicarboxylic acid diglycidyl, diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, butadiene epoxide, 3,4-epoxycyclohexylmethyl-(3,4- Epoxy) cyclohexanecarboxylate, bicyclohexene dioxide, 4,4'-di (1,2-epoxyethyl) diphenyl ether, 4,4'-di (1,2-epoxyethyl) biphenyl, 2 ,2-bis(3,4-epoxycyclohexyl)propane, diglycidyl ether of resorcin, diglycidyl ether of methylfluoroglycine, bis(2,3-epoxycyclopentyl)ether, 2-( 3,4-epoxy)cyclohexane-m-dioxane, bis(3,4-epoxy-6-methylcyclohexyl)adipate, N,N'-m-phenylenebis(4,5-epoxy-1, diepoxides such as 2-cyclohexane) dicarboimide;

Triglycidyl isocyanurate, triglycidyl ether of para-aminophenol, polyallyl glycidyl ether, 1,3,5-(1,2-epoxyethyl)benzene-2,2'-4,4'- Tetraglycidoxybenzophenone, tetraglycidoxytetraphenylethane, polyglycidyl ether of phenol novolac, polyglycidyl ether of cresol novolac, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane and trifunctional or higher epoxides such as these.

Among the above, examples of the epoxy compound include phenyl glycidyl ether, styrene oxide, diglycidyl 1,2-cyclohexanedicarboxylic acid, diglycidyl ether of bisphenol A, triglycidyl isocyanurate, and phenol. Since polyglycidyl ether of novolac, polyglycidyl ether of cresol novolac, etc. can be easily obtained industrially, it is preferable.

An epoxy compound may be used individually by 1 type, and may use 2 or more types together.

As a ratio of the epoxy compound in the polyisocyanurate raw material composition of this embodiment, more than 0 mol% and 20 mol% or less are illustrated, for example. The ratio of compound (I) in the polyisocyanurate raw material composition is preferably 0.001 mol% or more and 15 mol% or less, more preferably 0.005 mol% or more and 10 mol% or less, and 0.1 mol% or more and 7 mol% or less. more preferably. When the ratio of compound (I) is equal to or more than the lower limit of the above range, good reaction efficiency can be realized. Moreover, it will become easy to take balance with another component that the ratio of compound (I) is below the upper limit of the said range.

Polyfunctional isocyanate/epoxy compound =100/0.001-100/15 are preferable, as for the ratio (molar ratio) of the epoxy compound with respect to polyfunctional isocyanate, 100/0.005-100/10 are more preferable, 100/0.1-100/7 This is more preferable.

(optional ingredient)

The polyisocyanurate raw material composition of this embodiment may contain other components in addition to the said polyfunctional isocyanate, compound (I), and an epoxy compound. Examples of the other components include solvents, curing accelerators, silane coupling agents, antioxidants, mold release agents, defoamers, emulsifiers, thixotropic agents, smoothing agents, flame retardants, pigments, fillers, shrink softeners, and the like.

By heating the polyisocyanurate raw material composition of this embodiment, the trimerization reaction of polyfunctional isocyanate advances, and polyisocyanurate produces|generates. The compound (I) and the epoxy compound mainly function as catalysts for the trimerization reaction of polyfunctional isocyanate. Phosphorus catalysts generally have low hygroscopicity and suppress foaming during heating. However, when used as a catalyst for polyisocyanurate production, there is a problem that sufficient curability (yield) cannot be obtained due to low reactivity. However, compound (I) has a specific structure represented by the above general formula (I), as shown in Examples to be described later, and exhibits high reactivity when used as a catalyst for polyisocyanurate production reaction, and has sufficient curability. (yield) can be realized. That is, since compound (I) has low hygroscopicity and high reactivity as a catalyst, foaming is suppressed when thermosetting, and sufficient sclerosis|hardenability can be obtained.

«Second embodiment»

In one embodiment, the present invention provides a polyisocyanurate raw material composition comprising a polyfunctional isocyanate and compound (I).

(polyfunctional isocyanate)

The polyfunctional isocyanate is the same as that described in the description of the first embodiment. As for the preferable example of polyfunctional isocyanate, the thing similar to what was mentioned in the said 1st Embodiment is mentioned.

Among them, as the polyfunctional isocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, bis(isocyanatomethyl)cyclohexane, and modified polyisocyanates thereof are preferable.

Polyfunctional isocyanate may be used individually by 1 type, and may use 2 or more types together.

As a ratio of polyfunctional isocyanate in the polyisocyanurate raw material composition of this embodiment, 90 mol% or more and less than 100 mol% are illustrated, for example. The ratio of polyfunctional isocyanate in the polyisocyanurate raw material composition is preferably 95 mol% or more and 99.99 mol% or less, more preferably 98 mol% or more and 99.99 mol% or less, and more preferably 98 mol% or more and 99.95 mol% or less. desirable. If the ratio of polyfunctional isocyanate is more than the lower limit of the said range, favorable heat resistance can be implement|achieved. Moreover, it will become easy to take balance with another component that the ratio of polyfunctional isocyanate is below the upper limit of the said range.

(Compound (I))

Compound (I) is the same as described in the description of the first embodiment. Preferred examples of the compound (I) include the same compounds as those exemplified in the first embodiment.

Among these, in the compound (I), R ³ to R ⁵ in the general formula (I) are each independently a hydrogen atom, an alkoxy group having 1 to 4 carbon atoms, a monoalkylamino group having 1 to 4 carbon atoms, or a group having 2 to 8 carbon atoms. A compound that is a dialkylamino group is preferred.

Further, as the compound (I), a compound represented by the general formula (I-1) is preferable, and R ³ to R ⁵ in the general formula (I-1) are each independently a hydrogen atom and 1 to 4 carbon atoms. The compound which is an alkoxy group, a C1-C4 monoalkylamino group, or a C2-C8 dialkylamino group is more preferable.

In the above, the alkoxy group having 1 to 4 carbon atoms is preferably an alkoxy group having 1 to 3 carbon atoms, more preferably an ethoxy group or a methoxy group, and still more preferably a methoxy group. As each alkyl group which a C1-C4 monoalkylamino group or a C2-C8 dialkylamino group has, a C1-C4 alkyl group is preferable, A C1-C3 alkyl group is more preferable, A methylamino group or a dimethylamino group more preferably.

As a specific example of compound (I), the compound of phosphorus catalyst Nos. 12-59 of Tables 14-16 mentioned later is mentioned.

Compound (I) may be used individually by 1 type, and may use 2 or more types together.

As a ratio of compound (I) in the polyisocyanurate raw material composition of this embodiment, more than 0 mol% and 10 mol% or less are illustrated, for example. The ratio of compound (I) in the polyisocyanurate raw material composition is preferably 0.001 mol% or more and 5 mol% or less, more preferably 0.01 mol% or more and 2 mol% or less, and 0.05 mol% or more and 2 mol% or less. more preferably. When the ratio of compound (I) is equal to or more than the lower limit of the above range, good reaction efficiency can be realized. Moreover, it will become easy to take balance with another component that the ratio of compound (I) is below the upper limit of the said range.

Further, the ratio (molar ratio) of the compound (I) to the polyfunctional isocyanate is preferably polyfunctional isocyanate/compound (I) = 100/0.001 to 100/5, more preferably 100/0.01 to 100/2, and 100 /0.05 to 100/2 are more preferable.

(optional ingredient)

The polyisocyanurate raw material composition of the present embodiment may contain other components in addition to the polyfunctional isocyanate and compound (I). As another component, the thing similar to what was mentioned in the said 1st Embodiment is mentioned.

The polyisocyanurate raw material composition of this embodiment is mixed with an epoxy compound and heated, so that the trimerization reaction of polyfunctional isocyanate advances, and polyisocyanurate produces|generates. As an epoxy compound, the thing similar to what was described in description of the said 1st Embodiment can be used. The compound (I) and the epoxy compound mainly function as catalysts for the trimerization reaction of polyfunctional isocyanate, similarly to the polyisocyanurate raw material composition of the first embodiment. Since compound (I) has low hygroscopicity and high reactivity as a catalyst, foaming is suppressed when heated, and sufficient curability (yield) can be obtained.

[Kit for polyisocyanurate production]

The kit for producing polyisocyanurate of the present embodiment contains polyfunctional isocyanate, compound (I), and an epoxy compound.

As a kit of this embodiment, (a) polyfunctional isocyanate, (b) compound (I), (c) epoxy compound, (d) a composition containing polyfunctional isocyanate and compound (I), and (e) polyfunctional What has accommodated the composition containing isocyanate and an epoxy compound in different containers, combining suitably, is illustrated.

In the kit of this embodiment, each amount of polyfunctional isocyanate, compound (I), and epoxy compound accommodated in each container is not particularly limited, but the amount according to the mixing ratio for mixing each component at the time of production of polyisocyanurate It is preferable to

For example, the molar ratio of the total molar amount of the polyfunctional isocyanate contained in the kit of the present embodiment and the total molar amount of the compound (I) is polyfunctional isocyanate/compound (I) = 100/0.001 to 100/5 Preferably, 100/0.01 to 100/2 are more preferable, and 100/0.05 to 100/2 are still more preferable.

Further, for example, the molar ratio of the total molar amount of the polyfunctional isocyanate contained in the kit of the present embodiment and the total molar amount of the epoxy compound is preferably polyfunctional isocyanate/epoxy compound = 100/0.001 to 100/15, 100/0.005 to 100/10 are more preferable, and 100/0.1 to 100/7 are still more preferable.

The said container is not specifically limited, Any container may be sufficient. The material of the container should just not be corroded by the content, for example, glass, resin, a metal, etc. are mentioned.

«First embodiment» (Kit comprising (a), (b), (c))

In one embodiment, the present invention is a kit for preparing polyisocyanurate comprising (a) polyfunctional isocyanate, (b) compounds (I) and (c) an epoxy compound, wherein (a) to (c) are each Kits housed in different containers are provided.

(polyfunctional isocyanate)

The polyfunctional isocyanate is the same as that described in the description of the first embodiment in the section of "[Polyisocyanurate Raw Material Composition]". Preferred examples of the polyfunctional isocyanate include the same as those exemplified in the first embodiment of the "[Polyisocyanurate Raw Material Composition]" above.

(Compound (I))

Compound (I) is the same as that described in the description of the first embodiment in the item "[Polyisocyanurate raw material composition]". Preferred examples of the compound (I) include the same compounds as those exemplified in the first embodiment of the "[Polyisocyanurate Raw Material Composition]" above.

Moreover, it is preferable that the compound (I) is accommodated in the container in the state melt|dissolved in the solvent. A solvent will not be specifically limited if it can melt|dissolve compound (I), A well-known organic solvent etc. can be used.

(epoxy compound)

The epoxy compound is the same as that described in the description of the first embodiment in the section of "[Polyisocyanurate Raw Material Composition]". Preferred examples of the epoxy compound include those similar to those exemplified in the first embodiment of the term "[Polyisocyanurate Raw Material Composition]".

What is necessary is just to mix (a) polyfunctional isocyanate, (b) compound (I), and (c) epoxy compound which are contained in the kit of this embodiment at the time of manufacture of polyisocyanurate. By heating the said mixture, the trimerization reaction of polyfunctional isocyanate can advance and polyisocyanurate can be obtained.

«Second embodiment» (Kit comprising (d) and (c))

In one embodiment, the present invention is a kit for preparing polyisocyanurate comprising (d) a composition comprising a polyfunctional isocyanate and compound (I), and (c) an epoxy compound, wherein (d) and (c) provides kits each housed in a different container.

(Composition (d))

The kit of this embodiment contains the composition (henceforth "composition (d)") containing a polyfunctional isocyanate and compound (I).

The composition (d) is the same as the polyisocyanurate raw material composition according to the second embodiment described in the section of "[Polyisocyanurate raw material composition]".

(epoxy compound)

The epoxy compound is the same as the kit according to the first embodiment.

What is necessary is just to mix the composition (d) and (c) epoxy compound contained in the kit of this embodiment at the time of manufacture of polyisocyanurate. By heating the said mixture, the trimerization reaction of polyfunctional isocyanate can advance and polyisocyanurate can be obtained.

«Third embodiment» (Kit comprising (d) and (e))

In one embodiment, the present invention is a kit for preparing polyisocyanurate comprising (d) a composition comprising a polyfunctional isocyanate and a compound (I), and (e) a composition comprising a polyfunctional isocyanate and an epoxy compound, The (d) and (e) provide a kit accommodated in different containers, respectively.

(Composition (d))

The composition (d) is the same as the kit according to the second embodiment.

(Composition (e))

The kit of this embodiment contains the composition (henceforth "composition (e)") containing a polyfunctional isocyanate and an epoxy compound.

The polyfunctional isocyanate contained in the composition (e) is the same as that described in the description of the first embodiment of the "[Polyisocyanurate raw material composition]" section. Preferred examples of the polyfunctional isocyanate include the same as those exemplified in the first embodiment of the "[Polyisocyanurate Raw Material Composition]" above.

The polyfunctional isocyanate may be the same as the polyfunctional isocyanate contained in the composition (d), or may be different.

The epoxy compound contained in the composition (e) is the same as that described in the description of the first embodiment of the term "[Polyisocyanurate Raw Material Composition]". Preferred examples of the epoxy compound include those similar to those exemplified in the first embodiment of the term "[Polyisocyanurate Raw Material Composition]".

What is necessary is just to mix the composition (d) and composition (e) contained in the kit of this embodiment at the time of manufacture of polyisocyanurate. By heating the said mixture, the trimerization reaction of polyfunctional isocyanate can advance and polyisocyanurate can be obtained.

«Fourth embodiment» (Kit comprising (b) and (e))

In one embodiment, the present invention is a kit for preparing polyisocyanurate comprising (e) a composition comprising a polyfunctional isocyanate and an epoxy compound, and (b) a compound (I), wherein (e) and (b) provides kits each housed in a different container.

(Composition (e))

Composition (e) is the same as that of the kit according to the third embodiment.

(Compound (I))

Compound (I) is the same as the kit according to the first embodiment.

What is necessary is just to mix the composition (e) and (b) compound (I) contained in the kit of this embodiment at the time of manufacture of a polyisocyanurate. By heating the said mixture, the trimerization reaction of polyfunctional isocyanate can advance and polyisocyanurate can be obtained.

Each of the kits of the first to fourth embodiments may include any configuration in addition to the components exemplified above. Examples of the optional configuration include instructions for producing polyisocyanurate, a mold for casting the polyisocyanurate raw material composition, and the like. In addition, the polyfunctional isocyanate contained in (a) polyfunctional isocyanate contained in the kit of the first embodiment, or the composition (d) or composition (e) contained in the kit of the second to fourth embodiments is a block. In the case of polyfunctional isocyanate, the kit of the first to fourth embodiments may contain a reagent for deprotecting the blocked polyfunctional isocyanate as an optional configuration.

[Polyisocyanurate raw material cured product]

In one embodiment, the present invention provides a cured polyisocyanurate raw material obtained by heating a polyisocyanurate raw material composition comprising a polyfunctional isocyanate, a compound (I), and an epoxy compound. The polyisocyanurate raw material cured product contains unreacted polyfunctional isocyanate, dimer, catalyst, catalyst modified product, and other impurities in addition to polyisocyanurate produced from polyfunctional isocyanate.

The polyisocyanurate is not particularly limited as long as it has a structure in which a plurality of isocyanurate rings are arbitrarily linked through a divalent organic group. The structure of polyisocyanurate can be represented by the following general formula (II), for example.

[Wherein, R represents a divalent organic group, and n represents an integer of 2 or more. A plurality of R may be the same or different, respectively.]

In the general formula (II), R is a divalent organic group derived from polyfunctional isocyanate.

When the polyfunctional isocyanate used in the trimerization reaction is an aliphatic isocyanate, R is an aliphatic hydrocarbon group (eg, an alkylene group). When the polyfunctional isocyanate used for the trimerization reaction is an aromatic isocyanate, R becomes an aromatic hydrocarbon group (for example, an arylene group).

Polyisocyanurate has a structure in which an isocyanurate ring is randomly bonded through a divalent organic group, and it is difficult to specify the overall structure. The polyisocyanurate raw material hardened|cured material of this embodiment can contain several types of polyisocyanurate from which a structure and molecular weight differ. Further, the cured polyisocyanurate raw material of the present embodiment may contain the compound (I) and an epoxy compound described later, and a reaction product (modified product) thereof, and the like.

The polyfunctional isocyanate is the same as that described in the description of the first embodiment of the term "[Polyisocyanurate Raw Material Composition]". Preferred examples of the polyfunctional isocyanate include the same as those exemplified in the first embodiment of the "[Polyisocyanurate Raw Material Composition]" above.

Compound (I) is the same as that described in the description of the first embodiment in the item "[Polyisocyanurate raw material composition]". Preferred examples of the compound (I) include the same compounds as those exemplified in the first embodiment of the "[Polyisocyanurate Raw Material Composition]" above.

The epoxy compound is the same as that described in the description of the first embodiment in the section “[Polyisocyanurate Raw Material Composition]”. Preferred examples of the epoxy compound include those similar to those exemplified in the first embodiment of the term "[Polyisocyanurate Raw Material Composition]".

The polyisocyanurate raw material hardened|cured material of this embodiment can be obtained by mixing polyfunctional isocyanate, compound (I), and an epoxy compound, and heating it. "Heating" can be performed similarly to the heating process demonstrated in the term of "[Method for producing polyisocyanurate]" mentioned later.

The cured polyisocyanurate raw material of the present embodiment is composed of polyisocyanurate, the compound (I) and a compound represented by the following general formula (I') (hereinafter also referred to as “compound (I')”). At least one compound selected from the group consisting of may be included.

[In general formulas (I) and (I'), R ¹ and R ² represent a hydrogen atom. R ³ to R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, 2 to carbon atoms A dialkylamino group of 20, a carboxy group, a cyano group, a fluorinated alkyl group of 1 to 10 carbon atoms, or a halogen atom is represented. Each of the three R ³ to R ⁵ may be the same as or different from each other. However, ^{among the three R 3} to R ⁵ , at least one is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.]

It is preferable that they are 70 mass % or more and less than 100 mass %, for example, and, as for the ratio of the polyisocyanurate in the polyisocyanurate raw material hardened|cured material of this embodiment, it is more preferable that they are 80-99 mass %.

(Compound (I))

Compound (I) is the same as that described in the description of the first embodiment in the item "[Polyisocyanurate raw material composition]". Preferred examples of the compound (I) include the same compounds as those exemplified in the first embodiment of the "[Polyisocyanurate Raw Material Composition]" above.

(Compound (I'))

Compound (I') is an oxide of compound (I).

R ¹ to R ⁵ in the formula (I ') is the same as R ¹ to R ⁵ in the formula (I). ^{Preferred examples of R 3} to R ⁵ in the general formula (I') include the same ones cited as preferred examples ^{of R 3} to R ⁵ in the general formula (I). As compound (I'), the oxide of what was mentioned as a specific example of the said compound (I) is preferable.

The number of compounds (I') contained in the polyisocyanurate raw material hardened|cured material of this embodiment may be one, and 2 or more types may be sufficient as them.

The cured polyisocyanurate raw material of the present embodiment may contain only the compound (I), may contain only the compound (I'), or may contain both the compound (I) and the compound (I'). . When the cured polyisocyanurate raw material of the present embodiment contains both the compound (I) and the compound (I'), the compound (I') is an oxide of the compound (I).

It is preferable that the ratio of the sum total of compound (I) and compound (I') in the polyisocyanurate raw material hardened|cured material of this embodiment is 0.001-5 mass %, for example, It is 0.001-1 mass % more preferably.

(Epoxy compounds and their reactants)

The cured polyisocyanurate raw material of the present embodiment may contain other components in addition to polyisocyanurate and at least one compound selected from the group consisting of compound (I) and compound (I'). As the other component, for example, (i) an epoxy compound, (ii) a reaction product of an epoxy compound and a polyfunctional isocyanate, (iii) a reaction product of an epoxy compound and the compound (I), and (iv) a reaction product of an epoxy compound and an epoxy compound etc. (Hereinafter, (i)-(iv) may be collectively referred to as "epoxy compound etc.").

[epoxy compound]

The epoxy compound is the same as that described in the description of the first embodiment in the section “[Polyisocyanurate Raw Material Composition]”. Preferred examples of the epoxy compound include those similar to those exemplified in the first embodiment of the term "[Polyisocyanurate Raw Material Composition]".

[Reaction product of epoxy compound and polyfunctional isocyanate]

The reaction product of an epoxy compound and polyfunctional isocyanate is a compound which polyfunctional isocyanate and an epoxy compound react, and generate|occur|produces at the time of a heating reaction. The reaction product of an epoxy compound and polyfunctional isocyanate will not be specifically limited if it is a compound which an epoxy compound and polyfunctional isocyanate react and generate|occur|produce. As the reaction product, for example, a compound containing an oxazolidone ring is exemplified.

[Reaction product of epoxy compound and compound (I)]

The reaction product of the epoxy compound and the compound (I) is a compound generated by the reaction between the epoxy compound and the compound (I) during a heating reaction. The reaction product of the epoxy compound and the compound (I) is not particularly limited as long as it is a compound generated by the reaction of the epoxy compound and the compound (I). For example, when an epoxy compound is a compound represented by the following general formula (E), as a reaction product of an epoxy compound and a compound (I), the compound represented by the following general formula (E-1) is illustrated.

Of the formula ^(E-1), R 1 to R ⁵ are the same as R ¹ to R ⁵ in the formula (I). Each of the three R ³ to R ⁵ may be the same as or different from each other. However, ^{among the three R 3} to R ⁵ , at least one is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms. In formulas (E) and (E-1), Re ¹ is an organic group.]

For example, when the epoxy compound is phenyl glycidyl ether, Re ¹ in the general formulas (E) and (E-1) is a phenoxymethyl group.

[Reactant of an epoxy compound and an epoxy compound]

A reaction product of an epoxy compound and an epoxy compound (a reaction product between epoxy compounds) is a compound generated by reacting two or more epoxy compounds during a heating reaction. The reaction product of epoxy compounds will not be specifically limited if it is a compound which two or more epoxy compounds react and generate|occur|produce. For example, when an epoxy compound is a compound represented by the said general formula (E), the polymer which has a repeating unit represented by the following general formula (E-2) as a reaction product of an epoxy compound and an epoxy compound is illustrated.

[In formula (E-2), Re ¹ is an organic group.]

For example, when an epoxy compound is phenyl glycidyl ether, Re ¹ in the said General formula (E-2) turns into a phenoxymethyl group.

It is preferable that it is 0.001-30 mass %, for example, and, as for the ratio of the sum total of the epoxy compound in the polyisocyanurate raw material hardened|cured material of this embodiment, it is more preferable that it is 0.01-20 mass %.

As a polyisocyanurate raw material hardened|cured material of this embodiment, For example, 70 mass % or more and less than 100 mass % of polyisocyanurate (preferably 79 mass % - 99.98 mass %); Compound (I) and compound (I') as the total amount of more than 0 mass % and 5 mass % or less (preferably 0.001-1 mass %); And containing an epoxy compound etc. as the total amount more than 0 mass % and less than 30 mass % (preferably 0.01-20 mass %) etc. are illustrated.

Since the hardened|cured polyisocyanurate raw material of this embodiment is manufactured using compound (I) as a catalyst, there is little foaming and has sufficient hardness. Therefore, the polyisocyanurate raw material hardened|cured material of this embodiment can be used for various uses, such as a paint, an adhesive agent, a sealing material, and an optical component.

[Method for producing polyisocyanurate]

In one embodiment, the present invention provides a mixing step of mixing a polyfunctional isocyanate, a compound (I) represented by the general formula (I), and an epoxy compound, and a heating step of heating the mixture obtained in the mixing step. It provides a method for producing polyisocyanurate comprising.

≪Mixing process≫

A mixing process is a process of mixing polyfunctional isocyanate, compound (I), and an epoxy compound.

(polyfunctional isocyanate)

The polyfunctional isocyanate is the same as that described in the description of the first embodiment of the term "[Polyisocyanurate Raw Material Composition]". Preferred examples of the polyfunctional isocyanate include the same as those exemplified in the first embodiment of the "[Polyisocyanurate Raw Material Composition]" above.

(Compound (I))

Compound (I) is the same as that described in the description of the first embodiment in the item "[Polyisocyanurate raw material composition]". Preferred examples of the compound (I) include the same compounds as those exemplified in the first embodiment of the "[Polyisocyanurate Raw Material Composition]" above.

(epoxy compound)

The epoxy compound is the same as that described in the description of the first embodiment in the section “[Polyisocyanurate Raw Material Composition]”. Preferred examples of the epoxy compound include those similar to those exemplified in the first embodiment of the term "[Polyisocyanurate Raw Material Composition]".

The mixing ratio (molar ratio) of the compound (I) to the polyfunctional isocyanate is preferably polyfunctional isocyanate/compound (I) = 100/0.001 to 100/5, more preferably 100/0.01 to 100/2, and 100 /0.05 to 100/2 are more preferable.

As a mixing ratio (molar ratio) of the epoxy compound with respect to polyfunctional isocyanate, polyfunctional isocyanate/epoxy compound =100/0.001-100/15 are preferable, 100/0.005-100/10 are more preferable, 100/0.1-100 /7 is more preferable.

In the mixing step, the polyfunctional isocyanate, the compound (I), and the order of mixing the epoxy compound are not particularly limited, but from the viewpoint of suppressing the unintended progress of the reaction, the compound (I) and the epoxy compound are mixed first. It is preferable not to

The mixing process may be a process of mixing an epoxy compound with the mixture (d) of polyfunctional isocyanate and compound (I), for example. As the mixture (d), the polyisocyanurate raw material composition according to the second embodiment described in the section of "[Polyisocyanurate raw material composition]" can be used.

The mixing step may be, for example, a step of mixing the compound (I) with the mixture (e) of the polyfunctional isocyanate and the epoxy compound. As said mixture (e), the thing similar to the composition (e) contained in the polyisocyanurate production kit which concerns on 4th Embodiment demonstrated in the said "[kit for polyisocyanurate production]" can be used.

The mixing process may be a process of mixing the mixture (e) of polyfunctional isocyanate and an epoxy compound with the mixture (d) of polyfunctional isocyanate and compound (I), for example. As said mixture (d), the thing similar to the composition (d) contained in the polyisocyanurate production kit which concerns on 3rd Embodiment demonstrated in the said "[kit for polyisocyanurate production]" section can be used. In addition, as said mixture (e), the thing similar to the composition (e) contained in the polyisocyanurate manufacturing kit which concerns on 3rd Embodiment demonstrated in the said "[kit for polyisocyanurate manufacturing]" can be used. .

When polyfunctional isocyanate contains a blocked polyfunctional isocyanate, you may perform deprotection reaction of the blocked isocyanato group before a mixing process, after a mixing process, or during a mixing process. The deprotection reaction can be appropriately selected according to the type of protecting group that blocks the isocyanato group.

≪Heating process≫

A heating process is a process of heating the mixture obtained by the said mixing process.

After the said mixing process, the mixture of polyfunctional isocyanate, compound (I), and an epoxy compound is stirred suitably, and after pouring into a mold|type, a heating reaction is performed. The heating temperature should just be a temperature sufficient for the polyisocyanurate production reaction to proceed, for example, 40 to 240°C can be exemplified, and 60 to 200°C is preferable.

The heating time should just be sufficient time for the production|generation of polyisocyanurate, for example, 1 to 360 minutes can be illustrated, and 30 to 180 minutes are preferable.

You may perform heating in two steps. For example, in the first step, heating may be performed at a relatively low temperature, and in the second step, heating may be performed at a temperature higher than that in the first step. As heating temperature of the 1st stage, 60-120 degreeC is mentioned, for example, 70-110 degreeC is preferable. 1 to 180 minutes are mentioned, as for the time of the 1st stage heating, 30 to 150 minutes are more preferable. As heating temperature of the 2nd stage, 120-240 degreeC is mentioned, for example, 150-210 degreeC is preferable. 1 to 180 minutes are mentioned, as for the time of the heating of the 2nd stage, 30 to 150 minutes are more preferable. By performing heating in two steps, the curvature and crack accompanying cure shrinkage can be suppressed.

As mentioned above, polyisocyanurate or a polyisocyanurate raw material hardened|cured material can be manufactured. According to the manufacturing method of this embodiment, polyfunctional isocyanate trimerization reaction advances efficiently using compound (I) and an epoxy compound as a catalyst. Moreover, since compound (I) has low hygroscopicity, polyisocyanurate with little foaming or a polyisocyanurate raw material hardened|cured material can be obtained.

[Catalyst for polyisocyanurate production reaction]

In one embodiment, the present invention provides a catalyst for polyisocyanurate production reaction comprising a combination of compound (I) represented by the general formula (I) and an epoxy compound.

Further, in one embodiment, the present invention provides a polyisocyanurate production kit comprising a combination of the compound (I) represented by the general formula (I) and an epoxy compound as a catalyst for the polyisocyanurate production reaction. to provide.

Compound (I) is the same as that described in the description of the first embodiment in the item "[Polyisocyanurate raw material composition]". Preferred examples of the compound (I) include the same compounds as those exemplified in the first embodiment of the "[Polyisocyanurate Raw Material Composition]" above.

The epoxy compound is the same as that described in the description of the first embodiment in the section “[Polyisocyanurate Raw Material Composition]”. Preferred examples of the epoxy compound include those similar to those exemplified in the first embodiment of the term "[Polyisocyanurate Raw Material Composition]".

By using the combination of the compound (I) represented by the general formula (I) and the epoxy compound as a catalyst for the polyisocyanurate production reaction, foaming is suppressed when heated, and sufficient curability (yield) can be obtained. .

The present invention may also include the following aspects.

[1] A polyisocyanurate raw material composition comprising a polyfunctional isocyanate, a compound (I) represented by the following general formula (I), and an epoxy compound.

[In general formula (I), R ¹ and R ² represent a hydrogen atom. R ³ to R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, 2 to carbon atoms A dialkylamino group of 20, a carboxy group, a cyano group, a fluorinated alkyl group of 1 to 10 carbon atoms, or a halogen atom is represented. Each of the three R ³ to R ⁵ may be the same as or different from each other. However, ^{at least one of the three R 3} to R ⁵ is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.]

[2] A polyisocyanurate raw material composition comprising a polyfunctional isocyanate and a compound (I) represented by the following general formula (I).

[In general formula (I), R ¹ and R ² represent a hydrogen atom. R ³ to R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, 2 to carbon atoms A dialkylamino group of 20, a carboxy group, a cyano group, a fluorinated alkyl group of 1 to 10 carbon atoms, or a halogen atom is represented. Each of the three R ³ to R ⁵ may be the same as or different from each other. However, ^{at least one of the three R 3} to R ⁵ is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.]

[3] The polyisocyanu according to [1] or [2], wherein the ratio (molar ratio) of the compound (I) to the polyfunctional isocyanate is polyfunctional isocyanate/compound (I) = 100/0.001 to 100/5. Late raw material composition.

[4] The polyfunctional isocyanate is at least one selected from the group consisting of diphenylmethane diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, bis(isocyanatomethyl)cyclohexane, and modified polyisocyanates thereof. , The polyisocyanurate raw material composition according to any one of [1] to [3].

^{[5] R 3} to R ⁵ in the general formula (I) are each independently a hydrogen atom, an alkoxy group having 1 to 4 carbon atoms, a monoalkylamino group having 1 to 4 carbon atoms, or a dialkylamino group having 2 to 8 carbon atoms , The polyisocyanurate raw material composition according to any one of [1] to [4].

[6] A kit for preparing polyisocyanurate comprising (a) a polyfunctional isocyanate, (b) a compound represented by the following general formula (I), and (c) an epoxy compound, wherein (a) to (c) are Kits, each housed in a separate container.

[In general formula (I), R ¹ and R ² represent a hydrogen atom. R ³ to R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, 2 to carbon atoms A dialkylamino group of 20, a carboxy group, a cyano group, a fluorinated alkyl group of 1 to 10 carbon atoms, or a halogen atom is represented. Each of the three R ³ to R ⁵ may be the same as or different from each other. However, ^{among the three R 3} to R ⁵ , at least one is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.]

[7] (d) a composition comprising a polyfunctional isocyanate and a compound (I) represented by the following general formula (I), and (c) a kit for preparing polyisocyanurate comprising an epoxy compound, wherein (d) and (c) is a kit, each housed in a different container.

[In general formula (I), R ¹ and R ² represent a hydrogen atom. R ³ to R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, 2 to carbon atoms A dialkylamino group of 20, a carboxy group, a cyano group, a fluorinated alkyl group of 1 to 10 carbon atoms, or a halogen atom is represented. Each of the three R ³ to R ⁵ may be the same as or different from each other. However, ^{among the three R 3} to R ⁵ , at least one is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.]

[8] The ratio (molar ratio) of the compound (I) to the polyfunctional isocyanate in the composition of (d) is polyfunctional isocyanate/compound (I) = 100/0.001 to 100/5, [7] The kit for preparing polyisocyanurate described in.

[9] (d) a composition comprising a polyfunctional isocyanate and a compound (I) represented by the following general formula (I), and (e) a polyisocyanurate comprising a composition comprising a polyfunctional isocyanate and an epoxy compound For production A kit, wherein (d) and (e) are accommodated in different containers, respectively.

[In general formula (I), R ¹ and R ² represent a hydrogen atom. R ³ to R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, 2 to carbon atoms A dialkylamino group of 20, a carboxy group, a cyano group, a fluorinated alkyl group of 1 to 10 carbon atoms, or a halogen atom is represented. Each of the three R ³ to R ⁵ may be the same as or different from each other. However, ^{at least one of the three R 3} to R ⁵ is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.]

[10] (e) a composition comprising a polyfunctional isocyanate and an epoxy compound, and (b) a kit for preparing polyisocyanurate comprising a compound (I) represented by the following general formula (I), wherein (e) and (b) is a kit, each housed in a different container.

[In general formula (I), R ¹ and R ² represent a hydrogen atom. R ³ to R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, 2 to carbon atoms A dialkylamino group of 20, a carboxy group, a cyano group, a fluorinated alkyl group of 1 to 10 carbon atoms, or a halogen atom is represented. Each of the three R ³ to R ⁵ may be the same as or different from each other. However, ^{among the three R 3} to R ⁵ , at least one is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.]

[11] The polyfunctional isocyanate is at least one selected from the group consisting of diphenylmethane diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, bis(isocyanatomethyl)cyclohexane, and modified polyisocyanates thereof. , The kit for producing polyisocyanurate according to any one of [6] to [10].

^{[12] R 3} to R ⁵ in the general formula (I) are each independently a hydrogen atom, an alkoxy group having 1 to 4 carbon atoms, a monoalkylamino group having 1 to 4 carbon atoms, or a dialkylamino group having 2 to 8 carbon atoms ( However, the kit for polyisocyanurate production according to any one of [6] to [11], wherein both of ^{R 1} and R ^{2 do not become hydrogen atoms.}

[13] A cured polyisocyanurate raw material obtained by heating the polyisocyanurate raw material composition according to any one of [1] to [5].

[14] polyisocyanurate,

At least one compound selected from the group consisting of compound (I) represented by the following general formula (I) and compound (I') represented by the following general formula (I')

Containing, polyisocyanurate raw material cured product.

[In general formulas (I) and (I'), R ¹ and R ² represent a hydrogen atom. R ³ to R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, 2 to carbon atoms A dialkylamino group of 20, a carboxy group, a cyano group, a fluorinated alkyl group of 1 to 10 carbon atoms, or a halogen atom is represented. Each of the three R ³ to R ⁵ may be the same as or different from each other. However, ^{at least one of the three R 3} to R ⁵ is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.]

[15] Further, (i) an epoxy compound, (ii) a reaction product of an epoxy compound and a polyfunctional isocyanate, (iii) a reaction product of an epoxy compound and the compound (I), and (iv) a reaction product of an epoxy compound and an epoxy compound The cured polyisocyanurate raw material according to [14], comprising at least one compound selected from the group consisting of.

^{[16] R 3} to R ⁵ in the general formulas (I) and (I′) are each independently a hydrogen atom, an alkoxy group having 1 to 4 carbon atoms, a monoalkylamino group having 1 to 4 carbon atoms, or 2 to 8 carbon atoms The cured polyisocyanurate raw material according to [14] or [15], which is a dialkylamino group of

[17] Polyisocyanu comprising a mixing step of mixing a polyfunctional isocyanate, a compound (I) represented by the following general formula (I), and an epoxy compound, and a heating step of heating the mixture obtained in the mixing step A method of making a lattice.

[In general formula (I), R ¹ and R ² represent a hydrogen atom. R ³ to R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, 2 to carbon atoms A dialkylamino group of 20, a carboxy group, a cyano group, a fluorinated alkyl group of 1 to 10 carbon atoms, or a halogen atom is represented. Each of the three R ³ to R ⁵ may be the same as or different from each other. However, ^{at least one of the three R 3} to R ⁵ is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.]

[18] The method for producing polyisocyanurate according to [17], wherein the mixing step is a step of mixing the epoxy compound with the mixture (d) of the polyfunctional isocyanate and the compound (I).

[19] The method for producing polyisocyanurate according to [17], wherein the mixing step is a step of mixing the compound (I) with the mixture (e) of the polyfunctional isocyanate and the epoxy compound.

[20] The polyi according to [17], wherein the mixing step is a step of mixing the mixture (e) of the polyfunctional isocyanate and the epoxy compound with the mixture (d) of the polyfunctional isocyanate and the compound (I). A method for producing socyanurate.

[21] In any one of [17] to [20], wherein the mixing ratio (molar ratio) of the compound (I) to the polyfunctional isocyanate is polyfunctional isocyanate/compound (I) = 100/0.001 to 100/5 A process for the preparation of the polyisocyanurates described.

[22] The polyfunctional isocyanate is at least one selected from the group consisting of diphenylmethane diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, bis(isocyanatomethyl)cyclohexane, and modified polyisocyanates thereof. , The method for producing polyisocyanurate according to any one of [17] to [21].

^{[23] R 3} to R ⁵ in the general formula (I) are each independently a hydrogen atom, an alkoxy group having 1 to 4 carbon atoms, a monoalkylamino group having 1 to 4 carbon atoms, or a dialkylamino group having 2 to 8 carbon atoms , The method for producing polyisocyanurate according to any one of [17] to [22].

[24] The method for producing polyisocyanurate according to any one of [17] to [23], wherein the heating step is performed at a temperature of 40 to 240°C.

[25] The method for producing polyisocyanurate according to [24], wherein the heating step is a step of heating at 60 to 120° C. for 1 to 180 minutes, and then further heating at 120 to 240° C. for 1 to 180 minutes.

[26] A catalyst for a polyisocyanurate production reaction, comprising a combination of a compound (I) represented by the following general formula (I) and an epoxy compound.

[In general formula (I), R ¹ and R ² represent a hydrogen atom. R ³ to R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, 2 to carbon atoms A dialkylamino group of 20, a carboxy group, a cyano group, a fluorinated alkyl group of 1 to 10 carbon atoms, or a halogen atom is represented. Each of the three R ³ to R ⁵ may be the same as or different from each other. However, ^{at least one of the three R 3} to R ⁵ is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.]

[27] A kit for producing polyisocyanurate, comprising a combination of a compound (I) represented by the following general formula (I) and an epoxy compound as a catalyst for a polyisocyanurate production reaction.

[In general formula (I), R ¹ and R ² represent a hydrogen atom. R ³ to R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, 2 to carbon atoms A dialkylamino group of 20, a carboxy group, a cyano group, a fluorinated alkyl group of 1 to 10 carbon atoms, or a halogen atom is represented. Each of the three R ³ to R ⁵ may be the same as or different from each other. However, ^{among the three R 3} to R ⁵ , at least one is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.]

Example

Hereinafter, the present invention will be described in more detail by way of Examples and Comparative Examples, but the present invention is not limited by these Examples at all.

[Production and evaluation of cured polyisocyanurate raw material]

(Reference Examples 1 to 32, Reference Comparative Examples 1 to 69)

A mixture (d) of a polyfunctional isocyanate and a catalyst (compound (I) or another catalyst) and a mixture (e) of a polyfunctional isocyanate and an epoxy compound were prepared. The mixture (d) and the mixture (e) were mixed to prepare a polyisocyanurate raw material composition. The compounding ratio (molar ratio) of the polyfunctional isocyanate, catalyst, and epoxy compound is according to each reference example and reference comparative example in Tables 1 to 11, and the polyisocyanurate raw material composition of Reference Examples 1 to 32 and Reference Comparative Examples 1 to 69. got it

<Evaluation of gel time>

The polyisocyanurate raw material compositions of Reference Examples 1 to 32 and Reference Comparative Examples 1 to 69 were placed in a glass container, and heated to 80° C. in an oil bath (EOS-200RD, Asone Corporation).

While maintaining the temperature at 80° C., it was checked whether gelation occurred every 30 minutes, and the time until gelation was measured. In addition, the presence or absence of fluidity|liquidity was visually evaluated for gelatinization, and it was judged that it gelled when fluidity|liquidity disappeared.

The results are shown in Tables 1 to 11. The evaluation criteria in a table|surface are as follows.

Evaluation standard

(circle): Gelatinization was confirmed in less than 360 minutes.

x: Even if 360 minutes or more passed, gelatinization was not confirmed.

<Evaluation of foaming>

The polyisocyanurate raw material compositions of Reference Examples 1 to 32 and Reference Comparative Examples 1 to 69 were put in an aluminum container, and heated to 80° C. for 180 minutes with a circulating thermostat (VTR-111, Isuzu Seisakusho Co., Ltd.) for polyisocyanurate. Socyanurate raw material hardened|cured material was produced. The produced cured product was observed with a microscope (RH-2000, Hyrox, Inc.), and the number of bubbles in an arbitrary 1 cm x 1 cm square was measured.

The results are shown in Tables 1 to 11. The evaluation criteria in a table|surface are as follows.

Evaluation standard

○: The number of bubbles is less than 10

×: the number of bubbles is 10 or more

-: Not subject to evaluation (Polyisocyanurate raw material cured product cannot be produced (not cured))

The abbreviations of the compounds in Tables 1 to 11 indicate the compounds shown in Table 12, respectively.

In Reference Examples 1 to 32, good results were shown for either gel time or foaming.

On the other hand, in Reference Comparative Examples 1 to 69, since the gel time was long, it did not cure within 360 minutes, and a cured polyisocyanurate raw material could not be obtained, or a large amount of foaming was observed even when a polyisocyanurate raw material cured product was obtained. Reference Comparative Examples 61 to 69 used compound (I) as a catalyst and did not use an epoxy compound, but the gel time was long and a cured polyisocyanurate raw material could not be obtained.

From these results, in Reference Examples 1 to 32, foaming at the time of thermosetting was suppressed, and it was confirmed that sclerosis|hardenability was favorable. In addition, from the results of Table 11 (Reference Comparative Examples 61 to 69), it was confirmed that an epoxy compound was required for the polyisocyanurate production reaction to proceed.

[Evaluation of phosphorus catalyst]

For phosphorus catalysts TMPP, DMPP, TOAP, TPP, TOTP, TPTP, TPAP, DPCP, TCHP, TOCP, DPPP, DPPST, quantum chemical calculations based on density functional method and B3LYP/6-31G* method were performed. The level of the HOMO reflecting the lone pair of electrons on the phosphorus atom was calculated. Structural formulas of the phosphorus catalysts are shown below. Table 13 shows the results of quantum chemical calculations.

Hexamethylene diisocyanate, catalysts (catalysts No. 1 to 11) and phenyl glycidyl ether were blended in a molar ratio of 100:0.1:5, and the results of evaluating the gel time by the above method are shown in Table 13 together. Catalysts No. 9 to 11 with good gel time had a HOMO level of -0.190a.u. It was more than that. Among them, Nos. 9 to 10, which have shorter gel times than phosphorus catalyst No. 11, also had a higher HOMO level than No. 11. On the other hand, phosphorus catalysts No. 1 to 8, which did not cure within 360 minutes due to a long gel time, had a lower HOMO level than -0.190a.u. Therefore, it was found that the level of HOMO is a first indicator for screening a catalyst for a reaction for producing polyisocyanurate having a high reaction rate.

Phosphorus catalyst No. 5 and phosphorus catalyst No. 11 are phosphorus catalysts in which a methoxy group as a substituent is bonded to the para-position and the ortho-position of the benzene ring, respectively. Although both of them had the same level of HOMO, a large difference was observed in the reaction time. To investigate the cause, a transition state calculation was performed based on the density functional theory B3LYP/6-31+G* method, and the phosphorus catalyst nucleophilic attacked 1,2-ethyloxirane (epoxy compound) as a promoter. Activation barriers were calculated when In order to consider the solvent effect, a continuum model (PCM) calculation was performed which introduced the dielectric constant and solvation radius of chlorobenzene. The activation energy of phosphorus catalyst No. 5 was 33.79 kcal/mol, whereas the activation energy of phosphorus catalyst No. 11 was 32.17 kcal/mol. Therefore, the phosphorus catalyst No. 11 was in agreement with the experimental results (see Tables 1 to 11 and Table 13) that the activation barrier was small compared to the phosphorus catalyst No. 5 and the reaction was easy to proceed.

As a result of observing the structures in the calculation of the transition state of the phosphorus catalyst No. 5 and the phosphorus catalyst No. 11, the hydrogen atom of 1,2-ethyloxirane and the oxygen atom at the para or ortho position of the phosphorus catalyst hydrogen bond , it was found that 1,2-oxirane was attracted by the phosphorus catalyst molecule, and as a result, the distance between the phosphorus atom as the reaction point and the carbon of 1,2-ethyloxirane was shortened. In addition, in order to three-dimensionally interact with 1,2-ethyloxirane and the phosphorus catalyst, the lower the degree of electrical positivity of the atom directly bonded to the ortho-position carbon close to the phosphorus atom, the easier it is to interact. I get it. In fact, when calculating the average value of the Mulliken charges of atoms directly bonding to the carbon at the ortho position of the phosphorus atom (the average charge at the ortho position), the average charge at the ortho position of the phosphorus catalyst No. 5 is 0.1435, whereas The average charge at the ortho position of the phosphorus catalyst No. 11 was -0.1805, and it was confirmed that the average charge of the phosphorus catalyst No. 11 was lower.

From the above, it was found that the low degree of electron positivity of the atom directly bonded to the carbon at the ortho position of the phosphorus atom serves as a second index for screening the catalyst for the reaction for producing polyisocyanurate having a high reaction rate.

Here, the "average charge at the ortho position" is an average value of the Mullken charge of atoms directly bonding to a carbon atom among atoms bonding to the ortho position of three cyclic molecules directly bonding to a phosphorus atom. For example, in the said phosphorus catalyst No. 1 (TPP), the hydrogen atom couple|bonded with the carbon atom on both sides of the carbon atom couple|bonded with a phosphorus atom corresponds to it. Since the benzene ring is bonded to 3 phosphorus atoms, there are 6 corresponding atoms. The average of the Mulliken charges of these six atoms is defined as "the average charge at the ortho position".

The average charges of ortho positions of the phosphorus catalysts Nos. 1 to 11 and DMAPDPP (the following structure) were calculated, and the results are shown in Table 14 together with the levels of HOMO.

For the phosphorus catalysts shown in Table 14 above, the HOMO level was set on the abscissa (x-axis) and the average charge at the ortho position on the ordinate (y-axis), a region in which a highly reactive phosphorus catalyst exists was searched for. The results are shown in FIG. 1 . In FIG. 1, the number attached|subjected to each plot shows the phosphorus catalyst No. shown in Table 14. As shown in FIG. 1, phosphorus catalysts (phosphorus catalysts used in Reference Examples 1 to 32; phosphorus catalysts Nos. 9 to 11: black circles) showing good curability in the evaluation test of the polyisocyanurate raw material composition were y It was found to be located in the region of <28.5x+5.644 (x: level of HOMO/au; y: average charge of ortho-position). Therefore, if it is a phosphorus catalyst which satisfies the conditions of following formula (1), polyisocyanurate formation reaction advances favorably, and it is thought that it can be used suitably as a catalyst of a polyisocyanurate formation reaction. DMAPDPP of phosphorus catalyst No. 12 also satisfy|fills the conditions of following formula (1), and it was estimated that it can be used suitably as a catalyst of polyisocyanurate production|generation reaction. In fact, in the same manner as in the phosphorus catalyst No. 5, the activation energy of the phosphorus catalyst was 33.74 kcal/mol when the activation barrier was calculated when the phosphorus catalyst nucleophilically attacked 1,2-ethyloxirane (epoxy compound) as the promoter.

y<28.5x+5.644 … (One)

x: level of HOMO/a.u.

y: average charge at ortho positions

In addition, when the activation energy of phosphorus catalyst No. 15 shown in Table 15 is calculated, it is 20.64 kcal/mol, and the phosphorus catalyst satisfying the condition of formula (1) has a small activation barrier when the phosphorus catalyst nucleophilic attack the promoter. It was found that the reaction tends to proceed. The phosphorus catalyst having at least one amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms at the meta position or para position is an electron donating group. increases, and a phosphorus catalyst satisfying the condition of formula (1) is obtained. Among them, a phosphorus catalyst having an activation energy of 32.17 kcal/mol or less is preferable because it can be expected to exhibit an activity equivalent to or higher than that of phosphorus catalyst No. 11.

For other phosphorus catalysts, the average charge of the HOMO level and ortho position was calculated, and phosphorus catalysts satisfying the conditions of Equation (1) were searched for. As a result, phosphorus catalysts of phosphorus catalysts Nos. 13 to 59 shown in Tables 15 to 16 were found as phosphorus catalysts satisfying the conditions of formula (1). In Table 15 to 16, R ¹ to R ^5, R ¹¹ to R ^15, and R ²¹ to R ²⁵ is represented by the following general formula of R ¹ to R ^5, R ¹¹ to R ^15, and represented by R ²¹ to R ²⁵ Each substituent is represented, "H" represents a hydrogen atom, "OMe" represents a methoxy group, "NHMe" represents a monomethylamino group, and "NMe2" represents a dimethylamino group.

From the above, it is thought that, similarly to the phosphorus catalysts Nos. 9 to 11 used in Reference Examples 1 to 32, the phosphorus catalysts of the phosphorus catalysts Nos. 12 to 59 can also be suitably used as a catalyst for the polyisocyanurate production reaction. .

According to the present invention, there is provided a method for producing polyisocyanurate with little foaming and good curability during thermosetting, a polyisocyanurate raw material composition usable in the production method, and a kit for producing polyisocyanurate. In addition, there is provided a polyisocyanurate or polyisocyanurate composition with low foaming produced by the above production method. The polyisocyanurate or the cured polyisocyanurate raw material can be used for various applications such as paints, adhesives, sealing materials, and various molded articles.

Claims (16)

A polyisocyanurate raw material composition comprising a polyfunctional isocyanate, a compound (I) represented by the following general formula (I), and an epoxy compound.

[In general formula (I), R ¹ and R ² represent a hydrogen atom. R ³ to R ⁵ each independently represent a hydrogen atom, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms. Each of the three R ³ to R ⁵ may be the same as or different from each other. However, ^{at least one of the three R 3} to R ⁵ is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.] The polyisocyanurate raw material composition according to claim 1, wherein the ratio (molar ratio) of the compound (I) to the polyfunctional isocyanate is polyfunctional isocyanate/compound (I)=100/0.001 to 100/5. The polyfunctional isocyanate according to claim 1 or 2, wherein the polyfunctional isocyanate is diphenylmethane diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, bis(isocyanatomethyl)cyclohexane, and modified polyisocyanates thereof. At least one selected from the group, polyisocyanurate raw material composition. A kit for preparing polyisocyanurate comprising (a) polyfunctional isocyanate, (b) a compound represented by the following general formula (I), and (c) an epoxy compound, wherein (a) to (c) are different containers housed in the kit.

[In general formula (I), R ¹ and R ² represent a hydrogen atom. R ³ to R ⁵ each independently represent a hydrogen atom, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms. Each of the three R ³ to R ⁵ may be the same as or different from each other. However, ^{at least one of the three R 3} to R ⁵ is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.] (d) a composition comprising a polyfunctional isocyanate and a compound (I) represented by the following general formula (I), and (c) a kit for preparing polyisocyanurate comprising an epoxy compound, wherein (d) and (c) Each is housed in a separate container, the kit.

[In general formula (I), R ¹ and R ² represent a hydrogen atom. R ³ to R ⁵ each independently represent a hydrogen atom, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms. Each of the three R ³ to R ⁵ may be the same as or different from each other. However, ^{at least one of the three R 3} to R ⁵ is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.] (d) a polyisocyanurate preparation kit comprising a composition comprising a polyfunctional isocyanate and a compound (I) represented by the following general formula (I), and (e) a composition comprising a polyfunctional isocyanate and an epoxy compound, The (d) and (e) are each accommodated in a different container, the kit.

[In general formula (I), R ¹ and R ² represent a hydrogen atom. R ³ to R ⁵ each independently represent a hydrogen atom, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms. Each of the three R ³ to R ⁵ may be the same as or different from each other. However, ^{at least one of the three R 3} to R ⁵ is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.] (e) a composition comprising a polyfunctional isocyanate and an epoxy compound, and (b) a kit for preparing polyisocyanurate comprising a compound (I) represented by the following general formula (I), wherein (e) and (b) Each is housed in a separate container, the kit.

[In general formula (I), R ¹ and R ² represent a hydrogen atom. R ³ to R ⁵ each independently represent a hydrogen atom, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms. Each of the three R ³ to R ⁵ may be the same as or different from each other. However, ^{at least one of the three R 3} to R ⁵ is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.] A cured polyisocyanurate raw material obtained by heating the polyisocyanurate raw material composition according to any one of claims 1 to 3. a polyisocyanurate produced from a polyfunctional isocyanate;
Compound (I) represented by the following general formula (I), or a compound (I) represented by the following general formula (I) and a compound (I') represented by the following general formula (I');
epoxy compound
Containing, polyisocyanurate raw material cured product.

[In general formula (I) or (I'), R ¹ and R ² represent a hydrogen atom. R ³ to R ⁵ each independently represent a hydrogen atom, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms. Each of the three R ³ to R ⁵ may be the same as or different from each other. However, ^{among the three R 3} to R ⁵ , at least one is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.] Polyfunctional isocyanate, compound (I) represented by the following general formula (I), and a mixing step of mixing an epoxy compound, and a heating step of heating the mixture obtained in the mixing step, polyisocyanurate production Way.

[In general formula (I), R ¹ and R ² represent a hydrogen atom. R ³ to R ⁵ each independently represent a hydrogen atom, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms. Each of the three R ³ to R ⁵ may be the same as or different from each other. However, ^{among the three R 3} to R ⁵ , at least one is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.] The method for producing polyisocyanurate according to claim 10, wherein the mixing step is a step of mixing the epoxy compound with the mixture (d) of the polyfunctional isocyanate and the compound (I). The method for producing polyisocyanurate according to claim 10, wherein the mixing step is a step of mixing the compound (I) with the mixture (e) of the polyfunctional isocyanate and the epoxy compound. The method for producing polyisocyanurate according to any one of claims 10 to 12, wherein the heating step is performed at a temperature of 40 to 240°C. The method for producing polyisocyanurate according to claim 13, wherein the heating step is a step of heating at 60 to 120° C. for 1 to 180 minutes, and then further heating at 120 to 240° C. for 1 to 180 minutes. A catalyst for a production reaction for producing polyisocyanurate from polyfunctional isocyanate, comprising a combination of a compound (I) represented by the following general formula (I) and an epoxy compound.

[In general formula (I), R ¹ and R ² represent a hydrogen atom. R ³ to R ⁵ each independently represent a hydrogen atom, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms. Each of the three R ³ to R ⁵ may be the same as or different from each other. However, ^{at least one of the three R 3} to R ⁵ is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.] A kit for producing polyisocyanurate, comprising a combination of a compound (I) represented by the following general formula (I) and an epoxy compound as a catalyst for a reaction for producing polyisocyanurate from polyfunctional isocyanate.

[In general formula (I), R ¹ and R ² represent a hydrogen atom. R ³ to R ⁵ each independently represent a hydrogen atom, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms. Each of the three R ³ to R ⁵ may be the same as or different from each other. However, ^{at least one of the three R 3} to R ⁵ is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.]

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