JP2009203398A - Two-component urethane resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a two-component urethane resin composition which has practical usable time, cures at a high reaction rate, generates no foam, and can yield a cured product having excellent toughness. <P>SOLUTION: The two-component urethane resin composition includes (A) an isocyanate compound represented by formula (1) (wherein R<SB>1</SB>represents a polyvalent organic group, and s represents an integer of ≥2), (B) a compound having a plurality of isocyanate-reactive groups, and (C) a salt of an acidic phosphoric ester represented by formula (2) (wherein R<SB>2</SB>represents an organic group, and t represents 1 or 2) and an amine compound. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a two-component urethane resin composition that has a practical pot life, is cured at a high reaction rate, is free from bubbles, and can provide a cured product having excellent toughness. This two-component urethane resin composition is useful as various treatment agents (adhesives, coating agents, etc.).

  Conventionally, when a urethane resin composition is cured quickly, a metal catalyst typified by a tin-based catalyst has been often used (see Patent Document 1). Such a catalyst needs to be used in a large amount in order to develop desired physical properties (for example, toughness) in the cured product. However, when used in a large amount, the physical properties of the cured product are remarkably deteriorated over time, so that the long-term durability is poor and the amount that can be used is limited. And since the usage-amount is limited, it was a problem that the quantity of a catalyst required in order to complete reaction cannot be used, and the hardened | cured material which has a desired physical property cannot be obtained. On the other hand, an amine-based catalyst is known as a catalyst that does not cause deterioration of physical properties over time by using a sufficient amount of the catalyst (see Patent Document 1). However, when an amine-based catalyst is used, there is a problem that a large amount of bubbles are generated in the cured product regardless of the amount used.

  Thus, when a conventionally used catalyst is used as a curing catalyst, the amount of catalyst that can be used is limited, and it is difficult to obtain desired physical properties. In particular, it is very difficult to balance the pot life and curability (reaction rate). When trying to complete the curing reaction, the pot life is short and it is difficult to put to practical use. On the other hand, if priority is given to extending the pot life, the reaction rate tends to decrease, and it is difficult to obtain desired physical properties. That is, the present condition is that the two-pack type urethane resin composition which is excellent in all of quick-curing property, pot life, and the physical property of hardened | cured material has not been found.

Japanese Unexamined Patent Publication No. 1-111179

  Accordingly, the object of the present invention is to obtain a cured product having excellent toughness that is cured at a high reaction rate while having a practical pot life, and the generation of bubbles is remarkably suppressed. The object is to provide a liquid urethane resin composition.

  As a result of intensive studies to solve the above problems, the present inventors have used the “salt of an acidic phosphate ester and an amine compound” as a curing catalyst, while extending the pot life within a practical range. The present inventors have found that a cured product having excellent toughness can be obtained in which the amount of bubbles generated in the cured product is remarkably suppressed by curing at a high reaction rate. The present invention has been completed based on these findings and further research.

（式中、Ｒ₁は多価の有機基、ｓは２以上の整数を示す）
で表されるイソシアネート化合物（Ａ）と、複数のイソシアネート反応性基を有する化合物（Ｂ）と、下記式（２）

（式中、Ｒ²は有機基を示し、ｔは１又は２を示す）
で表される酸性リン酸エステルとアミン化合物との塩（Ｃ）からなる２液型ウレタン樹脂組成物を提供する。 That is, the present invention provides the following formula (1):

(Wherein R ₁ represents a polyvalent organic group, and s represents an integer of 2 or more)
The compound (B) having a plurality of isocyanate-reactive groups, the following formula (2)

(Wherein R ² represents an organic group, and t represents 1 or 2)
A two-component urethane resin composition comprising a salt (C) of an acidic phosphate ester and an amine compound represented by the formula:

（式中、Ａｒは芳香族環式基を示す。ｓは上記に同じ）
で表される芳香族ポリイソシアネート化合物が好ましく、なかでも、下記式（４）

（式中、Ｒ³は多価の有機基を示す。ｓは上記に同じ）
で表されるポリフェニルイソシアネート化合物が好ましく、特に、ポリイソシアネート化合物とポリオール化合物から得られる、末端にイソシアネート基を２個以上有するウレタンプレポリマーが好ましい。 As an isocyanate compound (A), following formula (3)

(In the formula, Ar represents an aromatic cyclic group. S is the same as above.)
Of the polyisocyanate compound represented by the following formula (4):

(Wherein R ³ represents a polyvalent organic group, s is the same as above)
The urethane prepolymer which has two or more isocyanate groups at the terminal obtained from a polyisocyanate compound and a polyol compound is particularly preferable.

（式中、Ｒ⁴は多価の有機基を示し、ｕは２以上の整数を示す）
で表されるポリオール化合物（Ｂ１）が好ましく、なかでも、下記式（５）

（式中、Ｒ⁴は多価の有機基を示し、ｕは２以上の整数を示す）
で表されるポリオール化合物（Ｂ１）及び下記式（６）

（式中、Ｒ⁵は多価の有機基を示し、Ｒ⁶、Ｒ⁷は、同一又は異なって水素原子又は有機基を示し、Ｒ⁸は有機基を示し、ｖは２以上の整数を示す。Ｒ⁶、Ｒ⁷、Ｒ⁸のうち少なくとも２つの基は互いに結合して、隣接する１又は２個の炭素原子とともに環を形成していてもよい）
で表されるケチミン化合物（Ｂ２）が好ましい。 As the compound (B) having a plurality of isocyanate-reactive groups, the following formula (5)

(Wherein R ⁴ represents a polyvalent organic group, and u represents an integer of 2 or more)
A polyol compound (B1) represented by formula (5) is preferable.

(Wherein R ⁴ represents a polyvalent organic group, and u represents an integer of 2 or more)
A polyol compound (B1) represented by the following formula (6)

(Wherein R ⁵ represents a polyvalent organic group, R ⁶ and R ⁷ are the same or different and represent a hydrogen atom or an organic group, R ⁸ represents an organic group, and v represents an integer of 2 or more. At least two of R ⁶ , R ⁷ and R ⁸ may be bonded to each other to form a ring together with adjacent 1 or 2 carbon atoms)
The ketimine compound (B2) represented by these is preferable.

  As the polyol compound (B1), a polyol compound having no polypropylene glycol skeleton is preferable.

  The ketimine compound (B2) is preferably a ketimine compound obtained by reacting an amine with diethyl ketone.

  As the salt (C) of the acidic phosphate ester and the amine compound, a salt obtained by reacting the acidic phosphate ester and the amine compound in a ratio of 1: 1 to 1: 0.2 (molar ratio) is preferable.

  If a sufficient amount of a conventional catalyst, for example, a tin-based catalyst, is used for the urethane resin composition to complete the curing reaction, the physical properties such as durability will deteriorate over time. It was. In addition, when an amine-based catalyst is used, foaming occurs with the curing reaction regardless of the amount added, and thus it is difficult to improve the physical properties of the cured product. On the other hand, in the two-pack type urethane resin composition of the present invention, the salt (C) of an acidic phosphate ester and an amine compound is used as a curing catalyst, and it is not necessary to use an amine-based catalyst. In the hardened | cured material obtained by hardening | curing a urethane resin composition, the problem of the bubble generation | occurrence | production caused by an amine catalyst was able to be solved. In addition, the salt (C) of an acidic phosphate ester and an amine compound does not deteriorate in physical properties over time even when a sufficient amount of catalyst is used to complete the curing reaction. It can be smoothly promoted and completed. Therefore, the curing reaction is performed at a high reaction rate, the final strength can be reached, and a cured product having excellent toughness can be obtained. Furthermore, as the compound (B) having a plurality of isocyanate-reactive groups, the pot life and reaction rate can be adjusted by selecting and using a predetermined compound from the viewpoint of reactivity with the isocyanate compound (A). it can. In the present invention, the final strength means the strength of the cured product in a state where the reaction is completed.

  The two-component urethane resin composition according to the present invention comprises an isocyanate compound (A), a compound (B) having a plurality of isocyanate-reactive groups, and a salt (C) of an acidic phosphate ester and an amine compound. .

[Isocyanate compound (A)]
The isocyanate compound (A) in the present invention is represented by the above formula (1). In the formula, R ¹ represents a polyvalent organic group, and s represents an integer of 2 or more.

The polyvalent organic group in R ¹ includes a polyvalent hydrocarbon group, a polyvalent heterocyclic group, a group in which two or more of these are bonded via or without a linking group. The carbon number of the organic group in R ^1, for example, 1 to 30, preferably 6 to 15. Examples of the linking group include an ether bond (—O—), a thioether bond (—S—), an amine bond (—NR′—), a carbonyl bond (—C (═O) —), and an ester bond (—C). (= O) -O-), carbonate bond, amide bond, urea bond, urethane bond and the like. R ′ represents an alkyl group.

  The polyvalent hydrocarbon group includes a polyvalent aliphatic hydrocarbon group, a polyvalent alicyclic hydrocarbon group, a polyvalent aromatic hydrocarbon group, and these polyvalent hydrocarbon groups. And polyvalent groups (sometimes referred to as “multivalent complex hydrocarbon groups”). As the polyvalent aliphatic hydrocarbon group, a divalent aliphatic hydrocarbon group such as an alkylene group can be used. Examples of the alkylene group include a linear alkylene group such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group, as well as an alkylene group having a branched chain or a substituent (for example, Propylene group, etc.).

The polyvalent alicyclic hydrocarbon group may be a polyvalent alicyclic hydrocarbon group having a monocyclic hydrocarbon ring, or a polyvalent alicyclic carbon group having a polycyclic hydrocarbon ring. It may be a hydrogen group. Examples of the monocyclic hydrocarbon ring include a cycloalkane ring having about 5 to 10 carbon atoms constituting a ring such as a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, and a cyclooctane ring. Moreover, as a polycyclic hydrocarbon ring, a bridged ring etc. are mentioned, for example. Examples of the bridge ring include a bicyclic hydrocarbon ring (for example, carbonization in pinane, pinene, bornane, norbornane, norbornene, bicyclo [3.2.1] octane, bicyclo [4.3.2] undecane, etc. Hydrogen rings, etc.), tricyclic hydrocarbon rings (eg adamantane, exotricyclo [5.2.1.0 ^2,6 ] decane, endotricyclo [5.2.1.0 ^2,6 ] decane, etc.) such as a hydrocarbon ring), tetracyclic hydrocarbon rings (e.g., such as a hydrocarbon ring in such tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecane), and others in.

  Specifically, examples of the divalent alicyclic hydrocarbon group having a cyclohexane ring include cycloalkylene such as 1,2-cyclohexylene group, 1,3-cyclohexylene group, and 1,4-cyclohexylene group. Groups. Examples of the divalent alicyclic hydrocarbon group having a norbornane ring include norbornane-diyl groups such as norbornane-2,3-diyl, norbornane-2,5-diyl and norbornane-2,6-diyl. Is mentioned.

  As the polyvalent aromatic hydrocarbon group, a divalent aromatic hydrocarbon group such as an arylene group can be used. As the arylene group, for example, a divalent aromatic hydrocarbon group having a benzene ring such as a phenylene group (for example, a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, etc.) And divalent aromatic hydrocarbon groups having a naphthalene ring such as a naphthylene group. In addition, as an aromatic ring in a polyvalent aromatic hydrocarbon group, in addition to a benzene ring and a naphthalene ring, 2 to 10 4 to 7-membered carbon rings such as azulene, indacene, anthracene, phenanthrene, triphenylene, and pyrene And a condensed carbocycle in which is condensed.

  Furthermore, examples of the polyvalent group (multivalent complex hydrocarbon group) in which these polyvalent hydrocarbon groups are combined include, for example, a divalent aliphatic hydrocarbon group (such as an alkylene group), a monocyclic group, and the like. A divalent alicyclic hydrocarbon group having a hydrocarbon ring or a polycyclic hydrocarbon ring (such as a cycloalkylene group or a norbornane-diyl group), a benzene ring or a divalent aromatic hydrocarbon group having a condensed carbocycle ( A divalent group (a divalent complex hydrocarbon group) in which a phenylene group, a naphthylene group, and the like) are appropriately combined. Examples of the divalent composite hydrocarbon group include a divalent composite hydrocarbon group in which an aliphatic hydrocarbon group such as an alkylene-phenylene group or an alkylene-phenylene-alkylene group and an aromatic hydrocarbon group are combined; alkylene -A divalent combination of an aliphatic hydrocarbon group such as a cycloalkylene group, an alkylene-cycloalkylene-alkylene group, an alkylene-norbornane-diyl group, an alkylene-norbornane-diyl-alkylene group, and an alicyclic hydrocarbon group. Examples include complex hydrocarbon groups. In the group in which these polyvalent complex hydrocarbon groups are combined, the alkylene moiety, phenylene moiety, cycloalkylene moiety, and norbornane-diyl moiety include the above-exemplified alkylene group, phenylene group, cycloalkylene group, norbornane-diyl group. Etc. can be used.

  Specifically, examples of the multivalent complex hydrocarbon group include a methylene-1,3-phenylene-methylene (m-xylylene) group, a methylene-1,3-cyclohexylene-methylene group, and a methylene-norbornane-2. , 5-diyl-methylene group, methylene-norbornane-2,6-diyl-methylene group, and in these groups, the methylene moiety is another alkylene moiety (eg, ethylene moiety, trimethylene moiety, propylene moiety, etc.). Groups and the like.

  The polyvalent heterocyclic group includes a monocyclic or polycyclic aromatic or non-aromatic heterocyclic ring containing at least one heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom. And a polyvalent heterocyclic group having a carbon atom at the binding site with the nitrogen atom shown in the formula.

  The above polyvalent hydrocarbon group or heterocyclic group may have a substituent (for example, a hydrocarbon group), and the substituent is reactive with an amine-reactive compound such as an epoxy resin. It is important not to have

The polyvalent organic group in R ¹ is preferably a polyvalent hydrocarbon group, and in particular, a polyvalent aromatic hydrocarbon group, a divalent combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group. These complex hydrocarbon groups are preferred.

  Moreover, s in the formula (1) represents an integer of 2 or more. That is, the isocyanate compound (A) is a polyvalent isocyanate compound. Although it will not restrict | limit especially if it is an integer greater than or equal to 2 as s, For example, it can select from the integer of 2-10 (preferably 2-6, More preferably, it is 2-4, Most preferably, it is 2). In addition, it is preferable that two or more isocyanate groups have an asymmetric reactivity because the reactivity can be improved.

  As the isocyanate compound (A) in the present invention, the aromatic polyisocyanate compound represented by the above formula (3) is a compound (B) having a plurality of isocyanate reactive groups (for example, a polyol compound (B1) or a ketimine compound). It is preferable in that it has a high reactivity with respect to (B2) enamine, which is an isomer of (B2), can exhibit fast curability, and can be cured at a high reaction rate. In the formula (3), Ar represents an aromatic cyclic group. s is the same as above.

  Examples of the aromatic hydrocarbon ring constituting the aromatic cyclic group in Ar include, for example, about 1 to 10 aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, a phenanthrene ring, an anthracene ring, and a naphthacene ring, or these Are groups bonded via or without a linking group. Among these, 1 to 5 aromatic hydrocarbon rings, particularly a benzene ring and a naphthalene ring are preferable. Ar may have a substituent, and examples of the substituent that Ar may have include an organic group (for example, a hydrocarbon group, a heterocyclic group, or a group in which two or more of these are bonded). Is mentioned.

  Examples of the hydrocarbon group as a substituent include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Examples of the aliphatic hydrocarbon group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, s-butyl group, n-pentyl group, 2-methylbutyl group, 3- Methylbutyl group, 2,2-dimethylpropyl group, hexyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3, Examples thereof include alkyl groups having about 1 to 20 carbon atoms such as 3-dimethylbutyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, dodecyl group, and octadecyl group. The alkyl group is preferably an alkyl group having 2 or more (for example, 2 to 6) carbon atoms, and more preferably an alkyl group having 2 to 4 carbon atoms.

  Examples of the alicyclic hydrocarbon group include a cycloalkyl group having about 5 to 10 carbon atoms constituting a ring such as a cyclohexyl group, and a polycyclic hydrocarbon ring (for example, a hydrocarbon ring in norbornane). Group having a bridged ring, etc.).

  As an aromatic hydrocarbon group, aryl groups, such as a phenyl group and a naphthyl group, etc. are mentioned, for example. Examples of the aromatic ring in the aromatic hydrocarbon group include a benzene ring and a condensed carbocyclic ring (for example, a condensed carbocyclic ring in which 2 to 10 4 to 7-membered carbocyclic rings such as a naphthalene ring are condensed). .

  The heterocyclic group as a substituent is a monocyclic or polycyclic aromatic or non-aromatic heterocycle containing at least one heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom. A heterocyclic group having a ring and having a carbon atom at the bonding site with the nitrogen atom shown in the formula can be given.

  The hydrocarbon group or heterocyclic group may have a substituent (for example, a hydrocarbon group), and the substituent has reactivity with an amine-reactive compound such as an epoxy resin. It is important not to.

  Examples of the aromatic polyisocyanate compound represented by the formula (3) include m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate, and 2,6. -Tolylene diisocyanate, naphthylene-1,4-diisocyanate, naphthylene-1,5-diisocyanate, 4,4'-diphenyl diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), polymeric MDI, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2 ' -Diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylproparate Diisocyanate, 3,3′-dimethoxydiphenyl-4,4′-diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, ω, ω′-diisocyanate 1,4-diethylbenzene, 1,3-bis (1-isocyanate-1-methylethyl) benzene, 1,4-bis (1-isocyanate-1-methylethyl) benzene, 1,3-bis (α, α- Dimethyl isocyanate methyl) benzene, and the like.

As the isocyanate compound (A) in the present invention, a polyphenyl isocyanate compound represented by the above formula (4) is particularly preferable. In formula (4), R ³ represents a polyvalent organic group. s is the same as above. Examples of the polyvalent organic group for R ³ include the same examples as those for R ¹ . Examples of the polyphenyl isocyanate compound represented by the formula (4) include 4,4′-diphenyl diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), polymeric MDI, 2,4 '-Diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate, etc. Can be mentioned.

The isocyanate compound (A) in the present invention is particularly preferably a urethane prepolymer having two or more isocyanate groups at the terminal, obtained from a polyisocyanate compound and a polyol compound. The polyisocyanate compound used as a raw material for the urethane prepolymer is represented by the above formula (1), in which R ¹ is a polyvalent aliphatic hydrocarbon group, a polyvalent alicyclic hydrocarbon group, a polyvalent In addition to the aromatic hydrocarbon group, an isocyanate compound which is a polyvalent complex hydrocarbon group can be mentioned. Among them, the aromatic polyisocyanate compound represented by the above formula (3) is preferable, and in particular, the above formula ( The polyphenyl isocyanate compound represented by 4) is preferred. When a urethane prepolymer having two or more isocyanate groups at the terminal is used as the isocyanate compound (A), the isocyanate compound (A), the compound (B) having a plurality of isocyanate-reactive groups, an acidic phosphate ester, and an amine compound The blending ratio of the salt (C) can be easily adjusted, and the curing rate can be easily adjusted.

  Examples of the polyisocyanate compound used as a raw material for the urethane prepolymer include dimers, trimers, reaction products or polymers of the isocyanate compounds listed in the above examples (for example, diphenylmethane diisocyanate dimers and trimers). Body, a reaction product of trimethylolpropane and tolylene diisocyanate, etc.) can also be used.

  As a polyol compound used as a raw material of a urethane prepolymer, a well-known and usual polyol compound can be used without being specifically limited. Preferred polyol compounds include at least one polyol compound selected from the group consisting of polyether polyols, polyester polyols, polyolefin polyols, and polycarbonate polyols.

  As the polyol compound used as a raw material for the urethane prepolymer, a polyol compound having no polypropylene glycol skeleton is preferable. When a polypropylene glycol is synthesized, a base catalyst is used. However, when the base catalyst remains in a polyol having a polypropylene glycol skeleton and a polyol compound having a polypropylene glycol skeleton is used as a raw material for a urethane prepolymer, a two-component type is used. Air bubbles are generated in the cured product obtained by curing the urethane resin composition, and the physical properties of the cured product tend to be reduced.

  As a polyol compound used as a raw material of the urethane prepolymer in the present invention, for example, a castor oil-based polyol can be used as a polyol compound having no polypropylene glycol skeleton. Castor oil-based polyols include castor oil, linear or branched polyester of castor oil fatty acid and polyol (low molecular polyol and / or polyether polyol), for example, diglyceride, monoglyceride of castor oil fatty acid, castor oil fatty acid and tri Mono-, di-, or triesters with methylolpropane can be used.

  In addition, as said low molecular weight polyol, for example, ethylene glycol, diethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, Hydrogenated bisphenol A, which is divalent and has a carboxyl group, such as dimethylolbutanoic acid, dimethylolpropanoic acid, etc., trivalent or higher (3-8 valent), such as glycerin, trimethylolpropane Hexanetriol, pentaerythritol, sorbitol and the like.

  As a weight average molecular weight of a polyol compound, it is 500-10000, for example, Preferably, it is 1000-5000. When the weight average molecular weight of the polyol compound is less than 500, the effect of imparting flexibility tends to be low, and the viscosity tends to increase. On the other hand, when it exceeds 10,000, it is necessary to add a large amount of catalyst to the prepolymer synthesis, and the physical properties tend to decrease.

  A polyol compound can be used individually or in combination of 2 or more types.

  The reaction method of the polyol compound used as the raw material of the urethane prepolymer and the polyisocyanate compound is not particularly limited, and a known method can be employed. For example, a urethane prepolymer having two or more isocyanate groups at the molecular chain terminals can be obtained by mixing a polyol compound and a polyisocyanate compound in a solvent or without a solvent.

  In the reaction, a polymerization catalyst can be used. As a polymerization catalyst, the well-known and usual polymerization catalyst (curing catalyst) used when making a polyol compound and a polyisocyanate compound react can be used. More specifically, examples of the polymerization catalyst include organic tin compounds, metal complexes, basic compounds such as amine compounds, organic acids, and organic phosphoric acid compounds.

  The molar ratio of the two components when the polyisocyanate compound and the polyol compound are reacted is, for example, 1.2 or more, preferably 1.5 or more, more preferably 2.0 or more as NCO / OH (molar ratio). is there. When NCO / OH (molar ratio) is less than 1.2, the molecular weight of the urethane prepolymer is increased, so that gelation or high viscosity is easily achieved. The reaction temperature is, for example, 5 to 100 ° C, preferably 60 to 85 ° C.

  The isocyanate group (NCO) content in the urethane prepolymer is, for example, about 0.3 to 50% by mass, and preferably about 0.3 to 40% by mass.

[Compound (B) having a plurality of isocyanate-reactive groups]
The compound (B) having a plurality of isocyanate-reactive groups may be a compound having two or more groups having reactivity with isocyanate groups. Examples of the compound having a plurality of isocyanate-reactive groups include polyols Examples include compounds, ketimine compounds, primary amines, secondary amines, thiols and the like. As the compound (B) having a plurality of isocyanate-reactive groups in the present invention, it is particularly preferable to use the polyol compound (B1) represented by the above formula (5). When the polyol compound (B1) is used as the compound (B) having a plurality of isocyanate-reactive groups, the reaction with the isocyanate compound (A) is remarkably caused by the salt (C) of the acidic phosphate ester and amine compound used as the catalyst. Since it is accelerated | stimulated, the toughness which was excellent in the hardened | cured material obtained can be provided.

(Polyol compound (B1))
The polyol compound (B1) as the compound (B) having a plurality of isocyanate-reactive groups in the present invention is represented by the above formula (5). In formula (5), R ⁴ represents a polyvalent organic group, and u represents an integer of 2 or more.

The number of carbon atoms of the polyvalent organic group for R ^4, for example, 1 to 800, preferably from 40 to 400. The polyvalent organic group in R ⁴ may have a hetero atom, and examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom. As the polyvalent hydrocarbon group, a saturated or unsaturated linear or branched polyvalent aliphatic hydrocarbon group (an alkylene group, an alkenylene group, an alkanetriyl group, an alkenetriyl group, etc.), Multivalent alicyclic hydrocarbon group (1,2-cyclopentylene group, 1,3-cyclopentylene group, 1,2-cyclohexylene group, 1,3-cyclohexylene group, 1,4-cyclohexylene A cycloalkylene group such as a cyclohexylidene group; a cycloalkylidene group such as a cyclohexylidene group; a multivalent bridge such as a norbornane-2,3-diyl group, norbornane-2,5-diyl group, norbornane-2,6-diyl group Cyclic hydrocarbon groups), polyvalent aromatic hydrocarbon groups (arylene groups such as phenylene groups such as 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, etc.), It includes polyvalent hydrocarbon groups bonded above.

  The u is not particularly limited as long as u is an integer of 2 or more, but is preferably 2 to 6, more preferably 2 to 4, and particularly preferably 2.

  The polyol compound (B1) is preferably at least one polyol compound selected from the group consisting of polyether polyols, polyester polyols, polyolefin polyols, and polycarbonate polyols.

  As the polyol compound (B1) in the present invention, a polyol compound having no polypropylene glycol skeleton is preferable. When a polypropylene glycol skeleton is synthesized, a base catalyst is used. However, when the base catalyst remains in a polyol compound having a polypropylene glycol skeleton and the polyol compound having a polypropylene glycol skeleton is used as the polyol compound (B1), 2 Air bubbles are generated in the cured product obtained by curing the liquid urethane resin composition, and the physical properties of the cured product tend to be reduced.

  Further, as the polyol compound (B1) in the present invention, a polyol compound having two or more hydroxyl groups having different reactivities can increase the reaction rate more rapidly and reach the final strength more quickly. It is preferable in that it can be performed.

  As the polyol compound (B1) in the present invention, for example, polytetramethylene glycol, castor oil-based polyol, and the like can be used. Among them, castor oil-based polyol has high reactivity and hardly absorbs water. It is preferable in that it is difficult to foam. Examples of the castor oil-based polyol include the same examples as those of the castor oil-based polyol cited as the raw material for the urethane prepolymer.

  The weight average molecular weight of a polyol compound (B1) is 50-10000, for example, Preferably, it is 500-5000. If this average molecular weight is less than 50, the curing rate tends to be too high and the pot life tends to be too short. On the other hand, when the weight average molecular weight exceeds 10,000, the curing rate tends to be too slow, and the curing tends to take a long time. A polyol compound (B1) can be used individually or in combination of 2 or more types.

  Moreover, it is preferable to use a ketimine compound (B2) with a polyol compound (B1) as a compound (B) which has a some isocyanate reactive group in this invention. When the polyol compound (B1) and the ketimine compound (B2) are used in combination, the curing rate can be accelerated and the final strength can be reached more quickly.

(Ketimine compound (B2))
The ketimine compound (B2) as the compound (B) having a plurality of isocyanate reactive groups in the present invention is represented by the above formula (6). In formula (6), R ⁵ represents a polyvalent organic group, R ⁶ and R ⁷ are the same or different and each represents a hydrogen atom or an organic group, R ⁸ represents an organic group, and v is an integer of 2 or more. Indicates. At least two groups out of R ⁶ , R ⁷ and R ⁸ may be bonded to each other to form a ring with adjacent 1 or 2 carbon atoms.

  In the urethane resin composition according to the present invention, when the ketimine compound (B2) is used as the compound (B) having a plurality of isocyanate-reactive groups, the primary amine obtained by hydrolysis of the ketimine compound (B2) is an isocyanate compound. Since the enamine compound, which is an isomer of the ketimine compound (B2), reacts with the isocyanate compound (A) earlier than the reaction with (A), it can exhibit fast curability.

The number of carbon atoms of the multivalent organic group in R ^5, for example, 1 to 1000, preferably 6-100. The number of carbon atoms of the organic group of R ^6, R ^7, for example, 1 to 6, preferably 1 to 3. The number of carbon atoms of the organic groups in R ^8, for example, 1-6, preferably 2-3.

（式中、Ｒ⁵、ｖは上記に同じ）
で表される１級アミン化合物と、下記式（８）

（式中、Ｒ⁶、Ｒ⁷、Ｒ⁸は上記に同じ。Ｒ⁶、Ｒ⁷、Ｒ⁸のうち少なくとも２つの基は互いに結合して、隣接する１又は２個の炭素原子とともに環を形成していてもよい）
で表されるケトン化合物とを反応させて得ることができ、前記１級アミン化合物のケチミン化率が８０％以上であることが好ましい。ケチミン化率が８０％を下回ると、ケチミン化合物の異性体であるエナミン化合物や水酸基よりイソシアネート基に対する反応性が高い１級アミンが多く残存するため、可使時間が短くなり過ぎる傾向がある。 The ketimine compound (B2) of the present invention has the following formula (7)

(Wherein R ⁵ and v are the same as above)
A primary amine compound represented by formula (8):

(Wherein R ⁶ , R ⁷ and R ⁸ are the same as above. At least two groups of R ⁶ , R ⁷ and R ⁸ are bonded to each other to form a ring with adjacent 1 or 2 carbon atoms. May be)
It is preferable that the ketimineization rate of the primary amine compound is 80% or more. When the ketiminization rate is less than 80%, enamine compounds which are isomers of ketimine compounds and primary amines having higher reactivity with respect to isocyanate groups than hydroxyl groups remain, so that the pot life tends to be too short.

(Primary amine compound)
In the primary amine compound represented by the formula (7), R ⁵ represents an organic group and corresponds to R ⁵ in the above formula (6). Examples of the organic group in R ⁵ include the same examples as the polyvalent organic group in R ¹ . Further, v in the formula (7) represents an integer of 2 or more, and corresponds to v in the formula (6).

  Primary amine compounds include aliphatic polyamines, alicyclic polyamines, aromatic polyamines, araliphatic polyamines, heterocyclic polyamines, and the like. Examples of the aliphatic polyamine include ethylenediamine, 1,3-trimethylenediamine, 1,4-tetramethylenediamine, 1,3-pentamethylenediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,2-propylenediamine, 1,2-butylenediamine, 2,3-butylenediamine, 1,3-butylenediamine, 2-methyl-1,5-pentamethylenediamine, 3-methyl-1,5-pentamethylene In addition to aliphatic diamines such as diamine, 2,4,4-trimethyl-1,6-hexamethylenediamine, 2,2,4-trimethyl-1,6-hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepenta Min, pentaethylenehexamine and the like. Further, as the aliphatic polyamine, a polyamine having a polyoxyalkylene skeleton such as a diamine having a polyoxyalkylene skeleton can also be used.

  Examples of the alicyclic polyamine include 1,3-cyclopentanediamine, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, -Amino-1-methyl-4-aminomethylcyclohexane, 1-amino-1-methyl-3-aminomethylcyclohexane, 4,4'-methylenebis (cyclohexylamine), 4,4'-methylenebis (3-methyl-cyclohexyl) Amine), methyl-2,3-cyclohexanediamine, methyl-2,4-cyclohexanediamine, methyl-2,6-cyclohexanediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) Cyclohexane, isophorone diamine, norbornane diamine { For example, alicyclic diamines such as 2,5-bis (aminomethyl) bicyclo [2.2.1] heptane, 2,6-bis (aminomethyl) bicyclo [2.2.1] heptane, etc.} It is done.

  Aromatic polyamines include m-phenylenediamine, p-phenylenediamine, 2,4-tolylenediamine, 2,6-tolylenediamine, naphthylene-1,4-diamine, naphthylene-1,5-diamine, 4, 4'-diphenyldiamine, 4,4'-diphenylmethanediamine, 2,4'-diphenylmethanediamine, 4,4'-diphenyletherdiamine, 2-nitrodiphenyl-4,4'-diamine, 2,2'-diphenyl Fragrances such as propane-4,4'-diamine, 3,3'-dimethyldiphenylmethane-4,4'-diamine, 4,4'-diphenylpropanediamine, 3,3'-dimethoxydiphenyl-4,4'-diamine Group diamine and the like.

  Examples of the araliphatic polyamine include 1,3-xylylenediamine, 1,4-xylylenediamine, α, α, α ′, α′-tetramethyl-1,3-xylylenediamine, α, α, α ′, α′-tetramethyl-1,4-xylylenediamine, ω, ω′-diamino-1,4-diethylbenzene, 1,3-bis (1-amino-1-methylethyl) benzene, 1,4 And aromatic aliphatic diamines such as -bis (1-amino-1-methylethyl) benzene and 1,3-bis (α, α-dimethylaminomethyl) benzene.

  As the primary amine compound, aliphatic polyamines, alicyclic polyamines, and araliphatic polyamines are preferable, and alicyclic polyamines are particularly preferable. A primary amine compound can be used individually or in combination of 2 or more types.

(Ketone compound)
In the ketone compound represented by the formula (8), R ⁶ , R ⁷ and R ⁸ each represent an organic group, and correspond to R ⁶ , R ⁷ and R ⁸ in the formula (6). At least two groups out of R ⁶ , R ⁷ and R ⁸ may be bonded to each other to form a ring with adjacent 1 or 2 carbon atoms.

Examples of the organic group for R ⁶ and R ⁷ include a hydrocarbon group, a heterocyclic group, and a group in which two or more of these are bonded. Examples of the organic group for R ⁸ include a hydrocarbon group, a heterocyclic group having a carbon atom at the bonding site with the carbonyl group shown in the formula, and a group in which two or more of these are bonded.

  Examples of the hydrocarbon group, the heterocyclic group, and a group in which two or more of these are bonded include the same examples as the organic group in the substituent that Ar may have.

At least two groups among R ⁶ , R ⁷ and R ⁸ may be bonded to each other to form a ring together with adjacent carbon atoms. Examples of such a ring include a cycloalkane ring having about 3 to 15 members such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cyclooctane ring, a cyclodecane ring, and a cyclododecane ring.

As —CH ₂ R ⁶ R ⁷ , —R ⁸ , at least one of them is a hydrocarbon group having 2 or more carbon atoms (for example, 2 to 6) (for example, an aliphatic hydrocarbon group, especially an alkyl such as an ethyl group or an isobutyl group). In this case, the other is preferably a hydrocarbon group having 1 to 6 carbon atoms (for example, an aliphatic hydrocarbon group, especially an alkyl group). In particular, when —CH ₂ R ⁶ R ⁷ and —R ⁸ are both hydrocarbon groups having 2 or more carbon atoms (for example, 2 to 6) (particularly aliphatic hydrocarbon groups, especially alkyl groups), the ketone compound is Since the enamine compound, which is an isomer of the ketimine compound (B2) obtained by the reaction, can react with the isocyanate compound (A) more quickly, it can exhibit excellent fast curability and initial adhesion. .

Representative examples of the ketone compound include, for example, dimethyl ketone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl butyl ketone, methyl isobutyl ketone, methyl t-butyl ketone, methyl s-butyl ketone, diethyl ketone, ethyl propyl ketone, ethyl Isopropyl ketone, ethyl butyl ketone, ethyl isobutyl ketone, ethyl t-butyl ketone, ethyl s-butyl ketone, ethyl pentyl ketone, ethyl hexyl ketone, ethyl heptyl ketone, ethyl octyl ketone, ethyl 2-ethylhexyl ketone, dipropyl ketone, propyl isopropyl ketone, Propyl butyl ketone, propyl isobutyl ketone, propyl t-butyl ketone, propyl s-butyl ketone, propyl pentyl ketone, pro Aliphatic ketones such as ruhexyl ketone, propyl heptyl ketone, propyl octyl ketone, propyl 2-ethylhexyl ketone, diisopropyl ketone, dibutyl ketone, diisobutyl ketone, di-t-butyl ketone, di-s-butyl ketone, dipentyl ketone, dihexyl ketone, etc. C _1-20 alkyl-C _1-20 alkyl ketone); and cyclic ketones such as cyclopentanone and cyclohexanone. A ketone compound can be used individually or in combination of 2 or more types. In the present invention, methyl isobutyl ketone, diethyl ketone, particularly diethyl ketone can be preferably used.

  The reaction between the primary amine compound and the ketone compound is not particularly limited, and a known method can be employed. For example, a primary amine compound and a ketone compound are mixed in the absence of a solvent or in the presence of a nonpolar solvent (for example, hexane, cyclohexane, toluene, benzene, etc.), then heated to reflux, and produced as necessary. This can be done by removing water azeotropically. In order to increase the reaction rate, a catalyst such as an acid catalyst may be used as necessary, and a dehydrating agent may be present in the system. The dehydrating agent is preferably added to the system when the reaction proceeds to some extent and the reaction rate becomes slow, from the viewpoint of economy and the like.

  The dehydrating agent is not particularly limited as long as it does not inhibit the reaction. For example, alkoxysilane compounds such as tetramethoxysilane and tetraethoxysilane; vinyl group-containing alkoxysilane compounds such as vinyltrimethoxysilane; tetramethoxy Examples thereof include silicone oligomers such as silane oligomers; silazane compounds such as hexamethyldisilazane; alkoxytitanium compounds such as tetrabutoxytitanium. The dehydrating agent is preferably a liquid that has no reactivity with amines.

  In this reaction, either one of the primary amine compound and the ketone compound (particularly the ketone compound) may be used in excess. The reaction temperature varies depending on the type of primary amine compound and ketone compound used, but is usually 50 to 200 ° C, preferably 100 to 160 ° C. After completion of the reaction, the remaining ketone compound, the solvent used, and the primary amine compound can be removed by distillation or the like.

  The ketimineization rate of the primary amine compound can be controlled by the charged molar ratio of the primary amine compound and the ketone compound, the reaction temperature, the reaction time, the type and amount of the catalyst and dehydrating agent, and the like. In addition, the ketiminization rate may be adjusted by purification after the reaction. A conventionally known method can be adopted as a purification method.

  The ketimine compound (B2) thus obtained may contain a ketimine compound having an unreacted primary amino group together with a ketimine compound having no amino group represented by the formula (5) which is the main product.

  In the present invention, the ketimine compound (B2) preferably has a ketimine conversion rate of 80% or more based on the primary amine compound that is the raw material. Although the ketiminization rate may be 80% or more by the reaction, the ketiminization rate may be adjusted to 80% or more by purification after the reaction. The ketiminization rate is preferably 90 to 95%. When the ketiminization rate is less than 80%, gelation or high viscosity tends to occur, and the pot life tends to be too short. The ketiminization rate can be determined by the method described later.

[Salt of acidic phosphate ester and amine compound (C)]
The salt (C) of an acidic phosphate ester and an amine compound in the present invention is a salt of an acidic phosphate ester represented by the above formula (2) and an organic amine compound. In formula (2), R ² represents an organic group, and t represents 1 or 2.

Examples of the organic group for R ² include the same examples as those of the organic group that Ar may have. The carbon number of the organic group of R ^2, for example, 1 to 30, preferably 4 to 20. Examples of the organic group in R ² of the present invention include an alkyl group having 2 or more carbon atoms (for example, 2 to 6) and a phenyl group, and an alkyl group having 2 to 4 carbon atoms is preferable.

  Examples of the acidic phosphate ester include methyl phosphate ester, dimethyl phosphate ester, ethyl phosphate ester, diethyl phosphate ester, isopropyl phosphate ester, diisopropyl phosphate ester, butyl phosphate ester, dibutyl phosphate ester, and 2-ethylhexyl phosphorus. Examples include acid esters, di (2-ethylhexyl) phosphate esters, isodecyl phosphate esters, and diisodecyl phosphate esters. These can be used alone or in admixture of two or more.

  The salt (C) of an acidic phosphate ester and an amine compound in the present invention can be obtained by reacting the acidic phosphate ester with an organic amine compound. As the organic amine compound, for example, amine compounds such as aliphatic amines, aromatic amines and basic nitrogen-containing heterocyclic compounds can be suitably used. Examples of the aliphatic amine include trialkylamines such as trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, triisobutylamine, tris-butylamine, tri-t-butylamine, tripentylamine, and trihexylamine; Dialkylamines such as dimethylamine, diethylamine, and dibutylamine; monoalkylamines such as methylamine, ethylamine, and butylamine; trimethanolamine, triethanolamine, tripropanolamine, triisopropanolamine, tributanolamine, tripentanolamine, Trialcoholamines such as isopentanolamine and trihexanolamine; dialcohols such as dimethanolamine and diethanolamine Triethanolamine; methanol amine, other such monoalcohols amines such as ethanolamine, ethylenediamine, diethylenetriamine and the like. Aromatic amines include, for example, N, N-dimethylaniline. Examples of the basic nitrogen-containing heterocyclic compound include morpholine, piperidine, pyrrolidine, diazabicycloundecene (1,8-diazabicyclo [5.4.0] undec-7-ene: DBU), diazabicyclononene (1, 8-diazabicyclo [5.4.0] nonec-7-ene: DBN), basic nitrogen-containing non-aromatic heterocyclic compounds such as N-methylmorpholine; pyridine, α-picoline, β-picoline, γ-picoline, quinoline And basic nitrogen-containing aromatic heterocyclic compounds. These can be used alone or in combination of two or more.

  In the present invention, examples of the organic amine compound include aliphatic amines (particularly triethylamine) such as trialkylamine and trialcoholamine, and basic nitrogen-containing non-aromatic heterocyclic compounds [particularly diazabicyclone. Decene (1,8-diazabicyclo [5.4.0] undec-7-ene: DBU)] and the like can be preferably used.

  As the usage-amount of the organic amine compound with respect to acidic phosphate ester at the time of making acidic phosphate ester and an organic amine compound react, it is 1-0.2 mol of organic amine compounds with respect to 1 mol of acidic phosphate esters, for example. Degree (preferably 0.5 to 0.2 mol).

  The salt (C) of an acidic phosphate ester and an amine compound in the present invention functions to strongly promote the reaction between the isocyanate compound (A) and the compound (B) having a plurality of isocyanate-reactive groups. Moreover, the salt (C) of an acidic phosphate ester and an amine compound does not cause deterioration of physical properties over time even when the amount used is increased. Therefore, an amount sufficient to complete the reaction between the isocyanate compound (A) and the compound (B) having a plurality of isocyanate-reactive groups can be used, and the reaction rate may decrease as the curing reaction proceeds. And the reaction rate does not decrease. In addition, when an amine-based catalyst is used, there is a problem that a large amount of bubbles are generated in the cured product. However, in the urethane resin composition according to the present invention, a salt of an acidic phosphate ester and an amine compound (C ) As a catalyst, and it is not necessary to use an amine-based catalyst.

  Furthermore, in the urethane bond reaction between the polyol compound (B1) as the compound (B) having a plurality of isocyanate-reactive groups and the isocyanate compound (A), it has an action of strongly promoting the reaction, Since it does not interfere with the urea bond reaction between the ketimine compound (B2) as the compound (B) having an isocyanate-reactive group and the isocyanate compound (A), it does not cause a rapid increase in initial viscosity and can be used for a long time. Can be extended to a practical range.

  The two-component urethane resin composition according to the present invention is cured when the two-component urethane resin composition is cured by utilizing the above-described characteristics of the salt (C) of an acidic phosphate ester and an amine compound. The pot life can be extended while suppressing a reduction in the reaction rate of the reaction, and a cured product having excellent toughness can be obtained by curing at a high reaction rate.

[Two-component urethane resin composition]
The two-component urethane resin composition according to the present invention comprises the isocyanate compound (A), a compound (B) having a plurality of isocyanate-reactive groups, and a salt (C) of an acidic phosphate ester and an amine compound. Features. The blending ratio [former: latter (molar ratio)] of the isocyanate compound (A) and the compound (B) having a plurality of isocyanate-reactive groups is about A / B = 0.5 to 1.2, preferably 0.8. It is about 8 to 1.0. When the above value is less than 0.5, the physical properties tend to decrease, whereas when the above value exceeds 1.2, foaming tends to occur easily. In addition, when using 2 or more types of compounds as a compound (B) which has several isocyanate reactive group, B is the total number of moles of the compound (B) which has several isocyanate reactive group to be used. For example, when the polyol compound (B1) and the ketimine compound (B2) are used as the compound (B) having a plurality of isocyanate-reactive groups, B in the above formula is (B1 + B2).

  As a compounding quantity of the salt (C) of acidic phosphate ester and an amine compound, it is about 0.01-10 mass parts with respect to 100 mass parts of isocyanate compounds (A), Preferably it is 0.5-5 masses. About a part. When the compounding quantity of the salt (C) of acidic phosphate ester and an amine compound exceeds 10 mass parts, there exists a tendency for a plastic effect to express and for physical properties to fall.

  In addition, the weight average molecular weight of the isocyanate compound (A) and the compound (B) having a plurality of isocyanate-reactive groups, the use amount of the salt (C) of an acidic phosphate ester and an amine compound, and the like are appropriately adjusted. Thus, it can be extended to the required range. Furthermore, when using the compound (B) which has 2 or more types of several isocyanate reactive group, each compound (B) which has a plurality of isocyanate reactive groups, and the reactivity with respect to an isocyanate compound (A) The pot life and the reaction rate can be adjusted by adjusting the use ratio (molar ratio) according to the above.

  The two-component urethane resin composition of the present invention includes, for example, the isocyanate compound (A), the compound (B) having a plurality of isocyanate-reactive groups, and a salt (C) of an acidic phosphate ester and an amine compound, If necessary, it can be prepared by mixing a dehydrating agent, a curing catalyst, and an adhesion-imparting agent. As the curing catalyst, for example, an organic acid (a carboxylic acid having a hydroxyl group is preferable), a tin-based catalyst, an amine-based catalyst, or the like can be used. In addition, since a castor oil type polyol has a hydroxyl group and a carboxyl group in the molecule, it is used as a carboxylic acid as a curing catalyst, and as a polyol compound (B1) as a compound (B) having a plurality of isocyanate-reactive groups. can do. Moreover, as an adhesive provision agent, an epoxy resin etc. (especially solid epoxy resin) can be used, for example. By adding an epoxy resin, a cured product having excellent toughness, heat resistance, light resistance and the like can be obtained.

  In addition to the above, the two-component urethane resin composition of the present invention includes additives [for example, fillers (calcium carbonate, kaolin, clay, talc, silica, silica sand, etc.), plasticizers, pigments (titanium oxide, carbon Black), dyes, anti-aging agents, ultraviolet absorbers, antioxidants, antistatic agents, flame retardants, adhesion-imparting agents, dispersants, thixotropic agents (for example, fumed silica, amide waxes, Vegetable oil derivatives, fibrillated fibers, etc.), reactive diluents, extenders, modifiers, polymer powders (eg, acrylic polymer powders, etc.)], and other latent hardeners (eg, other ketimine types) Compounds, aldimine compounds, oxazolidine compounds, etc.) and viscosity modifiers (for example, solvents such as ketones, aromatic hydrocarbons, aliphatic hydrocarbons, etc.) It may be. In addition, the two-component urethane resin composition has, for example, a modified silicone, a silyl group-terminated urethane polymer, a silyl group, and a main chain having a polyoxyalkylene skeleton, as long as the adhesiveness and adhesion are not impaired. Polymers, carboxylic acid vinyl ester compounds, and the like may be added. Moreover, these compounding ratios can be appropriately selected from known or commonly used ratios.

  The mixing of each component is preferably performed under an inert gas atmosphere (for example, under a nitrogen atmosphere) and / or under reduced pressure. Moreover, in order to remove the water | moisture content contained in an additive etc., you may mix, dehydrating by heating, pressure reduction, etc.

  The urethane resin composition according to the present invention is a two-component type, and is characterized by an isocyanate compound (A) and other compounds [a compound having a plurality of isocyanate-reactive groups (B), an acidic phosphate ester and an amine compound. And salt (C)] are sold in different containers, and are mixed when used. The two-component urethane resin composition according to the present invention is obtained by mixing two components, that is, an isocyanate compound (A) and other compounds [compounds having a plurality of isocyanate-reactive groups (B) and acidic phosphorus. The curing reaction starts by mixing the acid ester and the salt (C) of the amine compound].

  The two-component urethane resin composition according to the present invention includes an isocyanate compound (A), a urethane resin composition containing a compound (B) having a plurality of isocyanate-reactive groups, and an acidic phosphate ester as a curing catalyst. Since the salt (C) with an amine compound is used, when the two-component urethane resin composition according to the present invention is mixed, the curing reaction between the isocyanate compound (A) and the compound (B) having a plurality of isocyanate-reactive groups. In the initial stage, the viscosity does not increase rapidly, a practical pot life can be secured, and the curing reaction can be completed without lowering the reaction rate. And since it is not necessary to use an amine catalyst, the bubble which generate | occur | produces in hardened | cured material can be suppressed significantly. As a result, a cured product that reaches the final strength and has excellent toughness can be obtained.

  The two-component urethane resin composition of the present invention comprises an adhesive [for example, an adhesive for automobile interior, an adhesive for various vehicles (for example, an adhesive used for vehicles such as trains), an adhesive for building interior construction, and a building material. Adhesives, adhesives for electrical and electronic parts, furniture adhesives, household adhesives, etc.], coating agents [eg paints (eg concrete paints, metal paints, wood paints, tile paints, plastics) Paints, heavy-duty anti-corrosion paints, top coats, floor polishes, etc.), undercoats (undercoats), and binders (for example, inks, pigment prints, ceramic materials, non-woven fabrics, fiber sizing agents, rubber, wood flour) Etc.), sealing materials, sealing materials (sealers), potting materials, putty materials, primer materials, laminate materials, sizing agents, etc.

  As described above, the two-component urethane resin composition of the present invention can be used in a wide range of applications, and can exhibit adhesion (adhesiveness, adhesion, etc.) to a wide range of substrates. In addition, various physical properties (toughness, flexibility, adhesiveness, gloss, etc.) can be improved, and it can be used with excellent workability in various applications. In particular, it can exhibit excellent fast curability, and, for example, when used as an adhesive, it can improve the fit, so the time required for curing and temporary pressing during bonding is short, and the coated body The workability of bonding them together is good, and the working time can be greatly shortened. On the other hand, when used as a coating agent, the time required for curing during the formation of the coating layer (coating film) is short, and in this case, the workability for forming the coating layer on the coated body is good and the working time is greatly increased. Can be shortened.

  In addition, when using a two-pack type urethane resin composition as an adhesive, both coated bodies may be either porous or non-porous as coated bodies (applicable base materials), and the same The to-be-coated bodies made of these materials may be used, or the to-be-coated bodies made of different materials may be used. Moreover, when utilizing a two-component urethane resin composition as a coating agent, the to-be-coated body (applicable base material) for forming the coating layer is not particularly limited, and may be porous or non-porous. Good.

  More specifically, the two-component urethane resin composition of the present invention has good adhesion (adhesion) to various plastic materials in addition to inorganic materials (concrete, etc.) and metal materials (aluminum, stainless steel, etc.). Performance and adhesiveness). Therefore, the two-component urethane resin composition of the present invention is used in various applications (adhesion, coating film formation, etc.), for example, inorganic materials (eg, concrete, mortar, tile, stone, etc.), metal materials (eg, aluminum). , Copper, iron, stainless steel, etc.), wood materials (eg, wood, chipboard, particle board, hardboard, wood boards such as MDF, plywood, etc.), paper materials (eg, cardboard paper, paperboard, kraft paper, etc. Paper-like substances, processed paper such as moisture-proof paper, etc.), fiber materials (eg, non-woven fabrics, woven fabrics, etc.), leather materials, glass materials, porcelain materials, various plastic materials [eg, polyvinyl chloride, polyamide (nylon), Polyester (polyethylene terephthalate, polyethylene naphthalate, etc.), styrene resin (polystyrene, acrylonitrile) Butadiene-styrene copolymer, butadiene-styrene copolymer, etc.), polyurethane, olefin resin (polyethylene, polypropylene, ethylene-propylene copolymer, etc.), acrylic resin (polyacrylate ester, polymethacrylate ester, etc.) , Polycarbonate resin, etc.], rubber materials [e.g., natural rubber; olefin rubber (ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, etc.), styrene rubber (styrene-isoprene copolymer rubber). , Styrene-butadiene copolymer rubber, styrene-isoprene-styrene block copolymer rubber, styrene-butadiene-styrene block copolymer rubber, etc.), polyisoprene rubber, polybutadiene rubber, synthetic rubber such as silicon rubber, etc.] Various base materials It can be applied for. The shape of these base materials is not particularly limited, and may be any shape such as a film or sheet shape, a plate shape, a prism shape, or a column shape. Moreover, when a base material is formed with the plastic material, a foam etc. may be sufficient.

  In addition, when applying to these base materials, well-known thru | or usual methods, such as application | coating with a brush, a roller, spraying, immersion, etc., are employable. Moreover, after apply | coating the 2 liquid type urethane resin composition of this invention to a base material (a to-be-coated body, a to-be-coated body etc.), it can dry on various drying conditions (natural drying, forced drying, etc.). .

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited by these Examples.

The materials used in the examples and comparative examples are as follows.
[Isocyanate compound]
(1) Polyphenyl isocyanate (trade name “Sumijour 44V20”, manufactured by Sumika Bayer Urethane Co., Ltd .; sometimes referred to as “44V20”)
(2) Urethane prepolymer (the urethane prepolymer obtained by the following preparation method was used. It may be called "urethane prepolymer A")

[Polyol compound]
(1) Castor oil-based polyol (trade name “TLM”, manufactured by Toyokuni Oil Co., Ltd., number average molecular weight: about 900, average functional group number: 2.7, hydroxyl value: 168.3 mg-KOH / g; referred to as “TLM” May be)
(2) Polytetramethylene glycol (trade name “PTMG2000”, manufactured by Mitsubishi Chemical Corporation, weight average molecular weight: 2000, hydroxyl value: 57.2 mg-KOH / g; sometimes referred to as “PTMG”)

[Ketimine compound]
(1) Ketimine compound 1 (the ketimine compound obtained by the following preparation method was used. It may be referred to as “1,3-DEK type ketimine”)

[Acid phosphate ester]
(1) Diethyl phosphate (sometimes referred to as “Et-P-1”)
(2) Diethyl phosphate ester + ethyl phosphate ester (sometimes referred to as “Et-P-2”)
(3) Dibutyl phosphate ester (sometimes referred to as “Bu-P”)
(4) Isodecyl phosphate ester + diisodecyl phosphate ester (trade name “AP-10”, manufactured by Daihachi Chemical Co., Ltd .; sometimes referred to as “AP-10”)

[base]
(1) Triethylamine (sometimes referred to as “TEA”)
(2) Diazabicycloundecene (sometimes referred to as “DBU”)

[Other additives]
(1) Tin-based catalyst (trade name “Stan BL”, manufactured by Sansha Co., Ltd .; sometimes referred to as “Stan BL”)

Preparation Example 1 (Preparation of urethane prepolymer A)
40 g of TLM and 60 g of polyisocyanate (trade name “Sumijoule G412”, manufactured by Sumika Bayer Urethane Co., Ltd.) are mixed at room temperature (23 ° C.) and stirred at 50 ° C. for 3 hours to obtain urethane prepolymer A (Mw: 800, NCO: 15%) was obtained.

Preparation Example 2 (Preparation of ketimine compound 1)
1 mol of 1,3-bis (aminomethyl) cyclohexane (trade name “1,3-BAC”, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 4 mol of diethyl ketone (DEK) are placed in a flask, and water to be produced is added. While removing with a Dean-Stark trap, the reaction was conducted by refluxing for 12 hours at a temperature at which diethyl ketone (DEK) refluxed (120 to 150 ° C.), and it was confirmed that the reaction was completed by gas chromatography. Diethyl ketone (DEK) was removed by distillation under reduced pressure using an evaporator to obtain ketimine compound 1 (1,3-DEK type ketimine). The ketimination rate based on 1,3-bisaminomethylcyclohexane was 95% or more.

The ketiminization rate can be measured by the following method.
A reaction mixture containing a ketimine compound is dissolved in toluene, and the peak area of the ketimine compound having no primary amino group and the primary amino group n of the primary amine compound as a raw material are measured by gas chromatography measurement. The peak area A of the compound in which x of them are ketiminated and the sum of the peak areas are obtained, and the ketimination rate (% by mass) of the primary amine compound is calculated using the following formula (1).

The measurement conditions in the gas chromatography measurement are as follows.
(Measurement conditions for gas chromatography)
Measurement method: FID method Column temperature: After 1 minute at 80 ° C., the temperature is increased to 280 ° C. at a temperature increase rate of 10 ° C./min, and the condition is 280 ° C. for 1 minute. Temperature: 280 ° C. (Injection), 280 ° C. (Detector)
Carrier gas: helium (He) (flow rate: 30 ml / min), hydrogen (flow rate: 30 ml / min), air (flow rate: 400 ml / min)

Examples 1-13, Comparative Examples 1-8
The components shown in Tables 1 to 3 were mixed to obtain a urethane resin composition.

  About the obtained urethane resin composition, the following evaluation method evaluated the pot life, the reaction rate, and the presence or absence of foaming. The urethane resin composition according to the present invention generates heat while increasing the viscosity as the curing reaction proceeds. That is, the amount of heat generated (temperature increase) is considered to correspond to the number of reacted molecules (reaction rate). Therefore, the reaction rate can be indirectly observed by curing the urethane resin composition in the heat insulating container and observing the temperature change in the heat insulating container. Further, when the curing reaction is completed, no heat is generated and the temperature does not increase. That is, the longer the time (maximum temperature arrival time) required until the temperature rise curve becomes flat (when the maximum temperature is reached), the longer the curing reaction proceeds. After mixing the two-component urethane resin composition, the time that exists in the usable viscosity state is considered to be proportional to the maximum temperature attainment time, so it is indirectly possible by observing the maximum temperature attainment time. You can observe the usage time.

[Pot life]
About the urethane resin compositions (total amount 40 g) obtained in the examples and comparative examples, they were mixed in a heat-insulated container whose temperature was adjusted to 23 ° C., and immediately after that, the temperature change in the heat-insulated container was measured with a thermometer, The time (minutes) required to reach the maximum temperature after mixing was defined as the pot life.

[Reaction rate]
About the urethane resin compositions (total amount 40 g) obtained in the examples and comparative examples, they were mixed in a heat-insulated container whose temperature was adjusted to 23 ° C., and immediately after that, the temperature change in the heat-insulated container was measured with a thermometer, The curing reaction rates were compared by comparing the maximum temperature (° C) reached.

[With or without foaming]
The urethane resin compositions (total amount 40 g) obtained in the examples and comparative examples were applied on a plywood so as to have a thickness of 1 mm, and allowed to stand at room temperature 23 ° C. and 50% RH for 24 hours to obtain a cured product. Obtained. The obtained cured product was visually observed and the presence or absence of foaming was evaluated according to the following criteria.
Evaluation criteria No foaming was observed: ○
Slight foaming was observed:
Many foams were seen: ×

  For Examples and Comparative Examples using prepolymer A as the isocyanate compound (A) and TLM as the compound (B) having a plurality of isocyanate-reactive groups, the pot life (minutes) is the vertical axis and the maximum temperature (° C.) is FIG. 1 was prepared as the horizontal axis.

  As is apparent from Tables 1 to 3, the two-component urethane resin composition according to the present invention did not generate bubbles in the cured product. On the other hand, in Comparative Example 8, since an amine-based catalyst was used, a large amount of bubbles were generated in the cured product. Further, as apparent from FIG. 1, the two-component urethane resin composition according to the present invention uses a salt of an acidic phosphate ester and an organic amine compound as a curing catalyst, and therefore uses a tin-based catalyst as a catalyst. When compared with the urethane resin composition showing the same pot life, the maximum temperature is always higher and the reaction rate is higher. On the other hand, when the urethane resin compositions showing the same maximum temperature are compared, it can be seen that the pot life is always long and more practical. As described above, the two-component urethane resin composition according to the present invention has a practical pot life, cures at a high reaction rate, and produces a cured product having excellent toughness without generation of bubbles. You can see that In Comparative Example 8, since a large amount of bubbles was generated, no further examination (examination of pot life and maximum temperature (° C.)) was performed.

It is a graph which shows the evaluation test result of the pot life and reaction rate in an Example and a comparative example.

Claims (9)

Following formula (1)

(Wherein R ₁ represents a polyvalent organic group, and s represents an integer of 2 or more)
The compound (B) having a plurality of isocyanate-reactive groups, the following formula (2)

(Wherein R ² represents an organic group, and t represents 1 or 2)
A two-component urethane resin composition comprising a salt (C) of an acidic phosphate ester represented by Isocyanate compound (A) is represented by the following formula (3)

(In the formula, Ar represents an aromatic cyclic group. S is the same as above.)
The two-component urethane resin composition according to claim 1, which is an aromatic polyisocyanate compound represented by the formula: Isocyanate compound (A) is represented by the following formula (4)

(Wherein R ³ represents a polyvalent organic group, s is the same as above)
The two-component urethane resin composition according to claim 1, which is a polyphenyl isocyanate compound represented by the formula:   The two-component urethane resin composition according to any one of claims 1 to 3, wherein the isocyanate compound (A) is a urethane prepolymer obtained from a polyisocyanate compound and a polyol compound and having two or more isocyanate groups at the terminal. object. The compound (B) having a plurality of isocyanate-reactive groups is represented by the following formula (5)

(Wherein R ⁴ represents a polyvalent organic group, and u represents an integer of 2 or more)
The two-component urethane resin composition according to any one of claims 1 to 4, which is a polyol compound (B1) represented by: The compound (B) having a plurality of isocyanate-reactive groups is represented by the following formula (5)

(Wherein R ⁴ represents a polyvalent organic group, and u represents an integer of 2 or more)
A polyol compound (B1) represented by the following formula (6)

(Wherein R ⁵ represents a polyvalent organic group, R ⁶ and R ⁷ are the same or different and represent a hydrogen atom or an organic group, R ⁸ represents an organic group, and v represents an integer of 2 or more. At least two of R ⁶ , R ⁷ and R ⁸ may be bonded to each other to form a ring together with adjacent 1 or 2 carbon atoms)
The two-component urethane resin composition according to any one of claims 1 to 5, which is a ketimine compound (B2) represented by the formula:   The two-component urethane resin composition according to claim 5 or 6, wherein the polyol compound (B1) is a polyol compound having no polypropylene glycol skeleton.   The two-component urethane resin composition according to claim 6, wherein the ketimine compound (B2) is a ketimine compound obtained by reacting an amine with diethyl ketone.   The salt (C) of an acidic phosphate ester and an amine compound is a salt obtained by reacting an acidic phosphate ester and an amine compound in a ratio of 1: 1 to 1: 0.2 (molar ratio). The two-component urethane resin composition according to any one of -8.

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