WO2016104456A1

WO2016104456A1 - Polyurethane resin composition and polyurethane resin molded article

Info

Publication number: WO2016104456A1
Application number: PCT/JP2015/085727
Authority: WO
Inventors: 福田　誠; 上平　茂生; 倫弘小川
Original assignee: 富士フイルム株式会社
Priority date: 2014-12-26
Filing date: 2015-12-21
Publication date: 2016-06-30
Also published as: JPWO2016104456A1; JP6316455B2

Abstract

A polyurethane resin composition comprising thermoplastic polyurethane and at least one kind of chain-type iminoether group-containing compound selected from an iminoether compound represented by general formula (1) and a polymer thereof, and a molded article of the polyurethane resin. In general formula (1): R² represents an alkyl group, an aryl group or an alkoxy group; R³ represents an alkyl group or an aryl group represented by general formula (2) or (3) [wherein: R³¹ to R³³ independently represent a hydrogen atom or a substituent that may be bonded together to form a ring; R⁴¹ represents a substituent; n is an integer of 0 to 5, provided that when there are two or more R⁴¹s, these R⁴¹s may be either the same or different; and * represents a binding position to the nitrogen atom]; and R¹¹ to R¹³ independently represent a hydrogen atom, an alkyl group or an aryl group.

Description

Polyurethane resin composition and polyurethane resin molded article

The present disclosure relates to a polyurethane resin composition and a polyurethane resin molded article.

Polyurethane is excellent in various properties such as mechanical properties, abrasion resistance, elastic recovery and flex resistance, and can be melt-molded. Therefore, polyurethane is used in various applications as a substitute material for synthetic rubbers and plastics.
Furthermore, polyurethane is a material with high heat resistance, hydrolysis stability and abrasion resistance due to recent expansion of usage applications such as urethane foams such as sealing materials and heat insulating materials, shoe products, and automotive parts applications such as bumpers and headrests. There is a need for further improvement of

For example, Japanese Patent Application Laid-Open No. 2011-246550 proposes that a polyurethane having improved hydrolysis resistance and heat resistance be produced by adding a cyclic carbodiimide at the time of synthesis of the polyurethane.

However, as disclosed in Japanese Patent Application Laid-Open No. 2011-246550, the method of adding a cyclic carbodiimide at the time of synthesis of polyurethane does not lead to the improvement of a commercially available polyurethane, and is not a general method.

In addition, since polyurethane is thermally decomposed, molding at high temperatures is difficult. For example, in the case of injection molding using a polyurethane resin, the screw portion is carried out at 220 ° C. or lower even at high temperature, and it is about 230 ° C. at a part of the tip (nozzle). Therefore, if cyclic carbodiimide is added when molding using a commercially available polyurethane, the molding temperature of the polyurethane is usually less than 220 ° C., whereas the melting point of the cyclic carbodiimide is as high as 230 to 250 ° C. Therefore, it is difficult to react, and the improvement effect of heat resistance etc. is small.

The present invention has been made in view of the above-mentioned circumstances, and a polyurethane resin composition capable of producing a polyurethane resin molded article excellent in hydrolysis resistance and moldability even if general-purpose polyurethane is used Intended to be provided.
Another object of the present invention is to provide a polyurethane resin molded article excellent in hydrolysis resistance and moldability even when general-purpose polyurethane is used.

In order to achieve the above object, the following invention is provided.

<1> At least one chain-like iminoether group-containing compound selected from a thermoplastic polyurethane, an iminoether compound represented by the following general formula (1), and an iminoether compound represented by the general formula (1) And a compound.

In the general formula (1), R ² represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkoxy group which may have a substituent, and R ³ represents R ¹¹ represents an alkyl group represented by Formula (2) or an aryl group represented by the following General Formula (3), and R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl which may have a substituent Represents an aryl group which may have a group or a substituent.

In formula (2), R ³¹ , R ³² and R ³³ each independently represent a hydrogen atom or a substituent. R ³¹ , R ³² and R ³³ may be linked to each other to form a ring. In Formula (3), R ⁴¹ represents a substituent, and n represents an integer of 0 to 5. If R ⁴¹ there are a plurality, even more R ⁴¹ is the same as each other or different, may form a ring. In the general formulas (2) and (3), * represents a position to be bonded to a nitrogen atom.

<2> is an aryl group R ³ is represented by the general formula (3) in the general formula (1) polyurethane resin composition according to <1>.

The polyurethane resin composition as described in <1> or <2> whose iminoether compound represented by <3> General formula (1) is a chain-like iminoether group containing compound represented by following General formula (5) .

In formula (5), R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. R ²¹ represents a substituent, m represents an integer of 0 to 5, when R ²¹ there are a plurality, even more R ²¹ is the same as each other or different, a ring together You may form. R ⁴¹ represents a substituent, n represents an integer of 0 to 5, when R ⁴¹ there are a plurality, even more R ⁴¹ is the same as each other or different, a ring together You may form.

<4> Any one of <1> to <3>, wherein the multimer of the iminoether compound represented by the general formula (1) is a chain iminoether group-containing compound represented by the following general formula (6) The polyurethane resin composition as described in one.

In General Formula (6), R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent. R ⁴¹ represents a substituent, and n represents an integer of 0 to 5. If R ⁴¹ there are a plurality, even more R ⁴¹ is the same as each other or different, may form a ring. p represents an integer of 2 to 4, and L ¹ has an alkylene moiety which may have a substituent, an arylene moiety which may have a substituent, or a substituent at the end of bonding to a carbon atom It also represents a p-valent group which is a good alkoxylene moiety.

<5> Any one of <1> to <3>, wherein the multimer of the iminoether compound represented by the general formula (1) is a chain iminoether group-containing compound represented by the following general formula (7) The polyurethane resin composition as described in one.

In the general formula (7), R ² represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkoxy group which may have a substituent, and R ¹¹ and R ¹² And R ¹³ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. p represents an integer of 2 to 4, and p represents a p-valent group in which L ² is a arylene moiety which may have a substituent or a cycloalkylene moiety which may have a substituent. Represents

<6> Any one of <1> to <3>, wherein the multimer of the iminoether compound represented by the general formula (1) is a chain iminoether group-containing compound represented by the following general formula (8) The polyurethane resin composition as described in one.

In general formula (8), R ² represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkoxy group which may have a substituent, and R ⁴¹ represents a substituent And n represents an integer of 0 to 5. If R ⁴¹ there are a plurality, even more R ⁴¹ is the same as each other or different, may form a ring. p represents an integer of 2 to 4, and L ³ represents a p-valent group in which the bonding end with the oxygen atom is an alkylene part. In the alkylene moiety of L ³ , part or all of the hydrogen atoms may be substituted with an alkyl group which may have a substituent or an aryl group which may have a substituent.

<7> The polyurethane resin composition according to any one of <1> to <6>, which comprises 0.1 to 2.0 parts by mass of a chain iminoether group-containing compound with respect to 100 parts by mass of the thermoplastic polyurethane .

<8> The polyurethane resin composition according to any one of <1> to <7>, wherein the thermoplastic polyurethane is a polyester-based polyurethane.

<9> A polyurethane resin molded article molded using the polyurethane resin composition according to any one of <1> to <8>.

According to the present disclosure, it is possible to provide a polyurethane resin composition capable of producing a polyurethane resin molded article excellent in hydrolysis resistance and moldability, even when a general purpose polyurethane is used.
Further, according to the present disclosure, a polyurethane resin molded article excellent in hydrolysis resistance and moldability is provided even when a general purpose polyurethane is used.

Hereinafter, the polyurethane resin composition and the polyurethane resin molded article of the present disclosure will be specifically described. In the following description, “to” representing a numerical range means a range including numerical values described as the lower limit value and the upper limit value.

<Polyurethane resin composition>
The polyurethane resin composition of the present disclosure is represented by a thermoplastic polyurethane (hereinafter sometimes simply referred to as “polyurethane”), an iminoether compound represented by the following general formula (1), and a general formula (1) And at least one chained iminoether group-containing compound (hereinafter sometimes simply referred to as "chained iminoether group-containing compound") selected from multimers of iminoether compounds.

In addition, as for the "chain iminoether group-containing compound" in the present disclosure, the entire iminoether group (sometimes referred to as -N = C-O- or "iminoether moiety") contained in the iminoether compound has a cyclic structure. Iminoether compounds which are not incorporated into at least a portion of which constitute at least a part of the chain portion of the iminoether compound. In addition, with the multimer of the iminoether compound represented by the general formula (1), at least one partial structure linked to the chain iminoether group (-N = C-O-) in the general formula (1) is linked A chain iminoether group-containing compound synthesized via an iminoether compound represented by the general formula (1), which means a chain iminoether group-containing compound which has two or more partial structures other than a linking group In addition, a chain iminoether group-containing compound synthesized without passing through the iminoether compound represented by the general formula (1) is also included.

The polyurethane resin composition of the present disclosure can produce a polyurethane resin molded article excellent in hydrolysis resistance and moldability, even when a general-purpose polyurethane is used. The reason is presumed as follows.

Polyurethanes are mainly classified into polyester-based polyurethanes having a polyester-based polyol as a raw material and polyether-based polyurethanes having a polyether-based polyol as a raw material.
For example, in polyester-based polyurethanes, a trace amount of carboxylic acid is contained in the raw material polyester polyol, and the polyester portion is thermally decomposed during melt molding to form a carboxy group. Although the carboxy group promotes hydrolysis, the chain iminoether group-containing compound contained in the polyurethane resin composition of the present disclosure is more reactive than the cyclic iminoether compound, and reacts at the molding temperature of the polyurethane to form a carboxy group. It is believed that the hydrolysis resistance is improved by sealing the

When a resin composition containing a chain iminoether group-containing compound and a polyurethane is heated, melted and molded, for example, chain iminoether moiety and terminal carboxyl group of polyurethane (wave line indicates end of polyurethane) as in the following reaction scheme The amide compound and the carboxylic acid ester are reacted by reacting with a moiety other than a carboxy group), and the alkyl moiety linked to the iminoether group is cleaved to esterify and add to the carboxy group at the polyurethane end. Generate

Therefore, when it shape | molds using the resin composition containing a chain-like iminoether group containing compound and polyurethane, it is thought that it is suppressed that the molecular weight of a polyurethane increases, and the viscosity increase at the time of shaping | molding is suppressed.

On the other hand, a cyclic iminoether compound in which the iminoether moiety containing an iminoether group is cyclic is lower in reactivity than a chain iminoether group-containing compound, and when molded at a high temperature, a state in which polyurethane is added to the iminoether moiety It is considered that the viscosity of the polymer increases greatly as the molecular weight of the polymer increases. In particular, when the cyclic iminoether moiety is bifunctional or more (dimer or more), it is considered that a large number of polyurethanes are added to cause significant thickening.

(Synthesis method of imino ether compound)
As a method of synthesizing the iminoether compound represented by the general formula (1), a method in which an amide compound is imidoyl chloride, reaction with an alkoxide, and a method in which an aniline compound and an ortho ester compound are reacted. Although any method may be used as a synthesis method of the iminoether compound represented by General formula (1), it is preferable to use the method of making an aniline compound and an ortho ester compound react. A polyurethane resin composition to which an iminoether compound synthesized by a method of reacting an aniline compound and an ortho ester compound is added is preferable because hydrolysis resistance and color tone become better. It is considered that this is attributed to the absence of the coloring matter and the reagent and reaction product which deteriorate the hydrolysis resistance in the method of reacting the aniline compound with the ortho ester compound. Moreover, the method of reacting an aniline compound and an ortho ester compound is preferable also from the point which can synthesize | combine an imino ether compound by a short process.

The ortho ester compound used for the synthesis of the iminoether compound represented by the general formula (1) is preferably a compound represented by the following general formula (9).

In the general formula (9), R ⁴ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkoxy group which may have a substituent, R ⁵¹ and R ⁵² And R ⁵³ each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent.

Examples of ortho ester compounds used for the synthesis of iminoether compounds represented by the general formula (1) include trimethyl orthoacetate, triethyl orthoacetate, tripropyl orthoacetate, tributyl orthoacetate, tribenzyl orthoacetate, trimethyl orthoformate, Triethyl orthoformate, tripropyl orthoformate, tributyl orthoformate, tribenzyl orthoformate, trimethyl orthopropionate, triethyl orthopropionate, tripropyl orthopropionate, tributyl orthopropionate, tributyl orthopropionate, trimethyl orthobenzoate, trimethyl orthobenzoate And triethyl orthobenzoate, tributyl orthobenzoate, and tribenzyl orthobenzoate.

The ortho ester compound may be a commercially available product or may be synthesized. In the case of synthesis, it can be synthesized by imidating a nitrile compound such as hydrogen cyanide, acetonitrile, propionitrile, n-butyronitrile, benzonitrile or the like and reacting with an alcohol or a method of reacting trichlorobenzene with an alkoxide.

(Thermoplastic polyurethane)
The thermoplastic polyurethane used in the present disclosure is a rubber-like elastic body having a urethane group (—NHCOO—) in its molecular structure, and is also called a urethane rubber or a urethane resin.
Thermoplastic polyurethanes are generally constructed by the polyaddition reaction of long chain glycols (polyols), polyisocyanates and short chain glycols (chain extenders).

The type of polyurethane used in the present disclosure is not particularly limited, and may be polyester-based polyurethane or polyether-based polyurethane.
In particular, in polyester-based polyurethane, a trace amount of carboxylic acid is contained in the raw material polyester polyol, and the polyester portion is thermally decomposed during molding or moist heat to generate carboxylic acid. Since a carboxylic acid acts as a catalyst for hydrolysis, polyester-based polyurethanes are easily hydrolyzable, but it is believed that the chain iminoether group-containing compound seals the carboxylic acid during molding and in wet heat. Therefore, when the polyurethane resin composition of the present disclosure contains a polyester-based polyurethane as the polyurethane, the hydrolysis resistance can be significantly improved.

In the present disclosure, commercially available thermoplastic polyurethanes can be suitably used. As a commercially available thermoplastic polyurethane, for example, Milactolan (registered trademark) E 580 (polyester polyurethane, manufactured by Nippon Polyurethane Co., Ltd.), Milactolan (registered trademark) E 180 (polyester polyurethane, manufactured by Nippon Polyurethane Co., Ltd.), Milactolan (registered trademark) E 380 (Polyether-based polyurethane, manufactured by Nippon Polyurethane Co., Ltd.) and the like.

In addition, the thermoplastic polyurethane used in the present disclosure may be obtained synthetically. The manufacturing method of the thermoplastic polyurethane used by this indication is not specifically limited, A well-known method is applied suitably. For example, a method of mixing and stirring the polyol component, the chain extender component and the polyisocyanate component simultaneously (one-shot method), a method of adding the chain extender to the prepolymer formed from the polyol component and the polyisocyanate component, and mixing and stirring (Prepolymer method) etc. are illustrated.

The polyol component which is a long chain glycol having terminal active hydrogen is not particularly limited, and a known polyol component is exemplified. That is, polyester type, polyether type, polycarbonate type, acrylic type, silicone type, 1,4-polybutadiene type, 1,2-polybutadiene type, phenolic type, castor oil type etc. having a molecular weight of 500 to 6000, preferably 1000 to 3000 And various polyols, flame retardant polyols and the like.

As polyester-based polyols, caprolactone-based, adipate-based, copolyester-based polyols and the like are generally preferably used. Specifically, for example, polycaprolactone, polycarbonate polyol, or dicarboxylic acid such as adipic acid, isophthalic acid or terephthalic acid and ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, 1,6-hexanediol, trimethylolpropane, neole Examples thereof include condensation reaction products with polyols such as pentyl glycol.

Examples of polyether-based polyols include polypropylene glycol-based polyols, polyethylene glycol-based glycols or ethylene oxide-modified products thereof, amine-modified products, or polyoxytetramethylene glycol. These can be used alone or, if desired, in combination of two or more.

These polyol components are preferably used in a proportion of 30 to 90% by mass, more preferably 40 to 70% by mass, based on the total of the polyol component, the chain extender and the polyisocyanate component. When the polyol component is used in an amount of 30% by mass or more, the reduction in moldability tends to be suppressed, while when it is used in a proportion of 90% by mass or less, the reduction in hydrolysis resistance tends to be suppressed.

As an isocyanate component which can be used by this indication, there is no limitation in particular and well-known polyisocyanate can be illustrated.
Specifically, for example, aliphatic diisocyanates such as 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, etc. Aliphatic diisocyanates or aromatic diisocyanates such as xylylene diisocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate, 1,5-naphthyl diisocyanate, etc. can be exemplified. These may be used alone or in combination of two or more.

The polyisocyanate component is preferably used in a proportion of 5 to 70% by mass, more preferably 15 to 40% by mass, based on the total amount of the polyisocyanate component, the polyol component and the chain extender. By setting the blending amount of the isocyanate component to 70% by mass or less with respect to the above total amount, the decrease in moldability tends to be suppressed, and by setting the blending amount to 5% by mass or more, the hydrolysis resistance and the compression permanent resistance There is a tendency that the deterioration of the distortion characteristics is suppressed.

The chain extender is not particularly limited, and known chain extenders are exemplified. Specifically, for example, 1,4-butanediol, 1,6-hexanediol, 2,3-butanediol, p-phenylenedi (β-hydroxyethyl) ether, p-xylylene glycol, glycerin monoallyl ether, di- At least one of glycols such as methylol dihydropyran, diamines such as ethylenediamine, 3,3'-dichloro-4,4'-diaminodiphenylmethane and diethyltoluylene diamine, water, etc. is used.

Catalysts can also be used to make polyurethanes. As a catalyst used for manufacture of polyurethane, there is no limitation in particular and a well-known catalyst system can be used conveniently. Specific examples thereof include organic metal compounds such as tin-based, lead-based, iron-based and titanium-based and amine-based compounds. More specifically, for example, stannous octoate (II), dibutyltin diacetate, dibutyltin dilaurate, dibutyltin mercaptide, lead octenoate, etc., and amine catalysts such as triethylamine, N, N-dimethylcyclohexylamine N, N, N ', N'-tetramethylethylenediamine, N, N, N', N '', N ''-pentamethyldiethylenetriamine, tetramethylguanidine, diphenylamine, dinaphthylamine, 4,4'-bis ( α, α-Dimethylbenzyl) diphenylamine, 1,4-diazabicyclo [2.2.2] octane, N-methylmorpholine, 1,2-dimethylimidazole, triethanolamine, dimethylethanolamine, bis (dimethylaminoethyl) ether Non-patent literature such as: " Examples thereof include compounds described in “Polyurethane resin handbook” (edited by Keiji Iwata (Nippon Kogyo Shimbun Co., Ltd., September 25, 1987).

These catalysts are used in a proportion of 0.5 to 10 parts by mass, preferably 1 to 3 parts by mass, per 100 parts by mass of the total amount of polyurethane raw materials consisting of the polyol component, the polyisocyanate component and the chain extender. If the addition amount of the catalyst is 0.5 parts by mass or more, the effect of improving the heat resistance, the abrasion resistance and the hydrolysis resistance is observed, while if it is 10 parts by mass or less, foaming or strength, Degradation of mechanical properties such as elongation is suppressed.

The polyurethane formation reaction using each of the above components is performed, for example, by a one-shot method or a prepolymer method. In the one-shot method, a urethanization catalyst is added simultaneously with each component, or in the prepolymer formation step in the prepolymer method, and in the prepolymer method, a chain extender is then added and reacted.

The components are mixed and stirred, the polyurethane formation reaction proceeds, and the reaction product is heat-aged, crushed and granulated to obtain pellets of thermoplastic polyurethane which can be used in the present disclosure.

(Chain-like iminoether group-containing compound)
The chain iminoether group-containing compound used in the present disclosure is an iminoether compound represented by the following general formula (1) or a multimer of the iminoether compound represented by the general formula (1).

In the general formula (1), the alkyl group represented by R ² is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 12 carbon atoms. The number of carbon atoms of the alkyl group represented by R ^2, indicate the number of carbon that does not contain a substituent group. The alkyl group represented by R ² may be linear or branched. The alkyl group represented by R ² may be a cycloalkyl group. The alkyl group represented by R ² is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, sec-butyl, iso-butyl, n-pentyl, A sec-pentyl group, an iso-pentyl group, an n-hexyl group, a sec-hexyl group, an iso-hexyl group, a cyclohexyl group and the like can be mentioned. The alkyl group represented by R ² is more preferably methyl, ethyl, n-propyl, iso-propyl, iso-butyl or cyclohexyl.
The alkyl group represented by R ² may further have a substituent. Examples of the substituent include the above-mentioned alkyl group, aryl group, alkoxy group, halogen atom, nitro group, amido group, hydroxyl group, ester group, ether group, aldehyde group and the like.

The aryl group represented by R ² is preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 12 carbon atoms. Number of carbon atoms of the aryl group represented by R ^2, indicate the number of carbon that does not contain a substituent group. The aryl group represented by R ^2, a phenyl group, a naphthyl group can be exemplified a phenyl group is particularly preferred.
The aryl group represented by R ² may further have a substituent. As the substituent, the above-mentioned substituents, that is, an alkyl group, an aryl group, an alkoxy group, a halogen atom, a nitro group, an amido group, a hydroxyl group, an ester group, an ether group, an aldehyde group and the like can be exemplified. The substituent is not particularly limited as long as it does not interfere with the reaction of the iminoether group with the carboxy group.

The alkoxy group represented by R ² is preferably an alkoxy group having 1 to 20 carbon atoms, more preferably an alkoxy group having 1 to 12 carbon atoms, and an alkoxy group having 2 to 6 carbon atoms Is particularly preferred. Number of carbon atoms of the alkoxy group represented by R ^2, indicate the number of carbon that does not contain a substituent group. The alkoxy group represented by R ² may be linear, branched or cyclic. Preferred examples of the alkoxy group represented by R ² may be a group at the end of the alkyl group represented by R ² -O- is linked.
The alkoxy group represented by R ² may further have a substituent. As the substituent, the above-mentioned substituents, that is, an alkyl group, an aryl group, an alkoxy group, a halogen atom, a nitro group, an amido group, a hydroxyl group, an ester group, an ether group, an aldehyde group and the like can be exemplified. The substituent is not particularly limited as long as it does not interfere with the reaction of the iminoether group with the carboxy group.

R ³ represents an alkyl group represented by the above general formula (2) or an aryl group represented by the above general formula (3). In formula (2), R ³¹ , R ³² and R ³³ each independently represent a hydrogen atom or a substituent. When R ³¹ , R ³² and R ³³ are substituents, the substituents represented by R ³¹ , R ³² and R ³³ may be linked to each other to form a ring. Examples of the substituent include the above-mentioned alkyl group, aryl group, alkoxy group, halogen atom, nitro group, amido group, hydroxyl group, ester group, ether group, aldehyde group and the like. R ³¹ , R ³² and R ³³ may all be hydrogen atoms or may be the same substituent, or may be different substituents.
The alkyl group represented by the general formula (2) may be linear or branched. The alkyl group represented by the general formula (2) may be a cycloalkyl group.
In Formula (3), R ⁴¹ represents a substituent, and n represents an integer of 0 to 5. When n is 2 or more, a plurality of R ⁴¹ may be the same as or different from each other, and may be linked to each other to form a ring. As the substituent, the above-mentioned substituents, that is, an alkyl group, an aryl group, an alkoxy group, a halogen atom, a nitro group, an amido group, a hydroxyl group, an ester group, an ether group, an aldehyde group and the like can be exemplified. . n is more preferably 0 to 3, and still more preferably 0 to 2.

R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent. As the alkyl group and the aryl group, the alkyl group and the aryl group that can be taken by R ² can be similarly exemplified. R ¹¹ , R ¹² and R ¹³ may be bonded to each other to form a ring.

The polyurethane resin composition of the present disclosure may contain, as a chain iminoether group-containing compound, a multimer of the iminoether compound represented by General Formula (1). For example, a chain iminoether group-containing compound containing as a repeating unit a structure excluding at least one of R ² , R ³ or R ¹¹ to R ^{13 in} the general formula (1) is preferable.

The iminoether compound represented by the general formula (1) is preferably represented by the following general formula (4) from the viewpoint of easiness of synthesis.

In General Formula (4), R ² represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkoxy group which may have a substituent, and R ¹¹ and R ¹² And R ¹³ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. R ⁴¹ represents a substituent, and n represents an integer of 0 to 5. If R ⁴¹ there are a plurality, even more R ⁴¹ is the same as each other or different, may form a ring.

In the general formula (4), R ² , R ¹¹ , R ¹² and R ¹³ have the same meaning as each other in the general formula (1), and preferred ranges are also the same. In Formula (4), R ⁴¹ has the same meaning as R ⁴¹ in Formula (3), and the preferred range is also the same. n is preferably 0 to 3, and more preferably 0 to 2.

The iminoether compound represented by the general formula (1) is a chain iminoether group-containing compound in which R ³ in the general formula (1) is represented by the general formula (3) from the ease of synthesis, that is, It is preferable to be represented by Formula (5).

In the general formula ^(5), R ^{11, R 12} and ^{R 13} are the same as those in formula (1), and preferred ranges are also the same. In formula (5), R ⁴¹ has the same meaning as R ⁴¹ in formula (3), and the preferred range is also the same. The R ²¹ can also be exemplified the same substituents as ^{R 41} in the general formula (3).

In the general formula (5), n is preferably 0 to 3, and more preferably 0 to 2. m is preferably 0 to 3, and more preferably 0 to 2.

As the multimer of the iminoether compound represented by the general formula (1), a chain iminoether group-containing compound represented by the following general formula (6) is preferable from the ease of synthesis.

In General Formula (6), R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent. R ⁴¹ represents a substituent, and n represents an integer of 0 to 5. If R ⁴¹ there are a plurality, even more R ⁴¹ is the same as each other or different, may form a ring. p represents an integer of 2 to 4, and L ¹ has an alkylene moiety which may have a substituent, an arylene moiety which may have a substituent, or a substituent at the end of bonding to a carbon atom It also represents a p-valent group which is a good alkoxylene moiety. The alkylene moiety which may have a substituent may be a cycloalkylene moiety which may have a substituent.

In the general formula ^(6), R ^{11, R 12} and ^{R 13} are the same as those in formula (1), and preferred ranges are also the same. In Formula (6), R ⁴¹ has the same meaning as R ⁴¹ in Formula (3), and the preferred range is also the same. n is preferably 0 to 3, and more preferably 0 to 2.

In General Formula (6), L ¹ is an alkoxy moiety which may have a substituent, an alkylene moiety which may have a substituent, an arylene moiety which may have a substituent, or a substituent, at the end of the bond to a carbon atom Represents a p-valent group which is a ren moiety p is an integer of 2 to 4, and p is preferably 2 or 3. The alkylene moiety which may have a substituent may be a cycloalkylene moiety which may have a substituent.
Specific examples of the divalent group include, for example, an alkylene group which may have a substituent, an arylene group which may have a substituent, and an alkoxylene group which may have a substituent. Further, the terminal of the bond with the carbon atom is an alkylene moiety which may have a substituent, an arylene moiety which may have a substituent, or an alkoxylene moiety which may have a substituent, as a partial structure, -SO _2- , -CO-, substituted or unsubstituted alkylene moiety, substituted or unsubstituted alkenylene moiety, alkynylene moiety, substituted or unsubstituted phenylene moiety, substituted or unsubstituted biphenylene moiety, substituted or unsubstituted naphthylene And groups containing at least one selected from -O-, -S- and -SO-. The alkylene moiety which may have a substituent may be a cycloalkylene moiety which may have a substituent.
Preferably, for example, substituted or unsubstituted phenylene group, substituted or unsubstituted biphenylene group, substituted or unsubstituted naphthylene group, ethylene group, n-butylene group, substituted or unsubstituted cyclohexylene group, substituted or unsubstituted group -C ₆ H ₁₀ -C ₆ H _10- , substituted or unsubstituted -C ₆ H ₁₀ -CH ₂ -C ₆ H _10- , substituted or unsubstituted -C ₆ H ₄ -C (CH ₃ ) ₂ _-C ₆ H ₄ -, -C substituted or unsubstituted _{_{_{_{6 H 4 -CH 2 -C 6 H}}}} 4 -, substituted or unsubstituted _{_{-C 6 H 4 -C (O)}} -C 6 H 4 -, substituted or unsubstituted _{_{_{-C 6 H 4 -O-C 6}}} H 4 -, -C substituted or unsubstituted _{_{_{6 H 4 -S-C 6 H}}} 4 -, substituted or unsubstituted _-C 6 _H 4 -SO ₂ -C ₆ H ₄ -, also substituted Ku is unsubstituted _{_{_{_{-C 6 H 4 -C (CF 3}}}} ) 2 -C 6 H 4 -, substituted or unsubstituted _{_{-C 6 H 4 -NHC (O)}} -C 6 H 4 -, substituted or unsubstituted of _{_{_{_{-C 6 H 4 -O-C 6}}}} H 4 -C (CH 3) 2 -C 6 H 4 -O-C 6 H 4 -, substituted or unsubstituted _{_{_{-C 6 H 4 -O-C 6}}} H _{_{_{4 -C (O) -C 6 H}}} 4 -O-C 6 H 4 -, -C 6 H 4 substituted or unsubstituted _{_{_{_{-O-C 6 H 4 -SO 2}}}} -C 6 H 4 -O-C 6 _H ₄ -, _-C 6 H ₄ substituted or unsubstituted _{_{_{_{-O-C 6 H 4 -S-}}}} C 6 H 4 -O-C 6 H 4 -, -C 6 substituted or unsubstituted _H 4 -O- _{_{_{(C 6 H 4) 2 -O}}} -C 6 H 4 -, substituted or unsubstituted _{_{_{_{-C 6 H 4 -O-C 6}}}} H 4 -C (CF 3) 2 -C 6 H 4 -O-C 6 ₄ -, and the like.
As a specific example of a trivalent group, the group which remove | eliminated one hydrogen atom from the structure which has a substituent among the groups mentioned as an example of a bivalent group is mentioned, for example.
As a specific example of a tetravalent group, the group which remove | eliminated two hydrogen atoms from the structure which has a substituent among the groups mentioned as an example of a bivalent group is mentioned, for example.

In the present disclosure, by setting p in the general formula (6) to 2 to 4, a compound having two or more iminoether moieties in one molecule can be obtained, and a more excellent end capping effect can be exhibited. it can. Furthermore, the iminoether value (total molecular weight / number of iminoether groups) can be lowered by using a compound having two or more iminoether moieties in one molecule, and an iminoether compound can be efficiently reacted with a carboxy group. it can.

As a multimer of the iminoether compound represented by General formula (1), the chain-like iminoether group containing compound represented by following General formula (7) is also preferable from the easiness of a synthesis | combination.

In the general formula (7), R ² , R ¹¹ , R ¹² and R ¹³ have the same meanings as each other in the general formula (1), and the preferred ranges are also the same.

In the general formula (7), L ² represents a p-valent group which is an arylene moiety which may have a substituent or a cycloalkylene moiety which may have a substituent, at the end of the bond to the nitrogen atom. L ² is preferably a p-valent group in which the end of the bond to the nitrogen atom is an arylene moiety which may have a substituent. p is an integer of 2 to 4, and p is preferably 2 or 3.
Specific examples of L ² include an arylene group which may have a substituent, and a cycloalkylene group which may have a substituent. The end of the bond to the nitrogen atom is an arylene moiety which may have a substituent or a cycloalkylene moiety which may have a substituent, and as a partial structure, —SO ₂ —, —CO—, substituted or unsubstituted , An substituted or unsubstituted alkenylene moiety, an alkynylene moiety, a substituted or unsubstituted phenylene moiety, a substituted or unsubstituted biphenylene moiety, a substituted or unsubstituted naphthylene moiety, -O-, -S- and -SO- And groups containing at least one selected from
Preferably, for example, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted cyclohexylene group, a substituted or unsubstituted -C ₆ H ₁₀ -C ₆ H ₁₀ -, substituted or unsubstituted _{_{_{_{-C 6 H 10 -CH 2 -C 6}}}} H 10 -, substituted or unsubstituted _{_{_{_{-C 6 H 4 -C (CH 3}}}} ) 2 -C 6 H 4 -, substituted or unsubstituted _{_{_{_{-C 6 H 4 -CH 2 -C 6}}}} H 4 -, substituted or unsubstituted _{_{-C 6 H 4 -C (O)}} -C 6 H 4 -, substituted or unsubstituted _-C 6 H _{_{_{4 -O-C 6 H 4 -}}} , substituted or unsubstituted _{_{_{_{-C 6 H 4 -SC 6 H 4}}}} -, -C substituted or unsubstituted _{_{_{_{6 H 4 -SO 2 -C 6 H}}}} 4 -, substituted or unsubstituted _-C 6 _H 4 -C substitution _{_{_{_{CF 3) 2 -C 6 H 4}}}} -, substituted or unsubstituted _{_{-C 6 H 4 -NHC (O)}} -C 6 H 4 -, -C substituted or unsubstituted _{_{_{6 H 4 -O-C 6 H}}} 4 _{_{_{_{-C (CH 3) 2 -C 6}}}} H 4 -O-C 6 H 4 -, substituted or unsubstituted _{_{_{_{-C 6 H 4 -O-C 6}}}} H 4 -C (O) -C 6 H 4 -O -C ₆ H ₄ -, _-C 6 _H 4 substituted or unsubstituted _{_{_{_{-O-C 6 H 4 -SO 2}}}} -C 6 H 4 -O-C 6 H 4 -, substituted or unsubstituted _-C 6 H _{_{_{_{4 -O-C 6 H 4 -S}}}} -C 6 H 4 -O-C 6 H 4 -, -C 6 substituted or unsubstituted _{_{_{_{H 4 -O- (C 6 H 4}}}} ) 2 -O-C 6 H ₄ -, a substituted or unsubstituted _{_{_{_{-C 6 H 4 -O-C 6}}}} H 4 -C (CF 3) 2 -C 6 H 4 -O-C 6 H 4 -, and the like.

As a multimer of the iminoether compound represented by General formula (1), the chain-like iminoether group containing compound represented by following General formula (8) is also preferable from the easiness of a synthesis | combination.

In General Formula (8), R ² is synonymous with R ² in General Formula (1), and its preferable range is also the same. In Formula (8), R ⁴¹ has the same meaning as R ⁴¹ in Formula (3), and the preferred range is also the same. n is preferably 0 to 3, and more preferably 0 to 2. R ² may link to R ⁴¹ to form a ring.

In general formula (8), L ³ represents a p-valent group in which the end of the bond to the oxygen atom is an alkylene part. In the alkylene moiety of L ³ , part or all of the hydrogen atoms may be substituted with an alkyl group which may have a substituent or an aryl group which may have a substituent. p is an integer of 2 to 4, and p is preferably 2 or 3.
Specific examples of L ^3, include an alkylene group. The end of the bond to the oxygen atom is an alkylene moiety, and as a partial structure, -SO _2- , -CO-, a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, an alkynylene group, a substituted or unsubstituted Examples thereof include a group containing at least one selected from a phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted naphthylene group, -O-, -S- and -SO-.
Preferably, for example, ethylene group, n-butylene group, substituted or unsubstituted -CH ₂ -C (CH ₃ ) ₂ -CH _2- , substituted or unsubstituted -CH ₂ -C ₆ H ₄ -CH _2- , Etc.

The molecular weight (total molecular weight / number of iminoether groups) per iminoether group of the chain iminoether group-containing compound used in the present disclosure is preferably 1000 or less, more preferably 750 or less, and 500 or less Is more preferred. By setting the molecular weight per iminoether group to 1000 or less, it becomes possible to seal the terminal carboxy group of the polyurethane with a low addition amount.

Although the preferable specific example of the iminoether compound represented by General formula (1) and its multimer is shown below, the chain-like iminoether group containing compound which can be used by this indication is not limited to these.

The polyurethane resin composition of the present disclosure includes a polyurethane and at least one linear iminoether group-containing compound selected from an iminoether compound represented by the general formula (1) and an oligomer thereof, at the time of molding. Can be effectively suppressed, and a polyurethane resin molded product having hydrolysis resistance can be produced.
Moreover, the color taste of a molded object can also be controlled by adjusting the addition amount of a chain-like iminoether group containing compound.

The polyurethane resin composition of the present disclosure preferably contains 0.05 to 3 parts by mass of a chain iminoether group-containing compound with respect to 100 parts by mass of polyurethane. The hydrolysis resistance of the polyurethane resin molded article can be further improved by setting the addition amount of the chain iminoether group-containing compound to preferably 0.05 parts by mass or more with respect to 100 parts by mass of the polyurethane, 3 By setting it as mass part or less, the heat resistance and hydrolysis resistance of a polyurethane resin molding can be improved more.

In addition to the improvement of the hydrolysis resistance of the polyurethane resin molded product and the suppression of the thickening at the time of molding, from the viewpoint of suppressing the yellowish more effectively, a chain iminoether group-containing compound is added to 100 parts by mass of the polyurethane. It is more preferable to include 0.1 to 2.0 parts by mass.
In addition, although the polyurethane resin composition of this indication may use chain-like iminoether group containing compound individually by 1 type, and may use multiple types together, the chain-type iminoether group containing compound of multiple types may be used. When using together, it is preferable that a total amount is the said range.

The polyurethane resin composition of the present disclosure can be added to various additives such as a compatibilizer, a plasticizer, a weathering agent, an antioxidant, a heat stabilizer, a lubricant, and the like, as long as the effects of the present invention are not significantly impaired. The composition may contain an inhibitor, a brightener, a colorant, a conductive agent, an ultraviolet absorber, a flame retardant, a flame retardant aid, a pigment, a dye and the like.

The polyurethane resin composition of the present disclosure does not refuse to contain an end capping agent other than the iminoether compound described above, as long as the effects of the present invention are not significantly impaired. The polyurethane resin composition of this indication can also use together the terminal blocker chosen from a carbodiimide compound, an epoxy compound, and an oxazoline compound other than the iminoether compound mentioned above, for example.

<Polyurethane resin molding>
The method for producing a polyurethane resin molded product using the polyurethane resin composition of the present disclosure is not particularly limited, and a known molding method may be applied depending on the use. For example, the polyurethane resin composition of the present disclosure is used as a raw material, and molded into a molded article of a desired shape such as a sheet using an injection molding machine, an extruder, a casting machine or the like, preferably 5 to 24 at 80 to 150 ° C. Secondary crosslink (anneal) about time. Thereby, a polyurethane resin molded product excellent in hydrolysis resistance and moldability can be obtained.

The application of the polyurethane resin composition of the present disclosure is not particularly limited, and for example, it is suitably used for the production of polyurethane resin molded articles such as urethane foams such as sealing materials and heat insulators, shoe products, and automotive parts such as bumpers and headrests. Can.

Hereinafter, the present invention will be more specifically described by way of examples. The materials, amounts used, proportions, treatment contents, treatment procedures and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention is not limited to the examples shown below. In addition, "part" is mass reference | standard unless there is particular notice.

In the examples, first, the following exemplified compounds were synthesized as iminoether compounds.

Synthesis Example 1
<Synthesis of iminoether (1)>

In a 5 L three-necked flask, 600 g (2.80 mol) of triethoxymethylbenzene, 498 g (1.28 mol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 480 ml of toluene, 0.24 g of methanesulfonic acid The mixture was charged with 2.5 mmol) and stirred under heating reflux for 2 hours. The reaction system temperature was brought to 100 ° C. or lower, and the refluxed ethanol was removed by a Dean-Stark apparatus. After confirming the completion of the reaction by TLC (thin layer chromatography), the reaction solution was cooled to room temperature, methanol was added and crystallized to obtain 777 g (yield 95%) of iminoether (1). The obtained compound was identified by ¹ H-NMR.

Synthesis Example 2
<Synthesis of iminoether (2)>

In a 5 L three-necked flask, 512 g (2.80 mol) of trimethoxymethylbenzene, 498 g (1.28 mol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 480 ml of toluene, 0.24 g of methanesulfonic acid The mixture was charged with 2.5 mmol) and stirred under heating reflux for 2 hours. The reaction system temperature was adjusted to 100 ° C. or less, and the refluxed methanol was removed by a Dean-Stark apparatus. After completion of the reaction was confirmed by TLC, the reaction solution was cooled to room temperature and methanol was added to crystallize to obtain 745 g (yield 95%) of iminoether (2). The obtained compound was identified by ¹ H-NMR.

Synthesis Example 3
<Synthesis of iminoether (3)>

In a 5-L three-necked flask, 338 g (2.80 mol) of trimethyl orthoacetate, 498 g (1.28 mol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 480 ml of toluene, 0.24 g of methanesulfonic acid (2 .5 mmol) was added and stirred for 2 hours under heating and reflux. The reaction system temperature was adjusted to 100 ° C. or less, and the refluxed methanol was removed by a Dean-Stark apparatus. After completion of the reaction was confirmed by TLC, the reaction solution was cooled to room temperature, and methanol was added to crystallize to obtain 615 g (yield 92%) of iminoether (3). The obtained compound was identified by ¹ H-NMR.

Synthesis Example 4
<Synthesis of iminoether (4)>

In a 5 L three-necked flask, 512 g (2.80 mol) of trimethoxymethylbenzene, 310 g (1.28 mol) of 4,4'-diaminobenzanilide, 480 ml of toluene and 0.24 g (2.5 mmol) of methanesulfonic acid are charged, and heated to reflux. Stir for 2 hours below. The reaction system temperature was adjusted to 100 ° C. or less, and the refluxed methanol was removed by a Dean-Stark apparatus. After completion of the reaction was confirmed by TLC, the reaction solution was cooled to room temperature, and methanol was added to crystallize to obtain 504 g (yield 85%) of iminoether (4). The obtained compound was identified by ¹ H-NMR.

Synthesis Example 5
<Synthesis of iminoether (5)>

In a 5 L three-necked flask, 512 g (2.80 mol) of trimethoxymethylbenzene, 191.8 g (1.28 mol) of 4-aminoacetanilide, 480 ml of toluene and 0.24 g (2.5 mmol) of methanesulfonic acid are charged, and heated under reflux 2 Stir for hours. The reaction system temperature was adjusted to 100 ° C. or less, and the refluxed methanol was removed by a Dean-Stark apparatus. After completion of the reaction was confirmed by TLC, the reaction solution was cooled to room temperature and methanol was added to crystallize to obtain 309 g (yield 90%) of iminoether (5). The obtained compound was identified by ¹ H-NMR.

Synthesis Example 6
<Synthesis of iminoether (6)>

In a 5-L three-necked flask, 210 g (1.0 mol) of 4,4'-methylenebis (cyclohexylamine), 243 g (2.4 mol) of triethylamine and 1.0 L of dimethylacetamide are charged, and 336 g (2.4 mol) of benzoyl chloride in an ice bath After dropwise addition, the mixture was stirred at room temperature for 1 hour. 2.0 L of 1 mol / L hydrochloric acid water was added, and the mixture was stirred for 1 hour, and filtered to obtain 397 g (yield 95%) of an intermediate product (6-1). The obtained compound was identified by ¹ H-NMR.

In a 5 L three-necked flask, 300 g of the intermediate product (6-1) and 1.0 L of thionyl chloride were added, and after stirring at 65 ° C. for 2 hours, excess thionyl chloride was removed under reduced pressure. After cooling to room temperature, 1.0 ml of THF (tetrahydrofuran) was added, and 310 g (1.6 mol) of sodium methylate 28 mass% methanol solution (trade name: SM-28) was added dropwise under an ice bath, and then 1 hour at room temperature It stirred. After adding 1.5 L of ethyl acetate and 1.0 L of pure water, liquid separation was carried out, after drying with magnesium sulfate, the solid was obtained by concentrating. Thereto, 2.0 L of methanol was added, and stirred at room temperature for 1 hour, followed by filtration to obtain 288 g (yield 90%) of iminoether (6). The obtained compound was identified by ¹ H-NMR.

Synthesis Example 7
<Synthesis of iminoether (7)>

In a 5 L flask, 296 g (2.4 mol) of 2-aminobenzyl alcohol, 243 g (2.4 mol) of triethylamine and 1.5 L of dimethylacetamide are charged, and 203 g (1.0 mol) of terephthalic acid chloride is added in portions under an ice bath. After stirring for 1 hour, 2.0 L of 1 mol / L hydrochloric acid water was added, and the mixture was stirred for 1 hour, followed by filtration to obtain 357 g (yield 95%) of an intermediate product (7-1). The obtained compound was identified by ¹ H-NMR.

In a 5 L three-necked flask, 300 g (0.8 mol) of the intermediate product (7-1) and 1.0 L of thionyl chloride were added, and after stirring at 65 ° C. for 2 hours, excess thionyl chloride was concentrated and removed. After adding 1.0 L of methanol, 386 g (2.0 mol) of sodium methylate 28 mass% methanol solution (trade name: SM-28) is slowly added dropwise under an ice bath, and 1 hour at room temperature, 50 hours at 40 ° C. It stirred. The precipitate is filtered and methanol is removed under reduced pressure, and 1.5 L of ethyl acetate is added, separated, dried over magnesium sulfate, crystallized by adding methanol, and filtered to obtain an iminoether (7). 136 g (50% yield) were obtained. The obtained compound was identified by ¹ H-NMR.

Synthesis Example 8
<Synthesis of iminoether (8)>

A solution of 92.4 g (0.75 mol) of p-anisidine, 59 g (0.75 mol) of pyridine in 500 ml of N, N-dimethylacetamide under ice-cooling, 50 g (0.19 mol) of N, N-dimethyl trimesic acid trichloride A solution of 100 ml of acetamide was added dropwise. After heating up to room temperature, it stirred for 3 hours. The reaction solution was slowly added to 5 L of water to precipitate a solid. The solid was separated by filtration, and the obtained solid was dispersed in methanol and filtered again. This operation was repeated twice, and the obtained solid was dried to obtain 96.8 g (yield 97%) of an intermediate product (8-1).

A suspension of 26.3 g (50 mmol) of the intermediate product (8-1) in 100 ml of thionyl chloride was stirred for 3 hours while heating under reflux. After confirming that the reaction system became transparent, the mixture was further stirred for 2 hours. After thionyl chloride was distilled off, 200 ml of tetrahydrofuran was added, and 21.2 g (110 mol) of a sodium methylate 28% by mass methanol solution (trade name: SM-28) was added dropwise under ice-cooling. The temperature of the system was raised to room temperature, and after stirring for 10 minutes, ethyl acetate / water was added to separate the layers. The organic phase was washed with water and the organic phase was dried over magnesium sulfate. After the solvent was distilled off, purification was performed by silica gel column chromatography using a mixed solvent of ethyl acetate / hexane as an eluent. The solvent was distilled off to obtain 25.0 g (yield 88%) of iminoether (8). The obtained compound was identified by ¹ H-NMR.

<Synthesis of iminoether (9)>
Synthesis Example 9

Under ice-cooling, 95 g (0.5 mol) of benzoyl chloride was slowly added to a solution of 46.5 g (0.5 mol) of aniline and a solution of 44 g (0.6 mol) of pyridine in N, N-dimethylacetamide under ice cooling. The temperature of the reaction system was raised to room temperature, and the completion of the reaction was confirmed by TLC. After 50 ml of methanol was added, the reaction solution was slowly added to 5 liters of water to precipitate a solid. The solid was separated by filtration, and the obtained solid was dispersed in methanol and filtered again. This operation was repeated twice, and the obtained solid was dried to obtain 89.7 g (yield 91%) of an intermediate product (9-1).

A suspension of 9.9 g (50 mmol) of intermediate product (9-1) in 400 ml of thionyl chloride and a catalytic amount of N, N-dimethylformamide was stirred for 18 hours while heating under reflux. After confirming that the reaction system was completely dissolved, the mixture was further stirred for 2 hours. Thereafter, thionyl chloride was distilled off to obtain 10.8 g (quant.) Of an intermediate product (9-2).

After 2.0 g (50 mmol) of sodium hydride (60% by mass) was dispersed with hexane and allowed to stand, the supernatant hexane was removed with a Pasteur pipette. This operation was repeated twice and 50 ml of a tetrahydrofuran solution was added. Under ice-cooling, 1.6 g (25 mmol) of ethylene glycol was added. It confirmed visually that generation | occurrence | production of the bubble was complete | finished from system inside, and the tetrahydrofuran solution of ethylene dimethoxide was prepared.

150 ml of a tetrahydrofuran solution of 10.8 g (50 mmol) of the intermediate product (9-2) was cooled to −5 ° C., and the prepared tetrahydrofuran solution of ethylene dimethoxide was added dropwise. The temperature of the system was raised to room temperature, and after stirring for 30 hours, ethyl acetate / water was added to separate the layers. The organic phase was washed with water and the organic phase was dried over magnesium sulfate. After the solvent was distilled off, purification was performed by silica gel column chromatography using a mixed solvent of ethyl acetate / hexane as an eluent. The solvent was distilled off to obtain 6.5 g (yield 62%) of iminoether (9). The obtained compound was identified by ¹ H-NMR.

Example 1
1 part by mass of iminoether (1) is added to 100 parts by mass of Milactolan (registered trademark) E 580 (polyester-based polyurethane synthesized using caprolactone-based polyol as a raw material as a raw material, manufactured by Nippon Polyurethanes Co.) , Molded by injection molding machine under the forming conditions of nozzle temperature 190 ° C, cylinder front temperature 180 ° C, cylinder middle temperature 170 ° C, cylinder rear temperature 150 ° C, and sheet-like molded product (150 × 150 × 2 mm) And heated in an oven at 85 ° C. for 16 hours to prepare a test piece.

-Performance evaluation of polyurethane resin molding-
(Mod heat resistance: hydrolysis resistance)
The obtained test pieces were subjected to a moist heat aging test for 500 hours in an atmosphere at a temperature of 90 ° C. and a relative humidity of 95%. The elongation retention at break was determined and evaluated according to the following criteria. With respect to the breaking elongation of the test piece before storage, the breaking elongation of the test piece after storage under the above conditions was taken as a breaking elongation retention (%), and evaluated according to the following criteria. It can be said that the higher the fracture retention rate, the higher the hydrolysis resistance. The obtained results are shown in Table 1 below.
A: 90% or more B: 70% or more and less than 90% C: less than 70%

(Formability)
The resin pressure at the time of molding was confirmed by the pressure gauge of the extruder and evaluated according to the following criteria.
A: Increase in resin pressure is 0% or more and less than 50% in comparison with Comparative Example 1 B: Comparison with Comparative Example 1 is 50% or more and less than 100% in C: Comparison with Comparative Example 1 and resin 100% or more increase in pressure

(Color)
The obtained test pieces were visually evaluated according to the following criteria.
A: Yellowishness is equivalent to Comparative Example 1 and acceptable level.
B: Yellowishness is larger than Comparative Example 1 and unacceptable level.

Comparative Example 1
Test pieces were prepared and evaluated in the same manner as in Example 1 except that the iminoether (1) was not added.

[Examples 2 to 8, Comparative Examples 2 to 3, 6]
Test pieces were prepared and evaluated in the same manner as in Example 1 except that the compounds described in Table 1 were added instead of the iminoether (1).
The cyclic carbodiimide (1) and the cyclic carbodiimide (2) used in Comparative Examples 2 and 3 were synthesized with reference to JP 2011-256337A.

[Examples 9 to 12]
Test pieces were prepared and evaluated in the same manner as in Example 1 except that the addition amount of the iminoether (1) was changed as described in Table 1, respectively.

[Example 13]
Same as Example 1 except that Milactolan (registered trademark) E 580 (manufactured by Nippon Polyurethane Co., Ltd.) is changed to Milactolan (registered trademark) E 180 (polyester polyurethane synthesized from adipate based polyol as a raw material as a raw material, manufactured by Nippon Polyurethane Co., Ltd.) Test pieces were prepared and evaluated.

Example 14
Example 1 except that Milactolan (registered trademark) E 580 (manufactured by Nippon Polyurethane Co., Ltd.) is changed to Milactolan (registered trademark) E 380 (polyether polyurethane synthesized from polyether-based polyol as a polyol component, manufactured by Nippon Polyurethane Co., Ltd.) Test pieces were prepared and evaluated in the same manner as in.

Comparative Example 4
Test pieces were prepared and evaluated in the same manner as in Example 1 except that tetramethylenebisoxazoline (TMBO) having the following structure synthesized in the following Synthesis Example 10 was added instead of the iminoether (1) and added.

Synthesis Example 10
<Composition of TMBO>

In a 5-L flask, 500 g (2.47 mol) of diethyl adipate and 1500 g (9.9 mol) of ethanolamine were charged, and ethanol generated was distilled off while stirring at 170 ° C. for 1 hour. After cooling to room temperature, benzene and methanol were added for recrystallization, and filtration was performed to obtain 471 g (yield 82%) of an intermediate product TMBO-1. The obtained compound was identified by ¹ H-NMR.

185.7 g (0.8 mol) of TMBO-1 and 1.0 L of chloroform were charged into a 5 L three-necked flask, and 238 g (2.0 mol) of thionyl chloride was added dropwise under an ice bath, and the mixture was stirred at room temperature for 2 hours. After excess thionyl chloride is distilled off under reduced pressure, 1.0 L of methanol is added, and 771.7 g (4.0 mol) of a sodium methylate 28% by mass methanol solution (trade name: SM-28) is slowly added dropwise to obtain a room temperature The mixture was stirred at 40 ° C. for 30 hours under the condition of 2 hours. The reaction solution was cooled to room temperature, filtered, and the solvent was evaporated under reduced pressure. Then, 1.0 L of ethyl acetate was added, and after filtering, ethyl acetate was evaporated under reduced pressure. The obtained oily compound was distilled and purified at 128 ° C. and 133.3 Pa (1 Torr) to obtain 118 g (75% yield) of TMBO. The obtained compound was identified by ¹ H-NMR.

Comparative Example 5
Test pieces were prepared and evaluated in the same manner as in Example 1 except that Epocross (registered trademark) RPS (an oxazoline group-containing reactive polystyrene, manufactured by Nippon Shokubai Co., Ltd.) was added instead of the iminoether (1).

Resins used in Examples and Comparative Examples, chain iminoether group-containing compounds and comparative compounds and evaluation results are shown in Table 1 below. In addition, the symbol of resin in Table 1 means the following.
-PU-A: Milactolan E 580 (polyester polyurethane synthesized from caprolactone polyol as a polyol component) manufactured by Nippon Polyurethane Industry Co., Ltd.
-PU-B: Milactolan E 180 manufactured by Nippon Polyurethane Industry Co., Ltd. (Polyester-based polyurethane synthesized from adipate-based polyol as a polyol component)
-PU-C: Milactolan E 380 manufactured by Nippon Polyurethane Co., Ltd. (Polyether-based polyurethane synthesized from an ether-based polyol as a polyol component)

From the said Table 1, the polyurethane resin composition of each Example which added the chain-like iminoether group containing compound which concerns on this indication was excellent in hydrolysis resistance (wet heat resistance) and a moldability.
In Comparative Example 6, since the reactivity of the cyclic iminoether (7) is low, the hydrolysis resistance of the molded product is inferior, and it is considered that the moldability is lowered by the partial reaction, high molecular weight formation and thickening. .

The disclosure of Japanese Patent Application 2014-265717, filed December 26, 2014, is incorporated herein by reference in its entirety.
All documents, patents, patent applications, and technical standards described herein are specifically and individually indicated that each individual document, patent, patent application, and technical standard is incorporated by reference. To the same extent, incorporated herein by reference.

Claims

A thermoplastic polyurethane, and at least one chained iminoether group-containing compound selected from an iminoether compound represented by the following general formula (1) and a multimer of an iminoether compound represented by the general formula (1); A polyurethane resin composition comprising

In the general formula (1), R 2 represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkoxy group which may have a substituent, and R 3 represents R 11 represents an alkyl group represented by Formula (2) or an aryl group represented by the following General Formula (3), and R 11 , R 12 and R 13 each independently represent a hydrogen atom or an alkyl which may have a substituent Represents an aryl group which may have a group or a substituent.

In formula (2), R 31 , R 32 and R 33 each independently represent a hydrogen atom or a substituent. R 31 , R 32 and R 33 may be linked to each other to form a ring. In Formula (3), R 41 represents a substituent, and n represents an integer of 0 to 5. If R 41 there are a plurality, even more R 41 is the same as each other or different, may form a ring. In the general formulas (2) and (3), * represents a position to be bonded to a nitrogen atom.
The polyurethane resin composition according to claim 1, wherein R 3 in the general formula (1) is an aryl group represented by the general formula (3).
The polyurethane resin composition according to claim 1 or 2, wherein the iminoether compound represented by the general formula (1) is a chain iminoether group-containing compound represented by the following general formula (5).

In formula (5), R 11 , R 12 and R 13 each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. R 21 represents a substituent, m represents an integer of 0 to 5, when R 21 there are a plurality, even more R 21 is the same as each other or different, a ring together You may form. R 41 represents a substituent, n represents an integer of 0 to 5, when R 41 there are a plurality, even more R 41 is the same as each other or different, a ring together You may form.
4. The compound according to any one of claims 1 to 3, wherein the multimer of the iminoether compound represented by the general formula (1) is a chain iminoether group-containing compound represented by the following general formula (6). The polyurethane resin composition as described.

In General Formula (6), R 11 , R 12 and R 13 each independently represent a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent. R 41 represents a substituent, and n represents an integer of 0 to 5. If R 41 there are a plurality, even more R 41 is the same as each other or different, may form a ring. p represents an integer of 2 to 4, and L 1 has an alkylene moiety which may have a substituent, an arylene moiety which may have a substituent, or a substituent at the end of bonding to a carbon atom It also represents a p-valent group which is a good alkoxylene moiety.
The multimer of the iminoether compound represented by the general formula (1) is a chain iminoether group-containing compound represented by the following general formula (7) The polyurethane resin composition as described.

In the general formula (7), R 2 represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkoxy group which may have a substituent, and R 11 and R 12 And R 13 each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. p represents an integer of 2 to 4, and p represents a p-valent group in which L 2 is a arylene moiety which may have a substituent or a cycloalkylene moiety which may have a substituent. Represents
4. The compound according to any one of claims 1 to 3, wherein the multimer of the iminoether compound represented by the general formula (1) is a chain iminoether group-containing compound represented by the following general formula (8). The polyurethane resin composition as described.

In general formula (8), R 2 represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkoxy group which may have a substituent, and R 41 represents a substituent And n represents an integer of 0 to 5. If R 41 there are a plurality, even more R 41 is the same as each other or different, may form a ring. p represents an integer of 2 to 4, and L 3 represents a p-valent group in which the bonding end with the oxygen atom is an alkylene part. In the alkylene moiety of L 3 , part or all of the hydrogen atoms may be substituted with an alkyl group which may have a substituent or an aryl group which may have a substituent.
The polyurethane resin composition according to any one of claims 1 to 6, wherein the linear iminoether group-containing compound is contained in an amount of 0.1 to 2.0 parts by mass with respect to 100 parts by mass of the thermoplastic polyurethane.
The polyurethane resin composition according to any one of claims 1 to 7, wherein the thermoplastic polyurethane is a polyester-based polyurethane.
A polyurethane resin molded article molded using the polyurethane resin composition according to any one of claims 1 to 8.