JP2011122029A - One-pack type moisture curable resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a one pack-type moisture curable resin composition which ensures an appropriate pot life at room temperature while having storage stability and can be inexpensively produced. <P>SOLUTION: The one-pack type moisture curable composition includes a compound (A) having at least two 5-membered ring carbonate groups represented by formula (1) [wherein X is a residue of the compound (A)] in the molecule, and a ketimine compound (B) having a ketimine (C=N) bond led from a ketone or an aldehyde and an amine and a structure in which a branched carbon or a ring-member carbon is bonded to the α-position and/or the β-position of at least one of the carbon or the nitrogen of the ketimine group. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a one-component moisture-curable resin composition useful as an adhesive and a sealing material in the fields of civil engineering, construction, and building materials.

  The polyisocyanate compound reacts with a curing agent such as polyol or amine to form a urethane bond or a urea bond, and a cured product is obtained. The polyisocyanate compound forms a three-dimensional crosslinked structure by reaction with a curing agent, and becomes a polyurethane cured product excellent in high strength, high elongation, abrasion resistance, grease resistance, etc. It is used for sealants and adhesives.

  As a polyurethane cured product obtained by reacting a polyisocyanate compound and a curing agent, a one-component or two-component curable resin composition may be mentioned. Examples of the one-component curable resin composition include a curable resin composition containing a urethane prepolymer and a latent curing agent such as ketimine and oxazolidine. This one-component curable resin composition is a non-foaming material in which an amine regenerated by hydrolysis of a latent curing agent by moisture in the atmosphere reacts with a urethane prepolymer and is cured. Storage stability was poor, and an appropriate pot life could not be secured.

  In addition, in a two-component curable resin composition in which a urethane prepolymer and a curing agent such as an amine, polyol or acid anhydride are mixed at the time of use, the isocyanate compound reacts with moisture mixed during storage. In some cases, the storage stability decreased due to thickening, or the pot life was not sufficient under high temperature and high humidity.

  Therefore, a curable resin composition having a five-membered cyclic carbonate group in the molecule instead of an isocyanate group in the molecule has been proposed as a two-component curable resin composition. Since the curable resin composition is not affected by moisture during storage, it is intended to improve storage stability, pot life, adhesion, and water resistance (see, for example, Patent Document 1).

JP 2009-155407 A

  However, the composition is applied in a two-part curable resin composition, and using a five-membered cyclic carbonate group instead of an isocyanate group in the one-part type reacts with a curing agent amine, so that one-part type curing is used. There is a problem that the potable time cannot be secured while the storage resin composition has storage stability.

  In addition, storage stability is improved with a one-part curable resin composition rather than a two-part curable resin composition from the viewpoint of convenience in work, such as less time and effort for mixing a main agent and a curing agent during work, and reduction in manufacturing cost. There is a need for a resin composition that has a sufficient pot life at room temperature, has curability, and can be manufactured at low cost.

  In view of the above problems, an object of the present invention is to provide a one-component moisture-curable resin composition that can be produced at a low cost while ensuring an appropriate pot life at room temperature while having storage stability. To do.

（２） ５員環カーボネート基を少なくとも２つ有する化合物（Ａ）のＸが下記式（２）で示される基を有することを特徴とする上記（１）に記載の１液型湿気硬化性樹脂組成物。

（３） 前記ケチミン化合物（Ｂ）が、メチルイソプロピルケトン、又はジイソブチルケトンを用いて得られるものであることを特徴とする上記（１）又は（２）に記載の１液型湿気硬化性樹脂組成物。
（４） さらに、エポキシ樹脂（Ｃ）を含有することを特徴とする上記（１）〜（３）の何れか一項に記載の１液型湿気硬化性樹脂組成物。 The present invention includes the following (1) to (4).
(1) Compound (A) having at least two 5-membered cyclic carbonate groups represented by the following general formula (1) in the molecule;
A structure having a ketimine (C = N) bond derived from a ketone or aldehyde and an amine, and having a branched carbon or a ring member carbon bonded to the α-position and / or β-position of at least one of carbon and nitrogen of the ketimine group A one-component moisture-curable resin composition comprising: a ketimine compound (B).

(2) X of compound (A) having at least two 5-membered cyclic carbonate groups has a group represented by the following formula (2), and is a one-component moisture-curable resin as described in (1) above Composition.

(3) The one-component moisture-curable resin composition as described in (1) or (2) above, wherein the ketimine compound (B) is obtained using methyl isopropyl ketone or diisobutyl ketone. object.
(4) The one-component moisture-curable resin composition according to any one of (1) to (3), further comprising an epoxy resin (C).

  ADVANTAGE OF THE INVENTION According to this invention, while having storage stability, while being able to ensure moderate pot life at room temperature, the one-component type moisture curable resin composition which can be manufactured cheaply is provided. it can.

  Hereinafter, the present invention will be described in detail. Note that the present invention is not limited to the embodiments. In addition, constituent elements in the following embodiments include those that can be easily assumed by those skilled in the art or those that are substantially the same.

  The one-component moisture-curable resin composition of the present invention (hereinafter referred to as “the composition of the present invention”) has a compound having at least two 5-membered cyclic carbonate groups represented by the following general formula (1) in the molecule ( A), a ketimine (C═N) bond derived from a ketone or aldehyde and an amine, and a branched carbon or a ring member carbon at the α-position and / or β-position of at least one of carbon and nitrogen of the ketimine group And a ketimine compound (B) having a structure in which is bonded to a one-component moisture-curable resin composition.

[Compound (A) having at least two 5-membered carbonate groups]
The compound (A) having at least two 5-membered ring carbonate groups (hereinafter referred to as “compound (A)”) will be described.
In the present invention, the compound (A) is a compound having at least two 5-membered ring carbonate groups represented by the general formula (1).
Compound (A) can be prepared, for example, by reaction of diol with phosgene (reference, B. M. Trost and D. M. T. Chan., J. Org. Chem., 48, 3346 (1983), etc.), oxirane, etc. Reaction with β-lactone (T. Nishikubo, T. Iizuka, M. Iida and N. Isobe, Tetrahedron Lett., 27, 3741 (1986)), reaction with oxirane and carbon dioxide (WJ Peppel, Ind. Eng. Chem., 50, 767 (1958), N. Kihara and T. Endo, Macromolecules, 25, 4824 (1992)) and the like.

  Moreover, it is preferable that X of the said compound (A) has group shown by following formula (2). This is because the adhesiveness is particularly excellent.

  Conventionally, the polyisocyanate compound used to ensure storage stability in the one-component moisture-curable polyurethane composition has been expensive, but in the present invention, an inexpensive five-membered cyclic carbonate group is used instead of the polyisocyanate compound. Since the compound (A) which has this is used, cost can be reduced.

[Ketimine Compound (B)]
The ketimine compound (B) will be described.
In the present invention, a compound having a ketimine (C═N) bond derived from a ketone or aldehyde and an amine is referred to as a ketimine compound. In this specification, the ketimine compound is used in the sense that it includes an aldimine compound having a —HC═N bond, which is a reaction product of an aldehyde and an amine, in addition to a ketimine compound which is a reaction product of a ketone and an amine. It is done.

The ketimine compound (B) has a ketimine (C = N) bond synthesized from a ketone or aldehyde and an amine, and is branched to at least one α-position and / or β-position of carbon or nitrogen of the ketimine group. It has a structure in which carbon or ring member carbon is bonded. That is, it has a bulky group at the α-position and / or β-position of the ketimine (C═N) group. Here, the ring member carbon may be carbon constituting an aromatic ring or carbon constituting an alicyclic ring.
Examples of the ketimine compound (B) having a bulky group at the α-position and / or β-position of the ketimine (C═N) group include a ketimine (C═N) bond to which the bulky group is bound. Examples thereof include ketimine compounds having two or more in the molecule.

  When the ketimine compound (B) is produced, branched carbon or ring member carbon is introduced into the α-position and / or β-position of the carbon of the ketimine group, so that the branched hydrocarbon is introduced into the α-position and / or β-position of the carbonyl group. A ketone or aldehyde having a group or a cyclic hydrocarbon group is used. Examples of the ketone or aldehyde include diisopropyl ketone and ketones or aldehydes having a branched hydrocarbon group represented by the following formula (3); cyclic hydrocarbon groups such as propiophenone, benzophenone, benzaldehyde, and cyclohexanecarboxaldehyde. Examples thereof include ketones and aldehydes which can be used in combination.

In said formula (3), R < ⁸ > and R < ¹⁰ > represents a methyl group, an ethyl group, or a hydrogen atom each independently, R < ⁷ > represents a methyl group or an ethyl group, R < ⁹ > is C1-C6. Represents an alkyl group. However, R ⁹ can combine with R ⁷ or R ¹⁰ to form a ring. R ⁹ is bonded to R ⁷ to form a ring, and among the carbon atoms at the α-position of the carbonyl group, the carbon atom contained in the ring is bonded to R ⁷ or R ^{9 through} a double bond. In this case, R ⁸ is not present. When R ⁹ is bonded to R ⁷ or R ¹⁰ to form a ring, examples of the formed cyclic hydrocarbon include alicyclic hydrocarbons and aromatic hydrocarbons.

Examples of the ketone or aldehyde represented by the above formula (3) include methyl tert-butyl ketone (MTBK), methyl isopropyl ketone (MIPK), diisobutyl ketone, pivalaldehyde (trimethylacetaldehyde), and a branched carbon bonded to a carbonyl group. And isobutyraldehyde ((CH ₃ ) ₂ CHCHO).

  The ketimine compound (B) can be obtained by reacting the ketone or aldehyde with an amine. As the amine, a polyamine having two or more amino groups in the molecule is preferably used. Examples of the polyamine include 2,5-dimethyl-2,5-hexamethylenediamine, mensendiamine, 1,4-bis (2-amino-2-methylpropyl) piperazine, and propylene branched carbons at both ends of the molecule. Polyamines such as polypropylene glycol (PPG) having an amino group bonded thereto (for example, Jeffamine D230, Jeffamine D400, etc. manufactured by Sun Techno Chemical Co., Ltd.) can be used.

  In addition, the ketimine compound (B) uses a compound in which a bulky group is bonded to carbon of a ketimine group, and further methylene is bonded to nitrogen of the ketimine group, so that storage stability and curability (curing speed) are improved. It is preferable because a one-component moisture-curable resin composition excellent in both of the above can be obtained. When introducing a methylene group into the nitrogen of the ketimine group, a polyamine represented by the following formula (4) can be used.

Examples of the polyamine represented by the above formula (4) include ethylenediamine, propylenediamine, butylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenediamine, trimethylhexamethylenediamine, and N-aminoethyl. Piperazine, 1,2-diaminopropane, iminobispropylamine, methyliminobispropylamine, polyether skeleton dimethyleneamine H ₂ N (CH ₂ CH ₂ O) ₂ (CH ₂ ) ₂ NH ₂ (trade name) : Jepamine EDR148, manufactured by Sun Techno Chemical Co., Ltd.), a polyether skeleton diamine having a methylene group bonded to amine nitrogen, 1,5-diamino-2-methylpentane (trade name: MPMD, manufactured by DuPont Japan), Taxylenediamine (MXDA), polyamidoamine (trade name: X2000, manufactured by Sanwa Chemical Co., Ltd.), isophoronediamine, 1,3-bisaminomethylcyclohexane (trade name: 1,3BAC, manufactured by Mitsubishi Gas Chemical Company), 1 Examples include -cyclohexylamino-3-aminopropane, 3-aminomethyl-3,3,5-trimethyl-cyclohexylamine, norbornanediamine (trade name: NBDA, manufactured by Mitsui Chemicals) which is a diamine having a norbornane skeleton.
Of these, 1,3-bisaminomethylcyclohexane (1,3BAC), norbornanediamine (NBDA), metaxylylenediamine (MXDA), Jeffamine EDR148, and polyamidoamine are preferably used.

As the ketimine compound (B) obtained by reacting the ketone or aldehyde with the polyamine, specifically,
Obtained from methyl isopropyl ketone (MIPK) or methyl tert-butyl ketone (MTBK) and Jeffamine EDR148,
Those obtained from methyl isopropyl ketone (MIPK) or methyl tert-butyl ketone (MTBK) and 1,3-bisaminomethylcyclohexane (1,3BAC);
Those obtained from methyl isopropyl ketone (MIPK) or methyl tert-butyl ketone (MTBK) and norbornanediamine (NBDA);
Those obtained from methyl isopropyl ketone (MIPK) or methyl tert-butyl ketone (MTBK) and metaxylylenediamine (MXDA);
Preferred examples include those obtained from methyl isopropyl ketone (MIPK) or methyl tert-butyl ketone (MTBK) and polyamidoamine (X2000).
Among these, those obtained from MIPK or MTBK and NBDA, those obtained from MIPK and 1,3BAC are preferable because they exhibit excellent curability, and those obtained from MIPK or MTBK and X2000 However, it is preferably used because it exhibits excellent adhesion to wet surfaces.

  The ketimine compound (B) obtained from the combination of aldehyde and polyamine specifically includes pivalaldehyde, norbornanediamine (NBDA), 1,3-bisaminomethylcyclohexane (1,3BAC) or Jeffer. Min EDR148, combination with metaxylylenediamine (MXDA); with isobutyraldehyde, norbornanediamine (NBDA), 1,3-bisaminomethylcyclohexane (1,3BAC) or Jeffamine EDR148, metaxylylenediamine (MXDA) A combination of cyclohexanecarboxaldehyde and norbornanediamine (NBDA), 1,3-bisaminomethylcyclohexane (1,3BAC) or Jeffamine EDR148, metaxylylenediamine Those obtained from combinations of MXDA) is preferably exemplified.

  The ketimine compound (B) is reacted by heating and refluxing the ketone or aldehyde and the polyamine in the absence of a solvent or in the presence of a solvent such as benzene, toluene, xylene, etc., and removing the desorbed water by azeotropic distillation. Can be obtained.

In a conventional ketimine obtained from a general-purpose ketone such as methyl isobutyl ketone (MIBK) or methyl ethyl ketone (MEK) and an amine in which a methylene group is bonded to an amino group, the ketimine nitrogen is exposed, so that some basicity is obtained. Indicates. Therefore, the one-pack type moisture curable resin composition in which ketimine and an isocyanate compound are mixed has a problem in storage stability such that gelation proceeds during storage.
In contrast, the ketimine compound (B) used in the present invention has a bulky group in the vicinity of the ketimine nitrogen or the ketimine nitrogen, and the ketimine nitrogen is protected by a substituent, that is, due to steric hindrance, Its basicity is greatly weakened and exhibits excellent storage stability.
Furthermore, the ketimine compound (B) used in the present invention is easily decomposed into a raw material amine and a ketone or an aldehyde by contact with moisture in the air at the time of use. Excellent curability.

Further, even when a conventionally known ketimine is used as a latent curing agent, when an isocyanate compound having no bulky group near an isocyanate group such as TDI (tolylene diisocyanate) or XDI (xylene diisocyanate) is used, Although the curing speed is high, sufficient storage stability cannot be obtained, and it has been difficult to obtain a practical one-component moisture-curable resin composition.
On the other hand, in the present invention, by combining the ketimine compound (B) having a specific structure as described above and the compound (A) having at least two 5-membered cyclic carbonate groups, curability and storage stability are achieved. It was possible to make it compatible.

Since the compound (A) used in the present invention has at least two 5-membered cyclic carbonate groups bonded thereto, the steric hindrance increases. The mixture (composition) of such a compound (A) and the ketimine compound (B) having the above-mentioned specific structure is kept stable during storage in a container.
On the other hand, when the above composition comes into contact with air, the water molecules that are moisture are small, so that they easily attack the ketimine nitrogen without undergoing steric hindrance of the substituent, and the hydrolysis proceeds easily. The curing time of is fast.

When the composition of the present invention does not contain an epoxy resin (C), the content of the ketimine compound (B) in the composition of the present invention is an equivalent ratio (the five-membered carbonate group in the compound (A)). ) / (Ketimine bond C = N in ketimine compound (B)) is preferably 0.7 to 1.3, more preferably about 1.0.
Further, even when the composition of the present invention contains the epoxy resin (C), the equivalent ratio is the sum of the five-membered carbonate group in the compound (A) and the epoxy group in the epoxy resin (C)) / (ketimine). The ketimine bond C = N) in the compound (B) is preferably 0.7 to 1.3, more preferably about 1.0.
When the content of the ketimine compound (B) is in the above range, a composition having good storage stability and curability can be obtained.

[Epoxy resin (C)]
It is one of the preferred embodiments that the composition of the present invention further contains an epoxy resin (C). By containing the epoxy resin (C), the cured film can be strengthened, and excellent adhesion to mortar, metal and the like can be exhibited.
The epoxy resin (C) is not particularly limited as long as it is a resin composed of a compound having two or more oxirane rings (epoxy groups) in one molecule, and generally has an epoxy equivalent of 90 or more and 2000 or less. .
As the epoxy resin (C), a conventionally known epoxy resin can be used. For example, bisphenol A type, bisphenol F type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol S type, bisphenol AF type, biphenyl A bifunctional glycidyl ether type epoxy resin such as an epoxy compound having a bisphenyl group, a polyalkylene glycol type, an alkylene glycol type epoxy compound, an epoxy compound having a naphthalene ring, an epoxy compound having a fluorene group;
Polyfunctional glycidyl ether type epoxy resins such as phenol novolak type, orthocresol novolak type, DPP novolak type, tris-hydroxyphenylmethane type, trifunctional type, tetraphenylolethane type, etc .;
Glycidyl ester type epoxy resin of synthetic fatty acid such as dimer acid;
N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane (TGDDM), tetraglycidyl-m-xylylenediamine, triglycidyl-p-aminophenol, N, N-diglycidyl represented by the following formula (5) An aromatic epoxy resin having a glycidylamino group such as aniline;

Following epoxy compound having a tricyclo [5,2,1,0 ^2,6] decane ring represented by (6), specifically, for example, cresol or phenols, such as dicyclopentadiene and cresol An epoxy compound that can be obtained by a known production method of reacting epichlorohydrin after polymerization;

式中、ｍは、０〜１５の整数を表す。

In formula, m represents the integer of 0-15.

Cycloaliphatic epoxy resin; epoxy resin represented by Toray Rethiokol's Flep 10 epoxy resin having a sulfur atom in the main chain; urethane modified epoxy resin having urethane bond; polybutadiene, liquid polyacrylonitrile-butadiene rubber or acrylonitrile butadiene rubber Examples thereof include a rubber-modified epoxy resin containing (NBR).
These may be used alone or in combination of two or more.

Of the various epoxy resins exemplified above, it is preferable to use an epoxy resin having an aromatic ring in the skeleton because the physical properties (for example, tensile strength and the like) and adhesiveness of the resulting composition are better.
Moreover, as such an epoxy resin (C), commercially available products such as EP4100E manufactured by ADEKA, Epicoat 828, Epicoat 807, Epicoat 806, Epicoat 154, and Epicoat 630 manufactured by Japan Epoxy Resin Co., Ltd. can be used.

  The composition of the present invention may contain a polymer such as silicone and modified silicone together with the epoxy resin (C).

  Moreover, the composition of this invention can contain various additives as needed other than each component mentioned above in the range which does not impair the objective of this invention. Examples of additives include fillers, plasticizers, silane coupling agents, pigments, dyes, anti-aging agents, antioxidants, antistatic agents, flame retardants, adhesion promoters, stabilizers, dispersants, and solvents. Can be mentioned.

  Examples of the filler include organic or inorganic materials having various shapes. For example, calcium carbonate, fumed silica, calcined silica, precipitated silica, ground silica, fused silica; diatomaceous earth; iron oxide, zinc oxide, titanium oxide, barium oxide, magnesium oxide; magnesium carbonate, zinc carbonate; Kaolin clay, calcined clay; carbon black: these fatty acids, resin acids, fatty acid ester treated products and the like.

  Examples of the plasticizer include dioctyl phthalate (DOP), dibutyl phthalate (DBP); dioctyl adipate, isodecyl succinate; diethylene glycol dibenzoate, pentaerythritol ester; butyl oleate, methyl acetylricinoleate; tricresyl phosphate, phosphoric acid Trioctyl; propylene glycol polyester adipate, butylene glycol polyester adipate, etc. can be used. In addition, an acrylic polymer that is polymerized at a polymerization temperature of 150 ° C. or more and 350 ° C. or less and having a number average molecular weight of 500 or more and 5000 or less without using a chain transfer agent can be used.

  As the silane coupling agent, for example, trimethoxyvinylsilane and γ-glycidoxypropyltrimethoxysilane are particularly preferable because they are excellent in the effect of improving the adhesion to a wet surface and are general-purpose compounds.

  The pigment may be either an inorganic pigment or an organic pigment. For example, an organic pigment such as titanium oxide, zinc oxide, ultramarine blue, bengara, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride, sulfate inorganic pigment, azo pigment, copper phthalocyanine pigment, or the like can be used.

  The dye is not particularly limited, and conventionally known dyes can be used. For example, when the resin molded product is black, black dye, yellow dye, red dye, blue dye, and brown dye can be used.

Examples of the antiaging agent include hindered phenol compounds and hindered amine compounds.
Examples of the antioxidant include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA).
Examples of the antistatic agent include quaternary ammonium salts; hydrophilic compounds such as polyglycols and ethylene oxide derivatives.

Examples of the flame retardant include chloroalkyl phosphate, dimethyl / methylphosphonate, bromine / phosphorus compound, ammonium polyphosphate, neopentyl bromide-polyether, and brominated polyether.
Examples of the adhesion imparting agent include terpene resins, phenol resins, terpene-phenol resins, rosin resins, and xylene resins.
Examples of the stabilizer include fatty acid silyl esters and fatty acid amide trimethylsilyl compounds.

  The dispersant refers to a substance that makes a solid into fine particles and disperses it in a liquid, and examples thereof include sodium hexametaphosphate, sodium condensed naphthalenesulfonate, and a surfactant.

The method for producing the composition of the present invention is not particularly limited. For example, each of the above components is stirred in a roll, a kneader, an extruder, a universal agitator, a mixing mixer, etc. under reduced pressure or in an inert gas atmosphere such as nitrogen. Examples of the method include mixing by sufficiently kneading using an apparatus and uniformly dispersing.
The obtained composition of the present invention is stored in a closed container, and a cured product can be obtained at room temperature by using moisture in the air at the time of use.

Thus, the resin composition of the present invention is derived from the compound (A) having at least two 5-membered cyclic carbonate groups represented by the general formula (1) in the molecule, the ketone or aldehyde, and the amine. A ketimine compound (B) having a ketimine (C = N) bond and having a structure in which a branched carbon or a ring member carbon is bonded to at least one of the α-position and / or β-position of carbon or nitrogen of the ketimine group It is a one-component moisture-curable resin composition. In addition to the excellent adhesiveness possessed by the compound (A), by combining the excellent storage stability possessed by the ketimine compound (B), it is possible to ensure an appropriate pot life at room temperature while having storage stability. And excellent curability and adhesiveness can be secured.
The composition of the present invention is excellent in storage stability and curability at room temperature, and also excellent in adhesiveness to difficult-to-adhere members.
In addition, the composition of the present invention is a moisture-curing type and can be used as a one-pack type composition, so that the workability can be improved as compared with the two-pack type and used for a cured polyurethane product. Since the compound (A) having a 5-membered ring carbonate group is used in place of the polyisocyanate compound, the production cost can be reduced.
Accordingly, it is possible to provide a one-component moisture-curable resin composition that can ensure an appropriate pot life at room temperature while having storage stability and can be manufactured at low cost.

  The use of the composition of the present invention is not particularly limited. However, the composition of the present invention has the excellent characteristics as described above, and therefore, between the panel of the outer wall and the panel or tile, or between the window sash and the glass. It can be suitably used for a sealing material for construction, a structural adhesive in concrete and mortar, a crack injection material, and the like.

Moreover, the composition of this invention can be used conveniently as an adhesive agent for difficult-to-adhere members. Examples of the material of the hardly adhesive member to which the composition of the present invention can be applied include ABS resin, AES resin, aluminum baking coating, EPDM, soft vinyl chloride resins, glass, and SUS. These hard-to-adhere members are used in, for example, automobiles, vehicles, buildings, electronic parts, and the like.
Moreover, the composition of this invention can be used also for members other than a hardly-adhesive member.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
[Preparation of each component]
(1) Compound (A)
<Compound (A) 1>
As compound (A) 1, 100 parts by mass of polypropylene glycol (trade name: EXCENOL 3030, molecular weight 3000, manufactured by Asahi Glass Co., Ltd.) was dehydrated under reduced pressure at 110 ° C. for 5 hours. Thereafter, 100 parts by mass of dehydrated polypropylene glycol and 16.8 parts by mass of hexamethylene diisocyanate (trade name: 50M-HDI, manufactured by Asahi Kasei Chemicals) were mixed at a molar ratio of NCO / OH = 2.0. Was added at 5 ppm of tin catalyst and reacted at 90 ° C. for 3 hours under a nitrogen atmosphere. Then, 11.8 mass parts of glycerol carbonate was added, and it was made to react at the same temperature for further 3 hours, and carbonate urethane 1 ("compound (A) 1") was obtained. When the obtained compound (A) 1 was subjected to IR measurement, no absorption peak (2265 cm ⁻¹ ) attributed to the isocyanate group was observed.

<Compound (A) 2>
As compound (A) 2, 80 parts by mass of polypropylene glycol (trade name: EXCENOL 3030) and 20 parts by mass of diisononyl phthalate (trade name: DINP, manufactured by Shin Nippon Chemical Co., Ltd.) as a plasticizer are mixed, and at 110 ° C. under reduced pressure. Dehydrated for 5 hours. Thereafter, a mixture obtained by mixing 13.4 parts by mass of hexamethylene diisocyanate (trade name: 50M-HDI, manufactured by Asahi Kasei Chemicals Corporation) at a molar ratio of NCO / OH = 2.0 was added 5 ppm of tin catalyst, And reacted at 90 ° C. for 3 hours. Then, 9.4 mass parts of glycerol carbonate was added, and it was made to react at the same temperature for further 3 hours, and carbonate urethane 2 ("compound (A) 2") was obtained. When IR measurement of the obtained compound (A) 2 was performed, the peak of absorption (2265 cm ⁻¹ ) attributed to the isocyanate group was not observed.

(2) Ketimine compound (B)
<Ketimine Compound (B) 1>
As ketimine compound (B) 1, a ketimine group-containing compound represented by the following formula (7) synthesized from the following polyamine and the following ketone was used.
-Polyamine: Hexamethylenediamine (HMDA), manufactured by Wako Pure Chemical Industries, Ltd.-Ketone: Methyl isopropyl ketone (MIPK), manufactured by Wako Pure Chemical Industries, Ltd.

<Ketimine compound (B) 2>
As ketimine compound (B) 2, a ketimine group-containing compound represented by the following formula (8) synthesized from the following polyamine and the following ketone was used.
-Polyamine: Hexamethylenediamine (HMDA), manufactured by Wako Pure Chemical Industries, Ltd.-Ketone: Diisobutyl ketone (DIBK), manufactured by Wako Pure Chemical Industries, Ltd.

<Ketimine compound (B) 3>
As ketimine compound (B) 3, a ketimine group-containing compound represented by the following formula (9) synthesized from the following polyamine and the following ketone was used.
・ Polyamine: Norbornanediamine, manufactured by Mitsui Chemicals ・ Ketone: Methyl ethyl ketone, manufactured by Wako Pure Chemical Industries, Ltd.

(3) Epoxy resin (C)
Product name: EP4100E, manufactured by ADEKA

(4) Polyamine norbornanediamine (NBDA) (Mitsui Chemicals)

[Preparation of curable resin composition]
Each component shown in "Table 1" was blended in the addition amount (part by mass) shown in the same table, and these were uniformly mixed to prepare each composition shown in Table 1. The amount (parts by mass) of each component in each example and comparative example is shown in “Table 1”. The ketimine (B) 1, ketimine (B) 2, ketimine (B) 3 and polyamine were blended so as to be 1 equivalent with respect to the reactive functional group.

[Evaluation]
About each obtained composition, the evaluation test of the storage stability and the physical property after hardening (breaking strength, breaking elongation) was done by the method shown below. The results are shown in “Table 1”.

(Storage stability)
After measuring the viscosity of each composition immediately after compounding (viscosity immediately after compounding) obtained as described above, each composition immediately after compounding was put into a sealed container and the viscosity after storage at 40 ° C. for 10 days ( Viscosity after storage) was measured.
The storage stability was measured for each composition obtained as described above using an E-type viscometer at 25 ° C. and a rotation speed of 1 rpm.
As shown in the following formula (I), the storage stability is the viscosity (viscosity after storage) after storage at 40 ° C. for 10 days, measured by each composition immediately after mixing (viscosity immediately after mixing). Obtained from the divided value. If the storage stability was 5.0 or less, it was judged that the storage stability was good. Table 1 shows the storage stability test results.
Storage stability = (viscosity after storage) / (viscosity immediately after blending) (I)

(Physical properties)
Each composition was allowed to stand at 23 ° C. and 55% humidity for 7 days, then cured at 80 ° C. for 5 hours, and then punched with a JIS No. 3 dumbbell to prepare a test piece. The obtained test piece was subjected to a tensile test at a tensile speed of 50 mm / min using a tensile tester (AGS-10 kNG, manufactured by Shimadzu Corporation) in accordance with JIS K6251 to measure the breaking strength and breaking elongation. Table 1 shows the test results of breaking strength and breaking elongation.

    The combination of each component of each Example and each Comparative Example shown in Table 1 is as shown in Table 1.

  As shown in Table 1, compositions containing no ketimine compound (B) 1 or ketimine compound (B) 2 (Comparative Examples 1 and 2) were stored because they were cured immediately after blending the components shown in Table 1. Stability was bad. On the other hand, the compositions of Examples 1 to 6 containing the ketimine compound (B) 1 or ketimine compound (B) 2 were excellent in storage stability and good in physical properties after curing.

  As described above, the one-component moisture-curable resin composition according to the present invention has storage stability and can ensure an appropriate pot life at room temperature. For example, adhesives such as concrete and metal, sealing, etc. It can be used for materials.

Claims (4)

A compound (A) having at least two 5-membered cyclic carbonate groups represented by the following general formula (1) in the molecule;
A structure having a ketimine (C = N) bond derived from a ketone or aldehyde and an amine, and having a branched carbon or a ring member carbon bonded to the α-position and / or β-position of at least one of carbon and nitrogen of the ketimine group A one-component moisture-curable resin composition comprising: a ketimine compound (B).

The one-component moisture-curable resin composition according to claim 1, wherein X of the compound (A) having at least two 5-membered cyclic carbonate groups has a group represented by the following formula (2).

  The one-pack type moisture curable resin composition according to claim 1 or 2, wherein the ketimine compound (B) is obtained using methyl isopropyl ketone or diisobutyl ketone.   Furthermore, an epoxy resin (C) is contained, The 1 liquid type moisture curable resin composition as described in any one of Claims 1-3 characterized by the above-mentioned.