JP2003119373A - Moisture-curable polyurethane and/or epoxy resin composition, and storage stabilizer included in the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thixotropic moisture-curable polyurethane and/or epoxy resin composition excellent in storage stability, thixotropic properties, and having a rapid curing speed in processing and giving a cured product excellent in mechanical properties such as tensile strength or the like and to provide a storage stabilizer for the same. SOLUTION: The moisture-curable polyurethane composition comprises (A) a urethane prepolymer having two or more isocyanate groups in the molecule, (B) an inorganic filler as a storage stabilizer, and (C) an N-silyl amide compound expressed by formula (1): (R<1> -CONH)4-n -Si-R<2> n (In the formula R<1> is a 5-21C hydrocarbon group optionally including a hetero atom, R<1> is same or different in the case of n is 0, 1 or 2. R<2> is a 1-3C alkyl or alkoxy group, n is 0, 1, 2 or 3.) as a storage stabilizer, and (D) an epoxy resin and/or (E) a moisture-latent curing agent, and the moisture-curable epoxy resin composition comprising (D) the epoxy resin formulated with (C) the N-silyl amide and (E) the moisture-latent curing agent. Formula (1).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a moisture-curable polyurethane and / or epoxy resin composition suitable as a joint material, a sealant or an adhesive, and such a moisture-curable polyurethane and / or epoxy resin composition. The present invention relates to a storage stabilizer contained in.

An isocyanate compound having two or more isocyanate groups in the molecule forms a three-dimensional crosslinked structure by reaction with a curing agent such as amine and polyol, and has high strength, high elongation, abrasion resistance, grease resistance, etc. It becomes an excellent polyurethane cured product. When a repeating unit having an ether skeleton is present in the main chain of this isocyanate compound, a flexible cured product is obtained. Polyurethane compositions based on such urethane polymers have hitherto been used as joint materials, sealants,
Widely used as an adhesive. Such a urethane polymer having an isocyanate group reacts with moisture in the air and cures with decarbonation gas, so that it can be a one-pack type moisture-curable polyurethane composition. If a moisture latent curing agent that chemically blocks active hydrogen of the curing agent is used, curing can be controlled and foaming can be suppressed. Needless to say, the one-pack type moisture-curable polyurethane composition is highly useful because it has significantly improved workability as compared with a two-pack type polyurethane composition in which a main agent and a curing agent are mixed at the time of working.

By the way, when the moisture-curable polyurethane composition is used as a sealant or a joint material,
Good workability, but non-dripping property, that is, thixotropic (thixotropic, slump resistant) is required. This thixotropy is usually improved by using calcium carbonate as a filler and incorporating colloidal silica into the polyurethane composition.

Two types of calcium carbonate are known, usually heavy or light (colloidal calcium carbonate or precipitated calcium carbonate). Ground calcium carbonate is
As described above, it is used in combination with colloidal silica in a thixotropic one-pack type moisture-curable polyurethane composition. on the other hand,
Common light calcium carbonate has low storage stability and is not used in one-part moisture-curable polyurethane compositions.

Therefore, when light calcium carbonate having a large surface area is used in a one-pack type moisture-curable polyurethane composition, the calcium carbonate is used as a fatty acid ester (Japanese Patent No. 2652044) in order to ensure storage stability. Alternatively, it is necessary to perform surface treatment with a urethane compound (JP-A 1998-245221). Thereby, a one-pack type moisture-curable polyurethane composition having thixotropy can be provided. However, the use of these calcium carbonates does not always give high storage stability. In addition, the above-mentioned addition of colloidal silica inherently has the problems that foaming, cracking, and modulus become too high when the urethane composition is cured.

In view of such circumstances, the present inventor has previously found that a polyurethane composition containing calcium carbonate surface-treated with a fatty acid ester has a fatty acid silyl ester (Japanese Patent No. 2719105) or a fatty acid silyl ester group. Polysiloxane (Patent No. 2749763
No.) was added to improve storage stability. In particular, a polyurethane composition containing a fatty acid silyl ester enables the addition of light calcium carbonate and imparts thixotropy and storage stability.

On the other hand, the storage stability is also a serious problem in the one-pack type epoxy resin containing ketimine or oxazolidine as a latent curing agent. In response to this problem, WO98 /
Although the use of sterically hindered latent curing agents is disclosed in Japanese Patent No. 31722, these latent curing agents show high storage stability, but do not always give high satisfaction.

[0008]

Although the fatty acid silyl ester group is effective in both thixotropic and storage stability, the present inventors have found that the fatty acid silyl ester group is hydrolyzed to give a free carboxylic acid (fatty acid ) May occur. That is, since the fatty acid silyl ester group is more hydrolyzable than the isocyanate group, it is hydrolyzed during storage by the water contained essentially in calcium carbonate or the like used as a filler to generate a free carboxylic acid. Therefore, it has been found that in the case of a latent curing agent, particularly oxazolidine and ketimine, hydrolysis by the free acid is promoted and storage stability may be lowered.

Therefore, in particular, a storage stabilizer capable of further improving the storage stability of a thixotropic moisture-curable polyurethane composition containing an inorganic filler as compared with the current state, and a storage stabilizer containing this storage stabilizer. It is desired to develop a thixotropic moisture-curable polyurethane composition that is excellent in thixotropy, has a high curing rate during work, and can provide a cured product having excellent mechanical properties such as elongation.

Similarly, in the case of a one-pack type epoxy resin, the latent carboxylic acid is activated by the liberated carboxylic acid, the storage stability is lowered, and the epoxy resin is also liberated. It is activated by an acid and causes deterioration of storage stability. Therefore, especially the storage stability of the storage stability of the epoxy resin composition containing an inorganic filler can be further improved than the current state, and containing this storage stabilizer, with excellent storage stability,
The advent of a one-pack type epoxy resin composition capable of obtaining a cured product having a high curing rate during work and excellent mechanical properties is desired.

[0011]

The above-mentioned problems can be solved by the present invention described below. That is, the present invention is a storage stabilizer for polyurethane and / or epoxy resins, which comprises an N-silylamide compound having a functional group represented by the formula —CONH—Si≡.

The present invention also provides the formula (R ¹ -CONH) _4-n -Si-R ² _n (1) (wherein R ¹ has 5 carbon atoms which may contain a hetero atom).
To 21 hydrocarbon groups, and when n is 0, 1 or 2, R ¹ may be the same or different. R ² is an alkyl group or an alkoxy group having 1 to 3 carbon atoms,
n is 0, 1, 2 or 3. ) Is a storage stabilizer for moisture-curable polyurethane and / or epoxy resin comprising an N-silylamide compound.

The present invention also provides a urethane prepolymer (A) having two or more isocyanate groups in the molecule, and 1 to 30 parts by weight per 100 parts by weight of the urethane prepolymer (A).
0 parts by weight of the inorganic filler (B), 0.5 to 30 parts by weight of the N-silylamide compound (C) represented by the formula (1),
And a moisture-latent curing agent (E). Formula (R ¹ —CONH) _4-n —Si—R ² _n (1) (In the formula, R ¹ has 5 carbon atoms which may include a hetero atom.
To 21 hydrocarbon groups, and when n is 0, 1 or 2, R ¹ may be the same or different. R ² is an alkyl group or an alkoxy group having 1 to 3 carbon atoms,
n is 0, 1, 2 or 3. )

In the present invention, 0.5 to 30 parts by weight of the N-silylamide compound (C) represented by the formula (1) and 100% by weight of the epoxy resin (D), and the moisture latent curing agent (E) are used. ) Is contained in the moisture-curable epoxy resin composition. Formula (R ¹ —CONH) _4-n —Si—R ² _n (1) (In the formula, R ¹ has 5 carbon atoms which may include a hetero atom.
To 21 hydrocarbon groups, and when n is 0, 1 or 2, R ¹ may be the same or different. R ² is an alkyl group or an alkoxy group having 1 to 3 carbon atoms,
n is 0, 1, 2 or 3. )

In the present invention, the urethane prepolymer (A) having two or more isocyanate groups in the molecule, and 1 to 10 parts by weight per 100 parts by weight of the urethane prepolymer (A).
0 parts by weight of epoxy resin (D), 1 to 300 parts by weight of inorganic filler (B), 0.5 to 30 parts by weight of N-silylamide compound (C) represented by formula (1), and moisture potential A moisture-curable polyurethane composition containing a curing agent (E). Formula (R ¹ —CONH) _4-n —Si—R ² _n (1) (In the formula, R ¹ has 5 carbon atoms which may include a hetero atom.
To 21 hydrocarbon groups, and when n is 0, 1 or 2, R ¹ may be the same or different. R ² is an alkyl group or an alkoxy group having 1 to 3 carbon atoms,
n is 0, 1, 2 or 3. )

Further, the present invention contains 0.1 to 30 parts by weight of a moisture latent curing agent (E) selected from oxazolidine, ketimine, enamine and silyl mercaptan based on 100 parts by weight of the urethane prepolymer (A). 1 is a moisture-curable polyurethane composition.

Further, the present invention is a sealant or an adhesive comprising any of the above moisture-curable polyurethane and / or epoxy resin composition.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the moisture-curable polyurethane composition and / or epoxy resin composition of the present invention (hereinafter also simply referred to as a polyurethane composition), a storage stabilizer contained in the composition and the composition The usage of the product will be described in detail.

The moisture-curable polyurethane composition of the first aspect of the present invention comprises a urethane prepolymer (A), an inorganic filler (B) and an N-silylamide compound (C), and has mechanical properties such as tensile strength. With excellent
A moisture-curable polyurethane composition having a fast curing rate, thixotropy, excellent storage stability, and no significant change in the curing rate and thixotropy even after storage. By further adding a moisture latent curing agent (E) to the composition, a one-pack type moisture-curable polyurethane composition having no foaming and having excellent curability can be obtained. This polyurethane composition contains 1 to 300 parts by weight, preferably 10 to 300 parts by weight of an inorganic filler (B) per 100 parts by weight of the urethane prepolymer (A).
250 parts by weight of N-silylamide compound (C)
0.5 to 30 parts by weight, preferably 1 to 20 parts by weight. Moisture-latent curing agent (E) is 0.3-
It is contained in an amount of 20 parts by weight, preferably 0.5 to 10 parts by weight.

The one-pack type moisture-curable epoxy resin composition of the second aspect of the present invention comprises an epoxy resin (D), an N-silylamide compound (C), and a moisture-latent curing agent which produces a mercapto group or an amino group. Moisture-curable epoxy resin composition consisting of agent (E), which has excellent mechanical properties such as tensile strength, fast curing speed, and excellent storage stability, and does not cause significant changes in curing speed and thixotropy after storage. It is a thing. The conventional one-pack type moisture-curable epoxy resin composition using ketimine had a great problem in storage stability, but the epoxy resin composition of the second aspect successfully overcomes this problem. . This epoxy resin composition is N-based on 100 parts by weight of the epoxy resin (D).
0.5 to 30 parts by weight of the silylamide compound (C), preferably 1 to 20 parts by weight, 0.3 to 20 parts by weight, preferably 0.5 to 20 parts by weight of the moisture latent curing agent (E). It is contained in the ratio of.

The moisture-curable polyurethane composition of the third aspect of the present invention comprises a urethane prepolymer (A), an inorganic filler (B), an N-silylamide compound (C), and an epoxy resin (D), In addition to excellent mechanical properties such as tensile strength, it has excellent adhesiveness, fast curing speed, thixotropic property, and excellent storage stability. Moisture curing without significant changes in curing speed and thixotropic property after storage. Polyurethane composition.

In the third embodiment, even when a larger amount of the epoxy resin (D) than the urethane prepolymer (A) is used, the flexibility, compressive strength and tensile strength of the urethane cured product are exhibited. be able to. The compounding amount of the epoxy resin is appropriately determined depending on the curing rate of the obtained composition, the hardness of the composition after curing, the compression / tensile strength, etc. Usually, the epoxy resin (D) is the urethane prepolymer (A ) 1 to 100 parts by weight, and preferably 1 to 50 parts by weight, relative to 100 parts by weight. Especially when used for sealants, joint materials, etc., the amount of epoxy resin (D) is equal to that of urethane prepolymer (A) 1
1 to 50 parts by weight, preferably 1 to 3 parts by weight with respect to 00 parts by weight
It is preferably 0 part by weight. Components other than the epoxy resin (D) are the same as in the first embodiment.

Next, the urethane prepolymer which is the main ingredient of the polyurethane composition will be described. (A) Urethane Prepolymer In the present invention, as long as it has two or more isocyanate groups (NCO groups) in the molecule, it is possible to widely use urethane prepolymers that can be used as a main agent during normal polyurethane formation. . The urethane prepolymer is usually produced by the reaction of a polyol compound and an excess polyisocyanate compound (that is, NCO groups that are equimolar or more with respect to hydroxyl groups (OH groups)). The polyol compound is not particularly limited as long as it has two or more hydroxyl groups, and examples thereof include polyether polyols, polyester polyols, low molecular weight polyols, and other polyols.

The polyether polyol may be one kind or two kinds.
Propylene oxide,
1 of alkylene oxides selected from ethylene oxide, butylene oxide, styrene oxide, etc.
Examples thereof include those obtained by addition polymerization of one kind or two or more kinds. As the low molecular weight polyol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,
4-butanediol, pentanediol, neopentyl glycol, hexanediol, cyclohexanedimethanol, glycerin, 1,1,1-trimethylolpropane, 1,2,5-hexanetriol, sorbitol, pentaerythritol and other polyhydric alcohols, Resorcin, dihydroxystyrene and 4,4′-dihydroxyphenylpropane (bisphenol A), 4,
Aromatic diols having a bisphenol skeleton such as 4′-dihydroxyphenylmethane (bisphenol F), brominated bisphenol A, bisphenol S, and bisphenol AF, and hydrogenated products thereof are also included.

As the polyether polyol, specifically, polyoxypropylene glycol (PPG), polytetramethylene ether glycol (PTMEG), polyethylene glycol (PEG), polyoxypropylene triol, ethylene oxide / propylene oxide block copolymer. , A sorbitol-based polyol, a polyether polyol obtained from a diol having a bisphenol skeleton and an alkylene oxide, for example, a polyether polyol containing the bisphenol A unit and ethylene oxide or propylene oxide unit.

The polyester polyol is one or more of the above low molecular weight polyols, and glutaric acid, adipic acid, azelaic acid, maleic acid, fumaric acid, pimelic acid, suberic acid, sebacic acid, terephthalic acid, isophthalic acid, Pyromellitic acid, dimer acid, oligomeric acid,
Condensation polymer of one or more acids selected from hydroxycarboxylic acids such as castor oil, a reaction product of castor oil and ethylene glycol / propylene glycol; ring-opening of propion lactone, valerolactone, caprolactone, etc. Examples thereof include polymers having two hydroxyl groups at the ends.

Examples of polyester polyols include polyester polyols obtained from bisphenol A and castor oil, polyester polyols having a bisphenol skeleton obtained from bisphenol A, castor oil, ethylene glycol, and propylene glycol.

Further, polymer polyols having a carbon-carbon bond in the main chain skeleton such as acrylic polyols, polybutadiene polyols, hydrogenated polybutadiene polyols, and the aforementioned low molecular weight polyols can also be used. In addition, as an acrylic polyol, JP-A-60-2
Acrylic polyols synthesized by the special continuous bulk polymerization disclosed in Japanese Patent No. 15007 are also preferably exemplified.

Among the above-mentioned raw material polyols for urethane prepolymer, the number average molecular weight of 1,000 to 15, from the viewpoint of physical properties as a sealant of the composition after curing,
000, especially 1,000 to 10,000 polyether polyols are preferred. It may be a combination of two or more of the above-mentioned polyol compounds.

The raw material polyisocyanate compound for urethane prepolymer is not particularly limited as long as it has two or more isocyanate groups. Specifically, 2, 4
-Tolylene diisocyanate, 2,6-tolylene diisocyanate, phenylene diisocyanate, diphenylmethane-4,4'-diisocyanate, naphthalene-
Aromatic polyisocyanates such as 1,5-diisocyanate and triphenylmethane triisocyanate and hydrogenated compounds thereof; Aliphatic polyisocyanates such as ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate and hexamethylene diisocyanate; Alicyclic rings such as isophorone diisocyanate Formula polyisocyanates; aromatic ring-containing polyisocyanates such as xylylene diisocyanate and metatetramethyl xylylene diisocyanate are preferably exemplified. A combination of two or more of these may be used.

The urethane prepolymer is not particularly limited in its production method as long as it finally contains two or more free isocyanate groups in the molecule, but usually, the above-mentioned polyol compound is reacted with an excess polyisocyanate compound. It can be manufactured. The polyol compound and the polyisocyanate compound are used so that the ratio (NCO / OH) of the isocyanate groups in the polyisocyanate compound per one hydroxyl group in the polyol compound is usually 1.2 to 5.0, and the sealant is used. For use, preferably 1.5
Used to be ~ 2.4. When used in such an amount ratio, the viscosity of the urethane prepolymer is appropriate and the workability is good. For example, it can be performed by heating and stirring the polyol and the polyisocyanate in such an amount ratio at 50 to 100 ° C. At the time of the reaction, a urethane-forming catalyst such as an organic tin compound, an organic bismuth compound, or an amine can be used if necessary.

The urethane prepolymer used in the present invention has two or more molecular terminals consisting of free isocyanate groups, and the NCO number is an average number per molecule.
The number of NCOs per molecule of the urethane prepolymer is more preferably 2.2 or more. Further, the NCO number is preferably 0.4% or more, and more preferably 0.5% or more, when expressed in mass%. The polyurethane composition of the present invention can include two or more urethane prepolymers.

(B) Inorganic Filler In the present invention, the inorganic filler used in the polyurethane and / or epoxy resin composition is not particularly limited and is selected according to the purpose and application. Specifically, calcium carbonate, colloidal silica,
Silica anhydride, diatomaceous earth, carbon black, white carbon, clay, talc, titanium oxide, quick lime, kaolin,
Examples thereof include zeolite. Particularly, calcium carbonate is preferably used.

As the calcium carbonate, light calcium carbonate is mainly used when high thixotropy is required. In that case, those surface-treated with a fatty acid ester or a urethane compound are more preferably used. Further, heavy calcium carbonate is also used in combination for adjusting workability and physical properties of the cured product. Further, when high thixotropy is not required, ground calcium carbonate is mainly used.

In order to obtain the desired thixotropy, the inorganic filler is usually 1 to 300 parts by weight, preferably 10 to 25 parts by weight with respect to 100 parts by weight of the urethane prepolymer (A).
Used in a proportion of 0 parts by weight. If the amount of the inorganic filler exceeds the above amount and becomes too large, the viscosity tends to be too high and the workability tends to be deteriorated.

(C) N-Silylamide Compound The polyurethane and / or epoxy resin composition of the present invention contains an N-silylamide compound having a functional group represented by the formula —CONH—Si≡. That is, the polyurethane and / or epoxy resin composition of the present invention contains the N-silylamide compound represented by the formula (1). (R ¹ -CONH) _4-n -Si -R ² _n (1) (In the formula, R ¹ is a hydrocarbon group having 5 to 21 carbon atoms, preferably a hydrocarbon group having 11 to 20 carbon atoms. there. the hydrocarbon group, an oxygen, a time that .n also contain heteroatoms such as sulfur is 0, 1 or 2, R ¹ good .R ² be different even with the same carbon It is an alkyl group or an alkoxy group of the numbers 1 to 3, and n is 0, 1, 2 or 3.)

More specifically, the N-silylamide compound in the present invention is (R ¹ -CONH) _4-n -Si -R ²
_n and its partial hydrolysis-condensation products. These N-
The silylamide compound easily hydrolyzes to form an amide compound (R ¹ -CONH ₂ group-containing compound) and a silanol compound (HO-Si≡ group-containing compound). Therefore, a moisture-curable polyurethane and / or epoxy resin composition The water content can be easily removed. Therefore, it contributes to the improvement of storage stability. Further, the amide compound thus formed plays a role of improving thixotropy.

Specific examples of R ¹ include phenyl, benzyl, hexyl, heptyl, octyl, nonyl, decyl,
Pentadecyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, alkyl groups such as eicosyl, oleic acid residues, linoleic acid residues, acid residues such as linoleic acid residues, and the like. Of these, phenyl, pentadecyl, heptadecyl group and oleic acid residue are preferable. Specific examples of R ² are methyl, ethyl, propyl, methoxy, ethoxy and propoxy, and among them, methyl, ethyl, methoxy and ethoxy are preferable.

The method for synthesizing the N-silylamide compound is not particularly limited, but one example is a carboxylic acid amide containing an R ¹ group and a formula Si-R ² _n X _4-n (R ² and n are represented by the formula It can be synthesized from a halogenated silane compound represented by (1), where X is a halogen). Examples of the carboxylic acid amide include caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, and mericinic acid. Chain saturated fatty acids; unsaturated fatty acids such as caproic acid, oleic acid, cetoleic acid, sorbic acid, linoleic acid, and linolenic acid; amide derivatives of carboxylic acids selected from aromatic carboxylic acids such as benzoic acid and phenylacetic acid, or the like, or Combinations of two or more of these may be mentioned.
Particularly preferred are amide compounds of palmitic acid, stearic acid and oleic acid.

As the halogenated silane compound, tetrachlorosilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrichlorosilane, 2-chloroethyltrichlorosilane, ethyltrichlorosilane, 2-cyanoethyltrichlorosilane, allyltrichlorosilane, 3 -Bromopropyltrichlorosilane, methylvinyltrichlorosilane, ethylmethyldichlorosilane, trimethylbromosilane, divinyldichlorosilane, methyl-3,3,3-trifluoropropyldichlorosilane, isobutyltrichlorosilane, pentyltrichlorosilane, phenyltrichlorosilane, Methylphenyldichlorosilane, dimethylphenylchlorosilane, cyclohexyltrichlorosilane, benzyltrichlorosilane Amine, p-tolyltrichlorosilane, 6-trichlorosilyl-2-norbornene, 2-trichlorosilylnorbornane, 2- (4-cyclohexylnylethyl) trichlorosilane, dodecyltrichlorosilane, tetradecyltrichlorosilane, 1,2-bis ( Chlorosilane compounds such as trichlorosilyl) ethane, 1,2-bis (dimethylchlorosilyl) ethane, and 1,4-bis (dimethylchlorosilyl) benzene, 1,1,
3,3-Tetramethyl-1,3-dichlorosiloxane or a combination of two or more thereof can be used. Chlorosilane compounds are preferred.

The N-silylamide compound is obtained by combining the above-mentioned carboxylic acid amide and a halogenated silane compound with hexane, heptane, benzene, toluene, which does not have active hydrogen.
It is synthesized by using xylene, methylene chloride, chloroform or the like as a solvent and a tertiary amine such as triethylamine or pyridine as a dehydrochlorinating agent at room temperature to 100 ° C. Further, the N-silylamide compound can be synthesized by heating the above-mentioned carboxylic acid amide and the chlorosilane compound to 120 to 180 ° C. without using a dehydrochlorination agent and removing the generated hydrogen chloride gas. . Triethylamine, pyridine or the like can be used as a catalyst.

Among N-silylamide compounds, for example, an amide compound to which a trimethylsilyl group is bound, hexamethyldisilazane and the amide compound are distilled off at 80 to 150 ° C. in the presence of saccharin to distill off the produced ammonia. It can also be synthesized by reacting while.

When the N-silylamide compound of the present invention is incorporated into a moisture-curable polyurethane and / or epoxy resin composition containing an inorganic filler, the storage stability is enhanced as in the case of incorporating a silyl ester. You can Two or more N-silylamide compounds of the present invention may be used in combination. Particularly preferred N-silylamide compounds are N-trimethylsilylpalmitic acid amide, N-trimethylsilylstearic acid amide, N-trimethylsilyloleic acid amide and the like.

The N-silylamide compound (C) is
It is not known to improve the storage stability of moisture-curable polyurethane and / or epoxy resin compositions.
Therefore, the present invention also includes the use of the N-silylamide compound (C) as a storage stabilizer for moisture-curable polyurethane and / or epoxy resin compositions.

(D) Epoxy Resin The epoxy resin of the present invention is not particularly limited as long as it is a polyepoxy compound having two or more epoxy groups in one molecule.
For example, glycidyl ether type epoxy resin of bisphenol A and its derivatives, glycidyl ether type epoxy resin of glycerin, glycidyl ether type epoxy resin of polyalkylene oxide, glycidyl ether type epoxy resin of phenol novolac, glycidyl ester type epoxy resin of dimer acid, bisphenol Examples thereof include glycidyl ether type epoxy resins of F and modified resins thereof. Among these, glycidyl ether type epoxy resin of bisphenol A and its modified resin are preferably used. In the case of glycidyl ether type epoxy resin of bisphenol A, the average degree of polymerization is 1
It may be any of liquid, semi-solid and solid of 20 to 20. The effect of incorporating the epoxy resin into the polyurethane composition is as described above.

(E) Moisture Latent Curing Agent The polyurethane composition of the present invention is usually cured without using a curing agent. However, a moisture-latent curing agent may be used to accelerate the curing speed or suppress foaming.
The moisture latent curing agent can be used without particular limitation as long as it is generally contained in the one-pack type moisture curing polyurethane composition. Moisture-latent curing agents that are substantially inactive in the absence of water but produce primary amino groups, secondary amino groups or thiol groups upon contact with water (hydrolysis) are preferred, and oxazolidine , Ketimine,
Any moisture latent compound having one or a plurality of each structure of enamine or silyl mercaptan can be used without particular limitation. Specifically, oxazolidine, ketimine (including aldimine), enamine and silyl mercaptan are preferable.

The epoxy resin composition of the present invention, like polyurethane, is usually cured with a moisture latent curing agent. As the moisture latent curing agent, the same one as in the case of polyurethane is used. Those which generate a mercapto group or an amino group are suitable, and specifically, oxazolidine, ketimine (including aldimine), enamine and silylmercaptan are preferably used.

The oxazolidine may be any moisture latent compound having an oxazolidine ring, for example, Japanese Patent Publication No.
-35407, JP-B-58-5913, JP-A-7-
33853, JP-A-6-293821, JP-A-9-
Those disclosed in 278857, JP 2001-152080 A, and the like can be used. Specific examples include oxazolidine compounds represented by the following formula (2) and their derivatives.

[0049]

[Chemical 1]

In the formula, R ³ is a lower alkyl group such as a methyl group or an ethyl group. R ⁴ and R ⁵ are an aliphatic hydrocarbon group having 1 to 6 carbon atoms and an aromatic hydrocarbon group having 6 to 8 carbon atoms, which may contain a hetero atom. Specific examples include a methyl group, an ethyl group, a propyl group, an isobutyl group, an isopentyl group, a phenyl group, a 2,4-dimethylphenyl group and a p-methoxyphenyl group.
In addition, R ⁴ and R ⁵ may combine to form an alicyclic hydrocarbon group having 6 to 8 carbon atoms. R ⁶ represents a hydrogen atom, a methyl group or an alkylene group having a hydroxyl group. Some examples of suitable oxazolidines are given below.

[0051]

[Chemical 2]

The ketimine (or aldimine) may be any moisture-latent compound having an imino (= C = N-) bond obtained by the reaction of a ketone (or aldehyde) and an amine, for example, JP-A-2001-2753. Those disclosed in Japanese Laid-Open Publications can be used. A preferred ketimine has an imino bond derived from a ketone (or aldehyde) and an amine, and a branched carbon or ring member carbon is bonded to at least one α-position of carbon forming the imino bond or nitrogen forming the bond. Structures, that is, those having a bulky group at the α-position of the imino bond are mentioned. Here, the ring member carbon may be either a carbon forming an aromatic ring or a carbon forming an alicyclic ring. In particular, a bulky group is bound to the carbon that constitutes the imino bond, and methylene is bound to the nitrogen that constitutes the imino bond. It is preferable because a mold-curable composition can be obtained.

In the present invention, the ketimine having a bulky group as described above, specifically, a ketimine having two or more imino bonds to which the bulky group is bonded in the molecule,
A silicon-containing ketimine having a bulky group derived from a ketone or an aldehyde at the α-position of carbon of an imino bond and containing an amine component derived from an aminoalkylalkoxysilane, or a polycondensed ketimine thereof is mentioned. Among the above ketimines, those in which a bulky group is bonded to carbon of imino bond and methylene is bonded to nitrogen of imino bond are one liquid excellent in both storage stability and curability (curing speed). It is preferable because a mold-curable composition can be obtained.

Among the above-mentioned ketimines, methyl isopropyl ketone (MIP) is a preferred specific example.
K) or methyl t-butyl ketone (MTBK) and those obtained from Jeffamine EDR148 (registered trademark, sold by San Techno Chemical Co .: dimethylene amine having a polyether skeleton), methyl isopropyl ketone (MIP)
K) or methyl t-butyl ketone (MTBK),
1,3-bisaminomethylcyclohexane (1,3-B
AC), methyl isopropyl ketone (MIPK) or methyl t-butyl ketone (MTB).
K) and dimethylene amine having a norbornane skeleton (trade name: NBDA) (for example, ketimine compound used in Examples), methyl isopropyl ketone (MIPK) or methyl t-butyl ketone (MTB).
K) and metaxylylenediamine (MXDA), those obtained from methyl isopropyl ketone (MIPK) or methyl t-butyl ketone (MTBK), and polyamidoamine. Among these, those obtained from MIPK or MTBK and NBDA, and those obtained from MIPK and 1,3-BAC exhibit excellent curability. Also MIPK
Alternatively, those obtained from MTBK and polyamidoamine exhibit excellent adhesion to wet surfaces.

As the aldimine, a combination of pivalaldehyde with norbornanediamine (NBDA), 1,3-bisaminomethylcyclohexane (1,3-BAC) or Jeffamine EDR148, metaxylylenediamine (MXDA). A combination of isobutyraldehyde and norbornanediamine (NBDA), 1,3-bisaminomethylcyclohexane (1,3-BAC) or Jeffamine EDR148, metaxylylenediamine (MXDA); cyclohexanecarboxaldehyde and norbornanediamine (NBDA),
1,3-bisaminomethylcyclohexane (1,3-B
AC) or Jeffermin EDR 148, those obtained from a combination with metaxylylenediamine (MXDA) and the like are preferable.

Ketimines are silicon-containing ketimines derived from aminoalkoxysilanes. The ketimine is derived from a ketone or aldehyde having a bulky group in the α-position of the ketone or aldehyde. The form of the bulky group is the same as the ketimine. Details of the above-mentioned ketimine and its production raw materials, production method, and the like are described in detail in, for example, JP-A-2001-2753.

The enamine may be a moisture-latent compound having an enamine bond, for example, JP-A-7-28998.
Those disclosed in Japanese Patent Publication No. 9 can be exemplified. Silyl mercaptans are disclosed, for example, in JP-A-6-2716.
For example, those disclosed in Japanese Patent Publication No. 41 can be exemplified.

Among the above, oxazolidine and ketimine are preferably used. The polyurethane composition of the present invention contains the moisture latent curing agent (E) as described above in an amount of 0.1 to 3 with respect to 100 parts by weight of the urethane prepolymer (A).
It is preferable to contain 0 parts by weight, and further 1
It is more desirable to contain it in a proportion of about 20 parts by weight.

The moisture-curable polyurethane of the present invention and / or
Or the epoxy resin composition, further terpene resin,
Adhesiveness imparting agents such as phenolic resins, terpene-phenolic resins, rosin resins and xylene resins, and polymers such as silicone and modified silicone may be blended.

The moisture-curable polyurethane and / or epoxy resin composition according to the present invention may further contain a curing catalyst, if necessary, for the purpose of adjusting viscosity and physical properties.
Crosslinking agents, silane coupling agents, other fillers, plasticizers,
You may mix | blend a solvent, an adhesion promoter, a stabilizer, a coloring agent, etc.

Examples of the curing catalyst include titanic acid esters such as tetrabutyl titanate and tetrapropyl titanate; organic tin compounds such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate and tin naphthenate; octylic acid. Lead etc. are mentioned. The content of the curing catalyst is 0.002 per 100 parts by weight of the resin component (the total of the urethane prepolymer (A) and / or the epoxy resin (D)).
It is preferably 0.1 to 0.1 parts by weight. If it exceeds 0.1 parts by weight, the storage stability tends to decrease, and the thermal deterioration rate tends to increase.

A silane coupling may be included as an adhesion-imparting agent. As the silane coupling agent, widely used ones can be widely used, and examples thereof include an epoxy group-containing alkoxysilane. The epoxy group-containing alkoxysilane may be any compound having an epoxy group and a hydrolyzable alkoxysilyl group at the molecular end.

Among the epoxy group-containing alkoxysilanes, γ- (or 3-) glycidoxypropyltrimethoxysilane is preferably used. Also, silane coupling agents having no epoxy group such as chloropropyltrimethoxysilane, vinyltrichlorosilane, trimethoxyvinylsilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, and γ-methacryloxypropyltrimethoxysilane. Can be mentioned. Examples also include silane coupling agents having an amino group such as γ-aminopropyltrimethoxysilane and N- (β-aminoethyl) aminopropylmethyldimethoxysilane. In addition to the silane coupling agent, methyl silicate, ethyl silicate (specifically, M manufactured by Mitsubishi Chemical Corporation)
S51, MS56) and the like can be used to improve adhesion.

Various plasticizers can be used as the plasticizer. For example, dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butyl benzyl phthalate, butyl phthalyl butyl glycolate, and other phthalates; dioctyl adipate,
Aliphatic dibasic acid esters such as dioctyl sebacate; Polyalkylene glycol esters such as diethylene glycol dibenzoate and triethylene glycol dibenzoate; Phosphoric acid esters such as tricresyl phosphate and tributyl phosphate; Chlorinated paraffins; Alkyl Diphenyl; hydrocarbon oil such as partially hydrogenated terphenyl; process oils; alkylbenzenes and the like. The plasticizer is preferably added in an amount of 0 to 50 parts by weight with respect to 100 parts by weight of the urethane prepolymer (A).

Examples of the filler include vinyl chloride paste resin, glass balloons, vinylidene chloride resin balloons, acrylonitrile / methacrylonitrile resin balloons, and inorganic powder-treated products thereof.

Examples of the solvent include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, heptane and octane, petroleum solvents such as mineral spirits from gasoline to kerosene fraction, acetone and methyl ethyl ketone. , Ketones such as methyl isobutyl ketone, and ether esters such as cellosolve acetate and butyl cellosolve acetate.

Examples of the stabilizer include hindered phenol compounds and triazole compounds. Examples of the colorant include titanium white, carbon black, red iron oxide, and the like.

The polyurethane and / or epoxy resin composition of the present invention is moisture-curable and has the urethane prepolymer (A) or the epoxy resin (D) as the main component side,
It can also be used as a two-pack type in which the curing agent and / or the curing catalyst are mainly on the curing agent side. In that case, other components may be contained in either the main agent side or the curing agent side. However, the polyurethane and / or epoxy resin composition of the present invention is preferably used as a one-pack type sealant composition.

The method for producing the one-pack type polyurethane and / or epoxy resin composition is not particularly limited, and may be carried out in the same manner as the usual one-pack type polyurethane and / or epoxy resin composition, but the production is carried out for each component. It is preferably carried out in a state where the water content is low, and further in an anhydrous state. for that reason,
It is preferable that each component is sufficiently kneaded in an anhydrous state under reduced pressure using a stirrer such as a mixing mixer and uniformly dispersed to produce a composition. The N-silylamide compound of the present invention is preferably added at the initial stage of mixing in order to remove water in the composition.

[0070]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited to these examples. (Synthesis Example 1) <Synthesis of N-silylamide compound (1)> N-trimethylsilylstearic acid amide was synthesized from stearic acid amide and hexamethyldisilazane. The reaction formula is shown below. CH ₃ (CH ₂ ) ₁₆ CONH ₂ + 1/2 (CH ₃ ) ₃ SiNHSi (CH ₃ ) ₃ → CH ₃ (CH
₂ ) ₁₆ CONH-Si (CH ₃ ) ₃ + 1 / 2NH _{3 To} 800 g of stearic acid amide, 400 g of toluene and 0.5 g of saccharin were added, and dissolved by heating at 100 ° C. 260 g of hexamethyldisilazane was added dropwise to this,
After the dropping was completed, the mixture was heated at 130 ° C. for 4 hours. Thereafter, unreacted hexamethyldisilazane and toluene were distilled off under reduced pressure to obtain N-trimethylsilylstearic acid amide 1003.
g was obtained. N-trimethylsilylstearic acid amide has IR spectrum, ¹ H-NMR spectrum and M
The following structure was confirmed by S spectrum.

[0071]

[Chemical 3]

(Synthesis Example 2) <Synthesis of N-silylamide compound (2)> Synthesis Example 1
N-trimethylsilyloleic acid amide 1002 was prepared in the same manner as in Synthesis Example 1 except that 800 g of oleic acid amide was used instead of 800 g of stearic acid amide.
g was synthesized.

<(A) Synthesis of Urethane Prepolymer> Polyoxypropylene diol (average molecular weight 2000) 1
00 g, polyoxypropylene triol (average molecular weight 5000) 800 g, and metatetramethyl xylylene diisocyanate 140 g were mixed (at this time, NCO
/OH=1.8), the mixture was stirred and reacted at 90 ° C. in a N ₂ stream to synthesize a urethane prepolymer containing 1.8% of isocyanate groups.

Examples 1 to 6 and Comparative Examples 1 to 3 <Preparation of Polyurethane and / or Epoxy Resin Composition> The components shown below were used in the amounts shown in Table 1 and mixed with a universal mixer to prepare a mixture. A liquid polyurethane composition was prepared. As the polyurethane prepolymer (A), the one synthesized by the above method was used. (B) Sealets 200 (manufactured by Maruo Calcium) was used as calcium carbonate 1, and Super S (manufactured by Maruo Calcium) was used as calcium carbonate 2. As the (C) N-silylamide compound, N-trimethylsilylstearic acid amide or N-trimethylsilyloleic acid amide synthesized by the above method was used. As the silyl ester, KF-910 (manufactured by Shin-Etsu Chemical Co., Ltd .; viscosity: 35 mm ² / sec (60 ° C.), melting point: 45 ° C.) was used. As the (D) epoxy resin, DER332 (manufactured by Dow Chemical Co .; epoxy equivalent 173) was used. (E) As the latent curing agent oxazolidine, the one represented by the formula (3) was used. As the ketimine, the one represented by the formula (4) was used.

[0075]

[Chemical 4]

In addition to the components (A) to (E), the following components were blended. Plasticizer: UP-100 (manufactured by Toagosei Co., Ltd.) was used. Mineral spirits: A solvent (manufactured by Nisseki Mitsubishi) was used. Epoxy silane: A187 (manufactured by Unicar Japan Ltd.) was used.

With respect to the obtained polyurethane and / or epoxy resin composition, thixotropy, storage stability and mechanical properties were evaluated as follows. (1) The thixotropy was used to evaluate the initial thixotropy of the composition immediately after the preparation of the thixotropic polyurethane and / or epoxy resin composition. The thixo index was determined from the viscosity at 20 ° C as follows. The results are shown in Table 1. Using BS type viscometer No. 7 rotor, 20 ℃, 1
Each viscosity (cps) at rpm and 10 rpm was measured, and the viscosity ratio of 1 rpm / 10 rpm was used as a thixo index. The higher the thixo index value, the higher the thixotropic property.

(2) Curing Time (Tack Free Time) According to the method described in JIS A 5758, 20 ° C.,
The initial tack free time of the composition immediately after preparing the polyurethane and / or epoxy resin composition was measured under the atmosphere of 65% RH. The results are shown in Table 1.

(3) Storage stability The polyurethane and / or epoxy resin composition was stored in a closed container at 60 ° C. for 3 days, and then the thixo index and tack free time were measured. The results are shown in Table 1.

(4) Elongation (Eb) Polyurethane and / or epoxy resin composition
It was left to cure in an atmosphere of 0 ° C. and 65% RH for 7 days to be cured. The elongation (Eb) of this cured product was measured according to JIS K6251. The results are shown in Table 1.

[0081]

[Table 1]

[0082]

INDUSTRIAL APPLICABILITY The polyurethane and / or epoxy resin composition of the present invention exhibits initial thixotropy and curability, is excellent in storage stability, and has a cured product excellent in mechanical properties such as tensile strength. Give stable. Since the polyurethane and / or epoxy resin composition of the present invention contains an inorganic filler and has good thixotropy, it can be used as an ordinary flexible polyurethane and / or epoxy resin composition such as a sealant, a jointing material, an adhesive, etc. Although it can be widely used for applications, it is particularly suitable for applications such as sealants and joint materials. At that time, in particular, a sealant composed of a one-component polyurethane and / or an epoxy resin composition,
It can be suitably used as a joint material.

Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) // C09K 3/10 C09K 3/10 D Z F term (reference) 4H017 AA04 AA31 AB03 AB08 AC05 AD05 4J002 CD051 CD061 CD101 CD201 CK021 DA037 DE087 DE137 DE237 DJ007 DJ017 DJ038 DJ047 EX076 FD017 FD206 4J034 AA01 CA03 CA04 CA05 DF16 DF20 DF21 DF22 DF24 DG02 DG03 DG05 DG16 DK00 DP18 DP19 HA01 HA07 HA21 HC41 HC21 HC41 HC12 HC67 HC41 HC41 HC54 HC41 HC54 HC54 HC54 HC54 HC54 HC54

Claims (6)

[Claims] 1. A storage stabilizer for a polyurethane and / or epoxy resin, which comprises an N-silylamide compound having a functional group represented by the formula —CONH—Si≡. 2. A formula (R ¹ —CONH) _4-n —Si—R ² _n (1) (wherein R ¹ has 5 carbon atoms which may include a hetero atom).
To 21 hydrocarbon groups, and when n is 0, 1 or 2, R ¹ may be the same or different. R ² is an alkyl group or an alkoxy group having 1 to 3 carbon atoms,
n is 0, 1, 2 or 3. ) A storage stabilizer for moisture-curable polyurethane and / or epoxy resin, which comprises an N-silylamide compound represented by 3. A urethane prepolymer (A) having two or more isocyanate groups in the molecule, and 1 to 300 parts by weight of an inorganic filler (B), relative to 100 parts by weight of the urethane prepolymer (A), 0.5 A moisture-curable polyurethane composition containing 30 to 30 parts by weight of the N-silylamide compound (C) represented by the formula (1) and a moisture-latent curing agent (E). Formula (R ¹ —CONH) _4-n —Si—R ² _n (1) (In the formula, R ¹ has 5 carbon atoms which may include a hetero atom.
To 21 hydrocarbon groups, and when n is 0, 1 or 2, R ¹ may be the same or different. R ² is an alkyl group or an alkoxy group having 1 to 3 carbon atoms,
n is 0, 1, 2 or 3. ) 4. With respect to 100 parts by weight of the epoxy resin (D),
A moisture-curable epoxy resin composition containing 0.5 to 30 parts by weight of the N-silylamide compound (C) represented by the formula (1) and a moisture latent curing agent (E). Formula (R ¹ —CONH) _4-n —Si—R ² _n (1) (In the formula, R ¹ has 5 carbon atoms which may include a hetero atom.
To 21 hydrocarbon groups, and when n is 0, 1 or 2, R ¹ may be the same or different. R ² is an alkyl group or an alkoxy group having 1 to 3 carbon atoms,
n is 0, 1, 2 or 3. ) 5. A urethane prepolymer (A) having two or more isocyanate groups in the molecule, 1 to 100 parts by weight of an epoxy resin (D), and 1 to 300 parts by weight per 100 parts by weight of the urethane prepolymer (A). A moisture-curable polyurethane composition containing parts by weight of an inorganic filler (B) and 0.5 to 30 parts by weight of an N-silylamide compound (C) represented by the formula (1). Formula (R ¹ —CONH) _4-n —Si—R ² _n (1) (In the formula, R ¹ has 5 carbon atoms which may include a hetero atom.
To 21 hydrocarbon groups, and when n is 0, 1 or 2, R ¹ may be the same or different. R ² is an alkyl group or an alkoxy group having 1 to 3 carbon atoms,
n is 0, 1, 2 or 3. ) 6. A moisture latent curing agent (E) selected from oxazolidine, ketimine, enamine and silyl mercaptan is contained in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the urethane prepolymer (A). 3 or 5
The moisture-curable polyurethane composition described in 1.