JP2001081307A - One-component moisture-curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a one-component moisture-curable resin composition having excellent storage stability, good thixotropic property, high curing speed after taking out of a container and excellent adhesive strength and heat-resistance and useful as an adhesive, etc., in coating material, civil engineering and building fields. SOLUTION: The one-component moisture-curable resin composition contains (A) an isocyanate compound having a secondary carbon atom or tertiary carbon atom bonded to all isocyanate (NCO) groups in the molecule, (B) a ketimine having a ketimine (C=N) bond derived from ketone or aldehyde and amine and containing a branched carbon atom or a ring-forming carbon atom bonded to the α-position of at least one of the ketimine carbon or nitrogen and (C) calcium carbonate surface-treated with a urethane compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention is useful as an adhesive in the fields of paints, civil engineering and construction, which has excellent storage stability, has a high curing rate when taken out of a container, and has excellent adhesive strength and heat resistance. A one-component moisture-curable resin composition.

[0002]

2. Description of the Related Art It is known that an isocyanate compound reacts with a curing agent such as an amine at room temperature to form a urethane bond, whereby a cured product can be easily obtained. When the isocyanate compound and the amine are stored in a mixed state, there is a problem that a curing reaction proceeds during the storage and storage stability is deteriorated. For this reason, it is usually used as a so-called two-part type that is mixed during work. However, in recent years, isocyanate-based one-part type curable composition has been used because it is not necessary to adjust the mixing of the composition in on-site construction and it is easy to handle. Development of things is desired.

[0003] By the way, conventionally, the odor of the amine curing agent,
For the purpose of solving problems such as toxicity and improving convenience at the time of work, it has been studied to block (cap) an amine to form a latent curing agent. As an amine blocking technique, a ketimine obtained by blocking an amine with a ketone is known. Generally, a ketimine synthesized from an alkylenediamine and a ketone such as methyl isobutyl ketone and methyl ethyl ketone is known. Ketimine is a stable compound in the absence of water, and easily hydrolyzes to an active amine in the presence of water, so that it acts as a curing agent with moisture in the air.

[0004] However, even when the above-mentioned conventional general-purpose ketimine is used as a latent curing agent for the isocyanate compound, sufficient storage stability cannot be obtained due to progress of gelation during storage of the mixture. In order to impart thixotropic properties to the isocyanate-based one-part curable composition,
When commercially available surface-treated calcium carbonate is blended, the storage stability is further reduced. For this reason, the development of a one-pack moisture-curable resin composition that has excellent storage stability, has good thixotropic properties, has a high curing rate at room temperature due to moisture in the air, and further exhibits excellent adhesion. Is desired.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a coating composition which is excellent in storage stability, has thixotropic properties, has a high curing rate when taken out of a container, and has excellent adhesive strength and heat resistance. One object of the present invention is to provide a one-part moisture-curable resin composition useful as an adhesive or the like in the fields of civil engineering and construction.

[0006]

That is, the present invention provides:
(A) A ketimine (C = N) derived from an isocyanate compound having a structure in which a secondary or tertiary carbon is bonded to all isocyanate (NCO) groups in a molecule, (B) a ketone or an aldehyde, and an amine. A) a ketimine having a bond, wherein at least one of the ketimine carbon and nitrogen has a branched carbon or a ring-membered carbon bonded at the α-position;
(C) A one-pack moisture-curable resin composition containing calcium carbonate surface-treated with a urethane compound.

It is preferable that the composition further contains (D) an epoxy resin.

The urethane compound is preferably represented by the following formula (1).

Embedded image (Where X is a residue obtained by removing an isocyanate group from an isocyanate compound, or a residue obtained by removing an amino group from an amine compound, n is an integer of 1 to 4, R is a hydrocarbon group, and at least one of R Is a C ₈ or higher hydrocarbon group.)

The one-part moisture-curable resin composition comprises (D)
When the epoxy resin is not contained, the isocyanate compound 10 having a structure in which a secondary carbon or a tertiary carbon is bonded to all the isocyanate (NCO) groups in the molecule (A).
0 parts by weight, or when (D) an epoxy resin is contained, isocyanate having a structure in which secondary carbon or tertiary carbon is bonded to (A) all isocyanate (NCO) groups in the molecule. The calcium carbonate surface-treated with the urethane compound (C) is 50 to 2 with respect to 100 parts by weight of the compound and the epoxy resin (D) in total.
It is preferably contained in an amount of 00 parts by weight.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. (A) Isocyanate compound having a structure in which secondary or tertiary carbon is bonded to all isocyanate (NCO) groups in the molecule The isocyanate compound used in the present invention has all isocyanate (NCO) groups in the molecule. It has a structure attached to secondary or tertiary carbon. The group other than NCO bonded to the secondary or tertiary carbon is not particularly limited. For example, the group other than NCO is not particularly limited in its carbon number or bulkiness, and may contain a hetero atom such as O, S, or N. 2 which binds to tertiary carbon
The two groups may be the same or different from each other.

Such an isocyanate compound can be specifically represented by the following formula (2).

Embedded image In the formula, R ^c and R ^a are each independently an organic group that may contain O, S, and N, R ^b is a hydrogen atom or the organic group, and p is an integer of 1 or more.

Examples of the organic group include a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group and an alkylaryl group, and a group having a hetero atom selected from O, S and N, for example, ether, carbonyl, amide and the like. ,
Examples include an urea group (carbamide group) and an organic group containing a urethane bond. Among the above, ^Ra or ^Rb
The organic group represented by is preferably a methyl group.
Further, p is preferably 2 or more, that is, a polyfunctional isocyanate compound having two or more NCO groups to which the above-mentioned branched carbon is bonded in the molecule is preferable. In addition, the monoisocyanate compound with p = 1 is usually used by mixing with a polyisocyanate having p of 2 or more. Polyisocyanates can be used alone or in combination of two or more. It is a preferred embodiment to use a mixture of diisocyanate (p = 2) and triisocyanate (p = 3).

The isocyanate compound used in the present invention may have any structure as long as the isocyanate group has the structure specified above, and may be a so-called isocyanate monomer or a urethane prepolymer derived from a polyisocyanate monomer and a polyol. It may be a polymer.

Specific examples of the isocyanate monomer include a monoisocyanate compound (p = 1) such as m- or p-isopropenyl-α, α-dimethylbenzoyl isocyanate (TMI manufactured by Mitsui Cytec), m- or p-tetramethylxylylene diisocyanate (TMX
DI) and diisocyanate compounds (p = 2) such as isophorone diisocyanate. For the synthesis of the urethane prepolymer, diisocyanates are usually used among the above polyisocyanate monomers.

The polyol used for the synthesis of the urethane prepolymer is not particularly limited in its molecular weight and skeleton as long as it has two or more hydroxy groups. For example, those generally used as polyols such as low molecular weight polyhydric alcohols, polyether polyols, polyester polyols, and polymer polyols having a main chain composed of carbon-carbon bonds can be widely used.

As the urethane prepolymer, specifically, an adduct of a diisocyanate and a low molecular weight polyhydric alcohol,
Urethane prepolymers derived from diisocyanates, polyether polyols, polyester polyols and the like can be mentioned.

The low molecular weight polyhydric alcohols include, for example, ethylene glycol (EG), diethylene glycol, propylene glycol (PG), dipropylene glycol, (1,3- or 1,4-) butanediol, pentanediol, neone Pentyl glycol, hexanediol, cyclohexanedimethanol, glycerin, 1,1,1-trimethylolpropane (TMP),
Polyhydric alcohols such as 1,2,5-hexanetriol and pentaerythritol; and saccharides such as sorbitol.

Among such adducts of polyhydric alcohol and diisocyanate, adducts using trimethylolpropane (TMP) as polyhydric alcohol (polyol) (p = 3 in the above formula) are preferred. Specifically, 1,1,1-trimethylolpropane (TMP)
And tetramethylxylene diisocyanate (TMXD
The TMXDI.TMP adduct derived from I) is preferably mentioned.

As the above-mentioned adduct, those which are commercially available under the trade name of, for example, SEISEN 3160 (Mitsui Cytec) can also be used. Such an adduct is not necessarily a complete OH: NCO adduct and may contain unreacted raw materials.

The polyether polyol and polyester polyol used as the polyol during the synthesis of the urethane prepolymer are usually derived from the above low molecular weight polyhydric alcohols. In the present invention, those derived from aromatic diols are also preferably used. Can be The aromatic diols include a bisphenol A structure (4,4'-
Dihydroxyphenylpropane), a bisphenol F structure (4,4′-dihydroxyphenylmethane), a brominated bisphenol A structure, a hydrogenated bisphenol A structure, a bisphenol S structure, and a bisphenol AF structure having a bisphenol skeleton.

Examples of the polyether polyol derived from the above-mentioned polyhydric alcohols and / or aromatic diols include alkylene oxide derived from polyhydric alcohols such as ethylene oxide, propylene oxide and butylene oxide (tetramethylene oxide).
Those having one or more selected from styrene oxide and bisphenol skeletons can be mentioned. Specific examples of the polyether polyol include polyethylene glycol, polypropylene glycol (PPG), ethylene oxide / propylene oxide copolymer, polyteoramethylene ether glycol (PTMEG),
And sorbitol-based polyols. As a polyether polyol having a bisphenol skeleton,
A polyether polyol obtained from a diol having a bisphenol skeleton and a polyhydric alcohol, for example, a polyether polyol containing the bisphenol A structure and ethylene oxide and propylene oxide units can be used.

Examples of the polyester polyol include condensates of the above-mentioned polyhydric alcohols and / or aromatic diols with polybasic carboxylic acids (condensed polyester polyols), lactone polyols and polycarbonate diols. As the polybasic carboxylic acid forming the condensation polyester polyol,
Glutaric acid, adipic acid, azelaic acid, pimelic acid,
Examples include suberic acid, sebacic acid, terephthalic acid, isophthalic acid, dimer acid, other low molecular carboxylic acids, oligomeric acids, castor oil, and hydroxycarboxylic acids such as reaction products of castor oil and ethylene glycol.
As the lactone-based polyol, propion lactone,
Ring-opening polymers such as valerolactone; As the polyester polyol having a bisphenol skeleton, a polyester polyol obtained by using a diol having a bisphenol skeleton in place of the polyhydric alcohol or together with the polyhydric alcohol, for example, a polyester obtained from bisphenol A and castor oil Examples of the polyol include polyester polyols obtained from bisphenol A, castor oil, ethylene glycol, and propylene glycol.

In synthesizing the urethane prepolymer,
Further, polymer polyols having a carbon-carbon bond in the main chain skeleton, such as acrylic polyol, polybutadiene polyol, and hydrogenated polybutadiene polyol, can also be used. Two or more of the above polyols can be used in combination.

Preferable examples of the urethane prepolymer as described above include, for example, as a polyol, difunctional or trifunctional, or a polyfunctional (OH) mixture of these.
A polyfunctional urethane prepolymer obtained using polypropylene glycol or the like can be used.

Also preferred are urethane prepolymers having a bisphenol skeleton, and particularly preferred are urethane prepolymers having a bisphenol A skeleton. Specifically, as the polyol, a urethane prepolymer obtained by using a polyester polyol synthesized from bisphenol A and castor oil, a polyether polyol synthesized from bisphenol A and ethylene oxide, propylene oxide, or the like is preferably used. .

The urethane prepolymer may contain two or more kinds of polyol components, and may contain not only two or more kinds of bisphenol skeletons but also a polyol component having another structure together with the bisphenol skeleton. .

In the present invention, two or more of the above specific isocyanate compounds may be used in combination. Also, a general isocyanate compound other than the above may be used in a small amount as long as the object of the present invention is not impaired. For example, isocyanate compounds such as toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), and xylylene diisocyanate (XDI) can be used in combination. As it reduces stability, its usage is
(A) It is desirable that the content is less than 10 mol% based on the isocyanate compound having a structure in which a secondary carbon or a tertiary carbon is bonded to all isocyanate (NCO) groups in the molecule.

(B) Ketimine In the present invention, a compound having a C ＝ N bond derived from a ketone or aldehyde and an amine is referred to as ketimine,
Therefore, in the present specification, ketimine is -HC = N
It is used in a sense that also includes an aldimine having a bond.

The ketimine used in the present invention is a ketimine (C) derived from a ketone or aldehyde and an amine.
= N) bond, and has a structure in which a branched carbon or a ring member carbon is bonded to at least one α-position of the ketimine carbon or nitrogen. That is, ketimine C = α of N bond
Has a bulky group at each position. Here, the ring member carbon may be a carbon constituting an aromatic ring or a carbon constituting an alicyclic ring. In the present invention, as the ketimine having a bulky group as described above, specifically, a ketimine having two or more ketimine (C = N) bonds to which the bulky group is bonded in a molecule is exemplified.

In the above ketimine, the α of ketimine carbon
When a branched carbon or a ring-membered carbon is introduced at the position, a ketone or aldehyde having a branched hydrocarbon group or a cyclic hydrocarbon group at the α-position of the carbonyl group is used. Specifically, diisopropyl ketone, ketone having a branched hydrocarbon group represented by the following formula (3) or ketone having a cyclic hydrocarbon group such as aldehyde, propiophenone, benzophenone, benzaldehyde, and cyclohexanecarboxaldehyde; Aldehydes. These can be used in combination.

[0031]

Embedded image (Wherein, R ¹ : alkyl group having 1 to 6 carbon atoms R ² : methyl group or ethyl group R ³ : hydrogen atom, methyl group or ethyl group R ⁴ : hydrogen atom or methyl group)

As the ketone or aldehyde represented by the above formula (3), methyl t-butyl ketone (MTB
K), methyl isopropyl ketone (MIPK), pivalaldehyde (trimethylacetaldehyde), and isobutyraldehyde ((C
H ₃ ) ₂ CHCHO).

The above ketimine has two or more C ＝ N bonds in the molecule, and such a ketimine is usually obtained by using a polyamine having two or more amino groups in the molecule. In order to obtain a ketimine having a bulky group at the α-position of the ketimine nitrogen derived from the polyamine, for example, 2,5-dimethyl-2,5-hexamethylenediamine, mensendiamine, 1,4- Bis (2-amino-2-methylpropyl) piperazine, polypropylene glycol (PPG) having an amino group bonded to propylene branched carbon at both ends of the molecule (for example, Jeffamine D230 and Jeffamine D400 manufactured by San Techno Chemical Co., Ltd.)
Etc.) can be used.

Among the above-mentioned ketimines, those in which a bulky group is bonded to the ketimine carbon and methylene is bonded to the ketimine nitrogen, the above-mentioned secondary is attached to all the isocyanate (NCO) groups in the molecule (A). It is preferable to use together with an isocyanate compound having a structure in which carbon or tertiary carbon is bonded, because a one-part moisture-curable resin composition having particularly excellent both storage stability and curability (curing speed) can be obtained. In order to introduce a methylene group into the ketimine nitrogen, a polyamine represented by the following formula (4) can be used.

[0035]

Embedded image

Specific examples of the polyamine represented by the above formula (4) include ethylenediamine, propylenediamine,
Butylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenediamine, trimethylhexamethylenediamine, N-aminoethylpiperazine, 1,2-diaminopropane, iminobispropylamine, methyliminobispropylamine , H ₂ N (CH
Diamine having a polyether skeleton in which a methylene group is bonded to an amine nitrogen such as ₂ CH ₂ O) ₂ (CH ₂ ) ₂ NH ₂ (trade name: Jeffamine EDR148 manufactured by San Techno Chemical Co., Ltd.), 1,5-diamino-2-methylpentane (Trade name: MPMD manufactured by DuPont Japan), meta-xylene diamine (MXDA), polyamide amine (X20 manufactured by Sanwa Chemical Co., Ltd.)
00), isophoronediamine, 1,3-bisaminomethylcyclohexane (1,3BA manufactured by Mitsubishi Gas Chemical Company, Inc.)
C), 1-cyclohexylamino-3-aminopropane, 3-aminomethyl-3,3,5-trimethyl-cyclohexylamine, a diamine having a norbornane skeleton (NBDA manufactured by Mitsui Chemicals, Inc.) and the like. Among these, 1,3-bisaminomethylcyclohexane (1,3
BAC), norbornanediamine (NBDA), meta-xylylenediamine (MXDA), Jeffamine EDR
148 (trade name) and polyamidoamine are preferred.

Among the above ketimines, a preferred specific example is methyl isopropyl ketone (MIPK).
Or a product obtained from methyl t-butyl ketone (MTBK) and Jeffamine EDR148 (trade name: dimethyleneamine having a polyether skeleton); methyl isopropyl ketone (MIPK) or methyl t-butyl ketone (MTBK); Those obtained from -bisaminomethylcyclohexane (1,3BAC), those obtained from methyl isopropyl ketone (MIPK) or methyl t-butyl ketone (MTBK), and dimethyleneamine having a norbornane skeleton (trade name: NBDA); Methyl isopropyl ketone (MIPK) or methyl t-butyl ketone (MTBK) and meta-xylylenediamine (M
XDA), methyl isopropyl ketone (MIPK) or methyl t-butyl ketone (MTB).
K) and polyamidoamine (trade name: X2000). Among them, those obtained from MIPK or MTBK and NBDA, those obtained from MIPK and 1,3BAC,
Exhibits excellent curability. MIPK or MTBK
And X2000 exhibit excellent adhesion to wet surfaces.

Examples of ketimines obtained from a combination of an aldimine and a polyamine include pivalaldehyde, norbornanediamine (NBDA), 1,3-bisaminomethylcyclohexane (1,3BAC) or Jeffamine EDR148, metaxylylenediamine. (MXDA); isobutyraldehyde;
Norbornanediamine (NBDA), 1,3-bisaminomethylcyclohexane (1,3BAC) or Jeffamine EDR148, meta-xylylenediamine (MX
DA); cyclohexanecarboxaldehyde and norbornanediamine (NBDA), 1,3-
Preferred are those obtained from bisaminomethylcyclohexane (1,3BAC) or a combination with Jeffamine EDR148, meta-xylylenediamine (MXDA).

The ketimine as described above is reacted by heating a ketone or aldehyde and a polyamine in the absence of a solvent or in the presence of a solvent such as benzene, toluene, or xylene while azeotropically removing water to be eliminated. Can be obtained.

The ketimine used in the present invention has a bulky group at the α-position of the ketimine bond, and has a structure in which nitrogen is sterically hindered. Methyl isobutyl ketone (MIB
K), a conventionally known ketimine obtained from a general-purpose ketone such as methyl ethyl ketone (MEK) and an amine having a methylene group bonded to an amino group, show a certain degree of basicity because the ketimine nitrogen is exposed. Therefore, a one-pack type composition in which ketimine and an isocyanate compound are blended has a problem in storage stability such that gelation proceeds during storage.

On the other hand, the ketimine used in the present invention has a bulky group in the vicinity of the ketimine nitrogen or directly bonded to the nitrogen, and the ketimine nitrogen is protected by a substituent, that is, it is sterically hindered. , Its basicity is greatly reduced, and it exhibits excellent storage stability. In addition, the ketimine used in the present invention is easily decomposed into a raw material amine and a ketone or aldehyde by being brought into contact with the moisture in the air at the time of use. Express.

By the way, even when ketimine as described above is used as a latent curing agent, an isocyanate compound having no bulky group near an isocyanate group such as TDI (tolylene diisocyanate) and XDI (xylene diisocyanate) is used. However, although the curing speed was high, sufficient storage stability was not obtained, and it was difficult to obtain a practical one-part moisture-curable resin composition. On the other hand, in the present invention, by combining a ketimine having a specific structure as described above and an isocyanate compound having a bulky group bonded to an isocyanate group, both excellent curability and storage stability are achieved. Made it possible.

The isocyanate compound (A) having a structure in which a secondary carbon or a tertiary carbon is bonded to all the isocyanate (NCO) groups in the molecule used in the present invention has a bulky group bonded to the isocyanate group. When the bulky group is an electron donating group such as an alkyl group, the reactivity of the isocyanate group is low. The blend (composition) of such an isocyanate compound and the ketimine having the specific structure described above is kept stable during storage in a container. On the other hand, when the composition comes into contact with air, the water molecule, which is moisture, is small and easily attacks ketimine nitrogen without steric hindrance of the substituent, and hydrolysis proceeds easily. Therefore, the curing time of the one-part moisture-curable resin composition of the present invention is fast.

(C) Calcium Carbonate Surface-Treated with a Urethane Compound Conventionally, calcium carbonate blended in a one-part curable composition such as a urethane one-part sealant for imparting a far-reaching modification has a high storage stability. From the viewpoint of wettability, surface treatment with a fatty acid or a fatty acid ester has been performed. However, even if these surface-treated calcium carbonates are used, there is a problem that storage stability is not good. In the present invention, calcium carbonate surface-treated with a urethane compound (hereinafter referred to as surface-treated calcium carbonate) is used.
By using such a surface-treated calcium carbonate, the one-part moisture-curable resin composition of the present invention obtained has excellent storage stability and good curability.

The urethane compound used in the present invention is
A compound having at least one urethane bond (—NHCOO—) in a molecule, including a compound obtained by a reaction between an isocyanate and a polyol compound, a compound obtained by a reaction between an isocyanate and a carboxylic acid, and a urethane compound. And an isocyanate obtained by a reaction between isocyanate and isocyanate. As the isocyanate, an aromatic type, an aliphatic type, an alicyclic type,
A blend of more than one species can be used. As the polyol compound, those commonly used as polyols such as primary alcohols, secondary alcohols, alcohols such as phenol, polyether polyols, polyester polyols, and polymer polyols having a main chain composed of carbon-carbon bonds are widely used. Can be used.

The urethane compound used in the present invention is preferably a compound represented by the following formula (1) (hereinafter, referred to as a urethane compound of the formula (1)).

Embedded image In the formula, X represents a residue obtained by removing an isocyanate group from an isocyanate compound, or a residue obtained by removing an amino group from an amine compound. R is a hydrocarbon group, and at least one of R is a C ₈ or more hydrocarbon group. n is an integer of 1 to 4.

The method for synthesizing the urethane compound of the formula (1) is as follows.
A method of reacting an isocyanate compound (X- (NCO) _n ) with an alcohol (ROH), a method of reacting an isocyanate compound with a carboxylic acid, and a method of reacting carbonyl chloride (X- (OCOCl) _n ) with an amine. Can be used.

The isocyanate compound used in the synthesis of the urethane compound of the formula (1) is a compound having 1 to 4 isocyanate groups in the molecule, and all known isocyanate compounds used in the synthesis of urethane resins and the like are used. It is possible.

Specifically, examples of the monoisocyanate compound include phenyl isocyanate and stearyl isocyanate. Specific examples of the diisocyanate compound include aromatic isocyanates such as paraphenylene diisocyanate, tolylene diisocyanate, naphthalene diisocyanate, and 4,4'-diphenylmethane diisocyanate; aliphatic isocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, and octadecyl diisocyanate; Alicyclic isocyanates such as isophorone diisocyanate; aryl aliphatic isocyanates such as xylene diisocyanate; and modified isocyanates of the above isocyanates.

Specific examples of the triisocyanate compound include reaction products of the above-mentioned diisocyanate compound and the like with polyhydric alcohols such as glycerin, hexanetriol and trimethylolpropane, and tetramethylene diisocyanate and hexamethylene diisocyanate. Compounds having three isocyanate groups in one molecule obtained by forming a diisocyanate compound with an isocyanurate ring are exemplified. As the tetraisocyanate compound, specifically, a diurethane obtained by reacting the above-mentioned diisocyanate compound or the like with a dialcohol, and a compound having four isocyanate groups in one molecule obtained by reacting with two molecules of diisocyanate And the like. These isocyanate compounds
A single type or a combination of two or more types may be used.

The alcohol (ROH) used in the synthesis of the urethane compound of the formula (1) includes lower alcohols such as methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, heptanol, benzyl alcohol and allyl alcohol. And higher alcohols such as n-octyl alcohol, 2-ethylhexanol, nonyl alcohol, n-decyl alcohol, undecyl alcohol, n-tridecyl alcohol, mystyl alcohol, n-hexadecyl alcohol, and stearyl alcohol. As a combination of the above-mentioned isocyanate compound and alcohol, a combination of tolylene diisocyanate and stearyl alcohol is particularly preferable.

The carboxylic acids used in the synthesis of the urethane compound of the formula (1) include lauric acid, myristic acid,
Fatty acids such as palmitic acid, stearic acid, oleic acid, and behenic acid, and resin acids. As a combination of the above isocyanate compound and carboxylic acid,
A combination of tolylene diisocyanate and stearic acid is preferred.

The carbonyl chloride (X- (OCOCl) _n ) used in the synthesis of the urethane compound of the formula (1) includes methyl chlorocarbonate, ethyl chlorocarbonate, propyl chlorocarbonate, butyl chlorocarbonate, benzyl chlorocarbonate and chlorocarbonate. Octyl, nonyl chlorocarbonate, decyl chlorocarbonate, undecyl chlorocarbonate, okdadecyl chlorocarbonate,
And benzyl chlorocarbonate. Examples of the amine used for the synthesis of the urethane compound of the formula (1) include octylamine, laurylamine, stearylamine, oleylamine, m-phenylenediamine, p-phenylenediamine and the like.

The combination of carbonyl chloride and amine is particularly preferably a combination of m-phenylenediamine and octadecyl chlorocarbonate.

R in the above formula (1) is a hydrocarbon group, and at least one of R must be a hydrocarbon group having 8 or more carbon atoms. If there is no hydrocarbon group having 8 or more carbon atoms in one molecule, the storage stability of the composition containing the urethane compound of the above formula (1) is deteriorated.

The urethane compound used in the present invention, including the urethane compound of the formula (1), preferably has a melting point of 50 ° C. or higher. If the melting point is less than 50 ° C., the urethane compound may be dissolved during the production of the one-component moisture-curable resin composition.

The amount of the urethane compound used in the present invention, including the urethane compound of the formula (1), is not particularly limited.
-20% by weight, preferably about 2-10% by weight. If the amount is less than 1% by weight, the effect of the treatment cannot be obtained.

In the surface treatment of calcium carbonate used in the present invention, a carboxylic acid, a sulfonic acid, or a metal salt thereof may be used in addition to the urethane compound. Carboxylic acid, sulfonic acid, or the metal salt thereof and the urethane compound used in the present invention, in combination with the surface treatment of calcium carbonate, the one-part moisture curable resin of the present invention containing surface-treated calcium carbonate The storage stability of the composition is improved.

As carboxylic acids, sulfonic acids, or metal salts thereof (hereinafter also referred to as fatty acids, etc.), all of those generally used as a treatment agent for calcium carbonate can be used. Specific examples thereof include fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, and behenic acid; resin acids; sulfonic acids such as dodecylbenzenesulfonic acid; and metal salts thereof. As the metal in the metal salt, potassium, sodium,
Examples include aluminum, calcium, and magnesium. Among these, metal salts of fatty acids are particularly preferred.

The method of treating calcium carbonate using a carboxylic acid, a sulfonic acid or a metal salt thereof is not particularly limited. For example, calcium carbonate and a carboxylic acid, a sulfonic acid in a water slurry or a water-containing cake may be used. Or a method of vigorously stirring these metal salts with a mixer or the like. The amount of the carboxylic acid, sulfonic acid, or metal salt thereof is not particularly limited,
It is preferable to use carboxylic acid, sulfonic acid, or a metal salt thereof in an amount of about 0.5 to 10% by weight, preferably about 1 to 8% by weight, based on calcium carbonate. 0.5% by weight
If the amount is less than the above, the effect of the treatment cannot be obtained.

The untreated calcium carbonate for obtaining the surface-treated calcium carbonate used in the present invention includes BE
Those having a specific surface area of 3 m ² / g or more by the T method are used.
Among untreated calcium carbonate, precipitated calcium carbonate is particularly preferred. When such precipitated calcium carbonate is used, the thixotropic property of the surface-treated calcium carbonate used in the present invention obtained is excellent.

The method of adding a urethane compound or a fatty acid or the like used in the present invention for surface treatment of calcium carbonate is not particularly limited. For example, calcium carbonate or carbonate already treated with a fatty acid or the like may be used. A method of mixing calcium and the urethane compound used in the present invention and heating the mixture to a temperature equal to or higher than the melting point of the urethane compound (dry treatment); water slurry of calcium carbonate or calcium carbonate already treated with a fatty acid or the like; A method of mixing a urethane compound used for the above, heating the mixture to a temperature equal to or higher than the melting point of the urethane compound, dehydrating, drying, and pulverizing (wet treatment); When producing ordinary precipitated calcium carbonate, the particle size is preferably 100 μm or less. Add the urethane compound used in the present invention, and dry at a temperature equal to or higher than the melting point of the urethane compound. That method (fatty acids during this process, can be added at any location), and the like.

(D) Epoxy Resin The one-pack moisture-curable resin composition of the present invention can contain an epoxy resin. By containing the epoxy resin, the one-part moisture-curable resin composition of the present invention can exhibit excellent adhesiveness to mortar, metal, and the like. Further, even when the one-part moisture-curable resin composition of the present invention contains an epoxy resin, the storage stability is good and the strength of the cured product is extremely high. It is considered that the reason why the strength of the cured product is extremely high is that the reaction proceeds equally to the isocyanate compound and the epoxy resin. The epoxy resin that can be used in 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 novolak, glycidyl ester type epoxy resin of dimer acid, bisphenol And a glycidyl ether type epoxy resin of F. Among these, the glycidyl ether type epoxy resin of bisphenol A is suitably used as a general-purpose epoxy resin.

The content of the above-mentioned ketimine in the one-pack moisture-curable resin composition of the present invention may be expressed by an equivalent ratio of (isocyanate compound) when the one-pack moisture-curable resin composition of the present invention does not contain an epoxy resin. Isocyanate group in) /
(Ketimine bond C = N in ketimine) is 0.5-4.
It is preferably used so as to be 0, and more preferably 1.0 to
More preferably, it is 2.0. When the one-part moisture-curable resin composition of the present invention contains an epoxy resin, the equivalent ratio is (the sum of the isocyanate groups in the isocyanate compound and the epoxy groups in the epoxy resin) / (the ketimine bond in the ketimine C = N ) Is preferably 0.5 to 4.0, and more preferably 1.0 to 2.0. Within the above range, a composition having both good storage stability and curability can be obtained.

The content of the surface-treated calcium carbonate in the one-part moisture-curable resin composition of the present invention is adjusted so that the one-part moisture-curable resin composition of the present invention is epoxy-containing in order to obtain an appropriate initial thixotropic property and workability. When no resin is contained, the resin is preferably used in an amount of 50 to 200 parts by weight, more preferably 70 to 150 parts by weight, based on 100 parts by weight of the isocyanate compound. When the one-part moisture-curable resin composition of the present invention contains an epoxy resin, 50 to 20 parts by weight based on a total of 100 parts by weight of the isocyanate compound and the epoxy resin.
It is preferably used in an amount of 0 parts by weight, more preferably 70 to 150 parts by weight. If it exceeds 200 parts by weight, the viscosity becomes too high, and the workability tends to decrease.

The content of the epoxy resin that can be contained in the one-part moisture-curable resin composition of the present invention is preferably 5 to 1000 parts by weight, more preferably 10 to 500 parts by weight, based on 100 parts by weight of the isocyanate compound. preferable. Within this range, the obtained one-part moisture-curable resin composition of the present invention is excellent in curability, adhesiveness, mechanical strength and the like. In the present invention, a polymer such as silicone or modified silicone may be contained together with the epoxy resin.

Further, the one-pack moisture-curable resin composition according to the present invention may contain other additives such as a filler, a plasticizer, a silane coupling agent, a pigment, a dye, and the like, as long as the object of the present invention is not impaired. It may contain an antioxidant, an antioxidant, an antistatic agent, a flame retardant, an adhesion-imparting agent, a dispersant, a solvent, and the like.

Fillers include organic and inorganic fillers of various shapes, such as fumed silica, calcined silica, precipitated silica, crushed silica, and fused silica; diatomaceous earth; iron oxide, zinc oxide, titanium oxide, and barium oxide. , Magnesium oxide; magnesium carbonate, zinc carbonate;
Kaolin clay, calcined clay; or carbon black, or a fatty acid, resin acid, or fatty acid ester-treated product thereof can be used.

As plasticizers, dioctyl phthalate (DOP), dibutyl phthalate (DBP); dioctyl adipate, isodecyl succinate; diethylene glycol dibenzoate, pentaerythritol ester;
Butyl oleate, methyl acetyl ricinoleate; tricresyl phosphate, trioctyl phosphate; propylene glycol adipate polyester, butylene glycol adipate polyester, and the like can be used.

As the silane coupling agent, trimethoxyvinylsilane and γ-glycidoxypropyltrimethoxysilane are preferably used since they are particularly effective in improving the adhesion to wet surfaces and are general-purpose compounds. .

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

Examples of the antioxidants include hindered phenol compounds and hindered amine compounds. Examples of the antioxidant include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA). 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 a terpene resin, a phenol resin, a terpene-phenol resin, a rosin resin, and a xylene resin. The above components may be used in combination as appropriate.

The method for producing the one-part moisture-curable resin composition of the present invention from each of the above-mentioned components is not particularly limited. Preferably, each of the above-mentioned components is placed under reduced pressure or in an atmosphere of an inert gas such as nitrogen. It is preferable that the mixture is sufficiently kneaded using a stirring device such as a mixing mixer and uniformly dispersed. The obtained one-component moisture-curable resin composition is stored in a closed container, and a cured product can be obtained at room temperature by the moisture in the air at the time of use.

[0074]

EXAMPLES Next, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. <Synthesis of Isocyanate Compound> Tetramethylxylene diisocyanate (TMXDI, manufactured by Mitsui Cytec Co., Ltd.) and trifunctional PPG (Exenol 5030, manufactured by Asahi Glass Co., Ltd., molecular weight 5000) as a triol were prepared by NC.
O / OH was used at a molar ratio of 2.0, and the mixture was reacted with stirring at 80 ° C. for 8 hours in the presence of a tin catalyst to obtain an isocyanate compound containing 2.1% of isocyanate groups (urethane prepolymer). Polymer) was obtained. <Synthesis of isocyanate compound> Number average molecular weight 500
0 polypropylene glycol (Exenol 503)
0; manufactured by Asahi Glass Co., Ltd.) and diphenylmethane diisocyanate in a molar ratio of NCO / OH = 2.0 in the presence of a tin catalyst, and stirred and reacted at 80 ° C. for 10 hours to form an isocyanate group. Isocyanate compound (urethane prepolymer) containing 2.0%.

<Preparation of calcium carbonate surface-treated with urethane compound> The specific surface area by the BET method was 18 m ^2.
/ G of the precipitated calcium carbonate (360 g), a urethane compound represented by the following formula:

Embedded image Was added at room temperature for 15 minutes using a mixer.
The mixture was stirred and treated at 0 ° C. for 1 hour in a dry system to obtain calcium carbonate.

(Examples 1 to 4, Comparative Examples 1 to 6) The compounds shown in Table 1 were mixed at the ratios (weight ratios) shown in Table 1 to obtain compositions. The storage stability (rate of change in viscosity) and curability (curing time) of each of the obtained compositions were evaluated as follows. The results are shown in Table 1.

<Rate of viscosity change> Immediately after adjusting the above composition,
The initial viscosity is measured, and then the composition is stored in a closed container, and the viscosity of the composition after storage at 40 ° C. for 8 days is divided by the initial viscosity to obtain a viscosity change rate. <Curing time> The above composition was prepared and applied to one surface of glass with a coating thickness of 3 [mil] to form a test piece, and the test piece was placed on a dry time tester (Tayu Kikai Co., Ltd.). Adjust the needle tip so that the needle tip of the dry time tester touches the coated surface of the test piece, move the needle at 0.5 mm / sec under the conditions of 20 ° C. and 55% humidity, and apply the coated surface with the needle tip. Scratch. From the start of the movement of the needle until the change in the scratch (Gardner type dry time measurement method
In other words, it means that the curing proceeds further from the state where the composition of the applied coating portion is removed by the needle tip touching the coating surface, and only the depression due to the needle tip starts to remain on the coating surface.) The time is defined as a curing time (initial curing time).

[0078]

[Table 1]

<Compounds in Table> Epoxy resin: EPOXY EP4100E, epoxy equivalent = 190, manufactured by Asahi Denka Kogyo Co., Ltd. Calcium carbonate: Sealets 200 (surface treated with carboxylic acid ester) Calcium carbonate, manufactured by Maruo Calcium Co., Ltd. Surface-treated product by Maruo Calcium Co., Ltd. Ketimine: synthesized from norbornanediamine (NBDA) and methyl isopropyl ketone (MIPK). The chemical structural formula is shown below.

Embedded image Vinyl silane: A-171, Nippon Unicar Co., Ltd. Phosphite: JP-310, Johoku Chemical Co., Ltd. Tin catalyst: No. 918, plasticizer manufactured by Sankyoki Gosei Co., Ltd .: DOP

[0080]

The one-part moisture-curable resin composition of the present invention comprises:
It has good storage stability, has good thixotropic properties, and has a fast curing speed when it is taken out of the container.The epoxy resin contained has excellent adhesive strength, mechanical strength, Has heat resistance. Such one-part moisture-curable resin composition of the present invention can be used for stone, concrete,
It is useful as an adhesive for wood and metal, and as a sealing material.

Continued on the front page F-term (reference) 4J002 CD01W CD05W CD06W CK02X CK03X CK04X DE238 ER006 ER007 FB268 GH01 GJ01 4J034 CA17 CB01 DF01 DF11 DF21 DG02 DG03 DG04 DG05 DH01 DH05 HC14 HC12 HC04 HC71 HC73 QB12 RA07 RA08 RA10

Claims (4)

[Claims] (A) all isocyanates (N) in a molecule
A (CO) group having a ketimine (C = N) bond derived from an isocyanate compound having a structure in which a secondary carbon or a tertiary carbon is bonded to (B) a ketone or an aldehyde, and an amine; A one-component moisture-curable resin composition containing a ketimine having a structure in which a branched carbon or a ring member carbon is bonded to at least one α-position of nitrogen, and (C) calcium carbonate surface-treated with a urethane compound. 2. The one-part moisture-curable resin composition according to claim 1, further comprising (D) an epoxy resin. 3. The one-part moisture-curable resin composition according to claim 1, wherein the urethane compound is represented by the following formula (1). Embedded image (Where X is a residue obtained by removing an isocyanate group from an isocyanate compound, or a residue obtained by removing an amino group from an amine compound, n is an integer of 1 to 4, R is a hydrocarbon group, and at least one of R Is a C ₈ or higher hydrocarbon group.) 4. The method of claim 1, wherein the one-part moisture-curable resin composition comprises (D)
When the epoxy resin is not contained, the isocyanate compound 10 having a structure in which a secondary carbon or a tertiary carbon is bonded to all the isocyanate (NCO) groups in the molecule (A).
0 parts by weight, or when (D) epoxy resin is contained, isocyanate having a structure in which secondary carbon or tertiary carbon is bonded to (A) all isocyanate (NCO) groups in the molecule. The calcium carbonate surface-treated with the urethane compound (C) is 50 to 2 with respect to 100 parts by weight of the compound and the epoxy resin (D) in total.
The one-part moisture-curable resin composition according to any one of claims 1 to 3, which contains 00 parts by weight.