JP2000178455A - One-pack composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a one-pack composition with high storage stability, manifesting high tackiness/adhesion or firm adhesion through the action of moisture by making the composition include an acid anhydride group-contg. compound and a specific ketimine compound. SOLUTION: This one-pack composition is obtained by including (A) an acid anhydride group-contg. compound (pref. polybutadiene skeleton-bearing compound or the like) and (B) a ketimine compound prepared by reaction between (i) a ketone of formula I (R1 is a 1-6C alkyl; R2 is methyl or ethyl; R3 is H, methyl or ethyl) and (ii) a polyamine, pref. a compound of formula II [R4 is an organic group (optionally bearing O, S or N); n is >=2], and as necessary (C) a compound having two or more epoxy groups in the molecule and (D) an isocyanate group-contg. compound of formula III [R5 and R6 are each an organic group (optionally bearing O, S or N); R7 is H or an organic group (optionally bearing O, S or N); m is >=2].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a one-pack type composition having excellent storage stability, exhibiting good adhesive properties by moisture, and being useful as an adhesive or a curing agent in the fields of civil engineering and construction. About things.

[0002]

2. Description of the Related Art Conventionally, adhesive compositions using an acid anhydride resin as a base resin have been widely used as those having excellent adhesion to various base materials. None have sufficient storage stability. On the other hand, so-called moisture-curable one-component polyurethane resins that cure by moisture and room-temperature-curable one-component epoxy resins are also widely used as adhesives and adhesives such as sealing materials. However, none of these moisture-curable resin compositions simultaneously satisfied good adhesion to a substrate and sufficient storage stability as a one-pack composition.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a one-part composition which has excellent storage stability and exhibits good adhesiveness and adhesion by moisture.

[0004]

That is, the present invention provides a compound containing an acid anhydride group-containing compound and a ketimine compound obtained by reacting a ketone represented by the following formula (1) with a polyamine. A liquid composition is provided.

Embedded image R ¹ : any one selected from the group consisting of alkyl groups having 1 to 6 carbon atoms R ² : methyl group or ethyl group R ³ : hydrogen atom, methyl group or ethyl group

It is preferable that the polyamine is a compound represented by the following formula (2).

Embedded image R ⁴ : organic group (including groups having O, S and N) n: integer of 2 or more

Preferably, the acid anhydride group-containing compound is a compound having a polybutadiene skeleton.

Further, the present invention further provides a one-part composition containing a compound having at least two epoxy groups in a molecule.

Further, it preferably contains an isocyanate group-containing compound represented by the following formula (3).

Embedded image R ⁵ : Organic group (including group having O, S, N) R ⁶ : Organic group (including group having O, S, N) R ⁷ : Hydrogen atom or organic group (O, S, N) M: an integer of 2 or more

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to a one-pack composition which is excellent in storage stability and exhibits good adhesiveness and adhesion by moisture, and includes the following two embodiments. (1) A one-part composition containing an acid anhydride group-containing compound as a main component or one of the main components of the main component, and a ketimine compound as a latent curing agent. The main components other than the acid anhydride group-containing compound of the main agent include compounds having an epoxy group such as an epoxy resin (epoxy group-containing compound), compounds having an isocyanate group such as an isocyanate-terminated urethane prepolymer (isocyanate group-containing compound), and the like. Is mentioned. (2) A one-pack composition containing a ketimine compound and a compound containing an acid anhydride group of a monomer or an oligomer and used as a curing agent for a compound that is cured by an amine. The composition of the second embodiment can be used as a curing agent component of a one-pack type resin composition mainly composed of a compound curable by an amine other than the acid anhydride group-containing compound. Examples of the compound that is cured by an amine include an epoxy group-containing compound such as an epoxy resin, and an isocyanate group-containing compound such as an isocyanate-terminated urethane prepolymer.

The acid anhydride group-containing compound used in the one-part composition of the present invention (hereinafter referred to as the composition of the present invention) comprises an organic compound having an acid anhydride group. Either may be used. The acid anhydride group-containing compound is a compound containing, in the molecule thereof, carbon, hydrogen, and oxygen, or an organic compound constituting atom such as nitrogen, sulfur, and phosphorus. The acid anhydride group contained in the acid anhydride group-containing compound may be present at the terminal of the molecular skeleton or may be present in a side chain, and is not limited to its structure or molecular weight. In the compound containing an anhydride group, 1
On average, it preferably has 1 to 5 acid anhydride groups per molecule. The acid anhydride group-containing compound may have a functional group other than the acid anhydride group. For example, hydroxyl group, carboxyl group, saturated aliphatic alkyl group, unsaturated aliphatic alkyl group, alicyclic alkyl group, aromatic alkyl group, vinyl group, allyl group, alkoxyl group, silyl group, halogen group, phosphoric acid group, thioether Groups, thiol group, thiocarboxyl group, amide group, imide group, tertiary amino group, carbonate group, sulfonic acid group, carbonyl group, acryloyl group, methacryloyl group, urethane group and the like.

Specific examples of such an acid anhydride group-containing compound include phthalic anhydride, tetrabromophthalic anhydride,
Tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, 4- (4-methyl-3-pentenyl) tetrahydrophthalic anhydride, trialkyltetrahydro Phthalic anhydride, trimellitic anhydride, trimellitic anhydride triglyceride, trimellitic anhydride ethylene glycol ester, hydrogenated trimellitic anhydride, hydrogenated trimellitic anhydride triglyceride, hydrogenated trimellitic anhydride ethylene glycol ester, pyroanhydride Merritic acid, pyromellitic anhydride triglyceride, pyromellitic anhydride ethylene glycol ester, bensophenone anhydride-3,4
3 ', 4'-tetracarboxylic acid, chlorendic anhydride, pyromellitic dianhydride, methylcyclohexenedicarboxylic anhydride, methylcyclohexenetetracarboxylic anhydride, hymic anhydride, methylhymic anhydride, maleic anhydride, succinic anhydride Acid, dodecenyl succinic anhydride,
Unsaturation such as polyadipic anhydride, polyazelain anhydride, polysebacic anhydride, poly (ethyloctadecanedioic anhydride), poly (phenylhexadecandioic anhydride), linoleic acid, linolenic acid, and eleostearic acid Fatty acids or methyl esters thereof, addition products of triglycerides with maleic anhydride, ethylenic anhydrides such as itaconic anhydride, maleic anhydride and other copolymerizable monomers (for example, styrene, α-methylstyrene, acrylic Acid esters, methacrylic esters, acrylamide, methacrylamide, α-olefins, polyunsaturated fatty acid derivatives, vinyl ethers, vinyl acetate, ethylene, etc.), polybutadiene, polyisoprene, EPDM rubber, natural rubber, SBS, SEBS, SI
And maleic anhydride adducts of polymers having an unsaturated double bond in the main chain such as S. Furthermore, compounds in which the above-mentioned functional groups other than the acid anhydride group are bonded to these compounds are exemplified. These compounds may be used alone or in combination of two or more. Among these, as the acid anhydride group-containing compound contained in the composition of the first embodiment of the present invention, an acid anhydride group-containing compound having a main chain of polybutadiene is used for improving adhesion to glass or concrete. Preferred for reasons of excellence. As the acid anhydride group-containing compound contained in the composition of the second aspect of the present invention, maleic anhydride is preferred because of its high reactivity.

The method for producing the above-mentioned acid anhydride group-containing compound is not particularly limited. For example, polybutadiene, polyisoprene, EPDM rubber, natural rubber, SBS, SEBS, SBS
Examples thereof include a method in which a polymer having an unsaturated double bond in the main chain such as IS is subjected to an addition reaction with maleic anhydride. The composition of the first aspect of the present invention contains the above-mentioned acid anhydride group-containing compound, so that it has good tackiness due to moisture,
Develop adhesion. Further, the resin composition containing the composition of the second aspect of the present invention as a curing agent component exhibits good adhesiveness and adhesion due to moisture.

The ketimine compound used in the composition of the present invention is a compound having a large steric hindrance obtained by reacting the ketone represented by the above formula (1) with a polyamine.
Examples of the ketone used in the present invention include methyl isopropyl ketone and methyl t-butyl ketone.

Examples of the polyamine used in the present invention include ethylenediamine, propylenediamine, butylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenediamine, trimethylhexamethylenediamine, and N-aminoethylpiperazine. , 1,2
-Aliphatic polyamines such as diaminopropane, iminobispropylamine, methyliminobispropylamine, MPMD and metaxylylenediamine manufactured by DuPont Japan; Jeffamine EDR manufactured by Sun Techno Chemical Co.
148, such as isophorone diamine, 1,3-bisaminomethylcyclohexane, 1-cyclohexylamino-3-aminopropane, and 3-aminomethyl-3,3,5-trimethyl-cyclohexylamine. Alicyclic polyamines, diamines having a norbornane skeleton represented by NBDA manufactured by Mitsui Chemicals, Inc .; polyamideamines having an amino group at the molecular terminal of polyamide; 2,5-dimethyl-2,5-hexamethylenediamine; Diamine, 1,4-bis (2-
(Amino-2-methylpropyl) piperazine, Jeffamine D230 and Jeffamine D having a skeleton of polypropylene glycol (PPG) manufactured by San Techno Chemical Co.
400.

Among them, the polyamine is preferably a compound represented by the above formula (2). Specifically, among the above polyamines, in particular, 1,3-bisaminomethylcyclohexane, norbornanediamine, meta-xylylenediamine, and polyamidoamine are a ketimine compound synthesized using these, and the acid anhydride group-containing compound. Is particularly preferred because of excellent storage stability and particularly excellent curability. The composition comprises:
The composition of the first aspect of the present invention containing the acid anhydride group-containing compound as a main polymer, and a ketimine compound containing the resin other than the acid anhydride group-containing compound as a main polymer and the above-mentioned acid anhydride group-containing A composition according to the second aspect of the present invention, which comprises a curing agent.

As the above-mentioned ketimine compound, a ketimine compound obtained by combining each of the above-mentioned polyamines and each ketone such as methyl t-butyl ketone and methyl isopropyl ketone is preferably exemplified. The ketimine compound synthesized from the above polyamine, methyl isopropyl ketone, and methyl t-butyl ketone has a particularly excellent balance between curing speed and storage stability. Ketimine compounds synthesized from the above ketones and 1,3-bisaminomethylcyclohexane, norbornanediamine, metaxylylenediamine, and polyamidoamine are also particularly excellent in the balance between curing speed and storage stability. Excellent.

Specifically, Jeffamine EDR which is a diamine having a polyether skeleton manufactured by San Techno Chemical Co., Ltd.
148 and methyl isopropyl ketone,
One obtained from Jeffamine EDR148 and methyl t-butyl ketone, one obtained from 1,3-bisaminomethylcyclohexane and methyl t-butyl ketone, one obtained from NBDA and methyl isopropyl ketone manufactured by Mitsui Chemicals, Inc., Those obtained from 3-bisaminomethylcyclohexane and methyl isopropyl ketone,
Those obtained from NBDA and methyl t-butyl ketone,
A product obtained from Mitsubishi Gas Chemical's MXDA and methyl isopropyl ketone, a product obtained from Mitsubishi Gas Chemical's MXDA and methyl t-butyl ketone, a product obtained from Sanwa Chemical's X2000 and methyl isopropyl ketone, Examples include those obtained from W2000 X2000 and methyl t-butyl ketone. Among them, those obtained from NBDA and methyl isopropyl ketone manufactured by Mitsui Chemicals, Inc., those obtained from NBDA and methyl t-butyl ketone, and those obtained from 1,3-bisaminomethylcyclohexane and methyl isopropyl ketone are particularly preferable. Excellent curability. Further, those obtained from X2000 and methyl isopropyl ketone, and those obtained from X2000 and methyl t-butyl ketone have excellent adhesion to wet surfaces.

The above-mentioned ketimine compound is obtained by reacting the above-mentioned ketone and polyamine in the absence of a solvent or in the presence of a solvent such as benzene, toluene, xylene or the like by heating to reflux and removing elimination water by azeotropic distillation. Can be

The ketimine compound obtained by reacting the ketone represented by the above formula (1) with a polyamine has a bulky group near the double bond of the ketimine group, and thus has conflicting properties such as curing speed and storage stability. Meet. That is, a general-purpose ketone, methyl isobutyl ketone (MIBK),
Alternatively, when a ketimine compound is synthesized using a ketone having no substituent at the α-position of the ketone carbon, such as methyl ethyl ketone (MEK), the ketimine nitrogen is exposed, and thus shows a strong basicity. Therefore, a one-pack type resin composition containing such a ketimine compound is inferior in storage stability such as progress of gelation. A ketimine compound using a ketone represented by the above formula (1), for example, methyl isopropyl ketone, methyl t-butyl ketone, or the like as a raw material has a ketimine nitrogen protected by a substituent,
Steric hindrance greatly reduces its basicity. Using such a ketimine compound as a latent curing agent, as a main component of the main agent, or a one-part composition of the first embodiment of the present invention containing an acid anhydride group-containing compound as one of the main components of the main agent, Excellent in adhesiveness, curability and storage stability. Further, the resin composition containing the composition of the second aspect of the present invention containing the above-mentioned ketimine compound and the acid anhydride group-containing composition as a curing agent component has excellent adhesiveness, and has excellent curability and storage stability. Excellent.

The compound having at least two epoxy groups in the molecule (hereinafter also referred to as an epoxy group-containing compound) used in the present invention includes, for example, glycidyl ether type epoxy resin of bisphenol A and its derivatives, and glycidyl ether type of glycerin. Epoxy resin, polyalkylene oxide glycidyl ether type epoxy resin,
A glycidyl ether type epoxy resin of phenol novolak, a glycidyl ester type epoxy resin of dimer acid, a glycidyl ether type epoxy resin of bisphenol F and the like are exemplified. Among these, the glycidyl ether type epoxy resin of bisphenol A is suitably used as a general-purpose epoxy resin. The composition of the first embodiment containing such an epoxy group-containing compound has excellent adhesiveness after curing of the composition. Further, in the resin composition containing the composition of the second aspect of the present invention containing the epoxy group-containing compound as a main component of the main ingredient and the above-mentioned ketimine compound and acid anhydride group-containing compound as a curing agent component, With excellent wearability,
In particular, the effect of accelerating the curing is great and the curability is excellent.

Compound having an isocyanate group used in the present invention (hereinafter also referred to as isocyanate group-containing compound)
Is a compound having a large steric hindrance having at least two isocyanate groups having a large steric hindrance having at least one substituent at the α-position, and a chemical structural formula is given by the above formula (3). In the formula, R ⁵ and R ⁶ are O, S, an aromatic ring, an alkyl group, an arylalkyl group, or an organic group which may contain an N-containing group such as an amide, a urea group (carbamide group), or a urethane bond. is there. R ⁷ is a hydrogen atom or an organic group which may contain an N-containing group such as O, S, an aromatic ring, an alkyl group, an arylalkyl group, or an amide, a urea group (carbamide group), or a urethane bond. . As such an isocyanate group-containing compound, a commercially available product can be used, and examples thereof include MXDI and Seisen manufactured by Mitsui Cytec.

The isocyanate group-containing compound represented by the formula (3) may be a urethane prepolymer having two or more isocyanate groups obtained from a polyol and the above-mentioned isocyanate compound having a large steric hindrance. . Here, the polyol refers to a polyether polyol, a polyester polyol, other polyols, and a mixed polyol thereof.

Specifically, polyether polyols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3
-Butanediol, 1,4-butanediol, 4,4 ′
Dihydric alcohols such as -dihydroxyphenylpropane and 4,4'-dihydroxyphenylmethane; glycerin, 1,1,1-trimethylolpropane, 1,2,5
-Addition of one or more alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide and styrene oxide to one or more kinds of polyhydric alcohols such as hexanetriol and pentaerythritol; sugars such as sorbitol. And polyoxytetramethylene oxide.

The polyester polyols are roughly classified into condensed polyester polyols, lactone polyols, and polycarbonate diols. Specifically, ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, cyclohexanedimethanol, glycerin , 1,1,1-trimethylolpropane, or one or more other low molecular polyols, and glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, terephthalic acid, isophthalic acid, dimer acid, Alternatively, condensed polymers with one or more other low molecular carboxylic acids or oligomeric acids; ring-opened polymers such as propionlactone, valerolactone, and the like;

Further, other polyols include polyols having a main chain composed of carbon-carbon bonds, such as acrylic polyols, polybutadiene polyols, hydrogenated polybutadiene polyols, etc., ethylene glycol, diethylene glycol, propylene glycol, and the like.
Low molecular polyols such as dipropylene glycol, butanediol, pentanediol and hexanediol are also preferably exemplified.

In addition to the above polyols, polyols having a bisphenol structure may be used. When a polyol having a bisphenol structure is used, the composition of the first embodiment of the present invention containing the isocyanate group-containing compound represented by the formula (3) and the resin composition containing the composition of the second embodiment The product has excellent adhesiveness and excellent flexibility. The bisphenol structure is not particularly limited, and examples thereof include a bisphenol A structure, a bisphenol F structure, a brominated bisphenol A structure, a hydrogenated bisphenol A structure, a bisphenol S structure, and a bisphenol AF structure.

A urethane prepolymer synthesized using a compound having an isocyanate group having a large steric hindrance does not require a plasticizer for adjusting viscosity and modulus because of weak intermolecular hydrogen bonding.

The above-mentioned isocyanate group-containing compound has a bulky group near the isocyanate group, has a large steric hindrance of the isocyanate group, and further, when the bulky group is an electron donating group such as an alkyl group, Low reactivity of isocyanate groups. Therefore, a composition obtained by blending such an isocyanate group-containing compound having an isocyanate group having a large steric hindrance and a ketimine compound having a large steric hindrance is kept stable during storage in a container. on the other hand,
When the one-component resin composition containing the ketimine compound and the isocyanate group-containing compound is exposed to the air, small water molecules that are moisture easily attack ketimine nitrogen without steric hindrance of the substituent, Hydrolysis proceeds easily and has excellent curability. Therefore, the first invention of the present invention containing the above isocyanate group-containing compound as one of the main components of the main agent.
The composition according to the second aspect of the present invention, which comprises the isocyanate group-containing compound as a main component of the main agent and the ketimine and an acid anhydride group-containing compound as a curing agent component
The resin composition containing the composition of the embodiment has good storage stability and excellent curability. Further, such a composition has good flexibility after curing and also has excellent tackiness.

The amount of the ketimine compound in the one-pack composition of the first embodiment of the present invention is such that (anhydride group-containing compound) / (imino group of the ketimine compound) is 0.1 to 0.1 in equivalent ratio. It is preferably 5.0, more preferably 0.5 to 2.0. This is because storage stability and curability are both good in this range. A composition according to the first aspect of the present invention containing an acid anhydride group-containing compound and the above-mentioned ketimine compound having a large steric hindrance, and a resin composition containing the composition according to the second aspect of the present invention as a curing agent component Has good storage stability and excellent curability, and exhibits good adhesion and adhesion due to moisture.

The one-part composition of the first embodiment of the present invention may contain only the above-mentioned acid anhydride group-containing compound as a main component of the main ingredient, or may use another compound in combination. As such a compound, a compound which is cured by an amine generated by hydrolysis of a ketimine compound can be used. Preferably, the epoxy group-containing compound described above,
Examples include isocyanate group-containing compounds. In particular, it is preferable to contain an epoxy group-containing compound together with the acid anhydride group-containing compound because the adhesiveness becomes excellent. Further, it is preferable to include the above-mentioned isocyanate group-containing compound having a large steric hindrance because the flexibility is excellent, and particularly the curability and the storage stability are improved. In addition, as a main component of the main agent,
The above-mentioned acid anhydride group-containing compound, epoxy group-containing compound,
The first aspect of the present invention which comprises both isocyanate group-containing compounds
The one-part composition of the embodiment has excellent curability and storage stability, good adhesiveness and adhesion, and excellent flexibility after curing. In the composition of the first aspect of the present invention, the content of the epoxy group-containing compound and the isocyanate group-containing compound is not particularly limited, and the curability at the time when the curing reaction is completed, adhesiveness, flexibility, and the like. It may contain an amount according to the required properties, but the total amount is preferably 98% by weight or less, more preferably 95% by weight or less, of the resin component containing the acid anhydride group-containing compound. Is more preferred.
Within this range, the content ratio of the epoxy group-containing compound and the isocyanate group-containing compound to each other is arbitrary.

When the composition of the first embodiment of the present invention contains an acid anhydride group-containing compound, an epoxy group-containing compound and / or an isocyanate group-containing compound as the main component of the main ingredient, the compounding amount of the ketimine compound Is the equivalent ratio (the main functional group of the compound contained as the main component of the main agent)
/ (Imino group of ketimine compound) is preferably from 0.2 to 4.0, more preferably from 0.5 to 3.0. The main functional group of the compound contained as the main component of the main agent is a carbonyl group formed by ring-opening of an acid anhydride group in the case of an acid anhydride group-containing compound, an epoxy group in the case of an epoxy group-containing compound, An isocyanate group-containing compound represents an isocyanate group. Since the composition of the first aspect of the present invention is excellent in storage stability, adhesiveness, adhesion, and curability as described above, or is also excellent in adhesiveness and flexibility, an adhesive for a PVC sheet or the like is used. Can be suitably used as an adhesive, a sealing material, a paint, an adhesive, and the like.

The one-part composition according to the second aspect of the present invention is a composition comprising a ketimine compound and a compound containing an acid anhydride group,
It is a composition that can be used as a curing agent component of a one-pack resin composition containing a compound that cures with an amine as a main component. Preferred examples of the compound which is cured by the amine include the above-mentioned epoxy group-containing compound and isocyanate group-containing compound (including an isocyanate-terminated urethane prepolymer). The contents of the acid anhydride group-containing compound and the ketimine compound in the composition of the second aspect of the present invention are not particularly limited, but preferably the ketimine compound 1
0.1 to 3 parts by weight of the acid anhydride group-containing compound per 100 parts by weight.
0 parts by weight. In addition, the compounding amount of the ketimine compound is (equivalent ratio of (main functional group of compound contained as a main component of the main agent)) / (imino group of ketimine compound) in an equivalent ratio, preferably 0.2 to 4.0, more preferably The amount is preferably 0.5 to 3.0. Within this range, not only the curability is excellent, but also the storage stability is good. In addition,
The main functional group of the compound contained as the main component of the main agent means an epoxy group if it is an epoxy group-containing compound, and an isocyanate group if it is an isocyanate group-containing compound. In particular, when an epoxy resin is contained as a main component of the resin composition containing the composition of the second aspect of the present invention, such a resin composition has excellent storage stability, contains a ketimine compound as a curing agent component, and contains an acid anhydride group. Compared to the epoxy resin composition containing no compound, not only the adhesiveness and the adhesiveness but also the curability is particularly improved and accelerated. Further, when the above-mentioned urethane prepolymer is contained as a main component of the resin composition containing the composition of the second aspect of the present invention, it is particularly excellent in storage stability and also in flexibility after curing. Such a composition of the second aspect of the present invention can be suitably used as a curing agent and a curing accelerator for a compound that is cured by an amine.

The one-pack type composition of the first embodiment of the present invention and the one-pack type resin composition containing the one-pack type composition of the second embodiment of the present invention as a curing agent component may be used, if necessary. A curing accelerator may be used in combination. Examples of phosphites used as a curing accelerator include triphenyl phosphite, tris (nonylphenyl) phosphite, triethyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, and tris ( Tridecyl) phosphite, diphenylmono (2-
Ethylhexyl) phosphite, diphenylmonodecylphosphite, diphenylmono (tridecyl) phosphite, tetraphenyldipropyleneglycol diphosphite, tetraphenyltetra (tridecyl) pentaerythritol tetraphosphite, trilauryltrithiophosphite, bis (tridecyl) Pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, tristearyl phosphite, distearylpentaerythritol diphosphite, tris (2,4-di-t-butylphenyl) phosphite, hydrogenated bisphenol A Triesters such as pentaerythritol phosphite polymer. Further, di- or monoesters obtained by partially hydrolyzing these triesters are also exemplified. Of these, tetraphenyltetra (tridecyl) pentaerythritol tetraphosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite,
Distearyl pentaerythritol diphosphite, hydrogenated bisphenol A and pentaerythritol phosphite polymer have a particularly high accelerating effect and are preferably used.

When a triester is used among these phosphites, the amount added is 0.005 m to the main functional group of the compound contained as the main component of the main agent.
ol% or more, preferably 0.005 to 1.0 mo
1%. Here, the main functional group of the compound included as the main component of the main agent has the same meaning as the main functional group of the compound included as the main component of the main agent. When a di- or monoester obtained by partially hydrolyzing a triester is used, the amount of the di- or monoester is 0.005 to 50 mol% based on the main functional group of the compound contained as the main component of the main agent.
Preferably, it is 0.005 to 10 mol%. 0.0
If it is less than 05 mol%, there is no effect as an accelerator,
On the other hand, if the addition amount of the diester compound is more than 50 mol%, the storage stability is deteriorated. In addition, the one-pack type resin composition containing the composition of the first aspect of the present invention and the composition of the second aspect of the present invention as a curing agent component is an accelerator other than a phosphite as an accelerator. May be included.

The composition of the first embodiment of the present invention and the one-pack type resin composition containing the composition of the second embodiment of the present invention as a curing agent component may be used in combination with a silane coupling agent if necessary. May be. By containing a silane coupling agent, it is possible to obtain a resin composition that is excellent in balance between storage stability and curing speed, and also excellent in adhesion to a wet surface. The silane coupling agent is not particularly limited, and a conventionally known silane coupling agent can be used. For example, chloropropyltrimethoxysilane,
Trimethoxyvinylsilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, γ
-Methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane and the like. Of these, trimethoxyvinylsilane and 3-glycidoxypropyltrimethoxysilane are particularly preferably used because they have an excellent effect of improving the adhesion to a wet surface and are more general-purpose.

The content of these silane coupling agents is 0.1 to 20 parts by weight based on 100 parts by weight of the total of the compounds contained as the main components of the main ingredient, and preferably,
0.5 to 10 parts by weight. When the content is within the above range, the adhesiveness to the wet surface is preferably high because the shear stress at the time of fracture is high and the fracture rate of the base material is almost 100%.

The one-part resin composition containing the composition of the first aspect of the present invention and the composition of the second aspect of the present invention as a curing agent component is a silyl compound represented by the following formula (4). A compound having an ester group may be contained. By compounding a specific amount of such a compound having a silyl ester group, the curing time can be shortened without impairing the storage stability.

[0038]

Embedded image

In the formula, R is a hydrogen atom or a group having 1 carbon atom.
Represents up to 20 hydrocarbon groups. As the hydrocarbon group, specifically, methyl group, ethyl group, vinyl group, propyl group,
Linear hydrocarbon groups such as octyl group, lauryl group, palmityl group, stearyl group, allyl group and eicosyl group; branched hydrocarbon groups such as isopropyl group and isobutyl group;
Alicyclic hydrocarbon groups such as hexamethyl group; aromatic groups such as phenyl group and benzyl group; As R, a hydrocarbon group having 1 to 17 carbon atoms is particularly preferable because it has excellent storage stability and an effect of accelerating the curing reaction. When R is a hydrogen atom, storage stability is slightly difficult,
Conversely, when the number of carbon atoms is 18 or more, the effect of promoting the curing reaction is slightly reduced.

The compound having a silyl ester group is not particularly limited as long as the silyl ester group is a compound represented by the above formula (4).
It may be contained in any of the main chain terminal and the side chain, and may be contained in one or two or more. When two or more silyl ester groups represented by the formula (4) are contained in the compound, only one kind may be contained or they may be different from each other. The main chain of such a compound having a silyl ester group mainly comprises Si—O bonds. The main chain may be used alone or in combination of two or more. When the silyl ester group represented by the formula (4) is contained in the main chain, Si of the silyl ester group becomes Si in the main chain. Specific examples of the compound having such a silyl ester group include a compound represented by the following formula.

[0041]

Embedded image

In the above formula, the number p of repeating units of the silyl ester group is an integer of 1 or more. Examples of the method for producing the compound having a silyl ester group include polyhydrogensiloxane having an Si-H group such as poly (methylhydrogen) siloxane; linear saturated fatty acid such as formic acid and stearic acid; and caproleic acid. And unsaturated carboxylic acids such as benzoic acid, carboxylic acids such as alicyclic carboxylic acids such as naphthoic acid, or a copolymer of the above-described polyhydrogensiloxane and alkene, and the above-mentioned carboxylic acid. Acids can be synthesized by dehydration-condensation using a transition metal of Group VIII such as Pt or Ru alone or a chloride of these metals as a catalyst.

In the one-pack type resin composition containing the composition according to the first embodiment of the present invention and the composition according to the second embodiment of the present invention as a curing agent component, the compound having a silyl ester group is used. The content is preferably 0.05 to 10 parts by weight based on 100 parts by weight of the total of the compounds contained as the main component of the main ingredient. This is because the curing time is shortened without impairing the storage stability when the content is in the above range. In particular, 0.
The amount is preferably 1 to 8 parts by weight.

The one-pack type resin composition containing the composition of the first embodiment of the present invention and the composition of the second embodiment of the present invention as a curing agent component is provided within a range not to impair the object of the present invention. It may contain calcium carbonate. In particular, by containing the surface-treated calcium carbonate, the viscosity can be adjusted, and good initial thixotropy and storage stability can be obtained. As such calcium carbonate, conventionally known surface-treated calcium carbonate surface-treated with a fatty acid, a resin acid, or a fatty acid ester can be used. Specifically, as calcium carbonate surface-treated with fatty acids, as Calfine 200 (manufactured by Maruo Calcium Co.), Whiten 305 (heavy calcium carbonate, manufactured by Shiraishi Calcium Co.), and calcium carbonate surface-treated with fatty acid ester And Sealets 200 (manufactured by Maruo Calcium Co., Ltd.) are preferably used.

When surface-treated calcium carbonate is used as the calcium carbonate, if a ketimine compound having a relatively high polarity is used, thixotropy and storage stability are particularly excellent. Ketimine compounds represented by the following formulas (5) and (6) can be shown as ketimine compounds having relatively high polarity.

Embedded image R ⁸ : an organic group having at least one of O, S, N and an aromatic ring

Embedded image R ⁴ : organic group (including groups having O, S, and N)

Since the surface-treated calcium carbonate has a low surface polarity, when ketimine having the same low polarity is used, wetting occurs and thixotropy is reduced. In order to prevent this wetting, it is preferable to use ketimine having a relatively high polarity. In the ketimine represented by the formula (6), the substituents near the imine moiety are a methyl group and an isopropyl group, which are small to lower the polarity of the highly polar imine moiety. Therefore, good thixotropy and storage stability can be maintained without being affected by the ketimine skeleton (R ⁴ ). On the other hand, in the ketimine represented by the formula (5), the polarity of the imine moiety is low due to the methyl group and the t-butyl group. Therefore, the ketimine skeleton (R ⁸ ) must be highly polar. Such ketimines having relatively high polarity include Jeffamine EDR manufactured by San Techno Chemical Co., Ltd.
148, diamines having a xylylene skeleton represented by MXDA manufactured by Mitsubishi Gas Chemical Company, methyl isopropyl ketone, methyl t
-Ketimine synthesized from -butyl ketone, diamines having a norbornane skeleton represented by NBDA manufactured by Mitsui Toatsu Chemicals, diamines having a cyclohexane skeleton represented by 1,3-BAC manufactured by Mitsubishi Gas Chemical Company, and methyl isopropyl ketone And ketimines synthesized from methyl t-butyl ketone.

The amount of calcium carbonate added is 30 parts by weight based on the total of 100 parts by weight of the compound contained as the main component of the main ingredient.
The amount is preferably from 200 to 200 parts by weight, more preferably from 50 to 150 parts by weight. If the amount is less than 30 parts by weight, appropriate initial thixotropy and workability cannot be obtained. If the amount is more than 200 parts by weight, the viscosity increases and the workability deteriorates.

The composition according to the first aspect of the present invention comprises, besides the above-mentioned compounds, other additives such as a filler, a plasticizer, a thixotropic agent and a pigment within a range not to impair the object of the present invention. , A dye, an antioxidant, an antioxidant, an antistatic agent, a flame retardant, an adhesion promoter, a dispersant, a solvent, and the like. In the composition of the second aspect of the present invention, the above additives may be added to the composition of the present invention within a range not to impair the purpose of the present invention, but the composition of the present invention is used as a curing agent component. You may mix | blend with the main component of a one-pack type resin composition.

The filler which can be used in the present invention includes various forms of organic or inorganic fillers, such as fumed silica, calcined silica, precipitated silica, pulverized silica, fused silica; diatomaceous earth; Zinc, titanium oxide,
Barium oxide, magnesium oxide; calcium carbonate, magnesium carbonate, zinc carbonate; limestone clay, kaolin clay, calcined clay; or carbon black, or a fatty acid, resin acid, or fatty acid ester-treated product thereof.

Plasticizers usable in the present invention include dioctyl phthalate (DOP), dibutyl phthalate (DBP); dioctyl adipate, isodecyl succinate; diethylene glycol dibenzoate, pentaerythritol ester; butyl oleate, acetyl ricinoleic acid Methyl; tricresyl phosphate, trioctyl phosphate; propylene glycol adipate polyester, butylene glycol adipate polyester, and the like are used. These plasticizers may be used alone or in combination of two or more.

The thixotropy-conferring agents that can be used in the present invention include Aerosil (Nippon Aerosil Co., Ltd.)
) And Disparon (manufactured by Kusumoto Kasei Co., Ltd.). Examples of the antistatic agent include quaternary ammonium salts and hydrophilic compounds such as polyglycol and ethylene oxide derivatives.

The pigments that can be used in the present invention include inorganic pigments and organic pigments. Examples of the inorganic pigments include titanium dioxide, zinc oxide, ultramarine, red iron, lithopone, lead, cadmium, iron, cobalt, aluminum, and the like. Hydrochloride, sulfate and the like can be mentioned. Examples of the organic pigment that can be used in the present invention include an azo pigment and a copper phthalocyanine pigment.

Examples of the anti-aging agent that can be used in the present invention include compounds such as hindered phenols. Antioxidants that can be used in the present invention include:
Butylhydroxytoluene (BHT), butylhydroxyanisole (BHA) and the like can be mentioned. Examples of the flame retardant that can be used in the present invention include chloroalkyl phosphate, dimethyl methylphosphonate, bromine / phosphorus compound, ammonium polyphosphate, neopentyl bromide-polyether, brominated polyether and the like. Examples of the adhesion imparting agent that can be used in the present invention include terpene resins, phenol resins, terpene-phenol resins, rosin resins, xylene resins, and the like.

The method for producing the one-part composition according to the first and second aspects of the present invention is not particularly limited. Preferably, the above-mentioned components are mixed under reduced pressure or under a nitrogen atmosphere by using a mixing mixer or the like. It is preferable that the composition is sufficiently kneaded using a stirrer and uniformly dispersed to obtain a composition.

[0055]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. <Synthesis of Ketimine Compound> (Synthesis Example 1) Diamine having a norbornane skeleton (NBDA;
Mitsui Toatsu Chemicals Co., Ltd.) 100 g, 1.5 g equivalents of methyl isopropyl ketone 200 g, and toluene 20
0 g was placed in a flask, and the reaction was continued for 20 hours while removing generated water by azeotropic distillation to obtain ketimine A. (Synthesis Example 2) 200 g of methyl t-butyl ketone as ketone
Was carried out in the same manner as in Synthesis Example 1 except that was used, and ketimine B was obtained after 20 hours.

(Examples 1 to 5, Comparative Examples 1 and 2)
Were mixed at the compounding ratios shown in Table 1 to obtain the compositions described in Examples 1 to 5 and Comparative Examples 1 and 2, and the compositions were evaluated. The evaluation results are shown in Table 1 below.
Examples 1 to 4 are examples of the composition according to the first aspect of the present invention, and Example 5 is an example of the composition according to the second aspect of the present invention.

[0057]

[Table 1]

(1) Adhesiveness: After applying the compositions obtained in Examples and Comparative Examples to a slate plate, the composition was cured at 20 ° C. and a humidity of 55% for 40 minutes, and then a PVC sheet (10 ×) was applied. 5
cm ² ) to the composition (bonding area 8 × 5c)
m ² ). After 10 minutes, the PVC sheet is turned upside down and a weight (30 g) is attached to one end in the longitudinal direction of the PVC sheet, and the PVC sheet is naturally peeled off with the weight. The time (sec) until the entire PVC sheet was peeled off at that time was evaluated as tackiness. (2) Tack free time; time (hr) until the polyethylene film no longer adheres to the surface of the composition under the conditions of 20 ° C. and 55% humidity. (3) Viscosity increase: The viscosity of the composition after 1 day at 20 ° C. after blending was then stored at 60 ° C. for 1 day,
Is the value divided by the viscosity after one day.

<Each component in the table> Polybutadiene maleic anhydride: M-1000-20
(Nippon Oil Co., Ltd.) Epoxy resin: YD-128 (Toto Kasei) Urethane prepolymer: Exenol 3030 (Asahi Glass) 1000 g and TMXDI (Mitsui Cytec)
Calcium carbonate: Calfine 200 (manufactured by Maruo Calcium Co., Ltd.) Ketimine C: H-3 (manufactured by Yuka Shell Co., Ltd.)

[0060]

As is apparent from the above description, the one-pack composition of the first embodiment of the present invention has good storage stability,
It has excellent curability and exhibits good adhesiveness and adhesion due to moisture. Therefore, it can be suitably used as an adhesive, a sealing agent, a paint, etc. for a PVC sheet. Also,
The one-pack type composition according to the second aspect of the present invention is a one-pack type resin composition containing a compound which is excellent in storage stability and adhesion-imparting property, has excellent curing promotion effect, and is cured by an amine. It is suitably used as a curing agent component. Such a resin composition,
Excellent storage stability, curability, adhesiveness and adhesion.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 63/00 C08L 63/00 A C09J 109/00 C09J 109/00 163/00 163/00 // C09J 175 / 04 175/04 201/00 201/00 F-term (reference) 4J002 AC021 AC11W AC111 BB001 BB041 BB15W BB151 BB21W BB211 BC041 BC091 BE041 BF021 BG041 BG051 BG131 BH02W BH021 BP01W BP011 CK01X CK01X01 CK01X01 FD147 4J034 BA02 CA14 DG03 DG04 DG05 DG06 DG16 GA06 HA01 HA07 RA08 4J036 AA01 AB01 AD08 DC28 JA06 4J040 CA041 EC002 GA11 GA12 GA13 HC00 JA12 JB04

Claims (5)

[Claims] 1. A one-pack composition containing an acid anhydride group-containing compound and a ketimine compound obtained by reacting a ketone represented by the following formula (1) with a polyamine. Embedded image R ¹ : any one selected from the group consisting of alkyl groups having 1 to 6 carbon atoms R ² : methyl group or ethyl group R ³ : hydrogen atom, methyl group or ethyl group 2. The one-part composition according to claim 1, wherein the polyamine is a compound represented by the following formula (2). Embedded image R ⁴ : organic group (including groups having O, S and N) n: integer of 2 or more 3. The one-part composition according to claim 1, wherein the acid anhydride group-containing compound is a compound having a polybutadiene skeleton. 4. The one-pack composition according to claim 1, further comprising a compound having at least two epoxy groups in a molecule. 5. The one-pack composition according to claim 1, further comprising an isocyanate group-containing compound represented by the following formula (3). Embedded image R ⁵ : Organic group (including group having O, S, N) R ⁶ : Organic group (including group having O, S, N) R ⁷ : Hydrogen atom or organic group (O, S, N) M: an integer of 2 or more