JPH10182786A - Curable type composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition capable of providing a sufficient pot life, etc., regardless of the grade of precipitated calcium carbonate when mixing a curing agent by including a thiol group-containing polymer, an NCO group-containing compound, a specific curing catalyst and an organic sulfonic acid compound, etc., therein. SOLUTION: This composition is obtained by including (A) a polymer having >=2 thiol groups in the molecule, (B) a compound having >=2 isocyanate groups in the molecule, (C) a curing catalyst composed of a tertiary amine and/or an organometallic compound and (D) a filler, comprising precipitated calcium carbonate and treated with an organic sulfonic acid compound and/or a saturated fatty acid (salt). The resultant composition is capable of providing a composition having a sufficient pot life and a sufficient thixotropy when compounded with a curing agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable composition, and more particularly to a composition having a sufficient pot life and thixotropic content when a curing agent is mixed, regardless of the type of precipitated calcium carbonate used as a filler. It relates to a curable composition that can be provided.

[0002]

2. Description of the Related Art A polymer containing two or more thiol groups in one molecule is easily cured when mixed with an oxidizing agent, and the thiol group easily reacts with an epoxy group, an isocyanate group or the like to increase the molecular weight. From sealing materials, paints,
Widely used for adhesives. Examples of such a thiol group-containing polymer include a polysulfide polymer described in U.S. Pat. No. 2,466,963 and JP-A-4-36.
And the polysulfide polyether polymers described in US Pat.

In Japanese Patent Application Laid-Open No. Sho 52-125563, the above-mentioned polysulfide polymer is further disclosed in Japanese Patent Application Laid-Open No. 4-366.
No. 121 proposes a curable composition suitable for a sealing material, which is obtained by curing the polysulfide polyether polymer with an isocyanate compound, has less foaming, has good weather resistance, and can easily obtain a white cured product. Was done.

[0004]

SUMMARY OF THE INVENTION A compound for a curable composition for curing these thiol group-containing polymers with an isocyanate compound using a tertiary amine and / or an organometallic catalyst as a catalyst. In the case of preparing, sedimentable calcium carbonate can be used as a filler. However, depending on the varieties, the pot life is often short, the workability is deteriorated, or the thixotropy is sometimes deteriorated. When the pot life is short, it is improved by adding a carboxylic acid such as citric acid or stearic acid as a retarder and increasing the amount thereof, but there is a problem that the modulus of the cured product is significantly reduced. . In addition, when the thixotropic property is deteriorated, it is improved by increasing the mixing ratio of the precipitated calcium carbonate, but there is a problem that the pot life is shortened. For this reason, the conventional methods have a drawback that the variety of precipitated calcium carbonate to be used is limited and the versatility of blending is low.

Accordingly, an object of the present invention is to provide a thiol / isocyanate-based curable composition which has a sufficient pot life and a thixotropic content without depending on the type of precipitated calcium carbonate used as a filler. It is possible to provide a curable composition capable of obtaining a cured product expressing a sufficient modulus with good reproducibility after curing.
According to the present invention, the versatility of the formulation is significantly improved.

[0006]

Means for Solving the Problems As a result of intensive studies in view of the above-mentioned objects, the present inventors have found that a polymer having two or more thiol groups in the molecule can be used as a tertiary amine and / or an organometallic catalyst. When preparing a composition for a curable composition for curing with a compound having two or more isocyanate groups in the molecule, a predetermined amount of an organic sulfonic acid compound and / or thixotropy is provided as a curing retarder. Curing type that has sufficient pot life and thixotropy irrespective of the type of precipitated calcium carbonate used as a filler by incorporating a predetermined amount of saturated fatty acid as a filler, and expresses a sufficient modulus with good reproducibility even after curing. The present inventors have found that a composition can be obtained, and reached the present invention.

That is, the curable composition of the present invention comprises (a) a polymer having two or more thiol groups in a molecule, (b) a compound having two or more isocyanate groups in a molecule, (c) (1) a curing catalyst comprising (1) a tertiary amine and / or (2) an organic metal, and (d) (3) an organic sulfonic acid compound and / or (4) a saturated fatty acid (salt). I do.

Or (a) a polymer having two or more thiol groups in the molecule, (b) a compound having two or more isocyanate groups in the molecule, (c) (1) a tertiary amine and / or Or (2) a curing catalyst comprising an organic metal, and (e) (3) an organic sulfonic acid compound and / or (4)
A filler comprising precipitated calcium carbonate treated with a saturated fatty acid (salt).

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. [1] Polymer having two or more thiol groups in a molecule Polymer having two or more thiol groups in a molecule used in the present invention (hereinafter, simply referred to as thiol group-containing polymer)
The polymer skeleton portion of polyether, polythioether, polyester, acrylic copolymer, urethane copolymer, polyacetal, polybutadiene, polyisoprene, polyolefin, polychloroprene, polysulfide and those having the structure of these copolymers are preferable. . Particularly, a polysulfide polymer having a polysulfide structure and a polysulfide polyether polymer are preferable. The position of the thiol group is not particularly limited, but is preferably located at the end of the molecular skeleton. (1) polysulfide polymer polysulfide polymer, in the main chain, _{(b) - (C 2 H 4 OC} n H 2 n OC 2 H 4 -
Sx) -. (Here, n is an integer of 1 to 2, x contains a structural unit represented by is an integer from 1 to 5), and the end, (ii) _-C 2 _{H 4 OC n H 2 n OC 2 H} 4 -S
H (where n is an integer of 1 to 2).

[0010] Such a polysulfide polymer has fluidity at room temperature and has a number average molecular weight (Mn) of usually 10
0 to 200,000, preferably 400 to 50,
000. Preferred examples of such polysulfide polymers are described in U.S. Pat. No. 2,466,963. (2) polysulfide polyether polymer polysulfide polyether polymer, in the main chain ^{(c) - (R 1 O) m} - ( where, ^{R 1} is an alkylene group having 2 to 4 carbon atoms, m is 6
Shows an integer of ~ 200. A polyether moiety represented by), _{(d) - (C 2 H 4 OC} n H 2 n OC 2 H 4 -
Sx) -, and _{- (CH 2 CH (OH)} CH 2 -S
x) -. (Here, n is an integer of 1 to 2, x contains a structural unit represented by is an integer from 1 to 5), and the terminal, _(e) -C ₂ H 4 OC _{n H 2 n OC 2 H 4} -S
H and / or _{-CH 2 CH (OH) CH 2} -SH ( where, n is an integer of 1-2.) Are those having a thiol group represented by.

In this polysulfide polyether polymer, the polyether portion of (c) and the structural unit of (d) may be bonded in an arbitrary sequence, and the ratio thereof is-(R ¹ O ) M-component is 2 to 9
5 _{wt%, - (C 2 H 4} OC n H 2 n OC 2 H 4
—S _X ) —component is 3 to 70% by weight, and — (CH ₂ CH)
It is preferred that the content of the (OH) CH ₂ —S _X ) — component is 1 to 50% by weight. In addition, the content of the polysulfide-bonded Sx is preferably 1 to 60% by weight.

The number average molecular weight (Mn) of the polysulfide polyether polymer is usually from 600 to 200,0.
00, preferably 800 to 50,000.

Such a polysulfide polyether polymer can be produced, for example, by the method described in JP-A-4-363325. [2] Compound Having Two or More Isocyanate Groups in the Molecule The compound used in the present invention that contains two or more isocyanate groups in the molecule (hereinafter, simply referred to as an isocyanate group-containing compound) includes an organic polyisocyanate compound and / or Urethane prepolymers obtained by reacting an organic polyisocyanate compound with an active hydrogen-containing compound are preferred.

Specific examples of the organic polyisocyanate compound include tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate (crude MDI), xylylene diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate.

The active hydrogen-containing compounds include hydroxyl-terminated polyesters, polyvalent polyalkylene ethers, hydroxyl-terminated polyurethane polymers, acrylic polyols having hydroxyl groups introduced into acrylic copolymers, hydroxyl-terminated polybutadienes, polyvalent polythioethers, polyacetals, and the like. Aliphatic polyols, and alkanes including alkylene thiols having two or more SH groups, alkenes and aliphatic thiols, polysulfide polymers having terminal SH groups,
Diamines, including aromatic, aliphatic and heterocyclic diamines, and the like, and mixtures thereof.

As the urethane prepolymer, those obtained by reacting the above-mentioned active hydrogen-containing compound with an organic polyisocyanate compound under the condition of an excess of an isocyanate compound can be used.

In the present invention, the molar ratio (isocyanate group / thiol group) of the isocyanate group in the isocyanate group-containing compound to the thiol group in the thiol group-containing compound is 0.5 to 4.0, preferably 0.5 to 4.0. It mix | blends so that it may be set to 7-3.0. If the molar ratio is less than 0.5, the composition does not have a sufficiently high molecular weight, while if it exceeds 4.0, the cured product becomes hard and brittle, which is not preferable. [3] Tertiary amine, organometallic compound (1) Tertiary amine As the tertiary amine in the present invention, monoamines, diamines, triamines, polyamines, cyclic amines, alcohol amines, ether amines and the like are exemplified. Yes,
Specific examples include triethylamine, N, N-dimethylcyclohexylamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylpropane-1,3-diamine, N , N, N ', N'
-Tetramethylhexane-1,6-diamine, N, N,
N ', N ", N" -pentamethyldiethylenetriamine, N, N, N', N ", N" -pentamethyldipropylenetriamine, tetramethylguanidine, N, N-dipolyoxyethylenestearylamine, N, N -Dipolyoxyethylene tallow alkylamine, triethylenediamine, N, N'-dimethylpiperazine, N-methyl-N '
-(2 dimethylamino) -ethylpiperazine, N-methylmorpholine, N-ethylmorpholine, N- (N ',
N'-dimethylaminoethyl) -morpholine, 1,2-
Dimethylimidazole, dimethylaminoethanol, dimethylaminoethoxyethanol, N, N, N'-trimethylaminoethylethanolamine, N-methyl-
N '-(2hydroxyethyl) -piperazine, N- (2
(Hydroxyethyl) -morpholine, bis- (2-dimethylaminoethyl) ether, ethylene glycol bis-
(3 dimethyl) -aminopropyl ether and the like. Among them, an N, N-dipolyoxyethylene alkylamine compound is preferable because the residual tack of the cured product is small. Specific examples include N, N-dipolyoxyethylene stearylamine, N, N-dipolyoxyethylene tallow alkylamine, and the like. Two or more of these tertiary amines may be used. (2) Organometallic compound As the organometallic compound in the present invention, an organotin compound,
There are organic mercury compounds, organic lead compounds, etc.Specifically, tin octylate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin thiocarboxylate, dibutyltin maleate, dioctyltin mercaptide, dioctyltin thiocarboxylate Rate, phenylmercuric propionate, lead octenoate and the like. Among them, organotin compounds having little influence on discoloration and the like are preferable, and more preferably dialkyltin mercaptide and / or
Or dialkyltin dicarboxylates and / or dialkyltin bis (dicarboxylic acid monoalkyl ester) salts and / or
Or a dialkyltin (dicarboxylic acid) salt and the like.
Two or more of these organometallic compounds may be used.

The content of the curing catalyst (c) in the curable composition is preferably 0.001 to 5 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the polymer (a) having a thiol group. 005 to 3 parts by weight. Content 0.0
If the amount is less than 01 parts by weight, the curing does not proceed, and if it exceeds 5 parts by weight, the pot life becomes short, which is not preferable. [4] Organic sulfonic acid compound, precipitated calcium carbonate treated with the organic sulfonic acid compound Examples of the organic sulfonic acid compound in the present invention include alkylbenzene sulfonic acid, alkyl naphthalene sulfonic acid, dialkyl sulfosuccinic acid, alkyl sulfoacetic acid,
Alkanesulfonic acid, hydroxyalkanesulfonic acid,
α-olefin sulfonic acid and the like. Among them, alkylbenzene sulfonic acid is preferable because it has a large effect of delaying the pot life and a small decrease in the modulus of the cured product. The most preferred example is dodecylbenzenesulfonic acid, which is highly versatile as a surfactant.

The appropriate content of the organic sulfonic acid depends on the precipitated calcium carbonate used, and may not be contained if the curable composition has a sufficient pot life. In addition, when it is contained, the thixotropic content may decrease according to the amount. In such a case, both the thixotropic activity and the pot life can be optimized by using together with (4) the saturated fatty acid (salt). Specifically, the organic sulfonic acid and / or the saturated fatty acid (salt) is added to the above (a).
For 100 parts by weight of the polymer having a thiol group,
It is 0.01 to 10 parts by weight. If it is less than 0.01 part by weight, the effect as a retarder is small, and if it exceeds 10 parts by weight,
The effect of decreasing the modulus of the cured product increases.

In the present invention, the precipitated calcium carbonate treated with the above-mentioned organic sulfonic acid may be used as a filler, and the same effect as when it is contained as a compounding agent can be obtained. Even in this case, when thixotropic activity decreases, precipitated calcium carbonate treated in combination with the above (4) saturated fatty acid (salt) may be used.

The content of the precipitated calcium carbonate treated with the organic sulfonic acid is 10 parts by weight per 100 parts by weight of the polymer.
３００300 parts by weight. If the amount is less than 10 parts by weight, the thixotropic content is insufficient, and if it exceeds 300 parts by weight, the amount of the plasticizer increases and the polymer content becomes too low, which is not preferable in physical properties. [5] Saturated fatty acid (salt) compound, precipitated calcium carbonate treated with saturated fatty acid (salt) compound The saturated fatty acid (salt) compound in the present invention includes hexanoic acid, octanoic acid, decanoic acid, lauric acid, myristic acid, Palmitic acid, stearic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and the like, and sodium, calcium, magnesium salts thereof. Among them, C12
The above-mentioned saturated fatty acid (salt) compounds are preferable because they have a large thixotropy-imparting effect, and specific examples thereof include lauric acid, myristic acid, palmitic acid, stearic acid and the like, and sodium, calcium and magnesium salts thereof. The most preferred examples include stearic acid and salts thereof which are widely used and have a large number of carbon atoms.

The appropriate content of the above saturated fatty acid (salt) is
Depending on the precipitated calcium carbonate used, it may not be added if the curable composition has sufficient thixotropy. Further, when a fatty acid is contained, the modulus of the cured product may decrease in accordance with the amount thereof. In that case, both the thixotropic and the cured product modulus can be optimized by using the fatty acid salt or by using it together with the fatty acid salt. Further, as described above, it may be used in combination with an organic sulfonic acid to optimize the pot life. A specific amount is 0.01 to 10 parts by weight of the organic sulfonic acid and / or saturated fatty acid (salt) based on 100 parts by weight of the polymer (a) having a thiol group.
If the amount is less than 0.01 part by weight, the thixotropic effect is small. If the amount exceeds 10 parts by weight with a fatty acid, the effect of decreasing the modulus of the sealant increases. If the amount exceeds 10 parts by weight with a fatty acid salt, the effect on shortening the pot life is reduced. It is not preferable because it becomes too large.

Further, in the present invention, precipitated calcium carbonate treated with the above-mentioned saturated fatty acid (salt) may be used as a filler, and the same effect as incorporation as a compounding agent can be obtained. Even in this case, when the modulus of the cured product decreases, precipitated calcium carbonate treated alone or in combination with the fatty acid salt may be used. In order to optimize the pot life, precipitated calcium carbonate treated in combination with the organic sulfonic acid may be used.

The content of the precipitated calcium carbonate treated with the saturated fatty acid (salt) is 1 to 100 parts by weight of the polymer.
0 to 300 parts by weight. If the amount is less than 10 parts by weight, the thixotropic content is insufficient, and if it exceeds 300 parts by weight, the amount of the plasticizer increases and the polymer content becomes too low, which is not preferable in terms of physical properties. [6] Other Compounds (1) Filler The curable composition of the present invention is further improved in economy, workability when applying the composition, and physical properties after curing.
Fillers such as calcium carbonate, talc, clay, titanium oxide, silica and the like can be added. (2) Plasticizer The composition of the present invention comprising (a) the above-mentioned polysulfide polyether polymer as a polymer having two or more thiol groups in a molecule and a compound having two or more isocyanate groups in a molecule is conventionally used. Dioctyl phthalate (DOP), diheptyl phthalate (D
Since cheap phthalic acid esters such as HP) are compatible, it is possible to mix these additives. In addition, a plasticizer such as chlorinated paraffin and hydrogenated terphenyl can be blended.

[0025]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. [Synthesis Example 1] 1000 g of bifunctional polypropylene glycol (OH value: 56.4 mgKOH / g) obtained by adding propylene oxide to propylene glycol;
107 g of epichlorohydrin and 1.25 g of stannic chloride pentahydrate were charged into a reaction vessel and stirred at 80 to 90 ° C. for 3 hours. Further, a polysulfide polymer (trade name “Thiokol LP55” manufactured by Toray Thiokol Co., Ltd.)
After adding and mixing 1110 g, 89.9 g of sodium bisulfide (purity: 72.3%) was added, and the mixture was stirred at 80 ° C. for 2 hours. Thereafter, the salt was removed to obtain a pale yellow transparent polymer having a mercaptan content of 2.0% by weight and a viscosity of 80 poise (25 ° C.). [Examples 1 to 7] The polymer obtained in Synthesis Example 1 was added to Table 1
The types and amounts of catalysts and plasticizers shown in Table 1 and other fillers containing precipitated calcium carbonate, organic sulfonic acid, and saturated fatty acids were blended to obtain a base material for a sealing material. Table 2 shows the types and amounts of other fillers.

The base material was poured into a 100 cc polyethylene container, and the surface was smoothed.
The viscosity at one rotation and ten rotations was measured with a B-type viscometer B8U manufactured by KIMEC. The viscosity value of one rotation and the viscosity ratio expressed by the viscosity of one rotation / 10 the viscosity of one rotation were used as the thixotropic index.

A urethane prepolymer (isocyanate content 4.1) obtained by adding xylene diisocyanate to 390 parts by weight of the main ingredient and polypropylene glycol.
(% By weight) and 65 parts by weight were uniformly mixed at a constant temperature of 20 ° C. for about 10 minutes. The resulting mixture is 35 m high
m, 20 mm inside diameter, pour into an ethylene cup, smoothen the surface, and store at 20 ° C, 60 RH% humidity, and insert every hour using a penetration tester used in JIS K-2207. The degree was measured, and the time required to reach 350 was taken as the pot life. An aluminum plate treated with anodized sulfuric acid using this mixture was used as an adherend to JI.
An H-type specimen was prepared by a method according to SA-5758, and the 50% tensile stress after standard curing was measured in a room at 20 ° C. Table 3 shows the results. [Comparative Examples 1 to 3] As comparative examples, the same tests as in Examples 1 to 7 were performed for the case where no organic sulfonic acid or saturated fatty acid was added. Table 3 shows the results.

[0028]

[Table 1]

[0029]

[Table 2]

[0030]

[Table 3] As is clear from Table 3, the curable composition of the present invention can provide a compound having a sufficient pot life and thixotropy regardless of the type of the sedimentable calcium carbonate as a filler. A cured product expressing a sufficient modulus with good reproducibility is obtained.

[0031]

As described above in detail, the curable composition of the present invention is obtained by preparing a polymer having two or more thiol groups in a molecule by using a tertiary amine and / or an organometallic catalyst.
When preparing a composition for curing with a compound having two or more isocyanate groups in a molecule, a predetermined amount of an organic sulfonic acid compound as a curing retarder and / or a predetermined amount of a saturated fatty acid as a thixotropic agent are used. A cured product that has a sufficient pot life and thixotropic potential regardless of the type of the precipitated calcium carbonate as a filler and that exhibits a sufficient modulus even after curing with good reproducibility can be obtained. Such a curable composition significantly improves the versatility of the thiol / isocyanate-curable sealing material, paint and adhesive compounding composition.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08K 5/42 C08K 5/42 C08L 75/04 C08L 75/04 C09J 175/04 C09J 175/04 181/02 181/02 181 / 04 181/04 C09K 3/10 C09K 3/10 D

Claims (14)

[Claims] (1) a polymer having two or more thiol groups in a molecule; (b) a compound having two or more isocyanate groups in a molecule; (c) (1) a tertiary amine and / or Or a curable composition containing (2) a curing catalyst composed of an organic metal, and (d) (3) an organic sulfonic acid compound and / or (4) a saturated fatty acid (salt). 2. A polymer having two or more thiol groups in a molecule, (b) a compound having two or more isocyanate groups in a molecule, (c) (1) a tertiary amine and / or Or (2) a curing catalyst comprising an organic metal, and (e) (3) an organic sulfonic acid compound and / or (4)
A curable composition comprising a filler consisting of precipitated calcium carbonate treated with a saturated fatty acid (salt). 3. The curable composition according to claim 1, wherein (a) the polymer having two or more thiol groups in the molecule has a molecular weight of 600 to 200,000. Curable composition. 4. The curable composition according to claim 1, wherein the (a) molecule contains two or more thio-
Polymers having Le group - is, in the main chain, _{(b) - (C 2 H 4 OC} n H 2 n OC 2 H 4 -
S _x )-(where n is an integer of 1 to 2, x is an integer of 1 to 5), and (b) -C ₂ H _{4 OC n H 2 n OC 2 H} 4 -S
A curable composition, which is a polysulfide polymer having a thiol group represented by H (where n is an integer of 1 to 2). 5. The curable composition according to claim 1, wherein two or more thio- groups are present in the molecule (a).
Is a polymer having a (C)-(R ¹ O) m − (where R ¹ is an alkylene group having 2 to 4 carbon atoms, and m is 6).
Shows an integer of ~ 200. ) Represented by polyethylene - and ether moieties, _{(d) - (C 2 H 4 OC} n H 2 n OC 2 H 4 -
S _X) -, and _{- (CH 2 CH (OH)} CH 2 -S
_X) -. (Here, n is an integer of 1 to 2, x contains a structural unit represented by is an integer from 1 to 5), and, at the end, (e) _-C 2 H _{4 OC n H 2 n OC 2} H 4 -S
H and / or thio- represented by —CH ₂ CH (OH) CH ₂ —SH (where n is an integer of 1 to 2)
A curable composition, which is a polysulfide polyether polymer having a hydroxyl group. 6. The curable composition according to claim 1, wherein said (3) organic sulfonic acid compound is (5) an alkylbenzene sulfonic acid. 7. The curable composition according to claim 1, wherein the (4) saturated fatty acid (salt) compound is (6) a C12 or higher saturated fatty acid (salt) compound. Curable composition. 8. The curable composition according to any one of claims 1 to 7, wherein (d) is added to 100 parts by weight of the polymer having two or more thiol groups in the molecule.
A curable composition comprising (3) an organic sulfonic acid compound and / or (4) a saturated fatty acid (salt) in an amount of 0.01 to 10% by weight. 9. The curable composition according to any one of claims 1 to 8, wherein said (e) is added to 100 parts by weight of said polymer having two or more thiol groups in the molecule (a).
(3) Precipitating calcium carbonate treated with an organic sulfonic acid compound and / or (4) a saturated fatty acid (salt) is treated with 10-3
A curable composition characterized by containing 00% by weight. 10. The curable composition according to any one of claims 1 to 9, wherein (b) an isocyanate group of a compound having two or more isocyanate groups in a molecule; A curable composition characterized by having a molar ratio (isocyanate group / thiol group) to a thiol group in a polymer having two or more thiol groups of 0.5 to 4.0. 11. The curable composition according to claim 1, wherein said (5) alkylbenzene sulfonic acid is (7) dodecylbenzene sulfonic acid. 12. The curable composition according to claim 1, wherein said (6) saturated fatty acid (salt) compound having C12 or more is (8) stearic acid (salt). Curable composition. 13. A sealing material comprising the curable composition according to claim 1. 14. An adhesive comprising the curable composition according to claim 1.