JPH01278557A - Curable composition - Google Patents

Abstract

PURPOSE:To obtain the title composition outstanding in storage stability, heat resistance etc., suitable for sealers, adhesives, coatings, etc., by incorporating a thiol group-contg. polyether with each specified amount of a specific compound and a oxidizing agent. CONSTITUTION:The objective composition can be obtained by incorporating (A) 100pts.wt. of a thiol group-contg. polyether having in the molecule two or more thiol groups, with its main chain virtually constituted of recurring unit of the formula -R-O- (R is 2-4C alkylene), 500-100,000 (pref. 1,000-10,000) in molecular weight with (B) 1-50 (pref. 2-20)pts.wt. of an oxidizing agent (e.g., PbO2), and (C) 0.1-10 (pref. 0.3-2) pts.wt. of at least one compound selected from hindered phenolic compounds, hydroquinone-based compounds, amine-ketone-based compounds, aromatic secondary amine compounds, thiazole- based compounds and sulfur.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a curable composition, and more specifically, it has excellent storage stability, heat resistance, etc., and is suitable for use as a cooling agent, adhesive, paint, etc. The present invention relates to a curable composition.

[Conventional technology]

Polymers containing two or more thiol groups in one molecule are easily cured when mixed with an oxidizing agent, and are therefore used in healing materials, paints, and adhesives.

Examples of these thiol group-containing polymers include liquid polysulfite polymers described in U.S. Pat.
Thiol-terminated polyoxyalkylene polyol described in US Pat. No. 48,279, U.S. Pat. No. 3,923
．． A liquid polymer having a mercaptan group at the end described in No. 748, a polymer described in U.S. Pat. Poly(oxy/alkylene)poly(monosulfide) described in Japanese Patent Publication No. 52-34677
Polythiol, butane mercaptan polymer described in U.S. Pat. No. 3,282,901, U.S. Pat.
．． Mercapkun-containing polymers described in Japanese Patent Publication No. 523.985, Japanese Patent Publication No. 55-39261, Japanese Patent Publication No. 60-3
Examples include mercaptoorganopolysiloxanes described in No. 421 and the like.

In addition, as an oxidizing agent for a thiol group-containing polymer, Pb
O2, MnO2, NaBO2, etc. are used. These oxidizing agents are preferable because they have excellent ability to oxidize thiol groups and provide good elasticity.

[Problems that barking attempts to solve]

The mercaptan-terminated liquid polymer containing urethane bonds described in U.S. Pat. No. 3,923,748 is PbO2
Although it is easily cured with an oxidizing agent having a high oxidizing ability such as, there is a problem that the obtained cured product softens when exposed to high-temperature heating conditions.

Furthermore, the physical properties of poly(oxy/alkylene)poly(monosulfide)polythiol containing an ester bond described in Japanese Patent Publication No. 34677/1980 deteriorate when heated with PbO2 at high temperatures.

Furthermore, Special Publication No. 46-3389 and Special Publication No. 47-482
The polymer having a thiol group at the end described in No. 79 does not contain urethane bonds or ester bonds and essentially consists of ether bonds, thioether bonds, and disulfide bonds, but the cured product of this polymer by PB bonding However, they also have the disadvantage that their physical properties similarly deteriorate under long-term high-temperature heating conditions.

For this reason, PbD, which has the best curing ability, cannot be used for these thiol group-containing polymers.
Milder oxidizing agents and air oxidation promoting catalysts have been used in conjunction with air oxidation promoting catalysts, such as those described in No. 56.

The present invention is intended to solve the above-mentioned conventional problems, and its purpose is to provide a curable composition containing a thiol group-containing polyether that exhibits excellent heat resistance and does not soften or change its physical properties when heated at high temperatures. It is about providing something. Further, the present invention provides a curable composition that has stability during storage without impairing curability during construction.

[Failure to solve the problem]

As a result of extensive research in view of the above objectives, the present inventors have discovered that if a predetermined amount of a specific compound is added to a thiol group-containing polyether together with an oxidizing agent, it has good stability during storage and excellent heat resistance. The inventors discovered that it is possible to create a curable composition that gives a cured product, and came up with the present invention.

Zunawaji The curable composition of the present invention has (8) two or more -L thiol groups in the molecule, and the main chain is essentially -
Contains a repeating unit represented by R-C)- (R is an alkylene group having 2 to 4 carbon atoms) and has a molecular weight of 500 to 100.
000 thiol group-containing polyether, (B) 1 to 50 parts by weight of oxidizing agent and (C
) (a) hindered phenol compound, (b) hydroquinone compound, (C) amine-ketone compound, (d) aromatic secondary amine compound, (e) benzimidazole compound or its metal salt, ( f) At least one selected from a dicarbamate compound, (g) a guanidine compound, (h) a thiourea compound, (1) a thiazole compound, (j) a sulfenamide compound, (b) a thiuram compound, and (1) sulfur. It is characterized by containing 0.1 to 10 parts by weight of one compound.

The thiol group-containing polyether in the composition of the present invention (
8) has two or more thiol groups in one molecule and contains a repeating unit whose main chain is essentially -R-0- (R is an alkylene group having 2 to 4 carbon atoms), Molecular weight is 500
~100,000, particularly preferably 1.000-10
．． It is 000.

The thiol group-containing polyether used in the present invention may substantially contain ether bonds, thioether bonds, or disulfide bonds, but it is desirable that it essentially contain no urethane bonds or ester bonds.

The repeating unit in the thiol group-containing polyether is essentially represented by (-R-0-), where R is an alkylene group having 2 to 4 carbon atoms. The alkylene group R is not limited to a linear one, and may have an alkyne substituent such as a methyl group.

Preferred examples of such thiol group-containing polyethers include polyoxyalkylene polyols having a thiol group at the end and having a structure represented by the following general formula (1) described in Japanese Patent Publication No. 47-48279, and Patent No. 4.
Polymercuffrin having a structure represented by the following general formula (2) described in No. 092.293 and Japanese Patent Publication No. 4.6-3389 can be mentioned.

-(C1+2CH-0), -[:R2-C1]-C
) I2-3H... (1) R, DH -(C1+2CH+-port), -CH2C112CL
-3ll -(2)C[43 [However, in general formulas (1) and (2), R1 is hydrogen or methane]
The Li group, m, and n are integers of 2 to 100. ] The molecular weight of the above thiol group-containing polyether is 500 to 100.
Must be in the range 000. If the molecular weight is less than 500, the cured product will become brittle, and if it exceeds 100,000, the viscosity of the polymer will increase or the polymer will become solid, making it difficult to form a composition, which is not preferred.

The preferred molecular weight ranges from 1000 to 10.000. In addition, since it is easy to handle when making it into a composition,
Preferably, it is a liquid.

As the oxidizing agent (B) in the composition of the present invention, substances conventionally used as curing agents for thiol group-containing polymers can be used. Specific examples of these oxidizing agents include 2n02, Fed2, Pbo2, MgO2
, CaO2, BaO2, MnO2, TeO2, SeO2
, Pb30. ．． Inorganic peroxides such as 5rD2, Li, etc.
ZnO, FeO, Pb mouth, Fe2D3.5b20s
, Mg[], Co mouth, Ca mouth, Cu mouth, Ba
Inorganic oxides such as O, Na2Cry4, K2CrO, Na
2Cr20. , K2Cr2O7, NaC1 [ ], , Na
BO211202, K2C2O4, KMn mouth.

, inorganic oxidizing agents such as sodium percarbonate (2Na2CD3+3H2O2), penzoyl peroxite, dicumyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, t-butyl perbenzoate, sodium peracetate, Peroxides such as urea peroxide,
Examples include organic oxidizing agents such as nitrobenzene, dinitrobenzene, and baraquinonedioquine, but PbO2 is most preferred. The amount of these oxidizing agents added varies depending on the type of oxidizing agent, but for boat fishing, it is blended in an amount of 1 to 50 parts by weight per 100 parts by weight of the polymer of the present invention. If the amount of the oxidizing agent is less than 1 part by weight, the curing of the thiol group-containing polyether will be insufficient, and if it exceeds 50 parts by weight, the cured product may discolor, which is not preferred. The preferred amount added is 2 to 20 parts by weight.

Specific compounds (C) to be added to the composition of the present invention include (a) hindered phenol compounds, (b) hydroquinone compounds, (C) amine-ketone compounds, (d) aromatic secondary compounds. amine compound, (e) penzimidazole compound or its metal salt (f)
Examples include dithiocarbamate compounds, −〇 − =8= (g) guanidine compounds, thiourea compounds, (1) thiazole compounds, (j) sulfenamide compounds, (funds) thiuram compounds, and (1) sulfur. .

Here, the hindered phenol compound (a) is a compound represented by the following general formulas (3) to (6).

[R2, R3, R4, R in general formulas (3) to (6)
5, R6, and R7 are hydrogen or an alkyl group, X is carbon, nitrogen, an alkyl group, an alkylene group, or an alkylene amine group, Y, Y'' is an alkylene group, an alkyritene group, or sulfur, p is I There is an integer of ~3, and q is 1
-43, and r is an integer of 1-5. ] A specific example of this is 2,2″-methylenebis(4-
methyl-6-t-butylphenol), 2゜2'-methylenebis(4-ethyl-6-t-butylphenol),
l 1.3-tris(2-methyl-4-hydroquine-
5-tert-butylphenyl)butane, 1.3. 5-
Tris(3', 5'-n-t-butyl-4-hydroxy/bennru)ynanuric acid, butylidenebis(methyl-butylphenol), 3-(4'-hydroxy-3', 5'-di-t-butylphenyl) ) n-octadenyl propionate, tetrakis [methylene-3
-(3°,5”-t-butyl-4′-hydroquinphenyl)propionate comethane, 1.3.5-trimethyl-2,4,6-tris (3,5-t-butyl- 4-Hytroquine benzene, 4.4'-
Examples include thiobis(6-t-butyl-3-methylphenol).

In addition, (b) the hydroquinone compound has the following general formula (7
) is a compound represented by

B9 [In general formula (7), R8 and R9 are hydrogen or an alkyl group. ] Specific examples include hydroquinone, methylhydroquinone, t-butylhydroquinone 2,5-cyt
-butylhydroquinone, 2,5-di-monoamylhydroquinone, and the like.

In particular, adding hydroquinone not only improves heat resistance but also
This is preferable because it also provides good water resistance.

(C) The amine-ketone compound is a compound represented by the following general formula (8) [In the general formula (8), R1 is hydrogen or an alkoxy group, and R2, R3, and R4 are hydrogen or an alkyl group. .

] Specific examples include 6-nitoquine-1,2-dihydro-2,2,4-)limethylquinoline, poly(2,2,4
-) dimethyl-1,2-dihydroquinoline), and the like.

(d) The aromatic secondary amine compound has the following general formula (9)
It is a compound represented by the formula % or a@.

Q [General formula (9], α■, R,, R2, R3, R
4 is an alkyl group or an aryl group. ] Specific examples include phenyl-1-naphthylamine,
Octylated phenylamine, 4.4″-(α, α-
dimethylbenzyl)diphenylamine, N, N'
-No-2-naphthyl-p-phenylenediamine, N-phenyl-N''-(1,3-dimethylbutyl)-p-phenylenediamine, N-phenyl-N''-inpropyl-p-phenylenediamine, etc. Can be mentioned.

Further, (e) the benzoimitazole compound or its metal salt is a compound represented by the following -Kakuchi Ql) or 0.

In [-Satsuri Ql), 02), R5 is hydrogen or an alkyl group, and X is 5 or a metal in the R5 group. ] Specific examples thereof include 2-mercaptobenzimidazole, methyl-2-mercaptobenzimidazole, and 2-mercaptobenzimidazole.
Zinc salt of mercaptobenzimidasole, methyl-2
- Zinc salt of mercaptobenzimidazole, etc.

(f) The anti-thiocarhamate compounds are as follows - Killing 03)
This is a compound shown in

In 87 [-Sakatsu03), R6 and R7 are hydrogen, an alkyl group, or an aryl group, and R6 and R7 can form a heterocyclic structure together with a nitrogen atom. M is ■. , 1. ,Il,I
[B, rV. , vA, Vl, a metal in the group or piperidine or pipecoline. ] Specific examples include nickel diethyldithiocarbamate and disobutylsithiocarbamate.

Kel, zinc dibutyldithiocarbamate, zinc cybenzyldithiocarbamate, sodium dimethyldithiocarbamate, copper dimethyldithiocarbamate, ferric dimethyldithiocarbamate, tellurium diethyldithiocarbamate, pencumethylenedithiocarbamate piperidine salt, pipecolylcythiocarbamate Examples include pipecoline ruhamic acid salt.

= 15- (g) The guanidine compound is a compound represented by the following formula.

In [-Sakatsu04), R8 and R9 are an alkyl group or an aryl group. ] Specific examples include 1,3-phenylquanin,
Examples include no-0-tolylguanidine.

(l-1) The thiourea compound is a compound represented by the following -Sakatsu 〇5).

[--R1 and R2 are an alkyl group or an aryl group. ] Specific examples thereof include N,N'-diphenylthio-urea, trimethylthiourea, N,N'-diethylthiourea, and the like.

(1) Thiazole compounds are listed below - Killing 06) or 07)
It is a compound represented by

[-Katsu06), in α force, R3 is hydrogen, an alkyl group, an aryl group, or an alkyleneamine group, and n is 1
Or 2. ] Specific examples include 2-mercaptobenzthiazole, dibenzothiazyl disulfide, 2-(2″, 4′-
Examples include dinitrophenylthio)benzthianol.

('') The sulfenamide compound is a compound represented by -Kaku08) below.

In [-Sakatsu08), R4 is hydrogen, an alkyl group or a cycloalkyl group, R5 is an alkyl group or a cycloalkyl group, and R4 and R5 can form a heterocyclic structure together with a nitrogen atom. ] Specific examples include N-7 chlorohexyl-2-pentthiazolylsulfenamide, N-t-butyl-2-pentthiazolylsulfenamide, and N-oquinoneethylene-2-pentthiazolyl sulfenamide. Rusulfenamide, N, N'
Examples include 2-pentthiazolylsulfenamide and the like.

Moreover, (k) thiuram compound is a compound represented by the following -Katsu09).

In [-Sakatsu09), R6, R7, R8, and R9 are an alkyl group or a cycloalkyl group, and can form a heterocyclic structure together with the nitrogen atom. X is an integer from 2 to 4.

] Specific examples thereof include tetraethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, tetramethylthiuram monosulfide, and the like.

Furthermore, (1) sulfur is preferably powdered sulfur used for comb formulation.

Although it is sufficient to add only one kind of the above-mentioned compounds (a) to (1), two or more kinds can be mixed and added if necessary.

In particular, the addition of the above-mentioned compound (b) is preferable because even when the cured product is immersed in water, the physical properties do not deteriorate and the water resistance becomes good.

Furthermore, adding compound (a) (tora) improves both heat resistance and water resistance, which is preferable.

When blending any one of the above compounds (a) to (1) in the composition of the present invention, 0.1 to 10 parts by weight, preferably 0.3 to 2.0 parts by weight, per 100 parts by weight of the polymer. This is the middle part of the mold. If the amount of the compound in the blend is less than 0.1 part by weight, the stability and heat resistance of the composition will not be improved sufficiently;
If the content exceeds the heavy weight range, the physical properties of the composition may deteriorate or coloring may occur, which is not preferable.

The composition of the present invention further includes fillers such as calcium carbonate, talc, clay, titanium oxide, and silica for the purpose of improving economy, workability when applying the composition, and physical properties of the cured composition. , and plasticizers such as phthalate esters, chlorinated paraffins, and hydrogenated terphenyls.

The composition of the present invention contains the above components (A) to (C) in advance.
) may be mixed, but (A) + (C)
A two-component composition consisting of the main ingredient (B) and the curing agent (B) may be prepared and mixed at the time of use.

[For production]

The thiol group-containing polyether (A), which has two or more thiol groups in one molecule and whose main chain essentially contains repeating units represented by -R-〇-, is an oxidizing agent (B). When mixed with thiol group-containing polyether (A), it is easily cured and becomes an excellent elastic body, but furthermore, by adding the compound (C) to the base material containing the thiol group-containing polyether (A), good storage stability can be achieved. It is also possible to improve the heat resistance of the cured product.

The reason is considered to be as follows.

1) When the cured product is placed under high-temperature heating, radical oxidation etc. proceed due to the oxidizing agent remaining in the cured product, causing deterioration of the cured product, but the compound (C) suppresses this radical oxidation etc. Prevents deterioration of cured products.

2) In a two-component composition consisting of a main ingredient containing a thiol group-containing polyether (A) and a curing agent containing an oxidizing agent (B), the specific compound of the present invention (
By adding C), air oxidation of thiol groups can be suppressed and good stability during storage can be obtained.

〔Example〕

The present invention will be explained in more detail by the following examples=22- do.

Synthesis example ↓ Trifunctional polypropylene glycol obtained by adding propylene oxide to glycerin (Ko value 32.5)
800 g of shrimp chlorohydrin, 53.7 g of shrimp chlorohydrin, and 1.6 g of stannic chloride pentahydrate were placed in a 2β reaction vessel and stirred at 110° C. for 3 hours. Further, 464 g of hydrogen sulfide (purity 70%) was added, and the temperature was raised to 100°C. After stirring for 15 hours, the salt was removed to obtain a pale yellow transparent liquid polyether containing thiol groups. The sulfur content of the obtained thiol group-containing polyether was 15% by weight,
Mercaptan content was 1.2% by weight.

Examples 1 to 25 The thiol group-containing polyether obtained in Synthesis Example 1 was
The compound (C) of the present invention was blended with a plasticizer and a filler in the proportions shown in the table to obtain a main ingredient. On the other hand, pb02 (oxidizing agent) and a plasticizer were mixed in the proportions shown in Table 2 to prepare a curing agent. The obtained main ingredients and curing agent were mixed to form a 2m thick
The mixture was poured into a No. m mold and cured at 20° C. for 3 days and at 50° C. for 3 days (initial curing) to obtain a cured product in the form of a pellet. Regarding this cured product, ASTM D638-84T
Tensile test (tensile speed 50
0 mm/min), and the 100% modulus, breaking strength, and elongation were measured. At the same time, JAS K63
A hardness was measured according to 01. 14 more at 90℃
The same test was carried out after heating for one day. These results are summarized in Table 3 together with the storage stability of the base agent.

Table 1: Base compound formulation Table 2: Curing agent formulation -, ----26- (Note) (1): C, ・-==1.3.5-t'
J2 (3',5'-di-t-butyl-4-hydroxybenzyl)isocyanuric acid C2...1. , L 3Jl
(2-methy)shi-4-hitranslation5-t-buty)tofgoni)shi)butaneC3...Butyritenebis(methyl-butylphenol),...3-(4"-hydroxy-3") , 5"-di-t-butylbuenyl)propionic acid-n-butylbuenyl C9... 2,2"
- Methylene pis(4-methyl-6-t-butylphenol) C6, butylhydroquinone C7...6-Jtoxy~1,2-dihydro-2,
2,4-) Limethyl diamine CB...N,N''-di-2-naphthyl-p-fugonylenediamine C9...
・N-phenyl-N'-(13-dimethylbutyl)-p
-Phenylenediamine C+o 4,4" -(α
1 α-dimethy)benzyl)diphenylamine CI
+ ・・Octylated diphenylamine CI2
・・・ Nickel dibutyldithiocarbamate CI3
...Pentamethylene dithiocarbamic acid piperidine salt C142-mercaptobenzimidazole CI5
- Di-o-)lylguanidine Cu6- Tetramethylthiuram dried nosulfide C1□ - Dibenzothiazyl disulfide C,8-Ni oxydiethylene-2-benzothiazolyl sulfenamide C1゜ - N, N'
-diethylthio urea C20, powdered sulfur r7 C2+, tetrakis [methylene-3-(3'
, 5'-dyl-t-butyl-4'-hydroxyphenyl)
Propionate] Methane Moyo 1J6-Nitoxy 1,
2-dihydro2,2,4-trimethy) and quinoline (1 part by weight each) C22...t-butyl high 1! Rokinone right σ octyl chloride Schiff J nylamine (1 part by weight each) C23.
t-Butylhydroquinone Ayo σ2-Mercap!・Benzimidazole (1 part by weight) C24...tetrakis [methylene-3-(3',5°-di-t-butyl-4''-human oxyphenyl)propionate]
Methane, σN-oxydiethylene-2-benzothiazolylsulfenamide (1 part by weight each) C2S, high quinone and powdered sulfur (1 part by weight each) (2): A hardness (measured by jIS-6301) Examples 26 to 28 Sorted cured products were obtained in the same manner as in Examples 1 to 25. For the obtained sorted cured product, after initial curing, after initial curing and heating at 90°C for 14 days, and after initial curing and 20
After 7 days of immersion in ℃ water, a tensile test and hardness measurement were conducted in the same manner as in Examples 1 to 25. These results are summarized in Table 4.

-,,,-2,? - Comparative Examples 1 to 5 Cured products were produced in the same manner as in the above examples except that a composition to which the compound (C) of the present invention was not added and a composition to which a compound other than the compound (C) of the present invention was added were used. Created,
The same test was conducted. The results are shown in Table 5.

(Note) (1): I...bis [2-methyl-4-
(3" 10 alkyl (C, 2-,,) thiopropionyloxy) 5+ butyl phenyl sulbuhydro... pentaerythritol tetra [β-al+ru (12 Il+) thiopropionate ester" ha.
・Tris(monylphenyl)phosphite...
Alkanol (C+2-+6)/4,4'-isopropylidene diphenyl/triphenyl phosphite polycondensate (2): A hardness (measured by jIS K6301) -32- [Effects of the invention] Curable composition of the present invention can provide a cured product with good stability of the main ingredient during storage and excellent heat resistance, and is suitable for use in sealants, adhesives, paints, etc.

Claims (1)

[Claims] (1) (A) has two or more thiol groups in the molecule, and the main chain is essentially -R-O- (R has 2 to 2 carbon atoms)
1 to 50 parts by weight of (B) oxidizing agent to 100 parts by weight of a thiol group-containing polyether having a molecular weight of 500 to 100,000.
parts by weight, (C) 0.1 to 10 parts by weight of at least one compound selected from the following (a) to (1) (a) hindered phenol compound, (b) hydroquinone compound, (c) amine - ketone compound, (d) aromatic secondary amine compound, (e) benzimidazole compound or metal salt thereof, (f) dithiocarbamate compound, (g) guanidine compound, (h) thiourea compound, ( A curable composition comprising: i) a thiazole compound; (j) a sulfenamide compound; (k) a thiuram compound; and (l) sulfur.