JPH07310020A - One-pack type oxygen-setting resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition containing a specified SH group- containing polymer, a copper compound and an amine compound, having cold setting properties, capable of setting in a short time and useful as an adhesive, a sealant, a coating agent, etc. CONSTITUTION:This resin composition contains (A) an organic polymer having two or more SH groups in the molecule, e.g. a polymer having the main chain composed of a silicone, a polysulfide or a polyether and SH groups in an amount of >=2 per one molecule at the terminals, (B) a divalent copper compound such as copper (II) carbonate, copper (II) hydroxide or copper (II) acetylacetonate and (C) an organic amine compound such as a secondary amine or a tertiary amine. In addition, the respective components are contained preferably in a weight ratio satisfying A/B=100/0.001 to 100/5.0 and A/C=100/0.001 to 100/5.0.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a one-pack type oxygen-curable resin composition which is based on a polymer containing a mercapto group and can be used as an adhesive, a sealing material or a coating agent.

[0002]

2. Description of the Related Art A polymer having a mercapto group in its molecule has been used as a polysulfide, but it is common to oxidize a terminal mercapto group into a disulfide for curing thereof, and the reactivity of the mercapto group is utilized. Various curing methods have been considered. The curable resin composition containing a polymer having a mercapto group in the molecule includes a two-pack type in which a base containing the above polymer and a curing agent are mixed and cured immediately before use, and a polymer and a curing agent. Pre-mix with the catalyst, store in a closed container,
There are two types, one-pack type that is put out of the container at the time of use and cured by the surrounding atmosphere.

Among these, in the two-pack type resin composition, lead dioxide, which acts as an oxidant for the mercapto group of the polymer, organic peroxide, and the like are used as a curing agent. The two-pack type resin composition may cause various problems such as poor curing and deterioration of the physical properties of the cured product if it is not sufficiently mixed before use or if air bubbles are introduced during mixing. Need to be used after. On the other hand, in the one-pack type resin composition, since the mercapto group-containing polymer and the curing catalyst are mixed in advance, problems such as the two-pack type do not occur, and humidity in the air, ambient of oxygen, etc. Crosslinks and cures in the atmosphere. Therefore, the resin composition containing a polymer containing a mercapto group is gradually shifting from a two-pack type to a one-pack type.

[0004]

However, in the case of a one-pack type resin composition, as described above, it cures by utilizing the ambient atmospheric components such as moisture in the air that fluctuate geographically or seasonally. Therefore, there is a problem that the curing speed, the cured physical properties, etc. greatly vary depending on these. For example, in the case of moisture curing, curing may be significantly delayed and defective curing may occur when the humidity is low such as in a dry region or in winter. In order to improve the drawbacks of such a one-pack type resin composition, research on a curing method using oxygen in the air having a substantially constant concentration is underway. For example, JP-B-58-17549 discloses an oxygen-curable resin composition having a dithiocarbamic acid chelate compound of zinc and a β-diketone compound of manganese as a curing catalyst, and JP-B-4-15261. , An oxygen-curable resin composition using copper dimethyldithiocarbamate and ferric dimethyldithiocarbamate as a curing catalyst. However, these oxygen-curable resin compositions have the drawback that the curing catalyst contained in the resin composition gradually deactivates during storage, or the curing speed is very slow.

Further, as a method for accelerating the curing rate by utilizing moisture curing and oxygen curing, JP-A-57-38852 discloses a resin composition containing at the same time a moisture-activated metal peroxide. Is disclosed in Japanese Patent Laid-Open No. 5-1405.
Japanese Patent Publication No. 34-34 describes a composition in which a moisture-curable silicone or modified silicone sealing material is simultaneously mixed. However, in these resin compositions, since the part which depends on moisture curing is large in the end, the problems that occur during moisture curing as described above still remain, and satisfactory results have not been obtained.

[0006]

Therefore, in view of the present situation, the inventors of the present invention have made extensive studies to improve these problems of the one-pack type curable resin composition, and as a result,
One liquid that can reduce the effects of changes in various conditions such as ambient humidity during use, which is a drawback of conventional one-pack type curable resin compositions, and reduce changes in various properties of the resin composition such as curability. The present invention has been completed by finding a type oxygen-curable resin composition.

The present invention provides a one-pack type oxygen-curable resin composition which is cured well at room temperature by using an organic amine compound and a divalent copper compound as a curing catalyst in a polymer containing a mercapto group. The purpose is to do.
That is, the present invention provides (A) at least 2 per molecule.
An organic polymer having one or more mercapto groups, (B)
A one-pack type oxygen-curable resin composition comprising a divalent copper compound and an organic amine compound (C). The component (A) has at least one selected from the group consisting of silicone, polysulfide and polyether in the main chain, and at least 2 per molecule at the end.
It is characterized by containing one mercapto group. The component (B) is a divalent copper compound, and the component (C) is a secondary amine compound or a tertiary amine compound. Furthermore, the component (A) /
The component (B) has a weight ratio of 100 / 0.001 to 100 /
The weight ratio of the component (A) / component (C) is in the range of 100 / 0.001 to 100 / 5.0.

The present invention will be described in detail below. The organic polymer used in the present invention may be one having at least two mercapto groups in the molecule. Also,
The molecular weight of the organic polymer having two or more mercapto groups per molecule is 100 to 100,000, particularly 1,000.
The workability before curing and the physical properties after curing when the resin composition is up to 50,000 are good.

The organic polymer having two or more mercapto groups per molecule used in the present invention preferably contains at least one selected from the group consisting of silicone, polysulfide or polyether in the main chain. The organic polymer containing two or more mercapto groups per molecule containing silicone in the main chain can be obtained, for example, by synthesizing silicone and a thiol-based terminal silane coupling agent.

Examples of SH group-containing silicone obtained by modifying such silicone with a thiol-based silane coupling agent include SS10 (hydroxy-terminated silicone) (manufactured by Shin-Etsu Chemical Co., Ltd.) and A189 (thiol-based silane coupling agent). A compound synthesized from Nippon Unicar Co., Ltd. can be mentioned. This SH group-containing silicone is
As is well known, a hydroxy-terminated silicone and a mercaptoalkyltrialkoxysilane are reacted in the presence of a divalent tin catalyst (for example, tin (II) 2-ethylhexanoate) to give the following formula [1]. Synthesized as shown.

[0011]

[Chemical 1]

Besides, there is X-22-167B (molecular weight 3,300, manufactured by Shin-Etsu Chemical Co., Ltd.).

Compounds having polysulfide in the main chain include Thiokol LP31 (molecular weight 7,500),
Thiokol LP40 (molecular weight 4,000, all manufactured by Toray Thiokol Co., Ltd.) and the like can be mentioned.

Examples of the compound having a polyether in the main chain include Permapol P2 (manufactured by Nippon Shokubai Co., Ltd.).

In addition to this, US Pat. No. 2,466,963
-S- of solid polysulfide obtained by reacting an alkali polysulfide described in No. 1 with an organic polyhalogen compound.
Polymers having mercapto groups obtained by reducing part of S-bonds; US Pat. No. 3,923,748.
And polyoxyalkylene polysulfides described in JP-B-60-18687; US Pat. No. 3,71
1,452, mercaptan-terminated polyacrylates; S such as mercaptan-terminated poly (butadiene-acrylonitrile) described in U.S. Pat. No. 3,862,975.
Polymers containing H groups; US Pat. No. 3,817,93
No. 6 poly (oxyalkylene) -polyester-poly (monosulfide) -polythiol; polyoxyalkylene polymercaptans described in US Pat. No. 3,258,495; and the following general formula [2]. Examples thereof include poly (oxyalkylene glycol) having a mercapto group terminal.

[0016]

[Chemical 2] (In the formula, R represents a C _{1 to} C ₁₈ linear or branched alkylidene group, an alkylidyne group, an alkenylene group, an arylene group, or a cycloalkylene group, which may be substituted. Or represents an integer of 3.)

Specific examples of the divalent copper compound include copper (II) formate, copper (II) citrate, copper (II) tartrate, copper (II) oxalate, copper (II) acetate and copper benzoate. Compounds of carboxylic acid such as (II) with copper; copper complexes such as ammonium chloride copper (II), ammonium copper sulfate (II), potassium copper chloride (II), and copper acetylacetonate (II); copper bromide ( II), copper (II) chloride, copper borofluoride solution (II) and other copper halides; copper (II) oleate, copper (II) stearate, copper (II) naphthenate and other fatty acids and copper Compound; Copper sulfide (I
Copper sulfides such as I); copper hydroxides such as copper hydroxide (II); copper nitrate (II), copper pyrophosphate (II), copper carbonate (I)
I) etc. can be mentioned.

Of these, copper (II) carbonate, copper (II) hydroxide, copper (II) acetylacetonate, and copper chloride (I
I), copper nitrate (II), copper sulfide (II) and the like have high activity, and particularly copper (II) carbonate, copper (II) hydroxide, copper (II) acetylacetonate and the like are preferable. These divalent copper compounds may be used alone or in combination of two or more.

The organic amine compound is obtained by continuously reacting ammonia and alcohol by passing them through a dehydration catalyst such as silica-alumina, silica, titania, tungsten oxide, clay or various metal phosphates, and distilling the product. Method of separation by extraction; silver, nickel, which is placed under a hydrogen stream to keep ammonia and alcohol catalytic activity
A method of continuously reacting a metal such as copper as a dehydrogenation catalyst; a method of reacting ammonia with an aldehyde or a ketone in the presence of a hydrogenation catalyst, etc., and can be divided into monoamines, diamines, triamines, etc. .

Specifically, triethylamine, N, N-
Monoamines such as dimethylcyclohexylamine (DMEDA); N, N, N ', N'-tetramethylethylenediamine (TMEDA), N, N, N', N'-tetramethylpropane 1,3-diamine (TMPDA), etc. Diamines; N, N, N ', N ", N" -pentamethyldiethylenetriamine (PMDETA), N, N,
N ', N ", N" -pentamethyldipropylenetriamine (PMDPTA), tetramethylguanidine (TM
G) and other triamines; triethylenediamine (TE
A), N, N'-dimethylpiperazine (DMP), N-
Methyl, N '-(2-dimethylamino) -ethylpiperazine (TMNAEP), N-methylmorpholine, N.
(N ', N'-dimethylaminoethyl) morpholine (D
MAEMO), 1,2-dimethylimidazole (DMI
Z) and other cyclic amines; dimethylaminomethanol, diethylaminoethanol, dimethylaminoethoxyethanol (DMAEE), N, N, N′-trimethylaminoethylethanolamine (TMAEEA), N-methyl-N ′-(2-hydroxy) Ethyl) -piperazine (M
HEP), alcohol amines such as N- (2-hydroxyethyl) morpholine (HEMO); ether amines such as bis (2-dimethylaminoethyl) ether, ethylene glycol bis (3-dimethyl) -aminopropyl ether; Zabicyclooctane (DABCO),
1,8-diazabicyclo [5.4.0] -undecene-
7 (DBU) and the like.

As the organic amine compound used in the present invention, secondary amines and tertiary amines are preferable from the viewpoint of catalytic activity. Specifically, 1,8-diazabicyclo [5.
4.0. ] -Undecene-7 (DBU), tetramethylguanidine (TMG), diazabicyclooctane (DA
BCO) and the like are preferred because of their high activity. Among these, 1,8-diazabicyclo [5,4,0] -undecene-7 (DBU) and tetramethylguanidine (TM)
G) is preferable because it has a particularly high activity. The above organic amines may be used alone or in combination of two or more.

The amount of the above divalent copper compound added is 0.001 to 100 parts by weight per 100 parts by weight of the above-mentioned polymer having at least two mercapto groups per molecule.
The amount of the organic amine compound added is 0.001 to 5.0 with respect to 100 parts by weight of the polymer having at least two mercapto groups per molecule.
Parts by weight. The addition amount of the divalent copper compound is more preferably 0.01 to 0.8 parts by weight, and the addition amount of the organic amine compound is more preferably 0.01 to 0.8 parts by weight. When the amount of the copper (II) compound added is less than 0.001 part by weight, sufficient curability is not obtained when the curable resin composition is cured, and when it exceeds 5.0 parts by weight, storage stability deteriorates. This is because. Further, the amount of the organic amine compound blended is 0.0
If it is less than 01 parts by weight, sufficient curability cannot be obtained when the resin composition is cured, and if it exceeds 5.0 parts by weight, storage stability becomes poor.

The curable resin composition of the present invention comprises a filler, a plasticizer, an ultraviolet absorber, in addition to the above-mentioned components (A), (B) and (C), depending on the field of use of these compositions. , An adhesion promoter, a solvent and the like may be included.

As the filler, it is preferable to use an inorganic filler, and specific examples thereof include calcium carbonate, zeolite, clay, talc, fumed silica, precipitated silica and mica. These fillers may be in any shape such as particles, fibers and flakes, and when used in an amount of 50 to 150 parts by weight, the effect is remarkable in terms of workability and cured physical properties. These fillers may be used alone or in combination of two or more. As the plasticizer, phthalic acid esters, terephthalic acid esters, trimellitic acid esters, hydrocarbons and the like can be used, and specifically, dioctyl phthalate (DOP), phthalbenzyl phthalate, dioctyl adipate, trioctyl phosphate, etc. Is mentioned.

Examples of the ultraviolet absorber include 2-hydroxybenzophenone type, benzotriazole type, salicylate type, and titanium dioxide and 2-hydroxy-4-octoxybenzophenone. As the adhesion-imparting agent, a silane coupling agent, a titanium coupling agent, or the like can be used, and specific examples thereof include vinyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and isopropyltriisostearoyl titanate. . In the case of adding a solvent, toluene, aromatic hydrocarbons such as xylene, hexane, heptane, aliphatic hydrocarbons such as octane, and ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cellosolve acetate, butyl cellosolve acetate, etc. Ether esters and the like can be used.

The one-pack type oxygen-curable resin composition of the present invention is
It is manufactured as follows. To 100 parts by weight of the above-mentioned polymer having a mercapto group, 0.001 to 5.0 parts by weight of the above divalent copper compound, 0.001 to 5.0 parts by weight of the above organic amine compound, and 50 to 150 fillers. Add parts by weight, adjust the viscosity by diluting with a solvent or the like if necessary, and mix at 60 ° C. in a nitrogen atmosphere using, for example, a planetary mixer equipped with a vacuum device, to obtain the curable resin composition of the present invention. Get things. If desired, a plasticizer, a UV absorber, an adhesion promoter, etc. may be added. The curable resin composition produced as described above is stored by blocking oxygen by filling it with nitrogen or the like.

The one-pack type oxygen-curable resin composition of the present invention obtained as described above is shielded from the air and stored until the time of use, and cross-linked and cured by contacting with oxygen in the air at the time of use.
Let it be a resin cured product. Using the one-component oxygen-curable resin composition of the present invention, coating or adhering metal, stone, concrete, glass or the like, or construction as a sealing material for waterproof seal of double adiabatic windows or movable joints, etc. To do.

[0028]

EXAMPLES Examples of the present invention are shown below, but these examples are merely for explaining the present invention, and the present invention is not limited thereto.

In the embodiment of the present invention, 2 in one molecule
As an organic polymer having at least one mercapto group, L
P40 or LP31 (manufactured by Toray Thiokol Co., Ltd.),
Permapol P2 (manufactured by Nippon Shokubai Co., Ltd.) or the compound synthesized as in the above formula [1] was used.

Calcium carbonate is super # 1700
(Maruo Calcium Co., Ltd.) was used. Further, as an organic amine compound, tetramethylguanidine (TM
G, manufactured by Nippon Carbide Industry Co., Ltd., diazabicyclooctane (DABCO, manufactured by Sankyo Air Products Co., Ltd.),
1,8-diazabicyclo [5.4.0. ] -Undecene-7 (DBU, Sanyo Chemical Industry Co., Ltd.) and TEA were used.

(Example 1) In 100 parts by weight of LP40,
Calcium carbonate, DBU and cupric carbonate (copper carbonate (I
I)) was blended in the amounts shown in Table 1 and kneaded at 60 ° C. in a nitrogen atmosphere to obtain a one-pack type oxygen-curable resin composition of Example 1.

(Examples 2 to 4) LP3 in place of LP40
1. Permapol P2 or SH obtained as described above
In the same manner as in Example 1 except that the group-containing silicone was used,
The one-pack type oxygen-curable resin compositions of Examples 2 to 4 were obtained.

(Examples 5 to 7) One-pack type oxygen-curable resin compositions of Examples 5 to 7 were prepared in the same manner as in Example 1 except that TMG, DABCO or TEA was used as the organic amine compound replacing DBU. I got a thing.

(Examples 8 and 9) Example 8 was repeated in the same manner as in Example 1 except that the addition amounts of DBU and cupric carbonate were changed.
And 9 one-pack type oxygen-curable resin compositions were obtained.

(Examples 10 to 14) One part of Examples 10 to 14 was carried out in the same manner as in Example 1 except that other divalent copper compounds shown in Table 1 were used instead of cupric carbonate. A type oxygen-curable resin composition was obtained.

[0036]

[Table 1]

* LP31: Polysulfide (Toray Thiokol Co., Ltd.) LP40: Polysulfide (Toray Thiokol Co., Ltd.)
Permapol P2: Modified polysulfide (manufactured by Nippon Shokubai Co., Ltd.) SH group-containing silicone: Synthesized from silicone and thiol-based silane coupling agent DBU: 1,8-diazabicyclo [5.4.0. ] -Undecene-7 TMG: Tetramethylguanidine DABCO: Diazabicyclooctane TEA: Triethylamine TFT: Tack free time

(Comparative Examples 1 to 4) 100 parts by weight of LP40
In addition, as organic amine compounds, DBU, TMG, DABC
Resin compositions of Comparative Examples 1 to 4 were obtained in the same manner as in Example 1 except that O or TEA was blended in the amounts shown in Table 2.

Comparative Examples 5 to 11 Comparative Example 5 was carried out in the same manner as in Example 1 except that the compounds shown in Table 2 were added in the amounts shown in Table 2 in place of the divalent copper compound used in Examples. Resin compositions Nos. 11 to 11 were obtained.

[0040]

[Table 2]

* LP40: Polysulfide (manufactured by Toray Thiokol Co., Ltd.) DBU: 1,8-diazabicyclo [5.4.0. ] -Undecene-7 TMG: Tetramethylguanidine DABCO: Diazabicyclooctane TEA: Triethylamine TFT: Tack free time

(Evaluation of Physical Properties) As described above, Example 1
No. 14 to 14 and the resin compositions of Comparative Examples 1 to 11 were prepared and cured at room temperature, and a polyethylene film was applied to the surface of the resin composition so that they did not stick (tack free time, TFT ) Was measured to evaluate the curing characteristics. The results are shown in Tables 1 and 2.

As shown in Table 1, Examples 1 to 1 containing a divalent copper compound and an organic amine compound within the scope of the present invention.
The curable resin composition TFT of No. 4 had the longest curing time of 15 hours (Example 7) and the shortest of 5 minutes or less (Examples 1, 2 and 5), and the conventional mercapto group-containing resin composition. It was greatly shortened compared to. Further, it was also clarified that the TFT varies considerably depending on the combination of the divalent copper compound and the organic amine compound, and it was shown that the TFT can be properly used depending on the application by changing the combination of these compounds. On the other hand, as shown in Table 2, 2
Resin compositions of Comparative Examples 1 to 7 containing only one of an organic amine compound and another compound in place of a divalent copper compound, or Comparative Example 8 containing a divalent copper compound in an amount outside the scope of the present invention.
The TFTs of the resin compositions of Nos. 11 to 11 each had the shortest time of 20 hours (Comparative Examples 1 and 2), and the others took 3 days or more and required a long time to cure (Comparative Examples 3 and 11). Therefore,
From such a drastic shortening of the curing time, it is shown that the crosslinking and curing of the polymer having a mercapto group is promoted by the combined use of the divalent copper compound and the organic amine compound, and these compounds synergistically. It is thought that the substance acts to increase the catalytic activity.

[0044]

According to the present invention, the one-pack type of the present invention containing a polymer having a mercapto group, which is well cured by oxygen in the air at room temperature, a divalent copper compound and an organic amine compound. An oxygen-curable resin composition can be obtained. In addition, the one-pack type oxygen-curable resin composition of the present invention has a shorter curing time than conventional resin compositions and can be effectively used for various applications such as adhesives, sealing materials and coating agents.

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Claims (4)

[Claims] 1. A one-component liquid containing (A) an organic polymer having at least two mercapto groups per molecule, (B) a divalent copper compound, and (C) an organic amine compound. Type oxygen-curable resin composition. 2. The component (A) has at least one selected from the group consisting of silicone, polysulfide and polyether in the main chain, and contains at least two mercapto groups per molecule at the terminal. Item 1. A one-pack type oxygen-curable resin composition according to item 1. 3. The one-pack type oxygen-curable resin composition according to claim 1, wherein the component (C) is a secondary or tertiary amine. 4. The weight ratio of component (A) / component (B) is 100.
/0.001-100/5.0, (A) component / (C) component is 100 / 0.001-100 / 5.0 by weight ratio, One liquid in any one of Claim 1 thru | or 3. Type oxygen-curable resin composition.