JP3464721B2 - One-component oxygen-curable resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention is based on a silicone containing at least two mercapto groups per molecule, and is a one-pack type oxygen-curable resin composition which can be used as an adhesive, a sealing material or a coating agent. Regarding things.

[0002]

2. Description of the Related Art For a polymer having a mercapto group in its molecule, various curing methods utilizing the reactivity of the mercapto group have been considered. As its form, a two-pack type in which a base material having a polymer and a curing agent are mixed and cured immediately before use, a polymer and a curing catalyst are mixed in advance, stored in a closed container and stored, at the time of use. There are two types, one-pack type that is put out of the container and cured by the surrounding atmosphere.

Of these, in the two-pack type resin composition, lead dioxide, which acts as an oxidizing agent for the mercapto group of the polymer, and organic peroxides are used as a curing agent. But,
The two-component type resin composition may cause various problems such as insufficient curing before use, bubbles contained during mixing, poor curing, deterioration of physical properties of the cured product, and the like.
On the other hand, since the one-pack type resin composition has the mercapto group-containing polymer and the curing catalyst mixed in advance, there is no problem like the two-pack type, and the construction at the site is easy. For this reason, it is gradually shifting from the two-pack type to the one-pack type.

[0004]

However, in the case of a one-pack type resin composition, there is a method of crosslinking and curing by a surrounding atmosphere such as humidity and oxygen in the air. Since the conditions also change seasonally, there has been a problem that the curability, the physical properties of the cured product, 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, a curing method using oxygen whose concentration is almost constant in air has been studied.

For example, JP-B-58-17549 describes an oxygen-curable resin composition containing a dithiocarbamic acid chelate compound of zinc and a β-diketone compound of manganese as a curing catalyst, and JP-B-4-15261. The official gazette describes an oxygen-curable resin composition containing 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 is gradually deactivated during storage, or that the curing rate of the surface and deep areas 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 the moisture curing is large in the end, the problems that occur during the moisture curing as described above still remain,
I am not getting satisfactory results. Therefore, an object of the present invention is to reduce the influence of changes in various conditions such as ambient humidity at the time of use, which is a drawback of the conventional one-pack type curable resin composition, and to improve various characteristics of the resin composition such as curability. One object of the present invention is to provide a one-pack type oxygen-curable resin composition that can reduce the change in

[0008]

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,
It was found that when a trivalent iron compound and an organic amine are added to a silicone containing a mercapto group, a composition having good surface and deep curability can be obtained at room temperature due to oxygen in the air, and the present invention is completed. I arrived.

That is, the present invention is a one-pack type containing (A) a silicone having at least two mercapto groups per molecule, (B) a trivalent iron compound, and (C) an organic amine compound. An oxygen-curable resin composition is provided.
Weight ratio of component (A) / component (B) is 100 / 0.001
~ 100/10, (A) component / (C) component in a weight ratio of 1
It is preferably from 00 / 0.001 to 100 / 5.0.

The present invention will be described in detail below. The silicone used in the present invention may be one having at least two mercapto groups in one molecule.

Specific examples thereof include X-22-167B manufactured by Shin-Etsu Chemical Co., Ltd. As is known, a hydroxy-terminated silicone and a mercaptoalkyltrialkoxysilane are used as a divalent tin catalyst, For example, it can also be synthesized by reacting in the presence of tin dioctylate. Such mercapto group-containing silicones may be used alone or in combination of two or more kinds.

Further, the silicone having two or more mercapto groups per molecule used in the present invention may be used in combination with a polymer having two or more mercapto groups in the molecule. As a polymer that can be used together, Nippon Shokubai Co., Ltd., whose main chain is polypropylene glycol (PPG)
Examples include modified polysulfide (Permapol P2) manufactured by Toray Thiokol Co., Ltd., whose main chain is holisulfide (Thiocol LP), and the like.

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 represented by the following general formula (1). Examples thereof include poly (oxyalkylene glycol) having a mercapto group terminal.

[0014]

[Chemical 1]

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

The content of the mercapto group in the base mercapto group-containing polymer is 0.06 to 7% by weight, particularly 0.1 to 2% by weight, in view of workability and physical properties before curing. preferable.

Specific examples of the trivalent iron compound used in the present invention include iron (III) ammonium citrate, iron (III) ammonium sulfate, iron (III) ammonium oxalate, and iron.
(III) Acetylacetonate, iron (III) benzoylacetonate, iron chloride (III), iron (III) citrate, iron (III) decanoate, ethoxyiron (III), iron (III) ethylate, oxidative hydroxylation Iron (III), isopropoxy iron (III), iron naphthenate (III), iron nitrate (III), iron oxide (III), iron perchlorate (III), iron phosphate (III), phthalocyanine iron (III) ), Iron (III) sulfate, iron (III) dimethyldithiocarbamate, and the like.

Of these, iron (III) acetylacetonate, iron (III) dimethyldithiocarbamate and the like are particularly preferred because of their high activity. These trivalent iron compounds may be used alone or in combination of two or more. The addition amount of the trivalent iron compound used in the present invention is the above-mentioned polymer 10 having at least two mercapto groups per molecule.
0.001 to 10 parts by weight, particularly 0.
It is preferably from 01 to 5.0 parts by weight. When the amount of the trivalent copper compound added is less than 0.001 part by weight, sufficient curability cannot be obtained when the curable resin composition is cured, and 10
If it exceeds 5 parts by weight, the storage stability becomes poor.

The organic amine compound used in the present invention is 2
Preferably tertiary, tertiary amines and guanidines,
Specifically, triethylenediamine, N-methylmorpholine, 1,8-diazabicyclo [5.4.0] -undecene-7 (DBU), triethylamine, N, N-dimethylcyclohexylamine, N, N, N ', N'-tetramethylethylenediamine (TMEDA), N, N,
N ', N'-tetramethylpropane-1,3-diamine (TMPDA), N, N, N', N ", N" -pentamethyldiethylenetriamine (PMDETA), N, N,
N ', N ", N" -pentamethyldipropylenetriamine (PMDPTA), tetramethylguanidine (TM
G), N, N'-dimethylpiperazine (DMP), N-
Methyl-N '-(2-dimethylamino) -ethylpiperazine (TMNAEP), N. (N', N'-dimethylaminoethyl) morpholine (DMAEMO), 1,2-dimethylimidazole (DMIZ), diethylaminomethanol, dimethyl Aminoethoxyethanol (DMAE
E), N, N, N'-trimethylaminoethylethanolamine (TMAEEA), N-methyl-N '-(2-
Hydroxyethyl) -piperazine (MHEP), N-
(2-Hydroxyethyl) morpholine (HEMO), bis (2-dimethylaminoethyl) ether, ethylene glycol bis (3-dimethyl) -aminopropyl ether and the like can be mentioned.

Of these, secondary amines and tertiary amines and guanidines are preferred from the viewpoint of catalytic activity, and specifically, 1,8-diazabicyclo [5.4.0] -undecene-7 (DBU) and tetramethyl. Guanidine (TMG)
And the like are preferred because of their high activity. The above organic amines may be used alone or in combination of two or more.

The amount of the organic amine compound added is 0.001 to 5.0 parts by weight, particularly 0.05 to 2.0 parts by weight, based on 100 parts by weight of the silicone having at least two mercapto groups per molecule. It is preferably part by weight.
When the amount of the organic amine compound is less than 0.001 part by weight, sufficient curability cannot be obtained when the resin composition is cured,
If it exceeds 5.0 parts by weight, the 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.

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, and trioctyl phthalate. Octyl phosphate and the like can be 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 specifically,
Examples thereof include vinyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and isopropyltriisostearoyl titanate.

When a solvent is added, aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, heptane and octane, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, cellosolve acetate and butyl cellosolve. Ether ester such as acetate can be used.

As an example of the method for producing the one-pack type oxygen-curable resin composition of the present invention, a mercapto group-containing silicone is used.
A trivalent iron compound, an organic amine compound, and other compounding agents are added, and the viscosity is adjusted by diluting with a solvent or the like, if necessary, and at 60 ° C. in a nitrogen atmosphere, for example, a planetary mixer with a vacuum device, etc. It can be performed by mixing with. The curable resin composition produced as described above is stored by blocking oxygen by filling with nitrogen or the like until use, and is brought into contact with oxygen in the air at the time of use to be crosslinked and cured to obtain a resin cured product. The one-pack type oxygen-curable resin composition of the present invention is useful as an adhesive, a sealing material, a coating agent and the like.

[0029]

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
LP among organic polymers having one or more mercapto groups
40 is polysulfide manufactured by Toray Thiokol Co., Ltd., and Permapol is modified polysulfide manufactured by Nippon Shokubai Co., Ltd.

(Synthesis of SH group-containing silicone) A round-bottomed flask was charged with 1000 g of terminal hydroxydimethyl silicone having a molecular weight of about 35,000, and then 0.2 parts of tin dioctylate was added.
12 g of trimethoxy-3-mercaptopropylsilane was added thereto, and the mixture was reacted at 70 ° C. for 3.5 hours. After completion of the reaction, the by-product methanol and unreacted trimethoxy-3-mercaptopropylsilane were removed under the condition of 110 ° C./2 mmHg to obtain a colorless and transparent SH group-containing silicone having a viscosity of 23 Pa · s.

(Examples 1 to 9) The SH group-containing silicone synthesized above was mixed with the respective compounding agents in the amounts shown in Table 1 to obtain 60
The mixture was kneaded at 0 ° C. in a nitrogen atmosphere to obtain one-pack type oxygen-curable resin compositions of Examples 1-9.

[0033]

[Table 1]

Note) The amount of each composition component means parts by weight. LP40: Polysulfide (Toray Thiokol Co., Ltd.)
Permapol: modified polysulfide (Nippon Shokubai Co., Ltd.)
Plasticizer: butylbenzyl phthalate DBU: 1,8-diazabicyclo [5.4.0] -undecene-7 TMG: tetramethylguanidine TFT: tack free time

(Comparative Examples 1-10) 100 parts by weight of LP4
0, the organic amine compound shown in Table 2 is blended in the amount shown in Table 2, or the trivalent iron compound shown in Table 2 is added to Table 2.
Resin compositions of Comparative Examples 1 to 10 were obtained in the same manner as in Example 1 except that the amounts shown in Table 1 were added. The compositions of Comparative Examples 7 and 9 were immediately cured during or after the kneading and could not be applied.

[0036]

[Table 2]

Note) The amount of each composition component means parts by weight. Plasticizer: butylbenzyl phthalate DBU: 1,8-diazabicyclo [5.4.0] -undecene-7 TMG: tetramethylguanidine TFT: tack free time

Example 10 To 100 parts by weight of the SH group-containing silicone synthesized above, 80 parts by weight of calcium carbonate,
Plasticizer 10 parts by weight, DBU 0.6 parts by weight, iron (III)
Example 1 was compounded with 0.5 part by weight of acetylacetonate.
A resin composition of Example 10 was obtained in the same manner as in. The obtained resin composition was cured in an environment of a temperature of 20 ° C. and a humidity of 50%, and the cured film thickness was measured immediately after the initiation of curing.
The results are shown in Table 3 below.

(Comparative Examples 11 and 12) Resin compositions of Comparative Examples 11 and 12 were obtained in the same manner as in Example 10 except that LP40 or permapol was used in place of the SH group-containing silicone. The cured film thickness was measured in the same manner as in Example 10. The results are shown in Table 3 below.

[0040]

Note) The amounts of the composition components are parts by weight. LP40: Polysulfide (Toray Thiokol Co., Ltd.)
Permapol: modified polysulfide (Nippon Shokubai Co., Ltd.)
DBU: 1,8-diazabicyclo [5.4.0] -undecene-7 plasticizer: butylbenzyl phthalate

(Evaluation of Physical Properties) As described above, Example 1
The curable resin compositions of Nos. 10 to 10 and the resin compositions of Comparative Examples 1 to 8 were produced 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 to 3.

As described above, a system in which a trivalent iron compound and an organic amine compound are blended with a silicone having two or more mercapto groups in the molecule has a high catalytic activity in a small amount, and has a surface and deep-curing property. It can be seen that this is a good composition.

[0044]

Industrial Applicability According to the present invention, a trivalent iron compound and an organic amine compound based on a silicone having at least two mercapto groups in the molecule, which cures well with oxygen in the air at room temperature, are used. It is possible to obtain a one-pack type oxygen-curable resin composition containing the present invention. 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.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI C09K 3/10 C09K 3/10 G (56) References JP-A-53-85848 (JP, A) JP-A-57-38852 ( JP, A) JP 58-168658 (JP, A) Special table Sho 56-501603 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 83/00-83/16 C08K 3/00-13/08

Claims (2)

(57) [Claims] 1. A one-pack type comprising (A) a silicone having at least two mercapto groups per molecule, (B) a trivalent iron compound, and (C) an organic amine compound. Oxygen curable resin composition. 2. A weight ratio of component (A) / component (B) is 100.
/0.001-100/10, (A) component / (C) component are 100 / 0.001-100 / 5.0 by weight ratio, The one-pack oxygen-curable resin composition according to claim 1. .