JPH0415261B2 - - Google Patents

Description

[Detailed description of the invention]

FIELD OF INDUSTRIAL APPLICATION The present invention relates to one-component oxygen-curing compositions based on polymers containing SH groups. (Prior art and problems to be solved by the invention) Polymers containing SH groups can be cured in various ways by utilizing the reactivity of the SH groups, and are used in adhesives, sealants, photosensitive materials, etc. As a composition,
It is used in many applications and fields. The forms of these compositions include a two-component type, in which two components, a base containing a polymer containing an SH group and a curing agent, are mixed and cured immediately before use, and a two-component type, in which the polymer containing an SH group and a curing catalyst are mixed in advance. There are two types: one-component type, which is mixed and stored in a sealed container such as a cartridge, and when used, is taken out of the container and cured by the surrounding atmosphere. In the former two-component type, a compound that causes a curing reaction by reacting with an oxidizing agent such as lead dioxide or an organic peroxide or an SH group such as an epoxy resin is used as a curing agent. However, if the mixing is insufficient or the mixing ratio is not appropriate when mixing immediately before use, problems such as poor curing and deterioration of the physical properties of the cured product such as weather resistance and adhesion may occur. many. Also,
A defoaming step is required after mixing, and this work is complicated, and if incomplete, the inherent bubbles may cause blisters, dents, and poor adhesion. In order to solve these problems in terms of workability and physical properties, various one-component type curing compositions have been considered. That is, a polymer containing an SH group and a curing catalyst are mixed in advance to form one component, stored in a sealed container, taken out from the container when used, and exposed to moisture in the air, oxygen, ultraviolet rays, etc. This is a method of curing in the surrounding atmosphere. Curing due to humidity and ultraviolet rays is not a problem under certain controlled conditions, but under conditions that vary geographically and seasonally, such as outdoors, there is a problem that various properties such as curability and physical properties of the cured product vary greatly. It was hot.
That is, in the case of moisture curing, curing is significantly delayed in low humidity such as in dry regions or in winter, resulting in curing failure, and the composition does not function as a cured composition such as a sealant. Further, in the case of ultraviolet curing, similar problems occur when the amount of ultraviolet rays is low, such as in the shade or in winter. In order to improve the drawbacks of this one-component type,
No. 49582 discloses a catalyst system that combines zinc peroxide as a moisture curing catalyst, a metal chelate compound, and an amine-adsorbing molecular sieve. No satisfactory improvement was achieved in the changes in physical properties caused by the changes. The use of oxygen curing alone uses oxygen in the air whose concentration is almost constant, so it can improve the drawbacks of the one-component type with respect to the curing properties and stability of the physical properties of the cured product. No. 1, No. 2003-11-112 discloses a one-component oxygen-curing composition using a dithiocarbamic acid chelate compound of zinc and a beta-diketone compound of manganese as curing catalysts. However, these oxygen-curing compositions have the problem that the curing catalyst they contain gradually loses their activity during storage, and when used after storage, the curing speed decreases and curing failure occurs. . Storage stability is the most important performance requirement for one-component compositions, and improvements in this property have been strongly desired. In view of the current situation, the present inventors have conducted intensive research to improve these problems of one-component cured compositions, and as a result, have completed the present invention. Therefore, the present invention reduces changes in properties such as curability and physical properties of cured products due to changes in conditions such as ambient humidity and ultraviolet rays during use, which are disadvantages of conventional one-component curable compositions, Another object of the present invention is to provide a one-component oxygen-curing composition with improved curing rate and storage stability. (Means and effects for solving the problems) The present invention provides a polymer containing an SH group, and a compound having the general formula or (However, R ¹ and R ² are hydrogen or a hydrocarbon group having 1 to 18 carbon atoms, R ³ is a hydrocarbon group having 1 to 18 carbon atoms, x
is 1, 2, 3 or 4, M ¹ represents a metal from a group of the periodic table. ) at least one dithiocarbamic acid metal chelate compound (A) 0.001 to 10
Part by weight and general formula or (However, R ⁴ and R ⁵ are hydrogen or a hydrocarbon group having 1 to 18 carbon atoms, R ⁶ is a hydrocarbon group having 1 to 18 carbon atoms, y
is 1, 2, 3 or 4, and M ² represents b or a metal of group b of the periodic table. ) At least one dithiocarbamate metal chelate compound (B) represented by
0.001 to 10 parts by weight of a one-component oxygen curing composition. The SH group-containing polymer used in the present invention contains on average more than one SH group in the molecule, and can be obtained by various methods. To give one specific example, U.S. Patent No.
As described in No. 2466963, a solid polysulfide is synthesized by reacting an alkali polysulfide with an organic polyhalogen compound, and then a portion of the -S-S- bonds of the solid polysulfide is reduced with an alkali hydrosulfide. It can be obtained by More specific examples include U.S. Patent No. 3923748 and
60-18687; polyoxyalkylene polymercaptans as described in U.S. Pat. No. 3,258,495;
Poly(oxyalkylene)-polyester-poly(monosulfide) as described in U.S. Pat. No. 3,817,936
Polythiols, mercaptan-terminated polyacrylates as described in U.S. Pat. No. 3,711,452, U.S. Pat.
There are polymers containing SH groups, such as mercaptan-terminated poly(butadiene-acrylonitrile) described in No. 3,862,975. The dithiocarbamate metal chelate compound (A) used in the present invention is represented by the above general formula, and the metal M ¹ in the formula can be selected from at least one group metal. Among these, chelate compounds of iron, cobalt, or nickel are preferably used alone or in combination, and particularly suitable examples include ferric dimethyldithiocarbamate, ferric diethyldithiocarbamate, and ferric dibutyldithiocarbamate. , ferric N-pentamethylenedithiocarbamate, cobalt dimethyldithiocarbamate, cobalt diethyldithiocarbamate, cobalt dimethyldithiocarbamate, cobalt N-pentamethylenedithiocarbamate, nickel dimethyldithiocarbamate, nickel diethyldithiocarbamate, nickel dibutyldithiocarbamate, N - At least one dithiocarbamate metal chelate compound selected from nickel pentamethylene dithiocarbamate can be used. The amount of the dithiocarbamate metal chelate compound (A) ranges from 0.001 to 10 parts by weight per 100 parts by weight of the SH group-containing polymer. The dithiocarbamate metal chelate compound (B) used in the present invention is represented by the above general formula, and the metal M ² in the formula can be selected from at least one metal of b or group b. Among them, it is preferable to use copper or zinc chelate compounds alone or in combination, and particularly suitable examples include copper dimethyldithiocarbamate, copper diethyldithiocarbamate, copper dibutyldithiocarbamate, copper N-pentamethylenedithiocarbamate, At least one dithiocarbamate metal chelate compound selected from zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate, and zinc N-pentamethylenedithiocarbamate can be used. Dithiocarbamate metal chelate compound
The blending amount of (B) is in the range of 0.001 to 10 parts by weight per 100 parts by weight of the SH group-containing polymer. If the amount of the dithiocarbamate metal chelate compound (A) or the dithiocarbamate metal chelate compound (B) is less than 0.001 parts by weight, sufficient oxygen curability cannot be obtained. In addition, even if the blending amount exceeds 10 parts by weight, no improvement in curability commensurate with the blending amount is observed, and on the contrary, the workability decreases due to changes in the physical properties of the composition during storage, or the physical properties of the cured product change. This can easily lead to a decrease in Various other components can be added to the one-component oxygen-curing composition of the present invention. For example, fillers, pigments, plasticizers, viscosity modifiers, adhesion promoters, antioxidants, ultraviolet absorbers, solvents, etc. can be added depending on the field of use of the composition. (Effects of the Invention) The one-component oxygen-curing composition of the present invention has the features of a one-component type, such as ease of use, and the feature of an oxygen-curing type, that its curability is not affected by the surrounding atmosphere during curing. In addition, by using two types of dithiocarbamate metal chelate compounds together as a curing catalyst, the activity of the curing catalyst does not decrease even during storage of the composition, resulting in excellent storage stability and curing speed. The cured product can always stably exhibit excellent physical properties. Therefore, the composition of the present invention can be effectively used in various applications such as adhesives, sealants, photosensitive materials, paints, and sealants. (Example) The present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these examples. Note that all parts in the examples indicate parts by weight. Example 1 LP-32 (manufactured by Toray Thiokol Co., Ltd.) was used as the SH group-containing polymer and kneaded according to the following formulation to prepare a one-component oxygen-curing composition of the present invention. (Composition) Ingredients Parts by weight LP-32 100 Calcium carbonate 60 Titanium oxide 20 Dioctyl phthalate 40 Curing catalyst Ferric dimethyldithiocarbamate 0.8 Copper dimethyldithiocarbamate 0.5 After preparation, the resulting composition was sealed in a glass container with a lid. It was placed in a container and its performance was evaluated in the following manner. The results are shown in Table 1. Curing speed: Take out the composition from a sealed container, depth 20mm, width
It was filled in a 15 mm aluminum container, and the cured film thickness (mm) generated from the surface was measured at 20℃, 65%RH, and
Measured under the conditions of 20°C and 20%RH. Physical properties of cured product: Take out the composition from a sealed container and check JIS A 5758.
A mortar H-type test piece was prepared as described in 20℃ and 65℃.
%RH and after being left for 30 days under the conditions of 20℃ and 20%RH,
A tensile test was conducted in accordance with JIS A 5758, and 50% tensile stress (M ₅₀ ), tensile stress at break (T _b ), and elongation at break (E _b ) were measured. Storage Stability After leaving the composition in a closed container at 50℃ for 30 days, the curing rate was measured in the same manner as at 20℃ and 65%RH. compared with. Comparative Example 1 In the formulation of Example 1, 8 parts by weight of zinc peroxide, 0.5 parts by weight of zinc dibutyldithiocarbamate, and 1.0 parts by weight of manganese 2-ethylhexanoate were used as the curing catalyst to create a one-component curing composition for comparison. was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1. As shown in Table 1, the curing rate and the physical properties of the cured product varied depending on the humidity, and especially when the humidity was low, the curing rate was extremely slow and the physical properties of the cured product also decreased. Moreover, the storage stability was also insufficient. Example 2 Using Permapol P-785 (trade name of Nippon Shokubai Kagaku Kogyo Co., Ltd.) as a polymer containing an SH group,
A one-component oxygen curing composition of the present invention was prepared by kneading according to the following formulation. (Blending and disposal) Ingredients Parts by weight Permapol P-785 100 Calcium carbonate 320 Titanium oxide 30 Dioctyl phthalate 140 Curing catalyst Ferric dimethyldithiocarbamate 0.1 Zinc dibutyldithiocarbamate 0.3 Using the obtained composition, the same procedure as in Example 1 was carried out. I made an evaluation. The results are shown in Table 1.

[Table] As is clear from Table 1, the composition of the present invention was not affected by humidity and was found to provide sufficient curing speed and physical properties of the cured product even at low humidity of 20° C. and 20% RH. Furthermore, the curing rate did not change even after storage at 50°C for 30 days, indicating that it was a one-component oxygen-curing composition with excellent storage stability.

Claims (1)

[Claims] 1. A polymer containing an SH group, and the polymer 100
Per part by weight, general formula or (However, R ¹ and R ² are hydrogen or a hydrocarbon group having 1 to 18 carbon atoms, R ³ is a hydrocarbon group having 1 to 18 carbon atoms, x
is 1, 2, 3 or 4, M ¹ represents a metal from a group of the periodic table. ) at least one dithiocarbamic acid metal chelate compound (A) 0.001 to 10
Part by weight and general formula or (However, R ⁴ and R ⁵ are hydrogen or a hydrocarbon group having 1 to 18 carbon atoms, R ⁶ is a hydrocarbon group having 1 to 18 carbon atoms, y
is 1, 2, 3 or 4, and M ² represents b or a metal of group b of the periodic table. ) At least one dithiocarbamate metal chelate compound (B) represented by
A one-component oxygen curing composition comprising 0.001 to 10 parts by weight.