JPH09279047A - Room-temperature curing two-package composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a room-temperature curing two-package composition which can be rapidly cured and gives a cured material having rubber-like flexibility t eliminate such shortcomings of conventional modified silicone-based curable compositions that they do not rapidly cure and cannot be applied to a part where moisture hardly enters. SOLUTION: This composition consists of component A containing 100 pts.wt. modified silicone compound having at least one reactive silicon group in the molecule, 0.1-8 pts.wt. silanol condensation catalyst and 1.8-70 pts.wt. curing agent for epoxy resin, and component B containing 100 pts.wt. modified silicone compound, 25-75 pts.wt. epoxy resin and 0.1-20 pts.wt. water. Preferably, the component A and the component B respectively contain calcium carbonate in amounts of 5-150 pts.wt. and 5-100 pts.wt. based on 100 pts.wt. modified silicone compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a room temperature curable two-part mixed type composition which can be widely used in various fields such as adhesives and coating agents.

[0002]

2. Description of the Related Art Conventionally, as a room temperature-curable two-component mixed type composition, various rubbers have been added to the epoxy type curable composition in order to soften and impart flexibility to the composition. It is known that the main chain and / or side chain of an epoxy compound is modified with a urethane group or various rubbers.

Recently, for example, Japanese Patent Application Laid-Open No. 61-26872
No. 0 and JP-A-4-1220, a curable composition comprising a modified silicone, an epoxy resin, and an epoxy curing agent has been proposed as a composition exhibiting rubber elasticity. This kind of composition is used in an adhesive portion which is repeatedly subjected to distortion and stress by making use of its rubber properties, and greatly contributes to improvement of adhesive reliability and adhesive durability.

[0004]

However, while the above-mentioned modified silicone / epoxy resin / epoxy curing agent-based curable composition has the above-mentioned excellent properties, it has a slow curing rate at room temperature and low temperature. There has been a problem that the use is limited in the fields of bonding and assembling in the production line, coating, and painting in which quick curing is required.

Further, for adhesion at a place where it is difficult for moisture to enter (for example, adhesion between adherends having a large area, which are difficult to pass moisture such as metal), only the portion in contact with the surrounding air is cured. However, the cured product blocks moisture from reaching the inner uncured portion, and as a result, it takes a lot of time to completely cure the adhesive.

The object of the present invention is to overcome the above-mentioned drawbacks in that the conventional modified silicone-based curable composition does not cure rapidly and cannot be applied to a portion where moisture cannot easily enter.
An object of the present invention is to provide a room temperature curable two-part mixed type composition which can be rapidly cured and has a rubber-like flexibility.

[0007]

The room-temperature-curable two-component mixed composition according to the present invention comprises 100 parts by weight of a modified silicone compound having at least one reactive silicon group in one molecule, and a silanol condensation catalyst of 0. A agent containing 1 to 8 parts by weight and 1.8 to 70 parts by weight of a curing agent for epoxy resin;
It is composed of the agent B containing 25 to 75 parts by weight of an epoxy resin and 0.1 to 20 parts by weight of water with respect to 100 parts by weight of the modified silicone compound.

In a preferred embodiment of the invention, A
The agent contains 5 to 150 parts by weight of calcium carbonate with respect to 100 parts by weight of the modified silicone compound, and the agent B contains 5 to 100 parts by weight of calcium carbonate with respect to 100 parts by weight of the modified silicone compound.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Each constituent component of the composition of the present invention will be described in more detail below.

The modified silicone compound, which is one of the constituents of the agent A, has the function of imparting rubber-like flexibility to the cured product obtained from the composition of the present invention. It is a silicone compound having one reactive silicon group. Examples of the polymer compound used to form the skeleton of this compound include polyethers obtained by polymerization of cyclic ethers such as propylene oxide, ethylene oxide, and tetrahydrofuran;
Examples thereof include polyether series obtained by condensation of dibasic acid such as adipic acid and glycol or ring-opening polymerization of lactones. These polyether compounds are preferable in that they have good water resistance, are inexpensive, are easy to introduce a reactive silicon group into the molecular terminal, and are easy to handle as a liquid. Compounds having a reactive silicon group at least at one end of the polypropylene oxide are particularly preferred.

The modified silicone compound may have a functional group capable of reacting with an epoxy resin as long as it gives flexibility to the cured product obtained from the composition of the present invention.

Examples of the functional group capable of reacting with the epoxy resin include an amino group, a mercapto group, an epoxy group and a carboxyl group. Further, the reactive silicon group contains a silicon atom to which a hydrolyzable group or a hydroxyl group is bonded,
A group that can be crosslinked by a silanol condensation reaction. Examples of the hydrolyzable group include general groups such as a halogen atom, an alkoxy group, an acyloxy group, an aminooxy group, and a mercapto group, but the hydrolyzable group is mild and easy to handle. Is particularly preferable. A typical example of the reactive silicon group is described in JP-A-61-2.
And the methyldimethoxysilyl group as disclosed in 68720. The modified silicone compound as described above is specifically manufactured by Kanegafuchi Chemical Industry under the trade name "SAT20".
It is marketed as "0" or "SAT030".

The silanol condensation catalyst, which is another constituent of the agent A, acts as a catalyst for curing the modified silicone compound. Examples of the silanol condensation catalyst include dibutyltin dilaurate, dibutyltin dioxide,
Organotin catalysts such as dibutyltin phthalate, dibutyltin bisthioglycolic acid ester salt and dibutyldichloride are generally used. As the silanol condensation catalyst, a commercially available product "DEDC" manufactured by Sankoki Gosei Co., Ltd. can also be used. Dibutyltin phthalate is particularly preferred.

The mixing ratio of the silanol condensation catalyst is 0.1 to 8 parts by weight, preferably 0.5 to 5 parts by weight, and more preferably 1 to 4 parts by weight, based on 100 parts by weight of the modified silicone. If the compounding ratio of the silanol condensation catalyst is less than 0.1 parts by weight, a sufficient effect as a condensation catalyst of the modified silicone may not be exhibited and an uncured portion may remain. On the contrary, even if added in excess of 8 parts by weight. No improvement in the catalytic effect was observed, and the diluting action may occur.

The epoxy resin curing agent which is another component of the agent A is an aliphatic polyamine, a modified aliphatic polyamine, an amidoamine, a polyamide, an alicyclic polyamine, a modified alicyclic polyamine, a modified aromatic polyamine, Three
It is an amine compound such as a secondary amine, but is not limited to these amine compounds, and a general epoxy resin curing agent can be used. Specific examples of epoxy resin curing agents include polyethylene tetramine, tetraethylene pentamine, diethylaminopropylamine, N-aminoethylpiperazine, isophoronediamine, 2,4,6-tris (dimethylaminomethyl) phenol, and the like. From the viewpoint of physical properties of the cured product, a tertiary amine is desirable. As a curing agent for the epoxy resin, a tertiary amine compound “DMP-30” manufactured by Yuka Shell may be used.

The mixing ratio of the curing agent of the epoxy resin is 1.8 to 70 parts by weight with respect to 100 parts by weight of the modified silicone, and preferably 1.8 to 7 parts with respect to 100 parts by weight of the modified silicone.
It is 6 to 100 parts by weight with respect to 0 parts by weight and 100 parts by weight of the epoxy resin blended. The mixing ratio of the curing agent is 1.
If the amount is less than 8 parts by weight, a sufficient effect as a curing agent may not be obtained, and conversely, if the amount exceeds 70 parts by weight, the effect is not improved and the curing agent acts as a plasticizer and aggregates. It may lead to a decrease in strength.

The epoxy resin, which is one of the constituents of the agent B, acts to increase the strength of the adhesive after curing. Examples of the epoxy resin include epichlorohydrin-bisphenol A type epoxy resin, epichlorohydrin-bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, and urethane-modified epoxy resin. However, the epoxy resin that can be used in the composition of the present invention is not limited to the above examples, and generally used epoxy resins can be used. From the viewpoint of reactivity upon curing, it is preferable to use an epoxy resin having a plurality of epoxy groups in one molecule. A commercial product made by Yuka Shell Epoxy Co., Ltd. "Epicoat 82"
8 "can also be used.

The mixing ratio of the epoxy resin is 25 to 75 parts by weight, preferably 3 parts by weight based on 100 parts by weight of the modified silicone.
The amount is 0 to 70 parts by weight, more preferably 40 to 60 parts by weight. If the mixing ratio of the epoxy resin is less than 25 parts by weight, the reinforcing effect of the cured product may not be obtained and the adhesive strength may be lowered. On the contrary, if it exceeds 75 parts by weight, the cured product may become brittle.

Water, which is the other component of the agent B, is for promoting the curing of the above-mentioned modified silicone, and general industrial water or the like is used. The mixing ratio of water is 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the modified silicone. If the mixing ratio of water is less than 0.1 part by weight, the curing-accelerating effect of the modified silicone is low, and if it exceeds 20 parts by weight, water remains on the interface between the adhesive and the adherend when cured depending on the adherend. ,
The adhesive strength may not be sufficiently expressed, and the fractured state may be interface fracture.

The composition of the present invention may contain an inorganic filler. Examples of the inorganic filler include heavy calcium carbonate, colloidal light calcium carbonate, surface-treated finely powdered calcium carbonate, talc, mica powder, silica sand, carbon black, titanium oxide, etc., and those usually used for adhesives are used. it can. In particular, calcium carbonate-based fillers such as heavy calcium carbonate, colloidal light calcium carbonate and surface-treated finely powdered calcium carbonate are preferable.

Here, colloidal light calcium carbonate is light calcium carbonate in a special dispersed state,
It has an average particle diameter of 0.1 to 10 μm and an apparent specific gravity of about 0.2 g / ml.

The finely divided calcium carbonate is obtained by further pulverizing light calcium carbonate.
It has a mean particle size of 15 μm and an apparent specific gravity of 0.25 to 0.4 g / ml.

The surface-treated fine calcium carbonate is obtained by treating the surface of the above-mentioned colloidal light calcium carbonate with a fatty acid or rosin to make the surface hydrophobic.

As the calcium carbonate, hydrous calcium carbonate which has not been surface-treated can also be applied.

Since the modified silicone constituting the adhesive extremely dislikes the water content in the system during storage, the agent A containing the modified silicone contains calcium carbonate having a small water content, which has been surface-treated as described above. It is desirable to add.

As calcium carbonate, surface-treated calcium carbonate "Shiraenka CC" manufactured by Shiraishi Calcium Co., Ltd. and untreated calcium carbonate "Whiten S" manufactured by Shiraishi Calcium Co., Ltd.
Commercially available products such as "B" can also be used.

The blending ratio of calcium carbonate is 5 to 150 parts by weight of calcium carbonate per 100 parts by weight of the modified silicone compound in agent A, and 5 to 100 parts by weight of calcium carbonate in 100 parts by weight of the modified silicone compound of agent B. is there.

If the blending ratio of calcium carbonate is less than 5 parts with respect to 100 parts by weight of the modified silicone compound in each of the agents A and B, the cohesive force of the cured product will not be sufficiently expressed,
On the contrary, when the amount of the agent A exceeds 150 parts by weight and the amount of the agent B exceeds 100 parts by weight, the workability of the bonding work is deteriorated and the cured product is not adversely affected.

In the composition of the present invention, since the required amount of water is added to the agent B, sufficient adhesive strength can be obtained even when it is difficult to penetrate moisture such as adhesion between adherends having a large area and low moisture permeability. It is possible to obtain a sufficient cured product in a shorter time than in the case where water is not added at the time of other adhesion.

[0030]

Example 1 As a modified silicone resin, "CYRIL SAT030" manufactured by Kanegafuchi Chemical Industry Co., Ltd., "DEDC" manufactured by Sansha Machine Synthesis Co., Ltd. was used as a silanol condensation catalyst, and an oil-based shell was used as a curing agent for epoxy resin. Company's tertiary amine compound "DMP
-30 "and surface-treated calcium carbonate (" Shiraenka CC "manufactured by Shiraishi Calcium Co., Ltd.) as an inorganic filler,
The agent A was prepared at the blending ratio shown in Table 1.

On the other hand, "Epicoat 828" manufactured by Yuka Shell Epoxy Co., Ltd. was used as an epoxy resin, industrial water was used as water, and untreated calcium carbonate ("Whiten SB" manufactured by Shiraishi Calcium Co., Ltd.) was used as an inorganic filler. The agent B was prepared at the compounding ratio shown in Table 1.

In this way, room temperature curability consisting of agent A and agent 2
A liquid mixed type adhesive was prepared.

Examples 2 to 4 and Comparative Examples 1 to 3 Adhesives were prepared in the same manner as in Example 1 except that the mixing ratios of the constituents of agents A and B were changed to the values shown in Table 1. did.

[0034]

[Table 1]

Performance test a. Comparison of curing speeds 200 g of agent A and B which had been left in the atmosphere at 20 ° C in advance
Take 100 g of the agent and mix it to 200 g of the obtained adhesive.
The viscosity was determined from the value after 10 rotations of the adhesive after a lapse of a predetermined time at 20 ° C. with a B8U type viscometer. The results of Example 1 and Comparative Example 1 are shown in the graph of FIG.

As is apparent from this graph, the room temperature curable two-part composition according to the present invention was cured rapidly.

B. Storage stability of adhesive agent 200 g of agent A and B that have been left in the atmosphere at 20 ° C in advance
After taking 100 g of the agent and mixing it, the resulting adhesive was made to be able to block moisture by nitrogen purging, and after storing it in an oven at 40 ° C for 3 months, its appearance was evaluated by visual observation in two stages. did. The evaluation criteria for observation are as follows.

◯: No particular change x: Change in appearance such as thickening

The evaluation results are shown in Table 2.

C. Adhesive mixability The mixing difficulty when mixing agent A and agent B with a spatula,
It was evaluated on a two-grade scale based on the magnitude of the resistance applied to the spatula. The evaluation criteria for observation are as follows.

◯: Can be easily mixed ×: Mixing is difficult

The evaluation results are shown in Table 2.

D. Shear Tensile Strength 200 g of agent A and 100 g of agent B were mixed to prepare an adhesive. Two 25 mm × 150 mm (thickness 2 mm) aluminum plates were bonded with the above adhesive so that the bonding area was 25 mm × 20 mm, and cured at 20 ° C. for 7 days to prepare a test piece. Each aluminum plate constituting the test piece was pulled at a pulling speed of 200 mm / min, and the shearing tensile strength was calculated by converting the strength at that time per cm ² .

The results are shown in Table 2.

E. Initial adhesive strength development time After producing a test piece by the above method, a shear tensile strength test is conducted by the same test method as above, and the strength is 10 kg.
The time required to reach / cm ² was determined.

The evaluation results are shown in Table 2.

[0047]

[Table 2]

As is clear from Table 2, when the adhesives of the examples were used, good evaluation was obtained in all test items.

[0049]

INDUSTRIAL APPLICABILITY As described above, the room-temperature-curable two-component composition according to the present invention can be cured rapidly, and the cured product has rubber-like flexibility, and can be applied to a place where moisture is blocked. Since it is applicable, it is particularly effective for improving work efficiency and reliability when it is used as a flexible protective coating agent, potting agent, sealing agent, adhesive agent and the like.

[Brief description of drawings]

FIG. 1 is a graph showing the relationship between curing time and viscosity.

Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location C09J 163/00 JFL C09J 163/00 JFL // (C08L 101/10 63:00)

Claims (2)

[Claims] 1. To 100 parts by weight of a modified silicone compound having at least one reactive silicon group in one molecule, 0.1 to 8 parts by weight of a silanol condensation catalyst and 1.8 to 70 parts by weight of a curing agent for an epoxy resin. A room temperature-curable two-component mixture type composition comprising an agent A containing 10 parts by weight and an agent B containing 25 to 75 parts by weight of an epoxy resin and 0.1 to 20 parts by weight of water with respect to 100 parts by weight of the modified silicone compound. 2. The agent A contains 5 to 150 parts by weight of calcium carbonate based on 100 parts by weight of the modified silicone compound, and the agent B contains 5 to 100 parts by weight of calcium carbonate based on 100 parts by weight of the modified silicone compound. The composition as described.