JP2001152092A - Primer composition for jointing to two-component type silicone sealing material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a primer composition that shows sufficient adhesion, when the PIB sealing material is jointed to the two-component type silicone sealing material that was applied before a long period of time, and can give good adhesion in the case of the PIB sealing material to the base material, for example, anodically oxidized aluminum or the like. SOLUTION: The objective primer composition for jointing to the two- component type silicone sealing material comprises the primer basic components that is composed of a paraffin plasticizer solution including a silicone polymer that bears alkoxysilyl groups on the molecular chain ends and bears the alkylene structure as the main chain structure, an organic solvent, an organic titanic acid ester, a tin hardening catalyst and an aminosilane coupling agent, and additionally a ketimine silane coupling agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a two-component silicone-based sealing material which is pre-punched.
It is described as “PIB”. ) A primer composition for joining to a two-component silicone sealing material used when post-installing a sealing material, or a PIB-based sealing material, such as an inorganic material such as metal, ceramics, cement, or mortar, or a plastic. The present invention relates to a primer composition which imparts good adhesiveness by being filled in various base materials made of an organic material.

[0002]

2. Description of the Related Art Sealing materials used for sealing interior and exterior joints of buildings and vehicles, and around window frames, include:
There are various types such as a silicone type, a modified silicone type, a polysulfide type and a urethane type, and these are selected and used depending on the type of a base material and the type of joint to be applied. In particular, silicone-based sealing materials are excellent in surface weather resistance and durability, but have a problem of contamination due to seepage of silicone oil components around joints. In order to solve these problems, in recent years, a sealing material composed of a silicone-based polymer having a main chain structure of isobutylene, that is, a PIB-based sealing material has been used for heat resistance, weather resistance,
It has been developed as having excellent water resistance and paintability. This PIB-based sealing material has no defect of contamination due to exudation of a silicone oil component around joints of the conventional silicone-based sealing material, and is excellent in surface weather resistance and durability. It can be replaced by a sealing material.

On the other hand, at a site, a sealing material that has been deteriorated after a long time has passed since the construction is removed from the old sealing material when it is determined that the performance as the sealing material cannot be maintained in the future. Materials are installed. In such replacement of the sealing material, the old sealing material is not completely removed, so that the newly applied sealing material needs to adhere well to the old sealing material.

[0004] In the above replacement, PIB which replaces the conventional silicone-based sealing material described above.
Similarly, in the case of the system sealing material, it is necessary to be able to securely and firmly adhere to the two-component type silicone sealing material that has been previously applied. It is the primer that is important in imparting firm adhesion to the pre-sealed sealing material in this replacement.

However, in the sealing material industry,
There is no primer that exhibits good adhesion to a two-component silicone sealing material, and there has been a demand for the development of a primer in which a PIB-based sealing material exhibits good adhesion to a two-component silicone sealing material.

Under such circumstances, as primers for splicing to silicone-based sealing materials, JP-A-11-209701 and JP-A-11-209 are known.
No. 702 is disclosed. These are low molecular weight PIs
A primer comprising a B polymer, a silane coupling agent, an organic titanate, and a tin catalyst. In particular, Japanese Patent Application Laid-Open No. H11-209701 has a basic component containing an organic titanate. Kaihei 11
No. 209702 is an isocyanate group-containing silane coupling agent or an amino group-containing silane coupling agent containing a silane coupling agent as a basic component. In any case, the silane coupling agent is a primer that is an isocyanate group-containing silane coupling agent and an amino group-containing silane coupling agent. These primers are described in the above-mentioned publication as exhibiting good adhesiveness when a PIB-based sealing material is spliced with a silicone-based sealing material that has been previously applied. However, these primers show good adhesion when a post-punched PIB-based sealing material is passed on to a pre-shot silicone-based sealing material that has not passed for a long time after the application, but has passed for a long time after the application. P is applied to the silicone sealing material that has been pre-punched.
In the case where an IB-based sealing material is used, there is a problem that the adhesiveness is poor and not sufficient.

[0007]

The problem to be solved by the present invention is to provide a primer which solves the above problems. In other words, PI is applied to a two-component silicone-based sealing material
Shows sufficient adhesiveness when passing B-based sealing material (post-cast), and also provides extremely good adhesion when applying PIB-based sealing material to base materials such as alumite such as inorganic materials. The purpose of the present invention is to provide a primer composition.

[0008]

Means for Solving the Problems The inventors of the present invention have studied various materials for a primer composition for improving the adhesion to a PIB-based sealing material, and have particularly studied various silane coupling agents. They have found out that the silane coupling agent is extremely excellent and have found the means of the present invention.

That is, the means for solving the above-mentioned problems of the present invention is that, in the first aspect of the present invention, a ketimine-based silane coupling agent is added to a primer basic component containing a silicone-based polymer. It is a primer composition for splicing to a two-component silicone-based sealing material.

In the second aspect of the present invention, the primer basic component comprises a paraffin-based plasticizer solution containing a silicone-based polymer having an alkoxysilyl group at the molecular end and having a main chain structure of an alkylene structure, an organic solvent, and an organic titanate. 2. The method according to claim 1, comprising an ester, a tin-based curing catalyst and an amino-based silane coupling agent.
It is a primer composition for joining to a component-type silicone sealing material.

The basic components of the primer of the present invention include the above silicone polymer, an organic solvent such as toluene, xylene and hexane, an organic titanate such as tetranormal butyl titanate and tetraisopropyl titanate, and dibutyltin bisacetylacetonate. Curing catalyst with high silanol catalytic activity and N-β (aminoethyl)
An amino-based silane coupling agent such as γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, and N-phenyl-γ-aminopropyltrimethoxysilane is compounded. This primer basic component is based on 100 parts by weight of the silicone polymer.
100 to 5000 parts by weight of an organic solvent, 0.1 to 100 parts by weight of an organic titanate, 0.1 to 10 parts of a tin-based curing catalyst
0 parts by weight, amino silane coupling agent 0.1 to 10
0 parts by weight is preferred.

According to a third aspect of the present invention, there is provided a two-component silicone polymer, wherein the alkoxysilyl group is a methyldimethoxysilyl group and the alkylene structure of the main chain structure is polyisobutylene. It is a primer composition for joining to a silicone-based sealing material.

That is, the silicone polymer of the present invention having an alkoxysilyl group at the molecular terminal and having an alkylene structure in the main chain refers to at least one of a trialkoxysilyl group, an alkyldialkoxysilyl group and a dialkylalkoxysilyl group. Having a main chain structure of ethylene,
It is a polymer having an alkylene structure such as propylene, butylene and isobutylene and having a number average molecular weight of 1,000 to 30,000. Among them, the alkoxysilyl group is a methyldimethoxysilyl group, the alkylene structure of the main chain structure is polyisobutylene, and the number average molecular weight is 5,000 to 200.
Polymers that are 00 are particularly preferred as those of the present invention.

In the invention of claim 4, the ketimine silane coupling agent has a name of N- (1,3-dimethylbutylidene) -3- (trimethoxysilyl) -1-propanamine, N- (1, 3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, N- (1,
3-dimethylbutylidene) -3- (methyldimethoxysilyl) -1-propanamine, N- (1,3-dimethylbutylidene) -3- (methyldiethoxysilyl) -1-
The primer composition for splicing to a two-component silicone sealing material according to any one of claims 1 to 3, which is any of propaneamine.

This primer composition for joining has a ketimine-based silane coupling agent per 100 parts by weight of a silicone-based polymer in which the alkoxysilyl group is a methyldimethoxysilyl group and the alkylene structure of the main chain is polyisobutylene. It is a primer composition characterized by containing -5000 parts by weight. The effects of the present invention are excellent when blending in this range is performed.

That is, when the amount of the ketimine-based silane coupling agent is less than 1 part by weight, the improvement in the adhesiveness to the two-component silicone-based sealing material is small, and when the amount exceeds 5000 parts by weight, a general alumite such as alumite is used. Adhesion to an adherend may be reduced. Among them, particularly preferably 10 to 1000 parts by weight is most effective for the effect of the present invention.

The ketimine-based silane coupling agent in the present invention is a compound having the structure shown in Chemical formula ¹ , wherein R ¹ and R ² are each independently a monovalent linear or branched C ¹ -C ¹ compound. A hydrocarbon group such as an alkyl group, an alkene group, or an aromatic hydrocarbon group of 20, and R ³ is a divalent linear C 1-10 hydrocarbon group. R ⁴ is a lower alkyl group having 1 to 4 carbon atoms such as a methyl group and an ethyl group, and n is 0 or 1.

[0018]

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Further, when used for general adherends such as alumite or when used for pre-cast silicone sealing materials about 5 years after construction,
Those having excellent adhesion between these and PIB-based sealing materials include N- (1,3-dimethylbutylidene) -3- (trimethoxysilyl) -1-propanamine and N- (1,3
-Dimethylbutylidene) -3- (triethoxysilyl)
-1-propanamine, N- (1,3-dimethylbutylidene) -3- (methyldimethoxysilyl) -1-propanamine, N- (1,3-dimethylbutylidene) -3-
(Methyldiethoxysilyl) -1-propanamine, and when used for a pre-cast silicone sealant after about 10 years from the construction,
Those having excellent adhesiveness to the system sealing material include N- (1,3-dimethylbutylidene) -3- (trimethoxysilyl) -1-propanamine shown in Chemical formula 2 and N-
(1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine.

[0020]

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[0021]

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By the way, as a material composed of a system containing a ketimine compound, a sealing material containing a silane compound and a ketimine compound, and an adhesive such as an epoxy resin containing a modified silicone resin are known.
On the other hand, there are various types of materials in which various silane compounds are blended as silane primers. Most of these materials relate to improving the adhesiveness or adhesion between silicone rubber and various adherends or paints, and those relating to sealing materials. As
There has not been a product related to a primer for splicing to a silicone sealant.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION In describing an embodiment of a primer composition for splicing a two-component silicone sealing material of the present invention, a method for producing a best mode will be described. The silicone polymer as a primer basic component is a silylated polyalkylene polymer having an alkoxysilyl group at a molecular end and having a main chain structure of an alkylene structure. The alkoxysilyl group is a methyldimethoxysilyl group, the main chain structure is polyisobutylene, and the number average molecular weight is 5,000 to 5,000.
20,000 (hereinafter referred to as "PIB polymer"
That. ). Since this is commercially available, it will be described using this. This commercial product contains 10 to 40% by weight of a paraffin plasticizer called a process oil as a diluent in order to make the liquid easy to handle. 100 parts by weight of this PIB polymer is placed in a nitrogen gas flow device,
It is charged into a sealant manufacturing device equipped with a stirrer, a vacuum dehydrator and a heating device. This apparatus may be an apparatus for producing a urethane-based sealing material or a modified silicone-based sealing material. In this device, P diluted with the above process oil
The IB polymer is charged, and n-hexane as an organic solvent, an organic titanate, a tin-based curing catalyst, an amino-based silane coupling agent and the like are sequentially charged as a basic component while stirring, and a ketimine-based silane coupling is further added to the basic component. An agent is added and the mixture is homogenously mixed to obtain a primer composition.

[0024]

EXAMPLES In the examples shown in Table 1, 100 parts by weight of a silicone polymer having a number average molecular weight (hereinafter referred to as "Mn") of 5000 having a methyldimethoxysilyl group at the molecular end and a polyisobutylene main chain was used. 130 parts by weight of a paraffin-based plasticizer solution (trade name: Epion EP103S: manufactured by Kanegafuchi Chemical Industry Co., Ltd.), and n-hexane 5 as a solvent
00 parts by weight, tetra-n- as an organic titanate
25 parts by weight of butyl titanate (manufactured by Wako Pure Chemical Industries, Ltd.), dibutyltin bisacetylacetonate (trade name Neostan U-220: manufactured by Nitto Kasei) as a tin-based curing catalyst, amino-based silane coupling agent (trade name KBM573) : Shin-Etsu Chemical Co., Ltd.) as a basic component, and 10 parts by weight, 50 parts by weight of a ketimine-based silane coupling agent (trade name S340: manufactured by Chisso Corporation) as a basic component.
100 parts by weight of the three types were separately added, and three types of primer compositions of Example 1, Example 2, and Example 3 were obtained in the same order.

As a comparative example, in the preparation of the primer composition of the above example, a primer composition was obtained in the same manner as in the example using only the basic components without adding a ketimine silane coupling agent. (Preparation of sealing material base and curing agent)

On the other hand, a main agent and a curing agent for a polyisobutylene-based sealing material were prepared by the following method, and a tensile adhesion test was performed using this sealing material.

The preparation of the base material was carried out using a commercially available seal mixer, a 5 L planetary mixer equipped with a heating, stirring, depressurizing, and nitrogen gas flow apparatus (trade name: Planetary Mixer PLM5:
Inoue Seisakusho) has a paraffin-based process oil (trade name: Diana Process Oil PS-32) containing 100 parts by weight of a silicone-based polymer having a number average molecular weight of Mn: 20,000 and a methyldimethoxysilyl group at the molecular end and a polyisobutylene main chain. : Idemitsu Kosan Co., Ltd.) 50 parts by weight, colloidal calcium carbonate (trade name KR-6: Maruo Calcium Co., Ltd.) 145 parts by weight, epoxy resin (trade name Epicoat 828: Yuka Shell Epoxy Co., Ltd.) 5 parts by weight, glycerin 7 Parts by weight, 10 parts by weight of a glass balloon having an average particle diameter of 40 μm (trade name: Fuji Balloon H-35: manufactured by Fuji Silysia Ltd.), ultraviolet curable resin (trade name: Aronix M-30)
9: Toa Gosei Co., Ltd.) 3 parts by weight, UV absorber (trade name Tinuvin 327: Nippon Ciba Geigy Co., Ltd.) 1 part by weight, light stabilizer (trade name Sanol LS770: Sankyo Co., Ltd.) 1 part by weight, antioxidant ( 1 part by weight (trade name: Irganox 1010, manufactured by Nippon Ciba Geigy) was added, and the mixture was stirred at room temperature under a reduced pressure of 50 Torr for 30 minutes as a rough kneading step. Then, a paraffin-based process oil (trade name: Diana Process Oil PS-32: manufactured by Idemitsu Kosan Co., Ltd.)
20 parts by weight were added, and the mixture was stirred for 60 minutes under the condition of 50 Torr to obtain a main component of a two-component sealing material. In the present invention, stearic acid, which is a saturated acid, may be further mixed as a higher fatty acid having 10 to 20 carbon atoms, and may be mixed at the time of producing the main ingredient. Further, in the present invention, a polyhydric alcohol can be blended, and the polyhydric alcohol improves workability during construction.

The hardener was prepared by adding 15 parts by weight of tin octylate (trade name: Neostan U-28: manufactured by Nitto Kasei Co., Ltd.), 4 parts by weight of laurylamine (manufactured by Wako Pure Chemical Industries, Ltd.), paraffin-based process oil (trade name: Diana Process Oil PS
-32: 90 parts by weight of Idemitsu Kosan Co., Ltd., heavy calcium carbonate (trade name: Softon 3200: manufactured by Shiraishi Calcium Co., Ltd.) 9
0 parts by weight were added and mixed well to obtain a curing agent for a two-component sealing material.

[0029]

[Table 1]

(Adhesion test method) The adhesion test was evaluated by the following method. That is, as for the test piece, the surface of the alumite-treated aluminum (50 × 50 × 3 mm) was washed with toluene, and each primer of Table 1 was applied once to one test piece. The pre-cast silicone sealing materials (A) and (B) are silicone sealing materials actually constructed in a building, and (A) is a silicone sealing material that has passed 6 years after construction (product name SE- 792: Toray
(B) is a silicone-based sealing material (trade name: Tosseal 36) 13 years after construction.
1: GE / Toshiba Silicone Co., Ltd.). Each of these two types of silicone-based sealing materials (50 × 10 × 10 mm) was cut into two pieces with a cutter knife, and the thickness was reduced to half (5 × 10 × 10 mm).
0 × 10 × 5 mm), and the cut surface was used as a test surface. The surface was washed with toluene, and each of the primers in Table 1 was applied once to one specimen. A mixture of the base material of the PIB-based sealing material prepared above and a curing agent in a weight ratio of 10: 1 was sealed to a thickness of about 10 mm on the primer-coated surface left at 23 ° C. for 1 hour, and cured. I let it. The curing condition is 20 ° C. × 3 days. After curing, cut one end of the adhesive surface of the specimen with a cutter knife,
The B-based sealing material and the alumite-treated aluminum and silicone-based sealing materials were peeled by hand to determine whether they were bonded, and the adhesion to each adherend was evaluated. The evaluation was made in four stages of ◎, △, Δ, and ×.

◎ and ○ indicate that the adhesiveness is good and is in a practically sufficient range, は indicates that cohesive failure is caused by the peeling of the entire surface, and ○ indicates that the cohesive failure is caused in most parts by the peeling of the hand. On the other hand, △ and × have poor adhesion and are inadequate for practical use, and △ has interface failure in most parts,
× indicates that the interface is completely destroyed.

[0032]

As described above, the primer composition containing the ketimine-based silane coupling agent of the present invention can be used for a general adherend such as alumite or in a construction site for a long time. When used for a pre-filled silicone sealant,
It provides a remarkable improvement in the adhesiveness with the B-based sealing material, and provides an unprecedented superior effect.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J038 CL001 JC35 JC38 JC39 KA06 MA07 NA03 NA04 NA14 PB05 PB12 PC02 PC03 PC04 PC08 4J040 DJ031 HB02 HD36 HD41 HD42 KA23 LA06 LA07 LA08 MA02 MA05 MA06 MA10 NA12

Claims (4)

[Claims] 1. A primer composition for splicing to a two-component silicone sealing material, characterized by adding a ketimine-based silane coupling agent to a primer basic component containing a silicone-based polymer. 2. A primer basic component comprises a paraffin-based plasticizer solution containing a silicone-based polymer having an alkoxysilyl group at the molecular end and an alkylene structure in the main chain, an organic solvent, an organic titanate, and a tin-based curing agent. The primer composition for joining to a two-component silicone sealing material according to claim 1, comprising a catalyst and an amino silane coupling agent. 3. The two-component silicone sealing material according to claim 2, wherein the silicone polymer has a methyldimethoxysilyl group as the alkoxysilyl group and a polyisobutylene as the alkylene structure in the main chain structure. A primer composition for jointing. 4. The ketimine-based silane coupling agent comprises N
-(1,3-dimethylbutylidene) -3- (trimethoxysilyl) -1-propanamine, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-
Propanamine, N- (1,3-dimethylbutylidene)
-3- (Methyldimethoxysilyl) -1-propanamine or N- (1,3-dimethylbutylidene) -3- (methyldiethoxysilyl) -1-propanamine. Item 4. A primer composition for connecting to a two-component silicone sealing material according to any one of Items 1 to 3.