JP2007138096A - Primer composition for sealant application - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a primer composition for sealant application, highly adhesive to not only nonporous adherents such as metals or glass but also to so-called sparingly adhesive adherents coated with acrylic electrodeposition coatings or fluororesin coatings, among others, to provide such a primer composition highly adhesive to polyisobutylene-based sealants in particular. <P>SOLUTION: The primer composition for sealant application comprises (A) a hydrolyzable silyl group-containing polymer having acrylic skeleton, (B)an organopolysiloxane compound containing hydroxy and/or alkoxy groups bound to silicon atom, (C) an amino-containing silane compound, (D) a silanol condensation catalyst, and (E) an organic solvent. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a primer composition for construction of a sealing material, and more specifically, not only a non-porous adherend such as metal or glass, but also a so-called acrylic electrodeposition paint or fluororesin paint. The present invention relates to a primer composition for construction of a sealing material having good adhesion to a hardly adhesive adherend.

There are various types of sealing materials, such as silicones, modified silicones, polysulfides, urethanes, etc., used for sealing the interior and exterior joints of buildings and vehicles, and around window frames. Is selected and used depending on the type of member to be applied, the type of joint, the required performance, and the like. Among these, silicone sealants are widely used because they are excellent in surface weather resistance and durability. However, the silicone-based sealant has a problem in that the joint periphery is contaminated by the exudation of the silicone oil component after a long period of time has elapsed since construction.
Therefore, in recent years, polyisobutylene-based sealing materials that do not cause contamination of the joint periphery and are excellent in heat resistance, weather resistance, water resistance, and paintability have been attracting attention as replacements for silicone-based sealing materials. (Hereinafter, “polyisobutylene” may be referred to as “PIB”).

  On the other hand, in the construction of the sealing material for construction, not only the performance of the sealing material itself, but also the adhesiveness (adhesion) between the member constituting the joint part (adhered body) and the sealing material is important. A “primer” is used for imparting and improving the adhesion. In general, even when the same sealing material is used, it is necessary to use different primers depending on the adherend. Therefore, it is desired that the same primer can cope with as many adherends as possible. Depending on the type of sealing material and the material and type of the adherend, various components can be used as the primer. Especially in joints around glass where a high degree of weather resistance is required, a silicone-based primer can be used. Many silane-based primers containing a compound as a main component are used (see Patent Document 1).

Japanese Patent No. 2543760

However, these conventional silane-based primers are inferior in adhesiveness to so-called difficult-to-adhere adherends coated with acrylic electrodeposition paints or fluororesin paints that have become particularly popular in recent years. Therefore, further improvement of primer performance has been strongly desired. Further, when a PIB sealant is used instead of the silicone sealant, there is a problem that the adhesiveness is further inferior.
The present invention solves such problems, not only for non-porous adherends such as metal and glass, but also for so-called hardly adhesive adherends coated with acrylic electrodeposition paints or fluororesin paints, etc. Furthermore, the present invention is intended to provide a primer composition for constructing a sealing material having good adhesion.
In addition, the present invention provides a primer composition for construction of a sealing material that has good adhesion to PIB-based sealing materials that are expected to be used in applications where weather resistance is required in the future, among various sealing materials. It is something to be offered.

As a result of diligent research to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by blending a specific hydrolyzable polymer (A) into a silane-based primer, thereby completing the present invention. It came to do. That is, the present invention is as follows.
1. (A) 100 parts by weight of a hydrolyzable silyl group-containing polymer containing an acrylic skeleton, (B) 10 to 1800 parts by weight of an organopolysiloxane compound containing a hydroxyl group and / or an alkoxy group bonded to a silicon atom,
(C) 10 to 700 parts by weight of an amino group-containing silane compound,
(D) 0.1 to 700 parts by weight of a silanol condensation catalyst,
(E) A primer composition for constructing a sealing material, which is dissolved in an organic solvent.

2. The (A) hydrolyzable silyl group-containing polymer containing an acrylic skeleton is (A-1) a hydrolyzable silyl group-containing telechelic acrylic polymer and / or (A-2) an acrylic-containing modified silicone resin. Features 1. Primer composition for sealing material construction according to
3. 1. The sealing material is a polyisobutylene-based sealing material, Or 2. The primer composition for construction of a sealing material as described in 1.
According to the above means, the following operation can be obtained.

According to the primer composition for constructing a sealing material of the present invention, not only a non-porous adherend such as metal or glass but also a so-called hardly adhesive adherend coated with an acrylic electrodeposition paint or a fluororesin paint, etc. In contrast, an excellent effect can be obtained that a primer composition for construction of a sealing material having good adhesiveness can be obtained.
In addition, according to the primer composition for construction of a sealing material of the present invention, among various sealing materials, a primer composition for construction of a sealing material having good adhesion can be obtained, particularly with respect to a PIB-based sealing material. An excellent effect can be achieved.

Hereinafter, embodiments of the present invention will be described in detail. In addition, this invention is not limited only to these illustrations, Of course, a various change can be added in the range which does not deviate from the summary of this invention.
[About sealing materials]
Sealing materials are classified into polyurethane-based, silicone-based, modified silicone-based, polyisobutylene-based, acrylic urethane-based, polysulfide-based, and the like depending on the type of polymer used. These are cured by a chemical crosslinking reaction, but if classified according to the type of curing reaction, (1) polyurethane-based, acrylic urethane-based and polysulfide-based are (2) silanol-curable types Modified silicone systems and polyisobutylene systems are (3) silicone systems as dehydroxylamine curable types. In addition, as a product form, it is supplied in the form of a paper tube cartridge or the like that does not require mixing, and can be directly applied to the joint 1 There is a component type sealing material.
Among these, an example is shown below about the construction method of a 2 component-type polyisobutylene (PIB) type sealing material.

The two-component polyisobutylene-based sealing material comprises a base material mainly composed of a polyalkylene polymer (PIB polymer) having a hydrolyzable silyl group at the molecular end and a main chain structure of polyisobutylene, and a silanol curing catalyst. It consists of a hardening | curing agent to contain. And these base and hardening | curing agent are uniformly mixed with a stirrer for exclusive use of a sealing material in a construction site, a construction site, etc., and are filled in various joints.
After mixing the base and the curing agent, the hydrolyzable silyl group of the PIB polymer is activated by the silanol condensation catalyst, and is cured by a cross-linking reaction between the hydrolyzable silyl groups to form a rubber-like sealing material composition. .

[Primer composition]
[(A) Hydrolyzable silyl group-containing polymer containing acrylic skeleton]
In the present invention, (A) a hydrolyzable silyl group-containing polymer containing an acrylic skeleton (hereinafter sometimes referred to as “(A) acrylic-containing polymer”) means that the main chain skeleton is poly (meth) acrylic acid. A polymer comprising an alkyl ester and a polymer containing a hydrolyzable silyl group in the molecule.
(A) The main chain skeleton of the acrylic-containing polymer is composed of a poly (meth) acrylic acid alkyl ester copolymer. The (meth) acrylic acid alkyl ester monomer constituting the main chain skeleton is not particularly limited, and conventionally known (meth) acrylic acid alkyl ester monomers can be used.

(A) The hydrolyzable silyl group that the acrylic-containing polymer has in its molecule is represented by the formula: —SiX ₃ and / or —SiR ¹ (X) ₂ (wherein X represents a hydrolyzable group, and R ¹ represents A hydrolyzable silyl group represented by a substituted or unsubstituted organic group having 1 to 20 carbon atoms. The group represented by X in the above formula is a hydrolyzable group, and specific examples of the hydrolyzable group include a halogen group, a hydride group, an alkoxyl group, an acyloxy group, a ketoximate group, an amino group, an amide group, and an aminooxy group. , A mercapto group, an alkenyloxy group, and the like. Among these, an alkoxyl group is most preferable from the viewpoint of high reactivity and low odor. In the present invention, two or three groups X of the hydrolyzable silyl group may be different from each other.
(A) The molecular weight of the acrylic-containing polymer is not particularly limited, but the number average molecular weight is preferably 500 to 500,000, more preferably 1,000 to 100,000, and particularly preferably 2,000 to 20,000.

[(A-1) Hydrolyzable silyl group-containing telechelic acrylic polymer]
The (A-1) hydrolyzable silyl group-containing telechelic acrylic polymer in the present invention is a vinyl polymer having a hydrolyzable silyl group at the terminal, and is a (meth) acrylic acid alkyl ester (for example, (meta ) Ethyl acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobutyl (meth) acrylate, etc.) and / or alkoxyalkyl esters of (meth) acrylic acid (for example, (meth) acrylic acid 2- Methoxyethyl, 2-ethoxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, etc.) are synthesized as essential constituent units of the vinyl polymer. Specifically, it is produced by “atom transfer radical polymerization” proposed in Japanese Patent Application Laid-Open No. 2004-59782, which polymerizes vinyl monomers using an organic halide or a sulfonyl halide as an initiator and a transition metal complex as a catalyst. Curable resins are known.
(A-1) Hydrolyzable silyl group-containing telechelic acrylic polymers are commercially available, and they can be used in the present invention. As a commercial item, Kaneka brand name; SA100S, SA310S, OR100S etc. are mentioned, for example.

[(A-2) Acrylic-containing modified silicone resin]
The (A-2) acrylic-containing modified silicone resin in the present invention is a hydrolyzable silyl group-containing poly (meth) acrylic acid alkyl ester polymer (for example, alkyl includes methyl, ethyl, propyl, butyl, octyl, lauryl, etc. ) And a hydrolyzable silyl group-containing polyoxyalkylene polymer (for example, ring-opening polymer such as ethylene oxide, propylene oxide, tetrahydrofuran, etc.), or in the presence of a hydrolyzable silyl group-containing polyoxyalkylene polymer, A (meth) acrylic acid monomer, a (meth) acrylic acid alkyl ester monomer, a hydrolyzable silyl group-containing (meth) acrylic acid alkyl ester monomer, and the like are copolymerized. Specifically, Japanese Patent Publication No. 45-36319,
46-12154, 49-32673, JP-A-50-156599, 51-73561, 54-6096, 55-82123, 55-123620, 55-125121, Although curable resins generally referred to as modified silicone resins proposed in JP-A-55-131022, JP-A-55-135135 and JP-A-55-137129 are included, they are not particularly limited and are conventionally known The following polymers can be used.
(A-2) Acrylic-containing modified silicone resins are commercially available and can be used in the present invention. As a commercial item, Kaneka Co., Ltd. brand name; S943, S911, MA440, MA447, MA903 etc. are mentioned, for example.

[(B) Organopolysiloxane compound containing hydroxyl group and / or alkoxy group bonded to silicon atom]
In the present invention, (B) a hydroxyl group and / or alkoxy group-containing organopolysiloxane compound bonded to a silicon atom (hereinafter sometimes simply referred to as “(B) organopolysiloxane compound”) has, for example, an average unit of formula :

[Wherein, R ¹ is a monovalent hydrocarbon group (for example, an alkyl group such as methyl, ethyl, propyl, etc .; an alkenyl group such as vinyl, allyl, etc .; and those hydrogen atoms substituted with a halogen or a cyano group); R ² Is a hydrogen atom and / or alkyl group (methyl, ethyl, propyl, etc.); a is 0 to 2; and b is a value such that the number of hydroxyl groups or alkoxy groups bonded to silicon atoms in one molecule is one or more. In general, one or a mixture of two or more chlorosilanes or alkoxysilanes each having 0 to 2 monovalent hydrocarbon groups per silicon atom is mixed with water or water and an organic solvent. It can be produced by hydrolyzing in the presence of coexisting and removing by-product hydrochloric acid, alcohol and the like. In addition, these organopolysiloxane compounds may contain a phenyl group; an epoxy group; an amino group; a mercapto group; a methacryl group;
The (B) organopolysiloxane compound has a hydroxyl group when R ² is a hydrogen atom, and has an alkoxy group when R ² is an alkyl group. May coexist. For example, if an organopolysiloxane compound having an alkoxy group is partially hydrolyzed, a hydroxyl group and an alkoxy group coexist.

As these commercial items, for example, trade names manufactured by Shin-Etsu Chemical Co., Ltd .; KC-89S, KR-500, KR-510, X-41-1056, X-41-1810, X-40-2655A, X-40- 2671, Toray Dow Corning Silicone Co., Ltd. trade names; FZ-3704, PRX413, Colcoat Co., Ltd. trade names; ethyl silicate 28, ethyl silicate 40, ethyl silicate 48, methyl silicate 51, etc., and these are used. You can also
(B) The compounding amount of the organopolysiloxane compound is preferably 10 to 1800 parts by weight, more preferably 30 to 1600 parts by weight with respect to 100 parts by weight of the hydrolyzable silyl group-containing polymer containing (A) an acrylic skeleton. Is appropriate. When deviating from the range of 10 to 1800 parts by mass, in any case, adhesion to an adherend coated with an acrylic electrodeposition paint or a fluorine paint is lowered.

[(C) Amino group-containing silane compound]
As the (C) amino group-containing silane compound that can be blended in the primer composition according to the present invention, a known compound can be used within a range that does not impair the effects of the present invention.
Specific examples include, for example, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, aminophenyltrimethoxysilane, 4 -Amino-3-dimethylbutyltrimethoxysilane, 4-amino-3-dimethylbutylmethyldimethoxysilane, 4-amino-3-dimethylbutyltriethoxysilane, 4-amino-3-dimethylbutylmethyldiethoxysilane, N- Phenyl-γ-aminopropyltrimethoxysilane, N-naphthyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropylmethyldimethoxysilane, N-naphthyl-γ-aminopropylmethyldimethoxysilane, N- (n -Butyl)- γ-aminopropyltrimethoxysilane, N- (n-butyl) -γ-aminopropylmethyldimethoxysilane, N-ethyl-γ-aminopropyltrimethoxysilane, N-ethyl-γ-aminopropylmethyldimethoxysilane, N- Ethyl-aminoisobutyltrimethoxysilane, N-methyl-γ-aminopropyltrimethoxysilane, N-methyl-γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N- β (aminoethyl) -γ-aminopropyltriethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldiethoxysilane, N-3 -[Amino (dipropyleneoxy)] aminopropyltrimethoxy Sisilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, N- (6-aminohexyl) aminopropyltrimethoxysilane, N- (2-aminoethyl) -11-aminoundecyltrimethoxysilane, bis (trimethoxysilyl) Aminosilane compounds such as propyl) amine can be mentioned, but are not limited thereto. As these commercial products, Shin-Etsu Chemical Co., Ltd. trade names: KBE903, KBM903, KBM902, KBM9103, KBM602, KBE-603, KBM603, KBM-573, Nippon Unicar Corporation trade names; A-1170, A- link15 etc., Degussa-HulsAG brand name; DYNASYLAN1189 etc. are mentioned, These can also be used.

  (C) The compounding amount of the amino group-containing silane compound is preferably 10 to 700 parts by weight, more preferably 100 parts by weight of the hydrolyzable silyl group-containing polymer containing the acrylic skeleton (A). Is suitably 30 to 500 parts by weight. If the amount is less than 10 parts by weight, the adhesion to various adherends is lowered, and if it is more than 700 parts by weight, the curing of the interface may be delayed, such being undesirable.

[(D) Silanol condensation catalyst]
As the (D) silanol condensation catalyst that can be blended in the primer composition according to the present invention, a known compound can be used as long as the effects of the present invention are not impaired. Specific examples include organotin compounds, organotitanium compounds, organozirconium compounds, organometallic compounds such as organobismuth compounds, basic compounds such as amine compounds, and acidic compounds such as phosphate compounds. These may be used alone or in combination of two or more.
Among these, organometallic compounds are also preferred from the viewpoint of availability, and specifically, dibutyltin dilaurate, dioctyltin dimaleate, dibutyltin phthalate, stannous octylate, dibutyltin methoxide, dibutyltin diacetyl acetate, Organic tin compounds such as dibutyltin diversate, dibutyltin oxide, reaction product of dibutyltin oxide and phthalic acid diester, organic titanium compounds such as tetrabutyl titanate, tetraisopropyl titanate, titanium acetylacetonate, triethanolamine titanate, zirconium normal It is particularly preferable to use an organic zirconium compound such as propylate, zirconium normal butyrate, or zirconium monoacetyl acetate.

  As these commercial products, for example, trade names manufactured by Nitto Kasei Co., Ltd .; Stan BL, Stan No. 918, U202H, U-220H, U303, U700, U700ES, U-28, etc. (above, organotin compounds), product names manufactured by Nippon Soda Co., Ltd .; A-1, B-1, B-2, B-4 , Trade names made by Matsumoto Pharmaceutical Co., Ltd .; TC-100, TC-401, TC-750, etc. (above, organic titanium compounds), trade names made by Matsumoto Pharmaceutical Industries, Ltd .; ZA-40, ZA-60, ZC- 540, ZC-570, etc. (above, an organic zirconium compound) can be used, and these can also be used.

  The blending amount of the (D) silanol condensation catalyst is preferably 0.1 to 700 parts by weight, more preferably 0 with respect to 100 parts by weight of the hydrolyzable silyl group-containing polymer (A) containing an acrylic skeleton. 3 to 550 parts is appropriate. If the amount is less than 0.1 parts by weight, it takes time until the adhesiveness is developed, which is not practical. When the amount is more than 700 parts by weight, there is a problem in terms of storage stability such that precipitation occurs during storage of the primer.

[(E) Organic solvent]
(E) The organic solvent is used to dissolve the primer composition according to the present invention, and is soluble in the components (A) to (D) and wettability, volatility, and odor during the application work as a primer. Etc. are selected. Specific examples of such organic solvents include aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as n-hexane, heptane and methylcyclohexane, alcohols such as methanol, ethanol, isopropanol and butanol, Examples thereof include ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and butyl acetate, and halogenated hydrocarbons such as trichloroethylene and perchloroethylene.
These organic solvents are used alone or as a mixed solvent of two or more. Such an organic solvent is not necessarily required when the viscosity of the mixture of the components (A) to (D) is in a viscosity range that can be sufficiently used as a primer composition, but in many cases, the composition of the present invention is dissolved, Since it is advantageous to adjust the viscosity and concentration suitable for actual application work as a primer, the blending amount thereof is not particularly limited, and is an arbitrary amount.

In addition, as various additives that can be blended in the primer composition according to the present invention, powders and fillers such as calcium carbonate and silica, tackifiers (tackifiers), and the like within a range not impairing the effects of the present invention, Thixotropic agent, dehydrating agent, diluent, plasticizer, flame retardant, oligomer, anti-aging agent, UV absorber, pigment, titanate coupling agent, aluminum coupling agent, epoxy group-containing silane compound, mercapto group-containing silane compound , Known raw materials such as silicate compounds such as tetramethoxysilane, tetraethoxysilane, and ethyl polysilicate, and drying oils such as vinylsilane, isocyanurate silane, and tung oil, but are not limited thereto.
The primer composition of the present invention can be used as a primer composition for a sealing material or an adhesive. Among these, it is suitably used as a primer composition for a building sealing material, and examples thereof include a modified silicone type and a polysulfide type. Among these, a primer composition for a PIB type sealing material is particularly preferably used.

The invention is explained in more detail by means of examples. The present invention is not limited to the following examples.
[Adhesion test]
The prepared primer composition is applied to various adherends with a brush, dried at room temperature, and then a two-component polyisobutylene-based sealing material ("Bond Xeal IB" manufactured by Konishi Co., Ltd./"PIB "in the table) Notation) Two-component modified silicone sealant ("Bond MS seal" manufactured by Konishi Co., Ltd./"MS "in the table) or two-component polysulfide sealant (" Bond "manufactured by Konishi Co., Ltd.) “PS seal” / indicated in the table as “PS”) was applied to a thickness of 10 mm and cured at 23 ° C. × 3 days and 50 ° C. × 4 days. Subsequently, adhesiveness was evaluated by peeling off the adhesiveness of the sealing material coating film by hand. The test method was carried out in accordance with the 2004 version of the building sealing material handbook (edited by the Japan Sealant Industry Association) 6.2.1 (2) simple adhesion test. Specifically, a cellophane tape is pasted on a part of the adherend beforehand, and after the sealing material is cured, it is pulled by hand in the direction of 180 °, and the sealing material is cohesive failure or thin layer cohesive failure (evaluation result: ○ ) Is judged to have good adhesion. Further, when cohesive failure and interfacial failure were mixed (evaluation result: Δ), it was judged that the result was not preferable, although there may be no practical problem.

-Substrate used for evaluation Float glass plate ... JIS, R, 3202 Float glass Aluminum plate ... Silver anodized aluminum Acrylic baked coated steel plate ... Baking temperature 180 ° C
Fluoropolymer coated steel sheet ... Baking temperature 160 ° C
Acrylic electrodeposition coated aluminum plate… Sankyo Tateyama Aluminum Industry Co., Ltd.

Evaluation result: ○: Cohesive failure or thin layer cohesive failure of sealing material
Δ: cohesive failure or thin layer cohesive failure and interface failure of the sealing material
Mixed
×: Fracture at the interface between the sealing material and the adherend

Hereinafter, examples and comparative examples will be described in more detail.
[Example 1]
In a kettle equipped with a stirring blade, (A) 3 parts by mass of “SA100S (manufactured by Kaneka Corporation; hydrolyzable silyl group-containing telechelic acrylic polymer)” as an acrylic-containing polymer, and (B) “FZ- 3704 (manufactured by Toray Dow Corning Silicone Co., Ltd.), (C) “KBM603 (manufactured by Shin-Etsu Chemical Co., Ltd .; γ- (2-aminoethyl) aminopropyltrimethoxysilane) as an amino group-containing silane compound” ) "As 5 parts by mass, (D) 0.01 parts by mass of" Neostan U-220H (manufactured by Nitto Kasei Co., Ltd .; dibutyltin acetyl acetate) "as silanol condensation catalyst, (E) 40 parts by mass of isopropyl alcohol as organic solvent, Charge 40 parts by mass of n-hexane and 6 parts by mass of methylcyclohexane, mix by stirring To obtain a primer composition. The (A) acrylic-containing polymer “SA100S” was used after being dissolved and dispersed using a part of the solvent used in advance. Other (A) acrylic-containing polymers that appear in later examples were similarly used after being dissolved and dispersed using a part of the solvent to be used.
Using the prepared primer composition and the two-component polyisobutylene-based sealant, the above-described adhesion test was performed.

[Example 2]
Instead of 0.01 parts by mass of (D) silanol condensation catalyst “Neostan U-220H” in Example 1, 0.5 parts by mass of “Neostan U-220H” is used, and (E) the composition of the organic solvent is isopropyl alcohol 30. A primer composition was prepared in the same manner as in Example 1 except that the content was 25 parts by mass, 25 parts by mass of n-hexane, and 30 parts by mass of ethyl acetate, and an adhesion test was performed.
[Example 3]
Instead of 0.5 parts by mass of (D) silanol condensation catalyst “Neostan U-220H” in Example 2, 0.5 parts by mass of “Neostan U-220H” and “ZC-540 (manufactured by Matsumoto Pharmaceutical Co., Ltd .; zirconium) A primer composition was prepared in the same manner as in Example 1 except that the amount was 5 parts by mass of monoacetyl acetate) ”, and an adhesion test was performed. In addition, since ZC-540 contains 40-50% toluene and 10-20% 1-butanol in the product, the blending amounts described in the examples are those containing these solvents.

[Example 4]
A primer composition was prepared in the same manner as in Example 1, except that 0.01 parts by mass of (D) silanol condensation catalyst “Neostan U-220H” in Example 1 was changed to 6.5 parts by mass of “ZC-540”. Then, an adhesion test was conducted. The organic solvent composition was changed because the solubility was adjusted in accordance with the change of the silanol condensation catalyst.
[Example 5]
Instead of 0.5 parts by mass of (D) silanol condensation catalyst “Neostan U-220H” in Example 2, 0.5 parts by mass of “Neostan U-220H” and “B-1 (Nippon Soda Co., Ltd .; Tetra- n-Butyl titanate) A primer composition was prepared in the same manner as in Example 2 except that 5 parts by mass was used, and an adhesion test was performed.

[Example 6]
Instead of 0.01 parts by mass of (D) silanol condensation catalyst “Neostan U-220H” in Example 1, 0.5 parts by mass of “Neostan U-220H” and “B-1 (Nippon Soda Co., Ltd .; Tetra- n-Butyl titanate) A primer composition was prepared in the same manner as in Example 1 except that it was 15 parts by mass, and an adhesion test was performed.
[Comparative Example 1]
A primer composition was prepared in the same manner as in Example 4 except that (A) the acrylic-containing polymer “SA100S” in Example 4 was not blended, and an adhesion test was performed.

[Comparative Example 2]
A primer composition was prepared in the same manner as in Example 4 except that (D) the silanol condensation catalyst “Neostan U-220H” in Example 1 was not blended, and an adhesion test was performed.
Table 1 shows the composition of the primer compositions of Examples 1 to 6 and Comparative Examples 1 and 2 and the evaluation results of the adhesion test.
As is clear from the results in Table 1, the primer composition according to the present invention showed good adhesion to various adherends. On the other hand, the primer composition (Comparative Example 1) lacking the acrylic-containing polymer (A), which is a constituent requirement of the present invention, did not provide sufficient adhesion to an adherend having poor adhesion. In addition, (D) In the primer composition not containing the silanol condensation catalyst (Comparative Example 2), since the primer layer does not sufficiently cure, the primer layer partially cohesively breaks down in the adhesion test. Not expressed.

[Example 7]
In a kettle equipped with a stirring blade, (A) 3 parts by mass of “SA100S” as an acrylic-containing polymer, (B) 1 part by mass of “FZ-3704” as an organopolysiloxane compound, and (C) “Amino group-containing silane compound” 5 parts by mass of “KBM603”, (D) 0.5 part by mass of “Neostan U-220H” as a silanol condensation catalyst and 5 parts by mass of “B-1 (Nippon Soda Co., Ltd .; tetra-n-butyl titanate)” E) As an organic solvent, 40 parts by mass of isopropyl alcohol, 40 parts by mass of n-hexane and 6 parts by mass of methylcyclohexane were charged and mixed by stirring to obtain a primer composition.
Using the prepared primer composition and the two-component polyisobutylene-based sealant, the above-described adhesion test was performed.

[Example 8]
A primer composition was prepared in the same manner as in Example 7 except that 1 part by mass of (B) organopolysiloxane compound “FZ-3704” in Example 7 was replaced by 20 parts by mass of “FZ-3704”, and adhesion was performed. A sex test was performed.
[Comparative Example 3]
A primer composition was prepared in the same manner as in Example 4 except that (B) the organopolysiloxane compound “FZ-3704” in Example 5 was not blended, and an adhesion test was performed.

[Comparative Example 4]
A primer composition was prepared in the same manner as in Example 7, except that 0.1 part by mass of “FZ-3704” was used instead of 1 part by mass of (B) organopolysiloxane compound “FZ-3704” in Example 7. An adhesion test was conducted.
[Comparative Example 5]
A primer composition was prepared and bonded in the same manner as in Example 7 except that 60 parts by mass of “FZ-3704” was used instead of 1 part by mass of (B) the organopolysiloxane compound “FZ-3704” in Example 7. A sex test was performed.

[Example 9]
In Example 7, (B) 1 part by mass of the organopolysiloxane compound “FZ-3704” was replaced with 5 parts by mass of “FZ-3704”, and (C) the amino group-containing silane compound “KBM603” was replaced with 5 parts by mass. A primer composition was prepared in the same manner as in Example 7 except that 1 part by weight of “KBM603” was used, and an adhesion test was performed.
[Example 10]
A primer composition was prepared in the same manner as in Example 9 except that 1 part by mass of (C) amino group-containing silane compound “KBM603” in Example 9 was changed to 15 parts by mass, and an adhesion test was performed. It was.

[Comparative Example 6]
A primer composition was prepared in the same manner as in Example 5 except that the (C) amino group-containing silane compound “KBM603” in Example 5 was not blended, and an adhesion test was performed.
[Comparative Example 7]
A primer composition was prepared in the same manner as in Example 9 except that 0.1 parts by mass of “KBM603” was used instead of 1 part by mass of (C) amino group-containing silane compound “KBM603” in Example 9, and adhesiveness was improved. A test was conducted.
Table 2 shows the composition of the primer compositions of Examples 7 to 10 and Comparative Examples 3 to 7 and the evaluation results of the adhesion test.
As is clear from the results in Table 2, the primer composition according to the present invention showed good adhesion to various adherends. On the other hand, with the primer composition lacking the constituent requirements of the present invention (Comparative Examples 3 to 7), sufficient adhesiveness was not obtained.

[Example 11]
In a kettle with a stirring blade, (A) 3 parts by mass of “SA100S” as an acrylic-containing polymer, (B) 2.5 parts by mass of “KC-89S (manufactured by Shin-Etsu Chemical Co., Ltd.)” as an organopolysiloxane compound, (C) 5 parts by weight of “KBM603” as the amino group-containing silane compound, (D) 0.5 parts by weight of “Neostan U-220H” and 5 parts by weight of “B-1” as the silanol condensation catalyst, (E) Organic solvent As a starting material, 30 parts by mass of isopropyl alcohol, 25 parts by mass of n-hexane and 30 parts by mass of ethyl acetate were charged and mixed by stirring to obtain a primer composition.
Using the prepared primer composition and the two-component polyisobutylene-based sealant, the above-described adhesion test was performed.

[Example 12]
A primer composition was prepared in the same manner as in Example 11 except that the blending amount of (D) silanol condensation catalyst “Neostan U-220H” in Example 11 was changed to 1.5 parts by mass, and an adhesion test was performed. .
[Example 13]
A primer composition was prepared in the same manner as in Example 11 except that the blending amount of (D) silanol condensation catalyst “Neostan U-220H” in Example 11 was changed to 5 parts by mass, and an adhesion test was performed.

[Example 14]
A primer composition was prepared and bonded in the same manner as in Example 12 except that 3 parts by mass of (A) acrylic-containing polymer “SA100S” in Example 12 was changed to 3 parts by mass of “S943 (manufactured by Kaneka Corporation)”. A sex test was performed.
[Example 15]
A primer composition was prepared in the same manner as in Example 14 except that the amount of (D) silanol condensation catalyst “Neostan U-220H” in Example 14 was changed to 3 parts by mass, and an adhesion test was performed.

[Example 16]
A primer composition was prepared in the same manner as in Example 14 except that the amount of (D) silanol condensation catalyst “Neostan U-220H” in Example 14 was changed to 5 parts by mass, and an adhesion test was performed.
[Example 17]
A primer composition was prepared and bonded in the same manner as in Example 12 except that 3 parts by mass of “MA440 (manufactured by Kaneka Corporation)” was used instead of 3 parts by mass of (A) acrylic-containing polymer “SA100S” in Example 12. A sex test was performed.

[Comparative Example 8]
In Example 11, (A) the acrylic-containing polymer “SA100S” and (D) the silanol condensation catalyst “Neostan U-220H” were not blended, and (E) the composition of the organic solvent was 40 parts by mass of isopropyl alcohol and n-hexane 45. A primer composition was prepared in the same manner as in Example 11 except for changing to parts by mass, and an adhesion test was performed. In addition, this mixing | blending is equivalent to the structure of the prior art described in patent document 1. FIG.

[Comparative Example 9]
In Comparative Example 8, a primer composition was prepared in the same manner as in Comparative Example 8 except that 1.5 parts by mass of “Neostan U-220H” was further added as a (D) silanol condensation catalyst, and an adhesion test was performed.
Table 3 shows the composition of the primer compositions of Examples 11 to 17 and Comparative Examples 8 and 9 and the evaluation results of the adhesion test.
As is clear from the results in Table 3, the primer composition according to the present invention showed good adhesion to various adherends. On the other hand, with the primer composition corresponding to the configuration of the prior art described in Patent Document 1, sufficient adhesiveness could not be obtained.

[Example 18]
In a kettle equipped with a stirring blade, (A) 3 parts by mass of “SA100S” as an acrylic-containing polymer, (B) 1.25 parts by mass of “FZ-3704” as an organopolysiloxane compound, and “PRX-413 (Toray Dow Corning)・ Silicone Co., Ltd.) ”1.25 parts by mass, (C) 5 parts by mass of“ KBM603 ”as the amino group-containing silane compound, (D) 0.5 parts by mass of“ Neostan U-220H ”as the silanol condensation catalyst, and“ B-1 "5 parts by weight, (E) 30 parts by mass of isopropyl alcohol, 25 parts by mass of n-hexane and 30 parts by mass of ethyl acetate as an organic solvent were added and stirred to obtain a primer composition.
Using the prepared primer composition and the two-component polyisobutylene-based sealant, the above-described adhesion test was performed.

[Example 19]
Except for changing 1.25 parts by mass of (B) organopolysiloxane compound “FZ-3704” and “PRX-413” in Example 18 to 2.5 parts by mass of “FZ-3704”, A primer composition was prepared in the same manner as in Example 18, and an adhesion test was performed.
[Example 20]
A primer composition was prepared in the same manner as in Example 19 except that the blending amount of (B) organopolysiloxane compound “FZ-3704” in Example 19 was changed to 5 parts by mass, and an adhesion test was performed.

[Example 21]
In Example 20, (D) Silanol condensation catalyst “Neostan U-220H” 0.5 parts by mass and “B-1” 5 parts by mass were used as “ZC-540” 6.5 parts by weight, and (E) organic solvent A primer composition was prepared in the same manner as in Example 20 except that 40 parts by mass of isopropyl alcohol, 40 parts by mass of n-hexane, and 6 parts by mass of methylcyclohexane were used, and an adhesion test was performed.

[Comparative Example 10]
A primer composition was prepared in the same manner as in Example 20 except that (A) the acrylic-containing polymer “SA100S” in Example 20 was not blended, and an adhesion test was performed.
[Comparative Example 11]
A primer composition was prepared in the same manner as in Example 21 except that (A) the acrylic-containing polymer “SA100S” and (D) the silanol condensation catalyst “ZC-540” in Example 21 were not blended. went.

Table 4 shows the composition of the primer compositions of Examples 18 to 21 and Comparative Examples 10 and 11 and the evaluation results of the adhesion test.
As is clear from the results in Table 4, the primer composition according to the present invention showed good adhesion to various adherends. On the other hand, with the primer composition lacking the requirements of the present invention, sufficient adhesiveness could not be obtained.

In a kettle with a stirring blade, (A) 3 parts by mass of “SA100S” as an acrylic-containing polymer,
(B) 5 parts by mass of “FZ-3704” as the organopolysiloxane compound, 5 parts by mass of “KBM603” as the (C) amino group-containing silane compound, and (D) “Neostan U-220H” as the silanol condensation catalyst. 5 parts by mass and 5 parts by weight of “B-1” and (E) 85 parts by mass of n-hexane as an organic solvent were charged and mixed by stirring to obtain a primer composition.
[Example 22]
Using the prepared primer composition and a two-component polyisobutylene-based sealing material (indicated as “PIB” in the table), the above-described adhesion test was performed.
[Example 23]
Using the prepared primer composition and a two-component silicone sealant (indicated as “MS” in the table), the above adhesion test was performed.
[Example 24]
Using the prepared primer composition and a two-component modified polysulfide-based sealing material (indicated as “PS” in the table), the above-described adhesion test was performed.

Table 5 shows the composition of the primer compositions of Examples 22 to 24 and the evaluation results of the adhesion test.
As is clear from the results in Table 5, the primer composition according to the present invention showed good adhesion to various adherends even when various sealing materials were used.

  The primer composition for construction of a sealing material of the present invention is not only applied to non-porous adherends such as metal and glass, but also to so-called hardly adhesive adherends coated with acrylic electrodeposition paints or fluororesin paints. However, the present invention provides a primer composition for constructing a sealing material having good adhesiveness. In addition, among various sealing materials, it provides a primer composition for sealing material construction that has good adhesion to PIB-based sealing materials that are expected to be used in applications that require weather resistance in the future. Yes, it is industrially useful. In addition, there is a possibility that it can be applied and applied in the field of adhesives and coating agents.

Claims (3)

(A) 100 parts by weight of a hydrolyzable silyl group-containing polymer containing an acrylic skeleton,
(B) 10 to 1800 parts by weight of an organopolysiloxane compound containing a hydroxyl group and / or an alkoxy group bonded to a silicon atom;
(C) 10 to 700 parts by weight of an amino group-containing silane compound,
(D) 0.1 to 700 parts by weight of a silanol condensation catalyst,
(E) A primer composition for constructing a sealing material, which is dissolved in an organic solvent.   (A) The hydrolyzable silyl group-containing polymer containing an acrylic skeleton is (A-1) a hydrolyzable silyl group-containing telechelic acrylic polymer and / or (A-2) an acrylic-containing modified silicone resin. The primer composition for sealing material construction of Claim 1. The primer composition for constructing a sealing material according to claim 1 or 2, wherein the sealing material is a polyisobutylene-based sealing material.