JP2003013040A - Method for producing substrate/sealant joined product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a substrate/sealant joined product, by which the joint between the substrate and the sealant can be strengthened. SOLUTION: This method for producing the substrate/sealant joined product is characterized by comprising a process for coating the substrate with the first primer composition containing a urethane-based compound to form the first primer layer, a process for coating the first primer layer with the second primer composition containing a silane coupling agent and/a reactive silicone resin to form the second primer layer, and a process for coating the second primer layer with the sealant containing a polyisobutylene-based polymer having reactive silicon groups.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a base material / sealing material joint, and more particularly to a method for manufacturing a joint material comprising a sealing material containing a polyisobutylene polymer having a reactive silicon group and a base material. Regarding the method.

[0002]

2. Description of the Related Art A sealing material is a material applied to joints of members constituting a structural body such as a building or a vehicle or a gap between members for the purpose of enhancing airtightness and watertightness. As the sealing material, silicone-based, modified silicone-based, polysulfide-based, modified polysulfide-based, and polyurethane-based sealing materials have been widely used. In recent years, polyisobutylene-based polymers having a reactive silicon group (Japanese Patent Laid-Open No. 63- A sealing material (hereinafter referred to as "PIB sealing material") containing as a main component (6003 gazette, etc.) was developed, and due to its flexibility and high durability of the cured product, it is noted as a sealing material that can be applied to a wide range of applications. Has been done.

However, since the PIB sealing material does not always have sufficient adhesiveness to an object to be coated (hereinafter simply referred to as "base material"), the base material is treated with a primer before the PIB sealing material is applied. Is being considered. Examples of such a primer include, for example, JP-A-1
A primer composition containing a saturated hydrocarbon polymer such as a polyisobutylene polymer having a reactive silicon group, which is disclosed in JP-A-1-343429, can be mentioned.

[0004]

However, the primer composition disclosed in the above publication has the same main component as the PIB sealing material to be laminated thereon, so that the adhesion to the PIB sealing material is improved. On the other hand, there is a problem in that, in terms of adhesiveness to the base material, a significant improvement cannot be expected in comparison with the case where the PIB sealing material is directly applied. Such a problem is particularly remarkable when the substrate is a porous substrate.

The present invention has been made in view of the above problems of the prior art, and is a method of manufacturing a base material / sealing material joint, in which a base material is used when a PIB sealing material is used as the sealing material. Is a porous substrate /
Bonding between sealing materials can be strengthened, and
When stress is applied to the joint consisting of the sealant / base material, it suppresses the interface fracture between the base material / sealing material and causes the cohesive failure of the sealant, resulting in high breaking strength. It is an object of the present invention to provide a manufacturing method capable of obtaining a bonded product that exhibits the above-mentioned properties.

[0006]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the inventors of the present invention have used two types of primer compositions containing a specific compound to form two layers on a substrate. The inventors have found that the above object can be achieved by a method of applying a PIB sealing material after providing a primer layer, and completed the present invention.

That is, in the method for producing a base material / sealing material joint of the present invention, (1) a first primer composition containing a urethane compound is applied onto a base material to form a first primer layer. And (2) applying a second primer composition containing a silane coupling agent and / or a reactive silicone resin onto the first primer layer to form a second
And a step of (3) applying a sealing material containing a polyisobutylene-based polymer having a reactive silicon group onto the second primer layer.

The method for producing a base material / sealing material joint according to the present invention also includes (1) a method in which a urethane compound is contained on each of the facing surfaces of the base materials which are arranged to face each other with a gap therebetween. Coating the first primer composition to form a first primer layer, and (2) a second primer composition containing a silane coupling agent and / or a reactive silicone resin on the first primer layer. A step of applying a material to form a second primer layer, and (3) joining the facing second primer layers with a sealing material containing a polyisobutylene-based polymer having a reactive silicon group, It is characterized by including.

In the method for producing a substrate / sealing material joint of the present invention, the urethane compound is preferably a reactive urethane compound, and in such a case, the reaction of the reactive urethane compound is Before the end
It is preferable to apply the second primer composition. Moreover, it is preferable that the said base material is a porous base material.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below with reference to the accompanying drawings. In each figure, the same elements are designated by the same reference numerals, and overlapping description will be omitted.

FIG. 1 is a sectional view showing a first embodiment of a method for manufacturing a base material / sealing material joint product according to the present invention.
FIG. 1 (a) is a cross-sectional view of a base material 1 used in the present invention. The first base material 1 contains a urethane compound.
The first primer layer 11 is formed on the upper surface of the substrate 1 by applying the primer composition (hereinafter, simply referred to as “first primer composition”) (see FIG. 1B).
Then, a second primer composition containing a silane coupling agent and / or a reactive silicone resin (hereinafter, simply referred to as “second primer composition”) is applied onto the first primer layer 11. A second primer layer 21 is formed on the upper surface of the first primer layer 11 (FIG. 1C), and further, a sealing containing a polyisobutylene-based polymer having a reactive silicon group on the second primer layer 21. By applying the material, the second primer layer 2
The sealing material layer 31 is formed on the upper surface of the substrate 1 (see FIG.
(D)).

According to the first embodiment described above, the obtained base material / sealing material joint product has a base material 1, a first primer layer 11, a second primer layer 21, and a sealing material layer 31.
The first primer layer 11 may be formed on at least a part of the surface of the base material 1, and the second primer layer 21 may be a surface of at least a part of the first primer layer 11. The sealing material layer 31 may be formed on at least a part of the surface of the second primer layer 21.

FIG. 2 is a sectional view showing a second embodiment of the method for manufacturing a base material / sealing material joint product according to the present invention.
FIG. 2A is a cross-sectional view of the base material 1a and the base material 1b used in the present invention, and the base material 1a and the base material 1b are arranged so that their end faces face each other with a gap therebetween.
Each of the facing surfaces (opposing end surfaces) of the base material has a first
The first primer layer 11a is formed on the end surface of the base material 1a and the first primer layer 11b is formed on the end surface of the base material 1b by applying the primer composition of FIG. b)). Then, the first primer layer 11 is formed by applying the second primer composition on both layers.
A second primer layer 21a is formed on a, and a second primer layer 21b is formed on the first primer layer 11b (FIG. 2 (c)). Then, the second primer layer 21a and the second primer layer 21b facing each other are joined with a sealing material containing a polyisobutylene-based polymer having a reactive silicon group to form a bond between the second primer layer 21a and the second primer layer 21a. The sealing material layer 31 is formed between the second primer layers 21b (FIG. 2 (d)).

According to the second embodiment described above, in the obtained base material / sealing material joined product, the opposing end surfaces of the base material 1a and the base material 1b have the first primer layer 11a / the second primer layer 21a / The sealant layer 31 / the second primer layer 21b / the first primer layer 11b has a laminated structure. In addition, in the second embodiment, the base material 1a and the base material 1b may be the same base material or different base materials.
1a and the first primer layer 11b, the second primer layer 21a and the second primer layer 21b, respectively,
As long as the respective primer layers belong to the primer composition of the present invention, they may be the same or different. Further, as in the first embodiment, the first primer layer 11a (or the first primer layer 11b) is the base material 1a.
(Or the base material 1b) may be formed on at least a part of the surface, and the second primer layer 21a (or the second primer layer 21b) may be the first primer layer 11a (or the first primer layer 11b). It is sufficient if it is formed on at least a part of the surface of (1). Further, the sealing material layer 31 is
Second primer layer 21a and second primer layer 21
It suffices if both layers are bonded on at least a part of the surface of b.

FIG. 3 is a sectional view showing a third embodiment of a method for manufacturing a base material / sealing material joint product according to the present invention.
FIG. 3A is a cross-sectional view of the base material 1a and the base material 1b used in the present invention, and the base material 1a and the base material 1b are arranged so as to face each other with a gap therebetween. By applying the first primer composition to each of the opposing surfaces of the base material, the first primer layer 11a is formed on the lower surface of the base material 1a, and the first primer layer is formed on the upper surface of the base material 1b. 11b is formed (FIG. 3B). Then
By applying the second primer composition on both layers, the second primer layer 21a is formed on the first primer layer 11a, and the second primer layer 21b is formed on the first primer layer 11b. Are formed (Fig. 3
(C)). Then, the second primer layer 21a and the second primer layer 21b facing each other are joined with a sealing material containing a polyisobutylene-based polymer having a reactive silicon group to form a bond between the second primer layer 21a and the second primer layer 21a. The sealing material layer 31 is formed between the second primer layers 21b (FIG. 3D).

According to the third embodiment described above, in the obtained base material / sealing material joined product, the lower surface of the base material 1a and the upper surface of the base material 1b are the first primer layer 11a / the second primer layer 21a / Sealing material layer 31 / second primer layer 2
1b / first primer layer 11b has a structure joined by a laminate. In the third embodiment, the base material 1a and the base material 1b may be the same base material or different base materials, and the first primer layer 11a
And the first primer layer 11b and the second primer layer 2
Each of 1a and the second primer layer 21b may be the same or different as long as the respective primer layers belong to the primer composition of the present invention.
Further, similar to the first embodiment, the first primer layer 11
a (or the first primer layer 11b) may be formed on at least a part of the surface of the base material 1a (or the base material 1b), and the second primer layer 21a (or the second primer layer 21b) may be It may be formed on at least a part of the surface of the first primer layer 11a (or the first primer layer 11b). Further, the sealing material layer 31 may be formed by joining both layers on the surface of at least part of the second primer layer 21a and the second primer layer 21b.

FIG. 4 is a sectional view showing a fourth embodiment of the method for manufacturing a base material / sealing material joint product according to the present invention.
FIG. 4A is a sectional view of the base material 1a, the base material 1b, and the base material 1c used in the present invention.
b are arranged on the base material 1c so as to face each other with a gap therebetween. With this arrangement, the base material 1a and the base material 1b
Also, the base material 1c forms a U-shaped groove. Then, by applying the first primer composition to the surface of the U-shaped groove, the opposite end surfaces of the base material 1a and the base material 1b, and the base material 1c corresponding to the gap between the base material 1a and the base material 1b. The first primer layer 11 is formed on the surface of (see FIG. 4).
(B)). Then, the second primer composition is applied onto the first primer layer 11 to form the second primer layer 21 on the surface of the first primer layer 11 (FIG. 4C). Next, the sealing material layer 31 is formed by joining the facing second primer layers 21 with a sealing material containing a polyisobutylene-based polymer having a reactive silicon group (FIG. 4D).

According to the fourth embodiment described above, in the obtained base material / sealing material joined article, the U-shaped groove formed by the base material 1a, the base material 1b and the base material 1c has the first primer layer 1
It has a structure filled with the first and second primer layers 21 and the sealing material layer 31. In the fourth embodiment, the base material 1a, the base material 1b, and the base material 1c may be the same base material or different base materials. Also, the first
Similar to the embodiment, the first primer layer 11 is formed of the base material 1
It suffices that the second primer layer 21 is formed on at least a part of the facing end surfaces of a and the base material 1b, and the second primer layer 21 is formed on the surface of at least a part of the facing first primer layer 11. . Furthermore, the sealing material layer 31 may be formed by joining the two layers on the surface of at least a part of the second primer layer 21 facing each other. Therefore, the sealing material layer 31 does not have to be bonded to the second primer layer 21 on the base material 1c.

Next, a first primer composition, a second primer composition, a sealing material containing a polyisobutylene-based polymer having a reactive silicon group in the method for producing a substrate / sealing material joint of the present invention, and Each of the base materials will be described.

The first primer composition of the present invention contains a urethane compound as an essential component. The urethane compound in the present invention is a compound having a urethane bond in the molecule and having substantially no reactivity (hereinafter referred to as "non-reactive urethane compound") or a urethane bond or a urea bond is formed by reaction. The compound to be obtained (hereinafter referred to as "reactive urethane compound").

Examples of non-reactive urethane compounds include polyester polyols, polyether polyols, polycarbonate polyols, olefinic polyols and acrylic polyols, and aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates and the like. Polyisocyanate, polyurethane obtained by reacting the hydroxyl equivalent of the polyol is larger than the isocyanate equivalent of polyisocyanate, or a mixture of the above polyol with a compound having active hydrogen other than the hydroxyl group (for example, polyamine, polythiol, etc.) And a polymer obtained by reacting the above with the above polyisocyanate under the condition that the active hydrogen equivalent is larger than the isocyanate equivalent. For example, those dissolved in a solvent described below can be used, and the first primer layer can be formed by volatilizing the solvent after applying it to the substrate.

The reactive urethane compound may be a compound having a urethane bond before the reaction or a compound capable of forming a urethane bond or a urea bond only by the reaction. Further, the reactive urethane compound may be a compound capable of forming a urethane bond or a urea bond, and may be a compound which forms a bond other than the urethane bond or the urea bond by the reaction. Further, the reactive urethane compound may be a one-pack type reactive urethane compound or a two-pack type reactive urethane compound.

As a preferred example of the reactive urethane compound,
Examples thereof include a compound having an isocyanate group (preferably a compound having two or more isocyanate groups). When used in a one-pack type, such a compound forms a urea bond by reacting with water in the air, for example. . When the compound having an isocyanate group is used in a two-pack type,
Using a compound having an isocyanate group as a main agent and a compound having a group that reacts with an isocyanate group as a curing agent, the two are mixed to obtain a reaction product. Examples of the compound having a group capable of reacting with an isocyanate group include alcohol (preferably polyol), amine (preferably polyamine),
Examples thereof include carboxylic acid (preferably polycarboxylic acid), and a urethane bond, a urea bond, and an amide bond are respectively formed by the reaction by mixing. After the urethane bond, the urea bond, and the amide bond are formed, the reaction with the compound having an isocyanate group may further proceed to form an alohanate bond, a biuret bond, and an acylurea bond, respectively.

Among the reactive urethane compounds, the reactive urethane compounds having an isocyanate group include aromatic polyisocyanates such as diphenylmethane diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, and alicyclic polyisocyanates such as isophorone diisocyanate. , Alohanate-modified polyisocyanate and the like. Further, these polyisocyanates and polyester polyols, polyether polyols, polycarbonate polyols, olefinic polyols, polyols such as acrylic polyols are reacted under conditions such that the isocyanate equivalent of the polyisocyanate is equal to or more than the hydroxyl equivalent of the polyol. The resulting polyurethane prepolymer and compounds having active hydrogen other than hydroxyl groups (eg, polyamine, polythiol, etc.)
And a polymer obtained by reacting a mixture of the above-mentioned polyol and the above-mentioned polyol with the above-mentioned polyisocyanate under the condition that the isocyanate equivalent becomes equal to or more than the active hydrogen equivalent.
The terminal isocyanate group in the above-mentioned reactive urethane compound having an isocyanate group may be blocked by a known method.

In the present invention, it is preferable to use a reactive urethane compound as the urethane compound. This is because the use of the reactive urethane compound increases the adhesive force between the first primer layer and the base material, and as a result, tends to improve the binding force between the base material and the sealing material.

The first primer composition may be composed of only one or two or more of the urethane compounds described above, and contains a silane coupling agent used in the second primer layer described later. You may stay.

Further, the solvent may contain water or an organic solvent. Examples of the organic solvent include aliphatic hydrocarbon solvents such as hexane and heptane; alicyclic hydrocarbon solvents such as cyclohexane; aromatic solvents such as benzene, toluene and xylene; ketone solvents such as acetone and methyl ethyl ketone; chloroform. , Halogenated hydrocarbon solvents such as carbon tetrachloride; ester solvents such as ethyl acetate; ether solvents such as diethyl ether.

When a compound having an isocyanate group is used as the urethane compound, the above solvent is preferably a solvent containing no active hydrogen. Also,
In this case, amine catalysts such as triethylamine, tetramethylethylenediamine, triethylenediamine, dimethylaminoethanol, bis (2-dimethylaminoethyl) ether and organometallic catalysts such as stannas octoate, dibutyltin dilaurate and lead octenoate. May be contained in an appropriate amount.

As the method of applying the above-mentioned first primer composition to the substrate, known coating methods such as brush coating, roll coating and spray coating can be adopted. Although the first primer layer is formed on the substrate by such a coating method, it is preferable to remove volatile components such as a solvent from the first primer layer prior to forming the second primer layer. Further, the thickness of the first primer layer is preferably 1 to 500 μm in a state where volatile components are removed. If the thickness of the first primer layer is less than 1 μm, the adhesion between the base material and the sealing material tends to be insufficient, and if it exceeds 500 μm, it is economically disadvantageous.

When the first primer composition contains a reactive urethane compound (one-pack type or two-pack type), the first primer composition should be applied to the substrate before the reaction is completed. Is preferred. Moreover, it is preferable to apply the second primer composition before the reaction of the reactive urethane compound in the first primer composition applied to the substrate is completed. By adopting such a coating method,
It is possible to improve the adhesive strength between the base material and the first primer layer and the adhesive strength between the first primer layer and the second primer layer, and thus improve the bonding strength between the base material and the sealing material. it can.

Next, the second primer composition will be described. The second primer composition contains a silane coupling agent and / or a reactive silicone resin as essential components. In the present invention, the silane coupling agent means a compound having a hydrolyzable group and an organic group bonded to a silicon atom.

Examples of the hydrolyzable group in the silane coupling agent include a halogen atom, an alkoxy group, an acyloxy group, an alkenyloxy group, an amino group, a ketoximate group, an aminooxy group, a carbamoyl group and a mercapto group. Examples of the organic group include monovalent organic groups such as an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group. In particular, an organic group having an unsaturated double bond such as a vinyl bond or an epoxy group, Amino group, (meth)
A monovalent organic group substituted with a functional group such as an acryloyl group, a carboxyl group or a mercapto group is preferable.

Suitable silane coupling agents include vinyltriethoxysilane, vinyltrimethoxysilane,
A silane coupling agent having an unsaturated double bond such as γ- (methacryloyloxypropyl) trimethoxysilane; β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ- A silane coupling agent having an epoxy group such as glycidyloxypropylmethyldiethoxysilane; a silane coupling agent having a mercapto group such as γ-mercaptopropyltrimethoxysilane; γ-
Examples of the silane coupling agent having an amino group include aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and N-β (aminoethyl) γ-aminopropyltrimethoxysilane.

In the present invention, the reactive silicone resin means a reactive silicone resin having a group capable of reacting with an organic resin and a hydrolyzable silyl group or silanol group in one molecule. Examples of the group capable of reacting with the organic resin include an amino group, an epoxy group, a hydroxyl group, a mercapto group, a carboxyl group, an isocyanate group, and a (meth) acryloyl group. The group capable of reacting with the organic resin may be directly bonded to the silicon atom or may be bonded to the silicon atom via the organic group. Further, suitable reactive silicone resins include AP-133 and AP manufactured by Nippon Unicar Co., Ltd.
Z-730, APZ-6601, APZ-6612; Chisla Corp. Sila Ace MS3201, MS3202, M
S3301, MS3302, MS5101, MS510
2 etc. can be illustrated.

The second primer composition is one of the above-mentioned silane coupling agent and / or reactive silicone resin.
It may be one kind or two or more kinds. In addition, the second primer composition may contain a silane coupling agent having an amino group and / or a reactive silicone resin having an amino group, from the viewpoint of adhesiveness to the first primer layer and the sealing material. preferable.

The second primer composition may contain an organic solvent. Examples of the organic solvent include alcohol solvents such as ethanol and isopropanol; aliphatic hydrocarbon solvents such as hexane and heptane; alicyclic hydrocarbon solvents such as cyclohexane; aromatic solvents such as benzene, toluene, xylene; acetone. Ketone solvents such as methyl ethyl ketone; halogenated hydrocarbon solvents such as chloroform and carbon tetrachloride; ester solvents such as ethyl acetate; ether solvents such as diethyl ether;
From the viewpoint of storage stability of the silane coupling agent, an alcohol solvent is preferable.

As the method for applying the above-mentioned second primer composition to the substrate, the same method as for the first primer composition can be adopted. By such application, the second primer layer is formed on the first primer layer, but it is preferable to remove volatile components such as a solvent from the second primer layer prior to applying the sealing material. Further, the thickness of the second primer layer is preferably 1 to 500 μm in a state where volatile components are removed. When the thickness of the second primer layer is less than 1 μm, the adhesiveness between the base material and the sealing material tends to be insufficient, and the thickness is 500 μm.
If it exceeds, it is economically disadvantageous.

Next, a sealing material containing a polyisobutylene polymer having a reactive silicon group will be described.
In the present invention, the sealing material contains a polyisobutylene polymer having a reactive silicon group as an essential component.

The reactive silicon group in the polyisobutylene polymer means a group capable of forming a siloxane bond by reaction, and such a group is preferably a group represented by the following general formula (1).

[Chemical 1]

In the formula, R ¹ and R ² are alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and 7 to ² carbon atoms.
0 aralkyl group or (R ′) ₃ SiO— (R ′ is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different). The indicated triorganosiloxy group and X each represent a hydroxyl group or a hydrolyzable group. When there are two or more R ¹ , R ² and X, these may be the same or different. Also, a is an integer of 0 to 3 and b is 0.
Is an integer of 2 and m is an integer of 0 to 19, respectively. However, a + mb ≧ 1 must be satisfied.

When X is a hydrolyzable group, examples of such a group include a halogen atom, an alkoxy group, an acyloxy group, an alkenyloxy group, an amino group, a ketoximate group, an aminooxy group, a carbamoyl group and a mercapto group. Of these, alkoxy groups are particularly preferable. 1-6 are preferable and, as for carbon number of an alkoxy group, 1-4
Is more preferable. A methoxy group is particularly preferred as the alkoxy group.

The reactive silicon group may be directly bonded to the polyisobutylene polymer or may be bonded through a bond such as an ether bond, a thioether bond, an ester bond, a urethane bond or a urea bond. Further, the number of reactive silicon groups bonded to the polyisobutylene polymer may be 1 or more. In the present invention, the number of reactive silicon groups bonded to the polyisobutylene polymer is preferably 1.1 to 10, more preferably 1.1 to 5. The number of reactive silicon groups may not be an integer because it means an average value.

In the present invention, the polyisobutylene polymer means a polymer obtained by polymerizing a monomer containing isobutylene as an essential component. That is, the polyisobutylene-based polymer means an isobutylene homopolymer or a copolymer of an isobutylene monomer and another monomer. When the polyisobutylene polymer is a copolymer, the content ratio of the isobutylene monomer in all monomers forming the copolymer is preferably 50% by weight or more, more preferably 70% by weight or more.

Examples of the above-mentioned other monomers copolymerizable with the isobutylene monomer include olefins other than isobutylene, vinyl ethers, aromatic vinyl compounds, vinylsilanes, allylsilanes and the like. Specifically, 1
-Butene, 2-butene, 2-methyl-1-butene, 3-
Methyl-1-butene, pentene, 4-methyl-1-pentene, hexene, vinylcyclohexene, methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, chloroethyl vinyl ether, styrene, α
-Methylstyrene, dimethylstyrene, monochlorostyrene, dichlorostyrene, β-pinene, indene, vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, vinyltrimethoxysilane, divinyldichlorosilane, divinyldimethoxysilane, 1,3-divinyl-
Examples are 1,1,3,3-tetramethyldisiloxane, tetravinylsilane, allyltrichlorosilane, allyldimethylchlorosilane, allyltrimethylsilane, diallyldichlorosilane and 3-methacryloyloxypropylmethyldimethoxysilane.

The polyisobutylene-based polymer having a reactive silicon group is the above polyisobutylene-based polymer to which at least one reactive silicon group is bonded, but the polyisobutylene-based polymer is a copolymer. When a monomer having a methoxysilyl group or a chlorosilyl group is used as a monomer other than the isobutylene monomer, a polyisobutylene polymer having a reactive silicon group bonded can be obtained, and therefore a reactive silicon group can be further bonded to the polyisobutylene polymer. It is optional.

As a method for producing a polyisobutylene-based polymer having a reactive silicon group, for example, after synthesizing a polyisobutylene-based polymer having a vinyl group at a terminal, the vinyl group is reacted with a silicon hydride compound ( Hydrosilylation reaction) can be employed. In this case, the reactive silicon group is bonded to the polyisobutylene-based polymer via —CH ₂ —CH ₂ —.

The polyisobutylene-based polymer having a vinyl group at the terminal is obtained by, for example, adding a diene (for example, a diene having 4 to 30 carbon atoms) to a polymer obtained by polymerizing isobutylene (and optionally a copolymerization monomer). And the inifer method cited in JP-A-63-6003. Further, examples of the silicon hydride compound include compounds represented by the following general formula (2). In the formula, R ¹ , R ² , X, a, b and m
Is as defined above for R ¹ , R ² , X, a, b and m.

[Chemical 2]

The polyisobutylene polymer having a reactive silicon group used in the present invention is a polymer having a number average molecular weight (Mn) of 500 to 30,000 as measured by gel permeation chromatography (GPC). Is preferred, and a polymer of 1,000 to 15,000 is more preferred.

The sealing material in the present invention is one of the above-mentioned polyisobutylene-based polymers having a reactive silicon group.
Although it may be composed of one kind or two or more kinds, further, a filler such as calcium carbonate, talc, or an organic hollow body;
Curing accelerators such as tin compounds, bismuth compounds, phosphoric acid;
Adhesiveness imparting agents such as silane coupling agents and epoxy resins; Dehydrating agents such as alkyl orthoformates, alkyl orthoacetates and hydrolyzable organic silicon compounds; Thixotropic agents such as hydrogenated castor oil and fatty acid amides; Aliphatic hydrocarbons -Based solvents, aromatic hydrocarbon-based solvents, halogenated hydrocarbon-based solvents, solvents such as alcohols, ketones, esters and ethers; plasticizers such as phthalates, antioxidants such as hindered phenol-based antioxidants; benzo UV absorbers such as triazole-based UV absorbers; light stabilizers such as hindered amine-based light stabilizers; modulus adjusting agents such as trimethylsilyl ether; air oxidation curable compounds such as tung oil; inorganics such as iron oxide, chromium oxide, titanium oxide Pigments: Organic pigments such as phthalocyanine blue and phthalocyanine green may be included.

The sealing material in the present invention may be a one-pack type sealing material or a two-pack type sealing material. The one-pack type sealing material is a sealing material containing a polyisobutylene-based polymer having a reactive silicon group and a curing accelerator in the same compound, and is stored in a state where moisture is blocked and is in air when used. Contact with water to cause curing reaction. On the other hand, the two-component type sealing material is
A sealant composed of two components, a main component containing a polyisobutylene polymer having a reactive silicon group as a main component and a curing agent containing a curing accelerator as a main component, and the main component and the curing agent are kneaded at the time of use. This causes a curing reaction.

As a method for coating the above-mentioned sealing material on the second primer layer, any known sealing material coating method can be adopted. By applying the sealing material, the sealing material layer is formed on the second primer layer. When the sealing material layer is brought into contact with moisture, the curing reaction proceeds and becomes a cured product. The thickness of the sealing material layer is not particularly limited and can be appropriately determined according to the size of the gap between the base materials and the like.

Next, the substrate in the present invention will be described. Examples of the type of substrate used in the method for producing a substrate / sealing material joined article of the present invention include organic materials, inorganic materials, organic-inorganic composite materials, and metal materials, and their shapes are arbitrary, In the present invention, a porous substrate is preferred.

As the base material used in the present invention, a base material for building materials is particularly preferable. As such a base material, a precast concrete plate, an ALC panel, a GRC / cement extrusion molded plate, a ceramic siding, a stone headboard, a precast concrete. Itayaki, concrete wall, etc. are mentioned.

[0054]

EXAMPLES Hereinafter, preferred examples of the present invention will be described in more detail, but the present invention is not limited to these examples.

Example 1 50 mm × 50 mm × 12 m
Using a brush, a bond composition primer # 9 manufactured by Konishi Co., Ltd., which is a primer composition containing a urethane compound having an isocyanate group, is applied to a mortar plate of m, and dried at room temperature for 1 hour. A primer layer (first primer layer) having a thickness of about 20 μm was formed.

Then, using a brush on the first primer layer, a primer composition containing a reactive silicone resin, APZ-6601 manufactured by Nippon Unicar Co., Ltd. (solid content:
4.5%) was applied and dried at room temperature for 1 hour to form a primer layer (second primer layer) having a thickness of about 20 μm on the first primer layer.

Using the two mortar plates provided with the first and second primer layers thus obtained, an H-shaped test piece according to JIS A 1439 was produced by the method described below. That is, the two mortar plates are faced in parallel so that the second primer layers face each other, and a penguin seal 70 manufactured by Sunstar Giken Co., Ltd., which is a sealing material containing a polyisobutylene polymer having a reactive silicon group.
00 to bond the second primer layer and
7 days in a constant temperature and humidity bath with a humidity of 3% and a temperature of 50%
The sealing material was cured by holding it in a thermo-hygrostat at 65 ° C. and a humidity of 65% for 7 days.

Example 2 In place of Penguin Seal 7000 manufactured by Sunstar Giken Co., Ltd., Mylex Z manufactured by Yokohama Rubber Co., Ltd., which is a sealing material containing a polyisobutylene polymer having a reactive silicon group, was used. In the same manner as in Example 1, an H-type test piece according to JIS A 1439 was produced.

Comparative Example 1 After forming the first primer layer in the same manner as in Example 1, the first primer layer was
After bonding using a penguin seal 7000 manufactured by Sunstar Giken Co., Ltd. in the same manner as in Example 1, the mixture was cured, and JIS A was used.
An H-shaped test piece according to 1439 was produced.

(Comparative Example 2) In place of the Penguin Seal 7000 manufactured by Sunstar Giken Co., Ltd., Mylex Z manufactured by Yokohama Rubber Co., Ltd., which is a sealing material containing a polyisobutylene polymer having a reactive silicon group, was used. An H-type test piece according to JIS A 1439 was prepared in the same manner as in Comparative Example 1.

(Comparative Example 3) 50 mm × 50 mm × 12 m
A unicar company A, which is a primer composition containing a reactive silicone resin, using a brush on a mortar plate of m
PZ-6601 (solid content: 4.5%) was applied and dried at room temperature for 1 hour to form a primer layer (first primer layer) having a thickness of about 20 μm on a mortar plate. Next, the first primer layer was bonded using a penguin seal 7000 manufactured by Sunstar Giken Co., Ltd. in the same manner as in Example 1, and then cured to prepare an H-type test piece according to JIS A 1439.

(Comparative Example 4) In place of the Penguin Seal 7000 manufactured by Sunstar Giken Co., Ltd., a Mylex Z manufactured by Yokohama Rubber Co., Ltd., which is a sealing material containing a polyisobutylene polymer having a reactive silicon group, was used. An H-type test piece according to JIS A 1439 was prepared in the same manner as in Comparative Example 3.

(Comparative Example 5) Two 50 mm × 50 mm × 12 mm mortar plates not coated with the primer composition are placed in parallel and face each other in parallel, which is a sealing material containing a polyisobutylene polymer having a reactive silicon group. Joining was performed using a Penguin Seal 7000 manufactured by Star Giken Co., Ltd. and cured in the same manner as in Example 1 to prepare an H-type test piece according to JIS A 1439.

Comparative Example 6 In place of Penguin Seal 7000 manufactured by Sunstar Giken Co., Ltd., Mylex Z manufactured by Yokohama Rubber Co., which is a sealing material containing a polyisobutylene polymer having a reactive silicon group, was used. An H-type test piece according to JIS A 1439 was prepared in the same manner as in Comparative Example 5.

Tensile tests were carried out using the H-shaped test pieces obtained in Examples 1-2 and Comparative Examples 1-6, and 50% modulus (M50), breaking strength (Tmax), breaking elongation (E).
Was measured and the fracture mode was observed. When cohesive failure occurred only in the sealing material portion by the tensile test, the failure mode was set to CF100 (meaning 100% cohesive failure). Then, when the cohesive failure in the sealing material portion was X% out of the entire failure points, it was determined as CFX. Similarly, when the interface destruction occurred only at the mortar interface, the destruction mode was AF100 (meaning 100% interface destruction).

The obtained results are shown in Tables 1 and 2 below together with the types of the primer layer and the sealing material. In Table 1, "A" means Penguin Seal 7000 manufactured by Sunstar Giken Co., Ltd., and "B" means Milex Z manufactured by Yokohama Rubber Co., Ltd. Further, "C" means Bond Seal Primer # 9 manufactured by Konishi, and "D" is A manufactured by Unicar Japan.
It means PZ-6601.

[0067]

[Table 1]

[0068]

[Table 2]

[0069]

As described above, according to the present invention,
A method for manufacturing a base material / sealing material joint, wherein when a PIB sealing material is used as the sealing material, the bond between the base material / sealing material is strengthened even if the base material is a porous base material. When a stress is applied to the bonded product composed of the base material / sealing material / base material, the interface material between the base material / sealing material is suppressed from being fractured to cause cohesive failure of the sealing material. Therefore, it is possible to provide a manufacturing method capable of obtaining a bonded article exhibiting high breaking strength.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing a first embodiment of the present invention.

FIG. 2 is a sectional view showing a second embodiment of the present invention.

FIG. 3 is a sectional view showing a third embodiment of the present invention.

FIG. 4 is a sectional view showing a fourth embodiment of the present invention.

[Explanation of symbols]

1, 1a to 1c ... Base material, 11, 11a to 11b ... First primer layer, 21, 21a to 21b ... Second primer layer, 31 ... Sealing material layer.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09D 175/04 C09D 175/04 183/04 183/04 201/10 201/10 C09J 5/02 C09J 5 / 02 123/18 123/18 F-term (reference) 4D075 AE03 CA03 CA13 CA38 DA06 DA25 DB12 DB14 DB21 DB37 DC01 DC11 EA07 EA39 EA41 EB12 EB13 EB14 EB22 EB35 EB38 EB43 EC45 4H017 AA00 AA31 AB15 AC16 AD05 J01 038131 DG05 4 DG261 DG301 DL051 DL061 DL101 GA01 GA03 GA06 GA07 GA09 GA11 KA06 NA11 NA12 PA18 PA20 PB05 PB07 PC01 PC02 PC04 PC05 4J040 DA141 DA151 GA31 JA01 JA12 JA13 KA17 LA01 MA01 MA02 MA04 MA06 MA07 NA12 NA15 PA10 PA13

Claims (5)

[Claims] 1. A first substrate containing a urethane compound on a substrate.
Forming a first primer layer by applying the primer composition of 1., and applying a second primer composition containing a silane coupling agent and / or a reactive silicone resin on the first primer layer. Forming a second primer layer by applying a sealing material containing a polyisobutylene-based polymer having a reactive silicon group on the second primer layer. Method for manufacturing joined material of sealing material and sealing material. 2. A step of forming a first primer layer by applying a first primer composition containing a urethane-based compound to each of the facing surfaces of a base material that are arranged to face each other with a gap therebetween. A step of applying a second primer composition containing a silane coupling agent and / or a reactive silicone resin on the first primer layer to form a second primer layer; And a step of joining the primer layers with a sealing material containing a polyisobutylene-based polymer having a reactive silicon group, and a method for producing a base material / sealing material joined article. 3. The method for producing a base material / sealing material joined product according to claim 1, wherein the urethane compound is a reactive urethane compound. 4. The method for producing a substrate / sealing material joint product according to claim 3, wherein the second primer composition is applied before the reaction of the reactive urethane compound is completed. 5. The method for manufacturing a base material / sealing material joint product according to claim 1, wherein the base material is a porous base material.