JP2801641B2 - Surface joining method for ceramic plate etc. - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method of surface joining a porcelain plate, a glass plate or the like to a surface of concrete, blecast concrete, fiber reinforced cement or the like.

<Prior art> Conventionally, in a method of surface joining a porcelain plate material, a glass plate, etc. to the surface of concrete, precast concrete, fiber reinforced cement, etc., an adhesive or mortar made of a two-part epoxy resin composition curable at room temperature is used. The adhesive layer is made of a material having a low flexibility such as the above.

However, in such a conventional method, since the adhesive layer has poor flexibility, there are limitations on impact absorption, prevention of concrete cracks, and the like. In addition, since the adhesive is a two-pack type composed of a main agent and a curing agent, it is necessary to measure and mix the main agent and the curing agent at the time of use.

Recently, in order to strengthen the bonding strength, prevent intrusion of water, etc., and allow even a slight deformation of concrete, etc., use an adhesive mainly composed of epoxy-modified polysulfide etc. as an adhesive, apply this, and then concrete The method of casting or applying and then spreading silica sand and joining via silica sand has been performed in some cases. However, the adhesive having epoxy-modified polysulfide or the like as a main component has a heat resistance temperature of 80 ° C. Due to the degree of plasticity of the polysulfide itself and the thermosetting properties of the epoxy resin, the adhesive strength is strong but the hardness is high, the elasticity and deformability are poor, the shock absorption and crack followability are not sufficient, In some cases, fatigue and interface or cohesive failure occurred.

In addition, the epoxy-modified polysulfide adhesive is a two-pack type, and therefore has a problem in workability, such as applicability,
There is a drawback that low-temperature curability requires attention.

<Problems to be solved by the invention> The present invention has been made in view of the above facts,
Elastic joining while relieving or absorbing the difference in movements such as expansion and contraction due to mutual temperature difference, dry and wet difference, vibration displacement, etc. between the ceramic plate material, glass plate etc. and the back material such as concrete, Cracking of ceramic plate, glass plate, etc. due to them
The object of the present invention is to provide a surface joining method capable of preventing peeling, dropping, etc., and preventing birch, frost damage, etc. caused by intrusion of water into the gaps on the back surface of a ceramic plate, a glass plate, or the like. is there.

<Means for Solving the Problems> The present invention relates to a method of surface-bonding a porcelain plate, a glass plate, etc. to the surface of concrete, precast concrete, fiber reinforced cement, or the like. Applying a room temperature curable one-pack type epoxy resin composition having an elongation of 20 to 300%, and after the resin composition is cured, performing mortar application on the surface of the concrete, precast concrete, fiber reinforced cement, or the like, Alternatively, there is provided a surface joining method for a porcelain plate material or the like, characterized in that precast concrete, fiber-reinforced cement or the like is interposed and elasto-plastically joined.

Here, a surface bonding method for a ceramic plate material or the like in which the room temperature-curable one-pack type epoxy resin composition contains the following components (a) to (e) is preferable.

(A) epoxy resin (b) ketimine represented by formula 1 (Wherein R ¹ , R ² , R ³ and R ⁴ are hydrogen, an alkyl group having 1 to 6 carbon atoms or a phenyl group, X is an alkylene group having 2 to 6 carbon atoms or a non-adjacent group having 6 to 12 carbon atoms) (C) a modified silicone resin; (d) a catalyst for the modified silicone resin; (e) a silane compound. (Wherein, R ¹ is a monovalent hydrocarbon group having 1 to 12 carbon atoms, R ² is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 0 to 2). Surface bonding method such as a porcelain plate material which is a silicone resin having a decomposable silicon functional group at the end, the modified silicone resin is 10 parts by weight based on 100 parts by weight of the epoxy resin
A surface joining method for a ceramic plate material or the like that is included in an amount of up to 500 parts by weight is good.

Further, the silane compound is an aminoalkylalkoxysilane, an epoxyalkylalkoxysilane, a mercaptoalkylalkoxysilane or a copolymer thereof, and has a molecular weight of 2000 or less. A surface bonding method for a porcelain plate material or the like in which the silane compound is contained in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the epoxy resin is preferable.

In addition, a surface bonding method for a porcelain plate material or the like in which the room temperature-curable one-pack type epoxy resin composition further contains a dehydrating agent in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the epoxy resin is preferable.

 Hereinafter, the present invention will be described in detail.

 First, the present invention will be described with reference to the drawings.

According to the method of the present invention, as shown in FIG. 1, a room temperature-curable one-pack type epoxy resin composition 2 having an elongation after curing of 20 to 300% is applied to the back surface 1a of a ceramic plate 1 (A) (B). ), Curing and curing (C).

Next, the hardened and cured porcelain plate material 1 is supported at a predetermined position such as a concrete wall surface 3 serving as a back surface material via a mounting bracket 4 such as a trigger (D), and a mortar 5 is filled therebetween (E). Then, the bonding is completed by the hardening curing.

Alternatively, as shown in FIG. 2, a room temperature curable one-pack type epoxy resin composition 2 having an elongation after curing of 20 to 300% is applied to the back surface 1a of the porcelain plate material 1 (A) (B) and cured. Curing (C)
The made ceramic plate material 1 is set on a mold frame 6 with the back surface 1a facing upward, and a clip metal 7 and a trigger metal 8 are appropriately attached (D).
Here, precast concrete or fiber-reinforced cement 9 is cast (E), cured (F), and after curing, it is attached to a predetermined portion of the building 10 via a fitting 11 (G).

The application of the epoxy resin composition may be performed with an airless gun or a roller.

Further, the coating thickness is determined in consideration of expected displacement and the like.

Incidentally, the epoxy resin composition, it is preferable to use a cured product that adheres well to the ceramic plate material and the like, but in some cases, after the primer treatment of the ceramic plate material and the like, the epoxy resin composition is applied. Is also good.

In the present invention, since the room-temperature-curable one-pack type epoxy resin composition having an elongation after curing of 20 to 300% is used as the adhesive, the relative displacement caused by various causes between the porcelain plate and the like and the concrete and the like is reduced. Absorption can be alleviated, and both can be surface-sealed in a watertight, airtight, heat-resistant, and elastoplastic manner.
If the elongation after curing of the epoxy resin composition used is less than 20%, cracks are likely to occur in the adhesive layer, and the elongation is 300%.
%, Efflorescence tends to occur,
Adhesion also deteriorates.

In addition, efflorescence means that the leaching leaches from the ready-mixed concrete and contaminates the porcelain plate material and the like.

The porcelain plate and the like to which the method of the present invention is applied include a porcelain plate and a glass plate.

The epoxy resin composition used in the present invention is cured within 24 hours even at a low temperature of about 0 ° C., and after curing,
When concrete is poured in, especially when casting precast concrete or fiber reinforced cement
It is preferable to use a material which does not deteriorate to steam curing for several hours at ℃ and alkali generated, and can withstand high temperature, low temperature, alkali and other attacks thereafter.

If such an epoxy resin composition is used for a long time, it follows the in-plane displacement, and at the same time, retains its out-of-plane adhesive strength, exhibits practically sufficient strength for out-of-plane pressure, and is watertight and dense. In addition, elasto-plastic joining can be maintained.

Incidentally, the room-temperature-curable one-pack type epoxy resin composition used in the present invention may be any one as long as it has an elongation after curing of 20 to 300%, and will be described below (a) to (c).
A composition containing the component (e) can be mentioned as a representative.

As the epoxy resin of the component (a), for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin obtained by reacting bisphenol A, bisphenol F, bisphenol AD and the like with epichlorohydrin, etc. And, hydrogenated epoxy resin, glycidyl ester type epoxy resin, novolak type epoxy resin, urethane modified epoxy resin having a urethane bond, nitrogen-containing epoxy resin epoxidized metaxylene diamine and hydantoin,
Examples include, but are not limited to, rubber-modified epoxy resins containing polybutadiene or NBR.

The epoxy resin may be used alone or in combination of two or more.

The ketimine of the component (b) refers to a ketimine represented by the following formula 1.

(Wherein R ¹ , R ² , R ³ and R ⁴ are hydrogen, an alkyl group having 1 to 6 carbon atoms or a phenyl group, X is an alkylene group having 2 to 6 carbon atoms or a non-adjacent group having 6 to 12 carbon atoms) Ketimine is stable in the absence of water,
It becomes a primary amine by moisture and functions as a curing agent for epoxy resin. That is, ketimine is a latent curing agent. Thus, the storage stability of the room-temperature-curable one-pack type epoxy resin composition containing the components (a) to (e) is improved, and the curability during use is good.

Examples of such ketimines include 1,2-ethylenebis (isopentylideneimine), 1,2-hexylenebis (isopentylideneimine), 1,2-propylenebis (isopentylideneimine), p, p'- Examples thereof include biphenylenebis (isopropylideneimine), 1,2-ethylenebis (isopropylideneimine), 1,3-propylenebis (isopropylideneimine), and p-phenylenebis (isopentylideneimine).

The ketimine may be used alone or in combination of two or more.

The amount of ketimine used depends on the period during which the raw epoxy resin composition is stored, but generally, the amount of epoxy resin 100
It is 1 to 60 parts by weight, preferably 10 to 30 parts by weight based on parts by weight. If the amount is less than 1 part by weight, the curing rate becomes slow, which is not preferable. On the other hand, if it exceeds 60 parts by weight, the epoxy resin is easily cured at the time of storage, and the storage stability is unfavorably reduced.

The modified silicone resin of the component (c) refers to, for example, a silicone resin into which a functional group such as an amino group, a phenyl group, or an alkoxy group has been introduced, and has a hydrolyzable silicon functional group represented by the following formula 2 at the terminal. It is preferable to use a silicone resin having the same.

(Wherein, R ¹ is a monovalent hydrocarbon having 1 to 12 carbons, R ² is a monovalent hydrocarbon group having 1 to 6 carbons, and n is an integer of 0 to 2). And a silicone resin having a methyldimethoxysilyl group at a terminal, and the like, and commercially available products such as poly (methyldimethoxysilylethyl ether)
(MSP20A, manufactured by Kanegabuchi Chemical Industry Co., Ltd.) can be used.

One of these modified silicone resins may be used alone, or two or more of them may be used in combination.

Use of such a modified silicone resin is important for imparting flexibility to a cured product of the epoxy resin composition.

The curing of the modified silicone resin is performed by moisture in the air in the presence of a catalyst for the modified silicone resin.

The amount of the modified silicone resin used is 10 to 500 parts by weight, preferably 50 to 200 parts by weight, based on 100 parts by weight of the epoxy resin. If the amount is less than 10 parts by weight, the flexibility after curing of the epoxy resin composition is not sufficient. On the other hand, if the amount exceeds 500 parts by weight, the adhesiveness deteriorates, which is not preferable.

The modified silicone resin catalyst of the component (d) is a catalyst that cures the above modified silicone resin.

More specifically, a tin compound such as dibutyltin oxide, a metal salt of a carboxylic acid such as lead octylate, an amine salt such as cybutylamine-2-ethylhexoate, and the like are exemplified. May be used in combination.

The amount of the modified silicone resin catalyst used is 0.1 to 10 parts by weight based on 100 parts by weight of the modified silicone resin.

The silane compound of the component (e) refers to a so-called silane coupling agent represented by the following formula 3, or a reaction product of the coupling agent and a polymer.

R′Si (OR) ₃ (where R is an alkyl group and R ′ is an organic functional group such as an amino group, a mercapto group, a vinyl group, an epoxy group, etc.) It is preferable to use alkoxysilane, epoxyalkylalkoxysilane, mercaptoalkylalkoxysilane, or an alkoxysilane derivative that is a copolymer thereof.

More specifically, examples thereof include aminopropyltrimethoxysilane, a reaction product of aminopropyltrimethoxysilane with vinyltrimethoxysilane, and a reaction product of γ-glycidoxypropyltrimethoxysilane with polysulfide. Can be used.

The molecular weight of these silane compounds is preferably 2000 or less. If the molecular weight exceeds 2,000, the adhesiveness tends to deteriorate, which is not preferable.

The silane compounds may be used alone or in combination of two or more.

The amount of these silane compounds used is generally 0.1 to 50 parts by weight, preferably 1 to 100 parts by weight based on 100 parts by weight of the epoxy resin.
10 parts by weight. When the amount is less than 0.1 part by weight, the adhesiveness is deteriorated, which is not preferable.On the other hand, when the amount exceeds 50 parts by weight,
When used, ambient moisture reacts with the silane compound to make the modified silicone resin difficult to cure, and prevents ketimine from becoming a primary amine and functioning as a curing agent for the epoxy resin. This is not preferable because the curability of the room-temperature curable one-pack type epoxy resin composition deteriorates.

The above-mentioned room temperature-curable one-pack type epoxy resin composition includes component (a) epoxy resin, component (b) ketimine, component (c) modified silicone resin, component (d) catalyst for modified silicone resin, component (e) Although a silane compound is contained,
In addition, a dehydrating agent is preferably added.

The dehydrating agent suppresses the curing of the epoxy resin or the silicone resin due to the reaction of the ketimine or the modified silicone resin or the silane compound with water when the epoxy resin composition is not used, and improves the storage stability of the epoxy resin composition. Used to improve.

Examples of the dehydrating agent include vinyltrimethoxysilane, ethyl orthoformate and the like, and it is preferable to use 0.1 to 10 parts by weight based on 100 parts by weight of the epoxy resin.

The epoxy resin composition further, if necessary,
An antioxidant such as titanium oxide, a pigment such as carbon black, a filler such as calcium carbonate, and other additives such as an ultraviolet absorber and a plasticizer may be contained.

The room temperature-curable one-pack type epoxy resin composition comprises the component (a)
Epoxy resin, component (b) ketimine, component (c) modified silicone resin, component (d) catalyst for modified silicone resin,
The component (e) is produced by mixing a silane compound and additives such as a dehydrating agent by a conventional method, and is stored in a sealed container.

This epoxy resin composition is suitably used in the method of the present invention shown in FIGS. 1 and 2 without the presence of a primer.

<Examples> Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.

(Examples) (i) Production of room temperature-curable one-pack type epoxy resin composition Bisphenol A type epoxy resin (manufactured by Sumitomo Chemical Co., Ltd., trade name: ELA128) and poly (methyl) as a modified silicone resin in the ratios shown in Table 1. Dimethoxysilyl ethyl ether (manufactured by Kaneka Chemical Industry Co., Ltd., trade name MSP20A), calcium carbonate and titanium oxide were stirred at room temperature under reduced pressure (20 Torr or less) using a high-viscosity mixing stirrer. Next, vinyltrimethoxysilane (manufactured by Nippon Unicar, trade name A171) as a dehydrating agent and aminopropyltrimethoxysilane (manufactured by Nippon Unicar, trade name A1) as a silane compound
100), and the mixture was stirred under reduced pressure. Dibutyltin oxide dioctyl phthalate solution (manufactured by Sankyoki Seisaku Co., Ltd., trade name No.918) as a modified silicone resin catalyst, and ketimine (manufactured by Yuka Shell Epoxy Co., Ltd.) In the same manner, trade name H-3) or triethylenetetramine was added, and the mixture was stirred under reduced pressure to produce a one-part epoxy resin composition curable at room temperature.

(Ii) Evaluation The following evaluation was performed on the resin composition obtained in (i), and the results are shown in Table 1.

(1) Tack free time The resin composition was applied to a slate plate with a thickness of 5 mm, and the tack free time was measured.

(2) Storage stability Put the resin composition in a cartridge, store at 50 ° C,
Opened after the day, properties were evaluated according to the following criteria.

：: almost the same as the initial viscosity △: thicker than the initial viscosity ×: gelling (3) Hardness The resin composition was applied to a slate plate with a thickness of 5 mm and cured and cured (25 ° C., 50% RH, 7 days) Do) and about it, JI
Shore D hardness was measured according to SK 6301.

(4) Elongation The resin composition is applied to a polyethylene sheet with a thickness of 2 mm, cured and cured (25 ° C., 50% RH, 7 days), and punched out with a JIS K No. 3 dumbbell to form a JIS K 6301. According to the tensile test, the elongation at break was measured.

(5) Impact test The resin composition was applied to a ceramic plate (tile) (200 mm x 200 mm x 35).
mm) on the surface of 1 mm thick and cured (25 ° C, 50% R
H, for 7 days) to obtain test specimens. An iron ball (2.26 kg) was dropped from a height of 1 m on the surface of the test body where the cured resin layer was not provided, and the state of destruction of the cured resin layer was visually observed.

(6) Efflorescence test 0.5 m of the resin composition was applied to the inner surfaces 16, 17, and 18 of a water tank (50 mm x 50 mm x 35 mm) 15 made of a porcelain plate (tile) shown in Fig. 3.
It was applied with a thickness of m and cured by curing (25 ° C., 50% RH, 7 days). Next, a 6% aqueous solution of sodium sulfate was placed in the water tank 15, and the state of the effusion oozing out on the outer surface of the water tank was visually observed.

(7) Adhesiveness A resin composition is applied to one surface of a plate (200 mm x 200 mm x 35 mm) made of glass, aluminum, granite, tile, or mortar under the same conditions as in (5), cured, and cured. And

The test body was set on a frame material with the cured resin layer facing upward, a mortar was poured there, and cured at 20 ° C. and 60% RH for 14 days.

After curing, the adhesion was tested by hand peeling and evaluated according to the following criteria.

○: cohesive failure of cured resin △: partial interface failure between resin and plate ×: interface failure between resin and plate As is clear from Table 1, when the room-temperature-curable one-pack type epoxy resin composition specified by the method of the present invention is used, not only the properties of the resin composition, but also the flexibility and water resistance of the cured product and the mortar The adhesion was also excellent.

When a resin composition having a small elongation after curing was used (Comparative Example 1), cracks occurred due to impact because of poor flexibility.

On the other hand, when a resin composition having a large elongation after curing was used (Comparative Example 3), the adhesiveness was not sufficient.

Further, from Comparative Example 4, it was found that when a curing agent for an epoxy resin other than ketimine was used as a curing agent for a one-part epoxy resin composition curable at room temperature, storage stability was not sufficient.

<Effects of the Invention> The present invention is a method in which a cured product is a method of surface-bonding a porcelain plate or the like to concrete or the like using a room-temperature-curable one-component epoxy resin composition having high elasticity and deformability. The surface joint after construction is excellent in water tightness, air tightness, moisture proof, heat resistance, chemical resistance, etc., can maintain the required joint strength for a long time, and especially for porcelain plate (surface material) etc. and concrete Temperature difference, back and forth difference, vibration displacement,
The relative displacement due to expansion and shrinkage and other internal stress differences can be absorbed and mitigated by the low modulus elasticity of the cured epoxy resin itself, preventing cracking, peeling, falling, etc. of the surface material,
In addition, birch, frost damage and the like due to intrusion of water into the back gap can be prevented.

Further, the present invention can be applied to a case where a porcelain plate or the like is joined to vertical inner and outer wall surfaces, a ceiling surface, a floor surface, or the like, and is also applicable to a surface joint with a bleed concrete or a fiber reinforced cement.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a construction order explanatory view showing an example of the construction method of the present invention, FIG. 2 is a construction order explanatory view showing another construction example of the construction method of the present invention, FIG. FIG. 2 is a perspective view showing a water tank used for an Efro test. DESCRIPTION OF SYMBOLS 1... Ceramic plate material 1a... Back surface of ceramic plate material 2... Epoxy resin composition or cured product thereof 3... Concrete wall surface 4... Mounting metal fittings 5... Mortar 6. Frame, 7: Clip hardware, 8: Trigger, 9: Brecact concrete or fiber reinforced cement, 10: Construction, 11: Mounting bracket, 15: Water tank, 16, 17, 18 ... side

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) E04F 13/08 101 E04F 13/14

Claims (7)

(57) [Claims] 1. A method of surface joining a porcelain plate, a glass plate, etc. to the surface of concrete, precast concrete, fiber reinforced cement, etc., wherein the elongation after curing is 20 to 300% on the back surface of the porcelain plate, glass plate, etc. Room temperature curable one-part type epoxy resin composition, and after the resin composition is cured,
An interview with a porcelain plate or the like, characterized in that mortar is applied to the surface of the concrete, precast concrete, fiber reinforced cement, etc. Joint construction method. 2. The method according to claim 1, wherein the one-part epoxy resin composition curable at room temperature contains the following components (a) to (e). (A) epoxy resin (b) ketimine represented by formula 1 (Wherein R ¹ , R ² , R ³ and R ⁴ are hydrogen, an alkyl group having 1 to 6 carbon atoms or a phenyl group, X is an alkylene group having 2 to 6 carbon atoms or a non-adjacent group having 6 to 12 carbon atoms) (C) modified silicone resin (d) catalyst for modified silicone resin (e) silane compound 3. The modified silicone resin according to claim 2, wherein (Wherein, R ¹ is a monovalent hydrocarbon group having 1 to 12 carbon atoms, R ² is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 0 to 2). 3. The method according to claim 2, wherein the terminal is a silicone resin having a decomposable silicon functional group at its terminal. 4. The modified silicone resin is contained in an amount of 10 to 500 parts by weight based on 100 parts by weight of the epoxy resin.
Or the surface joining method of porcelain plate material or the like according to 3. 5. The method according to claim 2, wherein the silane compound is an aminoalkylalkoxysilane, an epoxyalkylalkoxysilane, a mercaptoalkylalkoxysilane or a copolymer thereof, and is an alkoxysilane derivative having a molecular weight of 2000 or less. Surface bonding method for porcelain plate etc. described in any of them. 6. The method according to claim 1, wherein the silane compound is an epoxy resin.
The surface joining method for a porcelain plate material or the like according to any one of claims 2 to 5, which is contained in an amount of 0.1 to 50 parts by weight relative to 0 parts by weight. 7. The method according to claim 7, wherein the dehydrating agent is an epoxy resin.
The surface joining method according to any one of claims 1 to 6, which is contained in an amount of 0.1 to 10 parts by weight based on parts by weight.