JPH11348013A - Tile fixing self-adhesive - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve a roughened surface bonding force by a method wherein a tile fixing self-adhesive consists of an alkali-soluble acrylic resin and a concrete hardening retarder. SOLUTION: A self-adhesive consists of an alkali-soluble acrylic resin, which is a copolymer containing a (meth)acrylate having an ether linkage, an α,β-unsaturated carboxylic acid or its salt and, when necessary, using in combination with a monomer copolymerizable with the monomer at the polymerization of the copolymer, and a concrete hardening retarder, which is a hydroxycarboxylic acid such as a gluconic acid, a tartaric acid, a citric acid, a malic acid or a galactonic acid and its salt or their salt. Thus, a roughened surface bonding force can be improved. At the manufacturing of a concrete plate, on which tiles are pasted in advance, the staining of the tile due to the setting of a cement paste can be prevented from developing.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive for fixing a tile, which is used when a tile is pre-attached to a precast concrete plate.

[0002]

2. Description of the Related Art In order to enhance aesthetics in buildings such as buildings, tiles are frequently used on outer walls, and in recent years, a method of manufacturing a concrete plate on which tiles are pasted in advance at a factory and assembling it on site, that is, a pre-installation method has been used. Has been adopted. For the concrete board used in the pre-adhesion method, a tile pack in which a required number of tiles are stuck in a matrix on a tape or sheet coated with an adhesive is produced, and concrete is poured on the back side of the tile. The mold is set on the inner surface of the mold as described above, then concrete is poured into the mold, cured, and after the concrete is hardened, the mold is dismantled. However, during the production of the concrete plate, after the concrete is poured into the formwork, a part of the concrete leaks from the joints of the tiles and wraps around the tile surface. There was a problem that required a lot of work. To solve such a problem, Japanese Patent Application Laid-Open No.
In JP 93227A, a water-soluble or alkali-soluble resin is used for the adhesive layer of the tape. Further, JP-A-8-118325 discloses a tape provided with a pressure-sensitive adhesive layer containing a concrete retarder for delaying the curing of concrete.

[0003]

However, in the technique disclosed in Japanese Patent Application Laid-Open No. Hei 6-193227, although the adhesive remaining on the tile can be washed away immediately after construction, the hardened concrete leaked to the tile surface is scraped off. Complicated work is required, and Japanese Patent Application Laid-Open No. 8-118325
In the technology disclosed in the publication, although the curing of concrete is delayed, when an acrylic pressure-sensitive adhesive, particularly an acrylic emulsion is used as the pressure-sensitive adhesive, the emulsion is
The tape substrate has a low heat resistance temperature and a low surface wetting tension, and is incompatible with the tape substrate, and has problems in drying properties and adhesion to the substrate.
In addition, since an acrylic resin containing an acrylate ester or the like as a main component is used, the concrete retarder hardly dissolves in the alkaline concrete paste.
It was necessary to add 15 to 40 parts by weight with respect to 00 parts by weight. As a result, it was found that there was a problem that the adhesive strength to the rough surface was inferior, and it was not yet satisfactory.

[0004]

In order to solve such a problem, the present inventors have sought to solve the above-mentioned problems by a tile fixing adhesive comprising an alkali-soluble acrylic resin and a setting retarder for concrete. The present invention has been completed.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described specifically. The alkali-soluble acrylic resin used in the present invention is not particularly limited as long as it is an acrylic resin soluble in an alkaline aqueous solution. Preferably, the solubility in a 3% by weight aqueous sodium hydroxide solution at 20 ° C. is 10% by weight or more, Further, it is 30 to 100% by weight. If the solubility is less than 10% by weight, the rate of dissolution of the concrete setting retarder into the concrete paste becomes undesirably low.

The solubility of the resin in water at 20 ° C. is preferably less than 10% by weight, more preferably 5% by weight or less. When the solubility is 10% by weight or more, the moisture resistance of the pressure-sensitive adhesive is inferior.

The method of controlling the solubility in the above-mentioned 3% by weight aqueous sodium hydroxide solution and water is not particularly limited, but the carboxylic acid group contained in the specific alkali-soluble acrylic resin described later is converted into sodium hydroxide, water, or the like. A method of partially neutralizing with an alkali such as potassium oxide may be used.

As the alkali-soluble acrylic resin,
For example, a (meth) acrylate having an ether bond,
A copolymer containing an α, β-unsaturated carboxylic acid or a salt thereof, and if necessary, a monomer copolymerizable with the above-mentioned monomer at the time of polymerization of the copolymer may be used in combination.

(Meth) acrylate having an ether bond is a compound in which an ether bond is introduced into (meth) acrylate by alkoxy or the like, and includes 2-ethoxyethyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, ethyl Examples thereof include carbitol acrylate and 2-butoxyethyl acrylate. Particularly, 2-ethoxyethyl acrylate and 2-methoxyethyl acrylate are preferably used.

The α, β-unsaturated carboxylic acids and salts thereof include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid and the like, and salts thereof such as sodium, potassium, magnesium, calcium and the like. And acrylic acid, methacrylic acid and the like are particularly preferably used.

It is also preferable to use other copolymerizable monomers in combination. Examples of the monomers include alkyl acrylates having 1 to 9 carbon atoms (methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, etc.), alkyl methacrylate (methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, 2-ethylhexyl methacrylate, etc.), vinyl acetate, acrylonitrile, methacrylonitrile, Styrene, hydroxyethyl acrylate, hydroxyethyl methacrylate,
There are hydroxypropyl acrylate, hydroxypropyl methacrylate, dimethylaminoethyl methacrylate, acrylamide, methacrylamide, methylol acrylamide, glycidyl methacrylate and the like. Among them, butyl acrylate, 2-ethylhexyl acrylate, methyl acrylate and vinyl acetate are preferably used.

The copolymerization ratio (weight ratio) of a (meth) acrylate having an ether bond to an α, β-unsaturated carboxylic acid or a salt thereof, or another copolymerizable monomer is 20 to 9
It is preferably from 8/2 to 10/0 to 78, more preferably from 30 to 60.
/ 3 to 7/33 to 67 are preferred. Outside the above range, alkali solubility becomes insufficient or water solubility becomes too large, which is not preferable.

The alkali-soluble acrylic resin used in the present invention can be easily produced by a method well known to those skilled in the art, such as radical copolymerization of the above components in an organic solvent.
Examples of the organic solvent used in the polymerization include aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate and butyl acetate, and aliphatic alcohols such as methanol, ethanol, n-propyl alcohol and iso-propyl alcohol. , Methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone and the like, and the polymerization catalyst used for radical polymerization,
Specific examples include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, cumene hydroperoxide and the like, which are ordinary radical polymerization catalysts. Further, the glass transition temperature (Tg) of the resin is preferably −20 ° C. or less.
If it exceeds -20 ° C, the adhesive strength tends to decrease, which is not preferred.

The alkali-soluble acrylic resin preferably has a weight average molecular weight of 200,000 to 1,000,000, more preferably 40,000.
10,000 to 700,000. If the weight average molecular weight is less than 200,000,
Insufficient cohesive force, problematic removability from tile,
If it exceeds 1,000,000, the production efficiency of the resin decreases, which is not preferable.

Examples of concrete setting retarders include (1) gluconic acid, tartaric acid, citric acid, malic acid,
Oxycarboxylic acids such as galactonic acid or salts thereof and salts thereof, (2) ketocarboxylic acids such as pyruvic acid, (3) sugar alcohols such as sorbitol and arabitol, (4) glucose, mannose, sucrose, etc. And (5) sodium silicofluoride, magnesium silicofluoride, lead nitrate, sodium phosphate, sodium iodide, sodium humate, tannin and the like.

The concrete retarder is used in an amount of 1 to 1 with respect to 100 parts by weight of the alkali-soluble acrylic resin.
It is preferable to mix 5 parts by weight, more preferably 3 to 10 parts by weight. If the compounding ratio is less than 1 part by weight, the effect of delaying the setting of the concrete paste is reduced when the thickness of the pressure-sensitive adhesive layer is small, and if it exceeds 15 parts by weight, the adhesive strength is undesirably reduced.

The adhesive for fixing tiles of the present invention contains the above-mentioned alkali-soluble acrylic resin and a setting retarder for concrete. The method for producing the adhesive is not particularly limited. Adding an aqueous solution of the curing retarder to an alcohol (methanol, ethanol, iso-propanol, etc.) solution of the base resin,
A method of stirring the mixture until the mixture becomes uniform is exemplified. In this case, the content of the alkali-soluble acrylic resin in the alcohol solution is preferably 30 to 60% by weight, more preferably 35 to 5% by weight.
0%. The amount of the set retarder in the aqueous solution of the concrete set retarder is about 10 to 40% by weight. Thus, the pressure-sensitive adhesive for fixing a tile of the present invention is obtained. Such a pressure-sensitive adhesive is usually used as a solution of the above-mentioned alcohol and water. However, the pressure-sensitive adhesive can be used even if the alcohol and water are distilled off.

The pressure-sensitive adhesive of the present invention can withstand use as a pressure-sensitive adhesive for fixing tiles as it is. However, in order to further improve pressure-sensitive adhesive performance (removability), 0.01 to 100 parts by weight of the pressure-sensitive adhesive is used. It is also preferable to add a crosslinking agent of up to 5 parts by weight, such as an epoxy-based, isocyanate-based, metal (aluminum, titanium, etc.) chelate-based,
Examples include amine-based cross-linking agents, and one or more are selected from these, and preferably include epoxy-based and metal-chelate-based cross-linking agents. Further, a coloring agent, a stabilizer, a filler, an adhesion improver, and the like can be added to the pressure-sensitive adhesive in addition to the crosslinking agent.

Next, a specific method of using the tile fixing adhesive will be described in detail below. First, the adhesive is applied on a substrate. The material of the substrate to be used is not particularly limited, for example, polyethylene, polypropylene,
Films such as polyethylene terephthalate can be used, and these films may be stretched. The thickness of the substrate is desirably about 15 to 200 μm. If the thickness is less than 15 μm, the stiffness becomes weak, and it becomes difficult to use the adhesive sheet for fixing tiles. If the thickness exceeds 200 μm, the outer diameter of the substrate roll becomes large, making it difficult to increase the length.

The thickness of the pressure-sensitive adhesive layer is preferably 15 to
100 μm. When the thickness of the pressure-sensitive adhesive layer is less than 15 μm, the effect of delaying the setting of the concrete paste is reduced, and when it exceeds 100 μm, it becomes difficult to form a pressure-sensitive adhesive tape or sheet.

In the present invention, as described above, the pressure-sensitive adhesive of the present invention is applied to at least one surface of a substrate and used for fixing a tile. An adhesive (adhesive) can be applied to the other surface of the substrate for the purpose of temporarily fixing to a mold or the like, and such an adhesive may be the adhesive of the present invention, but usually has excellent adhesive strength. Other adhesives (adhesives) are used. Thus, by providing the pressure-sensitive adhesive layers on both sides, it is also possible to constitute a tile fixing pressure-sensitive adhesive tape or sheet as a double-sided pressure-sensitive adhesive tape or sheet. In addition, release paper (release liner) may be laminated on the pressure-sensitive adhesive layer as needed.

An example of a method of applying the above-mentioned adhesive tape or sheet for fixing a tile to the production of a PC board will be described. First, tiles are arranged in a matrix on a flat surface. At this time, joints having predetermined dimensions are accurately formed, and temporary joints are embedded in the joints. Next, a tile fixing adhesive tape or sheet is attached so that the adhesive layer of the present invention is in contact with the tile surface to obtain a tile pack, which is set in a mold. Thereafter, the concrete is poured into the formwork, cured, and the concrete is hardened. After the concrete is hardened, the mold is removed, and then the adhesive tape or sheet for fixing the tile is peeled off.

At this time, the cement paste is leaking from the joint portion of the tile, but the concrete surface hardly progresses hardly because the concrete adhesive retardant is contained in the adhesive layer. Therefore, the concrete paste or the like adhering to the tile surface can be easily and reliably removed by washing with water or the like.

[0024]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below.
In the following description, “%” and “parts” are based on weight unless otherwise specified. Example 1 A four-necked round-bottomed flask was equipped with a reflux condenser, a stirrer, a dropping funnel and a thermometer, and charged with 50 parts of methanol. After heating and refluxing, 0.2 parts of azobisisobutyronitrile was used as a polymerization initiator. , And a mixture of 45 parts of 2-ethoxyethyl acrylate, 45 parts of n-butyl acrylate, 5 parts of acrylic acid, and 5 parts of vinyl acetate is added dropwise over 1 hour. After the reaction, methanol, iso-propanol, water (weight ratio:
40/45/15) to obtain a resin content of 40% to obtain an alkali-soluble acrylic resin (solution) having a weight average molecular weight of 550,000 and a glass transition temperature of -46 ° C. The solubility of the resin in a 3% aqueous sodium hydroxide solution at 20 ° C. was 95%. The solubility in water at 20 ° C. was 0.2%. The weight average molecular weight was determined by gel permeation chromatography, and the glass transition temperature was determined by a differential scanning calorimeter (DSC).

250 parts of the resin solution (100 parts of resin)
Was mixed with 12.5 parts of a 40% aqueous sucrose solution, and then mixed with an aluminum chelate-based curing agent (“COPONYL 5”).
792 "(manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) and mixed to obtain a tile fixing adhesive.

Using the pressure-sensitive adhesive, a pressure-sensitive adhesive sheet for fixing a tile was produced as follows, and the adhesive strength was evaluated. Thickness 4
The thickness after drying the adhesive for fixing the tile on one surface of a substrate made of a 0 μm stretched polypropylene film is 50 μm.
To prepare a pressure-sensitive adhesive sheet for fixing tiles, and the following evaluation was performed. (Adhesive Strength) Adhesive Strength to SUS The adhesive strength of the sheet to the stainless steel plate was determined by preparing a stainless steel plate (SUS304) and bonding the adhesive sheet to the stainless steel plate at 20 ° C. and 65% RH.
The 180 degree peel strength was measured based on the measuring method of the adhesive force of Z0237. -Rough surface adhesive strength The same evaluation was performed except that the adherend was made of a stainless steel plate and made into No. 280 sandpaper.

(Removability) Tile (size: 45 mm × 95)
mm) The adhesive sheet was stuck on the surface and the removability after leaving at 60 ° C. for 3 days was evaluated as follows. ◎ ・ ・ ・ No glue residue ○ ・ ・ ・ Slight glue residue on tile surface △ ・ ・ ・ Quite glue residue on tile surface × ・ ・ ・ Glue residue on most of tile surface

Further, a tile pack was produced using the above-mentioned pressure-sensitive adhesive as follows, and the delay effect was evaluated as follows.
After uniformly applying the tile fixing adhesive to one surface of a flat yarn base material (made of polyethylene) having a thickness of 110 μm,
After drying at 80 ° C. for 10 minutes, a pressure-sensitive adhesive sheet for fixing tiles having a thickness of 50 μm was produced. A plurality of tiles each having a size of 45 mm × 95 mm are attached to the sheet in a matrix so that the joint width becomes 5 mm.
A tile pack having a size of 00 mm × 600 mm was prepared.

The tile pack prepared as described above is set in a mold so that the side on which the tile is not bonded is overlapped on the bottom of the mold, and the instant cement ("Instant Sunday cement", A concrete paste containing 100 parts) and 250 parts of water was poured into a mold, cured at room temperature for 72 hours, and cured. Thereafter, the mold was released, and the adhesive sheet for fixing the tile was peeled off from the surface of the tile pack. (Delay effect) One hour after the tile fixing adhesive sheet was peeled off, the concrete leaking to the panel surface was washed off by washing with water, and the delay effect was evaluated as follows. ◎ ・ ・ ・ All leaked concrete was washed away.・ ・ ・: There were a few concrete fragments that could not be washed away with water washing, but they could be easily peeled off with a spatula. Δ: There were concrete fragments that could not be washed away with water, and could be peeled off with a spatula. ×: The tile surface was damaged when the spatula was not easily peeled off and forcibly removed.

Example 2 A tile fixing adhesive was obtained in the same manner as in Example 1 except that the addition of 3 parts of an aluminum chelate-based curing agent (“Corponyl 5792”, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) was omitted. This was carried out as in the example.

Example 3 The procedure of Example 1 was repeated, except that 12.5 parts of a 40% aqueous solution of sucrose was changed to 7.5 parts.
An adhesive solution for fixing a tile was obtained and evaluated in the same manner as in Example 1.

Examples 4 and 5, Comparative Example 1 An alkali-soluble acrylic resin having the composition shown in Table 1 was prepared in the same manner as in Example 1, and was evaluated in the same manner as in Example 1.

Comparative Example 2 The procedure of Example 1 was repeated except that the addition of the sucrose aqueous solution was omitted, and the same evaluation was performed. Table 2 shows the results of Examples and Comparative Examples.

[0034]

[Table 1]Alkali-soluble acrylic resin (A) * (B) * (C) * Tg (℃) Alkaline Water solubleSolubility ** *** Example 1 2-EEA AAc BA VAc-46 950 (40) (5) (50) (5) {2-EEA AAc BA VAc -46 950 (40) (5) (50) (5)} 3 2-EEA AAc BA VAc -46 950 (40) (5) (50) (5) 〃 42-EEA AAc BA VAc -46 100 3 (60) (10) (25) (5) ５ 52 -EEA AAc 2-EHA VAc -55 300(40) (5) (50) (5) Comparative Example 1 2-EEA AAc BA VAc -490 0 (20) (2) (73) (5) 22-EEA AAc BA VAc -46 950 (40) (5) (50) (5) Note) Figures in parentheses indicate parts by weight. Abbreviations are as follows. 2-EEA; 2-ethoxyethyl acrylate, AAc; acrylic acid, BA; n-butyl acrylate, VAc; vinyl acetate, 2-EHA; 2-ethylhexyl acrylate * (A); (meth) acrylate having an ether bond, B): α, β-unsaturated carboxylic acid or a salt thereof, (C); other copolymerizable monomer ** Solubility (%) in 3% aqueous sodium hydroxide solution at 20 ° C **** Water at 20 ° C Solubility (%)

[0035]

[Table 2] Adhesive force (g / inch) Removability Delay effect SUS Rough surface Example 1 1200 400 ◎ ◎ 〃 2 2000 800 ○ ◎ ３ 3 1500 500 ◎ ◎ 〃 1000 4 1000 350 ◎ ◎ 〃 5 1300 500 ◎ ○ Comparative Example 1 1100 550 × × 〃 2 1300 600 × × Note) SUS and rough surface (# 280 sandpaper) represent the adhesive strength between stainless steel and rough surface, respectively.

[0036]

The adhesive for fixing a tile according to the present invention is composed of an alkali-soluble acrylic resin and a setting retarder for concrete, so that it has excellent rough surface adhesion, and is used for producing a concrete board to which tiles are previously attached. No stain on tiles due to condensation.

Claims (6)

[Claims] 1. An adhesive for fixing a tile, comprising an alkali-soluble acrylic resin and a setting retarder for concrete. 2. The pressure-sensitive adhesive for fixing a tile according to claim 1, further comprising a crosslinking agent. 3. An alkali-soluble acrylic resin having a solubility in a 3% by weight aqueous sodium hydroxide solution at 20 ° C. of 10% by weight or more and a glass transition temperature of -20 ° C. or less. Item 3. The tile fixing adhesive according to Item 1 or 2. 4. A water solubility at 20 ° C. of 10
The pressure-sensitive adhesive for fixing a tile according to claim 3, wherein the adhesive is an alkali-soluble acrylic resin having a content of less than 10% by weight. 5. The compounding ratio of the concrete setting retarder is based on 100 parts by weight of the alkali-soluble acrylic resin.
The adhesive for fixing a tile according to any one of claims 1 to 4, wherein the amount is 1 to 15 parts by weight. 6. The method according to claim 1, wherein the alkali-soluble acrylic resin is a copolymer containing a (meth) acrylate having an ether bond, an α, β-unsaturated carboxylic acid or a salt thereof. The adhesive for fixing a tile according to the above.