JP3561411B2 - Tile fixing adhesive and tile fixing adhesive tape or sheet - Google Patents

Description

略号は以下のとおり。
２−ＥＥＡ；２−エトキシエチルアクリレート、ＡＡｃ；アクリル酸、ＢＡ；ｎ−ブチルアクリレート、ＶＡｃ；酢酸ビニル、２−ＥＨＡ；２−エチルヘキシルアクリレート
＊（Ａ）；エーテル結合を有する（メタ）アクリレート、（Ｂ）；α，β−不飽和カルボン酸又はその塩、（Ｃ）；その他の共重合可能なモノマー
＊＊２０℃における３％水酸化ナトリウム水溶液に対する溶解度（％）
＊＊＊２０℃における水に対する溶解度（％）
【００３５】
【表２】

【００３６】
【発明の効果】
本発明のタイル固定用粘着剤は、エーテル結合を有する（メタ）アクリレート、α，β−不飽和カルボン酸又はその塩、その他の共重合可能なモノマーの共重合比（重量比）が２０〜９８／２〜１０／０〜７８であるアルカリ可溶性アクリル系樹脂、コンクリート用硬化遅延剤よりなるので、粗面接着力に優れ、予めタイルが貼付けられたコンクリート板の製造時に、セメントペーストの凝結によるタイルの汚れがない。[0001]
TECHNICAL FIELD OF THE INVENTION
TECHNICAL FIELD The present invention relates to an adhesive for fixing a tile and an adhesive tape or sheet for fixing a tile, which are used when a tile is pre-attached to a precast concrete plate.
[0002]
[Prior art]
In order to enhance aesthetics in buildings such as buildings, tiles are frequently used for outer walls, and in recent years, a method of manufacturing a concrete plate on which tiles are pasted in advance in a factory and assembling it on site, that is, a pre-installation method has been adopted. Tipping method the concrete slab that is used, the number of tiles required to adhesive coated tapes and sheet manufactured tile pack affixed to a matrix, the concrete is pouring it on the back of the tile The mold is set on the inner surface of the mold, and 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, so that it is complicated to scrape off the hardened concrete leaked to the tile surface. There was a problem that required a lot of work.
In order to solve such a problem, JP-A-6-193227 uses a water-soluble or alkali-soluble resin for the adhesive layer of the tape. Further, Japanese Patent Application Laid-Open No. HEI 8-118325 discloses a tape provided with a pressure-sensitive adhesive layer containing a hardening retarder for concrete for delaying hardening of concrete.
[0003]
[Problems to be solved by the invention]
However, in the technique disclosed in JP-A-6-193227, although the adhesive remaining on the tiles can be washed out immediately after the construction, a complicated work for shaving off the hardened concrete leaked to the tile surface is required. In the technology disclosed in JP-A-8-118325, although the curing of concrete is delayed, when an acrylic adhesive, particularly an acrylic emulsion, is used as the adhesive, the emulsion has a low heat resistance temperature of the tape base material and causes surface wetting. It has poor compatibility with low tension materials, and has problems in drying properties and adhesion to substrates. Moreover, since an acrylic resin containing an acrylate ester or the like as a main component is used, the hardening retarder for concrete hardly dissolves in the alkaline concrete paste. On the other hand, it was necessary to add 15 to 40 parts by weight, and as a result, it was found that there was a problem that the adhesive strength to a rough surface was inferior, and it was still not satisfactory.
[0004]
[Means for Solving the Problems]
In order to solve such a problem, the present inventors have proposed a copolymerization ratio (weight ratio) of a (meth) acrylate having an ether bond, an α, β-unsaturated carboxylic acid or a salt thereof, and other copolymerizable monomers. ) Is 20 to 98/2 to 10/0 to 78, and an adhesive for fixing a tile comprising an alkali-soluble acrylic resin and a setting retarder for concrete solves the above-mentioned problems, and completed the present invention.
[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. Furthermore, it is 30 to 100% by weight. If the solubility is less than 10% by weight, the rate of dissolution of the hardening retarder for concrete into the concrete paste is undesirably low.
[0006]
Further, 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.
[0007]
The method for controlling the solubility in the above-mentioned 3% by weight sodium hydroxide aqueous solution or water is not particularly limited, but the carboxylic acid group contained in the specific alkali-soluble acrylic resin described later may be sodium hydroxide, potassium hydroxide or the like. Partially neutralized with an alkali.
[0008]
The alkali-soluble acrylic resin, d ether with binding (meth) acrylate, alpha, beta-unsaturated carboxylic acid or copolymers containing a salt, if desired copolymer during polymerization in the monomer and co A polymerizable monomer may be used in combination.
[0009]
(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 is 2-ethoxyethyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, or ethyl carbitol acrylate. , 2-butoxyethyl acrylate and the like, and particularly, 2-ethoxyethyl acrylate, 2-methoxyethyl acrylate and the like are preferably used.
[0010]
The α, β-unsaturated carboxylic acid or a salt thereof includes acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid and the like, and salts thereof such as sodium, potassium, magnesium and calcium. Particularly, acrylic acid, methacrylic acid and the like are preferably used.
[0011]
Further, it is also preferable to use another copolymerizable monomer in combination. Examples of the monomer 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, hydroxy Ethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, dimethylamino Chill methacrylate, acrylamide, methacrylamide, methylol acrylamide, there are glycidyl methacrylate, etc., among them, butyl acrylate, 2-ethylhexyl acrylate, methyl acrylate, vinyl acetate is preferably used.
[0012]
The copolymerization ratio (weight ratio) of the (meth) acrylate having an ether bond to an α, β-unsaturated carboxylic acid or a salt thereof, or another copolymerizable monomer is 20 to 98/2 to 10/0 to 78 . It is necessary that the ratio be 30 to 60/3 to 7/33 to 67. Outside the above range, alkali solubility becomes insufficient or water solubility becomes too large, which is not preferable.
[0013]
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-mentioned 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. The polymerization catalyst used for radical polymerization is azobisisobutyronitrile, benzoyl peroxide, di-t- Butyl peroxide, cumene hydroperoxide and the like are specific examples.
Further, the glass transition temperature (Tg) of the resin is preferably -20 ° C or lower, and if Tg exceeds -20 ° C, the adhesive strength tends to decrease, which is not preferable.
[0014]
The weight average molecular weight of the alkali-soluble acrylic resin is preferably from 200,000 to 1,000,000, and more preferably from 400,000 to 700,000. If the weight average molecular weight is less than 200,000, the cohesive strength is insufficient, and there is a problem in removability from the tile. If it exceeds 1,000,000, the production efficiency of the resin decreases, which is not preferable.
[0015]
Examples of the concrete retarder include (1) oxycarboxylic acids and salts thereof such as gluconic acid, tartaric acid, citric acid, malic acid, galactonic acid and salts thereof, and (2) ketocarboxylic acids such as pyruvic acid. , (3) sugar alcohols such as sorbitol and arabitol, (4) sugars such as glucose, mannose, and sucrose; and (5) sodium silicofluoride, magnesium silicofluoride, lead nitrate, sodium phosphate, sodium iodide, and humin. Acid sodium, tannin and the like.
[0016]
The hardening retarder for concrete is preferably blended in an amount of 1 to 15 parts by weight, more preferably 3 to 10 parts by weight, based on 100 parts by weight of the alkali-soluble acrylic resin. If the mixing 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.
[0017]
The tile fixing adhesive of the present invention contains the above alkali-soluble acrylic resin and a concrete setting retarder, and the method for producing the adhesive is not particularly limited. A method of adding an aqueous solution of the curing retarder to an alcohol (methanol, ethanol, iso-propanol, etc.) solution and stirring the mixture until the solution becomes uniform is mentioned. 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 50%. 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, but can be used even if the alcohol and water are distilled off.
[0018]
The pressure-sensitive adhesive of the present invention can sufficiently withstand use as a tile fixing pressure-sensitive adhesive as it is, but 0.01 to 5 parts by weight based on 100 parts by weight of the pressure-sensitive adhesive in order to further improve the pressure-sensitive adhesive performance (removability). It is also preferable to add a cross-linking agent of a part. Examples of the cross-linking agent include epoxy-based, isocyanate-based, metal (aluminum, titanium, etc.) chelate-based and amine-based cross-linking agents. Preferably, an epoxy-based or metal chelate-based crosslinking agent is used.
Further, a coloring agent, a stabilizer, a filler, an adhesion improver, and the like can be mixed with the pressure-sensitive adhesive in addition to the crosslinking agent.
[0019]
Next, a specific method for 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, films such as polyethylene, polypropylene, and 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, which is not preferable.
[0020]
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.
[0021]
Further, 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. It is possible to apply an adhesive (adhesive) to the other surface of the substrate for the purpose of temporary fixing to the surface of the substrate, and such an adhesive may be the adhesive of the present invention. An adhesive (adhesive) is 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. A release paper (release liner) may be laminated on the pressure-sensitive adhesive layer as needed.
[0022]
An example of a method of applying the above-mentioned adhesive tape or sheet for fixing a tile to the manufacture 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.
[0023]
At this time, the cement paste is leaking from the joint portion of the tile, but the concrete surface hardly progresses hardly because the pressure-sensitive adhesive layer contains a hardening retarder for concrete. Therefore, concrete paste and the like adhering to the tile surface can be easily and reliably removed by washing with water or the like.
[0024]
【Example】
Hereinafter, the present invention will be described specifically. In the following description, “%” and “parts” are based on weight unless otherwise specified.
Example 1
A 4-neck round bottom flask was equipped with a reflux condenser, a stirrer, a dropping funnel and a thermometer, 50 parts of methanol were charged, and after heating and refluxing, 0.2 parts of azobisisobutyronitrile was added as a polymerization initiator. 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 was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was reacted at ethyl acetate reflux temperature for 5 hours. Methanol, iso-propanol, water (weight ratio: 40/45/15), prepared so as to have a resin content of 40%, an alkali-soluble acrylic resin having a weight average molecular weight of 550,000 and a glass transition temperature of -46 ° C (solution) Got. 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 a gel permeation chromatography method, and the glass transition temperature was determined by a differential scanning calorimeter (DSC).
[0025]
After adding and mixing 12.5 parts of a 40% aqueous solution of sucrose to 250 parts of the resin solution (resin content: 100 parts), an aluminum chelate-based curing agent (“Corponyl 5792”, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) ) 3 parts were added and mixed to obtain a tile fixing adhesive.
[0026]
Using the pressure-sensitive adhesive, a pressure-sensitive adhesive sheet for fixing a tile was produced as follows, and the adhesive strength was evaluated.
The tile fixing pressure-sensitive adhesive was applied to one surface of a substrate made of a stretched polypropylene film having a thickness of 40 μm so that the thickness after drying became 50 μm, to produce a tile fixing pressure-sensitive adhesive sheet, and the following evaluation was performed.
(Adhesive strength)
Adhesive force 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 to determine the adhesive strength of JIS Z 0237. The 180 degree peel strength was measured according to the measurement method.
Rough Surface Adhesion The same evaluation was performed except that the adherend was made of a stainless steel plate and made into No. 280 sandpaper.
[0027]
(Removability)
The adhesive sheet was stuck on the surface of a tile (size: 45 mm x 95 mm), 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 [0028]
Further, a tile pack was produced using the above-mentioned pressure-sensitive adhesive as follows, and the retardation effect was evaluated as follows.
The above-mentioned adhesive for fixing a tile was uniformly applied to one surface of a flat yarn base material (made of polyethylene) having a thickness of 110 μm, and dried at 80 ° C. for 10 minutes to produce an adhesive sheet for fixing a tile having a thickness of 50 μm. A plurality of tiles each having a size of 45 mm × 95 mm were attached to the sheet in a matrix so that the joint width was 5 mm, and then cut to prepare a tile pack having a size of 300 mm × 600 mm.
[0029]
The tile pack prepared as described above is set in the mold so that the side on which the tile is not bonded is placed on the bottom of the mold, and the instant cement ("Instant Sunday Cement", manufactured by Home Chemical Industry Co., Ltd.) ) 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 tiles 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 retarding effect was evaluated as follows.
・ ・ ・: All leaked concrete was washed away.
○: There were a few pieces of concrete that could not be washed away with water, but they could be easily peeled off with a spatula.
Δ: There were concrete fragments that could not be washed away with water, and they could be peeled off with a spatula.
×: The tile surface was damaged when the spatula was not easily peeled off and forcibly peeled off.
[0030]
Example 2
In Example 1, the addition of 3 parts of an aluminum chelate-based curing agent (“Corponyl 5792”, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) was omitted, and a tile fixing adhesive was obtained in the same manner. .
[0031]
Example 3
The same procedure as in Example 1 was carried out except that 12.5 parts of a 40% aqueous solution of sucrose was changed to 7.5 parts in Example 1, to obtain an adhesive solution for fixing tiles, and evaluated in the same manner as in Example 1. Was done.
[0032]
Examples 4 and 5, Comparative Example 1
An alkali-soluble acrylic resin having the composition shown in Table 1 was prepared in accordance with Example 1, and evaluated in the same manner as in Example 1.
[0033]
Comparative Example 2
In Example 1, the same evaluation was performed by omitting the addition of the aqueous sucrose solution and performing the same evaluation.
Table 2 shows the results of Examples and Comparative Examples.
[0034]
[Table 1]

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 a 3% aqueous sodium hydroxide solution at 20 ° C.
*** Solubility in water at 20 ° C (%)
[0035]
[Table 2]

[0036]
【The invention's effect】
The adhesive for fixing a tile of the present invention has a copolymerization ratio (weight ratio) of (meth) acrylate having an ether bond, α, β-unsaturated carboxylic acid or a salt thereof, and another copolymerizable monomer. / 2-10 / 0-78, which is composed of an alkali-soluble acrylic resin and a concrete setting retarder, has excellent rough surface adhesion, and is used for producing a concrete plate to which a tile has been previously attached. There is no dirt.

Claims (6)

The copolymerization ratio (weight ratio) of the (meth) acrylate having an ether bond, the α, β-unsaturated carboxylic acid or a salt thereof, and other copolymerizable monomers is 20 to 98/2 to 10/0 to 78. An adhesive for fixing a tile, comprising an alkali-soluble acrylic resin and a setting retarder for concrete. 2. The tile fixing adhesive 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 DEG C. of 10% by weight or more and a glass transition temperature of -20 DEG C. or less is used. Adhesive for fixing tiles. The adhesive for fixing a tile according to claim 3, wherein the adhesive is an alkali-soluble acrylic resin having a solubility in water at 20 ° C of less than 10% by weight. The adhesive for fixing a tile according to any one of claims 1 to 4, wherein a mixing ratio of the curing retarder for concrete is 1 to 15 parts by weight based on 100 parts by weight of the alkali-soluble acrylic resin. A tile fixing pressure-sensitive adhesive tape or sheet obtained by laminating the tile fixing pressure-sensitive adhesive according to claim 1 on a substrate .