JPS59124976A - Adhesive sheet - Google Patents

Abstract

PURPOSE:To provide an adhesive sheet having excellent adhesion to wet surfaces, by applying an adhesive layers formed by a resin emulsion and an aqueous soln. of polyvalent metal salts on the surface of sheet-like materials. CONSTITUTION:An adhesive sheet which has an adhesive layer formed by a resin emulsion [e.g., that which contains a polymer with a glass transition point of 0 deg.C or below, consisting mainly of (meth)acrylate and an emulsion stabilizer (e.g., alkali metal salts, amine salts, or ammonium salts of a 12-20C aliph. carboxylic acid ] and an aq. neutral or alkaline soln. of polyvalent metal salts (e.g., an aq-soln. of CaCl2). Said sheet has excellent adhesion, particularly to wet surfaces.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an adhesive sheet that is excellent in adhesive application to wet surfaces.

BACKGROUND ART Adhesive sheets, which are formed by forming adhesive or pressure-sensitive adhesive layers on sheets of various materials, have been provided and are widely used for various purposes.

For example, adhesive sheets made of synthetic rubber, synthetic resin, rubber-asphalt, etc.
They are used by being attached to the surface of these structures when waterproofing them. This waterproofing construction method using an adhesive sheet is compared to other known waterproofing construction methods such as Alfalt waterproofing, paint film waterproofing, and sheet waterproofing.

It has many advantages, such as easy construction, no work at the construction site, and no generation of harmful substances that contaminate the environment. However, on the other hand, although the adhesive sheet shows good adhesion when the building block is dry, it either does not adhere at all when the building block is wet, or even if it does, it only shows extremely weak adhesive strength. However, it has a serious problem that it cannot be put to practical use.

An example of construction work that requires adhesion to wet surfaces is work for pasting adhesive sheets in places with poor ventilation, such as waterproofing work in tunnels. In this case, the structure is often wet, and in some cases it is not uncommon for some spring water or leakage water to flow down the surface of the structure. There has been a strong demand for an adhesive sheet that can provide good adhesion to other types of adhesives, and although many studies have been carried out to date to meet this demand, none has yet been found to be satisfactory.

In view of the above-mentioned problems of existing adhesive sheets, the present inventors continued their intensive research and as a result discovered a new emulsion-based adhesive composition and completed the present invention. The object of the present invention is to provide an adhesive sheet having excellent adhesive strength, especially to wet surfaces.

The above-mentioned object is an adhesive sheet characterized by having an adhesive layer formed on at least one side of a sheet-like material by a resin emulsion (B) and a neutral to alkaline polyvalent metal salt aqueous solution (B). is achieved.

In the emulsion adhesive used in the adhesive sheet of the present invention, resins that can be used as resin emulsions include natural rubber, chloroglene rubber, NBR,
Examples include rubbers such as SBR, acrylic rubber, synthetic resins such as (meth)acrylic ester polymers, and ethylene/vinyl acetate copolymers, among which (meth) shown by the following general formula (1) Polymers containing acrylic ester as a main component are preferred.

1 0H220-GOOR2---------(1) The (meth)acrylic ester represented by the above general formula (1) is roughly divided into acrylic ester and methacrylic ester, and the acrylic ester is 1 For example, acrylic acid methyl ester, Ak! J Jl/acid x tyl, :c stel, acrylic acid amyl ester, acrylic acid butyl ester, acrylic acid amyl ester, acrylic acid hexyl ester.

Acrylic et-2-ethylhexyl ester, acrylic acid n-octyl ester, acrylic acid decyl ester,
Acrylic acid lauryl varnish f J+/, acrylic acid cetyl ester, acrylic acid myristyl ester, acrylic acid stearyl ester.

Examples of acrylic acid cyclohexyl ester include methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl niscal methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, methacrylic acid n
-octyl ester, tesyl methacrylate, lauryl methacrylate ester.

Examples include myristyl methacrylate, cetyl methacrylate, stearyl methacrylate, and cyclohexyl methacrylate. In the present invention, not only homopolymers of these (meth)acrylic acid esters but also copolymers obtained by polymerizing two or more of these are also applicable in the same manner as homopolymers. The polymers applied to the present invention may be polymerized with these (meth)acrylic acid nystertopolymerizable ethylenically unsaturated oromonomers, as long as the original properties of the above polymers are not impaired. It also includes the resulting copolymer. The ethylenically unsaturated monomers applicable to the present invention include vinyls such as vinyl acetate, styrene and α-methylstyrene, nitriles such as acrylonitrile and methacrylonitrile, dibutyl maleate, vinyl persatate, Grindyl acrylate, glycidyl methacrylate l/-
However, copolymerizable esters include esters M such as Even if they are ethylenically unsaturated monomers, compounds containing sulfur groups such as sodium vinyl sulfonate, sulfonated styrene sodium salts, acrylic acid, and methacrylic acid.

Even if a carboxyl group-containing compound such as maleic acid or itaconic acid is copolymerized with a (meth)acrylic acid ester in a small amount, its properties can be drastically changed. Even if a system adhesive composition is prepared, the composition has poor adhesion to wet surfaces.)
Ru.

Therefore, these sulfone group-containing compounds and free carboxyl group-containing compounds are represented by the general formula (1) (
It is unsuitable as a copolymerization component of meth)acrylic acid ester.

The glass transition temperature of the polymer containing (meth)acrylic acid ester represented by the general formula (1) as a main component is preferably 0°C or lower, and particularly preferably -10°C or lower. When the glass transition temperature of the polymer is below 110°C, the strength of the film formed by agglomeration is strong and the adhesion is very high.In particular, it adheres strongly even to wet adherends, making it suitable. Get results.

The emulsion (g) according to the present invention comprises an emulsion stabilizer,
It is prepared by adding an adhesive strength enhancer to this as required. In the present invention, an alkali metal salt or amine salt of an aliphatic carboxylic acid having 12 to 20 carbon atoms is used as an emulsion stabilizer.

When an ammonium salt is applied, it promotes film formation through interaction with the polyvalent metal salt aqueous solution (B) of the present invention, as described below, and has excellent adhesive strength even on wet adherends. This is suitable because it expresses the following.

Examples of the aliphatic carbonic acids having 12 to 20 carbon atoms include saturated carboxylic acids such as lauric acid, myristic acid, palmitic acid, eicoic acid, and octadecanedicarboxylic acid, dodecenoic acid, myristoleic acid, palmitoleic acid, oleic acid, and gadoleic acid. Examples include unsaturated aliphatic carboxylic acids such as , eicosenoic acid, semi-hardened beef tallow fatty acid, tallow straight fatty acid, etc., and unsaturated fatty acids are particularly preferred from the viewpoint of adhesive strength to exposed substrates. In the present invention, it is preferable to use these carboxylic acids in the form of salts as emulsion stabilizers, and as such salts, alkali metal salts, amine salts, and ammonium salts all exhibit excellent adhesive strength, but especially Ammonium salts are preferred.

In the emulsion (g), the emulsion stabilizer is polymer 10
It is preferable to use α5 to 6.0 parts by weight per 0 parts by weight. If the amount of cL is too small (less than 5 parts by weight), adhesion to wet surfaces will be poor, and polymerization stability will be lacking during emulsion preparation, leading to the formation of aggregates and the like. On the other hand, if the amount exceeds 6.0 parts by weight, problems will arise in adhesion and water resistance.

The emulsion (5) according to the present invention contains a resin and an emulsion stabilizer as main components, and is usually carried out by the one-time charging polymerization method, the monomer sequential addition polymerization method, or the emulsion monomer sequential addition polymerization method. It is easily produced by addition method, seed polymerization method, etc.

The emulsion obtained as described above is used with the addition of an adhesive strength enhancer, if necessary. child! Examples of adhesive strength enhancers include rosin, modified rosin, esterified products of phenol fruit resin, resin, rosin and hyalkylphenol-modified xylene resin, derpene-phenol resin,
Terpene resins such as α and β pinene polymers, ++a aliphatic hydrocarbons, coumaron indene, methi 1/
Examples include carbon fiber resins, aromatic petroleum resins, and the like, which may be used alone or as a mixture of 2 f, fi or more.

Particularly preferred are esterified products of modified rosin and aliphatic hydrocarbon resins. These adhesive strength enhancers are preferably added to the 464 fat emulsion directly, in an emulsion state, or dissolved in a solvent such as toluene. By incorporating these adhesion strength agents, excellent adhesion effects such as improved adhesion under wet conditions, stable adhesion, less variation in apertures, and little dependence on temperature and open time are achieved. do. When blending the adhesive strength enhancer, add an emulsifier, water, etc. to prepare an emulsion, and mix it with the emulsion so that the solid content concentration of the adhesive strength strengthener emulsion is 5 to 70% by weight. It is better.

The emulsifier used in this case may be the same as or different from the emulsion stabilizer in emulsion (5), but more preferable results will be obtained if the emulsifier is the same.

In this way, the emulsion (5) of the present invention includes an emulsion containing an emulsion stabilizer and a resin, as well as an emulsion in which an adhesive strength enhancer or the like is appropriately added as necessary. The solid content concentration in the emulsion is preferably in the range of 60% to 95% (by weight).

Another important component of the present invention is a polyvalent metal salt aqueous solution (B).
There is. This functions as a film formation accelerator for the emulsion (g). These polyvalent metal salts include those in Periodic Table of Elements 1B, ]iA, 1lf3. l[B,
Examples include rVA, IVBlMA, or other salts of metals belonging to group II and acids, such as copper, magnesium, calcium, barium, zinc, aluminum, zirconia lumen, tin, manganese, or iron with formic acid, acetic acid, acetic acid, Organics such as acids 1? Salts with halogens such as , chlorine, bromine, iodine, etc. or inorganic acids such as C acids are preferred, among which neutral to alkaline salts such as calcium chloride are preferred. Chelate salts of these can also be used. The above-mentioned polyvalent metal salt is used after being dissolved in water or an aqueous medium such as water/alcohol, and the amount of the polyvalent metal salt used depends on the solid content concentration of the emulsion (A), the type of emulsion stabilizer, and the like.

It is determined by taking into account the strength of the adhesive and water resistance, etc. (
Although it is not possible to determine f, the solid content of the emulsion (ioo
It is preferable to add about 0.2 to 10 parts by weight to the heaviest part. These polyvalent metal salts are dissolved in water or an aqueous medium prepared by adding a hydrophilic solvent such as alcohol to water, and are used by adding a water-soluble polymer or a coloring pigment as necessary.

The emulsion and polyvalent metal salt aqueous solution (B) thus prepared are then applied to a sheet material to form an adhesive layer. Examples of sheet materials that can be used in the present invention include sheets of synthetic resins such as vinyl chloride, polyethylene, polypropylene, and polyester, sheets of rubbers such as butyl comb, ri:pDu, and asphalt sheets such as rubber asphalt. Can be mentioned. Furthermore, depending on the purpose of cutting, metals such as aluminum foil and copper foil, sheets of paper, cloth, and sheets of serotonin and the like may be used.

An adhesive layer made of the emulsion and the aqueous polyvalent metal salt solution (B) can be formed on these sheet-like materials by, for example, the following method.

(a) The emulsion (5) of the present invention and the polyvalent metal salt aqueous solution (B) (hereinafter abbreviated as (5) and (B)) are sprayed separately from a double-headed barrel, etc., and mixed in the air. .

(b) Brush the powder onto the surface of the sheet material in advance.

Apply with a roller, etc., and then spray (B) on when not dry.

(C) Apply (B) on the surface of a sheet-like object in advance with a brush, roller, spray, etc., and then spray the mixture in an undried state.

(d) Brush (B) onto the surface of the sheet material in advance.

Paint with a spray paint, then spray (5), then go back and spray (B).

The method of JL et al. to be selected should be determined as appropriate depending on the type and state of the adherend. It is not limited to.

Emulsion system V according to the present invention: The adhesive composition is applied to a sheet-like material by the above method to form an adhesive, but the aqueous polyvalent metal salt solution ( Second to the film formation promotion effect of B), the film formation of the adhesive layer starts immediately after application, and at the same time good adhesion is expected.

Therefore, the adhesive sheet of the present invention can be easily attached to a building frame without a drying process after applying the adhesive composition. Of course, the present invention does not limit the drying process after applying the adhesive composition, and it is a matter of course that the adhesive composition can be dried and used for various purposes. When drying,
Either natural drying or heat drying may be used.

The adhesive sheet of the present invention may be used by coating and forming an adhesive layer at the site of use immediately before use. , this may be rolled up into an o-le shape and used.
Alternatively, a release paper may be layered on the surface of the adhesive I, and a plurality of sheets may be laminated and troweled. Furthermore, the adhesive sheet of the present invention is not limited to those in which an adhesive layer is formed on one side of a sheet-like object, but also covers those in which an adhesive layer is formed on one side of a sheet-like object. 0 The structures to which the adhesive sheet of the present invention is applied are not particularly limited, but examples include concrete, mortar, cement bases such as V-stone, and plywood such as waterproof plywood. , asphalt board, metal, polyester, polystyrene.

There are synthetic resin boards such as ABS resin, and fiberboards such as .

The adhesive sheet of the present invention has excellent adhesive strength even on wet surfaces, which have been considered extremely difficult in the past. This one is especially good.

In order to make it easier to understand, in explaining this book-i@mei, we have mainly talked about waterproofing work for wet fan bodies in tunnels, but this is not limited to this. 'note? Of course, it can be shown. The adhesive sheet of the present invention can also be applied to structures other than AfJ tunnels, for example.

Underpasses, underground malls, basements, underground power plants, water tanks, waterways,
It can be conveniently used for various purposes such as waterproofing, corrosion prevention, and deep protection of wastewater treatment facilities, pools, skating rinks, bridges, and buildings, etc. Furthermore, these materials can be submerged underwater. Its industrial advantages are enormous, as it exhibits good adhesion even when used.

The following examples are given to specifically explain the present invention.
Means "parts by weight."

Example 1 Production method A of the following adhesive sheet using an adhesive composition consisting of the emulsion mixture listed in Table 1 of Volume 2 and a 5% calcium chloride water bath solution as a polyvalent metal salt aqueous solution (b). An adhesive sheet was prepared according to the following, and an adhesive test was conducted according to the adhesion test method below. Rice 6 Super Ester A75: Modified a rosin ester (
Arayo Kagaku ■) 1. Method for preparing adhesive sheets (1) Sheet) Using Truflo 01-Nitto Denko) on a vulcanized sheet of nibyl rubber and EPDM, after forming adhesive layers, cut into 25 x 201] m and serve. It was used as a sample.

(2) Application of adhesive: Emulsion (G) and polyvalent metal salt aqueous solution (B
) onto the surface of the sheet-like material (1).

At this time, the spray nozzle for the emulsion was 1.5 m thick, and the spray nozzle for the polyvalent metal salt aqueous solution (B) was 1.5 m long. The amount of emulsion (g) applied was approximately 300 I/-.

2. Adhesion test method (1) Structure: A 300 x 200 m piece of 7 lexipul board with a thickness of 3js was immersed in tap water for one day and night as a wet unit, and taken out immediately before the adhesion test, and the surface water was lightly wiped off) to serve as a specimen.

(2) Measuring method of adhesive strength: 300a immediately after pressing the adhesive sheet to the frame (1) after 1 minute has passed since the adhesive was applied to stop bleeding! 1
A 180° peel test was performed at a tensile rate of /min.

Table 2 Rice 1 Comparative Example 1.2. spray only resin emulsion.

Rice 2 The type of resin emulsion (5) is according to i (1).

Rice 3 Solid content ratio: parts by weight of calcium chloride per 100 parts by weight of solid content of emulsion (4) Example 2 As a skeleton, 1 sheet of 12 sheets and 1 sheet of calcium chloride sheet with a specific gravity of 1 layer and 1 portion of calcium chloride sheet with a thickness of 9 After being immersed in water day and night, the surface water was gently wiped off and the adhesive sheet 2 prepared in accordance with Example 1 was attached to the specimen to evaluate its adhesive strength. The results are shown in Table 6.

Example 6 Resin emulsion and l-chloroprene latex (
Hiroshi A Chemical Chloroprene Latex L'V60),
An emulsion-based adhesive composition was prepared in the same manner as in Example (1) except that a blended emulsion of EVA emulsion (Sumitomo Chemical Sumika 400) 10 double parts/(A-1) 90 double parts was used, and the composition An adhesion test was conducted on the adhesive sheet made using the following method. 5% calcium chloride aqueous solution into resin emulsion (g) solid content 100
The system using 0.7 parts solids per part showed good sheet adhesion and had the same OJ performance as the acrylic ester polymer Ogura.

Example 4 Using the resin emulsion (5) listed in Table 4 below and a polyvalent metal salt aqueous solution (10 tbsp calcium chloride water bath solution), the solid content ratio of the latter was 0.5. An adhesive composition was prepared by mixing the components in the same manner as in Example 1, and an adhesive sheet was produced using the composition in the same manner as in Example 1.

Table 4 I Chikyu Kodansei is made of a 500 x 200 ma flexible board with a thickness of 6 mm made of VC, and the above adhesive sheet is pasted in water, and after being immersed in water for 1 L1 immediately after pasting and after pasting. The adhesion strength was measured using the adhesion test method of Example 1 (2
), measurements were taken while immersed in water. The results are shown in Table 5.

The evaluation criteria for adhesive strength in the same table (same for the following examples) are as follows: li! J, j).

Adhesive strength evaluation criteria: x: 0 to 1.0 (kg/25wtb) Δ: 1
．． 0~1.5 (dirt/25μs) Q2 15~2.0 (#/2 5aa) ◎22.
0 or more (, 0 / 25) In place of the above-mentioned contact patch of the present invention, commercially available skin contact agents shown in Table 5 below were used separately. Example 1 Adhesion Test Method (1)
Approximately 3Of]g/m2 of sintered lj was added to the /-tab-shaped article described in
A test was conducted in the same manner as above using a test piece applied with a brush to ensure a sufficient amount. The results are shown in Table 5 as a comparison example.

Table 5 Application of adhesive layer) Time until application 1) Water-based adhesive: manufactured by Sumitomo 5M @ 2) I Futatsuka Electric Works C expansion 5) Solvent-based adhesive manufactured by Futatsuka Electric Works G) 4) Water-based Adhesive: Manufactured by Hoechst Synthesis 5) Cloth stick tape: Building block tape 6) Kiku double tape: Building block tape ((1) The red seal is a metaphorical example τ, lj.

Example j5 Adhesive sheet obtained in Actual Lm Example 4 (Trial j@A 7)
So, what is the 1j body listed in Table 6 of the book? Adhesion test 1 was carried out in exactly the same manner as in Example 4, except for the use of adhesives. The 11 lucky fruits are shown in Table 436.

Table 6 1) =) Roof. 01: Nitto Denko@Rubber 7-T Example 6 After applying the adhesive composition to a multi-sheet material by spraying, the temperature was 40°C.
An adhesive sheet was produced in exactly the same manner as in Example 4, Test 7, except that it was heated and dried for 24 hours. An adhesion test was conducted in the same manner as in Example 4 on the adhesive sheet 6 months after manufacture. The results are shown in Table 7.

Table 7 Example 7 The adhesive sheet obtained in Example 4 (test melon 7) was subjected to an adhesion test in exactly the same manner as in Example 1. The results are shown in Table 8.

Table 8 The red stamp means a comparative example.

Example 8 In each of the test specimens Nos. 1 to 4 shown in Table 2 of Example 1, 30 days, 100 days, and 30 days after applying the adhesive.
The adhesive strength of the products left at room temperature for 0 days was evaluated according to the adhesion test method in Example 1.
725 or more ◇ Applicant Kanebo NSC Co., Ltd. Procedural Amendment Honor (Method) April 28, 1980 Director General of the Specialty Commission Wakasugi No. 1] Odono No. 1, Incident Display 1982 255858 2, Name of the invention Adhesive sheet 3, Relationship to the shaft fixing case Patent applicant address Rikifubou Senri Building, No. 6, Senba 11-chome, Minoh City, Osaka Name Kanebo NSC Co., Ltd. Representative: Tatsuo Matsumoto (and one other company) 4, Agent Address: 5-17-4 Sumida, Sumida-ku, Tokyo 564
Patent Department, Kanebo Co., Ltd., 1-6-80 Tomobuchi-cho, Bejima-ku, Osaka City Phone: (06) 923-1143 5. Date of amendment order: June 29, 1980 (shipment date) 6. Increased brother due to amendment Document certifying power of representation (from Fujikura Kasei Co., Ltd.) and the entire specification.

a Contents of amendment (1) Document certifying power of attorney
Fujikura Kasei Co., Ltd.'s book) will be completed.

(2) The statement on the statement at the time of submission is attached to the attached statement.
(No change in content) We will make a correction.

9 List of attached documents (1) 1 power of attorney from Fujikura Kasei Co., Ltd. (2) 1 or more clearly written typed specifications regarding Patent Application No. 233838 of 1982

Claims (1)

[Claims] (1) A resin emulsion and a neutral to alkaline polyvalent metal salt aqueous solution (B
) An adhesive sheet comprising an adhesive layer formed by (2) The resin emulsion (4) contains a polymer whose main component is a (meth)acrylic acid ester and whose glass transition temperature is 0°C or lower, and an emulsion stabilizer. adhesive sheet. (6) The adhesive sheet according to claim (2), wherein the emulsion stabilizer is an alkali metal salt, amine salt, or ammonium salt of an aliphatic carboxylic acid having 12 to 20 carbon atoms. (4) The adhesive sheet according to claim (6), wherein the aliphatic carboxylic acid is an unsaturated aliphatic carboxylic acid. (5) Claims in which the resin emulsion (8) contains a polymer whose main component is a (meth)acrylic acid ester and whose glass transition temperature is 110°C or less, an adhesive strength enhancer, and an emulsion stabilizer. The adhesive sheet according to any one of items (1) to (4). (6) The adhesive sheet according to claim (5), wherein the adhesive strength enhancer is a modified rosin ester or an aliphatic hydrocarbon resin. (7) The adhesive sheet according to claim (5), wherein the emulsion stabilizer is an alkali metal salt, amine salt, or ammonium salt of an unsaturated aliphatic carboxylic acid having 12 to 20 carbon atoms. (8) The adhesive sheet according to any one of claims (1) to (7), wherein the polyvalent metal salt is calcium chloride. (9) Claims (1) to (8) in which the sheet-like material is a synthetic resin sheet, a rubber sheet, or asphalt.
Adhesive sheet described in any of the items◇