JPS5840377A - Pressure-sensitive aqueous adhesive - Google Patents

Abstract

PURPOSE:To provide a pressure-sensitive aqueous adhesive to be applied on wall surface, which shows only a small degree of decrease in adhesive power to uncured mortar due to outdoor exposure and forms a waterproof layer when cured, prepared by condensation of a high-molecular weight acrylic resin with a terpene resin emulsion. CONSTITUTION:The adhesive is prepared by mixing an acrylic resin emulsion obtained by dispersing an acrylic resin with a molecular weight of 300,000 or higher in water in the presence of a nonionic surfactant, with an emulsion of a terpene resin with a softening point of 100-150 deg.C, in the blend ratio of 1:0.5-1:2 by weight and adding, when necessary, a defoamer (e.g., polyglycol-based surfactant), a thickener (e.g., ammonium salt of macromolecular organic acid), an inorganic filler (e.g., CaCO3), etc. The adhesive is applied on plywood, metal plate, cement board, etc. and when dried, shows markedly reduced lowering of adhesive power to uncured mortar due to degradation of resistance to ultraviolet ray, water and heat, and when cured, causes the mortar layer and substrate to form a completely solid structure, with the adhesive layer serving as a waterproof layer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention describes the use of wall W for mortar finishing of walls of structures.
This is an improved water-based pressure sensitive W adhesive applied in the UK.

Conventionally, painting the exterior or interior walls of a structure involves pasting lath paper or rubber-based or '+-j+--based sheets on the base material, mechanically fixing the main legs and lath wire mesh, and
This is done either by spraying green mortar over it or without troweling. In this method, the wooden wire mesh and lath wire mesh are fixed using ordinary nails and staples, so water often flows to the back side through the nail holes and staple holes.

Recently, various types of adhesives have been used to bond raw mortar and walls together for the purpose of saving labor.
There is a disadvantage that the period until the right rear mortar is cast is limited. That is, glue the wall tffc11! When exposed to the outside of clothed dkAil, there is a problem in that the adhesive strength of the adhesive with fresh mortar deteriorates over time due to changes over time. In practice, the raw tartar is covered with a colored polyethylene sheet or the like, but this requires labor and has problems such as the covering sheet being damaged by wind and rain.

In order to solve this problem, the present invention uses an acrylic resin emulsion that is water-dispersed with an acrylic resin having a molecular weight of 30,000 or more and a nonionic surfactant, and an acrylic resin emulsion that has a softening temperature of 100 to 100,000 ljO.
A terpene resin emulsion that is water-dispersed with a nonionic surfactant such as a terpene resin at ℃ is mixed with a weight ratio of the acrylic resin and the terpene resin in the range of / : OJ ~ 1:0. The present invention provides a water-based pressure-sensitive adhesive.

In addition, the water-based pressure-sensitive adhesive is prepared by uniformly mixing the above-mentioned water-based pressure-sensitive adhesive conductive material, antifoaming agent, thickener, inorganic filler, etc. as required. A water-based pressure-sensitive adhesive is applied to the surface of organic or inorganic adherends such as metal plates, cement plates, and gypsum plates, and after drying, it can be bonded to raw mortar even when exposed to external violence. . In other words, UV deterioration, water resistance deterioration, heat resistance deterioration, etc. caused by outdoor cod
The decrease in adhesive strength with raw mortar caused by this is extremely small.
Also, after the raw mortar hardens, the crushed body and mortar layer are % total rc.
When integrated, the adhesive PIJ has the feature that it can become a waterproof layer.

The acrylic resin of the present invention comprises a copolymer having the following structural formula (referred to as basic acrylic resin in the present invention 1) q), methacrylic pentatyl ester, which is a monomer constituting the above copolymer, and It includes a copolymer obtained by copolymerizing at least one of styrene and vinyl acetate with acrylic acid ester.

The molecule S of the acrylic resin must be 30,000 or more, and if the molecular weight is less than 300,000, the VC will not have sufficient cohesive force and when used in a water-based pressure-sensitive adhesive, the adhesive force will be low, which poses a problem. In the case of styrene copolymerized saceta acrylic resin, if the styrene content exceeds 30% by weight, there will be problems with weather resistance, and when used as a water-based pressure-sensitive adhesive, there will be problems with adhesion to green mortar after outdoor exposure. be. In the case of acrylic resin copolymerized with vinyl acetate, if the content of vinyl acetate exceeds 301, there will be problems with water resistance, and when used as a water-based pressure-sensitive adhesive, this adhesive layer will not function as a waterproof coating. There is a function-LK problem. As described above, it is preferable for the acrylic resin of the present invention to have good weather resistance and water resistance, high cohesive force and high film strength, and surface adhesion since it is a pressure-sensitive MS adhesive.

Types of resins used with acrylic resin include coumaron Φ inch/resin, terpene phenol resin, p-tert-butylphenol/acetylene resin, phenol formaldehyde resin, terpene resin, xylene/formaldehyde resin, petroleum hydrocarbon resin, There are hydrogenated hydrocarbon resins, rosin derivatives, turpentine resins, etc., but they have problems such as weather resistance, heat resistance, water resistance, cost, and compatibility with various base materials and compatibility with acrylic resins. Delben resin is best than problem.

Also, since the softening temperature of Olben resin is estimated to be 10''C at maximum since it is used as a base material for mortar, a softening temperature # of 100°C is necessary.

Furthermore, when a water-based pressure-sensitive adhesive is prepared by using a material having a temperature of 100"C or less, the cohesive force of the adhesive decreases.

When a water-based pressure-sensitive adhesive is made using a resin with a softening temperature of 750°C or higher, the adhesive layer becomes hard and brittle, resulting in interfacial peeling between the mortar layer and the adhesive layer or between the adhesive layer and the base layer. occurs.

Considering the above points, a terpene resin having a softening temperature of 100 to 30°C is preferable as the resin for the water-based pressure-sensitive adhesive.

The acrylic resin S and terpene resin of the present invention are used in the form of an emulsion in which they are dispersed in water with a nonionic surfactant. It is selected appropriately depending on the conditions when used as a press-type adhesive, and a weight of 35 to .1 weight is usually used.
Standardly, a material with a weight of 100 g is used, but of course the present invention is not limited thereto. A water-based pressure-sensitive ii+s adhesive is prepared by mixing an acrylic resin emulsion and a terpene resin emulsion such that the weight ratio of the acrylic resin to the terpene resin ranges from /:O,S to /:K.

Furthermore, a water-based pressure-sensitive adhesive prepared by uniformly mixing and dispersing an antifoaming agent, a thickener (g), and an inorganic filler according to requirements is also preferable as a water-based pressure-sensitive S adhesive.

As the surfactant, it is preferable to use a nonionic surfactant in terms of water resistance, dispersibility, compatibility, and viscosity stability. As the nonionic surfactant, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, polyoxyethylene alkyl esters, norbitan alkyl esters, or polyoxyethylene sorbitan alkyls are used. The amount of surfactant to be used is 10 parts by weight or less per 100 parts by weight of acrylic resin or terpene resin.

In this case, the antifoaming agent is preferably a non-silicon type rather than used as an adhesive, and includes polyglycol type surfactants, polyether type surfactants, nonionic type surfactants, and the like. The amount of antifoaming agent used is usually 0.2 to 6 parts by weight per 1 part by weight of 100 parts of acrylic resin.

Ammonium salts of polymeric organic acids are used as thickeners.

Cellulose Sodium Glycolate, Potassium Salt of Vinyl Polymer (Modicol VE, US Nopco c
Hem Co., Ltd. (trade name), Bentonai F, and precipitated calcium carbonate. The amount of thickener used is generally 2 to 20 parts by weight per 100 parts by weight of the acrylic resin.

Calcium carbonate and clay as inorganic fillers.

These include talc, silica, asbestos, barium sulfate, and silica sand. The amount of inorganic filler used is usually 100% of acrylic resin.
The amount is 00 to 000 parts by weight. By using an inorganic filler, it is possible to dry quickly. That is, water-based adhesives normally dry at room temperature for a long time, but by introducing a filler, it becomes possible to dry them at a temperature of so-go°C for a short time. At the same time, the water-based pressure-sensitive adhesive forms an adhesive layer with few defects even when applied thickly.

The water-based pressure-sensitive adhesive obtained by mixing the above ingredients not only adheres well to raw mortar, but also has a water-based feel! The period during which the adhesive is applied to the adherend and dried and then placed in green mortar,
The green mortar has the advantage of not being affected by the outdoor exposure period before it is placed, and after the green mortar is placed, the mortar and the adherend are completely integrated, and the adhesive layer is a waterproof layer with appropriate moisture permeability. form.

The present invention will be explained in detail below with reference to Examples and Comparative Examples. Among the materials and chemicals used in these Examples and Comparative Examples, the following were used unless otherwise specified.

For acrylic resin emulsions, the molecular weight of the acrylic resin in the emulsion is then indicated in parentheses, and the line below that indicates the type of acrylic resin and the surfactant used in the emulsion.

Emulsions using basic acrylic resin as the acrylic resin are Acronal t/DP
Co., Ltd., product name), the emulsion using acrylic resin copolymerized with styrene is Acronal, 2? j-D
The emulsion using acrylic resin copolymerized with vinyl acetate (manufactured by Yuka Padeesh Co., Ltd., trade name) was Likapond P8-. 30θOA (manufactured by Chuo Rika Kogyo Co., Ltd., trade name) was used. Acrylic resin in acrylic resin emulsion ml f t! Unless otherwise specified, the weight is approximately 10%.

The softening temperature of the terpene resin is indicated in parentheses below the name, and the chemical structural formula of the resin is as shown in the following formula (I). This is a water-dispersed emulsion using a nonionic surfactant manufactured by Onna Yushi Kogyo Co., Ltd. (trade name).The concentration of terpene resin in the terpene resin emulsion is approximately 1! unless otherwise specified. be.

Nopco NXZ (manufactured by San Nopco Co., Ltd., trade name) was used as the antifoaming agent, and Gelton-30 (manufactured by Shiraishi Kogyo Co., Ltd., trade name) was used as the thickener.

Nonionic surfactants include polyoxyethylene monostearate (polyoxyethylene monostearate) as polyoxyethylene alkyl esters.
Nonion 8-4, Nippon Oil & Fats Co., Ltd. 1L%, trade name) is
Polyoxyethylene alkylpheno-A/polyoxyethylene 7-nonylphenol ether (
Nonion N8-. 2ob, manufactured by NOF (e), i
Product name) is polyoxyethylene stearyl ether (Nonion S) as a polyoxyethylene alkyl ether.
-2/j% Nippon Oil & Fats Co., Ltd., product name) is used.

All used items are shown in the double pupil area.

Next, examples and comparative examples will be shown.

Example-1 Acrylic resin emulsion (molecular weight 100,000) 100 (
, 8 acrylic resin, nonionic surfactant) Terpene resin emulsion 1OO (softening degree i3
o″C) Calcium carbonate KOθ Foaming agent
/ Thickener.

Total Li06 Comparative Example-1 Acrylic resin emulsion (molecular weight 1 million) 1
00 Terpene resin emulsion 100
(Softening temperature f/3117″C) Calcium carbonate: lOO antifoaming agent
l Thickener j Comparative Example-2 Acrylic resin emulsion (molecular weight 1 million) 10O terpene resin emulsion 100 (softening 1
14Fl130”C) Calcium carbonate CO00 antifoaming agent
l Thickener! Total 〇6 Examples-
2 Acrylic resin emulsion C min-ffjk1 million>
100 terpene resin emulsion 1
OO (softening temperature/30″C) Calcium carbonate -〇θ foaming agent
/ Thickener 5 Actual example-3 Acrylic resin emulsion (molecular weight 100,000) 1
0θ Chirchen Resin Emulsion 100 (
Softened part g i3o℃) Calcium carbonate coθ0 antifoaming agent
/ Thickener 5 Total 1IOt.

Comparative Example-5 Acrylic resin emulsion (molecular weight: 50,000) 100 (basic acrylic resin, nonionic surfactant) Terpene resin emulsion 100 (softening temperature/30°C
) Calcium carbonate Koθ0 antifoaming agent
l Thickener 5 Example-4 Acrylic resin emulsion (molecular weight J million) 1
00 (basic acrylic resin, nonionic surfactant) Derpene resin emulsion 1OO (softening part f
L/JO"C") Calcium carbonate Rich 0 antifoaming agent
l Thickener 3 Total 1IO4 Comparative Example-4 Acrylic resin emulsion (molecules 11/θ00,000) Hata 1
100 (basic acrylic resin, anionic surfactant)
Terpene resin emulsion 100 (softening temperature 130℃) Calcium carbonate Co0θ antifoaming agent
l Thickener j 11tIIO B Comparative Example-5 Acrylic 1111! Emulsion (molecular weight 1 million)
/θO (basic acrylic resin, nonionic surfactant) petroleum-based hydrocarbon resin emulsion 12
100 (Softening temperature/30°C) Calcium carbonate Koθ0 antifoaming agent
7 Total Li06 Comparative Example-6 Acrylic resin emulsion (molecular weight 1 million) 100 (
Basic acrylic resin, nonionic surfactant) Terpene resin emulsion 100 (softening temperature 90
°C) Calcium carbonate co.

Antifoaming agent/needle DaO6 comparative example-7 Acrylic resin emulsion (molecules @ 1 million) 100 (
Basic acrylic resin, nonionic surfactant) Terpene resin emulsion 100 (softening temperature 16
0°C) Calcium carbonate Rich 0 antifoaming agent
/ Thickener S Comparative Example-8 Acrylic resin emulsion (molecules @ ioo million) 100
(Basic acrylic resin, nonionic surfactant) Terpene resin emulsion lθ (softening temperature i
3o℃) Calcium carbonate 200 Antifoaming agent
l Thickener j ft, 34tA Comparative Example-9 Acrylic resin emulsion (molecular weight 1 million) 10O (
Basic acrylic resin, nonionic surfactant) Terpene resin emulsion 230 (softening temperature/J
O℃) Calcium carbonate KoOQ antifoaming agent
/ Thickener S The formulations of the above Examples and Comparative Examples are stirred at high speed to obtain a uniform paste-like water-based pressure-sensitive adhesive.

The adhesive strength thus obtained was measured for adhesive strength over time, water resistant adhesive strength, heat resistant adhesive strength, and moisture permeability, and the results are listed in Tables 1 to 4.

Test method [1] Adhesive strength over time 1-1 Preparation of specimen A water-based pressure-sensitive adhesive was applied to plywood and gypsum board with a thickness of 9 cm.
Apply at a ratio of /- and dry indoors day and night. This is then exposed outdoors.

After that, it was poured with green mortar to a thickness of 10 mm and left to cure indoors for two days, covered with polyethylene film. Thereafter, the polyethylene film was removed and the sample was cured indoors for S days before measurement.

1-2 Measurement method Sample area is /A (:112(tIX4(cm2) V
Make a cut in the mortar surface for Mr. C Naru. Next, attach the attachment with an epoxy resin adhesive and then measure the tensile speed at -〇〇 m1m1n.

There are 3 samples and the value is the average of the 3 samples.

[2] Water-resistant adhesive strength 2-1 Thickness of specimen fabrication? Water-based pressure-sensitive adhesive on Kagome plywood and gypsum board / K
Apply at a ratio of f/m20, - After drying day and night, apply 1
0TIII! Install IK.

After curing the raw mortar in the same manner as in 1-1, cover the exposed parts of the plywood and plaster board with a low-viscosity type epoxy resin adhesive. After the epoxy resin adhesive has hardened, it is immersed in water at room temperature. V during measurement
C is measured one hour after taking it out of the water.

2-2 Measurement method Same as 1-2 [3] Heat-resistant adhesive strength 5-1 Preparation of specimen Apply water-based pressure-sensitive adhesive to 9 m thick plywood and plasterboard / 9
Apply fresh mortar at a rate of 7m2 and dry for a day and night. /Q
Pour into tmli.

After curing the raw mortar, cure it in a constant temperature bath at 0°C in the same manner as in 1-1. At the time of measurement, take the sample out of the thermostatic chamber and let it stand indoors for y hours before measuring.

5-2 Measurement method Same as 1-2 [4] Measurement of moisture permeability (JIS-Z-0208Vc standard) 4-1 Preparation of specimen Apply water-based pressure-sensitive adhesive to waterproof plywood of thickness J and 3#. /face/m
The sample was coated at a ratio of 2:2 and dried at room temperature for one week.

4-2 Measurement method Cut the specimen into 70wa diameter pieces and fill an aluminum cup with anhydrous calcium chloride. The sample is then embedded with the adhesive layer facing up and sealed with wax. This is eo″C1 humidity f 90-
VC was left in a thermostatic oven at f=104 for 21 hours, and the moisture permeability was determined using the following formula.

8: Moisture permeable area t: Total time of one weighing interval during which the test was conducted However) The formulation of the mortar used in the above tests C11 to [3] was as follows.

Portland cement / θO standard sand −
〇〇Wed 60 total 3
1.0 or more, the following was found from the comparative example.

Preferred acrylic resins include basic acrylic resins, styrene of up to 30% by weight, or acrylic resins copolymerized with vinyl acetate.

The total content of styrene, vinyl acetate, or both is 3
If the weight exceeds 0 weight, problems will arise in weather resistance and water resistance.

In other words, when a water-based pressure-sensitive adhesive is made using an acrylic resin copolymerized with styrene in excess of 30% by weight, the longer it is exposed outdoors after the adhesive has been applied and dried, the stronger the adhesive strength with green mortar will be. descend. If a water-based pressure-sensitive adhesive is made using an acrylic resin copolymerized with vinyl acetate with a molecular weight exceeding 300,000 yen, water-based pressure-sensitive adhesive will have poor water resistance. The cohesive force after application of the agent becomes low.

There is no problem when the molecular weight is 300,000 or more.

When comparing L7 with a nonionic surfactant and an anionic surfactant for dispersing acrylic resin in water, the nonionic surfactant has better water resistance.

When using a cationic surfactant, the dispersibility and compatibility with other formulations and the viscosity stability of water-based pressure-sensitive adhesives are poor, so nonionic surfactants are considered to be better.

When comparing terpene resin and petroleum-based verticalized hydrogen resin, terpene resin is preferable because the adhesive strength value is higher. Also, if the softening temperature of terpene resin is lower than ioo℃. The adhesive force value will be low. On the other hand, if the softening temperature is higher than Izo℃, the adhesive layer becomes brittle after application and drying of the water-based pressure-sensitive adhesive, and interfacial peeling occurs between the adhesive layer and mortar @ Weight ratio of acrylic resin and terpene resin G/: 0. !
If the weight ratio is too large, interfacial peeling will occur between the base material and the adhesive layer. If the weight ratio of acrylic resin to terpene resin is too small, water resistance and heat resistance will be poor.

In particular, it shows an extreme decrease in water resistance. From the above, the acrylic resin should be a basic acrylic resin, styrene, vinyl acetate, or an acrylic resin with a total content of 30% by weight or less, with a molecular weight of J60,000 or more. An acrylic resin emulsion dispersed in water using a nonionic surfactant is preferred.

As the terpene resin, a terpene resin emulsion prepared by dispersing a terpene resin having a softening temperature of 100 to /jθ°C in water with a nonionic surfactant is preferred. The Kubon-based pressure-sensitive adhesive obtained through this process adheres well to green mortar regardless of the assimilation conditions after application and drying and the curing date, and is a water-based adhesive with excellent water resistance and heat resistance. It is a pressure sensitive adhesive. Another advantage is that it can be used in a wide range of materials, including organic or inorganic plywood, metal plates, cement plates, and gypsum plates.

Furthermore, after the green mortar has hardened, the water-based pressure-sensitive adhesive layer not only integrates the adherend with the mortar 1-, but also has the feature that the adhesive layer forms a waterproof layer with an appropriate permeability mW. There is.

Procedural amendment document Showa 5 ≦ Year/θ Month l Day 1, Case indication Showa S6 Patent application No. 13g and 09 No. 2, Title of invention Water-based pressure-sensitive adhesive 3, Person making the amendment Relationship with the case Patent application Hitohayakawa Rubber Co., Ltd. Telephone number (581) 2241 (main)

Claims (1)

[Scope of Claims] t An acrylic resin emulsion in which an acrylic resin with a molecular weight of 300,000 or more is dispersed in water with a nonionic surfactant, and a terpene resin with a softening degree of /θθ~/o″C in a nonionic surfactant. The terpene resin emulsion is water-dispersed with a water-dispersing agent, and the weight ratio of the acrylic resin and the terpene resin is
: A water-based pressure-sensitive adhesive characterized by having a mixture in the range of O, S to /knee. 2. The water-based pressure-sensitive type according to claim 1, wherein the acrylic resin is a copolymer resin containing up to 3011 Il of styrene, vinyl acetate, or styrene and vinyl acetate in a copolymerized form. glue. 5. Acrylic resin resin composition in which an acrylic resin with a molecular weight of 300,000 or more is dispersed in water with a nonionic surfactant, and Derben resin resin with a softening temperature of 100 to 30°C dispersed in water with a nonionic surfactant. The terpene resin emulsion has a weight ratio of the acrylic resin and the terpene resin:
0. ! f to l: A water-based pressure-sensitive adhesive in which a defoaming agent, a thickener, and an inorganic filler are added to the mixture in the range of f to l. 4. The above (polyglycol-based as f4/lII agent,
The above-mentioned acrylic resin 100 contains the residues of the polyether type surfactant G and the nonionic surfactant.
A special product characterized by being blended in a range of 0.2 to 6 parts by weight based on the heavy food portion! The water-based pressure-sensitive adhesive described in Section 5 of FF Haruyuki. 5 ammonium salt of a polymeric organic acid as the thickener;
A patent characterized in that seven or more selected from cellulose glycol iron sodium, bentonite g, and precipitated calcium carbonate are blended in an amount of 2 to 20 parts per 100 parts by weight of the acrylic resin. The water-based pressure-sensitive adhesive according to claim 5. ε Calcium carbonate as the inorganic filler. One species selected from clay, talc, silica, asbestos, barium sulfate, and silica sand must be blended with 100 M#MK of acrylic resin in a range of 100 -4θO weight part. A water-based pressure sensitive 111 adhesive according to claim 5. l Molecular weight of 300,000 or more σ) Acrylic resin resin FF Roujoy dispersed in water with acrylic resin nonionic surfactant,
Softening [1111'700~/!;0' A terpene resin emulsion obtained by dispersing Cn delben resin in water with a nonionic surfactant is mixed in a weight ratio of the acrylic resin and the terpene resin in the range of /: O, S to /: 2. , antifoaming agent Ol for 100 parts by weight of the acrylic resin
The water-based pressure-sensitive adhesive according to claim 5, characterized in that the water-based pressure-sensitive adhesive contains 6 parts by weight, 2 to 20 parts by weight of a thickener, and 200 to 609 parts by weight of an inorganic filler. .