JP2003073635A - Aqueous adhesive composition and adhered article therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous adhesive composition that can tightly bond a waterproof sheet to a cement material, and has excellent adhesion durability against water, and an adhered article therewith. SOLUTION: This aqueous adhesive composition comprises, as main components, a chloroprene latex obtained by polymerizing 100 parts by mass of chloroprene and 0.1-5 parts by mass of an ethylenically unsaturated carboxylic acid in the presence of 0.5-5 parts by mass of polyvinyl alcohol, a terpene-phenol resin, a rosin derivative and a metal oxide. The adhered article is formed by applying the aqueous adhesive to a cement material, and laminating a waterproof sheet thereon.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-based adhesive used in a work of fixing a waterproof sheet to a cementitious material during waterproofing of a building and an adhesive structure using the same.

[0002]

2. Description of the Related Art Conventionally, when joining a waterproof sheet to a cementitious material, a polychloroprene (CR) solvent-based adhesive is applied to the cementitious material and then the waterproof sheet is stretched. However, since an organic solvent such as toluene, ethyl acetate, or methyl ethyl ketone is used for the CR solvent-based adhesive, the organic solvent volatilizes in the workplace when the adhesive is applied,
It is not preferable in terms of worker safety and hygiene and environment, and reduction of organic solvent has been desired.

[0003]

DISCLOSURE OF THE INVENTION The present inventor has found that the conventional C
Provided is an adhesive and an adhesive structure which are free from the problems of safety and hygiene and environment as in the case of using an R solvent-based adhesive, and which are stronger than or equal to those of a conventional CR solvent-based adhesive. Is intended.

[0004]

Means for Solving the Problems As a result of repeated studies to achieve the above object, the present inventors have found that polyvinyl alcohol is present, and chloroprene and a specific amount of an ethylenically unsaturated carboxylic acid are polymerized. By using the obtained polychloroprene latex, terpene phenolic resin, rosin-based derivative and adhesive containing metal oxide as the main component, it is possible to firmly bond the waterproof sheet to the cementitious material and to have excellent water resistance. Invented

That is, the present invention contains a polychloroprene latex, a terpene phenol resin, a rosin derivative and a metal oxide as main components, and the polychloroprene latex contains 100 parts by mass of chloroprene and 0.1 of an ethylenically unsaturated carboxylic acid. It is a water-based adhesive consisting of chloroprene latex obtained by polymerizing 5 to 5 parts by mass in the presence of 0.5 to 5 parts by mass of polyvinyl alcohol. Also,
The present invention applies the above water-based adhesive to a cementitious material,
It is an adhesive structure characterized by laminating a waterproof sheet on it.

The present invention will be described in detail below. The waterproof sheet of the present invention is not particularly limited and, for example, a waterproof sheet that is commonly used in the construction field such as roofing of condominiums and the civil engineering field such as industrial waste landfill can be used. For example, ethylene-propylene rubber (EPD
M), nitrile rubber (NBR), polychloroprene rubber (CR), styrene-butadiene rubber (SBR), chlorosulphonated polyethylene rubber, ethylene-vinyl acetate copolymer rubber, etc., unvulcanized or vulcanized rubber sheet, Examples include soft vinyl chloride resin sheets and the like. Of these, EPDM vulcanized sheets are particularly preferable because they are excellent in durability and mechanical strength.

The cementitious material of the present invention is not particularly limited. For example, materials commonly used for construction such as slate, cement, mortar, concrete and asphalt can be mentioned.

The polychloroprene latex of the present invention is 2
-Chloro-1,3-butadiene (hereinafter referred to as "chloroprene") is a copolymer of an ethylenically unsaturated carboxylic acid monomer, and further contains one or more monomers copolymerizable with chloroprene. You may include as a copolymerization component.

Specific examples of the ethylenically unsaturated carboxylic acid in the present invention include acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic acid, citraconic acid, glutaconic acid, etc., which may be used alone or in combination with 2 It can also be used in combination with more than one type. In the present invention, acrylic acid and methacrylic acid are preferably used, and methacrylic acid is particularly preferably used.

The addition amount of the ethylenically unsaturated carboxylic acid in the present invention is 0.10 per 100 parts by mass of chloroprene.
It is 1 to 5 parts by mass, preferably 1 to 4 parts by mass. When the amount of the ethylenically unsaturated carboxylic acid added is less than 1 part by mass, the stability of the latex is poor and the production is difficult, and the adhesive properties are poor. If the amount of the ethylenically unsaturated carboxylic acid added exceeds 5 parts by mass, the water resistance of the adhesive structure will be poor.

Examples of the monomer copolymerizable with chloroprene in the present invention include 2,3-dichloro-1,3-
Examples thereof include butadiene, 1-chloro-1,3-butadiene, butadiene, isoprene, styrene, acrylonitrile, esters of acrylic acid, esters of methacrylic acid and the like, and two or more kinds may be used as necessary.

The polyvinyl alcohol in the present invention is not particularly limited, but one having a saponification degree in the range of 60 to 98 mol% is preferable. The degree of saponification is more preferably 75 to 95 mol%, and even more preferably 7
It is 8 to 89 mol%. The degree of polymerization of polyvinyl alcohol is preferably in the range of 200 to 3000. The degree of polymerization is more preferably 200 to 700, and even more preferably 200 to 550. Further, it may be a modified type (for example, an acetoacetylated type or a type having a polyethylene unit). When the polyvinyl alcohol is in this range, the polymerization operation can be stably performed, the stability of the obtained latex is excellent, and a stable latex can be obtained at a high concentration.

The addition amount of polyvinyl alcohol in the present invention is 0.5 to 5 parts by mass, preferably 2 to 4 parts by mass. When the amount of polyvinyl alcohol added is less than 0.5 parts by mass, the emulsifying power is insufficient and a large amount of aggregates are generated during the polymerization reaction. . On the other hand, if the amount exceeds 5 parts by mass, thickening occurs during the polymerization reaction, which hinders stirring and causes abnormal heat generation, which makes stable polymerization operation impossible.

The catalyst used in the polymerization of the polychloroprene latex of the present invention includes inorganic oxides such as potassium persulfate, ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides. Examples thereof include organic peroxides and the like. The use of potassium persulfate as the catalyst is preferred for stable polymerization. Further, potassium persulfate is preferably used in an aqueous solution of 0.1 to 5 mass%.

In order to enhance the activity of the catalyst used for the polymerization of the polychloroprene latex of the present invention, sodium sulfite, potassium sulfite, iron (II) oxide, anthraquinone β sodium sulfonate, formamidine sulfonic acid, L-ascorbic acid are used. Etc. can be added.

The polychloroprene in the present invention is
The toluene insoluble content (hereinafter gel content) content is not particularly specified, but it is preferably in the range of 10 to 60% by mass, and more preferably in the range of 15 to 50% by mass. If the gel content is less than 10% by mass, the adhesive strength will decrease. If the gel content exceeds 60% by mass, the initial adhesiveness and water resistance of the adhesive structure will deteriorate.

The gel content of polychloroprene can be controlled by the use of chain transfer agents. The chain transfer agent is not particularly limited as long as it is generally used in the production of polychloroprene, for example, long-chain alkyl mercaptans such as n-dodecyl mercaptan, n-octadecyl mercaptan and t-dodecyl mercaptan, diisopropyl xanthogen. Known chain transfer agents such as dialkylxanthogen disulfides such as disulfide and diethylxanthogen disulfide, and iodoform can be used.

Next, the polymerization temperature is preferably in the range of 0 to 55 ° C. in terms of polymerization control. In order to carry out the polymerization reaction more smoothly and safely, the polymerization temperature should be 30 to 50 ° C.
Is particularly preferable.

The final polymerization rate is preferably 80% by mass or more, and more preferably 90% by mass or more. At this time, when a large amount of residual chloroprene monomer is generated, it can be removed by a known method such as a demomerization step.

Further, for the purpose of controlling the polymerization rate and the polymerization rate, hydroquinone, pt-butylcatechol, diethylhydroxylamine, hydroquinone methyl ether,
2,6-di-t-butyl-4-methylphenol, 2,
2-methylenebis (6-t-4-methylphenol),
4,4-butylenebis (6-t-butyl-3-methylphenol), ethylenebis (oxyethylene) bis [3
-(5-t-Butyl-4-hydroxy-m-tolyl) propionate], octadecyl-3- (3,5-di-t
-Butyl-4-hydroxyphenyl) propionate,
Pentaerythritol tetrakis [3- (3,5-di-
t-butyl-4-hydroxyphenyl) propionate] and the like can be added as necessary.

In the present invention, the solid content concentration of the polychloroprene latex composition is preferably in the range of 40 to 65% by mass, more preferably 45 to 60% by mass. A higher solid content concentration gives a latex having a faster drying rate and more excellent initial adhesion. The solid content concentration can be adjusted by adjusting the ratio of the monomer and water during the polymerization, but can be adjusted by concentrating after the polymerization.

The chloroprene polymer in the present invention is acidic immediately after polymerization and is in an unstable normal state, so that the pH of the chloroprene polymer is 6 to 6.
It will be necessary to adjust to 10. PH is preferably 6.5 to 9.0. If the pH is less than 6, it may be easily deteriorated such as coagulation and separation after long-term storage. An alkaline solution having a pH of more than 10 is not preferable in terms of handling.

The pH adjuster in the present invention is used for the purpose of adjusting the pH of the chloroprene polymer latex just after the polymerization from acidic to neutral. For example, as a pH adjusting agent, sodium hydroxide, potassium hydroxide, a strongly basic substance such as diethanolamine or triethanolamine, sodium carbonate, potassium carbonate, trisodium phosphate, disodium hydrogen phosphate, tripotassium phosphate, hydrogen phosphate. Any one or more salts selected from basic salts such as dipotassium, tripotassium citrate, dipotassium hydrogen citrate, sodium acetate, potassium acetate, and sodium borate may be used in combination.

The method of adding the PH adjusting agent in the present invention is not particularly limited, and the PH adjusting agent powder can be added directly or diluted with water at an arbitrary ratio and added.

The polychloroprene latex of the present invention includes polyoxyethylene alkyl ether, polyoxyethylene alkylene alkyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether and polyoxyethylene. Alkyl allyl ether, polyoxyethylene derivatives such as polyoxyethylene-polyoxypropylene condensate, sorbitan monostearate, sorbitan monolaurate, sorbitan monopalmylate and other sorbitan fatty acid esters, glycerol monostearate, glycerol monooleate A glycerin fatty acid ester such as rate and a surfactant such as an aliphatic alkanolamide can be added.

The terpene phenolic resin of the present invention is not particularly limited. Examples thereof include copolymers of terpenes such as isoprene, α-pinene, β-pinene, limonene and phenols.

The form of the terpene phenolic resin of the present invention is not particularly limited. A solid may be used as it is, but an emulsion type is preferable because of excellent dispersibility.

The amount of the terpene phenolic resin of the present invention added (in terms of solid content) is preferably 10 parts by mass or more based on 100 parts by mass of the polychloroprene latex in solid content. If it is less than 10 parts by mass, the adhesive force and the initial adhesive force are insufficient.

The rosin derivative of the present invention is not particularly limited. Examples thereof include ester compounds such as gum rosin, wood rosin, tall oil rosin, hydrogenated rosin, disproportionated rosin, and polymerized rosin.

The form of the rosin derivative of the present invention is not particularly limited. A solid may be used as it is, but an emulsion type is preferable because of excellent dispersibility.

The amount of the rosin acid derivative of the present invention (calculated as solid content) is 100% solid content of polychloroprene latex.
It is preferably 10 parts by mass or more per part by mass. More preferably, it is 15 parts by mass or more. If it is less than 10 parts by mass, the water resistance and the initial adhesive strength are insufficient.

The total amount of the terpene phenol resin and the rosin derivative (based on the solid content) of the present invention is preferably 100 parts by mass or less per 100 parts by mass of the solid content of the polychloroprene latex. If the amount exceeds 100 parts by mass, the formation of the adhesive coating may be hindered, so that defective adhesion tends to occur.

Examples of the metal oxide in the present invention include zinc oxide, titanium oxide, alumina and zirconium oxide, boron oxide, tin oxide, chromium oxide, magnesium oxide and vanadium oxide. In particular, zinc oxide, titanium oxide, alumina and zirconium oxide are preferable as the metal oxide.

The amount of the metal oxide added is 0.1 to 100 parts by mass of polychloroprene latex in terms of solid content.
10 parts by mass is preferable, and 0.2 to 5 parts by mass or less is particularly preferable. If added in excess of 10.0 parts by mass, the initial adhesive strength will be reduced.

The water-based adhesive composition of the present invention includes calcium carbonate, barium sulfate, inorganic fillers such as silica and talc, plasticizers / softeners such as dibutyl phthalate and process oil, sodium polyacrylate, water-soluble polyurethane, Thickeners such as methylcellulose, curing accelerators such as isocyanates and diisocyanates, various antiaging agents, ultraviolet absorbers and antioxidants can be optionally blended.

The water-based adhesive composition of the present invention is prepared by mixing polychloroprene latex, terpene phenol resin, rosin derivative, metal oxide and the like, but the mixing device is not particularly limited, and it is a three-one motor. A known device such as a homogenizer, a media mill or a colloid mill can be used.

The bonded structure of the present invention is made by bonding a waterproof sheet to a cementitious material, but the bonding method is not particularly limited. For example, there is a method of applying a water-based adhesive to both sides of the cementitious material and the waterproof sheet and then laminating it, or a method of applying the adhesive only to the cementitious material and then applying the waterproof sheet, but the latter method is applied. The operation is easy to perform and is preferably used.

The waterproof sheet of the present invention may be treated with a primer. The primer is not particularly limited, and any of water dispersion type and solvent type may be used.

The cementitious material of the present invention may be subjected to a primer treatment before construction. The primer is not particularly limited. In most cases, the primer treatment of the cementitious material is carried out at the construction site, so it is preferable to use an aqueous primer. As the primer, a water-based adhesive composition as it is or diluted with water is more preferably used.

The water-based adhesive of the present invention can be applied by a known method such as brush coating, iron coating, spray coating, roll coater coating and bar coater coating.

The method for adhering the waterproof sheet to the cementitious material of the present invention is not particularly limited. For example, after applying the adhesive, leave it alone or dry the adhesive with a blower, etc.
Examples include a method of pressure bonding with a press device or the like.

[0042]

The present invention will be described below with reference to examples, but these examples do not limit the present invention. In addition,
In the following examples, parts and% are based on mass unless otherwise specified.

Example 1 Using a reactor having an internal volume of 30 liters, under a nitrogen stream, 94 parts by mass of water and polyvinyl alcohol (Dencapovar B-05, saponification degree 88 mol%, polymerization degree 550) 3.5. Put the mass part and heat (60
(° C) dissolved. After cooling this aqueous solution to near room temperature,
100 parts by mass of the chloroprene monomer, 1.4 parts by mass of methacrylic acid, and 0.3 part by mass of octyl mercaptan were added thereto. While maintaining this at 45 ° C, polymerization was carried out using sodium sulfite and potassium persulfate as initiators to obtain a polychloroprene latex. Final polymerization rate is 99.
It was 5%.

Next, a 10% aqueous sodium carbonate solution was added to this polychloroprene latex to adjust the pH to 8.
After adjusting to 0, a 20% aqueous solution of fatty acid alkanolamide (manufactured by Diamond Siamrock Chemical Co.) was added to 3
Part, 0.5 parts of 2,6-di-t-butyl 4-methylphenol emulsion (Cerosol H633 manufactured by Chukyo Yushi Co., Ltd.)
A CR latex having a solid content adjusted to 47% was obtained by adding mass parts (calculated as solid content).

Next, the following measurements were performed on this polychloroprene latex. [Measurement of gel content] A polychloroprene latex sample was freeze-dried and precisely weighed as A. Dissolved in toluene (0.6%
Was prepared), and the gel was separated using a centrifuge and a wire mesh of 200 mesh. 110 after gel-drying
It was dried in an atmosphere at 0 ° C. for 1 hour and weighed precisely to obtain B. The gel content was calculated according to the following formula. Gel content = B / A × 100 (%) The gel content of the CR latex was 40% by mass.

[Production of Water Adhesive Composition] CR latex 100 parts by mass (solid content), terpene phenolic resin (Tamanor E-100 manufactured by Arakawa Chemical Co., Ltd.) 30 parts by mass (solid content), rosin ester resin (Harima Kasei Co., Ltd. Hariesta SK-90D) 20 parts by mass (solid content conversion) and zinc oxide (Osaki Industry Co., Ltd. AZ-SW) 0.5 parts by mass (solid content conversion) by stirring and mixing with a three-one motor, and water-based adhesion. The agent was created.

[Initial adhesion peel strength] First, size 25 ×
For priming a 150 mm slate plate, the adhesive was diluted with water to a solid content concentration of 15% to undercoat evenly about 10 to 20 cc with a brush and dried at room temperature for 3 hours or more. Next, apply a water-based adhesive to the slate plate 150
It was applied with a g (solid content) / m ² brush and dried at room temperature for 1 hour. A rubber sheet made of EPDM was placed on a slate plate, and both adherends were pressure bonded with a hand roller. One hour after pressure bonding, the 180 ° peel strength was measured with a tensile tester under the condition of a tensile speed of 200 mm / min.

[Normal Adhesion Peeling Strength] Pressure was applied under the same conditions as described above, and after 120 hours, a tensile tester was used to pull at a pulling speed of 2
The 180 ° peel strength was measured under the condition of 00 mm / min.

[Water resistance] Press-bonding under the same conditions as above,
After 24 hours, it was immersed in water for 7 days, and a 180 ° peel strength was measured by a tensile test under the condition of a tensile speed of 200 mm / min.

Example 2 The same CR latex as in Example 1 (100 parts by mass (solid content)), terpene phenol resin (Tamanor E-100 manufactured by Arakawa Chemical Co., Ltd.) 20 parts by mass (solid content), rosin system 30 parts by mass of ester resin (Hariesta SK-90D manufactured by Harima Chemicals, Inc.) (solid content conversion), zirconium oxide (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.)
A water-based adhesive was prepared by stirring and mixing 5 parts by mass (converted to solid content) with a three-one motor.

Example 3 The same CR latex as in Example 1 (100 parts by mass (solid content)), terpene phenolic resin (Tamanor E-100 manufactured by Arakawa Chemical Co., Ltd.) 10 parts by mass (solid content conversion), rosin system 40 parts by mass of ester resin (Hariema SK-90D manufactured by Harima Chemicals, Inc.)
Further, 0.5 part by mass of zinc oxide (AZ-SW manufactured by Osaki Industry Co., Ltd.) (solid content conversion) was stirred and mixed with a three-one motor to prepare a water-based adhesive.

Comparative Example 1 100 parts by mass of CR latex as in Example 1 (as solid content), 50 parts by mass of terpene phenolic resin (Tamanor E-100 manufactured by Arakawa Chemical Co., Ltd. as solid content) and zinc oxide. (AZ-S made by Osaki Industry Co., Ltd.
W) 0.5 parts by mass (solid content conversion) was stirred and mixed with a three-one motor to prepare a water-based adhesive.

Comparative Example 2 100 parts by mass of CR latex as in Example 1 (solid content conversion), 40 parts by mass of rosin ester resin (Hariesta SK-90D manufactured by Harima Kasei Co., Ltd.) (solid content conversion) and zinc oxide. (AZ-S made by Osaki Industry Co., Ltd.
W) 0.5 parts by mass (solid content conversion) was stirred and mixed with a three-one motor to prepare a water-based adhesive.

[0054]

[Table 1]

[0055]

As is clear from Table 1, the water-based adhesive of the present invention is excellent in initial adhesive strength, normal adhesive strength and water resistance, and is therefore most suitable as an adhesive for waterproof sheets and cementitious materials.

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Claims (9)

[Claims] 1. A polychloroprene latex, a terpene phenolic resin, a rosin derivative and a metal oxide as main components, and the polychloroprene latex is 100 parts by mass of chloroprene and 0.1 to 5 parts by mass of an ethylenically unsaturated carboxylic acid. Parts of polyvinyl alcohol 0.5 to
A water-based adhesive composition having a pH adjusted to 6 to 10 after polymerization in the presence of 5 parts by mass. 2. The total amount of terpene phenol resin and rosin derivative (solid content) conversion is 100 parts by mass or less per 100 parts by mass of solid content of polychloroprene latex, and the amount of rosin derivative is 10 parts by mass or more. The water-based adhesive composition according to claim 1. 3. The water-based adhesive composition according to claim 1 or 2, wherein the metal oxide is any one of zinc oxide, titanium oxide, zirconium oxide, and aluminum oxide. 4. The gel content of polychloroprene is 10 to 10.
It is 60 mass%, The water-based adhesive composition of any one of Claims 1-3. 5. The amount of ethylenically unsaturated carboxylic acid is 1 to
It is 4 mass parts, The water-based adhesive composition in any one of Claims 1-4 characterized by the above-mentioned. 6. The degree of saponification of polyvinyl alcohol is 75.
% To 90 mol%, The water-based adhesive composition according to claim 1. 7. An adhesive structure characterized by applying a water-based adhesive composition according to any one of claims 1 to 6 to a cementitious material and then adhering a waterproof sheet. 8. The adhesive structure according to claim 7, wherein the cementitious material is surface-treated with an aqueous primer. 9. The waterproof sheet is surface-treated with a primer, according to claim 7 or 8.
The bonded structure according to the item.