JPH05311128A - Emulsion composition for foam - Google Patents

Abstract

(57) [Summary] [Purpose] To provide a foam emulsion composition capable of forming foam sheets, foam tapes, etc. having excellent strength, water resistance, weather resistance, compression recovery property, etc. [Structure] Foam emulsion composition Is composed of a mixture of (a) acrylic ester polymer emulsion and (b) polyurethane emulsion. This composition
It is preferably used as a foam sheet or foam tape.

Description

Detailed Description of the Invention

[0001]

The present invention relates to an adhesive foam sheet,
The present invention relates to an emulsion composition for foam, which can form a foam sheet, foam tape or the like useful as a material for an adhesive foam tape.

[0002]

2. Description of the Related Art Conventionally, bolts / nuts, rivets, spot welding, adhesives, double-sided adhesive tapes, etc. have been generally used for joining metals, plastics, wood, plywood, inorganic boards, fiber materials, etc. An adhesive foam sheet or an adhesive foam tape obtained by applying an adhesive to an olefin-based, urethane-based, acrylic-based foam sheet or foam tape is used for joining surfaces having large irregularities or different materials. Of these, especially for adhesive foam sheets or adhesive foam tapes,
A pressure-sensitive adhesive sheet based on acrylic foam is disclosed in JP-A-63-89585, and JP-A-47-30743.
Each of the publications describes an adhesive tape based on polyurethane foam. However, the pressure-sensitive adhesive sheet using an acrylic foam disclosed in JP-A-63-895585 is not sufficient in terms of general physical properties such as strength, water resistance and compression recovery property. In addition, JP-A-47-307
The pressure-sensitive adhesive tape using the polyurethane foam disclosed in JP-A No. 43-43 has a problem that it is deteriorated and hardened particularly because of poor weather resistance of the foam, and strength and adhesion to a substrate (for example, shear strength and peel strength) are reduced. there were. Furthermore, JP-A-3
JP-A-168260 proposes a pressure-sensitive adhesive tape having improved adhesion to a substrate by using a polyurethane-based foam that uses a polyol composition obtained by graft-polymerizing a vinyl monomer on a polyether. This adhesive tape needs to undergo a step of graft-polymerizing a vinyl monomer onto a polyether in order to obtain a polyol composition, and there is a problem in economical efficiency in a manufacturing process.

[0003]

Therefore, the present invention has been made in view of the above-mentioned conventional problems in the adhesive foam sheet and the adhesive foam tape, and the objects thereof are strength, water resistance, weather resistance and compression. An object of the present invention is to provide an emulsion composition for foams which can form foam sheets, foam tapes and the like having excellent recoverability.

[0004]

Means for Solving the Problems In the present invention, (a) an acrylic ester polymer emulsion and (b) a polyurethane emulsion are (a) / (b) in terms of solid content.
(B) The present invention relates to a foam emulsion composition obtained by mixing at a ratio of 95/5 to 5/95, and a foam sheet or foam tape formed from the composition.

The present invention will be described in detail below, which will clarify the purpose, constitution and effect of the present invention. The (a) acrylic ester polymer emulsion, which is one of the main components in the foam emulsion composition of the present invention, comprises an ester of acrylic acid or methacrylic acid and an aliphatic, alicyclic or aromatic unsubstituted alcohol. It is an emulsion containing a polymer obtained from an acrylic ester monomer. The term "unsubstituted" as used herein means having no groups other than hydrocarbon groups. (A) Examples of acrylic ester polymer emulsions include homopolymers of acrylic ester monomers, copolymers of two or more acrylic ester monomers, or 1
An emulsion composed of a copolymer of one or more kinds of acrylic ester monomers and one or more kinds of other monomers, and further a mixture of two or more kinds of homopolymers or copolymers thereof is mentioned. be able to.

As the acrylic ester monomer,
For example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, isobutyl acrylate, isobutyl methacrylate,
N-butyl methacrylate, pentyl acrylate, pentyl methacrylate, hexyl acrylate, hexyl methacrylate, heptyl acrylate, heptyl methacrylate,
2-ethylhexyl acrylate, octyl acrylate,
Octyl methacrylate, n-nonyl acrylate, isononyl acrylate, n-nonyl methacrylate, isononyl methacrylate, decyl acrylate, decyl methacrylate, undecyl acrylate, undecyl methacrylate,
Dodecyl acrylate, dodecyl methacrylate, n-amyl acrylate, isoamyl acrylate, n methacrylate
-Amyl, isoamyl methacrylate, lauryl acrylate, lauryl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate and the like can be mentioned. A preferred acrylic ester monomer is an acrylic acid alkyl ester or a methacrylic acid alkyl ester in which the alkyl group has 1 to 12 carbon atoms, and more preferably 1 to 4 carbon atoms.

The above-mentioned other monomers copolymerizable with the acrylic ester monomer include aromatic vinyl monomers, vinyl cyanide monomers, ethylenically unsaturated ester monomers, and ethylene. Ethylenically unsaturated ether monomer, ethylenically unsaturated sulfonic acid ester monomer, ethylenically unsaturated silane monomer, vinyl halide monomer, aliphatic conjugated diene monomer, etc. Unsaturated carboxylic acid, ethylenically unsaturated carboxylic acid anhydride, hydroxyl group-containing ethylenically unsaturated monomer, amino group-containing ethylenically unsaturated monomer,
Functional group-containing monomers such as amide group-containing ethylenically unsaturated monomers and epoxy group-containing ethylenically unsaturated monomers can be used.

Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, o-methylstyrene and p-
Methylstyrene, o-ethylstyrene, p-ethylstyrene, α-chlorostyrene, p-chlorostyrene, p-
Methoxystyrene, p-aminostyrene, p-acetoxystyrene, sodium styrenesulfonate, α-vinylnaphthalene, sodium 1-vinylnaphthalene-4-sulfonate, 2-vinylfluorene, 2-vinylpyridine, 4-vinylpyridine, etc. Can be mentioned.

Examples of the vinyl cyanide-based monomer include acrylonitrile, α-chloroacrylonitrile, α-methoxyacrylonitrile, methacrylonitrile, α-chloromethacrylonitrile, α-methoxymethacrylonitrile, vinylidene cyanide and the like. Is mentioned.

Examples of the ethylenically unsaturated alcohol ester include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl stearate, vinyl benzoate, allyl acetate, methallyl caproate, allyl laurate, allyl benzoate, alkyl. Examples thereof include vinyl sulfonate, allyl alkyl sulfonate, vinyl aryl sulfonate, and the like.

Examples of the ethylenically unsaturated ether monomer include methyl vinyl ether, ethyl vinyl ether,
Examples thereof include n-propyl vinyl ether, isopropyl vinyl ether, methyl allyl ether and ethyl allyl ether.

Examples of the ethylenically unsaturated sulfonic acid ester monomer include alkyl vinyl sulfonate and alkyl isoprene sulfonate.

Examples of the ethylenically unsaturated silane include vinyltriethylsilane, methylvinyldichlorosilane,
Examples thereof include dimethylallylchlorosilane and vinyltrichlorosilane.

Examples of the vinyl halide monomer include:
Examples thereof include vinyl chloride, vinylidene chloride, 1,2-dichloroethylene, vinyl bromide, vinylidene bromide and 1,2-dibromoethylene.

Examples of the aliphatic conjugated diene monomer include:
1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-neopentyl-1,3-butadiene, 2-chloro-1,3-
Butadiene, 1,2-dichloro-1,3-butadiene,
2,3-dichloro-1,3-butadiene, 2-bromo-
1,3-Butadiene, 2-cyano-1,3-butadiene, substituted linear conjugated pentadienes, linear and side chain conjugated hexadienes and the like can be mentioned.

Among the functional group-containing monomers, the ethylenically unsaturated carboxylic acid monomer is an ethylenically unsaturated monocarboxylic acid such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid or crotonic acid. Carboxylic acid or polycarboxylic acid or salts thereof; ethylenically unsaturated carboxylic acid anhydride monomers include fumaric acid, maleic acid and other ethylenically unsaturated polycarboxylic acid anhydrides; hydroxyl group-containing ethylenically unsaturated As the monomer, allyl alcohol, methallyl alcohol, hydroxymethyl acrylate, hydroxymethyl methacrylate, 1-hydroxyethyl acrylate, 1-hydroxyethyl methacrylate,
2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide, etc .;
Examples of the amino group-containing ethylenically unsaturated monomer include aminoethyl acrylate, aminoethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, β-aminoethyl vinyl ether, dimethylaminoethyl vinyl ether, vinylamine, vinylmethyl. Amine, vinyldimethylamine, allylamine, allyldimethylamine, methallyldiethylamine, etc .; amide group-containing ethylenically unsaturated monomers include acrylamide, methacrylamide, ethacrylamide, diacetone acrylamide, diacetone methacrylamide, crotonamide, itacon Amides of ethylenically unsaturated carboxylic acids such as diamides, methylitaconamides, maleindiamides; epoxy group-containing ethylenically unsaturated monomers include acrylic acid Glycidyl, mention may be made of glycidyl methacrylate, vinyl glycidyl ether, ethylene glycidyl esters or glycidyl ethers of ethylenically unsaturated alcohols of unsaturated carboxylic acids, such as allyl glycidyl ether.

The content of the other monomer in the copolymer of the acrylic ester and the other monomer used in the present invention is usually 0.5 to 50% by weight, preferably 1 to 50% by weight. It is 30% by weight.

Among the acrylic ester polymers used in the present invention, the preferred combination of monomers forming the copolymer is ethyl acrylate / methacrylic acid in the copolymer of acrylic ester monomers. Combinations of methyl (the same applies hereinafter), n-butyl acrylate / methyl methacrylate, 2-ethylhexyl acrylate / methyl methacrylate, ethyl acrylate / n-butyl acrylate / methyl methacrylate, and the like. In the case of a copolymer of an acrylic ester monomer and another monomer, n-butyl acrylate / styrene, ethyl acrylate, n-acrylate
At least one of butyl and 2-ethylhexyl acrylate / methyl methacrylate / N-methylol acrylamide, N-methylol methacrylamide, at least one of acrylic acid and methacrylic acid, and the like.

The (a) acrylic ester polymer emulsion used in the present invention is preferably produced by emulsion polymerization of an acrylic ester monomer, optionally with other monomers. Such emulsion polymerization is usually performed at 60 parts by weight based on 100 parts by weight of the total amount of the monomers.
~ 180 parts by weight of water, optionally in the presence of an emulsifier and a polymerization initiator, optionally a chain transfer agent, various electrolytes, pH
A regulator and the like are added to the mixture at 10 to 90 ° C, preferably 40
It is carried out by polymerizing at a temperature of -80 ° C for 5-40 hours. In emulsion polymerization, the monomers to be used can be added by an appropriate method such as batch addition, divided addition or continuous addition. In the divisional addition or continuous addition, the monomer can be added together with other addition components such as a polymerization initiator, or the other addition components are added in advance and only the monomer is divided. Alternatively, they can be added continuously. Further, the monomers to be added in portions or continuously can be emulsified in advance.

As the emulsifier, one or more kinds of anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, etc. are used, and these surfactants have fluorinated lipophilic groups. It can also be a fluorine-based surfactant. The anionic surfactant, alkali metal salts of fatty acids, sulfate ester salts of higher alcohols,
Polyoxyethylene alkyl ether sulphate, polyoxyethylene alkyl phenyl ether sulphate, fatty oil sulphate, aliphatic amine or amide sulphate, dibasic fatty acid ester sulphonate, aliphatic amide Sulfonates, alkyl or alkenyl sulfonates, alkylaryl sulfonates, alkyl sulfosuccinates, formalin condensed naphthalene sulfonates, phosphate ester salts of aliphatic alcohols, polyoxyethylene alkyl (phenyl) ether phosphates Ester salts and the like are used. Specific examples of the anionic surfactant include sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium diphenyl ether disulfonate, sodium succinate dialkyl ester sulfonate, and the like, and particularly sodium lauryl sulfate and sodium diphenyl ether disulfonate should be used. Thereby, the effect of the present invention is remarkably exhibited.

As the nonionic surfactant, polyoxyethylene alkyl ester, polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, glycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester and the like are used. ..

Furthermore, the chemical structure of the fluorine-based surfactant is basically the same as that of a normal surfactant, and examples thereof include carboxylate, sulfate and sulfonic acid as hydrophilic groups. Anionic surfactants having groups such as salts and phosphates, nonionic surfactants having polyoxyethylene groups as hydrophilic groups, cationic surfactants having groups such as amine salts and quaternary ammonium salts as hydrophilic groups Agents and amphoteric surfactants. Fluorosurfactants generally have high surface activity, and many of them exhibit a sufficient emulsifying action even if the lipophilic group has a smaller number of carbon atoms than general surfactants.
Examples of such fluorine-based surfactants include perfluoroalkylcarboxylic acid salts, perfluoroalkylsulfonic acid salts, perfluoroalkylphosphoric acid esters, perfluoroalkyltrimethylammonium salts, perfluoroalkylpolyoxyethylenes, perfluoroalkylbetaines. Etc.

The preferred amount of the emulsifier used is usually 0.5 to 10% by weight, based on the total amount of the monomers, and particularly 1 to
8% by weight is preferred. If the amount of emulsifier used is too small,
The stability of the emulsion tends to decrease due to the formation of coagulated substances, and the water resistance of the foam formed from the emulsion tends to decrease even if the amount is too large.

As the polymerization initiator, inorganic initiators such as potassium persulfate, ammonium persulfate and hydrogen peroxide, cumene hydroperoxide, isopropylbenzene hydroperoxide, paramenthane hydroperoxide, benzoyl peroxide, di- Examples thereof include organic initiators such as t-butyl peroxide, dilauroyl peroxide, azobisisobutyronitrile, asobisisovaleronitrile, azobisisocapronitrile, and azobis (phenylisobutyronitrile). .. The amount of the polymerization initiator used is 0.03 to the total amount of the monomers.
2 wt% is preferable, and 0.05 to 1 wt% is particularly preferable.

Further, a reducing agent, a chelating agent or the like may be added to accelerate emulsion polymerization. Examples of the reducing agent, sodium pyrobisulfite, sodium sulfite, sodium bisulfite, ferrous sulfate, glucose,
Formaldehyde sodium sulfoxylate, L-ascorbic acid and salts thereof and the like can be mentioned, and examples of the chelating agent include glycine, alanine, sodium ethylenediaminetetraacetate and the like.

As the chain transfer agent, 2,4-diphenyl-4-methyl-1-pentene component is preferably used.
Α-methylstyrene dimer, terpinolene, α-terpinene, γ-terpinene, dipentene, octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, dimethylxanthogen disulfide, diethylxanthogen disulfide, which is contained by weight% or more. Examples thereof include diisopropylxanthogen disulfide, tetremethylthiuram monosulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, dipentamethylthiuram disulfide and the like. A preferred chain transfer agent is n-dodecyl mercaptan. The amount of the chain transfer agent used is usually 15% by weight or less based on the total amount of the monomers.

The emulsion polymerization method for producing the (a) acrylic ester polymer emulsion used in the present invention has been described above. In the (a) acrylic ester polymer emulsion, at least the last stage of the polymerization is performed. It is also produced by a polymerization method other than the emulsion polymerization method, for example, a bulk polymerization method, a solution polymerization method, a precipitation polymerization method, a suspension polymerization method, a bulk-suspension polymerization method, or the like method in which an acrylic ester polymer obtained by emulsion polymerization is dispersed in an aqueous medium. Is something that can be done. Examples of the emulsifier used in this case include various surfactants used in the emulsion polymerization method described above.

The acrylic ester polymer used in the present invention has a glass transition point of -50 ° C to + 25 ° C.
It is preferably within the range. A particularly preferred glass transition point is -40 ° C to + 20 ° C. If the glass transition point is lower than -50 ° C, the foam tends to be too sticky to be handled, and the strength tends to be low. Meanwhile +
When the temperature is higher than 25 ° C, the foam becomes too hard and poor in flexibility, so that when it is used as a bonding material, the shear strength may be insufficient. The glass transition point is measured under the following conditions using a differential scanning calorimeter (DSC) manufactured by Rigaku Denki. About 5 g of acrylic ester polymer emulsion is thinly spread on a glass plate and dried at 25 ° C for 7 days to form a film. About the obtained film, temperature rising rate: 20 ° C /
The glass transition point is measured under measurement conditions of minutes, atmosphere: nitrogen, and sample amount: 20 mg.

The average particle size of the (a) acrylic ester polymer emulsion used in the present invention is 120 to
It is preferably in the range of 500 nm. A particularly preferable average particle size is 170 to 350 nm. Average particle size is 1
If it is less than 20 nm, the viscosity of the emulsion becomes too high, so that it becomes difficult to obtain an emulsion having a high solid content, and as a result, it tends to be difficult to obtain a good film. On the other hand, if it exceeds 500 nm, the water resistance and solvent resistance of the foam may be lowered. In addition, this average particle size was determined from the electron micrograph of the emulsion treated with uranyl acetate and osmic acid
It is the number average of 100 or more particles. (A) The average particle size of the acrylic ester polymer emulsion can be controlled by adjusting stirring conditions such as emulsion polymerization and the amount of the emulsifier used.

The (b) polyurethane emulsion, which is the other main component in the foam emulsion composition of the present invention, is a polyurethane resin and / or polyurethane elastomer finely emulsified and dispersed in an aqueous medium. The method for producing the (b) polyurethane emulsion is not particularly limited, but the diisocyanate component is emulsified in an aqueous medium in the presence of an emulsifier or a protective colloid, and the diol component is added with vigorous stirring. A method for obtaining a polyurethane emulsion by reacting, a solution of an _NCO- terminated prepolymer obtained from a diisocyanate component and a diol component in an organic solvent ₍ such as toluene ₎ is dispersed in an aqueous medium, and then a diamine component is added to extend the chain. To produce polyurethane, and then emulsify and disperse it by vigorously stirring in the presence of a large amount of emulsifier.By reacting the diol component and excess diisocyanate component in an organic solvent, an _NCO- terminated prepolymer is synthesized. , And then hydrophilic groups in the molecule (eg anionic groups, nonionic Group, a cationic group) with _NCO-reactive groups (e.g. hydroxyl, by reacting an internal emulsifier having an amino group) to synthesize an ionomer, and a method of this ionomer desolvation causes emulsified and dispersed in an aqueous medium Can be mentioned.

Examples of the diisocyanate component include toluene diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, xylene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate. Examples of the diol component include polyethylene glycol, polypropylene glycol, polyether glycol, polyester glycol, and polyether polyester glycol.

In the present invention, the mixing ratio of (a) acrylic ester polymer emulsion and (b) polyurethane emulsion is (a) /
(B) = 95/5 to 5/95. (A) Acrylic ester polymer emulsion exceeds 95% by weight (b)
If the polyurethane-based emulsion is less than 5% by weight, the normal state strength, water resistance strength, compression recovery property, etc. are particularly reduced.
If (a) the acrylic ester polymer emulsion is less than 5% by weight and (B) the polyurethane emulsion is more than 95% by weight, the weather resistance of the foam is particularly deteriorated. For example, when the foam is used as a pressure-sensitive adhesive foam sheet as a bonding material, Shear strength is low.

Further, the foam emulsion composition of the present invention can enhance the elasticity of the foam and further improve the compression recovery by adding a delayed coagulant or a heat-sensitive gelling agent. Specific examples of such a delayed coagulant or a heat-sensitive gelling agent include sodium fluoride, silica fluoride salts such as potassium fluoride, ammonium hydrogen carbonate, ammonium carbonate, ammonium chloride, ammonium salts such as ammonium acetate, Trypsin, protein, nitroparaffin, polyvinyl methyl ether, polypropylene glycol, methyl cellulose, hydroxyethyl cellulose, organopolysiloxane, alkylene oxide adduct of alkylphenol formalin condensate,
Examples thereof include low cloud point nonionic surfactants.

In order to improve various properties, the foam emulsion composition of the present invention contains, if necessary, a flame retardant, a cross-linking agent, a filler, a dye / pigment, an antioxidant, an ultraviolet absorber and a preservative. Further, additives such as a foaming agent, a foam stabilizer, an aromatic agent and a wax can be further blended.

Examples of the flame retardant include phosphoric acid ester type, halogen-containing phosphoric acid ester type, ammonium polyphosphate, antimony trioxide, zinc borate, barium metaborate, aluminum hydroxide, magnesium hydroxide and the like.

Examples of the cross-linking agent include phenol resin, urea resin, amino resin, aniline resin, melamine resin, epoxy resin, azo compound, isocyanate compound and zinc. By using these cross-linking agents, it is possible to further improve the compression recovery property and strength of the foam.

Examples of the filler include calcium carbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, barium hydroxide, basic zinc carbonate, basic lead carbonate, ferric hydroxide, silica sand, talc, clay and the like. Is mentioned.

Examples of the dyes and pigments include inorganic pigments such as titanium white, aniline black and phthalocyanine blue,
Organic pigments or dyes may be mentioned.

Examples of the antiaging agent include 4,4 '
-Dioctyldiphenylamine, tetrakis- [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, triethyleneglycol-bis [3- (3-t-butyl-5) -Methyl-4-hydroxyphenyl) propionate], tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, triphenylphosphite,
Examples thereof include tris (2-ethylhexyl) phosphite, tetraphenyldipropylene glycol diphosphite, cyclic neopentanetetraylbis (nonylphenylphosphite), and the like.

Examples of the ultraviolet absorber include pt
-Butylphenyl salicylate, 2-hydroxy-4-
Methoxybenzophenone, 2,2'-dihydroxy-4
-Methoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2,2 ',
4,4'-tetrahydroxybenzophenone, 2-
(2'-Hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy) -3 ', 5'-di-t
-Amylphenyl) benzotriazole, 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, ethyl-2-cyano-3,3-diphenylacrylate, 2-hydroxy-4-benzyloxybenzophenone, bis (2,2) , 6,6-Tetramethyl-4-piperidyl) sebacate, 8-benzyl-7,7,9,9-
Tetramethyl-3-octyl-1,2,3-triazaspiro [4,5] -undecane-2,4-dione, tetraxy (2,2,6,6-tetramethyl-4-piperidyl) -1,2, 3,4-butane tetracarboxylate and the like can be mentioned.

Examples of the preservatives include dihydroxydichlorodiphenylmethane, sodium pentachlorophenate, 2,3,4,6-tetrachloro-4- (methylsulfanyl) pyridine, 2,3,5,6-tetrachloro- 4- (methylsulfonyl) pyridine, bis (tributyltin) oxide, hexahydro-1,3,5-triethyl-s-triazine, 10,10'-oxybisphenoxyarsine, 1,2-benzisothiazoline-
3-one, dithio-2,2'-bis (benzmethylamide), N-dimethyl-N'-phenyl (N'-florodichloromethylthio) -sulfamide and the like can be mentioned.

Examples of the foaming agent include sodium lauryl sulfate, sodium alkyldiphenyl ether disulfonate, sodium polyoxyethylene alkylphenol ether sulfate and the like.

Examples of the foam stabilizer include ammonium stearate, alkyl sulfosuccinate, quaternary alkyl ammonium chloride and the like.

Examples of the fragrance include acetophenone, vanillin, coumarin, citronellal, organic carboxylic acid, methyl salicylate, geranyl acetate, geraniol, eugenol, terpineol, linalool, and lavenda oil.

Examples of the wax include polyethylene oxide wax, polypropylene oxide wax, glycol-modified polypropylene oxide wax, ethylene acrylic acid copolymer wax, and paraffin wax. A preferred wax is an oxidized polyethylene wax or the like.

The amount of these additives to be added is usually 5 to 50 parts by weight of the flame retardant and 0.1 to 100 parts by weight of the acrylic ester polymer emulsion (as solid content). -10 parts by weight, 2 to 200 parts by weight of filler,
0.1 to 10 parts by weight of dye and pigment is 0.05 to 5
Parts by weight, 0.05-5 parts by weight of ultraviolet absorber, 0.01-1 part by weight of preservative, 0.1-10 parts by weight of foaming agent, 0.1-10 parts by weight of foam stabilizer, aroma The agent is about 0.5 to 10 parts by weight and the wax is about 0.3 to 15 parts by weight.

The foam composition of the present invention contains a rubber latex such as natural rubber latex, styrene-butadiene rubber latex, acrylonitrile-butadiene rubber latex, chloroprene rubber latex, polyvinyl chloride emulsion, etc. It is also possible to mix a resin emulsion or the like such as a polystyrene-based emulsion, which may further improve various properties of the foam.

The total solid content of the foam emulsion composition containing the various additive components as described above is adjusted in consideration of the characteristics and application of the foam to be formed, workability during foam formation, and the like. It is preferably 55% by weight or more, more preferably 60% by weight or more. The total solid content is 5
If it is less than 5% by weight, the elasticity as a foam becomes low,
The use will be restricted. Further, if the total solid content is too high, it becomes difficult to maintain the dispersion stability of the emulsion composition, so the content is preferably 85% by weight or less.

Further, in the present invention, when a foam is formed from the foam emulsion composition, a thickener such as carboxymethyl cellulose, hydroxyethyl cellulose, sodium polyacrylate or the like is used,
The viscosity is adjusted to preferably 2,000 cps or higher, more preferably 2,500 to 70,000 cps.
If the viscosity of the emulsion composition is less than 2,000 cps, the foam density tends to be non-uniform and the thickness is 1 m.
It tends to be difficult to obtain foams of m or larger.
On the other hand, when the viscosity of the foam emulsion composition is too high, it becomes difficult to handle when forming the foam. In addition, the viscosity referred to here is measured by using a BM type viscometer and using a rotor No. Four
And a rotation speed of 12 rpm.

When forming a foam from the foam emulsion composition of the present invention, preferably a foaming agent and a foam stabilizer as described above are added, and a gas (preferably air) is added thereto to obtain an oaks mixer, It can be carried out continuously or discontinuously by mechanically stirring it with a whipper or the like. The expansion ratio varies depending on the use and characteristics of the foam, but is usually 1.5 to 10 times,
It is preferably 2 to 7 times.

Is the foam emulsion composition of the present invention?
The foam formed from this was applied to the substrate as needed.
After that, usually at a temperature of 100 to 170 ° C, usually for 10 minutes or less.
Above, preferably, it is heated and dried for about 15 to 40 minutes. Dry
The foam density after drying is 0.05-0.8g / cm3 Degree
Degree is preferred.

The form of the foam formed from the foam emulsion composition of the present invention is preferably a sheet or tape. In the present invention, when a sheet-like or tape-like foam is formed, it can be formed into a desired sheet or tape shape at the stage of forming the foam from the emulsion composition for foam, or can be wide or thick. The formed foam may be machined by cutting, cutting or the like to obtain a desired sheet or tape shape. These foam sheets or foam tapes can be subjected to secondary processing such as embossing, printing, lamination of decorative films, and the like.

By applying an adhesive to at least one surface of the foam sheet or foam tape of the present invention, an adhesive foam sheet or adhesive foam tape having excellent properties can be produced. The pressure-sensitive adhesive foam sheet and the pressure-sensitive adhesive foam tape can be appropriately selected in shape, thickness and the like depending on the application, purpose of use and the like. Further, if necessary, the surface not coated with the adhesive can be subjected to secondary processing such as empos, printing, lamination of a decorative film, and the like. It can be covered with a mold film or the like.

Examples of the adhesive include natural rubber and suture
Tylene butadiene rubber, polyvinyl ether, polyvinyl chloride
Various adhesives such as rubutyral and acrylic polymers are used
Water resistance, moisture resistance, weather resistance, foam
Acrylic polymer adhesive from the viewpoint of compatibility with
Agents are preferred. The coating amount of these adhesives depends on
Although it changes depending on the type of adhesive, application, etc.
50 or less per side of foam tape or foam tape
~ 100g (dry weight) / m2 It is a degree. Also, the above
Adhesives include rosin, rosin ester, coumarone resin,
Tackifiers such as terpene resins, fatty acid esters, animals and plants
In addition to softeners such as oils and fats, fillers, dyes and pigments, aging prevention
Other additives such as agents and stabilizers can also be added.

Further, between the foam and the pressure-sensitive adhesive, an undercoating agent layer having an affinity for both the foam and the pressure-sensitive adhesive used can be interposed. As this subbing agent,
Examples thereof include casein, polyvinyl alcohol and its derivatives, polyacrylamide, vinyl ether-maleic anhydride copolymer, and phenol resin.

The pressure-sensitive adhesive foam sheet and pressure-sensitive adhesive foam tape produced from the foam sheet or foam tape of the present invention are not only excellent in general physical properties such as strength, water resistance, weather resistance and compression recovery property, but also have good adhesion to a substrate. Etc., and can be widely used in each field where an adhesive sheet or adhesive tape is used. That is,
As itself or by joining with other materials, for example, automobile moldings, joining materials (for wood plywood, inorganic boards, wood, metals, plastics, etc.), interior materials (for floors, ceilings, walls) Etc.), damping material (for automobiles, audio, etc.),
Thermal insulation / insulation materials (for automobiles, audios, home appliances, constructions, etc.), soundproofing materials (for automobiles, audios, etc.), protective materials (for automobiles, aircraft, home appliances, audios, OA equipment, etc.) And the like can be suitably used.

The foam formed from the foam emulsion composition of the present invention has excellent characteristics as such, and therefore, it can be suitably used as a foam material even in forms other than sheets and tapes. can do.

The present invention will be described in more detail with reference to Examples and Comparative Examples below, but the present invention is not limited to these Examples. Where part and% are
Unless otherwise stated, it is based on weight.

【Example】

(1) Preparation of Emulsion Composition Using various acrylic ester polymer emulsions and polyurethane emulsions, a foaming agent (sodium lauryl sulfate), a foam stabilizer (ammonium stearate), a cross-linking agent (melamine resin) and a thickener. (Sodium polyacrylate) was blended to prepare a foam emulsion composition. The properties of each foam emulsion composition are shown in Table 1.

(2) Foam sheet and adhesive foam
Preparation of Sheet Air is blown into each foam emulsion composition shown in Table 1.
It was put in and foamed by mechanical stirring with a whipper.
After that, heat dry at 130 ° C for 30 minutes to close the foam.
0.3g / cm3 And 1.5 mm thick foam
Formed. Acrylic polymerization on this foam sheet
Apply body adhesive with 70g (dry weight) / m2
Then, an adhesive foam sheet was produced. (3) Physical properties of foam sheet and adhesive foam sheet
Evaluation Foam sheet and adhesive foam sheet obtained in (2) above
The various physical properties of the alloy were evaluated in the following manner. Criticism
Valency results are shown in Table 2.Normal strength Specimen obtained by cutting the foam sheet with No. 2 dumbbell
And use an autograph according to JIS K6301
Then, the tensile test was performed at a speed of 500 mm / min.Water resistance Specimens obtained in the same manner as normal strength are placed in room temperature water for 24 hours.
After soaking, a tensile test is conducted in the same manner as normal strength.
It wasWeatherability Foam sheet, carbon arc type weather resistance accelerated tester
After exposing at 63 ° C for 48 hours, visually inspect the surface.
It was observed and evaluated according to the following criteria. ○: No change △: Some yellowing ×: YellowingCompression recovery 4kg / cm2 for foam sheet Pressure of 10
After applying pressure for 10 minutes and releasing the pressure 10 seconds after the original thickness
The compression recovery was evaluated by the ratio (%).Shear strength 25mm x 25mm adhesive foam sheet, 5kg /
cm2 Pressed onto stainless steel SUS304 with pressure of
After curing at room temperature for 3 days, pull at a speed of 50 mm / min
Then, the shear strength was measured.180 degree peel strength Adhesive foam sheet with a width of 25 mm is 5 kg / cm2 of
Pressed onto stainless steel SUS304 with pressure, 3 at room temperature
After curing for a day, perform a tensile test at a speed of 50 mm / min.
No, the 180 degree peel strength was measured.

[0060]

[Table 1]

[0061]

[Table 2]

As is clear from Table 2, the foam sheet of the present invention is excellent in normal strength, water resistance, weather resistance and compression recovery. Moreover, the adhesive foam sheet made from the foam sheet has a peel strength of 180
The peel strength is extremely good. On the other hand, the foam sheet and the adhesive foam sheet obtained from only the acrylic ester polymer emulsion (Comparative Example 1) are inferior in physical properties other than weather resistance, and the foam sheet obtained from only the polyurethane emulsion (Comparative Example). In 2), the weather resistance is particularly poor, and the adhesive foam sheet has low shear strength and 180 degree peel strength.
As described above, the effect of the present invention achieved by using the acrylic ester polymer emulsion and the polyurethane emulsion in combination is the same as that of the foam sheet and the adhesive foam sheet obtained from the acrylic ester polymer emulsion and the polyurethane emulsion, respectively. By nature, it is unexpected.

[0063]

The foam sheet and foam tape formed from the emulsion composition for foams of the present invention are excellent in various physical properties such as strength, water resistance, weather resistance and compression recovery property, and the adhesive obtained from them. Foam sheets and adhesive foam tapes also have excellent adhesion to the substrate. Therefore, the foam formed from the emulsion composition for foam of the present invention is preferably in the form of a foam sheet or foam tape, and can be suitably used for various applications, and from these foam sheets or foam tapes The obtained adhesive foam sheet and adhesive foam tape are extremely useful in a wide range of fields such as automobiles, building materials, home appliances, and audios.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08L 75/04 NGG 8620-4J // (C08L 33/04 75:04) 8620-4J (72) Inventor Yasuhisa Watanabe 2-11-24 Tsukiji, Chuo-ku, Tokyo Within Nippon Synthetic Rubber Co., Ltd.

Claims (2)

[Claims] 1. An acrylic ester polymer emulsion (a) and a polyurethane emulsion (ii) are mixed in a solid content weight ratio of (ii) / (ii) = 95/5 to 5/95. A foam emulsion composition comprising: 2. A foam sheet or foam tape formed from the foam emulsion composition according to claim 1.