JP2007291362A - Adhesive composition and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive composition remarkably reducing aggregates and having excellent stability of viscosity and pH even when preserved over a long period and excellent adhesiveness in the adhesive composition composed of an aqueous emulsion (A) containing an ethylene-vinyl ester-based copolymer and an aqueous emulsion (B) containing a polyurethane and to provide a method for producing the adhesive composition. <P>SOLUTION: The adhesive composition comprises the aqueous emulsion (A) containing the ethylene-vinyl ester-based copolymer, the aqueous emulsion (B) containing the polyurethane and a polyoxyethylene alkyl ether (C) and/or a polyoxyethylene-polyoxypropylene condensate (D). The weight ratio of the (A)/(B) is (52/48) to (98.5/1.5) and the total weight (solid content) of the (C) and (D) is 0.05-0.75 pt.wt. based on 100 pts.wt. of the (A) and (B) [the total weight composing the (A) and (B)]. The method for producing the adhesive composition comprises mixing the (A) with (C) and/or (D) and then mixing the resultant mixture with the (B). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an adhesive composition obtained by blending an ethylene-vinyl ester copolymer emulsion and an aqueous polyurethane emulsion.

  An adhesive composition comprising an aqueous emulsion containing a copolymer of vinyl acetate and ethylene, which is one of ethylene-vinyl esters, and an aqueous emulsion containing polyurethane, as an adhesive composition excellent in normal adhesiveness and heat-resistant creep resistance Are disclosed in Patent Document 1 and Patent Document 2. And it is disclosed that this adhesive composition is suitable for adhesion | attachment with wood and a vinyl chloride sheet, and can be made to adhere | attach wood with polyolefin sheets, such as polyethylene and a polypropylene.

JP-A-60-163981 [Claims] JP-A-9-94811 [Claims]

As a result of studies by the present inventors, an adhesive composition obtained by directly blending an aqueous emulsion containing an ethylene-vinyl ester copolymer in a neutral to weakly acidic region and an aqueous polyurethane emulsion in an alkaline region is aggregated. It has become clear that the viscosity may increase when stored for a long time. Therefore, the pH of the ethylene-vinyl acetate copolymer emulsion in the neutral to weakly acidic region was adjusted using ammonia water in the vicinity of the pH of the polyurethane emulsion in the alkaline region, and the resulting adhesive composition was obtained. The product hardly agglomerated, and it was revealed that the viscosity did not increase even when stored for a long time. However, it has been clarified that the adhesive composition using aqueous ammonia has a low pH and a poor pH stability when stored for a long time.
An object of the present invention is to provide an adhesive composition comprising an aqueous emulsion containing an ethylene-vinyl ester copolymer and an aqueous emulsion containing a polyurethane. It is providing the adhesive composition which is excellent in this, and is excellent in adhesiveness, and its manufacturing method.

The present inventors have found that an adhesive composition containing a specific amount of a certain type of surfactant has excellent viscosity and pH stability and excellent adhesiveness even when stored for a long time.
That is, the present invention relates to an ethylene-vinyl ester copolymer-containing aqueous emulsion (A), a polyurethane-containing aqueous emulsion (B), and polyoxyethylene alkyl ether (C) and / or polyoxyethylene / polyoxypropylene condensation. An adhesive composition containing the product (D), wherein the weight ratio of the solid content of (A) / (B) is 52/48 to 98.5 / 1.5, and (C) and (D) Adhesive composition whose total weight (solid content) is 0.05 to 0.75 parts by weight with respect to 100 parts by weight (total weight constituting (A) and (B)) of (A) and (B) Things,
After mixing polyoxyethylene alkyl ether (C) and / or polyoxyethylene / polyoxypropylene condensate (D) with ethylene-vinyl ester copolymer-containing aqueous emulsion (A), polyurethane-containing aqueous emulsion (B Is a method for producing an adhesive composition.

  The adhesive composition of the present invention has almost no aggregate, and even when stored for a long time, the increase in viscosity and the decrease in pH are remarkably suppressed. Furthermore, even if the ethylene-vinyl ester copolymer emulsion is adjusted with ammonia water and then blended with a polyurethane emulsion, a pH adjustment step is not required before blending, and the copolymer can be easily produced. Moreover, when the adhesive composition of this invention is used as an adhesive agent, it will be excellent in adhesiveness in a normal state, and will be excellent in adhesiveness even if immersed in water for 24 hours.

Hereinafter, the present invention will be described in detail.
The ethylene-vinyl ester copolymer-containing emulsion (A) used in the present invention is an aqueous emulsion containing a copolymer containing structural units derived from ethylene and vinyl ester. The structural unit derived from ethylene in the copolymer is usually 5 to 70% by weight, and preferably about 10 to 35% by weight.
When the content of the structural unit derived from ethylene in the copolymer contained in (A) is 5% by weight or more, the film formability at room temperature of the obtained adhesive tends to be improved, and difficulties such as polyolefin It is preferable from the tendency that the adhesiveness to an adhesive base material improves, and it is preferable that it is 70 weight% or less from the tendency which heat resistance improves and adhesive strength tends to improve.

The vinyl ester used in (A) is a vinyl ester of monocarboxylic acid, and specifically, vinyl acetate, vinyl butyrate, vinyl propionate, vinyl pivalate, vinyl laurate, vinyl isononanoate, vinyl versatate. Examples include alkyl acid vinyl esters. Two or more kinds of vinyl esters may be used as the vinyl ester unit. Of the vinyl esters, vinyl acetate is preferred.
The content of the structural unit derived from the vinyl ester in the copolymer contained in (A) is 95 to 30% by weight, preferably 90 to 65% by weight. When the content is 95% by weight or less, it is preferable because the film-forming property of the aqueous emulsion at room temperature tends to be improved and the adhesion to difficult-to-adhere substrates such as polyolefins tends to be improved. On the other hand, the content of 30% by weight or more is preferable because heat resistance tends to be improved and adhesive strength tends to be improved.

As a monomer used in producing (A), in addition to ethylene and vinyl ester, a monomer that can be copolymerized with these and contains one ethylenic double bond in the molecule (hereinafter, In some cases, it may be a copolymerizable monomer). Specifically, vinyl halides such as vinyl chloride and vinyl bromide; vinylidene halides such as vinylidene chloride; vinylphosphonic acid and vinyl Vinyl compounds such as sulfonic acid and their salts; aromatic vinyl such as styrene, α-methylstyrene and chlorostyrene; (meth) acrylic acid such as methacrylic acid and acrylic acid; methyl (meth) acrylate, (meth) acrylic (Meth) acrylic acid esters such as butyl acid and 2-ethylhexyl (meth) acrylate; α, β- such as maleic acid, maleic anhydride, succinic acid and itaconic acid Saturated dicarboxylic acids; Nitriles such as (meth) acrylonitrile; Acrylamides such as N-methylolacrylamide and N-butoxymethylacrylamide; Conjugated dienes such as butadiene and isoprene; Allyl sulfonate, diallyl phthalate, triallyl cyanurate, tri Examples include allyl compounds such as allyl isocyanurate.
The content of structural units derived from the copolymerizable monomer in the copolymer contained in (A) is usually 20% by weight or less, preferably 10% by weight or less.

  (A) is a monomer different from ethylene, vinyl ester and copolymerizable monomer, and is a copolymerizable crosslinking monomer having two or more ethylenic double bonds (hereinafter referred to as crosslinking property). May be referred to as a monomer). As a result, a toluene insoluble matter is expressed. Examples of the crosslinkable monomer include diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, ethylene glycol diacrylate, allyl methacrylate, adipic acid diacrylate, and trimethylolpropane dimethacrylate. The content of the structural unit derived from the crosslinkable monomer in the copolymer contained in (A) is usually 5% by weight or less, preferably 3% by weight or less. The (A) containing a structural unit derived from a crosslinkable monomer tends to impart heat resistance to the resulting adhesive and improve the heat resistant creep of the adhesive.

(A) is obtained by emulsion polymerization. Here, as the emulsifier used in the production of (A), a protective colloid is preferably used, and an emulsifier composed only of the protective colloid is particularly preferable. Examples of the protective colloid include polyvinyl alcohols such as partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, carboxyl-modified polyvinyl alcohol, and silanol group-modified polyvinyl alcohol; hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose and the like. A cellulose derivative is mentioned. Among them, partially saponified polyvinyl alcohol and completely saponified polyvinyl alcohol are preferable, and 80-100 mol% saponified polyvinyl alcohol is particularly preferable.
The average polymerization degree of the protective colloid is usually 200 to 3000, and it is preferable to carry out emulsion polymerization using polyvinyl alcohols having an average polymerization degree of 250 to 2500 as the protective colloid.

ここで、 Ｎ： 固形分（％）
ｍ_０： 平底皿の質量（ｇ）
ｍ_１： 平底皿と試料との質量（ｇ）
ｍ_２： 平底皿と蒸発残留分との質量（ｇ） The solid content of the ethylene-vinyl ester copolymer and protective colloid in (A) is usually 40 to 78% by weight, preferably 43 to 75% by weight. When the solid content is 40% by weight or more, it is preferable because the formation of aggregates tends to be suppressed. When the solid content is 78% by weight or less, the gelation of the copolymer is suppressed and emulsion polymerization is easy. This is preferable.
The solid content in the present invention can be measured according to JIS K-6828.
That is, a flat bottom dish made of aluminum foil having a diameter of 50 mm is dried for 30 minutes with a forced circulation dryer at 140 ° C., allowed to cool to room temperature, and weighed with an accuracy of 1 mg. Weigh 1.0 ± 0.2 g of sample with a precision of 1 mg in a flat bottom pan and spread it uniformly. Transfer the sample flat bottom dish to a forced circulation dryer at 140 ° C., dry for 30 minutes, allow to cool to room temperature, weigh with an accuracy of 1 mg, and obtain the solid content by the following formula.

Here, N: solid content (%)
m ₀ : Mass of flat bottom pan (g)
m ₁ : Mass (g) of flat bottom plate and sample
m ₂ : Mass (g) of flat bottom pan and evaporation residue

  (A) The single cured product usually has a glass transition temperature of −25 to + 15 ° C., preferably −20 to + 10 ° C. When the glass transition temperature is −25 ° C. or higher, the heat resistance is improved, and when the temperature is 15 ° C. or lower, the film formability at room temperature tends to be improved.

(A) of this invention is about pH 4-7 normally. The pH in the above range is the pH range as produced by emulsion polymerization of (A), and an adhesive composition can be easily produced even if it is not prepared in the alkaline region equivalent to the polyurethane-containing aqueous emulsion (B). can do.
Further, it is preferable that the pH is adjusted to 7 or less because the storage stability of the adhesive composition in which the ethylene-vinyl ester copolymer emulsion is stably present and the pH change is small tends to be improved. .

  The polyurethane-containing aqueous emulsion (B) is an aqueous emulsion in which a polyurethane obtained by reacting a polyisocyanate compound, a polyol compound, and, if necessary, another compound is dispersed in water. Examples of the reaction include methods such as an acetone method, a prepolymer mixing method, a ketimine method, and a hot melt dispersion method.

The polyisocyanate compound is an organic polyisocyanate compound used in the production of ordinary polyurethane, such as 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate. 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, dicyclohexylmethane-4,4'-diisocyanate, methylcyclohexyl-2,4-diisocyanate, methylcyclohexyl-2,6-diisocyanate, xylylene diisocyanate, 1, 3-bis (isocyanate) methylcyclohexane, tetramethylxylylene diisocyanate, transcyclohexane-1,4-diisocyanate, lysine diisocyanate 2,4-toluylene diisocyanate, 2,6-toluylene diisocyanate, diphenylmethane-4,4'-diisocyanate, 1,5'-naphthene diisocyanate, tolidine diisocyanate, diphenylmethylmethane diisocyanate, tetraalkyldiphenylmethane Aromatic diisocyanates such as diisocyanate, 4,4'-dibenzyl diisocyanate, 1,3-phenylene diisocyanate; lysine ester triisocyanate, triphenylmethane triisocyanate, 1,6,11-undecane triisocyanate, 1,8- Isocyanate-4,4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tri Adducts of Chi trimethylolpropane and toluylene diisocyanate, and triisocyanates adducts such of trimethylol propane and 1,6-hexamethylene diisocyanate.
These may be used independently and 2 or more types may be used together.

  The polyol compound is a compound having two or more hydroxyl groups in the molecule used for normal polyurethane production, for example, ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol. Polyhydric alcohols, such as neopentyl glycol, trimethylol propane, glycerin; polyether polyols, such as polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol; adipic acid, sebacic acid, itaconic acid, maleic anhydride, terephthalic acid , Isophthalic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid and other dicarboxylic acids, ethylene glycol, diethylene glycol, propylene Recall, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,2-propanediol, 1,3-propanediol, 1,9-nonanediol, 3-methyl-1,5-pentane Polyester polyols obtained from polyol compounds such as diol, 1,3-propanediol, tripropylene glycol, trimethylolpropane and glycerin; polylactone-based polyester polyols such as polycaprolactone polyol and poly β-methyl-δ-valerolactone Polybutadiene polyol or hydrogenated product thereof, polycarbonate polyol, polythioether polyol, polyacrylate polyol and the like.

It is preferable to introduce a hydrophilic group into the molecule during the production of the polyurethane because the stability when the polyurethane contained in (B) is dispersed in water can be improved. Examples of the compound used for introducing a hydrophilic group include a nonionic hydrophilic group such as a structural unit derived from polyethylene glycol in the molecule, and a sulfonyl group, a carboxyl group, a hydroxyl group, a primary amino group (- NH ₂ ), a compound having at least one active hydrogen having reactivity with an isocyanate group, such as a secondary amino group (═NH) (hereinafter sometimes referred to as a hydrophilic group-containing compound), and the like.

Examples of the hydrophilic group-containing compound include 3,4-diaminobutanesulfonic acid, 3,6-diamino-2-toluenesulfonic acid, 2,6-diaminobenzenesulfonic acid, and N- (2-aminoethyl) -2. Examples include sulfonic acid-containing compounds such as aminoethylsulfonic acid; carboxylic acid-containing compounds such as 2,2-dimethylollactic acid, 2,2-dimethylolpropionic acid, and 2,2-dimethylolvaleric acid. A hydrophilic group containing compound may be used independently and 2 or more types may be used together.
(B) containing a hydrophilic group in the molecule obtained by using these hydrophilic group-containing compounds is called an ionomer structure, and has a surface-active ability in itself, so that it tends to disperse in water, This is preferable because the aqueous emulsion obtained by further emulsion polymerization of a monomer to an aqueous polyurethane emulsion tends to improve the water resistance.

The hydrophilic group is preferably an anionic group such as a sulfone group or a carboxyl group, and in particular, the sulfone group is preferred because it tends to further improve the water resistance of an aqueous emulsion obtained by emulsion polymerization of a monomer.
In general, the anionic group is preferably neutralized by a neutralizing agent. Examples of the neutralizing agent include tertiary amine compounds such as triethylamine and trietalamine; inorganic alkali compounds such as sodium hydroxide; ammonia and the like.

  A compound that is different from a hydrophilic group-containing compound for the purpose of chain extension and molecular weight adjustment as necessary when producing (B), and contains an active hydrogen capable of reacting with an isocyanate compound in the molecule May be used in combination. Examples of such compounds include polyvalent amine compounds such as ethylenediamine, 1,4-butanediamine, and 1,6-hexanediamine; tertiary amine-containing polyhydric alcohols such as triethanolamine, methanol, ethanol, and butanol. And monoalcohols.

As (B), a commercially available polyurethane-containing aqueous emulsion may be used as it is.
Specific examples include Hydran ECOS 3000, ADS-120, ADS-110, Sanyo Chemical Industries Uprene UXA-3005, Sumika Bayer Urethane U-53, U-54, U-56, etc., manufactured by Dainippon Ink and Chemicals, Inc. It is done.

  The weight ratio of the solid contents of (A) and (B) in the adhesive composition of the present invention is (A) / (B) = 52/48 to 98.5 / 1.5, preferably 88/12. ~ 97/3. The weight of (B) with respect to the total weight of the solids of (A) and (B) is preferably 48 or less because the heat resistance of the resulting adhesive tends to improve, and is 1.5 or more. And the adhesiveness with difficult-to-adhere substrates such as polyolefins tends to be improved.

The adhesive composition of the present invention contains polyoxyethylene alkyl ether (C) and / or polyoxyethylene / polyoxypropylene condensate (D).
(C) is an alkyl ether of polyethylene glycol. The average polymerization number of the structural unit (—CH ₂ —CH ₂ —O—) derived from polyethylene glycol as the polyoxyethylene alkyl ether is 7 to 49, and the carbon number of the alkyl part is 10 to 18 polyethylene glycol. When alkyl ether is used, it is preferable because aggregates of the adhesive composition tend to be reduced when (A) and (B) are mixed.
(C) is commercially available, and examples include Emulgen 1108, Emulgen 1118S-70, Emulgen 1135S-70, and Emulgen 1150S-70 manufactured by Kao Corporation. These commercially available products may be used as they are. Two or more types of (C) may be used.

(D) is a polyoxyethylene polyoxypropylene condensate. As (D), when a polyoxyethylene polyoxypropylene condensate having a molecular weight of 2000 to 27000 and containing 10 to 80% by weight of a structural unit derived from ethylene oxide is used, an adhesive is used when (A) and (B) are mixed. This is preferable because aggregates of the composition tend to be reduced.
(D) is commercially available, and examples thereof include Pluronic L-34, 44, 64 manufactured by Asahi Denka Kogyo Co., Ltd., and these commercially available products may be used as they are. Two or more kinds of (D) may be used.
Further, (C) and (D) may be used in combination.

In the adhesive composition, the total weight (solid content) of (C) and (D) is 100 parts by weight (the total weight constituting (A) and (B)) of (A) and (B). 0.05 to 0.75 parts by weight, preferably 0.05 to 0.6 parts by weight, particularly preferably 0.08 to 0.3 parts by weight. Here, the total weight constituting (A) and (B) means the weight of the entire aqueous emulsion composed of a solvent such as water and a solid content.
When the total weight of (C) and (D) is 0.05 parts or more, the tendency to reduce aggregates of the adhesive composition when mixing (A) and (B), and included in (A) Hydrolysis of the structural unit derived from the vinyl ester is suppressed, and as a result, the pH stability tends to be improved, and is preferably 0.75 part or less because the adhesive performance tends to be improved.

  The pH of the adhesive composition of the present invention is usually about 4-7. Within the above range, hydrolysis of the structural unit derived from the vinyl ester contained in (A) is suppressed, and as a result, the pH stability tends to be improved, which is preferable.

Examples of the adhesive composition of the present invention include thermosetting resins such as urea resin, melamine resin, and phenol resin, fillers such as clay, kaolin, talc, and calcium carbonate, antiseptics, rust inhibitors, and antifoaming agents. , Foaming agents, polyacrylic acid, polyether, methylcellulose, carboxymethylcellulose, polyvinyl alcohol, starch and other thickeners, viscosity modifiers, flame retardants, pigments such as titanium oxide, dibasic acid dimethyl succinate, adipic acid dimethyl A high boiling point solvent such as a plasticizer or the like may be blended.
Among them, the filler is recommended to be used for improving the flame retardancy and the coating property at the time of adhesion, and the amount used is usually 100 parts by weight of the solid content of the adhesive composition, About 1 to 500 parts by weight, preferably about 5 to 200 parts by weight.

  The adhesive composition of the present invention is prepared by mixing (B) with (A) and (C) and / or (D). (B) mixed with (C) and / or (D) and then mixed with (A), mixed with (A) and (B) and then mixed with (C) and / or (D) In comparison, the formation of aggregates tends to be significantly reduced, which is preferable.

The adhesive composition of the present invention may be used as it is as a one-pack type adhesive, but as the present adhesive, a blend of the adhesive composition of the present invention and a curing agent is suitable. is there.
Here, the curing agent is an isocyanate-based curing agent, specifically, diphenylmethane-4,4′-diisocyanate (MDI), tolylene diisocyanate (2,4-TDI, 2,6-TDI), Examples include hexamethylene diisocyanate (HDI), m-xylylene diisocyanate (XDI), oligomers thereof, and block types. Commercially available curing agents may be used as they are, specifically, Sumidur 44V20, N3300 made by Sumika Bayer Urethane, CR-60N made by Dainippon Ink and Chemicals, and the like.
The compounding quantity of the hardening | curing agent in an adhesive agent is 0.1-20 weight part with respect to 100 weight part of adhesive compositions (total weight which comprises an adhesive composition), Preferably it is 1-10 weight part. If it is 0.1 parts by weight or more, it is preferable because the heat resistant creep resistance and water resistance tend to be improved, and if it is 20 parts by weight or less, the usable time of the adhesive tends to be long, which is preferable.

The adhesive composition of the present invention or the substrate that can be bonded by the adhesive is a material that absorbs water, specifically, wood, plywood, medium density fiberboard (MDF), particle board, orientation. Examples include woody materials such as conductive strand boards; paper-based materials such as wallpaper and wrapping paper: cellulosic materials such as cotton cloth, linen, and rayon; and porous materials.
Furthermore, if one of the adhesive composition or the adhesive is bonded to a material that absorbs water, the other is a polyolefin such as polyethylene, polypropylene, or polystyrene; a plastic material such as polyester, polyether, or polyvinyl chloride; glass Alternatively, it may be bonded to a ceramic material such as ceramic.
Among them, a laminate formed by adhering a water-absorbing material and a polyolefin through the adhesive composition or adhesive of the present invention comprises an ethylene-vinyl acetate copolymer aqueous emulsion and a polyurethane aqueous emulsion. The laminate obtained through the adhesive composition is preferable in terms of normal adhesiveness and excellent in heat resistance creep resistance.

  Hereinafter, the present invention will be described in more detail with reference to examples. Parts and% mean weight basis unless otherwise specified. Moreover, solid content was performed with the measuring method according to JIS K-6828. Unless otherwise specified, the viscosity is a value measured at BL-60 rpm with a Brookfield viscometer (manufactured by Toki Sangyo Co., Ltd.) after adjusting the temperature in a 25 ° C. water bath.

Example 1
<Production example of ethylene-vinyl ester copolymer-containing aqueous emulsion (A)>
In a pressure-resistant container, in advance 160 parts of water, 180 parts of vinyl acetate, 8 parts of protective colloid, polyvinyl alcohol “Poval 217” (manufactured by Kuraray Co., Ltd., saponification degree 88 mol%, average polymerization degree 1700), protective colloid A solution in which 2.3 parts of certain “Poval 205” (manufactured by Kuraray Co., Ltd., saponification degree 88 mol%, average polymerization degree 500), 0.005 parts of ferrous sulfate heptahydrate and 0.4 parts of acetic acid was introduced. Next, the inside of the pressure vessel was replaced with nitrogen gas, and the inside of the vessel was heated to 60 ° C. and then pressurized to 4.6 MPa with ethylene. Next, 0.1 part of hydrogen peroxide aqueous solution and 0.6 part of sodium erythorbate were each diluted with water, and dripping was started. Subsequently, after confirming that the liquid temperature in the pressure vessel had risen, a solution prepared by dissolving 0.19 part of triallyl isocyanurate in 10 parts of vinyl acetate was added over 3 hours. During polymerization, the temperature in the reaction vessel is kept at 60 ° C. by controlling the temperature of the jacket. Further, an aqueous solution of hydrogen peroxide is added and stirred until the vinyl acetate concentration in the reaction solution becomes 1% or less. The ethylene gas of the reaction was removed to obtain an ethylene-vinyl acetate-polyfunctional monomer copolymer aqueous emulsion (A).
The resin composition of the obtained aqueous emulsion (A) is derived from polyvinyl alcohol, with 100 parts of structural units derived from vinyl acetate, 22 parts of structural units derived from ethylene, 0.1 parts of structural units derived from triallyl isocyanurate, The structural unit was 5.4 parts. The solid content of the aqueous emulsion (A) was 55.0% and the viscosity was 3000 mPa · s.

<Example of production of adhesive composition>
In a container, 150 g of (A) obtained in <Production example of ethylene-vinyl ester copolymer-containing aqueous emulsion (A)> and polyoxyethylene alkyl ether (C) as an Emulgen 1118S-70 manufactured by Kao Corporation 1.06 g of a solution ((C) -1)) adjusted to 20% concentration was mixed. Next, 50 g of polyurethane aqueous emulsion ECOS3000 manufactured by Dainippon Ink & Chemicals, Inc. was mixed in the container as the polyurethane-containing aqueous emulsion (B). The obtained adhesive composition had a pH of 5.4 and a viscosity of 1500 mPa · s. When the composition was stored at room temperature for 2 weeks, it had a pH of 5.4 and a viscosity of 1760 mPa · s. When the composition was stored at 50 ° C. for 2 weeks, it had a pH of 5.2 and a viscosity of 2450 mPa · s.

(Comparative Example 1)
In Example 1, a composition was obtained in the same manner as in Example 1 except that ((C) -1)) was not used and (A) and (B) were directly mixed. The composition obtained had a pH of 5.4 and a viscosity of 2430 mPa · s. When the composition was stored at room temperature for 2 weeks, it had a pH of 5.4 and a viscosity of 7800 mPa · s. When the composition was stored at 50 ° C. for 2 weeks, it had a pH of 5.2 and a viscosity of 10,000 mPa · s or more.

(Examples 2 to 4)
In place of Emulgen 1118S-70 ((C) -1)), pH and viscosity were measured in the same manner as in Example 1 except that (C) -1 to (C) -4 shown in Table 1 were used. . The results are summarized in Table 1 together with Example 1.

(Examples 5-6)
The pH and viscosity were measured in the same manner as in Example 1 except that (D) -1 to (D) -2 shown in Table 1 were used instead of Emulgen 1118S-70 ((C) -1)). . The results are summarized in Table 1 together with Example 1.

（Ｃ）−１：20%エマルゲン1118S-70、花王（株）製、ポリオキシエチレンアルキルエーテル
（Ｃ）−２：20%エマルゲン1108、花王（株）製、ポリオキシエチレンアルキルエーテル
（Ｃ）−３：20%エマルゲン1135S-70、花王（株）製、ポリオキシエチレンアルキルエーテル
（Ｃ）−４：20%エマルゲン1150S-60、花王（株）製、ポリオキシエチレンアルキルエーテル
（Ｄ）−１：20%プルロニックＬ-64、旭電化工業（株）製、ポリオキシエチレンポリオキシプロピレン縮合物
（Ｄ）−２：20%プルロニックＬ-44、旭電化工業（株）製、ポリオキシエチレンポリオキシプロピレン縮合物

(C) -1: 20% Emulgen 1118S-70, manufactured by Kao Corporation, polyoxyethylene alkyl ether (C) -2: 20% Emulgen 1108, manufactured by Kao Corporation, polyoxyethylene alkyl ether (C)- 3: 20% Emulgen 1135S-70, manufactured by Kao Corporation, polyoxyethylene alkyl ether (C) -4: 20% Emulgen 1150S-60, manufactured by Kao Corporation, polyoxyethylene alkyl ether (D) -1: 20% Pluronic L-64, manufactured by Asahi Denka Kogyo Co., Ltd., polyoxyethylene polyoxypropylene condensate (D) -2: 20% Pluronic L-44, manufactured by Asahi Denka Kogyo Co., Ltd., polyoxyethylene polyoxypropylene Condensate

(Comparative Examples 2 to 4)
It replaces with Emulgen 1118S-70 ((C) -1)), and it carries out similarly to Example 1 except using surfactant ((C ')-1-(C')-3) of Table 2. The pH and viscosity were measured. In Comparative Example 4, ammonia water was added to (A) of Example 1 and stirred to adjust the pH to 8 or higher, and then (B) was mixed, and no surfactant was used.
The results are summarized in Table 2 together with Comparative Example 1.

（Ｃ’）−１：20%ポイズ520、花王（株）製 特殊カルボン酸型高分子界面活性剤
（Ｃ’）−２：20%デモールＰ、花王（株）製 特殊カルボン酸型高分子界面活性剤
（Ｃ’）−３：25%アンモニア水

(C ')-1: 20% poise 520, special carboxylic acid type polymer surfactant manufactured by Kao Corporation (C')-2: 20% demole P, special carboxylic acid type polymer interface made by Kao Corporation Activator (C ')-3: 25% aqueous ammonia

<Example of production of adhesive>
10 parts of a mixture of DBE (dibasic acid ester (dimethyl succinate, dimethyl adipate, dimethyl glutamate), which is an organic solvent, is added to 100 parts of the adhesive composition of Example 1 (immediately after production), Thickener (SN thickener A-812, San Nopco Co., registered trademark, urethane-modified polyether, active ingredient 40%) diluted twice is added, and the viscosity (measured with BH-10) is about 10000 mPa・ Adjusted to s to obtain an adhesive.

<Adhesion test: normal peel strength>
After applying an aqueous emulsion to JAS1 water-resistant plywood to 110 g / m ² , Dai Nippon Printing non-vinyl chloride sheet WS-201E (polyolefin sheet thickness 0.16 mm) was pasted and degassed with a hand roller. After allowing to stand for 1 day while pressing at 5.4 × 10 ⁻³ MPa, the pressing was released and the laminate was further dried for 6 days to obtain a laminate.
The normal peel strength of the laminate was measured at a peel rate of 200 mm / min (Shimadzu Autograph). Further, the heat-resistant creep was adjusted to 80 ° C. and then peeled at a peeling angle of 90 ° and a load of 500 g / 25 mm, and the peel length after 24 hours was measured. The results are summarized in Table 3.

<Production Examples 1 to 6: Production Examples of Adhesives and Adhesion Tests>
Production Example 2 <Adhesive Production Example 1 except that instead of the adhesive composition of Example 1 (immediately after production), the adhesive composition of Example 1 was stored at 50 ° C. for 2 weeks. >, An adhesive was obtained, and the same adhesion test as in Example 1 was performed.
Production Example 3 was bonded in the same manner as <Adhesive Production Example 1> except that the adhesive composition of Example 5 (immediately after production) was used instead of the adhesive composition of Example 1 (immediately after production). An agent was obtained, and the same adhesion test as in Example 1 was performed.
Production Example 4 is <Adhesive Production Example 1> except that the adhesive composition of Example 5 was stored at 50 ° C. for 2 weeks instead of the adhesive composition of Example 1 (immediately after production). >, An adhesive was obtained, and the same adhesion test as in Example 1 was performed.
Production Example 5 was bonded in the same manner as <Adhesive Production Example 1> except that the adhesive composition of Comparative Example 1 (immediately after production) was used instead of the adhesive composition of Example 1 (immediately after production). An agent was obtained, and the same adhesion test as in Example 1 was performed.
The evaluation results of the adhesion test are shown in Table 3 together with Experimental Example 1.

（製造例６は接着剤組成物の粘度で１００００ｍＰａ・ｓより大きく接着剤の配合不良となり接着性試験実施できなかった。）

(Manufacturing Example 6 had a viscosity of the adhesive composition larger than 10,000 mPa · s, and the adhesive composition was poor and the adhesion test could not be performed.)

  As is clear from Table 3, the adhesive composition of the present invention can be easily prepared without adjusting the pH of the ethylene-vinyl ester copolymer emulsion. In addition, it is a stable blended aqueous emulsion with little change and a method for producing the same, in which the viscosity hardly increases even when stored for a long period of time, and the pH hardly decreases. The adhesive of the present invention is water-based, and can be used as a base emulsion for an adhesive for overlay plywood use.

(Examples 7 to 10 and Comparative Examples 5 to 8)
PH and viscosity were measured in the same manner as in Example 1 except that Emulgen 1118S-70 ((C) -1)) or Pluronic L-64 ((D) -1)) was used in the amounts shown in Table 4. . The results are shown in Table 4 together with Example 1.

（Ｃ）−１’：70%エマルゲン1118S-70、花王（株）製、ポリオキシエチレンアルキルエーテル
（Ｄ）−１’：100%プルロニックＬ-64、旭電化工業（株）製、ポリオキシエチレンポリオキシプロピレン縮合物

(C) -1 ′: 70% Emulgen 1118S-70, manufactured by Kao Corporation, polyoxyethylene alkyl ether (D) -1 ′: 100% Pluronic L-64, manufactured by Asahi Denka Kogyo Co., Ltd., polyoxyethylene Polyoxypropylene condensate

<Adhesion test: water peel strength>
A laminate was obtained in the same manner as in the normal state peel strength adhesion test.
Subsequently, the laminate was immersed in water for 24 hours and then measured at a peeling rate of 200 mm / min (Shimadzu Autograph) while still wet. Further, the heat-resistant creep was adjusted to 80 ° C. and then peeled at a peeling angle of 90 ° and a load of 500 g / 25 mm, and the peel length after 24 hours was measured. The results are summarized in Table 5.

<Production Examples 7 to 10: Adhesive Production Examples 7 to 10 and their adhesion tests>
Production Example 7 was bonded in the same manner as <Adhesive Production Example 1> except that the adhesive composition of Example 8 was used (immediately after production) instead of the adhesive composition of Example 1 (immediately after production). An agent was obtained, and the same adhesion test as in Example 1 was performed.
Production Example 8 is <Adhesive Production Example 1 except that instead of the adhesive composition of Example 1 (immediately after production), the adhesive composition of Example 8 was stored at 50 ° C. for 2 weeks. >, An adhesive was obtained, and the same adhesion test as in Example 1 was performed.
Production Example 9 was bonded in the same manner as <Adhesive Production Example 1> except that the adhesive composition of Comparative Example 6 (immediately after production) was used instead of the adhesive composition of Example 1 (immediately after production). An agent was obtained, and the same adhesion test as in Example 1 was performed.
Production Example 10 <Adhesive Production Example 1 except that the adhesive composition of Comparative Example 1 was stored at 50 ° C. for 2 weeks instead of the adhesive composition of Example 1 (immediately after production). >, An adhesive was obtained, and the same adhesion test as in Example 1 was performed.
The evaluation results of the adhesion test are shown in Table 5 together with Production Example 1.

The water peel resistance of the resin composition of Comparative Example 8 immediately after production and that stored for 2 weeks at 50 ° C. was inferior to that of Example 10.
Thus, in the adhesive composition, the total weight part of (C) and (D) is 100 parts by weight of (A) and (B) (total weight constituting (A) and (B)). On the other hand, it is preferable that it is 0.75 parts by weight or less because the water-resistant peel strength is excellent.

  According to the present invention, for woodworking, for paper processing, for wallpaper, for packaging, for (secondary) plywood, for construction sites, for construction factories, for laminating, for textiles, for home use, for civil engineering, for binding, etc. It can be used for a base emulsion such as a two-pack type, paint, etc., which uses a one-pack type adhesive and a curing agent in combination.

Claims (6)

  Contains an ethylene-vinyl ester copolymer-containing aqueous emulsion (A), polyurethane-containing aqueous emulsion (B), and polyoxyethylene alkyl ether (C) and / or polyoxyethylene-polyoxypropylene condensate (D) It is an adhesive composition, and the weight ratio of the solid content of (A) / (B) is 52/48 to 98.5 / 1.5, and the total weight (solid content) of (C) and (D) Is 0.05 to 0.75 parts by weight with respect to 100 parts by weight of (A) and (B) (total weight constituting (A) and (B)).   The adhesive composition according to claim 1, wherein the pH of the adhesive composition is 4-7.   The adhesive composition according to claim 1 or 2, wherein the emulsifier used in the production of (A) is only a protective colloid.   The adhesive agent containing the adhesive composition and hardening | curing agent in any one of Claims 1-3.   The laminated body formed by laminating | stacking the adhesive agent of Claim 4, or the adhesive composition in any one of Claims 1-3 between the material which absorbs water, and a plastic material.   After mixing polyoxyethylene alkyl ether (C) and / or polyoxyethylene / polyoxypropylene condensate (D) with ethylene-vinyl ester copolymer-containing aqueous emulsion (A), polyurethane-containing aqueous emulsion (B The manufacturing method of the adhesive composition which mixes.