Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F261/00—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
  • C08F261/02—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/24—Acids; Salts thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
  • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
  • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

Definitions

• the present invention relates to an aqueous emulsion containing a dispersoid, a dispersant and inorganic fine particles.
• the present invention also relates to a method for producing the aqueous emulsion.
• thermosetting resins such as melamine resin and urea resin, or N-monomers are required.
• Vinyl acetate resin emulsions obtained by copolymerizing crosslinkable monomers such as acrylamide have been used.
• all of these resins emit formaldehyde.
• Formaldehyde was known to be harmful, but the revision of the Building Standards Law prohibited or restricted the use of members that emit formaldehyde above a certain standard, so adhesion that emits formaldehyde more than ever. The use of agents and materials made with them tends to be avoided.
• acetoacetylated PVA in which an acetoacetyl group is introduced into polyvinyl alcohol (hereinafter abbreviated as PVA) is used as a protective colloid, and an acetoacetyl group-containing monomer and vinyl acetate are emulsified and copolymerized.
• PVA polyvinyl alcohol
• Patent Document 1 A method for improving water resistance and adhesive strength by cross-linking an acetoacetyl group has been studied (Patent Document 1).
• Patent Document 1 A method for improving water resistance and adhesive strength by cross-linking an acetoacetyl group has been studied (Patent Document 1).
• the polymer obtained by this method has a problem that the self-crosslinking reaction between acetoacetyl groups proceeds during storage, resulting in thickening and solidification. Improvement studies using additives have been conducted, but no effective method has yet been found.
• an unsaturated monomer unit having at least one monomer unit selected from an ethylenically unsaturated monomer unit and a diene-based unsaturated monomer unit as a main component and having a silyl group is used.
• a method using polymer fine particles contained in a small amount has been studied (Patent Document 2).
• the obtained polymer exhibits an excellent effect in terms of water resistance and adhesiveness.
• polymerization stability such as the unsaturated monomer having a silyl group destabilizing the polymerization and generating agglomerates.
• An object of the present invention is to provide an aqueous emulsion having excellent adhesiveness when used as an adhesive. Another object of the present invention is to provide a method for producing an aqueous emulsion having excellent polymerization stability.
• the present invention is completed by finding that an aqueous emulsion containing an ethylene-vinyl alcohol copolymer (B1) containing an ethylene unit as a dispersant (B) and further containing inorganic fine particles (C) can solve the above-mentioned problems. It came to.
• the above problem is an aqueous emulsion containing a dispersant (A), a dispersant (B) and inorganic fine particles (C); 95 to 99.95% by mass of unsaturated monomer units having no carboxyl group.
• a polymer (A1) containing 0.05 to 5% by mass of an unsaturated monomer unit having a carboxyl group is contained as a dispersoid (A), and the content of ethylene units is 1 mol% or more and less than 12 mol%.
• the ethylene-vinyl alcohol copolymer (B1) is contained as the dispersant (B), and the content of the dispersant (B) is 2 to 20 parts by mass with respect to 100 parts by mass of the dispersoid (A), and the inorganic fine particles.
• the problem is solved by providing an aqueous emulsion in which the content of (C) is 0.2 to 15 parts by mass with respect to 100 parts by mass of the dispersoid (A).
• the viscosity average degree of polymerization of the ethylene-vinyl alcohol copolymer (B1) is preferably 200 to 5000, and the saponification degree is preferably 80 to 99.7 mol%.
• the average particle size of the inorganic fine particles (C) is 10 to 500 nm. It is also preferable that the inorganic fine particles (C) are silica, zirconia or alumina. It is also preferable to further contain 0.1 to 5 parts by mass of a trivalent or tetravalent metal salt (D) in terms of metal element with respect to 100 parts by mass of the dispersoid (A).
• the subject is the method for producing the aqueous emulsion; after emulsion polymerization of an unsaturated monomer having no carboxyl group and an unsaturated monomer having a carboxyl group in the presence of the dispersant (B). It is also solved by providing a method for producing an aqueous emulsion, to which the inorganic fine particles (C) are added.
• the aqueous emulsion of the present invention has excellent adhesiveness when used as an adhesive. Further, since the production method of the present invention is excellent in polymerization stability, an aqueous emulsion with less agglutination can be obtained.
• the aqueous emulsion of the present invention contains a polymer (A1) containing an unsaturated monomer unit having no carboxyl group and an unsaturated monomer unit having a carboxyl group as the dispersoid (A), and contains ethylene units. It contains an ethylene-vinyl alcohol copolymer (B1) containing it as a dispersant (B), and further contains inorganic fine particles (C).
• the aqueous emulsion of the present invention is a polymer containing 95 to 99.95% by mass of unsaturated monomer units having no carboxyl group and 0.05 to 5% by mass of unsaturated monomer units having a carboxyl group.
• A1 is included as a dispersoid (A).
• the unsaturated monomer having no carboxyl group means a monomer composed of a compound having one or more carbon-carbon unsaturated bonds in the molecule and having no carboxyl group. Since this compound has a carbon-carbon double bond in the molecule, it can be addition-polymerized.
• the compound is not particularly limited, but for example, vinyl ester, (meth) acrylic acid ester, diene, olefin, (meth) acrylamide, (meth) acrylonitrile, aromatic vinyl compound, heterocyclic vinyl compound, vinyl ether, allyl.
• examples include compounds and polyfunctional acrylates. Of these, at least one unsaturated monomer selected from the group consisting of vinyl ester and diene is preferable, and vinyl ester is more preferable. These may be used alone or in combination of two or more.
• the vinyl ester is not particularly limited, and is, for example, vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl versatic acid, vinyl silicate, vinyl crotonate, vinyl decanoate, and hexane.
• the content of the unsaturated monomer unit having no carboxyl group in the polymer (A1) exceeds 99.95% by mass, heat-resistant adhesiveness and water-resistant adhesion when an aqueous emulsion is used as an adhesive.
• the sex is reduced.
• the content is preferably 99.9% by mass or less, and more preferably 99.5% by mass or less.
• the content is less than 95% by mass, agglomerates are generated during emulsion polymerization and the polymerization becomes unstable.
• the content is preferably 98% by mass or more.
• the unsaturated monomer having a carboxyl group is a monomer composed of a compound having one or more carbon-carbon unsaturated bonds in the molecule and having a carboxyl group.
• This compound can be addition-polymerized by having a carbon-carbon double bond in the molecule.
• the carboxyl group may be contained in the form of its anhydride.
• the compound is not particularly limited as long as the effects of the present invention are not impaired, and for example, carboxylic acids such as (meth) acrylic acid, crotonic acid, isocrotonic acid, citraconic acid, itaconic acid, maleic acid, maleic anhydride, and fumaric acid. Acid is mentioned.
• the (meth) acrylic acid refers to acrylic acid or methacrylic acid.
• the content of the unsaturated monomer unit having a carboxyl group in the polymer (A1) is less than 0.05% by mass, the heat-resistant adhesiveness and the water-resistant adhesiveness are lowered when the aqueous emulsion is used as an adhesive. do.
• the content is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more.
• the content exceeds 5% by mass, agglomerates are generated during emulsion polymerization and the polymerization becomes unstable.
• the content is preferably 2% by mass or less.
• the aqueous emulsion of the present invention contains an ethylene-vinyl alcohol copolymer (B1) having an ethylene unit content of 1 mol% or more and less than 12 mol% as a dispersant (B).
• the copolymer (B1) is a copolymer having an ethylene unit and a vinyl alcohol unit.
• the copolymer (B1) is obtained, for example, by saponifying a copolymer of ethylene and vinyl ester using an alkali catalyst or the like.
• vinyl esters include vinyl acetate, but other fatty acid vinyl esters (vinyl formate, vinyl propionate, vinyl valerate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl benzoate, etc. (Vinyl pivalate, vinyl versatic acid, etc.) can also be used.
• the content of ethylene units in the copolymer (B1) of the present invention is 1 mol% or more and less than 12 mol%. If the content of ethylene units is less than 1 mol%, the surface activity may be insufficient and the polymerization stability may be lowered, and the water-resistant adhesiveness may be lowered when used as an adhesive.
• the content of ethylene units is preferably 2 mol% or more, and more preferably 3 mol% or more. On the other hand, when the ethylene unit content is 12 mol% or more, a large amount of agglomerates are generated in the obtained aqueous emulsion, which makes filtration difficult.
• the ethylene unit content is preferably less than 10 mol%, more preferably less than 9 mol%.
• the ethylene unit content can be determined by a known method such as 1 H-NMR measurement.
• the saponification degree of the vinyl ester component of the copolymer (B1) is preferably 80 mol% or more, more preferably 90 mol% or more, further preferably 92 mol% or more, and 97 mol%.
• the above is particularly preferable.
• the saponification degree is preferably 99.7 mol% or less, more preferably 99 mol% or less.
• the degree of saponification can be determined by a known method such as 1 H-NMR measurement. Further, as long as the ethylene-vinyl alcohol copolymer has an average saponification degree in the above range, ethylene-vinyl alcohol copolymers having different saponification degrees may be used in combination.
• the viscosity average degree of polymerization of the copolymer (B1) (hereinafter, may be simply referred to as the degree of polymerization) may be within the range of the degree of polymerization of the copolymer generally used as a dispersant for emulsion polymerization.
• the degree of polymerization is 200 or more, stability during emulsion polymerization is sufficiently obtained, and when the degree of polymerization is 5000 or less, the solution viscosity during emulsion polymerization does not become too high, and stirring and heat removal are easy. It is preferable because it can be carried out.
• the degree of polymerization is a value obtained by the method described in JIS K 6726 (1994).
• the content of the dispersant (B) is 2 to 20 parts by mass with respect to 100 parts by mass of the dispersoid (A). When the content of the dispersant (B) is less than 2 parts by mass, sufficient stability during emulsion polymerization cannot be obtained.
• the content of the dispersant (B) is preferably 4 parts by mass or more.
• the content of the dispersant (B) exceeds 20 parts by mass, the water-resistant adhesiveness is lowered when the aqueous emulsion is used as the adhesive.
• the content of the dispersant (B) is preferably 11 parts by mass or less.
• the copolymer (B1) may contain a monomer unit other than the vinyl alcohol unit, the vinyl ester unit, and the ethylene unit as long as the effect of the present invention is not impaired.
• the content of the other monomer unit is preferably 6 mol% or less, more preferably 3 mol% or less, and further preferably 1 mol% or less.
• the copolymer (B1) may be used alone or in combination of two or more.
• the content of the inorganic fine particles (C) in the aqueous emulsion of the present invention is 0.2 to 15 parts by mass with respect to 100 parts by mass of the dispersoid (A).
• the content is preferably 0.5 parts by mass or more, and more preferably 0.8 parts by mass or more.
• the content exceeds 15 parts by mass, a large amount of agglomerates are generated in the obtained aqueous emulsion, which makes it difficult to apply.
• the agglomerates act as defects in the adhesive layer to reduce the adhesiveness.
• the content is preferably 12 parts by mass or less, and more preferably 10 parts by mass or less.
• the type of the inorganic fine particles (C) is not particularly limited, but silica, zirconia or alumina is preferably used. Silica is more preferably used because it is easily available. Among them, colloidal silica is more preferably used.
• the average particle size of the inorganic fine particles (C) is preferably 10 to 500 nm. If the average particle size of the inorganic fine particles (C) is less than 10 nm, the emulsion may thicken. The average particle size is more preferably 12 nm or more. On the other hand, when the average particle size of the inorganic fine particles (C) exceeds 500 nm, the inorganic fine particles (C) may not disperse well in the emulsion and aggregates may be generated. More preferably, the average particle size is 400 nm or less.
• the inorganic fine particles (C) are used in the form of a sol during emulsion polymerization.
• the average particle size is an arithmetic mean value of the particle size observed by a transmission electron microscope.
• the aqueous emulsion of the present invention preferably further contains a trivalent or tetravalent metal salt (D).
• the copolymer (B1) coordinates with the ions of the metal to form a chelate structure, and the copolymer (B1) is crosslinked via the metal ions to improve the water resistance of the aqueous emulsion. be able to.
• the salt (D) is further contained in an amount of 0.1 to 5 parts by mass in terms of metal element with respect to 100 parts by mass of the dispersoid (A).
• the content of the salt (D) is less than 0.1 parts by mass, when the aqueous emulsion is used as an adhesive, the heat-resistant adhesiveness may be lowered and the water-resistant adhesiveness may be lowered.
• the content of the salt (D) is preferably 0.5 parts by mass or more, and more preferably 1 part by mass or more.
• the content of the salt (D) exceeds 5 parts by mass, the water-resistant adhesiveness of the obtained aqueous emulsion may decrease.
• the content of the metal salt (D) is preferably 4 parts by mass or less, and more preferably 3.5 parts by mass or less.
• the type of salt (D) is not particularly limited.
• the trivalent or tetravalent metal ion in the salt (D) aluminum ion, titanium ion and zirconium ion are preferable. Among them, aluminum ion is a more preferable metal ion.
• Examples of the anion species in the salt (D) include inorganic acids such as nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid and carbonic acid; and organic acids such as acetic acid and lactic acid. Among them, inorganic acids are preferable, and nitric acid is more preferable.
• Examples of the salt (D) include a double salt containing ammonium, sodium, potassium and the like.
• the salt (D) is preferably aluminum nitrate, titanium lactate, or ammonium zirconium carbonate. Above all, when an aqueous emulsion is used as an adhesive, aluminum nitrate is more preferable from the viewpoint of obtaining more excellent heat-resistant adhesiveness and water-resistant adhesiveness.
• the aqueous emulsion of the present invention contains a polymer (A1) as a dispersoid (A), a copolymer (B1) as a dispersant (B), and inorganic fine particles (C), as long as the effects of the present invention are not impaired.
• other components other than the salt (D) may be contained.
• the other components include antifoaming agents, pH adjusters, solvents, pigments, dyes, preservatives, thickeners, cross-linking agents, plasticizers and the like.
• the content of the other component in the aqueous emulsion is usually 10% by mass or less.
• the solid content concentration of the aqueous emulsion of the present invention may be appropriately set according to the intended use, but is preferably 35 to 60% by mass. If the solid content concentration is less than 35% by mass, the viscosity of the aqueous emulsion is too low, and the particles may easily settle. The solid content concentration is more preferably 40% by mass or more. On the other hand, if the solid content concentration exceeds 60% by mass, aggregation may occur during emulsion polymerization. The solid content concentration is more preferably 58% by mass or less.
• the solid content concentration of the aqueous emulsion referred to here is a value obtained by [dry sample weight (g) / aqueous emulsion weight (g)] ⁇ 100.
• the method for producing the aqueous emulsion of the present invention is not particularly limited, but a suitable production method is an unsaturated monomer having no carboxyl group and an unsaturated single amount having a carboxyl group in the presence of the dispersant (B). This is a method of adding inorganic fine particles (C) after emulsion polymerization of the body.
• a water-soluble single initiator or a water-soluble redox-based initiator usually used for emulsion polymerization can be used. These initiators may be used alone or in combination of two or more. Of these, redox-based initiators are preferred.
• the water-soluble single initiator include azo-based initiators, hydrogen peroxide, and peroxides such as persulfates (potassium, sodium, or ammonium salts).
• a combination of an oxidizing agent and a reducing agent can be used as the redox-based initiator. Peroxide is preferable as the oxidizing agent.
• the reducing agent include metal ions and reducing compounds.
• a surfactant, a polymerization initiator, a reducing agent, a buffer, a degree of polymerization adjusting agent and the like which are usually used may be appropriately used as long as the effect of the present invention is not impaired.
• the dispersion medium in the emulsion polymerization is an aqueous medium containing water as a main component.
• the aqueous medium containing water as a main component may contain a water-soluble organic solvent (alcohols, ketones, etc.) that is soluble in any proportion with water.
• the "water-based aqueous medium containing water as a main component” is a dispersion medium containing 50% by mass or more of water. From the viewpoint of cost and environmental load, the dispersion medium is preferably an aqueous medium containing 90% by mass or more of water, and more preferably water.
• the dispersant in the method for producing an aqueous emulsion, it is preferable to add the dispersant to a dispersion medium to dissolve it by heating before starting emulsion polymerization, and then cool it to replace it with nitrogen. At this time, the heating temperature is preferably 80 to 100 ° C.
• the temperature of the emulsion polymerization is not particularly limited, but is usually 20 to 100 ° C, preferably 40 to 90 ° C, and more preferably 50 to 90 ° C.
• the aqueous emulsion of the present invention can be used for adhesive applications such as woodworking and paper processing, as well as for paints and fiber processing, and the adhesive application is particularly suitable. That is, the adhesive made of the aqueous emulsion of the present invention is a preferred embodiment.
• the aqueous emulsion obtained by the above method may be used as it is, or if necessary, other components (antifoaming agent, pH adjuster, solvent, pigment, dye, preservative, thickener, cross-linking agent) as described above may be used. , Plasticizer, etc.) may be added.
• the aqueous emulsion of the present invention has excellent adhesiveness when used as an adhesive.
• the aqueous emulsion of the present invention is also excellent in safety because it does not dissipate formaldehyde.
• the production method of the present invention is excellent in polymerization stability, an aqueous emulsion with less agglutination can be obtained.
• the solid content concentration of the aqueous emulsion, emulsion polymerization stability, and adhesion performance under various conditions were evaluated by the methods shown below.
• Solid content concentration 2-3 g of the aqueous emulsion obtained in Examples and Comparative Examples was precisely weighed to 4 digits after the decimal point with a precision balance, and then allowed to stand in a dryer at 100 degrees for 3 hours or more to remove water. A dry sample was obtained. The weight of the dry sample was precisely weighed to four digits after the decimal point with a precision balance, and the solid content concentration was calculated from the weight ratio of the dry sample and the aqueous emulsion according to the following formula.
• Solid content concentration (%) [Dry sample weight (g) / Aqueous emulsion weight (g)] x 100
• Emulsion Polymerization Stability 500 g of the aqueous emulsion obtained in Examples and Comparative Examples was filtered through a 60-mesh wire mesh, the filtration residue was weighed, and the ratio of the filtration residue to the mass of the aqueous emulsion was evaluated according to the following evaluation criteria. Evaluated in. It can be said that the smaller the filtration residue, the smaller the agglutination and the more stable the emulsion polymerization.
• C The filtration residue exceeded 2.0% by mass.
• D Filtration was difficult due to the presence of a large amount of filtration residue.
• the heat-resistant adhesiveness was evaluated in accordance with WATT'91.
• the obtained aqueous emulsion was applied to a European beech lumber (grain) at 200 g / m 2 and bonded to the above beech lumber to which the aqueous emulsion was not applied to obtain a test piece.
• the test piece was pressed at 20 ° C. with a load of 0.7 N / mm 2 for 2 hours. Then, after allowing to stand in a dryer at 80 ° C. for 1 hour, the test piece was taken out and the adhesive strength (unit: N / mm 2 ) was measured in a hot state.
• Example 1 Manufacturing of PVA-1)
• a polymerization vessel continuous polymerization tank equipped with a reflux condenser, a raw material supply line, a thermometer, a nitrogen inlet, a stirring blade, and a reaction liquid take-out line was used.
• the polymerization liquid was continuously taken out from the polymerization tank so that the liquid level in the polymerization tank became constant.
• the polymerization rate at the outlet of the polymerization tank was adjusted to 28%.
• the residence time of the polymerization tank was 5 hours.
• the temperature at the outlet of the polymerization tank was 60 ° C.
• the polymerization solution was recovered from the polymerization tank, and the unreacted vinyl acetate monomer was removed by introducing methanol vapor into the recovered solution to obtain a methanol solution (concentration: 30%) of an ethylene-vinyl acetate copolymer.
• the above ethylene-vinyl acetate copolymer (EVAc) / methanol solution (concentration 30% by mass) was fed as a saponification raw material solution at 4700 L / h, and sodium hydroxide / methanol solution (concentration 4% by mass) was fed as a saponification catalyst solution in 198 L. Feeded at / h.
• the fed saponification raw material solution and saponification catalyst solution were mixed, and the obtained mixture was placed on a belt and held at 40 ° C. for 18 minutes to allow the saponification reaction to proceed. Then, it was pulverized and dried to obtain an ethylene-vinyl alcohol copolymer (PVA-1) as a dispersant (B).
• PVA-1 ethylene-vinyl alcohol copolymer
• Table 1 shows the ethylene unit content, degree of polymerization and degree of saponification of PVA-1.
• the aqueous solution in which PVA-1 was dissolved was cooled, replaced with nitrogen, and then heated to 60 ° C. while stirring at 200 rpm. Then, 2.4 g of a 20% by mass aqueous solution of tartrate acid as a reducing agent and 3.2 g of a 5% by mass hydrogen peroxide solution as a polymerization initiator were added, and then 27 g of vinyl acetate (VAc) and 0.3 g of acrylic acid (AA) (AA).
• Acrylic acid corresponds to 1 part by mass with respect to 100 parts by mass of the total amount of vinyl acetate) as the dispersoid (A), and the polymerization was started.
• Example 2 Example 1 except that the amount of colloidal silica "LUDOX TM TMA" used as the inorganic fine particles (C) was 5.0 parts by mass or 12.0 parts by mass with respect to 100 parts by mass of the dispersoid (A).
• Aqueous emulsions (Em-2 and Em-3) were obtained in the same manner as above. The evaluation results of the aqueous emulsion are shown in Table 2.
• Example 4 The type of colloidal silica used as the inorganic fine particles (C) was changed to colloidal silica "LUDOX TM HSA” manufactured by WR Grace, and the amount added was 1.5 parts by mass with respect to 100 parts by mass of the dispersoid (A).
• An aqueous emulsion (Em-4) was obtained in the same manner as in Example 1 except that the salt (D) was not added.
• the evaluation results of the aqueous emulsion are shown in Table 2.
• “LUDOX TM HSA” is colloidal silica in which silica is colloidally dispersed in water, the average particle size of the silica is 24.0 nm, and the solid content concentration is 29.8% by mass.
• Example 5 Manufacturing of PVA-2) Except for changing the feed amount of ethylene, vinyl acetate and methanol, the amount of initiator to be added, the polymerization conditions such as the polymerization rate, and the feed amount and concentration of the EVAc solution and the saponification catalyst solution at the time of saponification as shown in Table 1.
• Table 1 shows the ethylene unit content, degree of polymerization and degree of saponification of PVA-2.
• aqueous emulsion Em-5 (Manufacturing and evaluation of aqueous emulsion Em-5) The amount of acrylic acid used was 0.5 parts by mass with respect to 100 parts by mass of vinyl acetate, PVA-2 as a copolymer (B1), 10 parts by mass with respect to 100 parts by mass of dispersoid (A), and salt (D). ), An aqueous emulsion (Em-5) was obtained in the same manner as in Example 1 except that 1.2 parts by mass of aluminum nitrate hexahydrate was used with respect to 100 parts by mass of the dispersoid (A). The evaluation results of the aqueous emulsion are shown in Table 2.
• Example 6 Manufacturing of PVA-3)
• the polymerization conditions such as the feed amount of ethylene, vinyl acetate and methanol, the amount of the initiator to be added, the polymerization rate, etc., and the feed amount and concentration conditions of the EVAc solution and the saponification catalyst solution at the time of saponification have been changed as shown in Table 1.
• An ethylene-vinyl alcohol copolymer (PVA-3) was produced by the same method as in Example 1 except for the above. Table 1 shows the ethylene unit content, degree of polymerization and degree of saponification of PVA-3.
• An aqueous emulsion (Em-6) was obtained in the same manner as in Example 1 except that 1.2 parts of aluminum nitrate hexahydrate was used with respect to 100 parts by mass of the dispersoid (A).
• the evaluation results of the aqueous emulsion are shown in Table 2.
• Example 7 The amount of acrylic acid used was 2 parts by mass with respect to 100 parts of vinyl acetate, PVA-3 was used as a copolymer (B1) by 7.5 parts by mass with respect to 100 parts by mass of the dispersoid (A), and inorganic fine particles (inorganic fine particles) were used. Colloidal silica "LUDOX TM TMA" was used as C) in an amount of 0.7 parts by mass with respect to 100 parts by mass of the dispersoid (A), and aluminum nitrate nineahydrate was used as the salt (D), and the dispersoid (A) 100 was used.
• aqueous emulsion (Em-7) having a solid content concentration of 48% by mass was obtained in the same manner as in Example 1 except that 3.2 parts by mass was used with respect to parts by mass.
• the evaluation results of the aqueous emulsion are shown in Table 2.
• Example 8 An aqueous emulsion (Em-8) was obtained in the same manner as in Example 7 except that 1.8 parts by mass of titanium lactate (relative to 100 parts by mass of the dispersant (A)) was added as the salt (D). Table 2 shows the results of various evaluations of the aqueous emulsion.
• Example 9 instead of acrylic acid, methacrylic acid (MAA) was added to 1.0 part by mass (relative to 100 parts by mass of vinyl acetate unit), and PVA-3 as a copolymer (B) was added to 7.5 parts by mass of dispersoid.
• An aqueous emulsion (Em-9) having a solid content concentration of 48% by mass was obtained in the same manner as in Example 1 except that 3.0 parts by mass of zirconium carbonate was used as the salt (D).
• the evaluation results of the aqueous emulsion are shown in Table 2.
• Comparative Example 1 Manufacturing of PVA-4) Except for changing the feed amount of ethylene, vinyl acetate and methanol, the amount of initiator to be added, the polymerization conditions such as the polymerization rate, and the feed amount and concentration of the EVAc solution and the saponification catalyst solution at the time of saponification as shown in Table 1.
• Table 1 shows the ethylene unit content, degree of polymerization and degree of saponification of PVA-4.
• aqueous emulsion Em-10 Manufacturing and evaluation of aqueous emulsion Em-10) An aqueous emulsion (Em-10) was obtained in the same manner as in Example 1 except that 7.5 parts by mass of PVA-4 was used as the copolymer (B1) with respect to 100 parts by mass of the dispersant (A).
• the evaluation results of the aqueous emulsion are shown in Table 2. In particular, in the water resistance test, the value was as low as 1.3 N / mm 2 , which was not sufficient.
• Comparative Example 2 An aqueous emulsion (Em-11) was obtained in the same manner as in Comparative Example 1 except that the inorganic fine particles (C) were not added.
• the evaluation results of the aqueous emulsion are shown in Table 2. In particular heat resistant adhesion and water-resistant adhesion evaluation, the value is respectively 1.7 N / mm 2, lower with 1.1 N / mm 2, is not sufficient adhesion.
• Comparative Example 3 Manufacturing of PVA-5)
• the polymerization conditions such as the feed amount of ethylene, vinyl acetate and methanol, the amount of the initiator to be added, the polymerization rate, etc., and the feed amount and concentration conditions of the EVAc solution and the saponification catalyst solution at the time of saponification have been changed as shown in Table 1.
• An ethylene-vinyl alcohol copolymer (PVA-5) was produced by the same method as in Example 1 except for the above. Table 1 shows the ethylene unit content, degree of polymerization and degree of saponification of PVA-5.
• aqueous emulsion Em-12 Manufacturing and evaluation of aqueous emulsion Em-12
• An aqueous emulsion (Em-12) was obtained in the same manner as in Example 1 except that 10 parts by mass of PVA-5 was used as a copolymer with respect to 100 parts by mass of vinyl acetate unit.
• PVA-5 10 parts by mass of PVA-5 was used as a copolymer with respect to 100 parts by mass of vinyl acetate unit.
• the evaluation results of the aqueous emulsion are shown in Table 2.
• Comparative Example 4 The amount of acrylic acid used was 0.5 parts by mass with respect to 100 parts by mass of vinyl acetate unit, PVA-3 as a copolymer (B1), and 7.5 parts by mass with respect to 100 parts by mass of dispersant (A).
• the salt (D) 1.2 parts by mass of aluminum nitrate hexahydrate was used with respect to 100 parts by mass of the dispersant (A), and the same as in Example 1 except that the inorganic fine particles (C) were not added.
• An aqueous emulsion (Em-13) having a solid content concentration of 48% was obtained.
• the evaluation results of the aqueous emulsion are shown in Table 2. In particular, in the evaluation of heat-resistant adhesiveness, the value was as low as 1.9 N / mm 2, and the heat-resistant adhesiveness was not sufficient.
• Comparative Example 5 Without using acrylic acid, PVA-2 was used as the copolymer (B1) in an amount of 7.5 parts by mass with respect to 100 parts by mass of the dispersoid (A), and both the inorganic fine particles (C) and the salt (D) were used.
• An aqueous emulsion (Em-14) having a solid content concentration of 48% was obtained in the same manner as in Example 1 except that it was not added.
• the valence results of the aqueous emulsion are shown in Table 2. In particular heat resistant adhesion and water-resistant adhesion evaluation, the value is respectively 1.5 N / mm 2, lower with 1.0 N / mm 2, is not sufficient adhesion.
• Comparative Example 6 The amount of acrylic acid used was 10 parts by mass with respect to 100 parts by mass of the vinyl acetate unit, PVA-2 was used as the copolymer (B1) with respect to 100 parts by mass of the dispersoid (A), and 7.5 parts by mass was used. Polymerization was attempted in the same manner as in Example 1 except that neither the inorganic fine particles (C) nor the salt (D) were added, but a large amount of agglomerates were generated and emulsion polymerization could not be performed.
• Comparative Example 7 The amount of acrylic acid used was 6 parts by mass with respect to 100 parts by mass of vinyl acetate unit, and polymerization was attempted in the same manner as in Example 1 except that neither inorganic fine particles (C) nor salt (D) were added. However, a large amount of agglomerates were generated and emulsion polymerization could not be performed.
• Comparative Example 8 The amount of acrylic acid used is 0.03 parts by mass with respect to 100 parts by mass of vinyl acetate unit, and the amount of colloidal silica "LUDOX TM TMA" used as inorganic fine particles (C) is added to 100 parts by mass of dispersoid (A).
• an aqueous emulsion (Em-17) was obtained in the same manner as in Example 1 except that 2.0 parts by mass was used.
• the evaluation results of the aqueous emulsion are shown in Table 2. In particular heat resistant adhesion and water-resistant adhesion evaluation, the value is respectively 1.7 N / mm 2, lower with 0.6 N / mm 2, is not sufficient adhesion.

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