WO2016043248A1 - 結合剤および水溶液 - Google Patents
結合剤および水溶液 Download PDFInfo
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- WO2016043248A1 WO2016043248A1 PCT/JP2015/076375 JP2015076375W WO2016043248A1 WO 2016043248 A1 WO2016043248 A1 WO 2016043248A1 JP 2015076375 W JP2015076375 W JP 2015076375W WO 2016043248 A1 WO2016043248 A1 WO 2016043248A1
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- binder
- polymer
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- carboxylic acid
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Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
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- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/24—Coatings containing organic materials
- C03C25/26—Macromolecular compounds or prepolymers
- C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C03C25/325—Polycarbonates
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
Definitions
- the present invention relates to a binder containing a polymer having a hydroxyl group.
- it is related with the binder containing the polymer which has a hydroxyl group useful as a binder of glass fiber or powder glass.
- the present invention also relates to an aqueous solution containing a polymer having a hydroxyl group.
- a heat-resistant molded body obtained by attaching a binder to glass fiber or the like and molding it into a mat shape is widely used as a heat insulating material for a residence, a warehouse, an apparatus, an apparatus, or the like.
- a phenol-formaldehyde binder is widely used as the binder.
- the phenol-formaldehyde binder has a problem that unreacted formaldehyde remains in the molded body and formaldehyde is released after construction of a house or the like. Therefore, binders that do not release formaldehyde have been studied.
- Patent Document 1 discloses a binder for mineral fibers characterized by comprising a vinyl copolymer (A) having an organic acid (salt) group (a) and a hydroxyl group and having a weight average molecular weight of 500 to 100,000. It is disclosed.
- the mineral fiber binder (1) does not contain formaldehyde, and there is no release of formaldehyde from a heat insulating material formed by bonding mineral fibers with the binder to form a mat, (2 ) Excellent adhesion to mineral fibers compared to conventional phenolic resins and excellent resilience to compression of the heat insulating material.
- the binders of the present invention those in the form of aqueous solutions or aqueous dispersions are environmentally compatible. It is disclosed that the present invention has an effect of exhibiting excellent physical properties such as adhesiveness even in a neutral region.
- Patent Document 2 discloses a glass fiber binder comprising (1) a reaction product of a polymerizable carboxylic acid or anhydride, or a mixture thereof, and a hydroxy C 2 to C 8 alkyl acrylate or methacrylate, or a mixture thereof. And (2) a binder characterized in that it comprises an aqueous solution with an alkali metal salt of a phosphorus-containing acid. Patent Document 2 discloses that the binder has a low viscosity when uncured and has structural rigidity when cured.
- Patent Document 3 includes at least two (co) polymer (A) having a carboxyl group or an acid anhydride group, a compound (B) having at least one hydroxyl group and at least one amino group, and water.
- the neutralization rate of the carboxyl group derived from the carboxyl group or acid anhydride group in (A) is 36 to 70 equivalent%, and the neutralization is neutralized by the amino group in (B)
- An aqueous binder for mineral fibers is disclosed.
- the aqueous binder for mineral fibers includes (1) no formaldehyde, (2) excellent water resistance and hydrolysis resistance, (3) excellent adhesion of mineral fibers, (4) the binder. It is disclosed that the mineral fiber laminate formed by bonding is excellent in the resilience against compression and has the effect of.
- JP 2006-89906 A Japanese National Patent Publication No. 10-509485 JP 2012-136612 A
- the present invention has been made by paying attention to the above circumstances, has good storage stability, and exhibits excellent binding power of glass fiber and powdered glass (for glass fiber and powdered glass composites).
- the object is to provide a binder capable of imparting good strength.
- the binder contains a predetermined polymer, so that the binder has good storage stability and the strength of the glass fiber or powder glass binder is good.
- the present invention has been completed based on these findings.
- the binder of the present invention comprises A binder comprising a polymer having a hydroxyl group
- the polymer includes a structural unit derived from a monomer represented by the general formula (1) and a structural unit derived from a monomer containing a carboxylic acid (salt) group
- the content of the structural unit derived from the monomer represented by the general formula (1) is 5 mol% to 40 mol% with respect to 100 mol% of the structural unit derived from all monomers
- the content of the structural unit derived from the monomer containing the carboxylic acid (salt) group is 60 mol% to 95 mol% with respect to 100 mol% of the structural unit derived from all monomers, 2 mol% or more of the carboxylic acid (salt) group contained in the polymer is neutralized with a volatile base and / or a non-volatile base, 0 mol% to 15 mol% of the carboxylic acid (salt) group contained in the polymer is neutralized with a nonvolatile base;
- the aqueous solution of the present invention comprises An aqueous solution containing a polymer having a hydroxyl group
- the polymer includes a structural unit derived from a monomer represented by the general formula (1) and a structural unit derived from a monomer containing a carboxylic acid (salt) group
- the content of the structural unit derived from the monomer represented by the general formula (1) is 5 mol% to 40 mol% with respect to 100 mol% of the structural unit derived from all monomers
- the content of the structural unit derived from the monomer containing the carboxylic acid (salt) group is 60 mol% to 95 mol% with respect to 100 mol% of the structural unit derived from all monomers, 2 mol% or more of the carboxylic acid (salt) group contained in the polymer is neutralized with a volatile base and / or a non-volatile base, 0 mol% to 15 mol% of the carboxylic acid (salt) group contained in the polymer is neutralized with a
- the bonded body of the present invention has a good storage stability, and the glass fiber and the powder glass can exhibit a good strength by being treated with the bonded body of the present invention. Therefore, the binder of the present invention can be usefully used as, for example, a binder for residential heat insulating materials.
- the binder of the present invention includes a polymer having a hydroxyl group, and the polymer includes a structural unit derived from the monomer represented by the general formula (1).
- the polymer which is an essential component of the binder of the present invention is also referred to as “polymer of the present invention”.
- R 1 represents a hydrogen atom or a methyl group
- R 2 represents an organic group having 2 to 20 carbon atoms.
- R 1 is preferably a methyl group. Since R 1 tends to be able to suppress moisture absorption deterioration when it is a methyl group, it can be a more preferable form.
- the upper limit of the number of carbon atoms contained in R 2 is preferably 12 or less, more preferably 8 or less, and particularly preferably 4 or less.
- examples of R 2 include a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, and a substituted or unsubstituted ether group.
- the above substituted alkylene group refers to a group in which part or all of the hydrogen atoms constituting the alkylene group are substituted with a substituent.
- the substituent includes an aryl group, a hydroxyl group, an alkoxy group, an amino group, an ester group, an amide group, a carboxyl group, a sulfonic acid group, and the like.
- the above-mentioned substituted aryl group refers to a group in which part or all of the hydrogen atoms constituting the aryl group are substituted with a substituent.
- the substituent includes an alkyl group, a hydroxyl group, an alkoxy group, an amino group, an ester group, an amide group, a carboxyl group, a sulfonic acid group, and the like.
- the above ether group includes a polyether group
- the substituted ether group refers to a group in which part or all of the hydrogen atoms constituting the ether are substituted with a substituent.
- the substituent includes an alkyl group, an aryl group, a hydroxyl group, an amino group, an ester group, an amide group, a carboxyl group, a sulfonic acid group, and the like.
- R 2 in the general formula (1) include —CH 2 CH 2 — group, —CH (CH 3 ) CH 2 — group, —CH 2 CH (CH 3 ) — group, —C (CH 3 ) 2 — group, —CH 2 CH 2 CH 2 — group, —CH (C 2 H 5 ) CH 2 — group, —C (C 2 H 5 ) (CH 3 ) — group, —CH 2 CH 2 CH Alkylene group such as 2 CH 2 — group, —CH (C 4 H 9 ) CH 2 — group; arylene group such as phenylene group, naphthyl group; —CH 2 CH 2 OCH 2 CH 2 — group, —CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 — group, —CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 — group, —CH (CH 3 ) CH 2 OCH (CH 3 ) CH 2 — group, —CH (CH 3 ) CH 2 OCH (CH 3
- the binder of the present invention When the binder of the present invention is used as a binder for glass fiber or powdered glass, the strength of the bonded body (referred to as glass fiber or powdered glass treated with the binder of the present invention) is improved, and moisture absorption deterioration since there is a tendency can be suppressed, the total number of carbon atoms contained in R 1 and R 2 is preferably 3 or more.
- the “structural unit derived from the monomer represented by the general formula (1)” means a structural unit formed by polymerization of the monomer represented by the general formula (1). means. However, if the monomer represented by the general formula (1) has the same structure as the structural unit formed by polymerization, a method other than polymerizing the monomer represented by the general formula (1) Are also included in the “structural unit derived from the monomer represented by the general formula (1)”.
- the structural unit derived from the monomer represented by the general formula (1) can be represented by the following general formula (2).
- R 1 represents a hydrogen atom or a methyl group
- R 2 represents an organic group having 2 to 20 carbon atoms.
- embodiments of R 1, R 2 in the general formula (2) preferred embodiment, aspects of the R 1, R 2 in the general formula (1), the same as the preferred embodiment.
- the polymer of the present invention has a structural unit derived from all monomers (a structural unit derived from a monomer represented by the general formula (1) and a structure derived from an unsaturated carboxylic acid monomer described later).
- the structural unit derived from the monomer represented by the general formula (1) is included in an amount of 5 mol% or more and 40 mol% or less with respect to 100 mol% of a unit and a structural unit derived from another monomer. It is preferable that it is contained in an amount of 10 mol% or more and 35 mol% or less, more preferably 15 mol% or more and 30 mol% or less. By including in the said range, it exists in the tendency for the intensity
- the polymer of the present invention may contain one type of structural unit derived from the monomer represented by the general formula (1), or may contain two or more types.
- the polymer of the present invention contains a structural unit derived from an unsaturated carboxylic acid monomer.
- the unsaturated carboxylic acid monomer is a monomer containing a carboxyl group and / or a salt thereof and a polymerizable carbon-carbon double bond, and specifically includes acrylic acid, methacrylic acid, croton Unsaturated monocarboxylic acids and salts thereof such as acids, ⁇ -hydroxyacrylic acid, ⁇ -hydroxymethylacrylic acid and derivatives thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid, methyleneglutaric acid, itaconic acid and the like; These salts (which may be monosalts or disalts) and the like are exemplified.
- the salt examples include metal salts, ammonium salts, and organic amine salts.
- the metal salt include salts of alkali metals such as sodium and potassium; alkaline earth metals such as calcium and magnesium; transition metals such as iron and aluminum;
- the organic amine salt include salts of alkylamines such as methylamine and n-butylamine; alkanolamines such as monoethanolamine, diethanolamine, triethanolamine and dipropanolamine; polyamines such as ethylenediamine and diethylenetriamine;
- the structural unit derived from an unsaturated carboxylic acid monomer is a structural unit formed by polymerizing an unsaturated carboxylic acid monomer, specifically, an unsaturated carboxylic acid type monomer.
- the polymer of the present invention may have a structural unit derived from an unsaturated carboxylic acid monomer in an amount of 60 mol% to 95 mol% with respect to 100 mol% of the structural unit derived from all monomers. Preferably, it is 65 mol% or more and 90 mol% or less, more preferably 70 mol% or more and 85 mol% or less.
- the polymer of the present invention may contain one type of structural unit derived from an unsaturated carboxylic acid monomer, or may contain two or more types of structural units. By including the structural unit derived from the unsaturated carboxylic acid monomer in the above range, the strength of the bonded body tends to be improved when the binder of the present invention is used for the binder of glass fiber or powder glass. It is in.
- the polymer of the present invention contains a carboxylic acid (salt) group, but 2 mol% or more of the carboxylic acid (salt) group contained in the polymer molecule of the polymer of the present invention is a volatile base and / or Neutralized with a non-volatile base. That is, 2 mol% or more is a carboxylic acid base neutralized with a volatile base and / or a nonvolatile base with respect to 100 mol% of the carboxylic acid (salt) group contained in the polymer of the present invention.
- 2 mol% or more and 50 mol% or less of the carboxylic acid (salt) group contained in the polymer molecule is neutralized with a volatile base and / or a non-volatile base, more preferably 5 mol%. It is from mol% to 40 mol%, more preferably from 8 mol% to 35 mol%.
- a volatile base means ammonia and an amine having a boiling point of less than 100 ° C. at 1 atm
- a non-volatile base means a base containing a metal atom such as alkali metal or alkaline earth metal, 1 An amine having a boiling point of 100 ° C. or higher at atmospheric pressure.
- the volatile base include ammonia, monomethylamine, dimethylamine, trimethylamine, isopropylamine, n-butylamine, triethylamine, and the like.
- Nonvolatile bases include alkali metal water such as sodium hydroxide and potassium hydroxide.
- Oxides hydroxides of alkaline earth metals such as calcium hydroxide; alkali metal carbonates such as sodium bicarbonate and sodium carbonate; alkanolamines such as monoethanolamine and diethanolamine; tributylamine and cyclohexylamine
- the Examples of the carboxylate base neutralized with a volatile base include —COONH 4 , and particularly preferred examples of the carboxylate base neutralized with a nonvolatile base include —COONa, —COOK, and —COONH. 2 (CH 2 CH 2 OH) 2 , etc. are exemplified and particularly preferred.
- the carboxylate base of the polymer of the present invention is neutralized with one kind of base (a volatile base or a non-volatile base), two or more kinds of bases (a volatile base and / or a non-volatile base) are used. May be neutralized with a base).
- 0 to 15 mol% of the carboxylic acid (salt) groups contained in the polymer are preferably neutralized with a nonvolatile base (that is, included in the polymer of the present invention).
- 0 mol% to 15 mol% is preferably neutralized with a non-volatile base with respect to 100 mol% of the carboxylic acid (salt) group), and 0 mol% to 12 mol% is neutralized with a non-volatile base It is more preferable that 0 mol% to 8 mol% is neutralized with a non-volatile base.
- 0 mol% to 50 mol% of the carboxylic acid (salt) groups contained in the polymer are neutralized with a volatile base (that is, the polymer of the present invention 0 mol% to 50 mol% is preferably neutralized with a volatile base with respect to 100 mol% of the carboxylic acid (salt) group contained), and 0 mol% to 40 mol% is a volatile base. More preferably, it is neutralized, and more preferably 0 to 35 mol% is neutralized with a volatile base.
- the polymer of the present invention is derived from a monomer other than the monomer represented by the general formula (1) and the unsaturated carboxylic acid monomer (hereinafter also referred to as “other monomer”). You may have a structural unit.
- Other monomers are not particularly limited, and specific examples include 3-allyloxy-2-hydroxypropanesulfonic acid, (meth) allylsulfonic acid, isoprenesulfonic acid, vinylsulfonic acid, styrenesulfonic acid, and the like.
- Sulfonic acid monomers such as salts of vinyl pyridine, vinyl imidazole, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminopropyl acrylate, aminoethyl methacrylate, diallylamine, diallyldimethylamine, and quaternized products and salts thereof
- Amino group-containing monomers such as N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-vinyl-N-methylformamide, N-vinyl-N-methylacetamide, N-vinyloxazolidone and the like
- Amide monomers such as (meth) acrylamide, N, N-dimethylacrylamide, N-isopropylacrylamide; 3- (meth) allyloxy-1,2-dihydroxypropane, 3-allyloxy-1,2- Unsaturated alcohol monomers such as dihydroxypropane, (meth)
- Examples of the salt include the same salts as those in the unsaturated carboxylic acid monomer.
- the structural unit derived from the other monomer is a structural unit formed by polymerization of the other monomer, specifically, the carbon-carbon double of the other monomer.
- the structure is a single bond.
- the other monomer is butyl acrylate (CH 2 ⁇ CHCOOC 4 H 9 )
- the structural unit derived from the other monomer is “—CH 2 —CH (COOC 4 H 9 ) —”. Can be represented.
- the polymer of the present invention preferably has 0 to 35 mol% of structural units derived from other monomers with respect to 100 mol% of structural units derived from all monomers. More preferably, it has more than mol% and 25 mol% or less, and more preferably has 0 mol% or more and 15 mol% or less.
- the polymer of the present invention may contain one type of structural unit derived from another monomer, or may contain two or more types of structural units.
- Each structural unit in the polymer of the present invention may be present randomly or may be present regularly such as in a block form.
- the polymer of the present invention has a weight-average molecular weight because the strength of the bonded body when the binder of the present invention is used as a binder for glass fiber or powdered glass tends to be improved and moisture absorption deterioration can be suppressed. 500 or more and 100,000 or less, preferably 1500 or more and 15000 or less, and more preferably 2000 or more and 10,000 or less. In addition, the said weight average molecular weight can be measured with the measuring method mentioned later.
- the polymer of this invention is manufactured including the process of superposing
- the monomer represented by the general formula (1), the unsaturated carboxylic acid monomer, and other monomers (hereinafter, also referred to as “all monomers”).
- the amount of the monomer represented by the general formula (1) is preferably 5 mol% to 40 mol%, more preferably 10 mol% to 35 mol%, with respect to the total use amount of 100 mol%.
- the content is 15 mol% to 30 mol%.
- the amount of the unsaturated carboxylic acid monomer used in the above process is preferably 60 mol% to 95 mol%, preferably 65 mol% to 90 mol, with respect to 100 mol% of the total amount of all monomers used.
- the mol% is more preferable, and 70 mol% to 85 mol% is still more preferable.
- the amount of other monomers used in the above process is preferably 0 mol% to 35 mol%, preferably 0 mol% to 25 mol%, based on 100 mol% of the total amount of all monomers used. More preferred is 0 mol% to 15 mol%.
- the polymerization in the polymerization step is performed by various conventionally known methods such as solution polymerization method, bulk polymerization, suspension polymerization method, reverse phase suspension polymerization method, cast polymerization method, thin film polymerization method, spray polymerization method, etc. Can be adopted. Although not particularly limited, solution polymerization is preferred.
- the polymerization step can be carried out either batchwise or continuously.
- a polymerization initiator is preferably used when performing polymerization.
- the polymerization initiator include hydrogen peroxide; persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate; dimethyl 2,2′-azobis (2-methylpropionate), 2,2′- Azobis (isobutyronitrile), 2,2′-azobis (2-methylpropionamidine) dihydrochloride, 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate Azo compounds such as 2,2'-azobis [2- (2-imidazolin-2-yl) propane], 2,2'-azobis (1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride
- Organic peroxides such as benzoyl peroxide, lauroyl peroxide, peracetic acid, di-t-butyl peroxide and cumene hydroperoxide are preferred
- the amount of the polymerization initiator used is preferably 0.1 g or more and 10 g or less, more preferably 0.1 g or more and 7 g or less with respect to 1 mol of the monomer (total monomer) used. More preferably, it is 0.1 g or more and 5 g or less.
- a chain transfer agent may be used as necessary.
- chain transfer agents include thiol chain transfer agents such as mercaptoethanol, thioglycolic acid, mercaptopropionic acid, and n-dodecyl mercaptan; halogens such as carbon tetrachloride, methylene chloride, bromoform, and bromotrichloroethane.
- Secondary alcohols such as isopropanol and glycerin; hypophosphorous acid (salts) such as hypophosphorous acid and sodium hypophosphite (including hydrates thereof); phosphorous acid and sodium phosphite Phosphorous acid (salt) such as sodium sulfite, potassium sulfite and the like; bisulfite (salt) such as sodium hydrogen sulfite and potassium hydrogen sulfite; dithionic acid (salt) such as sodium dithionite; And pyrosulfurous acid (salt) such as potassium sulfite.
- the said chain transfer agent may be used independently and may be used with the form of 2 or more types of mixtures.
- the amount of the chain transfer agent used is preferably 0 g or more and 20 g or less, more preferably 1 g or more and 15 g or less, with respect to 1 mol of the monomer (total monomer) used. More preferably, it is 1 g or more and 10 g or less.
- heavy metal ions may be used for the purpose of promoting the reaction.
- the heavy metal ion means a metal ion having a specific gravity of 4 g / cm 3 or more.
- the heavy metal ions are not particularly limited as long as they are included in the form of ions. However, it is preferable to use a method using a solution in which a heavy metal compound is dissolved because the handleability is excellent.
- heavy metal compound examples include molle salt (Fe (NH 4 ) 2 (SO 4 ) 2 ⁇ 6H 2 O), ferrous sulfate / pentahydrate, ferrous chloride, ferric chloride, manganese chloride, and the like. Illustrated.
- the amount of the heavy metal ion used is preferably 0 ppm or more and 100 ppm or less, more preferably 0 ppm or more and 50 ppm or less, based on the total amount of the polymerization reaction solution.
- the solvent preferably contains water, more preferably contains 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, based on the total amount of the solvent.
- Solvents usable in the polymerization step include water; lower alcohols such as methanol, ethanol and isopropyl alcohol; lower ketones such as acetone, methyl ethyl ketone and diethyl ketone; ethers such as dimethyl ether and dioxane; amides such as dimethylformaldehyde.
- These solvents may be used alone or in the form of a mixture of two or more.
- the amount of the solvent used is preferably 40 to 200% by mass with respect to 100% by mass of the monomer. More preferably, it is 45 mass% or more, More preferably, it is 50 mass% or more. Moreover, More preferably, it is 180 mass% or less, More preferably, it is 150 mass% or less. If the amount of the solvent used is less than 40% by mass, the molecular weight of the resulting polymer may be increased. If it exceeds 200% by mass, the concentration of the obtained polymer will be low, and the cost for storage and the like will be high. There is a risk.
- the polymerization in the above polymerization step is usually preferably performed at 0 ° C. or higher, and is preferably performed at 150 ° C. or lower. More preferably, it is 40 degreeC or more, More preferably, it is 60 degreeC or more, Most preferably, it is 80 degreeC or more. Moreover, More preferably, it is 120 degrees C or less, More preferably, it is 110 degrees C or less.
- the polymerization temperature does not necessarily need to be kept almost constant in the polymerization reaction.
- the polymerization is started from room temperature, the temperature is raised to a set temperature with an appropriate temperature increase time or rate, and then the set temperature is increased. You may make it hold
- the polymerization time in the polymerization step is not particularly limited, but is preferably 30 minutes to 420 minutes, more preferably 45 minutes to 390 minutes, still more preferably 60 minutes to 360 minutes, and most preferably 90 minutes to 300 minutes.
- the term “polymerization time” refers to the time during which a monomer is added unless otherwise specified in the case of batch polymerization.
- the acid group contained in the monomer during polymerization may not be neutralized, or part or all of it may be neutralized.
- the carboxylic acid (salt) group 100 of the unsaturated carboxylic acid monomer since it is easy to adjust the neutralization rate of the carboxylic acid (salt) group of the polymer of the present invention contained in the binder to the above range, the carboxylic acid (salt) group 100 of the unsaturated carboxylic acid monomer.
- the carboxylic acid base neutralized with a non-volatile base is 0 mol% to 15 mol% and the carboxylic acid base neutralized with a volatile base is 0 mol% to 50 mol with respect to mol%. % Is preferred.
- the polymerization step may be performed at a low degree of neutralization and adjusted to a desired degree of neutralization in the neutralization step.
- the pressure in the reaction system in the polymerization step may be any of normal pressure (atmospheric pressure), reduced pressure, and increased pressure, but in terms of molecular weight of the resulting polymer, the reaction may be performed under normal pressure or reaction. It is preferable to carry out under pressure while the system is sealed. Moreover, it is preferable to carry out under a normal pressure (atmospheric pressure) at the point of equipment, such as a pressurization apparatus, a pressure reduction apparatus, a pressure-resistant reaction container, and piping.
- the atmosphere in the reaction system may be an air atmosphere or an inert atmosphere. For example, the inside of the system may be replaced with an inert gas such as nitrogen before the start of polymerization.
- the polymer of the present invention is optional, but may be produced including steps other than the above polymerization step.
- steps other than the above polymerization step for example, an aging step, a neutralization step, a deactivation step of a polymerization initiator or a chain transfer agent, a dilution step, a drying step, a concentration step, a purification step, and the like can be mentioned.
- the binder of the present invention essentially contains the polymer of the present invention.
- the binder of the present invention preferably contains 1% by mass to 100% by mass of the polymer of the present invention with respect to 100% by mass of the binder of the present invention, more preferably 10% by mass to 97% by mass. More preferably, the content is from 95% by mass to 95% by mass.
- the binder of the present invention may contain only the polymer of the present invention, but the mechanical strength of the bonded body is further improved when the binder of the present invention is used as a binder for glass fibers or powdered glass. Because of the tendency, a phosphorus-containing compound may be included. The phosphorus-containing compound is considered to have an effect of promoting the crosslinking of the polymer of the present invention.
- Phosphorus-containing compounds include acid groups such as hypophosphorous acid (salt), phosphorous acid (salt), phosphoric acid (salt), pyrophosphoric acid (salt), polyphosphoric acid (salt), and organic phosphoric acid (salt) Examples of the compound (including these hydrates); organophosphorus compounds such as trimethylphosphine, triphenylphosphine, triphenylphosphine oxide; When the binder of this invention contains a phosphorus containing compound, these may be included 1 type or may be included 2 or more types. Examples of the salt include those described above.
- the content of the phosphorus-containing compound in the binder of the present invention is preferably 0% by mass to 20% by mass, more preferably 100% by mass of the polymer (the polymer of the present invention) contained in the binder of the present invention. May be 0.1 mass% to 10 mass%, more preferably 0.5 mass% to 7 mass%.
- the binder of the present invention may contain a curing accelerator other than the phosphorus-containing compound.
- curing accelerators other than phosphorus-containing compounds include proton acids (sulfuric acid, carboxylic acid, carbonic acid, etc.) and salts thereof (metal (alkali metal, alkaline earth metal, transition metal, 2B group, 4A group, 4B group, 4B group, 5B Group, etc.) salts, ammonium salts, etc.), metal (above) oxides, chlorides, hydroxides, alkoxides, etc., which may be used alone or in combination of two or more. May be.
- the binder of the present invention may contain, for example, 0% by mass to 20% by mass of a curing accelerator other than the phosphorus-containing compound.
- the binder of the present invention may contain a solvent.
- the solvent may be an organic solvent, but preferably contains water, and 50% by mass or more is preferably water based on the total amount of the solvent.
- the solvent is preferably contained in an amount of 0 to 99% by mass, more preferably 3 to 95% by mass, more preferably 5 to 5% by mass with respect to 100% by mass of the binder of the present invention. More preferably, the content is 90% by mass.
- the binder of the present invention is optional, but since the mechanical strength of the bonded body tends to be improved when the binder of the present invention is used as a binder for glass fiber or powdered glass, a crosslinking agent is used. May be included.
- the molecular weight is preferably 1000 or less, more preferably 500 or less, and particularly preferably 300 or less. preferable.
- the crosslinking agent include compounds having two or more hydroxyl groups and / or amino groups in one molecule.
- Preferred crosslinking agents include, for example, divalent alcohols (alcohols having two hydroxyl groups in the molecule) such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, and polyalkylene glycol; glycerin, polyglycerin, and erythritol Trihydric or higher alcohols such as xylitol and sorbitol (alcohols having three or more hydroxyl groups in the molecule); alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; polyamines such as ethylenediamine and diethylenetriamine; alkylene oxides on the polyamine And the like.
- divalent alcohols alcohols having two hydroxyl groups in the molecule
- glycerin, polyglycerin, and erythritol Trihydric or higher alcohols such as xylitol and sorbitol
- alkanolamines such as monoethanolamine, di
- the binder of the present invention contains the above crosslinking agent in an amount of 0 to 50 mol% with respect to 100 mol% of acid groups contained in the polymer (polymer of the present invention) contained in the binder of the present invention.
- the content is preferably 0 to 45 mol%, more preferably 0 to 40 mol%.
- the binder of the present invention includes inorganic fibers such as glass fibers, rock wool and carbon fibers; inorganic particles (inorganic powders) such as glass particles and mineral particles; organic fibers such as wool, cellulose, hemp, nylon and polyester; It can be used as a binder for organic particles such as nylon fine particles and polyester fine particles (organic powder); Preferably, it can be used as a binder for glass fibers or powdered glass.
- the treatment with the binder of the present invention requires a step of bringing the binder of the present invention into contact with a target substance (bonded substance) such as glass fiber or powdered glass.
- a target substance bonded substance
- the binder of the present invention contains a solvent
- the above step is carried out as it is or after adjusting the concentration or the like as desired, and (i) the binder of the present invention is impregnated, or (ii) )
- the binder of the present invention may be heated and melted to be brought into contact with the substance to be bonded.
- the above (i) or (ii) is preferable because it is easy to adjust the amount of the binder of the present invention to be added to the bound substance.
- the amount of the binder of the present invention added to the bound substance is such that the solid content of the binder of the present invention is 100% by mass of the bound substance.
- the content is preferably 1% by mass to 40% by mass, more preferably 1% by mass to 30% by mass, and still more preferably 1% by mass to 15% by mass.
- step (i) the “addition amount of the binding agent of the present invention to the substance to be bonded in the step of contacting with the substance to be bonded” means that in step (i) above, the substance actually adheres to the substance to be bonded after impregnating the substance to be bonded. In the step (ii), the amount of the binder actually adhered to the bound substance after being sprayed on the bound substance in the step (ii).
- the treatment with the binder of the present invention includes a step of heat-treating the bonded body obtained in the contacting step.
- the crosslinking reaction is promoted and the strength of the bonded body tends to be improved.
- the heat treatment step is preferably performed at 100 to 400 ° C, more preferably at 120 to 350 ° C, and further preferably at 150 to 300 ° C.
- the treatment with the binder of the present invention may include a step of drying the bonded body obtained in the step of contacting.
- the drying step may be performed under normal pressure or under reduced pressure.
- drying is performed by heating, the conditions are the same as in the heat treatment step.
- the treatment with the binder of the present invention may include a step of curing the conjugate obtained in the step of contacting.
- the binder of the present invention Since the binder of the present invention has good storage stability, the binder of the present invention can be applied to uses other than the binder. For example, it can be applied to various aqueous applications.
- the content of the structural unit derived from the monomer represented by the general formula (1) is 5 to 40 mol% with respect to 100 mol% of the structural unit derived from all monomers.
- the content of the structural unit derived from the monomer containing the carboxylic acid (salt) group is 60 to 95 mol% with respect to 100 mol% of the structural unit derived from all monomers, and is contained in the polymer.
- % Is neutralized with a volatile base, and the aqueous solution contains 20% by mass to 99.9% by mass of water (“aqueous solution of the present invention”) with the total amount of the aqueous solution being 100% by mass.
- aqueous solution of the present invention is also a preferred embodiment of the present invention.
- the preferred form of the aqueous solution of the present invention is the same as the binder of the present invention unless otherwise specified.
- the effective component of the binder was calculated from the aqueous solution after the completion of polymerization and the amounts of pure water, phosphorus-containing compound, nonvolatile base and volatile base added to the aqueous polymer solution.
- the active ingredient refers to the total amount of the polymer and the phosphorus-containing compound.
- the base was volatilized at the time of curing. Therefore, the active ingredient was calculated assuming that all carboxylic acid bases of the volatile base were carboxylic acid groups.
- ⁇ Content analysis of phosphorus-containing compounds (ion chromatography analysis)> The content of the phosphorus-containing compound was analyzed by ion chromatography under the following conditions.
- Device 762 Interface manufactured by Metrohm Detector: 732 IC Detector made by Metrohm Ion analysis method: suppressor method
- Eluent NaHCO3 water (2 g diluted to 2000 g with water) Flow rate: 1.0 mL / min.
- the cured binder test piece was prepared as follows. (I) Pure water was added to the binder to adjust the active ingredient to 35%. (Ii) Add the binder obtained in (i) above to glass beads having a particle size of 0.35 to 0.50 mm so that the active ingredient is 7.5% of the weight of the glass beads and mix well. did. (Iii) The mold obtained in (ii) is pressed into a 140 mm ⁇ 20 mm ⁇ 5 mm mold that has been subjected to mold release treatment, molded, dried in an oven at 200 ° C. for 30 minutes, then transferred to a desiccator and cooled for 30 minutes. I got a piece.
- ⁇ Production Example 1> In a 2.5 liter SUS separable flask equipped with a reflux condenser, a stirrer (paddle blade), and a thermometer, 171.7 g of pure water was charged (initial charge), and the temperature was raised to the boiling point under stirring. Next, 507.3 g (that is, 5.64 mol) of an 80% by mass aqueous acrylic acid solution (hereinafter referred to as “80% AA”) is added to the polymerization reaction system in a boiling point reflux state with stirring for 180 minutes and 50% by mass hydroxyethyl methacrylate.
- 80% AA 80% by mass aqueous acrylic acid solution
- 50% HEMA 50% HEMA 366.4 g (ie, 1.41 mol) for 180 minutes, 15 mass% sodium persulfate aqueous solution (hereinafter referred to as “15% NaPS”) 35.3 g, 195 minutes, 45 mass% 24.3 g of sodium hypophosphite aqueous solution (hereinafter referred to as “45% SHP”) is dripped from the tip nozzle through separate feeding paths at 18 minutes, followed by 95.1 g at 162 minutes, respectively, at two feed rates. did. The dropping of each component was continuously performed at a constant dropping rate except for 45% SHP.
- the obtained polymer aqueous solution (1) had a solid content of 54.0%, a weight average molecular weight (Mw) of 3500, and a SHP content of 1.0% by mass with respect to 100% by mass of the polymer.
- the dropping of each component was continuously performed at a constant dropping rate except for 45% SHP. After the completion of the 80% AA dropwise addition, the reaction solution was maintained at the boiling point reflux state (aged) for another 30 minutes to complete the polymerization.
- the obtained polymer aqueous solution (2) had a solid content of 65.0%, a weight average molecular weight (Mw) of 3500, and a SHP content of 1.0% by mass with respect to 100% by mass of the polymer.
- the obtained polymer aqueous solution (3) had a solid content of 53.0%, a weight average molecular weight (Mw) of 8200, and an SHP content of 3.6% by mass with respect to 100% by mass of the polymer.
- the obtained polymer aqueous solution (5) had a solid content of 49.2%, a weight average molecular weight (Mw) of 6400, and an SHP content of 1.2% by mass with respect to 100% by mass of the polymer.
- Example 1 The polymer aqueous solution (1) obtained in Production Example 1 (89.81 g), 45% SHP (3.34 g), 25% aqueous ammonia solution (1.43 g) (neutralized 5 mol% of acrylic acid), and pure water (5.42 g) were thoroughly stirred. A binder (1) with 50% active ingredient was obtained. The weight average molecular weight (Mw) of the polymer contained in the binder (1) was 3500, and the SHP content was 4.2% by mass with respect to 100% by mass of the polymer. It was 15.0 MPa when the mechanical strength of the test piece created by the above-mentioned method was evaluated.
- Mw weight average molecular weight
- the weight average molecular weight (Mw) after storing the binder (1) in a constant temperature layer at 50 ° C. for 20 days was 4130, and the increase rate of the weight average molecular weight (Mw) was 18%.
- the results are shown in Table 1.
- Example 2 The polymer aqueous solution (1) obtained in Production Example 1 (89) (81.81 g), 45% SHP (3.34 g), 25% ammonia aqueous solution (2.87 g) (neutralized 10 mol% of acrylic acid), and pure water (3.98 g) were thoroughly stirred. A binder (2) with an active ingredient of 50% was obtained. The weight average molecular weight (Mw) of the polymer contained in the binder (2) was 3500, and the SHP content was 4.2% by mass with respect to 100% by mass of the polymer. It was 17.3 MPa when the mechanical strength of the test piece created by the above-mentioned method was evaluated.
- Mw weight average molecular weight
- the weight average molecular weight (Mw) after storing the binder (2) in a constant temperature layer at 50 ° C. for 20 days was 3970, and the increase rate of the weight average molecular weight (Mw) was 13%.
- the results are shown in Table 1.
- Example 3 The polymer aqueous solution (1) obtained in Production Example 1 (89.81 g), 45% SHP 3.34 g, 25% aqueous ammonia solution 4.30 g (15 mol% neutralized acrylic acid) and 2.55 g of pure water were thoroughly stirred. A binder (3) with 50% active ingredient was obtained. The weight average molecular weight (Mw) of the polymer contained in the binder (3) was 3500, and the SHP content was 4.2% by mass with respect to 100% by mass of the polymer. It was 13.2 Mpa when the mechanical strength of the test piece created by the above-mentioned method was evaluated. The weight average molecular weight (Mw) after storing the binder (3) in a constant temperature layer at 50 ° C. for 20 days was 3900, and the increase rate of the weight average molecular weight (Mw) was 11%. The results are shown in Table 1.
- Example 4 The polymer aqueous solution (1) obtained in Production Example 1 (89) (81.81 g), 45% SHP (3.34 g), 25% aqueous ammonia solution (5.74 g (20 mol% neutralized acrylic acid)), and pure water (1.11 g) were thoroughly stirred. A binder (4) with 50% active ingredient was obtained. The weight average molecular weight (Mw) of the polymer contained in the binder (4) was 3500, and the SHP content was 4.2% by mass with respect to 100% by mass of the polymer. It was 14.1 MPa when the mechanical strength of the test piece created by the above-mentioned method was evaluated.
- Mw weight average molecular weight
- the weight average molecular weight (Mw) after storing the binder (4) in a constant temperature layer at 50 ° C. for 20 days was 3800, and the increase rate of the weight average molecular weight (Mw) was 9%.
- the results are shown in Table 1.
- Example 5 The polymer aqueous solution (1) obtained in Production Example 1 (88.44 g), 45% SHP 3.36 g, 48% sodium hydroxide aqueous solution 2.77 g (8 mol% neutralization of acrylic acid), and pure water 5.43 g The mixture was stirred to obtain a binder (5) of the present invention having an active ingredient of 50%.
- the weight average molecular weight (Mw) of the polymer contained in the binder (5) was 3500, and the SHP content was 4.2% by mass with respect to 100% by mass of the polymer.
- Mw weight average molecular weight
- the weight average molecular weight (Mw) after storing the binder (5) in a constant temperature layer at 50 ° C. for 20 days was 4180, and the increase rate of the weight average molecular weight (Mw) was 19%.
- the results are shown in Table 1.
- Example 6 The polymer aqueous solution (1) obtained in Production Example 1 (88.11 g), 45% SHP 3.36 g, 48% sodium hydroxide aqueous solution 3.45 g (10 mol% neutralized portion of acrylic acid), and pure water 5.08 g The mixture was stirred to obtain a binder (6) having an active ingredient of 50%.
- the weight average molecular weight (Mw) of the polymer contained in the binder (6) was 3500, and the SHP content was 4.2% by mass with respect to 100% by mass of the polymer. It was 15.6 MPa when the mechanical strength of the test piece created by the above-mentioned method was evaluated.
- the weight average molecular weight (Mw) after storing the binder (6) in a constant temperature layer at 50 ° C. for 20 days was 3980, and the increase rate of the weight average molecular weight (Mw) was 14%.
- the results are shown in Table 1.
- Example 7 Polymer aqueous solution (1) obtained in Production Example 1 86.47 g, 45% SHP 3.38 g, 48% sodium hydroxide aqueous solution 2.71 g (8 mol% neutralization of acrylic acid), 80% DEA 1.33 g (acrylic) The acid (2.5 mol% neutralized component) and 6.10 g of pure water were thoroughly stirred to obtain a binder (7) having an active ingredient of 50%.
- the weight average molecular weight (Mw) of the polymer contained in the binder (7) was 3500, and the SHP content was 4.2% by mass with respect to 100% by mass of the polymer.
- Mw weight average molecular weight
- the weight average molecular weight (Mw) after storing the binder (7) in a constant temperature layer at 50 ° C. for 20 days was 3940, and the increase rate of the weight average molecular weight (Mw) was 13%.
- the results are shown in Table 1.
- Example 8> The aqueous polymer solution (2) obtained in Production Example 2 (74.61 g), 45% SHP (3.34 g), 25% aqueous ammonia solution (11.47 g) (40 mol% neutralized with acrylic acid), and pure water (10.58 g) were thoroughly stirred. A binder (8) with an active ingredient of 50% was obtained. The weight average molecular weight (Mw) of the polymer contained in the binder (8) was 3500, and the SHP content was 4.2% by mass with respect to 100% by mass of the polymer. It was 13.3 MPa when the mechanical strength of the test piece created by the above-mentioned method was evaluated.
- Mw weight average molecular weight
- the weight average molecular weight (Mw) after storing the binder (8) in a constant temperature layer at 50 ° C. for 20 days was 3500, and the increase rate of the weight average molecular weight (Mw) was 0%.
- the results are shown in Table 1.
- Example 9 The polymer aqueous solution (1) obtained in Production Example 1 (89.12 g), 45% SHP (3.35 g), 48% sodium hydroxide aqueous solution (1.40 g neutralized with 4 mol% of acrylic acid) and 6.14 g of pure water The mixture was stirred to obtain a binder (9) having an active ingredient of 50%.
- the weight average molecular weight (Mw) of the polymer contained in the binder (9) was 3500, and the SHP content was 4.2% by mass with respect to 100% by mass of the polymer. It was 15.0 Mpa when the mechanical strength of the test piece created by the above-mentioned method was evaluated.
- the weight average molecular weight (Mw) after storing the binder (9) in a constant temperature layer at 50 ° C. for 20 days was 4210, and the increase rate of the weight average molecular weight (Mw) was 20%.
- the results are shown in Table 1.
- Example 10 The polymer aqueous solution (1) obtained in Production Example 1 (87.78 g), 45% SHP (3.36 g), 80% DEA (1.35 g) (2.5 mol% neutralized portion of acrylic acid) and 7.50 g of pure water were thoroughly stirred. A binder (10) with an active ingredient of 50% was obtained. The weight average molecular weight (Mw) of the polymer contained in the binder (10) was 3500, and the SHP content was 4.2% by mass with respect to 100% by mass of the polymer. It was 15.4 MPa when the mechanical strength of the test piece prepared by the above-mentioned method was evaluated. The weight average molecular weight (Mw) after storing the binder (10) in a constant temperature layer at 50 ° C. for 20 days was 4240, and the increase rate of the weight average molecular weight (Mw) was 21%. The results are shown in Table 1.
- ⁇ Comparative example 2> 86.47 g of the polymer aqueous solution (1) obtained in Production Example 1; 3.38 g of 45% SHP; 6.77 g of 48% sodium hydroxide aqueous solution (20 mol% neutralized portion of acrylic acid); 3.38 g of pure water
- the mixture was stirred to obtain a binder (C2) having an active ingredient of 50%.
- the weight average molecular weight (Mw) of the polymer contained in the binder (C2) was 3500, and the SHP content was 4.2% by mass with respect to 100% by mass of the polymer.
- the mechanical strength of the test piece prepared by the above method was evaluated and found to be 9.4 MPa.
- the weight average molecular weight (Mw) after storing the binder (C2) in a constant temperature layer at 50 ° C. for 20 days was 3680, and the increase rate of the weight average molecular weight (Mw) was 5%.
- the results are shown in Table 1.
- the weight average molecular weight (Mw) after storing the binder (C3) in a constant temperature layer at 50 ° C. for 20 days was 3500, and the increase rate of the weight average molecular weight (Mw) was 0%.
- the results are shown in Table 1.
- the weight average molecular weight (Mw) after storing the binder (C4) in a constant temperature layer at 50 ° C. for 20 days was 3500, and the increase rate of the weight average molecular weight (Mw) was 0%.
- the results are shown in Table 1.
- ⁇ Comparative Example 5> 94.34 g of the polymer aqueous solution (3) obtained in Production Example 3 and 5.66 g of pure water were sufficiently stirred to obtain a binder (C5) having an active ingredient of 50%.
- the weight average molecular weight (Mw) of the polymer contained in the binder (C5) was 8200, and the SHP content was 3.6% by mass with respect to 100% by mass of the polymer. It was 9.5 MPa when the mechanical strength of the test piece created by the above-mentioned method was evaluated.
- the weight average molecular weight (Mw) after storing the binder (C5) in a constant temperature layer at 50 ° C. for 20 days was 8200, and the increase rate of the weight average molecular weight (Mw) was 0%.
- Table 1 The results are shown in Table 1.
- the mixture was stirred to obtain a binder (R2) having an active ingredient of 35%.
- the weight average molecular weight (Mw) of the polymer contained in the binder (R2) was 5600, and the SHP content was 3.7% by mass with respect to 100% by mass of the polymer. It was 14.9 Mpa when the mechanical strength of the test piece created by the above-mentioned method was evaluated. When the hydrolysis resistance was evaluated, the mechanical strength was 13.0 MPa, and the strength retention was 87.2%.
- the results are shown in Table 2.
- the mixture was stirred to obtain a binder (R4) having an active ingredient of 35%.
- the weight average molecular weight (Mw) of the polymer contained in the binder (R4) was 6400, and the SHP content was 3.7% by mass with respect to 100% by mass of the polymer. It was 13.2 Mpa when the mechanical strength of the test piece created by the above-mentioned method was evaluated. When the hydrolysis resistance was evaluated, the mechanical strength was 9.9 MPa, and the strength retention was 75.0%.
- the results are shown in Table 2.
- the binder of the present invention can be usefully used as, for example, a binder for a heat insulating material for a house.
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Abstract
Description
水酸基を有する重合体を含む結合剤であって、
該重合体は、一般式(1)で表される単量体に由来する構造単位とカルボン酸(塩)基を含む単量体に由来する構造単位とを含み、
該一般式(1)で表される単量体に由来する構造単位の含有量は、全単量体に由来する構造単位100モル%に対し5モル%~40モル%であり、
該カルボン酸(塩)基を含む単量体に由来する構造単位の含有量は、全単量体に由来する構造単位100モル%に対し60モル%~95モル%であり、
該重合体に含まれるカルボン酸(塩)基の2モル%以上が揮発性の塩基および/または不揮発性の塩基で中和されており、
該重合体に含まれるカルボン酸(塩)基の0モル%~15モル%が不揮発性の塩基で中和されており、
該重合体に含まれるカルボン酸(塩)基の0モル%~50モル%が揮発性の塩基で中和されている。
水酸基を有する重合体を含む水溶液であって、
該重合体は、一般式(1)で表される単量体に由来する構造単位とカルボン酸(塩)基を含む単量体に由来する構造単位とを含み、
該一般式(1)で表される単量体に由来する構造単位の含有量は、全単量体に由来する構造単位100モル%に対し5モル%~40モル%であり、
該カルボン酸(塩)基を含む単量体に由来する構造単位の含有量は、全単量体に由来する構造単位100モル%に対し60モル%~95モル%であり、
該重合体に含まれるカルボン酸(塩)基の2モル%以上が揮発性の塩基および/または不揮発性の塩基で中和されており、
該重合体に含まれるカルボン酸(塩)基の0モル%~15モル%が不揮発性の塩基で中和されており、
該重合体に含まれるカルボン酸(塩)基の0モル%~50モル%が揮発性の塩基で中和されており、
該水溶液は、該水溶液の全量を100質量%として、水を20質量%以上、99.9質量%以下含む。
本発明の結合剤は、水酸基を有する重合体を含み、該重合体は、上記一般式(1)で表される単量体に由来する構造単位を含む。本発明の結合剤の必須成分である上記重合体を、以下、「本発明の重合体」ともいう。
本発明において、不飽和カルボン酸系単量体に由来する構造単位とは、不飽和カルボン酸系単量体が重合して形成される構造単位であり、具体的には、不飽和カルボン酸系単量体の炭素-炭素二重結合が単結合になった構造である。例えば、不飽和カルボン酸系単量体がアクリル酸(CH2=CHCOOH)である場合、不飽和カルボン酸系単量体に由来する構造単位は「-CH2-CH(COOH)-」で表すことができる。
本発明の結合剤は、本発明の重合体を必須に含む。
本発明の結合剤は、ガラス繊維、ロックウール、カーボン繊維等の無機繊維;ガラス粒子、鉱物粒子等の無機粒子(無機粉体);羊毛、セルロース、麻、ナイロン、ポリエステル等の有機物の繊維;ナイロン微粒子、ポリエステル微粒子等の有機物の粒子(有機物の粉体);等の結合剤として、使用することができる。好ましくはガラス繊維や粉末ガラスの結合剤として使用することができる。
本発明の結合剤による処理は、本発明の結合剤を、ガラス繊維や粉末ガラス等の対象物質(被結合物質)に接触させる工程を必須とする。上記工程は、本発明の結合剤が溶剤を含む場合には、そのままで、または所望により濃度等を調節して、(i)被結合物質を本発明の結合剤に含浸させるか、または(ii)被結合物質に本発明の結合剤を散布することにより、行うことが好ましい。本発明の結合剤が溶剤を含まない場合には、本発明の結合剤を加熱・溶融させて被結合物質に接触させても構わないが、処理物(被結合体)の強度にむらが生じやすくなる傾向にあるので、溶剤に溶解し、上記(i)または(ii)を行うことが好ましい。中でも、被結合物質に対する本発明の結合剤の添加量を調節しやすいことから、上記(ii)が好ましい。
本発明の結合剤は、良好な保存安定性を有することから、本発明の結合剤は、結合剤以外の用途にも適用可能である。例えば、各種水系用途に適用可能である。
重量平均分子量は、下記条件にて測定した。
装置:東ソー製 HLC-8320GPC
検出器:RI
カラム:東ソー製 TSK-GEL G3000PWXL
カラム温度:35℃
流速:0.5ml/min
検量線:創和科学社製 POLY SODIUM ACRYLATE STANDARD
溶離液:リン酸二水素ナトリウム12水和物/リン酸水素二ナトリウム2水和物(34.5g/46.2g)の混合物を純水にて5000gに希釈した溶液。
130℃に加熱したオーブンで結合剤を60分間放置して乾燥処理した。乾燥前後の重量変化から、重合完結後の水溶液の固形分(%)を算出した。
結合剤の有効成分は重合完結後の水溶液と、重合体水溶液に添加した純水、リン含有化合物、不揮発性の塩基、揮発性の塩基の添加量から計算した。ここで有効成分とは、重合体とリン含有化合物の合計量のことを指す。ただし揮発性塩基で中和を行った場合、硬化時に塩基は揮発するため、揮発性の塩基のカルボン酸塩基は全てカルボン酸基であるとして有効成分を算出した。
リン含有化合物の含有量は、下記条件にてイオンクロマト分析を行った。
装置:Metrohm社製 762 Interface
検出器:Metrohm社製 732 IC Detecter
イオン分析方式:サプレッサー法
カラム:Shodex IC SI-90 4E
ガードカラム:Shodex SI-90 G
カラム温度:40℃
溶離液:NaHCO3水(2gを水で2000gに希釈)
流速:1.0mL/min。
バインダー硬化物試験片は下記のようにして作成した。
(i)結合剤に純水を添加し、有効成分35%に調整した。
(ii)粒径0.35~0.50mmのガラスビーズに、上記(i)で得られた結合剤を、有効成分がガラスビーズ重量の7.5%となるように添加し、十分に混合した。
(iii)離型処理した140mm×20mm×5mmの型枠に(ii)で得られた混合物を押し入れて成型し、200℃のオーブンで30分間乾燥後、デシケータに移し30分冷却することで試験片を得た。
JISK7171に準じ、2mm/minの試験速度で曲げ強さを測定した。試験片3枚の曲げ強さを測定し、平均値を算出した。
上記方法で得られたバインダー硬化物試験片を40℃80%RHの恒温恒湿器内で3時間静置した。その後取り出し、23℃50%RHで1時間乾燥した。乾燥後の試験片について上記機械強度を測定し、強度の保持率から耐加水分解性を評価した。
還流冷却機、攪拌機(パドル翼)、温度計を備えた容量2.5リットルのSUS製セパラブルフラスコに、純水171.7gを仕込み(初期仕込)、攪拌下、沸点まで昇温した。次いで、攪拌下、沸点還流状態の重合反応系中に、80質量%アクリル酸水溶液(以下「80%AA」と称する)507.3g(すなわち5.64mol)を180分間、50質量%ヒドロキシエチルメタクリレート(以下「50%HEMA」と称する)366.4g(すなわち1.41mol)を180分間、15質量%過硫酸ナトリウム水溶液(以下「15%NaPS」と称する)35.3gを195分間、45質量%次亜リン酸ナトリウム水溶液(以下「45%SHP」と称する)24.3gを18分間とさらに続いて95.1gを162分間と2段階の供給速度で、それぞれ別々の供給経路を通じて先端ノズルより滴下した。それぞれの成分の滴下は、45%SHP以外は一定の滴下速度で連続的に行った。80%AAの滴下終了後、さらに30分間に渡って反応溶液を沸点還流状態に保持(熟成)して重合を完結せしめた。得られた重合体水溶液(1)の固形分は54.0%、重量平均分子量(Mw)は3500、SHPの含有量は重合体100質量%に対し1.0質量%だった。
還流冷却機、攪拌機(パドル翼)、温度計を備えた容量2.5リットルのSUS製セパラブルフラスコに、純水127.6gを仕込み(初期仕込)、攪拌下、沸点まで昇温した。次いで、攪拌下、沸点還流状態の重合反応系中に80%AA610.6g(すなわち6.78mol)を180分間、80%HEMA275.6g(すなわち1.70mol)を180分間、15%NaPS42.5gを195分間、45%SHP29.2gを18分間とさらに続いて114.5gを162分間と2段階の供給速度で、それぞれ別々の供給経路を通じて先端ノズルより滴下した。それぞれの成分の滴下は、45%SHP以外は一定の滴下速度で連続的に行った。80%AAの滴下終了後、さらに30分間に渡って反応溶液を沸点還流状態に保持(熟成)して重合を完結せしめた。得られた重合体水溶液(2)の固形分は65.0%、重量平均分子量(Mw)は3500、SHPの含有量は重合体100質量%に対し1.0質量%だった。
還流冷却機、攪拌機(パドル翼)、温度計を備えた容量2.5リットルのSUS製セパラブルフラスコに、純水168.0gを仕込み(初期仕込)、攪拌下、沸点まで昇温した。次いで攪拌下、沸点還流状態の重合反応系中に80%AA416.8g(すなわち4.63mol)を180分間、15%NaPS23.2gを195分間、45%SHP6.4gを18分間とさらに続いて30.3gを192分間と2段階の供給速度で、純水119.1gを重合開始92分後から88分間、それぞれ別々の供給経路を通じて先端ノズルより滴下した。それぞれの成分の滴下は、45%SHP以外は一定の滴下速度で連続的に行った。80%AAの滴下終了後、さらに30分間に渡って反応溶液を沸点還流状態に保持(熟成)して重合を完結せしめた。重合の完結後、反応溶液に80質量%ジエタノールアミン水溶液(以下「80%DEA」と称する)200.8g(アクリル酸の33mol%中和分)、45%SHP35.3gを攪拌下、滴下した。得られた重合体水溶液(3)の固形分は53.0%、重量平均分子量(Mw)は8200、SHPの含有量は重合体100質量%に対し3.6質量%だった。
還流冷却機、攪拌機(パドル翼)、温度計を備えた容量2.5リットルのSUS製セパラブルフラスコに、純水333.2gを仕込み(初期仕込)、攪拌下、沸点まで昇温した。次いで、攪拌下、沸点還流状態の重合反応系中に80質量%アクリル酸水溶液(以下「80%AA」と称する)416.7g(すなわち4.63mol)を180分間、ヒドロキシエチルメタクリレート(以下「HEMA」と称する)150.5g(すなわち1.16mol)を180分間、15質量%過硫酸ナトリウム水溶液(以下「15%NaPS」と称する)29.0gを195分間、45質量%次亜リン酸ナトリウム水溶液(以下「45%SHP」と称する)14.1gを18分間とさらに続いて56.5gを162分間と2段階の供給速度で、それぞれ別々の供給経路を通じて先端ノズルより滴下した。それぞれの成分の滴下は、45%SHP以外は一定の滴下速度で連続的に行った。80%AAの滴下終了後、さらに30分間に渡って反応溶液を沸点還流状態に保持(熟成)して重合を完結せしめた。得られた重合体水溶液(4)の固形分は52.0%、重量平均分子量(Mw)は5600、SHPの含有量は重合体100質量%に対し0.8質量%だった。
還流冷却機、攪拌機(パドル翼)、温度計を備えた容量2.5リットルのSUS製セパラブルフラスコに、純水234.7gを仕込み(初期仕込)、攪拌下、沸点まで昇温した。次いで攪拌下、沸点還流状態の重合反応系中に80%AA409.8g(すなわち4.55mol)を180分間、50質量%ヒドロキシエチルエタクリレート(以下「50%HEA」と称する)264.1g(すなわち1.14mol)を180分間、15%NaPS28.5gを195分間、45%SHP11.1gを18分間とさらに続いて51.8gを192分間と2段階の供給速度で、それぞれ別々の供給経路を通じて先端ノズルより滴下した。それぞれの成分の滴下は、45%SHP以外は一定の滴下速度で連続的に行った。80%AAの滴下終了後、さらに30分間に渡って反応溶液を沸点還流状態に保持(熟成)して重合を完結せしめた。得られた重合体水溶液(5)の固形分は49.2%、重量平均分子量(Mw)は6400、SHPの含有量は重合体100質量%に対し1.2質量%だった。
製造例1で得られた重合体水溶液(1)89.81g、45%SHP3.34g、25%アンモニア水溶液1.43g(アクリル酸の5mol%中和分)、純水5.42gをよく攪拌し、有効成分50%の結合剤(1)を得た。結合剤(1)に含まれる重合体の重量平均分子量(Mw)は3500、SHPの含有量は重合体100質量%に対し4.2質量%だった。上述の方法で作成した試験片の機械的強度を評価したところ、15.0MPaであった。結合剤(1)を50℃の恒温層内で20日間保存した後の重量平均分子量(Mw)は4130であり、重量平均分子量(Mw)の増加率は18%だった。
結果を表1に示した。
製造例1で得られた重合体水溶液(1)89.81g、45%SHP3.34g、25%アンモニア水溶液2.87g(アクリル酸の10mol%中和分)、純水3.98gをよく攪拌し、有効成分50%の結合剤(2)を得た。結合剤(2)に含まれる重合体の重量平均分子量(Mw)は3500、SHPの含有量は重合体100質量%に対し4.2質量%だった。上述の方法で作成した試験片の機械的強度を評価したところ、17.3MPaであった。結合剤(2)を50℃の恒温層内で20日間保存した後の重量平均分子量(Mw)は3970であり、重量平均分子量(Mw)の増加率は13%だった。
結果を表1に示した。
製造例1で得られた重合体水溶液(1)89.81g、45%SHP3.34g、25%アンモニア水溶液4.30g(アクリル酸の15mol%中和分)、純水2.55gをよく攪拌し、有効成分50%の結合剤(3)を得た。結合剤(3)に含まれる重合体の重量平均分子量(Mw)は3500、SHPの含有量は重合体100質量%に対し4.2質量%だった。上述の方法で作成した試験片の機械的強度を評価したところ、13.2MPaであった。結合剤(3)を50℃の恒温層内で20日間保存した後の重量平均分子量(Mw)は3900であり、重量平均分子量(Mw)の増加率は11%だった。
結果を表1に示した。
製造例1で得られた重合体水溶液(1)89.81g、45%SHP3.34g、25%アンモニア水溶液5.74g(アクリル酸の20mol%中和分)、純水1.11gをよく攪拌し、有効成分50%の結合剤(4)を得た。結合剤(4)に含まれる重合体の重量平均分子量(Mw)は3500、SHPの含有量は重合体100質量%に対し4.2質量%だった。上述の方法で作成した試験片の機械的強度を評価したところ、14.1MPaであった。結合剤(4)を50℃の恒温層内で20日間保存した後の重量平均分子量(Mw)は3800であり、重量平均分子量(Mw)の増加率は9%だった。
結果を表1に示した。
製造例1で得られた重合体水溶液(1)88.44g、45%SHP3.36g、48%水酸化ナトリウム水溶液2.77g(アクリル酸の8mol%中和分)、純水5.43gをよく攪拌し、有効成分50%の本発明の結合剤(5)を得た。結合剤(5)に含まれる重合体の重量平均分子量(Mw)は3500、SHPの含有量は重合体100質量%に対し4.2質量%だった。上述の方法で作成した試験片の機械的強度を評価したところ、14.5MPaであった。結合剤(5)を50℃の恒温層内で20日間保存した後の重量平均分子量(Mw)は4180であり、重量平均分子量(Mw)の増加率は19%だった。
結果を表1に示した。
製造例1で得られた重合体水溶液(1)88.11g、45%SHP3.36g、48%水酸化ナトリウム水溶液3.45g(アクリル酸の10mol%中和分)、純水5.08gをよく攪拌し、有効成分50%の結合剤(6)を得た。結合剤(6)に含まれる重合体の重量平均分子量(Mw)は3500、SHPの含有量は重合体100質量%に対し、4.2質量%だった。上述の方法で作成した試験片の機械的強度を評価したところ、15.6MPaであった。結合剤(6)を50℃の恒温層内で20日間保存した後の重量平均分子量(Mw)は3980であり、重量平均分子量(Mw)の増加率は14%だった。
結果を表1に示した。
製造例1で得られた重合体水溶液(1)86.47g、45%SHP3.38g、48%水酸化ナトリウム水溶液2.71g(アクリル酸の8mol%中和分)、80%DEA1.33g(アクリル酸の2.5mol%中和分)、純水6.10gをよく攪拌し、有効成分50%の結合剤(7)を得た。結合剤(7)に含まれる重合体の重量平均分子量(Mw)は3500、SHPの含有量は重合体100質量%に対し4.2質量%だった。上述の方法で作成した試験片の機械的強度を評価したところ、13.5MPaであった。結合剤(7)を50℃の恒温層内で20日間保存した後の重量平均分子量(Mw)は3940であり、重量平均分子量(Mw)の増加率は13%だった。
結果を表1に示した。
製造例2で得られた重合体水溶液(2)74.61g、45%SHP3.34g、25%アンモニア水溶液11.47g(アクリル酸の40mol%中和分)、純水10.58gをよく攪拌し、有効成分50%の結合剤(8)を得た。結合剤(8)に含まれる重合体の重量平均分子量(Mw)は3500、SHPの含有量は重合体100質量%に対し4.2質量%だった。上述の方法で作成した試験片の機械的強度を評価したところ13.3MPaであった。結合剤(8)を50℃の恒温層内で20日間保存した後の重量平均分子量(Mw)は3500であり、重量平均分子量(Mw)の増加率は0%だった。
結果を表1に示した。
製造例1で得られた重合体水溶液(1)89.12g、45%SHP3.35g、48%水酸化ナトリウム水溶液1.40g(アクリル酸の4mol%中和分)、純水6.14gをよく攪拌し、有効成分50%の結合剤(9)を得た。結合剤(9)に含まれる重合体の重量平均分子量(Mw)は3500、SHPの含有量は重合体100質量%に対し、4.2質量%だった。上述の方法で作成した試験片の機械的強度を評価したところ15.0MPaであった。結合剤(9)を50℃の恒温層内で20日間保存した後の重量平均分子量(Mw)は4210であり、重量平均分子量(Mw)の増加率は20%だった。
結果を表1に示した。
製造例1で得られた重合体水溶液(1)87.78g、45%SHP3.36g、80%DEA1.35g(アクリル酸の2.5mol%中和分)、純水7.50gをよく攪拌し、有効成分50%の結合剤(10)を得た。結合剤(10)に含まれる重合体の重量平均分子量(Mw)は3500、SHPの含有量は重合体100質量%に対し4.2質量%だった。上述の方法で作成した試験片の機械的強度を評価したところ、15.4MPaであった。結合剤(10)を50℃の恒温層内で20日間保存した後の重量平均分子量(Mw)は4240であり、重量平均分子量(Mw)の増加率は21%だった。
結果を表1に示した。
製造例1で得られた重合体水溶液(1)89.81g、45%SHP3.34g、純水6.85gをよく攪拌し、有効成分50%の結合剤(C1)を得た。結合剤(C1)に含まれる重合体の重量平均分子量(Mw)は3500、SHPの含有量は重合体100質量%に対し4.2質量%だった。上述の方法で作成した試験片の機械的強度を評価したところ、17.5MPaであった。結合剤(C1)を50℃の恒温層内で20日間保存した後の重量平均分子量(Mw)は4540であり、重量平均分子量(Mw)の増加率は30%だった。
結果を表1に示した。
製造例1で得られた重合体水溶液(1)86.47g、45%SHP3.38g、48%水酸化ナトリウム水溶液6.77g(アクリル酸の20mol%中和分)、純水3.38gをよく攪拌し、有効成分50%の結合剤(C2)を得た。結合剤(C2)に含まれる重合体の重量平均分子量(Mw)は3500、SHPの含有量は重合体100質量%に対し4.2質量%だった。上述の方法で作成した試験片の機械的強度を評価したところ、9.4MPaであった。結合剤(C2)を50℃の恒温層内で20日間保存した後の重量平均分子量(Mw)は3680であり、重量平均分子量(Mw)の増加率は5%だった。
結果を表1に示した。
製造例1で得られた重合体水溶液(1)66.47g、45%SHP3.63g、80%DEA15.59g(アクリル酸の38mol%中和分)、純水14.31gをよく攪拌し、有効成分50%の結合剤(C3)を得た。結合剤(C3)に含まれる重合体の重量平均分子量(Mw)は3500、SHPの含有量は重合体100質量%に対し4.2質量%だった。上述の方法で作成した試験片の機械的強度を評価したところ、10.3MPaであった。結合剤(C3)を50℃の恒温層内で20日間保存した後の重量平均分子量(Mw)は3500であり、重量平均分子量(Mw)の増加率は0%だった。
結果を表1に示した。
製造例2で得られた重合体水溶液(2)74.61g、45%SHP3.34g、25%アンモニア水溶液21.51g(アクリル酸の75mol%中和分)、純水0.54gをよく攪拌し、有効成分50%の結合剤(C4)を得た。結合剤(C4)に含まれる重合体の重量平均分子量(Mw)は3500、SHPの含有量は重合体100質量%に対し4.2質量%だった。上述の方法で作成した試験片の機械的強度を評価したところ、8.5MPaであった。結合剤(C4)を50℃の恒温層内で20日間保存した後の重量平均分子量(Mw)は3500であり、重量平均分子量(Mw)の増加率は0%だった。
結果を表1に示した。
製造例3で得られた重合体水溶液(3)94.34g、純水5.66gをよく攪拌し、有効成分50%の結合剤(C5)を得た。結合剤(C5)に含まれる重合体の重量平均分子量(Mw)は8200、SHPの含有量は重合体100質量%に対し3.6質量%だった。上述の方法で作成した試験片の機械的強度を評価したところ、9.5MPaであった。結合剤(C5)を50℃の恒温層内で20日間保存した後の重量平均分子量(Mw)は8200であり、重量平均分子量(Mw)の増加率は0%だった。
結果を表1に示した。
製造例4で得られた重合体水溶液(4)26.16g、45%SHP0.88g、25%アンモニア水溶液0.82g(アクリル酸の10mol%中和分)、純水12.14gをよく攪拌し、有効成分35%の結合剤(R1)を得た。結合剤(R1)に含まれる重合体の重量平均分子量(Mw)は5600、SHPの含有量は重合体100質量%に対し3.7質量%だった。上述の方法で作成した試験片の機械強度を評価したところ、15.8MPaであった。耐加水分解性の評価を実施したところ、機械強度は13.7MPaであり、強度の保持率は86.7%だった。
結果を表2に示した。
製造例4で得られた重合体水溶液(4)25.95g、45%SHP0.89g、48%水酸化ナトリウム水溶液0.40g(アクリル酸の4mol%中和分)、純水12.76gをよく攪拌し、有効成分35%の結合剤(R2)を得た。結合剤(R2)に含まれる重合体の重量平均分子量(Mw)は5600、SHPの含有量は重合体100質量%に対し3.7質量%だった。上述の方法で作成した試験片の機械的強度を評価したところ、14.9MPaであった。耐加水分解性の評価を実施したところ、機械強度は13.0MPaであり、強度の保持率は87.2%だった。
結果を表2に示した。
製造例5で得られた重合体水溶液(5)27.73g、45%SHP0.76g、25%アンモニア水溶液0.86g(アクリル酸の10mol%中和分)、純水10.65gをよく攪拌し、有効成分35%の結合剤(R3)を得た。結合剤(R3)に含まれる重合体の重量平均分子量(Mw)は6400、SHPの含有量は重合体100質量%に対し3.7質量%だった。上述の方法で作成した試験片の機械的強度を評価したところ、12.8MPaであった。耐加水分解性の評価を実施したところ、機械強度は10.0MPaであり、強度の保持率は78.1%だった。
結果を表2に示した。
製造例5で得られた重合体水溶液(5)27.52g、45%SHP0.75g、48%水酸化ナトリウム水溶液0.42g(アクリル酸の4mol%中和分)、純水11.11gをよく攪拌し、有効成分35%の結合剤(R4)を得た。結合剤(R4)に含まれる重合体の重量平均分子量(Mw)は6400、SHPの含有量は重合体100質量%に対し3.7質量%だった。上述の方法で作成した試験片の機械的強度を評価したところ、13.2MPaであった。耐加水分解性の評価を実施したところ、機械強度は9.9MPaであり、強度の保持率は75.0%だった。
結果を表2に示した。
Claims (2)
- 水酸基を有する重合体を含む結合剤であって、
該重合体は、一般式(1)で表される単量体に由来する構造単位とカルボン酸(塩)基を含む単量体に由来する構造単位とを含み、
該一般式(1)で表される単量体に由来する構造単位の含有量は、全単量体に由来する構造単位100モル%に対し5モル%~40モル%であり、
該カルボン酸(塩)基を含む単量体に由来する構造単位の含有量は、全単量体に由来する構造単位100モル%に対し60モル%~95モル%であり、
該重合体に含まれるカルボン酸(塩)基の2モル%以上が揮発性の塩基および/または不揮発性の塩基で中和されており、
該重合体に含まれるカルボン酸(塩)基の0モル%~15モル%が不揮発性の塩基で中和されており、
該重合体に含まれるカルボン酸(塩)基の0モル%~50モル%が揮発性の塩基で中和されている、
結合剤。
- 水酸基を有する重合体を含む水溶液であって、
該重合体は、一般式(1)で表される単量体に由来する構造単位とカルボン酸(塩)基を含む単量体に由来する構造単位とを含み、
該一般式(1)で表される単量体に由来する構造単位の含有量は、全単量体に由来する構造単位100モル%に対し5モル%~40モル%であり、
該カルボン酸(塩)基を含む単量体に由来する構造単位の含有量は、全単量体に由来する構造単位100モル%に対し60モル%~95モル%であり、
該重合体に含まれるカルボン酸(塩)基の2モル%以上が揮発性の塩基および/または不揮発性の塩基で中和されており、
該重合体に含まれるカルボン酸(塩)基の0モル%~15モル%が不揮発性の塩基で中和されており、
該重合体に含まれるカルボン酸(塩)基の0モル%~50モル%が揮発性の塩基で中和されており、
該水溶液は、該水溶液の全量を100質量%として、水を20質量%以上、99.9質量%以下含む、
水溶液。
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WO2022079946A1 (ja) * | 2020-10-16 | 2022-04-21 | 株式会社日本触媒 | ポリカルボン酸系重合体溶液の保管方法及び使用方法 |
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