JP6418847B2 - Nonionic polyhydric alcohol-containing binder - Google Patents

Description

  The present invention relates to a binder comprising a polymer having a hydroxyl group and a nonionic polyhydric alcohol. More specifically, the present invention relates to a binder containing a hydroxyl group-containing polymer and a nonionic polyhydric alcohol, which is useful as a binder for glass fibers and powdered glass.

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 or an appliance. As the binder, a phenol-formaldehyde binder is widely used. However, the phenol-formaldehyde binder has a problem in 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.
For example, Patent Document 1 discloses a glass fiber binder comprising (1) a reaction product of a polymerizable carboxylic acid or anhydride, or a mixture thereof, and a hydroxy C2-C8 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. The binder is disclosed to have a low viscosity when uncured and to have structural rigidity when cured.

  For example, U.S. Patent No. 6,057,836 includes (a) a polyacid containing at least two carboxylic acid groups, acid anhydride groups, or salts thereof; (b) a polyol containing at least two hydroxyl groups; and (c And a ratio of equivalents of the carboxylic acid group, acid anhydride group, or salt thereof: equivalents of the hydroxyl group is about 1 / 0.01. A curable aqueous composition wherein the carboxylic acid group, anhydride group, or salt thereof is neutralized to a range of about 35% or less with a non-volatile base. Has been. Patent Document 2 discloses that the curable aqueous composition is effective as a binder for a heat-resistant nonwoven fabric.

Japanese National Patent Publication No. 10-509485 JP-A-6-184285

  As described above, various binders such as glass fibers that do not contain formaldehyde have been proposed, but there has been a problem that the strength of the glass fibers treated with these binders is not sufficient.

  The present invention has been made by paying attention to the above circumstances, and expresses excellent bonding strength of glass fibers and powdered glass (giving good strength to a bonded body of glass fibers and powdered glass). The object is to provide possible binders.

  As a result of intensive investigations, the present inventors have found that the binder contains a predetermined polymer and a nonionic polyhydric alcohol, so that the strength of the glass fiber or powder glass binder is improved. Based on these findings, the present invention has been completed.

  That is, the present invention provides a binder comprising (i) a polymer having a hydroxyl group and (ii) a nonionic polyhydric alcohol, wherein the polymer is a monomer represented by the following general formula (1): It is a binder containing the structural unit derived from (1), and the structural unit derived from an unsaturated carboxylic monomer.

In the above general formula (1), R ₁ represents a hydrogen atom or a methyl group, and R ₂ represents an organic group having 2 to 20 carbon atoms.

By treating with the bonded body of the present invention, glass fibers and powdered glass can exhibit good strength. Therefore, the binder of the present invention can be usefully used as, for example, a binder for residential heat insulating materials.

Hereinafter, the present invention will be described in detail.
A combination of two or more preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

[Polymer having hydroxyl group]
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). Hereinafter, the polymer which is an essential component of the binder of the present invention is also referred to as “polymer of the present invention”.
In the above general formula (1), R ₁ represents a hydrogen atom or a methyl group, and R ₂ represents an organic group having 2 to 20 carbon atoms. When the binder of the present invention is used as a binder for glass fiber or powdered glass, the strength of the object to be bonded (referred to as glass fiber or powdered glass treated with the binder of the present invention) is improved, and moisture absorption is deteriorated. 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.

In the general formula (1), 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.

In the general formula (1), 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 substituted alkylene group means a group in which part or all of the hydrogen atoms constituting the alkylene group are substituted with a substituent. Here, 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 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. Here, 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 ether group includes a polyether group, and 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. Here, 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.

Specific examples of 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 ₂ CH ₂ — group, alkylene group such as —CH (C ₄ H ₉ ) CH ₂ — group, arylene group such as phenylene group, naphthyl group, etc .; —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 OCH 2 CH 2 - _{group, -CH (CH 3) CH 2} OCH (CH 3) CH 2 - group, _{-CH (CH 3) CH 2 OCH} (CH 3) CH 2 OC - _(CH 3) _{CH 2} ether groups such as, and the like.

  In the present invention, 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).

In the 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. Incidentally, 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 is a structural unit derived from all monomers (a structural unit derived from the monomer represented by the general formula (1) and a structural unit derived from other monomers described later) 100. It is preferable to contain 5 mol% or more and 40 mol% or less of the structural unit derived from the monomer represented by the general formula (1) with respect to mol%, and 10 mol% or more and 35 mol% or less. Is more preferable, and it is further more preferable to contain 15 mol% or more and 30 mol% or less. By including in the said range, it exists in the tendency for the intensity | strength of the to-be-bonded body at the time of using the binder of this invention for the binder of glass fiber or powder glass to improve.
The polymer of this invention may contain 1 type of structural units derived from the monomer represented by the said General formula (1), or may contain 2 or more types.

The polymer of the present invention includes 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, crotonic acid. , Α-hydroxyacrylic acid, α-hydroxymethylacrylic acid and derivatives thereof, unsaturated monocarboxylic acids and salts thereof; fumaric acid, maleic acid, methyleneglutaric acid, itaconic acid and other unsaturated dicarboxylic acids and these Salt (which may be mono- or di-salt); and the like.
Examples of the salt include metal salts, ammonium salts, and organic amine salts. Examples of 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; Examples of 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;

In the present invention, 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. It is a structure in which the carbon-carbon double bond of the monomer is a single bond. For example, when the unsaturated carboxylic acid monomer is acrylic acid (CH ₂ ═CHCOOH), the structural unit derived from the unsaturated carboxylic acid monomer is represented by —CH ₂ —CH (COOH) —. be able to.

  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 can have one or more structural units derived from an unsaturated carboxylic acid monomer. 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.

  Although the polymer of the present invention has an acid group (for example, a carboxylic acid (salt) group contained in a structural unit derived from an unsaturated carboxylic acid monomer), the acid contained in the polymer of the present invention It is preferable that 50-100 mol% is an unneutralized acid group (namely, acid type acid group) with respect to 100 mol% of groups. More preferably, it is 55-100 mol%, More preferably, it is 60-100 mol%. By being the said range, it exists in the tendency for the intensity | strength of the to-be-bonded body at the time of using the binder of this invention for the binder of glass fiber or powder glass to improve.

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-hydroxypropane sulfonic acid, (meth) allyl sulfonic acid, isoprene sulfonic acid, vinyl sulfonic acid, styrene sulfonic acid, and these. Sulfonic acid monomers such as salts of vinyl; 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 N- Bini Monomer; 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) allyl alcohol, and isoprenol; polyalkylene glycol monomers having a structure in which an alkylene oxide is added to the unsaturated alcohol monomer; butyl (meth) acrylate (Meth) acrylic acid alkyl ester monomers such as 2-ethylhexyl (meth) acrylate and dodecyl (meth) acrylate; unsaturated glycidyl compounds such as (meth) allyl glycidyl ether and glycidyl (meth) acrylate; Allyloxy-3-butoxypropane- -Monomers having a structure in which an alcohol is added to an unsaturated glycidyl compound such as ol; vinyl aryl monomers such as styrene, indene and vinylaniline; alkenes such as isobutylene and octene; vinyl acetate and vinyl propionate And the like. Moreover, when using the said other monomer, 1 type may be used independently or 2 or more types may be used together.
Examples of the salt include the same salts as those in the unsaturated carboxylic acid monomer.

In the present invention, the structural unit derived from the other monomer is a structural unit formed by polymerization of the other monomer, specifically, the carbon-carbon double bond of the other monomer. Is a structure with a single bond. For example, when 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 can have one or more structural units derived from other monomers.

  Each structural unit in the polymer of the present invention may be present randomly or may exist 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 1,500 or more and 15,000 or less, and more preferably 2,000 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 | polymerizing the monomer represented by the said General formula (1), an unsaturated carboxylic acid-type monomer, and another monomer as needed. It is preferable. In the above step, the monomer represented by the general formula (1), the unsaturated carboxylic acid monomer, and other monomers (hereinafter, also referred to as “all monomers”). The monomer represented by the general formula (1) is preferably 5 to 40 mol%, more preferably 10 to 35 mol%, more preferably 15 to 15 mol% with respect to the total use amount of 100 mol%. More preferably, it is 30 mol%. It is preferable that the usage-amount of the unsaturated carboxylic acid-type monomer in the said process is 60-95 mol% with respect to 100 mol% of the total usage-amount of all the monomers, and is 65-90 mol%. Is more preferable, and it is further more preferable that it is 70-85 mol%. The amount of other monomers used in the above process is preferably 0 to 35 mol%, more preferably 0 to 25 mol%, based on 100 mol% of the total amount used of all monomers. Preferably, it is 0-15 mol%, and it is still more preferable.

  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.

In the polymerization step, a polymerization initiator is preferably used when the polymerization is performed. Examples of 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 , 2,2′-azobis [2- (2-imidazolin-2-yl) propane], 2,2′-azobis (1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride, etc. An organic peroxide such as benzoyl peroxide, lauroyl peroxide, peracetic acid, di-t-butyl peroxide, cumene hydroperoxide and the like is preferable. Of these polymerization initiators, hydrogen peroxide and persulfate are preferable, and persulfate is most preferable. These polymerization initiators may be used alone or in the form of a mixture of two or more.
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.

In the polymerization step, a chain transfer agent may be used as necessary. Specific examples of 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 chain transfer agent may be used alone or in the form of a mixture of two or more.
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.

In the polymerization step, heavy metal ions may be used for the purpose of promoting the reaction. In the present invention, the heavy metal ion means a metal ion having a specific gravity of 4 g / cm 3 or more. By using heavy metal ions, the amount of polymerization initiator used can be reduced. 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. Examples of the heavy metal compound 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, and more preferably 0 ppm or more and 50 ppm or less with respect to the total amount of the polymerization reaction solution.

The polymerization step preferably uses a solvent. 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. Kind. These solvents may be used alone or in the form of a mixture of two or more.
As a usage-amount of a solvent, 40-200 mass% is preferable with respect to 100 mass% of monomers. 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 polymerization step is usually preferably performed at 0 ° C. or higher, and preferably 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. For example, 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 | maintain and you may carry out temperature fluctuation (temperature rise or temperature fall) with time during a polymerization reaction according to dripping methods, such as a monomer component and an initiator.

  The polymerization time in the polymerization step is not particularly limited, but is preferably 30 to 420 minutes, more preferably 45 to 390 minutes, still more preferably 60 to 360 minutes, and most preferably 90 to 300 minutes. . In the present invention, “polymerization time” represents the time during which a monomer is added unless otherwise specified.

  In the polymerization step, the neutralization rate of the acid groups contained in the monomer during polymerization (number of moles of neutralized acid groups / (number of moles of neutralized acid groups + unneutralized acid groups) Is preferably 0% or more and 30% or less, and more preferably 0% or more and 20% or less.

  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.

  Although the polymer of this invention is arbitrary, you may manufacture including processes other than the said polymerization process. 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.

[Nonionic polyhydric alcohol]
The binder of the present invention contains a nonionic polyhydric alcohol as an essential component. The nonionic property means that the molecule does not have an anionic group such as a carboxylic acid group, a sulfonic acid group or a phosphoric acid group, or a cationic group such as an amino group or a quaternary amine group. When the binder of the present invention contains a nonionic polyhydric alcohol, the strength of the bonded body of glass fiber or powder glass can be improved.
The nonionic polyhydric alcohol has the main role of acting as a crosslinking agent for the polymer of the present invention in the binder of the present invention. However, since the polyhydric alcohol is nonionic, the binding of the present invention. The storage stability tends to be improved by moderately interacting with the polymer of the present invention at the time of storage or crosslinking reaction of the agent, and the strength of the glass fiber or powder glass binder tends to be significantly improved. It is thought that it contributes to a certain thing.

  Examples of the polyhydric alcohol include divalent alcohols such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, and polyalkylene glycol (alcohol having two hydroxyl groups in the molecule); glycerin, polyglycerin, erythritol, and xylitol. And trivalent or higher alcohols such as sorbitol (alcohol having three or more hydroxyl groups in the molecule). A compound in which a part of hydroxyl groups of the trivalent or higher alcohol is esterified can also be used as the polyhydric alcohol as long as it has two or more hydroxyl groups in the molecule. The binder of the present invention may contain only one kind of polyhydric alcohol or two or more kinds. The polyhydric alcohol is preferably a dihydric alcohol, particularly preferably ethylene glycol or propylene glycol, because the strength of the glass fiber or powder glass combination tends to be further improved.

The polyhydric alcohol is preferably a water-soluble polyhydric alcohol. Here, water-soluble means that the solubility in water (g number dissolved in 100 g of water) at 20 ° C. is 3 g / 100 g-H ₂ O or more.

  The polyhydric alcohol has a tendency to further improve the strength of the bonded body of glass fiber or powdered glass. Therefore, the molecular weight is preferably 1000 or less, more preferably 500 or less, and 300 or less. Is particularly preferred.

[Binder of the present invention]
The binder of the present invention essentially contains a nonionic polyhydric alcohol and the polymer of the present invention.
The binder of the present invention may contain 1 to 50 mol% of polyhydric alcohol 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. Preferably, it contains 3 to 45 mol%, more preferably 5 to 40 mol%. By containing in the said range, it exists in the tendency which the intensity | strength of the coupling | bonding body of glass fiber or powder glass improves more.
The binder of the present invention preferably contains 50 to 99 mass%, more preferably 55 to 97 mass%, and more preferably 60 to 95 mass% of the polymer of the present invention with respect to 100 mass% of the binder. Further preferred. By containing in the said range, it exists in the tendency which the intensity | strength of the coupling | bonding body of glass fiber or powder glass improves more.

  The binder of the present invention may contain only the nonionic polyhydric alcohol and the polymer of the present invention. However, when the binder of the present invention is used as a binder for glass fibers or powdered glass, it is to be bonded. Since the mechanical strength of the body tends to be further improved, a phosphorus-containing compound may be included. The phosphorus compound is considered to have the 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 the present invention contains a phosphorus-containing compound, these may contain one kind or two or more kinds. 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 to 20% by mass, more preferably 0 with respect to 100% by mass of the polymer (the polymer of the present invention) contained in the binder of the present invention. 0.1 to 10% by mass, more preferably 0.5 to 7% by 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. The binder of this invention may contain 0-20 mass% of hardening accelerators other than the said phosphorus containing compound, for example.

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 binder of the present invention preferably contains 0 to 75% by mass, more preferably 30 to 70% by mass, and 30 to 60% by mass of the solvent with respect to 100% by mass of the binder of the present invention. Further preferred.

[Use of the binder of the present invention]
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.

[Method of using the binder of the present invention]
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. When 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) ) It is preferable to carry out by spraying the binder of the present invention on the substance to be bound. In the case where the binder of the present invention does not contain a solvent, the binder of the present invention may be heated and melted to be brought into contact with the substance to be bonded. Since it tends to be easy, it is preferable to carry out the above (i) or (ii) by dissolving in a solvent.
Among these, since it is easy to adjust the addition amount of the binder of the present invention to the bound substance, the above (i
i) is preferred.
In the step of bringing the binder of the present invention into contact with 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. It is preferably 1 to 40% by mass, more preferably 1 to 30% by mass, and further preferably 1 to 15% by mass. When the binder of the present invention is used in the above range, the mechanical strength of the bonded body tends to be improved.
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 above step (ii), it means the amount of the binder that actually adheres to the bound substance after being sprayed on the bound substance.

The treatment with the binder of the present invention preferably includes a step of heat-treating the bonded body obtained in the step of contacting. By performing the heat treatment, 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 120 to 350 ° C, and further preferably 150 to 300 ° C.

When the binder of this invention contains a solvent, the process by the binder of this invention may include the process of drying the to-be-coupled body obtained at the process made to contact. The drying step may be performed under normal pressure or under reduced pressure. When drying is performed by heating, the conditions are the same as those in the heat treatment step.

  When the binder of this invention contains a solvent, the process by the binder of this invention may include the process of curing the to-be-coupled body obtained at the process made to contact.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples.

<Measurement conditions of weight average molecular weight>
Device: Tosoh HLC-8320GPC
Detector: RI
Column: Tosoh TSK-GEL G3000PWXL
Column temperature: 35 ° C
Flow rate: 0.5 ml / min
Calibration curve: POLY SODIUM ACRYLATE STANDARD
Eluent: A solution obtained by diluting a mixture of sodium dihydrogen phosphate 12 hydrate / disodium hydrogen phosphate dihydrate (34.5 g / 46.2 g) to 5000 g with pure water.

<Method for measuring solid content of binder>
The binder was allowed to dry for 60 minutes in an oven heated to 130 ° C. The solid content (%) was calculated from the weight change before and after drying.

<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.
Apparatus: 762 Interface manufactured by Metrohm
Detector: 732 IC Detector manufactured by Metrohm
Ion analysis method: Suppressor method Column: Shodex IC SI-90 4E
Guard column: Shodex SI-90 G
Column temperature: 40 ° C
Eluent: NaHCO ₃ water (2 g diluted to 2000 g with water)
Flow rate: 1.0 mL / min.

<Creation of test piece for cured binder>
(I) Add water to the binder to adjust the solid content 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 solid content is 7.5% of the weight of the glass beads and mix thoroughly. To do.
(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. Get a piece.

<Mechanical strength of specimen>
According to JISK7171, the bending strength was measured at a test speed of 2 mm / min. The bending strength of three test pieces was measured, and the average value was calculated.

<Example 1>
In a 2.5-liter SUS separable flask equipped with a reflux condenser, a stirrer (paddle blade), and a thermometer, 155.1 g of pure water was charged (initial charge), and the temperature was raised to the boiling point under stirring. Next, 458.1 g (that is, 5.09 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 (hereinafter referred to as “below”). 330.9 g (referred to as “50% HEMA”) (ie 1.27 mol) for 180 minutes, 15% by weight sodium persulfate aqueous solution (hereinafter referred to as “15% NaPS”) 31.9 g for 195 minutes, 45% by weight 21.9 g of sodium phosphate aqueous solution (hereinafter referred to as “45% SHP”) was dropped from the tip nozzle through two separate feed paths at 18 minutes followed by 85.9 g at a feed rate of 162 minutes. 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. After the completion of the polymerization, 42.0 g of pure water, 31.6 g of ethylene glycol (that is, 0.51 mol, 10 mol% based on the carboxyl group), and 42.6 g of 45% SHP are added to the reaction solution, whereby the binder of the present invention is added. (1) was obtained. The aqueous solution had a solid content value of 53.0%, a weight average molecular weight (Mw) of 3500, and an SHP content of 4.2% by mass with respect to 100% by mass of the polymer. It was 19.2 MPa when the mechanical strength of the test piece created by the above-mentioned method was evaluated.

<Comparative Example 1>
In a 2.5 liter SUS separable flask equipped with a reflux condenser, a stirrer (paddle blade), and a thermometer, 163.5 g of pure water was charged (initial charge), and the temperature was raised to the boiling point under stirring. Next, under stirring, in the polymerization reaction system at the boiling point reflux state, 482.9 g (ie 5.37 mol) of 80% AA is 180 minutes, 348.8 g of 50% HEMA (ie 1.34 mol) is 180 minutes, and 33.6 g of 15% NaPS is 195. During the period, 23.1 g of 45% SHP was added for 18 minutes, and then 90.5 g was dropped from the tip nozzle through separate supply paths at 162 supply steps for 162 minutes. 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. After completion of the polymerization, 15.1 g of pure water and 42.5 g of 45% SHP were added to the reaction solution to obtain a comparative binder (1). The aqueous solution had a solid content value of 53.0%, a weight average molecular weight (Mw) of 3500, and an SHP content of 4.2% by mass with respect to 100% by mass of the polymer. It was 16.4 MPa when the intensity | strength of the test piece created by the above-mentioned method was evaluated.

<Comparative example 2>
In a 2.5-liter SUS separable flask equipped with a reflux condenser, a stirrer (paddle blade), and a thermometer, 293.9 g of pure water was charged (initial charge), and the temperature was raised to the boiling point with stirring. Then, under stirring, 80% AA 775.5 g (ie, 8.62 mol) is added for 180 minutes, 15% NaPS 41.0 g for 185 minutes, and 45% SHP 14.6 g for 18 minutes in the polymerization reaction system at the boiling point reflux state. .4 g was dropped from the tip nozzle through separate feed paths at 162 minutes and at two feed rates. 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. After the completion of the polymerization, 146.0 g of pure water, 107.0 g of ethylene glycol (that is, 1.72 mol, 20 mol% with respect to the carboxyl group), and 63.6 g of 45% SHP were added to the reaction solution, whereby a comparative binder (2 ) The aqueous solution had a solid content value of 53.0%, a weight average molecular weight (Mw) of 6100, and an SHP content of 5.3% by mass with respect to 100% by mass of the polymer. When the strength of the test piece prepared by the above-described method was evaluated, it was 10.5 MPa.

  Table 1 summarizes the evaluation results of the test pieces.

  From the results shown in Table 1, it is clear that the cured product of glass beads treated with the binder of the present invention has better strength than the cured product of glass beads treated with the conventional binder. It was.

Claims (3)

A binder comprising (i) a polymer having a hydroxyl group, and (ii) 1 to 50 mol% of a nonionic polyhydric alcohol with respect to 100 mol% of an acid group contained in the polymer, The coalescence is a structural unit derived from a monomer represented by the following general formula (1), a structural unit derived from an unsaturated carboxylic acid monomer, and a monomer represented by the general formula (1) And a structural unit derived from another monomer that is not any monomer of the unsaturated carboxylic acid monomer,
The said polymer is a binder containing the structural unit derived from the said other monomer 0 mol% or more and 35 mol% or less with respect to 100 mol% of structural units derived from all the monomers.

In the general formula (1), R ₁ represents a hydrogen atom or a methyl group, and R ₂ represents an organic group having 2 to 20 carbon atoms.   The polymer has a structural unit derived from the 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. The binder according to 1.   The binder according to claim 1 or 2 for inorganic fibers, inorganic particles, or organic particles.