JP2015067634A - Novel binder - Google Patents

Abstract

An object of the present invention is to provide a binder that exhibits an excellent binding force of glass fiber or powdered glass. A binder containing a polymer having an acid group, the polymer containing a structural unit derived from a monomer represented by the following general formula (1). In the above general formula (1), n represents a number of 1 to 5, and M independently represents a hydrogen atom, a metal atom, an ammonium group, or an organic ammonium group. [Selection figure] None

Description

  The present invention relates to a binder comprising a polymer having an acid group. In more detail, it is related with the binder containing the polymer which has an acid group useful as a binder of glass fiber or powder glass.

A heat-resistant laminated body formed by attaching a binder to glass fiber or the like is widely used as a heat insulating material for a residence, a warehouse, an apparatus or an appliance.
For example, in Patent Document 1, A) 5-100% by weight consists of an ethylenically unsaturated acid anhydride or an ethylenically unsaturated dicarboxylic acid whose carboxylic acid group can form an acid anhydride group, by radical polymerization. Formaldehyde-free aqueous linkage containing the resulting polymer and B) an alkanolamine having at least two hydroxyl groups, less than 1.5% by weight of a phosphorus-containing reaction accelerator relative to the sum of A) and B) Agents are disclosed. It is disclosed that the binder can be used as a binder for glass fiber fleece.

Special Table 2000-506940

  As described above, various binders such as glass fibers have been proposed, but from the demand for higher functionality of heat-resistant laminates, binders with better bonding power of glass fibers and powdered glass are desired. Is the actual situation.

  The present invention has been made by paying attention to the above-described circumstances, and an object thereof is to provide a binder that exhibits excellent glass fiber or powder glass binding strength.

  As a result of intensive studies, the present inventors have found that the binder contains a predetermined polymer, whereby the bonding strength of glass fibers and powdered glass is superior to conventional ones, and based on these findings. The present invention has been completed.

  That is, this invention is a binder containing the polymer which has an acid group, Comprising: This polymer is a binder containing the structural unit derived from the monomer represented by following General formula (1).

In the said General formula (1), n represents the number of 1-5, M represents a hydrogen atom, a metal atom, an ammonium group, and an organic ammonium group each independently.

The binder of the present invention exhibits excellent glass fiber or powder glass binding strength. Therefore, the binder of the present invention can be usefully used, for example, as a binder for glass fibers or powdered glass.

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 acid group]
The binder of this invention contains the polymer which has an acid group, and this polymer contains the structural unit derived from the monomer represented by the said 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 said General formula (1), although n represents the number of 1-5, Preferably it is 1 or 2. When n is 1, the monomer represented by the general formula (1) is itaconic acid (salt), and when n is 2, the monomer represented by the general formula (1) is methylene glutar Acid (salt).

In the general formula (1), M represents a hydrogen atom, a metal atom, an ammonium group, or an organic ammonium group. Examples of the metal atom include alkali metal atoms such as sodium atom and potassium atom; alkaline earth metal atoms such as calcium atom and magnesium atom; transition metal atoms such as iron atom and aluminum atom; Examples of the organic ammonium group include alkylamines such as methylamine and n-butylamine; alkanolamines such as monoethanolamine, diethanolamine, triethanolamine and dipropanolamine; polyamines such as ethylenediamine and diethylenetriamine; Illustrated. For example, in the case of ammonium residue M is derived from diethanolamine, diethanolamine base monomer acid represented by the general formula ^{(1), -C (= O} ) O - N + H 2 (CH 2 CH 2 OH) ₂ . The organic ammonium group is a group formed by neutralizing an organic amine with an acid.

  The polymer of the present invention has an acid group as described above, but 50 to 90 mol% is an unneutralized acid group (i.e., acid type) with respect to 100 mol% of the acid group contained in the polymer of the present invention. Acid group). More preferably, it is 55-85 mol%, More preferably, it is 60-80 mol%. By being within the above range, a machine of a bonded body (referred to as glass fiber or powder glass treated with the binder of the present invention) when the binder of the present invention is used as a binder for glass fiber or powdered glass Strength tends to improve.

  As will be described later, it is preferable that some of the acid groups contained in the polymer of the present invention are neutralized with an amine having at least two hydroxyl groups per molecule. Thereby, it exists in the tendency for the mechanical strength of the to-be-joined body at the time of using the binder of this invention for the binder of glass fiber or powder glass to improve. It is preferable that 10-50 mol% is neutralized with an amine having at least two hydroxyl groups per molecule, more preferably 15-45 mol, per 100 mol% of acid groups contained in the polymer of the present invention. %, And more preferably 20 to 40 mol%.

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)”.
Specifically, the “structural unit derived from the monomer represented by the general formula (1)” means that the carbon-carbon double bond of the monomer represented by the general formula (1) is carbon. The structural unit which became the single bond of carbon can be represented by following General formula (2).

In the said General formula (2), n represents the number of 1-5, M represents a hydrogen atom, a metal atom, an ammonium group, and an organic ammonium group each independently. The left and right asterisk marks in the general formula (2) represent atoms to which the structural unit of the general formula (2) is bonded, and are not included in the structural unit of the general formula (2).

  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 100 mol% or less of structural units derived from the monomer represented by the general formula (1) with respect to mol%, and 10 mol% or more and 100 mol% or less. Is more preferable, and it is further more preferable to contain 20 mol% or more and 100 mol% or less. By including in the said range, it exists in the tendency for the mechanical 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 may have a structural unit derived from a monomer other than the monomer represented by the general formula (1) (hereinafter also referred to as “other monomer”). .
The other monomers are not particularly limited, and specifically, unsaturated monomers such as acrylic acid, methacrylic acid, crotonic acid, α-hydroxyacrylic acid, α-hydroxymethylacrylic acid and derivatives thereof. Carboxylic acids and their salts, etc .; unsaturated dicarboxylic acids other than the monomer represented by the general formula (1) such as fumaric acid and maleic acid and their salts (even mono- and di-salts Sulfonic acid monomers such as 3-allyloxy-2-hydroxypropane sulfonic acid, (meth) allyl sulfonic acid, isoprene sulfonic acid, vinyl sulfonic acid, styrene sulfonic acid and salts thereof; vinyl pyridine, vinyl Imidazole, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminopropyl acrylate, aminoethyl Methacrylate, diallylamine, diallyldimethylamine, and amino group-containing monomers such as quaternized compounds and salts thereof; N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-vinyl-N-methylformamide, N -N-vinyl monomers such as vinyl-N-methylacetamide and N-vinyloxazolidone; Amide monomers such as (meth) acrylamide, N, N-dimethylacrylamide and N-isopropylacrylamide; 3- (meth) Unsaturated alcohol monomers such as allyloxy-1,2-dihydroxypropane, 3-allyloxy-1,2-dihydroxypropane, (meth) allyl alcohol, and isoprenol; alkylene oxide added to the above unsaturated alcohol monomers Polyalkylene glycol having the structure Monomers: (meth) acrylic acid alkyl ester monomers such as butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, etc .; vinylaryl monomer such as styrene, indene, vinylaniline Alkenes such as isobutylene and octene; vinyl carboxylates such as vinyl acetate and vinyl propionate; Moreover, said other monomer may be used individually by 1 type, or may use 2 or more types together. Examples of the salt include metal salts, ammonium salts, and organic amine salts.

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 ═CH ₂ COOC ₄ H ₉ ), the structural unit derived from the other monomer is —CH ₂ —CH ₂ (COOC ₄ H ₉ ). -, Can be represented by

  The polymer of the present invention preferably has 0 to 95 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 90 mol% or less, and more preferably has 0 mol% or more and 80 mol% or less.

  When the polymer of the present invention is a copolymer, each structural unit may be in a block shape, a random shape, or may exist regularly.

The weight average molecular weight of the polymer of the present invention is not particularly limited, but is preferably 1,000 or more and 500,000 or less, preferably 1,500 or more, preferably 100,000 or less, and 2,000 or more. 20,000 or less is more preferable.
In addition, the said weight average molecular weight can be measured with the measuring method mentioned later.

  The polymer of the present invention is preferably produced including a step of polymerizing the monomer represented by the general formula (1) and, if necessary, other monomers. In the above step, 5% of the monomer represented by the general formula (1) is used with respect to 100 mol% of the total amount of the monomer represented by the general formula (1) and the other monomer. It is preferable to set it as -100 mol%, It is more preferable to set it as 10-100 mol%, It is more preferable to set it as 20-100 mol%. On the other hand, the amount of the other monomer used in the above step is 0 to 95 mol with respect to 100 mol% of the total amount of the monomer represented by the general formula (1) and the other monomer. %, More preferably 0 to 90 mol%, and still more preferably 0 to 80 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.

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 0.1 g or more and 10 g or less with respect to 1 mol of the monomer (the monomer represented by the general formula (1) and other monomers) used It is preferably 0.1 g or more and 7 g or less, more preferably 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 the chain transfer agent 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 0 g or more and 15 g or less with respect to 1 mol of the monomer (monomer represented by the general formula (1) and other monomers) used. Is preferably 1 g or more and 10 g or less, more preferably 1 g or more and 7 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 10% or less, and more preferably 0% or more and 5% 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.

[Binder of the present invention]
The binder of the present invention may contain only the polymer of the present invention, but 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 fibers or powdered glass. Therefore, it is preferable to include a crosslinking agent. Examples of the crosslinking agent include compounds having at least two hydroxyl groups and / or amino groups in one molecule. As such compounds, polyols such as ethylene glycol, diethylene glycol, polyethylene glycol, glycerin and sorbitol; polyamines such as ethylenediamine, diethylenetriamine and hexamethylenediamine; one hydroxyl group and one amino group per molecule such as monoethanolamine and monopropanolamine Examples include compounds having a group; amines having at least two hydroxyl groups in one molecule such as diethanolamine, dipropanolamine, and triethanolamine. Among these, it is preferable to contain an amine having at least two hydroxyl groups per molecule.
The binder of the present invention preferably contains a crosslinking agent in an amount of 10 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. It is more preferably 15 to 45 mol%, and particularly preferably 20 to 40 mol%.

As described above, the binder of the present invention preferably contains an amine having at least two hydroxyl groups per molecule. Thereby, when the binder of this invention is used for the binder of glass fiber or powder glass, it exists in the tendency which the mechanical strength of the to-be-bonded body improves notably.
In the binder of the present invention, the amine having at least two hydroxyl groups per molecule may or may not be neutralized with an acidic substance. When the binder of the present invention is used as a binder for glass fiber or powdered glass, the curing reaction is likely to proceed. Therefore, some of the acid groups contained in the polymer of the present invention contain at least two molecules per one molecule. It is preferably neutralized with an amine having a hydroxyl group.

Since the binder of the present invention tends to improve the mechanical strength of the bonded body when the binder of the present invention is used as a binder for glass fibers or powdered glass, it preferably contains a curing accelerator.
As curing accelerators, proton acids [phosphoric acid compounds (phosphoric acid, phosphorous acid, hypophosphorous acid, phosphoric acid dihydride, polyphosphoric acid, alkylphosphinic acid, etc.), sulfuric acid, carboxylic acid, carbonic acid, etc.], And salts thereof [metal (alkali metal, alkaline earth metal, transition metal, 2B group, 4A group, 4B group, 5B group, etc.) salt, ammonium salt, etc.], metal (above) oxide, chloride , Hydroxides, alkoxides, and the like. These may be used alone or in combination of two or more.
The binder of the present invention preferably contains the curing accelerator in an amount of 0.1 to 20% by mass with respect to 100% by mass of the polymer (the polymer of the present invention) contained in the binder of the present invention. It is more preferable to contain 0.5-10 mass%, and it is most preferable to contain 1.6-7 mass%. 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.

  The binder of the present invention preferably contains 25 to 100% by mass, more preferably 30 to 70% by mass, and 40 to 70% by mass of the polymer of the present invention with respect to 100% by mass of the binder. 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, cotton, 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. When the binder of the present invention does not contain a solvent, the binder of the present invention may be heated and melted to come into contact with the substance to be bonded. However, the strength of the processed material (bonded substance) is uneven. Since it tends to be easy, it is preferable to carry out the above (i) or (ii) by dissolving in a solvent.
Among them, the above (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.
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.

When the binder of this invention contains a crosslinking agent, it is preferable that the process by the binder of this invention includes the process of heat-processing the to-be-bonded body obtained at the process made to contact. By performing the heat treatment, the crosslinking reaction is promoted and the mechanical 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 G4000PWXL, G3000PWXL
Column temperature: 40 ° 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 polymer>
The polymer composition (polymer composition 0.3 g + water 1.0 g) was left to dry in an oven heated to 150 ° C. for 20 minutes. The solid content (%) was calculated from the weight change before and after drying.

<Creating a cured product specimen with a binder>
(I) The aqueous polymer solution is adjusted to a solid content of 11%.
(Ii) Add the polymer aqueous solution obtained in (i) above to glass beads having a particle size of 0.35 to 0.50 mm so that the polymer solid content is 3% of the mass of the glass beads and mix thoroughly. To do.
(Iii) The mixture 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 110 ° C. for 45 minutes, transferred to a desiccator, and cooled for 30 minutes.
(Iv) After cooling, after heat treatment in an oven at 190 ° C. for 30 minutes, the sample is transferred to a desiccator and cooled for 30 minutes to obtain a test piece.

<Mechanical strength of specimen>
According to JIS K7171, 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>
A 1-liter separable flask equipped with a reflux condenser, a stirrer (paddle blade), and a thermometer was charged with 53.7 g of pure water (initial charge), and the temperature was raised to the boiling point with stirring. Next, 45 g (that is, 0.5 mol) of an 80% by mass acrylic acid aqueous 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 216.8 g of a 30% by mass itaconic acid aqueous solution. (Ie 0.5 mol) for 180 minutes, 15% by weight sodium persulfate aqueous solution (hereinafter referred to as “15% NaPS”) 5.01 g for 195 minutes, 45% by weight sodium hypophosphite aqueous solution (hereinafter “45% 1.1 g (referred to as “SHP”) (0.5 g / mol in terms of monomer charge) for 18 minutes, followed by 5.3 g for 192 minutes at two feed rates, each with separate feed routes It dripped from the tip nozzle through. 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, 11.7 g of 45% SHP was added to the reaction solution, and then 65.1 g (ie 0.5 mol) of an 80% by mass diethanolamine aqueous solution was gradually added dropwise to the reaction solution with stirring while the reaction solution was allowed to cool. Neutralization was performed (binder (1) of the present invention). The binder had a solid content value of 36.9% and a weight average molecular weight (Mw) of 5800. It was 21.46N when the intensity | strength of the test piece created by the above-mentioned method was evaluated.

<Example 2>
A 0.5 liter separable flask equipped with a reflux condenser, a stirrer (paddle blade), and a thermometer was charged with 123.7 g of pure water and 72.0 g of 2-methyleneglutaric acid (that is, 0.5 mol) (initial) The temperature was raised to 80 ° C. with stirring. Next, under stirring, 15 g NaPS 10.0 g for 60 minutes and 35 mass% sodium bisulfite aqueous solution (hereinafter referred to as “35% SBS”) 2.9 g for 60 minutes are separately provided in the polymerization reaction system at the boiling point reflux state. It dropped from the tip nozzle through the supply path. The dropping of each component was continuously performed at a constant dropping rate. After completion of the dropwise addition, the reaction solution was kept at 80 ° C. (ripening) for another 60 minutes to complete the polymerization. After completion of the polymerization, 9.1 g of 45% SHP was added to the reaction solution, and then 43.4 g of an 80% by mass diethanolamine aqueous solution (that is, 0.33 mol) was gradually added dropwise to the reaction solution with stirring while the reaction solution was allowed to cool. Neutralization was performed (binder (2) of the present invention). The binder had a solid content value of 41.7% and a weight average molecular weight (Mw) of 10,600. It was 19.42N when the intensity | 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, 231.8 g of pure water was charged (initial charge), and the temperature was raised to the boiling point with stirring. Next, under stirring, 611.8 g of 80% AA (that is, 6.8 mol) was added to the boiling point reflux polymerization reaction system for 180 minutes, and 32.3 g of 15% NaPS (0.71 g / mol when converted to the amount of monomer charged). 185 minutes, 45% SHP 11.6 g (0.77 g / mol in terms of monomer charge) for 18 minutes, followed by 46.1 g for 162 minutes, with two stages of supply. It dropped from the tip nozzle through the path. 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 kept at the boiling point reflux state (aged) for another 10 minutes to complete the polymerization. After completion of the polymerization, 187.4 g of pure water and 81.3 g of 45% SHP were added to the reaction solution, and then 297.8 g of an 80% by mass diethanolamine aqueous solution (33.3 mol% neutralized content of acrylic acid) while allowing the reaction solution to cool. ) Was gradually added dropwise to the reaction solution with stirring to effect neutralization (comparative binder (1)). The binder had a solid content value of 51.2% and a weight average molecular weight (Mw) of 6000. It was 16.12N when the intensity | strength of the test piece created by the above-mentioned method was evaluated.

<Comparative Example 2>
A 2.5-liter SUS separable flask equipped with a reflux condenser, a stirrer (paddle blade), and a thermometer was charged with 251.5 g of pure water (initial charge), and heated to the boiling point under stirring. Subsequently, 80% AA 624.0 g (that is, 6.9 mol) is added to the polymerization reaction system at the boiling point reflux state for 180 minutes with stirring, and 34.7 g of 15% NaPS (0.75 g / mol in terms of monomer input). For 195 minutes, 45% SHP 9.2 g (0.6 g / mol in terms of monomer charge) for 18 minutes, followed by 43.6 g for 192 minutes at a feed rate of two stages, 180. 2 g was dropped from the tip nozzle through a separate supply path for 88 minutes after 92 minutes from the start of polymerization. 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, 53.0 g of 45% SHP was added to the reaction solution, and then the reaction solution was allowed to cool, and 303.7 g of an 80% by mass diethanolamine aqueous solution (33.3 mol% neutralized portion of acrylic acid) was stirred and reacted. Neutralization was performed by gradually dropping into the solution (comparative binder (2)). The binder had a solid content value of 51.3% and a weight average molecular weight (Mw) of 8200. It was 17.51 N when the intensity | strength of the test piece created by the above-mentioned method was evaluated.
<Comparative Example 3>
A SUS separable flask having a capacity of 2.5 liters equipped with a reflux condenser, a stirrer (paddle blade), and a thermometer was charged with 179.5 g of pure water (initial charge), and heated to the boiling point with stirring. Then, under stirring, 80% AA 473.7 g (that is, 5.3 mol) is added to the boiling point reflux polymerization reaction system for 180 minutes, and 15% NaPS 26.4 g (0.75 g / mol in terms of monomer input) 195 minutes, 45% SHP 5.8 g (0.5 g / mol in terms of monomer input) for 18 minutes, followed by 28.1 g for 192 minutes at a feed rate of two stages, 160. 3 g was dropped from the tip nozzle through a separate supply path for 88 minutes after 92 minutes from the start of polymerization. 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 polymerization, 61.7 g of 45% SHP and 23.1 g of pure water were added to the reaction solution, and then the reaction solution was allowed to cool and 228.3 g of an 80% by mass diethanolamine aqueous solution (33.3 mol% neutralized content of acrylic acid). ) Was gradually added dropwise to the reaction solution under stirring to effect neutralization (comparative binder (3)). The binder had a solid content value of 49.7% and a weight average molecular weight (Mw) of 10,500. It was 18.25N when the strength of the test piece created by the above-mentioned method was evaluated.

<Comparative Example 4>
In a 2.5 liter SUS separable flask equipped with a reflux condenser, a stirrer (paddle blade), and a thermometer, 297.4 g of pure water and 192.2 g of maleic anhydride (hereinafter referred to as “MA”) (that is, 2.0 mol), 807.8% by weight diethanolamine aqueous solution 257.8 g (that is, 2.0 mol) was charged (initial charge), and the temperature was raised to the boiling point with stirring. Next, under stirring, in the polymerization reaction system at the boiling point reflux state, 176.5 g of 80% AA (that is, 2.0 mol) is added for 265 minutes, 56.4 g of 15% NaPS is supplied for 270 minutes, 35 mass% hydrogen peroxide (hereinafter “35% HP”). 47.1 g of pure water and 94.0 g of pure water were dropped from the tip nozzle through separate supply paths for 150 minutes after the start of polymerization. The dropping of each component was continuously performed at a constant dropping rate. After completion of the dropwise addition of 80% AA, the reaction solution was kept at the boiling point reflux state (aged) for an additional 55 minutes to complete the polymerization. After the completion of the polymerization, 14.5 g of 35% SBS and 64.1 g of 45% SHP were added to the reaction solution (comparative binder (4)). The binder had a solid content value of 45.5% and a weight average molecular weight (Mw) of 1500. It was 18.46N when the intensity | strength of the test piece created by the above-mentioned method was evaluated.

  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 superior mechanical strength compared to the cured product of glass beads treated with the conventional binder. became. Therefore, it became clear that the binder of this invention can be used usefully, for example as a binder of glass fiber or powder glass.

Claims (1)

A binder comprising a polymer having an acid group, wherein the polymer comprises a structural unit derived from a monomer represented by the following general formula (1).

In the said General formula (1), n represents the number of 1-5, M represents a hydrogen atom, a metal atom, an ammonium group, and an organic ammonium group each independently.