JP2017031393A - Aqueous binder for mineral fibers - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous binder which provides a mineral fiber laminate having excellent adhesivity of mineral fibers such as glass fibers and the like, heat-resistant laminate materials.SOLUTION: Provided are: an aqueous binder for mineral fibers comprising a copolymer containing an unsaturated (poly)carboxylic acid (anhydride) and an alkyl (C2-24) (meth)acrylate as constituent monomers, a crosslinking agent, and water, where a weight average molecular weight of the copolymer is 5,000 or more and less than 20,000; a mineral fiber laminate to which a cured material of the aqueous binder is adhered; and a method for producing a mineral fiber laminate, comprising heating and molding a mineral fiber laminate to which the aqueous binder is adhered.SELECTED DRAWING: None

Description

  The present invention relates to an aqueous binder for mineral fibers. More specifically, the present invention relates to an aqueous binder which is excellent in adhesiveness of mineral fibers such as glass fibers of a heat resistant laminate material and does not contain formaldehyde, and a mineral fiber laminate using the same.

  Conventionally, a mineral fiber laminate having heat resistance is composed of mineral fibers such as glass wool and rock wool, and is manufactured by molding the mineral fibers to which a binder is attached into a mat shape or the like by mechanical means. Widely used as a heat insulating material for various devices. As the binder, an aqueous binder made of a phenol resin, which is a condensate of a phenol compound and formaldehyde, has been conventionally used. However, the binder usually contains formaldehyde, and formaldehyde is not contained in a laminate using this binder. Due to the problem of being released into the environment, improved binders that do not contain formaldehyde have been proposed (see, for example, Patent Documents 1 and 2).

JP 2007-9206 A JP 2005-68399 A

However, the binder of Patent Document 1 is a composition containing an aqueous solution of an oligomer or co-oligomer of an ethylenically unsaturated carboxylic acid having a number average molecular weight of 300 to 900 and a polyol, but the adhesiveness of the binder is not sufficient. There wasn't.
Further, the binder of Patent Document 2 includes a polyacid containing at least two carboxylic acid groups, acid anhydride groups or salts thereof, a polyol containing at least two hydroxyl groups, and an alkyl having 5 or more carbon atoms. Although it is a binder made of an emulsion polymer having an ethylenically unsaturated acrylic monomer containing a group as a copolymer unit, since it contains an emulsion polymer, there is a problem that the adhesive is not sufficient because the sprayability of the binder is poor.
An object of the present invention is to provide an aqueous binder that solves the above-described problems and provides a mineral fiber laminate excellent in adhesion of mineral fibers such as glass fibers of a heat-resistant laminate material.

  The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention provides a co-polymer containing an unsaturated (poly) carboxylic acid (anhydride) (a1) and an alkyl (carbon number 2 to 24) ester (a2) of (meth) acrylic acid as constituent monomers. An aqueous binder (X) for mineral fibers comprising a coalescence (A), a crosslinking agent (B), and water, wherein the weight average molecular weight of (A) is 5,000 or more and less than 20,000; A method for producing a mineral fiber laminate in which the mineral fiber laminate to which the cured product of X) is adhered; the mineral fiber laminate to which the aqueous binder is adhered is heated and molded.

The aqueous binder for mineral fibers (X) of the present invention has the following effects.
(1) Excellent adhesion of mineral fibers.
(2) It imparts excellent flexibility to the mineral fiber laminate.
(3) It imparts excellent water resistance to the mineral fiber laminate.

[Copolymer (A)]
The copolymer (A) in the present invention comprises an unsaturated (poly) carboxylic acid (anhydride) (a1) and an alkyl (carbon number 2 to 24) ester (a2) of (meth) acrylic acid. Contains as a body.

(A1) is a (poly) carboxylic acid (anhydride) having 3 to 30 carbon atoms (hereinafter sometimes abbreviated as C) having one polymerizable unsaturated group. In the present invention, the unsaturated (poly) carboxylic acid (anhydride) means an unsaturated monocarboxylic acid, an unsaturated polycarboxylic acid and / or an unsaturated polycarboxylic anhydride.
Among the (a1), as the unsaturated monocarboxylic acid, aliphatic (C3-24, for example, acrylic acid, methacrylic acid, α-ethylacrylic acid, crotonic acid, isocrotonic acid), alicyclic ring-containing (C6-24, For example, cyclohexene carboxylic acid); unsaturated poly (2-3 or more) carboxylic acid (anhydride) include unsaturated dicarboxylic acid (anhydride) [aliphatic dicarboxylic acid (anhydride) (C4-24, eg malee Acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and anhydrides thereof), alicyclic dicarboxylic acid (anhydride) (C8-24, such as cyclohexene dicarboxylic acid, cycloheptene dicarboxylic acid, bicycloheptene dicarboxylic acid) Acid, methyltetrahydrophthalic acid, and anhydrides thereof)] and the like. (A1) may be used alone or in combination of two or more.
Of the above (a1), acrylic acid, methacrylic acid, maleic acid and maleic anhydride are preferred from the viewpoint of polymerizability with (a2) and the adhesion of mineral fibers, and more preferred are acrylic acid, methacrylic acid, Particularly preferred is acrylic acid.

(A2) is an alkyl (C2-24) ester of (meth) acrylic acid.
The (a2) includes: [ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, (meth) acrylic acid Dodecyl, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, eicosyl (meth) acrylate, 2-decyltetradecyl (meth) acrylate and (meth) ) Tetracosyl acrylate] and the like.
Among the above (a2), from the viewpoint of polymerizability with (a1) and adhesiveness of mineral fibers, the alkyl is preferably C2-20, and more preferably the alkyl is a straight chain of C3-16. Branched alkyl esters, particularly preferred are linear or branched alkyl esters in which the alkyl is C4-14.

  The weight ratio [(a1) / (a2)] of the monomers constituting (A) is preferably 40/60 to 99.99 from the viewpoints of adhesion of mineral fibers, water resistance and flexibility of the mineral fiber laminate. 9 / 0.1, more preferably 60/40 to 99.5 / 0.5, particularly preferably 70/30 to 99/1.

(A) may be a copolymer further comprising an unsaturated monomer (x) other than the monomers (a1) and (a2) as a constituent monomer as long as the effects of the present invention are not impaired.
Examples of the unsaturated monomer (x) include hydroxyalkyl (C1-5) (meth) acrylate, (meth) acrylamide, styrene, allylamine, (meth) acrylonitrile and the like.
The above (x) is preferably 20% by weight or less, more preferably 5% by weight or less, and particularly preferably 1% by weight or less, based on the total weight of (a1) and (a2).

Weight average molecular weight of (A) [hereinafter abbreviated as Mw. The measurement is based on a gel permeation chromatography (GPC) method described later. ] Is 5,000 or more and less than 20,000, preferably 6,000 to 19,000, and more preferably 7,000 to 18,000.
When the Mw is less than 5,000, the strength of the binder cured product is lowered and the adhesion of mineral fibers is deteriorated. On the other hand, when the Mw is 20,000 or more, the flexibility of the mineral fiber laminate is deteriorated.

The GPC measurement conditions for Mw and number average molecular weight (Mn) in the present invention are as follows.
<GPC measurement conditions>
[1] Apparatus: Gel permeation chromatography
[Model number “HLC-8120GPC”, manufactured by Tosoh Corporation]
[2] Column: “TSKgelG6000PWxl”, “TSKgel”
G3000PWxl "[both manufactured by Tosoh Corporation] are connected in series.
[3] Eluent: Methanol / water = 30/70 (volume ratio)
A solution in which 0.5% by weight of sodium acetate is dissolved.
[4] Reference material: polyethylene glycol (hereinafter abbreviated as PEG)
[5] Injection conditions: sample concentration 0.25% by weight, column temperature 40 ° C.

The copolymer (A) can be produced by a known solution polymerization method, and a solution polymerization method containing water is preferable from the viewpoint of productivity. As water content, it is preferable to use 40 mass% or more of water with respect to the total amount of solvent to be used, and it is preferable to use the total amount of the solvent to be used as water.
In the case of using an organic solvent, it may be removed after the polymerization and dissolved in water, or may be used as it is without removing the solvent. Organic solvents that can be used alone or with water include aqueous solvents (water solubility at 25 ° C. of 10 g / 100 g water), for example, ketones (acetone, methyl ethyl ketone (hereinafter abbreviated as MEK), diethyl ketone, etc.), Alcohol (methanol, ethanol, isopropanol, etc.) etc. are mentioned, Acetone, MEK, and isopropanol are preferable from the viewpoint of productivity. One or more organic solvents can be used.
The (A) is usually obtained as a solution (preferably an aqueous solution from an industrial point of view), and the content (% by weight) of (A) in the solution depends on productivity and handling in the production of an aqueous binder in the subsequent step. From the viewpoint of property, it is preferably 5 to 80%, more preferably 10 to 70%, and particularly preferably 20 to 60%.

(A) The polymerization temperature during production is preferably 0 to 200 ° C., more preferably 40 to 150 ° C., from the viewpoint of productivity and molecular weight control of (A).
The polymerization time is preferably 1 to 10 hours, more preferably 2 to 8 hours, from the viewpoint of reducing the residual monomer content in the product and productivity.
The end point of the polymerization reaction can be confirmed by the amount of residual monomer. The amount of residual monomer is preferably 5% or less, more preferably 3% or less, based on the weight of (A), from the viewpoint of adhesion of the binder to mineral fibers. The amount of residual monomer can be measured by gas chromatography.

[Crosslinking agent (B)]
The crosslinking agent (B) in the present invention includes an amine compound (B1) having no hydroxyl group, an amine compound (B2) having one hydroxyl group, a compound (B3) having two or more hydroxyl groups, and a mixture thereof. Can be mentioned.

  The amine compound (B1) not having a hydroxyl group is a poly (2 to 6 or more) amine having C2 or more and Mn 2,000 or less, an aliphatic polyamine (B11), an alicyclic polyamine (B12), a heterocyclic ring. And the formula polyamine (B13), aromatic polyamine (B14) and polyamide polyamine (B15).

  Examples of the aliphatic polyamine (B11) include aliphatic polyamines [C2-6 alkylenediamine (C2-10, for example, ethylenediamine, propylenediamine, hexamethylenediamine (1,6-hexanediamine)), polyalkylene (C2-6). ) Polyamines [C4-10, such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, iminobispropylamine, bis (hexamethylene) triamine]] and their alkyl (C1-4) substituents [ For example, dialkyl (C1-3) aminopropylamine, trimethylhexamethylenediamine, methyliminobispropylamine] and the like, alicyclic or heterocyclic-containing aliphatic polyamine [C5-20, such as 3,9-bis (3-aminopropyl). ) -2,4,8,10-tetraoxaspiro [5,5] undecane] and the like, and aromatic ring-containing aliphatic amines [C6-14, such as xylylenediamine, tetrachloro-p-xylylenediamine] and the like. Can be mentioned.

  Examples of the alicyclic polyamine (B12) include C6-20, such as 1,3-diaminocyclohexane, isophoronediamine, mensendiamine, and 4,4'-methylenedicyclohexanediamine (hydrogenated methylenedianiline).

  Examples of the heterocyclic polyamine (B13) include C4-20, such as piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, 1,4-bis (2-amino-2-methylpropyl) piperazine. .

  Aromatic polyamines (B14) include unsubstituted aromatic polyamines [C6-30, such as 1,2-, 1,3- and 1,4-phenylenediamine, 2,4′- and / or 4,4 ′. -Diphenylmethanediamine, crude diphenylmethanediamine (polyphenylpolymethylenepolyamine)], aromatic polyamines having a nucleus-substituted alkyl group [C1-C4 alkyl groups such as methyl, ethyl, n- and i-propyl, butyl, etc.] [C7- 30, for example 2,4- and 2,6-tolylenediamine, crude tolylenediamine, diethyltolylenediamine, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-bis (o -Toluidine), dianisidine], an aromatic polyamine having an imino group [C7-30, for example, 4,4'- (Methylamino) diphenylmethane, and 1-methyl-2-methylamino-4-aminobenzene] and the like.

  As the polyamide polyamine (B15), a low molecular weight obtained by condensation of a dicarboxylic acid (such as a dimer acid) and an excess (amino group / carboxyl group equivalent ratio of 2 or more) polyamine (such as the above-mentioned alkylene diamine, polyalkylene polyamine). (Mn 100-1,000) Polyamide polyamine is mentioned.

  Examples of the amine compound (B2) having one hydroxyl group include those having C2 or more and Mn 1,000 or less, and the following (B21) to (B23).

(B21) Monoalkanolamine C2-15, for example, ethanolamine, n-propanolamine, i-propanolamine, 6-amino-1-hexanol and the like.

(B22) Alkylene oxide (hereinafter abbreviated as AO) of (B1) (C2-4) 1 mol adduct C4 or more and Mn 1,000 or less, for example, ethylenediamine propylene oxide 1 mol adduct, 1,4-phenylenediamine Ethylene oxide 1 mol adduct, 2- (2-aminoethylamino) ethanol and the like.
(B23) Other than the above (B21) and (B22) C3-20, for example, N-methylethanolamine, N-ethylethanolamine, N-pentylhexanolamine may be mentioned.

  Examples of the compound (B3) having 2 or 3 hydroxyl groups include those having C4 or more and Mn 1,000 or less, and the following (B31) to (B34).

(B31) Dialkanolamine C4-10, for example, diethanolamine, diisopropanolamine, etc. are mentioned.

(B32) Trialkanolamine C6-15, for example, triethanolamine, triisopropanolamine, etc. are mentioned.

(B33) AO adduct of the above (B2) (addition mole number is 2 to 20 mol)
C6 or more and Mn 1,000 or less, for example, 2-20 mol AO adduct of diethylenetriamine, 2-20 mol AO adduct of tetramethylenepentamine, and the like.

(B34) C2 or more and Mn 1,000 or less poly (divalent to trivalent or higher) ols such as aliphatic polyols [of C2 to 12, such as ethylene glycol, propylene glycol, 1,3-propanediol, 2, 2-methyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-2,4-butanediol, 1,5-pentanediol, 3-methyl-1,5 -Pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 2-hydroxymethyl-2-methyl-1,3-propanediol, 2-ethyl-2-hydroxymethyl-2-methyl-1,3 -Propanediol, 1,2,6-hexanetriol]; alicyclic polyols [of C5-12, such as 1,3-cyclo Pentanediol, 1,4-cyclohexanediol]; sugars [of C6-12, such as glucose, fructose, mannitol, sorbitol, maltitol, sucrose]; and AO (C2-4) adducts of these polyols, etc. Can be mentioned.

  Of these (B1) to (B3), from the viewpoints of adhesion of mineral fibers, water resistance of the mineral fiber laminate, and flexibility, (B2) and (B3) are preferable, and (B21) is more preferable. , (B31) and (B32), particularly preferred are (B21) and (B31), and most preferred are isopropanolamine, diethanolamine and combinations thereof.

[Aqueous binder for mineral fibers (X)]
The aqueous binder (X) for mineral fibers of the present invention comprises the (co) polymer (A), a crosslinking agent (B) and water, and (B) for the carboxyl group (α) in (A). The equivalent ratio [(β) / (α)] of the total (β) of the primary amino group, secondary amino group and hydroxyl group is preferably from the viewpoint of the adhesiveness of the mineral fibers and the flexibility of the laminate. It is 2-1.5, More preferably, it is 0.4-1.0, Most preferably, it is 0.5 or more and less than 0.8.

The relevant quantity ratio [(β) / (α)] is obtained by measuring the primary and secondary amine values of (B) by the measurement method described later, and the hydroxyl value of (B) and the acid value of (A) by JISK-0070. It can obtain | require using the following formula from the result measured based on "the test value of the acid value of a chemical product, and a hydroxyl group."
In the following, each unit of amine value, hydroxyl value, and acid value is expressed in mgKOH / g.

Equivalent ratio = [Hydroxyl value of (B) + Secondary amine value of (B)] × [Weight of (B)]
/ [[Acid value of (A)] × [weight of (A)]]

<Method of measuring (B) 1st, 2nd amine value>
(B) [1] Total amine value (all A), [2] Tertiary amine value (3A) are measured by the method described later, and the first and second amine values (12A) are obtained from the following formula. .

(12A) = (All A)-(3A)

However, (12A): represents a 1,2 secondary amine value.
(Total A): Represents the total amine value.
(3A): represents a tertiary amine value.

[1] Method for measuring total amine value (total A) The total amine value is defined as mg of potassium hydroxide equivalent to hydrochloric acid required to neutralize primary, secondary and tertiary amines contained in 1 g of a sample. Numbers. Measured by the following method according to ASTM D2074.
(1) Weigh accurately the sample. (Sample amount: S ₁ g)
(2) Add and dissolve 30 mL of neutral ethanol [neutralized bromcresol green (BCG)].
(3) Titration with a 0.2 mol / L ethanolic hydrochloric acid solution (titer: f ₁ ), and the point at which the color changed from green to yellow is taken as the end point. (Titration volume: A ₁ mL)
(4) The total amine value (total A) is calculated from the following formula.

Total amine number (total A) = A ₁ × f ₁ × 0.2 × 56.108 / S ₁

[2] Method for measuring tertiary amine value (3A) The tertiary amine value (3A) is the amount of potassium hydroxide equivalent to perchloric acid required to neutralize the tertiary amine contained in 1 g of a sample. Numbers. Measured by the following method according to ASTM D2073.
(1) Weigh accurately the sample. (Sample amount: S ₃ g)
(2) Add 20 mL of acetic anhydride / acetic acid mixed solution (9/1) to dissolve, and let stand at room temperature for 3 hours.
(3) Add 30 mL of acetic acid, and titrate with a 0.1 mol / L perchloric acid / acetic acid solution (titer: f ₃ ) with a potentiometric titrator. (Titration volume: A ₃ mL)
(4) A blank test is performed as described above. (Titration volume: B ₁ mL)
(5) The tertiary amine value (3A) is calculated from the following formula.

Tertiary amine value (3A) = (A ₃ −B ₁ ) × f ₃ × 0.1 × 56.108 / S ₃

  The total content of (A) and (B) in the aqueous binder (X) of the present invention is preferably from 2 to 80 from the viewpoint of productivity of the mineral fiber laminate described later and uniform sprayability of the aqueous binder (X). % By weight, more preferably 4 to 70% by weight, particularly preferably 6 to 50% by weight.

  In addition to the above (A), (B) and water, the aqueous binder (X) of the present invention further contains a curing accelerator (C1), water repellent (C2), silane coupling agent (C3) and You may contain the at least 1 sort (s) of additive (C) chosen from the group which consists of a neutralizing agent (C4).

Examples of the curing accelerator (C1) include proton acids [phosphoric acid compounds (phosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, alkylphosphinic acid, etc.), carboxylic acids, carbonic acids, etc.], and salts thereof [metal ( Alkali metal, alkaline earth metal, transition metal, 2B group, 4A group, 4B group, 5B group, etc.) salt, etc.], metal (above) oxides, chlorides, hydroxides and alkoxides, titanium lactate And water-soluble organometallic compounds such as zirconyl acetate and the like. These may be used alone or in combination of two or more.
Of these, phosphoric acid compounds and salts thereof, titanium lactate, zirconyl acetate, and more preferred are phosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, alkylphosphinic acid, and the like from the viewpoint of curing speed. And salts of titanium lactate and zirconyl acetate, particularly preferably hypophosphorous acid.
The content of (C1) is preferably 0.1 to 20%, more preferably 0.3 to 15 based on the total weight of (A) and (B) from the viewpoint of curability and adhesiveness of mineral fibers. %, Particularly preferably 0.5 to 10%.

Examples of the water repellent (C2) include wax, heavy oil, and silicone oil. Examples of waxes include animal-derived waxes (such as beeswax, lanolin wax, shellac wax), plant-derived waxes (carnauba wax, wood wax, rice wax, candelilla wax, etc.), mineral-derived waxes (montane wax, ozokerite, etc.), petroleum Derived wax [paraffin wax, microcrystalline wax, etc.], synthetic wax [Fischer-Tropsch wax, polyethylene wax, polypropylene wax, polycarbonate wax, palm oil fatty acid ester, beef tallow fatty acid ester, stearic acid amide, diheptadecyl ketone, hardened castor oil, etc. These may be used alone or in combination of two or more.
Heavy oils include those composed of C15-120 paraffin or naphthene.
Examples of the silicone oil include reactive or non-reactive silicone oil.

  Of these, paraffin wax, polyethylene wax, polypropylene wax, and reactive silicone oil are preferable from the viewpoint of water repellency, and paraffin wax is particularly preferable.

Examples of the silane coupling agent (C3) include aminosilane coupling agents [γ-aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane. Etc.], and epoxy silane coupling agents [γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, etc.], which may be used alone or in combination of two or more.
The content of (C3) is preferably 0.1 to 2%, more preferably 0.2 to 2% based on the total weight of (A) and (B) from the viewpoint of the adhesiveness of the mineral fibers. .

The neutralizing agent (C4) is used to neutralize the alkaline component eluted from the mineral fiber. As (C4), ammonium salts of inorganic acids [ammonium sulfate, ammonium nitrate, ammonium sulfite, ammonium phosphate, ammonium phosphite, ammonium hypophosphite, ammonium polyphosphate, ammonium chloride, diammonium hydrogen phosphate, diphosphoric acid phosphate Ammonium hydrogen carbonate, ammonium hydrogen carbonate, ammonium thiosulfate, ammonium hyposulfite, ammonium chlorate, diammonium peroxodisulfate, ammonium aluminum sulfate, and the like. These may be used alone or in combination of two or more.
The content of (C4) is preferably 0.1 to 5% based on the total weight of (A) and (B) from the viewpoint of hydrolysis resistance of the mineral fiber laminate and adhesion of mineral fibers, Preferably it is 1-3%.

  The method for producing the aqueous binder (X) of the present invention is a method that can mix and disperse the (co) polymer (A), the crosslinking agent (B), water, and the additive (C) that is added if necessary. There is no particular limitation. The mixing time is usually 30 minutes to 3 hours, and uniform mixing of the aqueous binder (X) can be confirmed visually.

  Since the aqueous binder (X) of the present invention does not comprise a conventional phenol resin that is a condensate of a phenol compound and formaldehyde, it does not contain formaldehyde. Further, the aqueous binder (X) is extremely excellent in the adhesion of mineral fibers, the flexibility of the mineral fiber laminate, and the water resistance evaluated by the method described later.

The aqueous binder (X) of the present invention is suitably used as a binder for mineral fibers that are heat-resistant laminate materials.
Examples of the mineral fiber include glass fiber, slag fiber, rock wool, asbestos, and metal fiber.

[Mineral fiber laminate]
The mineral fiber laminate of the present invention is a mineral fiber laminate to which a cured product of the aqueous binder (X) is attached. That is, for example, the aqueous binder (X) is adhered to a mineral fiber and laminated to form a laminate, and then heated or molded, or the mineral fiber or its strand (fiber bundle) is laminated. It is obtained by spraying and adhering the aqueous binder (X) to the laminate, and heating and molding it.
Examples of the method for attaching the aqueous binder (X) to the mineral fiber or the laminate thereof include, for example, an air spray method or an airless spray method, a padding method, an impregnation method, a roll coating method, a curtain coating method, a beater deposition method, and a solidification method. Known methods such as the method can be mentioned.

  The amount of hardened material adhering to the aqueous binder (X) based on the weight of the mineral fibers (mineral fiber laminate) constituting the mineral fiber laminate is the adhesion of the mineral fibers, the smoothness of the laminate surface and the flexibility of the laminate, From the viewpoint of water resistance, it is preferably 0.4 to 40%, more preferably 1 to 20%, and particularly preferably 2 to 15%.

In the production of the mineral fiber laminate of the present invention, the aqueous binder (X) is usually adhered to the mineral fiber in an appropriate amount, and then heated, dried and cured.
The heating temperature is preferably 100 to 400 ° C., more preferably 200 to 350 ° C. from the viewpoints of adhesiveness, water resistance and coloration suppression of the laminate, and industrial viewpoint.
The heating time is preferably 2 to 90 minutes, more preferably 5 to 40 minutes, from the viewpoint of reaction rate and suppression of coloring of the laminate.

  The aqueous binder (X) of the present invention is excellent in the adhesion of mineral fibers and can impart excellent flexibility and water resistance to the mineral fiber laminate. This is because the composition of the copolymer (A) and the crosslinking agent (B) makes it easy for the binder melt to efficiently gather at the intersection of the mineral fibers during the curing process, and the curing proceeds intensively at the intersection. It is estimated that the cured resin has excellent resin properties.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these. In the following, parts and% represent parts by weight and% by weight, respectively.

[Production of (co) polymer (A)]
<Production Example 1>
The autoclave was charged with 350 parts of water and 250 parts of isopropanol [solvent], and nitrogen was substituted in the autoclave by bubbling nitrogen under stirring (gas phase oxygen concentration of 500 ppm or less). After raising the temperature to 82 ° C. while blowing nitrogen, 8.0 parts of 3-mercaptopropionic acid [chain transfer agent], 0.31 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) and 2,2 A solution [initiator] obtained by dissolving 1.26 parts of '-azobis (2-methylbutyronitrile) in 50 parts of isopropanol, 320 parts of acrylic acid (a1-1) and 55 parts of butyl acrylate (a2-1) Were simultaneously added dropwise over 2 hours and further stirred at 83 ° C. for 2 hours to carry out a polymerization reaction. Thereafter, isopropanol in the solution was removed, and water was added so that the nonvolatile content was 40%, to obtain an aqueous solution of the (co) polymer (A-1). (A-1) had an Mw of 13,000 and an acid value of 660.

<Production Examples 2, 3, 5, 7 to 11>
In Production Example 1, the same procedure as in Production Example 1 was carried out except that Table 1 was followed. Copolymers (A-2) to (A-3), (A-5), (A-7) to (A- 11) was obtained.

<Production Example 4>
The autoclave was charged with 500 parts of water and 0.068 part of iron sulfate as a solvent, and nitrogen was substituted in the autoclave by bubbling nitrogen under stirring (gas phase oxygen concentration of 500 ppm or less). The temperature was raised to 100 ° C. while blowing nitrogen, and then an aqueous solution [initiator] in which 15.2 parts of hydrogen peroxide (30% by weight aqueous solution) were dissolved in 50 parts of water and acrylic acid (a1-1) 349. 7 parts and a solution in which 0.35 part of butyl acrylate (a1-2) is mixed separately at the same time dropwise over 3 hours, and further stirred and polymerized at 100 ° C. for 2 hours. Water was added so that an aqueous solution of the copolymer (A-4) was obtained. (A-4) had an Mw of 13,000 and an acid value of 780.

<Production Example 6, Comparative Production Examples 1 and 2>
Production Example 4 was carried out in the same manner as in Production Example 4 except that Table 1 was followed to obtain aqueous solutions of Copolymer (A-6), (Ratio A-1), and (Ratio A-2).

  Table 1 shows the results of Production Examples 1 to 11 and Comparative Production Examples 1 and 2.

<Examples 1-33, Comparative Examples 1-2>
Each aqueous mineral fiber binder was prepared according to the composition (parts) shown in Tables 2 and 3. A test piece of a mineral fiber laminate was prepared using the binder in the following manner and evaluated by the methods described below. The results are shown in Tables 2 and 3.

<Making mineral fiber laminate>
A glass fiber laminate having a length × width × thickness of 30 cm × 30 cm × 1 cm and a density of 0.025 g / cm ³ is placed in a flat plate mold having a length × width × depth of 30 cm × 30 cm × 5 cm. I put it. Next, an aqueous binder having a cured product adhesion amount equivalent to 15% of the weight of the laminate was uniformly sprayed onto the laminate using an air spray. Thereafter, heat treatment (drying and curing) was performed for 40 minutes with a circulating air dryer at 220 ° C. to obtain a laminate (S-1) having a thickness of about 1 cm and a density of 0.029 g / cm ³ . In the same manner, a total of 5 laminates (S-1) were prepared.

(1) Evaluation of adhesiveness From each laminated body (S-1), five test pieces of length × width × thickness of 10 cm × 1.5 cm × 1 cm were cut out. Using these autographs [model number “AGS-500D”, manufactured by Shimadzu Corporation], the tensile strength was measured in accordance with “7.4 Tensile Strength” of JIS R3420 “Glass Fiber General Test Method” The average value of five test pieces was evaluated for adhesion based on the following criteria.
<Evaluation criteria>
☆: 500N / m ² or more ◎: less than 450N / m ² more than ^{500N / m 2 ○: 400N /} m 2 more than 450N / m less than ² △: 300N / m ² more than 400N / m ² less than ×: 300N / m less than ²

(2) Evaluation of water resistance Five test pieces having a length x width x thickness of 10 cm x 1.5 cm x 1 cm were cut out from each laminate (S-1). They were immersed in 25 ° C. tap water for 10 minutes. Then, it took out and left still on a sieve with an opening of 400 μm at 30 ° C. and 40% RH for 20 minutes.
The test piece was evaluated for water resistance according to the same evaluation criteria as in (1) above.

(3) Evaluation of flexibility Five test pieces having a length × width × thickness of 10 cm × 1.5 cm × 1 cm were cut out from each laminate (S-1). The thickness of the test piece was measured in units of 0.1 mm using a caliper (L0).
A stainless steel plate (length and width is the same as the test piece) was placed on these test pieces, and the thickness of the test piece after 10 seconds was measured under a load of 1.4 g / cm ² (L1). ).
Next, the stainless steel plate was removed, and the thickness of the test piece 60 seconds after the removal was measured (L2).
The degree of flexibility (%) was calculated from the following formula (1), and the degree of maintenance (%) was calculated from the formula (2), and the average value of five test pieces was evaluated based on the following criteria.

Flexibility (%) = [(L0) − (L1)] × 100 / (L0) (1)

Maintenance degree (%) = 100 − [(L0) − (L2)] × 100 / (L0) (2)

<Evaluation criteria>
☆: Softness degree 30% or more and maintenance degree 95% or more ◎: Softness degree 25% or more and less than 30% and maintenance degree 95% or more ○: Flexibility degree 20% or more and less than 25% and maintenance degree 95% or more △: Flexibility 15% or more and less than 20% and maintenance degree 95% or more ×: Flexibility degree less than 15% or maintenance degree less than 95%

  From the results of Tables 2 and 3, the aqueous binder for mineral fibers of the present invention is superior in the adhesiveness of mineral fibers and imparts excellent water resistance and flexibility to the mineral fiber laminate as compared with the comparative ones. I understand that.

  The mineral fiber aqueous binder (X) of the present invention is suitable for adhering mineral fibers (glass fibers, etc.) which are heat resistant laminate materials, and the mineral fiber laminate using the aqueous binder is a building. It is extremely useful because it can be applied to a wide range of fields as a heat insulating material, a heat insulating material, and a sound absorbing material for various devices.

Claims (11)

  Copolymer (A), crosslinked, comprising unsaturated (poly) carboxylic acid (anhydride) (a1) and alkyl (carbon number 2 to 24) ester (a2) of (meth) acrylic acid as constituent monomers An aqueous binder (X) for mineral fibers comprising an agent (B) and water, wherein the weight average molecular weight of (A) is 5,000 or more and less than 20,000.   The aqueous binder according to claim 1, wherein the weight ratio [(a1) / (a2)] of (a1) to (a2) is 40/60 to 99.9 / 0.1.   The aqueous binder according to claim 1 or 2, wherein (a1) is at least one selected from the group consisting of (meth) acrylic acid and maleic acid (anhydride).   The (B) is at least one selected from the group consisting of an amine compound (B1) having no hydroxyl group, an amine compound (B2) having one hydroxyl group, and a compound (B3) having two or more hydroxyl groups. The aqueous binder according to any one of claims 1 to 3.   The equivalent ratio [(β) / (α)] of the total (β) of the primary amino group, secondary amino group and hydroxyl group in (B) to the carboxyl group (α) in (A) is 0.2. It is -1.5, The aqueous binder in any one of Claims 1-4.   The aqueous binder according to any one of claims 1 to 5, wherein the total content of (A) and (B) is 2 to 80% by weight based on the weight of the aqueous binder.   The aqueous solution according to any one of claims 1 to 6, further comprising at least one additive (C) selected from the group consisting of a curing accelerator, a water repellent, a silane coupling agent, and a neutralizing agent. binder.   The mineral fiber laminated body to which the hardened | cured material of the aqueous | water-based binder (X) in any one of Claims 1-7 adhered.   The laminate according to claim 8, wherein a cured product adhesion amount of the aqueous binder is 0.5 to 30% by weight based on the weight of the mineral fiber laminate.   The laminate according to claim 8 or 9, which is used for a heat insulating material, a heat insulating material or a sound absorbing material.   The manufacturing method of the mineral fiber laminated body which heats and shape | molds the mineral fiber laminated body to which the aqueous | water-based binder in any one of Claims 1-7 adhered.