JP6133054B2 - Aqueous binder for mineral fiber - Google Patents

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 or the like by mechanical means. It is 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 (see, for example, Patent Document 1). However, since the binder usually contains formaldehyde and there is a problem that formaldehyde is released into the environment from a laminate using the binder, an improved binder not containing formaldehyde has been proposed (for example, Patent Document 2). 3).

JP 58-70760 A Japanese National Patent Publication No. 10-509485 JP 2007-2111161 A

However, although the binder of Patent Document 2 is composed of a copolymer of a carboxy functional monomer and a hydroxy functional monomer and an alkali metal salt catalyst of a phosphorus-containing acid, the water resistance and hydrolysis resistance of the binder are inferior. There is a problem in that the glass fiber mat that is bonded has a difficulty in restoring (described later) (the property that the thickness of the mat after the glass fiber mat is compressed returns to its original state).
Further, the binder of Patent Document 3 includes a polycarboxylic acid and a crosslinking agent containing an alcohol having an amino group and / or an imino group, and is contained in the crosslinking agent with respect to the number of moles of the carboxyl group in the polycarboxylic acid. The total number of moles of the hydroxyl group, amino group, and imino group is an aqueous binder having a molar ratio of 0.8 to 1.5, but there is a problem that the water resistance and hydrolysis resistance of the binder are poor.
The object of the present invention is to solve the above-mentioned problems, excellent adhesion of mineral fibers such as glass fibers of heat-resistant laminate materials, and does not contain formaldehyde, and is excellent in water resistance, hydrolysis resistance, and resilience. An object is to provide an aqueous binder for providing a mineral fiber laminate.

  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 an addition (co) polymer (A) having at least two carboxyl groups and / or latent carboxyl groups, at least two amino groups and / or imino groups, and hydroxyl groups. The total number of moles of amino groups and imino groups in (B1) with respect to the number of moles of carboxyl groups in (A), comprising a crosslinking agent (B) containing an amine compound (B1) that is not present and water Is a water-based binder for mineral fibers (X) having a ratio (γ1) of 0.3 to 1.5.

The aqueous binder for mineral fibers (X) of the present invention has the following effects.
(1) Excellent water resistance and hydrolysis resistance.
(2) Excellent mineral fiber adhesion.
(3) The mineral fiber laminate formed by bonding with the binder is excellent in compressibility.
(4) Does not contain formaldehyde.

[Addition (co) polymer (A)]
The addition (co) polymer (A) in the present invention has at least two carboxyl groups and / or latent carboxyl groups. Here, the latent carboxyl group means, for example, two carboxyl groups generated by hydrolysis of one acid anhydride group.
And, having at least two carboxyl groups and / or latent carboxyl groups means that at least two carboxyl groups, at least two latent carboxyl groups, or a sum of carboxyl groups and latent carboxyl groups Means having at least two groups.

  (A) is an addition polymerization of an unsaturated monomer (a) having a carboxyl group or an acid anhydride group, or an addition copolymer of (a) and other unsaturated monomer (x) other than (a) if necessary. It is obtained by polymerizing. Examples of (a) include the following and mixtures thereof:

  Among the unsaturated monomers (a1) having a carboxyl group among (a), unsaturated monocarboxylic acids [carbon number (hereinafter abbreviated as C) 3 to 20, such as (meth) acrylic acid, crotonic acid, cinnamic acid, Vinylbenzoic acid, 3-methyl-3-butenoic acid, 3-pentenoic acid, 4- and 5-hexenoic acid, 3-butenoic acid, monoalkyl (C1-8) esters of unsaturated dicarboxylic acids [C5-16, for example Maleic acid monoalkyl ester, fumaric acid monoalkyl ester, citraconic acid monoalkyl ester], unsaturated dicarboxylic acid monoester having a hydroxyl group [C5-20, for example, ethyl carbitol monoester of maleic acid, ethyl carbitol mono of fumaric acid Ester, glycol itaconate monoester], etc.], C4-20 (preferably C4-16) Dicarboxylic acid [C4-20 (preferably C4～16), such as maleic acid, fumaric acid, citraconic acid, and itaconic acid], and the like.

Among (a), as the unsaturated monomer (a2) having an acid anhydride group, an anhydride of the unsaturated dicarboxylic acid [C4-20 (preferably C4-16)] in (a1), for example, maleic anhydride And itaconic anhydride.
Of the above (a1) and (a2), (a1) is preferable from the viewpoint of the curing rate of the binder, and acrylic acid is more preferable.

As other unsaturated monomers (x) other than (a), the following may be mentioned.
(1) Amide monomer C3-18, such as (meth) acrylamide, N-alkyl (C1-5) (meth) acrylamide, alkoxy (C1-4) alkyl (C1-5) (meth) acrylamide, N, N-dialkyl (C1-5) (meth) acrylamide, aminoalkyl (C1-5) (meth) acrylamide, N-alkyl (C1-5) aminoalkyl (C1-5) (meth) acrylamide, N, N-dialkyl (C1 5) Aminoalkyl (C1-5) (meth) acrylamide, diacetone (meth) acrylamide, N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone;

(2) Acrylate monomers C3-30, such as alkyl (C1-18) (meth) acrylates and their lower alkyl (C1-4) ethers, hydroxyalkyl (C1-5) (meth) acrylates, aminoalkyl (C1-5) ) (Meth) acrylate, N-alkyl (C1-5) aminoalkyl (C1-5) (meth) acrylate, N, N-dialkyl (C1-5) (meth) acrylate, N-alkyl (C1-5) amino Alkyl (C1-5) aminoalkyl (C1-5) (meth) acrylate;

(3) Vinyl ether monomer C3-30, such as vinyl alkyl (C1-20) ether;
(4) Allyl monomer C3-10, such as N-allylamine, N, N-dialkyl (C1-5) allylamine;
(5) Nitrile monomer C3-10, such as (meth) acrylonitrile;

(6) Aliphatic unsaturated hydrocarbon monomer C2-30, such as ethylene, propylene, isobutylene, isoprene, butadiene;
(7) Aromatic vinyl monomer C8-30, for example, styrene, α-methylstyrene, p-methoxystyrene, vinyltoluene, p-hydroxystyrene, p-acetoxystyrene;
(8) Vinyl ester monomer C4-30, for example, vinyl acetate, vinyl propionate.
The above (x) may be used alone or in combination of two or more.

  Among the above (x), (2), (3), (6) and (7) are preferable from the viewpoint of the curing rate of the binder and the stability of the binder solution, and (2) is particularly preferable. Are hydroxyalkyl (C1-5) (meth) acrylate and alkyl (C1-5) (meth) acrylate.

The proportion (% by weight) of the monomer constituting (A) is usually 20% or more, preferably 40 to 100% from the viewpoint of adhesion between mineral fibers (hereinafter abbreviated as adhesive strength of binder), More preferably 60 to 100%; (x) is usually 80% or less, preferably 60% or less, more preferably 40% or less, particularly preferably 30% or less, most preferably 20% from the viewpoint of the adhesive strength of the binder. It is as follows.
As (a), each of (a1) and (a2) may be used alone or in combination. The weight ratio [(a1) / (a2)] when used in combination is preferably 50/50 or more, more preferably 70/30 or more, from the viewpoints of the curing speed and the adhesive strength of the binder.

Weight average molecular weight of (A) [hereinafter abbreviated as Mw. The measurement is based on a gel permeation chromatography (GPC) method described later. ] Is preferably from 500 to 100,000, more preferably from 1,000 to 80,000, particularly preferably from 5,000 to 50,000 from the viewpoint of the adhesive strength of the binder and the restoring force against compression of the mineral fiber laminate described below. 000.
The Gw GPC measurement conditions in the present invention are as follows.
<GPC measurement conditions>
[1] Apparatus: Gel permeation chromatograph
“HLC-8120GPC”, manufactured by Tosoh Corporation [2] Column: “TSKgel G6000PWxl”, “TSKgel”
G3000PWxl "[both manufactured by Tosoh Corporation] are connected in series.
[3] Eluent: 0.5% by weight of sodium acetate in methanol / water = 30/70 (volume ratio)
Dissolved with lithium.
[4] Reference material: polyethylene glycol [5] Injection conditions: sample concentration 0.25% by weight, column temperature 40 ° C.

  The number of carboxyl groups and / or latent carboxyl groups in (A) is preferably at least 2, preferably 3 to 2,000, more preferably 5 to 1, from the viewpoint of the adhesive strength of the binder and the water resistance of the binder. 000, particularly preferably 10 to 500.

The addition (co) polymer (A) can be produced by a known solution polymerization method, and an aqueous solution polymerization method is preferred from the viewpoint of productivity.
When an organic solvent is used, it may be removed after polymerization or may be used as it is without removing the solvent. Examples of the organic solvent include methyl ethyl ketone (hereinafter abbreviated as MEK), alcohol and the like, and MEK is preferable from the viewpoint of productivity.
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 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 the residual monomer is preferably 5% or less, more preferably 3% or less, from the viewpoint of the adhesive strength of the binder to the mineral fibers. The amount of residual monomer can be measured by gas chromatography.

[Crosslinking agent (B)]
The cross-linking agent (B) in the present invention contains the amine compound (B1), and for the purpose of improving the adhesive strength of the binder, the alkanolamine (B2) and / or polyol (B3) described later is added as necessary. You may make it contain.

  The amine compound (B1) in the present invention is a compound having at least two (preferably 3 to 6) amino groups and / or imino groups and having no hydroxyl group. In the present invention, the amino group means a primary amino group, and the imino group means a secondary amino group. If the number of the amino group and / or imino group is less than 2, the adhesive strength of the binder is lowered, and if it has a hydroxyl group, the hydrolysis resistance of the mineral fiber laminate is inferior.

The amine compound (B1) has C2 or more and a number average molecular weight (hereinafter abbreviated as Mn. Measurement is based on GPC under the same measurement conditions as Mw.) The following (B11) to (B15) are 2,000 or less. included.
(B11) Aliphatic polyamine (C2-18)
[1] Aliphatic polyamines [C2-6 alkylene diamines (for example, ethylenediamine, propylenediamine, hexamethylenediamine), polyalkylene (C2 to C6) polyamines [for example, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylene Hexamine, iminobispropylamine, bis (hexamethylene) triamine]]
[2] Substituted alkyl (C1-4) [for example, dialkyl (C1-3) aminopropylamine, trimethylhexamethylenediamine, 2,5-dimethyl-2,5-hexamethylenediamine, methyliminobispropylamine ]
[3] Alicyclic or heterocyclic ring-containing aliphatic polyamine [for example, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane]
[4] Aromatic ring-containing aliphatic amine (C8-15) (for example, xylylenediamine, tetrachloro-p-xylylenediamine);

(B12) Alicyclic polyamine (C4-15)
For example, 1,3-diaminocyclohexane, isophoronediamine, mensendiamine, 4,4′-methylenedicyclohexanediamine (hydrogenated methylenedianiline);
(B13) Heterocyclic polyamine (C4-15)
For example piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, 1,4 bis (2-amino-2-methylpropyl) piperazine;

(B14) Aromatic polyamine (C6-20)
[1] Unsubstituted aromatic polyamines such as 1,2-, 1,3- and 1,4-phenylenediamine, 2,4′- and 4,4′-diphenylmethanediamine, crude diphenylmethanediamine (polyphenylpolymethylenepolyamine) , Diaminodiphenylsulfone, benzidine, thiodianiline, bis (3,4-diaminophenyl) sulfone, 2,6-diaminopyridine, m-aminobenzylamine, triphenylmethane-4,4 ′, 4 ″ -triamine, naphthylene diene Amines;
[2] Aromatic polyamines having a nucleus-substituted alkyl group [C1-C4 alkyl group such as methyl, ethyl, n- and i-propyl, butyl, etc.], for example 2,4- and 2,6-tolylenediamine, crude tri Rangeamine, diethyltolylenediamine, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 4,4′-bis (o-toluidine), dianisidine, diaminoditolylsulfone, 1,3-dimethyl-2, 4-diaminobenzene, 1,3-diethyl-2,4-diaminobenzene, 1,3-dimethyl-2,6-diaminobenzene, 1,4-diethyl-2,5-diaminobenzene, 1,4-dibutyl- 2,5-diaminobenzene, 2,4-diaminomesitylene, 1,3,5-triethyl-2,4-diaminobenzene, 1,3,5-triisopropyl Lopyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 2,3-dimethyl-1 , 4-Diaminonaphthalene, 2,6-dimethyl-1,5-diaminonaphthalene, 2,6-diisopropyl-1,5-diaminonaphthalene and mixtures of these isomers [3] Aromatic polyamines having imino groups [above The aromatic polyamine of [1] to [2], wherein a part or all of —NH ₂ is replaced by —NH—R ′ (where R ′ is an alkyl group, for example, a lower alkyl group such as methyl or ethyl)]
For example, 4,4′-di (methylamino) diphenylmethane, 1-methyl-2-methylamino-4-aminobenzene;

(B15) Polyamide polyamine (Mn 100 to 2,000)
For example, a low molecular weight polyamide polyamine obtained by condensation of dicarboxylic acid (such as dimer acid) and an excess (amino group / carboxyl group equivalent ratio of 2 or more) polyamine (such as alkylene diamine, polyalkylene polyamine, etc.).

  Of the above (B1), from the viewpoint of the adhesive strength of the binder, (B11) and (B15) are preferred, aliphatic polyamines and low molecular weight polyamidoamines are more preferred, and polyalkylenes (C2-6) are particularly preferred. Polyamine, C2-6 alkylene diamine. The above (B1) may be used alone or in combination of two or more.

The alkanolamine (B2) in the present invention is a compound having C2 or more and Mn3,000 or less, having at least one hydroxyl group, and further having at least one amino group and / or imino group.
(B2) includes C2-20 hydroxylamine, an alkylene oxide (hereinafter abbreviated as AO) adduct of the amine compound (B1), a mixture thereof, and the like.

  Hydroxylamines include those having C2-20, such as those having one hydroxyl group [having an amino group [for example, monoethanolamine, isopropanolamine], those having an amino group and an imino group [for example, 2- (2-amino Ethylamino) ethanol] and the like, and those having two hydroxyl groups [those having an imino group (for example, diisopropanolamine, diethanolamine) and the like].

  AO adducts of amine compounds include C3 or more and Mn 3,000 or less, such as aliphatic amines [C1-10, such as methylamine, ethylamine, n- and i-propylamine, ethylenediamine, diethylenetriamine, triethylene. Tetramine, tetraethylenepentamine, pentaethylenehexamine], aromatic amine [C6-12, such as aniline, toluidine, xylylenediamine], alicyclic amine [C4-10, such as cyclopentylamine, cyclohexylamine], complex Examples include ring-containing amines [C4-10, such as piperazine] and AO adducts of the above hydroxylamines. The number of moles of AO addition is preferably 1 to 10 moles.

  AO includes C2-12 or higher (preferably C2-4) AO such as ethylene oxide, 1,2-propylene oxide, 1,2-, 2,3- and 1,3-butylene oxide, tetrahydrofuran. And 3-methyl-tetrahydrofuran), 1,3-propylene oxide, isobutylene oxide, C5-12 α-olefin oxide, substituted AO, such as styrene oxide, and combinations of two or more thereof (random addition and / or block addition) ) Is included.

Among the above (B2), from the viewpoint of the adhesiveness of the binder and the stability of the binder solution, those having an amino group of C2-20 hydroxylamine, and those having an amino group and an imino group are preferred. In combination with those, monoethanolamine, isopropanolamine, and diethanolamine are more preferable, and isopropanolamine and monoethanolamine are particularly preferable.
The above (B2) may be used alone or in combination of two or more.

  The polyol (B3) in the present invention is a compound having at least two hydroxyl groups and having no amino group and / or imino group. (B3) includes the following (B31) to (B37) of C2 or more and Mn2,000 or less.

(B31) Aliphatic polyol (C2-30)
Alkane polyols and intramolecular or intermolecular dehydrates such as ethylene glycol and its di- and trimers, propylene glycol and its di- and trimers, 1,3-propanediol, 2,2-dimethyl- and 2- Butyl-2-ethyl-1,3-propanediol, 1,3- and 1,4-butanediol, 2-methyl-2,4-butanediol, 1,5-pentanediol, 3-methyl-1,5 -Pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 2-ethyl-1,3-hexanediol, 2-hydroxymethyl-2-methyl- and 2-ethyl-2-hydroxymethyl-1, 3-propanediol, 1,2,6-hexanetriol, 2,2-bis (hydroxymethyl) -2,3-propanedioe , Glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol, poly (2-10) glycerin;

(B32) Alicyclic polyol (C5-12)
1,3-cyclopentanediol, 1,4-cyclohexanediol and the like;
(B33) Trialkanolamine (C6-12)
Triethanolamine, triisopropanolamine, etc .;
(B34) Sugars and their derivatives (C6-12)
Sucrose, glucose, fructose, mannitol, sorbitol, sorbitan, methyl glucoside, maltitol, etc .;
(B35) Aromatic ring-containing polyhydric alcohol (C10 or more and Mn1,000 or less)
Trisphenol compound [trade name “Trisphenol PA” [manufactured by Honshu Chemical Industry Co., Ltd.], etc.], etc .;
(B36) AO adduct of (B31) to (B35) (addition mole number 2 to 20)
(B37) AO adduct of the amine compound (B1) (addition mole number: 2 to 20).
Of the above (B3), from the viewpoint of adhesiveness of the binder, (B31), (B33) and (B34) are preferable, and glycerin, trimethylolpropane and sorbitol are more preferable.
The above (B3) may be used alone or in combination of two or more.

  The content (% by weight) in the crosslinking agent (B) is preferably 40% or more, more preferably 50% or more, particularly preferably 60% from the viewpoint of the water resistance and hydrolysis resistance of the binder of the amine compound (B1). -100%; The total of alkanolamine (B2) and polyol (B3) is usually 60% or less, preferably 50% or less, more preferably 40% or less from the viewpoint of hydrolysis resistance of the binder.

[Aqueous binder for mineral fibers (X)]
The aqueous binder for mineral fibers (X) of the present invention comprises the addition (co) polymer (A), a crosslinking agent (B) containing an amine compound (B1), and water, The ratio (γ1) of the total number of moles of amino groups and imino groups in (B1) to the number of moles of carboxyl groups in (B1) is 0.3 to 1.5, preferably 0.4 to 1.4, more preferably 0. .5 to 1.3. When the ratio (γ1) is less than 0.3 or exceeds 1.5, the adhesive strength of the binder, the water resistance and hydrolysis resistance of the mineral fiber laminate are deteriorated.

For the purpose of improving the adhesive strength of the binder, the crosslinking agent (B) may contain an alkanolamine (B2) and / or a polyol (B3) in addition to (B1) as described above. When the crosslinking agent (B) is a combination of (B1) and (B2) and / or (B3), the amino acid in (B2) and (B3) relative to the number of moles of the carboxyl group in (A) The ratio of the total number of moles of groups, imino groups and hydroxyl groups (γ2) is preferably 0.05 to 0.6, more preferably 0.1 to 0.5, and particularly preferably 0.15 to 0.4. The total of (γ1) and (γ2) is preferably 0.35 to 1.5, more preferably 0.4 to 1.4, and particularly preferably 0.45 to 1.3.
Further, (γ1) / [(γ1) + (γ2)] is preferably 0.4 or more, more preferably 0.5 or more, particularly preferably 0.6, from the viewpoint of hydrolysis resistance of the mineral fiber laminate. That's it.

The ratio (γ1) and the ratio (γ2) are determined by measuring the primary and secondary amine values of (B1) and (B2) as described later, the hydroxyl values of (B2) and (B3), and (A). The acid value can be determined from the result of measurement according to JIS K-0070 “Testing Method for Acid Value and Hydroxyl Group of Chemical Products” using the following formula.
In the following, each unit of amine value, hydroxyl value, and acid value is expressed in mgKOH / g.

Ratio (γ1) = [1,2 amine value of (B1)] × [weight of (B1)]
/ [[Acid value of (A)] × [weight of (A)]]

Ratio (γ2) = [[1,2 amine value of (B2) + hydroxyl value of (B2)] × [(B2)
Weight] + [hydroxyl value of (B3)] × [weight of (B3)]]
/ [[Acid value of (A)] × [weight of (A)]]

<Method for measuring 1,2-secondary amine value of (B1) and (B2)>
(1) Total amine value (All A) and [2] Tertiary amine value (3A) of (B1) and (B2) are measured by the method described later. 12A).

(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 the number of mg of potassium hydroxide equivalent to hydrochloric acid required to neutralize primary, secondary and tertiary amines contained in 1 g of a sample. Say. 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) Titrate with 0.2 mol / L ethanolic hydrochloric acid solution (titer: f ₁ ), and the point at which the color changed from green to yellow is the end point. (Titration volume: A ₁ mL)
(4) The total amine value (total A) is calculated from the following formula.

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

[2] Method of measuring tertiary amine value (3A) The tertiary amine value (3A) is the number of mg of potassium hydroxide equivalent to perchloric acid required to neutralize the tertiary amine contained in 1 g of a sample. Say. Measured by the following method according to ASTM D2073.
(1) Weigh accurately the sample. (Sample amount: S ₂ 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 ₂ ) with a potentiometric titrator. (Titration volume: A ₂ 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 ₂ −B ₁ ) × f ₂ × 0.1 × 56.108 / S ₂

  The total content of (A) and (B) in the aqueous binder (X) of the present invention is preferably 2 to 2 from the viewpoint of the productivity of the mineral fiber laminate described later and the uniform sprayability of the aqueous binder (X). 80% by weight, more preferably 2 to 70% by weight, particularly preferably 3 to 60% by weight.

  In the aqueous binder (X) of the present invention, in addition to the above (A), (B) and water, various other types may be used as needed for the purpose of further accelerating the curing rate of the binder during the production of the mineral fiber laminate described later. A curing accelerator (C) may be contained.

  The curing accelerator (C) preferably contains at least one metal selected from the metal group of Group 1, Group 2 and Group 3 of the periodic table from the viewpoint of the curability of the binder, and potassium, magnesium, calcium It is more preferable that it contains at least one metal selected from the group consisting of barium and ytterbium, particularly preferably magnesium or calcium.

  (C) containing a metal from Group 1 of the periodic table includes organic metal compounds such as organic acid salts, metal alkoxides or metal complexes (for example, acetylacetonate) of lithium, sodium, potassium, rubidium or cesium; (C) containing an inorganic metal compound such as a compound, metal hydroxide, carbonate, sulfate, nitrate, chloride, or fluoride, and including the Group 2 metal of the periodic table as beryllium, magnesium, Organometallic compounds such as organic acid salts, metal alkoxides or metal complexes (eg acetylacetonate) of calcium, strontium or barium; metal oxides, metal hydroxides, carbonates, sulfates, nitrates, chlorides or fluorides Inorganic metal compounds such as (C) containing the group 3 metal of the periodic table includes organometallic compounds such as scandium, ytterbium, yttrium or other rare earth organic acid salts, metal alkoxides or metal complexes (for example, acetylacetonate); And inorganic metal compounds such as metal hydroxides, carbonates, sulfates, nitrates, chlorides or fluorides. These may be used alone or in combination.

Of the above (C), bis (acetylacetonate) magnesium, magnesium stearate, calcium stearate, magnesium chloride, bis (acetylacetonato) barium, ytterbium triflate, and more preferred from the viewpoint of the curability of the binder. Magnesium compounds, particularly preferred are bis (acetylacetonate) magnesium and magnesium stearate.
The content of (C) is preferably 0.1 to 30% and more preferably 0.3 to 0.3% from the viewpoint of the curability of the binder and the adhesiveness of the binder, based on the total weight of (A) and (B). 10%, particularly preferably 0.5 to 5%.

  The aqueous binder for mineral fibers (X) of the present invention is an adhesive improver, viscosity modifier, antioxidant, ultraviolet absorber, stabilizer, plasticizer, wax, if necessary as long as the effects of the present invention are not impaired. One or more other additives (D) selected from the group consisting of pigments or dyes, antistatic agents, antibacterial agents, fungicides, fragrances, flame retardants, dispersants, film-forming aids, and wetting agents May be used in combination.

The total amount of the additive (D) used is preferably 50% or less based on the total weight of (A) and (B), preferably 0 from the viewpoint of the additive effect of each additive and the adhesive strength of the binder to mineral fibers. .5 to 20%.
The amount of each additive used based on the total weight of (A) and (B) is usually 10% or less for each of antioxidants, ultraviolet absorbers, stabilizers, antibacterial agents, fungicides and fragrances. From the same viewpoint, preferably 0.5 to 5%; plasticizer, wax, pigment or dye, antistatic agent, flame retardant, dispersant, film-forming aid and wetting agent are each usually 10% or less, and From the same viewpoint, it is preferably 1 to 5%.

  The production method of the aqueous binder (X) of the present invention includes an addition (co) polymer (A), an amine compound (B1), water, and an alkanolamine (B2), a polyol (B3), and a curing accelerator that are added if necessary. If it is a method which can mix and disperse an agent (C) and an additive (D), it will not specifically limit. 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 water resistance and hydrolysis 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 obtained by heating and molding a mineral fiber laminate to which the aqueous binder is adhered. Here, the thickness of the laminate is usually 1 to 1,000 mm, preferably 3 to 500 mm, and more preferably 5 to 300 mm from the viewpoint of productivity of the laminate and ease of handling.

  The adhesion amount (solid content) of the aqueous binder (X) based on the weight of the mineral fibers (mineral fiber laminate) constituting the mineral fiber laminate is determined by the adhesive strength of the binder, the smoothness of the laminate surface, and the flexibility of the laminate. From the viewpoint of restoring property to compression, it is preferably 0.4 to 40%, more preferably 0.5 to 30%, particularly preferably 1 to 25%, and most preferably 2 to 20%.

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 standpoint of restoration of the laminate, suppression of coloration of the laminate, and an industrial viewpoint.
The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes, from the viewpoint of reaction rate and suppression of coloration of the laminate.
In the aqueous binder (X) of the present invention, the carboxyl group derived from the carboxyl group and acid anhydride group in the addition (co) polymer (A) is an amino group and / or imino group in (B), and optionally a hydroxyl group. Can be cured to become a strong resin and exhibit an excellent binder function for bonding between mineral fibers.

Specifically, the mineral fiber laminate of the present invention is produced by the following method and procedure. Among these methods, the method [1] is preferable from the viewpoint of productivity.
[1] Method of spraying aqueous binder (X) on mineral fiber and heating and molding (1) The mineral composition is melted in a furnace and immediately fiberized using an air spray or an airless spray device. Spray the aqueous binder (X).
(2) The mineral fibers to which the aqueous binder (X) is attached are laminated to form a laminate, which is then heated and molded.
[2] Method of laminating mineral fibers or their strands (fiber bundles) to form a laminate, and spraying aqueous binder (X) on them and heating and molding (1) Mineral fibers or strands of mineral fibers (fiber bundles) Are laminated to form a laminate.
(2) The aqueous binder (X) is sprayed from above the laminate.
(3) The mineral fiber laminate to which the aqueous binder is attached is heated and molded.

The mineral fiber laminate of the present invention is excellent in water resistance and hydrolysis resistance. The water resistance is an evaluation of the influence of the water absorption of the binder on the adhesiveness and restorability, and can be evaluated by a water resistance test described later.
On the other hand, the hydrolysis resistance is an evaluation of the influence on the adhesiveness and restorability due to the hydrolyzability of the binder, and can be evaluated by a hydrolysis resistance test described later.

  The mineral fiber laminate of the present invention is excellent in resilience against compression. The restorability can be evaluated by a restorability test described later, and the restoration ratio in the restorability test of the mineral fiber laminate of the present invention is the function of maintaining the laminate (heat insulation, heat retention, sound absorption, etc.). From the viewpoint, it is preferably 85% or more, more preferably 90% or more.

  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.

The addition (co) polymer (A), amine compound (B1), alkanolamine (B2), polyol (B3), and curing accelerator (C) used in Examples and Comparative Examples are as follows.
(A-1): Polyacrylic acid (Mw 11,000, acid value 740) aqueous solution, nonvolatile content 50% (A-2): Acrylic acid / hydroxyethyl methacrylate (weight ratio = 90/6) copolymerization
Body (Mw 14,000, acid value 660) aqueous solution, non-volatile content 50%
(A-3): Polyacrylic acid (Mw 27,000, acid value 750) aqueous solution, nonvolatile content 50%
(A-4): Styrene / maleic acid (weight ratio = 47/53) copolymer (Mw 9,000, acid value 510) aqueous solution, nonvolatile content 40%
(A-5): Polyacrylic acid (Mw 35,000, acid value 745) aqueous solution, nonvolatile content 70%
(B1-1): Pentaethylenehexamine (B1-2): Tetraethylenepentamine (B1-3): 1,6-hexanediamine (B1-4): Isophoronediamine (B1-5): 1,2-phenylene Diamine (ratio B1-1): Pentylamine (B2-1): Isopropanolamine (B2-2): Monoethanolamine (B2-3): Diethanolamine (B3-1): Sorbitol (B3-2): Glycerin (C -1): Magnesium stearate (C-2): Magnesium chloride (C-3): Bis (acetylacetonato) barium

Examples 1-32 and Comparative Examples 1-6
An aqueous binder was prepared according to the composition (parts) shown in Tables 1 to 3. Using the aqueous binder, specimens of a cured binder and a mineral fiber laminate were prepared in the following manner, and evaluated by the methods described below.

[1] Performance evaluation of cured binder <Creation of a cured binder specimen>
An aqueous binder was added to glass beads having an average particle diameter of 1 mm so that the binder solid content was 2.5%, and mixed sufficiently. This was pressed into a mold of 80 mm × 15 mm × 6 mm that had been subjected to mold release treatment, molded, and heat-treated for 20 minutes with a circulating dryer at 250 ° C. to obtain a test piece. Ten test pieces were prepared.

<Performance evaluation method of binder cured product>
The obtained test piece was evaluated for performance according to the following method. The results are shown in Tables 1-3.
(1) Mechanical strength The bending strength was measured at a test speed of 50 mm / min according to JIS K7171. The bending strength of 5 test pieces was measured, and the average value was calculated.
(2) Hydrolysis resistance Five test pieces were allowed to stand for 2 days in a constant temperature and humidity chamber at 85 ° C. and 95% RH. Thereafter, it was taken out and dried at 30 ° C. and 50% RH for 7 days. The bending strength of the test piece after drying was measured in the same manner as in (1) above, and the hydrolysis resistance of the cured binder was evaluated.

[2] Performance evaluation of mineral fiber laminate <Preparation of mineral fiber laminate specimen>
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 was uniformly sprayed onto the laminate using an air spray so that the amount of solid content after drying was a predetermined amount with respect to the weight of the laminate. Thereafter, heat treatment was performed for 20 minutes in a circulating dryer at 250 ° C. to obtain a laminate test piece having a thickness of about 1 cm and a density of 0.030 g / cm ³ .

<Evaluation method of mineral fiber laminate>
The obtained test piece was evaluated for performance according to the following method. The results are shown in Tables 1-3.
(1) Adhesiveness of mineral fiber laminate Five test pieces having a length x width of 10 cm x 1.5 cm were cut out from the test piece, and these were cut out using JIS R3420 "General Test Method for Glass Fiber" using an autograph. The tensile strength was measured according to “7.4 Tensile Strength”, the average value of five test pieces was calculated, and the adhesiveness of the laminate was evaluated according to the following criteria.
<Evaluation criteria>
◎: 500 N / m ² or more ○: 400 N / m ² or more and less than 500 N / m ² Δ: 300 N / m ² or more and less than 400 N / m ² ×: Less than 300 N / m ²

(2) Restorability test after compression of mineral fiber laminate From the test piece, 5 test pieces having a length × width of 10 cm × 1.5 cm were cut out, and the thickness of the test piece was 0.1 mm using calipers. Measured to the unit. The test piece was placed on a stainless steel plate (10 cm × 2 cm × 0.1 cm), and a stainless steel plate (weight of about 95 g) of the same size was placed on the test piece and compressed. After leaving the test piece compressed by the weight of the stainless steel plate in an atmosphere of 30 ° C. and 50% RH for 5 days, the upper stainless steel plate was removed from the test piece and the thickness of the test piece immediately after removal (after compression) The thickness of the test piece) was measured. The restoration ratio (%) was calculated from the following formula, and the average value of five test pieces was evaluated according to the following criteria.

Restoration ratio (%) = (thickness of test piece after compression / thickness of test piece before compression) × 100

<Evaluation criteria>
◎: Restoration ratio is 90% or more ○: Restoration ratio is 85% or more and less than 90% △: Restoration ratio is 75% or more and less than 85% ×: Restoration ratio is less than 75%

(3) Water resistance test Ten test pieces having a length x width of 10 cm x 1.5 cm were cut out from the test piece and immersed in tap water at 30 ° C for 1 day. Thereafter, it was taken out and dried at 30 ° C. and 50% RH for 1 day. The test pieces after drying were evaluated for adhesion and restorability in the same manner as (1) and (2).

(4) Hydrolysis resistance test Ten test pieces each having a length × width of 10 cm × 1.5 cm were cut out from the test pieces, and these were left in a constant temperature and humidity chamber at 85 ° C. and 95% RH for 7 days. . Thereafter, it was taken out and dried at 30 ° C. and 50% RH for 7 days. The test pieces after drying were evaluated for adhesion and restorability in the same manner as (1) and (2).

  From Tables 1-3, the mineral fiber laminate molded using the aqueous binder for mineral fibers of the present invention is superior to the comparative example in the adhesiveness of the mineral fibers and the restorability after compression of the laminate, It turns out that it is excellent also in the adhesiveness after a water resistance and a hydrolysis resistance test, and the decompression | restoration property after compression.

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

Claims (9)

Addition (co) polymer (A) having at least two carboxyl groups and / or latent carboxyl groups, at least two amine compounds having an amino group and / or imino group and no hydroxyl group (B1) ) Containing a crosslinking agent (B) and water, and the ratio (γ1) of the total number of moles of amino groups and imino groups in (B1) to the number of moles of carboxyl groups in (A) is 0.3-1.5 der is, mineral fibers aqueous binder is 5,000 to 50,000 weight average molecular weight of (a) (X).   The crosslinking agent (B) is a combination of (B1) and an alkanolamine (B2) and / or polyol (B3), and the amino acid in (B2) and (B3) with respect to the number of moles of the carboxyl group in (A) The ratio (γ2) of the total number of moles of the group, imino group and hydroxyl group is 0.05 to 0.6, and the sum of (γ1) and (γ2) is 0.35 to 1.5. Aqueous binder.   The aqueous binder according to claim 1 or 2, wherein the total content of (A) and (B) in the aqueous binder (X) is 2 to 80% by weight.   Furthermore, the aqueous | water-based binder in any one of Claims 1-3 which contain a hardening accelerator (C).   A mineral fiber laminate obtained by heating the mineral fiber laminate to which the aqueous binder according to claim 1 is attached.   The mineral fiber laminate according to claim 5, wherein the solid content of the aqueous binder is 0.4 to 40% based on the weight of the mineral fiber laminate.   The mineral fiber laminate according to claim 5 or 6, wherein the restoration ratio in the restoration test is 85% or more.   The mineral fiber laminate according to any one of claims 5 to 7, which is used for a heat insulating material, a heat insulating material or a sound absorbing material.   A method for producing a mineral fiber laminate, comprising heating and molding the mineral fiber laminate to which the aqueous binder according to any one of claims 1 to 4 is attached.