JP5755626B2 - 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 Japanese Patent Laid-Open No. 2007-21111

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 relates to (co) polymer (A) having at least two carboxyl groups and / or acid anhydride groups, at least one hydroxyl group, at least one amino group and / or at least one. A crosslinking agent (B) containing the compound (B1) having an imino group and water, and (A) with respect to the number of moles of the carboxyl group derived from the carboxyl group and / or the acid anhydride group, The ratio (γ1) of the total number of moles of hydroxyl group, amino group and imino group in (B) is from 0.1 to less than 0.8, and the ratio of the total number of moles of amino group and imino group in (B) (γ2 ) Is an aqueous binder (X) for mineral fibers having 0.05 to 0.4.

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

  The aqueous binder for mineral fibers (X) of the present invention comprises at least two (co) polymer (A) having a carboxyl group and / or an acid anhydride group, at least one hydroxyl group, and at least one amino group. A crosslinking agent (B) containing a compound (B1) having a group and / or at least one imino group and water, and derived from a carboxyl group and / or an acid anhydride group in (A) The ratio (γ1) of the total number of moles of hydroxyl group, amino group and imino group in (B) to the number of moles of carboxyl group is 0.1 or more and less than 0.8, and the ratio of amino group and imino group in (B) The ratio (γ2) of the total number of moles is 0.05 to 0.4.

[(Co) polymer (A)]
The (co) polymer (A) in the present invention has at least two carboxyl groups and / or acid anhydride groups. That is, (A) has at least two carboxyl groups, at least two acid anhydride groups, or a total of at least two groups of carboxyl groups and acid anhydride groups.

  (A) polymerizes a polymerizable unsaturated monomer (a) having a carboxyl group and / or an acid anhydride group, or (a) and, if necessary, other polymerizable unsaturated monomers other than (a) ( It is obtained by copolymerizing x). Examples of (a) include the following and mixtures thereof.

  Among (a), the polymerizable unsaturated monomer (a1) having a carboxyl group is an unsaturated monocarboxylic acid [(meth) acrylic acid (acrylic acid and / or Methacrylic acid, the same shall apply hereinafter), crotonic acid, cinnamic acid, vinylbenzoic acid, alkenoic acid [C4-20 (preferably C4-13) such as vinylacetic acid, 3-methyl-3-butenoic acid, 3 -Pentenoic acid, 4- and 5-hexenoic acid], monoalkyl (C1-8) esters of unsaturated dicarboxylic acids [C4-16, such as maleic acid monoalkyl esters, fumaric acid monoalkyl esters, citraconic acid monoalkyl esters] , Monoesters of unsaturated dicarboxylic acids [C5-20, eg ethyl carbitol monoester of maleic acid, ethyl fumaric acid Ruby tall monoesters, itaconic acid glycol monoester], etc.], C4-20 (preferably C4～16) unsaturated dicarboxylic acids [maleic acid, fumaric acid, citraconic acid, and itaconic acid] and the like.

Among (a), as the polymerizable unsaturated monomer (a2) having an acid anhydride group, an anhydride of the unsaturated dicarboxylic acid [C4-20 (preferably C4-16)] in (a1), for example, anhydrous Examples include maleic acid 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.

Examples of other polymerizable unsaturated monomer (x) include the following C2-30.
(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 monomer C3-30, such as vinyl alkyl (C1-20) ether;
(4) Nitrile monomer C3-10, such as (meth) acrylonitrile;

(5) Aliphatic unsaturated hydrocarbon monomer C2-30, such as ethylene, propylene, isobutylene, isoprene, butadiene, etc .;
(6) C8-30 styrene monomer Styrene, α-methylstyrene, p-methoxystyrene, vinyltoluene, p-hydroxystyrene, p-acetoxystyrene, and the like;
(7) C3-30 vinyl ester monomer Vinyl acetate, vinyl propionate and the like.
The above (x) may be used alone or in combination of two or more.

  Of the above (x), from the viewpoint of the curability of the binder, the adhesive strength (hereinafter sometimes referred to as mechanical strength after binder curing) and the stability of the binder solution, (2), (3), (5), (6), more preferred is (2), and particularly preferred is alkyl (C1-18) (meth) acrylate.

The proportion (% by weight) of each monomer constituting (A) is usually 60% or more, and preferably 70 to 100 from the viewpoint of the adhesive strength of the binder to mineral fibers (hereinafter abbreviated as binder adhesive strength). %, More preferably 80 to 100%; (x) is usually 40% or less, preferably 30% or less, more preferably 20% or less from the viewpoint of the adhesive strength of the binder.
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 to 90/10, more preferably 70/30 to 85/5, from the viewpoint of the curing rate and 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 500 to 100,000, more preferably 1,000 to 80,000, particularly preferably 5,000, from the viewpoint of the adhesive strength of the binder to the mineral fibers and the resilience to the compression of the mineral fiber laminate described below. ~ 50,
000.
The GPC measurement conditions of Mw and the number average molecular weight (hereinafter abbreviated as Mn) 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)
Um dissolved.
[4] Reference material: polyethylene glycol (hereinafter abbreviated as PEG)
[5] Injection conditions: sample concentration 0.25%, column temperature 40 ° C.

  The number of carboxyl groups and / or acid anhydride groups in (A) is at least 2, preferably 3 to 2,000, more preferably 5 to 1,000, and particularly preferably 10 to 500. . When the number of the carboxyl groups and / or acid anhydride groups is less than 2, the adhesive strength, water resistance and hydrolysis resistance of the binder to the mineral fibers are deteriorated.

(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 ketones [methyl ethyl ketone (hereinafter abbreviated as MEK) and the like], alcohols [isopropanol and the like] and the like. From the viewpoint of productivity, ketones are preferable, and MEK is more preferable.
The (A) is usually obtained as a solution (preferably an aqueous solution), and the content (% by weight) of (A) in the solution is determined from the viewpoint of productivity and handleability during the production of the aqueous binder (X) in the subsequent step. Is preferably 5 to 80%, more preferably 10 to 70%, and particularly preferably 20 to 60%.

The polymerization temperature is preferably 0 to 200 ° C. from the viewpoint of productivity and (A) molecular weight control.
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 crosslinking agent (B) in the present invention includes the compound (B1). Compound (B1) includes at least one (preferably 1 to 10, more preferably 1 to 6) hydroxyl group, at least one (preferably 1 to 4) amino group and / or at least one ( Preferably it is a compound having 1-4 imino groups. In the present invention, the amino group means a primary amino group, and the imino group means a secondary amino group.
When the number of the hydroxyl groups is less than 1, the adhesive strength of the binder to the mineral fiber is reduced, and when the number of amino groups and / or imino groups in (B1) is less than 1, the water resistance and hydrolysis resistance of the binder are deteriorated. .

  Examples of (B1) include C2-20 hydroxylamine, amine alkylene oxide (hereinafter abbreviated as AO) adducts, and mixtures thereof.

Hydroxylamine includes C2-20, for example having one hydroxyl group [having an amino group [for example, monoethanolamine, isopropanolamine], having an amino group and an imino group [for example, 2- (2-aminoethylamino ) Ethanol] and the like, and those having two hydroxyl groups [those having an imino group (for example, diisopropanolamine, diethanolamine, etc.)].

AO adducts of amines include those having 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], aromatic amines [ C6-12, eg aniline, toluidine, xylylenediamine], alicyclic amines [C4-10, eg cyclopentylamine, cyclohexylamine], heterocycle containing amines [C4-10, eg piperazine] and AO addition of said hydroxylamines Things. AO addition mole number is 1
20 moles are preferred. Many of these amine AO adducts have an imino group.

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 these (B1), from the viewpoint of the curability of the binder and the stability of the binder solution, those having an amino group of C2-20 hydroxylamine, those having an amino group, and an imino group are preferred. In combination with those possessed, monoethanolamine and diethanolamine are more preferred, and monoethanolamine is particularly preferred.

The above (B1) may be used alone or in combination of two or more.
The ratio (mol%) of the amino group based on the total number of moles of amino group and imino group in (B1) (including one kind alone and two or more kinds in combination) is the adhesive strength of the binder to the mineral fiber and the water resistance of the binder From the viewpoint of the property and hydrolysis resistance, it is preferably 30% or more, more preferably 40% or more, and particularly preferably 50 to 100%.

The crosslinking agent (B) in the present invention contains the compound (B1), but for the purpose of improving the adhesive strength of the aqueous binder (X) of the present invention, a polyol (B2) may be contained as necessary. .
(B2) includes C2 or more and poly (n = 2 to 3 or more) ols having Mn of 1,000 or less, such as aliphatic polyols [of C2-12, such as ethylene glycol and its dimers and trimers, propylene Glycol and its dimer, trimer, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,3-butanediol 1,4-butanediol, 2-methyl-2,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 1, 6-hexanediol, 1,4-cyclohexanediol, 2-ethyl-1,3-hexanediol, 2-hydroxymethyl-2-methyl-1,3-propyl Pandiol, 2-ethyl-2-hydroxymethyl-2-methyl-1,3-propanediol, 1,2,6-hexanetriol, 2,2-bis (hydroxymethyl) -2,3-propanediol]; Cycloaliphatic polyols [C5-12, such as 1,3-cyclopentanediol, 1,4-cyclohexanediol]; trialkanolamines [C6-12, such as triethanolamine, triisopropanolamine]; saccharides [ C6-12, such as glucose, fructose, mannitol, sorbitol, maltitol, sucrose]; and AO (C2-4) adducts of these polyols. These may be used alone or in combination of two or more.

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

[Aqueous binder for mineral fibers (X)]
The aqueous binder for mineral fibers (X) of the present invention comprises the (co) polymer (A), a crosslinking agent (B) and water, and the carboxyl group and / or acid anhydride group in (A). The ratio (γ1) of the total number of moles of the hydroxyl group, amino group and imino group in (B) to the number of moles of the carboxyl group derived from is 0.1 or more and less than 0.8, preferably 0.2-0. 75, more preferably 0.3 to 0.7.
The ratio (γ2) of the total number of moles of amino groups and imino groups in (B) to the number of moles of carboxyl groups derived from the carboxyl group and / or acid anhydride group in (A) is 0. It is 05-0.4, Preferably it is 0.1-0.38, More preferably, it is 0.15-0.35.
When the ratio (γ1) is less than 0.1 and / or the ratio (γ2) is less than 0.05, the adhesive strength of the binder decreases, and the ratio (γ1) is 0.8 or more and / or the ratio (γ2) is 0. If it exceeds .4, the water resistance and hydrolysis resistance after curing the binder deteriorate.

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

Ratio (γ1) = [Hydroxyl value of (B) +1,2 secondary amine value of (B)] × [Weight of (B)]
/ [[Acid value of (A)] × [weight of (A)]]
Ratio (γ2) = [1,2 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] 2, tertiary amine value (23A), [3] tertiary amine value (3A) were measured by the method described below, and the following formula From the above, the primary and secondary amine values (12A) are obtained.
(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 for measuring 2, tertiary amine value (23A) 2, tertiary amine value (23A) is the amount of hydroxylation equivalent to hydrochloric acid required to neutralize the secondary or tertiary amine contained in 1 g of the sample. Refers to the number of mg of potassium. Measured by the following method according to ASTM D2074.
(1) Weigh accurately the sample. (Sample amount: S ₂ g)
(2) Neutral ethanol [Bromocresol Green (BCG, the same shall apply hereinafter) Neutral] 30 m
Add L and dissolve.
(3) Add 5 mL of 25% salicylaldehyde in ethanol and leave at room temperature for about 30 minutes.
(4) Titrate with 0.2 mol / L ethanolic hydrochloric acid solution (titer: f ₂ ), and the point at which the color changed from green to yellow is the end point. (Titration volume: A ₂ mL)
(5) The secondary and tertiary amine values (23A) are calculated from the following formula.

2, tertiary amine value (23A) = A ₂ × f ₂ × 0.2 × 56.108 / S ₂

[3] Method for 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 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

Further, the ratio (mol%) of the amino group based on the total number of moles of the amino group (namely, primary amino group) and imino group (namely, secondary amino group) in the (B) can be obtained from the following calculation formula. .
Ratio of amino group based on the total number of moles of amino group and imino group in (B) (mol%)
= (1A) × 100 / [(1A) + (2A)]

However, (1A): represents a primary amine value, and is obtained from the following formula.
(1A) = (All A)-(23A)
(2A): Represents a secondary amine value and is determined from the following formula.
(2A) = (23A)-(3A)

  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 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, further curing acceleration is required for the purpose of further accelerating the curing rate of the binder during the production of the mineral fiber laminate described later. An agent (C) may be contained.
(C) includes a protonic acid [phosphoric acid compound (phosphoric acid, phosphorous acid, hypophosphorous acid, phosphoric acid dihydride, polyphosphoric acid, alkylphosphinic acid, etc.), carboxylic acid, carbonic acid, etc.] and a salt 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, hydroxide Products and alkoxides, and these may be used alone or in combination of two or more.
Of these, phosphoric acid compounds and salts thereof, carboxylic acids and salts thereof are preferable from the viewpoint of curing speed, and phosphoric acid, phosphorous acid, hypophosphorous acid, phosphoric dihydride, polyphosphoric acid, alkyl are more preferable. Phosphinic acid and salts thereof and titanium lactate and zirconyl acetate, particularly preferred are salts of hypophosphorous acid.
The content of (C) is preferably 0.1 to 30%, more preferably 0.3 to 20%, particularly preferably 0.5 to 15% based on the total weight of (A) and (B). It is.

  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 (co) polymer (A), compound (B1), water, and optionally added polyol (B2), curing accelerator (C), additive ( There is no particular limitation as long as D) can be mixed and dispersed. 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 adhering the aqueous binder (X) to mineral fibers and laminating them to form a laminate, which is then heated and molded, or the mineral fibers or strands thereof It is obtained by laminating (fiber bundles) to form a laminate, attaching the aqueous binder (X) thereto, 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 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 the adhesion between the mineral fibers, the smoothness of the laminate surface, and the laminate From a viewpoint of a softness | flexibility and the restoring property with respect to compression, Preferably it is 0.4 to 40%, More preferably, it is 1 to 20%, Most preferably, it is 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 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 or acid anhydride group in the (co) polymer (A) reacts with the hydroxyl group, amino group and / or imino group in (B). In this way, the resin hardens to become a strong resin and can exhibit an excellent binder function for adhering 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 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. In the following, Examples 1 to 9 and 12 to 19 are referred to as Reference Examples 1 to 17, respectively.

The (co) polymer (A) used in Examples and Comparative Examples is as follows.
(A-1): Polyacrylic acid (Mw 13,000, acid value 700) aqueous solution, nonvolatile content 50% (A-2): Acrylic acid / hydroxyethyl methacrylate (weight ratio = 90/6) copolymerization
Body (Mw 11,000, acid value 660) aqueous solution, non-volatile content 50%
(A-3): Polyacrylic acid (Mw 27,000, acid value 750) aqueous solution, nonvolatile content 50%

Examples 1-17, Comparative Examples 1-4
An aqueous binder was prepared according to the composition (parts) shown in Tables 1 and 2. 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 which had been subjected to mold release treatment and molded, and heat-treated for 45 minutes with a circulating dryer at 230 ° 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 and 2.
(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 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 1 day. 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 having a solid weight equivalent to 20% after drying with respect to the weight of the laminate was uniformly sprayed onto the laminate using an air spray. Thereafter, heat treatment was performed for 45 minutes with a circulating dryer at 230 ° 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 and 2.
(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. 7.4 tensile strength "was measured, and the average value of five test pieces 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 after compression of mineral fiber laminate 5 pieces of a test piece having a length x width of 10 cm x 1.5 cm were cut out from the test piece, and the thickness of the test piece was measured in 0.1 mm units using calipers. Until measured. 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 Ten test pieces having a length × width of 10 cm × 1.5 cm were cut out from the test pieces and immersed in tap water at 45 ° C. for 5 days. 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 Ten test pieces each having a length × width of 10 cm × 1.5 cm were cut out from the test pieces, and left standing 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 1 day. The test pieces after drying were evaluated for adhesion and restorability in the same manner as (1) and (2).

From Tables 1 and 2, the mineral fiber laminate molded using the mineral fiber aqueous binder of the present invention is superior to the comparative example in the adhesion 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 restoring 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)

(Co) polymer (A) having at least two carboxyl groups and / or acid anhydride groups, having at least one hydroxyl group and at least one amino group and / or at least one imino group A hydroxyl group in (B) with respect to the number of moles of a carboxyl group derived from a carboxyl group and / or an acid anhydride group in (A), comprising a crosslinking agent (B) containing compound (B1) and water The ratio of the total number of moles of amino groups and imino groups (γ1) is 0.1 or more and less than 0.8, and the ratio of the total number of moles of amino groups and imino groups in (B) (γ2) is 0.05 to An aqueous binder (X) for mineral fibers, which is 0.4 , wherein (B1) is a combination of a hydroxylamine having 2 to 10 carbon atoms having an amino group and an imino group .   The aqueous binder according to claim 1, wherein the total content of (A) and (B) is 2 to 80% by weight.   The aqueous binder according to claim 1 or 2, wherein the proportion of amino groups based on the total number of moles of amino groups and imino groups in (B1) is 30 mol% or more.   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 and molding the mineral fiber laminate to which the aqueous binder according to any one of claims 1 to 4 is adhered.   The 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 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.