JP6230369B2 - Inorganic fiber mat and method for producing the same - Google Patents

Description

  The present invention relates to an inorganic fiber mat and a method for producing the same.

As a heat insulating material used for a wall of a house, an inorganic fiber mat such as rock wool or glass wool is used. These mats generally have inorganic fibers hardened with a phenol resin as a binder.
However, since phenol resin contains formaldehyde, formaldehyde is released into the atmosphere with the passage of time, causing a so-called sick house.

  Patent Documents 1 and 2 disclose acrylic resin binders that do not contain formaldehyde. However, these water-based binders have a high ratio of the total number of moles of functional groups that are hydroxyl groups, amino groups, and imino groups of the crosslinking agent to the number of moles of carboxyl groups contained in the binder, so that water resistance and hydrolysis resistance are high. It was inferior to.

  In response to this problem, Patent Documents 3 to 5 increase the hydrolysis resistance by reducing the molar ratio of the functional group of the crosslinking agent to the carboxyl group.

Japanese Patent Laid-Open No. 10-509485 Japanese Patent Laid-Open No. 2007-21111 JP 2013-117083 A JP 2013-136864 A JP 2013-151777 A

  An object of the present invention is to provide an inorganic fiber mat with improved water resistance or hydrolysis resistance and a method for producing the same.

  As a result of diligent research, the present inventors have been able to impart water repellency to the resulting cured product itself by reacting the functional groups of the resin contained in the reactive silicone oil and the binder, thereby providing water resistance or hydrolysis resistance. The present invention has been completed by finding that it can be enhanced.

According to the present invention, the following inorganic fiber mat and a method for producing the same are provided.
1. A water-based binder and reactive silicone oil are adhered to inorganic fibers,
A method for producing an inorganic fiber mat to be cured,
The aqueous binder is
(Co) polymer (A) having at least two selected from a carboxyl group and an acid anhydride group;
A crosslinking agent (B) containing a compound (B1) having at least two functional groups selected from a hydroxyl group, an amino group and an imino group;
A method for producing an inorganic fiber mat comprising water.
2. 2. The inorganic fiber according to 1, wherein the functional group of the compound (B1) contained in the crosslinking agent (B) of the aqueous binder is at least one hydroxyl group, at least one amino group and / or at least one imino group. Manufacturing method of mat.
3. The method for producing an inorganic fiber mat according to 1 or 2, wherein the aqueous binder further contains a curing accelerator (C).
4). The manufacturing method of the inorganic fiber mat in any one of 1-3 in which the said reactive silicone oil contains an epoxy group or an amino group.
5. The method for producing an inorganic fiber mat according to any one of 1 to 4, wherein the reactive silicone oil is an amine-modified silicone oil.
6). The manufacturing method of the inorganic fiber mat in any one of 1-5 whose quantity of the said reactive silicone oil is 0.02-8 weight part with respect to 100 weight part of said (co) polymers (A).
7). The manufacturing method of the inorganic fiber mat in any one of 1-6 whose said inorganic fiber is rock wool.
8). The molten mineral raw material is sprayed with the water-based binder together with air, and the fleece is formed on the first belt by depositing the fibers with the water-based binder attached thereto,
Moving the first belt carrying the fleece and moving the fleece from the first belt to the second belt at a predetermined position;
Move the second belt carrying the fleece and stack the fleece in place
8. The method for producing an inorganic fiber mat according to 7, wherein the stacked fleece is heated to cure the aqueous binder contained in the fleece.
An inorganic fiber mat obtained by the production method according to any one of 9.1 to 8.
A heat insulating material, heat insulating material or sound absorbing material comprising the inorganic fiber mat according to 10.9.

  ADVANTAGE OF THE INVENTION According to this invention, the inorganic fiber mat which improved water resistance or hydrolysis resistance, and its manufacturing method can be provided.

It is a figure which shows the manufacturing method of the rock wool mat concerning one Embodiment of this invention.

The inorganic fiber mat of the present invention can be produced by attaching an aqueous binder and reactive silicone oil to inorganic fibers and curing them by heating or the like.
The aqueous binder comprises at least two (co) polymer (A) having a carboxyl group and / or an acid anhydride group, and a compound having at least two functional groups selected from a hydroxyl group, an amino group and an imino group It contains a crosslinking agent (B) containing (B1) and water. By reacting the carboxyl group contained in the binder and the reactive silicone oil, water repellency can be stably imparted to the resulting cured product itself for a long period of time, and the water resistance or hydrolysis resistance of the inorganic fiber mat can be improved. .

  The amount of the reactive silicone oil is usually 0.02 to 8 parts by weight, preferably 0.03 to 5 parts by weight, more preferably 0.05 to 100 parts by weight of the (co) polymer (A). ~ 2 parts by weight.

  The inorganic fibers constituting the inorganic fiber mat may be mineral fibers such as rock wool and glass wool.

The reactive silicone oil has a functional group capable of reacting with the (co) polymer (A), for example, an epoxy group or an amino group. Specifically, monoamine-modified silicone oil, diamine-modified silicone oil, amino / polyether-modified silicone oil, epoxy-modified silicone oil, carbinol-modified silicone oil, mercapto-modified silicone, and the like can be used.
The reactive silicone oil may be any of a side chain type, a both terminal type, a single terminal type, and a side chain both terminal type.

  The reactive silicone oil may be added to the aqueous fiber and adhered to the inorganic fiber, or the reactive silicone oil may be adhered to the inorganic fiber together with the aqueous binder separately from the aqueous binder.

  The binder and the reactive silicone oil may be attached to the fiber together with air blowing during the production of the inorganic fiber, but are not limited thereto. For example, you may make it adhere after formation of a fleece (thin mat | matte before lamination | stacking) and a mat | matte (laminated body of fleece).

For example, an aqueous binder and a reactive silicone oil are attached to inorganic fibers and laminated to form a laminate, which is then heated and molded.
Examples of the method for attaching the aqueous binder to the mineral fiber or a laminate thereof include known methods such as an air spray method or an airless spray method, a padding method, a roll coating method, a curtain coating method, and a beater deposition method. .

  In the production of the inorganic fiber mat, the aqueous binder is usually adhered to a mineral fiber in an appropriate amount, and then heated and dried to be cured. Usually, heating is performed at 100 to 400 ° C. for 10 seconds to 60 minutes.

  The aqueous binder cures and becomes a strong resin by reacting the carboxyl group derived from the carboxyl group or acid anhydride group in the (co) polymer (A) with the functional group in the crosslinking agent (B). The function of an excellent binder for bonding fibers can be exhibited.

  The solid content of the binder is preferably 0.4 to 40% by weight, more preferably 0.4 to 20% by weight, still more preferably 1.0 to 10% by weight, based on the weight of the inorganic fiber mat. is there. If the amount is too small, the bonding strength is insufficient. If the amount is too large, the flexibility of the mat may be impaired.

As the aqueous binder used in the present invention, those described in Patent Documents 1 to 5 can be used, and those described in Patent Documents 3 to 5 can be particularly preferably used. Specifically, the uncured binder contains the following components (A) and (B) and water. In Patent Documents 3 to 5, the amount of the crosslinking agent (B) is small relative to the (co) polymer (A), and the crosslinking agent is 100% by weight in combination with the (co) polymer (A) and the crosslinking agent (B). (B) is, for example, 10 to 40% by weight or 15 to 25% by weight.
(A) (co) polymer having at least two carboxyl groups and / or acid anhydride groups (B) Compound (B1) having at least two functional groups selected from hydroxyl group, amino group and imino group Containing cross-linking agent

  Hereinafter, the components of the binder will be described.

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

  The (co) polymer (A) is obtained by polymerizing a polymerizable unsaturated monomer (a) having a carboxyl group and / or an acid anhydride group, or other than the monomer (a) and, if necessary, the monomer (a). The polymerizable unsaturated monomer (x) is copolymerized. Examples of the monomer (a) include the following and mixtures thereof.

  Among the monomers (a), as the polymerizable unsaturated monomer (a1) having a carboxyl group, an unsaturated monocarboxylic acid having 3 to 20 carbon atoms (hereinafter abbreviated as C) [(meth) acrylic acid (acrylic acid and / or Or methacrylic acid, the same shall apply hereinafter), crotonic acid, cinnamic acid, vinyl benzoic 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 fumarate Carbitol 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 the monomers (a), as the polymerizable unsaturated monomer (a2) having an acid anhydride group, an anhydride of an unsaturated dicarboxylic acid [C4-20 (preferably C4-16)] in the monomer (a1), for example, , Maleic anhydride and itaconic anhydride.
Of the monomers (a1) and (a2), the monomer (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 ether 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.
(8) Allyl monomers C3-10, such as N-allylamine, N-alkyl (C1-5) allylamine, N, N-dialkyl (C1-5) allylamine;
The monomer (x) may be used alone or in combination of two or more.

  Of the above monomers (x), (2) and (3) are preferable from the viewpoints 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. , (5), (6), more preferred is (2), and particularly preferred is alkyl (C1-18) (meth) acrylate.

  The proportion (% by weight) of each monomer constituting the (co) polymer (A) is such that the monomer (a) is usually 20% or more, and the adhesive strength of the binder to mineral fibers (hereinafter abbreviated as binder adhesive strength). To preferably 60% or more, 70 to 100%, more preferably 80 to 100%; monomer (x) is usually 20% or less, preferably 40% or less, 30% or less, more preferably from the viewpoint of the adhesive strength of the binder Is 20% or less.

[Crosslinking agent (B)]
The crosslinking agent (B) includes the compound (B1). The following compounds can be used as the compound (B1). Two or more kinds can be mixed and used.

Compound (B1-1)
At least one (preferably 1 to 10, more preferably 1 to 6) hydroxyl group, at least 1 (preferably 1 to 4) amino group and / or at least 1 (preferably 1 to 4). And a compound having an imino group. In the present invention, the amino group means a primary amino group, and the imino group means a secondary amino group.

Compound (B1-2)
A polyol having at least 2 (preferably 3 or more, more preferably 4 or more) hydroxyl groups.

Compound (B1-3)
A compound having at least two amino groups and / or imino groups.

  Examples of (B1-1) include C2-20 hydroxylamines, amine alkylene oxide (hereinafter abbreviated as AO) adducts, and mixtures thereof.

  Examples of hydroxylamine include C2-20 (preferably C1-6) alkyl alcohol amines, such as those having one hydroxyl group [having amino groups [eg monoethanolamine, propanolamine], amino groups, and imino groups. [For example, 2- (2-aminoethylamino) ethanol] and the like, and those having two hydroxyl groups [for example, those having an imino group (for example, dipropanolamine, 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, such as aniline, toluidine, xylylenediamine], alicyclic amines [C4-10, such as cyclopentylamine, cyclohexylamine], heterocyclic amines [C4-10, such as piperazine] and AO addition of said hydroxylamine 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 more (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, eg styrene oxide, and combinations of two or more thereof (random addition and / or block addition) included.

  Of these (B1-1), monoalcoholamines and dialcoholamines among C2-20 hydroxylamines are preferred from the viewpoint of the curability of the binder and the stability of the binder solution.

  The ratio (mol%) of amino groups based on the total number of moles of amino groups and imino groups in (B1-1) (including one kind alone and two or more kinds in combination) is the adhesive strength of the binder to the mineral fiber and the binder From the viewpoint of water resistance and hydrolysis resistance, it is preferably 30% or more, more preferably 40% or more, and particularly preferably 50 to 100%.

(B1-2) is, for example, C2 or more and Mn 1,000 or less poly (n = 2 to 3 or more) ol, such as aliphatic polyols [C2-12, such as ethylene glycol and its two or three amounts , 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 Propanediol, 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.
Of the above, propylene glycols and ethylene glycols are preferred because they add wettability and reduce adhesiveness when added to an aqueous resin solution, and propylene glycol is preferred because it is neither toxic nor flammable.

(B1-3) includes 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. It is.
(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.).

[Water-based binder]
Ratio of the total number of moles of hydroxyl groups, amino groups and imino groups in the crosslinking agent (B) to the number of moles of carboxyl groups derived from the carboxyl group and / or acid anhydride group in the (co) polymer (A) ( γ1) is usually 0.1 or more and 3 or less, and may be 0.1 or more and less than 0.8. The ratio (γ2) of the total number of moles of amino groups and imino groups in the crosslinking agent (B) is usually 0.03 to 1, and may be 0.05 to 0.4.
When γ1 is small, the hydrolysis resistance increases. The method of calculating | requiring said ratio of the number of moles is described in patent documents 3-5.

  The total content of the (co) polymer (A) and the crosslinking agent (B) in the aqueous binder is preferably 2 to 80% by weight from the viewpoint of the productivity of the inorganic fiber mat described later and the uniform sprayability of the aqueous binder, More preferably, it is 2-70 weight%, Most preferably, it is 3-60 weight%.

  In addition to the (co) polymer (A), the crosslinking agent (B) and water, the aqueous binder further contains a curing accelerator (C) if necessary for the purpose of further accelerating the curing rate of the binder. Also good.

The following substances can be used as the curing accelerator (C). Two or more kinds may be used in combination.
(C1) Protic acid [phosphoric acid compound (phosphoric acid, phosphorous acid, hypophosphorous acid, phosphoric acid dihydride, polyphosphoric acid, alkylphosphinic acid, etc.), carboxylic acid, carbonic acid etc.] and 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) oxides, chlorides, hydroxides and alkoxides .

(C2) Lewis acid containing one or more elements (c1) selected from the group consisting of boron, aluminum, tin, antimony, iron, zinc, titanium, zirconium, magnesium, beryllium, lead, bismuth and cobalt.
Protic acids such as sulfo group-containing compounds (for example, benzenesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, methanesulfonic acid, p-aminobenzenesulfonic acid, and salts thereof).

(C3) Organic metal compounds such as organic acid salts, metal alkoxides or metal complexes (for example, acetylacetonate) of lithium, sodium, potassium, rubidium or cesium; metal oxides, metal hydroxides, carbonates, sulfates, A curing accelerator comprising a Group 1 metal of the periodic table such as an inorganic metal compound such as nitrate, chloride or fluoride.
Organometallic compounds such as organic acid salts, metal alkoxides or metal complexes (eg acetylacetonate) of beryllium, magnesium, calcium, strontium or barium; metal oxides, metal hydroxides, carbonates, sulfates, nitrates, chlorides Or a curing accelerator containing a Group 2 metal of the periodic table such as an inorganic metal compound such as fluoride.
Scandium, ytterbium, yttrium or other rare earth organic metal compounds such as organic acid salts, metal alkoxides or metal complexes (eg acetylacetonate); metal oxides, metal hydroxides, carbonates, sulfates, nitrates, chlorides Or a curing accelerator containing a Group 3 metal of the periodic table such as an inorganic metal compound such as fluoride.

  The content of (C) is preferably 0.1 to 30%, more preferably 0.3 to 20%, particularly preferably based on the total weight of the (co) polymer (A) and the crosslinking agent (B). Is 0.5-15%.

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

  Since the aqueous binder used in 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.

[Rock wool mat]
The rock wool mat of the present invention is a mat made of a rock wool laminate, and the rock wool is adhered to each other by a hardened binder.
The manufacturing method of the rock wool mat of this invention is demonstrated using FIG. FIG. 1 is a diagram showing a method for producing a rock wool mat according to an embodiment of the present invention.
The melted raw material 1 is hung on a roll 11 that rotates at high speed. A binder is sprayed together with air onto a roll 11 that flows through the surroundings of the raw material 1, and the raw material 1 is made into a fiber and blown off to a steel belt (first belt) 13. Fibers accumulate on the steel belt 13 to form the fleece 3. The fleece 3 moves with the movement of the steel belt 13 and moves to a pendulum (second belt) 15 at a predetermined position. Thereafter, the fleece 3 further moves and moves onto the conveyor (third belt) 17 at a predetermined position. The laminated body 5 is formed by stacking fleece on the conveyor 17. The laminate 5 is passed through a curing furnace 19 to cure the binder, and the mat 7 is obtained.

The (co) polymer (A) usually has a weight average molecular weight of 1000 to 80000.
By including the (co) polymer (A) (low molecular weight (co) polymer) having a low weight average molecular weight (hereinafter also referred to as molecular weight) (for example, 2000 to 6500), the fleece adheres to the steel belt. It becomes easy to move from steel belt to pendulum.
By containing the (co) polymer (A) (high molecular weight (co) polymer) having a large molecular weight (for example, 6500 to 15000), the strength of the cured product is increased and the compression recovery rate is increased.
Therefore, when a mixture of a low molecular weight (co) polymer and a high molecular weight (co) polymer is used, it is easy to produce and the restoration rate can be maintained.

  The ratio of the low molecular weight (co) polymer and the high molecular weight (co) polymer is preferably 10 to 90:90 to 10, more preferably 20 to 80:80 to 20, and still more preferably 40 to 60: 60-40.

The weight average molecular weight is determined by gel permeation chromatography (GPC). The GPC measurement conditions are as follows.
<GPC measurement conditions>
[1] Apparatus: Gel permeation chromatograph [2] SB806M
Two HQ 8.0 mm (ID) × 30.0 cm (L) are connected in series.
[3] Eluent: 0.5% by weight of sodium acetate dissolved in methanol / water = 30/70 (volume ratio).
[4] Reference material: polyethylene glycol / polyethylene oxide (hereinafter abbreviated as PEG / PEO)
[5] Injection conditions: sample concentration 0.25%, column temperature 40 ° C.

  When spraying the aqueous binder together with air, the concentration of components other than water is 1 to 20% by weight, preferably 1 to 10% by weight.

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

The polymers (A), crosslinking agents (B), curing catalysts (C), and reactive silicone oil water repellents (D) used in Examples and Comparative Examples are as follows.
(A-1): Polyacrylic acid (Mw7500, acid value 700) aqueous solution, non-volatile content 50%
(A-2): Polyacrylic acid (Mw5700, acid value 700) aqueous solution, non-volatile content 50%
(B): Monopropanolamine (C): Sodium hypophosphite (D-1) Monoamine-modified silicone oil (D-2) Diamine-modified silicone oil

Examples 1-6
A polymer (A), a crosslinking agent (B), a curing catalyst (C), a reactive silicone oil (monoamine-modified silicone oil) (D), and water were mixed in the blending amounts shown in Table 1 to prepare an aqueous binder. Table 1 shows the parts by weight of the components (B) to (D) when the polymer (A) is 100 parts by weight. Using the aqueous binder, specimens of a cured binder and a mineral fiber mat were prepared in the following manner, and evaluated by the methods described below. The results are shown in Table 1.

[1] Performance evaluation of cured binder product <Preparation of test specimen of cured binder product>
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% by weight and mixed sufficiently. This was pressed into a 80 mm × 10 mm × 4 mm mold and molded, and heat-treated with a circulating dryer at 230 ° C. for 10 minutes to obtain a test piece. Ten test pieces were prepared.

<Performance evaluation method of binder cured product>
About the obtained test piece, performance evaluation was performed according to the following method.

(1) Mechanical strength According to JIS K7171, the bending strength was measured at a test speed of 2 mm / min and a distance between fulcrums of 64 mm. The bending strength of 5 test pieces was measured, and the average value was calculated.

(2) Hydrolysis resistance Five test pieces were left in a constant temperature and humidity chamber at 60 ° C. and 95% RH for 7 days. Thereafter, it was taken out and dried at 25 ° 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 average value was calculated to evaluate the hydrolysis resistance of the cured binder.

[2] Performance evaluation of mineral fiber mat <Preparation of mineral fiber mat specimen>
A rock wool mat was prepared by supplying the binder solution so that the binder solid content was 2.5% by weight by the method described above using the apparatus of FIG. The produced rock wool mat had a thickness of 5.5 cm and a density of 40 kg / m ³ .

<Performance evaluation method of mineral fiber mat>
The performance of the obtained rock wool mat was evaluated according to the following method. The results are shown in Table 1.
(1) Compression restoration test of mineral fiber mat Five test pieces each having a length × width × thickness 6 cm × 6 cm × 5.5 cm were cut out from the produced rock wool mat, and the thickness of the test piece was measured using a caliper. Measurement was performed to obtain a compression restoration test specimen. The compression restoration test specimen was compressed with an A & D universal testing machine so that the thickness of the specimen became 19.00 mm and left for 1 minute. Thereafter, the compressed state was released, and the thickness of the specimen was measured using a caliper. The thickness of the specimen was measured to the nearest 0.01 mm. The restoration rate (%) was obtained from the following formula, and the average value of 5 test pieces was calculated.
Restoration rate (%) = (thickness of test piece after compression / thickness of test piece before compression) × 100

(2) Hydrolysis resistance of mineral fiber mat From the produced rock wool mat, five test pieces each having a length x width x thickness of 6 cm x 6 cm x 5.5 cm were cut out, and the thickness of the test piece was measured using a caliper. It was measured. The test piece was allowed to stand for 7 days in a thermo-hygrostat under an atmosphere of 60 ° C. and 95% RH. Thereafter, the sample was taken out and dried at 25 ° C. and 50% RH for 1 day to obtain a compression restoration test specimen. The compression restoration test specimen was compressed with an A & D universal testing machine so that the thickness of the specimen became 19.00 mm and left for 1 minute. Thereafter, the compressed state was released, and the thickness of the specimen was measured using a caliper. The thickness of the specimen was measured to the nearest 0.01 mm. The restoration rate ratio (%) was obtained from the following formula, and the average value of 5 test pieces was calculated.
Restoration rate (%) = (thickness of test piece after compression / thickness of test piece before compression) × 100

Comparative Examples 1-3
As shown in Table 1, a cured binder was prepared and evaluated in the same manner as in Example 1 except that no reactive silicone oil was added. The results are shown in Table 1. As shown in Table 1, both the performance evaluation test of the cured binder and the evaluation test of the mineral fiber mat were inferior to those added with the reactive silicone oil.

  The inorganic fiber mat of the present invention can be used as a heat insulating material, a heat insulating material, a sound absorbing material or the like used in buildings and various devices.

DESCRIPTION OF SYMBOLS 1 Melted raw material 3 Fleece 5 Laminated body 7 Rock wool mat 11 Roll 13 Steel belt (1st belt)
15 Penjuram (second belt)
17 Conveyor (third belt)
19 Curing furnace

Claims (10)

To the inorganic fiber, an aqueous binder and a reactive silicone oil containing an amino group are attached,
A method for producing an inorganic fiber mat to be cured,
Saccharides are not attached to the inorganic fibers,
The aqueous binder is
(Co) polymer (A) having at least two selected from a carboxyl group and an acid anhydride group;
A crosslinking agent (B) other than a saccharide, comprising a compound (B1) having at least two functional groups selected from a hydroxyl group, an amino group, and an imino group;
A method for producing an inorganic fiber mat comprising water.   The functional group of the compound (B1) contained in the crosslinking agent (B) of the aqueous binder is at least one hydroxyl group, at least one amino group and / or at least one imino group. Manufacturing method of inorganic fiber mat.   The method for producing an inorganic fiber mat according to claim 1 or 2, wherein the aqueous binder further contains a curing accelerator (C). The method for producing an inorganic fiber mat according to claim 1, wherein the reactive silicone oil further contains an epoxy group . The method for producing an inorganic fiber mat according to any one of claims 1 to 4, wherein the reactive silicone oil is an amine-modified silicone oil selected from monoamine-modified silicone oil, diamine-modified silicone oil and amino-polyether-modified silicone oil. .   The method for producing an inorganic fiber mat according to any one of claims 1 to 5, wherein an amount of the reactive silicone oil is 0.02 to 8 parts by weight with respect to 100 parts by weight of the (co) polymer (A). .   The said inorganic fiber is rock wool, The manufacturing method of the inorganic fiber mat in any one of Claims 1-6. The molten mineral raw material is sprayed with the water-based binder together with air, and the fleece is formed on the first belt by depositing the fibers with the water-based binder attached thereto,
Moving the first belt carrying the fleece and moving the fleece from the first belt to the second belt at a predetermined position;
Move the second belt carrying the fleece and stack the fleece in place
The method for producing an inorganic fiber mat according to claim 7, wherein the stacked fleece is heated to cure the aqueous binder contained in the fleece. An inorganic fiber mat containing a cured binder for adhering inorganic fibers and the inorganic fibers to each other,
The binder is
Reactive silicone oil containing amino groups and
(Co) polymer (A) having at least two selected from a carboxyl group and an acid anhydride group;
An inorganic fiber mat comprising a reaction product with a crosslinking agent (B) other than a saccharide containing a compound (B1) having at least two functional groups selected from a hydroxyl group, an amino group, and an imino group .   A heat insulating material, a heat insulating material or a sound absorbing material comprising the inorganic fiber mat according to claim 9.

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