JP2012214948A - Binder for inorganic fiber nonwoven fabric - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a binder for an inorganic fiber nonwoven fabric which provides a nonwoven fabric pertaining uniform and excellent mechanical strength even if a coating weight of the binder is reduced, and excellent for its high yield rate in spraying the binder even in a manufacturing process of the inorganic fiber nonwoven fabric with low basis weight.SOLUTION: A binder for an inorganic fiber nonwoven fabric comprises a resin particle (A), a surface of which is at least partially coated with a hydrophilic fine particle (B). A number average primary particle diameter of (B) is 1-20 nm. A resin composing the resin particle (A) is preferably at least one selected from the group consisting of polyester resins, polyurethane resins, polyamide resins and polyvinyl acetate resins.

Description

  The present invention relates to a binder for inorganic fiber nonwoven fabric. More specifically, in the manufacturing process of inorganic fiber nonwoven fabric (glass chopped strand mat, etc., the same shall apply hereinafter), the yield rate at the time of spraying the binder than before (weight% of the binder adhered to the inorganic fiber laminate, The same shall apply hereinafter), and even if the amount of binder attached is reduced, the nonwoven fabric can maintain uniform and excellent mechanical strength (mechanical strength such as tensile strength; the same shall apply hereinafter). It is related with the binder for inorganic fiber nonwoven fabrics which can be performed.

  Conventionally, as an inorganic fiber nonwoven fabric binder, one using an unsaturated polyester resin pulverized by mechanical grinding (for example, see Patent Documents 1 and 2) is known.

JP-A-57-55931 JP 2003-301035 A

However, those described in Patent Documents 1 and ² are mats having a low basis weight [weight of mat per 1 m ² (weight of mat finally obtained by adding a binder to a glass chopped strand laminate) (weight per 100 g / m ² ), about half of the binder spread on the glass chopped strand laminate falls without adhering to the laminate, and there is a problem that the yield rate is poor, and improvement is eagerly desired. It was.
The object of the present invention is to provide an excellent yield rate at the time of binder spraying even in the production process of an inorganic fiber nonwoven fabric with a low basis weight, and even if the amount of binder attached is reduced, the uniform and excellent mechanical strength of the nonwoven fabric is maintained. Another object of the present invention is to provide a binder for an inorganic fiber nonwoven fabric that gives a nonwoven fabric.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have reached the present invention. That is, the present invention is the following four inventions.
(I) For inorganic fiber nonwoven fabrics comprising resin particles (A) in which at least a part of the particle surface is coated with hydrophilic fine particles (B), and the number average primary particle diameter of (B) being 1 to 20 nm. Binder (X).
(II) An inorganic fiber nonwoven fabric obtained by bonding an inorganic fiber laminate using the binder (X) of (I).
(III) An inorganic fiber reinforced plastic molded product obtained by molding the nonwoven fabric of (II) above as a reinforcing material.
(IV) In a method for producing a nonwoven fabric by spraying a binder on an inorganic fiber laminate, heating and melting, and then press-molding the laminate, and using the binder (X) of (I) above. A method for producing a fiber nonwoven fabric.

The binder (X) for inorganic fiber nonwoven fabric of the present invention has the following effects.
(1) Excellent yield rate during binder spraying.
(2) Uniform mechanical strength can be imparted to the inorganic fiber nonwoven fabric.

[Constituent Resin of Resin Particle (A)]
Although it does not specifically limit as resin which comprises the resin particle (A), For example, a polyester resin (PS), a polyurethane resin (PU), a polyamide resin (PA), a polyvinyl acetate resin (PV) etc. are mentioned. It is done. Of these, polyester resins and polyvinyl acetate resins are preferred from the viewpoint of adhesion to inorganic fibers, and polyester resins are particularly preferred.

[Polyester resin]
Polyester resins (PS) include polycondensates of poly (2-6 or more) carboxylic acids (including ester-forming derivatives) (a1) and low molecular polyols (a2), carboxyl groups and hydroxyl groups in the same molecule And a self-condensate of compound (a3) and a ring-opening polycondensate of lactone (a4).

  As the polycarboxylic acid (a1), aliphatic [carbon number (hereinafter abbreviated as C) 3 to 30, for example, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, tricarballylic acid] Aromatic [C8-30, such as phthalic acid, isophthalic acid, terephthalic acid, tetrabromophthalic acid, trimellitic acid, pyromellitic acid], and alicyclic polycarboxylic acids [C6-50, such as 1,3-cyclobutane Dicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2- and 1,4-cyclohexanedicarboxylic acid, 1,3- and 1,4-dicarboxymethylcyclohexane, dicyclohexyl-4,4′-dicarboxylic acid, dimer Acid]; ester-forming derivatives of these polycarboxylic acids [acid anhydrides (maleic anhydride, phthalic anhydride, etc. Lower alkyl (C1-4) ester [dimethyl ester (dimethyl terephthalate, etc.), diethyl ester (diethyl maleate, etc.), etc.], acid halide (terephthalic acid dichloride, etc.), etc .; and mixtures of two or more of these It is done. Of these, aliphatic polycarboxylic acids are preferable from the viewpoint of preventing coloring of the polyester resin.

The low molecular polyol (a2) is a number average molecular weight per hydroxyl group [hereinafter abbreviated as Mn. The measurement is based on the gel permeation chromatography (GPC) method under the measurement conditions described later. same as below. ] Is less than 300 (preferably a molecular weight of 31 or more and Mn 250 or less), and a divalent to 10-valent or higher (preferably 2-3) polyol can be used.
(A2) includes dihydric alcohol (a21), trivalent to 10-valent or higher polyhydric alcohol (a22), and alkylene oxides of these alcohols or polyvalent (divalent to trivalent or higher) phenols. (Hereinafter abbreviated as AO. C2-10) Low molar (2-10 mol) adduct (a23), and a mixture of two or more of these may be mentioned.

As AO, ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), 1,2-, 1,3- and 2,3-butylene oxide, tetrahydrofuran (hereinafter abbreviated as THF), styrene oxide, C5-10 or more alpha-olefin oxide, epichlorohydrin, and these 2 or more types combined use (block and / or random addition) are mentioned.
Among these AOs, preferred are EO, PO, and PO from the viewpoint of the mechanical strength of the inorganic fiber nonwoven fabric described later and the permeability to inorganic fibers such as styrene monomer in application to inorganic fiber reinforced plastic (FRP). These are combined.

  Examples of the dihydric alcohol (a21) include aliphatic alcohols [linear alcohols [C2-10, such as ethylene glycol, diethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1, 6-hexanediol (hereinafter abbreviated as EG, DEG, 1,3-PG, 1,4-BD, 1,5-PD, 1,6-HD)] and the like; branched chain alcohol [1,2- Propylene glycol, neopentyl glycol (hereinafter abbreviated as 1,2-PG, NPG, respectively), 3-methyl-1,5-pentanediol, 2,2-diethyl-1,3-propanediol, 1,2-, 1 , 3- and 2,3-butanediol, etc.]]; and a ring alcohol [C8 or more and less than Mn600, for example, an alicyclic alcohol 1,4-bis (hydroxymethyl) cyclohexane, etc.], araliphatic alcohols (m-and p- xylylene glycol and the like) and the like] and the like.

Specific examples of the trivalent to 10-valent or higher polyhydric alcohol (a22) include alkane polyols [C3 to 10 such as glycerin, trimethylolpropane, pentaerythritol, sorbitol (hereinafter abbreviated as GR, TMP, PE, SO, respectively). )], Intermolecular or intramolecular dehydrates of the alkane polyol [diPE, polyGR (degree of polymerization 2 to 8), sorbitan, etc.], saccharides and derivatives thereof (glycosides) (sucrose, methylglucoside, etc.) Can be mentioned.
Of the above (a21) and (a22), aliphatic alcohol is preferable from the viewpoint of the mechanical strength of the inorganic fiber nonwoven fabric, and 1,4-BD and NPG are more preferable.

Specific examples of the AO adduct (a23) include the AO low molar adducts of the above (a21) and (a22), and AO low molar adducts of polyvalent (divalent to trivalent or higher) phenols. It is done.
Examples of the polyhydric phenol include C6-18 dihydric phenols such as monocyclic dihydric phenols (hydroquinone, catechol, resorcinol, urushiol, etc.), bisphenol compounds (bisphenol A, -F, -C, -B, -AD). And -S, 4,4'-dihydroxydiphenyl-2,2-butane, etc.), dihydroxybiphenyl, and condensed polycyclic dihydric phenols [dihydroxynaphthalene (1,5-dihydroxynaphthalene, etc.), binaphthol, etc.]; and trivalent Or higher polyphenols such as monocyclic polyphenols (pyrogallol, phloroglucinol, etc.) and mono- or dihydric phenols (phenol, cresol, xylenol, resorcinol, etc.) and aldehydes (formaldehyde, glutaraldehyde, etc.) or Ketone (A A condensate with phenol (cretone or cresol novolak resin, resole intermediate, polyphenol obtained by condensation reaction of phenol and glyoxal or glutaraldehyde, polyphenol obtained by condensation reaction of resorcin and acetone, etc.).

  Specific examples of the compound (a3) having a carboxyl group and a hydroxyl group in the same molecule include C2-10, such as lactic acid, glycolic acid, β-hydroxybutyric acid, hydroxypivalic acid, hydroxyvaleric acid; and two or more of these. Of the mixture.

  Examples of the lactone (a4) include C4-15 (preferably C6-12), for example, ε-caprolactone, γ-butyrolactone, and γ-valerolactone.

In the present invention, the GPC is measured under the following conditions.
<GPC measurement conditions>
[1] Apparatus: HLC-8220 [manufactured by Tosoh Corporation]
[2] Column: TSKgel SuperMultipore HZ-M [Tosoh Corporation
Made]
[3] Eluent: Tetrahydrofuran [4] Reference material: Polystyrene [5] Injection conditions: Sample concentration 2.5 mg / ml, column temperature 40 ° C.

  Of the above polyester resins, polycarboxylic acid (a1) and low molecular polyol (a2) are preferable from the viewpoint of rapid polycondensation reaction and permeability of styrene and the like to inorganic fiber nonwoven fabrics in application to FRP and the like. More preferred is a polycondensation product of polycarboxylic acid (a1) and the above-mentioned AO low molar adduct (a23), and particularly preferred is a polyhydric phenol or aromatic compound having an aliphatic polycarboxylic acid and a ring. It is a polycondensate of an aliphatic alcohol with an AO low molar adduct.

The reaction temperature during the above polycondensation is usually 100 to 300 ° C, preferably 130 to 220 ° C. The polycondensation reaction is usually performed at normal pressure or reduced pressure (for example, 6 kPa or less).
Moreover, it is desirable to perform this reaction in inert gas atmosphere, such as nitrogen, from a viewpoint of coloring prevention of the polyester resin obtained.
The reaction equivalent ratio (carboxyl group / hydroxyl group equivalent ratio) of (a1) and (a2) during the polycondensation reaction is preferably 0.85 from the viewpoint of rapid polycondensation reaction and the stability of the resulting polyester resin. 1.4, more preferably 0.9 to 1.2.
The acid value (mgKOH / g. In the following, only numerical values are shown) of the polyester resin after the production is preferably 20 or less, more preferably 0 to 15 from the viewpoint of water resistance.

The polycondensation reaction may be either no catalyst or using an esterification catalyst.
Examples of the esterification catalyst include proton acid (phosphoric acid and the like), metal (alkali metal, alkaline earth metal, transition metal, 2B, 4A, 4B, and 5B metal) -containing compound [carboxylic acid (C2-4) salt, Carbonate, sulfate, phosphate, oxide, chloride, hydroxide, alkoxide, etc.].
Of these, carboxylate [2B, 4A, 4B and 5B group carboxylic acid (C2-4) salts], metal acid esters, oxides, and alkoxides are preferable from the viewpoint of reactivity. More preferable from the viewpoint of coloring prevention are zinc acetate, zirconyl acetate, tetrabutyl titanate, bis [2,2 ′-[(2-hydroxyethyl) imino-κN] -bis [ethanolate-κO]] titanate, antimony trioxide. And dibutyltin oxide.
The amount of esterification catalyst used is preferably from 0.005 to 3%, more preferably from the viewpoint of reactivity and coloration prevention, based on the total weight of the polycarboxylic acid (a1) and the low molecular weight polyol (a2). 01 to 1%.

In order to accelerate the reaction, an organic solvent can be added and refluxed. After completion of the reaction, the organic solvent is preferably removed.
The organic solvent is not particularly limited as long as it does not have active hydrogen such as a hydroxyl group, and examples thereof include hydrocarbons (toluene, xylene, etc.) and ketones (methyl ethyl ketone, methyl isobutyl ketone, etc.).

  The self-condensation reaction of the compound (a3) having the carboxyl group and the hydroxyl group in the same molecule and the ring-opening polycondensation reaction of the lactone (a4) are the reactions in the polycondensation reaction of the above (a1) and (a2). It can implement according to conditions.

  The weight average molecular weight of the polyester resin (PS) in the present invention (hereinafter abbreviated as Mw. The measurement is based on the GPC method under the above measurement conditions) is preferably 5 from the viewpoint of the mechanical strength of the inorganic fiber nonwoven fabric and the viscosity during heating and melting. From the same viewpoint, Mn is preferably 1,500 to 7,000, more preferably 2,000 to 6,000, more preferably from 10,000 to 60,000, more preferably from 10,000 to 55,000.

  The softening point of (PS) [measured in accordance with the ring and ball method (JIS K2207, “6.4 softening point test method” of “petroleum asphalt”)] is based on the prevention of adhesion of the inorganic fiber nonwoven fabric and the binder (X). From the viewpoint of the bondability between inorganic fibers and the workability of post-processing (fitness to a mold in application to FRP described later, the same applies hereinafter), preferably 80 to 150 ° C., more preferably 90 to 140. ° C.

  (PS) Glass transition temperature (hereinafter abbreviated as Tg, measured in accordance with JIS K7121, "Method for measuring plastic transition temperature") is measured using binder (X) blocking prevention and binder (X) Preferably from 40 to 60 degreeC, More preferably, it is 45 to 55 degreeC from a viewpoint of the bondability between the inorganic fibers by and workability of post-processing.

[Polyurethane resin]
The polyurethane resin (PU) includes a polyaddition product of poly (2 to 3 or more) isocyanate (b1) and an active hydrogen-containing compound (b2).

  Examples of the polyisocyanate (hereinafter abbreviated as PI) (b1) include diisocyanate (hereinafter abbreviated as DI) and trifunctional (hereinafter abbreviated as TI) or higher polyfunctional isocyanates such as carbon number (hereinafter abbreviated as C) (NCO). 6 to 20 aromatic PI; C2 to 18 aliphatic PI; C6 to 15 alicyclic PI; C8 to 15 araliphatic PI and modified products of these PI (Urethane groups, carbodiimide groups, allophanate groups, burette groups, uretdione groups, uretoimine groups, isocyanurate groups, oxazolidone group-containing modified products, etc.); and mixtures of two or more thereof.

  Examples of the aromatic PI include 1,3- and / or 1,4-phenylene DI, 2,4- and / or 2,6-tolylene DI (hereinafter abbreviated as TDI), crude TDI, 2,4′- and / Or 4,4'-diphenylmethane DI (hereinafter abbreviated as MDI), 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl- 4,4′-diisocyanatodiphenylmethane, crude MDI [crude diaminodiphenylmethane [a condensation product of formaldehyde and aniline, a mixture of diaminodiphenylmethane and a small amount (for example, 5 to 20% by weight) of a trifunctional or higher polyamine] A phosgenated product, generally called polyaryl PI (hereinafter abbreviated as PAPI). 1,5-naphthylene DI, 4,4 ', 4 "-triphenylmethane TI, m- and p-isocyanatophenylsulfonyl isocyanate.

  Examples of the aliphatic PI include ethylene DI, tetramethylene DI, hexamethylene DI (hereinafter abbreviated as HDI), dodecamethylene DI, 1,6,11-undecane TI, 2,2,4-trimethylhexamethylene DI, and lysine DI. (2,6-diisocyanatomethylcaproate), bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate Can be mentioned.

  Specific examples of the alicyclic PI include, for example, isophorone DI (hereinafter abbreviated as IPDI), dicyclohexylmethane-4,4 ′ and / or 2,4′-DI (hereinafter abbreviated as hydrogenated MDI), cyclohexylene DI, and methyl. Mention may be made of cyclohexylene DI, bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- and / or 2,6-norbornane DI.

  Specific examples of the araliphatic PI include m- and / or p-xylylene DI, α, α, α ′, α′-tetramethylxylylene DI.

  Specific examples of the modified product of PI include, for example, modified MDI (urethane modified MDI, carbodiimide modified MDI, trihydrocarbyl phosphate modified MDI), urethane modified TDI, burette modified HDI, isocyanurate modified HDI, isocyanurate modified IPDI and the like. Modified products of isocyanate and mixtures of two or more thereof [for example, combined use of modified MDI and urethane-modified TDI (isocyanate group-containing prepolymer)] are included. Among these, preferred are aliphatic and cycloaliphatic polyisocyanates, particularly HDI, IPDI, and hydrogenated MDI, from the viewpoint of less discoloration due to aging.

Examples of the active hydrogen-containing compound (b2) to be reacted with PI (b1) include a low-molecular polyfunctional active hydrogen-containing compound (b21) and a polymer polyol (b22).
Examples of the low molecular polyfunctional active hydrogen-containing compound (b21) include low molecular polyols and low molecular polyamines.

  As the low molecular polyol, the same one as the above (a2) can be used. Of the low molecular weight polyols, preferred are dihydric alcohols, more preferred are divalent aliphatic alcohols, and particularly preferred are 1,4-BD and NPG.

  Among the low molecular weight polyfunctional active hydrogen-containing compounds, the low molecular weight polyamine includes a diamine having a Mn per active hydrogen contained in the amino group of less than 300 (preferably a molecular weight of 30 or more and Mn 250 or less) and a trifunctional or higher functional group. Examples include polyamines, and those in which the isocyanate group of the polyisocyanate (b1) is replaced with an amino group.

  Examples of the diamine include aliphatic (ethylenediamine, hexamethylenediamine, etc.), alicyclic (4,4′-diamino-3,3′-dimethyldicyclohexylmethane, 4,4′-diamino-3,3′-dimethyldicyclohexyl, Diaminocyclohexane, isophoronediamine, etc.), aromatic (diethyltoluenediamine, etc.), araliphatic (xylylenediamine, α, α, α ′, α′-tetramethylxylylenediamine, etc.) and heterocyclic diamines (piperazine, etc.) Is mentioned.

Trifunctional or higher polyamines include polyalkylene (C2-6) polyamines (diethylenetriamine, triethylenetetramine, etc.), polyphenylmethane polyamines (condensation products of formaldehyde and aniline, etc.), and mixtures of two or more thereof. Is mentioned.
Among these low molecular weight polyamines, alicyclic and aliphatic diamines are preferable from the viewpoint of the mechanical strength of the inorganic fiber nonwoven fabric described later, and isophorone diamine and hexamethylene diamine are more preferable.

Among the active hydrogen-containing compounds (b2), as the polymer polyol (b22), a bivalent to tetravalent or higher (preferably 2-3 valent) polyol having a hydroxyl group equivalent of Mn300 or more can be used.
High molecular polyols include polyester polyols, polyether polyols, and mixtures of two or more thereof. The hydroxyl equivalent of the polymer polyol is preferably 300 to 10,000, more preferably 500 to 5,000, and particularly preferably 800 to 3,000, from the viewpoints of flexibility and mechanical strength of the glass chopped strand mat. .

  Examples of the polyester polyol include a condensed polyester polyol (polycondensate of a polyol and a polycarboxylic acid), a polylactone polyol (a ring-opening polymer of a lactone monomer using a polyol as an initiator), a polycarbonate polyol [a polyol and an alkylene ( C2-4) reaction product with carbonate (ethylene carbonate or the like), transesterification product of polyol and phosgenated carbonate or diphenyl carbonate]; and a mixture of two or more thereof.

  As the polyol constituting the polyester polyol, the low molecular polyol and / or the polyether polyol (described later) can be used.

The polycarboxylic acid constituting the condensed polyester polyol includes polycarboxylic acid and ester-forming derivatives thereof.
As polycarboxylic acid, aliphatic (2-6 valent, C3-30 polycarboxylic acid such as succinic acid, glutaric acid, maleic acid, fumaric acid, adipic acid, azelaic acid, sebacic acid, hexahydrophthalic acid), Aromatics (2-6 valent, C8-30 polycarboxylic acids such as ortho-, iso- and terephthalic acid, tetrabromo- and tetrachlorophthalic acid, trimellitic acid, pyromellitic acid) and alicyclic dicarboxylic acids (2 To 6-valent, C6-50 polycarboxylic acids such as 1,3-cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2- and 1,4-cyclohexanedicarboxylic acid, 1,3- and 1, 4-dicarboxymethylcyclohexane, dicyclohexyl-4,4′-dicarboxylic acid, dimer acid), ester formation thereof Derivatives [acid anhydrides (maleic anhydride, etc.), lower alkyl (C1-4) esters [dimethyl esters (dimethyl terephthalate, etc.), diethyl esters (diethyl maleate, etc.)], acid halides (terephthalic acid dichloride, etc.) And mixtures of two or more thereof.
Of these polycarboxylic acids, aliphatic polycarboxylic acids are preferred from the viewpoint of adhesion to inorganic fibers.

Examples of the lactone monomer constituting the polylactone polyol include C3-20 (preferably 4-12) lactones such as β-lactone (β-propiolactone, etc.), γ-lactone (γ-butyrolactone, etc.), and δ-lactone. (Δ-valerolactone, etc.), ε-lactone (ε-caprolactone, etc.), macrocyclic lactone (enanthlactone, undecanolactone, dodecalactone, etc.)], and mixtures of two or more of these.
Among these, γ-butyrolactone, ε-caprolactone, and mixtures thereof are preferable from the viewpoint of the mechanical strength of the inorganic fiber nonwoven fabric.

Among the polymer polyols, the polyether polyol includes an AO adduct of a compound having two or more active hydrogen atoms.
Examples of the compound having two or more active hydrogen atoms include low molecular polyols (above), polyhydric phenols (above), amines [primary monoamines such as alkyl or alkenylamines (C1-20), aromatic amines (aniline, etc.) ), Alkanolamine (hydroxyl alkyl group is C2-4), polyamine (above), heterocyclic polyamine such as piperazine, aminoalkyl (C2-4) piperazine (aminoethylpiperazine, etc.)] and the like.

  Of the polyurethane resin (PU) in the present invention, preferred from the viewpoint of flexibility and mechanical strength of the inorganic fiber nonwoven fabric is a polyaddition product of an aliphatic and / or alicyclic polyisocyanate and a polymer polyol, More preferred is a polyaddition product of alicyclic polyisocyanate and polyester polyol.

  The production of the polyurethane resin (PU) can be carried out by an ordinary method. The polyisocyanate (b1) and the active hydrogen-containing compound (b2) are all reacted together (one-shot method), and these reaction components are mixed. Examples thereof include a method in which a part is reacted in advance and subjected to a multistage reaction via an isocyanate group or a hydroxyl group-terminated urethane prepolymer (prepolymer method). Among these, preferred is a method of reacting an isocyanate group-terminated urethane prepolymer with the low molecular weight polyfunctional active hydrogen-containing compound (herein used as an extender and / or a crosslinking agent) from the viewpoint of viscosity during heating and melting and prevention of blocking. It is.

  The equivalent ratio (NCO / active hydrogen) of (b1) and (b2) in the one-shot method is usually 0.7 to 1.3 equivalents, preferably 0.8 to 1.2 from the viewpoint of viscosity during heating and melting. It is.

In addition, the isocyanate group-terminated urethane prepolymer in the prepolymer method is preferably formed by a reaction of polyisocyanate (b1) with a polymer polyol (b22) and, if necessary, the low-molecular polyfunctional active hydrogen-containing compound (b21). The In this case, the equivalent ratio (NCO / active hydrogen) of (b1) to (b22) and (b21) is usually 0.1 to 0.6 equivalent, preferably 0 to (b1) 1 equivalent. .2 to 0.5 equivalents, (b21) is usually 0 to 0.2 equivalents, preferably 0.05 to 0.10 equivalents.
The isocyanate group content of the isocyanate group-terminated urethane prepolymer is usually 0.5 to 10% by weight, preferably 1.5 to 6% by weight.

  Examples of the extender include dihydric alcohols (aliphatic alcohols, those having a ring), diamines (aliphatic, alicyclic, aromatic, araliphatic and heterocyclic diamines), and ketimine compounds of these diamines. [Ketimines of diamines and ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone (hereinafter abbreviated as MIBK)], and water. Of these, ketimine compounds are preferred from the viewpoint of the adhesiveness of polyurethane resin (PU) to inorganic fibers.

In the production of (PU), an end-capping agent for adjusting the molecular weight can be used as necessary. Examples of the end capping agent include a low molecular monool and a low molecular monoamine.
Low molecular monools include those of C1-10, such as aliphatic alcohols (methanol, ethanol, n- and i-propanol, n-butanol, 2-ethylhexanol, 1-octanol, etc.), araliphatic alcohols (benzyl). Examples of low molecular monoamines include C1-18, such as aliphatic monoamines [monoalkylamines (methylamine, ethylamine, propylamine, n-butylamine, etc.)].

  In addition, the Mw of the polyurethane resin (PU) is preferably 10,000 to 100,000, more preferably 1,5,000 to 60,000, from the viewpoint of the mechanical strength of the inorganic fiber nonwoven fabric and the viscosity at the time of heating and melting, From the same viewpoint, Mn is preferably 1,500 to 30,000, more preferably 2,000 to 20,000.

  The softening point of (PU) is preferably 60 to 150 ° C., more preferably 80 to 130 ° C., from the viewpoint of the bondability between inorganic fibers by the binder (X) and the workability of post-processing.

  The Tg of (PU) is preferably −40 to 40 ° C., more preferably −20 to 20 ° C. from the viewpoint of preventing blocking during storage of the binder (X) and the workability of post-processing.

[Polyamide resin]
Polyamide resin (PA) has the same polycondensation product of poly (2 to 6 or more) carboxylic acid (including ester-forming derivative) (c1) and low molecular weight polyamine (c2), carboxyl group and amino group Examples include a self-condensate of compound (c3) in the molecule and a ring-opening polycondensate of lactam (c4).

  Examples of the polycarboxylic acid (c1) include the same as the polycarboxylic acid (a1).

  As the low molecular weight polyamine (c2), a polyamine having a Mn per amino group of less than 300 (preferably a molecular weight of 30 or more and Mn250 or less), a bivalent to tetravalent or higher (preferably 2-3 valent) polyamine is used. it can. (C2) includes divalent amine (c21), trivalent to tetravalent or higher polyamine (c22), and a mixture of two or more thereof.

  Examples of the divalent amine (c21) include aliphatic diamine [linear amine (ethylenediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, etc.)]; branched diamine [3 -Methyl-1,5-pentanediamine, 2,2-diethyl-1,3-propanediamine, 1,2-, 1,3- and 2,3-butanediamine and the like]; alicyclic diamine [(1, 4-bis) diaminomethylcyclohexane, dimer diamine, isophorone diamine (hereinafter abbreviated as IPDA), dicyclohexylmethane-4,4 ′ and / or 2,4′-diamine (hereinafter abbreviated as PACM) and the like]; and araliphatic diamines [Diphenylmethane-4,4 ′ and / or 2,4′-diamine and the like].

Examples of the trivalent to tetravalent or higher polyamine (c22) include alkane polyamines [C4 to 10, for example, 3,3′-diaminodipropylamine, diethylenetriamine, triethylenetetramine, pentaethylenehexamine and the like].
Of the above (c21) and (c22), aliphatic diamines and alicyclic diamines are preferred from the viewpoint of mechanical strength of the inorganic fiber nonwoven fabric and prevention of coloring of the (PA) resin, and ethylenediamine, IPDA, PACM are more preferred. , Dimer diamine.

  Examples of the self-condensate of the compound (c3) having a carboxyl group and an amino group in the same molecule include C2-C10, for example, amino acid self-condensates such as glycine, alanine, glutamic acid, and γ-aminobutyric acid. Of these, glycine and alanine are preferred from the viewpoint of the mechanical strength of the inorganic fiber nonwoven fabric and the prevention of coloring of the polyamide resin (PA).

  As the lactam (c4), C3-20 (preferably 4-12) lactam, for example, β-lactam (β-propiolactam etc.), γ-lactam (γ-butyrolactam etc.), δ-lactam (δ-valero) Lactam, etc.), ε-lactam (ε-caprolactam, etc.), macrocyclic lactam (enantolactam, undecanolactam, laurolactam, etc.)], and mixtures of two or more thereof. Among these, γ-butyrolactam and ε-caprolactam are preferable from the viewpoint of the mechanical strength of the inorganic fiber nonwoven fabric.

  Among the above polyamide resins (PA), polycarboxylic acid (c1) and low molecular weight are preferable from the viewpoint of rapidity at the time of polycondensation reaction and permeability of styrene or the like to inorganic fiber nonwoven fabric in application to FRP and the like described later. A polycondensate with the polyamine (c2), more preferably a polycondensate of an alicyclic ring-containing polycarboxylic acid and an alicyclic ring-containing polyamine.

During the production of (PA), the reaction temperature during polycondensation is usually 100 to 300 ° C, preferably 130 to 220 ° C. The polycondensation reaction is usually carried out at normal pressure and then under reduced pressure (for example, 40 kPa or less) as necessary. The reaction is preferably carried out in an inert gas atmosphere such as nitrogen from the viewpoint of preventing (PA) coloring.
The reaction equivalent ratio (carboxyl group / amino group equivalent ratio) during the polycondensation reaction of (c1) and (c2) is preferably 0.6 from the viewpoint of rapid polycondensation reaction and the stability of the obtained (PA). It is -1.4, More preferably, it is 0.7-1.2.
The acid value of (PA) obtained is preferably 10 or less, more preferably 0 to 3, from the viewpoint of water resistance.

In the polycondensation reaction, an organic solvent can be added and refluxed to accelerate the reaction.
Examples of the organic solvent include those having no active hydrogen group such as a hydroxyl group and an amino group, for example, hydrocarbons (toluene, xylene, etc.) and ketones (methyl ethyl ketone, methyl isobutyl ketone, etc.).
The amount of the organic solvent used is usually 50% or less based on the total weight of (c1) and (c2), and preferably 5 to 25% from the viewpoint of productivity and safety. It is desirable to remove the organic solvent after completion of the reaction from the viewpoint of production of the inorganic fiber nonwoven fabric.

(PA) by the polycondensation reaction of (C1) and (C2) can be usually produced as follows. First, the amine component and the acid component are charged into a reaction vessel equipped with a cooling tube, a stir bar, a thermometer, and a nitrogen introduction tube, heated in a nitrogen atmosphere, and usually reacted at 130 to 220 ° C. for 4 to 6 hours. Then, if necessary, a polyamide resin can be produced by further reacting under reduced pressure of 5 to 40 kPa for 1 to 5 hours.
The self-condensation reaction of (c3) and the ring-opening polycondensation reaction of (c4) can be carried out according to the reaction conditions in the polycondensation reaction of (c1) and (c2).

  The Mw of the polyamide resin (PA) is preferably 4,000 to 60,000, more preferably 6,000 to 25,000, and Mn from the viewpoint of the mechanical strength of the inorganic fiber nonwoven fabric and the viscosity at the time of heat-melting the resin. Is preferably from 2,000 to 15,000, more preferably from 3,000 to 8,000 from the same viewpoint.

  The softening point of (PA) is preferably 60 to 150 ° C., more preferably from the viewpoints of preventing the adhesiveness of the inorganic fiber nonwoven fabric from being bonded, the bondability between the inorganic fiber strands by the binder (X), and the workability of post-processing. 80-130 ° C.

  The Tg of (PA) is preferably 30 to 60 ° C., more preferably 30 to 60 ° C. from the viewpoint of blocking prevention during storage of the binder (X), the bondability between the inorganic fiber strands by the binder (X), and the workability of post-processing. Is 45-55 ° C.

[Polyvinyl acetate resin]
The polyvinyl acetate resin (PV) includes a known vinyl acetate polymer or ethylene-vinyl acetate copolymer. The (co) polymer may be produced by (co) polymerizing raw material monomers, or a commercially available product of the (co) polymer may be used.
Among the commercially available products of the above (co) polymers, examples of vinyl acetate polymers include “Denkasacnar SN-17A” [trade name, manufactured by Denki Kagaku Kogyo Co., Ltd.] and the like, and ethylene-vinyl acetate co-polymers. Examples of the polymer include “EVAFLEX 550” [trade name, manufactured by Mitsui DuPont Polychemical Co., Ltd.].

  The Mw of the polyvinyl acetate resin (PV) is preferably 10,000 to 500,000, more preferably 20,000 to 400,000, from the viewpoint of the mechanical strength of the inorganic fiber nonwoven fabric and the viscosity at the time of heating and melting. , Mn is preferably 5,000 to 100,000, more preferably 10,000 to 70,000 from the same viewpoint.

  The softening point of (PV) is 30 to 90 ° C., more preferably 40 to 80 ° C., from the viewpoint of preventing stickiness of the inorganic fiber nonwoven fabric using the binder (X) and the bonding property between the strands by the binder (X). is there.

  The Tg of (PV) is preferably −40 to 30 ° C., more preferably −30, from the viewpoint of preventing blocking during storage of the binder (X) and the flexibility of the inorganic fiber nonwoven fabric using the binder (X). ~ 20 ° C.

[Resin particles (A)]
The resin particles (A) in the present invention are obtained by, for example, crushing machine “sample mill” [trade name, model number “SK-M10”, manufactured by Kyoritsu Riko Co., Ltd. same as below. ] Is usually pulverized at a rotational speed of 10,000 to 15,000 rpm for 1 to 5 minutes to form particles, and then sieved by combining sieves having different openings.

The volume average particle diameter [Dv] of the resin particles (A) in the present invention is preferably 50 to 500 μm from the viewpoint of powder flowability, dust generation of the binder (X) and mechanical strength of the inorganic fiber nonwoven fabric described later. More preferably, it is 75-350 micrometers, Most preferably, it is 100-250 micrometers.
Here, Dv can be obtained by a laser diffraction scattering method, and examples of the measuring apparatus include a particle size distribution measuring instrument [trade name “Microtrack MT3000II particle size analyzer”, manufactured by Nikkiso Co., Ltd.].

[Hydrophilic fine particles (B)]
In the binder (X) of the present invention, the hydrophilic fine particles (B) covering at least a part of the surface of (A) are at least one selected from the group consisting of silicon, aluminum, iron, titanium, magnesium, and zirconium. Examples thereof include oxides containing seed atoms, and fine particles composed of a mixture thereof.
Examples of the oxide include silicon dioxide, silicon oxide, aluminum oxide, iron oxide, titanium oxide, magnesium oxide, and zirconium oxide. Among these, from the viewpoint of blocking prevention in (A) and the yield rate at the time of spraying the binder, preferred are silicon oxide and titanium oxide.

  The amount of (B) used is preferably 0.01 to 5%, more preferably 0.05, based on the weight of (A), from the viewpoint of preventing blocking of the binder (X) and the bonding between inorganic fibers. -3%, particularly preferably 0.1-1%.

Here, the hydrophilicity in the hydrophilic fine particles (B) means a property that is easily wetted by water. Put 100 ml of water at 25 ° C. into a 200 ml beaker, and spray 0.1 g of fine particles on it. At this time, those in which the fine particles are immersed in water within 3 hours are defined as hydrophilic fine particles.
The hydrophobic fine particles refer to fine particles that do not meet the above definition of hydrophilic fine particles.

The number average primary particle diameter of (B) is 1 to 20 nm, and preferably 3 to 10 nm from the viewpoint of the specific surface area described later and the powder fluidity. When the particle diameter is less than 1 nm, it is difficult to obtain industrially, and when it exceeds 20 nm, the yield rate when the binder (X) is dispersed and the mechanical strength of the inorganic fiber nonwoven fabric are inferior.
The particle diameter can be obtained by analyzing an image of a transmission electron microscope (hereinafter referred to as TEM). As a measuring apparatus, TEM [model number “H-7100”, manufactured by Hitachi, Ltd.] and image analysis type particle size distribution are used. Measurement software [trade name “Mac-View”, manufactured by Mountec Co., Ltd.] and the like.

By adding and mixing the hydrophilic fine particles (B) to the resin particles (A), it is possible to obtain resin particles (A) that are at least partially coated with the hydrophilic fine particles (B).
Here, examples of the mixer include powder mixers such as a planetary mixer, a nauter mixer, and a tumbler mixer. Among these, from the viewpoint of mixing efficiency, a planetary mixer [for example, device name “HIVIS MIX”, model number “TK.HIVIS MIX F model.03”, manufactured by Special Rika Kogyo Co., Ltd., is used. same as below. ] Etc. are mentioned.
As mixing conditions, it is preferable to mix at 5-40 degreeC for 5 to 90 minutes from a viewpoint of productivity and the coverage of a hydrophilic microparticle (B).

The specific surface area of the resin particles (A) coated with the hydrophilic fine particles (B) by the BET method is preferably 0 from the viewpoint of the yield rate when the binder (X) is dispersed and the blocking property of the binder (X). .3 to 5.0 m ² / g, more preferably 0.8 to 3.0 m ² / g.
Here, examples of the specific surface area measuring apparatus in the BET method include a specific surface area measuring apparatus [trade name “Tristar 3020”, manufactured by Shimadzu Corporation].

The coverage of the resin particles (A) coated with the hydrophilic fine particles (B) by (B) is preferably 50% or more, more preferably 70% or more, from the viewpoint of the yield rate when the binder (X) is dispersed. Preferably it is 80% or more.
The coverage can be obtained by analyzing an image of a scanning electron microscope (hereinafter referred to as SEM). As a measuring apparatus, SEM [model number “JSM-7000”, manufactured by JEOL Ltd.] and image analysis type particle size distribution are used. Measurement software [trade name “Mac-View”, manufactured by Mountec Co., Ltd.] and the like.

[Inorganic fiber nonwoven fabric]
The inorganic fiber nonwoven fabric of this invention is comprised from the binder for inorganic fiber nonwoven fabrics containing the inorganic fiber laminated body and the resin particle (A) coat | covered with the hydrophilic fine particle (B).
Here, the inorganic fibers include mineral fibers obtained by fiberizing a melt such as stone, slag, glass, and carbon fibers.
The melt is formed by melting a mineral composition mixed with rocks or minerals having desired physical properties in a furnace. Specific examples of the mineral fiber include glass fiber, rock wool, stone wool and the like. Examples of these production methods include a centrifugal method (rotary method), a flame spraying method, a blow-off method, and the like, and are not particularly limited.
The carbon fiber is a fiber produced by carbonizing acrylic fiber or pitch (by-products such as petroleum, coal, coal tar, etc.) as a raw material at a high temperature, and the carbon fiber using the acrylic fiber is PAN (polyacrylonitrile). Carbon fibers using pitch and pitch are classified as pitch pitch.
Of the inorganic fibers, glass fibers are preferable from an industrial viewpoint.

Specifically, the inorganic fiber nonwoven fabric of the present invention can be produced by, for example, the following steps.
(1) An inorganic fiber laminate is obtained by spreading inorganic fibers on a wire mesh in a directional disorder so as to have a uniform thickness.
(2) A predetermined amount of tap water is sprayed by spraying so that the entire surface of the laminate is wetted from the upper or lower surface side of the laminate.
(3) A predetermined amount of the binder (X) is uniformly dispersed from the upper surface side of the laminated body and adhered.
(4) A predetermined amount of tap water is sprayed from the upper surface side by spraying so that the entire surface of the laminate is wetted, and a predetermined amount of binder (X) is uniformly sprayed and adhered.
(5) The step (4) may be repeated once or twice or more as necessary.
(6) After heating the binder (X) adhesion laminated body obtained at the process to said (5) at 85-200 degreeC for 1 to 10 minutes, it presses with the pressure of 0.01-5 MPa with a roll press machine. An inorganic fiber nonwoven fabric bonded with the binder (X) is obtained.

  The spray amount of tap water used in the above (2), (4) and (5) is based on the weight of the inorganic fiber laminate not containing the binder (X), respectively, and the adhesion of the binder (X) and the post-process From the viewpoint of easiness of drying, it is preferably 10 to 1000%, more preferably 20 to 700%.

  The yield rate (% by weight) at the time of spraying the binder (X) of the present invention on the inorganic fiber laminate is preferably 70% or more, more preferably 80% or more, particularly preferably from the industrial viewpoint of producing the inorganic fiber nonwoven fabric. Is 90% or more. The yield rate is measured by the method described later.

The amount (%) of the binder (X) based on the weight of the inorganic fiber laminate is determined by the mechanical strength and handling properties of the nonwoven fabric (flexibility, fit to a mold when creating an inorganic fiber reinforced plastic molded product described later, From the viewpoint of the same hereinafter, it is preferably 1 to 20%, more preferably 2 to 15%.
The adhesion amount of the binder (X) is determined by the ignition loss (%) of the inorganic fiber nonwoven fabric described later when the inorganic fiber is a high heat resistant material such as glass fiber, but the inorganic fiber is like the carbon fiber described later. When the ignition loss cannot be obtained, it can be obtained by directly measuring the amount of binder (X) adhering to the inorganic fiber laminate.

The unit weight (weight per unit area) of the inorganic fiber nonwoven fabric is usually 70 to 900 g / m ² , but preferably 80 to 250 g / m ² , more preferably from the viewpoint of improving the mechanical strength and yield of the nonwoven fabric. 90 to 160 g / m ² .

The difference between the maximum value and the minimum value of the tensile strength of the inorganic fiber nonwoven fabric of the present invention is preferably 45 N or less, more preferably 30 N or less, from the viewpoint of the flexibility of the nonwoven fabric and the uniformity of mechanical strength.
Moreover, the bending elastic modulus of the inorganic fiber nonwoven fabric of the present invention is preferably 0.5 to 3.0 MPa, more preferably 0.8 to 2.8 MPa from the viewpoint of mechanical strength and flexibility of the nonwoven fabric.

[Inorganic fiber reinforced plastic molded products]
The inorganic fiber reinforced plastic (FRP) molded product of the present invention is formed by molding the inorganic fiber nonwoven fabric of the present invention as a reinforcing material. The molding method of the molded product is not particularly limited, and examples thereof include a hand lay-up method, a spray-up method, a preform method, a matched die method, and an SMC method. Of these, for example, the hand lay-up method is usually performed according to the following procedure.
(1) A release agent is applied to the surface of the mold.
(2) A matrix resin (unsaturated polyester resin or the like) is applied to the surface of the mold at room temperature (15 to 25 ° C.) using a roller or the like so as to have a uniform thickness.
(3) The resin is gelled in a warm air oven adjusted to about 40 ° C.
(4) An inorganic fiber nonwoven fabric is fitted to the mold surface, a solution obtained by diluting the matrix resin with a styrene monomer or the like is laminated on the inorganic fiber nonwoven fabric with a roller or the like, and air is removed with a roller.
(5) The laminate is cured in a warm air oven.
(6) Take out from the mold to obtain a molded product.

As a matrix resin of a molded product obtained by the molding method including the hand lay-up method, a thermosetting resin (unsaturated polyester resin, vinyl ester resin, epoxy resin, phenol resin, polyurethane resin, silicon resin, modified acrylic resin, Furan resin, etc.) and thermoplastic resins (ABS resin, polycarbonate resin, polyethylene terephthalate resin, polyamide resin, polyetherimide resin, polyimide resin, etc.).
Among these, for example, in the case of the hand lay-up method, a thermosetting resin is used, and unsaturated polyester resins and vinyl ester resins are preferable from the viewpoint of workability during molding.

  EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited to these examples. In the examples, “part” means “part by weight” and “%” means “% by weight” unless otherwise specified.

Example 1 <Production of Binder (X-1)>
(1) Production of polyester resin (PS-1) In a reaction vessel, 3,365 parts of EO 2.2 mol adduct of bisphenol A, 1,123 parts of fumaric acid, 6 parts of dibutyltin oxide were charged, and 180 ° C. in a nitrogen atmosphere. For 4 hours. Thereafter, the temperature was raised to 200 ° C. and reacted at the same temperature for 6 hours under a reduced pressure of 2 kPa. After the acid value reached 16.0, the resin was taken out, cooled to room temperature, and polyester resin (PS- 1) was obtained. (PS-1) had Mw of 30,000, Mn of 2,800, a softening point of 116 ° C., and Tg of 53 ° C.
(2) Production of Resin Particles (A-1) 100 parts of (PS-1) was pulverized for 3 minutes at 12,500 rpm using a “sample mill”. The obtained resin powder was sieved with a sieve having an opening of 212 μm, and the resin powder that passed through the sieve was further sieved with a sieve having an opening of 75 μm to obtain resin particles (A-1) remaining on the 75 μm sieve. . Dv of (A-1) was 140 μm.
(3) Production of binder (X-1) (A-1) 10 parts of hydrophilic fine particles “AEROSIL 380” [trade name, manufactured by Nippon Aerosil Co., Ltd., silicon dioxide, number average primary particle size 7 nm] (B- 1) After adding 0.05 part, it mixed and obtained the binder (X-1) which consists of the resin particle (A-1) coat | covered with the hydrophilic fine particle (B-1). The specific surface area of the (X-1) in the BET method was 1.9 m ² / g, and the coverage was 85%.

Example 2 <Production of Binder (X-2)>
(1) Production of binder (X-2) (A-1) 10 parts of hydrophilic fine particles “AEROSIL 380S” [trade name, manufactured by Nippon Aerosil Co., Ltd., silicon dioxide, number average primary particle size 5 nm] (B- 2) After adding 0.05 part, it mixed and obtained the binder (X-2) which consists of the resin particle (A-1) coat | covered with the hydrophilic fine particle (B-2). The specific surface area of the (X-2) in the BET method was 1.5 m ² / g, and the coverage was 97%.

Example 3 <Production of Binder (X-3)>
(1) Production of binder (X-3) (A-1) 0.1 part of hydrophilic fine particles (B-1) was added to 10 parts, and then mixed and coated with hydrophilic fine particles (B-1). A binder (X-3) comprising the resin particles (A-1) was obtained. The specific surface area of the (X-3) in the BET method was 2.8 m ² / g, and the coverage was 100%.

Example 4 <Production of Binder (X-4)>
(1) Production of binder (X-4) (A-1) 10 parts of hydrophilic fine particles “AEROSIL 200” [trade name, Nippon Aerosil Co., Ltd., silicon dioxide, number average primary particle size 12 nm] (B- 3) After adding 0.05 part, it mixed and obtained the binder (X-4) which consists of the resin particle (A-1) coat | covered with the hydrophilic fine particle (B-3). The specific surface area of the (X-4) in the BET method was 0.65 m ² / g, and the coverage was 63%.

Example 5 <Production of Binder (X-5)>
(1) Production of polyurethane resin (PU-1) [Production of urethane prepolymer]
In a reaction vessel, 2,000 parts of polycaprolactone diol [trade name “Placcel 220”, manufactured by Daicel Chemical Industries, Ltd., Mn 2,000] was charged, heated to 110 ° C. under a reduced pressure of 0.4 kPa, and dehydrated for 1 hour. Went. Subsequently, 457 parts of IPDI were charged and reacted at 110 ° C. for 10 hours under a nitrogen atmosphere to obtain an isocyanate group-terminated urethane prepolymer (PP-1) having an isocyanate group content of 3.6%.
[Manufacture of extender]
In a reaction vessel, 50 parts of ethylenediamine and 50 parts of MIBK were charged and reacted at 50 ° C. for 1 hour to obtain (extender 1).

[Manufacture of polyurethane resin]
In a reaction vessel, 1,222 parts of (PP-1) and 2,481 parts of toluene were charged, and the temperature was raised to 65 ° C. in a nitrogen atmosphere to dissolve (PP-1). Next, 30 parts of (extender 1) was added dropwise over 15 minutes, and reacted at the same temperature for 3 hours. Thereafter, 36.5 parts of n-butylamine was added and reacted at the same temperature for 1 hour. Further, the mixture was heated up to 150 ° C., detolueneed at 2 kPa for 4 hours with stirring, and then taken out and cooled to room temperature to obtain a polyurethane resin (PU-1). (PU-1) had an Mw of 21,000, an Mn of 5,100, a softening point of 108 ° C, and a Tg of -15 ° C.

(2) Production of resin particles (A-2) After cooling 100 parts of (PU-1) in liquid nitrogen (-196 ° C., the same applies hereinafter) for 10 minutes, using a “sample mill”, the number of revolutions was 12, Milling was performed at 500 rpm for 3 minutes. Thereafter, resin particles (A-2) were obtained in the same manner as in Example 1. The Dv of (A-2) was 119 μm.

(3) Production of binder (X-5) (A-2) 0.05 part of hydrophilic fine particles (B-1) “AEROSIL 380” was added to 10 parts, and then mixed to obtain hydrophilic fine particles (B-1 ) To obtain a binder (X-5) composed of the resin particles (A-2) coated with. The specific surface area of the (X-5) in the BET method was 1.8 m ² / g, and the coverage was 77%.

Example 6 <Production of Binder (X-6)>
(1) Production of polyamide resin (PA-1) A reaction vessel was charged with 1,645 parts of dimer acid [trade name “EMPOL 1061”, manufactured by Cognis Japan Co., Ltd.], 540 parts of IPDA, and at 160 ° C. in a nitrogen atmosphere. The reaction was performed for 2 hours. Then, it was made to react at 180 degreeC and 200 degreeC for 2 hours each. Next, it was made to react under the reduced pressure of 5-6 kPa, and when the acid value became 2, after taking out, it cooled to room temperature and obtained polyamide resin (PA-1). In (PA-1), Mw was 19,000, Mn was 7,600, the softening point was 92 ° C, and Tg was 46 ° C.
(2) Production of Resin Particles (A-3) 100 parts of (PA-1) was pulverized for 3 minutes at 12,500 rpm using a “sample mill”. The obtained resin powder was sieved with a sieve having an opening of 212 μm, and the resin powder that passed through the sieve was further sieved with a sieve having an opening of 75 μm to obtain resin particles (A-3) remaining on the 75 μm sieve. . Dv of (A-3) was 155 μm.
(3) Manufacture of binder (X-6) (A-3) 10 parts of hydrophilic fine particles “TTO-51 (A)” [trade name, manufactured by Ishihara Sangyo Co., Ltd., titanium oxide, number average primary particle size 10 nm ] (B-4) After adding 0.1 part, it mixed and obtained the binder (X-6) which consists of the resin particle (A-3) coat | covered with the hydrophilic fine particle (B-4). The specific surface area of the (X-6) in the BET method was 0.75 m ² / g, and the coverage was 80%.

Example 7 <Production of Binder (X-7)>
(1) Production of resin particles (A-4) Ethylene-vinyl acetate copolymer resin [trade name “EVAFLEX550”, manufactured by Mitsui DuPont Polychemical Co., Ltd., Mw: 100,000, Mn: 23,000, softening point : 61 ° C., Tg: −26 ° C.] 100 parts of (PV-1) were cooled in liquid nitrogen for 10 minutes, and then ground using a “sample mill” at a rotational speed of 12,500 rpm for 3 minutes. Thereafter, resin particles (A-4) were obtained in the same manner as in Example 1, (2). Dv of (A-4) was 160 μm.

(2) Manufacture of binder (X-7) (A-4) After adding 0.05 part of hydrophilic fine particles (B-1) to 10 parts, they are mixed and coated with hydrophilic fine particles (B-1). A binder (X-7) comprising the resin particles (A-4) was obtained. The specific surface area of the (X-7) in the BET method was 1.7 m ² / g, and the coverage was 91%.

Example 8 <Production of Binder (X-8)>
(1) Production of resin particles (A-5) 100 parts of (PS-1) were pulverized for 3 minutes at 12,000 rpm using a “sample mill”. The obtained resin powder was sieved with a sieve having an opening of 323 μm to obtain resin particles (A-4) that passed therethrough. Dv of (A-4) was 225 μm.
(2) Production of binder (X-8) (A-5) Resin particles coated with hydrophilic fine particles (B-2) after adding 0.02 part of (B-2) to 10 parts A binder (X-8) comprising (A-5) was obtained. The specific surface area of the (X-8) in the BET method was 1.0 m ² / g, and the coverage was 86%.

Example 9 <Production of Binder (X-9)>
(1) Production of resin particles (A-6) 100 parts of (PS-1) were pulverized for 4 minutes at a rotation speed of 14,500 rpm using a “sample mill”. The obtained resin powder was sieved with a sieve having an opening of 125 μm, and the resin powder that passed through the sieve was further sieved with a sieve having an opening of 54 μm to obtain resin particles (A-6) remaining on the 54 μm sieve. . Dv of (A-6) was 105 μm.
(2) Production of binder (X-9) (A-6) 10 parts of hydrophilic fine particles “AEROSIL 130” [trade name, manufactured by Nippon Aerosil Co., Ltd., silicon dioxide, number average primary particle size 16 nm] (B- 5) After adding 0.45 part, it mixed and the binder (X-9) which consists of the resin particle (A-6) coat | covered with the hydrophilic fine particle (B-4) was obtained. The specific surface area of the (X-9) in the BET method was 4.8 m ² / g, and the coverage was 100%.

Example 10 <Production of Binder (X-10)>
(A-2) After adding 0.15 parts of hydrophilic fine particles “AEROSIL 255” [trade name, manufactured by Nippon Aerosil Co., Ltd., silicon dioxide, number average primary particle diameter 10 nm] (B-5) to 10 parts, By mixing, a binder (X-10) composed of resin particles (A-2) covered with hydrophilic fine particles (B-5) was obtained. The specific surface area of the (X-10) in the BET method was 3.0 m ² / g, and the coverage was 100%.

Comparative Example 1 <Production of Binder (X'-1)>
(A-1) After adding 10 parts of hydrophilic fine particles “AEROSIL 50” [trade name, manufactured by Nippon Aerosil Co., Ltd., silicon dioxide, number average primary particle size 30 nm] (B′-1) 0.05 part And a binder (X′-1) composed of resin particles (A-1) coated with hydrophilic fine particles (B′-1) was obtained. The specific surface area of the (X′-1) in the BET method was 0.6 m ² / g, and the coverage was 36%.

Comparative Example 2 <Production of Binder (X'-2)>
(A-1) After adding 10 parts of hydrophobic fine particles “AEROSIL R972” [trade name, manufactured by Nippon Aerosil Co., Ltd., silicon dioxide, number average primary particle size 16 nm] (B′-2) 0.05 part And a binder (X′-2) composed of resin particles (A-1) coated with hydrophobic fine particles (B′-2) was obtained. The specific surface area of the (X′-2) in the BET method was 1.2 m ² / g, and the coverage was 55%.

Comparative Example 3 <Production of Binder (X'-3)>
(A-1) 0.05 part of hydrophilic fine particles “Leosil QS-09” [trade name, manufactured by Tokuyama Corporation, silicon dioxide, number average primary particle size 23 nm] (B′-3) was added to 10 parts. Thereafter, mixing was performed to obtain a binder (X′-3) composed of resin particles (A-1) covered with hydrophilic fine particles (B′-3). The specific surface area of the (X′-3) in the BET method was 0.4 m ² / g, and the coverage was 42%.

Example 11 <Preparation of Glass Chopped Strand Nonwoven Fabric (GM-1)>
A glass strand for glass chopped strands (average strand count T = 30 tex, glass fiber density d = 2.5 g / cm ² , strand diameter K = 13.6 μm) was converted into a glass chopper [trade name “Glass Chopper”, Togiken The glass chopped strand was obtained by cutting into a length of about 5 cm. 30.0 g of the glass chopped strand obtained in a flat mold having a length of 75 cm × width 40 cm, which has been subjected to the mold release treatment, is dispersed in a directional disorder so as to have a uniform thickness to obtain a glass chopped strand laminate. Tap water (30 g) was sprayed uniformly by spraying from the upper surface side until the surface of the laminate was moistened.
Next, a binder (X-1) of 3.0 g [10.0 g / m ² per unit area] which is equivalent to 10% of the weight of the glass chopped strands dispersed was uniformly dispersed on the glass chopped strand laminate. Then, the binder was melted in a circulating dryer at 200 ° C. for 2 minutes, and then heated and pressed at a speed of 20 m / min with a roll type press machine (pressure 0.2 MPa) adjusted to 150 ° C. A glass chopped strand nonwoven fabric (GM-1) of 21 mm, a nonwoven fabric unit weight (weight per square meter) 109 g / m ² , and loss on ignition (measurement method will be described later) 8.6% was obtained. The loss on ignition is a value measured in accordance with “7.3.2 Loss on ignition” in JIS R3420 “General Test Method for Glass Fiber” described later.

Examples 12-20
In Example 11, glass chopped strand nonwoven fabrics (GM-2) to (GM-10) were obtained in the same manner as in Example 11 except that the binder (X-1) was replaced with another binder according to Table 1. .

Example 21 <Production of Carbon Fiber Nonwoven Fabric (NW-1)>
In Example 11, carbon fiber [trade name “Pyrofil TR30S3L”, PAN type, weight per 1 m of fiber: 200 mg / m, manufactured by Mitsubishi Rayon Co., Ltd.] was used instead of the glass strand. Then, a carbon fiber laminate was formed, and then tap water (30 g) was sprayed uniformly from the upper surface side of the laminate until the surface of the laminate became wet.
Next, a binder (X-1) of 3.0 g [10.0 g / m ² per unit area] corresponding to 10% of the weight of the carbon fiber is uniformly spread on the carbon fiber laminate, and 2.76 g A binder was attached to the carbon fiber laminate. Thereafter, in the same manner as in Example 10, a carbon fiber nonwoven fabric (NW-1) having a thickness of 0.28 mm and a unit weight of the nonwoven fabric of 109 g / m ² was obtained.

Comparative Example 4
A glass chopped strand nonwoven fabric (Example 11) was used in the same manner as in Example 11 except that (X′-1) was used instead of the binder (X-1) and the amount of binder to be dispersed was changed to 5.0 g. GM′-1) was obtained.

Comparative Examples 5 and 6
In the comparative example 4, the glass chopped strand nonwoven fabric (GM'-2) is the same as the comparative example 4 except that the binder (X'-1) is replaced with (X'-2) and (X'-3). , (GM′-3) was obtained.

  The inorganic fiber nonwoven fabric obtained above [glass chopped strand nonwoven fabric (abbreviated as GM in the present invention) and carbon fiber nonwoven fabric (abbreviated as NW in the present invention)] was evaluated according to the following method. The results are shown in Table 1.

<Evaluation method>
(1) Loss on ignition of GM (%)
This is a value measured in accordance with “7.3.2 Loss on ignition” of JIS R3420 “General test method for glass fiber”, and represents the ratio (%) of the amount of adhering binder excluding glass fiber based on the mat weight. The specific measurement procedure is as follows.
1) Put about 5g of the test piece in a magnetic crucible, dry at 105 ° C for 30 minutes, then cool to room temperature in a desiccator and measure the weight (m1) to the nearest 0.1 mg. The crucible containing the dried specimen was placed in an electric furnace whose temperature was adjusted to 625 ° C., burned for 5 minutes with the door open, then closed and burned for another 10 minutes. Thereafter, the magnetic crucible containing the test piece is taken out, allowed to cool to room temperature in a desiccator, and the weight (m2) is measured to the nearest 0.1 mg.
2) After drying the above crucible without a test piece at 105 ° C for 30 minutes, it is allowed to cool to room temperature in a desiccator, and the weight (m0) is measured to the nearest 0.1 mg.
3) The ignition loss is calculated from the following formula.

Loss on ignition (%) = 100 × [[(m1) − (m2)] / [(m1) − (m0)]]

(2) Yield rate (%) (Evaluation of yield when spraying binder)
The yield rate is calculated from the following formula.

Yield rate (%) = (W2 / W1) x 100

However, W1: Binder weight spread to the inorganic fiber laminate
W2: Weight of binder attached to inorganic fiber laminate In the case of GM, W2 is obtained from the following calculation formula.
W2 = GM weight × ignition loss / 100
For NW,
W2 is calculated | required from the weight difference of the laminated body before and behind binder distribution.

(3) Tensile strength (N) of inorganic fiber nonwoven fabric (evaluation of mechanical strength)
From each GM, 10 test pieces of vertical x horizontal 150 mm x 50 mm are cut out one by one, and the tensile strength is measured in accordance with “7.4 tensile strength” of JIS R3420 “Glass fiber general test method”. The average value of 10 pieces was obtained.

(4) Difference between maximum and minimum tensile strength of inorganic fiber nonwoven fabric (Evaluation of mechanical strength uniformity)
The difference between the maximum value and the minimum value of the tensile strength of 10 test pieces was determined and evaluated according to the following criteria.
<Evaluation criteria>
○: 30N or less △: More than 30N or less than 45N ×: More than 45N

  From the results of Table 1, the inorganic fiber nonwoven fabric obtained using the binder of the present invention has a better yield rate when spraying the binder than the inorganic fiber nonwoven fabric obtained using the comparative binder. It can be seen that the binder can impart uniform mechanical strength to the inorganic fiber nonwoven fabric.

  The inorganic fiber nonwoven fabric obtained by bonding the inorganic fiber laminate with the binder of the present invention is used as a reinforcing material for an inorganic fiber reinforced plastic molded article, and the molded article is an automobile member (molded ceiling material, etc.), a small size. Since it is applied to a wide range of fields such as hulls of ships (canoe, boat, yacht, motor boat, etc.), housing members (building materials, bathtubs, septic tanks, etc.), windmill blades, etc., it is extremely useful.

Claims (10)

  Binder for inorganic fiber nonwoven fabric (X) comprising resin particles (A) having at least a part of the particle surface coated with hydrophilic fine particles (B) and having a number average primary particle diameter of (B) of 1 to 20 nm (X ).   The binder according to claim 1, wherein the resin constituting (A) is at least one selected from the group consisting of a polyester resin, a polyurethane resin, a polyamide resin, and a polyvinyl acetate resin.   The binder according to claim 1 or 2, wherein the proportion of (B) based on the weight of (A) is 0.01 to 5% by weight. The binder according to any one of claims 1 to 3, wherein the resin particles (A) coated with the hydrophilic fine particles (B) have a specific surface area of 0.3 to 5.0 m ² / g.   The binder according to any one of claims 1 to 4, wherein (B) is an oxide containing at least one atom selected from the group consisting of silicon, aluminum, iron, titanium, magnesium and zirconium.   The binder according to any one of claims 1 to 5, wherein the inorganic fiber is at least one selected from the group consisting of mineral fibers and carbon fibers.   An inorganic fiber nonwoven fabric obtained by bonding an inorganic fiber laminate using the binder according to claim 1.   An inorganic fiber reinforced plastic molded product obtained by molding the nonwoven fabric according to claim 7 as a reinforcing material.   The molded article according to claim 8, wherein the plastic molded article is for automobile molded ceiling materials, small ship hulls, building materials, bathtubs, septic tanks or windmill blades.   In a method of spraying a binder on an inorganic fiber laminate, heating and melting, and press-molding the laminate to produce a nonwoven fabric, the binder (X) according to any one of claims 1 to 6 is used. A method for producing an inorganic fiber nonwoven fabric.