JP2014047445A - Binder for inorganic fiber nonwoven fabric - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a binder which does not contain an infusible component (gel), uniformly melts by being heated and thereby bonds inorganic chopped strand laminates, forms an inorganic fiber nonwoven fabric having uniform mechanical strength, and has adequate styrene solubility.SOLUTION: The binder for the inorganic fiber nonwoven fabric contains a polyester resin which has a constitutional unit that includes an acid component containing aromatic dicarboxylic acid and/or an ester-forming derivative thereof, and an alcohol component containing (poly) alkylene glycol.

Description

  The present invention relates to a binder for inorganic fiber nonwoven fabric. More specifically, the present invention relates to a binder for inorganic fiber nonwoven fabric that gives a uniform inorganic fiber nonwoven fabric having excellent mechanical strength.

An inorganic fiber nonwoven fabric is normally manufactured in the following steps.
(1) Several tens to several hundreds of inorganic single fibers (fiber diameter of about 10 to 25 μm) are bundled with a sizing agent to obtain strands.
(2) The strand is cut to a predetermined length to obtain an inorganic chopped strand (hereinafter abbreviated as inorganic CS).
(3) The inorganic CS is randomly dispersed and dispersed on a transport net that moves forward and backward at a constant speed to obtain an inorganic CS laminate.
(4) A predetermined amount of water is sprayed from the upper surface or the lower surface side of the inorganic CS laminate.
(5) An inorganic fiber nonwoven fabric is obtained by heating what is spread | dispersed the binder from the upper surface side of this laminated body in an oven chamber, combining inorganic CS with the fuse | melted binder, and also pressing.

  Conventionally, unsaturated polyester resins pulverized by mechanical pulverization (for example, see Patent Documents 1 to 3) have been known as binders for inorganic fiber nonwoven fabrics, and inorganic CS is obtained from an embossed roller-equipped sprayer or the like. On the laminate, an amount of binder adjusted according to the basis weight is dispersed. The dispersed binder does not usually contribute to the mechanical strength (tensile strength, etc., the same applies hereinafter) of the resulting inorganic fiber nonwoven fabric, but adheres and melts at the intersection of inorganic CS in the inorganic CS laminate. It is said that this has contributed mainly.

Japanese Patent No. 3857224 JP 2003-48255 A JP 2004-263124 A

Conventional binders often contain a polyester resin powder of a polycondensate of an alkylene oxide adduct of bisphenol A and an α, β-unsaturated dicarboxylic acid. This is because when the inorganic fiber reinforced plastic (FRP) described later is produced, the binder is required to have solubility in the styrene monomer for FRP.
The polyester resin has a problem that an unmelted component (gel) is generated. The polyester resin is finely pulverized by a pulverizer when used to form a powdery binder, but the contained gel particles are heated. Often does not melt.
As described above, in the production of the inorganic fiber nonwoven fabric, it is necessary to heat and melt the binder powder in the step (5). Therefore, when the binder powder containing such gel particles adheres to the inorganic CS intersection, the quality of the inorganic fiber nonwoven fabric ( Tensile strength and uniformity thereof). In addition, the gel particles are insoluble in styrene (a monomer component of the FRP resin solution) and have various industrial problems such as a decrease in strength of FRP.
The object of the present invention is to contain an inorganic chopped strand laminate by heating and uniformly melting without containing an infusible component (gel), giving an inorganic fiber nonwoven fabric with uniform mechanical strength, and having an appropriate styrene solubility. It is in providing the binder which has.
In the present invention, the binder having an appropriate styrene solubility means that the binder of the present invention is appropriately dissolved in a styrene monomer which is a diluent for a matrix resin such as an unsaturated polyester resin during FRP production. This means that the binder function of the inorganic fiber nonwoven fabric is maintained, it has an affinity with the matrix resin of FRP, and the fiber reinforced properties of the inorganic fiber nonwoven fabric in FRP are excellent. The solubility can be evaluated by a styrene solubility test described later.

  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 comprises a structural unit comprising an acid component (a) containing an aromatic dicarboxylic acid and / or an ester-forming derivative thereof (a1) and an alcohol component (b) containing a (poly) alkylene glycol (b1). It is the binder (X) for inorganic fiber nonwoven fabrics which contains the polyester resin (PS) to make.

The binder for inorganic fiber nonwoven fabric of the present invention has the following effects.
(1) It is uniformly melted by heating and does not contain an unmelted component (gel).
(2) Bonding inorganic chopped strand laminates to give an inorganic fiber nonwoven fabric with uniform mechanical strength.
(3) Since it has moderate styrene solubility, it is excellent in the fiber reinforcement property by the inorganic fiber nonwoven fabric in FRP.

[Polyester resin (PS)]
The polyester resin (PS) in the present invention is an aromatic dicarboxylic acid and / or an ester-forming derivative thereof [an acid anhydride, an acid halide, a lower alkyl (C1-4) ester, or the like. same as below. ] A polycondensate comprising as constituent units an acid component (a) containing (a1) and an alcohol component (b) containing (poly) alkylene glycol (b1).
Among (a1), the aromatic dicarboxylic acid has 8 to 20 carbon atoms (hereinafter abbreviated as C), such as ortho-, iso- and terephthalic acid, tetramethylterephthalic acid, 2,2'- and 4, 4'-biphenyldicarboxylic acid and the like; as ester-forming derivatives, anhydrides of the aromatic dicarboxylic acid (phthalic anhydride and the like), acid halides of the aromatic dicarboxylic acid (isophthalic acid dichloride, terephthalic acid dibromide and the like), And lower alkyl (C1-4) esters (eg, dipropyl phthalate, dimethyl isophthalate, dimethyl terephthalate).

  Of these (a1), preferred are isophthalic acid, terephthalic acid, terephthalic acid dimethyl ester, and phthalic anhydride from the viewpoint of the working environment during production and the styrene solubility of the (PS) resin.

As a polycarboxylic acid constituting the polyester resin (PS), in addition to (a1), an aliphatic, aromatic ring-containing, alicyclic-containing poly (bivalent to trivalent) or other than (a1) as long as the effects of the present invention are not impaired. More than that) carboxylic acids, their ester-forming derivatives, and mixtures thereof can be included.
The content of the polycarboxylic acid other than (a1) is usually 40 mol% or less based on the total number of moles of the acid component (a), and preferably 35 mol% or less from the viewpoint of the effect of the present invention. is there.

  Examples of the aliphatic polycarboxylic acid and ester-forming derivatives thereof (a2) include C2-30 and bivalent, such as glutaric acid, adipic acid, azelaic acid, sebacic acid, tricarballylic acid, maleic acid, Fumaric acid, itaconic acid, aconitic acid, succinic acid, and ester-forming derivatives thereof;

Aromatic ring-containing polycarboxylic acids other than (a1) and their ester-forming derivatives (a3) are C8-30, bivalent to tetravalent, such as homo-, homoiso- and homoterephthalic acid, phthalonic acid, Iso- and terephthalonic acid, trimellitic acid, pyromellitic acid, and ester-forming derivatives thereof;

Examples of the alicyclic-containing polycarboxylic acid and ester-forming derivatives thereof (a4) are C6-50, which are 2- to 3-valent, 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, cyclohexentricarboxylic acid, and ester-forming derivatives thereof.

  Among (a2) to (a4), from the viewpoint of compatibility with the aromatic dicarboxylic acid and / or its ester-forming derivative (a1) and from the viewpoint of appropriate solubility in the styrene monomer at the time of FRP preparation described below Preferred are (a2) and (a3), and more preferred are homo-, homoiso- and homoterephthalic acid.

  As the (poly) alkylene glycol (b1), the hydroxyl equivalent (molecular weight per hydroxyl group) is preferably 31 or more and the number average molecular weight [hereinafter abbreviated as Mn, from the viewpoint of optimum resin physical properties. The measurement is based on a gel permeation chromatography (GPC) method under the conditions described below. ] 300 or less, more preferably those having a molecular weight of 31 or more and Mn 250 or less can be used.

The GPC measurement conditions are as follows.
<GPC measurement conditions>
[1] Apparatus: HLC-8220 [manufactured by Tosoh Corporation]
[2] Column: TSKgel SuperMultipore HZ-M
[Made by Tosoh Corporation]
[3] Eluent: Tetrahydrofuran [4] Reference substance: PEG [when measuring (poly) alkylene glycol], polystyrene [when measuring substance other than (poly) alkylene glycol]
[5] Injection conditions: sample concentration 2.5 mg / ml, column temperature 40 ° C.

  (B1) includes ethylene glycol (EG), propylene glycol (PG), 1,4-butanediol (1,4-BD), 1,6-hexanediol (1,6-HD), neopentyl glycol ( NPG), diethylene glycol (DEG), dipropylene glycol (DPG), polyethylene glycol (PEG), polypropylene glycol (PPG), polytetramethylene glycol (PTMG) and the like.

  Of these (b1), EG, PG, DEG and DPG having a low hydroxyl equivalent are preferred from the viewpoint of the melting characteristics of the binder.

As the alcohol component (b) constituting the polyester resin (PS), in addition to the (poly) alkylene glycol (b1), a dihydric alcohol (b2) other than (b1) is necessary as long as the effects of the present invention are not impaired. Trivalent to 10-valent or higher polyhydric alcohol (b3), and alkylene oxide (hereinafter abbreviated as AO; C2 to 10) of these alcohols or polyhydric (divalent to trivalent or higher) phenols. (2-10 mol. The same shall apply hereinafter.) An adduct (b4), a mixture thereof and the like can be contained.
The content in the case of containing (b2) to (b4) is usually 40 mol% or less based on the total number of moles of the alcohol component (b), and preferably 35 mol% or less from the viewpoint of the effects of the present invention.

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 alpha-olefin oxide, epichlorohydrin, and these 2 or more types combined use (block and / or random addition) are mentioned.
Among these AOs, EO, PO, and a combination thereof are preferable from the viewpoint of the mechanical strength of the inorganic fiber nonwoven fabric described later and the permeability to the inorganic fiber nonwoven fabric such as styrene monomer in application to FRP. .

  Examples of the dihydric alcohol (b2) other than (b1) include aromatic ring-containing aliphatic alcohols [C8-15, such as m- and p-xylylene glycol]; alicyclic alcohols [C5-15, such as 1,2- 1,3- and 1,4-cyclohexanediol] and the like.

  Specific examples of the trivalent to 10-valent or higher polyhydric alcohol (b3) include alkane polyols [C3 to 10 such as glycerin, trimethylolpropane, pentaerythritol, sorbitol (hereinafter referred to as GR, TMP, PE, SO, respectively). Abbreviation)], intermolecular or intramolecular dehydration of the alkane polyol [C6-30, such as diPE, polyGR (degree of polymerization 2-8), sorbitan], saccharides and their derivatives (glycosides) (C6-20) For example, fructose, glucose, sucrose, methyl glucoside).

  Among the polyhydric phenols constituting the (b4), dihydric phenols include those of C6-18, such as monocyclic (hydroquinone, catechol, resorcinol, urushiol, etc.), condensed polycyclic [dihydroxynaphthalene (1,5 -Dihydroxynaphthalene etc.), binaphthol etc.], bisphenol compounds (bisphenol A, -F, -C, -B, -AD and -S, 4,4'-dihydroxydiphenyl-2,2-butane etc.), dihydroxybiphenyl; In addition, trihydric or higher polyhydric phenols include those having C6 or more and Mn 1,500 or less, such as monocyclic (pyrogallol, phloroglucinol, etc.), and mono- or dihydric phenols (phenol, cresol, xylenol, Resorcinol) and aldehydes (formaldehyde, glutarua) Dehydride etc.) or condensates with ketones (acetone etc.) (phenol or cresol novolac resin, resole intermediate, polyphenol obtained by condensation reaction of phenol and glyoxal or glutaraldehyde, polyphenol obtained by condensation reaction of resorcin and acetone Etc.).

  Of the above (b2) to (b4) other than (poly) alkylene glycol (b1), (b2) is preferable from the viewpoint of the melting characteristics of (PS) and the compatibility of the FRP resin and (PS) during FRP production. ) And (b4), more preferably an AO adduct of an aromatic ring-containing aliphatic alcohol and a polyhydric phenol, particularly preferably an AO adduct of p-xylylene glycol and bisphenol A.

The polyester resin (PS) of the present invention is obtained by a polycondensation reaction between the acid component (a) and the alcohol component (b).
In the polycondensation reaction, the reaction equivalent ratio (COOH / OH) of the carboxyl group (a) and the hydroxyl group (b) is preferably 0.85 from the viewpoint of rapid polycondensation reaction and stability of the resulting polyester resin. It is -2.0, More preferably, it is 0.90-1.5.

  The polycondensation reaction is usually performed at 190 to 250 ° C. under 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 (PS) obtained. In addition, when using the (poly) alkylene glycol whose boiling point is less than 190 degreeC, it is desirable to carry out under pressure from a viewpoint of obtaining the target polyester resin (PS) reliably.

In the polycondensation reaction, an esterification catalyst may be used.
Examples of the esterification catalyst include proton acid (phosphoric acid, etc.), metal (alkali metal, alkaline earth metal, transition metal, 2B, 4A, 4B, 5A, 5B metal, etc.)-Containing compound [carboxylic acid (C2-4) Salt, carbonate, sulfate, phosphate, oxide, chloride, hydroxide, alkoxide, etc.].
Of these, from the viewpoint of reactivity and prevention of coloring of the resulting polyester resin, preferred are metal-containing compounds, more preferred are carboxylic acid (C2-4) salts of 2B, 4A, 4B, 5A and 5B metals, Oxides and alkoxides, particularly preferred are zinc acetate, zirconyl acetate, tetrabutyl titanate, bis [2,2 ′-[(2-hydroxyethyl) imino-κN] -bis [ethanolate-κO]] titanate, antimony trioxide And dibutyltin oxide.
The use amount of the esterification catalyst is preferably 0.005 to 3% from the viewpoint of reactivity and prevention of coloring based on the total weight of the acid component (a) and the alcohol component (b) forming (PS). Preferably it is 0.01 to 1%.

In order to accelerate the reaction, an organic solvent can be added to the reaction system and refluxed. It is desirable to remove the organic solvent after completion of the reaction.
Examples of the organic solvent include those having no active hydrogen such as a hydroxyl group, such as hydrocarbons (toluene, xylene, etc.) and ketones (methyl ethyl ketone, methyl isobutyl ketone, etc.).

  Mn of (PS) is preferably 1,500 to 10,000, more preferably 2,500 to 7,000, from the viewpoint of the mechanical strength of the inorganic fiber nonwoven fabric described later and the melt viscosity at the time of heating and melting the binder. .

  (PS) softening point [measured according to the ring and ball method (JIS K2207, “petroleum asphalt” “6.4 softening point test method”). same as below. ] Is the prevention of the stickiness of the inorganic fiber nonwoven fabric, the moderate meltability of the binder during heating during the inorganic fiber nonwoven fabric manufacturing process, the workability of post-processing (fitness to mold in application to FRP described later, etc.) , The same shall apply hereinafter), preferably from 80 to 130 ° C, more preferably from 110 to 125 ° C.

  (PS) Glass transition temperature by differential thermal analysis [hereinafter abbreviated as Tg. The measurement conforms to JIS K7121, “Plastic transition temperature measurement method”. same as below. ] Is preferably 40 to 60 ° C., more preferably 45 to 55 ° C. from the viewpoints of blocking prevention during binder storage, workability in post-processing, and bonding at the intersections between inorganic CSs by the binder.

When (PS) is used as the binder (X) of the present invention, which will be described later, the carboxyl group and the hydroxyl group are the same as other polyester resins (QS) other than (PS) as long as the effects of the present invention are not inhibited as necessary. A self-condensate of the compound (c1) contained in the molecule, a ring-opening polycondensate of the lactone (c2), and the like can be used in combination.
The combined amount of (QS) is usually 30% or less based on the weight of (PS), preferably 20% or less, more preferably 10% or less from the viewpoint of the effect of the present invention.

Examples of (c1) include C2-10, such as lactic acid, glycolic acid, β-hydroxybutyric acid, hydroxypivalic acid, hydroxyvaleric acid, and mixtures of two or more thereof.
Of these, hydroxypivalic acid and hydroxyvaleric acid are preferred from the viewpoint of compatibility with (PS) and solubility in styrene monomer during FRP production.

Examples of the lactone (c2) include C3-20 (preferably 4-12) lactones such as β-lactone (β-propiolactone and the like), γ-lactone (γ-butyrolactone and the like), and δ-lactone (δ-valero). Lactones, etc.), ε-lactone (ε-caprolactone, etc.), macrocyclic lactones (enanthlactone, undecanolactone, dodecalactone, etc.), and mixtures of two or more of these.
Among these, γ-butyrolactone, ε-caprolactone, and a mixture thereof are preferable from the viewpoint of compatibility with (PS) and solubility in styrene monomer during FRP production.

  The self-condensation reaction of (c1) and the ring-opening polycondensation reaction of (c2) can be carried out according to the reaction conditions of the polycondensation reaction in the production of the polyester resin (PS).

  Mn of the polyester resin (QS) is preferably 2,500 to 7,000, more preferably 3,000 to 6,000, from the viewpoint of the mechanical strength of the inorganic fiber nonwoven fabric and the melt viscosity at the time of heating and melting the binder. .

[Polyester resin (PS) particles (A)]
When used as a binder, the polyester resin (PS) is pulverized to form polyester resin particles (A).
The (A) is a high-speed impact type pulverizer with a soundproof case equipped with a classification screen (0.2 to 3 mmφ round hole) (trade name “MIKRO-PULVERIZER”, model number “AP-BL”, Made by Hosokawa Micron Corporation. Hereinafter referred to as high-speed hammer mill. The particles having been passed through the classification screen are passed through the classification screen with a sieve having a different opening while continuously feeding at a feed rate of 11.4 to 13.8 g / min using It can be obtained by sieving by combination or the like.

  The volume average particle diameter Dv of (A) is preferably 60 to 350 μm, more preferably 120 to 250 μm, from the viewpoint of powder flowability and mechanical strength of the inorganic fiber nonwoven fabric. Here, Dv can be determined by a laser diffraction scattering method. As a measuring apparatus, for example, a particle size distribution measuring instrument [trade name “Microtrack MT3000II particle size analyzer”, manufactured by Nikkiso Co., Ltd.] (hereinafter abbreviated as “Microtrack”) Is mentioned.

[Inorganic fiber nonwoven fabric binder (X)]
The binder for inorganic fiber nonwoven fabric (X) of the present invention comprises the (PS) particles (A), and if necessary, an antiblocking agent (B1), a lubricant (B2), and a hydrophilicity imparting agent (B3). 1 type, or 2 or more types of additives (B) chosen from the group which consists of can be contained. These additives (B) are usually added after pulverizing and sieving (PS).
The total amount of (B) used is usually 8% or less based on the weight of (A), preferably from 0.01 to 5%, more preferably from the viewpoint of the effect of addition and the mechanical strength of the inorganic fiber nonwoven fabric. 1 to 3%.

Examples of the antiblocking agent (B1) include fine fatty acids or salts thereof, silicon or metal oxides, silicon or metal carbides, calcium carbonate, talc, organic resins, and mixtures thereof.
As higher fatty acids, C8-24 fatty acids such as lauric acid and stearic acid; as salts of higher fatty acids, alkali metals (Li, Na, K etc.), alkaline earth metals (Mg, Ca, Ba, etc.), Zn, Cu, Ni, Co and Al, etc .; silicon or metal oxides include silicon dioxide, silicon oxide, aluminum oxide, iron oxide, titanium oxide, magnesium oxide, zirconium oxide, etc .; silicon or Examples of metal carbides include silicon carbide and aluminum carbide; examples of organic resins include polyolefin resin, polyamide resin, poly (meth) acrylate resin, silicon resin, polyurethane resin, phenol resin, polytetrafluoroethylene resin, and cellulose powder. Is mentioned.
Of these, higher fatty acid metal salts and silicon or metal oxides are preferred from the viewpoint of blocking prevention and powder flowability of (A). Examples of commercially available silicon oxide include “AEROSIL 200”, “AEROSIL 380”, “AEROSIL R972” [trade names, all manufactured by Nippon Aerosil Co., Ltd.] and the like.

  The amount of (B1) used is usually 5% or less based on the weight of (A), preferably from 0.01 to 2%, more preferably from the viewpoint of preventing blocking of the binder and binding between inorganic CSs. ~ 1%.

Examples of the lubricant (B2) include wax, low molecular weight polyethylene, higher alcohol, higher fatty acid (metal salt), higher fatty acid ester, and higher fatty acid amide.
As the wax, carnauba wax and the like; As the low molecular weight polyethylene, polyethylene of Mn 1,000 to 10,000, etc .; As the higher alcohol, C10-24, such as stearyl alcohol; As the higher fatty acid ester, the above C8-24 Of higher fatty acids and poly (2-4) alcohol AO (C2-3) adducts (eg monostearate of EG EO 5 mol adduct); higher fatty acid amides include C10-40, eg stearin Examples include acid amides.
Among these, from the viewpoint of the powder fluidity of (A) and the bondability between inorganic CS, esters and higher fatty acid amides of higher fatty acids and polyhydric alcohol AO adducts are preferred.

  The amount of (B2) used is usually 5% or less based on the weight of (A), preferably from 0.01 to 2%, more preferably from the viewpoint of the powder flowability of (A) and the bondability between inorganic CSs. Is 0.1 to 1%.

As the hydrophilicity-imparting agent (B3), polyvinyl alcohol (Mn 1,000 to 10,000), carboxyl methyl cellulose, sodium alginate, PEG (Mn 200 to 20,000), PEG (Mn 100 to 2,000) chain-containing organopolysiloxane ( Mn 200-50,000), starch, sodium polyacrylate (Mn 500-20,000), (meth) acryloyl group-containing polymer having a quaternary ammonium base, and the like.
Among these, PEG and PEG chain-containing organopolysiloxane are preferred from the viewpoints of the affinity between water sprayed on the inorganic CS laminate described later and (X) and the binding property between inorganic CSs.

  The amount of (B3) used is usually 5% or less based on the weight of (A). From the viewpoint of the affinity between water (X) sprayed on the inorganic CS laminate described later and the binding property between inorganic CSs. To preferably 0.01 to 2%, more preferably 0.1 to 1%.

[Inorganic fiber nonwoven fabric]
The inorganic fiber nonwoven fabric of the present invention is obtained by bonding inorganic CSs in an inorganic CS laminate described later with the binder (X).
Here, the inorganic fibers include mineral fibers obtained by fiberizing a melt such as stone, slag, glass, and carbon fibers.

  The carbon fiber is a fiber formed by carbonizing an acrylic fiber or pitch (by-products such as petroleum, coal, coal tar, etc.) at a high temperature, and the carbon fiber using the acrylic fiber is polyacrylonitrile ( PAN) and carbon fibers using pitch are classified as pitch (PITCH).

  Of these inorganic fibers, glass fibers and carbon fibers are preferable from the viewpoint of adhesiveness with a matrix resin in application to FRP and the like, and glass fibers are more preferable.

Specifically, the inorganic fiber nonwoven fabric of the present invention can be produced by, for example, the following steps.
(1) An inorganic CS laminate is obtained by spreading inorganic CS on a wire mesh in a directional disorder so as to have a uniform thickness.
(2) A predetermined amount of water is sprayed by spraying from the upper surface and / or lower surface side of the laminate so that the entire surface of the inorganic CS laminate is uniformly wetted.
(3) A predetermined amount of binder is uniformly dispersed and adhered from the upper surface side of the inorganic CS laminate.
(4) A predetermined amount of water is sprayed from the upper surface side by spraying so that the entire surface of the inorganic CS laminate is moistened, and a predetermined amount of binder is uniformly dispersed and adhered.
(5) The step (4) may be repeated once or twice or more as necessary.
(6) The binder-adhered laminate obtained in the steps up to the above (5) is heated at 85 to 200 ° C. for 1 to 10 minutes and then adjusted to 70 to 230 ° C. by a pressure molding machine at 0.01 to 5 MPa. The binder is pressed (cooled press molding) at a pressure of 0.01 to 5 MPa with a press (hot press molding) or a roll press machine (roll temperature is adjusted to 0 to 30 ° C.) while cooling after the heating. An inorganic fiber nonwoven fabric bonded with is obtained.
The basis weight of the inorganic fiber nonwoven fabric (inorganic fiber nonwoven fabric weight per 1 m ² , unit is g / m ² ) is 40 to 950 depending on the application. For example, if it is for automobile ceiling materials, it is 40 to 200, preferably 80 to 150. Moreover, if it is for ships and building materials, it is 200-950, Preferably it is 300-600.

Here, the non-woven fabric refers to a chopped strand laminate that is bonded to a binder, heated and melted and then pressure-bonded, and has a thickness of about 0.05 to 2 mm.
For example, glass chopped strand mat [trade name: EM 100, basis weight: 100 g / m ² ] manufactured by Nippon Electric Glass Co., Ltd. as an inorganic fiber nonwoven fabric for automobile ceiling materials, and glass chopped manufactured by Central Glass Co., Ltd. for ships and building materials Examples thereof include a strand mat [trade name: ECM450-501, basis weight: 450 g / m ² ], a glass chopped strand mat [trade name: MC600A, basis weight: 600 g / m ² ] manufactured by Nitto Boseki Co., Ltd., and the like.

  The amount of water sprayed in (2), (4) and (5) of the above production process is based on the weight of the inorganic CS laminate not containing the binder, respectively, and the adhesion of the binder and easy drying in the subsequent process From the viewpoint of property, it is preferably 10 to 1,000%, more preferably 20 to 700%. The sprayed water adheres mainly at the intersections in the inorganic CS laminate, and the binder (X) of the present invention is excellent in adhesion with water at the intersections.

  The binder adhesion ratio based on the weight of the inorganic CS laminate [binder adhesion amount (%)] is determined according to the mechanical strength and handling properties of the inorganic fiber nonwoven fabric (flexibility, when creating an inorganic fiber reinforced plastic molded product described later) The preferred range is determined from the viewpoint of the fitability of the mold to the mold and the like. For example, if it is for automobile ceiling material, it is preferably 6 to 20%, more preferably 8 to 15%. Moreover, if it is for ships and building materials, Preferably it is 1 to 5%, More preferably, it is 2.5 to 4%.

  The coefficient of variation of the tensile strength of the inorganic fiber nonwoven fabric of the present invention is preferably 50% or less, more preferably 45% or less, from the viewpoint of the flexibility of the inorganic fiber nonwoven fabric and the uniformity of mechanical strength. The coefficient of variation is measured by the method described later.

[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 mold surface at room temperature (15 to 25 ° C.) using a roller or the like so as to obtain 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 “wt%” unless otherwise specified.

Example 1
(1) Production of polyester resin (PS-1) In a reaction vessel, PG 1,931 parts, EG 1,579 parts, terephthalic acid 5,852 parts, dibutyltin oxide 8 parts were charged and reacted at 180 ° C. for 4 hours in a nitrogen atmosphere. After that, the temperature was raised to 215 ° C., and the reaction was further continued for 5 hours. Thereafter, the mixture was reacted at the same temperature for 5 hours under a reduced pressure of 2 kPa. The product was taken out when the softening point reached 120 ° C., and then cooled to room temperature to obtain a polyester resin (PS-1). The characteristic values of (PS-1) are shown in Table 1.

(2) Production of (PS) particles (A-1) 2,000 parts of (PS-1) were pulverized using a high-speed hammer mill at a sample supply rate of 12 g / min and a hammer rotation speed of 12,500 rpm. The pulverized product was classified by passing through a 1.0 mmφ round hole classification screen attached to the exit of the pulverization part of the mill. The resin powder obtained by classification was sieved with a sieve having an opening of 350 μm, and (PS) particles (A-1) passed therethrough were obtained. Dv by Microtrack (hereinafter the same) was 230 μm.

(3) Production of binder (X-1) (A-1) 1,000 parts of an antiblocking agent (B-1) [trade name “AEROSIL 200”, manufactured by Nippon Aerosil Co., Ltd. same as below. ] After adding 2 parts, it mixed and obtained the binder (X-1) containing (PS) particle | grains (A-1).
(4) Production of inorganic fiber nonwoven fabric (NW-1) Glass strand [trade name “Roving ERS2310-821”, manufactured by Central Glass Co., Ltd. ] Was cut to a length of about 5 cm to obtain a glass chopped strand (glass CS). 24.5 g of the glass CS is sprinkled on the stainless steel wire net (conveying net) having a depth of 21 cm and a width of 27 cm so as to have a uniform thickness in a directionally uniform manner [stacked body weight (W-1): 24 0.5 g] was obtained. From the lower surface side of the laminate, the entire lower surface was sprayed by spraying to attach 7.3 g of tap water [30% based on the laminate weight (W-1)].
Next, lamination was performed using a powder spreader [trade name “Nikka K-III” manufactured by Nikka Corporation, hereinafter referred to as a powder spreader] with embossed rollers (Ayame # 22, roller diameter 60 mm). 0.55 g of binder (X-1) [2.2% based on the weight of the laminate (W-1)] was uniformly applied from the upper surface side of the body, and then a vibration test apparatus [trade name “3-axis vibration tester] MACS II ", manufactured by Yamato Science Co., Ltd., and so on. ], A vibration having a vibration displacement of 10 mm and a vibration cycle of 3 times / second was applied to the laminate for 2 seconds. Furthermore, tap water is sprayed on the entire upper surface from the upper surface side of the laminate, and 7.3 g of tap water [30% based on the weight of the laminate (W-1)] is adhered, and a powder spreader is further attached. Used, 0.20 g of binder (X-1) [0.8% based on the weight of the laminate (W-1)] was additionally adhered uniformly from the upper surface side of the laminate.
Then, it dried for 2 minutes with the drying machine adjusted to 200 degreeC, and also the binder was fuse | melted for 2 minutes continuously. Roll press machine [model name “EST roll press DIP-400E”, manufactured by Ebino Kosan Co., Ltd., and so on. ] (The surface temperature of the laminate immediately before pressing is 130 ° C., the surface temperature of the laminate immediately after pressing is 100 ° C., the pressing pressure is 0.4 MPa), and the binder adhesion amount is 3.0 based on the weight of the laminate (W-1). %, An inorganic fiber nonwoven fabric (NW-1) [size of (NW-1): length 210 mm × width 270 mm] having a basis weight of 450 g / m ² was obtained.

Example 2
(1) Production of polyester resin (PS-2) In a reaction vessel, 1,538 parts of an EO 2.2 mol adduct of bisphenol A, 1,897 parts of a PO3 mol adduct of bisphenol A, 4,900 parts of terephthalic acid, ethylene 1,352 parts of glycol and 15 parts of bis [2,2 ′-[(2-hydroxyethyl) imino-κN] -bis [ethanolate-κO]] titanate (hereinafter abbreviated as titanate catalyst) were charged at 190 ° C. in a nitrogen atmosphere. For 3 hours, then the temperature was raised to 220 ° C. and the reaction was further continued for 6 hours. Thereafter, the mixture was reacted at the same temperature for 4 hours under a reduced pressure of 2 kPa. After the softening point reached 127 ° C., the product was taken out and cooled to room temperature to obtain a polyester resin (PS-2). The characteristic values of (PS-2) are shown in Table 1.

(2) Production of (PS) particles (A-2) (PS) In the same manner as in Example 1 (2) except that (PS-1) in Example 1 (2) was replaced with (PS-2) (PS ) Particles (A-2) were obtained. Dv was 235 μm.

(3) Manufacture of binder (X-2) (PS) particle | grains are carried out similarly to Example 1 (3) except having replaced (A-1) with (A-2) in Example 1 (3). A binder (X-2) containing A-2) was obtained.

(4) Production of inorganic fiber nonwoven fabric (NW-2)
(NW-2) was obtained in the same manner as in Example 1 (4) except that (X-1) in Example 1 (4) was replaced with (X-2).

Example 3
(1) Production of polyester resin (PS-3) Into a reaction vessel, 929 parts of PG, 7,800 parts of terephthalic acid, and 8 parts of dibutyltin oxide were reacted at 180 ° C. for 4 hours in a nitrogen atmosphere, and then 220 ° C. The mixture was heated up to react for 4 hours. Thereafter, 235 parts of GR were charged and reacted at the normal pressure for 5 hours while maintaining the same temperature. Next, the mixture was reacted at the same temperature for 3 hours under a reduced pressure of 2 kPa. The product was taken out when the softening point reached 112 ° C., and then cooled to room temperature to obtain a polyester resin (PS-3). Table 1 shows the characteristic values of (PS-3).

(2) Production of (PS) particles (A-3) (PS) In the same manner as in Example 1 (2) except that (PS-1) in Example 1 (2) was replaced with (PS-3) (PS) ) Particles (A-3) were obtained. Dv was 225 μm.

(3) Production of binder (X-3) (PS) particles (PS) in the same manner as in Example 1 (3) except that (A-1) in Example 1 (3) was replaced with (A-3). A binder (X-3) containing A-3) was obtained.

(4) Manufacture of inorganic fiber nonwoven fabric (NW-3)
(NW-3) was obtained in the same manner as in Example 1 (4) except that (X-1) in Example 1 (4) was replaced with (X-3).

Example 4
(1) Production of polyester resin (PS-4) In a reaction vessel, 7,140 parts of DEG, 1,860 parts of EG, 9,053 parts of terephthalic acid, 5,381 parts of phthalic anhydride, and 20 parts of dibutyltin oxide were charged. After reacting at 180 ° C. for 2 hours in an atmosphere, the temperature was raised to 220 ° C. and reacted for 6 hours. Next, the mixture was reacted at the same temperature for 10 hours under a reduced pressure of 2 kPa. After the softening point reached 110 ° C., the product was taken out and cooled to room temperature to obtain a polyester resin (PS-4). The characteristic values of (PS-4) are shown in Table 1.

(2) Production of (PS) particles (A-4) (PS) In the same manner as in Example 1 (2) except that (PS-1) in Example 1 (2) was replaced with (PS-4) (PS) ) Particles (A-4) were obtained. Dv was 230 μm.

(3) Production of Binder (X-4) (PS) particles (PS) in the same manner as in Example 1 (3) except that (A-1) in Example 1 (3) was replaced with (A-4). A binder (X-3) containing A-4) was obtained.

(4) Manufacture of inorganic fiber nonwoven fabric (NW-4)
(NW-4) was obtained in the same manner as in Example 1 (4) except that (X-1) in Example 1 (4) was replaced with (X-4).

Example 5
(1) Manufacture of polyester resin (PS-5) In a reaction vessel, 932 parts of EG, 2,163 parts of maleic anhydride, 5,495 parts of terephthalic acid, and 15 parts of titanate catalyst were charged at 180 ° C. in a nitrogen atmosphere. After reacting for a period of time, the temperature was raised to 220 ° C. and reacted for 5 hours. Thereafter, the mixture was reacted at the same temperature for 4 hours under a reduced pressure of 2 kPa. After the softening point reached 122 ° C., the product was taken out and cooled to room temperature to obtain a polyester resin (PS-5). The characteristic values of (PS-5) are shown in Table 1.

(2) Production of (PS) particles (A-5) (PS) In the same manner as in Example 1 (2) except that (PS-1) in Example 1 (2) was replaced with (PS-5) (PS) ) Particles (A-5) were obtained. Dv was 225 μm.

(3) Production of Binder (X-5) (PS) particles (PS) in the same manner as in Example 1 (3) except that (A-1) in Example 1 (3) was replaced with (A-5). A binder (X-5) containing A-5) was obtained.

(4) Manufacture of inorganic fiber nonwoven fabric (NW-5)
(X-1) in Example 1 (4) was replaced with (X-5) and the glass strand was made of carbon fiber [trade name “Pyrofil TR30S3L”, PAN-based, basis weight 200 mg / m (weight per 1 m of fiber) (Mitsubishi Rayon Co., Ltd.)] (NW-5) was obtained in the same manner as in Example 1 (4) except that the strand was replaced.

Example 6
(1) Production of polyester resin (PS-6) 620 parts of EG, 1,234 parts of dimethyl terephthalate, 529 parts of phthalic anhydride, and 5 parts of titanate catalyst were charged in a reaction vessel and reacted at 180 ° C. for 2 hours in a nitrogen atmosphere. Then, the temperature was raised to 220 ° C. and reacted for 5 hours. Subsequently, the reaction was carried out at the same temperature for 6 hours under a reduced pressure of 2 kPa. Further, after returning to normal pressure, 100 parts of trimellitic anhydride was added and reacted at the same temperature for 30 minutes. When the softening point was 135 ° C., the product was taken out, cooled to room temperature, and polyester resin (PS- 6) was obtained. The characteristic values of (PS-6) are shown in Table 1.

(2) Production of (PS) particles (A-6) (PS) In the same manner as in Example 1 (2) except that (PS-1) in Example 1 (2) was replaced with (PS-6) (PS ) Particles (A-6) were obtained. Dv was 227 μm.

(3) Production of binder (X-6) (PS) particles (PS) in the same manner as in Example 1 (3) except that (A-1) in Example 1 (3) was replaced with (A-6). A binder (X-6) containing A-6) was obtained.

(4) Manufacture of inorganic fiber nonwoven fabric (NW-6)
(NW-6) was obtained in the same manner as in Example 1 (4) except that (X-1) in Example 1 (4) was replaced with (X-6).

Example 7
(1) Production of polyester resin (PS-7) In a reaction vessel, 4,590 parts of DEG, 6,225 parts of terephthalic acid, and 11 parts of dibutyltin oxide were allowed to react at 180 ° C. for 2 hours in a nitrogen atmosphere. The temperature was raised and reacted for 6 hours. Subsequently, the mixture was reacted at the same temperature for 8 hours under a reduced pressure of 2 kPa. When the softening point reached 73 ° C., the product was taken out and cooled to room temperature to obtain a polyester resin (PS-7). The characteristic values of (PS-7) are shown in Table 1.

(2) Production of (PS) particles (A-7) (PS) In the same manner as in Example 1 (2) except that (PS-1) in Example 1 (2) was replaced with (PS-7) (PS ) Particles (A-7) were obtained. Dv was 232 μm.

(3) Production of binder (X-7) (PS) particles (PS) in the same manner as in Example 1 (3) except that (A-1) in Example 1 (3) was replaced with (A-7). A binder (X-7) containing A-7) was obtained.

(4) Manufacture of inorganic fiber nonwoven fabric (NW-7)
(NW-7) was obtained in the same manner as in Example 1 (4) except that (X-1) in Example 1 (4) was replaced with (X-7).

Comparative Example 1
(1) Manufacture of polyester resin (PS'-1) A reaction vessel was charged with 3,455 parts of EO 2.2 mol adduct of bisphenol A, 1,123 parts of fumaric acid, and 6 parts of dibutyltin oxide, and 180 ° C. in a nitrogen atmosphere. For 5 hours. Thereafter, the mixture was reacted at the same temperature under a reduced pressure of 2 kPa for 5 hours, and when the softening point reached 115 ° C., the product was taken out and then cooled to room temperature to obtain a polyester resin (PS′-1). Table 2 shows the characteristic values of (PS′-1).

(2) Production of (PS) Particles (A′-1) Same as Example 1 (2) except that (PS-1) in Example 1 (2) was replaced with (PS′-1). (PS) particles (A′-1) were obtained. Dv was 230 μm.

(3) Production of binder (X′-1) (PS) In the same manner as in Example 1 (3) except that (A-1) in Example 1 (3) was replaced with (A′-1). A binder (X′-1) containing particles (A′-1) was obtained.

(4) Production of inorganic fiber nonwoven fabric (NW'-1)
An inorganic fiber nonwoven fabric (NW′-1) was obtained in the same manner as in Example 1 (4) except that (X-1) in Example 1 (4) was replaced with (X′-1).

Comparative Example 2
(1) Manufacture of polyester resin (PS'-2) In a reaction vessel, EO2.2 mol adduct of bisphenol A 11,269 parts, EG 3,003 parts, fumaric acid 7,191 parts, dibutyltin oxide 8 parts, The reaction was performed at 180 ° C. for 5 hours under a nitrogen atmosphere. Thereafter, the temperature was raised to 215 ° C., and the mixture was reacted at the same temperature for 7 hours under a reduced pressure of 2 kPa. After the softening point reached 120 ° C., the product was taken out, cooled to room temperature, and polyester resin (PS′-2 ) Table 2 shows the characteristic values of (PS′-2).

(2) Production of (PS) Particles (A′-2) Same as Example 1 (2) except that (PS-1) in Example 1 (2) was replaced with (PS′-2). (PS) particles (A′-2) were obtained. Dv was 225 μm.

(3) Production of binder (X′-2) (PS) In the same manner as in Example 1 (3) except that (A-1) in Example 1 (3) was replaced with (A′-2). A binder (X′-2) containing particles (A′-2) was obtained.

(4) Production of inorganic fiber nonwoven fabric (NW'-2)
An inorganic fiber nonwoven fabric (NW′-2) was obtained in the same manner as in Example 1 (4) except that (X-1) in Example 1 (4) was replaced with (X′-2).

Comparative Example 3
(1) Production of polyester resin (PS'-3) A reaction vessel was charged with 5,019 parts of an EO2 molar adduct of bisphenol A, 2,380 parts of terephthalic acid, and 8 parts of dibutyltin oxide, and 7% at 200 ° C. in a nitrogen atmosphere. After reacting for a period of time, the temperature was raised to 220 ° C. and reacted for 4 hours. Thereafter, the mixture was reacted at the same temperature for 10 hours under a reduced pressure of 2 kPa. The product was taken out when the softening point reached 123 ° C., and then cooled to room temperature to obtain a polyester resin (PS′-3). Table 2 shows the characteristic values of (PS′-3).

(2) Production of (PS) Particles (A′-3) As in Example 1 (2), except that (PS-1) in Example 1 (2) was replaced with (PS′-3). (PS) particles (A′-3) were obtained. Dv was 235 μm.

(3) Production of binder (X′-3) (PS) In the same manner as in Example 1 (3) except that (A-1) in Example 1 (3) was replaced with (A′-3). A binder (X′-3) containing particles (A′-3) was obtained.

(4) Manufacture of inorganic fiber nonwoven fabric (NW'-3)
An inorganic fiber nonwoven fabric (NW′-3) was obtained in the same manner as in Example 1 (4) except that (X-1) in Example 1 (4) was replaced with (X′-3).

Comparative Example 4
(1) Manufacture of polyester resin (PS'-4) In a reaction vessel, 930 parts of EG, 1,372 parts of maleic anhydride and 1 part of dibutyltin oxide were charged and reacted at 200 ° C for 7 hours in a nitrogen atmosphere, and then 220 ° C. The mixture was heated up to react for 6 hours. Thereafter, the mixture was reacted at the same temperature for 10 hours under a reduced pressure of 2 kPa. The product was taken out when the softening point reached 126 ° C., and then cooled to room temperature to obtain a polyester resin (PS′-4). Table 2 shows the characteristic value of (PS′-4).

(2) Production of (PS) Particle (A′-4) Same as Example 1 (2) except that (PS-1) in Example 1 (2) was replaced with (PS′-4). (PS) particles (A′-4) were obtained. Dv was 233 μm.

(3) Production of binder (X′-4) (PS) In the same manner as in Example 1 (3) except that (A-1) in Example 1 (3) was replaced with (A′-4). A binder (X′-4) containing particles (A′-4) was obtained.

(4) Manufacture of inorganic fiber nonwoven fabric (NW'-4)
An inorganic fiber nonwoven fabric (NW′-4) was obtained in the same manner as in Example 1 (4) except that (X-1) in Example 1 (4) was replaced with (X′-4).

  The inorganic fiber nonwoven fabric obtained above was evaluated for performance according to the following method. The results are shown in Tables 1 and 2.

<Evaluation method>
(1) Tensile strength (kgf) of inorganic fiber nonwoven fabric (evaluation of mechanical strength)
Five pieces of each inorganic fiber nonwoven fabric (210 × 270 mm) were prepared, and four test pieces each having a length of 150 mm × width 50 mm were cut out for each inorganic fiber nonwoven fabric to prepare a total of 20 test pieces. About these, the tensile strength was measured according to "7.4 tensile strength" of JIS R3420 "Glass fiber general test method", and the average value of 20 test pieces was obtained. In addition, when (PS) containing a non-melting component (gel) is used, it is reflected as a cause of the fall of tensile strength.

(2) Uniformity of tensile strength of inorganic fiber nonwoven fabric (Evaluation of uniformity of mechanical strength)
The standard deviation (σ) of the tensile strength of 20 test pieces in (1) was determined, the coefficient of variation of tensile strength was calculated from the following formula, and evaluated according to the following criteria. In addition, when (PS) containing a non-melting component (gel) is used, it is reflected as a cause of the uniformity fall of tensile strength.

Variation coefficient of tensile strength (%) = 100 × σ / average value of tensile strength

<Evaluation criteria>
○: 50% or less △: Over 50% over 60% ×: Over 60%

(3) Styrene solubility (seconds)
The styrene solubility of the binder was measured in accordance with JIS R3420 “Glass fiber general test method” (7.13 Styrene solubility of binder). The average value of the five test pieces was evaluated according to the following criteria.
<Evaluation criteria>
○: 15-20
Δ: 10 or more and less than 15 and more than 20 and 25 or less ×: Less than 10 and more than 25

  From the results of Tables 1 and 2, it can be seen that the binder of the present invention has a moderate styrene solubility and gives a uniform and excellent inorganic fiber nonwoven fabric as compared with the comparative one.

  The inorganic fiber nonwoven fabric formed by bonding inorganic CS with the binder of the present invention is used as a reinforcing material for inorganic fiber reinforced plastic molded products, and the molded products include automobile members (molded ceiling materials, etc.), small ships ( It is very useful because it can be applied to a wide range of fields such as hulls of canoes, boats, yachts, motor boats, etc., housing components (building materials, bathtubs, septic tanks, etc.), windmill blades, and the like.

Claims (6)

Polyester resin (PS) comprising as constituent units an acid component (a) containing an aromatic dicarboxylic acid and / or an ester-forming derivative thereof (a1) and an alcohol component (b) containing a (poly) alkylene glycol (b1) ) Binder for inorganic fiber nonwoven fabric (X). The binder according to claim 1, wherein the softening point of (PS) is 80 to 130 ° C. An inorganic fiber nonwoven fabric obtained by bonding an inorganic chopped strand laminate using the binder according to claim 1. An inorganic fiber reinforced plastic molded product obtained by molding the inorganic fiber nonwoven fabric according to claim 3 as a reinforcing material. The molded article according to claim 4, 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 for producing an inorganic fiber nonwoven fabric by spraying water and a binder on an inorganic chopped strand laminate, heating and melting the binder, and then pressing the laminate to produce an inorganic fiber nonwoven fabric, the binder (X) according to claim 1 or 2 The manufacturing method of the inorganic fiber nonwoven fabric characterized by using.