JP2011132499A - Binder for glass chopped strand mat - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a binder having a higher coupling efficiency onto a glass chopped strand intersecting point in a glass chopped strand laminate in comparison with a conventional binder, exhibiting excellent flexibility, and giving a uniform glass chopped strand mat having necessary mechanical strength. <P>SOLUTION: The binder for a glass chopped strand mat comprises a polyester resin powder (A) having a volume-average particle diameter Dv of 280-350 μm and a coefficient Cv of variation of volume-based particle diameter distribution of 10-35% as measured by the laser diffraction scattering method. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a powdery binder for glass chopped strand mats. More specifically, the present invention relates to a powdery binder that can be efficiently attached to a glass chopped strand intersection and can obtain a flexible glass chopped strand mat.

The glass chopped strand mat is usually obtained by the following method.
(1) Several ten to several hundred glass single fibers (fiber diameter of about 10 μm) are bundled with a sizing agent to obtain glass strands.
(2) The glass strand is cut into a predetermined length to obtain a bundle of glass chopped strands.
(3) The glass chopped strands are randomly distributed in directions on the transfer net to form a laminate.
(4) A binder powder is sprayed on the laminate and heated in an oven chamber so that the glass chopped strands are bonded with a fused binder and further pressed to obtain a glass chopped strand mat. The basis weight of the glass chopped strand mat (the amount of glass chopped strand used for the mat per 1 m ² , hereinafter the same) is usually 40 to 950 g / m ² . As the binder here, conventionally, many unsaturated polyester resins pulverized by mechanical pulverization have been used (see, for example, Patent Documents 1 and 2).

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

  However, since the conventional binder has a wide particle size distribution, not all of the particles are suitable for adhesion to the laminate of glass chopped strands. That is, even if the particles having a particularly small particle diameter are dispersed on the laminate, they adhere to the strands other than the intersection of the glass chopped strands, and the adhesion binder on the strand other than the intersection makes the mat hard. On the other hand, those having a particularly large particle size often fall through the gaps in the laminate without adhering to the glass chopped strand intersection of the laminate due to their own weight, There was a problem that a binder exceeding the required amount required from the performance aspect such as the mechanical strength of the original mat had to be supplied.

  The object of the present invention is to provide a glass chopped strand mat that has higher bonding efficiency on the glass chopped strand intersection in the glass chopped strand laminate than the conventional binder, is excellent in flexibility, is uniform, and has the required mechanical strength. Is to provide. Here and below, binding of the binder to the strand means that the binder adheres on the strand and is further fused by heating, pressing or the like to partially coat the strand.

  The inventors of the present invention have reached the present invention as a result of intensive studies to achieve the above object. That is, the present invention contains a polyester resin powder (A) having a volume average particle diameter Dv by laser diffraction scattering method of 280 to 350 μm and a volume-based particle diameter distribution variation coefficient Cv of 10 to 35%. It is a binder for glass chopped strand mats.

The glass chopped strand mat binder of the present invention has the following effects.
(1) The coupling efficiency on the glass chopped strand intersection in the glass chopped strand laminate is high.
(2) A glass chopped strand mat having excellent flexibility and uniform and necessary mechanical strength is provided.

[Polyester resin powder (A)]
The volume average particle diameter Dv of the polyester resin powder (A) in the present invention is 280 to 350 μm, preferably 290 to 340 μm, and more preferably 300 to 330 μm. When Dv is less than 280 μm, the ratio of the binder adhering to the strands other than the intersection of the strands increases, and the resulting mat becomes hard. When Dv exceeds 350 μm, the binder tends to fall from the gap between the laminates by its own weight. Since it is difficult to adhere to the body, the required amount of binder at the time of producing the mat increases.

  The proportion of particles having a volume reference particle diameter of 400 μm or more in (A) is preferably 20% by weight or less, more preferably 15% by weight or less, particularly preferably from the viewpoint of reducing the amount of binder falling from the gaps in the laminate. 10% by weight or less.

  The proportion of particles having a volume reference particle diameter of 250 μm or less in (A) is preferably 20% by weight or less, more preferably 15% by weight or less, particularly preferably 15% by weight or less, from the viewpoint of reducing the amount of binder adhering to the strand other than the strand intersection. Preferably it is 10 weight% or less.

  The variation coefficient Cv of the volume-based particle size distribution (A) is 10 to 35%, preferably 12 to 28%, and more preferably 13 to 25%. If the Cv is less than 10%, the productivity during binder production described later is poor, and if it exceeds 35%, the adhesion efficiency of the binder to the strand intersection decreases and the mat becomes hard. Here, Cv is obtained by the method described later, and the smaller the value, the narrower the volume-based particle size distribution.

  Here, the volume average particle diameter Dv, the volume reference particle diameter, and the variation coefficient Cv of the volume reference particle diameter distribution can all be obtained by a laser diffraction scattering method. Name "Microtrack 9320 HRA particle size analyzer", manufactured by Nikkiso Co., Ltd.].

  As the polyester resin of the polyester resin powder (A) in the present invention, a polycondensate of poly (n = 2 to 6) carboxylic acid (including anhydride and derivative) (a1) and a low molecular polyol (a2), Examples thereof include a self-polycondensate of compound (a3) having a carboxyl group and a hydroxyl group in the same molecule, and a ring-opening polycondensate of lactone (a4).

  Examples of the polycarboxylic acid (a1) include 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], aromatic [ C8-30, such as phthalic acid, isophthalic acid, terephthalic acid, tetrabromophthalic acid, tetrachlorophthalic acid, trimellitic acid, pyromellitic acid], and alicyclic polycarboxylic acids [C6-50, 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 And dimer acids]; ester-forming derivatives of these polycarboxylic acids [acid anhydrides (eg maleic anhydride) Phthalic anhydride), lower alkyl (C1 -4) ester [dimethyl ester (e.g. dimethyl terephthalate), such as diethyl ester, such as an acid halide (acid chloride, etc.)]; and mixtures of two or more thereof. Of these, aliphatic polycarboxylic acids and aromatic polycarboxylic acids are preferable from the viewpoint of compatibility between the polyester resin and the FRP resin matrix, and maleic acid, fumaric acid, terephthalic acid, and isophthalic acid are more preferable. is there.

  The low molecular polyol (a2) is a number average molecular weight per hydroxyl group [hereinafter abbreviated as Mn. Divalent to 10-valent or more (preferably 2 to 3 valent) polyols having a measurement by a gel permeation chromatography (GPC) method of less than 300 (preferably having a molecular weight of 31 or more and Mn 250 or less) 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 (1-10 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, EO, PO, and combinations thereof are preferable from the viewpoint of the mat strength described later and the permeability to glass fibers such as styrene monomer in application to glass fiber reinforced plastic (FRP). .

  Examples of the dihydric alcohol (a21) include aliphatic alcohols [linear alcohol (ethylene glycol, diethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol ( Hereinafter, EG, DEG, 1,3-PG, 1,4-BD, 1,5-PD, 1,6-HD)), etc.]; branched chain alcohol [1,2-propylene glycol, neo Pentyl glycol (hereinafter abbreviated as 1,2-PG and NPG, respectively), 3-methyl-1,5-pentanediol, 2,2-diethyl-1,3-propanediol, 1,2-, 1,3- and 2,3-butanediol, etc.]; and alcohol having a ring [alicyclic ring-containing alcohol (1,4-bis (hydroxymethyl) cyclohexane), etc. Include araliphatic (m-and p- xylylene glycol, etc.) is

  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 alcohols are preferable from the viewpoint of mat strength, and 1,4-BD, 1,6-HD and NPG are more preferable.

  Specific examples of the AO adduct (a23) include AO low molar adducts of the above (a21) and (a22), and AO low molarity of polyvalent (divalent to trivalent or higher) phenol having a ring. Valence products. The polyhydric phenol includes C6-18 dihydric phenol, such as monocyclic dihydric phenol (hydroquinone, catechol, resorcinol, urushiol, etc.), bisphenol (bisphenol A, -F, -C, -B, -AD and -S, dihydroxybiphenyl, 4,4'-dihydroxydiphenyl-2,2-butane, etc.), and condensed polycyclic dihydric phenols [dihydroxynaphthalene (eg, 1,5-dihydroxynaphthalene), binaphthol, etc.]; Octavalent or higher polyhydric phenols, such as monocyclic polyphenols (pyrogallol, phloroglucinol), and aldehydes or ketones (formaldehyde or cresol) of mono- or dihydric phenols (phenol, cresol, xylenol, resorcinol, etc.) Novo Click resins, resol intermediates, polyphenols obtained by condensation reaction of phenol with glyoxal or glutaraldehyde, and a polyphenol) obtained by condensation reaction of resorcin and acetone.

  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.

  Of the above polyester resins, polycarboxylic acid (a1) is preferable from the viewpoint of rapid polycondensation reaction and permeability of glass chopped strand mat (hereinafter sometimes simply referred to as “mat”) such as styrene. And a low-molecular polyol (a2) polycondensate, more preferably a polycondensate of polycarboxylic acids (a1) and (a23), particularly preferably a polyhydric phenol having an aliphatic polycarboxylic acid and a ring or It is a polycondensate of an araliphatic 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, 133 Pa or less). Moreover, it is desirable to perform this reaction in inert gas atmosphere, such as nitrogen, from a viewpoint of coloring prevention of a polyester resin. The reaction equivalent ratio (equivalent ratio of carboxyl group / hydroxyl group) 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 (unit is mg KOH / g, the same applies hereinafter) 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, carboxylates [2B, 4A, 4B and 5B metal carboxylic acids (C2-4) salts], oxides, and alkoxides are preferable from the viewpoint of reactivity. Further preferred from the viewpoint of low coloration of the product are antimony trioxide, monobutyltin oxide, tetrabutyl titanate, tetrabutoxy titanate, tetrabutyl zirconate, zirconyl acetate, and zinc acetate. The amount of the esterification catalyst used is not particularly limited as long as a desired molecular weight can be obtained, but the reactivity and the low colorability of the esterification catalyst are based on the total weight of the polycarboxylic acid (a1) and the low molecular polyol (a2). From the viewpoint, it is preferably 0.005 to 3%, more preferably 0.01 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 removed. The organic solvent is not particularly limited as long as it does not have active hydrogen such as a hydroxyl group. For example, hydrocarbon (toluene, xylene, etc.), ketone (methyl ethyl ketone, methyl isobutyl ketone, etc.), ester (ethyl acetate, Butyl acetate).

  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 constituting the polyester resin powder (A) in the present invention (hereinafter abbreviated as Mw. Measurement is based on the GPC method) and Mn are Mw from the viewpoint of the strength of the glass chopped strand mat and mechanical grindability. Preferably it is 20,000-65,000, More preferably, it is 35,000-55,000, Mn becomes like this. Preferably it is 4,000-6,000, More preferably, it is 4,500-5,500.

  The softening point of the polyester resin [measured in accordance with the ring and ball method (JIS K2207, “6.4 softening point test method” of “petroleum asphalt”)] prevents the glass chopped strand mat from exhibiting stickiness and performs post-processing operations. It is preferably 80 to 150 ° C., more preferably 90 to 140 ° C. from the viewpoints of properties and the viewpoint of melting of the binder and cooling and solidifying temperature during production of the glass chopped strand mat.

  The glass transition temperature of the polyester resin by differential thermal analysis (hereinafter abbreviated as Tg; measurement conforms to JIS K7121, “Measurement method of plastic transition temperature”) is used to prevent blocking during storage of the binder and to post-process the glass chopped strand mat. From the viewpoint of workability and from the viewpoints of melting of the binder and cooling and solidifying temperature during production of the glass chopped strand mat, it is preferably 40 to 60 ° C, more preferably 45 to 55 ° C.

  The polyester resin powder (A) of the present invention can be usually produced as follows. First, the above-mentioned alcohol component, acid component and catalyst (dibutyltin oxide, etc.) are charged into a reaction vessel equipped with a cooling tube, a stirring bar, a thermometer and a nitrogen introduction tube, and heated under a nitrogen atmosphere, usually 150 to 190. The reaction is carried out at 4 ° C. for 4 to 6 hours, and then the temperature is raised to 200 ° C. If necessary, the reaction is further usually carried out for 6 to 8 hours under reduced pressure of 1 to 4 kPa. The polyester resin can be obtained by taking it out.

  In order to further produce the polyester resin powder (A) from the polyester resin, the polyester resin is rotated at 10,000 to 15 using, for example, a sample mill [model number “SK-M10”, manufactured by Kyoritsu Riko Co., Ltd.]. The polyester resin powder (A) can be obtained by pulverizing at 1,000 rpm for 1 to 5 minutes to form particles, and then sieving by combining sieves having different openings.

[Additive (B)]
The binder for a glass chopped strand mat of the present invention containing the polyester resin powder (A) includes, in addition to (A), an antiblocking agent (B1), a lubricant (B2), and a hydrophilicity imparting agent as necessary. One or two or more additives (B) selected from the group consisting of (B3) can be contained. These additives (B) are usually added after pulverizing and sieving the polyester resin.
The total amount of (B) used is usually 8% or less based on the weight of the polyester resin powder (A), preferably from 0.01 to 5%, more preferably from the viewpoint of the effect of addition and the mechanical strength of the mat. 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. Examples of higher fatty acids include C8-24 (for example, lauric acid and stearic acid); examples of salts of higher fatty acids include alkali metals (Li, Na, K, etc.) and alkaline earth metals (Mg, Ca, Ba, etc.) of the above higher fatty acids. ), Zn, Cu, Ni, Co, Al, etc .; silicon or metal oxides such as silicon dioxide, silicon oxide, aluminum oxide, iron oxide, titanium oxide, magnesium oxide, zirconium oxide, etc .; Examples of organic resins include polyolefin resin, polyamide resin, poly (meth) acrylic resin, silicon resin, polyurethane resin, phenol resin, polytetrafluoroethylene resin, and cellulose powder. Of these, higher fatty acid metal salts and silicon or metal oxides are preferred from the viewpoint of the powder flowability of (A).

  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 0.1 to 2%, from the viewpoint of preventing blocking of the binder and interstrand binding. 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 wax, carnauba wax, etc .; As low molecular weight polyethylene, polyethylene of Mn 1,000-10,000, etc .; As higher alcohol, C10-24, such as stearyl alcohol; As fatty acid ester, C10-36 fatty acid [For example, esters of butyl stearate and higher fatty acids (C10-24) and AO (C2-3) adducts of polyhydric (2-4) alcohols (such as monostearate of EO 5 mol adducts of EG); Fatty acid amides include C10-40, such as stearic acid amide. Of these, esters and higher fatty acid amides of higher fatty acids and AO adducts of polyhydric alcohols are preferred from the viewpoint of the bondability between the glass strands.

  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 glass strands. 0.1 to 1%.

  As the hydrophilicity imparting agent (B3), polyvinyl alcohol (Mn 1,000 to 10,000), carboxyl methyl cellulose, sodium alginate, polyethylene glycol (hereinafter abbreviated as PEG) (Mn 200 to 20,000), PEG (Mn 100 to 2,000). ) -Containing organopolysiloxane (Mn 200 to 50,000), starch, sodium polyacrylate (Mn 500 to 20,000), quaternary ammonium base-containing (meth) acryloyl group-containing polymer, and the like. Of these, PEG and PEG chain-containing organopolysiloxane are preferable from the viewpoint of the bonding property between the glass strands.

  The amount of (B3) used is preferably 5% or less based on the weight of (A), preferably from the viewpoint of the affinity with water sprayed on the glass chopped strand laminate described below and the bonding properties between the glass strands. 0.01 to 2%, more preferably 0.1 to 1%.

[Glass chopped strand mat]
The glass chopped strand mat of the present invention is composed of a glass chopped strand mat binder containing a glass chopped strand laminate and a polyester resin powder (A). A binder-attached laminate is formed through a process consisting of binder spraying, and then the binder-attached laminate is manufactured by hot press molding or cooling roll press molding. Specifically, for example, it can be produced by the following steps.
(1) A glass chopped strand laminate is obtained by spraying glass chopped strands on a release-treated wire mesh so as to have a uniform thickness in a directional disorder.
(2) A predetermined amount of tap water is sprayed by spraying so that the entire surface on the back side is wet from the back side surface of the laminate.
(3) A predetermined amount of binder is uniformly dispersed from the front side surface of the laminated body and adhered.
(4) A predetermined amount of tap water is sprayed by spraying so that the entire surface of the front side surface of the laminate is wetted, and a predetermined amount of binder is uniformly dispersed and adhered.
The steps (3) to (4) may be performed once, or may be repeated twice or more.
(5) The binder-attached laminate obtained in (4) above is dried at 100 to 200 ° C. for 5 to 10 minutes, and the binder is fused to the glass chopped strands.
(6) A glass chopped strand mat bonded with a fused binder is obtained by pressing at a pressure of 0.01 to 5 MPa with a press machine adjusted to room temperature to 200 (preferably 50 to 150) ° C.

  The binding amount of the binder based on the weight of the glass chopped strand laminate required by the evaluation method described later is the mechanical strength and handling properties of the mat (flexibility, fit to the mold when creating a glass fiber reinforced plastic molded product described later) From the viewpoint of property, etc., the same applies hereinafter), it is preferably 1 to 10%, more preferably 2 to 8%.

  The amount of tap water sprayed in the above (2) and (4) is preferably 10 to 200 from the viewpoint of adhesion of the binder and ease of drying in the subsequent step, based on the weight of the glass chopped strand laminate. %, More preferably 20 to 150%.

In the image obtained by photographing from the front side and the back side of the glass chopped strand mat, the total area where the binder is fused to and coated on the glass chopped strand (diameter K μm) (hereinafter abbreviated as the total area of the fused coating). Of (S _A ), the ratio of the area where the binder is fused and coated on the strand within the radius K μm from the center of the intersection of the strand (hereinafter abbreviated as the intersection fusion-coated area) (S _C ) [In the following, it is abbreviated as the intersection fusion-bonding area ratio] (%) is preferably 60% or more, more preferably 63% or more, and particularly preferably 65 to 100% from the viewpoint of the flexibility of the mat. Here, the intersection fusion-covered area ratio (%) is calculated from the following equation based on the total fusion-covered area (S _A ) and the intersection fusion-covered area (S _C ) obtained by the evaluation method described later. Desired.

Intersection fusion coating area ratio (%) = 100 × S _C / S _A

  The bending elastic modulus of the glass chopped strand mat is preferably 0.5 to 3.0 Pa, more preferably 0.8 to 2.8 Pa from the viewpoint of the mechanical strength and flexibility of the mat.

  The mechanical properties of the glass chopped strand mat are desirably uniform throughout the mat. For example, the variation in bending elastic modulus (difference between the maximum and minimum bending elastic moduli of 10 test pieces) is preferably 0.2 Pa or less, more preferably 0.1 Pa or less.

The molding method of the glass fiber reinforced plastic molded article of the present invention 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) Apply a matrix resin (unsaturated polyester resin or the like) 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) A glass chopped strand mat 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 glass chopped strand mat 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.

  Examples of the matrix resin obtained by the molding method including the hand lay-up method include thermosetting resins (unsaturated polyester resins, vinyl ester resins, epoxy resins, phenol resins, polyurethane resins, silicone resins, modified acrylic resins, furan resins, 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 Hereinafter, although an Example demonstrates this invention further, this invention is not limited to these. In the following, “parts” and “%” represent parts by weight and% by weight, respectively.

Production Example 1 <Production of Polyester Resin Powder (A-1)>
(1) Production of polyester resin In a reaction vessel equipped with a cooling tube, a stir bar, a thermometer, and a nitrogen introduction tube, 3,365 parts of EO 2.2 mol adduct of bisphenol A, 1,123 parts of fumaric acid, dibutyltin oxide 6 parts were charged and reacted at 180 ° C. for 4 hours under a nitrogen atmosphere. Then, it was made to react under reduced pressure of 3-4 kPa, it heated up to 210 degreeC, and when it became the acid value 10, it cooled to 180 degreeC and took out, and polyester (P-1) was obtained.
(2) Production of polyester resin powder (A-1) (P-1) 100 parts of sample mill [device name “SK-M10”, manufactured by Kyoritsu Riko Co., Ltd., and the same shall apply hereinafter. For 3 minutes at a rotational speed of 12,500 rpm. The obtained resin powder is sieved with a sieve having an opening of 300 μm, and the resin powder having passed through the sieve is further sieved with a sieve having an opening of 250 μm to obtain a polyester resin powder (A-1) remaining on the 250 μm sieve. It was. (A-1) Mw is 35,000, Mn is 4,800, softening point is 114 ° C., Tg is 50 ° C., Dv is 280 μm, Cv is 23%, and the proportion of particles having a volume-based particle size of 250 μm or less. Was 15%, and the proportion of particles having a volume-based particle diameter of 400 μm or more was 10%.
(3) Manufacture of binder (X-1) (A-1) After adding 0.03 part of antiblocking agent [Brand name "Aerosil 200", Nippon Aerosil Co., Ltd., and the same below] to 10 parts, it mixed. Binder (X-1) was obtained.

Production Example 2 <Production of Polyester Resin Powder (A-2)>
(1) Production of polyester resin powder (A-2) (P-1) 100 parts were pulverized for 3 minutes using a sample mill at a rotational speed of 12,000 rpm. The obtained resin powder is sieved with a sieve having an opening of 355 μm, and the resin powder that has passed through the sieve is further sieved with a sieve having an opening of 250 μm to obtain a polyester resin powder (A-2) remaining on the 250 μm sieve. It was. Mw, Mn, softening point, and Tg of (A-2) are the same as (A-1), and values of other evaluation items are shown in Table 1.
(2) Manufacture of binder (X-2) (A-2) After adding 0.03 part of antiblocking agents to 10 parts, it mixed, and binder (X-2) was obtained.

Production Example 3 <Production of Polyester Resin Powder (A-3)>
(1) Production of polyester resin powder (A-3) (P-1) 100 parts were pulverized for 3 minutes at a rotation speed of 11,500 rpm using a sample mill. The obtained resin powder is sieved with a sieve having an opening of 425 μm, and the resin powder that has passed through the sieve is further sieved with a sieve having an opening of 250 μm to obtain a polyester resin powder (A-3) remaining on the 250 μm sieve. It was. Mw, Mn, softening point, and Tg of (A-3) are the same as (A-1), and the values of other evaluation items are shown in Table 1.
(2) Manufacture of binder (X-3) (A-3) After adding 0.03 part of antiblocking agents to 10 parts, it mixed, and binder (X-3) was obtained.

Production Example 4 <Production of polyester resin powder (A-4)>
(1) Production of polyester resin powder (A-4) (P-1) 100 parts were pulverized for 4 minutes at a rotation speed of 12,500 rpm using a sample mill. The obtained resin powder is sieved with a sieve having an opening of 355 μm, and the resin powder that has passed through the sieve is further sieved with a sieve having an opening of 300 μm to obtain a polyester resin powder (A-4) remaining on the 300 μm sieve. It was. Mw, Mn, softening point, and Tg of (A-4) are the same as (A-1), and values of other evaluation items are shown in Table 1.
(2) Manufacture of binder (X-4) (A-4) After adding 0.03 part of antiblocking agents to 10 parts, it mixed, and binder (X-4) was obtained.

Production Example 5 <Production of Polyester Resin Powder (A-5)>
(1) Production of polyester resin powder (A-5) 100 parts of (P-1) were pulverized for 4 minutes at a rotational speed of 12,000 rpm using a sample mill. The obtained resin powder is sieved with a sieve having an opening of 425 μm, and the resin powder that has passed through the sieve is further sieved with a sieve having an opening of 250 μm to obtain a polyester resin powder (A-5) remaining on the 250 μm sieve. It was. Mw, Mn, softening point, and Tg of (A-5) are the same as (A-1), and the values of other evaluation items are shown in Table 1.
(2) Manufacture of binder (X-5) (A-5) 0.03 part of antiblocking agent was added to 10 parts, and then mixed to obtain binder (X-5).

Production Example 6 <Production of Polyester Resin Powder (A-6)>
(1) Production of polyester resin powder (A-6) 100 parts of (P-1) were pulverized for 4 minutes at a rotational speed of 12,500 rpm using a sample mill. The obtained resin powder is sieved with a sieve having an opening of 300 μm, and the resin powder having passed through the sieve is further sieved with a sieve having an opening of 250 μm to obtain a polyester resin powder (A-6) remaining on the 250 μm sieve. It was. Mw, Mn, softening point, and Tg of (A-6) are the same as (A-1), and the values of other evaluation items are shown in Table 1.
(2) Manufacture of binder (X-6) (A-6) After adding 0.03 part of antiblocking agents to 10 parts, it mixed, and the binder (X-6) was obtained.

Production Example 7 <Production of Polyester Resin Powder (A-7)>
(1) In a reaction vessel equipped with a cooling tube, a stir bar, a thermometer and a nitrogen introduction tube, 4,366 parts of PO2.5 mol adduct of bisphenol A, 2,124 parts of 1,6-HD, terephthalic acid 1, 660 parts, maleic acid 44 parts, and dibutyltin oxide 6 parts were charged and reacted at 180 ° C. for 4 hours in a nitrogen atmosphere. Then, it was made to react under reduced pressure of 3-4 kPa, and it heated up to 210 degreeC, and when it became the acid value 7, it cooled to 180 degreeC and took out, and polyester (P-2) was obtained.
(2) Production of polyester resin powder (A-7) 100 parts of (P-2) were pulverized for 3 minutes at a rotational speed of 12,500 rpm using a sample mill. The obtained resin powder is sieved with a sieve having an opening of 300 μm, and the resin powder having passed through the sieve is further sieved with a sieve having an opening of 250 μm to obtain a polyester resin powder (A-7) remaining on the 250 μm sieve. It was. (A-7) Mw is 60,000, Mn is 5,200, softening point is 120 ° C., Tg is 43 ° C., Dv is 285 μm, Cv is 25%, and the proportion of particles having a volume-based particle size of 250 μm or less. Was 14%, and the proportion of particles having a volume-based particle diameter of 400 μm or more was 11%.
(3) Manufacture of binder (X-7) (A-7) After adding 0.03 part of antiblocking agents to 10 parts, it mixed, and the binder (X-7) was obtained.

Production Example 8 <Production of polyester resin powder (A-8)>
(1) Production of polyester resin powder (A-8) 100 parts of (P-2) were pulverized for 3 minutes at a rotation speed of 11,500 rpm using a sample mill. The obtained resin powder is sieved with a sieve having an opening of 425 μm, and the resin powder that has passed through the sieve is further sieved with a sieve having an opening of 250 μm to obtain a polyester resin powder (A-8) remaining on the 250 μm sieve. It was. Mw, Mn, softening point and Tg of (A-8) are the same as (A-7), and the values of other evaluation items are shown in Table 1.
(2) Production of binder (X-8) (A-8) 0.03 part of an anti-blocking agent was added to 10 parts and then mixed to obtain a binder (X-8).

Production Example 9 <Production of polyester resin powder (A-9)>
(1) Production of polyester resin powder (A-9) 100 parts of (P-2) were pulverized for 4 minutes at a rotational speed of 12,500 rpm using a sample mill. The obtained resin powder is sieved with a sieve having an opening of 355 μm, and the resin powder that has passed through the sieve is further sieved with a sieve having an opening of 300 μm to obtain a polyester resin powder (A-9) remaining on the 300 μm sieve. It was. Mw, Mn, softening point, and Tg of (A-9) are the same as (A-7), and the values of other evaluation items are shown in Table 1.
(2) Manufacture of binder (X-9) (A-9) After adding 0.03 part of antiblocking agents to 10 parts, it mixed, and binder (X-9) was obtained.

Production Example 10 <Production of Polyester Resin Powder (A-10)>
(1) Production of polyester resin powder (A-10) (P-2) 100 parts were pulverized for 4 minutes at a rotational speed of 12,500 rpm using a sample mill. The obtained resin powder is sieved with a sieve having an opening of 300 μm, and the resin powder having passed through the sieve is further sieved with a sieve having an opening of 250 μm to obtain a polyester resin powder (A-10) remaining on the 250 μm sieve. It was. Mw, Mn, softening point, and Tg of (A-10) are the same as (A-7), and the values of other evaluation items are shown in Table 1.
(2) Manufacture of binder (X-10) (A-10) 0.03 part of antiblocking agent was added to 10 parts, and then mixed to obtain binder (X-10).

Production Example 11 <Production of Polyester Resin Powder (A-11)>
(1) In a reaction vessel equipped with a cooling tube, a stir bar, a thermometer and a nitrogen introduction tube, 3,795 parts of PO 2.3 mol adduct of bisphenol A, 391 parts of EG, 1,160 parts of fumaric acid, dibutyltin oxide 6 The reaction was carried out at 180 ° C. for 4 hours under a nitrogen atmosphere. Then, it was made to react under reduced pressure of 3-4 kPa, and it heated up to 210 degreeC, and when it became the acid value 7, it cooled to 180 degreeC and took out, and polyester (P-3) was obtained.
(2) Production of polyester resin powder (A-11) (P-3) 100 parts were pulverized for 3 minutes using a sample mill at a rotational speed of 12,500 rpm. The obtained resin powder is sieved with a sieve having an opening of 300 μm, and the resin powder that has passed through the sieve is further sieved with a sieve having an opening of 250 μm to obtain a polyester resin powder (A-11) remaining on the 250 μm sieve. It was. (A-11) Mw is 60,000, Mn is 4,800, softening point is 108 ° C., Tg is 44 ° C., Dv is 283 μm, Cv is 22%, and the proportion of particles having a volume-based particle size of 250 μm or less. Was 12%, and the proportion of particles having a volume-based particle diameter of 400 μm or more was 9%.
(3) Manufacture of binder (X-11) (A-11) After adding 0.03 part of antiblocking agents to 10 parts, it mixed, and the binder (X-11) was obtained.

Production Example 12 <Production of Polyester Resin Powder (A-12)>
(1) Production of polyester resin powder (A-12) (P-3) 100 parts were pulverized for 3 minutes at a rotation speed of 11,500 rpm using a sample mill. The obtained resin powder is sieved with a sieve having an opening of 355 μm, and the resin powder that has passed through the sieve is further sieved with a sieve having an opening of 300 μm to obtain a polyester resin powder (A-12) remaining on the 300 μm sieve. It was. Mw, Mn, softening point, and Tg of (A-12) are the same as (A-11), and the values of other evaluation items are shown in Table 1.
(2) Manufacture of binder (X-12) (A-12) After adding 0.03 part of antiblocking agents to 10 parts, it mixed, and binder (X-12) was obtained.

Comparative Production Example 1 <Production of Polyester Resin Powder (A-1 ′)>
(1) Production of polyester resin powder (A-1 ′) (P-1) 100 parts were pulverized for 3 minutes at a rotation speed of 12,500 rpm using a sample mill. The obtained resin powder is sieved with a sieve having an opening of 212 μm, and the resin powder that has passed through the sieve is further sieved with a sieve having an opening of 106 μm, and the polyester resin powder (A-1 ′) remaining on the 106 μm sieve is obtained. Obtained. Mw, Mn, softening point, and Tg of (A-1 ′) are the same as (A-1), and values of other evaluation items are shown in Table 2.
(2) Manufacture of binder (X-1 ') After adding 0.03 part of antiblocking agents to 10 parts of (A-1'), it mixed and obtained binder (X-1 ').

Comparative Production Example 2 <Production of Polyester Resin Powder (A-2 ′)>
(1) Production of polyester resin powder (A-2 ′) (P-1) 100 parts were pulverized for 2 minutes at 12,000 rpm using a sample mill. The obtained resin powder is sieved with a sieve having an opening of 425 μm, and the resin powder that has passed through the sieve is further sieved with a sieve having an opening of 250 μm, and the polyester resin powder (A-2 ′) remaining on the 250 μm sieve is obtained. Obtained. Mw, Mn, softening point, and Tg of (A-2 ′) are the same as (A-1), and the values of other evaluation items are shown in Table 2.
(2) Manufacture of binder (X-2 ') 0.03 part of antiblocking agent was added to 10 parts of (A-2'), and then mixed to obtain binder (X-2 ').

Comparative Production Example 3 <Production of Polyester Resin Powder (A-3 ′)>
(1) Production of polyester resin powder (A-3 ′) (P-1) 100 parts were pulverized for 3 minutes at a rotational speed of 12,500 rpm using a sample mill. The obtained resin powder is sieved with a sieve having an opening of 150 μm, and the resin powder that has passed through the sieve is further sieved with a sieve having an opening of 106 μm, and the polyester resin powder (A-3 ′) remaining on the 106 μm sieve is obtained. Obtained. Mw, Mn, softening point, and Tg of (A-3 ′) are the same as (A-1), and values of other evaluation items are shown in Table 2.
(2) Manufacture of binder (X-3 ') 0.03 part of antiblocking agent was added to 10 parts of (A-3'), and then mixed to obtain binder (X-3 ').

Comparative Production Example 4 <Production of Polyester Resin Powder (A-4 ′)>
(1) Production of polyester resin powder (A-4 ′) (P-1) 100 parts were pulverized for 1 minute at a rotation speed of 11,500 rpm using a sample mill. The obtained resin powder is sieved with a sieve having an opening of 425 μm, and the resin powder that has passed through the sieve is further sieved with a sieve having an opening of 355 μm, and the polyester resin powder (A-4 ′) remaining on the sieve of 355 μm is obtained. Obtained. Mw, Mn, softening point, and Tg of (A-4 ′) are the same as (A-1), and values of other evaluation items are shown in Table 2.
(2) Manufacture of binder (X-4 ') 0.03 part of antiblocking agent was added to 10 parts of (A-4'), and then mixed to obtain binder (X-4).

Comparative Production Example 5 <Production of Polyester Resin Powder (A-5 ′)>
(1) Production of polyester resin powder (A-5 ′) (P-1) 100 parts were pulverized for 2 minutes using a sample mill at a rotational speed of 12,000 rpm. The obtained resin powder is sieved with a sieve having an opening of 425 μm, and the resin powder that has passed through the sieve is further sieved with a sieve having an opening of 300 μm, and the polyester resin powder (A-5 ′) remaining on the 300 μm sieve is obtained. Obtained. Mw, Mn, softening point, and Tg of (A-5 ′) are the same as (A-1), and values of other evaluation items are shown in Table 2.
(2) Production of binder (X-5 ′) 0.03 part of an antiblocking agent was added to 10 parts of (A-5 ′), and then mixed to obtain a binder (X-5 ′).

Comparative Production Example 6 <Production of Polyester Resin Powder (A-6 ′)>
(1) Production of polyester resin powder (A-6 ′) (P-2) 100 parts were pulverized for 3 minutes using a sample mill at a rotational speed of 12,500 rpm. The obtained resin powder is sieved with a sieve having an opening of 212 μm, and the resin powder that has passed through the sieve is further sieved with a sieve having an opening of 106 μm, and the polyester resin powder (A-6 ′) remaining on the sieve of 106 μm is obtained. Obtained. Mw, Mn, softening point and Tg of (A-6 ′) are the same as (A-7), and the values of other evaluation items are shown in Table 2.
(2) Manufacture of binder (X-6 ') 0.03 part of antiblocking agent was added to 10 parts of (A-6') and then mixed to obtain binder (X-6 ').

Comparative Production Example 7 <Production of Polyester Resin Powder (A-7 ′)>
(1) Production of polyester resin powder (A-7 ′) 100 parts of (P-2) were pulverized for 2 minutes at a rotational speed of 12,000 rpm using a sample mill. The obtained resin powder is sieved with a sieve having an opening of 425 μm, and the resin powder that has passed through the sieve is further sieved with a sieve having an opening of 250 μm, and the polyester resin powder (A-7 ′) remaining on the 250 μm sieve is obtained. Obtained. Mw, Mn, softening point, and Tg of (A-7 ′) are the same as (A-7), and the values of other evaluation items are shown in Table 2.
(2) Production of binder (X-7 ′) 0.03 part of an antiblocking agent was added to 10 parts of (A-7 ′), and then mixed to obtain a binder (X-7 ′).

Comparative Production Example 8 <Production of Polyester Resin Powder (A-8 ′)>
(1) Production of polyester resin powder (A-8 ′) 100 parts of (P-2) was pulverized for 2 minutes at a rotational speed of 12,000 rpm using a sample mill. The obtained resin powder is sieved with a sieve having an opening of 425 μm, and the resin powder that has passed through the sieve is further sieved with a sieve having an opening of 250 μm, and the polyester resin powder (A-8 ′) remaining on the 250 μm sieve is obtained. Obtained. Mw, Mn, softening point, and Tg of (A-8 ′) are the same as (A-7), and the values of other evaluation items are shown in Table 2.
(2) Production of Binder (X-8 ′) 0.03 part of an antiblocking agent was added to 10 parts of (A-8 ′) and then mixed to obtain a binder (X-8 ′).

Comparative Production Example 9 <Production of Polyester Resin Powder (A-9 ′)>
(1) Production of polyester resin powder (A-9 ′) (P-3) 100 parts were pulverized for 2 minutes at a rotation speed of 11,500 rpm using a sample mill. The obtained resin powder is sieved with a sieve having an opening of 425 μm, and the resin powder that has passed through the sieve is further sieved with a sieve having an opening of 250 μm, and the polyester resin powder (A-9 ′) remaining on the 250 μm sieve is obtained. Obtained. Mw, Mn, softening point, and Tg of (A-9 ′) are the same as (A-11), and the values of other evaluation items are shown in Table 2.
(2) Manufacture of binder (X-9 ') 0.03 part of antiblocking agent was added to 10 parts of (A-9'), and then mixed to obtain binder (X-9 ').

Comparative Production Example 10 <Production of Polyester Resin Powder (A-10 ′)>
(1) Production of polyester resin powder (A-10 ′) 100 parts of (P-3) were pulverized for 3 minutes at a rotational speed of 12,500 rpm using a sample mill. The obtained resin powder is sieved with a sieve having an opening of 250 μm, and the resin powder that has passed through the sieve is further sieved with a sieve having an opening of 212 μm, and the polyester resin powder (A-10 ′) remaining on the sieve of 212 μm is obtained. Obtained. Mw, Mn, softening point, and Tg of (A-10 ′) are the same as (A-11), and the values of other evaluation items are shown in Table 2.
(2) Manufacture of binder (X-10 ') 0.03 part of antiblocking agent was added to 10 parts of (A-10'), and then mixed to obtain binder (X-10 ').

Example 1 <Preparation of Glass Chopped Strand Mat (GM-1)>
A glass strand (average strand count T = 30 Tex, glass fiber density d = 2.5 g / cm ³ , glass strand diameter K = 123.6 μm) was made into a length of about 5 cm using a glass chopper manufactured by Togiken Co., Ltd. The glass chopped strand was obtained by cutting.
1.35 g of the glass chopped strands were sprayed on the stainless steel wire mesh that had been subjected to a release treatment of 15 cm in length × 20 cm in width so as to have a uniform thickness in a directionally disordered manner to obtain a laminate. Next, 2.7 g of tap water corresponding to 200% of the weight of the spread glass chopped strands was sprayed by spraying so that the entire back surface was uniformly wet from the back side surface of the laminate.
Next, 0.27 g of binder (X-1) corresponding to 20% of the weight of the dispersed glass chopped strands was uniformly dispersed on the laminate to obtain a binder-attached laminate.
Further, 2.7 g of tap water (equivalent to 200% of the weight of the spread glass chopped strand) is sprayed, and 0.14 g of binder (X-1), which is equivalent to 10% of the weight of the spread glass chopped strand, is added. It sprayed on this laminated body.
Thereafter, the glass chopped strand mat (GM-) having a basis weight of 45 g / m ^{2 was} obtained by drying with a constant temperature dryer at 200 ° C. for 6.5 minutes and pressing at a pressure of 0.5 MPa with a press heated to 85 ° C. 1) was obtained. The evaluation results of the mat are shown in Table 1.

Example 2, Comparative Examples 1-2
In Example 1, mats (GM-2) and (GM-) were used in the same manner except that binders (X-2) and (X-1 ′ to 2 ′) were used instead of binder (X-1). 1 ′ to 2 ′). Tables 1 and 2 show the evaluation results of the mat according to the evaluation items described later.

Example 3 <Preparation of mat (GM-3)>
A laminated body was obtained by spraying 13.5 g of the above-mentioned glass chopped strands in a directionally disordered and uniform thickness on a stainless steel wire mesh having a release treatment of 15 cm in length and 20 cm in width. Next, 2.7 g of tap water corresponding to 20% of the weight of the spread glass chopped strands was sprayed by spraying so that the entire back surface was wetted uniformly from the back side surface of the laminate.
Next, 0.27 g of binder (X-3), which is equivalent to 2% of the weight of the spread glass chopped strands, was sprayed uniformly on the laminate to obtain a binder-attached laminate.
Further, 2.7 g of tap water (equivalent to 20% of the weight of the spread glass chopped strand) is sprayed, and 0.14 g of binder (X-3), which is equivalent to 1% of the weight of the spread glass chopped strand, is added. It sprayed on this laminated body.
Thereafter, the glass chopped strand mat (GM-) having a basis weight of 450 g / m ^{2 was} obtained by drying with a constant temperature dryer at 200 ° C. for 6.5 minutes and pressing at a pressure of 0.5 MPa with a press heated to 85 ° C. 3) was obtained. The evaluation results of the mat are shown in Table 1.

Examples 4-5, Comparative Examples 3-4
In Example 3, mats (GM-4 to 5) were similarly obtained except that binders (X-4 to 5) and (X-3 ′ to 4 ′) were used instead of the binder (X-3). , (GM-3 ′ to 4 ′) were obtained. Tables 1 and 2 show the evaluation results of the mat according to the evaluation items described later.

Example 6 <Preparation of Mat (GM-6)>
27 g of the glass chopped strands were sprayed on the stainless steel wire mesh that had been subjected to a release treatment of 15 cm in length × 20 cm in width so as to have a uniform thickness in a directional disorder, thereby obtaining a laminate. Next, 2.7 g of tap water corresponding to 10% of the weight of the spread glass chopped strands was sprayed by spraying so that the entire back surface was wetted uniformly from the back side surface of the laminate.
Next, 0.27 g of binder (X-6) corresponding to 1% of the weight of the dispersed glass chopped strands was uniformly dispersed on the laminate to obtain a binder-attached laminate.
Further, 2.7 g of tap water (equivalent to 10% of the weight of the spread glass chopped strand) was sprayed, and 0.14 g of binder (X-6, which is equivalent to 0.5% of the weight of the spread glass chopped strand). ) Was sprayed on the laminate.
Then, the glass chopped strand mat (GM-) having a basis weight of 900 g / m ^{2 was} obtained by drying with a constant temperature drier at 200 ° C. for 6.5 minutes and pressing at a pressure of 0.5 MPa with a press heated to 85 ° C. 6) was obtained. The evaluation results of the mat are shown in Table 1.

Comparative Example 5
A mat (GM-5 ′) was obtained in the same manner as in Example 6, except that the binder (X-5 ′) was used instead of the binder (X-6). The evaluation results of the mat are shown in Table 2.

Example 7 <Preparation of mat (GM-7)>
A laminated body was obtained by spraying 3.3 g of the glass chopped strands on a stainless steel wire mesh having a length of 15 cm and a width of 20 cm and having a uniform thickness and a uniform thickness. Next, 2.7 g of tap water corresponding to 82% of the weight of the spread glass chopped strands was sprayed by spraying so that the entire back surface was wetted uniformly from the back side surface of the laminate.
Next, 0.23 g of binder (X-7) corresponding to 7% of the weight of the dispersed glass chopped strands was uniformly dispersed on the laminate to obtain a binder-attached laminate.
Further, 2.7 g of tap water (equivalent to 82% of the weight of the spread glass chopped strand) is sprayed, and 0.10 g of binder (X-7), which is equivalent to 3% of the weight of the spread glass chopped strand, is added. It sprayed on this laminated body.
Thereafter, the glass chopped strand mat (GM−) having a basis weight of 110 g / m ² was dried by pressing at a pressure of 0.5 MPa with a press machine heated to 85 ° C. for 6.5 minutes with a constant temperature dryer at 200 ° C. 7) was obtained. The evaluation results of the mat are shown in Table 1.

Example 8, Comparative Examples 6-7
In Example 7, mats (GM-8) and (GM-) were used in the same manner except that binders (X-8) and (X-6 ′ to 7 ′) were used instead of binder (X-7). 6 ′ to 7 ′). The evaluation results of the mat are shown in Tables 1 and 2.

Example 9 <Preparation of mat (GM-9)>
A mat (GM-9) was obtained in the same manner as in Example 3, except that the binder (X-9) was used instead of the binder (X-3). The evaluation results of the mat are shown in Table 1.

Example 10 <Preparation of mat (GM-10)>
6.9 g of the glass chopped strand was sprayed on the stainless steel wire mesh that had been subjected to a release treatment of 15 cm in length × 20 cm in width so as to have a uniform thickness in a directional disorder, thereby obtaining a laminate. Next, 2.7 g of tap water corresponding to 39% of the weight of the spread glass chopped strands was sprayed by spraying so that the entire back surface was uniformly wet from the back side surface of the laminate.
Next, 0.23 g of binder (X-10) corresponding to 3.4% of the weight of the dispersed glass chopped strands was uniformly dispersed on the laminate to obtain a binder-attached laminate.
Further, 2.7 g of tap water (equivalent to 39% of the weight of the spread glass chopped strand) was sprayed, and 0.10 g of binder (X-10 corresponding to 1.5% of the weight of the spread glass chopped strand). ) Was sprayed on the laminate.
Thereafter, the glass chopped strand mat (GM-) having a basis weight of 230 g / m ² was dried by pressing at a pressure of 0.5 MPa with a press machine heated to 85 ° C. for 6.5 minutes with a constant temperature dryer at 200 ° C. 10) was obtained. The evaluation results of the mat are shown in Table 1.

Comparative Example 8
A mat (GM-8 ′) was obtained in the same manner as in Example 10 except that the binder (X-8 ′) was used instead of the binder (X-10). The evaluation results of the mat are shown in Table 2.

Example 11 <Preparation of Mat (GM-11)>
9.0 g of the glass chopped strands were sprayed on the stainless steel wire mesh that had been subjected to a release treatment of 15 cm in length and 20 cm in width so as to have a uniform thickness in a directionally random manner to obtain a laminate. Next, 2.7 g of tap water corresponding to 30% of the weight of the spread glass chopped strands was sprayed by spraying so that the entire back surface was uniformly wet from the back side surface of the laminate.
Next, 0.23 g of binder (X-11) corresponding to 2.6% of the weight of the dispersed glass chopped strands was uniformly dispersed on the laminate to obtain a binder-attached laminate.
Further, 2.7 g of tap water (equivalent to 30% of the weight of the spread glass chopped strand) was sprayed, and 0.10 g of binder (X-11) corresponding to 1.1% of the weight of the spread glass chopped strand. ) Was sprayed on the laminate.
Thereafter, the glass chopped strand mat (GM-) having a basis weight of 300 g / m ^{2 was} obtained by drying with a constant temperature dryer at 200 ° C. for 6.5 minutes and pressing at a pressure of 0.5 MPa with a press heated to 85 ° C. 11) was obtained. The evaluation results of the mat are shown in Table 1.

Example 12 <Preparation of Matte (GM-12)>
18 g of the glass chopped strands were sprayed on the stainless steel wire mesh that had been subjected to a release treatment of 15 cm in length and 20 cm in width so as to have a uniform thickness in a directionally disordered manner to obtain a laminate. Next, 2.7 g of tap water corresponding to 15% of the weight of the spread glass chopped strands was sprayed from the back side surface of the laminate so that the entire back surface was uniformly wetted.
Next, 0.23 g of binder (X-12) corresponding to 1.3% of the weight of the dispersed glass chopped strands was uniformly dispersed on the laminate to obtain a binder-attached laminate.
Further, 2.7 g of tap water (equivalent to 15% of the weight of the spread glass chopped strand) was sprayed, and 0.10 g of binder (X-12 equivalent to 0.6% of the weight of the spread glass chopped strand). ) Was sprayed on the laminate.
Thereafter, the glass chopped strand mat (GM-) having a basis weight of 600 g / m ^{2 was} obtained by drying with a constant temperature dryer at 200 ° C. for 6.5 minutes and pressing with a press heated at 85 ° C. under a pressure of 0.5 MPa. 12) was obtained. The evaluation results of the mat are shown in Table 1.

<Evaluation items>
(1) Softening point (° C)
Measured with an automatic softening point tester [equipment name “ASP-5”, manufactured by Tanaka Scientific Instruments Manufacturing Co., Ltd.] in accordance with “6.4 Softening Point Test Method (Ring and Ball Method)” of JIS K2207 “Petroleum Asphalt” did.

(2) Glass transition temperature (Tg) (° C)
In accordance with JIS K7121 “Plastic Transition Temperature Measurement Method”, the measurement was performed according to [device name “RDC-220”, manufactured by Seiko Denshi Kogyo Co., Ltd.].

(3) Volume average particle diameter (Dv) of polyester resin powder, ratio (%) of each particle having a volume reference particle diameter of 400 μm or more and 250 μm or less in all particles of polyester resin powder
The particle size was measured by a laser diffraction scattering method using a particle size analyzer [device name “Microtrack 9320HRA particle size analyzer”, manufactured by Nikkiso Co., Ltd.].

(4) Volume based particle size distribution coefficient of variation (Cv) (%)
The coefficient of variation (Cv) is a value calculated from the following formula, and the standard deviation and the volume average particle size (Dv) are a particle size analyzer [device name “Microtrack 9320 HRA particle size analyzer”, manufactured by Nikkiso Co., Ltd. ] Was measured by a laser diffraction scattering method.

Cv = [standard deviation / Dv] × 100

(5) Binder binding amount (%)
It calculated | required in the following procedures.
(I) A test piece (length 50 mm × width 100 mm) was cut out from a part of the mat, cut into a magnetic crucible, dried at 105 ° C. for 30 minutes, and then allowed to cool to room temperature in a desiccator. The weight (m1) was measured to the nearest 0.1 mg. The magnetic crucible containing the test piece was placed in an electric furnace at 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 was taken out and allowed to cool to room temperature in a desiccator, and the weight (m2) was measured to the nearest 0.1 mg.
(Ii) An empty magnetic crucible containing no test piece was dried at 105 ° C. for 30 minutes, then allowed to cool to room temperature in a desiccator, and the weight (m0) was measured to the 0.1 mg unit.
(Iii) The binder binding amount (%) of the test piece was calculated from the following formula.

Binder binding amount (%) =
100 × [(m1) − (m2)] / [(m2) − (m0)]

(Iv) The same test pieces (i) to (iii) were performed on the same test pieces cut out from three portions of the mat different from the above (i), and the binder binding amount (%) of each test piece was calculated. did. The average value of the four values obtained was calculated and used as the binder binding amount (%) of the mat.

(6) Intersection fusion coating area ratio (%) [Binder binding efficiency on strand intersection]
It calculated | required in the following procedures.
(I) Dyeing of the binder fused to the glass strand of the mat A mat test piece (50 mm long × 100 mm wide) is immersed in an aqueous solution (dye solution) consisting of 1 g of rhodamine, 2 mL of 1% aqueous acetic acid and 98 mL of tap water at 47 ° C. Let stand for 2 hours. Thereafter, the test piece was taken out, and the staining solution was sufficiently rinsed with tap water to be removed.
(Ii) A portion of the surface of the mat (range of 1.74 mm in length × 1.3 mm in width) was magnified 175 using a microscope [device name “Digital HF Microscope VH-8000”, manufactured by Keyence Corporation]. A photograph was taken with a double lens [product name “VH-Z25”, depth of field 0.3 mm, manufactured by Keyence Corporation].
By analyzing the obtained image with image processing software [product name “WinROOF”, version 5.5, manufactured by Mitani Corp.], the total fusion coating area (S _A ) and the intersection fusion coating area ( S _c ) was determined, and the intersection fusion coating area ratio (%) was determined from the following equation. The area ratio was evaluated at 10 locations on each of the front and back surfaces by changing the place per mat, and the average value was calculated and used as the intersection fusion coating area ratio (%) of the mat. Note that the depth of field refers to the width within the range before and after the subject when the subject is focused with the camera.

Intersection fusion coating area ratio (%) = 100 × S _c / S _A

(7) Bending elastic modulus (flexibility evaluation) of mat (Pa)
Ten test pieces each having a length of 20 mm and a width of 100 mm were cut out from the mat and measured according to ASTM D256. The average value of 10 test pieces was evaluated according to the following criteria.
<Evaluation criteria>
○: 0.5 to 3.0
Δ: 0.1 or more and less than 0.5 and more than 3.0 and 4.0 or less ×: less than 0.1 and more than 4.0

(8) Variation in flexural modulus of mat (Evaluation of uniformity of mechanical properties) (Pa)
The difference between the maximum value and the minimum value of the bending elastic modulus of 10 test pieces in the evaluation of (7) above was obtained, and the uniformity of the bending elastic modulus was evaluated according to the following criteria.
<Evaluation criteria>
○: 0.2 or less △: more than 0.2 and less than 1.0 ×: 1.0 or more

  From the results of Tables 1 and 2, the glass chopped strand mat of the present invention has higher binder binding efficiency [intersection fusion coating area ratio (%)] on the glass chopped strand intersection than the comparative one, and is flexible. It can be seen that it has excellent and uniform mechanical strength. Therefore, the mat can greatly contribute to the improvement of workability such as the fitting property to the mold when producing the glass fiber reinforced plastic molded product.

  The glass chopped strand mat formed by bonding the glass chopped strand laminate with the binder of the present invention has a uniform mechanical strength and excellent flexibility and greatly contributes to improvement of workability such as fit to a mold. It is used as a reinforcing material for glass fiber reinforced plastic molded products, and the molded products include automobile members (molded ceiling materials, etc.), hulls of small vessels (canoe, boats, yachts, motor boats, etc.), houses It can be applied to a wide range of fields (such as bathtubs and septic tanks) and is extremely useful.

Claims (8)

A polyester resin powder (A) having a volume average particle diameter Dv by laser diffraction scattering method of 280 to 350 μm and a volume-based particle diameter distribution variation coefficient Cv of 10 to 35% is contained. Binder for glass chopped strand mat. The binder according to claim 1, wherein the proportion of particles having a volume-based particle diameter of 400 µm or more in (A) is 20 wt% or less. The binder according to claim 1 or 2, wherein the proportion of particles having a volume-based particle diameter of 250 µm or less in (A) is 20 wt% or less. A glass chopped strand mat obtained by bonding a glass chopped strand laminate with the binder according to claim 1. In the image obtained by photographing the surface of a glass chopped strand mat having a basis weight of 40 to 950 g / m ² , the total area (S _A ) of the binder fused to the glass chopped strand (diameter K μm) and covering it The mat according to claim 4, wherein the ratio of the area (S _C ) where the binder is fused and coated to the strand within the radius K μm from the center of the intersection of the strands is 60% or more. A glass fiber reinforced plastic molded product obtained by molding the mat according to claim 4 as a reinforcing material. The molded article according to claim 6, wherein the glass fiber reinforced plastic molded article is for automobile molded ceiling materials, small ship hulls, bathtubs or septic tanks. The method for producing a glass chopped strand mat by press-molding or heat-press-molding a binder-adhered laminate formed through a process comprising glass chopped strand spraying, water spraying, and binder spraying. A method for producing a glass chopped strand mat, characterized by using a binder.