JP2009263636A - Binder for glass chopped strand mats - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a binder for glass chopped strand mats which can be reduced in the amount of loading as compared with conventional binders and which can give glass chopped strand mats having requisite uniform strength. <P>SOLUTION: The binder for glass chopped strand mats includes a polyester resin powder (A) which exhibits a volume-mean diameter (D<SB>V</SB>) of 100 to 250 μm, a content of particles having volume-based diameters of 300 μm or above of 20 wt.% or below, and a coefficient (C<SB>V</SB>) of variation of the volume-based particle diameter distribution of 0.1 to 30%, as determined by the laser diffraction and scattering method. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a powdery binder for glass chopped strand mats. More specifically, a glass chopped strand mat that can maintain a mat strength (mechanical strength such as tensile strength, the same shall apply hereinafter) even when the binder amount is reduced, and that can create a flexible mat. It relates to a powdery binder.

The glass chopped strand mat is usually obtained by the following method.
(1) A glass strand is obtained by bundling several 10 to several hundred glass single fibers (fiber diameter of about 10 μm) with a sizing agent.
(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) The binder powder is sprayed on the laminate and heated in an oven chamber to bond the glass chopped strands with a binder to obtain a glass chopped strand mat.
As for this binder, conventionally, many unsaturated polyester resins pulverized by mechanical pulverization have been used (for example, Patent Document 1).

JP 2003-48255 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, particles having a particularly small particle diameter are less likely to adhere only to the surface layer of the laminate and reach the inner and back layers even when dispersed on the laminate, and as a result, the entire glass fiber. Inadequate binding results in a mat that is hard and hard, and the quality of the mat is impaired; on the other hand, those with a particularly large particle size often fall through the gaps of the laminate without adhering to the laminate, As a result, there is also a drawback that a binder exceeding the required amount required from the performance aspect such as the strength of the original mat must be supplied.

  An object of the present invention is to provide a binder that can provide a glass chopped strand mat that can be supplied in a smaller amount than conventional binders, is flexible, and has a required uniform strength.

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 is the volume average particle diameter D _V by a laser diffraction scattering method is 100 to 250 [mu] m, the proportion of particles having a volume-based particle size of at least 300μm is 20 wt% or less, and the particle diameter on a volume basis A binder for glass chopped strand mats, characterized in that it contains a polyester resin powder (A) having a coefficient of variation C _{V of} distribution of 0.1 to 30%.

The glass chopped strand mat binder of the present invention has the following effects.
(1) A uniform strength can be imparted to the glass chopped strand mat.
(2) Uniform strength can be imparted to the glass chopped strands with a smaller amount than in the past.
(3) A glass chopped strand mat having excellent flexibility is provided.

[Polyester resin powder (A)]
The polyester resin powder (A) of the present invention has a volume average particle diameter D _V of 100 to 250 μm, preferably 110 to 230 μm, and more preferably 120 to 220 μm. D _V is poor uniform adhesion raw binder to glass chopped strand laminate is less than 100 [mu] m, a glass chopped strand mat strength occurs variation becomes the quality is impaired, heavy dead weight of the binder exceeds 250 [mu] m, the laminate The amount of binder falling from the gap between the laminates without adhering to the laminate, and the number of binder particles per unit weight of the laminate is reduced, and the adhesion point between the laminate and the binder is reduced. The required amount of binder for mat production increases.

  The proportion of particles having a volume reference particle diameter of 300 μm or more in (A) is 20% by weight or less, preferably 15% by weight or less, more preferably 10% by weight or less. When the ratio exceeds 20% by weight, the binder itself is heavy and does not adhere to the laminate, and the binder falls from the gaps in the laminate, and the number of binder particles per unit weight of the laminate is small. Thus, since the adhesion point between the laminate and the binder is reduced, the strength of the glass chopped strand mat is lowered.

  The proportion of the particles having a volume reference particle diameter of 75 μm or less in (A) is preferably 20% by weight from the viewpoint of uniform adhesion of the binder to the glass chopped strand laminate, dust suppression, and flexibility of the resulting mat. Hereinafter, it is more preferably 10% by weight or less.

(Sometimes referred to a number average particle diameter) The number average particle diameter of (A) D _N is preferably from the viewpoint of reducing the binder amount in the uniformity and mats creation of a glass chopped strand mat strength 65～250Myuemu, more preferably 90-220 μm.

The ratio [D _V / D _N ] of the volume average particle diameter D _V and the number average particle diameter D _N of (A) is from the viewpoint of reduction of the amount of binder at the time of glass chopped strand mat preparation and uniformity of the mat strength. Preferably it is 1-1.5, More preferably, it is 1-1.3.

Further, the coefficient of variation C _V of the volume-based particle size distribution of (A) is 0.1 to 30%, preferably 1 to 28%, and more preferably 10 to 25%. When the _CV is less than 0.1%, the productivity of the binder is deteriorated, and when it exceeds 30%, the adhesion efficiency to the laminate is lowered, and the uniformity of the strength of the resulting mat is deteriorated. Here, the coefficient of variation C _V is obtained as described later, and the smaller the value, the narrower the volume-based particle size distribution.

Here, the volume average particle diameter D _V , the number average particle diameter D _N , the volume reference particle diameter, and the volume reference particle diameter distribution variation coefficient C _V can all be obtained by the laser diffraction scattering method, Is, for example, a particle size distribution analyzer [trade name “Microtrack 9320 HRA particle size analyzer”, manufactured by Nikkiso Co., Ltd.].

The shape of the particles constituting the polyester resin powder (A) in the present invention may be any of a spherical shape, an elliptical spherical shape, and an indefinite shape, and is not particularly limited, but it is a viewpoint of binder handling properties (powder fluidity). Therefore, a spherical shape or a shape close thereto is preferable. The number average circularity in the case of the shape is preferably 0.8 to 1.0, more preferably 0.85 to 1.0, particularly preferably 0.90 from the viewpoint of the powder fluidity of (A). 1.0.
Here, the circularity is a value calculated by the following equation, and can be measured and calculated by photographing particles with a microscope and image-processing the photograph [Ultra deep shape measuring microscope manufactured by Keyence Corporation] Image analysis with VK-8500 "and its accompanying shape analysis software" VK-H1A7 ", analysis with particle size / shape distribution measuring instrument" PITA-1 "manufactured by Seishin Co., Ltd.]. The number average circularity is a value obtained by a method described later.

Circularity = 4πF / L ² (where F: projected area of particle, L: projected peripheral length of particle)

In the present invention, the circularity of all the fine particles does not have to be in the above range, and the number average value of the circularity (number average circularity) may be in the above range.
Regarding the circularity, “Non-contact full-field strain measurement of concrete degradation / hardening process” committee research report, Chapter 3 Experiments and research using optical full-field measurement in the construction field, 3.6 It is explained in Aggregate shape evaluation using digital technology.

  Examples of the polyester resin of the polyester resin powder (A) in the present invention include polycondensates of polycarboxylic acids (a1) and low molecular polyols (a2), and compounds (a3) having a carboxyl group and a hydroxyl group in the same molecule. Self-polycondensate, ring-opening polycondensate of lactone (a4) and the like can be mentioned.

  Specific examples of the polycarboxylic acids (a1) include aliphatic polycarboxylic acids [functional group number 2-6, carbon number (hereinafter abbreviated as C) 3-30, such as succinic acid, glutaric acid, maleic acid, fumaric acid, adipine. Acid, azelaic acid, sebacic acid, hexahydrophthalic acid], aromatic polycarboxylic acid [functional number 2-6, C8-30, such as phthalic acid, isophthalic acid, terephthalic acid, tetrabromophthalic acid, tetrachlorophthalic acid, Trimellitic acid, pyromellitic acid], alicyclic-containing polycarboxylic acid [number of functional groups 2-6, 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′-dicarbo Acid and dimer acid]; ester-forming derivatives of these polycarboxylic acids [acid anhydrides (eg, maleic anhydride, phthalic anhydride), lower alkyl (C1-4) esters (dimethyl ester, diethyl ester, etc.) (eg, terephthalate) Acid dimethyl), acid halide (acid chloride, etc.)]; and mixtures of two or more thereof. Of these, aliphatic polycarboxylic acids are preferable from the viewpoint of preventing coloring of the polyester resin.

The low molecular polyol (a2) is a number average molecular weight per hydroxyl group [hereinafter abbreviated as Mn. The measurement is based on a gel permeation chromatography (GPC) method. ] Is less than 300 (preferably a molecular weight of 31 or more and Mn 250 or less), and a divalent to 10-valent or higher (preferably 2-3) polyol can be used.
(A2) includes dihydric alcohol (a21), trivalent to 10-valent or higher polyhydric alcohol (a22), and alkylene oxides of these alcohols or polyvalent (divalent to trivalent or higher) phenols. (Hereinafter abbreviated as AO. C2-10) Low molar (1-10 mol) adducts; and mixtures of two or more of these.

  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 α-olefin oxide, epichlorohydrin; and combinations of two or more thereof (block and / or random addition). Of these AOs, EO, PO, and a combination thereof are preferable from the viewpoint of mat strength and permeability of the styrene monomer or the like to the mat in application of the mat to glass fiber reinforced plastic (FRP).

  Specific examples of the dihydric alcohol (a21) include aliphatic alcohols [linear alcohols (ethylene glycol, diethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexane. Diol (hereinafter abbreviated as EG, DEG, 1,3-PG, 1,4-BD, 1,5-PD, 1,6-HD, etc.), etc.]; branched chain alcohol [1,2-propylene glycol, Neopentyl 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 a ring-containing alcohol [alicyclic ring-containing alcohol [1,4-bis (hydroxymethyl) cyclohexane, etc. Include araliphatic alcohols (m-and p- xylylene glycol and the like) and the like] 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.). It is done. Of the above (a21) and (a22), aliphatic alcohols are preferable from the viewpoint of mat strength, and 1,4-BD and NPG are more preferable.

Specific examples of the (a23) include the AO low molar adducts of the above (a21) and (a22), and the AO low molar adduct of polyvalent (divalent to trivalent or higher) phenol having a ring. It is done.
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 mono- or dihydric phenols (phenol, cresol, xylenol, resorcinol, etc.) aldehydes or ketones (formaldehyde, glutaraldehyde) , Guri Oxal, acetone) low condensates (eg phenol or cresol novolak resin, resole intermediate, polyphenol obtained by condensation reaction of phenol and glyoxal or glutaraldehyde, and 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.

  Lactones include those having C4-15 (preferably C6-12) such as ε-caprolactone, γ-butyrolactone, and γ-valerolactone.

  Of the above polyester resins, preferred are polycondensates of polycarboxylic acid (a1) and low-molecular polyol (a2), and more preferred from the viewpoint of rapid polycondensation reaction and permeability of styrene and the like into the mat. Is a polycondensation product of a polycarboxylic acid and an AO adduct of a polyhydric hydroxyl group-containing compound having a ring, and particularly preferred is an AO low-mole addition of an aliphatic polycarboxylic acid and a polyhydric phenol or araliphatic alcohol having a ring. It is a polycondensate with the product.

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). The reaction is desirably performed in an atmosphere of an inert gas such as nitrogen from the viewpoint of preventing coloring of the polyester resin.
The reaction equivalent ratio (equivalent ratio of carboxyl group / hydroxyl group) of (a1) and (a2) during the polycondensation reaction is preferably from the viewpoint of rapid polycondensation reaction and stability of physical properties of the resulting polyester resin. It is 0.7 to 1 / 1.1, more preferably 0.9 / 1 to 1.2 / 1. The acid value 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 esterification catalysts include protonic acids (phosphoric acid, etc.), metals (alkali metals, alkaline earth metals, transition metals, 2B, 4A, 4B and 5B metals), carboxylic acid (C2-4) salts, carbonic acid Examples include salts, sulfates, phosphates, oxides, chlorides, hydroxides, alkoxides, and the like.
Of these, from the viewpoint of reactivity, the preferred are carboxylic acid (C2-4) salts, oxides, alkoxides, and products of the 2B, 4A, 4B, and 5B metals, and more preferred from the viewpoint of low coloration of the product. Antimony oxide, 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 carried out by the polycarboxylic acid (a1) and the low molecular polyol (a2). It can carry out according to the reaction conditions in the polycondensation reaction.

  In the present invention, the weight average molecular weight (hereinafter abbreviated as Mw. The measurement is based on the GPC method) and Mn of the polyester resin constituting the polyester resin powder (A) and Mn are from the viewpoint of the strength and flexibility of the glass chopped strand mat. Preferably it is 5,000-50,000, More preferably, it is 10,000-45,000, Mn becomes like this. Preferably it is 400-4,500, More preferably, it is 800-4,000.

  The softening point of the polyester resin by the ring-and-ball method (JIS K2207, “Petroleum Asphalt”, “6.4 Softening Point Test Method”) is used to prevent the glass chopped strand mat from exhibiting tackiness and workability in post-processing, and From the viewpoint of the bondability between the glass chopped strands by the binder, it is preferably 80 to 150 ° C, more preferably 90 to 140 ° C.

  Glass transition temperature of the polyester resin by differential thermal analysis (hereinafter abbreviated as Tg; measurement conforms to JIS K7121, “Plastic Transition Temperature Measurement Method”) is used to prevent blocking during binder storage and to post-process glass chopped strand mats. From the viewpoint of workability, the temperature 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 rod, a thermometer and a nitrogen introduction tube, and heated under a nitrogen atmosphere, usually 150 to The mixture is reacted at 170 ° C. for 4 to 6 hours, and then heated to 200 ° C., and further reacted for 6 to 8 hours under reduced pressure of 3 to 4 kPa while confirming the acid value, and the acid value (unit: mgKOH / g) After becoming 20 or less, the polyester resin is obtained by cooling to 180 ° C. and taking out.

The method for further producing the polyester resin powder (A) from the polyester resin includes the following production methods (1) to (3). Among these, the production methods (1) and (2) are preferable from the industrial viewpoint, and the production method (2) is more preferable from the viewpoint of productivity.
(1) Pulverization method The polyester resin is pulverized for 3 to 5 minutes at a rotational speed of about 10,000 rpm using, for example, a sample mill [model number “SK-M10”, manufactured by Kyoritsu Riko Co., Ltd.] to form particles. Thereafter, the polyester resin powder (A) is obtained by sieving by combining sieves having different openings.

(2) Dispersion method An organic solvent [ester (ethyl acetate, butyl acetate, etc.), ketone (acetone, methyl ethyl ketone, methyl isopropyl ketone, etc.)] solution of the above polyester resin, using a disperser, water containing a dispersant. A method of obtaining a polyester resin powder (A) by dispersing in a medium to form a dispersion of the polyester resin, and separating and drying resin particles from the dispersion.

  Examples of the dispersant include anionic, cationic, nonionic and amphoteric surfactants, polymer-type dispersants, and combinations thereof.

  Examples of the anionic surfactant include those having a C8-24 hydrocarbon group as a hydrophobic group, such as ether carboxylic acid (salt) [(poly) oxyethylene (degree of polymerization = 1-100) lauryl ether acetate Na, etc.], (Ether) sulfate ester (salt) [Nauryl sulfate sulfate, (poly) oxyethylene (degree of polymerization = 1-100) lauryl sulfate Na etc.], sulfonate [dodecylbenzene sulfonate Na etc.], sulfosuccinate, (ether ) Phosphate ester (salt) [Naur lauryl phosphate, etc.], (Poly) oxyethylene (degree of polymerization = 1-100) Lauryl ether phosphate Na etc., Fatty acid salt (Na laurate etc.), Acylated amino acid salt [ Coconut oil fatty acid methyl taurine Na, etc.].

  Nonionic surfactants include aliphatic alcohol (C8-24) AO (C2-8) adducts (degree of polymerization = 1-100), polyvalent (divalent-10-valent or higher) alcohol fatty acids (C8- 24) Ester (glyceryl monostearate, etc.), fatty acid (C8-24) alkanolamide (1: 1 type coconut oil fatty acid diethanolamide, etc.), (poly) oxyalkylene (C2-8) (degree of polymerization = 1-100) Alkyl (C1-22) phenyl ether, (poly) oxyalkylene (C2-8) (degree of polymerization = 1-100) alkyl (C8-24) amine, alkyl (C8-24) dialkyl (C1-6) amine oxide, etc. Is mentioned.

  Examples of the cationic surfactant include quaternary ammonium type [stearyltrimethylammonium chloride and the like], amine salt type [diethylaminoethylamide stearate lactate and the like] and the like.

  Examples of amphoteric surfactants include betaine type [coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine and the like], amino acid type [β-laurylaminopropionic acid Na and the like] and the like.

Polymeric dispersants include polyvinyl alcohol, starch and derivatives thereof, cellulose derivatives (carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, etc.), carboxyl group-containing (co) polymers (polysodium acrylate, etc.), and JP-A-07- And polymer type dispersants having a urethane bond or an ester bond described in JP-A-133423 and JP-A-08-120041 [for example, polycaprolactone polyol and polyether diol linked with polyisocyanate, etc.] .
Mw of these polymer type dispersants is usually 3,000 to 1,000,000, preferably 5,000 to 100,000.

  Among these dispersants, nonionic surfactants and polymer dispersants are preferable from the viewpoint of preventing secondary aggregation after dispersion, and more preferable are those having a urethane bond or an ester bond described in the above publication. It is a molecular type dispersant.

The amount of the dispersant used is preferably 0.1 to 5%, more preferably 0.2 to 8% from the viewpoint of the dispersibility and granulation property of the resin based on the weight of the polyester resin; From the viewpoint that resin particles having a desired volume average particle diameter and circularity can be easily obtained based on the weight of the above, it is preferably 0.01 to 7%, more preferably 0.1 to 5%.
The amount of the aqueous medium composed of a dispersant and water with respect to the weight of the polyester resin is preferably 50 to 1,000%, more preferably from the viewpoint of the dispersibility of the polyester resin and the volume average particle diameter of the resin. 100 to 1,000%.
When the organic solvent solution of the polyester resin is dispersed in an aqueous medium containing a dispersant, the organic solvent solution may be heated to 40 to 100 ° C., if necessary, in order to reduce the viscosity.

  Examples of the disperser in (2) above include high-speed shearing, friction, high-pressure jet, and ultrasonic dispersers. Among these, a high-speed shearing disperser is preferable from the viewpoint that resin particles having a desired volume average particle diameter and circularity are easily obtained. When using a high-speed shearing disperser [for example, trade name “Ultra Disperser”, manufactured by Yamato Scientific Co., Ltd.], the rotational speed is preferably 1,000 to 30,000 rpm, more preferably from the same viewpoint as above. Is 2,000 to 10,000 rpm, and the dispersion time is preferably 0.1 to 5 minutes.

  The dispersion in the above (2) is filtered or separated by a known method using a filter press, a spatula filter, a centrifuge, etc., and a polyester resin powder (A) is obtained by drying the obtained resin particles. . The resin particles can be dried by a known method using an air circulation dryer, a spray dryer, a fluidized bed dryer or the like.

(3) Precipitation method A dispersant is added to the organic solvent solution in (2) as necessary, and a poor solvent (cyclohexane, petroleum ether, etc.) is gradually added, followed by mixing using the disperser, and precipitation. The resin particles are precipitated, or the resin particles are separated and dried by utilizing the difference in solubility of the organic solvent solution due to a temperature difference (for example, gradually cooling the organic solvent solution at a high temperature). To obtain a polyester resin powder (A).

  In this method, when the precipitated particles are coarse, a dispersant may be used, and examples of the dispersant include the same as the above (2). From the viewpoint of preventing secondary aggregation after resin particle dispersion, nonionic surfactants and polymer dispersants are more preferable, and polymer dispersants having urethane bonds or ester bonds described in the above publication are more preferable. is there. Examples of the disperser used in the present method (3) include the same as those in the above (2).

The amount of the dispersant used is preferably 0.1 to 5%, more preferably 0.2 to 8% from the viewpoint of the dispersibility and granulation property of the resin based on the weight of the polyester resin; From the viewpoint that resin particles having a desired volume average particle diameter are easily obtained based on the weight of the solvent, it is preferably 0.01 to 7%, more preferably 0.1 to 5%.
The amount of the dispersion medium composed of the dispersant and the solvent is preferably 50 to 1,000% from the viewpoint of the dispersibility of the polyester resin and the volume average particle diameter of the resin, based on the weight of the polyester resin. Preferably it is 100 to 1,000%.

  In this method (3), the cooling rate when utilizing the difference in solubility due to the temperature difference is preferably 2 ° C./min or less from the viewpoint of preventing secondary aggregation.

[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 anti-blocking 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, preferably 0.01 to 5%, more preferably 0.1 to 3%, based on the weight of the polyester resin powder (A).

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, such as lauric acid, stearic acid;
Examples of salts of higher fatty acids include salts of alkali metals (Na, K, Li, etc.), alkaline earth metals (Ca, Ba, Mg, etc.), Zn, Cu, Ni, Co and Al of the above higher fatty acids;
Examples of silicon or metal oxides include silicon dioxide, silicon oxide, aluminum oxide, iron oxide, titanium oxide, magnesium oxide, and zirconium oxide. Examples of the carbide include silicon carbide and aluminum carbide;
Examples of the organic resin include polyolefin resin, polyamide resin, poly (meth) acrylic resin, silicon resin, polyurethane resin, phenol resin, polytetrafluoroethylene resin, and cellulose powder.
Of these, metal salts of higher fatty acids and silicon or metal oxides are preferable from the viewpoint of powder flowability.

  The amount of (B1) used is usually 5% or less based on the weight of (A), preferably from 0.01 to 2.0, more preferably from the viewpoint of binder blocking prevention and glass fiber binding. -1.0%.

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, for example, stearic acid; As the higher fatty acid ester, C10-36, for example, Butyl stearate, polyhydric (2-4) alcohol AO (C2-3) adduct ester of higher fatty acid (C10-24) (monostearate of EG EO 5 mol adduct, etc.); ˜40, such as stearamide.
Among these, preferred from the viewpoint of glass fiber binding properties are higher fatty acid (C10-24) polyvalent (2-4) alcohol AO (C2-3) adduct esters and higher fatty acid amides.

  The amount of (B2) used is usually 5% or less based on the weight of (A), preferably from 0.01 to 2.0%, more preferably from the viewpoint of powder flowability and glass fiber bonding. 1 to 1.0%.

Examples of the hydrophilicity-imparting agent (B3) include polyvinyl alcohol (Mn 1,000 to 100,000), carboxymethyl 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 preferred from the viewpoint of glass fiber bonding.

  The amount of (B3) used is usually 5% or less based on the weight of the polyester resin, and is preferably 0.01 from the viewpoint of the affinity with water sprayed on the glass chopped strand laminate described below and the glass fiber binding properties. It is -2.0%, More preferably, it is 0.1-1.0%.

[Glass chopped strand mat]
The glass chopped strand mat of the present invention comprises a glass chopped strand laminate and a binder for glass chopped strand mat containing the polyester resin powder (A), and can be produced, for example, by the following steps.
(1) A glass chopped strand laminate is obtained by spraying glass chopped strands in a directionally disordered and uniform thickness in a release-treated flat plate mold.
(2) Spray approximately the same amount of tap water as the sprayed glass chopped strands with a spray bottle so that the surface of the glass chopped strands is sufficiently wet.
(3) A predetermined amount of glass chopped strand mat binder is uniformly adhered.
(4) The operations of (1) to (3) are repeated 1 to 3 times or more to obtain a laminate.
(5) A glass chopped strand mat bonded with a binder is obtained by pressing with a press heated to 150 to 170 ° C.

  The binding amount of the binder based on the weight of the glass chopped strand laminate is that of the mechanical strength and handling properties of the mat (flexibility, fit to a mold when forming a glass fiber reinforced plastic molded product described later, etc.). From the viewpoint, it is preferably 1 to 30%, more preferably 3 to 25%.

The weight (g / m ² ) of the glass chopped strand mat obtained in the above (5) is preferably 50 to 600, more preferably 100 to 500 from the viewpoint of the mechanical strength and handling properties of the mat.

  The ignition loss rate of the glass chopped strand mat determined from the calculation formula described below is preferably 90% or more, and more preferably 93% or more, from the viewpoint of reducing the amount of dropped binder and the required mechanical strength of the mat.

The difference between the maximum value and the minimum value of the tensile strength of the glass chopped strand mat is preferably less than 40N, more preferably 35N or less, and particularly preferably 30N or less, from the viewpoint of handling properties of the mat.
Here, the tensile strength is measured according to JIS R3420, which will be described later, and the difference between the maximum value and the minimum value of the tensile strength is the difference between the maximum value and the minimum value obtained for 10 test pieces. It is evaluated with.

Moreover, the glass fiber reinforced plastic molded article of the present invention is not particularly limited with respect to the molding method, 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.

As the matrix resin used in the molding method including the hand lay-up method, a thermosetting resin (unsaturated polyester resin, vinyl ester resin, epoxy resin, phenol resin, polyurethane resin, silicone 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 Hereinafter, although an Example demonstrates this invention further, this invention is not limited to these. In the following, parts and% indicate parts by weight and% by weight, respectively.

Production Example 1 <Production of Binder (X-1)>
(1) Manufacture of polyester resin In a reaction vessel equipped with a cooling tube, a stirring rod, 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 6 parts of oxide was charged and reacted at 180 ° C. for 4 hours in a nitrogen atmosphere. Thereafter, the temperature was raised to 200 ° C. and reacted for 5.5 hours under a reduced pressure of 3 to 4 kPa, then further raised to 210 ° C. and cooled to 180 ° C. when the acid value of the reaction product reached 16.0. To obtain (Polyester Resin-1).

(2) Manufacture of polyester resin powder (A-1) 100 parts of (polyester resin-1) were sample milled [equipment name “SK-M10”, manufactured by Kyoritsu Riko Co., Ltd., and so on. ] For 5 minutes at a rotation speed of 10,000 rpm. The obtained resin powder is sieved with a sieve having an opening of 180 μm, and the resin powder having passed through the sieve is further sieved with a sieve having an opening of 150 μm to obtain a polyester resin powder (A-1) remaining on the 150 μm sieve. It was.
Mw of (A-1) is 30,000, Mn is 2,800, softening point is 116 ° C., Tg is 53 ° C., volume average particle diameter (D _V ), ratio of particles of 300 μm or more to all particles Table 1 shows the ratio of the particles having a coefficient of variation (C _V ) of 75 μm or less to the total particles and the values such as (D _V ) / (D _N ).

(3) Manufacture of binder (X-1) (A-1) 10 parts of antiblocking agent [trade name “AEROSIL200”, manufactured by Nippon Aerosil Co., Ltd. ] After adding 0.03 part, it mixed and obtained binder (X-1).

Production Example 2 <Production of Binder (X-2)>
(1) Production of polyester resin powder (A-2) 100 parts of (polyester resin-1) 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 to obtain a polyester resin powder (A-2) remaining on the sieve of 212 μm. 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 Binder (X-3)>
(1) Manufacture of polyester resin powder (A-3) 100 parts of (polyester resin-1) was pulverized for 3 minutes at a rotational speed of 12,500 rpm using a sample mill, and the resulting resin powder was sieved with a 106 μm mesh. And a polyester resin powder (A-3) that passed through the sieve was obtained.
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 Binder (X-4)>
(1) Production of polyester resin powder (A-4) 100 parts of (polyester resin-1) were pulverized for 5 minutes at a rotational speed of 15,000 rpm using a sample mill, and the resulting resin powder was sieved with an opening of 160 μm. The polyester resin powder (A-4) remaining on the 150 μm sieve was obtained by further sieving the resin powder that passed through the sieve with a sieve having an opening of 150 μm. The softening point and Tg are the same as (A-1), and the 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 Binder (X-5)>
(1) Manufacture of polyester resin powder (A-5) 100 parts of (Polyester resin-1) are dissolved and mixed in 200 parts of ethyl acetate, and this is mixed with 14 mol of nonylphenol EO [trade name “Nonipol 200”, Sanyo Chemical Industries, Ltd. Same as below, manufactured by Co., Ltd. After adding a solution obtained by diluting 4 parts with 500 parts of water, the mixture was mixed at a rotation speed of 9,000 rpm for 5 minutes using a high-speed shearing disperser [trade name “Ultra Disperser”, manufactured by Yamato Scientific Co., Ltd.] . Next, this mixed liquid was charged into a reaction vessel, heated to 50 ° C., and ethyl acetate was distilled off under a reduced pressure of 20 to 30 kPa to obtain a resin particle dispersion comprising (polyester resin-1). Next, the resin particle dispersion was centrifuged, the supernatant was removed, and the process of adding water and centrifuging was repeated twice. The sedimented layer was dried under reduced pressure conditions of 50 ° C. and 1.3 kPa. 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 to obtain a polyester resin powder (A-5) remaining on the sieve of 212 μm. It was.
Mw, Mn, softening point and Tg of (A-5) were the same as (A-1), and the number average circularity was 0.93. The number average circularity was measured according to the method described later. 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 Binder (X-6)>
(1) Manufacture of polyester resin In (1) of manufacture example 1, after making it react for 1 hour instead of 5.5 hours of reaction under reduced pressure of 3-4 kPa, it heated up to 210 degreeC, and was further reacted. (Polyester resin-2) was obtained in the same manner as in Production Example 1 (1) except that the acid value was 19.0 when the acid value was 19.0.

(2) Production of polyester resin powder (A-6) Production Example 1 except that 100 parts of (Polyester Resin-2) was used in place of 100 parts of (Polyester Resin-1) in (2) of Production Example 1. A polyester resin powder (A-6) was obtained in the same manner as in (2).
Mw of (A-6) is 6,500, Mn is 2,300, softening point is 88 ° C., Tg is 48 ° C., and values of other evaluation items are shown in Table 1.

(3) 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 Binder (X-7)>
(1) Manufacture of polyester resin In (1) of manufacture example 1, after making it react for 8 hours instead of 5.5 hours of reaction under reduced pressure of 3-4 kPa, it heated up to 210 degreeC, and was further reacted. (Polyester Resin-3) was obtained in the same manner as in Production Example 1 (1) except that the acid value was 5.5 and was taken out after cooling to 180 ° C.

(2) Manufacture of polyester resin powder (A-7) Manufacture example 1 except having used 100 parts of (polyester resin-3) instead of 100 parts of (polyester resin-1) in (2) of manufacture example 1. In the same manner as in (2), a polyester resin powder (A-7) was obtained.
Mw of (A-7) is 40,000, Mn is 4,300, softening point is 130 ° C., Tg is 56 ° C., and values of other evaluation items are shown in Table 1.

(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.

Comparative Production Example 1 <Production of Binder (X'-1)>
(1) Manufacture of polyester resin powder (A'-1) 100 parts of (polyester resin-1) was pulverized for 3 minutes at a rotational speed of 12,500 rpm using a sample mill, and the resulting resin powder was sieved with an opening of 180 µm. Sieving with a sieve, a polyester resin powder (A′-1) that passed through the sieve was 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 1.
(2) Manufacture of binder (X'-1) (A'-1) After adding 0.03 part of antiblocking agents to 10 parts, it mixed and obtained binder (X'-1).

Comparative Production Example 2 <Production of Binder (X'-2)>
(2) Manufacture of polyester resin powder (A'-2) 100 parts of (polyester resin-1) was pulverized for 3 minutes at a rotational speed of 12,500 rpm using a sample mill, and the resulting resin powder was sieved with an opening of 150 µm. Sieving with a sieve, a polyester resin powder (A′-2) remaining on the sieve was 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 1.
(2) Manufacture of binder (X'-2) (A'-2) After adding 0.03 part of antiblocking agents to 10 parts, it mixed and obtained binder (X'-2).

Comparative Production Example 3 <Production of Binder (X'-3)>
(1) Production of polyester resin powder (A′-3) 100 parts of (polyester resin-1) were pulverized for 3 minutes at a rotational speed of 7,500 rpm using a sample mill, and the resulting resin powder was sieved with a mesh of 250 μm. And a polyester resin powder (A′-3) that passed through the sieve was 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 1.
(2) Manufacture of binder (X'-3) (A'-3) After adding 0.03 part of antiblocking agents to 10 parts, it mixed and obtained binder (X'-3).

Comparative Production Example 4 <Production of Binder (X′-4)>
(1) Production of polyester resin powder (A′-4) 100 parts of (polyester resin-1) 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 that has passed through the sieve is further sieved with a sieve having an opening of 250 μm, and the polyester resin powder (A′-4) remaining on the 250 μm sieve is obtained. Obtained.
Mw, Mn, softening point, and Tg of (A′-4) are the same as (A-1), and the values of other evaluation items are shown in Table 1.
(2) Manufacture of binder (X'-4) After adding 0.03 part of antiblocking agents to 10 parts of (A'-4), it mixed, and binder (X'-4) was obtained.

Comparative Production Example 5 <Production of Binder (X′-5)>
(1) Production of polyester resin powder (A′-5) 100 parts of (polyester resin-1) 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 106 μm, and the resin powder that has passed through the sieve is further sieved with a sieve having an opening of 75 μm, and the polyester resin powder (A′-5) remaining on the 75 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 1.
(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).

Example 1 <Preparation of Glass Chopped Strand Mat (GM-1)>
Glass strands for glass chopped strands (average strand count T = 30 tex, glass fiber density d = 2.5 g / cm ³ , glass strand diameter K = 13.6 μm) were used with a glass chopper manufactured by Togiken Co., Ltd. The glass chopped strand was obtained by cutting to a length of about 5 cm.
45.0 g of the glass chopped strands are sprayed in a directionally disordered uniform thickness into a 75 cm × 40 cm × 3 cm flat plate mold subjected to the mold release treatment, and then the surface of the sprayed body of the glass chopped strands is moistened. The tap water was sprayed to the extent by spraying.
Next, 1.35 g of binder (X-1) corresponding to 3.0% of the weight of the spread glass chopped strands was uniformly spread on the glass chopped strand spreader.
Furthermore, the operation of 45.0 g of glass chopped strands, tap water spraying, and 1.35 g of binder (X-1) was repeated twice in the same manner. As a result, a glass chopped strand laminate having a three-layer structure in which 4.05 g of binder (X-1) corresponding to 3.0% of the total amount of glass chopped strands was dispersed to 135.0 g was formed.
Thereafter, the film was hot-pressed at a speed of 1.5 m / min with a roll-type press heated to 150 ° C., and the thickness was 1.2 mm and the basis weight of the mat (the amount of glass chopped strand used for the mat per 1 m ² . The same.) A glass chopped strand mat (GM-1) having a weight loss of 2.70% by weight (93% loss on ignition) was obtained at 450 g / m ² .

The ignition loss (% by weight) is a value obtained in accordance with JIS R3420 described later. The specific procedure is as follows.
(1) About 5 g of a test piece is placed in a magnetic crucible, dried at 105 ° C. for 30 minutes, then allowed to cool to room temperature in a desiccator, and the weight (m1) is measured to the nearest 0.1 mg. The dried magnetic crucible containing a test piece was placed in an electric furnace adjusted to a temperature of 625 ° C., burned for 5 minutes with the door open, then closed, and burned for another 10 minutes. Thereafter, the magnetic crucible containing the test piece is taken out and allowed to cool to room temperature in a desiccator, and the weight (m2) is measured to the nearest 0.1 mg.
(2) About the said empty magnetic crucible which does not put a test piece, after drying for 30 minutes at 105 degreeC, it cools to room temperature within a desiccator, and measures a weight (m0) to a 0.1 mg unit.
(3) The ignition loss is calculated from the following formula.

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

The binder supply amount of the glass chopped strand mat used for FRP is often around 3% by weight of the weight of the glass chopped strand. Therefore, the binder supply amount was set to a weight equivalent to 3.0% of the weight of the glass chopped strand (that is, 2.91% of the weight of the obtained glass chopped strand mat), and the ignition loss rate was calculated from the calculation formula described later.
The ignition loss rate is preferably 90% or more, and more preferably 93% or more, from the viewpoint of reducing the amount of dropped binder and the required strength of the glass chopped strand mat.

Example 2 <Preparation of Glass Chopped Strand Mat (GM-2)>
In Example 1, except that the binder (X-1) was replaced with the binder (X-2), the thickness was 1.2 mm, the mat weight was 450 g / m ² , and the ignition loss was 2 A glass chopped strand mat (GM-2) of 64% (91% loss on ignition) was obtained.

Example 3 <Preparation of Glass Chopped Strand Mat (GM-3)>
In Example 1, except that the binder (X-1) is replaced with the binder (X-3), the thickness is 1.2 mm, the mat weight is 450 g / m ² , and the ignition loss is 2 A glass chopped strand mat (GM-3) of .75% (ignition loss 95%) was obtained.

Example 4 <Preparation of Glass Chopped Strand Mat (GM-4)>
In Example 1, the glass strand for the glass chopped strand is replaced with a glass strand having an average strand count T = 10 tex, a glass fiber density d = 2.5 g / cm ³ , and a strand diameter K = 71.4 μm. -1) was replaced with binder (X-2) in the same manner as in Example 1, thickness 1.1 mm, mat weight per unit area 450 g / m ² , ignition loss 2.65% (ignition loss rate) 91%) of glass chopped strand mat (GM-4) was obtained.

Example 5 <Preparation of Glass Chopped Strand Mat (GM-5)>
In Example 1, the glass strand for the glass chopped strand is replaced with a glass strand having an average strand count T = 120 tex, a glass fiber density d = 2.5 g / cm ³ , and a strand diameter K = 247.2 μm. -1) except that the binder (X-3) was replaced in the same manner as in Example 1, thickness 1.4 mm, mat weight per unit area 450 g / m ² , ignition loss 2.76% (ignition loss rate) 95%) of glass chopped strand mat (GM-5) was obtained.

Example 6 <Preparation of Glass Chopped Strand Mat (GM-6)>
In Example 1, except that the binder (X-1) was replaced with the binder (X-4), the thickness was 1.2 mm, the mat weight was 450 g / m ² , and the ignition loss was 2 A glass chopped strand mat (GM-6) having a loss of 0.81% (97% loss on ignition) was obtained.

Example 7 <Preparation of Glass Chopped Strand Mat (GM-7)>
In Example 1, except that the binder (X-1) was replaced with the binder (X-5), the thickness was 1.2 mm, the mat weight was 450 g / m ² , and the ignition loss was 2 in the same manner as in Example 1. A glass chopped strand mat (GM-7) of 0.83% (ignition loss rate 97%) was obtained.

Example 8 <Preparation of Glass Chopped Strand Mat (GM-8)>
In Example 1, by spraying once, 45.0 g of glass chopped strands were replaced with 5.0 g, 1.35 g of binder (X-1) was replaced with 0.15 g of binder (X-6), and this was performed three times. Except for this, a glass chopped strand laminate having a three-layer structure in which 0.45 g of binder (X-6) corresponding to 3.0% of the total amount of glass chopped strands was sprayed on 15.0 g of the total glass chopped strands. Formed body.
Thereafter, the glass chopped strand mat (GM) having a thickness of 0.3 mm, a mat weight of 50 g / m ² , an ignition loss of 2.62% by weight (ignition loss ratio of 90%) was obtained in the same manner as in Example 1. -8) was obtained.

Example 9 <Preparation of Glass Chopped Strand Mat (GM-9)>
In Example 1, by spraying once, 45.0 g of glass chopped strands were replaced with 58.0 g, 1.35 g of binder (X-1) was replaced with 1.74 g of binder (X-7), and this was performed three times. Except for this, a glass chopped strand laminate having a three-layer structure in which 5.22 g of binder (X-7) equivalent to 3.0% of the total glass chopped strands of 174.0 g was sprayed in the same manner as in Example 1. Formed body.
Thereafter, the glass chopped strand mat (GM) having a thickness of 1.6 mm, a mat weight of 580 g / m ² , a loss on ignition of 2.91% by weight (100% on loss of ignition) was heat-pressed in the same manner as in Example 1. -9) was obtained.

Comparative Example 1 <Production of Glass Chopped Strand Mat (GM'-1)>
In Example 1, except that the binder (X-1) was replaced with the binder (X′-1), the thickness was 1.2 mm, the mat weight was 450 g / m ² , and the ignition was carried out. A glass chopped strand mat (GM′-1) having a weight loss of 2.76% (ignition loss rate of 95%) was obtained.

Comparative Example 2 <Production of Glass Chopped Strand Mat (GM'-2)>
In Example 1, except that the binder (X-1) was replaced with the binder (X′-2), the thickness was 1.2 mm, the mat weight per unit area was 450 g / m ² , and the heat was high. A glass chopped strand mat (GM′-2) having a weight loss of 2.44% (ignition loss ratio of 84%) was obtained.

Comparative Example 3 <Preparation of Glass Chopped Strand Mat (GM'-3)>
In Example 1, except that the binder (X-1) was replaced with the binder (X′-3), the thickness was 1.2 mm, the mat weight was 450 g / m ² , and the heat was high. A glass chopped strand mat (GM′-3) having a weight loss of 2.55% (ignition loss rate of 88%) was obtained.

Comparative Example 4 <Production of Glass Chopped Strand Mat (GM'-4)>
In Example 1, the glass strand for the glass chopped strand is replaced with a glass strand having an average strand count T = 10 tex, a glass fiber density d = 2.5 g / cm ³ , and a strand diameter K = 71.4 μm. -1) was replaced with binder (X'-4) in the same manner as in Example 1, thickness 1.1 mm, mat weight per unit area 450 g / m ² , ignition loss 2.49% (ignition) A glass chopped strand mat (GM′-4) having a weight loss rate of 86% was obtained.

Comparative Example 5 <Production of Glass Chopped Strand Mat (GM′-5)>
In Example 1, except that the binder (X-1) was replaced with the binder (X′-5), in the same manner as in Example 1, the thickness was 1.2 mm, the mat weight per unit area was 450 g / m ² , and the heat was high. A glass chopped strand mat (GM′-5) having a weight loss of 2.73% (ignition loss rate of 94%) was obtained.

<Evaluation items>
The following items were evaluated and the results are shown in Table 1.
(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 by “RDC-220” [device name, manufactured by Seiko Denshi Kogyo Co., Ltd.].

(3) The volume average particle diameter (D _V ) of the polyester resin powder, the ratio (%) of each particle having a volume reference particle diameter of 300 μm or more and 75 μm or less in all particles of the polyester resin powder.
The measurement was performed by a laser diffraction scattering method using a “Microtrac 9320HRA particle size analyzer” [device name, manufactured by Nikkiso Co., Ltd.].
(4) Coefficient of variation of volume-based particle size distribution (C _V ) (%)
The coefficient of variation (C _V ) is a value calculated from the following formula, and the standard deviation and volume average particle diameter (D _V ) are measured by a laser diffraction scattering method using a “Microtrack 9320 HRA particle size analyzer”. did.

Coefficient of variation (C _V ) = [standard deviation / volume average particle diameter (D _V )] × 100

(5) Ratio of [volume average particle diameter (D _V ) / number average particle diameter (D _N )] (D _V ) and (D _N ) are values obtained by laser diffraction scattering using “Microtrack 9320 HRA particle size analyzer”. Measured by the method.

(6) Number average circularity Take a picture with the ultra deep shape measuring microscope “VK-8500” manufactured by Keyence Corporation, perform image analysis with the attached shape analysis software “VK-H1A7”, and obtain a number average circular shape. I asked for a degree.
Here, the number average circularity is a value obtained by measuring the circularity of each of 30 particles randomly picked up, repeating the number average operation 10 times, and simply averaging the obtained 10 values. It is.
(7) Loss on ignition (wt%)
This is a value measured in accordance with “7.3.2 Loss on ignition” of JIS R3420 “General test method for glass fiber” and represents the ratio (% by weight) of the binder adhering to the mat based on the weight of the mat. .

(8) Loss on ignition (%)
The ignition loss rate is calculated from the following equation.

Ignition loss rate (%) = [Ignition loss (% by weight) /2.91] × 100

(9) Tensile strength of glass chopped strand mat (N)
From each of the glass chopped strand mats (GM-1) to (GM-9) and (GM′-1) to (GM′-5), 10 test pieces cut into a width of 50 mm × a length of 150 mm were created, These were measured in accordance with “7.4 Tensile Strength” of JIS R3420 “General Test Method for Glass Fiber”. Specifically, the procedure was as follows.
(I) The test piece is allowed to stand for 1 hour under conditions of 25 ° C. and humidity 65% (standard atmosphere defined by JIS K7100).
(Ii) Grab both ends in the length direction of the test piece with the upper and lower clamps, and adjust the distance between the clamps to 100 mm.
(Ii) Using “Autograph AGS-500D” [device name, manufactured by Shimadzu Corporation], a tensile test is performed at a tensile speed of 100 mm / min, and the force required until the test piece breaks is defined as the tensile strength. .

(10) Measurement of glass chopped strand mat flexural modulus (flexibility evaluation) (MPa)
Ten test pieces each having a width of 20 mm and a length of 100 mm were cut from each of the glass chopped strand mats (GM-1) to (GM-9) and (GM′-1) to (GM′-5). These were measured according to ASTM D256.

<Evaluation criteria>
[1] Average value of tensile strength The average value of the tensile strength of 10 test pieces was determined and evaluated according to the following criteria.
○ Over 130N △ 70N or more and less than 130N × less than 70N

[2] Difference between maximum value and minimum value of tensile strength The difference between the maximum value and the minimum value of the tensile strength of 10 test pieces was determined and evaluated according to the following criteria.
○ Less than 40N Δ 40N or more and less than 80N × 80N or more [3] Tensile strength per ignition loss The average value of the tensile strength of 10 test pieces was divided by ignition loss (% by weight) and evaluated according to the following criteria. .
○ Over 50N △ 30N or more and less than 50N × less than 30N

[4] Average flexural modulus (evaluation of flexibility)
○ Less than 1.5 × 10 ⁻³ MPa Δ 1.5 × 10 ⁻³ MPa or more and less than 2.0 × 10 ⁻³ MPa × 2.0 × 10 ⁻³ MPa or more

As is apparent from Table 1, the glass chopped strand mat of the present invention has a higher ignition loss rate than the comparative conventional one, and therefore the binder has excellent adhesion efficiency, and the mat has strength (tensile strength). It can be seen that the strength is uniform and the strength is uniform throughout the mat. Moreover, since the comparative mat | matte inferior to mat | matte intensity | strength needs to increase the binder supply amount, it turns out that the binder of this invention can provide the intensity | strength required for a mat | matte uniformly with the usage-amount smaller than before.
Furthermore, from Table 1, the glass chopped strand mat of the present invention has an appropriate bending elastic modulus and excellent flexibility as compared with the comparative ones. Therefore, the glass chopped strand mat can be used as a molding die for producing a glass fiber reinforced plastic molded product using the mat. It can be seen that the fit can greatly contribute to the improvement of workability.

  A glass chopped strand mat formed by bonding a glass chopped strand laminate with the binder of the present invention is used as a reinforcing material for a glass fiber reinforced plastic (FRP) molded product, and the molded product is an automobile member (molded ceiling). Materials), hulls of small vessels (canoe, boat, yacht, motor boat, etc.), housing members (bathtubs, septic tanks, etc.), etc.

Claims (9)

A volume average particle diameter D _V is 100~250μm by a laser diffraction scattering method, the proportion of particles having a volume-based particle size of at least 300μm is 20 wt% or less, and variation coefficient of particle diameter distribution based on volume C A binder for glass chopped strand mats, comprising a polyester resin powder (A) in which _V is 0.1 to 30%. The binder according to claim 1, wherein the proportion of particles having a volume-based particle diameter of 75 µm or less in (A) is 20 wt% or less. (A) of the volume average particle diameter D _V and the number average particle diameter D _N ratio [D _V / D _N] is claim 1 or 2 wherein the binder is 1 to 1.5. The binder according to any one of claims 1 to 3, wherein the number average circularity of (A) is 0.8 to 1.0. A glass chopped strand mat obtained by bonding a glass chopped strand laminate with the binder according to claim 1. The mat according to claim 5, wherein the difference between the maximum value and the minimum value of the tensile strength of the mat is less than 40N. A glass fiber reinforced plastic molded product obtained by molding the mat according to claim 5 or 6 as a reinforcing material. The molded article according to claim 7, wherein the glass fiber reinforced plastic molded article is for automobile molded ceiling materials, small ship hulls, bathtubs or septic tanks. The binder according to any one of claims 1 to 4, wherein a glass chopped strand mat is produced by hot press molding a glass chopped strand laminate formed through the steps of glass chopped strand dispersion, water dispersion and binder dispersion. A method for producing a glass chopped strand mat, characterized in that