JP2009074228A - Binder for glass chopped strand mat - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a binder for glass chopped strand mats, providing the glass chopped strand mats having uniform strength and flexibility and excellent in post-processability, and capable of drastically reducing the required amount of the binder fed with little amount of the binder falling without adhering to a laminated body of the glass chopped strands. <P>SOLUTION: The binder for glass chopped strand mats contains spherical synthetic resin powder (A) having a number average circularity of 0.8-1.0, a volume average particle size of 100-400 μm, and containing 20 wt.% or less of particles having a particle size of less than 100 μm. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a powdery binder for glass chopped strand mats. More specifically, a binder that provides a glass chopped strand mat that is uniform, strong and flexible, and has good workability during subsequent processing operations (such as fitting the mat to the formwork during FRP molding). About.

  A glass chopped strand mat is usually a large number of glasses obtained by cutting glass strands formed by bundling 10 to several 100 glass single fibers having a fiber diameter of about 10 μm with a sizing agent into a predetermined length. After the chopped strands are dispersed and laminated in a directionally disordered manner on the transport net, the binder powder is dispersed on the laminate and heated in an oven chamber to bond the glass chopped strands with a binder. For this binder, conventionally, many unsaturated polyester resins pulverized by mechanical pulverization have been used (see, for example, Patent Documents 1 and 2).

However, since the conventional binder is pulverized by mechanical pulverization, the particle shape is indefinite, and the distribution width of the particle size (which will be used in the same meaning as the particle size below) is wide, so it is applied to the glass chopped strand mat. Even if a predetermined amount of binder powder to be supplied is supplied to the laminated body of glass chopped strands, the binder powder is unevenly deposited on the surface layer of the laminated body, resulting in insufficient binding of the glass fibers inside the glass chopped strand mat. Variations in strength and suppleness occur, the quality of the mat is impaired, and the workability during subsequent processing operations deteriorates.
On the other hand, there is a drawback that there is a binder that does not adhere to the laminated body of glass chopped strands and falls, and a predetermined amount or more of a binder that is originally required for the glass chopped strand mat must be supplied.
JP-A-57-55931 JP 2003-48255 A

  An object of the present invention is to provide a binder suitable for making a glass chopped strand mat that can substantially reduce the amount of the binder supplied, has a uniform strength and flexibility, and is excellent in the subsequent workability. There is to do.

The inventor of the present invention has arrived at the present invention as a result of intensive studies to achieve the above object.
That is, in the present invention, the number average circularity is 0.8 to 1.0, the volume average particle diameter by laser diffraction scattering method is 100 to 400 μm, and the content of powder particles less than 100 μm is 20% by weight or less. It is a binder for glass chopped strand mats characterized by containing spherical synthetic resin powder (A).

The spherical synthetic resin powder (A) constituting the binder for the glass chopped strand mat of the present invention has a spherical shape and a constant shape, and since the particle size distribution width is narrow, the binder uniformly adheres to the glass chopped strand laminate. Therefore, it is possible to effectively prevent variations in strength such as tensile strength of the glass chopped strand mat and flexibility such as bending resistance, which has been a problem in the past, and to apply to the formwork of the mat during FRP molding. Excellent workability after processing such as excellent formability (fitting).
Moreover, there are few binders which fall without adhering to the laminated body of a glass chopped strand compared with a conventional binder, and it has the effect that supply amount can be reduced.

The number average circularity of the spherical synthetic resin powder (A) in the present invention is 0.8 to 1.0, preferably 0.85 to 1.0, and more preferably 0.90 to 1.0.
Here, the circularity is a value calculated by the following formula, and can be measured and calculated by photographing particles with a microscope and image-processing the photograph [for example, a microscope VK-8500 manufactured by Keyence Corporation. , And image analysis using the accompanying shape analysis software VK-H1A7; 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: Projection perimeter of particle

If the number average circularity is less than 0.8, uniform adhesion to the laminate tends to be impaired. 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 may be in the above range.
Regarding circularity, the “Non-contact full-field strain measurement of concrete degradation and 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.

  (A) which comprises the binder for glass chopped strand mats of this invention requires that it is spherical and has a particle diameter of a fixed area | region, specifically, the number average circularity is 0.8-1. 0.0, the volume average particle diameter is 100 to 400 μm, and the content of powder particles less than 100 μm is required to be 20% by weight or less.

The spherical synthetic resin powder (A) in the present invention has a volume average particle diameter of 100 to 400 μm by a laser diffraction scattering method, and preferably 120 to 350 μm, from the viewpoint of uniform adhesion of the binder and reduction of falling of the binder. Preferably it is 130-300 micrometers, Most preferably, it is 135-250 micrometers.
The volume average particle diameter is measured with a particle size distribution measuring instrument [for example, Microtrack FRA particle size analyzer manufactured by Nikkiso Co., Ltd.] by a laser diffraction scattering method.
When the volume average particle diameter is less than 100 μm, the binder is dispersed and adhered exclusively to the surface of the laminated body of glass chopped strands, and the binding of the internal glass fibers becomes insufficient. As a result, the glass chopped strand mat has a variation in strength between the front side, the back side and the inside, and the quality of the mat is impaired. Further, if the volume average particle diameter exceeds 400 μm, the binder weight increases by the weight of the binder particles, and the amount of the binder that falls and dissipates through the gaps of the laminate without adhering to the laminate increases. The amount of binder attached per hit is reduced. As a result, it is necessary to supply more binder from the viewpoint of securing the performance of the glass chopped strand mat. As a result, the entire mat becomes hard and workability during subsequent processing operations deteriorates.

  The proportion of particles smaller than 100 μm in (A) is 20% by weight or less, preferably 15% by weight or less. If it exceeds 20% by weight, it will be dispersed and adhered exclusively to the surface of the laminate, resulting in insufficient binding of glass fibers, causing not only variation in strength on the front side, back side and inside of the glass chopped strand mat, but also dust. Occurs and the working environment deteriorates.

The softening point of the synthetic resin constituting the spherical synthetic resin powder (A) by the ring-and-ball method is such that the workability of the glass chopped strand mat during the subsequent processing operation (no inconvenient stickiness does not occur) and the mat molding temperature (set low). From the viewpoint of bonding between glass fibers, preferably 80 to 150 ° C, more preferably 90 to 140 ° C.
Here, the softening point is a value measured according to “6.4 Softening point test method (ring and ball method)” of JIS K2207 “Petroleum Asphalt”.

  As the composition of the synthetic resin constituting the spherical synthetic resin powder (A), the type of the synthetic resin is as long as the above-mentioned number average circularity, volume average particle diameter, and content of powder particles less than 100 μm are satisfied. Although it does not specifically limit, For example, a polyurethane resin (A1) and a polyester resin (A2) are mentioned.

The polyurethane resin (A1) is usually a resin obtained by polyaddition reaction of polyisocyanate (a1) and an active hydrogen-containing compound.
The polyisocyanate (a1) includes a diisocyanate and a trifunctional or higher polyfunctional isocyanate; for example, an aromatic having 6 to 20 carbon atoms (hereinafter abbreviated as C) (excluding carbon in the NCO group, the same applies hereinafter). Polyisocyanate (a11); C2-18 aliphatic polyisocyanate (a12); C6-15 alicyclic polyisocyanate (a13); C8-15 araliphatic polyisocyanate and modified products of these polyisocyanates ( a14) [urethane group, carbodiimide group, allophanate group, burette group, uretdione group, uretoimine group, isocyanurate group and oxazolidone group-containing modified product]; and a mixture of two or more thereof.

  Specific examples of the aromatic polyisocyanate (a11) include, for example, 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (hereinafter abbreviated as TDI), Crude TDI, 2,4′- and / or 4,4′-diphenylmethane diisocyanate (hereinafter abbreviated as MDI), 4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanate Natobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatodiphenylmethane, crude MDI [crude diaminodiphenylmethane [condensation product of formaldehyde and aniline, diaminodiphenylmethane and a small amount (for example, 5 to 20% by weight) Phosgenates of polyamines with tri- or higher functional groups, generally polyaryl poly It referred to as the isocyanate (hereinafter abbreviated as PAPI). 1,5-naphthylene diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate, m- and p-isocyanatophenylsulfonyl isocyanate.

  Specific examples of the aliphatic polyisocyanate (a12) include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (hereinafter abbreviated as HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2, and the like. 4-trimethylhexamethylene diisocyanate, lysine diisocyanate (2,6-diisocyanatomethylcaproate), bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2, 6-diisocyanatohexanoate is mentioned.

  Specific examples of the alicyclic polyisocyanate (a13) include, for example, isophorone diisocyanate (hereinafter abbreviated as IPDI), dicyclohexylmethane-4,4 ′ and / or 2,4′-diisocyanate (hereinafter abbreviated as hydrogenated MDI). Cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- and / or 2,6-norbornane diisocyanate. Specific examples of the araliphatic polyisocyanate include m- and / or p-xylylene diisocyanate and α, α, α ', α'-tetramethylxylylene diisocyanate.

  Specific examples of the modified polyisocyanate (a14) include modified MDI (urethane modified MDI, carbodiimide modified MDI, trihydrocarbyl phosphate modified MDI), urethane modified TDI, burette modified HDI, isocyanurate modified HDI, isocyanurate modified IPDI. And a mixture of two or more thereof [for example, combined use of modified MDI and urethane-modified TDI (isocyanate group-containing prepolymer)]. Of these, preferred are aliphatic and cycloaliphatic polyisocyanates, particularly HDI, IPDI, and hydrogenated MDI, which are less likely to discolor over time.

Examples of the active hydrogen-containing compound to be reacted with the polyisocyanate (a1) include a low-molecular polyfunctional active hydrogen-containing compound (a2) and a polymer polyol (a3).
Examples of the low molecular polyfunctional active hydrogen-containing compound (a2) include a low molecular polyol (a21) and a low molecular polyamine (a22).

The low molecular polyol (a21) is a number average molecular weight per hydroxyl group [hereinafter abbreviated as Mn. The measurement is based on a gel permeation chromatography (GPC) method. A polyol having a valence of less than 300 (preferably having a molecular weight of 31 or more and Mn of 250 or less) and a valence of 10 or more (preferably a valence of 2-3) can be used.
Examples of the low molecular polyol (a21) include dihydric alcohol (a211), trivalent to 10-valent or higher polyhydric alcohol (a212), and C2-10 alkylene oxide (hereinafter abbreviated as AO). Molar adducts; and mixtures of two or more thereof.

  As AO, ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), 1,2-, 1,3-, 1,4- and 2,3-butylene oxide, styrene oxide, C5-10 Or more α-olefin oxide, epichlorohydrin; and combinations of two or more thereof (block and / or random addition). Among these, EO, PO, and combinations thereof are preferable.

  Specific examples of the dihydric alcohol (a211) include aliphatic diols [linear diols (C2 to 10 such as ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol. 1,6-hexanediol, etc .; branched diols (C3-10, such as propylene glycol, neopentyl glycol, 3-methyl 1,5-pentanediol, 2,2-diethyl-1,3-propanediol) , 1,2-, 1,3- and 2,3-butanediol and the like]; and a diol having a cyclic group [C8 or more and less than Mn600, such as 1,4-bis (hydroxymethyl) cyclohexane, m- and of p-xylylene glycol, dihydric phenol (such as bisphenol A) ( Li) such as polyoxyalkylene ethers (C2-4 alkylene group)] can be mentioned.

Specific examples of the trivalent to 10-valent or higher polyhydric alcohol (a212) include alkane polyols (C3-30, such as glycerin, trimethylolpropane, pentaerythritol, sorbitol, and their intermolecular or intramolecular dehydrates [ Dipentaerythritol, polyglycerin (degree of polymerization 2 to 8), sorbitan etc.], saccharides and derivatives thereof (glycosides) (sucrose, methyl glucoside etc.).
Of these (a21), preferred are aliphatic diols, and more preferred are 1,4-butanediol and neopentyl glycol.

  The low molecular polyamine (a22) as the low molecular polyfunctional active hydrogen-containing compound (a2) has a diamine having an Mn of less than 300 (preferably a molecular weight of 30 or more and Mn 250 or less) per active hydrogen contained in the amino group ( and a polyamine (a222) in which the isocyanate group of the polyisocyanate (a1) is replaced with an amino group.

  Specific examples of the diamine (a221) include aliphatic diamine (ethylenediamine, hexamethylenediamine, etc.), alicyclic diamine (4,4′-diamino-3,3′-dimethyldicyclohexylmethane, 4,4′-diamino-3). , 3′-dimethyldicyclohexyl, diaminocyclohexane, isophoronediamine, etc.), aromatic diamine (diethyltoluenediamine, etc.), araliphatic diamine (xylylenediamine, α, α, α ′, α′-tetramethylxylylenediamine, etc. ) And heterocyclic diamines (such as piperazine).

Specific examples of the polyamine (a222) include polyalkylene (C2-6) polyamine (diethylenetriamine, triethylenetetramine, etc.), polyphenylmethane polyamine (condensation product of formaldehyde and aniline, etc.); and a mixture of two or more thereof Is mentioned.
Of these (a22), from the viewpoint of the strength of the glass chopped strand mat, alicyclic diamines and aliphatic diamines are preferred, and isophorone diamine and hexamethylene diamine are particularly preferred.

As the polymer polyol (a3) to be reacted with the polyisocyanate (a1), a divalent to tetravalent or higher (preferably 2-3) polyol having a Mn of 300 or more per hydroxyl group can be used.
The polymer polyol (a3) includes a polyester polyol (a31), a polyether polyol (a32), and a mixture of two or more thereof. The Mn per hydroxyl group of the polymer polyol (a3) is preferably 300 to 10,000, more preferably 500 to 5,000, from the viewpoint of the flexibility of the glass chopped strand mat and the strength of the glass chopped strand mat. Particularly preferred is 800 to 3,000.

  Examples of the polyester polyol (a31) include a condensed polyester polyol (a311) (by polycondensation of a polyol and a polycarboxylic acid); a polylactone polyol (a312) (a ring-opening polymerization of a lactone monomer using a polyol as an initiator). Polycarbonate polyol (a313) [reaction of polyol with alkylene (C2-4) carbonate (such as ethylene carbonate), transesterification of polyol with phosgenated carbonate or diphenyl carbonate]; and two or more of these Of the mixture.

  As the polyol in (a311), (a312), and (a313), one or more of low molecular polyols [for example, (a21) described above] and / or polyether polyols (for example, (a32) described later) can be used.

The polycarboxylic acid (a3111) in the condensed polyester polyol (a311) includes not only the polycarboxylic acid itself but also an ester-forming derivative thereof.
Specific examples of the polycarboxylic acids (a3111) include aliphatic polycarboxylic acids (polycarboxylic acids having 2 to 6 functional groups and C3-30, such as succinic acid, glutaric acid, maleic acid, fumaric acid, adipic acid, and azelaic acid. , Sebacic acid, hexahydrophthalic acid), aromatic polycarboxylic acids (2-6 functional groups, C8-30 polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, tetrabromophthalic acid, tetrachlorophthalic acid, Trimellitic acid, pyromellitic acid, etc.), alicyclic dicarboxylic acids (polycarboxylic acids having 2 to 6 functional groups and C6-50, such as 1,3-cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-dicarboxymethylcyclohexyl 1,4-dicarboxymethylcyclohexane, dicyclohexyl-4,4′-dicarboxylic acid and dimer acid); their ester-forming derivatives [anhydrides, lower alkyl (C1-4) esters (dimethyl esters, diethyl esters) Etc.), acid halides (such as acid chlorides), such as maleic anhydride, phthalic anhydride, dimethyl terephthalate]; and mixtures of two or more thereof. Of these, aliphatic polycarboxylic acids are preferred from the viewpoint of the softening point of the binder.

  Examples of the lactone monomer in the polylactone polyol (a312) include C3-20 (preferably 4-12) lactones such as β-lactone (eg, β-propiolactone), γ-lactone (eg, γ-butyrolactone), δ- Lactones (such as δ-valerolactone), ε-lactones (such as ε-caprolactone), macrocyclic lactones (such as enanthlactone, undecanolactone, dodecalactone)]; and mixtures of two or more thereof. Among these, γ-butyrolactone, ε-caprolactone, and mixtures thereof are preferable from the viewpoint of the strength of the glass chopped strand mat.

  The polyether polyol (a32) includes those having a structure in which AO is added to a compound having two or more active hydrogen atoms. Examples of the compound having two or more active hydrogen atoms include low molecular polyols [for example, (a21)]; divalent phenols [for example, bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.), monocyclic phenols ( Catechol, hydroquinone, etc.)]; amines [primary monoamines, such as alkyl or alkenylamines (C1-20), anilines, alkanolamines (C2-4 of hydroxylalkyl groups) (such as those listed below as terminators), polyamines Examples thereof include (a22) and heterocyclic polyamines such as piperazine, aminoalkyl (C2-4) piperazine (aminoethylpiperazine, etc.)] and the like.

  Among the polyurethane resins (A1) in the present invention, those preferred from the viewpoint of the flexibility and strength of the glass chopped strand mat are aliphatic polyisocyanate (a12) and / or alicyclic polyisocyanate (a13) and polymer polyol ( It is a polyaddition reaction product with a3), and more preferred is a polyaddition reaction product of alicyclic polyisocyanate (a13) and polyester polyol (a31).

  The production of the polyurethane resin (A1) can be carried out by a usual method, a method in which the active hydrogen-containing compound and the polyisocyanate (a1) are all reacted together (one-shot method), and a part of these reaction components For example, and a multi-stage reaction via an isocyanate group or a hydroxyl group-terminated urethane prepolymer (a) (prepolymer method). From the viewpoint of the volume average particle diameter of (A), a prepolymer method, particularly an isocyanate group-terminated urethane prepolymer and a low molecular weight polyfunctional active hydrogen-containing compound (a2) (here used as an extender and / or a crosslinking agent) And / or a method of reacting a terminator.

The isocyanate group-terminated urethane prepolymer is preferably formed by reacting the polyisocyanate (a1) with the high-molecular polyol (a3) and, if necessary, the low-molecular polyfunctional active hydrogen-containing compound (a2). In this case, the equivalent ratio of (a1) to (a2) and (a3) is usually 0 to 0.2 equivalent, preferably 0.05 to 0.10 equivalent with respect to (a1) 1 equivalent, (A3) is usually 0.1 to 0.6 equivalent, preferably 0.2 to 0.5 equivalent.
The isocyanate group content of the isocyanate group-terminated urethane prepolymer is usually 0.5 to 10% by weight, preferably 1.5 to 6% by weight.

  Examples of the extender include the dihydric alcohol (a211) (aliphatic diol, diol having a cyclic group, etc.) mentioned in the description of (a21), and the diamine (aliphatic diamine, alicyclic diamine) mentioned in (a22). , Aromatic diamines, araliphatic diamines, heterocyclic diamines, etc.), ketimine compounds of these diamines [ketimines of diamines and ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone (hereinafter abbreviated as MIBK)], and water Is mentioned. Of these, ketimine compounds are preferred from the viewpoint of the volume average particle diameter of (A).

  Examples of the crosslinking agent include trivalent to 10-valent or higher polyhydric alcohols (a212) (glycerin, trimethylolpropane, etc.) mentioned in the description of (a21), and polyamines (a222) (diethylenetriamine) mentioned in (a22). And triethylenetetramine).

  Examples of the terminator include monoamines having one or two C2-4 hydroxyalkyl groups and aliphatic (including alicyclic and aliphatic) monoamines having no hydroxyl group.

Monoamines having one or two hydroxyalkyl groups as terminators include monoalkanolamines [C2-4, such as monoethanolamine, monopropanolamine]; dialkanolamines [C4-8, such as diethanolamine, dipropanolamine. And a mixture of two or more thereof.
Of these, dialkanolamine is preferable from the viewpoint of strength and softening point of the glass chopped strand mat, and particularly preferable are diethanolamine and dipropanolamine. [In some cases, when an isocyanate group is present in an excess equivalent to the amino group, the hydroxyl group also participates in the reaction with the isocyanate group and acts as an extender and a crosslinking agent. ]

Aliphatic monoamines [mono- and di-cycloalkyl (C5-18) amines such as cyclopentylamine, cyclohexylamine, etc.], aliphatic monoamines [mono- and monocyclic] having no hydroxyl group as a terminator. And di-alkyl or alkenyl (C1-20) amines such as methylamine, ethylamine, propylamine, butylamine, octylamine, 2-ethylhexylamine, nonylamine, oleylamine, N-methylbutylamine, diethylamine, dibutylamine and the like] and these The mixture of 2 or more types of these is mentioned.
Among these, preferred from the viewpoint of the strength of the glass chopped strand mat are aliphatic monoamines having no hydroxyl group, and particularly preferred are butylamine, octylamine, 2-ethylhexylamine, and dibutylamine.

The charging ratio of the extender, terminator and crosslinking agent to the isocyanate group-terminated urethane prepolymer is a predetermined weight average molecular weight [hereinafter abbreviated as Mw. The measurement is based on the GPC method. ] Within a range in which the polyurethane resin is formed.
For example, the equivalent ratio of the extender to 1 equivalent of isocyanate groups in the isocyanate group-terminated urethane prepolymer is preferably 0.05 to 1.5 equivalents, more preferably 0.1 to 1.2 equivalents. The equivalent ratio of the terminator is usually 0 to 0.4 equivalent, preferably 0.05 to 0.3 equivalent, and the equivalent ratio of the crosslinking agent is usually 0 to 0.4 equivalent, preferably 0.02. -0.2 equivalents.
Further, the equivalent ratio of the total of the extender, the terminator, and the crosslinking agent with respect to 1 equivalent of the isocyanate group of the isocyanate group-terminated urethane prepolymer is preferably 0.1 to 2.3 equivalents, more preferably 0.3 to 1.7. Is equivalent.

  In addition, Mw of the polyurethane resin (A1) is usually 10,000 or more, preferably 15,000 to 1,000,000, and Mn is usually 1,000 or more, preferably 1,500 to 500,000. is there.

  The terminal group of the polyurethane resin (A1) is usually a hydroxyl group or an amino group, not an isocyanate group.

As a method of obtaining the polyurethane resin (A1) in a spherical shape of the present invention,
(1) A method of forming a spherical particle during a resin formation reaction step to obtain a resin dispersion,
(2) A method of precipitating a resin from a resin solution.

When the resin composition of the spherical synthetic resin powder (A) in the present invention is a polyurethane resin (A1), as a method for producing the particles,
(1) A method in which an aqueous dispersion of a polyurethane resin is formed in water containing a dispersant, and resin particles are separated and dried from the aqueous dispersion to obtain a powder (A) (for example, JP-A-07-133423 and JP (Methods described in each of Kohei 08-120041).
(2) A non-aqueous dispersion of polyurethane resin is formed in an organic solvent (n-hexane, cyclohexane, n-heptane, etc.) that does not dissolve the polyurethane resin, and the resin particles are separated and dried from the non-aqueous dispersion to obtain a powder (A ) (For example, the method described in JP-A No. 04-255755).
Among these, the method (1) is preferable in that fine particles having a desired shape and particle diameter can be easily obtained without using a large amount of an organic solvent.

  The method (1) includes a method of obtaining resin fine particles by reacting an isocyanate group-terminated urethane prepolymer with an extender and, if necessary, a terminator and a crosslinking agent in an aqueous medium in the presence of a dispersant.

For example,
(1-1) A production method in which an isocyanate group-terminated urethane prepolymer and an extender are dispersed with a disperser in water containing a dispersant,
(1-2) A production method in which an isocyanate group-terminated urethane prepolymer, an extender and a stopper are dispersed in water containing a dispersant by a disperser,
(1-3) The manufacturing method etc. which disperse | distribute an isocyanate group terminal urethane prepolymer with the disperser in the water containing a dispersing agent, an extending | stretching agent, and a terminator as needed are mentioned.
Among these, the method (1-1) is preferable from the viewpoint of reducing the number average circularity to 1.0 and reducing powder particles of less than 100 μm.

  Examples of the dispersant used include anionic, cationic, nonionic and amphoteric surfactants, polymeric dispersants, and combinations thereof.

  Examples of the anionic surfactant include ether carboxylic acids having C8-24 hydrocarbon groups or salts thereof ((poly) oxyethylene (degree of polymerization = 1-100) lauryl ether sodium acetate, etc.), C8-24 hydrocarbons. Sulfate ester or ether sulfate ester having a group thereof or a salt thereof [sodium lauryl sulfate, (poly) oxyethylene (degree of polymerization = 1-100) sodium lauryl sulfate, (poly) oxyethylene (degree of polymerization = 1-100) lauryl sulfate Triethanolamine, (poly) oxyethylene (degree of polymerization = 1-100) coconut oil fatty acid monoethanolamide sodium sulfate, etc.], sulfonates having C8-24 hydrocarbon groups [sodium dodecylbenzenesulfonate, etc.], C8 Sulfo having 1 or 2 hydrocarbon groups of ~ 24 Succinate, phosphate ester or ether phosphate ester having C8-24 hydrocarbon group or salt thereof [sodium lauryl phosphate, (poly) oxyethylene (degree of polymerization = 1-100) sodium lauryl ether phosphate, etc. ], Fatty acid salts having a C8-24 hydrocarbon group [sodium laurate, triethanolamine laurate, etc.] and acylated amino acid salts having a C8-24 hydrocarbon group [coconut oil fatty acid methyl taurine sodium, coconut oil fatty acid] Sarcosine sodium, coconut oil fatty acid sarcosine triethanolamine, N-coconut oil fatty acid acyl-L-glutamic acid triethanolamine, N-coconut oil fatty acid acyl-L-glutamic acid sodium, lauroylmethyl-β-alanine sodium, 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) Esters [glyceryl monostearate, sorbitan monolaurate, etc.], fatty acids (C8-24) alkanolamides [1: 1 type coconut oil fatty acid diethanolamide, 1: 1 type lauric 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 and alkyl ( C8-24) Dialkyl (C1-6) amine oxide [lauryl dimethylamine oxide etc.] etc. are mentioned.

  Cationic surfactants include quaternary ammonium salt type [stearyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, ethyl lanolin sulfate fatty acid aminopropylethyl dimethyl ammonium, etc.], amine salt type [diethylamino stearate] Ethylamide lactate, dilaurylamine hydrochloride, oleylamine lactate, etc.].

  Amphoteric surfactants include betaine-type amphoteric surfactants [coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, laurylhydroxy Sulfobetaine, lauroylamidoethylhydroxyethylcarboxymethylbetaine hydroxypropyl sodium phosphate, etc.] and amino acid type amphoteric surfactants [sodium β-laurylaminopropionate, etc.].

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

  Among these dispersants, preferred from the viewpoint of preventing secondary aggregation after dispersion are a polymer-type dispersant and a nonionic surfactant, and more preferred are urethane bonds or ester bonds described in the above publication. It has a polymer type dispersant.

  The amount of the dispersant used is usually 0.1 to 5% (hereinafter, unless otherwise specified,% represents% by weight), preferably 0.2 to 4%, based on the solid content of the polyurethane resin. Further, the dispersant is preferably 0.01 to 5%, more preferably 0.1 to 3% based on the weight of water. If it is 0.01 to 5%, resin fine particles having a preferable volume average particle diameter are easily obtained. Moreover, the usage-amount of the dispersing agent solution which consists of a dispersing agent and water with respect to the weight of an isocyanate group terminal urethane prepolymer becomes like this. Preferably it is 50 to 1,000%, More preferably, it is 100 to 1,000%. If it is 50 to 1,000%, the dispersion state of the isocyanate group-terminated urethane prepolymer tends to be good, and resin fine particles having a preferable volume average particle diameter are easily obtained. If necessary, the isocyanate group-terminated urethane prepolymer may be heated to 40 to 100 ° C. in order to reduce the viscosity. Also, ester solvents (ethyl acetate, butyl acetate, etc.), ketone solvents (acetone, methyl ethyl ketone, MIBK, etc.), chlorine solvents (dichloromethane, dichloroethane, trichloroethane, etc.) and / or aromatic solvents (toluene, xylene, etc.) ) Or the like may be added in an amount of 50% by weight or less based on the isocyanate group-terminated urethane prepolymer.

As a method for dispersing the isocyanate group-terminated urethane prepolymer in water containing a dispersant, a method using a known disperser such as a high-speed shearing method, a friction method, a high-pressure jet method, or an ultrasonic method is preferable. Of these, a more preferable method is a method using a high-speed shearing disperser.
When a high-speed shearing disperser is used, the number of rotations is preferably 1,000 to 30,000 rpm, more preferably 2,000 to 10,000 rpm. The dispersion time is preferably 0.1 to 5 minutes. If the rotation speed and dispersion time are within these ranges, resin particles having a preferable volume average particle diameter can be easily obtained.

  The reaction time of the isocyanate group-terminated urethane prepolymer, the extender and the terminator is not particularly limited, and is appropriately selected according to the reactivity and reaction temperature. For example, when the reaction temperature is 30 ° C., it is usually 1 to 40 hours, preferably 5 to 20 hours. In the manufacturing method of this invention, reaction temperature is 0-80 degreeC normally, Preferably it is 20-60 degreeC.

  The dispersion is filtered or separated using a known equipment such as a filter press, a spatula filter, a centrifuge, and the resulting particles are dried to obtain a polyurethane resin (A1) powder. The particles can be dried using a known facility such as a circulating dryer, a spray dryer, or a fluidized bed dryer.

On the other hand, the case where the resin composition of the spherical synthetic resin powder (A) in the present invention is a polyester resin (A2) will be described below.
Examples of the polyester resin (A2) of the spherical synthetic resin powder (A) in the present invention include polycarboxylic acids [for example, the aforementioned polycarboxylic acids (a3111)] and low molecular polyols (for example, the aforementioned (a21)). Examples include condensates and polycondensates of the compound (a41) having a carboxyl group and a hydroxyl group in the same molecule.

Specific examples of the compound (a41) having a carboxyl group and a hydroxyl group in the same molecule include C2-6, such as lactic acid, glycolic acid, β-hydroxybutyric acid, hydroxypivalic acid, hydroxyvaleric acid; and two or more of these. Of the mixture.
Of the polyester resin (A2), from the viewpoint of the strength and suppleness of the glass chopped strand mat, a polycondensate of polycarboxylic acids (a3111) and a low molecular polyol (a21) is preferred, and more preferred are: It is a polycondensate of an aliphatic polycarboxylic acid and an AO low molar adduct of an araliphatic diol.

  The temperature during the polycondensation of the polyester resin (A2) is usually 100 to 300 ° C, preferably 130 to 220 ° C. The atmosphere during the polymerization is desirably performed in the presence of an inert gas such as nitrogen. The equivalent ratio of polycarboxylic acids and polyols at the time of polymerization is equivalent ratio of carboxylic acid group / hydroxyl group, and preferably 1 / 0.7 to 1 / 1.1. The acid value after polycondensation is preferably 20 or less.

  The Mw of the polyester resin (A2) is preferably 5,000 to 50,000 from the viewpoints of the strength and flexibility of the glass chopped strand mat.

  When the resin constituting the spherical synthetic resin powder (A) is a polyester resin (A2), the glass transition temperature by differential thermal analysis (hereinafter abbreviated as Tg) is usually 40 to 60 ° C., prevention of blocking during storage and later From the viewpoint of workability at the time of processing work, it is preferably 45 to 55 ° C.

When the spherical synthetic resin powder (A) is a polyester resin (A2), the production method thereof is as follows:
(1) Disperse polyester resin (A2) dissolved in an aqueous solvent in advance with an ester solvent such as ethyl acetate or butyl acetate, or a ketone organic solvent such as acetone, methyl ethyl ketone or methyl isopropyl ketone in an aqueous medium. Then, a method of forming a water dispersion of (A2) and separating and drying resin particles from this water dispersion to obtain a powder.
(2) A poor solvent (cyclohexane, petroleum ether, etc.) is gradually mixed with the organic solvent solution to precipitate insolubilized fine particles, or the organic solvent solution (toluene, ethylene glycol, etc.) For example, the organic solvent solution is gradually cooled to precipitate fine particles, and the resin fine particles are separated and dried to obtain a powder.
Among these, the method (1) is preferable in that fine particles having a desired shape and particle diameter can be easily obtained without using a large amount of an organic solvent.

  As the dispersant to be used, the same dispersant as that for obtaining the above-mentioned polyurethane resin (A1) as a spherical powder can be used. Among the above-mentioned dispersants, preferred are a polymeric dispersant and a nonionic surfactant. It is an agent.

The amount of the dispersant used is usually 0.1 to 10% by weight, preferably 0.2 to 8% by weight, based on the solid content of the resin. Further, the dispersant is preferably 0.01 to 7% by weight, more preferably 0.1 to 5% by weight with respect to water. If it is 0.01 to 7% by weight, resin fine particles having a preferable volume average particle diameter can be easily obtained.
Moreover, the usage-amount of the dispersing agent solution which consists of a dispersing agent and water with respect to the weight of a polyester resin (A2) becomes like this. Preferably it is 50 to 1,000 weight%, More preferably, it is 100 to 1,000 weight%. If it is 50 to 1,000% by weight, the dispersion state of the polyester resin (A2) tends to be good, and resin fine particles having a preferable volume average particle diameter are easily obtained.
If necessary, the organic solvent solution of the polyester resin (A2) may be heated to 40 to 100 ° C. in order to reduce the viscosity.

As a method for dispersing the polyester resin (A2) in water containing a dispersant, the high-speed shearing method, the friction method, the high-pressure jet method, This is a method using a known disperser such as an ultrasonic type. Among these, a more preferable method is a method using a high-speed shearing type disperser.
When a high-speed shearing disperser [for example, Ultra Disperser manufactured by Yamato Scientific Co., Ltd.] is used, the rotational speed is preferably 1,000 to 30,000 rpm, more preferably 2,000 to 10,000 rpm. The dispersion time is preferably 0.1 to 5 minutes. If the rotation speed and dispersion time are within these ranges, resin particles having a preferable volume average particle diameter can be easily obtained.

  The dispersion is filtered or separated using a known equipment such as a filter press, a spatula filter, a centrifuge, and the resulting particles are dried to obtain a polyester resin powder. The particles can be dried using a known facility such as a circulating dryer, a spray dryer, or a fluidized bed dryer.

The glass chopped strand mat binder of the present invention containing the spherical synthetic resin powder (A) includes, in addition to (A), the above-described dispersant, and, if necessary, an anti-blocking agent (B1), curing acceleration. One or more additives (B) selected from the group consisting of the agent (B2) and the flame retardant (B3) can be contained. These additives (B) may be previously contained in the resin powder (A) or may be added at the time of use.
The purpose of (B2) is to accelerate curing when the glass chopped strand mat is hardened with a matrix resin (such as an unsaturated polyester resin) and processed into FRP.

Examples of the anti-blocking agent (B1) include fine fatty acids or salts thereof, silicon or metal oxides, silicon or metal carbides, or a mixture or composite composition thereof.
Examples of higher fatty acids include C8-24, such as capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and 12-hydroxystearic acid;
As salts of higher fatty acids, salts of alkali metals (sodium, potassium, lithium, etc.), alkaline earth metals (calcium, barium, magnesium, etc.), zinc, copper, nickel, cobalt and aluminum of the above higher fatty acids;
Silicon or metal oxides include silicon dioxide (orthorhombic, cubic, hexagonal and monoclinic), silicon oxide (amorphous, etc.), aluminum oxide, iron oxide, titanium oxide, magnesium oxide, zirconium oxide Examples of the carbide include silicon carbide and aluminum carbide.
Examples of commercially available products of (B1) include Aerosil R972, Aerosil 200 [all trade names, manufactured by Nippon Aerosil Co., Ltd.], Leorosil [trade names, manufactured by Tokuyama Co., Ltd.], and the like.
Among these (B1), from the viewpoint of the powder fluidity of (A), metal salts of higher fatty acids and silicon or metal oxides are preferable.

  The amount of (B1) used is usually 10% or less based on the weight of (A), preferably from 0.01 to 8% from the viewpoint of antiblocking properties of (A) and glass chopped strand binding properties of (A). More preferably, it is 0.1 to 5%.

Examples of the curing accelerator (B2) include metal soaps and amine compounds.
As metal soap, cobalt naphthenate, cobalt octenoate, barium naphthenate, manganese octenoate, etc .;
Examples of the amine compound include N, N-dimethylaniline, O-toluidine, morpholine and the like.
Of these (B2), amine compounds are preferred from the viewpoint of compatibility with the resin.

  The amount of (B2) used is usually 10% or less based on the weight of (A), preferably from 0.0001 to 7.5%, more preferably 0 from the viewpoint of curing speed and resin adhesion to glass fibers. 0.001 to 5%.

Examples of the flame retardant (B3) include organic and inorganic flame retardants.
Organic flame retardants include phosphates [aromatic monophosphates (tricresyl phosphate, etc.), aromatic diphosphates [resorcinol bis (diphenyl phosphate), etc.]], aromatic ring-containing halogen compounds (decabromodiphenyl ether, tetrabromobisphenol A, etc.) Etc.).
Examples of inorganic flame retardants include antimony compounds and metal hydroxides.
Antimony compounds include antimony trioxide and antimony pentoxide;
Examples of the metal hydroxide include magnesium hydroxide and aluminum hydroxide.
Of these (B3), an organic flame retardant is preferable from the viewpoint of compatibility with the resin.

  The amount of (B3) used is usually 20% or less based on the weight of (A), preferably 0.5 to 10%, more preferably 1 from the viewpoint of flame retardancy and prevention of inhibition of the unsaturated polyester curing. 0.0 to 5%.

The glass chopped strand mat of the present invention can be produced, for example, by the following procedure.
(1) A glass chopped strand is dispersed in a flat plate mold subjected to a release treatment so as to have a uniform thickness in a directional disorder.
(2) Spray tap water of approximately the same amount as the glass chopped strand of (1) by spraying so that the surface of the glass chopped strand is sufficiently moistened.
(3) A predetermined amount of glass chopped strand mat binder is uniformly dispersed.
(4) The above operations (1) to (3) are repeated 1 to 3 times or more.
(5) A glass chopped strand mat is obtained by pressing with a press machine heated to 115 to 170 ° C.

When the volume average particle diameter of the spherical synthetic resin powder (A) constituting the binder of the present invention is D (μm), the diameter K (μm) of the glass chopped strand obtained from D and the following formula (1) The ratio [D / K] is preferably 0.1 / 1 to 4/1, more preferably 0.5, from the viewpoint of the strength and uniformity of the glass chopped strand mat and the reduction in the amount of binder at the time of forming the mat. / 1 to 3/1, particularly preferably 1.3 / 1 to 2/1.

K = 20 × [10T / (dπ)] ^1/2 (1)

In the formula, K represents the diameter of the glass chopped strand, that is, the diameter when a strand in which about 10 to several hundred glass single fibers are converged is regarded as a cylinder, and T represents the average strand count (tex) of the glass chopped strand. , D represents the density (g / cm ³ ) of the glass fiber, and π represents the circumference.

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

Production Example 1 <Production of polyurethane resin spherical powder (A1-1)>
1) Production of Dispersant In a reaction vessel equipped with a stir bar and a thermometer, 787 parts of polycaprolactone diol (Mn 2,000), PO / EO random adduct of propylene glycol (Mn 4,000, PO / EO weight ratio = 50/50) 800 parts were charged and dehydrated under reduced pressure at 120 ° C. The water content after dehydration was 0.05%. Subsequently, 55.5 parts of HDI, 65.5 parts of hydrogenated MDI, and 0.6 part of dibutyltin dilaurate were added and reacted at 80 ° C. for 5 hours to obtain (Dispersant-1).

2) Production of urethane prepolymer 2,000 parts of polycaprolactone diol (Mn 2,000) was charged into a reaction vessel equipped with a stir bar and a thermometer, and heated to 110 ° C. under a reduced pressure of 0.4 kPa for 1 hour. Dehydration was performed. Subsequently, 457 parts of IPDI were added and reacted at 110 ° C. for 10 hours to obtain an isocyanate group-terminated urethane prepolymer [prepolymer (a-1)] having an isocyanate group content of 3.6%.

3) Production of extender In a reaction vessel, 50 parts of ethylenediamine and 50 parts of MIBK were charged and reacted at 50 ° C. for 5 hours to obtain (chain extender-1).

4) Production of polyurethane resin spherical powder (A1-1) 50 parts of the obtained prepolymer (a-1) and 0.6 part of (chain extender-1) were mixed and (dispersant-1) After adding a solution obtained by diluting 2 parts into 250 parts of water, Ultra Disperser [manufactured by Yamato Scientific Co., Ltd.] was used and mixed for 1 minute at 9,000 rpm. After mixing, the mixture was poured into a reaction vessel equipped with a stir bar and a thermometer, and reacted at 50 ° C. for 10 hours. Next, the blocking agent Aerosil R972 [manufactured by Nippon Aerosil Co., Ltd.] same as below. 0.5 part was added, and it filtered and dried and obtained spherical powder (A1-1) 50 parts of spherical polyurethane resin.
The polyurethane resin constituting (A1-1) has a Mw of 50,000, a softening point of 98 ° C., a Tg of −45 ° C., and a volume average measured by the laser diffraction scattering method (A1-1). The particle diameter was 218 μm, the content of particles having a particle size of less than 100 μm was 9%, and the number average circularity measured by image processing with a microphotograph (hereinafter the same) was 0.91.

Production Example 2 <Production of Polyester Resin Spherical Powder (A2-1)>
1) Production of polyester In a reaction vessel equipped with a cooling tube, a stirring bar, a thermometer and a nitrogen introduction tube, 3,530 parts of PO2 molar adduct of bisphenol A, 545 parts of neopentyl glycol, 1,670 parts of fumaric acid, dibutyl 3 parts of tin oxide was charged and reacted at 180 ° C. for 4 hours in a nitrogen atmosphere. Then, it heated up to 200 degreeC, it was made to react under reduced pressure of 3-4 kPa, and when it became acid value 12.0, it cooled and took out to 180 degreeC, and obtained (polyester-1). Mw of (Polyester-1) was 24,000, the softening point was 113 ° C, and Tg was 46 ° C.

2) Production of spherical powder of polyester resin 100 parts of the above (Polyester-1) was dissolved and mixed in 200 parts of ethyl acetate, and nonylphenol EO 14 mol adduct [Nonipol 200, manufactured by Sanyo Chemical Industries, Ltd. same as below. ] After adding a solution obtained by diluting 4 parts to 500 parts of water, Ultra Disperser [manufactured by Yamato Scientific Co., Ltd.] same as below. And was mixed for 5 minutes at 9,000 rpm.
Subsequently, this mixed liquid was transferred to a reaction vessel equipped with a stir bar and a thermometer, heated to 50 ° C., and ethyl acetate was distilled off under a reduced pressure of 20 to 30 kPa, thereby obtaining a particle dispersion composed of (polyester-1). It was. Next, the particle dispersion was centrifuged, and the process of adding water and centrifuging was repeated twice. Then, 1 part of an anti-blocking agent Aerosil R972 was added and dried to obtain a spherical powder of a spherical polyester resin (A2- 1) 100 parts were obtained.
The volume average particle diameter of (A2-1) was 193 μm, the content of particles less than 100 μm was 11%, and the number average circularity was 0.93.

Production Example 3 <Production of Polyester Resin Spherical Powder (A2-2)>
1) Production of polyester In a reaction vessel equipped with a cooling tube, a stir bar, a thermometer and a nitrogen introduction tube, 3,365 parts of an EO 2.2 mol adduct of bisphenol A, 1,123 parts of fumaric acid, dibutyltin oxide 6 And the reaction was carried out at 180 ° C. for 4 hours in a nitrogen atmosphere. Thereafter, the temperature was raised to 200 ° C., the reaction was performed under a reduced pressure of 3 to 4 kPa, the temperature was raised to 210 ° C., and when the acid value reached 16.0, the product was cooled to 180 ° C. and taken out to obtain (Polyester-2). It was. Mw of (Polyester-2) was 36,000, the softening point was 116 ° C, and Tg was 53 ° C.

2) Manufacture of spherical powder of polyester resin After 100 parts of the above (Polyester-2) was dissolved and mixed in 200 parts of ethyl acetate, a solution obtained by diluting 4 parts of nonylphenol EO 14 mol adduct to 500 parts of water was added. The mixture was mixed for 5 minutes at 9,000 rpm using an ultradisperser. Next, this mixed liquid was transferred to a reaction vessel equipped with a stir bar and a thermometer, heated to 50 ° C., and ethyl acetate was distilled off under a reduced pressure of 20 to 30 kPa to obtain a particle dispersion composed of (polyester-2). It was. Next, the particle dispersion was centrifuged, and the process of adding water and centrifuging was repeated twice. Then, 1 part of an anti-blocking agent Aerosil R972 was added and dried to obtain a spherical powder of a spherical polyester resin (A2- 2) 100 parts were obtained.
The volume average particle diameter of (A2-2) was 206 μm, the content ratio of particles less than 100 μm was 8%, and the number average circularity was 0.95.

Production Example 4 <Production of Polyester Resin Spherical Powder (A2-3)>
100 parts of the above (Polyester-1) was dissolved and mixed in 200 parts of ethyl acetate, and after adding a solution obtained by diluting 6 parts of nonylphenol EO 14 mol adduct with 550 parts of water, using an ultradisperser, rotating The mixture was mixed at several 10,000 rpm for 5 minutes. In the same manner as in Production Example 2, a particle dispersion composed of (Polyester-1) was obtained.
Further, in the same manner as in Production Example 2, 100 parts of spherical polyester resin spherical powder (A2-3) was obtained. The volume average particle diameter of (A2-3) was 135 μm, the content of particles less than 100 μm was 17%, and the number average circularity was 0.97.

Production Example 5 <Production of Polyester Resin Spherical Powder (A2-4)>
100 parts of (Polyester-2) is dissolved and mixed in 100 parts of ethyl acetate, and after adding a solution obtained by diluting 3 parts of nonylphenol EO 14 mol adduct to 500 parts of water, use an ultradisperser and rotate. The mixture was mixed at several 9,000 rpm for 5 minutes. In the same manner as in Production Example 2, a particle dispersion composed of (Polyester-2) was obtained.
Further, in the same manner as in Production Example 2, 100 parts of spherical polyester resin spherical powder (A2-4) was obtained. The volume average particle diameter of (A2-4) was 225 μm, the content of particles less than 100 μm was 7%, and the number average circularity was 0.87.

Comparative Production Example 1 <Production of pulverized polyester resin (A2'-1)>
100 parts of (Polyester-1) obtained in Production Example 2 was mechanically pulverized with a sample mill, and 1 part of an anti-blocking agent Aerosil R972 was added to obtain 95 parts of a pulverized polyester resin (A2′-1). The volume average particle diameter of (A2′-1) was 223 μm, the content of particles less than 100 μm was 26%, and the number average circularity was 0.56.

Comparative Production Example 2 <Production of pulverized polyester resin (A2'-2)>
100 parts of (Polyester-2) obtained in Production Example 3 was mechanically pulverized with a sample mill, and 1 part of Aerosil R972 as an antiblocking agent was added to obtain 95 parts of a pulverized polyester resin (A2′-2). The volume average particle diameter of (A2′-2) was 157 μm, the content of particles less than 100 μm was 56%, and the number average circularity was 0.71.

Example 1 <Production of Glass Chopped Strand Mat (GM-1)>
A glass strand for glass chopped strand (average strand count T = 30 tex, glass fiber density d = 2.5 g / cm ² , strand diameter K = 13.6 μm) is about 5 cm using a glass chopper manufactured by Togiken Co., Ltd. Cut into lengths to obtain glass chopped strands. The meanings of K, T, and d here are the same as described above.
45.0 g of the glass chopped strand obtained in the 75 cm × 40 cm flat plate mold subjected to the mold release treatment was sprayed in a directionally disordered uniform thickness, and then sprayed until the surface of the glass chopped strand was moistened. Tap water was sprayed.
Further, 1.35 g of binder (A1-1) corresponding to 3.0% of the weight of the glass chopped strand [in the following, the symbol of the binder is the same as the symbol of the resin powder constituting the binder. ] Was uniformly sprayed on the glass chopped strands. Furthermore, 45.0 g of glass chopped strand spraying, tap water spraying, and 1.35 g of binder spraying were repeated twice. Therefore, a three-layer structure was formed in which 4.05 g of binder corresponding to 3.00% of the total glass chopped strands was sprayed on 135.0 g.
After that, it was heated and set at a speed of 1.5 m / min with a roll type press machine heated to 150 ° C., thickness 1.2 mm, mat unit weight 450 m / m ² per square meter, ignition loss 3.91 g. A glass chopped strand mat (GM-1) was obtained.

The loss on ignition is a value measured according to “7.3.2 Loss on ignition” of JIS R3420 “General Test Method for Glass Fiber”.
The ignition loss is usually 90% or more, preferably 93% or more of the binder amount (% by weight) spread on the glass chopped strands. If the loss on ignition is lower than 90% of the amount of binder spread, there will be a lot of falling binder and the strength of the glass chopped strand mat will be insufficient. In order to eliminate this mat strength deficiency, it is necessary to increase the supply amount of the binder, resulting in an increase in cost during mat production.

Example 2 <Preparation of Glass Chopped Strand Mat (GM-2)>
A glass chopped strand mat (GM-) having a thickness of 1.2 mm, a mat unit weight of 449 g / m ² per square meter, and a loss on ignition of 3.93 g, except that the binder (A2-1) was used. 2) was obtained.

Example 3 <Preparation of Glass Chopped Strand Mat (GM-3)>
A glass chopped strand mat (GM-) having a thickness of 1.2 mm, a unit weight of the mat of 450 g / m ² per square meter, and an ignition loss of 3.91 g, except that the binder (A2-2) was used. 3) was obtained.

Example 4 <Preparation of Glass Chopped Strand Mat (GM-4)>
A glass chopped strand mat (GM-) having a thickness of 1.2 mm, a unit weight of the mat of 450 g / m ² per square meter, and an ignition loss of 3.97 g, except that the binder (A2-3) was used. 4) was obtained.

Example 5 <Preparation of Glass Chopped Strand Mat (GM-5)>
A glass chopped strand mat (GM-) having a thickness of 1.2 mm, a unit weight of the mat of 450 g / m ² per square meter, and an ignition loss of 3.87 g, except that the binder (A2-4) was used. 5) was obtained.

Comparative Example 1 <Preparation of Glass Chopped Strand Mat (GM'-1)>
A thickness of 1.2 mm, 1 in the same manner as in Example 1 except that the binder (A2′-1) was used.
A glass chopped strand mat (GM′-1) with a unit weight of 448 g / m ² g of the mat per square meter and an ignition loss of 3.55 g was obtained.

Comparative Example 2 <Production of Glass Chopped Strand Mat (GM'-2)>
A glass chopped strand mat (GM) having a thickness of 1.2 mm, a unit weight of the mat per square meter of 448 g / m ² , and a loss on ignition of 3.43 g, except that the binder (A2′-2) was used. '-2) was obtained.

The evaluation method in the present invention is as follows.
<Softening point>
Based on “6.4 softening point test method (ring and ball method)” of JIS K2207 “petroleum asphalt”, Tanaka Scientific Instruments Manufacturing Co., Ltd. automatic softening point tester ASP-5 was used.

<Tg>
In accordance with JIS K7121 “Plastic transition temperature measurement method”, the measurement was performed by RDC-220 manufactured by Seiko Instruments Inc.

<Volume average particle size and content of particles less than 100 μm>
It was measured with a Nikkiso Microtrac FRA particle size analyzer.

<Number average circularity>
Photographs were taken with a Keyence microscope VK-8500, and image analysis was performed with the attached shape analysis software VK-H1A7 manufactured by the same company, and the number average circularity was determined.
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.

<Amount of falling binder>
A value obtained by subtracting the loss on ignition of the glass chopped strand mats (GM-1) to (GM′-2) of Examples and Comparative Examples from the amount of the binder supplied to the glass chopped strands was defined as a falling binder amount (g).

Falling binder amount (g) = Binder supply amount-ignition loss

<Measurement of tensile strength of glass chopped strand mat>
Each of the glass chopped strand mats (GM-1) to (GM′-2) of Examples and Comparative Examples was cut into 350 mm × 65 mm to prepare 10 test pieces, and these were prepared as JIS R3420 “Glass Fiber General Test Method”. Of “7.4 Tensile Strength”. Table 1 shows the average value of 10 sheets and the difference between the maximum value and the minimum value.

<Flexibility of glass chopped strand mat>
Each of the glass chopped strand mats (GM-1) to (GM′-2) of Examples and Comparative Examples was cut into 2 cm × 15 cm to prepare 10 test pieces, and these were made according to JIS L1096 “General Textile Testing Method”. It was measured according to “8.19.1 Bending / softening A method (45 ° cantilever method)”. The bending resistance is represented by the length (mm) that the specimen moved, and Table 1 shows the average value of 10 sheets and the difference between the maximum value and the minimum value.

  As is apparent from Table 1, the glass chopped strand mat binders of Examples 1 to 5 of the present invention have a much smaller amount of dropped binder than the binders of Comparative Examples 1 and 2, and reduce the binder supply amount. You can see that Moreover, it turns out that the obtained glass chopped strand mat is excellent in strength (tensile strength) and flexibility (flexibility), and its variation is small.

  The glass chopped strand binder of the present invention provides a chopped strand mat excellent in later processing workability, so that the hulls of small ships such as canoes, boats, yachts and motor boats, bathtubs in ordinary houses, septic tanks, etc. It can be used effectively for plastic (FRP) molded products and is extremely useful.

Claims (7)

Spherical synthetic resin having a number average circularity of 0.8 to 1.0, a volume average particle diameter by laser diffraction scattering method of 100 to 400 μm, and a content of powder particles of less than 100 μm of 20% by weight or less A binder for glass chopped strand mats, comprising powder (A). The binder according to claim 1, wherein (A) has a softening point of 80 to 150 ° C by a ring and ball method. The binder according to claim 1 or 2, wherein (A) comprises a polyurethane resin (A1). The binder according to claim 1 or 2, wherein (A) comprises a polyester resin (A2) having a glass transition temperature of 40 to 60 ° C. Furthermore, the binder in any one of Claims 1-4 formed by containing the 1 type (s) or 2 or more types of additive (B) chosen from the group which consists of a blocking inhibitor, a hardening accelerator, and a flame retardant. A glass chopped strand mat obtained by bonding a glass chopped strand laminate with the binder according to claim 1. The binder according to any one of claims 1 to 5, 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