JP5198507B2 - Binder for glass chopped strand mat - Google Patents

Description

  The present invention relates to a powdery binder for glass chopped strand mats. More specifically, the mat strength (mechanical strength such as tensile strength, the same applies hereinafter) and mat quality (fiber adhesion on the front and back surfaces of the mat, the same applies hereinafter) are maintained even when the binder amount is reduced. It relates to a powdery binder for glass chopped strand mats.

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) Water is sprayed on the laminate.
(5) The binder powder is spread on the laminate, heated in an oven chamber to dry the moisture and melt the binder, then pressed with a press machine, and cooled and solidified to bond the glass chopped strands with a binder. A glass chopped strand mat is obtained.
As the binder here, conventionally, many unsaturated polyester resins pulverized by mechanical pulverization have been used (see, for example, Patent Documents 1 and 2). Since these particles have a too wide particle size distribution and are biased toward the coarse particles to be used as they are, the volume average particle size of 150 to 250 μm, which is usually most suitable for applying to a glass chopped strand mat after pulverization, is used. Sifted into powder. A powder having a volume average particle diameter in this range is usually obtained by using a sieve having a size of 250 to 355 μm.

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

However, mats using conventional binders do not sufficiently melt the binder when heated, and a large amount of unmelted binder remains, so that all of the binder sprayed on the glass chopped strand laminate contributes efficiently to glass fiber bonding. There was a problem of not doing.
As a solution to this, there is a method of further increasing the heating temperature. However, additional energy costs are required, and cooling solidification is not easy even when the binder is sufficiently melted, resulting in poor bonding between the glass chopped strands. There is a problem that the quality of the mat obtained is lowered. As a countermeasure, it is conceivable to reduce the mat production line speed for cooling and solidifying the binder, but there are industrial problems such as productivity. In addition, although a method using a binder with a low softening point is also mentioned, since a decrease in the softening point is usually accompanied by a decrease in the glass transition temperature, the machine grindability at the time of binder powder production deteriorates, resulting in an obstacle to productivity. In addition, blocking is likely to occur when the binder powder is stored, resulting in problems such as lack of storage stability.

  The object of the present invention is to provide excellent strength and quality without reducing the productivity of glass chopped strand mats, machine grindability during binder powder production, and storage stability of binder powder, and with less usage than conventional binders. It is providing the binder for glass chopped strand mats which can obtain the glass chopped strand mat which has this.

  The inventors of the present invention have reached the present invention as a result of intensive studies to achieve the above object. That is, the present invention contains a polyester resin (A) having an alkylene oxide adduct (a) and a dibasic acid (b) of a bisphenol compound as structural units and having a difference between the glass transition point and the softening point of 60 ° C. or less. It is a binder for glass chopped strand mats.

  The binder for glass chopped strand mats of the present invention can be melted and cooled and solidified smoothly and can save energy, and is less used than before without impairing the mechanical grindability and the storage stability of the binder during binder powder production. By the amount, the glass chopped strand mat has an effect that uniform and excellent mechanical strength and excellent mat quality (fiber adhesion on the front and back surfaces of the mat) can be imparted.

[Polyester resin (A)]
The polyester resin (A) in the present invention is composed of an alkylene oxide (hereinafter abbreviated as AO) adduct (a) and a dibasic acid (b) of a bisphenol compound, and has a glass transition point and a softening point (hereinafter, respectively). Difference between Tg and Tm) is 60 ° C. or less, preferably 50 ° C. or less, more preferably 45 ° C. or less. When the difference between Tg and Tm exceeds 60 ° C., the quality of the mat is lowered, and the balance between the mechanical grindability of (A) and the storage stability of the binder powder and the meltability of the binder is deteriorated.

  Here, Tg (° C.) is a numerical value obtained by differential thermal analysis (measurement conforms to JIS K7121, “Plastic Transition Temperature Measurement Method”), (A) mechanical grindability, storage stability of binder powder. From the viewpoint of the post-processability of the glass chopped strand mat described below, it is preferably 35 to 60 ° C, more preferably 40 to 58 ° C, and particularly preferably 45 to 55 ° C.

  Tm (° C.) is a numerical value obtained by the ring-and-ball method (measurement conforms to “6.4 softening point test method” of JIS K2207, “Petroleum Asphalt”), and prevents the glass chopped strand mat from exhibiting stickiness. From the viewpoint of the post-processing property of the mat and the binding property of the glass chopped strand laminate, the temperature is preferably 90 to 120 ° C, more preferably 95 to 105 ° C.

  Moreover, the melt viscosity at 150 ° C. of (A) is preferably 5 to 50 Pa · s, more preferably 7 to 45 Pa · s from the viewpoint of the bondability of the glass chopped strand laminate. Here, melt viscosity was measured based on JIS K7117 using an “RB-80H viscometer” and an H4 rotor [both manufactured by Toki Sangyo Co., Ltd.].

The AO adduct (a) of the bisphenol compound in the present invention is mainly composed of 1 mol of the AO adduct (a1) per each hydroxyl group of the bisphenol compound from the viewpoint of storage stability and melt viscosity of the polyester resin powder described later. (A) includes the following (a1) to (a3). Here, the main component means that the content based on the weight of (a) is 85% or more.
(A1) 1 mol of AO adduct per each hydroxyl group of bisphenol compound (a2) 2 mol or less of AO adduct per hydroxyl group of bisphenol compound [except for (a1)]
(A3) AO adduct exceeding 2 mol per hydroxyl group of bisphenol compound

  The content of each component based on the weight of (a) is 85% or more of (a1), the machine grindability of (A), the storage stability of the binder powder, and the uniform and excellent machine of the resulting glass chopped strand mat From the viewpoint of strength, it is preferably 92% or more, more preferably 95% or more, particularly preferably 98% or more; (a2) is 1% or less, preferably 0.8% or less, more preferably 0 from the same viewpoint as above. .5% or less, particularly preferably 0.2% or less; (a3) is 14% or less, preferably 7.2% or less, more preferably 4.5% or less, particularly preferably 1.% from the same viewpoint as described above. 8% or less.

The content of each component of (a1) to (a3) based on the weight of (a) can be measured, for example, under the following conditions by a liquid chromatography (LC) method.
<LC method measurement conditions>
LC system: LC-20AD [manufactured by Shimadzu Corporation]
Column: CAPCELL PAK C18 [made by Shiseido Co., Ltd., inner diameter 4.6 mm ×
Length 250mm]
Eluent: acetonitrile / water = 30/70 (vol%)
Flow rate: 1 ml / min
Detector: SPD-M20A [manufactured by Shimadzu Corporation]
Detection wavelength: 275 nm
Injection volume: 2 μl

As a bisphenol compound which comprises (a), carbon number (henceforth C) 12-23 (preferably 12-19, more preferably 12-15), for example, bisphenol A, -F, and -S are mentioned.
Among these, bisphenol A and -F are preferable from the viewpoint of compatibility with the matrix resin in the glass fiber reinforced plastic molded article described later.

AO constituting (a) includes C2-12 (preferably 2-4), such as ethylene oxide, 1,2-propylene oxide, 1,2-, 2,3- and 1,3-butylene oxide, tetrahydrofuran and 3-methyl-tetrahydrofuran (hereinafter abbreviated as EO, PO, BO, THF and MTHF), 1,3-propylene oxide, isoBO, C5-12 α-olefin oxide, substituted AO (styrene oxide, epihalohydrin, etc.) Can be mentioned.
Of these, a single AO such as EO or PO is preferable from the viewpoint of the machine grindability of (A) and the storage stability of the binder powder.

(A) can be produced by adding AO to a bisphenol compound in an aqueous medium in the presence of an alkaline catalyst.
The amount of the aqueous medium used is preferably 5 to 100%, more preferably 10 to 60% based on the weight of the bisphenol compound from the viewpoint of reducing by-products.
Alkaline metal catalysts [alkali metal (Na, K, Li, etc.) hydroxide (sodium hydroxide, potassium hydroxide, lithium hydroxide, etc.), alkali metal (Na, K, Li, etc.) alcoholate (C1 2, eg sodium methylate, potassium methylate), metallic sodium etc.], amine catalyst (C3-15, eg trimethylamine, triethylamine, tributylamine), tetraalkyl (C4-12 alkyl group) ammonium hydroxide (tetramethylammonium And the like). Of these, alkali metal catalysts are preferable from the viewpoint of reducing by-products, more preferable are sodium hydroxide, potassium hydroxide, and lithium hydroxide, and particularly preferable are sodium hydroxide and lithium hydroxide.

The usage-amount of an alkaline catalyst is 0.05-20% normally based on the weight of a bisphenol compound, Preferably it is 0.1-10%.
As a method of adding AO to a bisphenol compound, a bisphenol compound, an aqueous medium and an alkaline catalyst are charged into an autoclave reaction vessel, the inside of the reaction vessel is replaced with nitrogen, the temperature is raised to a predetermined temperature while stirring, and AO is dropped. The method of making it react on normal pressure or pressurization (normally 0.5 Mpa or less) conditions, charging gradually, etc. is mentioned.
The reaction temperature is preferably 60 to 120 ° C., more preferably 60 to 110 ° C. from the viewpoint of productivity and reduction of by-products, and the reaction time is usually 2 to 8 hours.

The AO adduct (a) of a bisphenol compound in the present invention can be usually produced by the following procedure.
(1) In the presence of an alkaline catalyst, 1.5 to 2 mol of AO is added dropwise to 1 mol of a bisphenol compound, and then reacted for 1 to 2 hours. Thereafter, partial neutralization (preferably 20 to 99 mol%, more preferably 40 to 90 mol%) of the alkaline catalyst is performed. Examples of the acid used for neutralization include inorganic acids (phosphoric acid, hydrochloric acid, sulfuric acid, etc.) or organic acids (acetic acid, lactic acid, maleic acid, paratoluenesulfonic acid, etc.).
(2) After partial neutralization, an additional amount of AO in which the total AO dropping amount from (1) is 2 to 2.8 (preferably 2.2 to 2.6) mol is further added dropwise, and then 1 React for ~ 2 hours.
(3) Sampling is performed, and the contents of (a1) to (a3) are measured by the LC method, and it is confirmed that (a1) is a main component. The procedure (3) may be performed after the AO addition reaction in the procedure (1) as necessary.
(4) After the above confirmation, the aqueous medium is separated and removed, further washed with water, treated with an adsorbent and filtered, and then dehydrated to obtain (a).

  As the dibasic acid (b) in the present invention, aliphatic dibasic acid (C3-30, such as succinic acid, maleic acid, glutaric acid, fumaric acid, adipic acid, azelaic acid, sebacic acid), aromatic dibasic acid (C8-30, such as phthalic acid, isophthalic acid, terephthalic acid, tetrabromophthalic acid, tetrachlorophthalic acid), alicyclic dibasic acid (C6-50, such as 1,3-cyclobutanedicarboxylic acid, 1,3- Cyclopentanedicarboxylic acid, 1,2- and 1,4-cyclohexanedicarboxylic acid, 1,3- and 1,4-dicarboxymethylcyclohexane, dicyclohexyl-4,4′-dicarboxylic acid and dimer acid); Ester-forming derivatives of acids [acid anhydrides (eg maleic anhydride, phthalic anhydride, etc.), lower alkyl (C1-4) ester (Dimethyl ester, diethyl ester, etc.) (e.g., dimethyl terephthalate), such as an acid halide (acid chloride, etc.)]; and mixtures of two or more thereof. Of these, aliphatic dibasic acids are preferable from the viewpoint of preventing coloring of the polyester resin (A).

The polyester resin (A) is produced by the polycondensation reaction of the above (a) and (b). The reaction temperature during the polycondensation is not particularly limited, but is usually 100 to 300 ° C, preferably 130 to 220 ° C. The polycondensation reaction is usually performed under 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 (carboxyl group / hydroxyl group equivalent ratio) of (a) and (b) during the polycondensation is preferably 0.9 from the viewpoint of rapid polycondensation reaction and stability of physical properties of the resulting polyester resin. / 1 to 1.4 / 1, more preferably 0.9 / 1 to 1.2 / 1.
The acid value of the polyester resin (A) (unit is mgKOH / g. In the following, only numerical values are shown) 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.
Among these, preferred from the viewpoint of reactivity is more preferred from the viewpoint of low colorability of carboxylic acid (C2-4) salts, oxides, alkoxides, and products of 2B, 4A, 4B, 5A and 5B metals. Are antimony trioxide, mono- and dibutyltin oxide, tetrabutyl titanate, tetrabutoxy titanate, tetrabutyl zirconate, zirconyl acetate, zinc acetate.
The amount of the esterification catalyst used is not particularly limited as long as a desired molecular weight can be obtained, but is preferably from the viewpoint of reactivity and low coloring based on the total weight of (a) and (b). 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 usually 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).

  Weight average molecular weight and number average molecular weight of the polyester resin (A) [hereinafter abbreviated as Mw and Mn, respectively. All measurements are performed by gel permeation chromatography (GPC). ] Is preferably 5,000 to 30,000, more preferably 6,500 to 28,000, particularly preferably 7, from the viewpoint of the mechanical strength of the glass chopped strand mat, the meltability of the binder, and the mechanical grindability. 000 to 25,000, Mn is preferably 2,000 to 4,000, more preferably 2,500 to 3,500.

[Binder for glass chopped strand mat]
The binder for glass chopped strand mats of the present invention comprises the polyester resin (A) powder. Although it does not specifically limit as a manufacturing method of this (A) powder, From the industrial viewpoint, the manufacturing method by mechanical grinding | pulverization is preferable.

[Additive (D)]
If necessary, the binder of the present invention can be used in combination with at least one additive (D) selected from the group consisting of an antiblocking agent (D1), a lubricant (D2) and a hydrophilicity imparting agent (D3). The additive (D) may be added before the pulverization after the production of the polyester resin (A), or may be added after the pulverization.
The total amount of (D) used is usually 8% or less, preferably 0.01 to 5%, more preferably 0.1 to 3% based on the weight of (A).

Examples of the anti-blocking agent (D1) 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, for example, lauric acid, stearic acid; as salts of higher fatty acids, alkali metals (Na, K, Li, etc.) and alkaline earth metals (Ca, Ba, Mg, etc.) of the above higher fatty acids , Zn, Cu, Ni, Co, Al, etc .; silicon or metal oxides include silicon dioxide, silicon oxide, aluminum oxide, iron oxide, titanium oxide, magnesium oxide, zirconium oxide, etc .; Examples of carbides include silicon carbide and aluminum carbide; examples of organic resins include polyolefin resin, polyamide resin, poly (meth) acrylic resin, silicon resin, polyurethane resin, phenol resin, polytetrafluoroethylene resin, and cellulose powder. It is done.
Of these, metal salts of higher fatty acids and silicon or metal oxides are preferable from the viewpoint of powder flowability.

  The amount of (D1) used is usually 5% or less based on the weight of (A), preferably from 0.01 to 2%, more preferably from the viewpoint of preventing binder blocking and binding to glass fibers. ~ 1%.

Examples of the lubricant (D2) 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, stearyl alcohol; As the higher fatty acid ester, C10-36, for example, Butyl stearate, polyvalent (2-4) alcohol AO (C2-3) adduct ester of higher fatty acid (C10-24) [for example, monostearate of EO 5 mol adduct of ethylene glycol (hereinafter abbreviated as EG)]; The higher fatty acid amide includes C10-40, such as stearic acid amide.
Among these, from the viewpoint of the bonding property with glass fiber, polyhydric (2-4) alcohol AO (C2-3) adduct esters of higher fatty acids (C10-24) and higher fatty acid amides are preferred.

  The amount of (D2) used is usually 5% or less based on the weight of (A), preferably from 0.01 to 2%, more preferably from the viewpoint of powder flowability and binding to glass fibers. ~ 1%.

As the hydrophilicity imparting agent (D3), 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 salt-containing (meth) acryloyl group-containing polymer, and the like.
Of these, PEG and PEG chain-containing organopolysiloxane are preferred from the viewpoint of bonding with glass fibers.

  The amount of (D3) used is usually 5% or less based on the weight of (A), and is preferably 0 from the viewpoint of hydrophilicity with water sprayed onto the glass chopped strand laminate described below and binding properties with glass fibers. 0.01-2%, more preferably 0.1-1%.

[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 a polyester resin (A) powder, 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) After spraying tap water, which is approximately half the weight of the spread glass chopped strands, with a spray (water spraying operation) so that the surface of the laminate is sufficiently wet, the laminate is turned upside down.
(3) A predetermined amount of a glass chopped strand mat binder is sprayed on the laminate and uniformly adhered.
(4) The water spraying operation of (2) is performed once more, and a predetermined amount of the binder is sprayed on the laminated body and uniformly adhered.
(5) The operation of the above (4) is repeated 0 to 2 times or more to obtain a laminate having a binder attached thereto.
(6) The obtained laminate is placed in a circulating dryer at 200 ° C. to remove moisture.
(7) A glass chopped strand mat bonded with a binder is obtained by pressing with a press adjusted to room temperature to 45 ° C.

  The binding amount of the binder based on the weight of the glass chopped strand laminate is preferably 1 to 30%, more preferably 2 to 25%, and particularly preferably 3 to 20% from the viewpoint of the mechanical strength and handling properties of the mat.

The weight (g / m ² ) of the glass chopped strand mat obtained after the step (7) is preferably 50 to 1,000, more preferably 75 to 900, particularly preferably from the viewpoint of the mechanical strength and handling properties of the mat. Is 100-500.

  The uniformity of the mechanical strength of the glass chopped strand mat is indicated by the small difference between the maximum and minimum values of tensile strength, and the difference between the maximum and minimum values of tensile strength indicates the handling properties of the mat. From the viewpoint, it is preferably 40N or less, more preferably 35N or less, particularly preferably 30N or less. 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.

  Whether or not the glass chopped strand mat of the present invention has excellent mechanical strength with a smaller amount of use than the conventional binder is indicated by, for example, the tensile strength per ignition loss (% by weight) described later. The tensile strength per ignition loss (% by weight) is preferably 40 N or more, more preferably 45 N or more, and particularly preferably 50 N or more.

[Glass fiber reinforced plastic molded products]
The molding method of the glass fiber reinforced plastic molded article of the present invention is not particularly limited, and examples thereof include a hand lay-up method, a spray-up method, a preform method, a matched die method, and an SMC method. Among these, for example, the hand lay-up method is usually performed in the following procedure.
(1) A release agent is applied to the surface of the mold.
(2) Use a roller or the like at room temperature (15 to 25 ° C.) so as to obtain a uniform thickness.
Apply unsaturated polyester resin.
(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 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.

The matrix resin used in the molding method including the hand lay-up method is 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 from the viewpoint of workability during molding, unsaturated polyester resins and vinyl ester resins are preferable.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these. In the following, parts and% represent parts by weight and% by weight, respectively.
Moreover, (a1)-(a3) shall mean the following.
(A1): 1 mol of AO adduct per each hydroxyl group of bisphenol compound (a2): 2 mol or less of AO adduct per hydroxyl group of bisphenol compound [provided that (a1) is excluded)
]
(A3): AO adduct of more than 2 mol per hydroxyl group of bisphenol compound

Production Example 1 <Production of Binder (X-1)>
(1) Manufacture of EO adduct (a-1) of bisphenol A 228 parts (1 mol) of bisphenol A and 228 parts of water were charged into a glass autoclave equipped with a dropping and stirring device, and after substitution with nitrogen, 90 The temperature was raised to 0 ° C., and bisphenol A was dispersed in water. To this, 3 parts of sodium hydroxide was added, nitrogen substitution was performed again, and 88 parts (2 mol) of EO was added dropwise over about 4 hours, and reacted at 90 ° C. and a pressure of 0.2 MPa or less.
One hour after the completion of the dropping, 1.4 parts of phosphoric acid was added to neutralize part of the sodium hydroxide, and 22 parts (0.5 mol) of EO was further added dropwise over about 2 hours. The reaction was performed at a pressure of 0.2 MPa or less. One hour after the completion of the additional dropping, the content based on the total weight of (a1), (a2), and (a3) in the contents was confirmed, and (a1) 95%, (a2) 0.5%, (A3) 4.5%. The content was measured according to the LC method (hereinafter the same).
The product was heated to 90 ° C. to remove the aqueous phase. Further, 300 parts of water was added and stirred at 90 ° C. for 1 hour, and then the aqueous phase containing by-products (EG, diethylene glycol, etc.) was separated and removed. Adsorbent [trade name “KYOWARD 600”, manufactured by Kyowa Chemical Industry Co., Ltd. same as below. 120 parts were added, and the mixture was stirred for 1 hour and filtered. The filtrate was dehydrated under reduced pressure at 130 ° C. and 1.3 kPa for 2 hours to obtain an EO adduct (a-1) of bisphenol A. The hydroxyl value of (a-1) (unit is mgKOH / g. Only numerical values are shown below) was 353.

(2) Production of polyester resin (A1) (a-1) 3,365 parts, fumaric acid 1,123 parts, dibutyltin oxide 6 in a reaction vessel equipped with a cooling tube, a stirring bar, a thermometer and a nitrogen introduction tube The polyester resin (A1) was obtained by charging the reaction solution at 180 ° C. in a nitrogen atmosphere for 6 hours.

(3) Manufacture of polyester resin powder (A1-1) (A1) 100 parts of sample mill [device 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 was sieved with a sieve having an opening of 355 μm to obtain a polyester resin powder (A1-1) that passed through the sieve.

(4) Production of binder (X-1) (A1-1) 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 EO adduct (a-2) of bisphenol A In (1) of Production Example 1, instead of 88 parts (2 moles) of EO, 79.2 parts (1.8 moles) of EO were used, and 22 parts of additional EO were added. Except that 8.8 parts (0.2 mol) of EO was used instead of (0.5 mol), it was carried out in the same manner as (1) of Production Example 1, and the EO adduct (a-2) of bisphenol A was obtained. Obtained. The hydroxyl value of (a-2) was 355, and the contents of (a1) to (a3) in (a-2) were (a1) 100%, (a2) 0%, and (a3) 0%. .

(2) Production of polyester resin (A2) Production Example 1 except that (a-2) 3,346 parts were used instead of (a-1) 3,365 parts in Production Example 1 (2). A polyester resin (A2) was obtained in the same manner as (2).

(3) Manufacture of polyester resin powder (A2-1) In (3) of manufacture example 1, it replaced with 100 parts of polyester resin (A1), and used 100 parts of polyester resin (A2). A polyester resin powder (A2-1) was obtained in the same manner as 3).

(4) Manufacture of binder (X-2) (A2-1) After adding 0.03 part of antiblocking agents to 10 parts, it mixed and obtained binder (X-2).

Production Example 3 <Production of Binder (X-3)>
(1) Production of EO Adduct (a-3) of Bisphenol A In (1) of Production Example 1, 79.2 parts (1.8 mol) of EO was used instead of 88 parts (2 mol) of EO, and additional EO22 EO adduct of bisphenol A (a-3), except that 35.2 parts (0.8 mol) of EO was used instead of 0.5 parts (0.5 mol). Got. The hydroxyl value of (a-3) is 352, and the contents of (a1) to (a3) in (a-3) are (a1) 92%, (a2) 0.8%, (a3) 7.2. %Met.

(2) Production of polyester resin (A3) In Production Example 1 (2), Production Example 1 except that (a-3) 3,375 parts were used instead of (a-1) 3,365 parts. A polyester resin (A3) was obtained in the same manner as (2).

(3) Production of polyester resin powder (A3-1) Production method 1 (3) except that 100 parts of polyester resin (A3) was used instead of 100 parts of polyester resin (A1) in Production Example 1 (3). A polyester resin powder (A3-1) was obtained in the same manner as 3).

(4) Manufacture of binder (X-3) (A3-1) 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 EO adduct (a-4) of bisphenol A In (1) of Production Example 1, instead of 88 parts (2 moles) of EO, 66 parts (1.5 moles) of EO, 22 parts of additional EO ( EO adduct (a-4) of bisphenol A was obtained in the same manner as in (1) of Production Example 1 except that 57.2 parts (1.3 mol) of EO was used instead of 0.5 mol). It was. The hydroxyl value of (a-4) was 350, and the contents of (a1) to (a3) in (a-4) were (a1) 85%, (a2) 1%, and (a3) 14%. .

(2) Manufacture of polyester resin (A4) In (2) of Production Example 1, (a-4) 3,394 parts were used instead of (a-1) 3,365 parts. A polyester resin (A4) was obtained in the same manner as (2).

(3) Production of polyester resin powder (A4-1) Production Example 1 (3) except that 100 parts of polyester resin (A4) was used instead of 100 parts of polyester resin (A1) in Production Example 1 (3). A polyester resin powder (A4-1) was obtained in the same manner as 3).

(4) Manufacture of binder (X-4) (A4-1) 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) Production of PO adduct (a-5) of bisphenol A In (1) of Production Example 1, PO 116 parts (2 mol) was added dropwise instead of EO 88 parts (2 mol), and the addition was completed for 2 hours. Later, 1.4 parts of phosphoric acid was added to neutralize part of the sodium hydroxide, and 46.4 parts (0.8 moles) of PO were added dropwise instead of 22 parts (0.5 moles) of additional EO. Except having been made, it carried out similarly to (1) of manufacture example 1. Two hours after the completion of the additional dropping, the content based on the total weight of (a1), (a2), and (a3) in the contents was confirmed, and (a1) 90%, (a2) 1%, (a3 ) 9%. Further, in the same manner as in Production Example 1 (1), the filtrate after the adsorbent addition treatment was dehydrated under reduced pressure at 100 ° C. and 1.3 kPa for 2 hours to obtain a bisphenol A PO adduct (a-5). The hydroxyl value of (a-5) was 322.

(2) Production of Polyester Resin (A5) In Production Example 1 (2), (a-5) 3,689 parts were used instead of (a-1) 3,365 parts, and a nitrogen atmosphere was used at 180 ° C. After making it react for time, it heated up to 200 degreeC and obtained the polyester resin (A5) like (2) of manufacture example 1 except having made it react under reduced pressure of 3-4 kPa for 5 hours.

(3) Production of Polyester Resin Powder (A5-1) Production Example 1 (3) except that 100 parts of polyester resin (A5) was used instead of 100 parts of polyester resin (A1) in Production Example 1 (3). A polyester resin powder (A5-1) was obtained in the same manner as 3).

(4) Manufacture of binder (X-5) (A5-1) After adding 0.03 part of antiblocking agents to 10 parts, it mixed, and binder (X-5) was obtained.

Production Example 6 <Production of Binder (X-6)>
(1) Production of polyester resin (A6) In Production Example 1 (2), (a-2) 3,346 parts were used instead of (a-1) 3,365 parts, and at 180 ° C. in a nitrogen atmosphere, A polyester resin (A6) was obtained in the same manner as in Production Example 1 (2) except that the reaction was performed for 3 hours.

(2) Production of Polyester Resin Powder (A6-1) Production Example 1 (3) except that 100 parts of polyester resin (A6) was used instead of 100 parts of polyester resin (A1) in Production Example 1 (3). A polyester resin powder (A6-1) was obtained in the same manner as 3).

(3) Manufacture of binder (X-6) (A6-1) After adding 0.03 part of antiblocking agents to 10 parts, it mixed and obtained binder (X-6).

Comparative Production Example 1 <Production of Binder (X'-1)>
(1) Production of EO adduct (a′-1) of bisphenol A In Production Example 1, (1), except that EO 220 parts (5 mol) were used instead of the additional EO 22 parts (0.5 mol). Was carried out in the same manner as in Production Example 1 (1) to obtain an EO adduct (a′-1) of bisphenol A. The hydroxyl value of (a′-1) is 345, and the contents of (a1) to (a3) in (a′-1) are (a1) 74.5%, (a2) 0.5%, (a3 ) 25%.

(2) Production of Polyester Resin (A′1) In Production Example 1 (2), (a′-1) 3,443 parts were used instead of (a-1) 3,365 parts, and 180 ° in a nitrogen atmosphere. The polyester resin (A′1) was treated in the same manner as in Production Example 1 (2) except that the reaction was performed at 5 ° C. for 5 hours, the temperature was raised to 200 ° C., and the reaction was performed for 5 hours under reduced pressure of 3 to 4 kPa. Obtained.

(3) Manufacture of polyester resin powder (A'1-1) Manufacture except having used 100 parts of polyester resin (A'1) instead of 100 parts of polyester resin (A1) in manufacture example 1 (3). A polyester resin powder (A′1-1) was obtained in the same manner as in Example 1 (3).

(4) Manufacture of binder (X'-1) After adding 0.03 part of antiblocking agents to 10 parts of (A'1-1), it mixed, and binder (X'-1) was obtained.

Comparative Production Example 2 <Production of Binder (X'-2)>
(1) Production of EO adduct (a′-2) of bisphenol A In (1) of Production Example 1, EO 308 parts (7 mol) was used instead of EO 88 parts (2 mol), and additional EO was added dropwise. Except that it was not, it was carried out in the same manner as (1) of Production Example 1 to obtain an EO adduct (a′-2) of bisphenol A. The hydroxyl value of (a′-2) is 358, and the contents of (a1) to (a3) in (a′-2) are (a1) 60%, (a2) 20%, and (a3) 20%. there were.

(2) Manufacture of polyester resin (A'2) In (2) of manufacture example 1, (a'-2) 3,318 parts are used instead of (a-1) 3,365 parts, and it is 180 in nitrogen atmosphere. The polyester resin (A′2) was treated in the same manner as in Production Example 1 (2) except that the reaction was carried out at 5 ° C. for 5 hours, the temperature was raised to 200 ° C., and the reaction was carried out under reduced pressure of 3-4 kPa for 4 hours. Obtained.

(3) Production of polyester resin powder (A′2-1) Production Example 1 except that polyester resin (A′2) was used in place of 100 parts of polyester resin (A1) in Production Example 1 (3). A polyester resin powder (A′2-1) was obtained in the same manner as (3).

(4) Production of binder (X′-2) 0.03 part of an antiblocking agent was added to 10 parts of (A′2-1), and then mixed to obtain a binder (X′-2).

  Acid values, Mw, Mn, Tm, Tg, melt viscosity at 150 ° C., mechanical grindability, and binder of the polyester resins (A1) to (A6) and (A′1) to (A′2) obtained above The results of storage stability of (X-1) to (X-6) and (X′-1) to (X′-2) are shown in Table 1.

Example 1 <Preparation of Glass Chopped Strand Mat (GM-1)>
A glass strand for glass chopped strand (average strand count: 30 tex, glass fiber density: 2.5 g / cm 3) is cut into a length of about 5 cm using a glass chopper manufactured by Togiken Co., Ltd. Got.
135.0 g of the glass chopped strand is sprayed in a directionally disordered uniform thickness into a 75 × 40 × 3 cm flat plate mold subjected to the mold release treatment, and then the surface of the laminated body of the glass chopped strand is moistened. After spraying tap water (about 68 g) by spraying to the extent, the laminate was turned upside down.
Next, 2.03 g of binder (X-1) corresponding to 1.5% of the weight of the dispersed glass chopped strands was uniformly dispersed on the glass chopped strand laminate.
Further, about 68 g of tap water was sprayed thereon, and then 2.03 g of binder (X-1) was sprayed uniformly. Thereafter, the binder is melted in a circulating dryer at 200 ° C. for 2 minutes and further pressed at a speed of 20 m / min with a roll type press machine (clearance between rolls 200 μm, pressure 0.2 MPa) adjusted to 45 ° C. Thus, the thickness is 0.69 mm, the basis weight of the mat (the amount of glass chopped strand used for the mat per 1 m ² , the same applies hereinafter), 450 g / m ² , loss on ignition (measurement method will be described later) 2.90% Glass chopped strand mat (GM-1) was obtained.

Examples 2-6, Comparative Examples 1-2
According to Table 1, each glass chopped strand mat (GM-2) to (GM-6), (GM ′) having a basis weight of 450 g / m ² was used in the same manner as in Example 1 except that the binder usage was changed. -1) to (GM′-2) were obtained. The thickness of each mat is shown in Table 1.

<Evaluation items>
The following items were evaluated and the results are shown in Table 1.
[Evaluation of polyester resin]
(1) Softening point (Tm) (° C)
Based on JIS K2207, “6.4 Softening Point Test Method (Ring and Ball Method)” of “Petroleum Asphalt”, using an automatic softening point tester [device name “ASP-5”, manufactured by Tanaka Scientific Instruments Manufacturing Co., Ltd.] It was measured.
(2) Glass transition point (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) Melt viscosity at 150 ° C. (Pa · s)
The measurement method is as described above.
(4) Machine grindability 100 parts of polyester resin was ground for 5 minutes at a rotation speed of 10,000 rpm using a sample mill. The obtained resin powder was sieved with a sieve having an opening of 355 μm, and the weight of the polyester resin powder that passed through the sieve was measured and evaluated according to the following criteria.
<Evaluation criteria>

○ 50 parts or more △ 30 parts or more and less than 50 parts × less than 30 parts

(5) Storage stability 100 parts of binder powder is placed in a 300 ml graduated cylinder (inner diameter 40 mm), and a 100 g cylindrical weight slightly smaller than the inner diameter of the graduated cylinder is placed on the powder and placed in a constant temperature bath at 45 ° C. After heating for 1 hour, the weight was removed, the measuring cylinder was tilted, and the blocking resistance of the binder powder was evaluated according to the following criteria.
<Evaluation criteria>

○ Easily flows and has excellent blocking resistance.
Δ Slightly lacking fluidity and partially blocking.
X Blocking is recognized as a whole without fluidity.

[Evaluation of glass chopped strand mat]
(1) Loss on ignition of mat (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. . The specific measurement 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] The empty magnetic crucible without a test piece is dried at 105 ° C. for 30 minutes, then allowed to cool to room temperature in a desiccator, and the weight (m0) is measured to the nearest 0.1 mg.
[3] The ignition loss is calculated from the following formula.

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

(2) Tensile strength of mat (N)
Ten test pieces each having a width of 50 mm and a length of 150 mm were cut out from each glass chopped strand mat, and these were measured in accordance with “7.4 Tensile Strength” of JIS R3420 “Glass Fiber General Test Method”. The average value of 10 test pieces was taken as the tensile strength of the glass chopped strand mat. In addition, the adhesion amount of the binder was calculated | required by the ignition loss of said (3). Specifically, the tensile strength was measured by the following procedure.
(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 10 mm.
(Iii) 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. .

<Evaluation criteria>
[1] Average value of tensile strength The average value of the tensile strength of 10 test pieces was obtained and evaluated according to the following criteria.
<Evaluation criteria>

○ 130N or more △ 100N or more and less than 130N × less than 100N

[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.
<Evaluation criteria>

○ 40N or less △ More than 40N 80N or less × More than 80N

[3] Tensile strength per ignition loss (% by weight) The average tensile strength of 10 test pieces was divided by the ignition loss (% by weight) and evaluated according to the following criteria.
<Evaluation criteria>

○ 40N or more △ 30N or more and less than 40N × less than 30N

(3) Pencil hardness of mat front and back (Evaluation of fiber adhesion)
The pencil hardness was measured in accordance with JIS K5600, a scratch test was performed by applying a load from directly above the pencil fixed at 45 degrees, and the degree of glass fiber falling (fiber adhesion) was evaluated according to the following criteria.
<Evaluation criteria>

4B 4B pencil does not drop fibers, 3B pencil does not drop fibers 5B 5B pencil does not drop fibers 4B pencil causes fibers to drop 6B 6B pencil In this case, the fiber does not fall off, but the 5B pencil causes the fiber to fall off. × 6B or more pencil causes the fiber to fall off.

  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)

Glass chopped strand mat comprising a polyester resin (A) having an alkylene oxide adduct (a) and a dibasic acid (b) of a bisphenol compound as structural units and having a difference between the glass transition point and the softening point of 60 ° C. or less. Binder. The binder according to claim 1, wherein (a) contains 85% by weight or more of 1 mol of alkylene oxide adduct (a1) per each hydroxyl group of the bisphenol compound. The binder according to claim 1 or 2, wherein the glass transition point of (A) is 40 to 60 ° C. The softening point of (A) is 90-120 degreeC, The binder in any one of Claims 1-3. The binder according to claim 1, wherein (A) has a melt viscosity at 150 ° C. of 5 to 50 Pa · s. A glass chopped strand mat obtained by bonding a glass chopped strand laminate with the binder according to claim 1. A glass fiber reinforced plastic molded product obtained by molding the mat according to claim 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. In the method of manufacturing the glass chopped strand mat by press-molding after heating the glass chopped strand laminated body formed through the process which consists of glass chopped strand dispersion | spreading, water dispersion | distribution, and binder dispersion | distribution, Any one of Claims 1-5 A method for producing a glass chopped strand mat, characterized by using a binder.