JP4454481B2 - Glass fiber and glass fiber reinforced acrylonitrile / butadiene / styrene copolymer resin molding using the same - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a reinforcing glass fiber provided with a sizing agent including a urethane resin and an acrylonitrile / styrene copolymer resin, and a resin molded body reinforced by the glass fiber, and in particular, a resin molding of a warm water washing toilet seat The present invention relates to a material that can be suitably used for products.

  Conventionally, glass fiber reinforced acrylonitrile / butadiene / styrene copolymer resin (GFR-ABS resin) in which acrylonitrile / butadiene / styrene copolymer resin (ABS resin) is reinforced with glass fiber is the mechanical strength of ABS resin. In addition to formability and surface appearance, it is widely used because of its excellent mechanical strength by strengthening with glass fiber.

  As a method for molding this GFR-ABS resin, a method of melting and kneading a glass fiber chopped strand (CS) and a thermoplastic resin into a pellet and then injection-molding it is generally used. It is finely cut and the reinforcing effect by the fibers is not sufficient.

  Therefore, a method is adopted in which a glass fiber and a thermoplastic resin dry blended are directly supplied to an injection molding machine to obtain a GFR-ABS resin molded product so that the glass fiber is not cut as finely as possible by injection molding. In this molding method, in particular, a sizing agent is attached to the surface of the glass fiber in order to improve the appearance of the molded body and to prevent so-called fluffing that the glass fiber becomes cottony.

  Even in the case of GFR-ABS resin, similar to the reinforced fiber resin using other resins, the mechanical strength is greatly different due to the effect of interfacial adhesion between the glass and the resin. The selection of the agent becomes extremely important.

  For example, Patent Document 1 proposes that 50 to 1 part by weight of glass fiber treated with an epoxy-based, urethane-based, or acrylic-based sizing agent is added as a sizing agent to a thermoplastic resin.

  Further, in Patent Document 2, when reinforcing a matrix resin of acrylonitrile / styrene copolymer resin (AS resin) and ABS resin with glass fiber, AS resin or ABS resin and urethane resin are used as a glass fiber sizing agent. It is described that the mechanical strength of the fiber-reinforced resin body is large and the glass fiber is less fuzzy by using.

In Patent Document 3, an epoxy resin having an epoxy equivalent of 900 or more, an AS resin, and a silane coupling agent are used as a sizing agent, so that the glass fiber has excellent sizing property, and the molded product has hue and mechanical strength. It is described that it is excellent.
Japanese Patent Laid-Open No. 10-316832 Japanese Patent Publication No. 5-4349 JP 7-33484 A

  In a molded product obtained by dry blending a bundle of glass fibers using a sizing agent described in the above document with an ABS resin and directly molding it with an injection molding machine, the bundled glass fibers are undissolved. The glass fibers were not finely dispersed and the glass fibers were undispersed, and the undispersed portions of the glass fibers were exposed on the surface, resulting in poor surface appearance and surface smoothness. Therefore, when glass fiber non-dispersion occurs on the surface of the molded product seal part, etc., the unevenness of the molded product surface caused by the above problem causes a gap at the joint part with other members, and water leakage is likely to occur. Is desired.

  Therefore, the object of the present invention is to improve the defibration property of the bundled glass fibers by dry blending the bundled glass fibers with the ABS resin and directly forming the glass fibers by an injection molding machine. To provide a glass fiber capable of obtaining a molded article having excellent mechanical strength, excellent surface appearance, and excellent surface smoothness as a molded article, and a molded article using the same. is there.

The above object is achieved by the present invention described below. That is, the present invention has the following gist.
(1) A glass fiber to which a sizing agent containing a urethane resin and an acrylonitrile / styrene copolymer resin is applied, wherein the urethane resin has a softening temperature of 100 ° C. or less.
(2) Glass fiber as described in (1) whose acrylonitrile styrene copolymer resin is 30-300 mass parts with respect to 100 mass parts of urethane resin in the said sizing agent.
(3) Glass fiber as described in (2) whose acrylonitrile styrene copolymer resin is 40-120 mass parts with respect to 100 mass parts of urethane resins in the said sizing agent. (4) The glass fiber according to any one of (1) to (3), wherein the acrylonitrile / styrene copolymer resin is non-crosslinked.
(5) The glass fiber according to any one of (1) to (4), wherein the sizing agent is 0.5 to 2.0 parts by mass with respect to 100 parts by mass of the glass fiber.
(6) A glass fiber reinforced acrylonitrile / butadiene / styrene copolymer resin comprising the glass fiber according to (1) to (5) and an acrylonitrile / butadiene / styrene copolymer resin, wherein the acrylonitrile / butadiene / styrene resin is used. Glass fiber reinforced acrylonitrile / butadiene / styrene copolymer obtained by dry blending the glass fiber to 5 to 250 parts by mass with respect to 100 parts by mass of the copolymer resin and directly molding by an injection molding machine. Polymer resin molding. (7) A glass fiber reinforced acrylonitrile / butadiene / styrene copolymer resin comprising the glass fiber according to (1) to (5) and an acrylonitrile / butadiene / styrene copolymer resin, the acrylonitrile / butadiene / styrene resin. The glass fiber is dry blended so that the glass fiber is 5 to 250 parts by mass and the additive selected from metal soap, fatty acid esters and polyethylene glycol is 1 to 10 parts by mass with respect to 100 parts by mass of the copolymer resin. A glass fiber reinforced acrylonitrile / butadiene / styrene copolymer resin molding obtained by direct molding using an injection molding machine.

The glass fiber of the present invention contains a urethane resin and an acrylonitrile / styrene copolymer resin as a sizing agent.
By using the urethane resin, it is suitable for preventing fluff of glass fibers, and particularly for preventing fluff of chopped strands obtained by cutting glass fibers to a specific length.

  The softening temperature of the urethane resin in the sizing agent is important, and the softening temperature is 100 ° C. or lower, preferably 50 to 90 ° C. When the softening temperature exceeds 100 ° C., a glass fiber reinforced acrylonitrile / butadiene / styrene copolymer resin molded article obtained by using glass fiber and matrix resin as acrylonitrile / butadiene / styrene copolymer resin (ABS resin) ( In the GFR-ABS resin molded body), many glass lumps in which the bundled glass fibers are undispersed are present, and the surface appearance of the molded body is inferior. In particular, in the case of so-called direct molding in which the chopped strand obtained by cutting the glass fiber to a specific length and an ABS resin are dry blended and directly molded by an injection molding machine, the non-dispersion becomes remarkable and the surface appearance is inferior. It is not preferable.

  According to the knowledge of the present inventor, by setting the softening temperature of the urethane resin to 100 ° C. or less, the heating of 180 to 240 ° C., which is the molding temperature of the acrylonitrile / butadiene / styrene copolymer resin, is effective for the bundled glass fibers. It is presumed that the bundled glass fibers are defibrated in the process of melting and kneading the urethane resin as a sizing agent immediately after the introduction of the hopper, and the undispersion is greatly reduced.

The urethane resin is not particularly limited as long as the softening temperature is 100 ° C. or less. In the present invention, the polyurethane resin is composed of a polymer polyol, an organic diisocyanate, and optionally a chain extender and / or a crosslinking agent. Conventionally known ones derived from can be used. The urethane resin is usually used as an aqueous solution such as an emulsion or a dispersion, or an aqueous dispersion.
The softening temperature here refers to a film formed from the sizing agent, measured by a flow tester, and the flow start temperature as the softening temperature.

  Specific examples of the polymer polyol include, for example, polyester polyol (for example, polyethylene adipate diol, polybutylene adipate diol, polyethylene butylene adipate diol, polyneopentyl adipate diol, polyneopentyl terephthalate diol, polycaprolactone diol, polyvalerolactone diol, Polyhexamethylene carbonate diol); polyether polyol [polyethylene glycol, polypropylene glycol, polyoxyethyleneoxypropylene glycol, polyoxytetramethylene glycol, EO and / or propylene oxide (hereinafter referred to as PO) adduct of bisphenols, etc.], etc. Is mentioned.

Specific examples of organic diisocyanates include, for example, 2,4′- or 4,4′-diphenylmethane diisocyanate (MDI), 2,4- or 2,6-tolylene diisocyanate (TDI), 4,4′-dibenzyl diisocyanate. Aromatic diisocyanates such as 1,3- or 1,4-phenylene diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate; aliphatic diisocyanates such as ethylene diisocyanate, hexamethylene diisocyanate (HDI), lysine diisocyanate; isophorone It is mentioned and mixtures of two or more thereof; - diisocyanate (IPDI), 4, 4 'dicyclohexylmethane diisocyanate (H ₁₂ MDI) cycloaliphatic diisocyanates such as Kill. Among these, preferred are _{MDI, TDI, HDI, H 12} MDI and IPDI.

  The chain extender and / or cross-linking agent used as necessary includes active hydrogen-containing compounds having a number average molecular weight of less than 60 to less than 500, such as polyhydric alcohols [ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4. -Butanediol, 1,6-hexanediol, 3-methylpentanediol, diethylene glycol, neopentyl glycol, 1,4-bis (hydroxymethyl) cyclohexane, 1,4-bis (hydroxyethyl) benzene, 2,2-bis Divalent alcohols such as (4,4′-hydroxycyclohexyl) propane; Trivalent alcohols such as glycerin and trimethylolpropane; Pentaerythritol, diglycerin, α-methylglucoside, sorbitol, xylit, mannitol, dipentaene 4- to 8-valent alcohols such as sitolitol, glucose, fructose and sucrose], polyhydric phenols (polyphenols such as pyrogallol, catechol and hydroquinone; bisphenols such as bisphenol A, bisphenol F and bisphenol S) ), Water, polyamine [aliphatic polyamine (ethylenediamine, hexamethylenediamine, diethylenetriamine, etc.), alicyclic polyamine (isophoronediamine, 4,4′-dicyclohexylmethanediamine, etc.), aromatic polyamine (4,4′-diaminodiphenylmethane) Etc.), alicyclic polyamines (such as xylylenediamine), hydrazine or derivatives thereof, etc.].

  In the present invention, the mechanical strength of the GFR-ABS resin molding is improved by using acrylonitrile / styrene copolymer resin (AS resin) as a glass fiber sizing agent. The AS resin in the sizing agent is preferably 30 parts by mass or more and 300 parts by mass or less with respect to 100 parts by mass of the solid content of the urethane resin. When the value is less than 30 parts by mass, the mechanical strength of the molded product is inferior, and when it exceeds 300 parts by mass, the dispersibility of the glass fibers in the molded product is inferior. If the AS resin of the sizing agent is 40 to 120 parts by weight, more preferably 100 parts by weight, which is substantially the same as 100 parts by weight of the solid content of the urethane resin, a GFR-ABS resin molded article obtained by using this Improves the surface smoothness.

Although it does not specifically limit as AS resin used for a sizing agent, It is preferable that it is non-crosslinked AS resin. As used herein, the non-crosslinked resin refers to a resin that is not a crosslinked resin that is crosslinked by dehydration condensation reaction between linear polymers by allowing an aldehyde condensable compound such as N-methylolacrylamide to be present in the AS resin. Say.
When a cross-linked AS resin is used, the cross-linked AS resin covers the surface of the glass fiber and strengthens the focusing property. As a result, the glass tends to be undispersed in the GFR-ABS resin molded product. The appearance may be inferior.
If it is non-crosslinked AS resin, the convergence is moderate, glass undispersed hardly occurs in the GFR-ABS resin molding, and the surface appearance of the molding is excellent.

  As a component of the sizing agent used in the present invention, it is preferable to contain a silane coupling agent used for the surface treatment of glass fibers. Preferable specific examples include γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -N′-β- (aminoethyl)- Aminosilanes such as γ-aminopropyltriethoxysilane and γ-anilinopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane Epoxysilanes, vinyltrimethoxysilane, vinylsilanes such as N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-chloropropyltrimethoxy Examples include silane, γ-mercaptopropyltrimethoxysilane, etc. Can. Two or more types of these coupling agents can be used. Of the above, monoaminosilane or diaminosila is preferably used as the silane coupling agent, and the above monoaminosilane is particularly preferable from the viewpoint of color tone.

  Furthermore, it is preferable to contain a surfactant as a component of the sizing agent of the present invention. As the surfactant, nonionic surfactants such as ethylene oxide propylene oxide copolymers, synthetic alcohols, natural alcohols, fatty acid esters, and distyrenated phenols can be used.

  In addition to the above components, the sizing agent of the present invention preferably contains a fatty acid amide, a quaternary ammonium salt or the like as a lubricant. Examples of the fatty acid amide include dehydration condensates of polyethylene polyamines such as diethylenetriamine, triethylenetetramine, and tetraethylenepentamine with fatty acids such as lauric acid, myristic acid, palmitic acid, and stearic acid. Further, as the quaternary ammonium salt, alkyltrimethylammonium salts such as lauryltrimethylammonium chloride can be used in combination. Furthermore, the sizing agent of the present invention can contain an antistatic agent typified by an inorganic salt such as lithium chloride or potassium iodide, or a quaternary ammonium salt such as an ammonium chloride type or an ammonium ethosulphate type.

  The sizing agent used in the present invention is preferably the urethane resin, AS resin, if necessary, a silane coupling agent, and, if necessary, other film formers, for example, mixed in an aqueous medium, and then preferably Is easily obtained by mixing auxiliary agents such as surfactants, lubricants and antistatic agents.

  In the present invention, when a glass fiber bundle is treated with a sizing agent having the specific composition described above, the sizing agent needs to be applied to a glass fiber bundle composed of glass filaments immediately after being spun from a bushing. .

  The average fiber diameter of the glass filament forming the glass fiber bundle to be treated with the sizing agent of the present invention is preferably 6 to 23 μm, more preferably 10 to 16 μm. The glass fiber bundle preferably contains 100 to 4000 glass filaments, particularly preferably 800 to 3000 glass filaments in one fiber bundle.

  The adhesion amount of the sizing agent used in the present invention to the glass fiber bundle is preferably 0.5 to 2 parts by mass in terms of solid content (ignition loss) with respect to 100 parts by mass of the glass fiber. If the value is less than 0.5 parts by mass, the mechanical strength of the molded article is inferior, and if it exceeds 2 parts by mass, no more mechanical strength can be obtained, which is economically undesirable. Therefore, 0.7 to 1.5 parts by mass is particularly preferable.

  In the present invention, the glass fiber bundle treated with the sizing agent is wound on a drum or the like in a wet state, and then the wound fiber bundle is drawn out, preferably cut into 1.5 to 13 mm. Alternatively, a wet chopped strand can be obtained by cutting a glass fiber bundle as it is without winding it around a drum. The wet chopped strand is then dried. Although the drying temperature and time are arbitrary, the drying is preferably performed at a temperature of 120 to 180 ° C., preferably 10 seconds to 10 minutes, so that excess water is removed.

  The glass fiber bundle produced and cut as described above is impregnated with a molten thermoplastic resin to produce a fiber-reinforced molding material or a thermoplastic resin molding. As the thermoplastic resin, the ABS resin is most likely to exhibit the effects of surface smoothness and mechanical strength of the resulting molded article, and then the AS resin is suitably employed.

  Furthermore, the fiber-reinforced molding material or the thermoplastic resin molded body may contain an additive selected from metal soap, fatty acid esters, and polyethylene glycol in addition to the glass fiber and the thermoplastic resin. The content of the additive is not particularly limited as long as it does not hinder the effects of the present invention, but it is 1 to 10 parts by mass with respect to 100 parts by mass of the thermoplastic resin without impairing mechanical strength, and at the time of molding. This is preferably employed because it has the effect of improving the dispersibility of the glass fiber and the thermoplastic resin and reducing the friction during molding resin flow.

  The molding material of a thermoplastic resin such as ABS resin, or the glass content in the molded body is preferably 5 to 250 parts by mass, more preferably 15 to 100 parts by mass with respect to 100 parts by mass of the resin. When the glass content of the molding material exceeds 250 parts by mass, the impregnation with the thermoplastic resin tends to be insufficient, and after mixing with the matrix resin, the dispersibility of the glass fibers is poor during direct injection molding. On the other hand, if the glass content of the molding material is less than 5 parts by mass, considering the glass content of the current glass fiber reinforced thermoplastic resin product, the strength cannot be increased by the glass fiber, and the practicality is low.

  When producing a GFR-ABS resin molded article using an ABS resin as a thermoplastic resin, for example, while plasticizing the ABS resin melted from a screw extruder, the chopped strand is supplied to this. Melt and knead. The melt-kneaded product is formed into a linear reinforced ABS resin body, and then cut with a pelletizer or the like to once produce a GFR-ABS resin molding material, and then the GFR-ABS resin molding material is put into an injection molding machine. To obtain a molded body. In addition to this method, the chopped strand and the ABS resin are dry blended and put into an injection molding machine to form a molded product, or the chopped strand and the ABS resin are directly blended without being blended, and the injection molding machine is used. And direct injection molding to obtain a molded product. The present invention is extremely excellent in the dispersibility of the glass fibers in the molded article even in the method of injection blending by chopped strands and ABS resin and direct injection molding, which is originally inferior in dispersibility of the glass fibers. A molded body can be obtained.

By using the glass fiber of the present invention, a molded article having excellent surface appearance and mechanical strength can be obtained. That is, as shown in the Examples and Comparative Examples described later, the molded product has less undispersed glass fibers compared to the molded product using glass fibers using specific urethane and acrylonitrile / styrene copolymer resin in the prior art. Thus, a molded article having excellent surface appearance and excellent mechanical strength can be obtained.
Moreover, the molded object excellent in surface smoothness is obtained by adjusting moderately the component ratio of a urethane resin and an acrylonitrile styrene copolymer resin.

The present invention will be described more specifically with reference to the following examples. However, it should be understood that the present invention should not be construed as being limited to such examples.
For Examples 1 to 5 and Comparative Examples 1 to 3, except that the sizing agent in the chopped strand was prepared in the following conditions using the following matrix resin, except that the raw materials having the following contents were prepared in the amounts shown in Table 1. Molded bodies were obtained and evaluated for mechanical strength and appearance.

(Bundling agent component)
AS resin A: non-crosslinked type acrylonitrile-styrene-acrylic acid ester ternary system
AS resin B: cross-linking type acrylonitrile-styrene-acrylic acid ester ternary system (containing N-methylolacrylamide as a functional group)
Urethane resin A softening point 70 ° C .: polyol component: polyester polyol), isocyanate component: (isophorone diisocyanate)
・ Urethane resin B softening point 110 ° C .: polyol component: polyester polyol), isocyanate component: (isophorone diisocyanate)
・ Aminosilane coupling agent: γ-aminopropyltriethoxysilane ・ Lubricant: Carnauba wax

(Chopped strand)
Glass filament average diameter 13μm, 2400 bundling,
Sizing agent adhesion amount (ignition loss, listed in Table 1), cutting length 3 mm

(Matrix resin)
ABS resin (Flame retardant grade for injection molding MFR60)
Molding material: 100 parts by mass of matrix resin, 33 parts by mass of glass fiber

(Injection molding conditions)
Clamping: 850t, cylinder temperature: 210 ° C, mold: 65 ° C, rotation speed: 55rpm, back pressure: 30MPa

The physical properties of the molded articles obtained in Examples and Comparative Examples are shown in “Table 1”. The evaluation methods of the softening temperature of urethane resin, tensile strength for mechanical strength evaluation, Charpy impact strength, and appearance state in “Table 1” are as follows.
-Evaluation of softening temperature of urethane resin: A film of urethane emulsion was prepared, and the flow start temperature was measured with a flow tester CFT-500D manufactured by Shimadzu Corporation.
-Tensile strength (MPa): Measured according to ISO 527-1, 2
Charpy impact strength (kg / mm ² ): Measured according to ISO 179-1,2.
Appearance state: The number of undispersed portions of the glass fiber appearing on the surface of the 0.5 m ² shaped body was visually confirmed.
The results in “Table 1” were evaluated as ◎ when the number of undispersed portions of the glass fiber was 3 or less, ◯ when 4 to 6 or less, and × when 6 or more.
-Surface smooth state: The number of undispersed portions of the glass fiber appearing on the surface of the molded body was visually confirmed.
The results in "Table 1" are ◎ when the undispersed portion of the glass fiber is zero, △ when the undispersed portion of the glass fiber is slightly seen, and when the undispersed portion of the glass fiber is clearly seen. It evaluated as x.

The glass fiber according to the present invention can be used as a glass fiber for a glass fiber reinforced acrylonitrile / butadiene / styrene copolymer resin molding. The glass fiber reinforced acrylonitrile / butadiene / styrene copolymer resin molding according to the present invention can be used for resin moldings such as toilet seats.

Claims (7)

A glass fiber to which a sizing agent including a urethane resin and an acrylonitrile / styrene copolymer resin is applied, wherein the urethane resin has a softening temperature of 100 ° C. or less. The glass fiber according to claim 1, wherein the acrylonitrile / styrene copolymer resin is 30 to 300 parts by mass with respect to 100 parts by mass of the urethane resin in the sizing agent. The glass fiber according to claim 2, wherein the acrylonitrile / styrene copolymer resin is 40 to 120 parts by weight with respect to 100 parts by mass of the urethane resin in the sizing agent. The glass fiber according to any one of claims 1 to 3, wherein the acrylonitrile / styrene copolymer resin is non-crosslinked. The glass fiber according to any one of claims 1 to 4, wherein the sizing agent is 0.5 to 2.0 parts by mass with respect to 100 parts by mass of the glass fiber. A glass fiber reinforced acrylonitrile / butadiene / styrene copolymer resin comprising the glass fiber according to claim 1 and an acrylonitrile / butadiene / styrene copolymer resin, the acrylonitrile / butadiene / styrene copolymer resin 100. Glass fiber reinforced acrylonitrile / butadiene / styrene copolymer resin molding obtained by dry blending such that the glass fiber is 5 to 250 parts by mass with respect to parts by mass and directly molding by an injection molding machine . A glass fiber reinforced acrylonitrile / butadiene / styrene copolymer resin comprising the glass fiber according to claim 1 and an acrylonitrile / butadiene / styrene copolymer resin, the acrylonitrile / butadiene / styrene copolymer resin 100. The glass fiber is dry-blended so that the glass fiber is 5 to 250 parts by mass, and the additive selected from metal soap, fatty acid esters, and polyethylene glycol is 1 to 10 parts by mass, and an injection molding machine. A glass fiber reinforced acrylonitrile / butadiene / styrene copolymer resin molded article obtained by direct molding by the above method.