JP5253816B2 - Chopped strand and fiber-reinforced crystalline polyester resin molding material using the same - Google Patents

Description

  The present invention relates to a chopped strand for obtaining a crystalline polyester resin molded article having excellent moldability and a fiber-reinforced crystalline polyester resin molding material containing the chopped strand.

  Thermoplastic resins are widely used as molded body materials from the viewpoint of processability and lightness. Chopped strands obtained by cutting glass strands of several hundred to several thousand bundles while applying a bundling agent containing a synthetic resin emulsion, a silane coupling agent, etc. to this thermoplastic resin. A fiber reinforced thermoplastic resin in which is used as a reinforcing material is suitably employed because of its excellent mechanical strength. Among thermoplastic resins, fiber reinforced polyester resins using crystalline polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polylactic acid are excellent in heat resistance, chemical resistance, mechanical properties, and electrical properties.

However, among polyester resins, crystalline polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polylactic acid have a relatively high glass transition point compared to other resins, and the mold temperature is the crystallization temperature of the crystalline polyester resin. If it is not raised to the vicinity, the crystalline polyester resin does not crystallize sufficiently, or the speed of crystallization of the resin itself is slow, so that the moldability is poor. Therefore, Patent Document 1 discloses crystallization promotion selected from polyethylene terephthalate, glass fiber, an inorganic filler, and a polyalkylene glycol having a molecular weight of 5,000 or less or a polyhydric alcohol or an epoxy compound thereof. By using an agent, molding can proceed to the surface layer of the molded body even when molded at a lower mold temperature than before, and a molded body with a beautiful molded body surface and good shape stability can be obtained. A polyester resin composition is described.
Japanese Patent Publication No.54-148833

  However, although the polyester resin composition described in Patent Document 1 is excellent in moldability from the point of promoting crystallization of the polyester resin, polyalkylene glycol or polyhydric alcohol is contained in the polyester resin composition (in the molding material). Including a large amount of crystallization accelerator such as 1 to 15% by mass causes a decrease in mechanical strength (including long-term decrease) of the molded body, and also during molding and when the molded body is heated. There was a problem that the processability of the molded body was inferior due to the generated gas.

  Accordingly, the present invention has been made in view of the above problems, and the object of the present invention is excellent in moldability during molding when blended with a crystalline polyester resin to form a molding material, and at the time of molding. An object of the present invention is to provide a chopped strand that generates less gas and has excellent processability of the resulting molded body, and a fiber-reinforced crystalline polyester resin molding material using the chopped strand.

The above object is achieved by the present invention described below. That is, in the present invention, a silane coupling agent (component a), polyethylene glycol (component b), an epoxy resin (component c), and a urethane resin (component d) are attached, and the number average of the component (b) When the molecular weight is 200 to 5,000, and the total amount of the components (a), (b), (c) and (d) as a solid content is 100% by mass, the component (b) The chopped strand for mix | blending with crystalline polyester resin characterized by the ratio of 5-45 mass% being provided.

In the present invention, the component (a), the component (b), the component (c) and the component (d) are 0.6 to 2.0 in 100% by mass of the chopped strand as a total amount as a solid content. The number average molecular weight of the component (b) is 500 to 3,000; the component (b) is a solid content in 100% by mass of the chopped strand. It is preferable to adhere in the ratio of 0.1 to 1% by mass.

Further, the present invention cuts a reinforcing fiber to which a sizing agent containing at least a silane coupling agent (component a) is added, and the cut reinforcing fiber has a polyethylene glycol having a number average molecular weight of 200 to 5,000. A post-treatment agent containing at least (component b) is applied, and the sizing agent and / or the post-treatment agent further contains an epoxy resin (component c) and / or a urethane resin (component d), When the total amount of the (a) component, (b) component, (c) component, and (d) component as the solid content is 100% by mass, the ratio of the (b) component is 5 to 45% by mass. The manufacturing method of the chopped strand for mix | blending with the crystalline polyester resin characterized by these is provided.

Moreover, this invention contains the silane coupling agent (a component), the polyethyleneglycol (b component) whose number average molecular weight is 200-5,000, an epoxy resin (c component), and a urethane resin (d component). A chopped strand manufacturing method for cutting a reinforcing fiber to which a sizing agent is applied, wherein the solid content of the component (a), the component (b), the component (c) and the component (d) in the sizing agent When the total amount is as 100 mass%, the ratio of the said (b) component is 5-45 mass%, The manufacturing method of the chopped strand for mix | blending with the crystalline polyester resin characterized by the above-mentioned is provided.

  The present invention also provides a fiber-reinforced crystalline polyester resin molding material characterized in that the chopped strands of the present invention are dispersed in a crystalline polyester resin and the reinforcing fiber content is 5 to 60% by mass. .

  In the molding material of the present invention, the component (b) is preferably contained at a ratio of 0.02 to 0.3% by mass in 100% by mass of the fiber-reinforced crystalline polyester resin molding material. .

  According to the present invention, when blended with a crystalline polyester resin to form a molding material, the moldability is excellent during molding, the gas generation during molding is small, and the processability of the resulting molded article is excellent. A strand and a fiber-reinforced crystalline polyester resin molding material using the strand can be provided.

Next, the present invention will be described in more detail with reference to the best mode for carrying out the invention. The chopped strand of the present invention is characterized in that a silane coupling agent (component a), polyethylene glycol (component b), an epoxy resin (component c), and a urethane resin (component d) are attached.
Hereinafter, in the present specification, the amounts of such silane coupling agent (a component), polyethylene glycol (b component), epoxy resin (c component) and urethane resin (d component) adhering to the chopped strand are particularly mentioned. Unless otherwise indicated, it means the amount of solid content as shown in Tables 2-1 and 2-2 of Examples described later.

  Examples of the reinforcing fiber used in the chopped strand of the present invention include glass fiber and carbon fiber, and it is preferable to use glass fiber from the viewpoint of workability and low cost. The reinforcing fiber preferably has an average fiber diameter (average diameter of filaments constituting the reinforcing fiber) of 6 to 23 μm, and more preferably 9 to 16 μm. The number of filaments in the reinforcing fiber is preferably 100 to 4,000, more preferably 800 to 3,000. According to this, it is easy to disperse the chopped strands in the crystalline polyester resin that is the matrix resin, and the reinforcing fiber content of the crystalline polyester resin molding material is easy to adjust.

  As the silane coupling agent which is the component (a) used in the present invention, a silane coupling agent conventionally used for surface treatment of reinforcing fibers can be used. Preferred specific examples include γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, γ-anilinopropyltrimethoxy Aminosilanes such as silane; epoxy silanes such as γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; vinyltrimethoxysilane, N-β- (N-vinylbenzyl) Vinylsilanes such as aminoethyl) -γ-aminopropyltrimethoxysilane; γ-methacrylic Trimethoxysilane, .gamma.-chloropropyl trimethoxy silane, .gamma. such mercaptopropyltrimethoxysilane may be mentioned. Two or more kinds of these components (a) can be used.

  As the component (a), among the above, aminosilanes are preferable, among which monoaminosilane and diaminosilane are more preferable, and among these, monoaminosilane is most preferable because it has little adverse effect on the color tone of the reinforcing fiber. And the quantity of (a) component made to adhere to chopped strand (reinforced fiber) is 1-30 mass in 100 mass% of total amounts of (a) component, (b) component, (c) component, and (d) component. %, And more preferably 5 to 15% by mass. When the component (a) is less than 1% by mass, the adhesion between the chopped strand and the crystalline polyester resin tends to be inferior, and it is difficult to obtain a sufficient reinforcing effect when the molding material of the present invention is used as a molded body, If the component (a) exceeds 30% by mass, the color tone of the chopped strands may turn yellow, and the adhesiveness with the crystalline polyester resin is inferior.

  In the present invention, the polyethylene glycol used as the component (b) is chopped at a ratio of 5 to 45% by mass in the total amount of 100% by mass of the components (a), (b), (c) and (d). It is characterized by adhering to the strand, more preferably adhering at a ratio of 10 to 30% by mass. If the amount of the component (b) is less than 5% by mass, the effect of lowering the crystallization temperature of the crystalline polyester resin in the molding material containing the chopped strands is not preferable. If it exceeds 45% by mass, the mechanical strength and long-term maintenance of the molded body made of the molding material of the present invention are not sufficient, and gas is easily generated during molding of the molded body, which is not preferable.

  The component (b) has a number-average molecular weight of 200 to 5,000, the effect of lowering the crystallization temperature of the crystalline polyester resin in the molding material of the present invention, and the mechanical properties of the molded product obtained therefrom. Necessary for long-term maintenance of strength, and more preferably 500 to 3,000. When the number average molecular weight of the component (b) is less than 200, the decomposition and volatilization of the component (b) starts at a temperature lower than the processing temperature of the resin, so that the concentration of the component (b) in the molded body is reduced. In addition, the amount of gas generated increases during processing and molding, which is not preferable in terms of the workability of the molding material and the physical properties of the obtained molded body, and is not preferable because the mechanical strength of the obtained molded body is reduced. On the other hand, when the number average molecular weight of the component (b) exceeds 5,000, the mechanical strength of the molded article and its long-term maintenance are not sufficient, which is not preferable.

  The epoxy resin used as the component (c) in the present invention is not particularly limited, and examples thereof include bisphenol A type epoxy resins and novolac type epoxy resins. The component (c) is preferably attached to the chopped strand in a ratio of 50 to 90% by mass in the total amount of 100% by mass of the components (a) to (d), more preferably 70 to 85% by mass. It is adhering in the ratio which occupies. When the proportion of the component (c) is less than 50% by mass, the mechanical strength of the molded product obtained from the molding material cannot be sufficiently obtained, whereas the proportion of the component (c) is not suitable. If it exceeds 90% by mass, the adhesion amount of the other components such as the component (a) in the chopped strand decreases, so the adhesion between the chopped strand and the crystalline polyester resin tends to be inferior, and the mechanical strength of the molded body Is not preferred because it tends to decrease.

  The urethane resin used as the component (d) in the present invention is to improve the converging property of the filaments of the reinforcing fibers constituting the chopped strand, and includes a polymer polyol, an organic diisocyanate, and, if necessary, a chain extender and / or A conventionally known one derived from a crosslinking agent can be preferably used, and is preferably used in the form of an aqueous dispersion such as an emulsion or a dispersion.

  Specific examples of the polymer polyol include, for example, polyester polyol (polyethylene adipate diol, polybutylene adipate diol, polyethylene butylene adipate diol, polyneopentyl adipate diol, polyneopentyl terephthalate diol, polycaprolactone diol, polyvalerolactone diol, Polyhexamethylene carbonate diol, etc.) and polyether polyols (polyethylene glycol, polypropylene glycol, polyoxyethyleneoxypropylene glycol, polyoxytetramethylene glycol, ethylene oxide and / or propylene oxide adducts of bisphenols, etc.).

Specific examples of the organic diisocyanate include aromatic diisocyanates [2,4- or 4,4-diphenylmethane diisocyanate (MDI), 2,4- or 2,6-tolylene diisocyanate (TDI), 4,4. -Dibenzyl diisocyanate, 1,3- or 1,4-phenylene diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate (XDI), etc.], aliphatic diisocyanate [ethylene diisocyanate, hexamethylene diisocyanate (HDI), lysine diisocyanate Etc.], cycloaliphatic diisocyanates [isophorone diisocyanate (IPDI), 4,4-dicyclohexylmethane diisocyanate (H ₁₂ MDI), etc.], and two or more of these are used in combination. Also good.

  As the chain extender and / or the crosslinking agent, an active hydrogen-containing compound having a number average molecular weight of 60 to less than 500 is preferable. For example, a polyhydric alcohol [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 ( 4,4-hydroxycyclohexyl) propane and other dihydric alcohols; glycerin, trimethylolpropane and other trihydric alcohols; pentaerythritol, diglycerin, α-methylglucoside, sorbitol, xylit, mannitol, dipentaerythritol, glu , Fructose, sucrose, etc., polyhydric phenols (pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, etc.), polyamines (ethylenediamine, hexamethylenediamine, diethylenetriamine) Aliphatic polyamines such as isophorone diamine, 4,4-dicyclohexylmethane diamine, etc .; Aromatic polyamines such as 4,4-diaminodiphenyl methane; Arocycloaliphatic polyamines such as xylylenediamine, hydrazine or derivatives thereof Etc.) and water.

  In the present invention, it is particularly preferable to use xylylene diisocyanate (hereinafter referred to as “XDI”) among the above-mentioned organic diisocyanates as the isocyanate component of the component (d). When the component (d) in which the isocyanate component is composed of XDI is used, it is easy to improve the converging property of the filament of the reinforcing fiber constituting the chopped strand, the amount of fluff of the chopped strand can be suppressed, and (d ) Since the high converging property can be imparted even if the content of the component is relatively small, the content of the component (c) can be increased, and a chopped strand having a high reinforcing effect can be obtained.

  Moreover, as the polymer polyol component, the above polyol having a number average molecular weight of 500 to 6,000 is preferable, and more preferably 800 to 3,000. And the (d) component comprised by the polycaprolactone diol and XDI is more preferable since it is excellent in the convergence property of the reinforcing fiber filament in a chopped strand. And (d) component is chopped strand in the ratio which occupies 0.5-30 mass% in the total amount 100 mass% of (a) component, (b) component, (c) component, and (d) component. It is preferable that it adheres, More preferably, it adheres in the ratio which occupies 5-25 mass%. When the component (d) is less than 0.5% by mass, it is difficult to maintain the focusing property. On the other hand, when the component (d) exceeds 30% by mass, the mechanical strength of the molded article tends to be inferior. Absent.

  The components used for adhering to the chopped strand in the present invention include the above components (a), (b), (c) and (d) as essential components. Various additives such as an agent, a lubricant, and an antistatic agent can be used.

  As the surfactant, nonionic surfactants are preferable, and examples thereof include ethylene oxide propylene oxide copolymers, synthetic alcohols, natural alcohols, fatty acid esters, and distyrenated phenols.

  Examples of the lubricant include fatty acid amides and quaternary ammonium salts. 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. Moreover, as a quaternary ammonium salt, lauryl trimethyl ammonium chloride, an alkyl trimethyl ammonium salt, etc. can be used.

  Examples of the antistatic agent include inorganic salts such as lithium chloride and potassium iodide, and quaternary ammonium salts such as ammonium chloride type and ammonium ethosulphate type.

  In 100% by mass of the chopped strand and the total of the component (a), the component (b), the component (c) and the component (d) (hereinafter also referred to as “the total amount of the chopped strand”), the component (a) and the component (b) The component (c) and the component (d) are preferably attached to the chopped strand so that the total amount thereof accounts for 0.6 to 2.0% by mass, and 1.0 to 1.8% by mass. It is more preferable to make it adhere so that it may become a ratio. When the total adhesion amount of the component (a), the component (b), the component (c) and the component (d) is less than 0.6% by mass, the mechanical strength of the molded product obtained from the molding material is not sufficiently improved. On the other hand, if the total adhesion amount of the component (a), the component (b), the component (c) and the component (d) exceeds 2.0% by mass, it is not preferable because the cost of the chopped strand obtained is increased. .

  Moreover, it is preferable that said (b) component has adhered in the ratio which occupies 0.1-1 mass% in the said chopped strand whole quantity 100 mass%, and a more preferable adhesion amount is 0.1-0.8. % By mass. When the adhesion amount of the component (b) is less than 0.1% by mass, the effect of lowering the crystallization temperature at the time of molding the crystalline polyester resin is poor, which is not preferable. On the other hand, when the adhesion amount exceeds 1% by mass, the molding material is used. This is not preferable since the mechanical properties of the molded product obtained from the above are deteriorated and gas is generated during processing.

  In the present invention, the method for producing chopped land is not particularly limited, and various conventionally known methods can be used. For example, taking glass fiber as an example, molten glass is drawn out from a number of nozzles attached to the bottom of the bushing to form a glass filament, and a sizing agent is applied to the glass filament with an applicator or spray to form a glass strand. The sizing agent at this time may contain all of the above-mentioned (a) component, (b) component, (c) component and (d) component, or at least the (a) component as described later. May be contained. In the case of containing all of (a) component, (b) component, (c) component and (d) component, the sizing agent comprises (a) component, (b) component, (c) component and (d) component, It can be prepared by blending in a solid content ratio such that the adhesion amount of each component in the chopped strand is the above ratio, and mixing in an aqueous medium such as water. At this time, the various additives are mixed together as necessary. Moreover, it is preferable that the total solid content concentration of a sizing agent is about 1-10 mass%.

  The glass strand obtained above is cut into a length of 1.5 to 13 mm. At that time, the glass strand may be wound once and then cut, or may be cut as it is without being wound. Next, the process proceeds to a drying step of the cut glass strand, but a post-treatment agent described later may be applied before the drying step. The drying temperature and drying time are arbitrary and not particularly limited. However, in order to efficiently carry out the drying process without impairing the converging property of the glass filaments constituting the chopped strand, the drying temperature is 120 to 220 ° C. and the drying time is 10 It is preferable to set it for 2 to 10 minutes.

  In the present invention, a particularly preferable method for producing chopped land is to apply a sizing agent containing at least the component (a) to a reinforcing fiber strand (for example, the above glass strand), and the reinforcing fiber strand as described above. The post-treatment agent containing at least the component (b) is applied to the cut reinforcing fiber strand, and then dried as described above. In addition, when a post-treatment agent is applied to the cut reinforcing fiber strand, a method as described in JP-T-2003-505322, that is, the cut reinforcing fiber strand is put into a rotating drum. A method of rolling the cut reinforcing fiber strands by rotating the rotating drum after spraying the post-treatment agent can be employed.

  At that time, the sizing agent and / or the post-treatment agent further contains the component (c) and / or the component (d). And in the chopped strand obtained, when the total amount of said (a) component, (b) component, (c) component, and (d) component is 100 mass%, the ratio of (b) component is 5-45 mass. The blending amounts of the component (a), the component (b), the component (c) and the component (d) in the sizing agent and the post-treatment agent are adjusted so as to be%. The method for preparing the sizing agent and the post-treatment agent is the same as the method for preparing the sizing agent.

  As described above, by applying a sizing agent containing at least the component (a) to the reinforcing fiber strand first, and then applying a post-treatment agent containing at least the component (b) to the chopped strands cut thereafter, Compared with the case where (a) component, (b) component, (c) component and (d) component are all blended in the sizing agent, polyethylene glycol as component (b) is the crystallization temperature of the crystalline polyester resin. The effect of improving the moldability of the molding material by lowering or increasing the crystallization is enhanced. In addition, since the component (b) is not blended in the sizing agent, the sizing property of the filaments constituting the chopped strands is increased, and when the chopped strands are used, the generation of fuzz is reduced and the handling property is improved.

  The sizing agent in the above particularly preferred method may contain the component (c) and / or the component (d) in addition to the essential component (a). The post-treatment agent may contain the component (c) and / or the component (d) in addition to the essential component (b). Moreover, when this sizing agent contains the component (c) and the component (d) in addition to the component (a), the post-treatment agent may contain the component (c) and the component (d). , May not be contained. When the post-treatment agent contains the component (c) and the component (d) in addition to the component (b), the sizing agent may contain the component (c) and the component (d). It does not have to be contained.

  Similarly to the above, the sizing agent and the post-treatment agent should be prepared by blending them in a solid content ratio such that the adhesion amount of each component in the chopped strand becomes the above ratio and mixing in an aqueous medium such as water. Can do. In addition, when blending component (c) or component (d) in both the sizing agent and the post-treatment agent, the total blending amount is set so that the amount finally adhered to the chopped strand is the above ratio. However, the amount may be divided into a sizing agent and a post-treatment agent. In addition, it is preferable to mix | blend the urethane resin which is (d) component with both a sizing agent and a post-processing agent. As a result, the converging properties of the filaments constituting the chopped strands are enhanced, the generation of fluff when the chopped strands are heated in the kneading step with the resin is reduced, and the handleability is improved.

  Also in the sizing agent in the above particularly preferable method, the total solid concentration is preferably about 1 to 10% by mass. Moreover, it is preferable that the total solid content concentration of said post-processing agent is about 10-80 mass%, and it is more preferable that it is 30-70 mass%. When the component (c) and / or the component (d) is added to the component (b) in the post-treatment agent, the proportion of the component (b) when the total solid content of the post-treatment agent is 100% by mass Is preferably 5 to 95% by mass.

  The chopped strand of this invention is obtained as mentioned above. Moreover, the fiber reinforced crystalline polyester resin molding material of this invention is obtained by disperse | distributing said chopped strand in the melted crystalline polyester resin.

  In the present invention, the method for producing the fiber-reinforced crystalline polyester resin molding material is not particularly limited, and various conventionally known methods can be used. For example, while the crystalline polyester resin melted from the screw extruder is plasticized, the chopped strand is supplied and melt kneaded. The melt-kneaded product is molded into a linear fiber-reinforced crystalline polyester resin molding, and then cut with a pelletizer or the like to obtain a fiber-reinforced crystalline polyester resin molding material. Further, a fiber-reinforced crystalline polyester resin molding material can be obtained by a known method using an injection molding machine.

  Moreover, as a reinforcement fiber content rate in a molding material, the ratio which occupies 5-60 mass% in a molding material is preferable, More preferably, it is the ratio which occupies 7-50 mass%. If the reinforcing fiber content is less than 5% by mass, the molded product obtained from the molding material has poor mechanical strength and is not suitable for practical use. On the other hand, if the reinforcing fiber content exceeds 60% by mass, the manufacturing cost of the molding material increases. Therefore, it is not preferable.

  In the fiber-reinforced crystalline polyester resin molding material of the present invention, the component (b) is contained at a ratio of 0.02 to 0.3% by mass in 100% by mass of the total amount of the fiber-reinforced crystalline polyester resin molding material. It is preferable. If the content is less than 0.02% by mass, the effect of lowering the crystallization temperature of the crystalline polyester resin when molding the crystalline polyester resin molding material is not sufficient, which is not preferable. If it exceeds 3% by mass, the mechanical properties of the crystalline polyester resin molded article are deteriorated, long-term maintenance is not sufficient, and gas is not preferable during molding.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, these examples are illustrative of embodiments of the present invention and are not intended to limit the scope of the present invention. In the text, “%” is based on mass.
[Production of chopped strand (CS)]
(Examples 1-7 and Comparative Examples 1-9)
3,000 glass fibers with an average diameter of 10 μm are bundled, and a sizing agent (aqueous dispersion, solid content is the total amount of each component in Table 1 below) prepared by using the following raw materials and blended in Table 1 below. The glass strand was made to adhere in the amount described in Table 2 below per 100 parts by mass of the glass fiber. Thereafter, these glass strands were cut to a length of 3 mm and then dried using a hot air dryer to obtain chopped strands of Examples and Comparative Examples. In addition, the component (b) used in Comparative Examples 8 and 9 was not included in the sizing agent, but was included when a molding material was produced with an extruder using a chopped strand and a crystalline polyester resin, which will be described later. .

(Examples 8 and 9)
3,000 glass fibers with an average diameter of 10 μm are bundled, and a sizing agent (aqueous dispersion, solid content is the total amount of each component in Table 1 below) prepared by using the following raw materials and blended in Table 1 below. The glass strand was made to adhere in the amount described in Table 2 below per 100 parts by mass of the glass fiber. Thereafter, these glass strands are cut to a length of 3 mm, the following post-treatment agent is sprayed on the glass strands cut in the rotating drum as described above, and adhered in the amounts described in Table 2 below. After rolling continuously, it was dried using a hot air dryer to obtain a chopped strand of the example. The post-treatment agent used in Example 8 is an aqueous solution containing 20% PEG 1000 (trade name), and the post-treatment agent used in Example 9 is 20% PEG 1000 (trade name) and urethane resin. It is an aqueous solution containing 8%.

(Bundling agent ingredients)
-(A) component: (gamma) -aminopropyl triethoxysilane-(b) component:
Polyethylene glycol (PEG) 200: number average molecular weight 200 (manufactured by Sanyo Chemical Industries, Ltd., trade name: PEG 200)
Polyethylene glycol (PEG) 1000: number average molecular weight 1,000 (manufactured by Sanyo Chemical Industries, Ltd., trade name: PEG1000)
Polyethylene glycol (PEG) 2000: Number average molecular weight 2,000 (manufactured by Sanyo Chemical Industries, Ltd., trade name: PEG2000)
Polyethylene glycol (PEG) 4000: number average molecular weight 4,000 (manufactured by Sanyo Chemical Industries, Ltd., trade name: PEG 4000)
Polyethylene glycol (PEG) 6000: number average molecular weight 6,000 (manufactured by Sanyo Chemical Industries, Ltd., trade name: PEG 6000)
-Component (c): Novolac type epoxy resin-Component (d): Urethane resin synthesized using dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI) and aromatic polyester polyol-Phosphoric ester metal Salt: Asahi Denka Kogyo Co., Ltd., trade name: NA-11
-Disproportionated rosin metal salt: Arakawa Chemical Industries, Ltd., trade name: Pine Crystal KM-1500
Lubricant: Degussa Goldschmitt Cation Softener / Sorbitol Surfactant: Mitsui Chemicals, trade name: NU-6

Using each of the chopped strands obtained in the above Examples and Comparative Examples and a polyethylene terephthalate resin (trade name; “Dianite MA521H”, manufactured by Mitsubishi Rayon Co., Ltd.), using a twin screw extruder with a screw diameter of 35 mm, the molding temperature A pellet-like fiber-reinforced polyethylene terephthalate resin molding material having a glass content of 29 to 31% was obtained at 280 ° C. The content ratio of the component (b) in each molding material is as shown in Table 3 below. Further, the crystallization temperature (Tc) of each molding material was measured by the following method, and from the crystallization temperature in Comparative Example 1 containing no component such as component (b), the crystallization in other Examples and Comparative Examples A value (ΔTc) obtained by subtracting the temperature was obtained and used as an index of the degree of decrease in the crystallization temperature of the polyethylene terephthalate resin.
<Crystalization temperature>
The pellet-shaped molding material was sliced into a flaky sample, and the crystallization temperature was measured using DSC (differential scanning calorimetry) under conditions of a heating rate of 10 ° C./min and nitrogen gas of 20 ml / min. .

The fiber reinforced polyethylene terephthalate resin molding materials of Examples 1 to 9 and Comparative Examples 1 to 9 are each injection molded at a clamping load of 75 tons, a cylinder temperature of 280 ° C., and a mold of 140 ° C. The molded items thus obtained were evaluated for the following items, and the results are shown in Table 4 below.
[Performance evaluation of fiber reinforced polyethylene terephthalate resin moldings]
<Tensile strength measurement>
It was measured by a method based on ASTM D-638 and judged to be good if it was 130 MPa or more.
<Pressure cooker test (PCT)>
The test piece was allowed to stand for 50 hours in a thermostatic / humidifier with a temperature of 120 ° C. and a humidity of 100%, and then the tensile strength was measured by a method based on ASTM D-638, and the retention rate was calculated. If the retention rate was 30% or more at 50 hr, it was judged that the hydrolysis resistance was good.
<IZOD impact strength measurement>
It measured with the method based on ASTM D-256 with a 1/8 inch notch, and judged that it was favorable if it was 70 J / m or more.
Measurement was carried out by a method according to ASTM D-256 without a 1/8 inch notch, and it was judged to be good if it was 400 J / m or more.

For each of the chopped strands of Examples 1, 2, 3, 8, and 9 and Comparative Example 1, the degree of fluff generation during heating and kneading was measured by the following method, and used as an index of good handling properties. The results are shown in Table 5 below.
[Evaluation of the degree of fluff generation during heating and kneading of chopped strands]
1,000 g of chopped strands are weighed, put into a sealed container heated to a temperature of 50 ± 5 ° C., kneaded for 5 minutes by rotating a twin screw provided in the sealed container, and then chopped strands. Was passed through a metal mesh having a mesh size of 4 mm, and the amount of fluff remaining on the mesh was weighed to determine the degree of fluff generation.

  As seen in Table 4, Comparative Example 3 (example in which the blending ratio of component (b) exceeds the range of the present invention), Comparative Example 4 (example in which the molecular weight of component (b) exceeds the range of the present invention), Comparative Example 8 (Example in which component (b) is blended in resin instead of chopped strand) and Comparative Example 9 (same as Comparative Example 8) have low tensile strength retention before and after the pressure cooker test, and are resistant to hydrolysis. The evaluation of sex was inferior. On the other hand, in Examples 1 to 9 of the present invention, the hydrolysis resistance was all good. Moreover, as seen in Table 3, Comparative Example 4, Comparative Examples 5 to 7 (example in which component (b) is not blended) and Comparative Example 8 (component (b) adhered to chopped strands in the examples) In an example in which an amount equivalent to that in the resin was blended with the resin), the crystallization temperature was hardly lowered, and no improvement in injection moldability was observed. On the other hand, in Examples 1 to 9 of the present invention, the effect of lowering the crystallization temperature was exhibited, and the improvement of injection moldability was recognized. Further, Examples 2, 4, 5, and 7 have different molecular weights of the component (b), but even within the scope of the present invention, the crystallization temperature is lowered when the component (b) is not high in molecular weight. It can be seen that the effect tends to be high.

  When Example 2 in Table 3 and Examples 8 and 9 are compared, the latter has a greater effect of lowering the crystallization temperature in spite of the same component (b) content. This is the effect by the manufacturing method of this invention especially preferable, ie, the method of providing (b) component with a post-processing agent. Moreover, when the said Table 5 is seen, Example 9 which mix | blended urethane resin with both the bundling agent and the post-processing agent has little generation | occurrence | production of the fluff at the time of heat kneading | mixing, and (b) Since a component is not used, bundling property is high. It is equivalent to Comparative Example 1. Thus, it can be seen that not only the bundling agent but also the post-treatment agent is blended with urethane resin, so that the bundling property of the glass filament constituting the chopped strand is increased and the handling property of the chopped strand is improved.

  The chopped strand of the present invention improves the moldability when obtaining a fiber-reinforced crystalline polyester resin molding material, and suppresses gas generation during molding and heating of the resulting molded body.

Claims (8)

A silane coupling agent (component a), polyethylene glycol (component b), an epoxy resin (component c), and a urethane resin (component d) are attached, and the number average molecular weight of the component (b) is 200-5, When the total amount of the components (a), (b), (c) and (d) is 100% by mass, the ratio of the component (b) is 5 to 45. A chopped strand for blending with a crystalline polyester resin, characterized in that it is a mass%. The component (a), the component (b), the component (c), and the component (d) are attached in a proportion of 0.6 to 2.0% by mass in 100% by mass of the chopped strand as a total amount of solids. The chopped strand according to claim 1.   The chopped strand according to claim 1, wherein the number average molecular weight of the component (b) is 500 to 3,000. The chopped strand according to claim 1, wherein the component (b) is attached in a proportion of 0.1 to 1% by mass as a solid content in 100% by mass of the chopped strand. A reinforcing fiber to which a sizing agent containing at least a silane coupling agent (component a) is added is cut, and at least polyethylene glycol (b component) having a number average molecular weight of 200 to 5,000 is added to the cut reinforcing fiber. A post-treatment agent contained therein, the sizing agent and / or the post-treatment agent further contains an epoxy resin (component c) and / or a urethane resin (component d), the component (a), ( Crystallinity characterized in that when the total amount of the components b), (c) and (d) as the solid content is 100% by mass, the proportion of the component (b) is 5 to 45% by mass . A method for producing chopped strands for blending with a polyester resin . A sizing agent containing a silane coupling agent (component a), a polyethylene glycol (component b) having a number average molecular weight of 200 to 5,000, an epoxy resin (component c), and a urethane resin (component d) is applied. A method of producing chopped strands for cutting the reinforced fibers, wherein the total amount of the (a) component, (b) component, (c) component and (d) component in the sizing agent as a solid content is 100 A method for producing chopped strands for blending in a crystalline polyester resin , wherein the proportion of the component (b) is 5 to 45% by mass when the mass is% by mass.   A fiber-reinforced crystalline polyester resin molding material, wherein the chopped strand according to any one of claims 1 to 4 is dispersed in a crystalline polyester resin, and the reinforcing fiber content is 5 to 60% by mass. . The component (b) is in 100% by mass of the fiber-reinforced crystalline polyester resin molding material,
The fiber-reinforced crystalline polyester resin molding material according to claim 7, which is contained at a ratio of 0.02 to 0.3% by mass as a solid content.