JP2965715B2 - Glass fiber mat and glass fiber reinforced nylon reaction injection molded product - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glass fiber mat used for a reinforced nylon reaction injection molded article and a glass fiber reinforced nylon reaction injection molded article, and more particularly to a mat fixed with a specific surface treatment agent and the mat. The present invention relates to a glass fiber reinforced nylon reaction injection molded product reinforced with a mat.

[0002]

2. Description of the Related Art Conventionally, glass fiber mats are produced by melting and spinning raw materials such as clay and lime to form monofilaments.
For the purpose of satisfying the ease of spinning and the workability in the post-process, the surface is treated with a surface treatment agent containing polyvinyl acetate or unsaturated polyester as a main component, the required number is bundled, and then the unsaturated polyester or polyacetic acid is obtained. Glass fibers are fixed with a binder such as vinyl to form a mat.

On the other hand, nylon resins for reaction injection molding are:
Since the molding cycle is short and the mechanical properties, heat resistance, abrasion resistance and the like are excellent, these properties are exploited to be used in a wide range of fields. It is also common practice to mix short glass fibers having a length of about 1 mm or less as a reinforcing material in the nylon resin.

However, there is a limit in improving the mechanical properties such as strength and rigidity of the molded product of short glass fiber, and in order to achieve further improvement, a mat in which relatively long glass fiber is fixed with a binder is used. Use as a reinforcement is also being considered. However, when a conventional glass mat used for FRP, such as an unsaturated polyester resin, is used, the molded product becomes brown, the appearance is significantly reduced, and the strength of the molded product is reduced. Furthermore, there is a disadvantage that the inherent characteristics of reaction injection molding cannot be utilized due to the delay of the reaction during molding. The cause of such an abnormality is that the conventional glass fiber surface treatment agent and / or binder causes an abnormal reaction with the catalyst and / or cocatalyst in the raw material of the nylon resin for reaction injection molding. . In order to solve this problem, it is conceivable to use glass fibers without a surface treatment agent and / or a binder. Such glass fibers can prevent discoloration of a molded product, but have a strong binding force and flexibility of the glass fibers. However, there is a drawback that workability is remarkably reduced due to lack of adhesiveness, and adhesiveness is extremely poor.

[0005]

SUMMARY OF THE INVENTION In view of the above facts, the present inventors have made intensive studies to solve this drawback, and as a result, as a surface treatment agent for glass fibers used in glass fiber reinforced nylon reaction injection molded articles. Using a composition containing an epoxy-modified acrylic copolymer, a polyoxyethylene-type nonionic surfactant and an amino group-containing silane coupling agent, surface-treating the glass fibers, and then arranging the glass fibers in a random mat state. It has been found that, by reinforcing with a glass fiber mat fixed with a binder that does not dissolve in lactams as a binder, a superior glass fiber reinforced nylon reaction injection molded product that has never been obtained before can be obtained, and the present invention has been completed. Was.

[0006]

That is, the present invention provides a composition containing an epoxy-modified acrylic copolymer, a polyoxyethylene type nonionic surfactant and an amino group-containing silane coupling agent as a surface treatment agent for glass fibers. Is provided on a glass fiber, the glass fiber is surface-treated, the glass fiber is arranged in a sheet shape, and the glass fiber is fixed with a binder that does not dissolve in lactams.

[0007] The present invention also provides a glass fiber reinforced nylon reaction injection molded article reinforced with the above glass fiber mat.

The epoxy-modified acrylic copolymer used for the surface treatment agent for glass fibers of the present invention includes acrylic acid ester and acrylic acid, acrylic acid ester and acrylamide, acrylic acid and maleic acid, acrylic acid and methacrylic acid, acrylic acid And those obtained by neutralizing a copolymer resin such as maleic acid and styrene with an amine and adding a water-soluble epoxy resin thereto. The compounding amount is preferably 0.5 to 10% by weight based on the surface treatment agent.

Examples of the polyoxyethylene type nonionic surfactant include alkyl polyoxyethylene ethers such as polyoxyethylene lauryl ether, polyoxyethylene ethers of sorbitan esters such as polyoxyethylene sorbitan monooleate, and alkyl allyl formaldehyde condensed polyoxy. Examples include ethylene ether, polyoxyethylene polyoxypropyl alkyl ether, polyoxyethylene ether of glycerin ester, polyethylene glycol fatty acid ester, polyoxyethylene fatty acid amide, polyoxyethylene alkylamine, and fatty acid alkanolamide. The compounding amount is preferably 0.01 to 1.0% by weight based on the surface treatment agent.

As for the amino group-containing silane coupling agent, γ-aminopropyltriethoxysilane, γ-aminopropyl
(2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride, γ-anilinopropyltrimethoxysilane, γ-
Ureidopropyltriethoxysilane, γ-aminopropyltrimethoxysilane and the like are listed. The compounding amount is preferably 0.01 to 1.0% by weight based on the surface treatment agent.

Further, in addition to the above, a softener, an antistatic agent, water and the like may be contained. These compositions can be treated into glass fibers using a known surface treatment apparatus for producing glass fibers. The amount of the surface treatment agent for the glass fiber is generally 0.3 to 1.5% by weight as a solid content, and drying and baking are performed as necessary.

The binder has a softening point or a melting point of preferably 50 ° C. or more and 150 ° C. or less and does not dissolve in lactams. Here, the lactams are γ-butyrolactam, δ-valerolactam, ε-caprolactam, ζ-enantholactam, η-caprylactam, ω
-Refers to laurolactam and the like. The binder is specifically one or more of saponified ethylene-vinyl acetate copolymer, polyamide resin and methacrylic resin. As a saponified ethylene-vinyl acetate copolymer,
A saponified copolymer of 5 to 20 mol% of vinyl acetate is preferred. As the polyamide resin, a versamide type obtained by reacting a polyamine with a binary fatty acid as a raw material and a nylon type obtained by methoxymethylating amide group hydrogen of a copolymer such as nylon 6, 6-6, or 6-10 are used. Is raised. As methacrylic resin, polymethyl methacrylate, methyl methacrylate and methyl acrylate, ethyl acrylate, butyl acrylate, styrene,
Acrylic nitrile, butadiene binary or ternary copolymers or blends thereof are listed. As the properties of these binders, powders having an average particle diameter of 100 μm to 400 μm (preferably 200 μm to 300 μm) can be generally used. Emulsified ones can also be used if necessary. The amount of the binder attached to the glass fiber mat is 3 to 15% by weight. When the softening point or melting point of the binder is less than 50 ° C., the holding stability of the mat is deteriorated, and the fixing force of the binder is reduced by the resin heated at the time of molding. It flows with the resin, and the value of the molded article is lost. On the other hand, when the temperature exceeds 150 ° C., a high temperature is required at the time of producing the mat-like material, which is economically undesirable.

As the nylon reaction injection molding resin, known resins such as lactams and modified products thereof, catalysts and cocatalysts can be used as they are.

[0014]

EXAMPLES The present invention will be described in detail below with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Examples 1 to 5 Treated glass fibers were drawn out from a number of nozzles attached to the bottom of the bushing, and melted glass was drawn out. Is expressed in terms of% by weight, and the remainder is water.) Was wound up while being applied through an applicator, and the wound up was heated and dried. At this time, the solid content of the treating agent was 0.6% by weight. The treated glass fiber is cut into 10 cm by a cutting device, dropped on a moving conveyor, and deposited in a sheet shape. Next, the powdered binder shown in Table 1-1 was sprinkled on the deposited glass fiber, heated and baked, and then cooled to produce a sheet-like glass fiber mat. The amount of the binder attached was 7.0% by weight.

The above-mentioned treated glass fiber mat and a nylon RIM raw material (product name: UBE nylon RIM grade UX Ube Industries, Ltd.) containing ε-caprolactam, a catalyst, a cocatalyst, etc., and a glass content of about 30% by weight A molded article was produced under the curing conditions of 150 ° C. for 3 minutes with the following composition. Table 1-2 shows the characteristic results of the molded product.

[0017]

[0018]

Comparative Examples 1 to 10 Glass fiber mats and molded articles were prepared in the same manner as in Examples 1 to 5, except that the conventional surface treatment agents shown in Tables 2-1 and 3-1 were used. Tables 2-2 and 3-2 show the characteristic results of the molded articles at that time.

[0020]

[0021]

[0022]

[0023]

Examples 6 to 8 As Examples 6 to 8, the characteristic results of molded articles produced in the same manner as in Example 5 except that the binders shown in Table 4-1 were used are shown in Table 4 It is shown in FIG.

[0025]

[0026]

Comparative Example 11 Table 4 shows the characteristic results of a molded article produced in the same manner as in Example 5 except that a polyester resin was used as a binder.
-2.

[0028]

The glass fiber reinforced nylon reaction injection molded article using the glass fiber mat according to the present invention has excellent appearance and surface curability of the molded article, and also has good mechanical properties of the molded article. The industrial value is extremely large.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI B29K 77:00 D06M 15/263 105: 08 C08L 77:00 D06M 101: 00 (72) Inventor Toshio Kamimi Kinu, Moka-shi, Tochigi 6, Moka Plant, Fuji Fiber Glass Co., Ltd. (72) Inventor Tetsuo Kita 1-4-1, Chuo, Wako-shi, Saitama Pref. Honda Technical Research Institute, Inc. (56) References JP-A-2-130115 (JP) JP-A 1-222111 (JP, A) JP-A 63-4911 (JP, A) JP-A 62-7513 (JP, A) JP-A 62-86026 (JP, A) 4-144722 (JP, A) JP-A-3-187717 (JP, A) JP-A-48-49850 (JP, A) JP-A 64-1933 (JP, U) (58) Fields investigated (Int. Cl. ⁶ , DB name) B29C 45/00-45/84 C08J 5/08 CFG C03C 25/02 D06M 15 / 263

Claims (2)

(57) [Claims] Claims 1. After treating a glass fiber with a composition containing an epoxy-modified acrylic copolymer, a polyoxyethylene type nonionic surfactant and an amino group-containing silane coupling agent as a surface treatment agent for the glass fiber, A glass fiber mat comprising glass fibers arranged in a sheet and fixing the glass fibers with a binder that does not dissolve in lactams. 2. After treating a glass fiber with a composition containing an epoxy-modified acrylic copolymer, a polyoxyethylene type nonionic surfactant and an amino group-containing silane coupling agent as a surface treatment agent for the glass fiber, A glass fiber reinforced nylon reaction injection molded product in which glass fibers are arranged in a sheet and reinforced with a mat in which the glass fibers are fixed with a binder that does not dissolve in lactams.