JPH05507676A - Size composition for impregnating filament strands - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Size composition technical field for impregnating filament strands The present invention provides highly loaded ed) relates to size compositions useful for impregnating impregnated fiber strands. Further In one of its special aspects, the present invention provides thermoplastic resin powder impregnated glass or fiber struts. Regarding the

Background technology The production of impregnated fibers and the application of thermoplastic resins to the fibers are known. fibers like this is coated with thermoplastic resin after the fiber strands are formed.

Sizing compositions typically used as coatings for glass fibers are Gate matata was also applied to the surface of the fibers after the fibers were formed. Typically, the size group Glass fibers are first manufactured by applying a thin layer of a compound onto the surface of bare glass fibers. It is necessary to The size composition is based on glass fibers and fibers treated with sizing agents. It needs to be compatible with the subsequently applied resin. The size composition is galamata Can be used to improve the bonding relationship between fibers and polymer resins or thermoplastics. Ru. The glass fibers are then collected into strands and the strands are passed around a take-up bobbin. The yarn is wound around a string to form a substantially cylindrical package, commonly referred to as a “thread package.” Form. Then, to dry the size composition applied to the surface of the glass fibers The yarn package is then air-dried or exposed to high temperatures. Then the glass fiber The fibers are impregnated with a thermoplastic resin to form an impregnated thread or cord.

However, it is difficult to produce high-performance thermoplastic resin-impregnated fiber strands. Have difficulty. Typically, the composition consists of a bonding relationship between a thermoplastic resin and glass fibers. Contains various processing aids to help improve the process. However, these processing aids The agent remains in the impregnated strand. Processing aid is clean thermoplastic resin impregnated glass If fibers are desired, for example, high performance thermoplastic resin impregnated fiber strands can be made. It is an undesirable material when used for construction.

fibers without the need for non-aqueous solvents, fluidized beds, sheaths or time-consuming manufacturing methods For impregnating the strands with thermoplastic resin, such as may be applied during the forming process. Significant time and cost savings would be achieved if a beneficial size composition were available. Probably.

In addition, it can be used when blended directly with thermoplastic resins during the glass fiber forming process. The size composition used yields qualitatively pure thermoplastic resin-impregnated glass strands. It is profitable to get.

Disclosure of invention According to the invention, a thermoplastic resin and a binder or film-forming agent and a thickener ( or rheology modifiers). A slurry composition is provided. The slurry composition of the present invention comprises a stable polymer. “Involves the use of labile processing components together with stable polymers to obtain prepregs.

The slurry composition is applied to glass fibers during a fiber forming operation. Thus, the present invention The composition can be applied as a glass fiber size during a fiber forming operation and the resulting size The thermoplastic resin-impregnated glass fibers are then processed into glass fiber-reinforced products. Can be processed.

According to the present invention, in order to obtain a thermoplastic resin reinforced fiber strand, the size is first applying the sizing composition to the glass fibers and then sizing the resulting sized glass. There is no need to impregnate the fibers with a compatible polymer resin. of the present invention The slurry composition is coated with a sizing agent impregnated with a compatible polymeric resin matrix. give the glass fibers. Impregnated glass fibers contain undesirable processing materials. First, it is beneficial for a wide variety of high-performance glass-reinforced end-use products.

These and other aspects and advantages of the invention are described in detail below. It becomes clear after considering the detailed explanation.

Brief description of the drawing Figure 1 is a graph showing thermogravimetric analysis of a slurry containing polyphenylene sulfide. be.

Figure 2 is a graph showing thermogravimetric analysis of glass fibers impregnated with the slurry shown in Figure 1. It's rough.

The best way to carry out the invention The present invention provides an improved filament that is pre-impregnated with a thermoplastic polymer during the filament forming operation. Slurry composition useful for producing yarn or strands (towards filaments) Regarding products.

The invention is compatible with any glass fiber commonly used to reinforce polymer resins. . As used herein, the term "garamata fiber" refers to one or more fibers of molten glass. These galamata fibers are formed due to the attenuation of the flow and are held together during the forming process. Refers to filaments that are formed into strands when assembled. Also , the term refers to the process of applying and/or heating a large number of strands together. forming rabbets, such as woven fabrics formed from glass fiber strands, threads or cords; Refers to yarns and cords made into cloth and non-woven fabrics.

The individual components used in the practice of the invention are commercially available and thus the features of the invention can be easily blended with each other in preparing formulations embodying the following.

Generally, the compositions of the present invention include a carrier solvent, usually water, a coupling agent, and a binder. processing aids such as mixtures or film formers, thickeners or rheology modifiers; matrix thermoplastic dispersed during sizing to form slurry May contain resin powder.

Any suitable coupling agent may be used in the successful practice of this invention. cupri The binder creates adhesion between the matrix I-IJ resin, provides strength, and absorbs the matrix in the slurry. Acts to provide retention of trix resin. One of the suitable coupling agents Examples are silanes such as diamine silane (Z6020 from Dow Corning). Ru. The turnip agent may be included in an amount of about 1.2% by weight of the slurry mixture.

Any suitable labile binder may be used. Also, unstable thickeners are the same as binders. It may be a material. A binder or film-forming agent is a fibre-forming agent during the fiber-forming process. Assists in handling and processing of lament. Suitable binders or film formers include e.g. For example, epoxy, polyester, polyvinyl acetate, polyvinyl alcohol, acrylic or a thermoplastic resin powder particle that has the ability to bind to fibers after water evaporation. suspend the particles in a slurry with other chemicals or by itself, and then Other chemicals that bind to fibers. One example of a suitable labile binder is polyethylene. It is an oxide. The binder ranges from about 1.0 to about 1.2% by weight of the slurry mixture. included in the amount of

Any suitable unstable thickener may be used. The thickener is made of thermoplastic resin powder particles. Acts as a rheology modifier so that it actually adheres to the fibers. using thickener Otherwise, the thermoplastic resin powder particles will leave the application while the carrier solvent leaves the fiber. It may remain in the controller's roll. The result is on the applicator roll of powder, which in turn quickly results in fiber breakage.

The thermoplastic resin is dispersed during sizing in the form of fine particles. One example of resin is polyphenylene sulfide. In a preferred embodiment, the powder particle size is less than about 125 microns. According to the invention, the resin powder is the final prepreg yarn. or may be applied to the filament in an amount ranging from about 5 to about 50% by weight of the strand. .

According to the present invention, the sizing composition has thermoplastic resin powder particles suspended in a slurry. do. The slurry composition of the present invention has all the ingredients in their liquid state without stirring. It is best produced by blending. Uniform coverage of composition may be applied to the glass fibers in any suitable manner during the fiber forming process. present invention The composition is disclosed in co-pending U.S. Patent No. No. 7/269.089 (filed March 12, 1984, now abandoned). (a continuation of U.S. Patent No. H071024°953) (all of these glass fibers by the method described in (the disclosure of which is expressly incorporated herein by reference). It is preferably applied to the surface of.

The resulting slurry composition is sufficiently liquid to be applied to the fibers during the fiber forming operation. be. Each fiber is coated with the slurry mixture as the fiber is formed and is immediately coated with the slurry mixture. the location of their formation where normal size compositions are typically applied (e.g. The fibers are coated near the fibers (between the sheath and the spindle where the fibers are wound as a package). .

In one fiber forming process, continuous fibers emerge from a bush and are dipped into a slurry. Impregnated with a final slurry.

Also useful for producing organic or inorganic fillers, e.g. conductive rovings It is contemplated by the present invention that metallic fillers may also be used with thermoplastic polymer powder particles. within the intended range. These fillers are characterized by the fact that each powder particle has a polymer and Can be premixed to contain fillers or added separately to the slurry as a powder. Ru.

The resulting impregnated strands may be chopped before or after drying and subjected to operations such as injection molding. It can be used for production. Continuous thermoplastic impregnated strands can be filament wound or It can be pultruded to obtain a thermoplastic fiber reinforced end-use product.

High performance thermoplastic resin is used as Mad 177 resin in fiber reinforced compositions. shows advantages over thermosetting polymers when These advantages include good high temperature performance , by using resin strands. This is a high performance reinforced with continuous fibers. Particularly useful for thermoplastics. The present invention is based on pre-impregnation with such thermoplastic resin. Describe the strands.

Thermoplastic resin powder is dispersed in water. Usually the surface active side is added to water and powdered Helps moisturize. Thickeners, typically water-soluble polymers, are added to increase the viscosity of the liquid phase do. Other additives such as silane coupling agents may also be added to the aqueous suspension (also known as (referred to as "slurry"). This slurry is used as the right size, As disclosed in co-pending U.S. patent application Ser. No. 07/269.089, cited above. as applied to the glass fibers as they are formed. thickener, it heat It is thermally decomposed into volatile products at a temperature lower than the decomposition temperature of plastic resin powder. selection and that even after this thermoplastic is fused, this thermoplastic It decomposes in the presence of this thermoplastic without seriously degrading the properties of the resin. this Examples of such binders are polyethylene oxide, hydroxypropyl cellulose , starch, and hydroxyethylcellulose. In addition, this thickener is a binder. The binder binds the thermoplastic resin powder to the fiber strands after drying. used to hold and therefore give impregnated strands with good integrity . The binder may also be an additional ingredient added to the slurry. However However, the thickener selected is also thermally degradable. Also, the wetting agent selected should be Volatile or thermally decomposable at temperatures.

Once the slurry is applied to the glass fibers, the formed package is dried. Continued The thermoplastic resin-impregnated fiber is heated to a temperature higher than the fusion temperature of the thermoplastic resin powder. The result is that the powder is completely or partially fused, or that there is no need to rely on a binder. is retained in the fibers. This heating step may include partial decomposition of unstable components. or may be preceded by, thus increasing the melting temperature of the thermoplastic. The decomposition of unstable components is completed at higher or lower temperatures. These works - Any of the above may be combined with a modification of the thermoplastic such as "curing 2" or "annealing". May be combined.

Polyphenylene sulfide powder (Ry from Phillips Chemical Company) A fine powder (<125 microns) of a high-performance thermoplastic resin such as t-on) H is Disperse in an aqueous solution of a wetting agent in a proportion of . 1200 parts water, 4 parts Taj Tergitol Nin Foam 2 x ( (from Union Carbide). Stir these together and add 800 parts by weight Add Vl, stir until good wetting and add 14800 parts by weight of water. and stir.

This slurry was poured into a 115-mesh sieve little by little to remove coarse fractions and powder. Separate into fine fractions. Pass the slurry through a sieve, collect and let it settle for at least 12 hours. make it rain The settled powder is collected by passing it through a 115 mesh. Also, The upper liquid (hereinafter referred to as water/surf) is collected.

Prepare a slurry with the following composition. IJ) passing through 115 mesh (equivalent to dry powder) 1200 parts, water/surf 2764 parts, polyethylene Oxide (Polyox WS from Union Carbide) Add 48 parts of R205 and mix well until uniform. This is 31.1% to give a slurry containing solids. When the glass fibers are formed, they are coat with a slurry of Transfer the slurry to a regular sieve fitted with a doctor blade. Apply with a double applicator and adjust film thickness with an applicator roll. .

Two forming packages with 2000 filaments/strands were prepared as follows: Make it like this.

Package #1 Total amount of solids relative to glass - 21.1% Package #2 Total amount of solids to glass = 20.0% Package #1 was dried for 1 day under indoor conditions. dry The package (after replacing the cardboard forming tube with steel) was then heated to 300°C. Place in air oven for 1 hour. Polyphenylene sulfide is fused and polyoxyethylene Polyphenylene oxide thermally decomposes into volatile substances, and polyphenylene oxide further decomposes into volatile substances. Cures into a high molecular weight polymer. When the package is removed from the oven and allowed to cool, the Strands of impregnated glass are easily removed from the package despite the large amount of impregnated resin It can be rolled out.

The strands are filament wound in a mold to form a unidirectional composite.

The strands can then be compression molded into an end-use product. 80142kg /cm2 (114k psi) Indicates that it has a property.

Dry package #2 like package #1, but with polyphenylene sulfur. Before fusing the strands, the strands are wound around the plate to form a unidirectional layer. next Place the plate in an air oven at 300°C as done for package #1 above. Leave it for 1 hour. The unidirectional layer is fused to the sheet, which is then combined into a unidirectional composite material. Can be used for compression molding. The measured bleeding strength is 111,436 kg/cm2 ( 120,0OOpsi), which also exhibits beneficial mechanical properties.

Example 2 Polyphenylene sulfide powder (Lidone Vl from Phillips Chemical Company) A fine powder (<125 microns) of a high performance thermoplastic resin such as Disperse in an aqueous solution of the agent. 1200 parts by weight of water, 1 part of 4 parts Tajitor Nin - Form 2x (from Union Carbide). 800 parts by weight of Lydone Vl Add 14,800 parts by weight of water and stir until good wetting. Stir. Pour this slurry into a 115-mesh sieve little by little to separate the powder into coarse particles. Separate into graded and finely classified substances. Pass the slurry through a sieve and collect at least 1 Let settle for 2 hours. Collect the settled powder by passing it through a 115 mesh. . Prepare a slurry with the following composition. Ridon Vl passing through 115 mesh ( (equivalent to dry powder) 1200 parts, water/surf 2764 parts, polyethylene Oxide (Polyox 11sR205 from Union Carbide) 42 and 48 parts of diamine silane (26020 from Dow Corning) were added. Ru. This gives a slurry containing 31.8% solids. Garamata fibers are formed During the process, they are coated with the slurry described above. slurry, doctor blade Adjust the film thickness by applying with a regular size applicator attached. Adjust with tar roll. Forming pad with 2000 filaments/strands Make a cage.

Package #1 Total amount of solids relative to glass - 26.2% Package indoors Dry under the following conditions for one day. Wrap the strands around the plate to form a unidirectional layer. Next Place the plate in an air oven at 300°C for 1 hour. polyphenylene sulfide The polyoxyethylene oxide thermally decomposes into volatile substances, and the polyethylene oxide Phenylene oxide is further cured into a high molecular weight polymer. Remove the package from the oven. When grown and cooled, the unidirectional layer fuses into a sheet, forming a unidirectional composite material. Can be used for compression molding. Measured bending strength varies from 10,545 to 10,545 depending on molding conditions. 13357 kg/sq cm (150,000-190.0OOpsi) useful Shows mechanical properties.

Thermogravimetric analysis (TGA), as shown in Figures 1 and 2, shows that unstable components during thermal decomposition are Verify removal. In the first series of tests, the samples were heated at a uniform rate of 20°C/min. and record the weight of the sample as a function of temperature.

Figure 1 shows that pure polyphenylene sulfide (PPS) hardly decomposes below 300°C. It is shown that there is no change in temperature and that there is negligible weight loss up to 500°C. on the other hand, Polyethylene oxide used as an unstable thickener and binder decomposes at 200℃ It started to vaporize almost completely by the time the temperature reached 400°C. The solid curve is , shows the weight loss of the dry slurry as the temperature increases. From 200℃ to point A The weight loss is due to loss of polyethylene oxide in the slurry. Above point A, The weight loss of the residual PPS in the dried slurry is approximately the same as that of pure PPS. be.

In another thermogravimetric analysis shown in FIG. Exposure of the dried glass to a temperature of 300°C (for 1 hour in a 300°C oven) to simulate the thermal history of placed dry impregnated glass). The weight of the sample is as follows Met. As seen in Figure 2, within 5 to IO minutes, most of the volatile substances are Decomposed and volatile substances removed. After 1 hour there was no further weight loss.

Recorded weight loss (100-98,2) = 18% for polyethylene oxide, Due to the loss of small amounts of volatile content in the PPS and residual moisture in the strands.

Although preferred formulations of the present invention have been described, those skilled in the art will appreciate that various modifications can be made. I beg you. These improvements are claimed to include all equivalent formulations, compositions, etc. Matches the widest range.

○J Summary book Contains resin.

ms! jI Inquiry 1h or T Hai Is Q1102499 International Search Report

Claims (2)

[Claims] 1. At least a portion of the surface of the glass fiber is formed during formation of the glass fiber. coated with a residue resulting from evaporation of water from an aqueous composition applied to the surface. based on the weight of the aqueous composition, the aqueous composition comprising: from about 30 to about 50% by weight of polyphenylene having an average particle size of about 125 microns or less sulfide thermoplastic resin powder, about 0.005-5.0% by weight diamine silane a coupling agent, about 0.5-5.0% by weight of a polyethylene oxide thickener; Glass fibers consisting essentially of water-based surfactants. 2. At least a portion of the surface of the glass fiber is made of 29.66% by weight polyphenylene. sulfide, 1.04% by weight polyethylene oxide, 1.18% by weight dia water from an aqueous composition consisting of minsilane and 68.18% by weight water surfactant. Glass fibers coated with residue resulting from evaporation.