JPH01268762A - Fiber-containing massive colored resin composition and production thereof - Google Patents

Abstract

PURPOSE:To obtain the subject resin composition useful as a raw material or reinforcing material for composite materials, by applying a liquid containing a binder, whiskers and colorant to fibers, mixing the resultant fibers with a matrix resin, cutting the mixture in a wet state to provide a massive form and drying the resultant masses. CONSTITUTION:The objective composition produced by applying a liquid containing (B) 0.5-10pts.wt. one or more resins selected from epoxy, phenolic, polyamide, urethane and unsaturated polyester resins as a binder, (C) whiskers, (D) a colorant and, as necessary, a granular carbon material to (A) 100pts.wt. one or more fibers selected from carbon, glass and aramid fibers and mixing (E) 60-1,000pts.wt. matrix resin (which is a solid at ordinary temperature) simultaneously or after the application, cutting or dividing the resultant mixture into masses in a wet state and drying the obtained masses.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a fiber-containing bulk colored resin composition and a method for producing the same.

The fiber-containing bulk colored resin composition of the present invention is useful as a raw material for composite materials whose main material is resin, and as a reinforcing material for such composite materials. It can be colored.

Carbon fibers, glass fibers, aramid fibers, and the like are used to impart electrical conductivity to resins, cement, etc., and to improve their mechanical properties, molded dimensional stability, and the like.

To give a more specific explanation using carbon fiber as an example, the fiber length is 1 m or less, which has been treated with a binding agent, with the main purpose of not only improving the strength of the composite material, but also imparting conductivity and improving sliding properties. are blended into the base material of the composite partner.

Such improvements in physical properties are achieved by the added sizing agent improving the adhesion between the base material and the carbon fibers. Conventional surface treatment of carbon fibers with a sizing agent involves applying a liquid containing a sizing agent to carbon fibers in the form of long fibers, mats, tows, etc., drying them, winding them around a bobbin, and cutting them. This is done by using short fibers.

However, the surface treatment of carbon fibers according to such conventional techniques has the following drawbacks.

(a) Since the carbon fibers are cut after being treated with a sizing agent, no sizing agent is applied to the cut end surface.

Therefore, the physical properties of the composite material cannot be sufficiently improved.

(b) Dust is generated when cutting carbon fibers, which worsens the working environment.

(c) Carbon fiber is conductive, so the short fiber processing machine's operation panel and surrounding switch boxes must be sealed to prevent electrical leakage and electric shock.

The above problems, except for (c), also apply to glass fibers and aramid fibers.

Taking the example of blending short carbon fibers into resin, the short carbon fibers are usually pelletized through the following pelletizing process.
Although they are mixed into resins, each has its own problems.

(i) Add the required amount of short carbon fibers to resin pellets or resin powder, disperse them uniformly using a high-speed rotating mixer, extrude them into a rope shape while kneading them under heat and pressure, and after cooling, 3 to 5 mm. The pellets are then cut into pellets consisting of short carbon fibers and resin.

In this case, the fibers are likely to break in the high-speed rotating mixer, and the sizing agent attached to the fibers may be detached. Therefore, improvements in physical properties of composite materials obtained using such pellets are insufficient.

(ii) Add the required amount of short carbon fibers to resin pellets or resin powder, disperse uniformly with a high-speed rotating mixer, then extrude into a rope shape while kneading under heat and pressure, and cut into 3 to 5 mm pieces. The pellets are then cooled and dried to form pellets consisting of short carbon fibers and resin.

Also in this case, since a high-speed rotating mixer is used, the same problem as in (i) above occurs.

(i i i) A certain age of resin pellets or resin powder and short carbon fibers are continuously put into an extrusion molding machine, kneaded under heat and pressure, molded into a rope shape, and after cooling, 3
Cut into pieces of ~5 mm to make pellets.

In either case, it is necessary to knead the resin and carbon fibers under heat and pressure to form pellets.

The above problems regarding carbon fibers also apply to glass fibers and aramid fibers, with some exceptions.

Means for Solving the Problems The inventor of the present invention has conducted various studies in view of the problems of the prior art as described above, and has developed a block colored resin composition consisting of carbon fibers, a sizing agent, whiskers, a coloring agent, and a matrix resin. It has been found that the problems of the prior art can be greatly reduced or substantially eliminated if the article is manufactured in a wet state. Furthermore, it has been found that when the solution or dispersion used at this time also contains a colored additive component, the composite material can be easily colored uniformly and clearly.

That is, the present invention provides the following composition and method for producing the same.

(a) 100 parts by weight of at least one type of fiber selected from the group consisting of carbon fiber, glass fiber and aramid fiber, (b) epoxy resin, phenol resin, polyamide resin, urethane resin and unsaturated polyester resin as a binding agent. 0.5 to 10 parts by weight of at least one resin selected from the group consisting of (c) matrix resin 60 to 1
000 parts by weight of a fiber-containing bulk colored resin composition comprising (d) whiskers and (e) a coloring agent.

(2) The fiber-containing bulk colored resin composition according to item 1 above, which further contains a granular carbon material.

■ (a) At least one type of fiber selected from the group consisting of carbon fiber, glass fiber, and aramid fiber, and (b) epoxy resin, phenol resin, polyamide resin, urethane resin, and unsaturated polyester resin as a binding agent. A liquid containing at least one resin selected from the group, (d) whiskers and (e) a coloring agent is applied, and (c) a matrix resin is mixed at the same time or after this application, and cutting or dividing in a wet state. A method for producing a fiber-containing bulk colored resin composition, which comprises curing the composition into a block and then drying the composition.

The carbon fibers, glass fibers, and aramid fibers used in the present invention are not particularly limited in shape, raw material, etc. for example,
In the case of carbon fibers, they may be long fibers, tow-like fibers, or mat-like fibers, and their raw materials may be coal-based, petroleum-based, or organic fiber-based.

As the sizing agent used in the present invention, epoxy resins, phenol resins, polyamide resins, urethane resins, unsaturated polyester resins, and the like are used in the form of solutions, dispersions, and the like. The concentration of these convergence agents in liquids such as solutions and dispersions is not particularly limited, but is usually about 1 to 10% by weight. Moreover, two or more types of convergence agents may be used in combination. In the present invention, the sizing agent refers to something that has the function of aggregating fibers and maintaining the aggregated state.

The solvent or liquid medium for the resin is not particularly limited,
Examples include water, toluene, ethanol, and methyl ethyl ketone. These solvents or liquid mediums may be appropriately selected depending on the type of sizing agent used.

As the whiskers used in the present invention, white whiskers such as potassium titanate whiskers and aluminum oxide whiskers are preferable from the viewpoint of reinforcing effects and masking effects. If only a masking effect is to be achieved, a powder such as titanium dioxide may be used.

Examples of the coloring agent used in the present invention include titanium oxide, cadmium red, cadmium yellow, cobalt blue, and perinone pigment (red).

The matrix resin used in the present invention includes those that are solid at room temperature, such as polyamide resin, polyphenylene sulfide resin, polyacetal resin, and polypropylene resin. In addition, in the present invention, the matrix resin refers to a matrix resin when manufacturing carbon fiber reinforced resin (CF RP) using the bulk colored resin composition according to the present invention.
Refers to something that can be used as a matrix for CFRP.

In the present invention, granular carbon materials such as mesocarbon microbeads and carbon black can be blended in order to impart functions such as sliding properties and conductivity.

In the composition of the present invention, the sizing agent is generally used in an amount of 0.65 to 10 parts by weight, preferably 1 to 8 parts by weight, per 100 parts by weight of fibers such as carbon fibers.

If the amount of binding agent is too small, the shape retention of the fibers will be insufficient, whereas if the amount of binding agent is excessive,
Inhibits reinforcing hardening by fibers.

In the present invention, whiskers are also used to improve the physical properties of the composite material and the color development, but the amount used varies depending on the type of fiber, the degree of coloring, the properties of the colorant used, etc. , it is not possible to define it unambiguously, but it is determined according to the purpose of use. For example, by blending potassium titanate whiskers, even when black carbon fibers are used, the mechanical strength of the composite material can be improved and a beautiful color can be imparted. In this case, the amount used is preferably about 20 to 100 parts by weight based on 100 parts by weight of carbon fiber.

If the amount of the colorant is too small, the coloring will be insufficient, whereas if it is in excess, the physical properties of the composite material may be deteriorated. The amount of coloring agent used is also determined depending on the purpose, as in the case of the whiskers described above. Generally, the amount of colorant used varies depending on the degree of masking effect of the whiskers used, even when the same colorant is used to produce the same color. - For example, when carbon fiber is used as the fiber and potassium titanate is used as the whisker, the amount of cadmium yellow used as the coloring agent is about 2 to 30 parts by weight per 100 parts by weight of carbon fiber.

The amount of granular carbon material used in the present invention varies widely depending on the purpose, but is usually 30 to 90 parts by weight per 100 parts by weight of carbon fiber.
It's in a prize that weighs about 0 parts by weight. When imparting electrical conductivity to a carbon fiber composite material, it is desirable that the lower limit be about 30 parts by weight of the granular carbon material per 100 parts by weight of carbon fibers in order to ensure uniform dispersion. Conversely, in order to ensure that the powder exhibits its properties as a sliding material, it is necessary to add 90% of the granular carbon material to 100 parts by weight of carbon fiber.
It is also possible to use up to about 0 parts by weight.

The method of the present invention is carried out as follows. First, fibers such as carbon fibers are immersed in a solution, dispersion, etc. of a sizing agent containing a colorant and whiskers, or a solution, dispersion, etc. of a sizing agent containing a colorant and whiskers is sprayed onto the fibers. Colorants, whiskers and binding agents are applied to the fibers by means of. Next, a dryer, rollers,
After removing excess liquid by any means such as a centrifuge,
Both matrix resins are mixed and extruded using a mixer, an extruder, etc., and the mixture is cut or divided into predetermined sizes (for example, 4 mm in diameter and 5 mm in length) in a wet state. The cut or divided lumps retain their shape due to the presence of the sizing agent. If it is dried, its handling becomes even easier. Most preferably, the excess liquid is removed using a dryer. When removing the liquid by other means, care must be taken because, for example, only the coloring material may be removed and the composition may vary or become non-uniform.

The mixing of the colorant, whisker and matrix resin in the present invention is not limited to the above order.

For example, it is also possible to add a matrix resin to the liquid in advance. However, it is preferable to mix in the above order because mixing can be performed most uniformly.

Further, the order in which the granular carbon material is mixed is not limited, but in order to achieve uniform mixing and prevent generation of dust during operation, it is preferable to mix the granular carbon material into the sizing agent liquid.

The process of producing a block composition from a mixture is conveniently carried out using a mixing extruder similar to a mincing mixer, since the fibers are cut at the same time as compression, and pea-sized blocks are directly obtained. .

Effects of the Invention Since the fiber-containing bulk coloring composition of the present invention contains a colorant and a matrix resin, a fiber-reinforced resin of a desired color can be obtained by directly molding the composition without adding a matrix resin. Of course, it is also possible to change the composition of the molded article by further adding matrix resin, coloring agent, etc. prior to molding.

Moreover, the addition of whiskers compensates for the decrease in performance due to the mixing of colorants, and the whiskers exhibit a masking effect, so even when carbon fibers are used, a uniform and beautifully colored fiber-reinforced resin can be obtained.

In addition, since the fiber-containing colored bulk resin composition of the present invention is produced in a wet state, it prevents deterioration of the working environment due to the generation of floating dust during production, as well as electrical leakage and electric shock (in the case of carbon fibers) due to attached dust. be done. Even when molding is performed using this, no dust is generated.

Furthermore, by using the composition of the present invention, molding manufacturers do not need to prepare fibers, colorants, whiskers, and matrix resin separately, nor do they need equipment to mix them. Since colored fiber-reinforced resin molded products can be produced, the economic effect is extremely large.

Furthermore, when using the composition of the present invention, the fibers are supplied to the molding machine while being uniformly included in the composition, so a molded product with stable quality in which the fibers are uniformly dispersed in the matrix resin can be produced. As a result, the phenomenon of fiber blocking, which is often a problem with fiber-reinforced resins, is prevented.

EXAMPLES Examples will be shown below to further clarify the features of the present invention.

In the following, "parts" and "%" represent "parts by weight" and "% by weight," respectively.

Example 1 A sizing agent solution was prepared by adding 280 g of water to 9 g of a 50% aqueous solution of a water-soluble epoxy resin, and further adding 25 g of potassium titanate whiskers and 2.5 g of perinone pigment (red). Next, after impregnating 75 g of matte pitch-based carbon fiber with the sizing agent liquid, 6-nylon powder (average particle size 1
00μm) 150g were mixed uniformly, pre-dried with hot air at 80℃ to adjust the wet state, placed in a mixer/extruder, and extruded into a strand with a diameter of 4mm.
It was cut into 5 mm length pieces and dried at 150°C for 2 hours.

The weight of the obtained fiber-containing blocky red resin composition was 249
It was g.

Example 2 To 9 g of a 50% aqueous solution of a water-soluble epoxy resin, 2 g of an epoxy resin curing agent and 280 g of water were added and stirred, and further 25 g of potassium titanate whiskers and 5 g of cadmium yellow were added to prepare a sizing agent solution. Next, after impregnating 75 g of matte pitch-based carbon fiber with the sizing agent liquid, 150 g of 6-nylon powder (average particle size 100 μm) was mixed uniformly and pre-dried with hot air at 80° C. to adjust the wet state. and put it in the mixer/extruder, and
After extruding into 5 mm strands, cut into 5 mm lengths,
It was dried at 120°C for 2.5 hours.

The weight of the obtained fiber-containing blocky yellow resin composition was 251
It was g.

Example 3 Fiber-containing blocky blue resin composition 25 was prepared in the same manner as in Example 1 except that cobalt blue was used as the colored additive component.
Obtained 0g.

Example 4 Example 1 except that a mixture of equal amounts of mat-like pitch-based carbon fiber and mat-like glass fiber is used as the fiber material.
In the same manner as above, a red blocky carbon fiber-glass fiber-epoxy resin composition was obtained.

Example 5 280 g of water was added to 9 g of a 50% aqueous solution of water-soluble epoxy resin, and further 25 g of potassium titanate whiskers, 25 g of mesocarbon microbeads, and perinone pigment (
A sizing agent liquid was prepared by adding 2.5 g of red). Next, after impregnating 75 g of matte pitch-based carbon fibers with the sizing agent liquid, 1 lb. of 6-nylon powder (average particle size 100 μm) was added.
Mix 50g uniformly, pre-dry with hot air at 80℃ to adjust the wet state, put in a mixer extruder, extrude into strands with a diameter of 4mm, cut into 5mm lengths, and heat at 150℃ for 2 hours. Dry.

The weight of the obtained fiber-containing blocky red resin composition was 273
It was g.

Example 6 2 g of an epoxy resin curing agent and 280 g of water were added to 9 g of a 50% aqueous solution of water-soluble epoxy resin, stirred, and further mixed with 25 g of potassium titanate whiskers, 2 carbon flakes, and
A sizing agent solution was prepared by adding 5 g of stent and 5 g of cadmium yellow. Next, mat-like Pi-Tutsi carbon fiber 7
After impregnating 5 g of the sizing agent liquid, 150 g of 6-nylon powder (average particle size 100 μm) was mixed uniformly, the wet state was adjusted using a roller, and the mixture was placed in a mixer/extruder to form strands with a diameter of 4 mm. After extrusion, length 5
It was divided into mm pieces and dried at 120°C for 2.5 hours.

The weight of the obtained fiber-containing blocky yellow resin composition was 256
It was g.

Example 7 Fiber-containing blocky blue resin composition 27 was prepared in the same manner as in Example 5 except that cobalt blue was used as the colored additive component.
5g was obtained.

Example 8 A red blocky carbon fiber-glass fiber-epoxy resin composition was prepared in the same manner as in Example 5, except that an equally coarse mixture of mat-like pitch-based carbon long fibers and mat-like glass fibers was used as the fiber material. I got something.

(that's all)

Claims (3)

[Claims] (1) (a) 100 parts by weight of at least one type of fiber selected from the group consisting of carbon fiber, glass fiber and aramid fiber, (b) epoxy resin, phenol resin as a binding agent,
At least one resin selected from the group consisting of polyamide resin, urethane resin and unsaturated polyester resin
．． A fiber-containing bulk colored resin composition comprising 5 to 10 parts by weight, (c) 60 to 1000 parts by weight of a matrix resin, (d) whiskers, and (e) a coloring agent. (2) The fiber-containing bulk colored resin composition according to claim 1, further containing a granular carbon material. (3) (a) At least one type of fiber selected from the group consisting of carbon fiber, glass fiber and aramid fiber, (b) epoxy resin, phenol resin as a binding agent,
Applying a liquid containing at least one resin selected from the group consisting of polyamide resin, urethane resin and unsaturated polyester resin, (d) whiskers and (e) coloring agent, and (c) at the same time or after this application. A method for producing a fiber-containing bulk colored resin composition, which comprises mixing a matrix resin, cutting or dividing it into blocks in a wet state, and then drying the mixture.