JP6570104B2 - Colored prepreg and tubular body - Google Patents

Description

  The present invention relates to a colored prepreg composed of reinforcing fibers and a colored matrix resin and a tubular body using the colored prepreg.

As a manufacturing method for coloring a fiber reinforced resin material (so-called prepreg) formed by impregnating a reinforced fiber with a matrix resin, there is the following method.
(1) There is a manufacturing method in which only the matrix resin is colored (Patent Document 1).
(2) There is a manufacturing method in which only reinforcing fibers are colored (Patent Document 2).
(3) There is a manufacturing method of overlapping colored sheets (Patent Document 3).

JP-A-6-200053 (paragraph number [0010]) Japanese Patent Laid-Open No. 4-18308 (the second page, upper left column, the 10th line to the 17th line) JP 2011-236274 A

  (1) Even when the matrix resin is colored only, the reinforcing fiber also has a unique color. Therefore, even if the matrix resin is given a desired color, depending on the color of the reinforcing fiber, the desired matrix resin When coloring is made thin or turbid to form a molded product such as a fiber reinforced resin material (prepreg), sufficient color developability may not be obtained.

Accordingly, there is a method of mixing a concealing material together with a coloring material for the purpose of diminishing the inherent color of the reinforcing fiber or for the purpose of concealment (Japanese Patent Laid-Open No. 3-1119038). The coloring material interferes and sufficient color developability cannot be obtained.
Therefore, as in Patent Document 1, a layer containing a concealing material is used as a lower layer, a layer containing a coloring material is used as an upper layer, and an isolation layer is provided between them. In the coloring material layer, a reinforcing fiber having high transparency is used. It was necessary to take measures such as using it.

  (2) On the other hand, it is possible to apply other colors to the surface of the reinforcing fiber, but depending on the type of the reinforcing fiber, there are some which cannot be colored or become problematic when colored. For example, carbon fiber and aramid fiber are fiber types that are difficult to color.

  (3) In order to eliminate such difficulties, generally, painting and printing are used. However, in this case, a dedicated coating device and a process for applying them are required, and there are aspects of poor production efficiency and a sufficient coating thickness is required, so that the base material for the colored fiber reinforced composite material becomes heavy. However, there are aspects that are not sufficient when there is a demand for weight reduction.

  Moreover, since such dedicated coating apparatuses and processes for applying them are required, a considerable number of processes are required, and if the number of manufacturing rods is not large, there is a risk that manufacturing costs may be disadvantageous.

  (4) Considering the points as described above, there is a method in which the present applicant puts a colored sheet on the prepreg as in the invention described in Patent Document 3, but in terms of manufacturing process and manufacturing cost In need of further improvement.

  The object of the present invention is to eliminate the disadvantages of the prior art, and can be adopted even when a highly chromogenic reinforced fiber type is used without losing the original performance and characteristics of the fiber reinforced resin material. The present invention provides a simple colored prepreg.

〔Constitution〕
The characteristic configuration of the invention according to claim 1 is a prepreg formed by impregnating a reinforcing resin group with a matrix resin mixed with a pigment that suppresses the coloring property inherent to the reinforcing fiber and imparts coloring property to the resin itself.
The pigment mixed in the matrix resin is impregnated from the front side of the reinforcing fiber group, a part of which is captured by the reinforcing fiber, and the remaining part moves to the back side and is distributed in the reinforcing fiber group. A colored prepreg in which the mixing density of the pigment is greater than the mixing density in the back half,
The pigment is a glass flake made of a glass substrate having a color developing layer on the surface, or a metal flake made of a metal substrate having a color developing layer on the surface, and has a light coherent color development , and its effect Is as follows.

[Action]
That is, since the surface side half is higher than the back side half in terms of the density of the pigment, if the front side half is used for the display surface, the colored prepreg can be highly colored.

〔effect〕
Therefore, it is not necessary to adopt a complicated configuration in which a layer containing a concealing material and a layer containing a coloring material are overlapped via an isolation layer, and manufacturing restrictions such that a transparent fiber is required. In addition, high color developability can be obtained without being inhibited by the color inherent to the matrix resin and the reinforcing fibers, and desired color can be easily obtained regardless of the hard-to-color strengthening resin.
Also, even if the ratio of the pigment to the matrix resin is the same, it can be accumulated on the surface side half, so that it can exhibit the same color developability as that mixed at a higher ratio, and there are few pigments Can provide an effective coloring function.

[Action]
That is, since the front surface side is higher than the back surface side in terms of the density of the pigment, if the front surface side is used as a display surface, a colored prepreg can be made highly colored.
On the other hand, if the low-density side is used as the display surface, the density increases toward the opposite side, thereby increasing the depth of the color.

〔effect〕
Therefore, it is not necessary to adopt a complicated configuration in which a layer containing a concealing material and a layer containing a coloring material are overlapped via an isolation layer, and manufacturing restrictions such that a transparent fiber is required. In addition, high color developability can be obtained without being inhibited by the color inherent to the matrix resin and the reinforcing fibers, and desired color can be easily obtained regardless of the hard-to-color strengthening resin.
Even if the ratio of the pigment to the matrix resin is the same, the degree of integration can be changed from the front side to the back side, so the back and front can be selected arbitrarily compared to those uniformly dispersed Can be used.

[Action]
In other words, the glass flakes themselves are transparent, providing a strong gloss and transparency. By changing and adjusting the coating material that forms the color-developing layer, the color of the matrix resin is vividly developed. Can be made.
In addition, the metal flakes provide various colors by the color developing layer, and ensure the color developability of the matrix resin.

〔effect〕
Therefore, it is not necessary to adopt a complicated configuration in which a layer containing a concealing material and a layer containing a coloring material are overlapped via an isolation layer, and manufacturing restrictions such that a transparent fiber is required. In addition, high color developability can be obtained without being inhibited by the color inherent to the matrix resin and the reinforcing fibers, and desired color can be easily obtained regardless of the hard-to-color strengthening resin.
By adopting glass flakes or metal flakes, it is possible to obtain color development utilizing light coherence and the like, so it is possible to obtain a colored prepreg made of a colored matrix resin having various color developability.

〔Constitution〕
The characteristic configuration of the invention according to claim 2 is formed by impregnating the reinforcing fiber group with a colored matrix resin formed by mixing the pigment in a ratio of 0.04% to 17% with respect to the resin. The operational effects are as follows.

[Action]
That is, by mixing the pigment at a volume ratio of 0.04% to 17% with respect to the matrix resin, even if the reinforcing fiber has a unique color, it exhibits a color development different from the color of the reinforcing fiber. A colored prepreg could be obtained.

〔effect〕
Therefore, it is not necessary to adopt a complicated configuration in which a layer containing a concealing material and a layer containing a coloring material are overlapped via an isolation layer, and manufacturing restrictions such that a transparent fiber is required. In addition, high color developability can be obtained without being inhibited by the color inherent to the matrix resin and the reinforcing fibers, and desired color can be easily obtained regardless of the hard-to-color strengthening resin.

[Function and effect]
Even if the reinforcing fiber has a specific color by mixing the pigment at a ratio of 0.04% to 17% by volume with respect to the matrix resin exhibiting a liquid in which the solid content has been dissolved, the color of the reinforcing fiber A colored prepreg exhibiting a color different from that of the sample was obtained.

On the other hand, if the mixing ratio of the pigment is set to a ratio exceeding 17%, the mixing of the pigment and the resin does not become uniform, and a sufficient fluidity cannot be obtained due to the dumpling shape. However, there was a risk of not going well.
Therefore, by mixing the resin and the pigment, the resin and the pigment could be satisfactorily mixed by increasing the viscosity of the resin and obtaining sufficient fluidity.

A pigment is mixed in the resin in advance to form a colored matrix resin, and the colored matrix resin is formed into a liquid type at a high temperature.
A colored prepreg is produced by impregnating the colored matrix resin by pouring the liquid material of the colored matrix resin from the surface side orthogonal to the direction in which the reinforcing fibers are aligned.
In this way, the colored matrix resin is made into a liquid state, and a colored prepreg in which the surface side is higher than the back side in the density of the pigment by adopting a pouring method from the surface side orthogonal to the alignment direction of the reinforcing fiber group. It became easier to manufacture.
Therefore, if the surface side is used for the display surface, it can be made highly colored as a colored prepreg.

  As a result, it is not necessary to adopt a complicated configuration in which a layer containing a concealing material and a layer containing a coloring material are overlapped via an isolation layer, and a transparent reinforcing fiber is required. There is no restriction, and it is possible to obtain high color development without being inhibited by the color inherent to the matrix resin or the reinforcing fiber, and it is possible to easily obtain a desired color development regardless of the difficult-to-color reinforcing resin.

〔Constitution〕
A characteristic configuration of the invention according to claim 3 is a colored matrix resin sheet material formed into a sheet shape by mixing the pigment in a ratio of 0.04% to 17% volume ratio with respect to a liquid epoxy resin. This is because it is formed by superposing and impregnating a group of carbon fibers aligned in one direction in a high temperature state.

[Function and effect]
That is, even if the reinforcing fiber has a specific color by mixing the pigment at a ratio of 0.04% to 17% by volume with respect to the matrix resin exhibiting a liquid in which the solid content is dissolved, the reinforcing fiber A colored prepreg exhibiting a color development different from the above color could be obtained.

On the other hand, if the mixing ratio of the pigment is set to 17% or more, the mixing of the pigment and the resin is not uniform, and it becomes a dumpling shape and sufficient fluidity is not obtained, so that the superposition with the reinforcing fiber is successful. There was also a fear of not.
Therefore, by mixing the resin and the pigment, the resin and the pigment could be satisfactorily mixed by increasing the viscosity of the resin and obtaining sufficient fluidity.

A colored matrix resin is formed by previously mixing the pigment into the resin, and the colored matrix resin is formed into a hot melt type sheet that exhibits adhesiveness at a high temperature.
The colored matrix resin sheet material is superposed on the reinforcing fiber group and impregnated by applying a high temperature (for example, using a laminating method or the like) to produce a colored prepreg.

  Therefore, it is not necessary to adopt a complicated configuration in which a layer containing a concealing material and a layer containing a coloring material are overlapped via an isolation layer, and there is a manufacturing restriction that a transparent fiber is required as a reinforcing fiber. In addition, high color developability can be obtained without being inhibited by the color inherent to the matrix resin and the reinforcing fibers, and desired color development can be easily obtained regardless of the hardly colored reinforcing resin.

〔Constitution〕
The characteristic constitution of the invention according to claim 4 is that coloring is performed by adding one pigment having a single color to the other pigment having a color different from that of the one pigment and mixing the combined pigment in the above-described ratio. It is in the point which forms matrix resin, The effect is as follows.

[Function and effect]
In other words, a prepreg produced by mixing pigments of different colors and impregnating the matrix resin has a higher hiding ability for the reinforcing fiber color and exhibits higher color development and decorativeness than a single color.

〔Constitution〕
The characteristic configuration of the invention according to claim 5 is that it is a tubular body made of the colored prepreg according to any one of claims 1 to 4 , and the function and effect thereof are as follows.

[Function and effect]
In other words, a colored prepreg with a high coloring property can be molded to obtain a tubular body, so that the surface coating of the tubular body can be minimized, and the increase in weight due to painting can be suppressed, and the painting process can be shortened. Can be planned.

〔Constitution〕
The characteristic configuration of the invention according to claim 6 is that it is a tubular body in which the colored prepreg according to any one of claims 1 to 4 is coated, and the function and effect thereof are as follows. is there.

[Function and effect]
In other words, although it is a colored prepreg with high color developability, various decorations can be further applied by coating the surface.

[First Embodiment]
A colored prepreg used for a bicycle frame, a tubular body such as a golf shaft or a fishing rod, or clothes or footwear will be described.
The colored prepreg is formed by impregnating a reinforcing fiber bundle in which reinforcing fibers are aligned in one direction with a matrix resin containing a coloring element.
Here, as the reinforcing fiber, carbon fiber is preferable, but glass fiber, alumina fiber, aramid fiber and the like can be mentioned, and these can be used alone or in combination.

  In terms of the specifications of the carbon fiber, it is preferable that the tensile elastic modulus is 100 to 800 GPa and the tensile strength is 2000 to 7000 MPa. The fiber diameter constituting the reinforcing fiber alignment sheet is 5 μm to 12 μm, and the number of filaments is preferably 500 to 24,000, and more preferably 1000 to 6000.

The matrix resin may be a cured product of a thermosetting resin or a thermoplastic resin. Examples of the thermosetting resin include an epoxy resin, a vinyl ester resin, an unsaturated polyester resin, and a phenol resin. When carbon fibers are used as the reinforcing fiber bundle, an epoxy resin is optimal from the viewpoint of adhesiveness.
As described above, the selected reinforcing fiber bundle is impregnated with the matrix resin to produce a colored fiber reinforced composite.

  The manufacturing of the matrix resin according to the embodiment of the present invention employs a general manufacturing method. That is, the following steps are performed. Here, an epoxy resin such as a bisphenol A-type epoxy resin and other compositions are charged into a kneader or a stirring device such as a planetary mixer. A curing agent or the like is mixed into the mixture which is heated at 80 to 160 ° C. and stirred and mixed, and the temperature is lowered to about 60 ° C. to obtain a desired epoxy resin molded product.

  As the epoxy resin, in addition to the above-described bisphenol A type epoxy resin, for example, brominated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, stilbene type epoxy resin, biphenyl type epoxy resin, bisphenol A novolak Type epoxy resin, cresol novolac type epoxy resin, diaminodiphenylmethane type epoxy resin, polyphenyl base epoxy resin such as tetrakis (hydroxyphenyl) ethane base, fluorene-containing epoxy resin, triglycidyl isocyanurate, heteroaromatic ring (for example, triazine ring) Epoxy resin containing epoxy resin; aliphatic glycidyl ether type epoxy resin, aliphatic glycidyl ester type epoxy resin, alicyclic Glycidyl ether type epoxy resin, aromatic epoxy resins such as alicyclic glycidyl ester type epoxy resins. These may be used alone or in combination of two or more.

  Examples of the curing agent include aromatic amines (eg, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, benzyldimethylamine, dimethylaminomethylbenzene), aromatic acid anhydrides (eg, phthalic anhydride, trimellitic anhydride). Acid, pyromellitic anhydride, etc.), phenolic resins, phenol novolac resins, heteroaromatic ring-containing amines (eg, triazine ring-containing amines), etc .; aliphatic amines (eg, ethylenediamine, diethylenetriamine, triethylene) Tetramine, tetraethylenepentamine, iminobispropylamine, bis (hexamethylene) triamine, 1,3,6-trisaminomethylhexane, polymethylenediamine, trimethylhexamethylenediamine, polyether Diamine), alicyclic amines (isophoronediamine, menthanediamine, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) 2,4,8,10-tetraoxaspiro (5,5) undecane) Non-aromatic curing agents such as adducts, bis (4-amino-3-methylcyclohexyl) methane, bis (4-aminocyclohexyl) methane, modified products thereof, and the like, and aliphatic polyamidoamines composed of polyamines and dimer acids. Can be mentioned. These may be used alone or in combination of two or more.

[Another implementation structure of reinforcing fiber group]
(1) The arrangement in which the carbon fibers and the like are aligned in one direction as the reinforcing fiber group has been described, but a so-called cross sheet in which reinforcing fibers are arranged in different directions and crossed and knitted may be employed.
(2) Alternatively, a so-called non-woven fabric in which the orientation is freely set and randomly entangled without arranging the reinforcing fibers may be employed. A typical manufacturing process for creating a nonwoven fabric comprises a first stage for creating a fleece and a second stage for joining the fleece.
(A) As a first-stage fleece forming method, there is a dry method (for example, airlaid method). The reinforcing fiber is cut short and formed into a sheet while flowing in an air stream.
(B) As the second stage fleece bonding method, a needle punch method, a stitch bond method, or the like can be used. A non-woven fabric is formed by piercing a needle with a barb against the fleece formed in a sheet shape and mechanically coupling it.
(C) As a nonwoven fabric, what laminated | stacked many layers what arrange | positioned the reinforced fiber to 4 axial directions is included.

Usable pigments include natural pigments and synthetic pigments (synthetic dyes, synthetic pigments). Synthetic pigments are mainly used, and azo dyes and cyanine pigments are typically used. Examples of the synthetic pigment include inorganic pigments such as iron oxide, titanium yellow, and chromium oxide, and organic pigments such as azo pigments, quinacridone series, and dioxazine series.
There are two types of pigments, inorganic pigments and organic pigments, due to their composition. Further, inorganic pigments include natural inorganic pigments that are processed products of minerals and synthetic inorganic pigments that are chemically synthesized. In addition, organic pigments that have been used for a long time include those that use insoluble dye precursors taken from plants as pigments, and those obtained by rake dyes extracted from plants and animals. Most of what is currently used industrially are synthetic organic pigments established by the petroleum industry.

Here, the form which uses the glass flake and metal flake which are inorganic pigments is demonstrated.
The glass flake is a thin glass substrate coated with a thin metal, or a glass substrate coated with iron oxide or the like. The color development varies depending on the coating material and the coating thickness.

  The layer coated on the glass substrate develops color using light interference and exhibits a specific color development. This coating layer is referred to as a coloring layer.

The manufacturing method is as follows.
(1) The molten glass is thinly stretched to make transparent and flat flakes.
(2) Next, various metals and metal oxides are coated.

Here, the glass flakes used are those called “Metashine” (a bright inorganic pigment) manufactured by Nippon Sheet Glass, and include the following.
(1) It is coated with TiO ₂ and exhibits high transparency and iris color (code No. 1020RS / RY / RR / RG). It has a rectangular shape with a substrate specific gravity of about 2.5, a substrate thickness of 1 μm, and a long dimension (representing an average particle size) of 20 μm. In addition, some of the long dimensions have dimensions of 30 to 120 μm.
Titanium oxide TiO ₂ and the glass substrate are transparent, and the coating layer of titanium oxide exhibits high color developability due to light interference, and is useful as a paint.
By the way, RS / RY / RR / RG of variety No. exhibits color development of silver, yellow, red and blue, respectively, and the optical path difference related to light interference is adjusted by changing the thickness of the coating layer. .

  (2) Ag is coated to a thickness of 20 to 60 μm and exhibits a silver color due to silver having a high visible light reflectance (code No. 5480PS). It has a rectangular shape and has a specific gravity of about 2.5, a thickness of 5 μm, and a long dimension of 480 μm. The substrate thickness is 1 μ and the long dimension is 25 μm to 230 μm.

(3) Fe ₂ O ₃ is coated to a thickness of 70 to 110 μm and exhibits the following color development (code No. 1030TY / TZ / TP / TA). It has a rectangular shape with a specific gravity of about 2.5, a substrate thickness of 1 μ, and a long dimension of 30 μ. In addition, some have a length of 80 μ as the long dimension.
Incidentally, TY / TZ / TP / TA of the product type No. exhibits colors of gold, bronze, kappa, and rasset, respectively.

Along with glass flakes, metal flakes are also used.
Here, the metal flake to be used is a product name “ELG” manufactured by NEO, and includes the following.
Similarly, metal flakes are obtained by thinly coating a metal substrate such as Ni or Fe ₂ O ₃ on a thin metal substrate such as aluminum, and the shape and other specifications are the same as glass flakes.

  The above-mentioned metal flake (LG) is a metal powder produced by a vacuum deposition method, and a protective layer of a metal thin film surrounds a metal substrate and is colored. The particle size is 110 to 120 μm for both red and blue.

Other examples of usable synthetic organic pigments include azo pigments and polycyclic pigments, and the following pigments are used. As the azo pigment, a transparent type of benzidine yellow exhibiting a medium yellow color, brilliant carmine 6B exhibiting a bluish red, and the like, represented by a phthalocyanine pigment as a polycyclic pigment,
(A) Yellow: isoidolinone, quinophthalone, isoindoline, anthraquinone, anthrone, xanthene (b) Orange: diketopyrrolopyrrole, perylene, anthraquinone (anthrone), perinone, quinacridone, indigoid (c) Red: anthraquinone, quinacridone, di Ketopyrrolopyrrole, perylene, perinone, indigoid (d) Purple (菫): Dioxazine, quinacridone, perylene, indigoid, anthraquinone (anthrone), xanthene (e) Blue: phthalocyanine, anthraquinone, indigoid (f) Green: phthalocyanine, azomethine And perylene.

As the inorganic pigment, a synthetic inorganic pigment is used, and examples thereof include synthetic iron oxide red, cadmium yellow, nickel titanium yellow, strontium yellow, hydrated chromium oxide, chromium oxide, cobalt aluminate, and synthetic ultramarine blue.
(A) Red pigment: red lead, iron oxide red (b) Yellow pigment: yellow lead, zinc yellow (zinc yellow 1 type, zinc yellow 2 type)
(C) Blue pigment: ultramarine blue, prussian blue (potassium ferrocyanide)

Next, the process of mixing the resin and the pigment will be described.
The mixing time of the pigment is not limited as long as the resin component melts and can be easily stirred (80 ° C. to 160 ° C.). The resin and the pigment may be selected and mixed one by one, but a plurality of types of pigments may be mixed with a single type of resin. Among the plural types, even if they are of the same type, those having different colors are considered.

The volume ratio of the resin and the pigment related to the mixing concentration is 0.04% to 17%, desirably 2% to 5%. Depending on the flowability of the resin and the specific gravity of the resin and the pigment, the possible mixing ratio of the resin and the pigment differs. However, even if the mixing ratio of the pigment to the resin exceeds 17%, there is a significant difference in color development. There is no. On the other hand, when the mixing ratio increases, the resin and the pigment do not fuse well, and a lump may be formed. Therefore, there is a correlation between the viscosity of the resin and the weight ratio of the pigment.
As described above, when the resin and the pigment are mixed, a fixed colored sheet material is formed by the mixture.
When the color developability of the pigment is evaluated, it can be said that the color developability is better as the ratio is larger in the weight ratio between the resin and the pigment.
The shape of the pigment is not particularly limited, but is preferably a flat plate having a width of 5 to 25 μm and a length of 50 to 150 μm.

Next, the manufacturing process of the fiber reinforced colored resin material (colored prepreg) will be described.
(1) The carbon fibers are aligned in one direction, aligned in a belt shape, and sent to a predetermined position. On the other hand, the matrix resin mixed with the above-mentioned pigment such as glass flakes is liquefied by heat treatment and stored in a tank or the like.
(2) The liquefied matrix resin is poured toward the moving carbon fiber group while feeding the carbon fiber group arranged in a belt shape to the matrix resin supply unit.
(3) Then, the matrix resin poured into the surface of the carbon fiber group rubs between the carbon fiber groups while being conveyed, and oozes out to the back surface of the carbon fiber group.
(4) Thereby, the carbon fiber group can be impregnated with the matrix resin, and a prepreg is created.
(5) By the way, when the glass flakes mixed in the matrix resin sink into the carbon fiber group, the carbon fiber is inhibited from settling and gradually reaches the back surface of the carbon fiber group. Captured by carbon fiber. As a result, in the thickness direction of the prepreg, the amount of glass flakes staying on the surface side is large, and the density is increased.
(6) The density of the glass flakes is higher in the half on the front side than in the back side in the thickness direction of the prepreg, but when the glass flakes are captured by the carbon fiber at a certain ratio. The density gradually increases from the back surface to the front surface.

  In addition to the manufacturing method as described above, a generally used hot melt method may be employed. That is, in this case, instead of dropping the matrix resin in a liquid state, a method of forming the matrix resin in a strip shape is adopted.

The method is as follows.
The carbon fibers are aligned in one direction and arranged in a band shape, and the upper epoxy resin sheet is overlapped on the upper side and the lower epoxy resin sheet is overlapped on the lower side, and these laminates are rearranged by the first feed roll. Transport to process. The laminate conveyed by the pair of upper and lower first feed rolls is heated by the hot platen and is driven and conveyed by the pair of upper and lower heating and pressure rolls.

  A cover material such as a cover film or scream cloth is superposed on the laminate sent by a heat and pressure roll, sent to a take-up roll by a pair of upper and lower second feed rolls, and wound as a prepreg by a take-up roll. Taken.

  When the resin sheet is disposed only on the lower side with respect to the reinforcing fiber group, the process paper is supplied from the upper side of the reinforcing fiber group instead of the upper resin sheet, and the upper process paper, the reinforcing fiber group, and the lower side are supplied. The resin sheets are superposed by a first feed roll and supplied and conveyed to a hot platen as a laminate. The process paper is wound on the lower conveyance side after receiving the conveyance action of the heating and pressing roll. Thereby, a prepreg is manufactured.

〔Example〕
1. Step (1) for mixing pigment in resin (1) As the resin, a liquid bisphenol A type epoxy resin, a solid bisphenol A type epoxy resin, or a polyfunctional epoxy resin is used alone or in combination.
(2) As the pigment imparting color developability, metashine (glass), which is glass flakes as inorganic pigments, pearl, and LG (aluminum), which is aluminum flakes as inorganic pigments, are appropriately selected and used.
(3) As described later, the mixture is charged into a stirrer at a predetermined volume ratio, and the temperature is raised to 120 ° C. where stirring is easy, and stirring is performed.
(4) Confirm that the melting of the resin component and the diffusion of the pigment have become uniform, lower the temperature to 80 ° C. or less while continuing the stirring, add a predetermined amount of curing agent and curing accelerator, and the pigment is uniform To obtain a mixture of resin and pigment.
(5) When the mixture is obtained, as described above, the mixture is heated to prepare a liquid colored matrix resin. Alternatively, a solid colored matrix resin sheet is obtained from the mixture by a reverse roll coater manufacturing method.

2. Step (6) of Forming Prepreg from Colored Resin and Reinforced Fiber Group Next, a colored prepreg is obtained by aligning carbon fibers in one direction and dropping a liquid colored matrix resin. Alternatively, the colored prepreg is obtained by superposing the colored matrix resin sheet and impregnating the resin into the carbon fiber by heating and pressing.

[Evaluation of colored prepreg]
From the above, the color development was evaluated. In this case, the test results using metal flakes (aluminum metallic: trade name Elgi NEO), glass flakes (trade name: Meta Shine), and pearl are described below.

(1) For samples 1 to ³ , a single-color glass flake (trade name: Metashine) (specific gravity 2.54 g / cm ³ ) with an epoxy resin (specific gravity 1.22 g / cm ³ ) at a concentration of 0 .1 wt%, 5.0 wt%, and 30.0 wt% mixed were used.

For (2) the sample 4-6, the epoxy resin (specific gravity of 1.22 g / cm ^3), single color Pearl (specific gravity 3.00 g / cm ^3), concentration 0.1 wt%, 5.0 wt% What was mixed in the ratio of 30.0 wt% was used.
(3) For samples 7-9, the epoxy resin (specific gravity of 1.22 g / cm ^3), a single color of Aluminum Metal flakes (trade name: Eruji NEO) (specific gravity 2.70 g / cm ^3), concentration What mixed in the ratio of 0.1 wt%, 5.0 wt%, 30.0 wt% was used.

(4) For Sample 10, the epoxy resin (specific gravity of 1.22 g / cm ^3), the blue and red Aluminum Metal flakes (trade name: Eruji NEO) (specific gravity 2.70 g / cm ^3), concentration 5 A mixture of 0.01 wt% was used.

Next, the difference in the color development state depending on the type of glass flakes or metal flakes as a pigment, or the form of further coating the colored prepreg will be described.
(1) The glass flakes described above are used. In other words, a silver-coated one made of Nippon Sheet Glass with a thickness of 20 to 60 μm is used.
In this case, it is a so-called monotone, and if it is used alone as a colored prepreg, if it feels unsatisfactory, the following pigment is further mixed.
In other words, a material that is coated with Fe ₂ O ₃ made of Nippon Sheet Glass to a thickness of 70 to 110 μm and exhibits a bronze color is used. By mixing these bronze glass flakes, depth is added to the hue, and an excellent color feeling is exhibited without painting.
(2) However, since the colored prepreg mixed with glass flakes exhibiting a silver color is monotone, it is possible to decorate it and obtain a more vivid color.
Therefore, a desired color clear coating can be applied after a rod for fishing rod is manufactured with a colored prepreg mixed with glass flakes exhibiting a silver color.
(3) Moreover, the thing using a metal flake also shows a favorable coloring state. A colored prepreg is formed with a colored matrix resin mixed with aluminum flakes. A rod for a fishing rod is manufactured using this colored prepreg. Also in this case, as described in (1), the color developability is high so that clear coating or the like is not required.

[Another implementation structure]
(1) As the colored prepreg produced in the above-described manufacturing process, a long sheet having a width of about 1 m has been described, but a short sheet having a width of about 1 mm to 15 mm, a so-called prepreg tape. May be.

  (2) As a method for producing a colored prepreg, resin sheets are arranged on the upper and lower sides of the reinforcing fiber group and they are polymerized. However, the resin sheet is arranged on only one of the upper and lower sides, or the upper resin sheet or You may take the manufacturing method which superposes | polymerizes a lower resin sheet and a reinforced fiber group.

  (3) In the above prepreg, a form using a scream cloth is described. For example, when the prepreg is used for a fishing rod or the like, if the strength against crushing destruction is not required, the scream cloth is used. There is no need.

  (4) As a method for producing a colored prepreg, an immersion method may be used. That is, even if a method is adopted in which the colored resin material is stored in a molten state in the immersion tank, the reinforcing fiber group is immersed in the immersion tank, and the resin material is sufficiently attached to the reinforcing fiber group. Good. If the reinforcing fiber group is formed in a band shape, it can be sequentially immersed and a continuous process can be performed.

  (5) The colored prepreg can be applied not only to a cylindrical shape such as a fishing rod but also to shoes and clothes.

  The present invention is applied to bicycle frames, wheel rims, golf shafts, fishing rods, rackets such as tennis and badminton, and other colored prepregs processed into clothing and the like.

Claims (6)

In a prepreg formed by impregnating a group of reinforcing fibers with a matrix resin mixed with a pigment that suppresses the coloring property inherent to the reinforcing fibers and imparts coloring properties to the resin itself,
The pigment mixed in the matrix resin is impregnated from the front side of the reinforcing fiber group, a part of which is captured by the reinforcing fiber, and the remaining part moves to the back side and is distributed in the reinforcing fiber group. A colored prepreg in which the mixing density of the pigment is greater than the mixing density in the back half,
The pigment is a colored prepreg which is a glass flake made of a glass substrate having a color developing layer on the surface or a metal flake made of a metal substrate having a color developing layer on the surface and having a light coherent color .   The colored prepreg according to claim 1, wherein the reinforcing fiber group is impregnated with a colored matrix resin formed by mixing the pigment in a proportion of 0.04% to 17% by volume with respect to the resin.   A carbon fiber in which the pigment is mixed into a liquid epoxy resin at a ratio of 0.04% to 17% by volume, and a colored matrix resin sheet material formed into a sheet shape is aligned in one direction at a high temperature. The colored prepreg according to claim 1, which is formed by superposing and impregnating the group.   4. A colored matrix resin is formed by adding one pigment having a single color to another pigment having a color different from that of the one pigment, and mixing the combined pigments in the above-described ratio. The colored prepreg according to any one of the above.   The tubular body which consists of a colored prepreg as described in any one of Claims 1-4.   The tubular body which has coated the surface of the coloring prepreg as described in any one of Claims 1-4.