JPH0270730A - Colored filament of fiber-reinforced plastic - Google Patents

Abstract

PURPOSE:To provide a colored filament of a fiber-reinforced plastic excellent in long-term discoloration resistance, heat resistance, film appearance, etc., by coating the surface of a filament of a fiber-reinforced plastic with a fluorinated resin coating material of a specified composition and curing the resin. CONSTITUTION:A fluorinated copolymer comprising 30-70wt.% at least either chlorotrifluoroethylene or tetrafluoroethylene, 10-50wt.% cyclohexyl vinyl ether, 2-50wt.% alkyl vinyl ether, 3-25wt.% hydroxyalkyl vinyl ether and 0-45wt.% other components is mixed with a curing agent comprising a polyisocyanate compound and/or an aminoplast compound and a pigment. The obtained fluorinated resin coating material is applied to the surface of a filament of a fiber-reinforced plastic and cured to produce a colored filament.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] This invention relates to a colored filament made of fiber-reinforced plastic that has long-term fading resistance, heat resistance, and excellent coating appearance.

[Conventional technology]

Colored fiber-reinforced plastic (rFRP) colored filaments are generally made of organic or inorganic pigments dispersed in resin, and a colored paint film is applied to the outer peripheral surface of the FRP colored filament. There are two types of . Among these, those in which a colored coating film is formed on the outer peripheral surface of a colored filament made of FRP are excellent in terms of gloss and appearance. This FRP colored filament with a colored coating film is used in various fields, and one of its uses is as a tension member for an optical fiber cable.

[Problem that the invention seeks to solve]

In particular, the optical fiber cable mentioned above is an overhead ground wire (OPG).
When used as W), the tension member has long-term fading resistance and heat resistance.

Corrosion resistance and chemical resistance are required, and it is required to maintain a high level of good condition for a long period of time under harsh environments. For example, in optical fiber cables used as overhead ground wires, the FRP colored tension members may fade due to exposure to high atmospheres in the summer, or may fade due to high heat caused by lightning strikes etc. This is causing problems.

This invention was made in view of the above circumstances, and it is a colored filament made of FRP that can maintain its initial state even if it is exposed to a high temperature atmosphere for a long period of time, or even if it is exposed to high heat instantly. Its purpose is to provide.

[Means for Solving the Problems] The colored filament made of FRP of the present invention is a colored filament made of FRP in which a fluorine-containing resin paint is applied to the surface of the filament made of FRP and cured. As the fluorine-containing resin paint, a composition containing the following (A) to (C) as essential components is used.

(A) 30 to 70 Iiffi% of at least one of chlorotrifluoroethylene and tetrafluoroethylene;
A fluorine-containing copolymer comprising 10 to 50% by weight of cyclohexyl vinyl ether, 2 to 50% by weight of alkyl vinyl ether, 3 to 25% by weight of hydroxyalkyl vinyl ether, and 0 to 45% by weight of other comonomers.

(B) At least one of a polyvalent isocyanate compound and an aminoplast compound.

(C) Pigment.

[Function] The present inventors focused on a fluorine-containing resin paint as a paint that can maintain excellent paint film properties in a high-temperature atmosphere or under instantaneous high heat, and applied it to a colored paint film on a colored filament made of FRP. In order to use it, we conducted a series of studies. As a result, they discovered that the initial objective could be achieved by using a special fluorine-containing resin coating containing the above (A) to (C) as essential components, and the present invention was achieved.

The FRP colored filament of the present invention comprises a fluorine-containing copolymer having a special composition as described above (component A), at least one of a polyvalent isocyanate compound and an aminoblast compound (component B), and a pigment (component B). It is obtained by using a fluorine-containing resin paint containing the essential component (component) and an FRP filament to which it is coated.

Examples of the resin used for the FRP filament include thermosetting resins such as unsaturated polyester resin, epoxy resin, and vinyl ester resin. Further, as the reinforcing fibers, inorganic fibers such as glass fibers, carbon fibers, and metal fibers, organic fibers such as aramid fibers, etc. can be used as appropriate.

These may be used alone or in combination without any problem.

The colored coating film formed on the outer peripheral surface of the above FRP filament body is
It is necessary not only to have excellent fading resistance and heat resistance, but also to have excellent coatability and adhesion to the FRP filament.

Furthermore, when used as a tension member for optical fibers, it may be bent.
The colored coating film formed on the outer circumferential surface of the FRP filament is also required to be flexible so that it can follow the bending of the filament. From this point of view, in the present invention, a fluorine-containing resin coating coated on the outer circumferential surface of the FRP filament body includes the above-mentioned components (A) to (C) as essential components.

Component (A) in the above fluorine-containing resin paint includes 30 to 70% by weight (hereinafter abbreviated as "%") of one or both of chlorotrifluoroethylene and tetrafluoroethylene, and 10 to 50% of cyclohexyl vinyl ether.
, a fluorine-containing copolymer containing 2 to 50% of alkyl vinyl ether, 3 to 25% of hydroxyalkyl vinyl ether, and 0 to 45% of other comonomers.

The content of one or both of chlorotrifluoroethylene and tetrafluoroethylene in the component (A) needs to be set within the range of 30 to 70%, preferably 35 to 65%. In other words, if the content of these substances is below the above range, the weather resistance and fading resistance of the coating film will not only be insufficient (and the production of paint will become difficult.On the other hand, if the content is below the above range) However, manufacturing becomes difficult.

Cyclohexyl vinyl ether needs to be set within a range of 10 to 50%, preferably 12 to 45%. This is because if the content is less than the above range, the hardness of the coating film will decrease, whereas if it exceeds the content, the adhesiveness of the FRP colored filament will be lacking.

It is necessary to set the alkyl vinyl ether in a range of 2 to 50%, preferably 5 to 40%. If this content is below the above range, the flexibility of the coating will decrease,
On the other hand, if it exceeds this, the FRP coloring-resistant filament will lack adhesion and fading resistance. As such alkyl vinyl ether,
Those containing a linear or branched alkyl group having 2 to 8 carbon atoms are used, and those containing a linear or branched alkyl group having 2 to 4 carbon atoms are preferably used.

The content of hydroxyalkyl vinyl ether must be set within the range of 3 to 25%, preferably 5 to 20%.

When this content exceeds the above range, the solubility of the fluorine-containing copolymer itself in organic solvents decreases, and the flexibility of the coating film also decreases. Conversely, if it falls below the above range,
This is because the durability and adhesion of the coating film decrease.

The fluorine-containing copolymer as component (A) used in this invention is obtained by copolymerization using the above-mentioned raw materials, and its molecular structure contains structural units derived from the above-mentioned raw materials. Contains. Such a fluorine-containing copolymer may optionally contain structural units based on comonomers other than the above four types of structural components. Examples of such comonomers include ethylene, propylene, isobutylene, vinyl chloride, vinylidene chloride, methyl methacrylate, butyl acetate, and the like.

In this invention, one or both of the polyvalent isocyanate compound and the aminoplast compound of the component (B) are used as the curing agent component of the fluorine-containing copolymer of the component (A). Examples of polyvalent isocyanate compounds include aliphatic or alicyclic diisocyanates such as hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, hydrogenated diphenyl diisocyanate, and hydrogenated xylylene diisocyanate, or biuret forms, dimers, and dimers thereof. Typical examples include reaction products between excess amounts of these isocyanate compounds and low molecular weight polyols such as ethylene glycol, glycerin, trimethylolpropane, and pentaerythritol. By mixing these polyvalent isocyanate compounds with the component (A) in a predetermined ratio, a two-component coating material that can be cured even at room temperature can be obtained.

In addition, block isocyanate compounds obtained by masking the above polyvalent isocyanate compounds with masking agents such as phenols, alcohols, oximes, lactams, amines, amides, etc. can also be used, and in this case also the above (A)
It can be mixed with the other components in a predetermined ratio to create a one-component paint that can be cured by baking. Moreover, the above-mentioned aminoplast compounds can also be used as curing agents. An aminoplast compound is a condensation product of an amino compound such as melamine, urea, benzoguanamine, or acetoguanamine and an aldehyde compound, or a compound obtained by further etherifying this condensation product with an alcohol such as butanol. When using aminoplast compounds as curing agents,
By mixing this with the above component (A) in a predetermined ratio, or by using it in combination with the above polyvalent isocyanate compound and mixing it with the above (A) component in a predetermined ratio, a one-component paint that can be cured by baking can be obtained. Become.

The fluorine-containing resin paint used in this invention includes the above (
In addition to component A) and component (B), a pigment is used as component (C). Examples of such pigments include titanium oxide, cobalt, nickel, antimony, zinc compounds, phthalocyanine blue benzidine yellow, quartz powder, alumina oxide, precipitated barium sulfate, and the like.

The fluorine-containing resin paint used in this invention includes:
In addition to the above components (A) to (C), an organic solvent that dissolves these components is used. Such organic solvents include:
Examples include hydrocarbon solvents (xylene toluene, etc.), ester solvents (butyl acetate, etc.), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), and alcohol solvents (methanol, ethanol, butanol, etc.).

In addition to the above-mentioned raw materials, other additives may be used in the fluororesin-containing paint of the present invention, if necessary. Examples of such additives include dispersants 9, surface conditioners, thickeners, and the like.

FRP is made of fluorine-containing resin paint made from the above ingredients.
When painting the manufactured filament, use air spray,
Methods such as shower coat brushing, roll painting, and ironing are used as appropriate. The curing conditions for the above paint are as follows: drying at room temperature, drying at 100 to 150°C for 10 to
The temperature is set for 30 minutes or 2 to 10 minutes at 100 to 230°C, thereby baking and hardening and forming a colored coating film on the outer peripheral surface of the FRP filament. The thickness of the coating film in this case is preferably about 1 to 25 μm.

〔Effect of the invention〕

As described above, the F Rp '5J5 part striatum of the present invention uses the above-mentioned special fluorine-containing resin paint,
Because it forms a coating on the outer surface, the coating hardly fades even if it is exposed to a high atmosphere for a long time or exposed to high heat instantly, and exhibits a high gloss color. Moreover, it follows the bending of the FRP colored filaments well and does not cause cracks.

Next, examples will be described together with comparative examples.

[Example 1] Ethyl vinyl ether 17 and hydroxybutyl vinyl ether 13 were dissolved in a mixed solvent of 40 parts of xylene and 115 parts of methyl isobutyl ketone, and then 40 parts of titanium oxide was added and kneaded. A curing agent consisting of 8 parts of hexamethylene diisocyanate and 0.01 part of dibutyltin dilaurate was mixed with this to obtain a paint.

The obtained paint was spray-painted on the surface of an FRP filament with a diameter of 3.0 mm, dried at 80 °C for 6 hours, and a 15μ
A colored FRP striatum having a white coating film of m was obtained.

[Example 2] 35 parts of chlorotrifluoroethylene 35 parts of cyclohexyl vinyl ether 5 parts of ethyl vinyl ether 25 parts of hydroxybutyl vinyl ether were used. A colored FRP striatum was obtained in the same manner as in Example 1 except for the above.

[Example 3] 65 parts of chlorotrifluoroethylene, 10 parts of cyclohexyl vinyl ether, 22 parts of ethyl vinyl ether, and 3 parts of hydroxybutyl vinyl ether were used. A colored FRP striatum was obtained in the same manner as in Example 1 except for the above.

[Example 4] So parts of chlorotrifluoroethylene, 20 parts of cyclohexyl vinyl ether, 17 parts of ethyl vinyl ether, and 13 parts of hydroxyalkyl vinyl ether were dissolved in a 60% xylene solution.

To 100 parts of the above solution, 30 parts of N-n-butoxymethylacrylamide and 0.1 part of para-toluenesulfonic acid were added and reacted at 120°C for 2.5 hours, and 40 parts of xylene was added to the obtained product. added.

While maintaining this solution at 80°C, 24 parts of a monomer mixture consisting of 25% methyl methacrylate, 60% cyclohexyl methacrylate, 3% acrylic acid, 12% hydroxyethyl methacrylate, and azobisisobutyrochloride were added. A mixture of 0.5 part of nitrile was added dropwise over 2.5 hours to cause a reaction. Furthermore, 0.5 part of azobisisobutyronitrile was added, the temperature was raised to 90°C, and the mixture was stirred and reacted for 3.5 hours.
A very slightly emulsified solution with a hydroxyl value of 12) at 1°C was obtained.

To 100 parts of this polyol resin solution, 6 parts of isobutyl etherified melamine solution, 30 parts of xylene, 3 parts of butyl acetate.
A coating material was prepared by kneading and dispersing 0.3 parts of a surface conditioner, 20 parts of titanium oxide, and 5 parts of Pigment Yellow 53. The obtained coating material was spray-painted onto the surface of an FRP filament having a diameter of 3.0 mm and dried by heating at 150°C for 30 minutes to obtain a colored FRP filament having a yellow coating.

[Comparative Example 1] In a reaction vessel equipped with a stirrer, a thermometer, and a condenser,
Add 388 parts of dimethyl terephthalate, 91 parts of ethylene glycol, 98.5 parts of glycerin, and 0.2 parts of zinc acetate, heat to 130-140°C to distill off low-boiling reactants, and then gradually raise the temperature. The mixture was heated to 240°C while further distilling off low-boiling reactants. In this reaction system, (H
30 parts of a fluorine-containing carboxylic acid having the structure OOC(CH2) 5CFt CHFCFz ) was added and reacted for about 30 minutes. Subsequently, the pressure was reduced to remove unreacted alcohol components, and when the reaction product became viscous (acid value at this time was 1 or less), xylene was added to form a solution with a solid content of 40%. Tetrabutyl titanate was added in an amount of 3% based on the solid content of this solution, and the mixture was uniformly mixed and stirred to form a paint.

30 parts of titanium oxide was added to the obtained paint, and this was used to obtain a colored FRP filament having a white paint film.

[Comparative Example 2] Bisphenol A type epoxy resin (epoxy equivalent: 190
0, softening temperature 125°C) 100 parts, amine curing agent (
3.0 parts of dicyandiamide), and an organic solvent (meta-
Add 270 parts of para-cresol/xylene-7/3),
Further, 20 parts of titanium oxide was added, and the same procedure as in Example 1 was carried out to obtain a colored FRP filament having a white coating film.

The colored FRP striatum obtained in the above examples and comparative examples was
The following table shows the results of a deterioration test conducted at 50°C for 400 hours.

(Hereafter, the remainder is white)

Claims (1)

[Claims] (1) A colored fiber-reinforced plastic filament formed by applying a fluorine-containing resin paint to the surface of the fibre-reinforced plastic filament and curing it, wherein the fluorine-containing resin paint comprises:
A colored striatum made of fiber-reinforced plastic characterized by using a material containing the following (A) to (C) as essential components. (A) 30 to 70% by weight of at least one of chlorotrifluoroethylene and tetrafluoroethylene, 10 to 50% by weight of cyclohexyl vinyl ether, 2 to 50% by weight of alkyl vinyl ether, 3 to 25% by weight of hydroxyalkyl vinyl ether, and other comonomers. A fluorine-containing copolymer consisting of 0 to 45% by weight. (B) At least one of a polyvalent isocyanate compound and an aminoplast compound. (C) Pigment.