JP2002050249A - Method for manufacturing surface-coated wire material and surface-coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method which can provide surface-coated wire material with no liquid-dripping and a high-efficiency productivity, and a composition for coating wire material whose composition is excellent in strength and extension, and yields no liquid drips at the temperatures 80-250 deg.C even though the composition is liquid at ordinary temperatures. SOLUTION: A method for manufacturing a surface-coated wire material in which method a coating composition comprising a curing thermosetting resin composition, which can be cured by ultraviolet irradiation, is applied on the surface of wire material, and the surface of the coating composition is cured preliminarily by ultraviolet irradiation, and subsequently the coating composition is completely cured by a heat treatment, and a composition for coating wire material used in the above-mentioned method for manufacturing surface-coated wire material in which the above-mentioned coating composition comprises (a) epoxy prepolymer resin, (b) a radical-polymerization component, (c) a photo- radical polymerization initiator, and (d) an epoxy curing agent to be thermally activated.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a surface-coated wire and a composition for coating a wire used in the method.

[0002]

2. Description of the Related Art Curable epoxy resins include adhesives, paints,
It is used for various coating materials, etc., and requires various cured product characteristics for each application. For example, Japanese Patent Application Laid-Open No. 7-11105 exemplifies an epoxy resin composition containing an inorganic filler, which is mainly used for an electric insulating coating material. Japanese Patent Application Laid-Open No. 7-268278 discloses a cured product of an epoxy resin composition comprising an epoxy resin and a phenol resin curing agent as a bonding wire covering material for a semiconductor device.

However, since the curable epoxy resin described in the above publication is a powder or a composition containing a large amount of solvent, it must be applied by spraying the curable epoxy resin composition. However, the workability was poor because of the necessity of paying attention to the exhaustion of the volatile solvent. In addition, especially in applications such as adhesives, paints, and various coating materials, liquefaction of a curable epoxy resin, improvement of pot life, shortening of curing time, etc. are required to improve productivity. Things have excellent strength,
You must maintain flexibility. In particular, when the wire is coated with an epoxy resin that is liquid at room temperature using a curing agent activated by heat, the wire is usually cured at a temperature of 80 to 250 ° C. At that time, the viscosity of the resin decreases. However, there is a problem that so-called liquid dripping occurs.

[0004]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a method of manufacturing a surface-coated wire capable of providing a surface-coated wire with high productivity without liquid dripping in view of the above-mentioned current state of the wire coating technology, strength, and strength. An object of the present invention is to provide a composition for coating a wire used in the method for producing a surface-coated wire, which is excellent in elongation, does not cause liquid dripping at a temperature of 80 to 250 ° C even when it is liquid at normal temperature.

[0005]

In order to achieve the above object, a method for producing a surface-coated wire according to the present invention comprises a coating composition comprising a thermosetting resin composition curable by ultraviolet irradiation on the surface of the wire. The method is characterized in that an object is applied, the surface of the coating composition is preliminarily cured by irradiation with ultraviolet rays, and then the coating composition is completely cured by heat treatment.
Further, the composition for coating a wire used in the method for producing a surface-coated wire according to the present invention includes: (a) an epoxy prepolymer resin; (b) a radical polymerizable component;
(C) a photo-radical polymerization initiator; and (d) an epoxy curing agent activated by heat. Hereinafter, the present invention will be described in more detail.

In the method for producing a surface-coated wire according to the present invention, as long as it is a thermosetting resin composition curable by ultraviolet irradiation, it can be used as a coating composition without any particular limitation. Any of two-pack type may be used. 2
In the case of a liquid coating composition, a predetermined amount of the main agent and the curing agent is uniformly stirred and defoamed, the coating composition is applied to the surface of the wire, and the surface of the coating composition is previously irradiated with ultraviolet rays. After curing, a heat treatment is performed to completely cure the coating composition, whereby a surface-coated wire can be obtained.

The wire coating composition of the present invention is used as a preferred coating composition in the method of producing a surface-coated wire of the present invention. As the epoxy prepolymer resin (a), generally used epoxy resins can be widely used. For example, epichlorohydrin-
Bisphenol A type epoxy resin, epichlorohydrin-bisphenol F type epoxy resin, hydrogenated epichlorohydrin-bisphenol A type epoxy resin, novolak type epoxy resin, glycidylamine type epoxy resin, glycidyl ether type epoxy resin, urethane modified epoxy resin, etc. In particular, a bisphenol A type epoxy resin having a good balance between performance and cost is more preferably used.

A preferred specific example of the bisphenol A type epoxy resin is, for example, a product name “Epicoat 80”.
6, 807, 815, 827, 828 ”(Epicoat 800 series) (both manufactured by Yuka Shell Epoxy Co., Ltd.), and“ Epomix R series ”such as trade name“ Epomix R139, R140 ”(Mitsui Oil Chemical Industry Co., Ltd. ", trade name" Araldite GY-250, GY-2
"Araldite GY series" (both manufactured by Nippon Ciba Geigy) and the like. You. The bisphenol type epoxy resin may be used alone,
Two or more types may be used in combination.

The above (b) radical polymerizable component means a radical polymerizable polymer in addition to a radical polymerizable monomer, and includes acrylic monomers and polymers, and vinyl ether monomers. And polymers, ene-thiol-based polymers, maleimide-based polymers, unsaturated polyester / styrene-based copolymers, and the like. For example, acrylic monomers as acrylic monomers and acrylates at the ends as acrylic polymers Urethane resin having a group, etc., and specific examples thereof include, for example, trade name “Ankaletz 2364”
(Manufactured by BTR Japan).

The photo-radical polymerization initiator (c) is 2,2-dimethoxy-1,2-diphenylethane-
1-one, bis (2,4,6) -trimethylbenzoyl) -phenylphosphinoxide and the like.

The epoxy curing agent activated by heat (d) includes a combination of an acid anhydride and a catalyst (such as a tertiary amine, a metal salt, or imidazole).
Examples of acid anhydrides are dodenyl succinic anhydride, phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic acid, pyromellitic anhydride, pyromellitic anhydride,
Nadic anhydride and the like.

(A) an epoxy prepolymer resin, (b)
The wire coating composition of the present invention containing a radically polymerizable component, (c) a photoradical polymerization initiator, and (d) an epoxy curing agent activated by heat as essential components, is used for treatment such as light shielding and storage in a cool and dark place. Can be made into a one-pack type, but taking storage stability into consideration, the agent A is composed of (a) an epoxy prepolymer resin, (b) a radical polymerizable component, and B
It is preferable to use a two-pack type agent comprising (c) a photo-radical polymerization initiator and (d) an epoxy curing agent activated by heat.

The agent A may be, if necessary, a reactive diluent, a non-reactive diluent, a softener, a plasticizer, a surfactant, an adhesion-imparting agent, or a coupling within a range not to impair the achievement of the object of the present invention. Agents, fillers, colorants, stabilizers, antioxidants, defoamers,
One or more of various additives such as thixotropic agents may be contained.

The method for producing the agent A is not particularly limited. For example, using a known mixer such as a universal mixer or a kneader, the essential components (a) an epoxy prepolymer resin and (b) a radical polymerization A predetermined amount of a sex component, and
By uniformly stirring and mixing one or two or more predetermined amounts of the various additives to be contained as necessary,
A desired agent A can be obtained.

In the agent B, if necessary, a softener, a plasticizer, a surfactant, an adhesion-imparting agent, a coupling agent, a filler, a colorant, and a stabilizer, as long as the object of the present invention is not hindered. One or more of various additives such as an antioxidant, an ultraviolet absorber, an antifoaming agent, and a modifier may be contained. The method for producing the agent B is not particularly limited. For example, using a conventionally known stirring mixer such as a universal mixer or a kneader, the essential components (c) a photo-radical polymerization initiator, and (d) activation by heat. A desired curing agent can be obtained by uniformly stirring and mixing a predetermined amount of the epoxy curing agent to be used and one or more predetermined amounts of the various additives to be contained as necessary.

The mixing ratio of the main agent and the curing agent is not particularly limited, but (a) of the agent A and a functional group capable of forming a bond with the active hydrogen of the epoxy prepolymer resin and (d) of the agent B The reactive group of the epoxy curing agent activated by the reaction is within an equivalent of ± 30%, the functional group of the photocurable resin which is the (b) radical polymerizable component of the agent A, and the (c) photoradical polymerization of the agent B It is preferable that the amount of radicals generated by the initiator is within an equivalent of ± 30%. If it exceeds ± 30%, the elongation and mechanical strength of the cured product may be reduced.

(Action) According to the method for producing a surface-coated wire of the present invention, first, the surface of the coating composition is preliminarily cured by light irradiation, and then the coating composition is completely cured by heat treatment. The surface coated wire can be provided with high productivity without liquid dripping. At this time, if the composition for coating a wire rod of the present invention is used, the epoxy resin composition having necessary strength and elongation and having excellent productivity, particularly an epoxy resin composition which is liquid at room temperature, is 80 to 250. It becomes possible to produce a surface-coated wire at a temperature of ° C. without causing liquid dripping.

[0018]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. (Example 1) [Adjustment of main agent and curing agent] Each raw material was weighed at a ratio shown in Table 1 below, and mixed while stirring and defoaming until it became uniform. Each of the main ingredients and the curing agent of No. 3 were prepared.

[Evaluation Method] Liquid dripping test The composition for coating a wire obtained by mixing a main agent and a curing agent was applied to a steel wire to a thickness of about 1 mm, irradiated with 24 mW ultraviolet rays for 1 minute, and then cured by heating at 200 ° C. for 5 minutes. The presence or absence of liquid dripping was visually confirmed.

2. Tensile strength and elongation Based on JISK-7113 "Plastic tensile test method", the test was performed using the No. 1 test piece shown in FIG. First, a wire coating composition obtained by mixing and defoaming a main agent and a curing agent was cast into a mold, irradiated with 24 mW ultraviolet rays for 1 minute, and then cured at 200 ° C. for 5 minutes to obtain a test piece. The test piece was set on a tensile tester and pulled at 10 mm / min. The tensile strength was defined as the tensile strength (N / mm ² ) by dividing the breaking strength of the test piece by the cross-sectional area of the test piece. In the present invention, 1
(N / mm ² ) or more is desirable. For elongation, a 50 mm mark was drawn at the center of the parallel portion of the test piece, and the elongation between the mark lines when the test piece was broken was divided by 50 mm to obtain elongation (%). In the present invention, about 10 to 15 (%) is desirable. These results are shown in Table 1 together with the mixing of the raw materials.

[0021]

[Table 1]

[0022]

According to the method for producing a surface-coated wire of the present invention, a coating composition comprising a thermosetting resin composition curable by ultraviolet irradiation is applied to the surface of the wire, and the coating composition is irradiated by ultraviolet irradiation. Surface is pre-cured, and then the coating composition is completely cured by a heat treatment, so that the coating composition can be completely cured with high productivity without liquid dripping. . Further, at this time, by using the wire coating composition of the present invention, for example, an epoxy resin composition having sufficient strength and elongation necessary for a PC rope coating material, and having excellent productivity, particularly at room temperature. A liquid epoxy resin composition,
An epoxy resin composition that does not cause liquid dripping at a temperature of 250 ° C. makes it possible to produce a surface-coated wire. That is, the composition for coating a wire of the present invention comprises (a) to
It contains the specific raw material (d) and is easy to handle because it is in a liquid state, has a sufficient pot life at room temperature, and cures in a short time at high temperatures, and thus has excellent workability.

[Brief description of the drawings]

FIG. 1 is a test piece for measuring tensile strength and elongation.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) H01B 3/40 H01B 3/40 CG F term (Reference) 4E070 AC01 BG06 BG12 EA05 4J038 DB041 DB042 DB061 DB062 DB071 DB072 DB151 DB481 DB482 FA061 FA062 FA081 FA082 FA111 FA112 FA181 FA182 FA261 FA262 FA281 FA282 JA33 JA75 JB01 JB32 JC21 KA03 NA24 NA27 PA17 PA19 PB06 PB09 PC02 5G305 AA02 AA11 AB36 BA09 CA15 CB13 CB15 CB16 CC325 CD08 CD08 5

Claims (2)

[Claims] 1. A coating composition comprising a thermosetting resin composition curable by irradiation with ultraviolet light is applied to the surface of a wire, and the surface of the coating composition is pre-cured by irradiation with ultraviolet light, and then heated. A method for producing a surface-coated wire, wherein the coating composition is completely cured by a treatment. 2. The coating composition according to claim 1, wherein (a) an epoxy prepolymer resin, (b) a radical polymerizable component, (c) a photoradical polymerization initiator, and (d) an epoxy curing agent activated by heat. The composition for coating a wire used in the method for producing a surface-coated wire according to claim 1, comprising: