KR20090009017A - Polyisocyanate generator for cable and vanish compositions - Google Patents

Abstract

A polyisocyanate generator for cable and a vanish composition containing the same are provided to obtain an environment-friendly varnish by reducing bad smell and stoving temperature and containing environment solvents such as n-methylpyrolidone, dibasic ether, and 1- methoxy -2- propanol. A polyisocyanate generator for cable is represented by the chemical formula 1. In the chemical formula 1, R1 is the formula (a) or their derivatives, and R2 and R3 are independently C1-5 alkyl group or C6-10 aryl group.

Description

Polyisocyanate regenerator for insulated wire and varnish composition containing the same {POLYISOCYANATE GENERATOR FOR CABLE AND VANISH COMPOSITIONS}

The present invention relates to a polyisocyanate regenerator for insulated wire and a varnish composition containing the same, in particular a regenerator of isocyanate in a thermosetting polyurethane resin for improving malodor occurring during insulation coating of wires and a new polyisocyanate regenerator. One relates to a polyurethane enamel varnish composition for insulated wire.

In general, the polyurethane varnish in forming an insulating coating of the electric wire is a phenolic acid in the polyester polyol and dihydric or trivalent free isocyanate prepared by the reaction of phthalic acid or adipic acid and derivatives thereof with dihydric or trivalent alcohol. It is prepared by dissolving isocyanate blocked with volatile alcohols such as phenol and the like in a solvent.

The insulated wire manufactured by applying and baking the polyurethane varnish thus formed on the copper wire of the wire is superior to the insulated wire obtained by applying and baking the insulating coating of other synthetic resins having different electrical characteristics, chemical resistance, and cold resistance. Although there is an advantage that can be directly soldered without peeling, isocyanate blocked with volatile alcohol causes many odors and environmental pollution due to the regeneration of volatile alcohol and shortens the lifetime of the oxidation catalyst of platinum and vanadium. Causes a rise.

In order to solve the problems of the prior art as described above, the present invention provides a regenerated body of isocyanate in a thermosetting polyurethane resin and a new polyurethane isocyanate regenerated polyurethane enamel containing the new polyisocyanate regenerated to improve the odor generated during the insulation coating of the wire It is an object to provide a varnish composition.

It is another object of the present invention to provide an environmentally friendly varnish by reducing odor and baking temperature while maintaining existing characteristics.

In order to achieve the above object, the present invention provides a polyisocyanate regenerator characterized in that represented by the following formula (1).

[Formula 1]

,R1 in Formula 1 is

,

,

,

또는 이들의 유도체이고,

,

,

Or derivatives thereof,

R2 and R3 are each independently an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R2 and R3 may form a ring with each other.

In another aspect, the present invention provides a varnish composition for insulated wire, comprising a polyisocyanate regenerator of the formula (1).

 In another aspect, the present invention provides a varnish composition for insulated wire, comprising 100 parts by weight of the polyisocyanate regenerator of Formula 1 to 25 to 40 parts by weight of polyol and 30 to 70% by weight of the total solids.

Polyurethane varnish containing polyisocyanate regenerator and polyol according to the present invention is a polyisocyanate regenerated blocked by reacting isocyanate with alkyl oxime, N-methyl pinolidon, dibasic ether, 1-methoxy-2- By producing varnish as the main solvent using environmentally friendly solvents such as propanol to suppress the occurrence of odor at the time of coating and baking on copper wire, it is possible to be baked at low temperature to achieve productivity and energy savings.

The present invention is characterized by the use of alkyl oximes for isocyanates. In addition, it is preferable to use environmentally friendly solvents such as N-methylpyrrolidone, dibasic ether, 1-methoxy-2-propanol, which does not use methacresol, and to reduce odor and VOC, thereby making it an environmentally friendly polyurethane. It is to prepare varnish.

Polyisocyanate regenerator for insulated wire of the present invention is characterized by the above formula (1). The polyisocyanate regenerator may be prepared by dropping an alkyl oxime dropwise to one molecule of diisocyanate with attention to heat generation as shown in Scheme 1 below.

Scheme 1

In Scheme 1, R1, R2 and R3 are the same as above.

The reaction temperature during the reaction is 50 ~ 200 ℃, preferably 50 ~ 150 ℃. If it is less than 50 ° C, the reaction hardly proceeds, and if it exceeds 200 ° C, unwanted side reactions sometimes occur, resulting in coloring of the polyisocyanate produced.

The polyisocyanate regenerator of the present invention is a polyisocyanate in which part or all of the isocyanate groups are blocked with an alkyl oxime, and the alkyl oxime is preferably formaldehyde, acetaldehyde, acetoxime, methyl ethyl ketoxime, cyclo Hexone oxime or the like is used to improve the electrical properties, chemical resistance and cold resistance of the varnish composition for insulation conductivity.

In another aspect, the present invention provides a varnish composition for insulated wire, characterized in that it comprises a polyisocyanate regenerator of the general formula (1), preferably 25 to 40 parts by weight of a polyol to 100 parts by weight of the polyisocyanate regenerator of the general formula (1) Part, and may comprise a solvent to 30 to 70% by weight total solids.

As the polyol in the varnish composition for insulated wire of the present invention, a polyol commonly known in the art may be used, and it is preferable to use a polyester polyol. The polyol reacts with the polyisocyanate and regenerator to form a urethane. The polyol is included in an amount of 25 to 40 parts by weight based on 100 parts by weight of the polyisocyanate regenerator. It is preferable to include 29 to 34 parts by weight. If the amount of the polyol is less than or exceeds the above range, the content ratio of the polyisocyanate to NCO becomes too small or too large so that urethane formation of desired physical properties is not achieved.

More preferably, the polyol and the polyisocyanate regenerator are preferably reacted in the range of 1: 1.1 to 1: 1.2 equivalent ratio. When mixed in such an equivalence ratio, the urethane bond is well formed, thereby obtaining a urethane insulating varnish having solderability of desired characteristics.

In addition, as the solvent for the polyol and the polyisocyanate in the insulating varnish composition of the present invention, it is preferable to use an environmentally friendly solvent such as N-methyl pinolinidone, dibasic ether, 1-methoxy-2-propanol as the main solvent. The amount of solvent determines the total amount of solids of the insulating varnish. If it is included too little or too much, the desired workability cannot be obtained. Preferably, the solvent may be included so that the total solid content of the varnish composition for dielectric insulation of the present invention is 30 to 70% by weight. More preferably, the total solid content is 35 to 45% by weight. In addition, the auxiliary solvent may be used xylene, xylene, or solvent-naphtha (solvent-naphtha).

In addition, the varnish composition for insulated wire of the present invention may further include an additive such as a reaction promoter usually included in the varnish composition for insulated wire. The additive may be included in the range of 0.01 to 5 parts by weight, respectively, in 100 parts by weight of the polyisocyanate. Specific examples of the additive include reaction compounds such as Sn compounds, tertiary amine compounds, quick stone gum compounds, and organic zinc compounds. These compounds dissociate block agents to promote curing by dissociating block isocyanates and polyols. Do it. Dibutyltin dilaurate (DBTDL: Dibutyltin dilaurate) is effective as a Sn compound with high catalytic effect due to low temperature curing and low temperature solderability. However, it has a moderate catalytic effect in consideration of economical aspects and heat resistance of enamel coating. Zn-Oactate can be used. As another additive, an epoxy resin may be used for scratching resistance, and a nylon resin may be used for improving flexibility.

The varnish composition for insulated wire of the present invention not only has excellent electrical resistance, chemical resistance and cold resistance, but also improves odor generated during insulation coating of the wire, reduces baking temperature, and has environmentally friendly characteristics.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

Example 1

250 g of 4,4-dimethylmethane diisocyanate was added to a 1 L four-necked flask, and heated to 40 ° C., and 179.6 g of methylethylketoxime was added dropwise for 4 hours without exceeding 90 ° C. to synthesize polyisocyanate. . Here, 140 g of polyester polyol having 245 hydroxyl groups and 60% solids, 100 g of N-methylpyrrolidone, 35 g of dibasic ether, 65 g of 1-methoxy-2-propanol, 65 g of xylene and a reaction accelerator The organic zinc compound was added with 1.2% of the resin, followed by stirring to prepare a urethane insulating enamel varnish having a solid content of 40% viscosity of 0.65 poise.

Example 2

Polyisocyanate regenerated urethane insulation was performed in the same manner as in Example 1 except that 250 g of L-MDI (2,4,4,4-dimethylmethane diisocyanate mixture) was used instead of 4,4-dimethylmethane diisocyanate. Enamel varnishes were prepared.

[Comparative Example]

180 g of D-380-60B polyol of Gangnam Hwaseong Co., 136 g of Methacresol, 162 g of Xylene, catalyst in 180 g of TD-1400T of Kangnam Hwasung Co. 3.5 g was added to prepare a urethane insulating enamel varnish.

The varnishes of Examples 1 and 2 and Comparative Examples were applied and baked on a 1.0 φ mm copper wire to prepare a polyurethane enameled wire under the following working conditions.

Softening Furnace Temperature: 510 ℃

Soburo Inlet Temperature: 310 ℃

Soburo outlet temperature 360 ℃

Speed: 14m / min

The characteristics of the enameled wire obtained under the above conditions were evaluated according to KS C 3107, and the results are shown in Table 1 below.

TABLE 1

Experiment item Example 1 Example 2 Comparative example Pinhole Good Good 3EA Film defect Good Good crack Breakdown 7.21 kv 6.5 kv 5.8 kv Internal softening temperature 230 ℃ 190 ℃ 205 ℃ Thermal shock resistance Good Good crack Tanδ 122 ℃ 105 ℃ 93.5 ℃ Solderability Good Good Bad

In addition, the insulating enamel varnish prepared according to Example 1 and Comparative Example was measured according to ISO 11890-2. The results are shown in Table 2 below.

TABLE 2

Test Items Measurement Sample Amount of volatile organic solvent VOCs Example 1 387.8 g / L Comparative example 834.2 g / L

In addition, the results of analyzing the odor by the odor process test method (small chamber method: indoor air quality process test method) of the insulating enamel varnish prepared according to Example 1 and Comparative Examples are shown in Table 3.

TABLE 3

Measurement Sample Result (unit: dilution factor) Example 1 3730 Comparative example 11800

As can be seen from Tables 1 to 3, it was confirmed that the varnish composition containing the polyisocyanate regenerator of the present invention has excellent insulation breakdown, softening resistance, and the like, and can suppress odor generation during the process.

Claims (5)

Polyisocyanate regenerator, characterized in that represented by the formula (1): [Formula 1]

R1 in Formula 1 is

,

,

,

Or derivatives thereof, R2 and R3 are each independently an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms. The method of claim 1, The polyisocyanate regenerator, characterized in that each of the oxime at the end of the formula (1) is independently acetaldehyde, acetoxime, methyl ethyl ketoxime, or cyclohexanone oxime. A varnish composition for insulated wire, comprising the polyisocyanate regenerator according to claim 1. The method of claim 3, wherein 100 parts by weight of the polyisocyanate regenerator according to claim 1; 25 to 40 parts by weight of polyol; And Varnish composition for insulated wire, comprising a solvent so that the content of the total solid content is 30 to 70% by weight. The method of claim 4, wherein The solvent is a varnish composition for insulated wire, characterized in that at least one selected from the group consisting of N-methylpyrrolidone, dibasic ether, 1-methoxy-2-propanol and the like.