JP2001354947A - Quickly curing two-component castable fixing agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a castable fixing agent which as repairability enabling dismantling without damaging electrical wiring, or the like, is excellent in impregnating properties, and is quickly cured, enabling other assembling steps to be carried out on the same line. SOLUTION: This fixing agent mainly comprises a (meth)acrylic ester and has a gelation time at 25 deg.C of 10-60 sec. A wiring part obtained by using the fixing agent is also provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to sealing air and rainwater from leaking when electric wiring or a telegraph cable is penetrated through a wall or a wall in an automobile, electric equipment, shipbuilding, construction or other fields. The present invention relates to a novel fast-curing two-component fixing agent used by injecting into a gap. More specifically, the present invention relates to a two-pack type fast curing agent which has excellent repairability when electric wiring or communication cables are renewed, and has low viscosity and excellent penetration into gaps such as wire bundles. . Because of its rapid curing properties, it can be used particularly suitably for the production of wiring parts for automobiles or electric devices mass-produced on a continuous production line.

[0002]

2. Description of the Related Art When an electric wiring or the like is to penetrate a wall of a building or a wall of an automobile or electric equipment, the electric wiring or the like is usually passed through a pipe-like or container-like cover having a through hole. It is common. Epoxy resins, urethane resins, polyester resins, and the like have been used to seal the gap between the cover and the wiring or the gap between the wirings. However, these resins generally have low impregnating properties due to high viscosity, and have insufficient airtightness such as water leakage. In addition, it generally takes a long time to cure, so that it is difficult to manufacture wiring components such as a wire harness on the same conveyor line as other assembling work. further,
Cured resin that has been used in the past has too strong an adhesion to the wire coating, or the cured resin is too strong and has poor repairability when renewing the wiring. Alternatively, there is a possibility that the incidental parts may be damaged.

[0003]

After passing electric wiring or the like through a pipe-shaped or container-shaped cover having a through hole,
A fixing agent that can be suitably used for the purpose of injecting and curing into the gap between the cover and the electric wiring and sealing it, and has a repairing property that can be disassembled without damaging the electric wiring, etc. The purpose of the present invention is to provide an injection-fixing agent which can be cured by using the same line as another assembly process.

[0004]

Means for Solving the Problems A low-viscosity (meth) acrylic acid ester as a main component, and if necessary, a (meth) acrylic modified urethane oligomer is blended to adjust the viscosity and the hardness of the cured product to thereby improve the impregnation and repairability. Properties. In addition, by using an organic peroxide and a specific curing accelerator together, the work time can be significantly reduced by gelling in 10 minutes to 60 seconds at 25 ° C. and several minutes even at a low temperature near 0 ° C. And completed the present invention. The fast-curing two-pack type injection fixing agent of the present invention contains 50 to 100 parts by weight of a (meth) acrylate, 0 to 45 parts by weight of an acryl-modified urethane oligomer, and 0.1 to 0.1 parts by weight of a compound having a vinyl group and a carboxyl group. 100 parts by weight of a mixture consisting of 5.0 parts by weight is divided into solution A and solution B, and 0.3 to 5 parts by weight of an organic peroxide is used in solution A, and tertiary amine, mercaptan, β-diketone, and triketone are used in solution B. , Carboxylic anhydride,
It is obtained by blending a total of 0.1 to 2 parts by weight of one or more curing accelerators selected from urea derivatives, organic vanadium compounds, and organic cobalt compounds. Further, if necessary, a polymerization inhibitor and an antifoam leveling agent may be added at 0.05 to 2.
It is prepared by mixing 0 parts by weight with both liquids.

[0005] The (meth) acrylate in the composition of the present invention is a monofunctional acrylate or methacrylate having one or two hydroxyl groups, ether groups or glycidyl groups in the molecule, or a hydroxyl group,
It is not necessary to have an ether group or a glycidyl group.
It is a trifunctional acrylate or methacrylate, and is composed of one or a mixture of two or more of these (meth) acrylates.

Examples of the main (meth) acrylic acid esters that can be used include the following. Here, methacrylic ester is mainly exemplified, but acrylic ester can also be used.

2-hydroxyethyl methacrylate, 2
-Hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, phenoxyethyl methacrylate, 1,4-butanediol dimethacrylate, 1,6
-Hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, trimethylolpropane trimethacrylate, glycerin dimethacrylate, 2-
Hydroxy-3-acryloyloxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycidyl methacrylate, 2-methacryloyloxyethyl acid phosphate, ethylene glycol dimethacrylate, polyalkylene glycol dimethacrylate, methoxyethylene glycol methacrylate, methoxypolyalkylene glycol Methacrylate, phenoxyethylene glycol methacrylate, phenoxypolyalkylene glycol methacrylate, 3
-Chloro-2-hydroxypropyl methacrylate, trimethylolpropane, bisphenol A ethylene oxide adduct diacrylate and the like.

The (meth) acryl-modified urethane oligomer in the composition of the present invention is a compound obtained by reacting a polyether isocyanate oligomer or a polyester isocyanate oligomer with a (meth) acrylate ester having a hydroxyl group. Examples include NK Oligo U-340A manufactured by Shin-Nakamura Chemical.

The compound having a vinyl group and a carboxyl group in the composition of the present invention is, for example, a monoester of a (meth) acrylic acid ester or a maleic acid having a carboxyl group, such as 2-methacryloyloxyethyl succinic acid. , 2-methacryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl 2-hydroxypropylphthalic acid, monoethyl maleate and the like.

The organic peroxide in the composition of the present invention is a ketone peroxide, a hydroperoxide, a diacyl peroxide, or a peroxydicarbonate which can be cured at a relatively low temperature, for example, methyl ethyl ketone peroxide, acetylacetone. Examples include peroxide, methyl acetoacetate peroxide, methyl cyclohexanone peroxide, cyclohexanone peroxide, cumene hydroperoxide, benzoyl peroxide, and bis (4-tbutylcyclohexyl) peroxycarbonate.

[0011] The curing accelerator in the composition of the present invention is:
Tertiary amine, mercaptan, β-diketone, triketone,
These are carboxylic anhydrides, thiourea compounds, organic vanadium compounds, and organic cobalt compounds, and one or a mixture of two or more of these curing accelerators can be used. Examples include dimethylaniline, dimethylbenzylamine, dimethylparatoluidine, saccharin, 2-mercaptophenol, 2-mercaptobenzothiazole, benzoylacetone, acetylacetone, 1,3-cyclohexanedione, 2,3,4pentanetrione, 2-acetylcyclo Examples include pentanone, phthalic anhydride, ethylene thiourea, vanadium oxide diacetylacetonate, vanadium oxide triacetylacetonate, and cobalt naphthenate. In the composition of the present invention, one or a mixture of two or more selected from tertiary amines, mercaptans, β-diketones, triketones, carboxylic anhydrides, and thiourea compounds, and an organic vanadium compound or an organic cobalt compound are selected. It is particularly preferable to use one kind of curing accelerator in combination, since the addition amount is small and a short gelation time can be obtained.

The method of using the fast-curing two-pack type injecting and fixing agent of the present invention can be suitably carried out with a general two-pack injecting machine having a mixing section with a static mixer at the tip. Further, since the viscosity of the liquid is low, it is possible to use a collision-mixing type injection machine in which the liquid A and the liquid B collide before leaving the pipe and before reaching the wiring cover. The use of this impingement mixing type injection machine is economical because there is no mixing section in the apparatus and there is no risk of blockage, and there is no wear of the static mixer and the like.

[0013]

Next, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

Example 1 2-hydroxyethyl methacrylate 40
Parts by weight, 18.4 parts by weight of methoxypolyethylene glycol 400 acrylate, 0.4 parts by weight of 2-methacryloyloxyethyl succinic acid, 37.5 parts by weight of a methacryl-modified urethane oligomer (a reaction product of an isocyanate oligomer and 2-hydroxyethyl methacrylate) , 3.6 parts by weight of cumene hydroperoxide, 0.03 parts by weight and 0.10 parts by weight of a polymerization inhibitor and a defoaming leveling agent, respectively, and stirred and mixed at room temperature to obtain a liquid A. Next, 44 parts by weight of 2-hydroxyethyl methacrylate,
Methoxy polyethylene glycol 400 acrylate 2
0.6 parts by weight of the mixture is heated to 50-60 ° C., and 0.06 parts by weight of vanadium (IV) oxide diacetylacetonate, 0.3 parts by weight of dimethylaniline, 0.3 parts by weight of ethylenethiourea are stirred. Was dissolved. Subsequently, 34.7 parts by weight of a methacryl-modified urethane oligomer, 0.03 part by weight of a polymerization inhibitor and 0.03 part by weight of a defoaming leveling agent were added.
10 parts by weight were mixed to obtain a liquid B. The viscosities of both liquids A and B were 80 mPa · s and 85 mPa · s, respectively, and the gelation time at 25 ° C. of a 1: 1 mixture by weight ratio was 30 seconds. The cured product hardness after 1 hour was rubbery with a Shore A hardness of 40.

Examples 2 to 8 In the same manner as in Example 1, solutions A and B were prepared according to the formulations shown in Table 1, and the viscosity, gel time and hardness were measured. Table 1 shows the results.

[Table 1]

Claims (6)

[Claims] 1. A fast-curing, two-pack injection-fixing agent comprising (meth) acrylic acid ester as a main component and having a gelling time of 10 to 60 seconds at 25 ° C. 2. A monofunctional (meth) acrylate having one or two of a hydroxyl group, an ether group and a glycidyl group in the molecule or a hydroxyl group, an ether group and a glycidyl group in the molecule. 2 to 3 functional (meth) acrylates which may not have a group, and one or two of these (meth) acrylates
2. The fast-curing, two-part injectable fixative according to claim 1, comprising a mixture of at least two kinds. 3. The method according to claim 1, wherein the (meth) acrylate is 50 to 10%.
A mixture 100 comprising 0 parts by weight, 0 to 45 parts by weight of a (meth) acryl-modified urethane oligomer, and 0.1 to 5.0 parts by weight of a compound having a vinyl group and a carboxyl group.
A part by weight is divided into the liquid A and the liquid B, and the organic peroxide is added to the liquid A in an amount of 0.
2. The fast-curing two-part injection fixing agent according to claim 1, wherein 3 to 5 parts by weight and 0.1 to 2.0 parts by weight of a curing accelerator are added in advance to the liquid B, and the mixture is used immediately before injection. 4. A curing accelerator comprising one or more compounds selected from tertiary amines, mercaptans, β-diketones, triketones, carboxylic anhydrides or thiourea derivatives, and an organic vanadium compound or an organic cobalt compound. 2. The fast-curing two-pack injection fixing agent according to claim 1, which is used in combination with any one of them. 5. The liquid A and the liquid B before mixing each have a viscosity of 50 to 200 mPa · s, and the Shore A after curing.
2. The fast-curing two-part injection fixing agent according to claim 1, having a hardness of 20 to 100. 6. A wiring obtained by using a fast-curing two-pack type injection-fixing agent, which is mainly composed of (meth) acrylate and has a gel time of 10 to 60 seconds at 25 ° C. parts.