JPS6017358B2 - Adhesive or adhesive composition - Google Patents

Description

[Detailed Description of the Invention] In recent years, with the revision of the Electrical Appliance and Material Control Law, adhesive or non-adhesive tape or sheet insulators used for insulating coils, etc. must have a thickness of 0.30 mm or more as a base material. .

However, if the base material is made thicker, it becomes stiffer, and it is difficult to adhere to the object to be insulated during insulation work, resulting in poor taping workability.Furthermore, there is a drawback that the base material peels off after use due to the repulsive force after insulation work.

Generally, to solve this problem, softeners such as phthalic acid ester, phosphoric acid ester, benzoic acid methylamide,
In this case, plasticizers such as sulfoamide are used.
When used in the summer when the temperature is 3-0 or above, there are problems such as the adhesive coming out from the edge of the tape and the adhesive transferring to the back surface of the tape. The present invention solves the above-mentioned problems and provides an adhesive or a pressure-sensitive adhesive composition that has a softening effect and is used for adhesive or pressure-sensitive adhesive tapes that do not cause smearing. The present invention has a terminal hydroxyl group or a terminal carboxyl group, and a 1,2 bond structure is
, 4-bond structure, and a polyfunctional isocyanate obtained by reacting trimethylolpropane with toludine diisocyanate.

The above-mentioned polybutadiene is added in an amount of 5 to 10 parts by weight based on 10 parts by weight of the acrylic adhesive or pressure-sensitive adhesive having a carboxyl group. If the amount is 5 parts by weight, the resulting tape or sheet will become stiff and will peel off after being wound into a coil or the like. The adhesive or pressure-sensitive adhesive composition of the present invention (hereinafter referred to as pressure-sensitive adhesive composition) has a fibrous porous substance as a base material, and an adhesive tape for applying the pressure-sensitive adhesive composition thereon, and a base material of the same or different type. It is used in non-adhesive tapes made by laminating base materials of the same or different types together, and laminated adhesive tapes in which a pressure-sensitive adhesive composition is applied to base materials laminated together. The acrylic adhesive containing a carboxyl group used in the present invention is a copolymer of acrylic ester and acrylic acid with a non-volatile content of 30 to 40% with toluene etc., such as Aron S-1511. × (manufactured by Toagosei Chemical Industry Co., Ltd.,
40% non-volatile content).

The polyfunctional isocyanate obtained by reacting trimethylolpropane and toluidine diisocyanate is used as the isocyanate in the present invention because it has better storage stability as an adhesive than ordinary toluidine diisocyanate. For example, there is Coronate L (manufactured by Nippon Polyurethane Industries, non-volatile content 75%).

As the polyfunctional isocyanate, it is preferable to use a trifunctional isocyanate obtained by reacting 1 mol of trimethylolpropane and 3 mol of toluidine diisocyanate. - If a polyfunctional isocyanate is not used, bleeding will occur from the end of the tape.

The polyfunctional isocyanate is used in an amount of 10 parts by weight or less, based on the weight of the acrylic adhesive or pressure-sensitive adhesive 10, but preferably in a range of 1 to 4 parts by weight.

Polyptadiene having a terminal hydroxyl group or a terminal carboxyl group is used because the terminal functional group and isocyanate are excellent in stability of the adhesive when applied, and the adhesive reacts easily during the drying process. This is because the flexibility of the adhesive tape can be improved, and it can also be given the characteristic of not becoming stale even at 30 qo.

Furthermore, the bonding structure of polybutadiene used here was limited because of its compatibility with the acrylic adhesive. In other words,
In the bonding structure of the polybutadiene primary mirror skeleton, 1,
If the number of 4-bond structures (including cis, trans) is larger than that of 1 and 2-bond structures, the compatibility with acrylic adhesives will be extremely poor, and the adhesive will become cloudy and separate after blending. This is because when the number of 1.2 bond structures is greater than the 1,4 bond structure, the compatibility with the acrylic pressure-sensitive adhesive becomes very good, and the pressure-sensitive adhesive after blending becomes transparent. 1,2 bond structure with terminal hydroxyl group or terminal carboxyl group
As shown in the following formula, the polybutadiene with a larger amount than the bond structure has a molecular weight in the range of 1,000 to 10,000, among which the terminal hydroxyl group has NissoPBG-100
0 (manufactured by Nippon Soda, non-volatile content 100%), terminal carboxyl groups include NissoPBC-1000 (manufactured by Nippon Soda, non-volatile content 100%), and the like.

or HOOC-- or--C〇〇day where a+b+c: 2 b>a+c n=10-100 The adhesive or pressure-sensitive adhesive composition of the present invention may be added with a solvent such as toluene or methyl ethyl ketone, or a xylene resin, if necessary. You may also add a tackifier such as.

Examples of the present invention will be described.

Note that the parts by weight described below indicate parts by weight of non-volatile components.

Comparative Example 1 Trifunctional isocyanate (Coronate L: Japan Polyurethane) obtained by reacting 1 mol of trimethylolpropane and 3 mol of toluidine diisocyanate, with a cloud content of 10 acrylic pressure-sensitive adhesives (Aron S-1511X: manufactured by Toagosei Kogyo Co., Ltd.) (hereinafter referred to as Santomikan Isocyanate) (hereinafter referred to as Santomikan Isocyanate) was mixed with 0.30-thick printer paper (PLP-
40.30 (manufactured by Ohira Paper Industries) and after drying (10
0 coating), laminated with 0.025 inch thick polyethylene terephthalate film (Lumirror: manufactured by Toray Industries),
Thereafter, a mixture of 10 parts by weight of the above-mentioned acrylic adhesive and 2 parts by weight of trifunctional isocyanate was applied to the linter paper side and dried (dry for 100 nights/pillow coating). It is treated with a backside treatment agent (KS-70 manufactured by Inshinetsu Chemical Co., Ltd.) (dry for 2 days/final treatment) and rolled up to make adhesive tape.

Comparative Example 2 100 parts by weight of the acrylic adhesive used in Comparative Example 1, 4 parts by weight of trifunctional isocyanate, 1,2 bond structure without functional group: 90%, 1,4 bond structure: 1
Polybutadiene consisting of 0 (NissoPBB-100
and average molecular weight 1000 (manufactured by Nippon Soda), and coated on IJ printer paper with a thickness of 0.3 mm and dried (coated 100 coats/meter with dry coating) to a thickness of 0.025 mm. The same procedure as in Comparative Example 1 was carried out to prepare an adhesive tape.

Comparative Example 3 100 parts by weight of the acrylic adhesive used in Comparative Example 1, 4 parts by weight of the trifunctional isocyanate, and 1
, 2 bond structure: 20%, 1,4 bond structure: 80% polybutadiene (PolyPbR-4 group T, average molecular weight: 4000: manufactured by Idemitsu Petrochemical) 6 parts by weight were mixed,
This was coated on linter paper with a thickness of 0.3 mm and dried (dry coated at a rate of 100 mm) and then laminated with a polyethylene terephthalate film having a thickness of 0.025 mm.The same operation as in Comparative Example 1 was performed and the mixture was laminated. Make adhesive tape.

Comparative Example 4 100 parts by weight of the acrylic adhesive used in Comparative Example 1, 4 parts by weight of trifunctional isocyanate, and 1
A copolymer of polybutadiene (PolyPbCS-15, average molecular weight 3600:
A. R. C. 0chemicalCO. Coated on linter paper with a thickness of 0.30 mm, and after drying (100 coats per coat in dry condition) was laminated with a polyethylene terephthalate film on the 0.025 side, as in Comparative Example 1. Perform the following steps to make adhesive tape.

Here, a+b=2 n=10-100 Comparative Example 5 100 parts by weight of the acrylic adhesive used in Comparative Example 1, 4 parts by weight of the trifunctional isocyanate, and a terminal carboxyl group, 1,2 bond structure: 20 %, 1,4 bond structure 80
% of acrylonitrile (Hycar CTBN, average molecular weight 3300: B.F.
alCo. Comparative Example Perform the same operation as step 1 to make adhesive tape.

Here, a-b Ni 2 n Ni 10 to 100 Comparative Example 6 100 parts by weight of the acrylic adhesive used in Comparative Example 1, 4 parts by weight of trifunctional isocyanate, and further having a terminal hydroxyl group,
1.2 Bond structure: 90%, 1. Mixing 11 parts by weight of polybutadiene (NissoPBG-1000, average molecular weight 1000: manufactured by Nippon Soda) consisting of 10% of Reiki structure;
This was coated on a printer paper with a thickness of 0.3 mm and dried (100 coatings per dry coat), then glued onto a polyethylene terephthalate film with a thickness of 0.025 mm and adhered in the same manner as in Comparative Example 1. make tape.

Example 1 100 parts by weight of the acrylic adhesive used in Comparative Example 1, 4 parts by weight of the trifunctional isocyanate, and 1
, 2-bond structure: 90%, 1,4-bond structure: 10% by weight of polybutadiene 6 was mixed, and this was coated on linter paper with a thickness of 0.3 mm. After drying (dry for 100 evenings/final coating) A polyethylene terephthalate film having a side thickness of 0.025 mm was laminated and the same operation as in Comparative Example 1 was performed to make an adhesive tape.

Example 2 100 parts by weight of the acrylic adhesive used in Comparative Example 1, 4 parts by weight of the trifunctional isocyanate, and a terminal carboxyl group, 1,2 bond structure: 90%, 1,4 bond structure: 10% polybutadiene (NissoP)
BC-loo average molecular weight 1000: Nippon Soda) 100
Parts by weight were mixed and this was coated on linter paper with a side thickness of 0.30. After drying (drying for 100 evenings/pillow coating), it was laminated with a polyethylene terephthalate film with a side thickness of 0.025 and the same operation as in Comparative Example 1 was performed. Glue together to make adhesive tape.

Comparative Example 7 100 parts by weight of the acrylic adhesive used in Comparative Example 1, having a terminal carboxyl group, 1,2 bond structure: 90%, 1,
4-bond structure: Mix parts by weight of polybutadiene 6 consisting of 10%, coat this on a 0.3-inch thick printer paper and dry it (100 coatings per dry coat). The same procedure as in Comparative Example 1 was carried out to prepare an adhesive tape.

Example 3 100 parts by weight of the acrylic adhesive used in Comparative Example 1, 4 parts by weight of Sanfukan isocyanate, and a terminal carboxyl group containing 1,2 bond structure: 90%, 1,4 bond structure: 10%
A five-layer mixture of polybutadiene consisting of 0.
After coating and drying on linter paper with a thickness of 3.
The adhesive tape was then laminated with a polyethylene terephthalate film having a thickness of 0.025 mm, and the same operation as in Comparative Example 1 was performed to prepare an adhesive tape.

Comparative Example 8 100 parts by weight of the acrylic adhesive used in Comparative Example 1, 4 parts by weight of the trifunctional isocyanate, and a terminal carboxyl group, 1,2 bond structure: 90%, 1,4 bond structure: 10
4 parts by weight of polybutadiene consisting of 0.0% by weight were mixed.
After coating on 3W thick linter paper and drying (100% dry)
The adhesive tape was then laminated with a polyethylene terephthalate film having a side thickness of 0.025 mm and the same operation as in Comparative Example 1 was performed to make an adhesive tape.

Example 4 100 parts by weight of the acrylic adhesive used in Comparative Example 1, 2. 1,2-bond structure with a terminal carboxyl group: 90%, 1,4-bond structure:
604 parts by weight of polybutadiene consisting of 10% are mixed;
This was coated on a 0.030 foot thick printer paper and dried (dry for 100 evenings/final coating), then laminated with a 0.025 skin thick polyethylene terephthalate film and the same operation as in Comparative Example 1 was carried out. Make adhesive tape.

Example 5 100 parts by weight of the acrylic adhesive used in Comparative Example 1, 1. 1,2-bond structure with a terminal carboxyl group: 90%, 1,4-bond structure:
Mix 60 parts by weight of polybutadiene consisting of 10%, coat this on linter paper with a thickness of 0.03 cm, dry it (dry coating for 100 coats), and glue it with a polyethylene terephthalate film with a skin thickness of 0.025 mm. An adhesive tape is prepared by performing the same operation as in Comparative Example 1.

Table 1 shows the test results of the obtained adhesive tape.

Boat.

○ Ship test method is JIS C 23 spot and JIS C 2107
According to.

Special test methods are as follows. (*1) Glue a sample of 1 length x 2 ribs on a stainless steel plate, hang a load of 500 meters perpendicularly to it in 40 qo, and observe the deviation between the stainless steel plate and the sample after 6 minutes.

The judgment method is NG if the slippage falls, ○K if the slippage does not fall.
And so.

(*2) J. According to the Do vs. method.

Run-up distance: 10 degrees, test distance: 10 on a 30 degree slope
I did it with my enemy.

The determination method was based on the diameter of a steel ball that could rest on the adhesive surface of the adhesive tape. For example, 10 indicates a diameter of 10/32 inch. (*3) 40oo-90%R as adhesive tape
．． It was left in the H chamber, and after 2 hours it was taken out, and the tape was immediately pulled out from the end face and the tape was peeled off to observe whether the adhesive had migrated to the back of the eye.

As for the judgment method, cases where there was loosening from the end face or transfer of the adhesive to the back of the eye were judged as NG, and cases other than that were judged as OK. 1st
The test method is shown in the figure. In FIG. 1, 1 is the end surface of the adhesive tape, 2 is its back surface, and 3 is its adhesive surface. (*4) Cut two pieces of adhesive tape to the size of a 25.4 x 63.5 sail, and glue them together evenly with both adhesive sides facing inside to use as a sample for Gurley flexibility measurement. Measured using a device.

Figure 2 shows the test method. In Figure 2, 4 is a clip;
5 is a sample, 6 is a flexibility measuring needle, and 7 is its trajectory. (
*6) Create a model coil by uniformly wrapping a ◇0.2 willow urethane enameled wire around a 10-rib glass rod, taking care not to loosen both ends of the enameled wire.

Thereafter, an adhesive tape having a width of 1 specific rib is wrapped half a time or once and a half and left for 230 minutes without being subjected to external force, and after 3 days the distance of peeling is measured. The judging method was OK if the peeling distance was within 4 ribs, and NG if the peeling distance was other than that.

Figures 3 and 4 show the test methods for half-turning and once-half-turning, respectively. In Figures 3 and 4, 8 is a glass rod, 9 is a urethane enameled wire, 10 is an adhesive tape, 1
1 indicates the peeling distance. As shown in Table 1, the adhesive tape obtained using the adhesive or pressure-sensitive adhesive composition of the present invention can be made flexible even when thickened by arbitrarily changing the blending ratio, and can be used in high temperature and high humidity environments. Even in an atmosphere of

[Brief explanation of the drawing]

Figure 1 is a schematic diagram of the discoloration test conducted in the example, Figure 2
The figures are schematic diagrams of the flexibility test conducted in the example, Figures 3 and 4.
The figure is a schematic diagram of a model coil peelability test. Explanation of symbols, 1...End face of adhesive tape, 2...
... Back side of adhesive tape, 3 ... Adhesive surface of adhesive tape, 4 ... Clip, 5 ... Sample (2 pieces), 6 ... Flexibility measuring needle, 7. ...Flexibility measuring needle trajectory, 8...Glass rod, 9...Urethane enameled wire, 10...Adhesive tape, 1 1...
...Peeling distance. Figure 1 Figure 2 Figure 3 Figure 4

Claims (1)

[Claims] 1 5 to 100 parts by weight of polybutadiene, which has a terminal hydroxyl group or a terminal carboxyl group and has more 1,2 bond structure than 1,4 bond structure, and trimethylolpropane per 100 parts by weight of acrylic adhesive or pressure-sensitive adhesive having carboxyl group. An adhesive or pressure-sensitive adhesive composition containing a polyfunctional isocyanate obtained by reacting toluidine diisocyanate with toluidine diisocyanate.