JPH05179216A - Polychloroprene adhesive composition - Google Patents

Abstract

PURPOSE:To provide a solvent-type chloroprene adhesive composition satisfying both thixotropic properties and adhesion by using a specific modified chloroprene polymer and a specific thermally reactive phenol-formaldehyde resin. CONSTITUTION:(A) 100 pts.wt. of a modified chloroprene polymer containing 0.01 to 5wt.% of COOH group in the molecule, (B) 10 to 200 pts.wt., preferably 20 to 150 pts.wt. of a thermally reactive phenol-formaldehyde resin containing more than 30 mole %, preferably 30 to 60 mole % of methylol group, when the total of methylol, methylene ether and methylene groups is regarded as to be 100 mole %, (C) 5 to 15 pts.wt., based on 100 pts.wt. of (B), of a basic metal oxide or hydroxide such as MgO or ZnO, when needed, further, other thixotropic agent such as basic magnesium carbonate are dispersed in an organic solvent such as toluene or ethyl acetate to give the subject composition containing 10 to 50wt.% of non-volatile components.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a solvent-type polychloroprene-based adhesive composition having improved flow characteristics.

Due to their excellent properties, polychloroprene-based solvent-based adhesives are used in many industrial fields such as shoemaking, woodworking,
Used in architecture, automobiles, home appliances, etc. Of these, in construction, there are many constructions of vertical parts regardless of interior and exterior,
Since the solvent-type adhesive has fluidity, the coating layer is likely to flow down and cause poor adhesion. Also, when working with a high-viscosity adhesive using an applicator, etc., the adhesive flows down from the nozzle when moving to the next step, so-called stringing is seen, and the adhesive is also applied to unnecessary parts. Will be attached and cause a decrease in commercial value, for example. Therefore, the adhesive for this purpose is required to have such characteristics that it can work smoothly during application, the obtained coating film does not sag, and the adhesive does not cause stringing. Such characteristics are so-called thixotropic properties, and these adhesives are required to have thixotropic properties.

[0003]

2. Description of the Related Art Several methods for improving the thixotropy of solvent-type polychloroprene adhesives are known.
For example, there is a method of blending a compounding chemical imparting thixotropic property, or a method of using polychloroprene having thixotropic property. The former includes basic magnesium carbonate (for example, Tokusil T, trade name, Tokuyama Soda Kogyo Co., Ltd.), dry process white carbon (for example, Aerosil 380, trade name, manufactured by Nippon Aerosil Co., Ltd.), organic bentonite (for example, NEW D ORBEN manufactured by Shiraishi Co., Ltd. ) And the like, and the latter includes polychloroprene containing microgel (for example, Y-20E of Toso Corporation). When these methods are used, the manufacturing method is complicated or the adhesiveness (for example,
There is a problem in the selectivity of the adherend) or the cohesive force is reduced. Alternatively, there is a drawback that it is difficult to satisfy both thixotropy and adhesive strength.

[0004]

DISCLOSURE OF THE INVENTION The present inventors have completed the present invention as a result of intensive research aimed at solving these problems all at once. That is, the present invention uses a modified chloroprene polymer of a certain type and a thermoreactive phenol formaldehyde resin of a certain type, whereby a solvent-type polychloroprene satisfying both thixotropy and adhesive strength by a conventional production method. A system adhesive composition is provided.

[0005]

Means for Solving the Problems That is, the present invention provides (1)
100 parts by weight of a chloroprene polymer containing a carboxyl group represented by the general formula —COOH in the molecule and (2) methylol when the sum of methylol group, methylene ether group and methylene group in all molecules is 100 mol%. Base is 30-6
10 to 200 parts by weight of the thermoreactive phenol formaldehyde resin, which is 0 mol%, and (3) 5 to 15 parts by weight of the basic metal oxide or hydroxide, based on 100 parts by weight of the thermoreactive phenol formaldehyde resin. The present invention relates to a solvent-type polychloroprene-based adhesive composition having thixotropy, which is obtained by dissolving a composition consisting of 1 part and 2 parts in an organic solvent. The details will be described below.

In a solvent type polychloroprene adhesive composition, a chloroprene polymer having a carboxyl group represented by the general formula --COOH in the molecule of the present invention (hereinafter referred to as carboxyl modified CR) is in the molecule. 0.01
It is a chloroprene polymer containing ˜5.0 wt% of carboxyl groups. Using this carboxyl modified CR,
Methods for increasing the initial adhesive strength, high-temperature adhesive strength, etc. are already known and have been put to practical use in the adhesive industry field. This method is considered to utilize the chemical reactivity between the carboxyl group and the metal oxide for improving the adhesive strength. Further, a method of increasing the initial adhesive strength or high temperature adhesive strength by using a chelate reaction of a heat-reactive phenol formaldehyde resin (hereinafter referred to as a resin) with a metal oxide is already known, and is known in the adhesive industry field. It has been put to practical use.

On the other hand, the present invention provides a solvent-type polychloroprene-based adhesive composition containing (1) 100 parts by weight of carboxyl-modified CR and (2) 100 mol% of the sum of methylol group, methylene ether group and methylene group in all molecules. And the methylol group is 30 mol% or more, preferably 30 to 60 mol%
10 to 200 parts by weight of resin, preferably 20 to 150
Parts by weight and (3) basic metal oxide or hydroxide is resin 1
Thirotropic property is imparted by coexistence with 5 to 15 parts by weight with respect to 00 parts by weight, which is a solvent-type polychloroprene system satisfying both thixotropic property and adhesive force by a conventional production method. An adhesive composition is provided. In order to impart thixotropic properties, coexistence of carboxyl-modified CR, resin and basic metal oxide or hydroxide is indispensable, and thixotropic properties cannot be imparted even if any of them is lacking.

In the present invention, a compounding agent which imparts ordinary thixotropic properties, such as basic magnesium carbonate, dry process white carbon, organic bentonite, etc., or polychloroprene containing a microgel imparting thixotropic properties is used in combination. You can also

First, a method for producing the solvent-type polychloroprene adhesive composition according to the present invention will be described.

The carboxyl-modified CR can be used alone or as a blend of the carboxyl-modified CR and a chloroprene polymer which is usually used in adhesives. The resin is a methyl group when the sum of the resin, methyl group, methylene ether group and methylene group in all molecules is 100 mol%.
The resin having less than 30 mol% of ruthenium groups can be used alone or in combination of two or more. The amount of the resin used in the adhesive can be increased or decreased according to the application of the adhesive, but is generally 10 to 200 parts by weight based on 100 parts by weight of carboxyl-modified CR or 100 parts by weight of the chloroprene polymer.

To form a chelate with the resin, the basic metal oxide or hydroxide is added in a proportion of 5 to 15 parts by weight based on 100 parts by weight of the resin.

Examples of the basic metal oxide and hydroxide include MgO, CaO, Mg (OH) ₂ and Ca (OH) _2.
And other metal oxides such as CdO, PbO, Z
nO, TiO ₂ , etc., and 1 to 10 parts by weight of one kind or two or more kinds of metal oxides is added to 100 parts by weight of the chloroprene polymer, if necessary. Generally MgO, Zn
O is used.

The organic solvent used for preparing the present adhesive can be any carboxyl-modified CR and any resin that can dissolve the resin, and includes hydrocarbons, chlorinated hydrocarbons, ketones and esters. These may be used alone or in combination depending on the purpose of use.

Specific examples of these organic solvents include hydrocarbons such as benzene, toluene, xylene, cyclohexane, n-hexane, n-heptane, petroleum benzine, gasoline and petroleum spirit. Chlorinated hydrocarbons include methylene chloride, chloroform,
Carbon tetrachloride, 1,1,1-trichloroethane, dichloroethane and the like. Examples of the ketones include acetone, methyl ethyl ketone, methyl-n-propyl ketone, and the like. Esters include propyl formate, ethyl acetate,
Examples include acetic acid-n-propyl acetate, isopropyl acetate and acetic acid-n-butyl acetate.

The adhesive is prepared by preparing a chelate reaction solution prepared from an organic solvent, a resin, and a basic metal oxide, and dissolving the carboxyl-modified CR therein, or by dissolving the carboxyl-modified CR in the organic solvent. And there is a method of dissolving resin and basic metal oxide at once,
Either method can be used. The non-volatile content of the adhesive can be adjusted according to the desired application, but is generally between 10 and 10.
It is 50% by weight.

The mol% of the methylol group in the resin used in the present invention is 2% by dissolving the alkylphenol in heavy acetone.
Nuclear magnetic resonance device “FX-10” manufactured by JEOL Ltd. at 3 ° C.
0 ”by means of ¹³ C-NMR analysis means, methylol group (—CH ₂ OH), methylene ether group (—CH ₂ OCH ₂ —), methylene group (—CH) in all molecules.
_2- ) was measured and the mol% of methylol group was calculated.

[0017]

EXAMPLES The present invention is described below with reference to examples, but the present invention is not limited thereto. In the text,
All parts are parts by weight unless otherwise specified.

In the following examples, thixotropy and adhesive strength were measured by the following methods. (Thixotropic property) When measuring the viscosity of a fluid by changing the rotor rotation speed of a Brookfield viscometer, if the viscosity is the same even if the rotor rotation speed is changed, it is a so-called Newtonian fluid, and if not, it is a non-Newtonian fluid. ,
If the viscosity measured at high rpm is low, it is called a thixotropic fluid. Therefore, in the present invention, the adhesive composition adjusted to 23 ° C. is used as No. 3 rotor, 6 rpm and N using a Vismetron “single cylinder viscometer” manufactured by Toshiba System.
o. The viscosity was measured at 60 rpm with 4 rotors, and the thixotropy was evaluated by this size with the value calculated using the following formula as the thixotropy index. Thixotropic index = measured viscosity at 6 rpm (cps)
Viscosity (cps) at / 60 rpm (Adhesive strength) Two No. 9 canvas with a width of 100 mm x 150 mm were used as adherends, and the adhesive was applied to each by brush, and the open time was set to 15 to 30 minutes. After that, stick each other and press with a hand roller, 25mm × 15
The cut test piece was cut to 0 mm. Next, the test piece is kept at room temperature (2
Instron tensile tester (UTO Baldwin UT) at a head speed of 200 mm / min.
M-4-100) was used to measure the T-peel adhesion strength at normal temperature and high temperature (80 ° C).

Example 1 100 parts of commercially available carboxyl-modified CR skyprene 510 (manufactured by Tosoh Corporation) and MgO (manufactured by Kyowa Chemical Industry Co., Ltd.) were added to a dual-arm kneader [S1-1 manufactured by Moriyama Seisakusho Co., Ltd.]. Kyowamag 150] 4 parts, ZnO [Sakai Chemical Industry Co., Ltd. Zinca-20] 5 parts, antiaging agent [Kawaguchi Chemical Industry ANTAGE BHT] 2 parts 8 inch roll for rubber kneading [Kansai roll ( Manufactured by K.K.) and 100 parts of resin containing 48 mol% of methylol group in advance, M
gO, 10 parts, and a mixed solvent (226 parts of toluene, 75 parts of cyclohexane, 75 parts of ethyl acetate) were stirred and mixed at room temperature for 24 hours, and a chelate reaction solution was prepared.
Table 1 shows the results of the measurement of thixotropy and adhesive strength of the adhesive composition obtained by mixing and dissolving for a period of time.

Example 2 Table 1 shows the results of exactly the same procedure as in Example 1 except that the resin used in Example 1 was a resin having a methylol group of 40 mol%.
Shown in.

Example 3 Example 1 was repeated except that the commercially available carboxyl-modified CR skyprene 510L was replaced with a commercially available carboxyl-modified CR skyprene 510L (manufactured by Tosoh Corporation).
Table 1 shows the results of exactly the same as above.

Example 4 The same result as in Example 1 except that the commercially available carboxyl-modified CR skyprene 510 in Example 1 was replaced with the commercially available carboxyl-modified CR skyprene 580 (manufactured by Tosoh Corporation). Is shown in Table 1.

Example 5 In Example 1, except that 50 parts of commercially available carboxyl-modified CR skyprene 510 was used and 50 parts of commercially available CR skyprene G-40S for adhesives (manufactured by Tosoh Corporation) was used as a blend. Table 1 shows the results of exactly the same as in Example 1.

Example 6 Except for Example 1, except that 25 parts of commercially available carboxyl-modified CR skyprene 510 was used, and 75 parts of commercially available CR skyprene G-40S for adhesive was used as a blend. The results obtained in the same manner are shown in Table 1.

Example 7 In Example 1, 50 parts of commercially available carboxyl-modified CR skyprene 510 was used, and 50 parts of commercially available CR skyprene G-40S for adhesive was used as a blend to make 50 parts of resin. Table 1 shows the results obtained in exactly the same manner as in Example 1 except for the above.

Example 8 In Example 1, 50 parts of commercially available carboxyl-modified CR skyprene 510 was used, and 50 parts of commercially available CR skyprene G-40S for adhesive was used as a blend to make 150 parts of resin. Table 1 shows the results obtained in exactly the same manner as in Example 1 except for the above.

Example 9 In Example 1, commercially available carboxyl-modified CR skyprene 510 was used in an amount of 50 parts, and commercially available adhesive CR skyprene G-40S, 25 parts, commercially available microgel-containing CR.
Table 1 shows the results of exactly the same operation as in Example 1 except that 25 parts of Skype Prene Y-20E (manufactured by Tosoh Corporation) was used in the blend.

Example 10 In Example 1, 50 parts of commercially available carboxyl-modified CR skyprene 510 was used, and 50 parts of commercially available CR skyprene G-40S for adhesive was used as a blend to prepare a dry process white carbon. Table 1 shows the results obtained in exactly the same manner as in Example 1 except that 10 parts of (trade name Aerosil 380 manufactured by Nippon Aerosil) was added.

Example 11 In Example 1, 50 parts of commercially available carboxyl-modified CR skyprene 510 was used, and 50 parts of commercially available CR skyprene G-40S for adhesive was used in a blend to prepare a basic magnesium carbonate (Tokuyama). Soda Industry Co., Ltd. product name Tokushi
Table 1 shows the results obtained in exactly the same manner as in Example 1 except that 10 parts of T) was added.

Example 12 In Example 1, 50 parts of commercially available carboxyl-modified CR skyprene 510 was used, and 50 parts of commercially available CR skyprene G-40S for adhesive was used as a blend to prepare an organic bentonite (manufactured by Shiraishi Kogyo Co., Ltd.). NEW D ORBEN) 1
Table 1 shows the result of exactly the same operation as in Example 1 except that 0 part was added.

COMPARATIVE EXAMPLE 1 The same results as in Example 1 except that the commercially available carboxyl-modified CR skyprene 510 in place of the commercially available carboxyl CR skyprene G-40S in Example 1 was used. 2 shows.

As is clear from Table 2, thixotropy cannot be imparted even when a resin having a methylol group of 30 mol% or more is used when the carboxyl-modified CR is not used.

Comparative Example 2 In Example 1, 50 parts of commercially available carboxyl-modified CR skyprene 510 was used, and 50 parts of commercially available CR skyprene G-40S for adhesive was used in a blend, and the resin was 17 mol of a methylol group. Table 2 shows the results of exactly the same operation as in Example 1 except that the resin was changed to 0.1%.

Comparative Example 3 In Example 1, 50 parts of commercially available carboxyl-modified CR skyprene 510 was used, and 50 parts of commercially available CR skyprene G-40S for adhesive was used as a blend, and the resin was 26 mol of methylol groups. Table 2 shows the results of exactly the same operation as in Example 1 except that the resin was changed to 0.1%.

Comparative Example 4 The same result as in Example 1 except that the resin having 26 mol% of methylol groups in Example 1 was used.
Shown in.

As is clear from Table 2, thixotropy cannot be imparted even when the carboxyl-modified CR is used when a resin having less than 30 mol% of methylol groups is used.

Comparative Example 5 In Example 1, instead of the commercially available carboxyl-modified CR skyprene 510, commercially available adhesive CR skyprene G-40S (75 parts) and commercially available microgel-containing CR skyprene Y-20E (25 parts) were used. Table 2 shows the results obtained in exactly the same manner as in Example 1 except that was used in the blend.

Comparative Example 6 In Example 1, a commercially available CR skyprene G-40S for adhesive was used in place of the commercially available carboxyl-modified CR skyprene 510, and 10 parts of dry process white carbon Aerosil 380 was added. Table 2 shows the results of exactly the same operation as in Example 1 except for the above.

COMPARATIVE EXAMPLE 7 In Example 1, commercially available CR skyprene G-40S for adhesive was used in place of the commercially available carboxyl-modified CR skyprene 510, and 10 parts of basic magnesium carbonate Toxyl T was added. Table 2 shows the results of exactly the same operation as in Example 1 except for the above.

Comparative Example 8 In Example 1, a commercially available CR skyprene G-40S for adhesive was used in place of the commercially available carboxyl-modified CR skyprene 510, and organic bentonite / NEW D was used.
Table 2 shows the results obtained in exactly the same manner as in Example 1 except that 10 parts of ORBEN was added.

As is clear from Table 2, when carboxyl-modified CR is not used, CR containing microgel or basic magnesium carbonate, dry process white carbon,
It can be seen that the addition of organic bentonite hardly imparts thixotropy.

[0042]

[Table 1]

[0043]

[Table 2]

[0044]

The polychloroprene-based adhesive composition satisfying the requirements of the present invention satisfies both thixotropy and adhesive performance.

Claims (1)

[Claims] 1. A chloroprene polymer 100 containing a carboxyl group represented by the general formula --COOH in the molecule (1).
10 to 200 parts by weight of (2) a thermoreactive phenol formaldehyde resin having a methylol group of 30 to 60 mol% when the sum of methylol group, methylene ether group and methylene group in all molecules is 100 mol%. Parts and (3) a basic metal oxide or hydroxide in an amount of 5 to 15 parts by weight based on 100 parts by weight of a thermoreactive phenol formaldehyde resin, dissolved in an organic solvent. A solvent-based polychloroprene-based adhesive composition having thixotropic properties.