JPS6037150B2 - Chloroprene latex adhesive - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to chloropresolatex adhesives, and more specifically, the resins used therein are not dispersed in water by adding an emulsifier, but are carbonized. The hydrogen resin itself is modified to make a part of the hydrocarbon resin a polymer activator, self-solubilized or self-emulsified, and mixed with chloroprene latex (hereinafter referred to as CRL) to form an adhesive.After film formation, it is tackified. A hydrocarbon resin self-solubilizing liquid or self-emulsifying liquid (hereinafter referred to as a resin self-dispersing liquid) serves as a hydrocarbon resin self-dispersing liquid.

This invention relates to a chloroprene latex adhesive (hereinafter referred to as "CRL adhesive") that has improved initial adhesive strength (so-called rise), final adhesive strength, and workability by using a chloroprene latex adhesive (hereinafter referred to as CRL adhesive). Conventionally, solvent-type chloroprene adhesives have been widely used because of their excellent adhesive properties and quick rise time.

However, since solvent-based chloroprene adhesives use large amounts of organic solvents, they pose problems such as the risk of fire and explosion, as well as denaturation, and in recent years, they have also had drawbacks such as environmental pollution due to the release of large amounts of solvent. Furthermore, the development of a CRL adhesive has been strongly desired from the viewpoint of resource conservation. In general, solvent-type chloroprene adhesives are oil-soluble adhesives with softening points of 50 to 170°C, such as chloroprene rubber and tackifiers such as alkylphenol resins, terbenphenol resins, coumarindene resins, xylene resins, rosins and their derivatives, and petroleum resins. It is obtained by dissolving the imparting agent in an organic solvent.
However, simply changing the above-mentioned adhesive to a water-dispersible type does not provide excellent performance, and various studies have been made. For example, Hakama Kosho 51-39262, Hakama Sekisho 51-12513
How to improve CRL as shown in 6, Japanese Patent Application Laid-open No. 49-970
In order to emulsify conventional solvent-based tackifiers such as 5351-100137 without using a solvent, there is a method of mixing liquid resin, vegetable oil, and high boiling point solvent.
A method of using water-based acrylic resin as a dispersant as in Samurai Sekisho 49-970, or JP-A-52-93A5.
Good performance cannot be obtained with conventional solvent-based petroleum resins, such as resins obtained by copolymerizing chain conjugated dienes with C81C, o styrenes, or modified products thereof, with emulsifiers. Techniques have been developed to add and use it as an emulsion. However, even with the above-mentioned improved technology, it cannot be said that the conventional disadvantages of CRL adhesives, such as adhesive strength, quick rise time, and workability, have been sufficiently improved. was desperately needed.

In view of the current situation, the present inventors have developed a material with excellent adhesive strength.
As a result of intensive study to develop a CRL adhesive that has a quick rise and good workability, it was discovered that the problem lies in the emulsification method rather than the type of resin. A resin self-dispersion liquid in which a part of the hydrocarbon resin is made polymeric active by neutralization with an organic amine aqueous solution, thereby self-solubilizing or self-emulsifying the hydrocarbon resin, is prepared by C.
By mixing it with RL, it has far superior performance compared to solvent-based chloroprene adhesives, and by changing the ratio of resin self-dispersion liquid and CRL, it can be made into various forms from low viscosity latex to paste. It was discovered that the present invention could be obtained, and the present invention was completed.

That is, the present invention adds Q8 unsaturated acid or its anhydride to CRL and ordinary aliphatic (mainly C5), aromatic (mainly C9), or copolymer (mainly C5-C9) hydrocarbon resins. The present invention relates to a CRL adhesive obtained by blending a resin self-dispersion obtained by neutralizing an acid-modified resin obtained by neutralizing an ammonia aqueous solution with an aqueous solution of an organic amine compound and then adding water to adjust the solid content.

Ordinary CRLs are sufficient as CRLs used in the present invention, and are commercially available under trade names such as Skyprene (manufactured by Toyo Soda Co., Ltd.), Denka Chloroprene (manufactured by Denki Kagaku Co., Ltd.), and Neobrene (manufactured by Showa Neobrene Co., Ltd.). You can use things.

On the other hand, the hydrocarbon resin used in the present invention is a commercially available hydrocarbon resin or petroleum resin. Friedel-Crafts such as BF3 and its sickle AIC13 are made by using crab fraction (C9 crab fraction) as raw material oil and a fraction having a boiling point in the arbitrary range of 140-20 and 0 (usually C9 crab fraction) as raw material oil. A resin having a bromine number of 20 or more obtained by polymerization using a type catalyst is used.

In the present invention, since the addition of Q8 unsaturated acid is an essential condition, it is necessary for the hydrocarbon resin to have a certain degree of bromine value, but if it is too high, problems such as aging properties may occur after use as an adhesive. Yes, the required bromine number is 20 to 10 times better.
is 30-70. Examples of such resins include Betrozin #80 (manufactured by Mitsui Petrochemicals) Neopolymer, L-9
0 (manufactured by Nippon Petrochemical Co., Ltd.) (all C9 resin) High Resin #
60, #90 (manufactured by Toho Oil Resin Co., Ltd.) (all G-C9 resins) / - Red TIO0, GIO0 (manufactured by Mitsui Petrochemical Co., Ltd.) Escorets 1102, Escorets LTA (manufactured by Tonen Petroleum Engineering Co., Ltd.) Quinton A-100, B- 170 (manufactured by Nippon Zeon Co., Ltd.) (hereinafter referred to as G resin) and other commercially available resins can be used.

Among them, in terms of reactivity with acids and stability of dispersion, Vetrogin #80 Neopolymer L-9 and HiResin #60
, #90 are preferred. The Q8 unsaturated acids and their anhydrides used in the present invention include acrylic acid, methacrylic acid, maleic acid, itaconic acid, maleic anhydride, itaconic anhydride, etc., but the reaction between the hydrocarbon resin and the Q8 unsaturated acid is A commonly used method is sufficient.

If too little acid is used, a stable resin dispersion cannot be obtained, and if too much is used, the amount of amine required for neutralization increases, causing problems such as environmental pollution due to amine emission and affecting the water resistance of the adhesive. The saponification value of acid-modified resin is 20-10.
0, more preferably 30-60. In the present invention, the acid-modified resin thus obtained is neutralized with aqueous ammonia or an aqueous solution of an organic amine compound, and is used after being self-soluble or self-emulsifying. When used as an adhesive, the presence of amine salts or ammonium salts in the film will have a negative effect on the water resistance of the adhesive, so as a neutralizing agent, use a method that is thinly dispersed during drying and does not exist in the film in the form of a salt. For this purpose, ammonia, lower amines having 1 to 4 carbon atoms such as methylamine and ethylamine, and morpholines are preferable, and morpholines are more preferable. Therefore, alkali metal hydroxides cannot be used. The concentration of the neutralizing agent is preferably 10 to 90%, more preferably 30 to 70%. This is because if it is less than 10%, the particles of the dispersion become coarse, which adversely affects adhesive performance, and if it is more than 90%, the viscosity is high during phase inversion, resulting in poor workability. The amount of neutralizing agent used is 70 to 150% of the saponification value of the acid-modified resin, preferably 8.
It is 0-120%. If it is less than 70%, the stability will be poor when used as an adhesive, and if it is more than 150%, the amount of amine used will be large and the odor of amine will be intense.

During this neutralization, a solvent may be used to lower the viscosity of the acid-modified resin, but it is not preferable to use a large amount.
Furthermore, commonly used nonionic or anionic emulsifiers may be used, but if the amount is too large, it will have a negative effect on the adhesive performance, so use of a large amount should be avoided.

As described above, the present invention involves acid-modifying a part of the currently commonly used hydrocarbon resin and neutralizing it with an aqueous ammonia solution or an aqueous solution of an organic amine compound to produce a hydrocarbon resin by itself without using an emulsifier. It solubilizes or self-emulsifies, and the ammonia or amine used after applying the adhesive disperses and does not exist as a salt, but becomes an undissociated acid, which has a strong affinity with polychloroprene, making it compatible ( It forms a uniform film with good mixability and excellent water resistance, contributing to initial adhesion and tackiness. Hold-up 5
The method of using acid addition resins or their amide modified products such as methylamine, diethylamine, and ammonia as a tackifier, which is described as part of 2-93445, involves emulsifying these modified resins with an emulsifier to form an emulsion. This resin is fundamentally different from the present invention, as it is used as a resin and is inferior in performance to unmodified resins.

As described above, the CRL adhesive using the resin self-dispersion liquid obtained by the method of the present invention has superior adhesive strength, quick rise time, excellent water resistance, and excellent stability compared to solvent-based adhesives. ing.

Furthermore, by changing the blending ratio of the resin self-dispersion liquid and CRL, it is possible to change the adhesive strength from a low-viscosity aqueous solution to a paste-like one without changing the adhesive strength. It has the characteristic of being compatible. The adhesive according to the present invention has the above-mentioned two components as main ingredients, and it goes without saying that other additives such as anti-aging agents and fillers may be added thereto.

The present invention will be explained in more detail with reference to Examples below. (Synthesis of acid-modified resin) Reference example 1 Neopolymer L90 (manufactured by Nippon Petrochemicals Co., Ltd.) 100 kg was charged into a flask and heated and melted at 20°C, then 3 kg of maleic anhydride was charged and reacted at 200 kg for 5 hours to effect the addition. The resin obtained had a softening point of 103.5°C and a saponification value of 32.

Reference Example 2 An acid-added resin is obtained by reacting HiResin #90 (manufactured by Toho Oil Resin Co., Ltd.) for 100 minutes and maleic anhydride for 5 hours in the same manner as in Reference Example 1.

This resin had a softening point of 119.5°C and a saponification value of 46. (Preparation of resin dispersion) Reference Example 3 100 parts of the resin of Reference Example 1 was heated and melted, and 20 parts of Butyl Cellosolve was added thereto to form a homogeneous solution.

To this, add 5.3 mL of 28% ammonia aqueous solution to 80 to 9 mL of aqueous solution.
Gradually drop it to make a uniform dispersion.Finally, reduce the solid content to 40%.
Add water and adjust accordingly. Reference Example 4 100 mm of the resin obtained in Reference Example 2 was heated and melted, and 15 mm of butyl cellosolve was added thereto to form a homogeneous solution.

Add a 30% aqueous solution of formolin to this for 10 minutes at 80-90℃.
Gradually add the mixture dropwise to make a uniform dispersion. Finally, add water and adjust to 40% garden type. Reference Example 5 90 parts of the resin and 10 parts of the rosin from Reference Example 1 were melted and heated, and 15 parts of butyl cellosolve was added thereto to form a uniform solution.

A 10% aqueous solution of KOH was gradually added dropwise to this at 80 to 90° C. to form a uniform emulsion. Finally, add water to adjust the solids content to 40%. Reference Example 6 Similarly to Reference Example 5, the resin of Reference Example 2 was made into a uniform emulsion in a KOH aqueous solution for 4 days.

Reference Example 7 Hi-Resin 090 90 ml and Rosin 10 ml were melted and heated, and solvent naphtha 15 ml was added thereto to form a uniform solution.

A 10% aqueous solution of KOH is gradually added dropwise to this mixture at 80 to 90° C. to form a uniform emulsion. Finally, add water to adjust the solids content to 40%. Example 1 A CRL adhesive was prepared by mixing 5 parts of the resin dispersion of Reference Example 3 and 10 parts of chloroprene latex (Denka Chloroprene LA50, manufactured by Denki Kagaku Co., Ltd.).

Example 2 C in the same manner as in Example 1 using the resin dispersion of Reference Example 4
RL adhesive was created.

[Comparative Examples 1, 2, 3] [Resin dispersion using an emulsifier] CRL was carried out in the same manner as in Example 1 using the resin dispersions of Reference Examples 5, 6, and 7.
Created adhesive.

Apply the CRL adhesive created above to No. 9 canvas canvas (12
09: JISL-3102) Coat each canvas to a thickness of 250 mm/cm, leave it for 10 minutes (open time 10 minutes), and roll the two canvases back and forth 5 times with a 5K9 pressure roll. After being crimped and cured at 25 qo for 7 days, it was peeled off at a speed of 30 m/min to measure the adhesive strength.

The results are shown in Table 1.

Table 1: Results of using the present invention and emulsifier The results show that the CRL adhesive of the present invention has superior adhesive strength compared to when an emulsifier such as potassium rosinate soap is used.

Example 3 In contrast to the resin dispersion obtained in Reference Example 2, chloroprene latex (Denka Chloroprene LA-50:
(manufactured by Denki Kagaku Co., Ltd.) to obtain CRL adhesive.

The obtained adhesive was applied to canvas-canvas, buna-puna, and iron-to-iron at a rate of 250 min/s, respectively, and after being left for the respective times shown in Table 2, a pressure of 5 k9 was applied.

- Measure the adhesion force after crimping by reciprocating 5 times with a 2500°C and curing for 7 days at a pressure of 2500mm (Tensile speed: Peeling 300 ribs/min, Number of strips 2.5 sides/min. The results are shown in Table 2. Table 2 Examples 4 1 plate part of the resin dispersion obtained in Reference Example 3 and 10 parts of chloroprene latex (Skyprene #402: manufactured by Toyo Soda Co., Ltd.)
A CRL adhesive was prepared by mixing 0 parts.

The CRL adhesive obtained in Examples 3 and 4 was applied to two pieces of canvas to a thickness of 250 mm/mm, left for 10 minutes, and then pressed back and forth 5 times with a 5K9 pressure roll. , and measure the adhesive strength by varying the curing time. The results are shown in FIG. 1 in comparison with commercially available products.

'1} Adhesive obtained in Example 3 ■ Adhesive obtained in Example 4 (3} Commercially available solution-type chloroprene adhesive As a result, the method of the present invention has a lower initial adhesive strength ( It can be seen that both the rise and final adhesive strength are excellent.

Example 5 Chloroprene latex (Denka Chloroprene LA-50, manufactured by Denki Kagaku Co., Ltd.) was mixed in various proportions to the resin dispersion obtained in Reference Example 2 to prepare CRL adhesives.

The viscosity of this adhesive is measured in the same manner as in Example 1 for pH and adhesive strength.

The results are shown in Table 3.

There is no major difference in adhesive strength despite slight changes in viscosity, and it can contribute to improving workability.

Table 3

[Brief explanation of drawings]

FIG. 1 shows the change in adhesive strength when the curing time of the adhesive in Examples 3 and 4 was changed.

Claims (1)

[Claims] 1 A modified hydrocarbon resin obtained by reacting a hydrocarbon resin with a bromine number of 20 or more with an α,β unsaturated carboxylic acid or its anhydride is neutralized with an aqueous ammonia solution or an aqueous solution of an organic amine compound to self-solubilize or self-solubilize. A chloroprene latex type adhesive characterized in that it is emulsified and then chloroprene latex is added.