JPS6026511B2 - coaching composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to coating compositions using chlorinated polymers.

More specifically, the present invention relates to a coating composition using chlorinated polymethylbentene, which dissolves well in inexpensive general-purpose solvents and has excellent heat resistance and thermal stability.

Chlorinated polyolefins obtained by chlorinating general-purpose polymers such as rubber, polyethylene, and polypropylene in chlorine-resistant solvents form films with excellent weather resistance, water resistance, and chemical resistance, so they are used in clear lacquers, paints, It is widely used as a main component of coating compositions such as inks and adhesives.

However, these existing chlorinated polyolefins
Because they soften at ~200°C, paints, inks, adhesives, etc. that use these as vehicles have poor heat resistance, so they are usually used in combination with a resin with a high softening point or with a thermosetting resin. In reality, the heat softening properties are improved by methods such as the above, and therefore, there is a strong demand for improvement in the heat resistance of these chlorinated polyolefins. In other words, in order to improve coating workability and increase printing speed, the drying temperature during line coating and printing is increasing, but in this case, the coating surface becomes soft due to heat, causing blocking, creep, and scratches. There are many problems such as problems when this occurs and a decrease in printing effectiveness.

In addition, there is an urgent need to improve not only the softening point but also the heat resistance of the commonly used chlorinated polyolefins, such as the fact that the clear film is easily discolored by heat or light. On the other hand, these existing chlorinated polyolefins have been added to rubber adhesives to improve creep resistance, but in recent years, creep resistance at higher temperatures has been improved in applications such as automobiles and aircraft. Therefore, there is a desire for additive resins that are miscible with rubber adhesives, have a high softening temperature, and are thermally stable. On the other hand, it is desired to reduce the amount of solvent remaining in the ink film after printing from the viewpoint of preventing air pollution and occupational safety and health, but conventionally known chlorinated polyolefins do not have sufficient solvent release properties. , was not satisfactory.

The present inventors aimed to improve the drawbacks of these conventionally known chlorinated polyolefins.
Melt index in 9 is 8-7 females/10 h
Chlorinated polymethyl obtained by uniformly chlorinating crystalline poly-4-methylbentene-1 (ASTMD1238-651) to a chlorine content of 5% by weight or more in a solution state that is uniformly dissolved in a chlorine-resistant solvent. Bentene dissolves well in inexpensive general-purpose solvents such as xylene, toluene, Solvesso 10 Finger, etc., just like conventional chlorinated polyolefins, and is more heat resistant and thermally stable than conventional chlorinated polyolefins. The inventors discovered that the properties are significantly superior, leading to the present invention.

A chlorinated polymer obtained by chlorinating an amorphous polymer (amorphous polymer) obtained by cationic polymerization of 4-methylbesothene-1 to a chlorine content of 25 to 5% by weight is known (US Pat. No. 3,484,423). .

Also, 4-methylbentene-1 is converted into Ziegler-Nat
Isotactic (crystalline) poly-4-methylbentene-1 obtained by polymerization with ta (Zigler-Natta) catalyst
A chlorinated polymer containing 5 to 61% by weight of chlorine obtained by pulverizing the dough and suspending the dough in carbon tetrachloride at room temperature and chlorinating it is known [J. PolymerSci
．． 55.169-180 (1961)].

However, the chlorinated polymer obtained by suspending this crystalline poly-4-methylbentene-1 in carbon tetrachloride and chlorinating it has a high degree of chlorination and a high softening temperature, but when heated in air, it becomes extremely The viscosity decreases,
It causes a large weight loss due to dehydrochlorination, and its resistance to thermal decomposition is significantly inferior to that of commonly used chlorinated polymers such as polyvinyl chloride, so that no effective use can be found for it. Therefore, the present inventors conducted various experiments regarding the chlorination of the above-mentioned 4-methylbentene-1 amorphous polymer and crystalline polymer.
Chlorinated polymethylbentene, which is obtained by uniformly chlorinating crystalline poly4-methylbentene-1 (38-65T) in a solution state to a chlorine content of 50% by weight or more, has extremely high general resistance as a coating composition. After learning that it is a polymer, we came up with the present invention. That is, the present inventors investigated homogeneous chlorination of crystalline poly-4-methylbentene-1, which had not been attempted before, and found that the melt index at 5k9 at 260oC was 8 to 70k9/10hjn (ASTMD
Crystalline poly(4-methylbentene-1), which is 12 spots (65T), is completely dissolved in carbon tetrachloride under pressure at a temperature above its boiling point, and chlorine gas is passed through this solution to obtain an arbitrary chlorine content. Uniformly chlorinated poly-4 with
As a result of obtaining -methylbentene-1 and examining its properties, we found that among these homogeneously chlorinated polymers, the chlorine content was particularly low.
% by weight or more, it has an extremely high softening temperature that is at least as good as the chlorinated polymer produced by the previously known heterogeneous chlorination method, and in terms of thermal stability, Not only compared to chlorinated poly-4-methylbentene-1, but also compared to other conventionally known chlorinated polymers such as polyvinyl chloride, chlorinated polyvinyl chloride, chlorinated rubber, chlorinated polyethylene, chlorinated polypropylene, etc. The present invention was completed based on the discovery that it is far superior.

The substance of the present invention is a chlorinated polymer obtained by homogeneous chlorination of crystalline poly-4-methylbentene-1, which has not been tried before. When various coating compositions were prepared using this substance, hardness and toughness were improved. We learned that it has particularly excellent properties related to heat resistance, and also has good heat resistance, that is, thermal deformation resistance and thermal decomposition resistance, and good solvent separation properties that could not be achieved with conventional chlorinated polyolefin compositions. The present invention provides novel and useful coating compositions, such as paints, printing inks, OP varnishes, adhesives, etc., containing the substances of the present invention.

The present invention will be explained in detail below.

The substance of the present invention has a melt index of 8 to 7 females/hin (ASTMD
Crystalline poly-4-methylbentene-1, which is 12 spots-65T), is uniformly dissolved in a chlorinated resistant solvent such as carbon tetrachloride under pressure at a temperature above the boiling point of the solvent, and chlorine gas is added to the solution. It is produced by maintaining a uniformly dissolved state throughout the process and chlorinating until the chlorine content exceeds 5% by weight.

At this time, the reaction can be carried out smoothly and in a short time in the presence of organic peroxides, diazo compounds, etc. that are commonly used as chlorination catalysts, or by using light or radiation as a catalyst. In the present invention, the melt index of the raw material crystalline poly-4-methylbentene-1 is 26030,5k9.
The reason why the crystalline poly-4-methylbentene-1 in this melt index range is limited to 8 to 7 females/1 melon under load is that the melt index range is 130oo, 3.5k9/normal or below at temperature and pressure up to room temperature and normal pressure. This is because it can be uniformly dissolved in chlorinated resistant solvents such as carbon tetrachloride under certain conditions.

In addition, in the present invention, the chlorine content in the homogeneously chlorinated product of crystalline poly-4-methylbentene-1 is set to 5% by weight or more because a degree of chlorination below this level does not result in the thermal properties characteristic of the present invention. This is because they are not fully satisfied. The substance of the present invention obtained by homogeneous chlorination in a chlorination-resistant solvent as described above is
The chlorinated polymer is isolated by a known method such as steam distillation or precipitation using a solvent (non-solvent) that does not dissolve the chlorinated polymer, and then dissolved in a solvent suitable for use as a coating composition. It may be a coaching composition, but
In addition, the desired solvent-based coating composition can be obtained by a direct solvent substitution method or the like without isolating the substance of the present invention from the reaction solution after chlorination.

Below, the experimental results regarding various properties of the substance of the present invention, such as stability at high temperatures, resistance to thermal decomposition, and resistance to thermal deformation, are shown. Table I From this, it can be seen that the substance of the present invention has excellent stability at high temperatures.

When polyvinyl chloride resin is used in a coating composition, it undergoes dehydrochlorination in an avalanche manner when exposed to high temperatures, whereas the substance of the present invention has a direct relationship between time and weight loss and does not cause avalanche dehydrogenation. I don't.

Next, the present invention will be explained in detail based on examples.

Example 1 Melt index is 1 kg and 70 g
/1 hin (ASTM○12 paper 165T) 2 types 4
-Methylbentene-1 isotactic polymer is dissolved in carbon tetrachloride of 20 pieces each, and 2k9/
After sufficiently dissolving under the pressure of 110 oo and air purging, chlorination was carried out by blowing gaseous chlorine from the bottom of the reactor while irradiating it with light.

A white powder was obtained by steam distilling the chlorinated reaction liquid, which was appropriately sampled to a target degree of chlorination of 50 to 75%. The results of examining the chlorine content, solution viscosity, softening temperature, and thermal decomposition resistance of this product are shown below.

For comparison, a comparative test was conducted with commercially available chlorine rubber. Taiichi 2 Solution quality: 40Wt commercial solution shows centiboise at 25°C: Measured by melting point side stagnation device Thermochromic property: Storage stability of Tobuta discoloration varnish after 30 minutes at 180°C 20% Torrei customer liquid Test to see if rust has formed after 5 days at room temperature by dipping a nail in water) ○・・・・・・・・・・・・・・・Rust has formed×・・・・・・・・・・・・- Rust occurrence As can be seen from Table 2, the material of the present invention has an extremely high softening temperature and thermal stability.

Furthermore, in order to clarify this thermal stability quantitatively, B in Table 2, commercially available polychlorinated pinyl resin, commercially available chlorinated rubber 162
Table 3 shows the results of actually measuring the relationship between heating time in air open at ℃ and weight loss.

Table-3 PV0...Skin/Reagent (Katayama Chemical Industry Keikai Shikikai Morishi) and polyvinyl chloride resin) Chlorinated rubber...Commercially available Kinutsuri 1
It will be understood from Table 3 that the material of the present invention is much more thermally decomposable than commercially available chlorinated rubber or commercially available vinyl chloride resin.

Example 2 [Printing ink] Using the above Example B, an ink for grapia printing was prepared.

That is, prepare a 20% toluene solution with 1 part of resin and 7 parts of toluene, and add pigment (carmine string N Toyo Ink Manufacturing KK) to this.
Product) log was added and kneaded for 2 hours with a sand mill, and then coated on coated paper with a constant solid content of the ink.
~7 ink films were formed. After sufficiently drying this at room temperature, color development, heat resistance, and storage stability of the ink were tested. Table 4 Color development: determined by color density Heat resistance: Place coated base paper on the ink surface, apply a heat seal bar set to each temperature, press 20k9/base, 1 tochi stage, and then leave to cool for at least 3 minutes. The paper was judged based on the state of the paper when it was peeled off.

◎-No paper peeling ○-5% or less △-30% or less×-5
Storage stability of 0% or more: Rust on tin cans or gelation of ink at 5 and 0 and change in flow state at -1 and 0.

Example 3 [Releasability of solvent from clear coating] Quick release of solvent from coating films that usually contain a large amount of resin, such as ink, lacquer, and OP varnish, is important for achieving the original performance early, as well as improving hygiene. This is also necessary from the above, and the solvent releasability of the substance of the present invention was compared with the following compositions.

．． Table-5 Residual rate of toluene (Tsutomu) Conditions: Toluene solution with 20% resin content in a 9-diameter bedding dish: 5-0
．． 1 g was accurately weighed and measured, and measurements were made for the case of air drying at 2 pi 0 for 18 h and the case of drying at 60°C.

The amount of residual toluene was determined using P-xylene as an internal standard. Example 4 [〇P2] An OP varnish containing a small amount of chlorinated paraffin using the inventive substance B of Example 1 was prepared, and the pencil hardness of the dry film was measured.

Note that chlorinated rubber is shown as a comparative example as a currently used quick-drying heat-resistant OP varnish. Table 6: Dry film temperature (at room temperature) As can be seen from Table 6, coating compositions with excellent surface hardness can be obtained by using the substance of the present invention.

Furthermore, in practical terms, it would be useful if it could be added to various resins commonly used in compositions to improve heat blocking properties and surface hardness, but the substances of the present invention often conflict with chlorinated rubber, chlorinated polypropylene, etc. Therefore, they could be combined and used together.
Example 5 [Paint] In addition to the properties described above, sufficient film resistance is an essential condition for a paint.

Therefore, a top coat was prepared using C and E prepared in Example 1 and chlorinated rubber, and changes in whiteness due to UV irradiation were monitored.

The paint composition and test piece preparation method are as follows. Paint Composition A test piece was prepared by kneading the paint with the above composition in a sand mill, applying an undercoat of Epozinc on Sandplast Slope, and painting the top with a brush.

After the test plate was air-dried for 7 days, the test piece attached to a rotating drum was irradiated with a 20 W mercury lamp from a distance of 30 m, and the whiteness was monitored at predetermined intervals.

Mino-7UV Washishoryo Dark and White Heronfish {eSevere...%) Table 7
As is clear from the above, the paint containing the substance of the present invention has light resistance that is as good as, if not superior to, that of chlorinated rubber. Example 6 [Application as a flame retardant] A combustible polyolefin was blended with polyethylene in the following composition and a combustion test was conducted.

Composition: Mix the above compositions thoroughly and roll two rolls (surface temperature: 1
45q0) for 1 minute and then molded into a sheet (medium 1 skin, thickness lm/m, length 10 skin) JISK-69
A combustion test was conducted according to No. 11.

Table 8 Results of flammability test From the above results, the substance of the present invention has the effect of making elutritable plastic (polyethylene) self-extinguishing, has the same effect as chlorinated paraffin used for this purpose, and has the same effect as chlorinated paraffin used for this purpose. It turns out that there is no.

Claims (1)

[Claims] 1 Melt index at 260℃ and 5kg is 8
~70g/10min (ASTMD1238-65T)
A coating composition comprising chlorinated polymethylpentene obtained by uniformly chlorinating crystalline poly-4-methylpentene-1 in a solution state to a chlorine content of 50% by weight or more.