JPH03199275A - Coating film-forming composition - Google Patents

Abstract

PURPOSE:To obtain the title flexible, heat-resistant composition by suspending a poly 4-methylpentene-1 polymer etc., in an aqueous medium followed by chlorination. CONSTITUTION:Poly 4-methylpentete-1 and/or alpha-olefin 4-methylpentene-1 polymer(s) is suspended in an aqueous medium followed by chlorination so as to come to >=50wt.% in the chlorinate content, thus giving the objective composition.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a chlorinated 4-methylpentene-1 resin having flexibility and heat resistance as a film-forming composition for inks, paints, OP varnishes, etc. It is something.

[Conventional technology]

The chlorinated 4-methylpentene-1 resin is poly-4-methylpentene-1 and/or α-olefin 4-
It is a substance produced by chlorinating methylpentene-1 polymer. These chlorinated 4-methylpentene-1 resins not only have excellent weather resistance, water resistance, and chemical resistance, but also have extremely superior heat resistance compared to conventional chlorinated polyolefins. It is widely used as a binder for printing inks or as a heat-resistant OP varnish.

[Problem to be solved by the invention]

However, since the chlorinated 4-methylpentene-1 resin, which is chlorinated in a chlorine-resistant solvent using the conventional manufacturing method, is a homogeneous chlorine compound, when it forms a film, it is hard and brittle, resulting in poor bending resistance. has been pointed out.

Various improvement measures have been proposed to improve this bending resistance. For example, JP-A-58-45266 discloses that chlorinated poly-4-methylpentene-1 is polymerized with an acrylic monomer to impart flexibility. Alternatively, there are practical examples where soft resins such as plasticizers are used in combination to provide physical flexibility. However, these methods of imparting flexibility are based on chlorinated 4-methylpentene-1
This results in a substantial reduction in the heat resistance, which is a characteristic of the resin, and a satisfactory improvement measure has not been achieved.

[Means to solve the problem]

In view of the above circumstances, the present invention has been developed to
The object of the present invention is to provide a chlorinated 4-methylpentene-1 resin that has flexibility.

As a result of various studies, the inventors of the present invention have found that, in the step of chlorinating poly-4-methylpentene-1 and/or α-olefin-4-methylpentene-1 polymers, if the process is carried out in an aqueous medium, powder resin The present invention was developed based on the fact that the surface is easily chlorinated and a heterogeneous reactant is easily formed.

That is, chlorinated 4 chlorinated in a conventional chlorine-resistant solvent
-Methylpentene-1 polymer has a narrow molecular weight due to its homogeneous reaction, and therefore it has become a resin that forms a hard film, but when chlorinated in an aqueous medium, a heterogeneous reactant is formed, and the degree of chlorination increases. This means that a flexible chlorinated resin can be obtained because it can have a wide width and also has a wide molecular weight. At that time, if the suspension is circulated with a circulation pump or a ball mill or the like is placed in the middle of the circulating liquid and the powder resin surface is mechanically peeled off and renewed while being chlorinated, heat resistance may be impaired depending on the degree of chlorination. This means that a chlorinated 4-methylpentene-1-based resin can be obtained which has arbitrary flexibility.

If the resin used in the present invention has many voids inside the polymer particles or has a small particle size, unnecessary uneven chlorination can be avoided, which is a favorable condition for producing the effects of the present invention. .

The reason why the chlorine content is set to 50% by weight or more in the present invention is that if it is less than 50% by weight, the heat resistance, which is a feature of the present invention, cannot be obtained.

〔Example〕

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

Example 1 500 parts of pure water and 8 g/l0 of Ml were placed in a glass reactor.
100 parts of 4-methylpentene-1 homopolymer (ASTM D123B-65T) was added, the inside of the container was purged with nitrogen while stirring, and then chlorine was blown in at 90°C while irradiated with light at normal pressure. Chlorination was performed.

At this time, in order to prevent the resin particles from forming agglomerates, the suspension is circulated by a circulation pump, and a ball mill is installed in the middle of the circulation system to mechanically peel and renew the powder resin surface while chlorinating it. The pulverization treatment was carried out continuously during the reaction.

When the average chlorine content reached 54% by weight, the chlorination reaction was stopped, residual chlorine was removed, and the sample was dried to obtain a sample.

Example 2 500 parts of pure water and 15 parts of decene-1 were placed in a glass reactor.
Ml containing no1% is 36g/IOiin (ASTM
D123B-657) 4-methyl pliers and 100 parts of Sea 1 copolymer were added, the inside of the container was stirred and flushed with nitrogen, and chlorine was blown in at 90°C while irradiated with light at normal pressure to perform chlorination. Ta. At this time, in order to prevent the resin particles from forming agglomerates, the suspension is circulated by a circulation pump, and a ball mill is installed in the middle of the circulation system to mechanically peel and renew the powder resin surface while chlorinating it. , in reaction 2
The grinding process was performed in a time cycle of 1 hour. When the average chlorine content reached 62% by weight, the chlorination reaction was stopped, residual chlorine was removed, and the sample was dried to obtain a sample.

Example 3 500 parts of pure water and 10 no. of ethylene were placed in a glass reactor.
Ml containing 1% is 70g/IO+nin (ASTM 0
1238-657) ethylene/4-methylpentene-
After adding 100 parts of 1 copolymer and purging with nitrogen while stirring the inside of the container, the container was heated to 90°C while being irradiated with light at normal pressure.
Chlorination was carried out by blowing chlorine.

When the average chlorine content reached 68% by weight, the chlorination reaction was stopped, residual chlorine was removed, and the sample was dried to obtain a sample.

Comparative Example 1 Ml is 54g/IOiin (ASTM D123B-
65T) 4-methylpentene-1 homopolymer 100
Dissolve g in 5 liters of quaternary hydrogenated carbon and heat at 85°C under normal pressure.
After sufficient dissolution, chlorination was performed while irradiating with light. When the chlorine content reached 60% by weight, the chlorination reaction was stopped, residual chlorine was removed, and white powder was obtained by steam distillation.

Comparative Example 2 Ml containing 15n+o1% of decene-1 was 36g/lOn
+jn (ASTM D+238-657) 4-methylpentene-! Take 100 g of copolymer and dissolve it in 52% tetranomialized carbon under a pressure of 2 kg/ad.
After sufficiently dissolving at 0° C., chlorination was performed while irradiating with light. When the chlorine content reached 65% by weight, the chlorination reaction was stopped, residual chlorine was removed, and white powder was obtained by steam distillation.

Analysis of solution viscosity, average molecular weight/molecular weight dispersity, softening temperature, and thermal decomposition resistance for the samples obtained in Examples 1 to 3 and Comparative Examples 1 to 2, and a 20% toluene solution of each sample was also applied to polished mild steel plates. Coating to (SPCCll53141 cold rolled B, 0.8x50X 150m/m), 1
After air drying day and night, layer resistance + To resistance.

Table 1 shows the results of the impact resistance test.

In addition, gravure printing ink was prepared using each sample.

That is, a 20% toluene solution was prepared with 18 g of resin and 72 g of toluene, 10 g of pigment (Carmino 6BN: Toyo Ink Manufacturing K K product) was added thereto, and the mixture was kneaded in a sand mill for 2 hours.The solid content of the ink was kept constant and coated paper was prepared. The ink film was coated to form an ink film of 5 to 7 microns. After sufficiently drying this at room temperature, various tests were conducted on color development, heat resistance, and ink storage stability. The results are shown in Table 2.

Table - ■ Various analysis results Note 1) Dissolution viscosity Shows the centivoise at 25°C of 40% heavy toluene solution.

Note 2) Average molecular weight: G with polystyrene as standard,
Measured values by P, C,.

3) Dispersity/Mw/Mn Mt-mF & average molecular weight Mn...Number average molecular weight Note 4) Softening temperature: Measured by melting point measuring device.

Note 5) Thermochromic property: Discoloration after heating at 180°C for 30 minutes.

Note 6) Flexibility: 180° with 172φ inch mandrel
The condition of the bent paint film was examined.

Note 7) Impact resistance: DuPont type impact tester, striking core 1/2
Using a φ inch load of 500g, 50cI for surface striking
11, and in the case of lining, it was dropped from 25 cm.

Table 2 Physical properties of printing ink [Effects of the invention] From Tables 1 and 2, the composition of the present invention has self-flexibility, and other physical properties are inferior to those obtained by the conventional uniform chlorination method. It can be seen that it has properties that do not have

Note 1) Color development: Determined by color density ○...Good color development 2
) Heat resistance: A coated base paper was placed over the ink, a heat seal bar set at each temperature was applied and pressed, and the coated base paper was left to cool for 30 minutes or more, and then the paper was peeled off and fixed.

◎...No paper peeling ○...Paper peeling 5% or less△...Paper peeling 30% or lessNote 3) Storage stability: When ink is stored in a tin can, rust on the tin can or ink gel at 50℃ Changes in the flow state at -10°C (t,.

○...Good

Claims (2)

[Claims] (1) Poly-4-methylpentene-1 and/or α
- A flexible heat-resistant film-forming composition obtained by suspending an olefin/4-methylpentene-1 polymer in an aqueous medium and chlorinating it to a chlorine content of 50% by weight or more. (2) The composition according to claim 1, which is chlorinated while being pulverized.