JPH0670091B2 - Novel hydroxyl group-containing chlorinated polyolefin, its manufacturing method and composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel hydroxyl group-containing chlorinated polyolefin, its production method and composition. Specifically, it is possible to give a cured product having rubber-like elasticity and excellent properties in solvent resistance, heat resistance, weather resistance and electrical properties by crosslinking and curing with various curing agents. The present invention relates to a hydroxyl group-containing chlorinated polyolefin, a method for producing the same, and a composition using the same.

[Problems to be Solved by Prior Art and Invention]

Since polyolefins are non-polar and crystalline, they do not adhere to conventional coating compositions and are difficult to paint, print and adhere to polyolefins. The most commonly used methods at present are to use a chlorinated polyolefin as the main component of the coating composition, and after subjecting the surface of the polyolefin to oxidation treatment for the purpose of improving the compatibility and surface wettability with the coating composition. On the other hand, there is a method of painting, printing or adhering, but this method is difficult to apply depending on the type of coating composition and the surface state of the polyolefin, and the adhesiveness is not completely satisfactory. Further, as an attempt to obtain a coating composition having good adhesion to the surface of polyolefin without oxidation treatment, petroleum-based resins and cyclized rubbers disclosed in JP-B-49-18089 and JP-B-49-5214 are used. , A modified alkyd resin, an acrylic resin, an ethylene-vinyl acetate copolymer resin or the like and a chlorinated polyolefin resin. However, although they have good adhesion to polyolefins, they have limited practical surface hardness, and have no oil resistance or solvent resistance. It's just being done.

Further, in order to produce a coating composition having adhesion to polyolefin and having good coating hardness, oil resistance and solvent resistance, for example, as shown in JP-A-56-50971. Attempts have been made to impart oil resistance and solvent resistance by blending a crosslinking component in a resin composition mainly composed of chlorinated polyolefin and cyclized rubber,
Generally, a polyisocyanate compound, a known compound having a cross-linking agent effect such as a melamine resin or an epoxy resin has poor compatibility with a chlorinated polyolefin or a cyclized rubber, and a urethane bond, an amide bond or the like has an adhesive property to a polyolefin surface. It is not suitable because it significantly inhibits, and the oxidation polymerization type resin component such as oil-modified alkyd resin and boiled polybutadiene is compatible with chlorinated polyolefin and cyclized rubber, but does not cause deformation of the polyolefin. Sufficient cross-linking and hardening cannot be expected in the temperature range commonly used for adhesion and adhesion.

Further, a polymer containing a hydroxyl group in its molecule, such as a polyhydroxypolyolefin produced by anionic polymerization as disclosed in JP-A-49-114692, has a stable hydroxyl group when chlorinated. However, as shown in the comparative example of the present invention, even if the chlorinated product is used as a coating material, sufficient curing behavior is not exhibited.

[Means for Solving the Problems]

The present invention has been made in order to solve such a problem, and is a chlorinated polyolefin containing a hydroxyl group having a chlorine content of 15 to 55% by weight, which is characterized by chlorinating an oxidized polyolefin and then reducing it. The present invention also provides a method for producing the same and a coating composition using the same, and has the intended purpose.

The present invention will be described in detail below.

That is, the present invention relates to a novel chlorinated polyolefin having at least one hydroxyl group at both ends of the molecule, its production and composition, and more specifically to 190 ° C.
Polyolefin resin having a melt viscosity of 10 to 10,000 cps, such as crystalline polypropylene, amorphous polypropylene, polybutene-1,4-methylpentene-1, low or high density polyethylene, ethylene-propylene copolymer, etc. Alternatively, two or more kinds of them are mixed and melted by heat or dissolved in an aliphatic hydrocarbon solvent and subjected to thermal degradation while introducing oxygen or ozone to introduce a carbonyl group into the molecule. During thermal degradation, examples of radical generators include di-tert-butyl peroxide, tert-butyl hydroperoxide, dicumyl peroxide, benzoyl peroxide, and tert-butyl peroxide.
Peroxides such as butylperoxybenzoate, methylethylketone peroxide, 2,5-dimethyl-2,5-di-tert-butylperoxyhexyne-3 and azonitriles such as azobisisobutyronitrile and azobisisopropionitrile It is possible to increase the rate of degradation by using a class. The polyolefin used in the present invention is
If the melt viscosity at 190 ° C is 10 cps or less, when used as a paint, ink, binder, or adhesive, the cohesive force of the film is weak and the required performance cannot be obtained. Further, if the melt viscosity at 190 ° C. is 10,000 cps or more, the viscosity becomes high in these applications and the workability is poor.

In this way, the oxidized polyolefin that has been thermally degraded using oxygen or ozone is dissolved in a chlorine-based solvent, and chlorine is added at a temperature of 0 to 130 ° C under pressure or normal pressure in the presence of a catalyst or under irradiation of ultraviolet rays. Blow gas to chlorinate.

The chlorinated product of the carbonyl group-containing polyolefin is dissolved in an aromatic solvent such as toluene or xylene, or an aliphatic solvent such as methyl ethyl ketone or tetrahydrofuran, and the carbonyl group is reduced to a hydroxyl group using a reducing agent such as a metal hydride. Examples of commonly used reducing agents include lithium aluminum hydride, sodium aluminum hydride, sodium borohydride, diisobutylaluminum hydride, lithium borohydride, borane derivatives and the like.

INDUSTRIAL APPLICABILITY The novel hydroxyl group-containing chlorinated polyolefin of the present invention provides a resin composition having good color developability, adhesiveness and storage stability, and by crosslinking and curing it with an isocyanate or other various curing agents, paints, inks, etc. It is possible to provide a coating film composition that is useful as an adhesive, a binder, an adhesive, and the like.

〔Example〕

Next, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

Example 1 About 50 g of isotactic polypropylene having a melt viscosity of about 2000 cps at 190 ° C. was placed in a three-necked flask equipped with a stirrer, an oxygen inlet and a cooling tube, and carbon tetrachloride of about 1 was added.
Was completely dissolved at 80 ° C., 0.5 g of di-tert-butyl peroxide was added, and a degradation reaction was carried out for 5 hours while passing oxygen at 200 cc / min. The carbon tetrachloride reactor thus obtained was put into hot water to obtain solid oxidized polypropylene.

Furthermore, 30 g of this product was charged into the chlorination reactor, and 1
After carbon tetrachloride was added and dissolved at 80 ° C, gaseous chlorine was blown from the bottom of the reactor while irradiating ultraviolet rays until the degree of chlorination reached 15 wt%.

After completion of the reaction, the solvent carbon tetrachloride was distilled off by an evaporator and replaced with tetrahydrofuran (hereinafter referred to as TF)) to obtain a 20 wt% THF solution. This product (20wt% THF solution)
100 g was put in a three-necked flask equipped with a stirrer, a reducing agent charging port and a cooling tube, 800 g of THF was added and the temperature was kept constant at 60 ° C., 0.1 g of lithium aluminum hydride was charged for 10 minutes, and reduction was performed for about 1 hour. The reaction was carried out. After the reaction, the product was obtained by adding it to a large amount of methanol and filtering the white precipitate.

After drying, the excess product was prepared into a 20% toluene solution.

Example 2 Example 1 was followed except that the chlorination degree was 30 wt%.

Example 3 Example 1 was followed except that the chlorination degree was 55 wt%.

Comparative Example 1 50 g of a commercially available oxidized polypropylene having a number average molecular weight of 1000 to 2000 (manufactured by Sanyo Chemical Industry Co., Ltd., trade name "TS-200") was charged into a chlorination reaction apparatus, carbon tetrachloride of 1 was added and dissolved at 80 ° C. After that, while irradiating with ultraviolet rays, gaseous chlorine was blown from the bottom of the reactor until the degree of chlorination reached 15 wt%. After completion of the reaction, carbon tetrachloride as a solvent was distilled off with an evaporator and replaced with toluene to prepare a 20 wt% solution.

Comparative Example 2 Comparative Example 1 was followed except that the chlorination degree was 30 wt%.

Comparative Example 3 A polyhydroxypolyolefin having a number average molecular weight of 2500 was synthesized by the method described in JP-A-49-114692, 50 g of which was charged into a chlorination reactor, and carbon tetrachloride (1) was added and dissolved at 80 ° C. Then, while irradiating with ultraviolet rays, gaseous chlorine was blown from the bottom of the reactor until the degree of chlorination reached 15 wt%.

After completion of the reaction, carbon tetrachloride as a solvent was distilled off with an evaporator and replaced with toluene to prepare a 20 wt% solution.

Example 4 A 20 wt% toluene solution of each of the hydroxyl group-containing chlorinated polyolefin copolymer or the oxidized chlorinated polypropylene copolymer obtained in Examples 1, 2, and 3 and Comparative Examples 1, 2, and 3.
Titanium oxide 4g, carbon black 0.1g and Epicoat 828 (manufactured by Shell Kagaku Co., Ltd.) 1.6g were mixed with 200g, kneaded in a sand mill for 1 hour, diluted with toluene to an appropriate viscosity, and washed with toluene. Board (2 x 50 x
80 mm) was spray coated to a film thickness of 5-10 μm.

Five minutes later, a two-component curable urethane paint (manufactured by NOF CORPORATION)
Spray coating to a film thickness of 30-40μ, air-dry at room temperature for 15 minutes, and then force dry at 80 ° C for 30 minutes.
After standing at room temperature for 24 hours, the coating film was tested for physical properties. The results are shown in Table-1.

Test method Adhesion: 100 pieces of gougin that reach the base at 1 mm intervals were made on the coated surface, and a cellophane adhesive tape was adhered onto it and peeled off in the 180 ° direction, and it was judged by the extent to which the coating film remained.

Accelerated weathering resistance: A carbon arc type sunshine weather meter was used. The glossiness was measured by 60 ° specular reflection and the whiteness was measured by a hunter.

Hot water resistance: The coated plate was immersed in hot water at 40 ° C for 120 hours and 240 hours, and the state of the coating film was examined.

Gasoline resistance: Rubbing the coated surface with absorbent cotton impregnated with Nisseki Regular Gasoline 50 times and examining the state of the coating film.

Methanol resistance: Cotton wool was soaked in methanol and the coated surface was rubbed 100 times to examine the state of the coating film.

Evaluation criteria in the table ◎ Good ○ Almost good △ Somewhat bad × Bad × × Very bad Example 5 Copolymerization of hydroxyl group-containing chlorinated polyolefins obtained in Examples 1, 2, 3 and Comparative Examples 1, 2, 3 20 wt% toluene solution of coalesced or oxidized chlorinated polypropylene copolymer
After dispersing 100 g and 28 g of titanium dioxide in a sand mill for 3 hours, 7.9 g of isocyanate curing agent Coronate EH (manufactured by Nippon Polyurethane Industry Co., Ltd.) and 2.7 g of 10% zinc octylate solution as an accelerator were added, and No. 4 Ford Cup 13
A polypropylene plate EP-A2 (manufactured by Mitsui Toatsu Kagaku Co., Ltd.) was spray-coated with the viscosity adjusted with toluene so as to be about 15 seconds. After leaving it for about 15 minutes at room temperature, forcibly drying it at 80 ° C. for 30 minutes and allowing it to stand in the room for 1 week, the coating film was tested. The results are shown in Table 2. The test method and the evaluation criteria in the table are the same as in Table-1.

[Advantages of the Invention] The hydroxyl group-containing chlorinated polyolefin of the present invention is novel, and by crosslinking and curing it with various curing agents, it can be used for paints, inks, binders,
It is possible to provide a coating film composition useful as an adhesive and is of great industrial value.

Claims (6)

[Claims] 1. A hydroxyl group-containing chlorinated polyolefin having a chlorine content of 15 to 55% by weight, which is obtained by chlorinating an oxidized polyolefin and then reducing it. 2. A hydroxyl group-containing chlorinated polyolefin having a chlorine content of 15 to 55% by weight according to claim 1, wherein the oxidized polyolefin is obtained by thermally decomposing the polyolefin with oxygen or ozone. 3. The chlorine content of 15 to 5 according to claim 2, wherein the polyolefin has a melt viscosity at 190 ° C. of 10 to 10,000 cps.
5% by weight of hydroxyl group-containing chlorinated polyolefin. 4. A chlorine characterized by oxidizing a polyolefin to give a carbonyl-containing polyolefin, then chlorinating the carbonyl-containing polyolefin, and then reducing part or all of the carbonyl groups to hydroxyl groups using a reducing agent. A method for producing a hydroxyl group-containing chlorinated polyolefin having a content of 15 to 55% by weight. 5. A coating material containing a hydroxyl group-containing chlorinated polyolefin having a chlorine content of 15 to 55% by weight, which is obtained by chlorinating an oxidized polyolefin and then reducing the same,
Coating composition for inks, binders, adhesives, etc. 6. A paint obtained by crosslinking and curing an active ingredient of a chlorinated polyolefin containing a hydroxyl group having a chlorine content of 15 to 55% by weight, which is obtained by chlorinating an oxidized polyolefin and then reducing it. Coating composition for inks, binders, adhesives, etc.