JPH05271323A - Cross-linking of oxidation-modified chlorinated polyolefin and its use - Google Patents

Abstract

PURPOSE:To provide a process for producing a cross-linked product of an oxidation-modified chlorinated polyolefin applicable to various substrates as a binder resin such as coating material, ink, primer and adhesive. CONSTITUTION:The objective cross-linked product of an oxidation-modified chlorinated polyolefin is produced by oxidizing a polyolefin with air, oxygen, ozone, etc., during the chlorination reaction of the polyolefin to introduce functional groups into a chlorinated polyolefin and cross-linking the functional groups with a compound having >=2 isocyanate groups, epoxy groups, hydroxyl groups, etc., in one molecule.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a crosslinkable oxidatively modified chlorinated polyolefin, a crosslinked product thereof, a process for producing the same, and a composition using the same, more specifically, various plastics including polyolefin and various Provided are various crosslinkable compositions for paints, primers and printing inks or adhesives which can be applied to substrates such as metal, paper, wood and concrete.

[0002]

2. Description of the Related Art Chlorinated polyolefins such as chlorinated polypropylene, chlorinated polyethylene and chlorinated rubber can be easily dissolved in an inexpensive solvent. The solution can be applied, sprayed, dipped, etc. The work is easy and quick drying, the coating film obtained from the solution is acid resistant,
Alkali resistance, weather resistance, and flame retardancy are excellent, and those having a chlorine content in the range of 5 to 50 wt% have excellent properties such as exhibiting good adhesion to a polyolefin resin having poor adhesion. It is used in various fields as a very useful modified resin. Examples thereof include paints, primers, printing inks, coating agents for films and sheets, and adhesives.

However, these chlorinated polyolefins generally have the following drawbacks, and cause various difficulties and limitations in their application. That is, these are poor solvent resistance of the coating film, insufficient strength of the film,
Those with a high chlorine content are brittle and must use a large amount of plasticizer, while those with a low chlorine content have a low softening temperature, so the coating film may peel off even under hot water conditions. It has drawbacks such as poor affinity to the surface of polar substances and difficulty in adhering to metals and wood.

In order to improve these drawbacks, Japanese Patent Publication No. 51
No. 24316 discloses a method of grafting a monomer having a functional group onto a chlorinated polyolefin.
No. 27968 and JP-A No. 62-95372 disclose a method of grafting a chlorinated polyolefin with an acrylic monomer having a hydroxyl group and then crosslinking with an isocyanate compound. A method of grafting the contained acrylic monomer and then crosslinking with an epoxy compound has been proposed.
However, these methods have a drawback that the graft polymerization rate of the above-mentioned monomer to the chlorinated polyolefin is extremely low and a homopolymer is produced, so that a sufficient crosslinked coating film of the chlorinated polyolefin cannot be obtained.

Further, in JP-B-63-50381 and JP-B-1-16414, a chlorinated carboxyl group-containing chlorinated polyolefin obtained by grafting an unsaturated acid anhydride onto a polyolefin is cross-linked with an epoxy compound. Although a method has been proposed, this method also has the disadvantage that the rate of the crosslinking reaction is essentially slow.

An object of the present invention is to provide an oxidatively modified chlorinated polyolefin capable of solving the above problems, a crosslinked product thereof, and a method for producing the same. The present invention is also various plastics and various metals including polyolefin,
It is also an object to provide various compositions for paints, primers and printing inks or adhesives which are crosslinkable and can be applied to substrates such as paper, wood and concrete.

[0007]

The present inventors have made an oxidation-modified chlorinated polyolefin that has been subjected to an oxidation treatment using at least one or two or more selected from air, oxygen and ozone during the chlorination reaction of the polyolefin. (I) 2 per molecule
Or more isocyanate groups and / or epoxy groups and / or
Alternatively, the inventors have found that a method of crosslinking with a compound (II) having a hydroxyl group solves the above-mentioned problems, and completed the present invention.

[0008]

The oxidation-modified chlorinated polyolefin used in the present invention includes crystalline polypropylene, amorphous polypropylene, polybutene-1, polypentene-1,4-methylpentene-1, low density or high density polyethylene and ethylene-propylene copolymer. Polymers, ethylene-propylene-diene copolymers, natural rubber, polyolefins such as polyisoprene are dispersed or dissolved in water or a medium such as carbon tetrachloride or chloroform, and added with a radical generating catalyst or under irradiation of ultraviolet rays. Chlorination is carried out in the temperature range of 50 to 120 ° C under atmospheric pressure or atmospheric pressure, and air, oxygen or ozone may be mixed with gaseous chlorine at the beginning, in the middle, or at the end of chlorination, simultaneously, separately or alternately. Obtained by blowing on.

The progress of oxidation of the oxidation-modified polyolefin is
It can be judged that the absorption around 1730 cm ^-1 measured by an infrared spectrophotometer increases. The degree of oxidation can be confirmed by the functional group index measured by the scale of the following formula, and in order to carry out the present invention, the functional group index is preferably 1 or more.

The compounds having two or more isocyanate groups per molecule used as the crosslinking agent of the present invention include aromatic, aliphatic and alicyclic organic diisocyanates, such as tolylene diisocyanate and xylene diisocyanate. 1,5-naphthalene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6
-Hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, 4,4-dicyclohexylmethane diisocyanate, 1,4-cyclohexyl diisocyanate and the like. In addition, these organic diisocyanates,
It may be used after being modified into an isocyanate derivative such as a buret body, an isocyanurate body or a trimethylolpropane adduct body. Furthermore, if the compound has two or more isocyanate groups per molecule, such as a urethane resin having a free isocyanate group obtained by reacting a polymer polyol such as a polyether polyol or a polyester polyol with the above organic diisocyanates. Can be used.

Examples of the compound having an epoxy group include bisphenol A type and bisphenol F type epoxy resins and polyhydric alcohol glycidyl ether types, such as ethylene glycol glycidyl ether, propylene glycol glycidyl ether, glycerol polyglycidyl ether, and sorbitol polyglycidyl ether. Etc., and cycloaliphatic epoxy resins obtained by oxidizing olefins with peracid. In addition, an acrylic epoxy compound obtained by copolymerizing glycidyl (meth) acrylate and other (meth) acrylates, etc., 2 per molecule
Any compound having at least one epoxy group can be used.

Examples of the compound having a hydroxyl group include diols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,4-pentanediol, 1,6-hexanediol and 2,5-hexanediol, and glycerin, There are polyhydric alcohols such as trimethylolethane, trimethylolpropane and pentaerythritol. Further, a compound having two or more hydroxyl groups per molecule, such as a polymer polyol such as a polyether polyol or a polyester polyol, can be used.

In order to accelerate the crosslinking reaction of the present invention, a third
Basic amines such as pyridine, quinoline, triethylamine, and 1,8-diazo-bicyclo-undecene-7 and organometallic catalysts such as zinc octylate and di-n-butyltin dilaurate may be added. ..

The composition of the present invention mainly comprises a crosslinkable composition containing the above-mentioned oxidation-modified chlorinated polyolefin (I) and compound (II) as a main binder resin and a crosslinked product of (I) and (II). The composition containing the binder resin can be used as it is as a coating agent or an adhesive, but a pigment, a solvent, and other additives are added and kneaded.
It can be dispersed and used as paint or ink. or,
The composition by itself shows balanced performance,
If necessary, alkyd resin, acrylic resin, polyether resin, polyester resin, urethane resin and the like may be further added and used.

A feature of the present invention is that a functional group is introduced into a chlorinated polyolefin by oxidizing the polyolefin with chlorination reaction with air, oxygen, ozone or the like, and this functional group is added per molecule. By improving the solvent resistance, toughness, heat resistance, moisture resistance, etc. of the coating film, which was a drawback of chlorinated polyolefin, by crosslinking with a compound having two or more isocyanate groups, epoxy groups, hydroxyl groups, etc. is there.

Although the functional group introduced into the chlorinated polyolefin is not clear, it is considered that a carbonyl group, a carboxyl group, an acid chlorate group, a peroxide group, a peroxide chlorate group or the like is formed during the oxidation treatment. Further, since functional groups are considered to be generated during the cleavage reaction of the polyolefin, it is considered that these functional groups are introduced into the terminal of the chlorinated polyolefin molecule.

[0017]

EXAMPLES The present invention will now be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

(Prototype Example-1) Melt index is 14
g / 10 min (Measurement method: ASTM D1238-62
4 kg of isotactic polypropylene of T) was uniformly dissolved in 80 liters of carbon tetrachloride under pressure, and 100 to 11
Chlorination was performed by blowing chlorine gas while irradiating ultraviolet rays at a temperature of 0 ° C. When the chlorine content reached about 20 wt%, the chlorine gas was changed to a mixed gas having a chlorine / air volume ratio of about 10/90, and chlorination was performed gently while performing an oxidation treatment. While tracking the above-mentioned functional group index with an infrared spectrophotometer in the middle of the oxidation treatment, the functional group index was 9.5 and 18.
7, the chlorine content is 27.3 wt% and 31.8 wt% respectively
Was sampled, carbon tetrachloride was distilled off and replaced with toluene to obtain an oxidation-modified chlorinated polypropylene having a nonvolatile content of 40 wt%.

(Prototype Example-2) The melt index is 70.
g / 10 min (measuring method: JIS K6760) 4 kg of polyethylene was chlorinated under the same conditions as in Prototype Example-1,
When the chlorine content reached about 50 wt%, a mixed gas having a chlorine / oxygen volume ratio of about 45/55 was blown to perform oxidation treatment and chlorination. According to the method of Prototype Example-1, the functional group indexes are 31.2 and 40.5 and the chlorine contents are 6 respectively.
Samples of 9.5 wt% and 69.8 wt% were withdrawn, carbon tetrachloride was separated by steam distillation and dried to obtain powder of oxidation-modified chlorinated polyethylene.

(Examples-1 and 2 and Comparative Examples-1 and 2) A paint was prepared using the oxidation-modified chlorinated polypropylene obtained in Prototype Example-1 and a polypropylene plate TX-933A (manufactured by Mitsubishi Petrochemical Co., Ltd.) was prepared. ) Was spray painted. After being dried at room temperature for 15 minutes, forcedly dried at 80 ° C. for 30 minutes and allowed to stand in the room for 1 week, the coating film was tested. The results are shown in Table 1. The paint formulation is shown in Table 2.

[0021]

[Table 1]

Test method ○ Adhesion 100 grids that reach the substrate at 1 mm intervals were made on the coated surface, and cellophane adhesive tape was adhered on top of them for 180
It was peeled off in the direction of ° and judged by the extent to which the coating film remained.

○ Warm Water Resistance The coated plate was immersed in warm water of 40 ° C. for 120 hours and 240 hours, and the state of the coating film was examined.

Gasoline resistance (rubbing 100 times) The absorbent cotton was soaked with gasoline and the coated surface was rubbed 100 times to examine the state of the coating film. (Dip 2 hours) Scratch reaching the substrate on the coated surface (×
Mark) was put in, and it was dipped in gasoline for 2 hours and the state of the coating film was examined.

Bending Resistance The state of the coating film was examined by bending 180 ° with a 1 / 2φ inch mandrel.

○ Impact resistance The impact resistance was examined with a DuPont type impact tester, using a hammer core ½φ inch and a load of 500 g, and dropping it from a height of 50 cm on the coated surface to examine the state of the coating film.

[0027]

[Table 2]

○ Paint preparation method The resin and titanium dioxide obtained in Prototype Example-1 were subjected to 1 in a sand mill.
After kneading for a time, a cross-linking agent and an accelerator were added, and the viscosity was adjusted with xylene so that the temperature was 13 to 15 seconds / 20 ° C. in a No. 4 Ford cup. In the case of Comparative Example, the viscosity was adjusted without adding a crosslinking agent and an accelerator.

(Examples 3 and 4 and Comparative Examples 3 and 4) White ink and red ink were prepared with the oxidation-modified chlorinated polypropylene obtained in Prototype Example-1 and coated on Manila coated paper with coating rod # 4. I worked. After drying at room temperature for 1 day, heat resistance was measured. The results are shown in Table 3. The ink formulation is shown in Table 4.

[0030]

[Table 3]

○ Heat resistance test method of ink After a high-quality paper was placed on the ink surface and a heat seal bar set at each temperature was pressure-bonded for ² kg / cm ² -10 seconds, it was left standing for 30 minutes or more to peel it off. It was judged by the condition of the coated surface at that time.

[0032]

[Table 4]

Ink Preparation Method According to the ink formulation of Table 4, the resin obtained in Prototype Example-2 was dissolved in toluene, the pigment was mixed, and the mixture was kneaded in a sand mill for 2 hours. Next, a crosslinking agent and an accelerator were added, and the viscosity was adjusted with toluene using a No. 3 Zahn cup so that the temperature was 20 to 25 seconds / 20 ° C. In the case of Comparative Example, the viscosity was adjusted without adding a crosslinking agent and an accelerator.

[0034]

From the results shown in Table 1, the coating films of Comparative Examples 1 and 2 are extremely inferior in hot water resistance and gasoline resistance, but by crosslinking as in Examples 1 and 2, It can be seen that the property of is significantly improved. In addition, the results shown in Table 3 also show that the heat resistance is improved by crosslinking, which shows that the present invention is useful.

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[Procedure amendment]

[Submission date] July 1, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Title of invention

[Correction method] Change

[Correction content]

Title: Crosslinked product of oxidatively modified chlorinated polyolefin and process for producing the same

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction content]

The progress of oxidation of the oxidatively modified chlorinated polyolefin can be judged by the fact that the absorption around 1730 cm ^-1 measured by an infrared spectrophotometer increases. The degree of oxidation can be confirmed by the functional group index measured by the scale of the following formula, and in order to carry out the present invention, the functional group index is preferably 1 or more.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0024

[Correction method] Change

[Correction content]

○ Gasoline resistance (rubbing 100 times) Soaked absorbent cotton with gasoline,
The coated surface was rubbed 100 times to examine the state of the coating film. (Dip 2 hours) Scratch reaching the substrate on the coated surface (×
Mark) was put in, and it was dipped in gasoline for 2 hours and the state of the coating film was examined.

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Claims (5)

[Claims] 1. During the chlorination reaction of a polyolefin, any one of air, oxygen, and ozone, or two or three thereof.
An oxidation-modified chlorinated polyolefin (I) obtained by oxidation treatment with a seed mixture is crosslinked with a compound (II) having two or more isocyanate groups and / or epoxy groups and / or hydroxyl groups per molecule. And a method for producing a crosslinked product of an oxidation-modified chlorinated polyolefin (I). 2. The method for producing a crosslinked product according to claim 1, wherein the chlorine content of the oxidation-modified chlorinated polyolefin (I) is 5 to 75 wt%. 3. A paint comprising the oxidation-modified chlorinated polyolefin (I) and compound (II) according to claim 1 as a main binder resin, or the crosslinked product of the above (I) and (II) as a main binder resin. , Primer, printing ink, adhesive composition. 4. A chlorination reaction of a polyolefin, which is obtained by oxidation treatment with any one or more of air, oxygen and ozone, and has two or more isocyanate groups and / or epoxy groups per molecule. And / or an oxidation-modified chlorinated polyolefin crosslinkable with a compound having a hydroxyl group. 5. The method for producing the oxidation-modified chlorinated polyolefin according to claim 4.