JP2001114960A - Acid-modified chlorinated polyolefin composition with good solvent resistance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an acid-modified chlorinated polyolefin composition which has improved storage stability, adhesion to polyolefins, and solvent resistance in comparison with a conventional chlorinated polyolefin and is used for coating materials and primers. SOLUTION: This solvent-resistant acid-modified chlorinated polyolefin composition is prepared by compounding 100 pts.wt. acid-modified chlorinated polyolefin with 0.1-10 pts.wt. material selected from among metal soaps, inorganic acids, organometallic compounds, hydrotalcite compounds, and their mixtures. The acid modified chlorinated polyolefin has a chlorine content of 5-50 wt.% and a content of a grafted α,β-unsaturated carboxylic anhydride of 1-10 wt.% and is prepared by partially opening part of the rings of grafted α,β-unsaturated carboxylic anhydride units with water.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a polyolefin resin, for example, polypropylene, polyethylene, ethylene-
Propylene copolymers, ethylene-propylene-acid-modified chlorinated polyolefins used as primers for molded products or films of polyolefin resins such as ethylene-propylene-diene copolymers, and more specifically, molded products of these polyolefin resins, sheets, The present invention relates to an acid-modified chlorinated polyolefin composition used as a coating resin having excellent adhesion to a film and gasohol resistance and a binder resin for a primer.

[0002]

2. Description of the Related Art In recent years, plastics have many advantages such as high productivity, wide design freedom, light weight, rust prevention and impact resistance. It is often used as a material for such applications.
In particular, polyolefin resins are inexpensive and moldable,
It has many excellent properties such as chemical resistance, heat resistance, water resistance, and good electrical properties, so it is widely used as an industrial material, and is expected to grow in demand in the future. is there. However, polyolefin resins are different from polar synthetic resins, such as polyurethane resins, polyamide resins, acrylic resins, and polyester resins, in that they are non-polar and crystalline, making them difficult to paint and bond. Having.

[0003] For the coating and bonding of such a hard-to-adhere polyolefin resin, a low chlorinated polyolefin having a strong adhesive force to the polyolefin resin has conventionally been used as a binder resin. For example, Japanese Patent Publication 46-2
No. 7489 proposes a chlorinated isotactic polypropylene chlorinated to 20 to 40% by weight as a binder resin for a printing ink of a polypropylene film.
Japanese Patent Publication No. 50-35445 and Japanese Patent Publication No. 50-37688
Chlorinated propylene-ethylene copolymers chlorinated to 4040% by weight have been proposed as binder resins for printing inks and adhesives for polyolefins. Also, JP-A-57-36128, JP-B-63-50381, JP-A-59-36128
JP-166534, JP-B-63-36624 and the like describe low-chlorinated polypropylene or low-chlorinated propylene-α-olefin containing carboxylic acid and / or carboxylic anhydride having a chlorine content of 5 to 50%. Copolymers have been proposed as primers for painting polyolefin-based molded articles and binder resins for coating.

In recent years, primers for polyolefin-based molded articles have been required to have not only adhesiveness but also solvent resistance, particularly gasohol resistance. However, the above-mentioned acid-modified chlorinated polyolefin has gasohol resistance. However, it is not enough and improvement is desired. The present inventors have filed Japanese Patent Application No. 10-309609.
No. 4 proposed a binder resin for a polyolefin resin having improved solvent resistance, but this resin still had insufficient gasohol resistance.

On the other hand, the low chlorinated polyolefins described above are obtained by dispersing or dissolving various polyolefins in water or a chlorinated solvent and then chlorinating by blowing a chlorine gas. Are introduced unevenly. As a result, these low-chlorinated polyolefins become unstable, and have the disadvantage that they are degraded with dehydrochlorination when exposed to ultraviolet light or high heat. Therefore, the addition of a stabilizer is essential.

[0006] A stabilizer is also added to polyvinyl chloride resin, which is one of the chlorinated resins, together with chlorinated polyolefins. However, "Polyvinyl chloride, its chemistry and industry" (Asakura Shoten Co., Ltd., Showa 41) (Published 3rd edition on January 25) include metal chlorides such as calcium stearate and lead stearate, inorganic acid salts such as lead oxide and tribasic lead sulfate, dibutyltin dilaurate and dibutyl as stabilizers for polyvinyl chloride resin. It is described that organometallic compounds such as tin malate, epoxidized soybean oil, and epoxy compounds such as glycidyl ether of glycerin can be used.

As a stabilizer for chlorinated polyolefins,
Although the above stabilizers can be used, JP-B-57-31756, JP-B-60-49654, JP-A-6-306227, JP-A-7-73362, JP-A-10-036601 , JP10
Most of the stabilizers are epoxy compounds, as shown in JP-A-204372.

As a simple chlorinated polyolefin stabilizer, an epoxy compound can maintain long-term stability. However, when the polyolefin has a functional group which reacts with an epoxy group in the molecular chain, for example, carboxylic acid or carboxylic anhydride When an epoxy compound is added to an acid-modified chlorinated polyolefin containing a carboxylic acid, the carboxylic acid reacts with an epoxy group. Particularly, when a diepoxy compound is added, there is an adverse effect such as thickening.

[0009] To solve this problem, Japanese Patent Application Laid-Open No. 9-235433 discloses a monoepoxy compound having improved long-term storage stability. However, even with such a composition, although the storage stability as an acid-modified chlorinated polyolefin is improved, a problem has been pointed out that the gasohol resistance of a primer using this acid-modified chlorinated polyolefin decreases with time. ing.

[0010]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems, and is excellent in adhesion to polyolefin and gasohol resistance, and has improved the stability over time of these physical properties. It is intended to provide a chlorinated polyolefin composition.

[0011]

That is, the present inventors have found that the chlorine content is 5 to 50% by weight, the graft amount of α, β-unsaturated carboxylic anhydride is 1 to 10% by weight, Α,
An acid-modified chlorinated polyolefin obtained by partially opening a part of β-unsaturated carboxylic acid anhydride with water,
For 100 parts by weight, an acid-modified chlorinated polyolefin composition comprising 0.1 to 10 parts by weight of a metal soap, an inorganic acid salt, an organic metal compound or a hydrotalcite compound alone or in a mixture of 0.1 to 10 parts by weight, based on the polyolefin The present inventors have found that they have good adhesion and solvent resistance and have stability over time, and have accomplished the present invention.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION As a raw material of the present invention, crystalline polypropylene or a propylene-α-olefin copolymer containing 50 to 98 mol% of a propylene component can be used. The propylene-α-olefin copolymer is obtained by copolymerizing α-olefin with propylene as a main component, and can be used as either a block copolymer or a random copolymer. As the α-olefin component, for example, ethylene, 1
-Butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, and the like. The content of propylene component is optimally 50-98 mol%,
If it is less than 50 mol%, the adhesion to polypropylene decreases. On the other hand, if it exceeds 98 mol%, the flexibility of the coating film deteriorates.

The acid-modified chlorinated polyolefin of the present invention is obtained by introducing an α, β-unsaturated carboxylic anhydride and chlorine into the above-mentioned polyolefin resin, and further partially converting the α, β-unsaturated carboxylic anhydride with water. It is obtained by ring opening, and can be produced by the following three methods. That is, (1) a polyolefin resin is preliminarily graft-polymerized with an α, β-unsaturated carboxylic anhydride, and then the α, β-unsaturated carboxylic anhydride is partially ring-opened with water, followed by a chlorination reaction. (2) After preliminarily graft-polymerizing an α, β-unsaturated carboxylic anhydride to a polyolefin resin and performing a chlorination reaction, partially opening the α, β-unsaturated carboxylic anhydride with water. How to ring,
(3) In this method, after chlorinating the polyolefin resin, an α, β-unsaturated carboxylic anhydride is graft-polymerized, and the α, β-unsaturated carboxylic anhydride is partially ring-opened with water.

To illustrate a specific production method, in the first method, first, an α, β-unsaturated carboxylic anhydride is graft-copolymerized on a polyolefin resin. A method in which the above resin is heated and melted to a melting point or higher to cause a reaction (melting method), a method in which the above resin is dissolved in an organic solvent, and then heated and stirred in the presence of a radical generator to cause a reaction (a solution method), etc. Can be performed by a known method.

In the case of the melting method, a Banbury mixer,
Since the reaction is performed in a short time at a temperature of not less than the melting point and not more than 300 ° C. using a kneader, an extruder or the like, there is an advantage that the operation is simple.

On the other hand, in the solution method, it is desirable to use an aromatic solvent such as toluene or xylene as an organic solvent. No problem. The radical generator used in the reaction can be appropriately selected from known ones, and an organic peroxide compound is particularly desirable.

Examples of the above-mentioned organic peroxide compounds include di-t-butyl peroxide, dicumyl peroxide, t-butyl cumyl peroxide, benzoyl peroxide, dilauryl peroxide, cumene hydroperoxide and t-butyl peroxide. -Butyl hydroperoxide,
1,1-bis (t-butylperoxy) -3,5,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) -cyclohexane, cyclohexanone peroxide, t-butylperoxybenzoate, t- Butylperoxyisobutyrate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisopropylcarbonate, cumylperoxyoctoate And the like.

However, in the case of the solution method, it is necessary to replace the above-mentioned solvent with a chlorinated solvent such as chloroform when performing a chlorination reaction after graft copolymerizing an α, β-unsaturated carboxylic anhydride. In the first method, the melting method is more preferable.

Further, in order to improve the gasohol resistance, gel permeation chromatography (GP
It is desirable that the component having a weight average molecular weight of 2,000 or less measured with C) as a standard is 2% or less. In this method, low molecular weight components can be removed by extracting the resin grafted with the α, β-unsaturated carboxylic anhydride in a polar solvent such as acetone or methyl ethyl ketone under heating.

The subsequent partial ring opening of the α, β-unsaturated carboxylic acid anhydride grafted to the polyolefin resin with water is carried out by adding the α, β-unsaturated carboxylic acid anhydride-grafted resin to water. For example, and a method of leaving in an atmosphere of high humidity.

In the subsequent chlorination reaction, α, β-unsaturated carboxylic anhydride is graft-copolymerized, and the partially ring-opened polyolefin resin is dissolved in a chlorinated solvent such as chloroform. 50-14 under normal pressure or pressure under irradiation, or in the presence or absence of a catalyst
This is performed by blowing chlorine gas in a temperature range of 0 ° C. The reaction solution after the completion of the chlorination reaction is obtained by replacing chloroform, which is a chlorinated solvent, with an aromatic solvent such as toluene or xylene by utilizing a difference in boiling point, and in addition, an ester solvent, a ketone solvent, or the like. May be used as a mixture.

After the acid-modified chlorinated polyolefin is solidified by the following method, it may be dissolved in the above solvent such as toluene or xylene.

In the second method, a polyolefin resin is preliminarily graft-polymerized with an α, β-unsaturated carboxylic acid anhydride and subjected to a chlorination reaction, and then partially subjected to α, β-unsaturated carboxylic acid anhydride with water. The method of ring-opening is carried out by graft-polymerizing an α, β-unsaturated carboxylic anhydride onto a polyolefin resin in advance in the same manner as in the first method, then performing a chlorination reaction in the same manner as in the first method, and removing the solvent. The solvent is changed to a solvent such as toluene or xylene, and water is added to the solution to partially open the grafted α, β-unsaturated carboxylic anhydride.

After performing the third method, chlorination reaction,
In the method of graft-polymerizing an α, β-unsaturated carboxylic anhydride and further opening the ring with water, first, a polyolefin resin is dissolved in a chlorinated solvent such as chloroform, and the chlorination reaction is performed in the same manner as in the first method. After the production of the chlorinated polyolefin resin, the solvent is changed to a solvent such as toluene or xylene, and then the α, β-unsaturated carboxylic anhydride is subjected to graft copolymerization in the presence of the organic peroxide. The reaction can be carried out at a temperature of not lower than 50 ° C. and not higher than the boiling point of the solvent. Further, water is added to the solution to partially open the grafted α, β-unsaturated carboxylic anhydride.

In the first, second and third methods, the α, β-unsaturated carboxylic acid anhydride graft-copolymerized with the polyolefin resin, when used as a primer resin,
It is for imparting adhesion to the top coat, for example, maleic acid, citraconic acid, itaconic acid, anhydrides of aconitic acid and the like can be exemplified, but considering the graftability to polyolefin resin, maleic anhydride is Most suitable.

In the present invention, the amount of the α, β-unsaturated carboxylic anhydride introduced by graft copolymerization is from 1 to 10
% By weight is optimal. When the amount is less than 1% by weight, adhesion between the obtained primer composition and the top coat is not sufficiently obtained. When the amount is 10% by weight or more, when used as a primer, the moisture resistance tends to decrease.

The amount of ring opening by water can be determined by the absorbance ratio of the absorption derived from the acid anhydride to the absorption derived from the carboxylic acid in the infrared absorption spectrum. This will be described by taking maleic anhydride as an example.

The absorption derived from maleic anhydride is 1780 cm -1
And the absorption derived from maleic acid opened by water is
It is at 1710cm-1. When the grafted maleic anhydride opens, the absorbance at 1780 cm-1 decreases, the absorption appears at 1710 cm-1 and the absorbance at 1710 cm-1 increases as the ring opening proceeds. Therefore, the absorption derived from maleic anhydride (abs
1780cm-1) and absorption derived from maleic acid (abs1710cm-1)
The degree of ring opening can be defined by the ratio (abs1710cm-1) / (abs1780cm-1). The absorbance ratio (abs1710cm-1) / (abs1780cm-
When 1) is in the range of 0.05 to 100, the solvent resistance is good, but outside this range, the solvent resistance becomes poor. When maleic anhydride reacts with the epoxy compound to open the ring, an absorption at 1710 cm-1 and an absorption derived from an ester group appear at 1730 cm-1. Even if maleic anhydride is ring-opened, an increase in absorption at 1730 cm-1 is not preferable because solvent resistance deteriorates.

The lower the chlorine content of the acid-modified chlorinated polyolefin resin, the better the adhesion to the polypropylene resin, but the lower the solubility in organic solvents, and the lower the flowability at low temperatures. Also, when the chlorine content increases, the adhesion to the polypropylene-based resin decreases. Therefore, the chlorine content is optimally 5 to 50% by weight, preferably 10 to 30% by weight.

Further, the obtained acid-modified chlorinated polyolefin resin was subjected to gel permeation chromatography (GP
It is preferable that the weight average molecular weight measured by C) using polystyrene resin as a standard is 30,000 to 220,000. Below 30,000, the cohesive strength of the resin is insufficient and 220,000
The above is not preferable because the spray workability is reduced.
Further, it is preferable for the gasohol resistance that the component having a molecular weight of 2000 or less be 2% or less.

In the present invention, a metal soap, an inorganic acid salt, an organic metal compound or a hydrotalcite compound is used alone or in combination as a stabilizer. Metal soaps include lithium stearate, sodium stearate, magnesium stearate, calcium stearate, calcium laurate, calcium 2-ethylhexylate, calcium ricinoleate, calcium ethyl acetoacetate, zinc stearate, zinc laurate, lead stearate, Examples thereof include dibasic lead stearate and lead naphthenate.

Examples of the inorganic acid salts include tribasic lead sulfate, basic lead sulfite, and basic lead silicate sulfate.

Examples of the organometallic compounds include dibutyltin dilaurate and dibutyltin distearate.

Further, the hydrotalcite compound is
It is a non-stoichiometric compound represented by the following general formula. Formula: ^{_{[M 2+ 1-X M 3+ X}} (OH) 2 ] ^{X +} [A ^n- _{X / ^N} · mH
₂ O] ^X- where, M ²⁺ : Mg ²⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ Zn
Divalent metals such as ²⁺ . M ³⁺ : A trivalent metal such as Al ³⁺ , Fe ³⁺ , Cr ³⁺ , Co ³⁺ , and In ³⁺ . ^{A n-: OH -, F -} , Cl -, Br -, NO 3 -, CO 3 2-, S
^{_{O 4 2-, Fe (CN)}} 6 3-, CH 3 COO-, oxalate ion, n-valent anion such as Sarichin ion. x is in the range of 0 <x ≦ 0.33.

Among these hydrotalcite compounds,
Particularly preferably used is Mg _4.5Al_Two(OH)₁₃CO_Three・
3.5H_TwoO or Mg₆Al_Two(OH)₁₆CO_Three・ 4H_TwoIs represented by the formula of O
is there. The above stabilizers may be used in combination, for example,
For example, a hydrotalcite compound and the above metal soaps
Some lithium stearate, sodium stearate,
Magnesium stearate, calcium stearate, etc.
May be used together. Hydrotalcite compounds
And the above inorganic salts, tribasic lead sulfate, basic sulfurous acid
Lead and basic lead silicate sulfate may be used in combination. Also high
Drotarsite compounds and the above organometallic compounds
Dibutyltin dilaurate, dibutyltin distearate
May be used in combination.

The composition of the present invention has a chlorine content of 5 to 50% by weight and a grafting amount of α, β-unsaturated carboxylic anhydride of 1%.
To 10% by weight of an acid-modified chlorinated polyolefin, wherein a part of the grafted α, β-unsaturated carboxylic anhydride is ring-opened with water, based on 100 parts by weight of the acid-modified chlorinated polyolefin. And 0.1 to 10 parts by weight of a metal soap, an inorganic acid salt, an organometallic compound or a hydrotalcite compound alone or as a mixture. That is, if the amount of these stabilizers is less than 0.1 part by weight, sufficient stability cannot be obtained, and if the amount exceeds 10 parts by weight, the composition does not become a transparent coating when dried to form a transparent coating.

These stabilizers may be added to the reaction solution after the completion of the chlorination reaction, or may be added after replacing the chlorination solvent such as chloroform with a solvent such as toluene.
It is preferable to add the stabilizer which is solid at room temperature after dissolving and dispersing it in a chlorinated solvent such as chloroform or a solvent such as toluene in advance.

The acid-modified chlorinated polyolefin composition of the present invention may be stored or transported in a solid form, and used by dissolving it in a solvent when forming a coating. An example of the solidification method in that case will be described. Water is added to the reaction solution in which the chlorination reaction has been completed in the first method, or the reaction solution in which the chlorination reaction has been completed in the second method, or the reaction solution in which the graft polymerization has been completed in the third method. The reaction can be achieved by adding a hydrotalcite compound or the like to the reaction solution and then drying with a drum dryer. Further, in place of the drum dryer, the reaction solvent was completely removed by a vented extruder provided with a vent port for distilling off the reaction solvent under reduced pressure, and the solid of the acid-modified chlorinated polyolefin composition was extruded into a strand, It can also be achieved by pelletizing with an underwater cutter or a water-cooled pelletizer. Further, a method of further adhering a fine powder of a hydrotalcite compound or the like to the surface of a solidified pellet by adding a hydrotalcite compound is also effective from the viewpoint of pellet stability and blocking prevention.

The solid acid-modified chlorinated polyolefin composition is used in a state of being dissolved in an organic solvent at the time of use. The solution concentration may be appropriately selected depending on the application,
If the solution concentration is too high or too low, the coating workability is impaired, so the resin concentration is preferably 5 to 30% by weight. The solvent to be used is preferably an aromatic solvent such as toluene and xylene; in addition, an ethyl acetate and an ester solvent such as butyl acetate;
Ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, aliphatic solvents such as n-hexane and heptane, and alicyclic solvents such as cyclohexane, methylcyclohexane and ethylcyclohexane can be used. Furthermore, in order to enhance the storage stability of the resin solution, alcohols such as methanol, ethanol, and isopropyl alcohol, and propylene glycol ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, and propylene glycol tertiary butyl ether may be used alone or in combination. 1 to the above solvent by mixing above
It is preferable to add 20%.

The production of a solution of the acid-modified chlorinated polyolefin composition can be carried out by converting chlorinated solvent such as chloroform to the above-mentioned solvent such as toluene by utilizing the difference in boiling points.

Specifically, after the chlorination reaction is completed, the chlorination reaction solvent such as chloroform is distilled off under reduced pressure, replaced with toluene, xylene, or the like, and then added with a hydrotalcite compound or the like. However, after a certain amount of the chlorination reaction solvent is distilled off and then a hydrotalcite compound or the like is added, the solvent may be replaced with toluene or xylene.

The resin composition according to the present invention may be used after being coated as it is, or may be used after adding a solvent, a pigment and other additives. In addition, the composition alone exhibits well-balanced coating film properties.If necessary, a cyclized rubber, a petroleum resin, a coumarone indene resin, a chlorinated polyolefin resin, an acrylic resin, an alkyd resin, or the like is further added. Can be used.

[0043]

The present invention is characterized in that a metal soap, an inorganic acid salt, an organic metal compound or a hydrotalcite compound is used alone as a stabilizer in an acid-modified chlorinated polyolefin partially ring-opened with water. Another advantage is that, when used in combination, the primer using an acid-modified chlorinated polyolefin, which has been inadequate than the conventional one, has dramatically improved solvent resistance and long-term stability of physical properties.

Conventionally, epoxidized compounds have been used as stabilizers for chlorinated polyolefins, but when the chlorinated polyolefin has a functional group which reacts with an epoxy group in the molecular chain, various harmful effects are caused. For example, when a diepoxy compound is used, cross-linking between molecular chains occurs, causing problems such as thickening and gelling. In addition, since the ester group generated by the reaction between the carboxylic acid and the epoxy compound has a high solubility in a solvent, the primer using the acid-modified chlorinated polyolefin has a problem that the solvent resistance is reduced.

Further, even when a modification reaction or the like utilizing the reaction of an acid-modified chlorinated polyolefin with a carboxylic acid or a carboxylic anhydride is carried out, if a reaction with an epoxy compound has already occurred at the time of storage, the carboxylic acid as a functional group is not obtained. Due to the decrease or disappearance of the acid or carboxylic anhydride, there is a problem that sufficient modification cannot be performed.

The present invention has the following advantages with respect to such a problem. (1) The acid-modified chlorinated polyolefin partially ring-opened with water has a higher polarity than the non-ring-opened chlorinated polyolefin, thereby improving the solvent resistance. (2) By using metal soaps, inorganic acid salts, organometallic compounds or hydrotalcites compounds which do not react with carboxylic acid or carboxylic anhydride as a stabilizer,
It can be kept in a carboxylic acid or carboxylic anhydride state for a long time.

[0047]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

(Production Example 1) The melt viscosity at 180 ° C. was about
Into a three-necked flask equipped with a stirrer, a dropping funnel and a condenser for refluxing monomers, 6 kg of an ethylene-propylene copolymer having an ethylene content of 3 mol% at 2500 mPa · s, and kept constant at 180 ° C. It melted completely in the oil bath. After performing nitrogen replacement in the flask for about 10 minutes, 240 g of maleic anhydride was added over about 5 minutes while stirring, then 24 g of di-tert-butyl peroxide was dissolved in 100 ml of heptane, and the solution was dropped from the dropping funnel. It took about 30 minutes.
At this time, the inside of the system was kept at 180 ° C., and the reaction was continued for another 1 hour.
Unreacted maleic anhydride was removed over 30 minutes. Next, this ethylene-propylene copolymer grafted with maleic anhydride was charged into methyl ketone ethyl 12 kg,
After stirring at 80 ° C for 2 hours, remove methyl ethyl ketone
Dry at 12 ° C. for 12 hours. At this time, the graft amount of maleic anhydride was 2.9% by weight. Next, this maleic anhydride grafted ethylene-propylene copolymer is heated to 50 ° C.
It was left under an atmosphere of 90% humidity for 2 weeks to open maleic anhydride.

Next, this resin was charged into a glass-lined reaction vessel, 100 L of chloroform was added, and 2 kg / cm ² -110
After sufficiently dissolving under the condition of ° C, chlorine gas is blown in from the bottom of the reactor while irradiating ultraviolet rays, and chlorine content is 21.3% by weight.
Reaction solution (A) was obtained. The weight average molecular weight was 65,000, and components having a weight average molecular weight of 2000 or less were 1%.

(Production Example 2) 6 kg of an ethylene-propylene copolymer having a melt viscosity at 180 ° C. of about 2100 mPa · s and an ethylene content of 3 mol% was cooled with a stirrer, a dropping funnel and a monomer for reflux. The mixture was placed in a three-necked flask equipped with a tube and completely melted in an oil bath kept constant at 180 ° C. After performing nitrogen replacement in the flask for about 10 minutes, 300 g of maleic anhydride was added over about 5 minutes while stirring, then 30 g of di-tert-butyl peroxide was dissolved in 100 ml of heptane, and the solution was dropped from a dropping funnel. It took about 30 minutes. At this time, the inside of the system was maintained at 180 ° C., and the reaction was further continued for 1 hour. Then, unreacted maleic anhydride was removed over about 30 minutes while reducing the pressure inside the flask with an aspirator. Next, this ethylene-propylene copolymer grafted with maleic anhydride was charged into 12 kg of methyl ketone ethyl, stirred at 80 ° C. for 2 hours, and then dried at 70 ° C. for 12 hours except for methyl ethyl ketone.

Next, this product was subjected to a chlorination reaction according to the method of Production Example 1 to obtain a reaction solution (B) having a chlorine content of 22.4% by weight and a grafted amount of maleic anhydride of 3.8% by weight. The weight average molecular weight was 56000, and components having a weight average molecular weight of 2000 or less were 1%.

<Examples 1 to 5, Comparative Examples 1 and 2> Reaction solution A
Then, after adding each of the stabilizers shown in Table 1 previously dissolved and dispersed in chloroform, the reaction solvent was completely removed with a vented extruder equipped with a vent port for distilling off chloroform under reduced pressure. The chlorinated polypropylene composition was extruded into strands, cooled with water, and pelletized with a water-cooled pelletizer (Model: KM-150, manufactured by Katsu Seisakusho Co., Ltd.).
A propylene copolymer solid was obtained. Absorbance ratio (abs1710
cm-1) / (abs1780cm-1) were all 2.0.

<Examples 6 to 10, Comparative Examples 3 and 4> Reaction solution
Add 3 L of water to B, stir for 3 hours, concentrate with an evaporator, add each of the stabilizers shown in Table 1 previously dissolved and dispersed in chloroform, and replace chloroform, which is the reaction solvent, with toluene. And the solids concentration is 20
By weight (toluene solution), seven types of maleic anhydride-modified chlorinated ethylene-propylene copolymers were obtained. Absorbance ratio (ab
s1710cm-1) / (abs1780cm-1) were all 1.3.

<Examples 11 to 15> After the reaction solution B was concentrated by an evaporator, the stabilizers shown in Table 1 previously dissolved and dispersed in chloroform were added, and the reaction solvent chloroform was added to toluene. After substitution, five types of maleic anhydride-modified chlorinated ethylene-propylene copolymers having a solid content of about 30% by weight (toluene solution) were obtained. 100 ml of water was added to 10 L of each toluene solution, followed by stirring for 3 hours. Thereafter, the solid content concentration was adjusted to 20% by weight (toluene solution). Absorbance ratio (abs1710cm-1) / (abs1780cm-
1) were all 1.5.

<Comparative Examples 5 to 6> After the reaction solution B was concentrated by an evaporator, each of the epoxy compounds shown in Table 1 previously dissolved in chloroform was added, and chloroform as a reaction solvent was replaced with toluene. Two types of maleic anhydride-modified chlorinated ethylene-propylene copolymers having a solid content of about 30% by weight (toluene solution) were obtained. 100 ml of water was added to 10 L of each toluene solution, followed by stirring for 3 hours. Thereafter, the solid content concentration was adjusted to 20% by weight (toluene solution). Absorbance ratio (abs1710cm-1) / (abs1780cm-
1) were all 1.4.

<Comparative Examples 7 to 13> After the reaction solution B was concentrated by an evaporator, the stabilizers shown in Table 1 previously dissolved and dispersed in chloroform were added, and the reaction solvent chloroform was replaced by toluene. Thus, seven types of maleic anhydride-modified chlorinated ethylene propylene copolymers having a solid content of 20% by weight (toluene solution) were obtained. Ring opening operation with water was not performed. Absorbance ratio (abs1710cm-
1) / (abs1780cm-1) was all 0.02.

[0057]

[Table 1]

<Paint Test 1> Examples 1 to 5 and Comparative Example 1
100 g of a resin solution prepared by dissolving the solid product prepared in Examples 2 to 2 into a 20% solution by dissolving it in toluene, or the resin solution immediately after production prepared in Examples 6 to 15 and Comparative Examples 3 to 13 (solid content of 20%).
%) 10 g of titanium dioxide was added to 100 g, and the mixture was kneaded with a sand mill for 3 hours. The viscosity was adjusted with xylene at 13 to 15 seconds / 20 ° C with a No. 4 Ford cup, and a polypropylene plate (T
(X-933A, manufactured by Mitsubishi Chemical Corporation) using an air spray gun so that the film thickness was about 10 μm. Next, a two-component curable urethane paint was applied (film thickness: about 30 μm). 30 at 80 ° C
After drying for minutes, it was left at room temperature for 24 hours to evaluate the physical properties. Table 2 shows the results of the primer test.

<Paint Test 2> The paint used in Paint Test 1 was used.
After leaving at 40 ° C for 10 days, the paint is
(TX-933A, manufactured by Mitsubishi Chemical Corporation) using an air spray gun so that the film thickness was about 10 μm. Next, a two-component curable urethane paint was applied (film thickness: about 30 μm). 3 at 80 ° C
It was dried for 0 minutes and left at room temperature for 24 hours to evaluate its physical properties.
Table 2 shows the results of the primer test.

<Coating Test 3> Examples 1 to 5 and Comparative Example 1
The solid product prepared in the above-mentioned 2 was left at 40 ° C. for 10 days, and then dissolved in toluene to prepare a 20% solution, or the resin solution prepared in Examples 6 to 15 and Comparative Examples 3 to 13 was dissolved in 40%. A test piece was prepared and evaluated for physical properties in the same manner as in the paint test 1, except that a test piece left at 10 ° C for 10 days was used. Table 2 shows the results of the primer test.

[0061]

[Table 2]

● Adhesion 100 cross grids reaching the base at 1 mm intervals on the painted surface
A cellophane adhesive tape was adhered thereon and peeled off in the 180 ° direction, and the degree of the remaining coating film was judged.

Solvent resistance Painted plates were converted to regular gasoline / methanol = 9/1 (v / v)
After immersion for 0 minutes, the state of the coating film was observed.

[0064]

According to the results shown in Table 2, when an epoxy compound is used as a stabilizer, gasohol properties are good immediately after production of an acid-modified chlorinated polyolefin even when used as a primer. However, when stored for a long period of time, or when a long time has elapsed after the production of the coating material, the gasohol resistance is reduced. On the other hand, when metal soaps, inorganic acid salts, organometallic compounds or hydrotalcite compounds are used, gasohol resistance is good even after long-term storage.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/56 C08K 5/56 C08L 51/06 C08L 51/06 (72) Inventor: Isao Onodera Iwakuni, Yamaguchi Prefecture 2-8-1 Iidacho Nippon Paper Industries Co., Ltd. Chemical Development Laboratory (72) Inventor Kazunori Shiraishi 2-8-1 Iidacho, Iwakuni-shi, Yamaguchi Prefecture Nippon Paper Industries Co., Ltd. Chemical Development Laboratory (72) Inventor Urata Keiji 2-8-1 Iida-cho, Iwakuni-shi, Yamaguchi Prefecture Nippon Paper Industries Co., Ltd. Chemicals Research Laboratory F-term (reference) 4J002 BN101 DE286 DG046 DJ006 EG026 EG036 EG046 EZ046 FD036 GH00 GH01 4J100 AA02Q AA03P AA04Q AA07Q AA01AQAAQAAQA CA04 CA31 HA21 HA42 HA61 HC29 HC30 HC36

Claims (6)

[Claims] 1. An acid-modified chlorinated polyolefin having a chlorine content of 5 to 50% by weight and a grafted amount of an α, β-unsaturated carboxylic anhydride of 1 to 10% by weight, wherein the grafted α, For 100 parts by weight of the acid-modified chlorinated polyolefin in which a part of the β-unsaturated carboxylic anhydride is ring-opened with water, metal soaps, inorganic acid salts, organometallic compounds or hydrotalcite compounds are used. 0.1 alone or mixed
An acid-modified chlorinated polyolefin composition having good solvent resistance, which is blended in an amount of from 10 to 10 parts by weight. 2. An absorbance ratio (abs17) in the spectrum of an acid-modified chlorinated polyolefin measured by infrared absorption spectroscopy.
The acid-modified chlorinated polyolefin composition having good solvent resistance according to claim 1, wherein (10 cm-1) / (abs1780 cm-1) is 0.05 to 100. 3. The acid-modified chlorinated polyolefin composition having good solvent resistance according to claim 1, wherein a component having a molecular weight of 2,000 or less as measured by gel permeation chromatography is 2% or less. 4. The raw material of the acid-modified chlorinated polyolefin,
The acid-modified chlorinated polyolefin composition having good solvent resistance according to any one of claims 1 to 3, wherein the composition is crystalline polypropylene or a propylene-α-olefin copolymer containing 50 to 98 mol% of a propylene component. 5. The composition according to claim 1, wherein the α, β-unsaturated carboxylic anhydride is maleic anhydride. 6. The composition according to claim 1, wherein the acid-modified chlorinated polyolefin composition is a solidified product.