JP2001114961A - Binder resin composition and its preparation method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel binder resin composition. SOLUTION: This composition comprises an organic solvent and a carboxyl- group-containing chlorinated syndiotactic polyolefin resin having a chlorine content of 0.1-40 wt.%, a content of a grafted α,β-unsaturated carboxylic acid and/or its anhydride of 0.5-10 wt.%, and a wt. average mol.wt. of 30,000-220,000. A carboxyl-group-containing chlorinated syndiotactic polyolefin produced by using a metallocene compound has a good liquid state even when the chlorine content is low, and is excellent in adhesion to polyolefin materials and in solvent resistance.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a binder resin composition used for painting a polyolefin molding and a method for producing the same.

[0002]

2. Description of the Related Art Plastics are widely used in recent years as materials for automobile parts, electric parts, building materials and the like because they have many advantages such as light weight, rust prevention and wide design flexibility. In particular, polyolefin resins are widely used as industrial materials because they have many excellent properties such as low cost, excellent moldability, chemical resistance, heat resistance, water resistance, and good electrical properties, The demand is expected to grow in the future. However, unlike synthetic resins having polarity, polyolefin resins also have the drawback that coating and bonding are difficult because they are non-polar and crystalline.

As a pretreatment for painting or bonding, a method of activating the surface of a molded article by plasma treatment or gas flame treatment, or a method of painting a primer (undercoat) containing chlorinated polyolefin as a main component is known. Has been adopted.

[0004] For the coating of polypropylene bumpers for automobiles, for example, JP-A-57-36128 and JP-B-63-36624 disclose a primer composition containing a chlorinated modified polyolefin as a main component.

[0005] Although chlorinated primers have excellent adhesion to polyolefins,
Recently, with the increase in rigidity of the material, there has appeared a material that does not have sufficient adhesion of a primer, and the conventional chlorinated polyolefin-based resin cannot sufficiently cope with the primer.

[0006] As described above, at present, a strong adhesive force cannot be obtained for some materials with the conventional chlorinated polyolefin resin or its derivative.

[0007]

The above-mentioned primer composition and the like proposed so far have been obtained by chlorinating isotactic polypropylene (IPP) produced using a Ziegler-Natta catalyst as a polymerization catalyst. The main component was tactic polypropylene. In recent years, metallocene compounds have been developed as polymerization catalysts for polyolefins, and are disclosed in JP-A-7-138325 and JP-A-7-138325.
No. 149975 discloses a polymerization example of syndiotactic polypropylene (SPP) produced using a metallocene compound as a polymerization catalyst. This SPP has a narrower molecular weight distribution than IPP, and can control the molecular weight arbitrarily.
It is characterized by having a low glass transition point and is excellent in transparency when formed into a resin molded product.

[0008] One method of using the SPP is disclosed in
JP 18016 discloses examples of adhesives using chlorinated products of syndiotactic polypropylene. However, since these adhesives are simply chlorinated syndiotactic polypropylene, they have the drawback that they do not adhere to the topcoat when used as a primer when painting PP moldings. I have.

An object of the present invention is to provide a binder resin composition having excellent solvent solubility, excellent adhesion to a polypropylene-based material, and excellent adhesion to a top coat.

[0010]

Means for Solving the Problems The present inventors have found that the content of chlorine is 0.1 to 40% by weight, and the amount of grafting of α, β-unsaturated carboxylic acid and / or its anhydride is 0.5 to 10% by weight ( However, when the chlorine content is 10 to 40% by weight and the amount of grafted α, β-unsaturated carboxylic acid and / or acid anhydride is 1 to 10%
Weight%), weight average molecular weight 30,000-2
The above problem has been solved by a binder resin composition comprising a carboxyl group-containing chlorinated syndiotactic polyolefin resin of 20000 and an organic solvent.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The polyolefin resin as a raw material of the present invention is a syndiotactic polyolefin produced using a metallocene catalyst as a polymerization catalyst. Syndiotactic polypropylene (SPP) or a propylene-α-olefin copolymer produced using a metallocene catalyst as a polymerization catalyst can be used alone or as a mixture of two or more.

The α-olefin component used in the propylene-α-olefin copolymer is, for example, ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 3-methyl-1-pentene and 1-methyl-1-pentene. At least one kind selected from hexene,
Α-olefins having 2 or 4 to 6 carbon atoms are preferred, and the ratio of the propylene component to the α-olefin component in the copolymer is not particularly limited, but the propylene component is desirably 50 mol% or more.

[0013] The metallocene catalyst used herein is the second metallocene catalyst.
Random copolymerization with narrower molecular weight distribution compared to conventional Ziegler-Natta catalysts in the polymerization of olefins.This catalyst combines a metallocene compound of a Group 4 transition metal with methylaluminoxane obtained by hydrolyzing trimethylaluminum. It has the characteristics that it has excellent properties and a narrow composition distribution, and has a wide range of copolymerizable comonomers.

The syndiotactic polyolefin resin used in the binder resin composition of the present invention can be produced by a known method using a metallocene catalyst. As a specific resin, tiaro (trade name of syndiotactic polypropylene manufactured by Mitsui Chemicals, Inc.) can be used.

The binder resin composition of the present invention can be obtained by introducing an α, β-unsaturated carboxylic acid and / or an acid anhydride thereof and chlorine into the above syndiotactic polyolefin resin. It can be manufactured by two methods. That is, after the graft polymerization of α, β-unsaturated carboxylic acid and / or an acid anhydride thereof onto the syndiotactic polyolefin resin in advance, a chlorination reaction (first method) and a chlorination reaction are performed. Then, α, β-unsaturated carboxylic acid and / or its acid anhydride is graft-polymerized (second method).

The specific manufacturing method will be described below.
In the first method, first, a method of graft copolymerizing an α, β-unsaturated carboxylic acid or an anhydride thereof onto a syndiotactic polyolefin resin is performed by heating and melting the resin to a melting point or higher in the presence of a radical generator. A known method such as a method of reacting (melting method), a method of dissolving the resin in an organic solvent, and heating and stirring in the presence of a radical generator to cause a reaction (solution method) can be used.

In the case of the melting method, a Banbury mixer,
Since the reaction is carried out in a short time at a temperature not lower than the melting point and not higher than 400 ° C. by using a kneader or an extruder, 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-butylcumyl 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-butylperoxyisopropyl carbonate,
Cumyl peroxy octoate and the like.

However, in the case of the solution method, after the α, β-unsaturated carboxylic acid and / or its anhydride is graft-copolymerized, when the next chlorination reaction is carried out, chlorination of chloroform or the like from the above solvent is carried out. Since it is necessary to replace with a solvent, the melting method is preferred in the first method.

In the subsequent chlorination reaction, a syndiotactic polyolefin resin obtained by graft copolymerizing an α, β-unsaturated carboxylic acid and / or an acid anhydride thereof is dissolved in a chlorinated solvent such as chloroform. It is carried out while irradiating or by blowing gaseous chlorine in the presence of the above-mentioned organic peroxide.

In the second method, in which a chlorination reaction is carried out and then an α, β-unsaturated carboxylic acid and / or an acid anhydride thereof is graft-polymerized, first, a syndiotactic polyolefin resin is treated with chlorine such as chloroform. After dissolving in a system solvent and performing a chlorination reaction in the same manner as in the first method to produce a chlorinated syndiotactic polyolefin resin, the solvent is changed to a solvent such as toluene or xylene, and then the α, β- Graft copolymerization of a saturated carboxylic acid and / or an acid anhydride thereof is performed in the presence of the above-mentioned 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.

In the first method and the second method, the purpose of graft copolymerizing an α, β-unsaturated carboxylic acid and / or an anhydride thereof with a syndiotactic polyolefin resin is to prepare a binder resin composition of the present invention. This is because when using as a primer, adhesion to the top coat is imparted. Chlorinated polyolefins are inherently low in polarity,
When used as it is as a primer (undercoat), it has good adhesion to the PP material, but hardly adheres to highly polar topcoats (eg, polyurethane paint, melamine paint). Therefore, it is important to increase the polarity of the chlorinated polyolefin by graft copolymerizing an α, β-unsaturated carboxylic acid and / or an acid anhydride thereof.

Α, β-unsaturated carboxylic acids and
/ Or as the acid anhydride, for example, maleic acid,
Examples thereof include citraconic acid, itaconic acid, aconitic acid and their acid anhydrides, acrylic acid, methacrylic acid, fumaric acid, mesaconic acid, etc., and maleic anhydride is most suitable in consideration of the graftability to a polyolefin resin.

In the present invention, the amount of the α, β-unsaturated carboxylic acid and / or its anhydride to be introduced by graft copolymerization is optimally 0.5 to 10% by weight. 0.5% by weight
If the amount is less than the above, sufficient adhesion between the obtained primer composition and the top coat is not obtained. If the amount is more than 10% by weight, the moisture resistance tends to decrease when used as a primer.

The lower the chlorine content of the carboxyl group-containing chlorinated syndiotactic polyolefin resin, the better the adhesion to the polypropylene resin, but the lower the solubility in organic solvents, and the higher the chlorine content. The chlorine content is optimally 0.1 to 40% by weight, preferably 1 to 30% by weight, because the adhesion to the polypropylene resin is reduced.

The weight average molecular weight of the obtained carboxyl group-containing chlorinated syndiotactic polyolefin resin measured by gel permeation chromatography (GPC) was 30 based on polystyrene resin as a standard.
It is preferably from 000 to 220,000. If it is less than 30,000, the cohesive strength of the resin is insufficient, and if it is more than 220,000, spray workability is undesirably reduced.

The composition of the present invention is usually used by dissolving it in an organic solvent. The solution concentration may be appropriately selected depending on the application, but 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 used is preferably an aromatic solvent such as toluene and xylene. In addition, an ester solvent such as ethyl acetate and butyl acetate, a ketone solvent such as methyl ethyl ketone and methyl isobutyl ketone, and a solvent such as n-hexane and heptane Aliphatic solvents such as aliphatic solvents, 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. It is preferable to mix the above and add 1 to 20% to the above solvent.

The binder resin composition of the present invention is a resin composition dissolved in an organic solvent. The production of the resin composition is possible by converting a chlorinated solvent such as chloroform as a reaction solvent into the above-mentioned solvent by utilizing a difference in boiling points. Further, after adding an epoxy compound or the like as a stabilizer to the reaction solution after the reaction, the mixture is supplied to an extruder with a vent having a suction part for solvent removal on a screw shaft part, solidified, and dissolved in the solvent. Is also good. The method of solidification is a known method already known, for example, a vented extruder equipped with a submerged cut pelletizer at the outlet of the extruder,
It can be carried out using a vented extruder, a pelletizer for cutting strand-shaped resin, and the like.

The chlorinated polyolefin used in the binder resin composition of the present invention deteriorates with dehydrochlorination when exposed to ultraviolet light or high heat. If the chlorinated polyolefin is degraded by dehydrochlorination, the coloring of the resin will cause the deterioration of the working environment due to the release of hydrochloric acid as well as the deterioration of the physical properties such as the decrease in adhesion to the PP material. is there. Particularly preferred as stabilizers are epoxy compounds.

The epoxy compound is not particularly limited, but is preferably compatible with the chlorinated resin and has an epoxy equivalent of 10
Epoxy compounds having about 0 to 500 and having one or more epoxy groups in one molecule can be exemplified. For example, epoxidized soybean oil and epoxidized linseed oil obtained by epoxidizing a vegetable oil having a natural unsaturated group with a peracid such as peracetic acid. Epoxidized fatty acid esters obtained by epoxidizing unsaturated fatty acids such as oleic acid, tall oil fatty acid and soybean oil fatty acid. Epoxidized alicyclic compounds represented by epoxidized tetrahydrophthalate. Bisphenol A or a polyhydric alcohol condensed with epichlorohydrin, for example, bisphenol A glycidyl ether, ethylene glycol glycidyl ether, propylene glycol glycidyl ether, glycerol polyglycidyl ether, sorbitol polyglycidyl ether and the like are exemplified. Also, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, sec-butyl phenyl glycidyl ether, tert-butyl phenyl glycidyl ether, typified by phenol polyethylene oxide glycidyl ether, etc. Monoepoxy compounds are exemplified. Further, used as a stabilizer of polyvinyl chloride resin, calcium stearate, metal soaps such as lead stearate, organic metal compounds such as dibutyltin dilaurate, dibutylmalate, and hydrotalcite compounds can also be used. These may be used in combination.

The binder resin composition according to the present invention may be used as it is by coating, but may be a solvent, a pigment,
Other additives may be added and used. Further, the composition alone shows well-balanced coating film properties, but if necessary, cyclized rubber, petroleum resin, cumarone indene resin,
Chlorinated polyolefin resin, acrylic resin, alkyd resin and the like may be further added and used.

[0034]

[Action] One of the features of syndiotactic polypropylene (SPP) is that it has slightly lower crystallinity and a lower softening temperature than isotactic polypropylene (IPP). Therefore, even if the chlorine content is extremely low, the solubility in the solvent is good. Moreover, since the chlorine content can be set low, the adhesion to the polyolefin-based material is also good. It is also considered that the overcoat adhesion was obtained by increasing the polarity of the resin by graft copolymerizing the α, β-unsaturated carboxylic acid and / or its anhydride.

SPP has a very narrow molecular weight distribution (Mw /
Mn = about 2). In the present invention, it has been found that the narrow molecular weight distribution of the chlorinated SPP contributes to high adhesion. That is, the low molecular weight component is disadvantageous to the adhesion to the material and the gasoline resistance, and the chlorinated IPP containing a large amount of the low molecular weight component has poor solvent resistance and the like.

[0036]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.

[Example 1] Syndiotactic polypropylene (MI: 3.7 g / 10 mi manufactured by SPP Mitsui Chemicals, Inc.)
n) is supplied to a twin-screw extruder (L / D = 34, φ40 mm, first barrel to seventh barrel), the residence time is 10 minutes, and the barrel temperature is 350 ° C (first barrel).
Thermal decomposition was carried out in a barrel (7th barrel to 7th barrel) to obtain an SPP having a melt viscosity at 190 ° C. of about 2000 mPa · s. 5 kg of this resin was heated and dissolved at 190 ° C. in a four-necked flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel. After performing nitrogen replacement in the flask for 10 minutes, 250 g of maleic anhydride was added over about 5 minutes with stirring, and di-radical was used as a radical generator.
20 g of t-butyl peroxide was added dropwise over about 30 minutes.
After the reaction was further continued for 30 minutes, unreacted maleic anhydride was removed while reducing the pressure in the flask with an aspirator. Next, this product was charged into a glass-lined reaction vessel, 50 L of chloroform was added thereto, and gaseous chlorine was blown from the bottom of the reaction vessel while irradiating ultraviolet rays under a pressure of ² kg / cm ² to chlorinate. Six extractions were performed on the way, and chloroform, which was a solvent, was distilled off by an evaporator. Then, a 30% by weight toluene solution of chlorinated SPP modified with maleic anhydride by replacing with toluene was obtained. Epicoat 828 (manufactured by Yuka Shell Epoxy Co., Ltd.) was added as a stabilizer in an amount of 4% based on the resin. Table 1 shows the chlorine content, the grafted amount of maleic anhydride, and the weight average molecular weight of the obtained resin. The obtained resin solution was allowed to stand at room temperature for one month, but no change was observed in the liquid state and appearance.

The obtained resin solution (solid content 30%) or 1
After 100g of the resin solution (solid content 30%) which had been left for a month and 20g of titanium dioxide were kneaded with a sand mill for 3 hours, the viscosity was adjusted with xylene to 13-15 seconds / 20 ° C with a NO. A test plate extruded with tactic polypropylene (MI: 3.7 g / 10 min, manufactured by Mitsui Chemicals, Inc.) has a film thickness of about 10 with an air spray gun.
It was painted to a thickness of μm. Next, a two-component curable urethane paint was applied (film thickness: about 30 μm). It was dried at 80 ° C. for 30 minutes and left at room temperature for 24 hours to evaluate its physical properties. Table 2 shows the results of the primer test.

The paint whose viscosity was adjusted as described above was applied to an ultra-high-rigidity polypropylene plate (TX-933A, manufactured by Mitsubishi Chemical Corporation) with an air spray gun so that the film thickness became about 10 μm. Next, a two-part curable urethane paint was applied
(Thickness: about 30 μm). It was dried at 80 ° C. for 30 minutes and left at room temperature for 24 hours to evaluate its physical properties. Table 3 shows the results of the primer test.

[Example-2] Syndiotactic polypropylene (MI: 3.7 g / 10 mi manufactured by SPP Mitsui Chemicals, Inc.)
n) Charge 5 kg into a glass-lined reaction vessel, and add 50 L
Was added, and gaseous chlorine was blown from the bottom of the reaction vessel while irradiating with ultraviolet rays under a pressure of ² kg / cm ² to perform chlorination. Six extractions were performed on the way, and chloroform, which was a solvent, was distilled off with an evaporator and replaced with toluene to obtain a 30% by weight toluene solution of chlorinated SPP. Each chlorine content 14.2, 18.2, 20.8, 22.3, 25.1, 32.2
wt%.

333 g of a 30% toluene solution of chlorinated SPP having a chlorine content of 6 levels obtained by the above reaction was stirred,
Each was charged into a four-necked flask equipped with a condenser, a thermometer and a dropping funnel, and heated to 90 ° C. with stirring. 10 g, 8 g, 6 g, 4 g, 4 g, and 5 g of maleic anhydride were added and dissolved, and 4 g, 4 g, 3 g, 5 g, 1 g, and 1 g of benzoyl peroxide were added as radical generators to start the reaction. did. After stirring at 90 ° C. for 3 hours, the solution concentration was adjusted to 30% with toluene. Epiol SB (manufactured by NOF Corporation) was added as a stabilizer in an amount of 4% based on the resin.

Table 1 shows the chlorine content, the grafted amount of maleic anhydride, and the weight average molecular weight of the obtained resin. The obtained resin solution was allowed to stand at room temperature for one month, but no change was observed in the liquid state and appearance. Further, a primer test was performed in the same manner as in Example 1. The results are shown in Tables 2 and 3.

[Example-3] Syndiotactic polypropylene (MI: 3.7 g / 10 mi manufactured by SPP Mitsui Chemicals, Inc.)
n) For 10 kg, resin pellets mixed at a ratio of 0.6 kg of maleic anhydride and 0.2 kg of di-t-butyl peroxide were mixed in a twin-screw extruder (L / D = 34, φ40 mm, first barrel to seventh barrel). , Seventh
The barrel was equipped with a vent for deaeration) to carry out the reaction. The reaction was carried out at a residence time of 10 minutes and a barrel temperature of 190 ° C. (first to seventh barrels). In the seventh barrel, the remaining unreacted maleic anhydride was removed by a vacuum operation. The resulting product has a melt viscosity at 190 ° C of about 3000 mPas and a maleic anhydride-modified SPP having a grafting amount of maleic anhydride of 4%.
I got

5 kg of this resin was charged into a glass-lined reaction vessel, 50 L of chloroform was added, and gaseous chlorine was blown from the bottom of the reaction vessel while irradiating with ultraviolet rays under a pressure of ² kg / cm ² to chlorinate. Six extractions were performed on the way, and chloroform, which was a solvent, was distilled off by an evaporator. Then, a 30% by weight toluene solution of chlorinated SPP modified with maleic anhydride by replacing with toluene was obtained. Epicoat 828 (manufactured by Yuka Shell Epoxy Co., Ltd.) was added as a stabilizer in an amount of 4% based on the resin.

Table 1 shows the chlorine content, the grafted amount of maleic anhydride, and the weight average molecular weight of the obtained resin. The obtained resin solution was allowed to stand at room temperature for one month, but no change was observed in the liquid state and appearance. Further, a primer test was performed in the same manner as in Example 1. The results are shown in Tables 2 and 3.

Comparative Example 1 The melt viscosity at 190 ° C. was about 23
00 kg / s isotactic polypropylene (IPP) 5 kg
Was heated and dissolved at 190 ° C. in a four-necked flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel. After purging with nitrogen in the flask for 10 minutes, 250 g of maleic anhydride was added over about 5 minutes while stirring, and 20 g of di-t-butyl peroxide as a radical generator was added dropwise over about 30 minutes. After the reaction was further continued for 30 minutes, unreacted maleic anhydride was removed while reducing the pressure in the flask with an aspirator. Next, this product was charged into a glass-lined reaction vessel, 50 L of chloroform was added thereto, and gaseous chlorine was blown from the bottom of the reaction vessel while irradiating ultraviolet rays under a pressure of ² kg / cm ² to chlorinate. On the way, extraction was performed four times, and chloroform as a solvent was distilled off by an evaporator, and a 30% by weight toluene solution of chlorinated IPP modified with maleic anhydride by replacement with toluene was obtained. Epiol SB (manufactured by NOF Corporation) as a stabilizer, 4% of resin
Was added.

Table 1 shows the chlorine content, the grafted amount of maleic anhydride, and the weight average molecular weight of the obtained resin. The obtained resin solution was allowed to stand at room temperature for one month, but no change was observed in the liquid state and appearance. Further, a primer test was performed in the same manner as in Example 1. The results are shown in Tables 2 and 3.

Comparative Example 2 Syndiotactic Polypropylene (MI: 3.7 g / 10 min, manufactured by SPP Mitsui Chemicals, Inc.)
The twin screw extruder (L / D = 34, φ40mm, 1st barrel to 7th barrel)
And a thermal degradation was carried out under the conditions of a residence time of 10 minutes and a barrel temperature of 350 ° C. (first to seventh barrels) to obtain SPP having a melt viscosity at 190 ° C. of about 2000 mPa · s. Then this SPP5kg
Was charged into a glass-lined reaction vessel, 50 L of chloroform was added, and gaseous chlorine was blown from the bottom of the reaction vessel while irradiating with ultraviolet rays under a pressure of ² kg / cm ² to chlorinate. The solvent was extracted four times on the way, and chloroform, which was a solvent, was distilled off using an evaporator. Then, the solvent was replaced with toluene to obtain a 30% by weight toluene solution of chlorinated SPP. Epicoat 828 (made by Yuka Shell Epoxy Co., Ltd.) as a stabilizer
Was added to the resin at 4%.

Table 1 shows the chlorine content and the weight average molecular weight of the obtained resin. The obtained resin solution was allowed to stand at room temperature for one month, but no change was observed in the liquid state and appearance. Further, a primer test was performed in the same manner as in Example 1. The results are shown in Tables 2 and 3.

[Comparative Example 3] The same operation as in Example 1 was carried out to obtain 6 levels of chlorinated SPP modified with maleic anhydride having a chlorine content in the range of 14 to 34 wt%. No compound was added.

Table 1 shows the chlorine content and the weight average molecular weight of the obtained resin. When this resin solution was allowed to stand at room temperature for one month, all the resin solutions turned reddish brown.
A primer test was carried out in the same manner as in Example 1 for the resin solution immediately after the production and the resin solution left at room temperature for one month. The results are shown in Tables 2 and 3.

[0052]

【table 1】

[0053]

[Table 2]

[0054]

[Table 3]

[0055]Adhesiveness  Make 100 grids that reach the base at 2 mm intervals on the painted surface,
Adhere the cellophane adhesive tape on top of it and move it 180 °
It was determined by the degree of peeling and remaining of the coating film.・Gasoline resistance  Painted plate to regular gasoline / ethanol = 9/1 (v / v) 12
After immersion for 0 minutes, the state of the coating film was observed.・Moisture resistance  Immerse the coated board in 40 ° C warm water for 240 hours,
The adhesion was examined.

[0056]

According to the results of Table 1, the chlorinated product of SPP is good in liquid even if the chlorine content is low. From the results of Table 2, the chlorinated SPP containing carboxyl group shows good adhesion to SPP material and overcoating. Carboxyl group-containing chlorinated IP
It turns out that it is better than P. Further, from the results in Table 3, it was found that the carboxyl group-containing chlorinated SPP had excellent adhesion to the conventional ultra-rigid PP material. These results indicate that the carboxyl group-containing chlorinated syndiotactic polyolefin of the present invention is a useful resin as a binder resin.

Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat II (Reference) C09D 151/06 C09D 151/06 163/00 163/00 F term (Reference) 4J002 BB241 BN051 BN091 CD052 CD162 EA016 EA026 EA056 EE026 EL027 4J028 AA01A AB00A AB01A AC01A AC08A AC09A AC10A AC18A AC19A AC20A AC26A AC27A AC28A BA00A BA01B BB00A BB01B BC25B EB02 EB05 EB08 EB09 EB10 GA12 4J038 CB091 CB171 DB02 GA02 4DB02 DB02 DB02 GA02 PB05 PB07 PB09 PC08

Claims (4)

[Claims] A chlorine content of 0.1 to 40% by weight, and a grafting amount of α, β-unsaturated carboxylic acid and / or an acid anhydride thereof of 0.5 to 10% by weight (provided that the chlorine content is 10 to 40% by weight). % And a grafting amount of α, β-unsaturated carboxylic acid and / or an acid anhydride thereof is 1 to 10% by weight), and a carboxyl group-containing chlorinated syndiotactic having a weight average molecular weight of 30,000 to 220,000. A binder resin composition comprising a tic polyolefin resin and an organic solvent. 2. The binder resin composition according to claim 1, further comprising an epoxy compound as a stabilizer. 3. A syndiotactic polyolefin produced using a metallocene compound as a polymerization catalyst,
α, β-unsaturated carboxylic acid and / or its acid anhydride
After graft copolymerization of 0.5 to 10% by weight, the chlorine content is 0.1%.
Chlorinated up to 40% by weight (however, chlorine content is 10-40%)
%, And the grafting amount of the α, β-unsaturated carboxylic acid and / or acid anhydride thereof is 1 to 10% by weight), and the carboxyl group-containing chlorinated syndio having a weight average molecular weight of 30,000 to 220,000. A method for producing a binder resin composition, comprising dissolving an tactic polyolefin resin in an organic solvent. 4. After chlorinating a syndiotactic polyolefin produced using a metallocene compound as a polymerization catalyst to a chlorine content of 0.1 to 40% by weight,
0.5 to 10 unsaturated carboxylic acids and / or their anhydrides
Wt% graft copolymerized (however, chlorine content is 10-40
%, And the grafting amount of the α, β-unsaturated carboxylic acid and / or acid anhydride thereof is 1 to 10% by weight), and the carboxyl group-containing chlorinated syndio having a weight average molecular weight of 30,000 to 220,000. A method for producing a binder resin composition, comprising dissolving an tactic polyolefin resin in an organic solvent.