JP2003327761A - Aqueous dispersion, its manufacturing method and use - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new aqueous dispersion which can realize a high solid content and has good adherence to a polyolefin base material and good gasohol resistance even during low-temperature baking. <P>SOLUTION: The aqueous dispersion contains a dispersion of: a carboxy group-containing chlorinated propylene random copolymer having a chlorine content of 5-40 wt.%, a graft amount of an α,β-unsaturated carboxylic acid or its anhydride of 0.1-20 wt.%, and a weight-average molecular weight of 10,000 to 300,000; and a stabilizer. Its manufacturing method and use are provided. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous dispersion used when coating various types of poorly-adhesive resin moldings such as polypropylene. More specifically, it relates to a primer, a coating material, an ink, and an aqueous dispersion suitable for use as an adhesive when adhering the molded article to another substrate.

[0002]

2. Description of the Related Art Polyolefin resins such as polypropylene have high chemical stability, are inexpensive, have a good balance of physical properties, and are recyclable, so that they are molded parts for automobile parts, household appliances, and miscellaneous goods. The amount of use is increasing mainly in. However, olefin resins are non-polar and have the drawback that they are difficult to paint and bond. Therefore, it is common to use chlorinated polypropylene or acid-modified chlorinated polypropylene as a primer, or as a constituent element of paints, inks, and adhesives.

Conventionally, this chlorinated resin was used by dissolving it in an aromatic organic solvent such as toluene or xylene.
From the viewpoint of environmental problems and safety and hygiene, water-based attempts have been widely made (Japanese Patent Publication No. 8-6009, Japanese Patent Laid-Open No. 5-209006, Japanese Patent Laid-Open No. 5-209006).
6-80738, Patent 2769958, WO90 / 12656, etc.). But,
These water-based resins have a problem that a great deal of energy and time are required compared with solvent-based resins in a drying / baking process after coating on a substrate.

In order to solve this problem, it has been required to make the chlorinated resin aqueous dispersion liquid into a high solid and to cope with low temperature baking. On the other hand, the high rigidity of polyolefin base materials is progressing, and especially under low temperature baking conditions of about 80 to 90 ° C, sufficient adhesion cannot be obtained with conventional aqueous dispersions of chlorinated resin, making it difficult to respond. It has become to. Further, in automotive parts applications, it is required to have gasohol resistance and the like, and it is more difficult to deal with it.

A method of lowering the softening temperature of the raw material polypropylene is effective as one of means for coping with low temperature baking. However, in order to lower the softening temperature in the conventional polymerization method using a Ziegler-Natta catalyst, ethylene or other It is necessary to increase the composition ratio of the α-olefin, and as a result, physical properties such as adhesion and gasohol resistance are deteriorated. If the molecular weight of the chlorinated resin is increased in order to suppress the deterioration of physical properties, poor dispersion may occur due to an increase in melt viscosity in the hydration process, or the viscosity of the final product obtained may increase, making it unsuitable for high solidification.

Further, conventional polypropylene, a copolymer of propylene and ethylene or other α-olefin has a wide molecular weight distribution and a wide molecular weight distribution after acid modification or chlorination, but the presence of a relatively low molecular weight component. As a result, adhesion and solvent resistance are reduced. In particular, the deterioration of gasohol resistance is remarkable, and in order to improve it, a step of removing low molecular weight components by extraction with a solvent or the like is required, which is uneconomical.

On the other hand, syndiotactic polypropylene (hereinafter, SPP) produced by using a metallocene catalyst.
Has a low softening temperature and a narrow molecular weight distribution, and a technique of a primer made of a chlorinated resin using this SPP is disclosed (Japanese Patent No. 3045498). But,
Since most of the base materials are mainly composed of isotactic polypropylene (IPP) produced by using Ziegler-Natta type catalyst, sufficient adhesion cannot be obtained.

As described above, the conventional aqueous dispersion using a chlorinated resin has not been able to obtain good adhesion and gasohol resistance while being compatible with high solidification and low temperature baking.

[0009]

DISCLOSURE OF THE INVENTION The present invention is a novel material which can be made into a high solid and has excellent gas-hole resistance and adhesion to various poorly-adhesive resin base materials such as polypropylene even at low temperature baking. The purpose is to provide an aqueous dispersion.

The inventors of the present invention have conducted extensive studies in order to solve this problem, and as a result, carboxy-containing chlorinated propylene-based random copolymers originating from a propylene-based random copolymer polymerized in the presence of a metallocene catalyst are found. We have found that an aqueous dispersion of a polymer solves this problem. Furthermore, it was found that the aqueous dispersion of the present invention not only exhibits good adhesion to polypropylene substrates, but also to other difficult-to-adhere substrates such as PET.

[0011]

According to the present invention, the following (1) to (8) are provided. (1) Carboxyl group-containing chlorinated propylene having a chlorine content of 5 to 40% by weight, an α, β-unsaturated carboxylic acid or an anhydride thereof grafted amount of 0.1 to 20% by weight, and a weight average molecular weight of 10,000 to 300,000. An aqueous dispersion comprising a random copolymer and a stabilizer. (2) Further contains a surfactant and a basic substance (1)
The aqueous dispersion described. (3) After or before graft copolymerizing 0.1 to 20% by weight of α, β-unsaturated carboxylic acid or its anhydride to a propylene-based random copolymer produced using a metallocene compound as a polymerization catalyst, Chlorine content is chlorinated to 5 to 40 wt%, weight average molecular weight of carboxyl group-containing chlorinated propylene random copolymer having a weight average molecular weight of 10,000 to 300,000, the production of an aqueous dispersion characterized by dispersing in water Method. (4) The method for producing an aqueous dispersion according to (3), wherein a surfactant and a basic substance are further added to the carboxyl group-containing chlorinated propylene random copolymer and dispersed in water. (5) A primer using the aqueous dispersion according to (1) or (2). (6) A paint using the aqueous dispersion according to (1) or (2). (7) An ink using the aqueous dispersion according to (1) or (2). (8) An adhesive using the aqueous dispersion according to (1) or (2).

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION A propylene random copolymer as a raw material of the present invention is obtained by copolymerizing propylene as a main component with another α-olefin as a comonomer using a metallocene catalyst as a polymerization catalyst. Is a propylene-based random copolymer. Commercially available products such as Novatec (manufactured by Nippon Polychem Co., Ltd.) can also be used.

As the other α-olefin which is a comonomer, at least one kind can be selected from the group consisting of ethylene or an olefin having 4 or more carbon atoms. Examples of the olefin having 4 or more carbon atoms include 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and the like. By using a metallocene catalyst, the range of comonomer that can be copolymerized can be expanded as compared with the Ziegler-Natta catalyst.

As the metallocene catalyst used here, known ones can be used. Specifically, a catalyst obtained by combining the following components (A) and (B) and, if necessary, (C) is desirable. Component (A): A metallocene complex which is a transition metal compound of Groups 4 to 6 of the periodic table having at least one conjugated five-membered ring ligand. Component (B): A cocatalyst (ion-exchange layered silicate) capable of activating the metallocene complex (A) by reacting the compound (B) with the metallocene complex (A). Component (C); an organoaluminum compound.

The propylene random copolymer of the present invention can be produced by a known method (JP 2001-206914 etc.). For example, propylene, ethylene,
The production is carried out while continuously supplying alkylaluminum and a metallocene catalyst while supplying hydrogen.

The propylene random copolymer of the present invention preferably has a melting point (hereinafter, Tm) measured by a differential scanning calorimeter (hereinafter, DSC) of 115 to 165 ° C., and the olefin composition and polymerization conditions can be appropriately selected. . If it is higher than 165 ° C, the solvent solubility is lowered. If the temperature is lower than 115 ° C, the adhesion to the material will decrease. More preferably, it is a low melting point propylene random copolymer having a melting point of 115 to 135 ° C.

For the measurement of Tm by DSC in the present invention, a DSC measuring device manufactured by Seiko Denshi Kogyo Co., Ltd. was used to measure 20 mg of a sample of about 5 mg.
Melting peak temperature and melting end temperature when melted at 0 ° C for 5 minutes, cooled to 40 ° C at a rate of 10 ° C / min to crystallize, and then further heated to 200 ° C at 10 ° C / min to melt It was evaluated by.

The propylene random copolymer of the present invention is thermally degraded by a known method in the presence of a radical generator at a temperature of melting point or higher and 350 ° C. or lower using a Banbury mixer, kneader, extruder or the like. Alternatively, those which are not thermally degraded may be used alone or in combination.
The radical generator used in the reaction can be appropriately selected from known ones, and organic peroxide compounds are particularly desirable.

Examples of the organic peroxide compounds include di-t-butyl peroxide, dicumyl peroxide, t-butyl cumyl peroxide, benzoyl peroxide, dilauryl peroxide, cumene hydroperoxide and t. -Butyl hydroperoxide,
1,1-bis (t-butylperoxy) -3,5,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) -cyclohexane, cyclohexanone peroxide, t-butylperoxybenzoate, t- Butyl peroxyisobutyrate, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxy-2-ethyl hexanoate, t-butyl peroxy isopropyl carbonate,
Examples include cumyl peroxy octoate.

In the present invention, the propylene random copolymer obtained as described above may be used alone or in combination of a plurality of types. Especially Tm
Is preferably in the range of 115 to 165 ° C. Further, a mixture of other polyolefins such as IPP and SPP can also be used. Depending on the application, IPP or SPP can be mixed up to 50% by weight in all the resins.

The carboxyl group-containing chlorinated propylene random copolymer of the present invention can be obtained by introducing α, β-unsaturated carboxylic acid and chlorine into the above propylene random copolymer. It can be produced by the following two methods. That is, after preliminarily graft-polymerizing α, β-unsaturated carboxylic acid or an anhydride thereof to a propylene-based random copolymer, a method of performing a chlorination reaction (first method), and after performing a chlorination reaction α,
This is a method (second method) of graft-polymerizing β-unsaturated carboxylic acid or its anhydride. The first method is superior in various physical properties of the final aqueous dispersion.

The specific manufacturing method will be illustrated below.
In the first method, first, a method of graft copolymerizing α, β-unsaturated carboxylic acid or an anhydride thereof to a propylene-based random copolymer can be graft-polymerized with or without a radical initiator, but the initiator It is preferable to use, for example, it is preferable to use an organic peroxide such as benzoyl peroxide, dicumyl peroxide, lauroyl peroxide, di-t-butyl peroxide, cumene hydroperoxide. The type and amount of the radical initiator can be appropriately selected depending on the reaction conditions, but it is desirable to use about 0.1 to 5% by weight based on the propylene random copolymer (solid content). If it is less than the above range, the graft reaction rate is lowered, and if it is more than that, side reactions such as reduction of the graft reaction rate, internal cross-linking and reduction of molecular weight occur. A method in which the resin is heated to a melting point or higher in the presence of a radical generator to cause a reaction (melting method), and the resin is dissolved in an organic solvent, and then heated and stirred in the presence of a radical generator to cause a reaction. It can be performed by a known method such as (solution method).

In the case of the melting method, a Banbury mixer,
Since the reaction is carried out in a short time at a temperature of not lower than the melting point and not higher 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 the organic solvent, but in addition to this, an ester solvent, a ketone solvent or the like may be partially mixed and used. It doesn't matter. The radical generator used in the reaction can be appropriately selected from known ones, and organic peroxide compounds are particularly desirable. As the organic peroxide compound, those mentioned above can be used.

In the case of the solution method, after the α, β-unsaturated carboxylic acid or its anhydride is graft-copolymerized, when the chlorination reaction is carried out, the above solvent is volatilized and replaced with a chlorinated solvent such as chloroform. The melting method is preferable in the first method because it is necessary.

The subsequent chlorination reaction can be easily carried out by a known method. For example, a propylene-based random copolymer obtained by graft-copolymerizing an α, β-unsaturated carboxylic acid or an anhydride thereof is dispersed or dissolved in a medium such as water or chloroform, and pressurized in the presence of a catalyst or under ultraviolet irradiation. Alternatively, it is carried out by blowing chlorine gas under atmospheric pressure in the temperature range of 50 to 130 ° C. If the temperature is lower than 50 ° C, the chlorination reaction becomes non-uniform and the solvent solubility is deteriorated. If the temperature is higher than 130 ° C, the molecular weight is lowered during the chlorination reaction and the adhesiveness and printability are deteriorated.

In the second method of carrying out a chlorination reaction and then graft-polymerizing an α, β-unsaturated carboxylic acid or an anhydride thereof, a propylene random copolymer is first added to a chlorine-based solvent such as chloroform. To produce a chlorinated propylene-based random copolymer by chlorination reaction in the same manner as in the first method, the solvent is changed to a solvent such as toluene, xylene, and then α, β-unsaturated carboxylic acid. Alternatively, the anhydride is subjected to graft copolymerization in the presence of the above organic peroxide. The reaction temperature can be carried out at a temperature of 50 ° C. or higher and the boiling point of the solvent or lower.

In the first method and the second method, α,
The β-unsaturated carboxylic acid or its anhydride, the order of addition of the initiator, the method and the like can be appropriately selected. It is also possible to remove the residual monomers by providing a pressure reduction step at the end of the reaction.

The present invention is characterized in that various physical properties are excellent without providing a low molecular weight component removing step such as solvent extraction. However, it is of course possible to remove the low molecular weight component. When removing low molecular weight components, it is preferable to carry out after graft polymerization of α, β-unsaturated carboxylic acid or its anhydride.

In the present invention, the purpose of graft-copolymerizing an α, β-unsaturated carboxylic acid or its anhydride with a propylene random copolymer is to use a topcoat paint when the aqueous dispersion of the present invention is used as a primer. This is because it imparts adhesiveness with and further enhances dispersibility in water. Chlorinated polyolefin has a low polarity by nature, and when used as it is as a primer (undercoating agent), it has good adhesion to PP materials, but adhesion to highly polar topcoat paints (e.g. polyurethane paint, melamine paint). There is almost no sex. Therefore, it is important to increase the polarity of the chlorinated polyolefin by graft-copolymerizing α, β-unsaturated carboxylic acid or its anhydride. Further, by increasing the polarity of the chlorinated polyolefin, the adhesion to various other non-adhesive substrates such as PET is also imparted.

Examples of the α, β-unsaturated carboxylic acid or its anhydride that can be used include maleic acid, citraconic acid, itaconic acid, aconitic acid and their anhydrides, acrylic acid, methacrylic acid, fumaric acid and mesaconic acid. Can be exemplified. These unsaturated carboxylic acids or their anhydrides can be used alone or in combination, but maleic anhydride is most suitable in consideration of graftability to polyolefin resin.

In the present invention, the amount of the α, β-unsaturated carboxylic acid or its anhydride introduced by graft copolymerization is 0.1 with respect to the raw material propylene random copolymer.
~ 20 wt% is optimal. If the content is less than this range, a good aqueous dispersion cannot be obtained, and the adhesiveness and the like decrease.
On the other hand, if the amount is too large, unreacted unsaturated carboxylic acid or its anhydride is generated in a large amount, and the water resistance is deteriorated, which is not preferable. More preferably, it is 1.0 to 10% by weight.
The graft weight% of the α, β-unsaturated carboxylic acid or its anhydride can be determined by the alkali titration method or the FT-IR method.

The lower the chlorine content of the chlorinated propylene-based random copolymer containing a carboxyl group, the better the adhesion to the polypropylene resin, but if it is too low, the softening point and melting point of the resin will increase, so low-temperature baking will occur. The adhesiveness at that time is reduced. Also, if the chlorine content becomes higher, the adhesion to polypropylene resin will decrease, so the chlorine content will be 5-40%.
Optimally, wt%, preferably 15-30 wt%. The degree of chlorination of the carboxyl group-containing chlorinated propylene random copolymer is determined by titration according to JIS K 7210.

The carboxyl group-containing chlorinated propylene random copolymer used in the present invention has a weight average molecular weight (Mw) of 10,000 to 300,000. If it is less than 10,000, the cohesive force of the resin is insufficient, and if it exceeds 300,000, the handling of the ink and the adhesive is deteriorated, which is not preferable.
The Mw in the present invention is a value measured by gel permeation chromatography (hereinafter, GPC, standard substance: polystyrene resin).

When the chlorinated polyolefin is exposed to ultraviolet rays or high heat, it deteriorates with dehydrochlorination. In particular, when heated in the emulsification process or subjected to mechanical shearing force, it is easy to dehydrochlorinate. When the carboxyl group-containing chlorinated propylene random copolymer is deteriorated by dehydrochlorination, the resin is colored and the physical properties such as the adhesion to the PP substrate are deteriorated. Addition of a stabilizer is indispensable because it causes deterioration and deterioration of working environment. Epoxy compounds are particularly preferred as stabilizers. The epoxy compound is not particularly limited, but those compatible with the chlorinated resin are preferable, and the epoxy equivalent is 100.
Examples thereof include epoxy compounds having about 1 to 500 and having at least one epoxy group in one molecule. 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, soybean oil fatty acid,
Cyclohexene oxide, α-pinene oxide, 3,
Aliphatic epoxy compounds such as 4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, condensed with bisphenol A or polyhydric alcohol and epichlorohydrin, for example, bisphenol A glycidyl ether, ethylene glycol glycidyl ether, propylene glycol glycidyl Examples thereof include ether, glycerol polyglycidyl ether, sorbitol polyglycidyl ether and the like. Others, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether,
Examples are monoepoxy compounds represented by allyl glycidyl ether, phenyl glycidyl ether, s-butylphenyl glycidyl ether, t-butylphenyl glycidyl ether, and phenol polyethylene oxide glycidyl ether. Also used as a stabilizer of polyvinyl chloride resin, calcium stearate, metal soaps such as lead stearate, dibutyltin dilaurate, organometallic compounds such as dibutylmalate, hydrotalcite compounds can also be used, These may be used in combination.

The amount of the epoxy compound used can be appropriately selected depending on the epoxy equivalent and the use conditions, but is 0.1% based on the weight of the carboxyl group-containing chlorinated propylene random copolymer.
~ 10 wt% is preferred. If it is less than 0.1% by weight, it has no effect as a stabilizer, and if it is more than 10% by weight, not only it is uneconomical, but also physical properties may be deteriorated. Epoxy compounds can be added before the emulsification step to capture free hydrochloric acid generated by heat or mechanical shearing force, or by adding a separately epoxidized epoxy compound after emulsification, the pH can be adjusted by free hydrochloric acid during storage or use. Can also be adjusted so that does not change.

In the present invention, the aqueous dispersion containing the carboxyl group-containing chlorinated propylene random copolymer dispersed therein means an emulsion, and can be obtained by a known method. For example, a carboxyl group-containing chlorinated propylene random copolymer is melted at about 100 ° C., a stabilizer, a small amount of an organic solvent, and if necessary, a surfactant and a basic substance are melted and kneaded, and then 80 to 98. ℃
It is possible to use a method in which water is added to form a W / O emulsion, and then phase is changed to an O / W emulsion while adding water.

As the emulsifying device, for example, a cylindrical reactor provided with an anchor type stirring blade or a Maxblend type stirring blade, or a device equipped with a high speed stirring device such as a homogenizer or a disper, for example, Harmotech ( It is possible to use M-Technique), Hibis Dispermix (made by Tokushu Kika Kogyo), Combimix (made by Tokushu Kika Kogyo), and a twin-screw extruder. It is also possible to emulsify at a temperature of 100 ° C or higher under pressure using a device such as an autoclave equipped with a stirring device.

In the present invention, the use of a surfactant at the time of emulsification has the effect of obtaining a more stable aqueous dispersion, and is particularly preferably used when an aqueous dispersion having a high concentration is obtained. As the surfactant, polyoxyalkylene alkyl ester, polyoxyalkylene alkyl ether,
Examples thereof include nonionic surfactants such as polyoxyalkylene alkyl phenyl ether, sucrose ester, sorbitan alkyl ester, sorbitan fatty acid ester, propylene glycol ester, polyglycerin ester, fatty acid alkanolamide, fatty acid monoglyceride and polyoxyalkylene alkylamine. Anionic surfactants, cationic surfactants and amphoteric surfactants can be used in combination with the above nonionic surfactants to improve the dispersibility of the aqueous dispersion, but the water resistance of the coating film is significantly reduced. Therefore, it is limited to very small amounts. The kind and the amount of addition of the surfactant can be appropriately selected, but are 5 to 3 with respect to the carboxyl group-containing chlorinated propylene random copolymer.
0 wt% (relative to solids) is preferred. If less than this,
If the stability of the aqueous dispersion becomes poor, and if it is too large, the water resistance remarkably decreases, which is not preferable.

Further, when the carboxyl group-containing chlorinated propylene random copolymer is emulsified by using the above surfactant together with a basic substance, the carboxyl group is neutralized with the basic substance to improve the dispersibility in water. Can be made. As the basic substance, sodium hydroxide, potassium hydroxide, sodium carbonate, ammonium carbonate, potassium carbonate, ammonia, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine,
Ethanolamine, propanolamine, diethanolamine, N-methyldiethanolamine, dimethylamine, diethylamine, triethylamine, N, N-dimethylethanolamine, 2-dimethylamino-2-methyl-1-propanol, 2-amino-2-methyl-1 −
Examples thereof include propanol and morpholine.
The type and amount of the basic substance used can be appropriately selected, but the pH of the aqueous dispersion is designed to be 6 to 9.5, preferably 7 to 8.5. If the pH is lower than 6, the dispersibility will be reduced, and if it is higher than 9.5, the elimination of hydrochloric acid will be significantly unfavorable.

The concentration of the aqueous dispersion of the present invention may be appropriately selected depending on the application. If the concentration of the dispersion liquid is too high or too low, the coating workability is impaired. Therefore, the solid content concentration of the carboxyl group-containing chlorinated propylene random copolymer is from 5 to 60.
wt% is preferred.

The aqueous dispersion according to the present invention can be used as a primer, a paint, an ink or an adhesive which can be applied to films, sheets and molded products made of various types of poorly adherent resins such as polypropylene and PET. It may be used by coating as it is, but within a range not impairing the effects of the present invention, a solvent for increasing the drying speed, a pigment,
Other additives such as a viscosity modifier, a primary rust preventive, an antifoaming agent, a wettability improver, a flow aid, and a fungicide may be added in a necessary amount. Further, the coating film obtained from the aqueous dispersion shows balanced physical properties by itself, but if necessary, other aqueous resins such as aqueous urethane resin, aqueous blocked isocyanate, aqueous epoxy resin, aqueous acrylic resin,
An aqueous phenol resin, an aqueous amino resin, an aqueous alkyd resin, an aqueous chlorinated rubber, an aqueous silicone resin or the like may be further added and used.

[0043]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited thereto.

[Measurement Method of Physical Properties] MFR (Melt Flow Rate) Measured by the melt flow rate (condition: 230 ° C., weighted 2.16 kgf) of JIS-K-6758 polypropylene test method. -Tm Using a DSC measuring device manufactured by Seiko, a sample (about 5 mg) was taken and melted at 200 ° C for 5 minutes. After that, up to 40 ℃ 10 ℃ /
After cooling at a rate of min to crystallize, further 2 at 10 ° C / min
The temperature was raised to 00 ° C. and the melting peak temperature and melting end temperature at the time of melting were evaluated. -Chlorine content measured according to JIS-K7229. -Mw GPC (standard material: polystyrene resin). -Unsaturated carboxylic acid or its anhydride graft amount: Determined by the alkali titration method. -Viscosity Measured using a B-type viscometer. The rotation speed is 60 rpm and the # 2 rotor is used. -Average particle size Measured using Zetasizer 3000HS (Sysmex Corporation).

Prototype Example 1 Propylene Random Copolymer Produced Using Metallocene Catalyst (Novatech, Nippon Polychem Co., Ltd. MFR = 7.0 g / 10 min, Tm = 125 ° C.) 100
By weight, 4 parts by weight of maleic anhydride powder (manufactured by NOF CORPORATION) and 2 parts by weight of di-t-butyl peroxide were kneaded.
After that, twin-screw extruder (L / D = 60, φ15mm, 1st barrel ~ 8th
Barrel), residence time 5 minutes, rotation speed 300 rpm, barrel temperature 120 ℃ (1st and 2 barrel), 180 ℃ (3rd and 4th barrel), 100 ℃ (5th barrel), 130 ℃ ( The reaction was carried out under the conditions of (6th to 8th barrel), and the pressure reduction treatment was carried out on the 6th, 7th and 8th barrels to obtain a maleic anhydride modified propylene random copolymer. 2 kg of this resin was put into a glass-lined 50 L reaction kettle, and 20 L of chloroform was added. 2kg / cm ²
Gaseous chlorine was blown from the bottom of the reaction vessel to chlorinate while irradiating ultraviolet rays under the pressure. I pull it out on the way,
Chloroform as a solvent was distilled off by an evaporator to adjust the solid content to 30% by weight. Stabilizer (t-butylphenyl glycidyl ether) was added to the chloroform solution in an amount of 1.5% by weight relative to the resin, and then the twin-screw extruder (L / D = 34,
φ40mm, 1st barrel ~ 7th barrel), the residence time is 1
0 minutes, rotation speed 50 rpm, barrel temperature 90 ℃ (1-6 barrel),
Solidification was performed under the condition of 70 ° C (7th barrel). 1st, 4th,
A pressure reduction treatment was carried out with 5 and 6 barrels to obtain a maleic anhydride-modified chlorinated propylene-based random copolymer.

The maleic anhydride-modified chlorinated propylene-based random copolymer obtained had an Mw of 77,000, a maleic anhydride graft weight of 2.4% by weight, and a chlorine content of 20.5% and 15.6% by weight. was gotten.

[Prototype Example 2] Propylene Random Copolymer Produced Using Metallocene Catalyst (Novatech, Nippon Polychem Co., Ltd. MFR = 7.0 g / 10 min, Tm = 125 ° C.) 100
3 parts by weight of powdery maleic anhydride (manufactured by NOF Corporation) and 2 parts by weight of 2,5-dimethyl-2,5-di (t-butylperoxy) hexane were kneaded. After that, twin screw extruder (L / D = 60,
φ15mm, 1st barrel ~ 8th barrel), the residence time is 5
Min, rotation speed 300 rpm, barrel temperature 120 ℃ (1st and 2 barrel), 170 ℃ (3rd and 4th barrel), 120 ℃ (5th barrel), 13
The reaction was carried out under the condition of 0 ° C (6th to 8th barrel) and the pressure reduction treatment was carried out in the 6th, 7th and 8th barrels to obtain a maleic anhydride modified propylene random copolymer. 2 kg of this resin was put into a glass-lined 50 L reaction kettle, and 20 L of chloroform was added. While irradiating ultraviolet rays under the pressure of 2kg / cm ² ,
Gaseous chlorine was blown from the bottom of the reaction kettle for chlorination. Chloroform was extracted on the way and chloroform as a solvent was distilled off by an evaporator to adjust the solid content to 30% by weight.
Stabilizer (t-butylphenyl glycidyl ether) was added to the chloroform solution in an amount of 1.5% by weight with respect to the resin, and then the mixture was supplied to a twin-screw extruder (L / D = 34, φ40 mm, first barrel to seventh barrel), Residence time 10 minutes, rotation speed 50 rpm, barrel temperature 90 ℃
Solidification was performed under the conditions of (first to sixth barrels) and 70 ° C (seventh barrel). Reduced pressure was applied to the first, fourth, fifth, and sixth barrels to obtain a maleic anhydride-modified chlorinated propylene-based random copolymer.

The maleic anhydride-modified chlorinated propylene random copolymer thus obtained had an Mw of 120,000, a maleic anhydride graft weight of 2.0% by weight, and a chlorine content of 20.7.
Two types, 1% by weight and 15.5% by weight, were obtained.

[Prototype Example 3] SPP (MFR = 3.7 g / 10 min, T
m = 130 ℃) twin-screw extruder (L / D = 34, φ40mm, 1st barrel ~
(7th barrel), the residence time is 10 minutes, the barrel temperature is 35
Thermal degradation is performed under the condition of 0 ℃ (1st barrel ~ 7th barrel), and 190
A resin having a melt viscosity of about 2000 mPa · s at ℃ was obtained. Substituting the obtained resin with the propylene-based random copolymer produced using the metallocene catalyst in Prototype Example 1,
Maleic anhydride modified chlorinated SP by the same operation as prototype 1
P was obtained. The weight average molecular weight of the obtained maleic anhydride-modified chlorinated SPP was 58,000, and the maleic anhydride graft weight was 2.8% by weight, and the chlorine contents were 20.4% and 15.5% by weight.
Two types were obtained.

[Prototype Example 4] A propylene-ethylene copolymer (ethylene content 5%, melt viscosity 830 mPa · s / 180 ° C., Tm = 126 ° C.) obtained by using a Ziegler-Natta catalyst in Prototype Example 1 By replacing the propylene random copolymer produced by using a metallocene catalyst, a maleic anhydride-modified chlorinated propylene-ethylene copolymer was obtained by the same operation as in Prototype Example 1. The weight average molecular weight of the obtained maleic anhydride-modified chlorinated propylene-ethylene copolymer was 66,0.
At 00, the weight of maleic anhydride grafted was 2.5% by weight, and two types of chlorine contents were obtained, 20.5% by weight and 15.8% by weight.

Example 1 A maleic anhydride modified chlorinated propylene random copolymer obtained in Prototype Example 1 was placed in a 2 L 4-necked flask equipped with a stirrer, a cooling tube, a thermometer and a dropping funnel. 200g of which chlorine content is 20.5% by weight, surfactant (ESOMIN T / 25, made by Lion) 33
g, a stabilizer (stearyl glycidyl ether) 8 g, and xylene 36 g were added, and the mixture was kneaded at 120 ° C. for 30 minutes. Next, 8-amino-2-methyl-1-propanol 8g was added over 5 minutes, and after hold | maintaining for 5 minutes, 90 degreeC warm water 970g was added over 40 minutes. After depressurizing treatment to remove xylene, the mixture was cooled to room temperature with stirring to obtain an aqueous dispersion. The solid content of the aqueous dispersion was 30% by weight, pH = 7.0, the viscosity was 97 mPa · s / 25 ° C., and the average particle size was 220 nm.

[Example 2] The maleic anhydride-modified chlorinated propylene-based random copolymer in Example 1 was replaced with the one having a chlorine content of 15.6% by weight obtained in Prototype Example 1, and a surfactant was used as eleminol NA. -120 (manufactured by Sanyo Kasei) was replaced with the same procedure as in Example 1 to obtain an aqueous dispersion. The solid content of the aqueous dispersion is 30% by weight, pH = 7.3, and the viscosity is 148 mPa · s / 2.
The temperature was 5 ° C, and the average particle size was 254 nm.

[Example 3] The same procedure as in Example 1 was carried out except that the maleic anhydride-modified chlorinated propylene random copolymer in Example 1 was replaced with the one having a chlorine content of 20.7% by weight obtained in Prototype Example 2. An aqueous dispersion was obtained in each operation. The solid content of the aqueous dispersion is 30% by weight, pH = 7.7, and the viscosity is 102 mPas.
/ 25 ° C, and the average particle size was 243 nm.

[Example 4] The maleic anhydride-modified chlorinated propylene random copolymer in Example 1 was replaced with the one having a chlorine content of 15.5% by weight obtained in Prototype Example 2, and the surfactant was used as eleminol NA. In place of -120 (manufactured by Sanyo Kasei), an aqueous dispersion was obtained in the same manner as in Example 1. The solid content of the aqueous dispersion is 30% by weight, pH = 7.1, and the viscosity is 2
It was 05 mPa · s / 25 ° C., and the average particle size was 354 nm.

Comparative Example 1 An aqueous dispersion was prepared in the same manner as in Example 1 using the maleic anhydride-modified chlorinated syndiotactic polypropylene having a chlorine content of 20.4% by weight obtained in Prototype Example 3. . The physical properties of the obtained aqueous dispersion are as follows: solid content 30% by weight, pH = 6.9, viscosity 94 mPa · s / 25 ° C.
And the average particle diameter was 194 nm.

Comparative Example 2 An aqueous dispersion was prepared in the same manner as in Example 2 using the maleic anhydride-modified chlorinated syndiotactic polypropylene having a chlorine content of 15.5% by weight obtained in Prototype Example 3. . The physical properties of the obtained aqueous dispersion are as follows: solid content 30% by weight, pH = 7.5, viscosity 237 mPa · s / 25
C., and the average particle size was 241 nm.

Comparative Example 3 Maleic anhydride-modified chlorinated propylene having a chlorine content of 20.5% by weight obtained in Prototype Example 4
Using an ethylene copolymer, an aqueous dispersion was prepared in the same manner as in Example 1. With regard to the physical properties of the obtained aqueous dispersion, the solid content was 30% by weight, pH = 7.2, the viscosity was 67 mPa · s / 25 ° C., and the average particle size was 83 nm.

Comparative Example 4 Maleic anhydride-modified chlorinated propylene having a chlorine content of 15.8% by weight obtained in Prototype Example 4
An aqueous dispersion was prepared in the same manner as in Example 2 except that the ethylene copolymer was used. With respect to the physical properties of the obtained aqueous dispersion, the solid content was 30% by weight, pH = 7.5, the viscosity was 205 mPa · s / 25 ° C., and the average particle size was 262 nm.

[Performance Test] Examples 1 to 4, Comparative Examples 1 to 4
After adding 1.5% by weight of 1% aqueous solution of Surflon S-141 (manufactured by Seimi Chemical Co., Ltd.) as a wettability improver (to the aqueous dispersion) to the aqueous dispersions obtained in step 1, the following heat seal strength test and primer were performed. Tests and various substrate adhesion tests were conducted. The results are shown in Tables 1 and 2.

○ Heat-seal strength test Corona surface-treated stretched polypropylene film was
The sample was applied using a # 8 Meyer bar and dried at room temperature for 15 hours. Overlapping the coated surfaces, No. 276 Heat Seal Tester (Yasuda Seiki Seisakusho) 1.5kg / cm
² , heat sealing was performed under the conditions of 90 ° C and 10 seconds. Each test piece was cut to have a width of 1 cm, peeled off using a tensile tester under the conditions of 5 kg weight and 100 mm / min, and the peel strength was measured. The test was performed 3 times, and the average value was used as the result.

○ Primer test An ultra-high rigidity polypropylene plate whose surface was wiped with isopropanol was spray-coated so as to have a dry film thickness of 10 to 15 μm and dried at 90 ° C. for 30 minutes. Then 2
Liquid type topcoat white paint is applied by spraying so that the dry film thickness is 45 or more and 50 μm or less, and left at room temperature for 15 minutes, then at 90 ° C.
It was baked for 30 minutes. After allowing the test piece to stand at room temperature for 3 days, the following test was performed. -Make 100 squares that reach the base at 2 mm intervals on the adhesive coated surface,
A cellophane adhesive tape was adhered on it and peeled off in the direction of 180 °, and the extent to which the coating film remained was evaluated.・ Register the gasohol resistance test piece to regular gasoline / ethanol = 9/1 (v / v).
It was immersed for 0 minutes and the state of the coating film was observed. -Hot water resistance The test piece was immersed in hot water of 40 ° C for 240 hours, and the state and adhesion of the coating film were examined.

○ Adhesion test for various base materials Spray coating was applied to various base materials whose surfaces were wiped with isopropanol so that the dry film thickness was 10 to 15 μm, and 8
It was dried at 0 ° C for 10 minutes. Next, a two-component topcoat silver paint was spray-applied so that the dry film thickness was 45 or more and 50 μm or less, allowed to stand at room temperature for 15 minutes, and then baked at 80 ° C. for 20 minutes. After allowing the test piece to stand at room temperature for 3 days, 2
100 grids that reach the substrate at an interval of mm were made, and a cellophane adhesive tape was adhered onto it and peeled off in the 180 ° direction, and the extent to which the coating film remained was judged.

[0063]

[Table 1]

[0064]

[Table 2]

[0065]

From the above results, the aqueous dispersion of the maleic anhydride-modified chlorinated propylene random copolymer of the present invention shows good physical properties even under conditions of drying at a low temperature of 80 or 90 ° C. and heat treatment. I know that It can also be used for high solidification.

On the other hand, the aqueous dispersion of chlorinated SPP modified with maleic anhydride is inferior in adhesiveness, and due to this, both gasohol resistance and hot water resistance are lowered. Further, an aqueous dispersion of a maleic anhydride-modified chlorinated propylene-ethylene copolymer using a Ziegler-Natta catalyst has a relatively good adhesiveness when baked at 90 ° C, but has a wide molecular weight distribution, and is suitable for solvents and Due to the presence of low molecular weight components that are weak in water, both gasohol resistance and warm water resistance decrease. In the adhesion test conducted by baking at 80 ° C., the adhesion of Comparative Examples 2 and 4 in which the degree of chlorination is decreased tends to further decrease due to the decrease in polarity and the increase in softening temperature.

Therefore, unlike the conventional aqueous dispersion obtained by simply using a low-melting-point polyolefin as a raw material, the aqueous dispersion containing the carboxyl group-containing chlorinated propylene random copolymer of the present invention has a lower degree of chlorination, It is a useful resin that can produce a high-solid aqueous dispersion even when a high molecular weight chlorinated resin is used, and exhibits excellent physical properties for various substrates even under low-temperature baking conditions. It proves to be effective for inks, inks and adhesives.

Front page continuation (51) Int.Cl. ⁷ identification code FI theme code (reference) C09D 7/12 C09D 7/12 11/02 11/02 123/26 123/26 151/06 151/06 C09J 11/02 C09J 11/02 123/26 123/26 151/06 151/06 F Term (reference) 4J002 BN101 CD162 DE286 EG036 EG046 EL026 EL046 EZ046 FD036 GH01 GJ01 HA07 4J038 CB171 CP031 CP051 HA116 HA276 JB01 KA08 MA08 MA10 PC08 4J039 AD01 AD01 BA16 BA29 BC33 BE22 CA06 4J040 DA181 DL061 DL101 HA146 HA196 HC01 JA03 KA38 MA10 4J100 AA02Q AA03P AA04Q AA16Q AA17Q AA19Q CA04 CA31 DA01 DA09 HA21 HA57 HC29 HC30 JA01 JA03

Claims (8)

[Claims] 1. A carboxyl group-containing chlorine having a chlorine content of 5 to 40% by weight, an α, β-unsaturated carboxylic acid or an anhydride thereof grafted amount of 0.1 to 20% by weight, and a weight average molecular weight of 10,000 to 300,000. An aqueous dispersion comprising a propylene-based random copolymer and a stabilizer dispersed therein. 2. The aqueous dispersion according to claim 1, further comprising a surfactant and a basic substance. 3. A propylene-based random copolymer produced by using a metallocene compound as a polymerization catalyst, α, β
A chlorine content of 5 to 40 after or before the graft copolymerization of 0.1 to 20% by weight of an unsaturated carboxylic acid or its anhydride.
Chlorinated up to wt%, weight average molecular weight 10,000 to 300,0
A method for producing an aqueous dispersion, wherein the chlorinated propylene-based random copolymer having a carboxyl group of 00 is dispersed in water. 4. The method for producing an aqueous dispersion according to claim 3, wherein a surfactant and a basic substance are further added to the carboxyl group-containing chlorinated propylene random copolymer and dispersed in water. 5. A primer using the aqueous dispersion according to claim 1. 6. A paint using the aqueous dispersion according to claim 1. 7. An ink using the aqueous dispersion according to claim 1. 8. An adhesive using the aqueous dispersion according to claim 1.