JP3468897B2 - Aqueous composition emulsion of modified chlorinated polyolefin and use thereof - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention relates to a polyolefin resin,
For example, a chlorinated polyolefin used for the purpose of coating a propylene homopolymer, an ethylene-propylene copolymer, an ethylene-propylene-butene copolymer as a main component, a molded product, the same film, or the same fiber product. A method for producing and using an aqueous composition emulsion of a modified product, more specifically, it is applied to a molded product and a film of a polyolefin resin as a primer or as a one-coat finish to be used as a paint, ink or adhesive. As a sufficient adhesion obtained by coating the surface of the polyolefin substrate with an organic solvent such as trichloroethane without steam cleaning or degreasing, the appearance of the coating film and the interlayer adhesion to the base coat or the top coat, the resistance A water-based composition of modified chlorinated polyolefins that gives good coating properties such as solvent resistance and moisture resistance. ® relates emissions of preparation and use.

[0002]

2. Description of the Related Art Conventionally, since a polyolefin resin is generally crystalline and does not have a highly reactive functional group on the surface, it is difficult to adhere or coat the polyolefin resin substrate. In order to improve this, some attempts have been made to improve the adhesion of the coating film by modifying the resin surface with a physical method such as acid treatment, corona discharge or plasma treatment. However, in these cases, the process becomes complicated or a huge capital investment is required. In addition, it is difficult to say that the effects that have been found in the complicated processes and capital investment described above are necessarily obtained. From this point of view, the present inventors have found that as a polyolefin composition used for improving physical properties such as adhesion to a polyolefin material and pigment dispersibility, acrylic oligomers and / or polydiene are added to polyolefins such as chlorinated polyolefins. Method of using a composition obtained by graft-copolymerizing compounds in a solution system (JP-A-3-221512) and polyolefins such as chlorinated polyolefin in an aqueous system (meth)
The inventors have invented a method (JP-A-5-209006) using a composition obtained by graft-copolymerizing acrylic monomers and / or oligomers thereof. However, although the above method has shown considerable effects and solved many problems, with the recent rapid progress in resin material synthesis technology, polyolefin-based materials including a large number of difficult-to-adhesive types have been rapidly marketed. It has become available. Therefore, the inventors of the present invention have conducted extensive research on water-based composition emulsions of modified chlorinated polyolefins having excellent adhesion to polyolefin-based resins. On the other hand, as a surface treatment agent for activating the surface of a polyolefin-based resin substrate, an invention in which a terpene-based solvent is mixed with a solution system such as halogenated polyolefin (Japanese Patent Laid-Open No. 53-1424).
71).

[0003]

As described above, the present invention further improves the adhesiveness to various polyolefin resin substrates, the properties of the ink composition or other coating film, and therefore the present invention The present invention provides an aqueous composition emulsion of a chlorinated polyolefin-modified product, which is an improvement of the prior invention of the present applicant, and the present invention is an aqueous composition emulsion of a chlorinated polyolefin-modified product of the applicant of the present invention. Was completed by blending a terpene-based compound or terpene-based composition with, and vaporized the surface of the polyolefin-based resin substrate with a chlorine-based organic solvent such as trichloroethane, which is one of the substances that cause ozone depletion in the atmosphere. Has good adhesiveness to the polyolefin-based resin substrate without washing or degreasing, for example, used for automobile bumpers It is used for surface coating or adhesion of low-polarity substances such as for reolefin-based primer, or for use as base resin for inks, interlayer adhesion with base coat or top coat, solvent resistance, moisture resistance, etc. The purpose is to improve various physical properties or adhesiveness of the.

[0004]

The present invention provides an aqueous emulsion of a chlorinated polyolefin modified product obtained by modifying a chlorinated polyolefin with a (meth) acrylic monomer and / or a (meth) acrylic oligomer, and at least one mono-monomer. It is an aqueous composition emulsion of a chlorinated polyolefin-modified product, characterized by being prepared by blending an aqueous solution containing a terpene (C ₁₀ H ₁₆ ). The present invention also provides a water-based emulsion of a modified chlorinated polyolefin obtained by modifying a chlorinated polyolefin with an α, β-unsaturated carboxylic acid or an anhydride thereof, with at least one monoterpene (C ₁₀ H
₁₆ )) and an aqueous solution containing
It is an aqueous composition emulsion of a modified chlorinated polyolefin. In a preferred embodiment of the present invention, 0.1 to 100 parts by weight of an aqueous solution of a monoterpene is mixed with 100 parts by weight of an aqueous emulsion of a chlorinated polyolefin modified product. The aqueous composition emulsion of the chlorinated polyolefin modified product of the present invention is used for coating a polyolefin resin base material,
It is preferably used for adhesion and printing ink. The present invention is further characterized in that, when applied to a polyolefin resin substrate, the above-mentioned chlorinated polyolefin-modified water-based composition emulsion is applied to the substrate without steam cleaning or degreasing with a chlorine organic solvent. And the use of the aqueous composition emulsion.

[0005]

[Chemical 1]

In the present invention, an aqueous composition emulsion is obtained by blending an aqueous solution containing at least one monoterpene (C ₁₀ H ₁₆ ) with an aqueous composition emulsion of a modified chlorinated polyolefin. This composition
It is a composition having a coating film physical property that adheres to a polyolefin substrate without vapor cleaning or degreasing with a chlorine-based organic solvent such as trichloroethane when coating or coating a plastic molded product having a polyolefin as a substrate. The reason for this is that, according to the results of research conducted by the present inventors, monoterpenes have strong penetrability with respect to polyolefins and also have adhesiveness, so that the surface of the polyolefin material is activated. That is, a polymer having a functional group associated with a monoterpene penetrates into the surface layer of the polyolefin and is compatibilized therewith, and further, since there is stickiness, the adhesion is strengthened.

The monoterpene (C ₁₀ H used in the present invention
Examples of ₁₆ ) include, for example, α-pinene, β-pinene and α-pinene.
Limonene, β-ferrandran, 7-methyl-3-methylene-1,6-octadiene, 2,2-dimethyl-3-
Methylene norbornene, 3,7,7-trimethylbicyclo [4,1,0] hept-3-ene and the like may be used as a composition of two or more of these, and the boiling point is usually 250 ° C.
The following are preferred: When the monoterpene is added to the water-based composition emulsion of the modified chlorinated polyolefin, it is added after being made water-based. The aqueous solution of monoterpene is prepared by blending monoterpene with a surfactant, water, higher alcohol, lanolin and the like. The content of the monoterpene in the aqueous solution is appropriately 1 to 99% by weight, and the particularly preferable content is 10 to 50% by weight.

The water-based composition emulsion of the modified chlorinated polyolefins, which is the subject of the present invention, is a component used for imparting adhesiveness as a coating film physical property. Α-, such as propylene, 1-butene, 4-methyl-1-pentene
Resins, rubber-like substances, and the like, which are copolymers or homopolymers of olefinic unsaturated hydrocarbons, are used. Specifically, the constituent elements thereof are a propylene-α-butene copolymer and an ethylene-propylene-diene copolymer. Polymers, ethylene-propylene copolymers, ethylene-1-butene copolymers, ethylene-vinyl acetate copolymers, polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, etc., Resins chlorinated up to 5 to 50% by weight of polyolefins are preferably used. Further, as a constituent polyolefin, a copolymer of two or more kinds of the above-mentioned α-olefin and a conjugated or non-conjugated diene, for example, an ethylene-propylene-butadiene copolymer, an ethylene-propylene-dicyclopentadiene copolymer, Further, a copolymer of α-olefin and a conjugated or non-conjugated diene, for example, propylene-butadiene copolymer, browylene-ethylidene norbornene copolymers, etc., a copolymer of a monomer such as a building monomer and an α-olefin, and The partially saponified product, the above-mentioned copolymer, or a composition comprising two or more kinds thereof is used. Further, a modified polyolefin resin obtained by introducing a carboxysyl group, a hydroxyl group, an acid anhydride or the like into these can also be used. The modification of the polyolefin with α, β-unsaturated carboxylic acid or its acid anhydride is carried out by a known method. For example, a propylene-ethylene-1-butene copolymer is dissolved in toluene, and then maleic anhydride and a peroxide are added dropwise to the flask while keeping the reaction temperature at 111 ° C. for reaction. The obtained reaction liquid may be added to a non-solvent such as methanol to be resinized and dried. When the present invention is carried out using this maleic anhydride-modified polyolefin, the adhesion and solvent resistance are further improved.

The aqueous composition emulsion of the modified chlorinated polyolefins in the present invention comprises, for example, a polyolefin such as chlorinated polyolefin and / or a (meth) acrylic oligomer dissolved in a (meth) acrylic monomer. It is obtained by a method such as dispersion in an aqueous medium and then suspension polymerization. The (meth) acrylic monomers used in the above method are preferentially selected from those which easily dissolve polyolefins and (meth) acrylic oligomers. For example, methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth) acrylate, normal butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate -, Mono-functional (meth) acrylates such as stearyl (meth) acrylate, benzyl (meth) acrylate and isobornyl (meth) acrylate
, Maleic anhydride, (meth) acrylic acid, dimethylaminoethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, acrylamide, etc. The functional monomers, styrenes such as styrene, chloromethylstyrene, α-methylstyrene, etc. may be used alone or in admixture of two or more kinds. Here, (meth) acrylic is an abbreviation for acrylic and methacrylic.

Further, the (meth) acrylic oligomers have, as a typical feature, those having a certain repeating unit in the molecule and having at least one or two or more double bonds in the molecule. Further, of course, those that should be called macromers or macromonomers are included, but ordinary macromers or macromonomers (hereinafter referred to as macromonomers etc.) refer to those having a double bond at the end of the molecule. However, those having a functional group such as a hydroxyl group or a carboxyl group at both ends of the molecule are also included. These macromonomers have a molecular weight in the range of several hundreds to 10,000, and the physical properties of the coating film of the copolymer obtained and the stability of the emulsion differ depending on the type of macromonomer used and the molecular weight.

Examples of the above (meth) acrylic oligomers include, in addition to macromonomers, caprolactone-modified (meth) acrylate oligomers, terminal hydroxyl group-containing (meth) acrylate oligomers, oligoesters ( (Meth) acrylate, urethane (meth) acrylate
And epoxy (meth) acrylate. Among these, those containing a hydroxyl group, a carboxyl group, an acid anhydride group or an amino group are also included. These (meta)
Acrylic oligomers are monofunctional monomers described above,
One or more types of monomers from styrene etc.
Made using. In suspension polymerization of the chlorinated polyolefin-modified product in an aqueous composition emulsion, it is necessary to make the droplets of the monomer solution uniform and fine particles. At this time, if an emulsifier is used and a homogenizer is used, the purpose can be more easily achieved. Typical examples of emulsifier surfactants include aromatic compounds such as polyoxyethylene alkylphenyl ether, higher alkyl compounds such as polyoxyethylene alkyl ether, and fatty acid derivative compounds such as polyoxyethylene fatty acid ester. Nonionic surfactants, polyoxyethylene alkyl (or alkylphenyl) ether sulfate ester salts, dialkyl sulfosuccinate sodium salts, higher alcohol sulfate ester soda and other anionic surfactants, and the like. You may use together 1 type (s) or 2 or more types of surfactant among these. Rather, it is often the case that two or more kinds of anionic and / or nonionic surfactants having different HLBs are used to give better results. As a polymerization initiator used at the time of polymerization, a peroxide type such as benzoylperoxide and an azobis type such as azobisisobutyronitrile can be used.

Further, in order to control the degree of polymerization,
The use of a chain transfer regulator has the advantage that the degree of polymerization can be significantly reduced and the chain length can be made uniform. As the chain transfer regulator, mercaptans and disulfides are used. Examples of mercaptans include n-dodecyl mercaptan, n-tetradecyl mercaptan, n-decyl mercaptan, t-decyl mercaptan, t-tetradecyl mercaptan, t-hexadecyl mercaptan and 3-ethoxypropanethiol. Examples of disulfides include bis-2-aminodiphenyl disulfide, bis-2-dibenzothiazoyl disulfide, and diisopropyl xanthogen disulfide. As a suspension polymerization method, polyolefins such as chlorinated polyolefin in which a polymerization initiator is dissolved, (meth)
While dripping an emulsion (hereinafter referred to as a pre-emulsion) obtained by homogenizing a solution containing an acrylic monomer and / or a (meth) acrylic oligomer and an aqueous solution in which an emulsifier is dissolved, into a reaction can containing deionized water. Polymerization with stirring in a nitrogen atmosphere.

Further, the emulsion targeted for the aqueous composition emulsion of the above-mentioned chlorinated polyolefin-modified product is an unsaturated carboxylic acid such as maleic anhydride as described above.
A solution of a polyolefin-based polymer modified by 5 to 10 Wt% or a chlorinated product thereof is used, if necessary, with monoethylamine, diethylamine, monobutylamine, triethylamine, triethanolamine, aqueous ammonia, dibutylamine, tributylamine, 2-amino-2. -Methyl-
Amino alcohols such as 1-propanol, caseo-
It can be obtained by neutralizing in the presence of an aqueous solution of a strong alkali such as Da or Kakekari, and forcibly emulsifying with water, a surfactant and the like. In that case, those obtained by removing the contained solvent by a method such as concentration under reduced pressure are also included.

When 0.1 to 100 parts by weight of an aqueous solution of a monoterpene is added to 100 parts by weight of an aqueous emulsion of the chlorinated polyolefin-modified product obtained by the above method, it is possible to form a polyolefin molded product such as polypropylene or a film. Improves adhesion and gloss of coating film. If the compounding ratio of the aqueous solution of monoterpene is less than 0.1 part by weight, it is difficult to obtain the effect of improving the adhesion to the polyolefin, and if it exceeds 100 parts by weight, the drying speed becomes slow and the workability deteriorates. Therefore, it cannot be used in the present invention.
It is preferably 1 to 50 parts by weight.

[0015]

EXAMPLES The present invention will now be described by way of Examples and Production Examples, but the present invention is not limited to these.

[Production Example 1] Neugen EA-19 was added to 120 g of deionized water.
6 g of 0D (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd .: polyoxyethylene alkylphenyl ether) was added to obtain a uniform and transparent aqueous solution (a). Power Blender-500 ULTR
D-Limonene (Kanto Chemical Co., Inc. reagent) 50 with a 500 ml cup fixed to AII (Sakuma Seisakusho Co., Ltd.)
g, 126 g of an aqueous solution (a) and 15 g of lanolin were charged, and the mixture was emulsified at 10,000 rpm for 3 minutes at room temperature to obtain an aqueous composition containing a tenpen-based oligomer as a main component.

[0016]

[Production Example 2] Aqueous terpene-based oligomers were prepared by changing d-limonene to turpentine oil (Kanto Chemical Co., Inc. reagent: α-pinene as a main component) under exactly the same operation and conditions as in Production Example 1.
A composition containing as a main component was obtained.

[0017]

[Production Example 3] 500 g of normal butyl methacrylate,
Macromonomer AW-6 (manufactured by Toagosei Kagaku Co., Ltd .: isobutyl methacrylate molecular weight 6000 macromonomer) 100 g, methacrylic acid 15 g, chlorinated polypropylene (manufactured by Toyo Kasei Co., Ltd .: Hadren 14-LW)
P: Chlorine content 27%) 200 g was placed in a 2-liter four-necked flask equipped with a stirrer, dissolved at 80 ° C. until uniform, and then cooled to 50 ° C., and Nipa-BO (NOF CORPORATION) Company: benzyl peroxide paste) 6.
2 g and 0.6 g of t-dodecyl mercaptan were added to obtain a uniform solution (ii). In addition, in 909 g of deionized water, 49 g of Neugen EA-190D (Daiichi Kogyo Seiyaku Co., Ltd .: polyoxyethylene alkylphenyl ether) and 33 g of Neoperex No6 (Kao Co., Ltd .: sodium dodecylbenzenesulfonate paste) are added. And add
A uniform and transparent aqueous solution (C) was obtained. The solutions (b) and (c) were put in a 5 liter polyethylene cup and homogenized with a homogenizer (HV-SL manufactured by Tokushu Kika Kogyo Co., Ltd.) at 2000 rpm for 30 minutes, and then # 400S.
It was filtered with a US wire mesh to obtain a pre-emulsion. Deionized water 30 in a 2 liter 4-neck flask equipped with a dropping funnel.
After charging 0 g of the system and sufficiently replacing the inside of the system with nitrogen, the temperature of the system was raised to 63 ° C. by an oil bath and the pre-emulsion was uniformly added to the dropping funnel over 3 hours while stirring.
The reaction was carried out and the mixture was aged for 6 hours at 63 ° C. The obtained emulsion was filtered through a # 400 wire mesh. This emulsion has a non-volatile content of 39.8% by weight and an emulsion viscosity of 0.25 poise.

[0018]

[Manufacturing Examples 4 to 6] The kinds of monomers (mixtures) and kinds of chlorinated polyolefins used under the same operations and conditions as in Manufacturing Example 3 were changed. The composition of the obtained emulsion is shown in [Table 1].

[0019]

[Table 1] (1) NB; normal butyl methacrylate L; lauryl methacrylate M; methyl methacrylate (2) 14-LWP; Toyo Kasei Kogyo Co., Ltd. chlorinated polypropylene (chlorine content: 27.2%) 16-LP; Toyo Kasei Co., Ltd. Chlorinated polypropylene (chlorine content: 32.0%)

[0020]

Example 1 100 g of the emulsion obtained in Production Example 3
The coating film physical properties of the composition obtained by blending 10 g of the composition containing the aqueous tenpen-based oligomer obtained in Production Example 1 as the main component are shown in [Table 3].

[0021]

[Table 3] (1) Addition rate: to emulsion composition (Production Examples 1-28,
Comparative Examples 1-7) wt%. (2) Adhesion: Polypropylene plate (Mitsui Noblen SB-E
100 mm x 50 by press molding 3
mm, thickness 2 mm) surface is washed thoroughly with tap water and dried. The liquids blended in Examples 1 to 28 and Comparative Examples 1 to 7 were diluted to a resin concentration of 12% by weight and kept at 25 ° C. while being air-type spray gun (F-88 manufactured by Meiji Kikai Seisakusho Co., Ltd.).
(Type) Spray coating was carried out from a distance of 30 cm with a spray pressure of 2.0 kg / cm ² G. The coating thickness was 5 to 10 μ (resin base). Drying was performed at 80 ° C. for 30 minutes, and after returning to room temperature, 24 hours passed was tested. The evaluation was performed according to JIS K5400, cut tape method (◯: good, ×: bad). (3) Gloss: Spray-paint on the washed polypropylene plate described in (1), apply to a thickness of 5 to 10 μ (resin base), and dry at 80 ° C. for 30 minutes. After being returned to room temperature and passed for 24 hours, it was used for the test. As the gloss meter, a gloss meter IG-310 manufactured by Horiba Ltd. was used. (4) Interlayer adhesion: Spray-paint on the washed polypropylene plate described in (1) to apply it to a thickness of 5 to 10 μ (resin base), and dry at 80 ° C. for 30 minutes. Then, Retan PG-80 (urethane paint manufactured by Kansai Paint Co., Ltd.) is applied to a thickness of 50 to 60 μ (resin base). Furthermore, after drying at 80 ° C. for 30 minutes and returning to room temperature, 24 hours have passed, the test is conducted. Evaluation is JIS
Evaluation was carried out according to K5400, cut tape method (◯: good, ×: bad). (5) Moisture resistance: Spray-painted on the washed polypropylene plate described in (1) to a thickness of 5 to 10 μm (resin base) and dried at 80 ° C. for 30 minutes. Then, Retan PG-80 (urethane paint manufactured by Kansai Paint Co., Ltd.) is applied to a thickness of 50 to 60 μ (resin base). Further, a piece dried at 80 ° C. for 30 minutes is used as a coated piece. After the test piece was left for 240 hours in a constant temperature layer kept at 40 ° C. and 95% relative humidity, the adhesion was evaluated according to JIS K5400, cut tape method (◯: good, ×: bad). (6) Solvent resistance: Spray-paint on the water-washed polypropylene plate described in (1), apply to a thickness of 5 to 10 µ (resin base), and dry at 80 ° C for 30 minutes. afterwards,
Retan PG-80 (urethane paint manufactured by Kansai Paint Co., Ltd.) is applied to a thickness of 50 to 60 μ (resin base). Further, a piece dried at 80 ° C. for 30 minutes is used as a coated piece. Immerse absorbent cotton in a mixed solvent of methyl ethyl ketone / toluene = 8/2 weight ratio, and apply 100 to the coated surface.
Rubbing was repeated and the state of the coating film was examined (◯: good, ×: bad). (7) Peel strength: The liquid blended in Examples 1 to 28 and Comparative Examples 1 to 7 was applied to a 60 μ biaxially stretched polypropylene film untreated surface (manufactured by Toyobo Co., Ltd.) so that the coating amount was 10 g / m ^2. Then, after drying at room temperature for 24 hours, 60 μ biaxially oriented polypropylene film Doshi heat seal (130
The peeling strength was measured by Tensilon. (8) Serotope peeling test of ink coated surface: Examples 1-2
8. An ink was prepared with the emulsion compositions of Comparative Examples 1 to 7 and applied on a 60 μ biaxially oriented polypropylene film untreated surface (manufactured by Toyobo Co., Ltd.) so that the coating amount was 10 g / m ^2, and then at room temperature for 24 hours. After drying, cellophane tape was attached, and the peeled state when peeled off at once was evaluated (◯: good, ×: bad).

[0022]

Comparative Example 1 The coating film physical properties of the emulsion obtained in Production Example 3 are shown in [Table 3].

[0023]

Example 2 100 g of the emulsion obtained in Production Example 3
Table 3 shows the coating film physical properties of the composition obtained by adding 10 g of the mixture containing, as a main component, the aqueous terpene-based oligomer obtained in Production Example 2.

[0024]

Examples 3 to 16 100 g of the emulsions obtained in Production Examples 3 to 6 were obtained by blending the composition containing the aqueous terpene-based oligomer obtained in Production Example 1 or 2 as a main component or. The coating film physical properties of the composition are summarized in [Table 3].

[0025]

[Comparative Examples 2 to 4] The coating film properties of the emulsions obtained in Production Examples 4 to 6 are summarized in [Table 3].

[0026]

[Production Example 7] Chlorinated polypropylene "HARDREN 13
-LB "(manufactured by Toyo Kasei Co., Ltd .: chlorine content 26
%, Resin concentration 20% toluene solution) 1000 g, Nisso polybutadiene EP-1054 (manufactured by Nippon Soda Co., Ltd. polybutadiene: number average molecular weight; 1000, containing epoxy group in the molecule) 12 g, maleic anhydride 2 g. It was put into a 2 liter four-necked flask equipped with a thermometer and a cooling tube, and the solution temperature was adjusted to 90 ° C. with stirring and heating, and then the space in the system was sufficiently replaced with nitrogen, at the end of the reaction. The nitrogen stream was maintained at a constant flow rate. Then, 2 g of benzoylperoxide was added, and after 1 hour, 1 g,
After 2 hours and 3 hours, 1 g each was added. Furthermore, the mixture was reacted for 2 hours while heating and stirring at the same temperature to obtain a modified chlorinated polypropylene composition solution (d). Also,
Neoperex No. is added to 950 g of deionized water. 6 to 50 g
A homogeneous and transparent aqueous solution (e) was obtained by the addition. Solution (d) 1000 g in a 5 liter polyethylene cup,
(E) Put 950 g and 12 g of ammonia water (manufactured by Wako Pure Chemical Industries, Ltd .: 25% grade reagent special grade) into a homogenizer.
2000r with (Special Machine Chemical Co., Ltd .: HV-SL)
After being uniformly dispersed at pm for 30 minutes, it was filtered through a # 400 SUS wire mesh to obtain an emulsion (f). In addition, the evaporator
The emulsion (f) was concentrated under reduced pressure using to remove the contained toluene. The obtained emulsion was filtered through a # 400 wire mesh. This emulsion has a non-volatile content of 36.2% by weight and an emulsion viscosity of 3.2 poise.

[0027]

[Manufacturing Examples 8 and 9] Emulsions were obtained by the same operation and conditions as in Manufacturing Example 7, except that the amount of maleic anhydride was changed. The modified composition is shown in [Table 2].

[0028]

[Table 2]

[0029]

Example 17 Emulsion 100 obtained in Production Example 7
Table 3 shows the coating film properties of the composition obtained by adding 10 g of the composition containing the aqueous terpene-based oligomer obtained in Production Example 1 as a main component to g.

[0030]

Comparative Example 5 The coating film physical properties of the emulsion obtained in Production Example 7 are shown in Table 3.

[0031]

Example 18 Emulsion 100 obtained in Production Example 7
The coating film physical properties of the composition obtained by adding 10 g of the composition containing the aqueous terpene-based oligomer obtained in Production Example 2 as the main component to g are shown in [Table 3].

[0032]

Examples 19 to 28 Compositions obtained by blending 100 g of the emulsions obtained in Production Examples 7 to 9 with the composition containing the aqueous terpene-based oligomer obtained in Production Example 1 or 2 as a main component or The coating film physical properties of the products are summarized in [Table 3].

[0033]

[Comparative Examples 6 and 7] The coating film properties of the emulsions obtained in Production Examples 8 and 9 are summarized in [Table 3]. Further, in [Table 3], inks were prepared by using the emulsion compositions of Examples 1 to 28 and Comparative Examples 1 to 7, and a coating amount of 10 g / a on a 60 μ biaxially oriented polypropylene film untreated surface (manufactured by Toyobo Co., Ltd.). m
^The results obtained by applying a coating of ² and drying at room temperature for 24 hours and then performing a cellotepe peeling test using cellophane tape are also shown. The formulation of the ink is shown in [Table 4].

[0034]

[Table 4] Cyanimble-S-2010 (Dainichiseika Co., Ltd., organic pigment) BYK-032 (BYK Chemie, defoamer)

[0035]

When a composition based on a terpene oligomer or a mixture thereof is added to an aqueous composition emulsion of a chlorinated polyolefin modified product, an aqueous composition of a chlorinated polypropylene modified product of chlorinated polypropylene is added. It can be seen that the adhesion of the product emulsion to polyolefin molded products such as polypropylene and / or the same film, the gloss of the coating film, the interlayer adhesion, the moisture resistance and the solvent resistance are obviously improved as shown in [Table 3]. .

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI C08L 45:00) (72) Inventor Ryozo Oda 2900 Sone Town, Takasago City, Hyogo Prefecture Toyo Kasei Kogyo Co., Ltd. Chemicals Research Laboratory (56) References JP-A-59-4637 (JP, A) JP-A-8-41263 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08J 3/03-3/07 C08L 23 / 26-23/28 C09D 123/26-123/28 C09J 123/26-123/28

Claims (7)

(57) [Claims] 1. An aqueous emulsion of a modified chlorinated polyolefin obtained by modifying a chlorinated polyolefin with a (meth) acrylic monomer and / or a (meth) acrylic oligomer, and at least one monoterpene (C).
An aqueous composition emulsion of a modified chlorinated polyolefin, which is characterized by being mixed with an aqueous solution containing ₁₀ H ₁₆ ). 2. An aqueous solution containing at least one monoterpene (C ₁₀ H ₁₆ ) in an aqueous emulsion of a modified chlorinated polyolefin obtained by modifying a chlorinated polyolefin with an α, β-unsaturated carboxylic acid or an anhydride thereof. A water-based composition emulsion of a chlorinated polyolefin-modified product, characterized by comprising: 3. The chlorinated polyolefin according to claim 1, wherein 0.1 to 100 parts by weight of an aqueous solution of a monoterpene is added to 100 parts by weight of an aqueous emulsion of a modified chlorinated polyolefin. A water-based composition emulsion of a modified product. 4. The aqueous composition emulsion of the modified chlorinated polyolefin according to claim 1 or 2, which is used for coating a polyolefin resin base material. 5. The water-based composition emulsion of the modified chlorinated polyolefin according to claim 1 or 2, which is used for adhering a polyolefin resin substrate. 6. The water-based composition emulsion of the chlorinated polyolefin-modified product according to claim 1, which is for a printing ink of a polyolefin-based resin substrate. 7. A water-based chlorinated polyolefin modified product according to claim 1, which is applied to a polyolefin resin substrate without vapor cleaning or degreasing with a chlorine organic solvent. Use of an aqueous composition emulsion, characterized in that the composition emulsion is applied.