JP3468896B2 - Method for stabilizing modified polyolefin solution or dispersion - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a surface of a polyolefin material, which is used as a coating for a molded product or a film of a polyolefin resin, is applied as a primer or with a one-coat finish, and is used as a paint, an ink or an adhesive. Is applied to the surface of the polyolefin material without vapor cleaning or degreasing with an organic solvent such as trichloroethane to give a good coating film such as adhesion, weather resistance, coating film appearance, and solvent resistance. Modified polyolefin solution or dispersion The present invention relates to a method of stabilizing a liquid (dispersion) (hereinafter collectively referred to as a modified polyolefin solution).

[0002]

2. Description of the Related Art Conventionally, a chlorinated polyolefin (mainly a low chlorinated product having a chlorination degree of 20 to 40% by weight) and a monomer such as a (meth) acrylic monomer (abbreviation of acrylic monomer or methacrylic monomer) are used as a polymerization initiator. And / or in the presence of a chain transfer agent, when a polymerization reaction is carried out in a solution state of an ordinary organic solvent such as toluene, generally, (1) as a primer, polypropylene (P
They are inadequate in adhesiveness to a base material or to a propylene-based copolymer base material, and are inferior in so-called interlayer adhesion to a top coat resin or the like. Further, (2) the one-coat paint or the one for the same coating has insufficient adhesion to a PP or propylene-based copolymer base material, poor pigment dispersibility and poor weather resistance. In order to improve these physical properties, chlorinated polyolefins are copolymerized with (meth) acrylic monomers and / or oligomers, etc. for primers or one-coat paints, adhesives, vehicles for inks or other coatings. As an invention relating to use, JP-A-3-22512
JP-A-4-23839, JP-A-4-8746,
There is JP-A-5-255653.

[0003]

Chlorinated polyolefin (CPO), especially chlorinated polypropylene (CPP) or CPO having a chlorine content of 20 to 40% by weight, is used as (meth) acrylic monomer, styrene monomer, vinyl acetate. When modified with a monomer or a versatic acid, a vinyl ester, or a mixed monomer composed of two or more kinds of the above monomers, etc., when prepared as a solution with an ordinary organic solvent, for example, a single solvent such as toluene or xylene , Phase separation may occur depending on long-term storage. Further, a toluene or xylene solution of a non-crystalline or low crystalline polyolefin such as a propylene-butene-maleic anhydride copolymer or an ethylene-vinyl acetate copolymer is likely to cause phase separation similarly to the above. On the other hand, recently, trichloroethane (TCE), an effective solvent due to pollution problems
Due to social demands that regulate the production and sale of ozone-depleting substances such as TCE, it has already been decided in 1995 that the production and movement of ozone-depleting substances such as TCE will be prohibited. From this point of view, it has been desired that a long-term stable solution of a solution or dispersion of a polyolefin-modified product such as the above-mentioned chlorinated polyolefins appears.

The present invention is directed to the stability of modified polyolefin solutions for coating primers, coatings, adhesives, adhesive primers, vehicles for inks and other coating agents used in other applications, eg room temperature stability, low temperature stability. And improving the physical properties of the solution such as the stability of long-term storage, and the adhesiveness of the coating film obtained by using the stable modified polyolefin solution having the improved physical properties of the solution, and the coating properties such as the gloss of the coating film. The purpose is to improve.

[0005]

The present invention provides a modified polyolefin solution or dispersion obtained by copolymerizing a polyolefin (I) with a (meth) acrylic monomer (IV) and a (meth) acrylic macromonomer (V). A method for stabilizing, wherein the solution or dispersion is a polyolefin (I)
Is a solution or a dispersion of an organic solvent that dissolves, and the solubility parameter (δ) by CM Hansen is 8.0 to 10.0 with respect to the solution or the dispersion. (Cal / cm ³ ) ^1/2 , and C.I. M. The hydrogen bonding force component (δ _h ) which is one component of the three-dimensional solubility parameter by Hansen is 2.
A method for stabilizing a modified polyolefin solution or dispersion, which comprises blending at least one organic solvent having a concentration of 0 to 6.0 (cal / cm ³ ) ^1/2 .

Preferably, the above-mentioned solubility parameter (δ) is 8.0 to 10.0 (cal / cm ³ ) ^1/2 and the hydrogen bonding force component (δ _h ) is 2.0 to. 6.0
The organic solvent having (cal / cm ³ ) ^1/2 is selected from n-butyl acetate, isobutyl acetate, methyl isobutyl ketone, cyclohexanone and tetrahydrofuran.

In the present invention, (δ) and (δ _h ) are as described in J.
BRANDRUP and E.I. H. IMMERGUT, PO
LYMER HANDBOOK (1989) (VII /
519-VII / 557), and the calculated value is based on the HANDBOOK. Page. VII / 526 ~ VII / 557
Listed solubility parameter values (SolubilityP
It was calculated using the parameter Value).
Here, (δ) and (δ _h ) are represented by the following formulas, and their calculated values for various organic solvents are shown in Table 1.

[0008]

[Formula 1]

Where ΔE: total evaporation energy (cal / mol) Vm: molar volume (cm ³ / mol) ΔEd, ΔEp, ΔEh: dispersion of evaporation energy, dipole efficiency, hydrogen bonding force δ _d , δ _p , δ _h : Dispersion power, dipole efficiency, hydrogen bonding force component of the solubility parameter, that is, (δ _h ) is a hydrogen bonding component of (δ).

[0010]

[Table 1]

According to the study by the present inventors, (δ) is 8.
0 to 10.0 (cal / cm ³ ) ^1/2 and (δ _h ) is 2.
If (δ) and (δ _h ) are outside the range of 0 to 6.0 (cal / cm ³ ) ^1/2 , the stabilization of the modified polyolefin solution, which is the object of the present invention, cannot be achieved. That is, when the value of (δ) is less than 8.0, the polarity of the solvent is lowered and the solubility in the polyolefin (I) itself is lost.
On the other hand, when the value of (δ) exceeds 10.0, for example, a (meth) acrylic monomer (IV) and / or (containing a functional group (polar group such as —OH, —COOH, maleic anhydride group) and / or ( It also does not dissolve even relatively highly polar (homo) polymers, which are mainly produced as a by-product from the (meth) acrylic macromonomer (V). Further, when (δ _h ) is less than 2.0 or (δ _h ) exceeds 6.0, the high polarity part and low polarity part of the polymer of the present invention are not dissolved. Generally, the polyolefin (I) is composed of (meth) acrylic monomers whose polarity is (meth).
Polymers composed of polyolefin (I) and (meth) acrylic monomers, etc., which are remarkably low in polarity compared to the polarities of acrylic polymers, are difficult to compatibilize because both polymer components repel each other, and a uniform solution is obtained. It is difficult and the stability of the solution is poor. However, in general, as a method of compatibilizing polymers, (A) graft polymerization is performed to stabilize incompatible components. There is a method of stabilizing the system by adding a compatibilizing agent (B), but the polyolefin (I) in the present invention adopts a modification technique for simultaneously realizing the above (A) and (B). This is intended to achieve the desired compatibilization. That is, (meth) acrylic monomers which are easily compatible with both the acrylic polymer and the polyolefin (I) are selected, and the (meth) acrylic monomer (IV) and the (meth) acrylic macromonomer are added to the polyolefin (I). When (V) is copolymerized, a graft polymer is produced, and this portion is easily compatible with the polyolefin in the organic solvent.

Polyolefin (I) to which the present invention is directed
Is a component used to impart adhesiveness as a coating film physical property, and (a) ethylene, propylene, 1-
Examples thereof include resins and rubber-like substances made of a copolymer or homopolymer of an α-olefin unsaturated hydrocarbon such as butene and 4-methyl-1-pentene. Specifically, propylene-α
-Butene copolymer, ethylene-propylene-diene copolymer, ethylene-propylene copolymer, ethylene-1-
Butene copolymer, ethylene-vinyl acetate copolymer, polyethylene, poly-4-methyl-1 pentene and the like can be mentioned. Alternatively, it may be a resin chlorinated to 5 to 50% by weight of the above polyolefins.

Further, as the (b) polyolefins, copolymers of two or more kinds of the above α-olefins with conjugated or non-conjugated dienes, for example, ethylene-propylene-butadiene copolymer, ethylene-propylene-dicyclo. Pentadiene copolymer, ethylene-propylene-ethylidene norbornene copolymer, ethylene-propylene-1,5-
Hexadiene copolymers, (c) copolymers of α-olefins and conjugated or non-conjugated dienes, such as propylene-butadiene copolymers, propylene-ethylidene norbornene copolymers, (d) building monomers, etc. The copolymer of the monomer of (1) and α-olefin and its partially saponified product, (e) the above-mentioned copolymer, or a composition comprising two or more thereof is used. Further, a modified polyolefin resin in which a carboxyl group, a hydroxyl group or an acid anhydride group is introduced into these is also used. The modification of the polyolefin with the α, β-unsaturated carboxylic acid (II) and / or its acid anhydride (III) can be easily carried out by an ordinary reaction method. For example, a propylene-ethylene-1-butene copolymer is dissolved in toluene, and maleic anhydride and a peroxide are added dropwise to the flask while the reaction temperature is kept at 111 ° C to carry out the reaction. The obtained reaction liquid may be put into a non-solvent such as methanol to be resinified and dried. When this maleic anhydride-modified polyolefin is used in a coating composition comprising the solution of the present invention, the physical properties of the coating film are further improved.

The α, β-unsaturated carboxylic acid (II) and / or its acid anhydrides (III) used in the present invention include monocarboxylic acid type compounds such as acrylic acid, methacrylic acid and crotonic acid. There are aliphatic carboxylic acids having 6 or less carbon atoms, and in the dicarboxylic acid system, for example, there are aliphatic carboxylic acids such as maleic acid, fumaric acid, citraconic acid, and itaconic acid. Unsaturated carboxylic acid which it has, etc. are also used. Examples of the unsaturated acid of this system include acid anhydrides such as maleic anhydride and fumaric anhydride.

Further, as the (meth) acrylic monomer (IV) which is the object of the solution stabilization method of the present invention, those which easily dissolve the polyolefin (I) and the (meth) acrylic oligomer are preferentially selected. For example, methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth) acrylate, normal butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) ) Monofunctional (meth) acrylates such as acrylate and isobornyl (meth) acrylate; dimethylaminoethyl (meth) acrylate, 2
-Monofunctional (meth) acrylates having a functional group such as hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate and acrylamide; selected from styrenes such as styrene, chloromethylstyrene and α-methylstyrene A single type or a mixture of two or more types of monomers is preferably used. Especially polyolefins (I)
Examples of the monomer that easily dissolves are, for example, methacrylates such as cyclohexyl methacrylate, 2-ethylhexyl methacrylate, and lauryl methacrylate, acrylates such as butyl acrylate and isobornyl acrylate, vinyl esters such as vinyl ester of versatic acid, and paramethylstyrene. And the like, such as styrenes. On the contrary, examples of the monomer in which the polyolefins (I) are difficult to dissolve include polar compound monomers containing methacrylates such as methyl methacrylate, 2-hydroxyethyl methacrylate, and glycidyl methacrylate.

Further, the (meth) acrylic macromonomer (V) which is the object of the solution stabilization method of the present invention usually means one having a double bond at the end of the molecule, and a hydroxyl group or a carboxyl group at both ends of the molecule. Those having a functional group such as a group are also included. The molecular weight of these macromonomers is in the range of several hundreds to 10,000, and the types of macromonomers used,
The physical properties of the coating film of the copolymer obtained and the stability of the emulsion differ depending on the molecular weight. In addition to macromonomers and the like, caprolactone-modified (meth) acrylate-based oligomers, terminal hydroxyl group-containing (meth) acrylate oligomers, oligoester (meth) acrylates, urethane (meth) acrylates, epoxy (meth) acrylates and the like can be mentioned. Among these, those containing a hydroxyl group, a carboxyl group, an acid anhydride group or an amino group are also included. The (meth) acrylic macromonomer (V) also includes liquid rubbers made of polybutadiene or polyisoprene. For example, polybutadiene having a molecular weight of 500 to 4,000 having a functional group such as an epoxy group, a carboxyl group, a hydroxyl group, an amino group or an amide group in the molecule of a 1,4- or 1,2-structure and / or at the terminal of the molecule. And / or polyisoprenes and the like.

The modified polyolefin targeted by the present invention comprises a polyolefin (I), a (meth) acrylic monomer (IV) and a (meth) acrylic macromonomer (V).
It can be obtained by solution polymerization. As a polymerization initiator used at the time of polymerization, a peroxide type such as benzoyl peroxide and an azobis type such as azobisisobutyronitrile are used. Furthermore, if a chain transfer regulator is used to control the degree of polymerization, the degree of polymerization can be significantly reduced and the chain length can be made uniform. As the chain transfer regulator, mercaptan,
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, 3-ethoxypropanethiol, and disulfides. Examples thereof include bis-2-aminodiphenyl disulfide, bis-2-dibenzothiazoyl disulfide, diisoprovirzanthogen disulfide and the like. As the polymerization method, the above-mentioned polymerization initiator and / or polymerization regulator may be dissolved in advance in a solution of polyolefin (I) such as toluene or xylene, or may be added in the polymerization process. ) A solution of the acrylic monomer (IV) and the (meth) acrylic macromonomer (V) is dropped into the reaction vessel while stirring and polymerizing in a nitrogen atmosphere.

It is 1) that a solution of the above-mentioned modified polyolefin in an ordinary organic solvent causes layer separation during storage in a container or the like.
The graft ratio at the time of modification is considerably low due to the presence of foreign substances mixed in the raw material and the effect of oxygen remaining in the system, and a polymer group having a composition mainly composed of polyolefin (I) and mainly (meth) Acrylic monomer (IV) and /
Or, the polymer group consisting of the (meth) acrylic macromonomer (V) becomes incompatible, or 2) the graft ratio at the time of modification is satisfactory, but since it is stored in a container for a long time, This is a case where layer separation occurs or is predicted to occur due to a difference in specific gravity between polymer groups and / or a difference in behavior with respect to a solvent.

According to the results of studies conducted by the present inventors, a solvent showing good results when added in the above cases is as follows.
(Δ) and (δ _h ) are within the above ranges as shown in Table 1. Examples thereof include solvents such as esters such as n-butyl acetate and isobutyl acetate, ketones such as methyl isobutyl ketone and cyclohexanone, ethers such as tetrahydrofuran and the like, which have a so-called intermediate hydrogen bonding strength. As a matter of course, the polarity of the polymer of the polyolefin (I) and the hydrogen-bonding force components (δ) and (δ _h ) of its solubility parameter, or the (meth) acrylic monomer (IV) and / or (meth) acrylic macromonomer Although it depends on (δ) and (δ _h ) of the polymer group consisting of (V), basically, the above solvent group, for example, esters such as n-butyl acetate and isobutyl acetate, methyl isobutyl ketone, etc. Solvents having a so-called intermediate hydrogen bonding force, such as ketones such as cyclohexanone and ethers such as tetrahydrofuran, can be good addition solvents. Of course, as shown in Table 1, the above-mentioned good additive solvents include C.I. M. The solubility parameter (δ) according to Hansen is 8.0 to 10.0 (cal / cm ³ ).
^1/2 and C.I. M. The hydrogen bonding force component (δ which is one component of the three-dimensional solubility parameter by Hansen
_h ) is an organic solvent having 2.0 to 6.0 (cal / cm ³ ) ^1/2 , and may be a mixed solvent obtained by mixing the organic solvent with another organic solvent. As used herein, the mixed solvent is one of the solvents (δ) and (δ _h ) in the above range.
Refers to a mixed solvent of one or more kinds of other solvents and one or more kinds of other solvents, and the kind of the other solvent used at this time is polyolefin (I),
(Meth) acrylic monomer (IV) and / or (meth)
It is preferable that the acrylic macromonomer (V) can be partially or completely dissolved. For example, when the (meth) acrylic polymer contains a hydroxyl group of 50 KOHmg / g or more, it is a solvent selected from the group of solvents having a strong hydrogen bond centering on alcohols such as isoprobe alcohol and propylene glycol. In addition, when 5 to 100% by weight of the solvent is added to the added solvent, the stabilization of the solution is significantly increased.

As a method of addition, it is preferable to add and mix at room temperature or a predetermined temperature of 25 ° C. or higher. Where 10
If the temperature in the system is too low, not more than 0 ° C., the modified polyolefin will gel or settle to increase the viscosity, so the mixing temperature should be room temperature or higher. Furthermore, the addition amount is 1 to the resin amount of the modified polyolefin.
200% by weight is desirable, and more preferably 5 to 100% by weight. Here, when the above-mentioned amount of the solvent is added to the modified polyolefin solution having a predetermined resin concentration, the resin concentration is naturally lowered, but in order to adjust the resin concentration to a desired value, toluene or xylene, etc., in an amount corresponding to the amount of the solvent added in advance is used. Is removed by a method such as concentration under reduced pressure, and then a predetermined solvent may be added.

The modified polyolefin solution stabilized by the above method and conditions has a layer separation of 6 when stored at room temperature.
The layer separation occurs only to such an extent that it does not occur at all for a month or there is no problem in practical use. On the other hand, as for the coating film performance, as described above, it is the state of suppressing the phase separation that stabilizes the solution state, and the film-forming process of the modified polyolefin solution stabilized by the above method is xylene or toluene. Unlike a solution consisting only of a solvent having a weak hydrogen bonding force such as, for example, or a mixture thereof, it is performed more ideally, so that the gloss is very good, the coating film has few defects, and thus PP.
The adhesion to propylene-based copolymers is remarkably improved.

The present invention will be described below with reference to examples.

Production Example 1 "Hardlen 14-LLB" (Chlorinated polypropylene manufactured by Toyo Kasei Co., Ltd .: chlorination rate; 27% by weight, solid content; 30) in a flask equipped with a stirrer, a thermometer and a cooling tube.
% By weight, weight average molecular weight; 40,000, toluene solution) 100% by weight, Nisso polybutadiene G-1000
(Polybutadiene manufactured by Nippon Soda Co., Ltd .: number average molecular weight;
1,000 g, containing hydroxyl groups at both ends of the molecule), 35 g of toluene, and 0.3 g of benzoyl peroxide were added, and the nitrogen in the reaction vessel was sufficiently replaced. I kept it. Next, the temperature is raised to 85 ° C., and the mixture is stirred at 85 ° C. for 2 hours. Then, 6.0 g of Praxel FA4 (acrylic oligomer manufactured by Daicel Chemical Industries, Ltd., hydroxyl value 98, molecular weight 570), AN
2.0 g of 6 (Toagosei Chemical Industry Co., Ltd. macromonomer, methacryloyl group-terminated styrene-acrylonitrile macromonomer, molecular weight 6,000), AW-6S
(Toagosei Kagaku Kogyo Co., Ltd., macromonomer, methacryloyl group-terminated isobutyl methacrylate macromonomer, molecular weight 6,000, 50 wt% toluene solution) 1.0 g, and methyl methacrylate 5.0 g as a mixture, solid content in toluene solution What was made into 30 weight% is dripped over 1 hour. Then, 0.1 g of benzoyl peroxide was added, and the mixture was stirred at 85 ° C. for 3 hours to complete the copolymerization reaction in a total of 6 hours. 50 ° C after completion of copolymerization reaction
After cooling and filtration, a modified chlorinated polyolefin solution was obtained.

Production Example 2 In a flask equipped with a stirrer, a thermometer and a cooling tube, "Hardlen CY-9020" (Toyo Kasei Kogyo Co., Ltd. chlorinated polypropylene: chlorination rate; 20% by weight, solid content; 2)
0 wt%, number average molecular weight; 7,000, toluene solution)
100% by weight, Nisso polybutadiene TEAI-1000
(Polybutadiene manufactured by Nippon Soda Co., Ltd .: number average molecular weight;
1,000 g, containing urethane groups at both ends of the molecule), 35 g of toluene, 0.3 g of benzoyl peroxide were added, nitrogen substitution in the reaction vessel was sufficiently performed, and thereafter, an atmosphere under a nitrogen stream in all reaction steps. Kept at. Next, the temperature is raised to 85 ° C., and the mixture is stirred at 85 ° C. for 2 hours. Next, 6.0 g of 2-ethylhexyl methacrylate, 2.0 g of AN6 (macromonomer manufactured by Toagosei Chemical Industry Co., Ltd., methacryloyl group-terminated styrene-acrylonitrile macromonomer, molecular weight 6,000), AW-6S (Toagosei Chemical Industry Co., Ltd.) 1.0 g of a macromonomer manufactured by Co., Ltd., a methacryloyl group-terminated isobutyl methacrylate macromonomer, a molecular weight of 6,000, and a toluene solution of 50% by weight), and 5.0 g of cyclohexylmethacrylate as a mixture to obtain a solid content of 20% by weight in a toluene solution. The thing is dripped over 1 hour. Then, 0.1 g of benzoyl peroxide was added, and the mixture was stirred at 85 ° C. for 3 hours to complete the copolymerization reaction in a total of 6 hours. After the completion of the copolymerization reaction, it was cooled to 50 ° C. and filtered to obtain a modified chlorinated polyolefin solution.

Production Example 3 "Hardlen 13-LB" (Chlorinated PP manufactured by Toyo Kasei Co., Ltd .: chlorination degree; 26% by weight, resin concentration; 20)
%, Weight average molecular weight: 7,000,) 100 g, macromonomer AW-6S (macromonomer manufactured by Toa Gosei Chemical Industry Co., Ltd., molecular weight 6,000 of methacryloyl group-terminated isobutyl methacrylate macromonomer, 50% toluene solution) While stirring and heating a mixture of 2 g and cyclohexyl methacrylate 0.4 g, the solution temperature is 90 ° C.
After that, the space in the system was sufficiently replaced with nitrogen, and the nitrogen stream was kept at a constant flow rate until the end of the reaction. Then, 0.2 g of benzoyl peroxide was added, 0.1 g after 1 hour, and 0.1 g after 2 hours and 3 hours.
The mixture was added and further reacted at the same temperature for 2 hours while stirring under heating to obtain a modified chlorinated polyolefin solution having a resin concentration of 21.3% by weight.

Production Example 4 Propylene-butene copolymer (75 mol% propylene component, weight average molecular weight; 15,000, 12 wt% toluene solution) in a flask equipped with stirrer, thermometer and cooling tube.
100 g of toluene, 35 g of toluene, and 0.3 g of benzoyl peroxide were added, and the atmosphere in the reaction vessel was sufficiently replaced with nitrogen, and the atmosphere in the nitrogen stream was kept in all reaction steps thereafter. Next, the temperature is raised to 85 ° C. and the mixture is stirred for 2 hours. Then,
6.0 g of 2-ethylhexyl methacrylate, 5.0 g of 2-hydroxyethyl methacrylate and AN6
(Toa Synthetic Chemical Industry Co., Ltd. macromonomer, methacryloyl group terminal styrene-acrylonitrile macromonomer, molecular weight 6,000) 2.0 g, AW-6S (Toa Synthetic Chemical Industry Co., Ltd. macromonomer, methacryloyl group terminal isobutyl methacrylate macro) monomer,
Molecular weight 6,000, 50 wt% toluene solution) 1.0
g and maleic anhydride as a mixture of 0.3 g, a toluene solution having a solid content of 12% by weight was added dropwise over 1 hour. Then, 0.1 g of benzoyl peroxide was added, and the mixture was stirred at 85 ° C. for 3 hours to complete the copolymerization reaction in a total of 6 hours. After the completion of the copolymerization reaction, it was cooled to 50 ° C. and filtered to obtain a modified polyolefin solution.

[0027]

[Table 2]

Example 1 In 100 g of the modified chlorinated polyolefin solution produced in Production Example 1 above, a separated substance was observed in the lower layer in a storage container (made of glass) after 3 months from the production. 1.1 kg in a content of 15 kg was isolated as the isolate. All of these were transferred to another container, sealed, and heated in a water bath until the internal temperature reached 40 ° C. to obtain a uniform solution. Furthermore, the temperature in the system is raised to 50 ° C,
2 kg of toluene was distilled off using an evaporator. Then, in this concentrated liquid, n-butyl acetate [δ = 8.51,
δ _h = 3.08, both in units of (cal / cm ³ ) ^1/2 , and so on]: cyclohexanone (δ = 9.58, δ _h =
2.49) = 2: 1 (weight ratio) mixed solvent 2k
g and mixed well. After storing for 6 months in a warehouse kept at 15 to 35 ° C., it was confirmed that no isolate was found in the container. The results are shown in Table 3.

Example 2 In 100 g of the modified chlorinated polyolefin solution (in a glass sample bottle) produced in Production Example 2 above, a separated substance was observed in the lower layer after 3 months from the production. Contents 1
0.6 kg out of 5 kg was isolated as the isolate.
All of these were transferred to another container, sealed, and heated in a water bath until the internal temperature reached 50 ° C. to obtain a uniform solution. Furthermore, the temperature in the system was raised to 55 ° C., and 3 kg of toluene was distilled off using an evaporator. Then, 3 kg of cyclohexanone was added to this concentrated liquid and mixed well. After storing for 6 months in a warehouse kept at 15 to 35 ° C., it was confirmed that no isolate was found in the container. The results are shown in Table 3.

Example 3 In 100 g of the modified chlorinated polyolefin solution produced in Production Example 3 (in a glass sample bottle), 3 months after the production, a separated substance was observed in the lower layer. Contents 15
0.3 kg / kg was isolated as the isolate. All of these were transferred to another container, sealed, and heated in a water bath until the internal temperature reached 50 ° C. to obtain a uniform solution.
Furthermore, the temperature in the system was raised to 55 ° C., and 1 kg of toluene was distilled off using an evaporator. Then, 1 kg of tetrahydrofuran (δ = 9.90,
δ _h = 3.9) was added and mixed well. 15-35 ° C
After storing it for 6 months in a warehouse kept at 1, no separation was confirmed in the container. The results are shown in Table 3.

Example 4 Modified polyolefin solution 1 produced in Production Example 4 above
In the case of 00 g (in a glass sample bottle), a separated substance was observed in the lower layer after 3 months from the production. 0.6 kg in a content of 15 kg was isolated as the isolate. All of these were transferred to another container, sealed, and heated in a water bath until the internal temperature reached 50 ° C. to obtain a uniform solution. Furthermore, the temperature in the system was raised to 55 ° C., and 3 kg of toluene was distilled off using an evaporator. Then, in this concentrated liquid, cyclohexanone: isopropyl alcohol = 8: 2
(Weight ratio) of 3 kg was added and mixed well. 15-35
After storing for 6 months in a warehouse kept at ℃, when confirmed, no isolate was confirmed in the container. The results are shown in Table 3.
It was shown to.

[0032]

[Table 3]

1) Composition: weight ratio. B: Acetic acid n-
Butyl, C; cyclohexanone, TF; tetrahydrofuran, I; isopropyl alcohol, X; xylene, T
O: toluene, EB: ethylbenzene, TL: tetralin.

2) Addition amount: Shown as a weight% with respect to the resin amount of the modified polyolefin solution.

3) Solution state: visually determined in a transparent container.

4) Adhesion: polypropylene plate (hereinafter P
Abbreviated as P plate. Mitsui Noblen SB-E3 is prepared by
Press-molded 100 mm x 50 mm, thickness 2 m
The surface of m) is thoroughly washed with tap water and dried. Dilute the modified polyolefin solution to 7% by weight with thinner and add 25
While maintaining the temperature at ℃, using an air spray gun (Meiji Kikai Seisakusho Co., Ltd. F-88 type), the air pressure is 2.
Spray coating was performed from a distance of 30 cm at 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. Evaluation is JIS K540
According to the OX cut tape method. ⊚: Good (even on 10 points, even if the same X part is peeled off with cellophane tape 5 times, the coating film is not scratched or peeled at all), ○: Approximately good (on a maximum of 10 points, Even if the same X location is peeled off twice with cellophane tape, the coating film is not scratched or peeled off at all. △: Slightly bad (with a perfect score of 10, peeling off the same X location twice with cellophane tape) And the coating is scratched or peeled off slightly).

5) Gloss: Polypropylene plate (hereinafter, PP
Abbreviated as a plate. Mitsui Noblen SB-E3 is press-molded by a conventional method, and is 100 mm x 50 mm, thickness 2 m.
The surface of m) is thoroughly washed with tap water and dried. Dilute the emulsion concentration to 20% by weight with deionized water, and add 25
While maintaining the temperature at ℃, using an air spray gun (Meiji Kikai Seisakusho Co., Ltd. F-88 type), the air pressure is 2.
Spray coating was performed from a distance of 30 cm at 0 kg / cm ² G. The coating thickness was 5 to 10 μ (resin base). Drying was performed at 80 ° C. for 30 minutes, the temperature was returned to room temperature, and 24 hours passed, which was used for the test. As the gloss meter, a gloss meter IG-310 manufactured by Horiba Ltd. was used.

6) Adhesion between layers-1: 5) Washing with P
Spray coating on P plate, PP plate, thickness 5 ~ 10μ
(Resin base), and dried at 80 ° C. for 30 minutes. Thereafter, Retan PG-80 (urethane paint manufactured by Kansai Paint Co., Ltd.) is applied so as to have a thickness of 100 to 150 μ (resin base). Further, after drying at 80 ° C. for 30 minutes and returning to room temperature for 24 hours, a test piece is used. After leaving the test piece for 24 hours in an atmosphere kept at 20 ± 1 ° C. and a relative humidity of 30 ± 3%, 4).
Adhesion is evaluated by the method described in.

7) Interlayer adhesion-2: 5) Washing with P
Spray coating on P plate, PP plate, thickness 5 ~ 10μ
(Resin base), and dried at 80 ° C. for 30 minutes. After that, Flex-1211 (melamine paint manufactured by Kansai Paint Co., Ltd.) is applied to a thickness of 100 to 150 μ (resin base). Further, after drying at 120 ° C. for 30 minutes and returning to room temperature for 24 hours, a test piece is used. 20 ± 1 ℃ and relative humidity 30 ± 3%
After leaving the test piece for 24 hours in the atmosphere kept at
The adhesion is evaluated by the method described in 4).

Comparative Example 1 Using the same modified chlorinated polyolefin solution as in Example 1, the same operation as in Example 1 was carried out to obtain a uniform concentrate 1.
3 kg was obtained. Here, 2 kg of xylene (δ = 8.8
0, δ _h = 1.5) and mixed well,
It was stored in a warehouse kept at 35 ° C for 1 month. Upon confirmation at that point, the isolate was identified in the container exactly as it was when the isolate was first identified in the modified chlorinated polyolefin solution.

Comparative Example 2 In 100 g of the modified chlorinated polyolefin solution (in a glass sample bottle) produced in Production Example 2 above, a separated substance was observed in the lower layer after 3 months from the production. Contents 1
0.6 kg out of 5 kg was isolated as the isolate.
All of these were transferred to another container, sealed, and heated in a water bath until the internal temperature reached 50 ° C. to obtain a uniform solution. Furthermore, the temperature in the system was raised to 55 ° C., and 3 kg of toluene was distilled off using an evaporator. Then toluene _{(δ = 8.91, δ h =} 1.0) in the concentrate was thoroughly mixed by adding 3kg a. After storing for 3 months in a warehouse kept at 15 to 35 ° C., it was confirmed that the separated product was regenerated in the container.

Comparative Example 3 In 100 g of the modified chlorinated polyolefin solution (in a glass sample bottle) produced in Production Example 3 above, a separated substance was observed in the lower layer after 3 months from the production. Contents 1
0.3 kg in 5 kg was isolated as the isolate.
All of these were transferred to another container, sealed, and heated in a water bath until the internal temperature reached 50 ° C. to obtain a uniform solution. Furthermore, the temperature in the system was raised to 55 ° C., and 1 kg of toluene was distilled off using an evaporator. Then, 1 kg of ethylbenzene (δ = 8.80, δ
_h = 0.7) was added and mixed well. After storing for 1 month in a warehouse kept at 15 to 35 ° C., it was confirmed that the separated substance was again confirmed in the container.

Comparative Example 4 Modified Polyolefin Solution 1 Produced in Production Example 4 above
In the case of 00 g (in a glass sample bottle), a separated substance was observed in the lower layer when 3 months passed after the production. Contents 15kg
0.6 kg of was isolated as the isolate. All of these were transferred to another container, sealed, and heated in a water bath until the internal temperature reached 50 ° C. to obtain a uniform solution. Furthermore, the temperature in the system was raised to 55 ° C., and 3 kg of toluene was distilled off using an evaporator. The tetralin _{(δ = 9.50, δ h =} 1.4) to 3kg in this concentrate
Add and mix well. After storing for 6 months in a warehouse kept at 15 to 35 ° C., it was confirmed that the same isolate was found in the container.

[0044]

According to the present invention, the modified polyolefin solution contains C.I. M. The solubility parameter δ according to Hansen is 8.0 to 10.0 (cal / cm ³ ) ^1/2 , and the hydrogen bonding force component δ _h which is one component of the three-dimensional solubility parameter according to him is 2.0. ~ 6.0 (cal / c
By adding and mixing an organic solvent of m ³ ) ^1/2 ,
The solution has room temperature stability of 6 months or more, layer separation is suppressed to the extent that it can be stored as a uniform solution or has no problem in practical use, and has long-term storage stability. On the other hand, as the physical properties of the coating film, a one-coat finished coating film or a primer coating film can be obtained by coating or coding on a polyolefin-based molded product or film and drying it in the temperature range from room temperature to 160 ° C. The resulting coating film has excellent adhesion,
Good various physical properties such as good physical properties such as gloss were obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-59-138271 (JP, A) JP-A-60-38436 (JP, A) JP-A-3-221512 (JP, A) JP-A-5- 112751 (JP, A) JP 5-239292 (JP, A) JP 5-279431 (JP, A) JP 6-179850 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 255/00 C08L 51/06

Claims (2)

(57) [Claims] 1. A method for stabilizing a solution or dispersion of a modified polyolefin obtained by copolymerizing polyolefin (I) with (meth) acrylic monomer (IV) and (meth) acrylic macromonomer (V), The solution or dispersion is a solution or dispersion with an organic solvent that dissolves polyolefin (I), and the solubility parameter by CM Hansen for the solution or dispersion. (Δ) is 8.0 to 10.0 (cal / cm ³ ) ^1/2 , and C.I. M. The hydrogen bonding force component (δ _h ) which is one component of the three-dimensional solubility parameter by Hansen is 2.
A method for stabilizing a modified polyolefin solution or dispersion, which comprises blending at least one organic solvent having a concentration of 0 to 6.0 (cal / cm ³ ) ^1/2 . 2. The solubility parameter (δ) is 8.0 to 1.
0.0 (cal / cm ^{3) 1/2,} and hydrogen bonding components ([delta] _h) is an organic solvent that is ^{2.0~6.0 (cal / cm 3) 1/2} , acetic acid n- 2. A material selected from butyl, isobutyl acetate, methyl isobutyl ketone, cyclohexanone and tetrahydrofuran.
A method for stabilizing a modified polyolefin solution or dispersion as described.