JP2596884B2 - Binder resin solution composition with good low-temperature fluidity - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyolefin resin,
For example, the present invention relates to a binder resin composition used for the purpose of protection or cosmetics such as polypropylene, polyethylene, ethylene propylene copolymer, ethylene propylene diene copolymer, etc. More specifically, it has excellent adhesion to these sheets, films and molded products. Paints, primers, printing inks,
Alternatively, the present invention relates to a binder resin solution composition for an adhesive.

[0002]

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

[0003] For the coating and bonding of such a hard-to-adhere polyolefin resin, a low chlorinated polyolefin having a strong adhesive force to the polyolefin resin has conventionally been used as a binder resin. For example, Japanese Patent Publication No. 46-274
No. 89 proposes chlorinated isotactic polypropylene chlorinated to 20 to 40% by weight as a binder resin for a printing ink of a polypropylene film.
Japanese Patent Publication No. 50-35445 and Japanese Patent Publication No. 50-37688
Chlorinated propylene-ethylene copolymers chlorinated to 4040% by weight have been proposed as binder resins for printing inks and adhesives for polyolefins.

Further, Japanese Patent Application Laid-Open No. Sho 57-36128, Japanese Patent Publication No. Sho 63-5
No. 0381, JP-A-59-166534, JP-B-63-36624
Japanese Patent Application Publication No. JP-A-2005-64103 discloses a low-chlorinated polypropylene or a low-chlorinated propylene-α-olefin copolymer having a carboxylic acid and / or carboxylic anhydride having a chlorine content of 5 to 50%, which is a polyolefin-based molded product. It has been proposed as a coating primer or a binder resin for coating.

Further, JP-A-1-110580 discloses a terpolymer comprising an unsaturated carboxylic acid monomer containing a carboxylic acid and / or a carboxylic anhydride, an unsaturated vinyl ester monomer and ethylene. Chlorinated terpolymers chlorinated to 3 to 50% by weight have been proposed as binder resins for adhesives of polyolefin resins.

In general, the lower chlorinated polyolefins described above tend to have lower adhesion to polyolefins and lower solvent resistance as the chlorine content increases. Therefore, it is preferable to set the chlorine content as low as possible. However, if the chlorine content is too low, the solution state deteriorates and the viscosity increases or gels during storage, so that the workability such as coating and spray coating deteriorates remarkably. Even if the chlorine content of the low-chlorinated polyolefin is set within a range that does not impair workability such as coating and spray coating, the fluidity of the solution will deteriorate when stored at low temperatures, and handling at low temperatures in winter. Great restrictions on work. It is possible to improve the low-temperature fluidity by lowering the solution concentration of the low-chlorinated polyolefin, but if the concentration is low, it becomes difficult to disperse the pigment when processing it into ink or paint, and the transportation cost increases. Cause problems.

[0007]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems and provides a low-chlorinated polyolefin with good adhesion to polyolefin and low solvent resistance without impairing the low-temperature fluidity and workability of the polyolefin. An object of the present invention is to provide an excellent binder resin solution for paints, primers, printing inks or adhesives.

[0008]

That is, the present inventors have found that the weight ratio of alicyclic hydrocarbon having 5 to 9 carbon atoms to aromatic hydrocarbon is in the range of 10:90 to 90:10. A binder resin solution obtained by dissolving a chlorinated polyolefin having a chlorine content of 12 to 26% by weight to a solid content concentration of 15 to 40% by weight in a mixed solvent shows good low-temperature fluidity and workability, Further, they have found that they have excellent adhesion and solvent resistance to polyolefin, and have accomplished the present invention.

The alicyclic hydrocarbon having 5 to 9 carbon atoms used in the present invention includes, for example, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane,
Ethylcyclopentane, dimethylcyclopentane, cycloheptane, ethylcyclohexane, dimethylcyclohexane, methylethylcyclopentane, trimethylcyclopentane, cyclooctane, cyclononane, etc., a hydrocarbon solvent having one alicyclic structure in the molecule Say that. These solvents can be used alone or in combination of two or more. The alicyclic hydrocarbon preferably has 5 to 9 carbon atoms. When the number of carbon atoms is 4 or less, the boiling point is too low, and when the number of carbon atoms is 10 or more, the boiling point is too high, so that the solvent is not suitable.

[0010] The aromatic hydrocarbon used in the present invention is:
For example, benzene, toluene, xylene, ethylbenzene, isopropylbenzene and aromatic solvent naphtha having a boiling point range of 120 to 200 ° C obtained by fractionation of coal tar gas oil, and hydrocarbons having one benzene ring in the molecule Refers to a system solvent. These solvents can be used alone or in combination of two or more.

As the solvent for the binder resin solution of the present invention, a mixed solvent of an alicyclic hydrocarbon and an aromatic hydrocarbon is used. The optimal weight mixing ratio of alicyclic and aromatic hydrocarbons is
When the ratio is in the range of 10:90 to 90:10, a binder resin solution having good low-temperature fluidity can be obtained. When a solvent other than an alicyclic hydrocarbon and an aromatic hydrocarbon is mixed into the mixed solvent, the effect of the present invention is not reduced if the amount is small, but the effect is large if mixed in a large amount. May be reduced. The amount of the mixture that reduces the effect differs depending on the properties of each solvent, but in order to carry out the present invention, it is necessary that the solvent system contains 70% by weight or more of the mixed solvent.

The chlorine content of the chlorinated polyolefin used in the present invention varies depending on the type of the raw material polyolefin before chlorination, but is most preferably 12 to 26% by weight. Chlorine content
If the content is less than 12% by weight, the solubility in the mixed solvent becomes poor, and good low-temperature fluidity cannot be obtained. On the other hand, if the chlorine content is higher than 26% by weight, the adhesion to polyolefins and the solvent resistance deteriorate, which is not preferable.

When the raw material is chlorinated polypropylene, which is crystalline polypropylene, the optimum chlorine content is 18 to 26% by weight. The optimum chlorine content is also 18 to 26% by weight for a carboxyl group-containing chlorinated polypropylene containing carboxylic acid and / or carboxylic acid anhydride as a raw material of crystalline polypropylene.

When the raw material is a chlorinated propylene-α-olefin copolymer which is a propylene-α-olefin copolymer containing 50 to 97 mol% of a propylene component, the optimum chlorine content is 12 to 26% by weight. is there. Suitable for propylene-α-olefin copolymer containing 50 to 97 mol% of propylene component and carboxyl group-containing chlorinated propylene-α-olefin copolymer containing carboxylic acid and / or carboxylic anhydride. The chlorine content is between 12 and 26% by weight.

When the starting material is a chlorinated terpolymer, which is a terpolymer comprising an unsaturated carboxylic acid monomer, an unsaturated vinyl ester monomer and ethylene, the optimum chlorine content is 15 to 25% by weight. is there.

The crystalline polypropylene which is the raw material of the present invention is an isotactic polypropylene having a weight average molecular weight of 10,000 to 300,000.

The propylene-α-olefin copolymer which is a raw material of the present invention is mainly composed of propylene and α
-An olefin is copolymerized, and either a block copolymer or a random copolymer can be used. Examples of the α-olefin component include ethylene, 1-butene,
Examples thereof include 1-pentene, 1-hexene, 1-heptene, 1-octene, and 4-methyl-1-pentene. The content of the propylene component is optimally from 50 to 97 mol%, and if it is less than 50 mol%, the adhesion to polypropylene decreases. On the other hand, if it exceeds 97 mol%, the flexibility of the coating film deteriorates.

The terpolymer, which is the raw material of the present invention, is obtained by copolymerizing an unsaturated carboxylic acid monomer, an unsaturated vinyl ester monomer, and ethylene by a known method such as a high-pressure radical polymerization method, a solution polymerization method, or an emulsion polymerization method. It is polymerized. Examples of the unsaturated carboxylic acid monomer component include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, maleic anhydride, and itaconic anhydride. Examples of the unsaturated vinyl ester monomer include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and the like.

The content of the unsaturated carboxylic acid monomer is from 1 to
10% by weight is optimal. If it is less than 1%, the content of the polar group in the composition becomes too small to obtain sufficient adhesiveness,
Those exceeding 10% gel during the chlorination. The content of the unsaturated vinyl ester monomer is optimally 1 to 50% by weight. If less than 1%, the effect of improving the adhesiveness is not recognized,
If it exceeds 50% by weight, the advantages of the ethylene polymer such as processability, flexibility and mechanical strength are lost.

Crystalline polypropylene and propylene-α
-A method of graft-polymerizing an unsaturated carboxylic acid monomer to an olefin copolymer is a method in which the polyolefin is heated and melted to a temperature equal to or higher than its melting point in the presence of a radical generator to cause a reaction (melting method), and the polyolefin is dissolved in an organic solvent. After that, the reaction can be carried out by a known method such as a method of heating and stirring in the presence of a radical generator to cause a reaction (solution method).

In the case of the melting method, a Banbury mixer,
Using a kneader, extruder, or the like, the reaction is performed at a temperature of not less than the melting point and not more than 300 ° C. On the other hand, in the solution method, it is preferable to use an aromatic solvent such as toluene or xylene as a reaction solvent. The reaction temperature is 100-180 ° C,
There is a feature that a uniform graft polymer can be obtained with few side reactions.

Examples of the radical generator used in the reaction include benzoyl peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, dicumyl peroxide, tert-butyl peroxybenzoate, methyl ethyl ketone peroxide, cumene hydroperoxide. Organic peroxide such as peroxide, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4
-Dimethylvaleronitrile), 2,2'-azobis (4
-Methoxy-2,4-dimethylvaleronitrile) and the like.

As the unsaturated carboxylic acid monomer used in the reaction, the above-mentioned monomers can be used as they are. Content of unsaturated carboxylic acid monomer is 1 to 10% by weight
Is optimal. If it is less than 1%, the content of the polar group in the composition becomes too small to obtain sufficient adhesiveness, and if it exceeds 10%, it gels during chlorination.

Crystalline polypropylene and propylene-α
The method of graft-polymerizing the unsaturated carboxylic acid monomer to the chlorinated olefin copolymer may be carried out according to the above-mentioned solution method, and the reaction temperature is preferably from 80 to 110 ° C. If the temperature is too low, the progress of the reaction will be slow, and if the temperature is too high, the chlorinated polyolefin will be undesirably decomposed. The content of the unsaturated carboxylic acid monomer is 1
~ 10% by weight is optimal. If it is less than 1%, the content of the polar group in the composition becomes too small to obtain sufficient adhesiveness, and if it exceeds 10%, the grafting reaction becomes insufficient,
Because unreacted unsaturated carboxylic acid monomers remain in the system, good physical properties cannot be obtained.

The chlorination of polyolefin can be easily carried out by a usual reaction method. For example, polyolefin is dispersed or dissolved in water or a medium such as carbon tetrachloride or chloroform,
This is carried out by blowing chlorine gas at a temperature of 50 to 120 ° C. under pressure or normal pressure in the presence of a catalyst or under irradiation of ultraviolet rays.

When the binder resin solution of the present invention is produced, the above-mentioned chlorinated polyolefin may be dried and then dissolved in a mixed solvent of an alicyclic hydrocarbon and an aromatic hydrocarbon. After the completion of the reaction, the chlorination reaction solvent such as carbon tetrachloride or chloroform may be distilled off and replaced with the mixed solvent. The solid content of the binder resin solution is preferably 15 to 40% by weight. If the amount is less than 15% by weight, problems such as difficulty in dispersing the pigment when processing into ink or paint and increase in transportation cost occur. If it exceeds 40% by weight, the low-temperature fluidity deteriorates, and the handling operation at low temperatures in winter is greatly restricted, which is not preferable.

[0027]

The feature of the present invention is to further improve the properties of a low-chlorinated polyolefin having good adhesion to polyolefins. In other words, the lower the chlorine content of a low-chlorinated polyolefin, the better the adhesion to the polyolefin and the improved solvent resistance.However, the solution state deteriorates and the gel becomes thickened during storage, and the fluidity at low temperatures becomes poor. Deteriorate. For this reason, workability such as coating and spray coating is significantly deteriorated, and handling work at a low temperature in winter is greatly restricted, but a low-chlorinated polyolefin in a poor solution state as in the present invention is converted to an alicyclic hydrocarbon. By dissolving in a mixed solvent composed of styrene and an aromatic hydrocarbon, a binder resin solution having a good solution state, excellent low-temperature fluidity, and good adhesion to polyolefin and excellent solvent resistance can be obtained.

This effect of the mixed solvent can be estimated from the model structure of the chlorinated polypropylene as follows.

[0029]

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[0030]

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[0031]

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Formula 1 shows chlorinated polypropylene in which one chlorine atom is contained in 2 units of propylene.
The chlorine content is calculated to be about 30%. Similarly, chemical formula 2 is a case where one unit of chlorine is contained in three units of propylene, and the chlorine content is about 22%. Similarly, Chemical Formula 3 is a case where one chlorine atom is contained in 4 units of polypropylene, and the chlorine content is about 17.5.
%.

Although polypropylene is a thermoplastic resin, it is non-polar and crystalline and does not dissolve in aromatic hydrocarbons at room temperature. When a chlorine atom is bonded to polypropylene, the polarity is increased and the crystallinity is reduced, so that the polypropylene is dissolved in an aromatic hydrocarbon even at room temperature. When the chlorinated polypropylene of Chemical Formula 1, Chemical Formula 2, or Chemical Formula 3 is dissolved in an aromatic hydrocarbon, the low-temperature fluidity is improved in the order of Chemical Formula 1, Chemical Formula 2, Chemical Formula 3 within the chlorination degree range. (The higher the degree of chlorination, the better the low-temperature fluidity), and the more chlorine-bonded propylene units, the easier it is to dissolve in aromatic hydrocarbons. That is, it can be said that the propylene unit to which chlorine is bonded is easily dissolved in the aromatic hydrocarbon. On the other hand, when a chlorinated polypropylene having a low chlorination degree as shown in Chemical formula 3 is dissolved in a mixed solvent of an alicyclic hydrocarbon and an aromatic hydrocarbon, the low-temperature fluidity becomes good, so that the alicyclic hydrocarbon is made of chlorine. Suggests that the solubility is good even for a propylene unit to which is not bonded.

In the low chlorinated polyolefin, since the degree of chlorination is low, a unit having a high polarity to which chlorine is bonded and a nonpolar unit to which chlorine is not bonded are localized. Therefore, it seems to be effective to use a solvent having good solubility in each unit as a mixed solvent. That is, the weight ratio of alicyclic hydrocarbon to aromatic hydrocarbon is 10:90 to 90:
By dissolving the low-chlorinated polyolefin in a mixed solvent in the range of 10, a binder resin solution composition having good adhesion to polyolefin, excellent solvent resistance, and good low-temperature fluidity can be obtained. I guess it was.

The binder resin composition of the present invention can be used for paints and inks such as polyolefin films and sheets and molded articles.
It can be used as a binder resin such as an adhesive and a heat sealant. The modified chlorinated polyolefin obtained by copolymerizing the unsaturated carboxylic acid monomer of the present invention can also be used as a polyolefin-based primer for bumper coating. When coating a polyolefin bumper, the substrate surface was washed with trichloroethane vapor to make it easier for the primer to adhere, but trichloroethane was regulated as an ozone depleting substance. In many cases, steam cleaning is not performed. Since the adhesive property to polyolefin is remarkably improved, the vanider resin composition of the present invention shows good primer performance even to a polyolefin-based bumper which is not subjected to trichloroethane vapor cleaning.

The binder resin composition of the present invention may be used as it is after being coated, but it can be used as a paint or ink after kneading and dispersing by adding a pigment, a solvent and other additives. The vanider resin alone exhibits well-balanced coating film properties, but if necessary, alkyd resin, acrylic resin, polyacryl polyol, polyester resin, polyester polyol, polyether resin, polyether polyol, polyurethane resin , Chlorinated polyolefins and the like may be further added and used.

[0037]

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

(Trial Production Example-1) Melt Index: 14 g
300 g / min (measured according to ASTM D1238-62T) of isotactic polypropylene was charged into a glass-lined reaction vessel, and 5 L of carbon tetrachloride was added and sufficiently dissolved under a pressure of ² kg / cm ² . Thereafter, while irradiating ultraviolet rays, chlorine gas was blown from the bottom of the reactor to perform a chlorination reaction. Two kinds of reaction solutions having different chlorine contents were drawn out, and carbon tetrachloride as a reaction solvent was removed by drying under reduced pressure to obtain chlorinated polypropylene solids having chlorine contents of 25% by weight and 30% by weight.

(Trial Production Example 2) Isotactic polypropylene 500 having a melt viscosity of about 2600 cps at 180 ° C.
g was placed in a three-necked flask equipped with a stirrer, dropping funnel and condenser for refluxing the monomers, and was completely melted in an oil bath kept constant at 180 ° C. After about 10 minutes of purging with nitrogen in the flask, 20 g of maleic anhydride was added over about 5 minutes while stirring, and then di-tert-
2 g of butyl peroxide was dissolved in 10 ml of heptane and charged from a dropping funnel over about 30 minutes. At this time,
After maintaining the temperature at 180 ° C. and continuing the reaction for another 1 hour, unreacted maleic anhydride was removed over about 30 minutes while reducing the pressure in the flask with an aspirator. Next, this product was subjected to a chlorination reaction in accordance with the method of Prototype Example 1 to obtain a maleic anhydride-modified chlorinated polypropylene having a chlorine content of 22% by weight and 27% by weight.

(Prototype Example-3) Melt index is 200
g / 10min (measured according to JIS K6730), and a terpolymer containing 91% of ethylene, 5.7% of ethyl acrylate, and 3.3% of maleic anhydride was prepared as a trial production example-1.
Chlorination reaction according to the method described above, the chlorine content is 20% by weight
And a solid of 28% by weight of a chlorinated terpolymer was obtained.

(Examples 1 to 4 and Comparative Examples 1 to 10) The chlorinated polyolefins obtained in Prototype Examples 1, 2, and 3 were converted to aromatic hydrocarbons, alicyclic hydrocarbons, and other Dissolved in the solvent. The mixing ratio is shown in Table 1. Table 2 shows the solution state (low-temperature fluidity) of each chlorinated polyolefin solution stored in an atmosphere at 0 ° C. to 25 ° C.

(Example-5 and Comparative Example-11) Example-1
Chlorinated polypropylene solution (chlorine content: 25%, mixed solvent of toluene / cyclohexane) and the chlorinated polypropylene solution of Comparative Example-8 (chlorine content: 30%, toluene alone) were not treated with a coating rod # 4. Each was applied to a polypropylene film (hereinafter referred to as untreated PP), dried at room temperature for 24 hours, and then subjected to a heat seal strength test. In the heat seal strength test, the coated surfaces were overlapped, heat sealed at 120 ° C.-1 kg / cm ² for 1 second under pressure bonding conditions, and after 24 hours, a 180 ° peel strength test was performed with Tensilon (tensile speed: 50mm / min). The results are shown in Table 3.

(Example-6 and Comparative Example-12) Example-3
Chlorinated terpolymer solution (chlorine content: 20%, mixed solvent of toluene / methylcyclohexane) and chlorinated terpolymer solution of Comparative Example-10 (chlorine content: 28%, toluene alone) From untreated PP, linear low-density polyethylene (hereinafter referred to as LLDPE), low-density polyethylene (hereinafter referred to as LDPE), high-density polyethylene (hereinafter HDPE)
) And a heat seal strength test was performed. The test conditions were exactly the same as in Example 5, except that the heat sealing temperature of the polyethylene film was 90 ° C. The results are shown in Table 3.

(Example-7 and Comparative Example-13) Example-2
Maleic anhydride-modified chlorinated polyolefin solution (chlorine content: 22%, mixed solvent of toluene / cyclohexane) and maleic anhydride-modified chlorinated polypropylene solution of Comparative Example-9 (chlorine content: 27%, toluene alone) 100g
And Epicoat 828 (epoxy resin, epoxy equivalent: 184-194, Shell Chemical Co., Ltd.) as a stabilizer.
1.0 g, 10 g of titanium dioxide as a pigment and 0.2 g of carbon black were mixed, and the pigment was dispersed in a sand mill for 1 hour. The viscosity was adjusted with a Ford cup # 4 at 13 to 14 seconds / 20 ° C. with toluene. Then, a polypropylene plate (TX-933A, manufactured by Mitsubishi Yuka Co., Ltd.) washed with water was spray-coated so as to have a film thickness of about 10 μm. After a few minutes, the two-component curable urethane paint is spray-coated so that the film thickness becomes 30 to 40 μm, dried at room temperature for about 15 minutes, then forcibly dried at 80 ° C. for 30 minutes, and left still at room temperature for 24 hours. The coatings were tested. The results are shown in Table 4.

[0045]

[Table 1]

[0046]

[Table 2]

[0047]

[Table 3]

[0048]

[Table 4]

Coating film test method : Adhesion: A gobang pattern was formed on the coated surface at intervals of 1 mm to reach the substrate, and a cellophane adhesive tape was adhered on it to obtain 180 °
It was peeled off in the direction, and the number of remaining streaks was examined. Gasoline resistance: Put a scratch on the painted surface to reach the substrate, immerse in regular gasoline at 25 ° C for 2 hours,
The state of the coating film was examined. Water resistance: The film was immersed in warm water of 40 ° C. for 240 hours to examine the state of the coating film. Moisture resistance: The film was left in an atmosphere of 50 ° C. and a relative humidity of 98% for 240 hours, and the state of the coating film was examined.

[0050]

【The invention's effect】

(From the results in Table 2) In Examples 1-3, chlorinated polyolefins having a low chlorine content were dissolved in a mixed solvent of an alicyclic hydrocarbon and an aromatic hydrocarbon.
° C) The fluidity is all good. On the other hand, Comparative Examples-1 to
No. 6 is obtained by dissolving the chlorinated polyolefin in a single solvent of an alicyclic hydrocarbon or an aromatic hydrocarbon, but the low-temperature fluidity is inferior in any case.
This indicates that dissolving in a mixed solvent of an alicyclic hydrocarbon and an aromatic hydrocarbon improves the low-temperature fluidity more than dissolving it in a single solvent.

In Example 4, a chlorinated polyolefin having a low chlorine content was dissolved in a solvent system containing 20% of a solvent (ethyl acetate) other than a mixed solvent of an alicyclic hydrocarbon and an aromatic hydrocarbon. However, the low-temperature fluidity was good. On the other hand, Comparative Example-7 was obtained by dissolving a chlorinated polyolefin having a low chlorine content in a solvent system containing 30% or more of a solvent (ethyl acetate) other than the above mixed solvent. I have. From this, the mixed solvent of the alicyclic hydrocarbon and the aromatic hydrocarbon is at least in the solvent system.
It can be said that it is necessary to contain 70% or more.

In order to dissolve the chlorinated polyolefin in a single solvent of aromatic hydrocarbon and to improve the low-temperature fluidity, the chlorine content of the chlorinated polyolefin should be relatively high as in Comparative Examples -8 to 10. There is a need to.

(From the results in Tables 3 and 4)
7 and Comparative Examples -11 to 13 are chlorinated polyolefins having a relatively high chlorine content and exhibiting good low-temperature fluidity with a single solvent of an aromatic hydrocarbon, and a mixed solvent of an alicyclic hydrocarbon and an aromatic hydrocarbon. This is a comparison of the physical properties of chlorinated polyolefins having a low chlorine content and exhibiting good low-temperature fluidity. The results in Tables 3 and 4 indicate that the lower the chlorine content of the chlorinated polyolefin, the better the heat seal strength, adhesion, gasoline resistance, and the like.

That is, the present invention relates to a method of converting a chlorinated polyolefin having a low chlorine content, which was originally difficult to use due to poor low-temperature fluidity and extremely poor workability, with a mixed solvent of an alicyclic hydrocarbon and an aromatic hydrocarbon. By improving low temperature fluidity,
It can be seen that it is possible to obtain a usable binder resin solution having good physical properties.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication location C09J 123/28 JCM C09J 123/28 JCM

Claims (15)

(57) [Claims] 1. A chlorinated polyolefin having a chlorine content of 12 to 26% by weight, and (b) a chlorinated polyolefin having a chlorine content of 12 to 26% by weight.
100% by weight of a mixed solvent having a weight mixing ratio of an alicyclic hydrocarbon having 5 to 9 carbon atoms and an aromatic hydrocarbon in a range of 10:90 to 90:10, and in the resin solution composition A binder resin solution composition having good low-temperature fluidity, wherein the solid content concentration of the binder resin is 15 to 40% by weight. 2. The binder resin solution composition according to claim 1, wherein the chlorinated polyolefin is a chlorinated polypropylene obtained by chlorinating crystalline polypropylene to a chlorine content of 18 to 26% by weight. 3. The chlorinated polyolefin is characterized in that the chlorinated polypropylene obtained by chlorinating the crystalline polypropylene to a chlorine content of 18 to 26% by weight has at least one kind selected from carboxylic acids and / or carboxylic anhydrides. The binder resin solution composition having good low-temperature fluidity according to claim 1, which is a carboxyl group-containing chlorinated polypropylene obtained by grafting 1 to 10% by weight of a saturated carboxylic acid monomer. 4. A carboxyl group-containing polypropylene obtained by grafting 1 to 10% by weight of at least one unsaturated carboxylic acid monomer selected from carboxylic acid and / or carboxylic anhydride onto crystalline polypropylene, wherein the chlorinated polyolefin is chlorine. The binder resin solution composition having good low-temperature fluidity according to claim 1, which is a chlorinated polypropylene having a carboxyl group chlorinated to a content of 18 to 26% by weight. 5. A chlorinated propylene-α-olefin copolymer obtained by chlorinating a propylene-α-olefin copolymer having a propylene component of 50 to 97 mol% to a chlorine content of 12 to 26% by weight. The binder resin solution composition having good low-temperature fluidity according to claim 1, 6. A chlorinated polyolefin obtained by chlorinating a propylene-α-olefin copolymer having a propylene component of 50 to 97 mol% to a chlorine content of 12 to 26% by weight. With at least one unsaturated carboxylic acid monomer selected from carboxylic acids and / or carboxylic anhydrides
The binder resin solution composition having good low-temperature fluidity according to claim 1, which is a carboxyl group-containing chlorinated polypropylene obtained by grafting at 10% by weight. 7. The chlorinated polyolefin is a propylene-α-olefin copolymer containing 50 to 97 mol% of a propylene component and at least one unsaturated compound selected from carboxylic acids and / or carboxylic anhydrides. 2. A carboxyl group-containing chlorinated polyolefin obtained by grafting a carboxylic acid monomer with 1 to 10% by weight of a carboxyl group-containing polypropylene to a chlorine content of 12 to 26%. Binder resin solution composition. 8. The chlorinated polyolefin is at least one selected from carboxylic acids and / or carboxylic anhydrides.
The low-temperature fluidity-good polyolefin according to claim 1, wherein the terpolymer comprising an unsaturated carboxylic acid monomer, an unsaturated vinyl ester monomer and ethylene is chlorinated to a chlorine content of 15 to 25% by weight. Binder resin solution composition. 9. The terpolymer comprises 1 to 10% by weight of at least one unsaturated carboxylic acid monomer selected from carboxylic acids and / or carboxylic acid anhydrides, and contains 1 to 10% by weight of unsaturated vinyl ester monomer. The binder resin solution composition having good low-temperature fluidity according to claim 8, wherein the amount is from 50 to 50% by weight. 10. A coating material for polyolefin films, sheets and molded products, comprising the binder resin solution composition having good low-temperature fluidity according to claim 1 as an active ingredient. 11. An ink for a polyolefin film, sheet, or molded article, comprising the binder resin solution composition having good low-temperature fluidity according to claim 1 as an active ingredient. 12. An adhesive for a polyolefin film, sheet or molded product, comprising the binder resin solution composition having good low-temperature fluidity according to claim 1 as an active ingredient. 13. A heat sealant for a polyolefin film, sheet, or molded product, comprising the binder resin solution composition having good low-temperature fluidity according to claim 1 as an active ingredient. 14. A primer for coating a polyolefin resin, comprising the binder resin solution composition having good low-temperature fluidity according to any one of claims 3, 4, 6 to 9 as an active ingredient. 15. A chlorinated polyolefin having a chlorine content of 12 to 26% by weight in a total solvent of 70 to 100% by weight.
Is dissolved in a mixed solvent having a weight mixing ratio of an alicyclic hydrocarbon having 5 to 9 carbon atoms and an aromatic hydrocarbon in a range of 10:90 to 90:10, and has good low-temperature fluidity. Of preparing a novel binder resin solution composition.