JP2003192725A - Binder resin and coating material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coating material such as a coating, an ink, an adhesive and a primer, which excels in adhesion and water-resistant adhesion for particularly a polyolefin resin, as well as to provide a binder resin suitable for the coating material. <P>SOLUTION: The coating material contains the binder resin which is characterized in that it comprises a modified cyclized polymer (C) obtained by addition reaction of an α,β-ethylenically unsaturated dicarboxylic acid anhydride (B) to a cyclized product of a conjugated diene polymer having a cyclization ratio of 30-95% (A), that the addition amount of the above (B) to the above (C) is 0.1-10 wt.%, and that the proportion of the added acid anhydride group (I) to the total amount of the (I) and the dicarboxylic acid group (II) formed by hydrolysis of the acid anhydride group is 60 wt.% or more. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a binder resin and a coating material, and more particularly, a coating material such as a paint, an ink, an adhesive, a primer and the like, which has excellent adhesion to a polyolefin resin and water-resistant adhesion, and the coating material. And a binder resin suitable for.

[0002]

2. Description of the Related Art It is known that isoprene-based rubber such as natural rubber and synthetic isoprene rubber is easily cyclized in the presence of an acid catalyst. Also, some reports have been made on the application of the cyclized rubber thus obtained to a coating material.

For example, a polyolefin obtained by using a cyclized rubber obtained by cyclizing a low molecular weight conjugated diene polymer or copolymer with an acid catalyst as a vehicle resin, and optionally adding a plasticizer, a dispersant and the like. Printing inks or coating compositions for films or moldings have been proposed. It is described therein that if a cyclized rubber is used as a vehicle resin, a coating film having excellent adhesion and fir resistance can be formed (see, for example, Patent Document 1).

Further, a surface treating agent comprising a mixture of one or more selected from the group consisting of halogenated polyolefin, halogenated rubber and cyclized rubber and a mixed solvent containing a terpene solvent is used to produce a polyolefin. It is described that when the surface of a resin molded product is modified, a molded product having a surface with good adhesion and easy secondary processing such as painting and printing can be obtained (for example, see Patent Document 2).

Further, when the low molecular weight conjugated diene polymer is cyclized, a low molecular weight isoprene polymer having a cis-1,4 bond content of 70% or more and a molecular weight of 10,000 to 150,000 is obtained as an anhydrous polymer. Maleic acid or a derivative thereof is added in an amount of 0.3 to 12 per isoprene monomer unit of the polymer.
A method for producing a modified cyclized polymer using a modified polymer added with mol% has been proposed. Then, it is described that by adopting this production method, a modified cyclized polymer having excellent adhesion to a polyolefin resin and compatibility with a polar resin, and thus suitable for printing ink, paint, etc. can be obtained (for example, , Patent Document 3.).

As described above, various studies have been made on the application of a conjugated diene polymer cyclized product or a modified cyclized polymer thereof as a constituent of paints and inks for polyolefin resins. However, even if any of the conventionally proposed ones is added as a binder to paints, inks, etc., the effect of improving the adhesion to polyolefin resin molded products by them is insufficient, and the adhesion after immersion in water is insufficient. In some cases, it was inferior in water resistance (water resistance adhesion).

[0007]

[Patent Document 1] JP-A-51-12827

[Patent Document 2] JP-A-53-142471

[Patent Document 3] JP-A-57-145103

[0008]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide coating materials such as paints, inks, adhesives, and primers which are particularly excellent in adhesion to polyolefin resin and water-resistant adhesion, and a binder suitable for the coating material. To provide a resin.

[0009]

DISCLOSURE OF THE INVENTION The present inventors have focused on a modified cyclized polymer obtained by subjecting a conjugated diene polymer cyclized product to an addition reaction with an α, β-ethylenically unsaturated dicarboxylic acid anhydride. As a result of intensive studies, the cyclization rate, the addition amount of α, β-ethylenically unsaturated dicarboxylic acid anhydride, the added α,
By using a specific modified cyclized polymer in which the ratio of acid anhydride groups in β-ethylenically unsaturated dicarboxylic acid anhydride is adjusted, it was found that the above object can be achieved, and the present invention has been completed. .

Thus, according to the present invention, the cyclization rate is 30.
To 95% of a conjugated diene polymer cyclized product (A) is added to an α, β-ethylenically unsaturated dicarboxylic acid anhydride (B) to obtain a modified cyclized polymer (C). The addition amount of (B) to C) is 0.1 to 10% by weight, and the added acid anhydride group (I) and the dicarboxylic acid group () formed by hydrolysis of the acid anhydride group ( I
Provided is a binder resin characterized in that the ratio of (I) to the total amount of I) is 60% by weight or more.

Further, according to the present invention, there is provided a coating material containing the binder resin.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The binder resin and coating material of the present invention will be described in detail below.

(Binder Resin) In the binder resin of the present invention, α, β-ethylenically unsaturated dicarboxylic acid anhydride (B) is added to the cyclized product of conjugated diene polymer (A) having a cyclization rate of 30 to 95%. Modified cyclized polymer (C) obtained by reaction
It consists of Here, the “cyclization rate” of the cyclized product of the conjugated diene polymer means the ratio of the amount of double bonds remaining after cyclization to the amount of double bonds before cyclization. The amount of double bonds before and after the cyclization reaction is measured by proton NMR.

As the conjugated diene polymer which is a raw material for producing the cyclized product (A), a polymer obtained by polymerizing a conjugated diene monomer by a known method may be used. The content of the conjugated diene monomer unit in the conjugated diene polymer is preferably 70% by weight or more,
It is more preferably 80% by weight or more, and particularly preferably 95% by weight or more. As the conjugated diene monomer, 1,3-
Butadiene, isoprene, 2,3-dimethyl-1,3-
Butadiene, 2-phenyl-1,3-butadiene, 1,
3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3
-Octadiene, 3-butyl-1,3-octadiene,
Examples include chloroprene. Among these, 1,3
-Butadiene and isoprene are preferred, with isoprene being more preferred.

The conjugated diene polymer may be a copolymer of the above-mentioned conjugated diene monomer and a copolymerizable monomer. Examples of the monomer copolymerizable with the conjugated diene monomer include styrene, α-methylstyrene, p-methylstyrene, p-phenylstyrene, p-methoxystyrene, chloromethylstyrene, m-fluorostyrene and vinylnaphthalene. Aromatic vinyl compounds of olefins such as propylene, isobutylene, vinyl chloride and vinylidene chloride; Among these, aromatic vinyl compounds are preferable, and styrene and α-methylstyrene are more preferable.

The weight average molecular weight of the conjugated diene polymer is not particularly limited, but the weight average molecular weight measured by GPC (gel permeation chromatography method, polystyrene conversion value) is 30,000 to 500,000.
Is preferably in the range of 50,000 to 300,
The range of 000 is more preferable. If the weight average molecular weight is too small, the resulting modified cyclized polymer may have poor adhesion to the polyolefin resin. Conversely, if it is too large, the viscosity of the modified polymer in a solution will be high and the coating process will be uneven. May be easier to remove.

The cyclized product (A) of the conjugated diene polymer is produced by cyclizing the conjugated diene polymer using a known acid catalyst (cyclization catalyst). Specifically, it is produced by bringing the conjugated diene polymer and the cyclization catalyst into contact with each other in an inert solvent.

As the cyclization catalyst, for example, sulfuric acid; fluoromethanesulfonic acid, difluoromethanesulfonic acid, p
-Sulfonic acids such as toluene sulfonic acid and their anhydrides, organic sulfonic acid compounds such as alkyl esters; boron trifluoride, boron trichloride, tin tetrachloride, titanium tetrachloride, aluminum chloride, diethyl aluminum monochloride, bromide Metal halides such as aluminum, antimony pentachloride, tungsten hexachloride, iron chloride;
And so on.

The inert solvent used in the cyclization reaction is not particularly limited, but examples thereof include aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; n-pentane and n.
Chain aliphatic hydrocarbons such as -hexane, n-heptane, and n-octane; cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane; and the like. Of these, hydrocarbons having a boiling point of 70 ° C. or higher are preferable. Further, the solvent used for the polymerization reaction of the conjugated diene polymer may be used as it is. In this case, a cyclization catalyst is added to the polymerization reaction liquid after the polymerization to cyclize the polymer.

The reaction temperature, reaction time, amount of catalyst used, etc. in the cyclization reaction may be appropriately determined according to the desired cyclization rate. The reaction temperature is preferably 20 to 200 ° C, and 5
0-150 degreeC is more preferable, and 80-100 degreeC is especially preferable. The reaction time is preferably 1 to 20 hours, and 2 to 15
Time is more preferable and 3 to 10 hours is particularly preferable.

It is essential that the cyclization rate of the cyclized product of the conjugated diene polymer (A) is 30 to 95%. If the cyclization rate is too small or too large, it is difficult to achieve the object of the present invention. The cyclization rate is preferably 50 to 90%, more preferably 60 to 85%. The degree of cyclization (n) of the cyclized product, that is, the connection of the rings in the cyclized product is not particularly limited, and is usually in the range of n = 1 to 3.

The conjugated diene polymer cyclized product (A) may be further hydrogenated, if necessary. This hydrogenation method is not particularly limited and can be performed in the presence of a known hydrogenation catalyst and hydrogen.

The conjugated diene polymer cyclized product (A) contains α, β
-The modified cyclized polymer (C) is obtained by the addition reaction of the ethylenically unsaturated dicarboxylic acid anhydride (B).

The α, β-ethylenically unsaturated dicarboxylic acid anhydride (B) has an ethylenic carbon-carbon unsaturated bond in the molecule, and a carboxylic acid group is bonded to each of two adjacent carbon atoms. However, it is not particularly limited as long as they form an acid anhydride structure. Examples of the α, β-ethylenically unsaturated dicarboxylic acid anhydride (B) include maleic anhydride, itaconic anhydride, aconitic anhydride, and the like. Among them, maleic anhydride can be preferably used.

The method of adding the acid anhydride (B) to the cyclized product (A) is not particularly limited, and known reaction conditions generally classified into an ene addition reaction or a graft polymerization reaction may be adopted. Usually, the addition reaction is easily carried out by heating (A) and (B) in the presence or absence of a solvent (solid phase reaction) in the presence or absence of a radical catalyst. You can

The solvent used in this addition reaction is
For example, the same solvent as the above-mentioned cyclization reaction can be used. Examples of radical catalysts include di-tert-butyl peroxide, tert-butyl hydroperoxide, dicumyl peroxide, benzoyl peroxide, tert-butyl peroxide benzoate, methyl ethyl ketone peroxide, and di-tert.
-Peroxides such as butyldiperphthalate; azonitriles such as azobisisobutyronitrile; and the like.

The modified cyclized polymer (C) thus produced corresponds to the cyclized conjugated diene polymer (A) and the α, β-ethylenically unsaturated dicarboxylic acid anhydride (B) as the raw materials. The amount of (B) added to (C) is 0.1 to 10% by weight. If the added amount is small, the adhesiveness tends to be poor, and conversely, if the added amount is large, the water resistant adhesiveness tends to be poor. This addition amount is preferably 0.2 to 8% by weight, and more preferably 0.3 to 5% by weight. Here, the "addition amount" of (B) is calculated based on the acid value of the modified cyclized polymer (C).

The acid anhydride group in the modified cyclized polymer (C) is
It is easily hydrolyzed by the presence of water and converted into a free dicarboxylic acid group. That is, by addition of water or artificial water in the addition reaction atmosphere, in the modified cyclized polymer (C), addition derived from α, β-ethylenically unsaturated dicarboxylic acid anhydride (B), Acid anhydride group (I)
And the dicarboxylic acid group (II) formed by hydrolysis of the acid anhydride group coexists. The acid value is measured by titrating such an acid anhydride group (I) and a dicarboxylic acid group (II).

In the modified cyclized polymer (C), it is essential that the ratio of (I) to the total amount of the acid anhydride group (I) and the dicarboxylic acid group (II) is 60% by weight or more. This proportion is preferably 70% by weight or more, and more preferably 80% by weight or more. If this ratio is low, it is difficult to achieve the object of the present invention. Here, the ratio of the acid anhydride group (I) is obtained based on the peak intensity ratio of the acid anhydride group and the carboxylic acid group in the infrared spectroscopy.

In the modified cyclized polymer (C), in order to increase the ratio of (I), the operation is carried out in the absence of water in the addition reaction step and the step of obtaining the polymer after the addition reaction. Is essential. Further, the dicarboxylic acid group formed by hydrolysis of the acid anhydride group is dehydrated by heating to be converted into an acid anhydride group, so that a modified cyclized polymer having a low ratio of the above (I), Preferably, in an atmosphere of an inert gas such as nitrogen or helium or under reduced pressure, heat treatment (for example, a temperature of 160 to 180 ° C., a treatment time of 30 minutes to 4 hours) is performed to increase the ratio of (I). It is also possible.

The weight average molecular weight (GPC method, polystyrene conversion value) of the modified cyclized polymer (C) is usually 5,000.
~ 600,000, preferably 22,000-370,
000, more preferably 37,000 to 230,000
Is.

The binder resin of the present invention is preferably used as a binder to be mixed with various coating materials such as adhesives, primers, paints and inks.

(Coating Material) The coating material of the present invention contains the binder resin described above and covers at least a part of the surface of the molded article. The coating material is not particularly limited, but specifically, for example, an adhesive, a primer,
Examples include paints and inks. After coating with the coating material of the present invention, secondary processing may be further performed, if desired.

A primer, which is one type of adhesive, is a pretreatment agent used when another coating agent (for example, a general paint or adhesive) is applied to the surface of a molded article. The primer is a composition in which a binder resin and, if necessary, an additive, are dissolved or uniformly dispersed in a solvent, and by blending the binder resin according to the present invention, the surface of the molded article and other coating materials are Adhesion can be improved.

The content of the binder resin of the present invention in the primer composition is not particularly limited, but is usually 5 to 95% by weight, preferably 10 to 90% by weight, more preferably 15% by weight.
~ 80% by weight. In the composition, in addition to the binder resin of the present invention, for example, other kinds of olefin resin, acrylic resin, urethane resin, epoxy resin, melamine resin, alkyd resin, chlorinated olefin resin, silicone rubber, acrylic rubber, etc. A binder can be used together.

Examples of the additives for the primer include pigments, fillers, antioxidants, ultraviolet absorbers, defoamers, thickeners, dispersants and surfactants. The blending amount may be appropriately determined depending on the kind of the additive, the purpose of use, and the like.

The solvent for the primer is not particularly limited as long as it can dissolve or disperse the binder resin. Examples of the solvent usually used include aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, ketone solvents, alcohol solvents, ether solvents, halogen solvents, aqueous solvents and the like. Among these, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, ketone solvents, and aqueous solvents can be preferably used from the viewpoints of solubility and volatility of the binder resin.

The paint or adhesive applied to the surface of the molded article pretreated with such a primer is not particularly limited. As the paint, acrylic paint, polyester paint, alkyd melamine paint, polyurethane paint, polyester melamine paint and the like can be preferably used. As the adhesive, an epoxy adhesive, a urethane adhesive, an acrylic adhesive, a cyanoacrylate instant adhesive or the like can be preferably used.

The paint is generally a binder resin, a pigment,
It contains a solvent and optionally additives. The binder resin is a component having a function of fixing the pigment on the surface of the molded product. When the binder resin of the present invention is added to the coating material,
The pigment can be firmly fixed to the surface of the molded product. The content of the binder resin in the coating material is not particularly limited, but is usually 5 to 95% by weight, preferably 10 to 90% by weight, more preferably 15 to 80% by weight.

In addition to the binder resin of the present invention, another kind of binder resin such as an acrylic resin, a urethane resin, an epoxy resin, a melamine resin, an alkyd resin and the like can be blended in the paint.

As the paint pigment, a coloring pigment such as an organic pigment or an inorganic pigment, a rust preventive pigment or the like is used. The pigment concentration in the paint may be determined depending on the type of pigment and the color strength. The solvent for coating material is not particularly limited as long as it can uniformly dissolve or disperse the binder, the pigment and, if necessary, the additive, and the same solvent as the above-mentioned primer solvent can be used. Further, as additives for paints, thixotropic agents, antioxidants, ultraviolet absorbers, defoamers, thickeners, dispersants, surfactants and the like are used.

The molded article to which the coating material of the present invention can be applied is not particularly limited, but a polyolefin resin molded article is preferable, and a polypropylene resin molded article is more preferable. As a polyolefin resin,
Polypropylene resins such as propylene homopolymers, propylene-ethylene copolymers, propylene-butene copolymers, propylene-octene copolymers; ethylene homopolymers; norbornene polymers and hydrogenated products thereof;
Cyclic conjugated diene-based polymers and hydrogenated products thereof; and the like. The molding method and shape of the molded article are not particularly limited, and for example, a molded article having a desired shape molded by an injection molding method, an extrusion molding method, a blow molding method, or the like can be used.

The primer, which is a kind of the coating material of the present invention, can remarkably improve the adhesion between the paint or the adhesive to be overcoated and the resin molded product, particularly the polyolefin resin molded product. , Molded parts for automobiles, etc .; packaging materials; containers for beverages, cosmetics, etc .; sports equipment materials such as sports shoes, golf balls; civil engineering and construction materials such as sheet waterproofing materials, gaskets, sealing materials, etc. Can be used for processing. Among them, it can be preferably used for surface modification treatment of automobile materials such as exterior materials such as bumpers, mat guards, weather strips, glass run channels; interior materials such as instrument panels, grommets and airbags.

Further, the coating material, which is a kind of the coating material of the present invention, can remarkably improve the adhesion to resin molded products, particularly polyolefin resin molded products, so that it is a molded member for electric, electronic, automobile, etc. packaging. Materials: Beverages, cosmetics, etc .; Sports equipment materials such as sports shoes and golf balls; Civil engineering materials such as sheet waterproofing materials, gaskets and sealing materials; Among them, it can be preferably used for coating automotive materials such as exterior materials such as bumpers, mat guards, weather strips, glass run channels; interior materials such as instrument panels, grommets and airbags.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. Parts and% in these examples are by weight unless otherwise specified.

(1) Weight average molecular weight of polymer The weight average molecular weight of the polymer was determined as a standard polystyrene equivalent by the GPC method.

(2) Cyclization rate of the cyclized product of the conjugated diene polymer The peak areas of double bond-derived protons before and after the cyclization reaction of the conjugated diene polymer were measured by proton NMR analysis. Then, the ratio of the double bond remaining in the cyclized product was calculated. Then, the cyclization rate (%) was determined by the following formula: (100-ratio of double bond remaining in cyclized product).

(3) Ratio of acid anhydride group in modified polymer The peak intensity (1760 to 1780 cm ^-1 ) of the acid anhydride group was measured by Fourier transform infrared spectrum, and the acid anhydride was measured by the calibration curve method. The content of groups was determined. Similarly, the peak intensity (1700 cm ⁻¹ ) of the carboxylic acid group was measured, and the content of the dicarboxylic acid group was measured by the calibration curve method. From these, the ratio of acid anhydride groups to the total amount of acid anhydride groups and dicarboxylic acid groups was determined.

(4) Acid value The acid value of the modified polymer and the polyester were measured according to the method described in "Standard Method for Analyzing Fats and Oils" (Japan Oil Chemistry Association) 2, 4, 1-83. (5) Hydroxyl value The hydroxyl value of polyester is "standard oil and fat analysis test method".
(Japan Oil Chemistry Association) 2, 4, 9, 2-83 It measured according to the method.

(6) Cross-cut test (initial adhesion test) After coating the molded plate, 2 mm on the coated surface using a cutter
Eleven cuts that reach the substrate at intervals were made, and 11 similar cuts were made so as to intersect at right angles, and 100 2mm square grids were made. Adhere the cellophane adhesive tape on the grid and peel it off in the direction of 45 °,
The number of squares on which the painted surface remained was examined. (7) Water Resistance Adhesion Test After immersing a coated plate in warm water of 40 ° C. for 240 hours, the above-mentioned cross-cut test was conducted to check the number of cross-cuts on which the coated surface remained.

(8) Accelerated weather resistance test An accelerated weather resistance test was conducted for a certain period of time using a carbon arc lamp type sunshine weather meter, and the gloss retention rate (%) was 100 before the accelerated weather resistance test. Indicate. The gloss was determined as a specular reflectance (%) according to JIS K5400 7.6 with an incident angle from the light source of 60 degrees.

(9) Flowability of primer and paint Ford cup N specified in JIS K 5400
o. In accordance with Method 4, it was expressed as a flowing time at 20 ° C.

(Example 1) Polyisoprene (cis-1,4-structure isoprene unit 86) was placed in a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas inlet tube.
%, Trans-1,4-structure isoprene unit 12%,
3,4-Structure isoprene unit 2%, weight average molecular weight 13
6,000) 100 parts was cut into a 10 mm square and charged together with 1570 parts of toluene. After replacing the inside of the flask with nitrogen, the mixture was heated to 85 ° C. in an oil bath and stirred to dissolve polyisoprene in toluene. After completely dissolving, 3.9 parts of p-toluenesulfonic acid was added, and stirring was continued while keeping the solution at 85 ° C. to carry out a cyclization reaction. After 5 hours, 400 parts of ion-exchanged water was added to stop the cyclization reaction. Three
After standing for 0 minutes, the oil layer was separated. This oil layer was washed 3 times with 400 parts of ion-exchanged water and then centrifuged at a rotation speed of 300 rpm to remove water. Further, the oil layer was heated to 130 ° C. to completely remove water.

While stirring the toluene solution containing the cyclized product thus obtained, 2.5 parts of maleic anhydride was added to 5 parts thereof.
It was charged at a constant speed over a period of minutes. After the addition reaction was performed at a reaction temperature of 160 ° C. for 4 hours, the reaction solution was mixed with 2,6-di-tert.
-Injected into 3000 parts of an acetone solution containing 1% butylphenol to recover the precipitate. This was dried under reduced pressure to obtain a modified cyclized polymer A. Table 1 shows the cyclization rate, weight average molecular weight, maleic anhydride addition amount, and acid anhydride group ratio of the modified cyclized polymer A.

Example 2 As polyisoprene, cis-1,4-structure isoprene unit 73%, trans-1,
It is composed of 22% of 4-structured isoprene units and 5% of 3,4-structured isoprene units and has a weight average molecular weight of 107,000.
And the amount of p-toluenesulfonic acid was 3.6 parts, and the same cyclization reaction was carried out as in Example 1. Then, the modified cyclized polymer B was obtained by treating this cyclization reaction solution in the same manner as in Example 1 except that the amount of maleic anhydride was 2.0 parts. Cyclization rate of modified cyclized polymer B,
Table 1 shows the weight average molecular weight, the amount of maleic anhydride added, and the ratio of acid anhydride groups.

Example 3 As polyisoprene, cis-1,4-structure isoprene unit 30%, trans-1,
Same as Example 1, except that 4-structured isoprene unit 14%, 3,4-structured isoprene unit 56%, and weight average molecular weight 252,000 were used and the amount of p-toluenesulfonic acid was 3 parts. It processed and the cyclization reaction was performed. Next, a modified cyclized polymer C was obtained by treating this cyclization reaction solution in the same manner as in Example 1 except that the amount of maleic anhydride was 2.8 parts. Table 1 shows the cyclization rate, weight average molecular weight, maleic anhydride addition amount, and acid anhydride group ratio of the modified cyclized polymer C.

Example 4 Instead of polyisoprene, polybutadiene (cis-1,4-structured butadiene unit 26
%, Trans-1,4-structured butadiene unit 18%,
1,2-Structured butadiene unit 56%, weight average molecular weight 2
10,000) and the amount of toluene is 1620 parts,
After polybutadiene was dissolved in toluene, the temperature was kept at 23 ° C., 2.78 parts of benzyl chloride and 1.8 parts of ethylaluminum dichloride were added in place of p-toluenesulfonic acid, and 20 parts of methanol was added 12 minutes after the addition. The cyclization reaction was carried out in the same manner as in Example 1 except that the reaction was stopped. Next, a modified cyclized polymer D was obtained by treating this cyclization reaction solution in the same manner as in Example 1 except that the amount of maleic anhydride was 1.5 parts. Table 1 shows the cyclization rate, weight average molecular weight, maleic anhydride addition amount, and acid anhydride group ratio of the modified cyclized polymer D.

Comparative Example 1 p-toluenesulfonic acid 1.
A cyclization reaction was carried out by the same procedure as in Example 1 except that 9 parts were used. Next, a modified cyclized polymer E was obtained by treating this cyclization reaction solution in the same manner as in Example 1 except that the amount of maleic anhydride was 2.0 parts. Table 1 shows the cyclization rate, weight average molecular weight, maleic anhydride addition amount, and acid anhydride group ratio of the modified cyclized polymer E.

(Comparative Example 2) This comparative example is described in JP-A-57-1.
It carried out with reference to Japanese Patent No. 45103. In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube, polyisoprene (cis-1,4-structure isoprene unit 73%, trans-1,4-structure isoprene unit 22%, 3% , 4-structure isoprene unit (5%, weight average molecular weight: 107,000) was cut into 10 mm square and charged with 1570 parts of toluene. After replacing the inside of the flask with nitrogen, the flask was heated to 80 ° C. in an oil bath, and polyisoprene was dissolved in toluene under stirring. After completely dissolving, 7.2 parts of maleic anhydride was added, the solution was kept at 180 ° C., and the reaction was continued for 1 hour. Then, the reaction solution was 3,000 parts of 2,6-di-tert-butylphenol 1% acetone solution. And the precipitate was collected and dried under reduced pressure to obtain a maleated isoprene polymer.

100 parts of the maleated isoprene polymer was redissolved in 300 parts of toluene, 3.6 parts of p-toluenesulfonic acid was added, the solution was maintained at 85 ° C., and stirring was continued to carry out the cyclization reaction. After about 5 hours, 400 parts of ion-exchanged water was added to stop the reaction. After standing for 30 minutes, the separated oil layer was separated. This oil layer was washed 3 times with 400 parts of ion-exchanged water. The oil layer was put into 1000 parts of a 2,6-di-tert-butylphenol 1% methanol solution, and the precipitate was recovered and dried under reduced pressure to obtain a modified cyclized polymer F.
Table 1 shows the cyclization rate, weight average molecular weight, maleic anhydride addition amount, and acid anhydride group ratio of the modified cyclized polymer F.

(Comparative Example 3) Polyisoprene (cis-1,4-structure isoprene unit 86 was added to a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube.
%, Trans-1,4-structure isoprene unit 12%,
3,4-Structure isoprene unit 2%, weight average molecular weight 1
36,000) 100 parts was cut into a 10 mm square and charged together with 1570 parts of toluene. After substituting the inside of the flask with nitrogen, the flask was heated to 85 ° C. in an oil bath, and polyisoprene was dissolved in toluene under stirring. After completely dissolved,
Add 3.9 parts of p-toluenesulfonic acid, and add 85 to the solution.
The temperature was kept at 0 ° C. and stirring was continued to carry out the cyclization reaction. After about 5 hours, 400 parts of ion-exchanged water was added to stop the reaction.
After standing for 30 minutes, the separated oil layer was separated. Oil layer 40
After washing 3 times with 0 part of deionized water, rotation speed 300r
Water was removed by centrifugation at pm. Further oil layer 13
Water was completely removed by heating to 0 ° C.

While stirring the solution containing the cyclized product thus obtained, 2.0 parts of maleic anhydride was added at a constant rate over 5 minutes, and the reaction was continued at 160 ° C. for 4 hours.
The reaction solution is 2,6-di-tert-butylphenol 1%
Acetone / water = 8/2 Add to 3000 parts of solution,
The precipitate was collected and dried under reduced pressure to obtain modified cyclized polymer G. Table 1 shows the cyclization rate, weight average molecular weight, maleic anhydride addition amount, and acid anhydride group ratio of the modified cyclized polymer G.

[0063]

[Table 1]

(Examples 5 to 8 and Comparative Examples 4 to 6) Preparation of Molded Plates Using the resin materials shown in Table 2, three kinds of molded plates X to Z (50 mm × 80 mm × 3 mm) were prepared by injection molding. . The molded plate Y was injection-molded using the raw materials shown in Table 2 which were mixed by a Henschel mixer, melt-kneaded by a twin-screw extruder and pelletized.

[0065]

[Table 2]

Preparation and Evaluation of Primer Using the modified cyclized polymers A to G obtained in Examples 1 to 4 and Comparative Examples 1 to 3 as a binder resin, a high speed stirrer was used according to the primer formulation shown in Table 3. After mixing for 10 minutes with (dispar), the flowability is adjusted to 13
It diluted with toluene so that it might become 14 seconds, and 7 types of primers were prepared.

Using a spray gun having a diameter of 1.0 mm and a spray pressure of 3.5 to 5.0 MPa, each of the molded plates X to Z, which was thoroughly washed with water and dried, had a film thickness of 10 μm. Each primer of 3 was spray coated. 5 minutes later,
Two-component curing type urethane metallic paint (product name RB-212 (base paint) and product name RB-288 (clear paint), manufactured by Nippon Bee Chemical Co., Ltd.) with a film thickness of 40 μm
2 coats were applied using the same spray gun as above. After drying at 23 ° C for 15 minutes, 3 at 80 ° C
It was dried in a non-circulating dryer for 0 minutes. After standing at room temperature for 3 days, a cross-cut test and a water resistance adhesion test were performed, and the results are shown in Table 3.

[0068]

[Table 3]

The following can be seen from Table 3. The primer of Comparative Example 4 using the modified cyclized polymer E having a cyclization rate lower than the range specified in the present invention, and the modified cyclized polymer F having a ratio of acid anhydride groups lower than the range specified in the present invention. When a resin molded article is pretreated with the primers of Comparative Examples 5 and 6 using G and G, the adhesion and water resistance of the paint applied thereafter are inferior. Compared to these comparative examples,
When the resin moldings are pretreated with the primers of Examples 5 to 8 using the modified cyclized polymers A to D in the range specified in the present invention, the coating composition applied thereafter has excellent adhesion and water resistance. ing.

(Example 9) (Preparation of polyester for blending paint) In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a diversion tube and a nitrogen gas inlet tube, 800 parts of terephthalic acid and 2-butyl- 770 parts of 2-ethyl-1,3-probandiol, 72.7 parts of pentaerythritol and 0.
Charge 80 parts, stir while introducing nitrogen gas, and remove water and a part of unreacted monomer generated during the reaction, and raise the temperature from 200 ° C to 240 ° C over 6 hours to react. Let After that, the reaction was continued for 3 hours while dehydrating at 240 ° C. under a reduced pressure of 50 mmHg. The obtained polyester has a weight average molecular weight of 43,000, an acid value of 0.35 mgKOH / g, and a hydroxyl value of 46 mgKOH / g.
Met.

(Preparation of paint) 50 parts of the above polyester,
30 parts of titanium oxide as a white pigment, modified cyclized polymer A25
Parts and 125 parts of xylene were mixed and kneaded with a sand grinder mill for 1 hour, then the flowability was reduced to 13
Further diluted with xylene for 14 seconds to prepare a white paint. The molded plate X washed with water was spray-coated with a white paint to a film thickness of 40 μm using the above-mentioned spray gun, dried at 23 ° C. for 15 minutes, and then at 80 ° C., 3
Drying was performed for 0 minutes in a non-circulating dryer. After standing at room temperature for 7 days, a cross-cut test, a water resistance adhesion test and an accelerated weathering test were performed. The results are shown in Table 4.

Example 10 and Comparative Example 7 A white paint was prepared and evaluated in the same manner as in Example 9 except that the modified cyclized polymer A was changed to B or E, respectively.
Table 4 shows the results of the cross-cut test, the water-proof adhesion test and the accelerated weathering test.

[0073]

[Table 4]

From Table 4, the following can be seen. Modified cyclized polymer E having a cyclization rate lower than the range specified in the present invention
The coating material of Comparative Example 7 using is inferior in adhesion and water resistance adhesion to a polyolefin resin molded product. On the other hand, the paints of Examples 9 and 10 using the modified cyclized polymer in the range specified in the present invention are excellent in adhesion and water resistance adhesion to the polyolefin resin molded article, and
It gives a coated surface that retains its luster for a long period of time.

[0075]

Industrial Applicability According to the present invention, there are provided coating materials such as paints, inks, adhesives, and primers, which are particularly excellent in adhesion to polyolefin resins and water-resistant adhesion, and binder resins suitable for the coating materials.

Continued front page    F-term (reference) 4J038 CP081 GA06 PA07 PC08                 4J040 DL141 GA07 MA11                 4J100 AA03Q AA06Q AB00Q AB02Q                       AB03Q AB04Q AB07Q AC03Q                       AC04Q AS01P AS02P AS03P                       AS04P AS06P AS07P BA02Q                       BB01Q BB07Q BC43P BC43Q                       BC55H CA31 DA01 HA61                       HC29 HC30 HC36 HC54 HE14                       JA01 JA03 JA07

Claims (3)

[Claims] 1. A modified cyclization obtained by subjecting a conjugated diene polymer cyclized product (A) having a cyclization rate of 30 to 95% to an α, β-ethylenically unsaturated dicarboxylic acid anhydride (B) for addition reaction. The polymer (C) has an addition amount of the (B) to the (C) of 0.1 to 10% by weight, and the added acid anhydride group (I) and the acid anhydride group are hydrolyzed. A binder resin, wherein the ratio of (I) to the total amount of dicarboxylic acid groups (II) formed by decomposition is 60% by weight or more. 2. A coating material containing the binder resin according to claim 1. 3. The coating material according to claim 2, which is an adhesive or a paint.