JPH06108004A - Coating composition - Google Patents

Abstract

PURPOSE:To provide a coating compsn., a printing ink, or an adhesive compsn. which exhibits excellent properties when applied to a film, a sheet, or a molded article of a plastic. CONSTITUTION:A coating compsn. contains a resin which is obtd. by oxidizing a chlorinated polyolefin with air, oxygen, ozone, etc., during the chlorination of a polyolefin, reacting the oxidized chlorinated polyolefin with an org. disocyanate and a high-molecular polyol to give a urethane-modified chlorinated polyolefin, and grafting a monomer having at least one ethylenic unsatd. bond in the molecule and/or a monomer having at least one ethylenic unsatd. bond and at least one hydroxyl group in the molecule onto the urethane-modified chlorinated polyolefin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating composition used for the purpose of protecting various types of plastics and making them more beautiful. More specifically, the present invention relates to a polyolefin resin, polyurethane resin, polyamide resin, acrylic resin, polyester resin. The present invention relates to a resin composition for paints and printing inks or adhesives, which exhibits various physical properties for films, sheets or molded products of various synthetic resins such as resins.

[0002]

2. Description of the Related Art Plastics have many advantages such as high productivity, wide design freedom, light weight, rust prevention, and impact resistance. Therefore, in recent years, plastics have been widely used as materials for automobile parts, electric parts, building materials, etc. It is used. In particular, polyolefin-based resins are widely used as industrial materials because they are inexpensive and have many excellent properties such as moldability, chemical resistance, heat resistance, water resistance, and good electrical properties. It is one of the materials with the highest expectations for elongation.

However, unlike a synthetic resin having a polarity, such as a polyurethane resin, a polyamide resin, an acrylic resin, a polyester resin, a polyolefin resin is non-polar and crystalline, so that it is difficult to coat or bond it. Has the drawback

Therefore, conventionally, the adhesion has been improved by activating the surface of the polyolefin resin molded article by plasma treatment or gas flame treatment, but this method involves complicated steps and requires a large amount of equipment and time. However, due to the complexity of the shape of the molded product and the influence of pigments and additives in the resin,
It has drawbacks such as variations in the surface treatment effect.

As a method of coating without such a pretreatment, various primer compositions such as those used for coating polypropylene bumpers of automobiles have been proposed, but this involves a very complicated two-coat finish.

As a coating composition for one-coat finishing, there are chlorinated polyolefins and cyclized rubbers having a strong adhesive force to a polyolefin resin, but weather resistance,
Moisture resistance, gasoline resistance, etc. are inferior and sufficient coating performance is not shown. Therefore, attempts have been made to mix and use acrylic resins and alkyd resins having good paint properties.
However, since acrylic resin and alkyd resin originally have poor compatibility with chlorinated polyolefin, the gloss of the coating film decreases,
This causes problems such as a marked loss of appearance.

[0007] In order to improve these drawbacks, JP-A-58-719
As seen in JP 66, a coating composition obtained by copolymerizing an acrylic monomer and a chlorinated polyolefin,
As seen in JP-A-59-27968, a chlorinated polyolefin-modified hydroxyl group-containing acrylic copolymer obtained by copolymerizing a chlorinated polyolefin with an acrylic monomer having a hydroxyl group, and an isocyanate compound as an essential component. And a hydroxyl group-containing acrylate-modified chlorinated copolymerized with an acrylic monomer having a hydroxyl group in the presence of a chlorinated polyolefin and a liquid rubber as seen in JP-A-62-95372. Adhesive resin compositions composed mainly of polyolefin and isocyanate compounds,
No. 4-92009 discloses a coating composition obtained by reacting a hydroxyl-containing chlorinated polyolefin obtained by graft-copolymerizing a chlorinated polyolefin and a monomer containing at least one hydroxyl group with an organic diisocyanate or a high-molecular polyol. is there.

However, since these compositions inherently have poor reactivity with chlorinated polyolefins and acrylic monomers, white turbidity or two-layer separation occurs even when copolymerized, and a uniform and transparent solution is not formed. I can't get it. Further, in Japanese Patent Application No. 4-102119, "oxidized chlorinated polyolefin cross-linked product and its production method" is characterized in that chlorinated polyolefin that has been subjected to oxidation treatment is cross-linked with a cross-linking agent having an isocyanate group, an epoxy group, or a hydroxyl group. However, in this method, since the coating film is improved by adding a cross-linking agent to form a cross-linked coating film, the flexibility, appearance, durability, etc. originally required for a vanider resin are inferior. However, it is not always a well-balanced binder resin.

Further, prior to the present invention, the inventors of the present invention proposed a binder resin composition in which a urethane structure was introduced by reacting an oxidatively treated chlorinated polyolefin with a polymer polyol or an organic diisocyanate (Japanese Patent Application No. 4-241252). However, the urethane-modified chlorinated polyolefin was not a resin that satisfied the high gloss, toughness, pigment dispersibility, etc. required for a one-coat finishing resin.

[0010]

DISCLOSURE OF THE INVENTION The present invention solves the above problems by modifying a chlorinated polyolefin, and is far superior to conventional modified chlorinated polyolefins in coatings, primers, It is an object to provide a binder resin such as a printing ink or an adhesive. It is also an object to provide a production method for obtaining a uniform and transparent modified product of chlorinated polyolefin when modifying the chlorinated polyolefin.

[0011]

Means for Solving the Problems That is, the present inventors have found that during the chlorination reaction of a polyolefin, the chlorination is carried out by oxidation treatment using at least one or two or more selected from air, oxygen and ozone. Resin (IV) obtained by reacting polyolefin (I) with organic diisocyanate (II) and polymer polyol (III), and a monomer further containing at least one ethylenically unsaturated bond in one molecule. And / or 1
At least one ethylenically unsaturated bond and hydroxyl group in the molecule
The present inventors have found that a coating composition obtained by graft-copolymerizing individual contained monomers achieves the above object, and has completed the present invention.

The oxidation-treated chlorinated polyolefin (I) used in the present invention is crystalline polypropylene, amorphous polypropylene, polybutene-1, polypentene-1,
Polyolefins such as 4-methylpentene-1, low-density or high-density polyethylene, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, natural rubber, and polyisoprene are mixed with water or carbon tetrachloride or chloroform. Dispersed or dissolved in a medium such as the above, under irradiation of a radical generating catalyst or ultraviolet rays, under pressure or normal pressure at 50 to 120 ° C.
Chlorination in the temperature range of
Alternatively, it can be obtained by blowing air, oxygen, or ozone with gaseous chlorine at the end of chlorination, simultaneously, separately, or alternately.

Oxidized chlorinated polyolefin (I)
Oxidation progressed at 1730 cm ^-1 measured by infrared spectrophotometer
It can be judged by the increase in absorption in the vicinity. The degree of oxidation can be confirmed by the functional group index measured by the scale of the following formula 1, and in order to carry out the present invention, the functional group index is preferably 1 or more.

[0014]

[Equation 1]

The chlorine content of the oxidised chlorinated polyolefin (I) is preferably in the range of 5 to 75 wt% because the solution state deteriorates if it is too low or too high. or,
Those having a chlorine content of less than 5 to 50% by weight show good adhesion to the polyolefin resin having poor adhesion. On the other hand, the one having a chlorine content of 50 to 75 wt% has good adhesion to polar materials and also excellent ultraviolet resistance.

The organic diisocyanate (II) used in the present invention includes aromatic, aliphatic and alicyclic diisocyanates, such as tolylene diisocyanate,
Xylene diisocyanate, 1,5-naphthalene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,
2,4-trimethylhexamethylene diisocyanate,
There are isophorone diisocyanate, 4,4-dicyclohexylmethane diisocyanate, 1,4-cyclohexyl diisocyanate and the like.

The polymer polyol (II used in the present invention
Examples of I) include polyether polyols and polyester polyols. Examples of the polyether polyols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polycarbonate diols, and bisphenol A obtained by adding ethylene oxide or propylene oxide. There are glycols that can be used.

Polyester polyols include polycondensation of dicarboxylic acids such as adipic acid, maleic acid, succinic acid, fumaric acid, phthalic acid and sebacic acid with glycols such as ethylene glycol, neopentyl glycol and 1,8-octamethylenediol. There are adipates that can be obtained by this, for example, polyethylene adipate, polybutylene adipate, polyhexamethylene adipate and the like.
Further, polycaprolactone diols obtained by ring-opening polymerization of lactone can also be used.

As a reaction method of the chlorinated polyolefin (I) which has been subjected to the oxidation treatment of the present invention with the organic diisocyanate (II) and the polymer polyol (III), a conventionally known method for producing a urethane prepolymer resin may be used. However, since the terminal functional group must be a hydroxyl group, the isocyanate group / hydroxyl group molar ratio must be less than 1.0, and preferably 0.1 to 0.9.

The solvent used in the reaction is preferably an aromatic solvent such as toluene or xylene, and an ester solvent such as ethyl acetate or butyl acetate, a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone, ethanol, isopropanol, etc. Alcohol-based solvents such as n-butanol, aliphatic solvents, cycloaliphatic solvents and the like may be used in combination.

As another method according to the above reaction method, after reacting the compound (V) having at least one epoxy group in the molecule with the chlorinated polyolefin (I) which has been subjected to the oxidation treatment, ( There is also a method of reacting (II) with (III).

The epoxy compound (V) used at this time is a glycidyl ether type of monoalcohol or polyhydric alcohol, for example, butyl glycidyl ether, phenyl glycidyl ether, ethylene glycol glycidyl ether, propylene glycol glycidyl ether, sorbitol polyglycidyl ether, and the like. Bisphenol A
Type and bisphenol F type epoxy resins and the like, and other cycloaliphatic epoxy resins obtained by oxidizing olefins with peracid. Further, at least 1 in the molecule, such as an acrylic epoxy compound obtained by copolymerizing glycidyl (meth) acrylate and other (meth) acrylates.
Any compound containing a single epoxy group can be used.

The resin (IV) obtained by the above method further contains a monomer containing at least one ethylenically unsaturated bond in one molecule and / or an ethylenically unsaturated bond and a hydroxyl group in one molecule. The reaction method of graft-copolymerizing at least one monomer is as follows. Resin (IV) is appropriately diluted with a solvent and mixed, a polymerization initiator is added and then heated, and the monomer is gradually added. The basic process is to react while
The resin (IV) and the monomer may be mixed in advance, a polymerization initiator may be added, and the mixture may be heated to react.

Examples of the polymerization initiator include peroxides such as benzoyl peroxide and di-tert-butyl peroxide, and azonitriles such as azobisisobutyronitrile.

The monomer containing at least one ethylenically unsaturated bond in one molecule used in the present invention is
For example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth)
There are acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, glycidyl (meth) acrylate, styrene, vinyl acetate, (meth) acrylonitrile, etc., and ends of polystyrene and poly (meth) acrylate. A compound such as a macromonomer having a polymerizable (meth) acryloyl group can also be used.

Further, the monomer containing at least one ethylenically unsaturated bond and one hydroxyl group in one molecule is, for example, 2-
There are hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, etc., and the above-mentioned hydroxyl group-containing (meth) acrylate is esterified with caprolactone (poly) caprolactone-modified (meth). Acrylate (eg, Daicel Chemical Industries, Ltd., trade name Praxel F
A, Praxel FM series, etc.) can also be used. or,
Esters obtained by reacting α, β unsaturated carboxylic acids or their anhydrides with diols, 1,4-butene glycol, allyl alcohol, etc. A unit amount having an ethylenically unsaturated bond and a hydroxyl group in one molecule Any body or compound can be used.

The content of the resin obtained from the chlorinated polyolefin (I) contained in the coating composition of the present invention is 5 to 90.
wt% is preferred. If it is less than 5 wt%, the adhesion to polyolefin is poor, and if it is more than 90 wt%, the physical properties of the coating film are poorly balanced.

The coating composition of the present invention is blended with an isocyanate compound as a curing agent, so that gasoline resistance, weather resistance, moisture resistance, and hot water resistance (boil, retort) are obtained.
It is possible to improve coating film physical properties required for paints and inks. As the isocyanate compound used at this time,
The above-mentioned organic diisocyanates can be used, but it is more preferable to modify these organic diisocyanates into isocyanate derivatives such as buret, isocyanurate, and trimethylolpropane adduct.

The coating composition of the present invention may be used by coating as it is, but it may be used as a paint or an ink after kneading and dispersing by adding a pigment, a solvent and other additives. Further, it can be used as a primer for adhesion or coating of various plastics such as polypropylene resin.

The coating composition shows a balanced coating property by itself, but if necessary, alkyd resin, acrylic resin, polyacrylic polyol, polyester resin, polyester polyol, polyether resin, poly Ether polyol, polyurethane resin, chlorinated polyolefin and the like may be further added and used.

[0031]

The feature of the present invention is that a functional group is introduced into the chlorinated polyolefin by oxidizing the polyolefin during the chlorination reaction with air, oxygen, ozone, etc.,
It is considered that when the functional group and the organic diisocyanate, the monomer having an unsaturated bond, and the like react with certainty, the obtained resin becomes a uniform and transparent solution.

Furthermore, since the obtained resin contains chlorinated polyolefin, urethane prepolymer, and acrylic component, the chlorinated polyolefin exhibits good adhesion to the polyolefin resin, and urethane is applied to the coating film. It imparts tough flexibility, and acrylic acts as a component that imparts hardness and abrasion resistance, resulting in a coating composition that is well-balanced and unique.

Although the functional group introduced into the chlorinated polyolefin is not clear, a carbonyl group,
The formation of a carboxyl group, an acid chloro group, a peroxide group, a peroxide chlor group, etc. is considered. Further, since functional groups are considered to be generated during the cleavage reaction of the polyolefin, it is considered that these functional groups are introduced at the terminal of the chlorinated polyolefin molecule.

For obvious reasons, it is not possible to react the chlorinated polyolefin (I) which has been subjected to the oxidation treatment with the compound (V) containing an epoxy group and then to carry out the urethanization reaction of the reaction system. It has the effects of accelerating the reaction rate and stabilizing the reaction system.

[0035]

EXAMPLES The present invention will now be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

(Prototype Example-1) 4 kg of isotactic PP having a number average molecular weight of 5,000 was uniformly dissolved in 80 liters of carbon tetrachloride under pressure, and chlorine gas was blown while irradiating with ultraviolet rays at a temperature of 100 to 110 ° C. Chlorination was performed. When the chlorine content reached about 20 wt%, the chlorine gas was changed to a mixed gas with a chlorine / air volume ratio of about 10/90, and chlorination was performed slowly while performing an oxidation treatment. While tracing the above functional group index with an infrared spectrophotometer during the oxidation treatment, a sample with a functional group index of 15.5 and a chlorine content of 30.2 wt% was extracted,
Distill off carbon tetrachloride and replace with toluene.
% Chlorinated PP was obtained.

(Prototype Example-2) 2 kg of isotactic PP having a number average molecular weight of 15,000 was chlorinated under the same conditions as in Prototype Example-1, and when the chlorine content reached about 20 wt%, chlorine /
Oxidation treatment and chlorination were performed by blowing a mixed gas having an oxygen volume ratio of about 25/75. Following the method of prototype example-1,
Functional group index 16.5, chlorine content 31.8wt%, non-volatile content
50% by weight of oxidized chlorinated PP was obtained.

(Prototype Example-3) 500 g of isotactic PP having a number average molecular weight of 5,000 was charged into a glass-lined reaction kettle, 8 liters of carbon tetrachloride was added, and the temperature was adjusted to 1
After sufficiently dissolving at 10 ° C. and a pressure of 2 kg / cm ² , chlorine gas was introduced from the bottom of the reaction vessel while irradiating with ultraviolet rays until the chlorine content became 30 wt%. Next, carbon tetrachloride was distilled off and replaced with toluene to obtain a chlorinated PP having a nonvolatile content of 50 wt%.

(Example-1) In a flask equipped with a stirrer, a thermometer, and a cooling tube for refluxing a monomer, the oxidized chlorinated PP (nonvolatile content 50 wt%) obtained in Prototype Example-1 was placed.
%) 210 g, hexamethylene diisocyanate 9.6 g,
Product name Clapol P-1010 (Kuraray Co., Ltd., 3-methylpentane adipate high-molecular diol, molecular weight 1,00
0) 75 g was added, and after reacting at 85 ° C. for several hours, 204.6 g of toluene was added. Next, benzoyl peroxide
Add 1.5g and stir at 85 ° C for 30 minutes, then add 84.6g of cyclohexyl acrylate and 35.4g of 2-hydroxyethyl acrylate over about 3 hours and carry out graft copolymerization reaction for about 7 hours to make it uniform and transparent. A different reaction product (nonvolatile content 50 wt%) was obtained.

Next, 100 g of the obtained reaction product and titanium dioxide
After kneading 26 g in a sand mill for 2 hours, 12.7 g of an isocyanate curing agent N3390 (made by Bayer, hexamethylene diisocyanate type, isocyanurate body) was added, and N was added.
o.4 With Ford cup, adjust the viscosity with xylene to 13 ~ 15 seconds / 20 ℃, polypropylene plate, TX-933A
Spray-painted (manufactured by Mitsubishi Petrochemical Co., Ltd.). After being dried at room temperature for 15 minutes, forcedly dried at 80 ° C. for 30 minutes and allowed to stand in the room for 1 week, the coating film was tested. The results are shown in Table 1.

(Example-2) 210 g of chlorinated PP (nonvolatile content: 50 wt%) obtained by the oxidization treatment obtained in Prototype Example-2, hexamethylene diisocyanate 5.9 g, Praxel L-212AL
(Manufactured by Daicel Chemical Industries, Ltd., caprolactone-based polymer diol, molecular weight 1,200) 75 g, toluene 200.9 g, benzoyl peroxide 1.5 g, methyl methacrylate 5
Example-1 with a compounding ratio of 0.7 g, lauryl methacrylate 33.9 g, and 2-hydroxyethyl acrylate 35.4 g.
The reaction was carried out according to the above method to obtain a uniform and transparent reaction product (nonvolatile content 50 wt%). Next, 100 g of the obtained reaction product, 26 g of titanium dioxide, an isocyanato curing agent desmodul Z43
A paint preparation and a coating film test were carried out in the same manner as in Example 1 with a compounding ratio of 21.5 g of 70 (Isophorone diisocyanate type, isocyanurate body, manufactured by Bayer). The results are shown in Table 1.

Comparative Example-1 Chlorinated P obtained in Prototype Example-3
Using P (nonvolatile content 50 wt%), the reaction was carried out in the same proportion as in Example-2 to obtain an opaque reaction product. Further Examples-
The paint preparation and the coating film test were conducted in the same manner as in 2. The results are shown in Table 1.

[0043]

[Table 1]

Coating film test method ○ Adhesion 100 grids that reach the substrate at 1 mm intervals were made on the coated surface, and cellophane adhesive tape was adhered on top of them to make 180 °
It was peeled off in the direction and judged by the extent to which the coating film remained.

Accelerated weathering resistance A carbon arc type sunshine weather meter was used. The glossiness was measured by 60 ° specular reflection, and the whiteness was measured by a hunter.

○ Resistance to warm water Immerse the coated plate in warm water of 40 ° C for 120 hours and 240 hours,
The state of the coating film was examined.

○ Gasoline resistance (rubbing 100 times) The absorbent cotton was impregnated with gasoline and the coated surface was rubbed 100 times to examine the state of the coating film. (Dip 2 hours) Scratch that reaches the substrate on the coated surface (×
Mark) was put in, and it was dipped in gasoline for 2 hours and the state of the coating film was examined.

Bending resistance: The state of the coating film was examined by bending 180 ° with a 1/2 φ inch mandrel.

○ Impact resistance Impact resistance It is a DuPont type impact tester, and the impact core is 1 / 2φ inch,
The state of the coating film was examined by using a load of 500 g and dropping it from a height of 50 cm on the coated surface.

(Example-3) An ink was prepared using the reaction product obtained in Example-1, and uncoated polypropylene film (hereinafter referred to as untreated PP) and corona discharge treated polypropylene film (hereinafter treated) were coated with coating rod # 4. PP), polyethylene terephthalate film (hereinafter PE)
(Referred to as T) and a nylon film (hereinafter referred to as NY), and dried at room temperature for 24 hours, and then subjected to cellophane tape peeling test and heat seal strength test using a cellophane adhesive tape. The results are shown in Table 2. The ink formulation is shown in Table 3.

(Example-4) The same test as in Example-3 was conducted on the reaction product obtained in Example-2. The results are shown in Table 2.

Comparative Example-2 The same test as in Example-3 was conducted on the reaction product obtained in Comparative Example-1. The results are shown in Table 2.

(Comparative Example-3) Trade name Sanbren IB-45
The same test as in Example-3 was carried out using 0 (polyurethane resin, nonvolatile content 30 wt%, manufactured by Sanyo Chemical Co., Ltd.).
The results are shown in Table 2.

[0054]

[Table 2]

Cellophane tape peeling test A cellophane adhesive tape was attached to the ink-coated surface and peeled off at a stretch to determine the peeled state.

Heat seal strength test: Overlap the ink coated surfaces and make 1 at 110 ° C-1 kg / cm ² .
Heat sealing was performed under pressure bonding conditions for 2 seconds, and after 24 hours, a 180 ° peel strength test was performed using Tensilon. (Pulling speed 5
(0 mm / min)

[0057]

[Table 3] -Sambrene IB-450 has a non-volatile content of 30 wt% (methyl ethyl ketone / isopropanol = 2/1 solution) -Titanium dioxide (Ishihara Sangyo Co., Ltd., rutile type R-820) -Carmine 6BN (Toyo Ink Mfg. Co., Ltd., azo type) Organic pigment)

[0058]

【The invention's effect】

(From the results of Table 1) Resins obtained by urethane-modifying chlorinated PP oxidized as in Examples 1 and 2 and further graft-copolymerized with an acrylic monomer have excellent properties as compared with conventional ones. , Adhesion, appearance, gasoline resistance, weather resistance,
It can be seen that the coating film is very well balanced without sacrificing flexibility and the like. On the other hand, even if the mere chlorinated PP is variously modified as in Comparative Example-1, good physical properties cannot be obtained.

(From the results in Table 2) Chlorinated P of Comparative Example-2
It can be seen that the P-based ink shows almost good adhesion to the PP film, but the PET and NY films have no adhesion. Further, the polyurethane-based ink of Comparative Example-3 is PE.
Although it adheres to the T and NY films, it does not have sufficient adhesion to the PP film. Examples 1 and 2 have good adhesion to both PP film, PET and NY film, and it can be seen that the products of the present invention are highly versatile ink resins.

Claims (7)

[Claims] 1. A chlorinated polyolefin (I) which has been subjected to an oxidation treatment with at least one or two or more selected from air, oxygen and ozone during a chlorination reaction of a polyolefin, an organic diisocyanate (II) and The resin (IV) obtained by reacting the polymer polyol (III) is further added with a monomer containing at least one ethylenically unsaturated bond in one molecule and / or an ethylenically unsaturated bond in one molecule. And a coating composition comprising a resin obtained by graft copolymerizing a monomer containing at least one hydroxyl group as a constituent element. 2. An organic diisocyanate (II) and a polymer after the compound (V) containing at least one epoxy group in the molecule is reacted with the oxidatively treated chlorinated polyolefin (I) according to claim 1. A resin (IV) obtained by reacting a polyol (III) with a monomer further containing at least one ethylenically unsaturated bond in one molecule and / or an ethylenically unsaturated bond and a hydroxyl group in one molecule. A coating composition comprising a resin obtained by graft-copolymerizing a monomer containing at least one of the above. 3. The coating composition according to claim 1 or 2, wherein the chlorine content of the oxidized chlorinated polyolefin is 5 to 75 wt%. 4. The coating composition according to any one of claims 1 to 3, wherein the resin (IV) is obtained by reacting in a molar ratio of isocyanate group / hydroxyl group of 0.1 to 0.9. 5. A coating composition containing 5 to 90 wt% of a resin obtained from the chlorinated polyolefin (I) which has been subjected to the oxidation treatment according to claim 1 in an amount of 5 to 90% by weight.
The coating composition according to the item. 6. A resin composition for paints and printing inks or adhesives, characterized in that an isocyanate compound is added as a curing agent to the coating composition according to any one of claims 1 to 5. 7. A resin (IV) obtained by reacting (I) with (II) and (III), further comprising a monomer and / or a monomer containing at least one ethylenically unsaturated bond in one molecule. A resin for coating composition according to any one of claims 1 to 5, wherein a monomer containing at least one ethylenically unsaturated bond and at least one hydroxyl group in one molecule is graft-copolymerized. Manufacturing method.