JP2838076B2 - Method for producing binder resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the production of paints, primers and binder resin compositions for printing inks or adhesives which can be applied to various types of plastics, various metals, paper, wood, concrete and other substrates. About the method.

[0002]

2. Description of the Related Art Chlorinated polyolefins such as chlorinated polypropylene, chlorinated polyethylene and chlorinated rubber can be easily dissolved in inexpensive solvents.
Easy work such as immersion and quick drying. The coating film obtained from the solution is excellent in acid resistance, alkali resistance, weather resistance, and flame retardancy. Since it has excellent properties such as good adhesion to adhesive polyolefin resins, it is widely used as an extremely useful modified resin in various fields. For example, paints, primers, printing inks, coating agents for films and sheets, adhesives and the like.

[0003] However, these chlorinated polyolefins have the following disadvantages in common, and cause various difficulties and limitations in application. That is, these are that the solvent resistance of the coating film is poor, the strength of the film is insufficient,
Those with a high chlorine content are brittle and must use a large amount of a plasticizer, and those with a low chlorine content have a low softening temperature, so that the coating film peels and falls off even under conditions of about hot water, It has drawbacks such as poor affinity for the polar substance surface and difficulty in adhering metals, wood, etc.

To improve these disadvantages, various methods have been proposed for modifying chlorinated polyolefins. For example, JP-A-58-71966 discloses a composition obtained by copolymerizing an acrylic monomer and a chlorinated polyolefin as a coating or adhesive for a hardly adherent polyolefin-based resin molded product. No. 27968, a composition obtained by blending an isocyanate compound with a chlorinated polyolefin-modified hydroxyl-containing acrylic copolymer obtained by copolymerizing an acrylic monomer having a hydroxyl group and a chlorinated polyolefin,
JP-A-62-59372 discloses a composition comprising a hydroxyl group-containing acryl-modified chlorinated polyolefin and an isocyanate compound copolymerized with an acrylic monomer having a hydroxyl group in the presence of a chlorinated polyolefin and a liquid rubber. Etc. However, these compositions are inherently poor in reactivity between the chlorinated polyolefin and the acrylic monomer, so that even when copolymerized, cloudy or two-layer separation occurs, and a uniform and transparent solution cannot be obtained. . Further, the coating film is hard and has poor impact resistance and bending resistance, so that it cannot be said that the coating film is well-balanced.

On the other hand, in order to protect the package contents for food packaging, polypropylene (hereinafter referred to as PP), polyethylene (hereinafter referred to as PE), polyethylene terephthalate (hereinafter referred to as PET), nylon (hereinafter referred to as NY) are used. Are used as composite films by lamination. A large number of inks for lamination used for packaging have been used depending on the type of film, but today, the inks for lamination have been broadly classified into two types. That is, an ink composition mainly containing chlorinated PP and chlorinated ethylene vinyl acetate copolymer used for PP film and an ink composition mainly containing urethane resin mainly used for PET and NY films. .

An ink composition containing a chlorinated PP and a chlorinated ethylene-vinyl acetate copolymer as a main binder is disclosed, for example, in Japanese Patent Publication No. Sho 60-31670. This composition has good ink adhesion to an untreated PP film, and also shows good adhesion when printed by lamination using the PP extrusion lamination method, but it shows good adhesion to PET and NY films. Has poor adhesion and is not suitable for these films as printing inks for lamination.

As described in JP-A-62-15336 and JP-A-62-153367, the latter ink compositions containing a urethane resin as a main binder are films having polarities such as PET and NY. Shows good adhesiveness, but has no adhesion to an untreated PP film, and printing by the PP extrusion lamination method is impossible.

An ink resin suitable for both printing by the PP extrusion lamination method and lamination printing of PET, NY film, etc. is disclosed in
No. 85226, JP-A-64-85227, JP-A-1-252606, JP-A-1-2922020
JP, JP-A-4-18470, JP-A-4-77
No. 511, for example.

These proposals relate to a polyurethane-modified chlorinated PP which is obtained by reacting chlorinated PP with various functional group-containing monomers or oligomers or polymers having a radical polymerizable double bond and then urethane-forming the chlorinated PP. . However, this method also has a poor reactivity between the chlorinated PP and the compound having a radical polymerizable double bond as described above, so that the obtained reactant causes cloudiness or two-layer separation, and a uniform and transparent solution is obtained. It is difficult to obtain a functional group uniformly in each molecule of the chlorinated PP by this type of radical reaction. That is, if an attempt is made to introduce a functional group into each molecule of the chlorinated PP, a segment of the chlorinated PP having two or more functional groups is generated, which may cause gelation during the urethane-forming reaction.
If only two functional groups are to be introduced into each molecule of the chlorinated PP, the chlorinated PP segments into which the functional groups are not introduced are present. It is difficult to become a good ink resin.

[0010]

SUMMARY OF THE INVENTION The present invention solves the above problems by modifying chlorinated polyolefin, and is far superior to conventional chlorinated polyolefin modified products, such as paints, primers, and the like. An object is to provide a binder resin such as a printing ink or an adhesive. Another object of the present invention is to provide a method for producing a uniform and transparent modified chlorinated polyolefin when modifying the chlorinated polyolefin.

Prior to the present invention, the present inventors cross-linked an oxidized chlorinated polyolefin with a cross-linking agent having an isocyanate group, an epoxy group or a hydroxyl group. The invention of "the manufacturing method" has already been proposed in Japanese Patent Application No. 4-102119. However, this method aims to improve the coating by adding a crosslinking agent to form a crosslinked coating,
Various physical properties such as flexibility, appearance, and durability, which are originally required for the binder resin, are inferior, and it is difficult to say that the binder resin is always balanced.

[0012]

The present inventors have further studied and found that during the chlorination reaction of polyolefin,
At least one or two selected from air, oxygen, and ozone
After reacting a chlorinated polyolefin (I) oxidized using at least one species with a compound (IV) containing at least one epoxy group in the molecule, a polymer polyol (II) and an organic diisocyanate (III) And a chain extender were reacted, and if necessary, a binder resin composition obtained by adding a reaction terminator was found to achieve the above object, and the present invention was accomplished.

The oxidized chlorinated polyolefin (I) used in the present invention comprises crystalline polypropylene, amorphous polypropylene, polybutene-1, polypentene-1,
Polymethyls such as 4-methylpentene-1, low-density or high-density polyethylene, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, natural rubber, polyisoprene, etc. can be prepared by adding water or carbon tetrachloride or chloroform. Dispersing or dissolving in such a medium as described above, and under irradiation of a radical generating catalyst or ultraviolet light, under pressure or normal pressure, from 50 to 12
The chlorination is carried out in a temperature range of 0 ° C. and is obtained by blowing air, oxygen or ozone simultaneously or separately or alternately with gaseous chlorine from the beginning, from the middle or at the end of the chlorination. Can be

Oxidized chlorinated polyolefin (I)
The oxidation progress of 1730 cm was measured with an infrared spectrophotometer.
Can be determined by absorption at around ^-1 increases, and the degree of oxidation can be confirmed by a functional group index measured by a measure of the formula functional group index to implement the present invention are one or more Is preferred.

[0015] The chlorine content of the oxidized chlorinated polyolefin (I) is preferably in the range of 5 to 75 wt%, since the solution state is deteriorated if it is too low or too high.
Further, those having a chlorine content of 5 to 50% by weight show good adhesion to a poorly adherent polyolefin resin. on the other hand,
Those having a chlorine content of 50 to 75 wt% have good adhesion to polar materials and also have excellent ultraviolet resistance.

The polymer polyol (I) 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. Examples of polyester polyols include glycols and the like, and dicarboxylic acids such as adipine, maleic acid, succinic acid, fumaric acid, phthalic acid, and sebacic acid and ethylene glycol, neopentyl glycol, and 1,8-octamethylenediol. There are adipates obtained by polycondensation of glycols, 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.

The organic diisocyanate (III) used in the present invention includes aromatic, aliphatic and alicyclic diisocyanates, such as tolylene diisocyanate, xylene diisocyanate, 1,5-naphthalene diisocyanate, and 1,4-diisocyanate. Tetramethylene diisocyanate, 1,
Examples include 6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, 4,4-dicyclohexylmethane diisocyanate, and 1,4-cyclohexyl diisocyanate.

Epoxy compound (IV) used in the present invention
Glycidyl ether type of monoalcohol or polyhydric alcohol, such as butyl glycidyl ether, phenyl glycidyl ether, ethylene glycol glycidyl ether, propylene glycol glycidyl ether, sorbitol polyglycidyl ether, bisphenol A type and bisphenol F type epoxy resin, etc. And cyclic aliphatic epoxy resins obtained by oxidizing olefins with a peracid. Further, any compound containing at least one epoxy group in the molecule, such as an acrylic epoxy compound obtained by copolymerizing cricidyl (meth) acrylate and other (meth) acrylates, can be used.

As the chain extender used in the present invention, diols and diamines can be used. Typical examples of the diol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,4-pentanediol, and the like. Representative diamines such as 1,6-hexanediol and 2,5-hexanediol include ethylenediamine, propylenediamine, hexamethylenediamine, 2,2,4-trimethylhexamethylenediamine, isophoronediamine, 4 , 4-dicyclohexylmethanediamine and the like.

The reaction terminator used in the present invention includes:
Monoalcohols such as methanol, ethanol and isopropanol, monoethylamine, n-propylamine,
There are monoamines such as n-butylamine. Also, amino alcohols such as ethanolamine, propanolamine and butanolamine can be used.

The method for obtaining the binder resin according to the present invention comprises reacting (I) with a compound (IV) containing at least one epoxy group in the molecule, and then reacting (II) with (III)
May be reacted under conditions of an excess of isocyanate groups,
The molecular weight may be further increased by using a chain extender. Further, a reaction terminator may be used to stop the reaction of the terminal isocyanate group of the obtained prepolymer. Examples of the reaction solvent include aromatic solvents such as toluene and xylene; ester solvents such as ethyl acetate, propyl acetate and butyl acetate; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; and alcohols such as ethanol, isopropanol and n-butanol. The system solvents can be used alone or as a mixture.

Further, after reacting (I) and (IV),
The polyurethane resin (V) can also be carried out according to the above reaction method. For the polyurethane resin (V), a conventionally known method for producing a polyurethane resin may be used. For example, an organic diisocyanate is excessively added to the above-mentioned high molecular polyol component, that is, NCO / OH exceeds 1.0 mol, preferably Can be reacted in the range of 1.1 to 2.0 moles, and if it is necessary to further increase the molecular weight, a chain extender can be used to produce a polyurethane resin (V) having at least one isocyanate group in one molecule. it can.

The binder resin of the present invention is prepared by blending an isocyanate compound as a curing agent to obtain a coating film and other properties required for paints and inks such as gasoline resistance, moisture resistance, weather resistance, and hot water resistance (boiling and retorting properties). Can be improved. As the isocyanate compound used at this time, the above-mentioned organic diisocyanates can be used,
These organic diisocyanates are converted into puret,
It is more preferable to use it after modifying it with an isocyanate derivative such as an isocyanurate compound and a trimethylolpropane adduct compound.

The binder resin of the present invention may be used as it is after being coated, but may be used as a paint or ink after kneading and dispersing by adding a pigment, a solvent and other additives. The binder 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.

A feature of the present invention is that a functional group is introduced into the chlorinated polyolefin by oxidizing the polyolefin with air, oxygen, ozone or the like during the chlorination reaction, and this functional group is combined with the organic diisocyanate. The object of the present invention is to modify the urethane with a polymer polyol or the like by applying the reaction. According to this method, it is possible to reliably introduce a urethane chain into the chlorinated polyolefin,
It is considered that the obtained binder resin becomes a uniform and transparent solution.

Although the functional group to be introduced into the chlorinated polyolefin is not clear, formation of a carbonyl group, a carboxyl group, an acid chlor group, a peroxide group, a peroxide chlor group or the like during the oxidation treatment is considered. Further, since it is considered that a functional group is generated during the cleavage reaction of the polyolefin, it is considered that these functional groups are introduced into the terminal of the chlorinated polyolefin molecule. When a chlorinated polyolefin having a functional group introduced at the molecular end is urethanized with an organic diisocyanate and a polymer polyol, the resulting binder resin does not become a network polymer, but a straight-chain having good viscosity. It is considered to be a polymer.

Although the reason for this is not clear, the urethane-forming reaction after previously reacting the oxidized chlorinated polyolefin (I) with the compound (IV) containing an epoxy group is difficult in the reaction system. It has the effect of accelerating the reaction rate and stabilizing the reaction system.

Further, by increasing the molecular weight using a chain extender, the obtained composition can have cohesiveness and flexibility. When a diol is used as a chain extender, a urethane bond (-NH
COO-), and the urethane bond may further react with an isocyanate depending on conditions to form an allophanate bond. When a diamine is used as a chain extender, a urea bond (—NHCONH)
-), And the active hydrogen of the urea bond reacts with the isocyanate to form a burette bond. Thus, the formed urethane bond or urea bond is -NH
It is considered that a tough film is formed by the hydrogen bond between-and -CO, and at the same time, it has a high polarity and thus greatly contributes to the adhesion.

[0029]

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 is 14 g
/ 10min (Measurement method: ASTM D1238-62T) 4 kg of isotactic PP is uniformly dissolved in 80 liters of carbon tetrachloride under pressure, and chlorine gas is blown while irradiating ultraviolet rays at a temperature of 100 to 110 ° C to perform chlorination. went. About 20 chlorine content
When the amount of chlorine gas reaches about 1 wt%, the volume ratio of chlorine gas to air is about 1%.
The gas mixture was switched to 0/90, and chlorination was performed slowly while performing oxidation treatment. In the course of the oxidation treatment, the above-mentioned functional group index was traced by an infrared spectrophotometer, and samples having a functional group index of 11.5 and chlorine contents of 27.3 wt% and 31.2 wt% were withdrawn, and carbon tetrachloride was distilled off. Then, toluene was substituted, and oxidized chlorinated PP having a nonvolatile content of 50 wt% was obtained.

(Trial Production Example-2) Melt index is 70 g
/ 10min (Measurement method: JIS K6760) 4kg PE example
Chlorination is carried out under the same conditions as in 1, and the chlorine content is about 50 wt%.
When the temperature reached, a mixed gas having a volume ratio of chlorine / oxygen of about 45/55 was blown thereinto to perform oxidation treatment and chlorination. In accordance with the method of Prototype Example 11, a sample having a functional group index of 31.2 and 40.5 and a chlorine content of 69.5 wt% and 69.8 wt%, respectively, was taken out, carbon tetrachloride was separated by steam distillation, dried, and oxidized. A chlorinated PE powder was obtained.

Example 1 Oxidized chlorinated PP obtained in Prototype Example 1 (chlorine content: 31.2 wt%, functional group index: 11.
5, nonvolatile content 50wt%) 180g, trade name Epicoat 828
5.4 g of bisphenol A type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd.) was charged into a flask equipped with a stirrer, a thermometer, and a cooling tube for refluxing the monomer.
After reacting at 85 ° C for 1 hour, trade name Clapol P-2010
210 g (3-methylpentane adipate, manufactured by Kuraray Co., Ltd., molecular weight: 2,000) and 47.8 g of isophorone diisocyanate were added and allowed to react for several hours. Then cool to 50 ° C and add toluene
After adding 336.1 g and 340.9 g of methyl ethyl ketone, performing a chain extension reaction with 12 g of isophoronediamine and cooling, 85.2 g of isopropyl alcohol was added to obtain a uniform and transparent binder resin (nonvolatile content 30 wt%). Next, the ink was adjusted with the binder resin, and the coated rod # 4 was applied to an untreated PP film, a corona-discharge treated PP film, a PET film, and a NY film, and dried at room temperature for 24 hours. A cellophane tape peeling test and a heat seal strength test were performed. Table 1 shows the results
Shown in The formulation of the ink is shown in Table 2.

(Comparative Example-1) Trade name: Supercron 80
3MW (chlorinated polypropylene, chlorine content 29.5wt%,
A mixture of non-volatile content 20wt%, Sanyo Kokusaku Pulp Co., Ltd.) and trade name Supercron BX (chlorinated ethylene vinyl acetate copolymer, chlorine content 18wt%, non-volatile content 20wt%, Sanyo Kokusaku Pulp Co., Ltd.) A test similar to that of Example-1 was performed. Table 1 shows the results.

(Comparative Example-2) Trade name: Sambren IB-4
A test similar to that of Example-1 was conducted with 50 (polyurethane resin, nonvolatile content 30 wt%, manufactured by Sanyo Chemical Industry Co., Ltd.).
Table 1 shows the results.

[0035]

[Table 1]

Cellophane tape peeling test A cellophane adhesive tape was adhered to the ink-coated surface, and the peeling state of the coated surface was determined at a stretch.・ Heat seal strength test The ink-coated surfaces are superimposed on each other and heated at 110 ° C-1kg / 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 50
mm / min)

[0037]

[Table 2]

Supercron 803 MW and Supercron BX are toluene solutions. Sambrene IB-450 is methyl ethyl ketone / isopropyl alcohol = 2/1
solution.・ Titanium dioxide (Ishihara Sangyo Co., Ltd., rutile type R-8)
20) ・ Carmine 6BN (Toyo Ink Mfg. Co., Ltd., azo organic pigment) ・ Meat condition: Kneading with sand mill for 2 hours

(Example-2) Oxidized chlorinated PP obtained in Prototype Example-1 (chlorine content: 27.3 wt%, functional group index: 11.
5, nonvolatile content 50wt%) 420g, Epicoat 828 12.6g
Was placed in the same flask as in Example 1, and allowed to react at a temperature of 85 ° C. for 1 hour. Then, 90 g of Placcel L-220AL and 27.4 g of isophorone diisocyanate were added and reacted for several hours.
Next, the mixture was cooled to 50 ° C., 531.8 g of toluene was added, and a chain extension reaction was performed with 9.5 g of isophoronediamine. Then, 1.0 g of N-butylamine and 76 g of isopropyl alcohol were added to stop the reaction, and a uniform and transparent binder resin ( A nonvolatile content of 30% by weight) was obtained. Next, a primer is adjusted with the binder resin, and P
P-plate (TX-933A, manufactured by Mitsubishi Yuka Co., Ltd.) with a film thickness of 5
It was spray-coated so as to have a thickness of 1515 μm. After a few minutes, the two-part curable urethane paint and one-part curable melamine paint of each paint maker are spray-coated to a thickness of 30 to 40 μm, respectively, and dried at room temperature for 15 minutes. In the case of the one-component curable melamine paint, it was forcibly dried at 120 ° C. for 30 minutes. After standing at room temperature for 24 hours, the coating film was tested. Table 3 shows the results. The formulation of the primer is shown in Table 4.

(Example-3) Oxidized chlorinated PP obtained in Prototype Example-1 (chlorine content 31.2 wt%, functional group index 11.
5, nonvolatile content 50wt%) 480g, Epicoat 828 12g,
201060 g of Clapol P, isophorone diisocyanate
26.2 g, toluene 494.1 g, isophorone diamine 8 g, n-
The same reaction as in Example 2 was carried out at a blending ratio of 1.0 g of butylamine and 76 g of isopropyl alcohol to obtain a uniform and transparent binder resin (nonvolatile content: 30% by weight). Hereinafter, the same test as in Example-2 was performed. Table 3 shows the results.

(Comparative Example-3) Supercron 82 (trade name)
2 (acid anhydride-modified chlorinated PP, chlorine content 24.5 wt%, nonvolatile content 20 wt%, manufactured by Sanyo Kokusaku Pulp Co., Ltd.), and the same test as in Example-2 was performed. Table 3 shows the results.

[0042]

[Table 3]

Paint A-1: 2 manufactured by Kansai Paint Co., Ltd.
Liquid-curable urethane paint ・ Paint A-2: One-part curable melamine paint made by Kansai Paint Co., Ltd. ・ Paint B-1: Two-part curable urethane paint made by Nippon Paint Co., Ltd. ・ Paint B-2: Nippon Paint ( Co., Ltd. One-component curable melamine paint

[0044]

[Table 4]

Primer preparation method Knead for 1 hour with a sand mill and use Ford Cup N0.4
Adjust the viscosity with xylene for 10 to 12 seconds. Test method ○ Adhesion Make 100 grids that reach the substrate at 1 mm intervals on the painted surface, and adhere cellophane adhesive tape on top of it and make 180 °
The film was peeled off in the direction, and the degree of the remaining coating film was determined. ○ Gasoline resistance Scratch (marked by X) reaching the substrate was put on the coated surface, immersed in gasoline for 2 hours, and the state of the coating film was examined. ○ Flex resistance Using a 1/2 φ inch mandrel in an atmosphere of −20 ° C, 180
° The state of the bent coating film was examined. ○ Impact resistance Using a DuPont impact tester in an atmosphere of -20 ° C,
An impact test was performed under the conditions of 2 φ inches, a load of 500 g, and a height of 50 cm, and the state of the coating film was examined.

Example 4 Oxidized chlorinated PE obtained in Prototype Example 2 (chlorine content: 69.5 wt%, functional group index: 31.
2) 200 g, Epicort 828 8 g, 50 g of high-molecular polyol synthesized from adipic acid and 1,4-butanediol (butane adipate, molecular weight 2,000), 22.5 g of isophorone diisocyanate, 389 g of toluene, 389 g of isophorone diamine
The same reaction as in Example 2 was carried out at a mixing ratio of 7.5 g and 43 g of isopropyl alcohol to obtain a uniform and transparent binder resin (nonvolatile content: 40 wt%). Next, a white ink and a red ink are adjusted with the binder resin, and a coating rod #
4 and coated on Manila coated paper. After drying at room temperature for one day, the heat resistance was measured. Table 5 shows the results. The ink formulation is shown in Table 6.

(Example-5) Oxidized chlorinated PE obtained in Prototype Example-2 (chlorine content 69.8 wt%, functional group index 40.
5) 200g, Epicoat 828 8g, Clapol P-2010
25 g, isophorone diisocyanate 17.3 g, toluene
The same reaction as in Example 2 was carried out at a mixing ratio of 347 g, isophoronediamine 6.2 g, and isopropyl alcohol 38 g, and a uniform and transparent binder resin (nonvolatile content 40 wt%)
I got Thereafter, the same test as in Example-4 was performed. Table 5 shows the results.

(Comparative Example-4) Trade name: Supercron 90
The same test as in Example-4 was conducted by adjusting the ink with 7MA (manufactured by Sanyo Kokusaku Pulp Co., Ltd., chlorinated PE, chlorine content: 69 wt%). Table 5 shows the results.

[0049]

[Table 5]

○ Test method for heat resistance of ink When a high-quality paper is placed on the ink surface and a heat seal bar set at each temperature is pressed at 2 kg / cm ^{2 for} 10 seconds, and then left standing for 30 minutes or more and peeled off Judgment was made based on the state of the coated surface.

[0051]

[Table 6]

Carmine 6BN: azo organic pigment, manufactured by Toyo Ink Manufacturing Co., Ltd. Isocyanate compound: Desmodur Z43
No. 70, isocyanate curing agent, isophorone diisocyanate, isocyanurate ・ Accelerator: di-n-butyltin dilaurate ○ Ink preparation method Mix the pigment according to the ink formulation in Table 6, and use a sand mill.
Time for meat. Next, a crosslinking agent and an accelerator were added.
The viscosity was adjusted with toluene so that the temperature was 20 to 25 seconds / 20 ° C. in a 3 Zahn cup.

[0053]

(From the results in Table 1) Chlorinated P of Comparative Example 1
The P / chlorinated ethylene vinyl acetate copolymer ink binder resin shows good adhesion to PP film, but has no adhesion to PET and NY films and is far from practical strength. The polyurethane-based binder resin of Comparative Example 2 adheres to PET and NY films, but does not have sufficient adhesive strength to PP films. The product of the present invention is P
It can be seen that this is a highly versatile ink binder resin having good adhesiveness to both P film, PET and NY films.

(From the results in Table 3) The acid anhydride-modified chlorinated PP of Comparative Example 3 is a commercially available primer for a PP bumper, but has selectivity in the adhesion to an existing topcoat paint. In addition, bending resistance and impact resistance at low temperatures are poor. The binder resin of the present invention has good physical properties such as gasoline resistance and moisture resistance, and can be said to be a well-balanced PP resin primer excellent in adhesion to existing paints and low-temperature physical properties.

(From the results in Table 5) The heat resistance of the binder resin of the present invention is improved as compared with commercially available chlorinated PE by blending an isocyanate compound as a curing agent, and the present invention is useful. You can see that there is.

Continuation of the front page (51) Int.Cl. ⁶ Identification symbol FI C09D 175/04 C09D 175/04 C09J 123/28 C09J 123/28 175/04 175/04 (56) References JP-A-6-41488 (JP) JP-A-4-161402 (JP, A) JP-A-1-252606 (JP, A) JP-A-9-20817 (JP, A) Patent 2551894 (JP, B2) (58) Int.Cl. ⁶ , DB name) C08G 18/00-18/87 C08F 8/00-8/50

Claims (3)

(57) [Claims] 1. A chlorinated polyolefin (I) oxidized by using at least one or more selected from air, oxygen and ozone during a chlorination reaction of the polyolefin.
And reacting the compound (IV) containing at least one epoxy group in the molecule, reacting the polymer polyol (II) and the organic diisocyanate (III), and then reacting with a chain extender. A method for producing a binder resin composition. 2. A chlorinated polyolefin (I) oxidized by using at least one or more selected from air, oxygen and ozone during the chlorination reaction of the polyolefin.
And a compound (IV) containing at least one epoxy group in the molecule, then reacting the polymer polyol (II) and the organic diisocyanate (III), then reacting with a chain extender, and further reacting A method for producing a binder resin composition, comprising adding a terminator. 3. The process for producing a binder resin composition according to claim 1, wherein the chlorine content of the oxidized chlorinated polyolefin (I) is 5 to 75% by weight.