JP2848588B2 - 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 a resin composition used for the purpose of protecting and cosmetically protecting various plastics, and more particularly, to a polyolefin resin, a polyurethane resin, a polyamide resin, an acrylic resin, and a polyester resin. Resin compositions for coatings, printing inks and adhesives that exhibit excellent gasoline resistance, weather resistance, moisture resistance, hot water resistance (boiling, retort properties), etc., for films, sheets or molded products of various synthetic 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. Used. In particular, polyolefin resins are inexpensive and have many excellent properties such as moldability, chemical resistance, heat resistance, water resistance, and good electrical properties, and are widely used as industrial materials. Elongation is one of the most promising materials.

However, unlike a synthetic resin having a polarity, such as a polyurethane resin, a polyamide resin, an acrylic resin, and a polyester resin, a polyolefin resin is nonpolar and crystalline, so that painting and bonding are difficult. Has the disadvantage of saying

Therefore, conventionally, the surface of a polyolefin-based resin molded article is activated by plasma treatment or gas flame treatment to improve the adhesion. However, this method has a complicated process and requires a large amount of equipment and time. Loss due to the complexity of the molded product and the effects 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 found in automotive bumper coating have been proposed, but this involves a 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 polyolefin-based resins.
Moisture resistance, gasoline resistance, etc. are poor and do not show sufficient coating film performance. For this reason, attempts have been made to use a mixture of acrylic resin and alkyd resin having good paint properties.
However, acrylic resin and alkyd resin originally have poor compatibility with chlorinated polyolefin, so the gloss of the coating film decreases,
Problems such as remarkably impairing the appearance are caused.

To improve these disadvantages, Japanese Patent Application Laid-Open No. 58-719
As seen in No. 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-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 Paint composition or a hydroxyl group-containing acrylic-modified chlorinated copolymerized with an acrylic monomer having a hydroxyl group in the presence of a chlorinated polyolefin and a liquid rubber as shown in JP-A-62-95372. Adhesive resin composition containing polyolefin and isocyanate compound as main components
No. 4-92009 describes a coating composition obtained by reacting a chlorinated polyolefin and a hydroxyl-containing chlorinated polyolefin obtained by graft copolymerization of a monomer containing at least one hydroxyl group with an organic diisocyanate or a polymer polyol. is there.

However, these compositions are inherently poor in reactivity between the chlorinated polyolefin and the acrylic monomer, so that even when copolymerized, opacity or two-layer separation occurs, and a uniform and transparent solution is produced. I can't get it. In Japanese Patent Application No. 4-102119, a cross-linked oxidized chlorinated polyolefin and a method for producing the same are characterized by cross-linking an oxidized chlorinated polyolefin 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 crosslinking agent to form a crosslinked coating film, the flexibility, appearance, durability, etc., which are originally required for the bandider resin, are inferior. However, it is not necessarily a balanced binder resin.

Furthermore, prior to the present invention, the present inventors have proposed a binder resin composition having a urethane structure introduced by reacting an oxidized 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 satisfying the high gloss, toughness, pigment dispersibility, etc. required for a resin for one-coat finishing.

[0010]

The present invention solves the above-mentioned problems by modifying a chlorinated polyolefin, which 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.

[0011]

That is, the inventors of the present invention have developed a chlorination reaction which is oxidized using at least one or more selected from air, oxygen and ozone during the chlorination reaction of polyolefin. A resin (IV) obtained by reacting a polyolefin (I) with an organic diisocyanate (II) and a polymer polyol (III), and a monomer 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 resin composition comprising a resin obtained by graft copolymerization of a monomer contained therein and an isocyanate compound achieves the above object, and have accomplished the present invention.

The oxidized chlorinated polyolefin (I) used in the present invention includes crystalline polypropylene, amorphous polypropylene, polybutene-1, polypentene-1,
4-methylpentene-1, low-density or high-density polyethylene, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, natural rubber, polyolefins such as polyisoprene, and water or carbon tetrachloride or chloroform. Disperse or dissolve in such a medium as described above, and 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 from the beginning, from the middle,
Alternatively, at the end of the chlorination, it is obtained by blowing air, oxygen or ozone simultaneously or separately or alternately with gaseous chlorine.

Oxidized chlorinated polyolefin (I)
The oxidation progress of 1730 cm ^-1 measured by infrared spectrophotometer
This can be determined by the increase in absorption in the vicinity. In addition, the degree of oxidation can be confirmed by a functional group index measured on 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]

The chlorine content of the oxidized chlorinated polyolefin (I) is preferably in the range of 5 to 75% by weight, since the solution state is deteriorated 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 poorly adherent polyolefin resins. 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 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,
Examples include isophorone diisocyanate, 4,4-dicyclohexylmethane diisocyanate, and 1,4-cyclohexyl diisocyanate.

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 to bisphenol A. Glycols and the like.

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 obtained by the reaction, 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 method of the present invention for reacting the oxidized chlorinated polyolefin (I) with the organic diisocyanate (II) and the high molecular polyol (III) may use a conventionally known method for producing a urethane prepolymer resin. However, since the terminal functional group needs to be a hydroxyl group, the molar ratio of isocyanate group / hydroxyl group needs to 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 and xylene, and an ester solvent such as ethyl acetate and butyl acetate, a ketone solvent such as methyl ethyl ketone and methyl isobutyl ketone, ethanol, isopropanol, and the like. Alcohol solvents such as n-butanol, aliphatic solvents, cycloaliphatic solvents and the like may be used in combination.

As another method carried out according to the above reaction method, after the compound (V) containing at least one epoxy group in the molecule is reacted with the oxidized chlorinated polyolefin (I) (II) ) And (III) to give the resin (VI).

The epoxy compound (V) used in this case includes glycidyl ethers of monoalcohols and polyhydric alcohols, such as butyl glycidyl ether, phenyl glycidyl ether, ethylene glycol glycidyl ether, propylene glycol glycidyl ether, sorbitol polyglycidyl ether, and the like. Bisphenol A
And epoxy resins of bisphenol F type, and cyclic aliphatic epoxy resins obtained by oxidizing olefins with peracid. Further, at least one compound in a molecule such as an acrylic epoxy compound obtained by copolymerizing glycidyl (meth) acrylate and other (meth) acrylates.
Any compound containing two epoxy groups can be used.

The resin (IV) obtained by the above method further comprises a monomer containing at least one ethylenically unsaturated bond in one molecule and / or a monomer having an ethylenically unsaturated bond and a hydroxyl group in one molecule. The reaction method for graft copolymerization of at least one monomer is as follows. Resin (IV) is appropriately diluted with a solvent, mixed, and heated after adding a polymerization initiator. The basic process is to react while reacting,
The resin (IV) and the monomer may be mixed in advance, and after adding a polymerization initiator, the mixture may be heated and reacted.

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

The monomer used in the present invention which contains at least one ethylenically unsaturated bond in one molecule includes:
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 the terminal of polystyrene or poly (meth) acrylate A compound such as a macromonomer having a (meth) acryloyl group that can be polymerized into a polymer can also be used.

Further, a monomer containing at least one ethylenically unsaturated bond and a hydroxyl group in one molecule may be, for example, 2-
There are hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and the like. (Poly) caprolactone-modified (meth) obtained by esterifying the above hydroxyl-containing (meth) acrylate with caprolactones. Acrylate (for example, Daicel Chemical Industries, Ltd., trade name Placcel F)
A, Plaxel FM series, etc.) can also be used. or,
Esters obtained by reacting α, β unsaturated carboxylic acids or anhydrides thereof with diols, 1,4-butene glycol, allyl alcohol, and other monomers having an ethylenically unsaturated bond and a hydroxyl group in one molecule Any substance or compound can be used.

The content of the resin obtained from the chlorinated polyolefin (I) contained in the resin composition of the present invention is 5 to 90 wt.
% Is preferred. If the amount is less than 5% by weight, the adhesion resistance to the polyolefin is inferior, and if it is more than 90% by weight, the balance of physical properties of the coating film is deteriorated.

The resin composition of the present invention contains gasoline resistance, weather resistance, moisture resistance and hot water resistance (boiling and retorting properties) by blending an isocyanate compound as a curing agent.
For example, it is possible to improve the properties of a coating film required for paints and inks. As the isocyanate compound used at this time,
Although the above-mentioned organic diisocyanates can be used, it is more preferable that these organic diisocyanates are used after being modified into an isocyanate derivative such as a burette, isocyanurate, or trimethylolpropane adduct.

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

The resin composition alone exhibits well-balanced coating film properties, but if necessary, alkyd resin, acrylic resin, polyacryl polyol, polyester resin, polyester polyol, polyether resin, polyether A polyol, a polyurethane resin, a chlorinated polyolefin or the like may be further added and used.

A feature of the present invention is that during the chlorination reaction of the polyolefin, a functional group is introduced into the chlorinated polyolefin by oxidizing the polyolefin with air, oxygen, ozone, etc. It is considered that the resulting resin becomes a uniform and transparent solution when the monomer having a saturated bond reacts reliably.

Further, the chlorinated polyolefin, urethane prepolymer, and acrylic component are introduced into the obtained resin, so that the chlorinated polyolefin exhibits good adhesion to the polyolefin resin, and the urethane is applied to the coating film. Acrylic provides a coating composition having a tough flexibility and acts as a component for imparting hardness and abrasion resistance.

Although the functional group introduced into the chlorinated polyolefin is not clear, a carbonyl group,
Formation of a carboxyl group, an acid chlor group, a peroxide group, a peroxide chlor group and the like can be 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.

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) having an epoxy group in advance and then carry out the urethane reaction. It has the effect of accelerating the reaction rate and stabilizing the reaction system.

[0035]

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.

(Prototype Example-1) 4 kg of isotactic PP having a number average molecular weight of 5,000 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. Chlorination was performed. When the chlorine content reached about 20 wt%, the chlorine gas was switched to a mixed gas having a chlorine / air volume ratio of about 10/90, and chlorination was performed slowly while performing the oxidation treatment. In the course of the oxidation treatment, a sample having a functional group index of 15.5 and a chlorine content of 30.2 wt% was withdrawn while tracking the above functional group index with an infrared spectrophotometer.
The carbon tetrachloride was distilled off and replaced with toluene.
% Of oxidized chlorinated PP was obtained.

(Trial Production Example 2) 2 kg of isotactic PP having a number average molecular weight of 15,000 was chlorinated under the same conditions as in Trial Production 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. Hereinafter, according to the method of prototype example 1,
Functional group index 16.5, chlorine content 31.8wt%, non-volatile content
An oxidized chlorinated PP of 50% by weight was obtained.

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

Example 1 In a flask equipped with a stirrer, a thermometer and a condenser for refluxing monomers, the oxidized chlorinated PP obtained in Trial Production Example 1 (non-volatile content: 50 wt.
%) 210 g, hexamethylene diisocyanate 9.6 g,
Trade name Klapol P-1010 (manufactured by Kuraray Co., Ltd., 3-methylpentane adipate polymer diol, molecular weight 1,00)
0) 75 g was charged and reacted at 85 ° C. for several hours, and then 204.6 g of toluene was added. Next, benzoyl peroxide
After charging 1.5 g and stirring at 85 ° C. for 30 minutes, 84.6 g of cyclohexyl acrylate and 35.4 g of 2-hydroxyethyl acrylate are added over about 3 hours, and the graft copolymerization reaction is further performed for about 7 hours, and the resulting mixture is uniform and transparent. The 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 isocyanate curing agent N3390 (Bayer, hexamethylene diisocyanate, isocyanurate) was added.
o. Adjust viscosity with xylene so that the temperature becomes 13 to 15 seconds / 20 ° C with a 4 Ford cup, and use a polypropylene plate, TX-933A.
(Mitsubishi Yuka Co., Ltd.) was spray painted. After drying at room temperature for 15 minutes, forcibly drying at 80 ° C. for 30 minutes, and leaving it to stand indoors for one week, the coating film was tested. Table 1 shows the results.

(Example 2) 210 g of the oxidized chlorinated PP (nonvolatile content: 50 wt%) obtained in Prototype Example-2, 5.9 g of hexamethylene diisocyanate, Plaxel L-212AL
75 g of caprolactone-based polymer diol (manufactured by Daicel Chemical Industries, Ltd., molecular weight 1,200), toluene 200.9 g, benzoyl peroxide 1.5 g, methyl methacrylate 5
Example-1 was prepared at 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 method described in (1) to obtain a uniform and transparent reaction product (nonvolatile content: 50 wt%). Next, 100 g of the obtained reactant, 26 g of titanium dioxide, isocyanate curing agent Desmodur Z43
Paint preparation and coating film tests were carried out in the same manner as in Example 1 at a blending ratio of 21.5 g of 70 (Bayer, isophorone diisocyanate, isocyanurate). Table 1 shows the results.

Comparative Example 1 Chlorinated P Obtained in Prototype Example 3
Using P (non-volatile content: 50 wt%), the reaction was carried out at the same blending ratio as in Example 2 to obtain an opaque reactant. Further Example-
In the same manner as in 2, paint preparation and coating film tests were performed. Table 1 shows the results.

[0043]

[Table 1]

Coating film test method ○ Adhesion 100 cross-cuts reaching the substrate at 1 mm intervals were made on the coated surface, and a cellophane adhesive tape was stuck on it and 180 °
The film was peeled off in the direction, and the degree of the remaining coating film was determined.

○ Accelerated weather resistance A carbon arc type sunshine weatherer meter was used. Gloss was measured at 60 ° specular reflection, and whiteness was measured with a hunter.

○ Warm water resistance The coated plate was immersed 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) Gasoline was impregnated with absorbent cotton and the coated surface was rubbed 100 times to examine the state of the coating film. (2 hours of soaking) Scratch reaching the substrate on the painted surface (×
Mark) and immersed in gasoline for 2 hours to examine the state of the coating film.

Bending resistance The film was bent 180 ° with a 1/2 φ inch mandrel, and the state of the coating film was examined.

○ Impact resistance Impact resistance A DuPont type impact tester was used.
Using a load of 500 g, the film was dropped from a height of 50 cm onto the coated surface, and the state of the coated film was examined.

[0050]

【The invention's effect】

(From the results in Table 1) The resin obtained by subjecting the chlorinated PP oxidized as in Examples -1 and -2 to urethane modification and then graft copolymerizing an acrylic monomer is superior to the conventional resin. , For example, adhesion, appearance, gasoline resistance, weather resistance,
It can be seen that the coating film is very balanced without impairing the flexibility and the like. On the other hand, even if various chlorinated PPs are variously modified as in Comparative Example 1, good physical properties cannot be obtained.

──────────────────────────────────────────────────の Continuation of front page (51) Int.Cl. ⁶ Identification symbol FI C08F 8/20 C08F 8/20 283/00 283/00 (56) References JP-A-4-88037 (JP, A) JP Hei 1-292062 (JP, A) JP-A-60-123523 (JP, A) JP-A-60-92375 (JP, A) JP-A-49-48780 (JP, A) (58) Fields investigated (Int) .Cl. ⁶ , DB name) C08L 51/08 C09D 11/10 C09D 151/08 C09J 151/08 C08F 283/00-283/14

Claims (8)

(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 a polyolefin, an organic diisocyanate (II) and A resin containing at least one ethylenically unsaturated bond in one molecule and / or a monomer having at least one ethylenically unsaturated bond in the resin (IV) obtained by reacting the polymer polyol (III) A resin composition comprising a resin obtained by graft copolymerizing a monomer having at least one hydroxyl group with an isocyanate compound. 2. An organic diisocyanate (II) and a polymer after reacting a compound (V) containing at least one epoxy group in the molecule with the oxidized chlorinated polyolefin (I) according to claim 1. Resin (VI) obtained by reacting polyol (III) with a monomer containing at least one ethylenically unsaturated bond in one molecule and / or a monomer having one or more ethylenically unsaturated bonds in one molecule. A resin composition comprising a resin obtained by graft copolymerizing a monomer containing at least one isocyanate compound and an isocyanate compound. 3. The resin composition according to claim 1, wherein the chlorine content of the oxidized chlorinated polyolefin is 5 to 75% by weight. 4. The resin according to claim 1, wherein the resin (IV) or the resin (VI) is obtained by reacting at a molar ratio of isocyanate group / hydroxyl group in the range of 0.1 to 0.9. Composition. 5. The resin obtained from the oxidized chlorinated polyolefin (I) according to claim 1 in a resin composition.
The resin composition according to any one of claims 1 to 4, wherein the content of the resin composition is from 90 to 90% by weight. 6. A resin composition for coatings comprising the resin composition according to claim 1. 7. A resin composition for printing inks, comprising the resin composition according to claim 1. 8. A resin composition for an adhesive, comprising the resin composition according to any one of claims 1 to 5.