JPS5927968A - Coating resin composition - Google Patents

Abstract

PURPOSE:To provide a resin compsn. capable of yielding a coating excellent in prolonged adhesion and solvent resistance to polyolefinic substrates, by incorporating a particular chlorinated polyolefin-modified graft acrylic copolymer and an isocyanate compd. CONSTITUTION:A coating compsn. which contains an isocyanate compd. and a chlorinated polyolefin-modified acrylic copolymer contg. hydroxyl groups, obtained by copolymn., in the presence of a chlorinated polyolefin (a) with a degree of chlorination of 50wt% or lower, of a vinyl monomeric mixture (b) comprising 1-40wt% hydroxyl group-contg. monomer (b-1), 10-99wt% (meth)acrylate (b-2), and 0-50wt% other monomers copolymerizable therewith (b-3) at a rate of monomeric mixture (b)/ chlorinated polyolefin (a) of 90/10-10/90 (wt. ratio in solid content).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a novel and useful paint opening (I
Regarding acids, 8' (specifically, polyolefin-based products such as untreated polyolefin molded articles or films containing a specific chlorinated polyolefin-modified acrylic graft copolymer and an incyanate-based compound as essential components) The present invention relates to a coating resin composition that functions as a primer for a substrate and has good adhesion and solvent resistance so that it can be used in one coat.

Conventional paints made from alkyd resins, acrylic resins, and epoxy resins have almost no adhesion to polyolefin base materials such as molded products or films made from crystalline polyolefins with low polarity. .

As a method for coating such a polyolefin group (MII A), as a primer, for example, a maleic anhydride-modified product of actactic polypropylene or a maleic acid-modified product of an ethylene-propylene copolymer has been proposed.

However, although these modified products have good adhesion to polyolefin pattern materials, they have poor adhesion to top coats, and when used as clear paints, they are difficult to coat.
Q has the drawbacks of being cloudy and having extremely poor pigment dispersibility.

1.Although it is also known to use chlorinated polyolefin itself as a primer and acrylic resin as a top coat, this method is
・There are drawbacks such as deterioration in interlayer adhesion, properties, solvent resistance, and long-term durable adhesion.

Furthermore, although it is known to use chlorinated polyolefin itself as a top coat, it has the disadvantage that the hardness and solvent resistance of the coating film are significantly poor, making it impractical.

By the way, a resin composition for paint that has improved long-term adhesion to polyolefin plugging materials and improved coating performance such as top coat solvent resistance and hardness is a combination of chlorinated polyolefin and acrylic resin composition. Although compositions consisting of a combination of 1 and 2 are effective, such compositions include the following problems.

Of course, when the chlorination rate exceeds 50% by weight (hereinafter simply abbreviated as %), the compatibility between the chlorinated polyolefin and the acrylic J (polymer improves, but the coating film formed It can be said that its practical use is extremely difficult due to its reduced adhesion and solvent resistance.

On the other hand, in order to improve this adhesion, the chlorination rate is 5.
Although it is possible to improve adhesion by using chlorinated polyolefin of 0% or less, for example around 35%,
On the other hand, the lack of compatibility with the acrylic co-tiX combination results in extremely poor stability of the paint, which again makes it difficult to use.

However, in view of the various drawbacks mentioned above, the present inventors have conducted extensive research to improve the compatibility between isocyanate compounds and chlorinated polyolefin-modified acrylic copolymers with a chlorination rate of 50% or less. As a result, a vinyl monomer mixture containing a hydroxyl-containing monomer and a (meth)acrylic acid ester as essential component compounds was polymerized (obtained by polymerization) in the presence of a chlorinated polyolefin. When using a chlorinated polyolefin-modified hydroxyl group-containing acrylic copolymer, the compatibility is 1!Extremely high (sagging, and polyolefin-based)^Excellent long-term adhesion to materials and solvent resistance @film physical properties The present invention was completed by discovering that it is possible to obtain a paint having the following properties.

In the presence of the chlorinated polyolefin (8) with a chlorination rate of 50% or less according to the present invention, 1 to 401 tR% of the water r1'2 group-containing monomer (b-1), (meth)acrylic 10 to 99% by weight of acid ester (b-2) and 0 to 50% of other copolymerizable monomer (b-3) (vinyl yarn monoplane mixture pile consisting of % by weight), monomer body mixture (b)
/chlorinated polyolefin (nl = 90/10~10
/ 90- (Solid content ■ (? Ratio) Joint ■ [Salt-+monocarbon 17 i Refine modified hydroxyl group-containing acrylic system J 1 (hereinafter referred to as chlorinated polyolefin modified product Δ)) and an incyanate compound (B) as essential components.

Here, typical examples of the hydroxyl-containing monomer (b-1) include β-hydroxyethyl (meth)acrylate, β-hydroxypropyl (meth)acrylate, and β-hydroxypropyl (meth)acrylate.
-Human l” xisoprop lJ building (meth)acrylate,
Examples include β-human U xybutyl (meth)acrylate.

In addition, typical examples of the (meth)acrylic ester (b-2) include MEG (meth)acrylate,
Examples include ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, and cyclohexyl (meth)acrylate.

Furthermore, the other copolymerizable monomers (b-
Typical examples of 3) include styrene, vinyl acetate,
(meth)acrylonitrile, (meth)acrylamide, di-7setone acrylamide, dimethylaminoedyl methacrylate, or diesters of unsaturated digroups Ji such as dibutyl fumale-1, simeglu maleate or dibdel itaconate. There are various types.

This 1. It is also possible to partially use monomers containing functional 11-PJ, Q such as [crab, acid), (and Grindylno acid), (acrylic acid, etc.), and representative monomers include acrylic acid. , methacrylic acid, maleic acid, fumaric acid, glycidyl acrylate, glycidyl methacrylate, β-
Examples include methylglycidyl methacrylate.

On the other hand, the chlorinated polyolefin (al is a homopolymer or copolymer of α-olefin such as ethylene, propylene, -butene, 3-methyl-1-butene, 3-medylene-1-pentene, or α- Cofat copolymers of olefins and other monomers, such as ethylene-vinyl acetate, ethylene-butadiene, and ethylene-acrylic acid ester copolymers, are provided and chlorinated, but chlorinated Suitable examples include polyethylene, chlorinated polypropylene, chlorinated ethylene-propylene copolymer, and chlorinated ethylene-vinyl acetate copolymer.

In addition, it is preferable to use a chlorinated polyolefin ta+ having a chlorination rate of 50% or less, and if this chlorination rate exceeds 50%, the polyolefin type;! it:
This is not preferable because the adhesion to +4 will decrease, and the chlorination rate is determined by taking into account coating film performance such as adhesion, flexibility, and hardness, and a range of 15 to 40% is the most balanced. Particularly preferred as it provides a coating with a certain mllQ performance.

The chlorinated polyolefin modified product (A) used in obtaining the composition of the present invention is as described above (b-1
), (b-2), and even (b-3) are obtained by copolymerizing and copolymerizing bl in the presence of chlorinated polyolefin (8). The solid content weight ratio of the monomer mixture (b)/chlorinated polyolefin (al) is 90/10 to 10/90, preferably 85
/15 to 60/40 is preferable.

If the amount of chlorinated polyolefin (8) is too small, the adhesion to the polyolefin binder will be reduced, and if it is too large, the solvent resistance of the paint will be significantly reduced, so both are preferable. do not have.

In addition, in order to obtain such a chlorinated polyolefin modified product (Δ), known and commonly used polymerization methods can be used as they are; The polymerization initiator, such as benzoyl peroxide or azobisisobutyronitrile, can be obtained by solution polymerization using azobisisobutyronitrile.

Typical isocyanate compounds used in obtaining the composition of the present invention include tolylene diisocyanate, hexamethylene diisocyanate, and isophoric diisocyanate.
diisocyanates such as diisocyanate and polycoalcohol adducts with these diisocyanates, but more preferably 1-duranate as a derivative of hexamethylene diisocyanate having a biuret structure. 24A-100J (Asahi Kasei Kogyo 0...product), "Desmodur N" (a product of Bayer AG, West Germany), or "Coronet 1-IEIIJ" (Boriurekun Kogyo G11) as an adduct of hexamethylene diisocyanate and cyanuric acid.
l products) etc.

Thus, the composition of the present invention contains the above-mentioned chlorinated polyolefin modified product (A') and isocyanate compound (B), respectively.
The amount of these two essential components depends on the amount of isocarbon in component (B).
The ratio of IJ hydroxyl Jk number in the 7 nate dry number/(Δ) component is preferably in the range of 0.5 / 1 to 1, 2 / 1, and if it is outside this range, A coating film with excellent solvent resistance and weather resistance (11) is no longer visible.

The composition of the present invention thus obtained has not only excellent compatibility, but also long-term adhesion, interlayer adhesion with the top coat (=J adhesion, and excellent coating performance in solvent resistance). However, the adhesion is further strengthened.
If necessary, unmodified chlorinated polyolefins may be added to the compositions of the present invention in order to achieve the desired results.

Because the composition of the present invention is excellent as described above, it can be used in a wide range of applications as a coating composition for various polyolefin base materials. It may also be used as a top coat 1 for various structures.

Alternatively, it may be used as a primer to improve the printability of polyolefin films, or may be used as a binder for some printing inks.

The composition of the present invention is thus a polyolefin thread material, such as a homoelectrolyte or a copolymer of α-olefin with methylene, propylene, 1-butene, 3-methyl-1-butene, 3-methyl-1-pentene, etc. It can be used repeatedly for coating molded products or films of polymers or copolymers of these α-molefins and other vinyl yarn monomers, or various other 43 materials, especially titanium oxide, talc,
Or, it exhibits adhesion to polyolefin molded articles containing various fillers such as silica.

The coating composition of the present invention may be used as a clear coating for painting, or may be mixed with a pigment or a leveling agent and used as an enamel coating.

Next, the present invention will be explained in detail with reference to Reference Examples, Examples, and Comparative Examples. Unless otherwise specified, all parts and figures are based on weight.

Reference Example 1 (li of chlorinated polyolefin modified product (A)
Example I) In a reactor equipped with a stirrer and a cooler,
Charge 50 parts of Birdren 14 LL old (chlorinated polyolefin manufactured by Toyo Kasei Kogyo 0; chlorination rate = 28%, solids content - 30%) and 80 parts of toluene, and raise the temperature inside the vessel to 80°C. Raise the temperature and add methyl methacrylate to it.
1.70 parts, 9 parts of isobutyl methacrylate, 5 parts of β-hydroxoethyl meccrylate, and methacrylic ts
A vinyl monomer mixture consisting of 1 part of x and a solution of 0.4 part of azobisisobutyronitrile in 35 parts of toluene were heated for 3 hours under oil. After being maintained at the same temperature for 10 hours, a chlorinated polyolefin modified product (A-1) (8) having a solid content (hereinafter abbreviated as NV) of 40.8% was prepared.

Reference Example 2 (Same -L) The amount of chlorinated polyolefin used was changed to 66, G y++, while the amount of methyl methacrylate was changed to 65 parts, and 0.5 parts was added to 23.4 parts of toluene. N
Chlorinated polyolefin modified product with V40.2% (A-2
> obtained.

Reference Example 3 (same as above) The amounts of methyl methacrylate and β-hydroxyethyl methacrylate were changed to 60 parts and 10 parts, while 0.4 part of azobisisobutyronitrile was added to 30 parts of toluene/811 'i! A modified chlorinated polyolefin (Δ-3) having an NV of 40° and 5% was obtained in the same manner as in Reference Example 1, except for using the dissolved product obtained by using the same method.

Reference example 4 (same 2) [Instead of Birdren 14 LLBJ, 37.5 parts of ``
Super Chron 507J (Choyang Kokusaku Pulp G11l
chlorinated polypropylene; chlorination rate = 60%; NV =
40%) while using 0.4 parts in 47.5 parts of toluene.
A comparative chlorinated polyolefin with an N V of 40.5% was prepared in the same manner as in Reference Example 1, except that part of the azobis-f-tubyronitrile was dissolved, and the dissolved product was changed to be used. Δ'-1) was obtained.

Reference Example 5 (Same as above) A comparative example with an N V of 40.8% was prepared in the same manner as Reference Example 3, except that acrylonitrile from the same car was used instead of β-hydroxyethyl methacrylate. A modified chlorinated polyolefin (A'-2) was obtained.

Examples 1 to 4 and Comparative Example 1.2 After the chlorinated polyolefin modified product and titane oxide were milled in a sand mill at the blending ratios shown in Table 1, an isocyanate compound was blended, Rock I with thinner
Various paints were prepared by performing viscosity opening in an I+ cup for 15 seconds.

Next, each of these paints was individually coated with "Noblen DC-3".
A 3-thick sheet made of 8J (polypropylene manufactured by Mitsubishi Yuka 91) was spray-coated and then force-dried at 580° C. for 30 minutes.

The adhesion of each of these paints to polyolefin W-A (initial adhesion) and the fact that these paint films were left for 6 months.
The following is a summary of Tanora's goban test (side 1 fire adhesion) and the gasoline resistance and alcohol resistance of each coating film.
Shown in the same table.

As is clear from the results in Table 1, 6 Otsu failure 1jllδ (
Adhesion to the lyolefin-based W material (initial 44 can? f raw) was also good, and the coating film obtained using the →l forming oxide in the present invention (other 6 Gobanme test after leaving the sword (lJI Ku attached 1g-) Moni 1
T, durability (= J adhesion is maintained, and
Coating 11Q Q> hJ It is known that the gasoline resistance and alcohol resistance are also good.

Claims (1)

[Scope of Claims] (Δ) In the presence of chlorinated polyolefin (ol) with a chlorination rate of 50% or less, 1 to 40% by weight of the hydroxyl-containing monomer (b-1), (meth) A vinyl monomer mixture (b) consisting of 10 to 99% by weight of acrylic molten ester (b-2) and 0 to 50% by weight of other copolymerizable monomer (b-3), mixture (b)/chlorinated polyolefin f81 = 90/1
A chlorinated polymolefin-fitting hydroxyl group-containing acrylic copolymer obtained by copolymerization at a ratio of 0 to 10/90 (solid content weight ratio), and (B) isocyanate-1 compound as essential components. A paint resin composition comprising: a paint resin composition having good adhesion to a polyolefin binder.