JPH0318657B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a resin composition for coatings, and more particularly to polyolefin resin compositions such as untreated polyolefin molded products and films, which contain a chlorinated polyolefin and a specific vinyl copolymer as essential film-forming components. The present invention relates to a resin composition for paint that has good adhesion and solvent resistance and functions as a primer and one coat on materials. Conventional paints made of alkyd, acrylic, epoxy resins, etc. have almost no adhesion to molded products or films made of crystalline polyolefins, which have low polarity. As a method for coating polyolefin materials, primers such as atactic polypropylene modified with maleic anhydride and ethylene-propylene copolymer modified with maleic acid have been proposed. However, although these have good adhesion to polyolefin materials, they have poor interlayer adhesion with top coats, and when used as clear paints, the paint film becomes cloudy, so they can only be applied to enamel paint systems containing pigments. There is. Additionally, a method is known in which chlorinated polyolefin itself is used as a primer and acrylic resin is applied to the top coat, but this method is said to reduce interlayer adhesion with the top coat, solvent resistance, and long-term durable adhesion. There are drawbacks. Furthermore, although it is known to use chlorinated polyolefin itself as a top coat, it is impractical because the hardness and solvent resistance of the coating film are significantly deteriorated. It has long-term adhesion to polyolefin materials, maintains interlayer adhesion with top coat, and has excellent solvent resistance.
Resin compositions made of chlorinated polyolefin and acrylic copolymer are effective as coating resin compositions with improved coating performance such as curing. The compositions formed include the following problems. That is, the chlorination rate is 50% by weight (hereinafter abbreviated as %)
If it exceeds the range, the compatibility between the chlorinated polyolefin and the acrylic copolymer will improve, but the adhesion and solvent resistance of the formed coating film will deteriorate, making it difficult to use it practically. On the other hand, it is possible to improve adhesion by using a chlorinated polyolefin with a chlorination rate of 50% or less, for example around 35%, but it lacks compatibility with the acrylic copolymer.
The stability of the paint becomes extremely poor, making it difficult to use it practically. However, as a result of intensive research by the present inventors in order to further improve the compatibility of essential film-forming components between chlorinated polyolefin and a specific vinyl copolymer, as well as to improve the adhesion to polyolefin materials, the molecule The addition reaction product of a vinyl polymer and an allyl compound having a functional group that can undergo an addition reaction, that is, an allyl group-containing vinyl copolymer, has excellent compatibility with chlorinated polyolefins and has excellent compatibility with materials. The present invention was completed based on the discovery that adhesion and gasoline resistance were also good. That is, the present invention provides an allyl compound having one or more functional groups selected from the group consisting of a hydroxyl group, a carboxyl group, and a glycidyl group, and a hydroxyl group, a carboxyl group, which can react with each of these functional groups,
10 to 90 parts by weight of an allyl group-containing vinyl copolymer (A) obtained by reacting a vinyl polymer having one or more functional groups selected from the group consisting of glycidyl groups and carboxylic anhydride groups; , 90 to 10 parts by weight of chlorinated polyolefin (B) and 0.01 parts by weight of curing catalyst (C)
~1 part by weight and 0 of the polyisocyanate compound (D)
The object of the present invention is to provide a resin composition for coating material containing 20 parts by weight in the proportions as described above, which has good adhesion to polyolefin molded articles and also has good solvent resistance. Here, the allyl group-containing vinyl polymer (A), which is the first component of the composition of the present invention, is generally prepared by reacting a vinyl polymer having a carboxyl group in the side chain with, for example, allyl glycidyl ether. However, as an alternative method, a carboxyl group-containing allyl compound such as a monoester of a dibasic acid such as succinic acid, maleic acid or fumaric acid with allyl alcohol or ethylene glycol monoallyl ether, and glycidyl Reaction with group-containing vinyl polymers, or ethylene glycol monoallyl ether, trimethylolpropane mono-,
Even if an allyl group is introduced into the side chain by reacting a diallyl ether compound or a mono-, di-, or triallyl ether compound of pentaerythritol, a hydroxyl group-containing vinyl polymer, and a diisocyanate compound such as hexamethylene diisocyanate. good. Furthermore, an allyl group may be introduced into the side chain by reacting an allyl compound containing a hydroxyl group or a methylol group with a vinyl polymer containing a carboxylic anhydride group. In this way, an allyl compound having an allyl group and one or more functional groups selected from a hydroxyl group, a carboxyl group, and a glycidyl group in one molecule, and a hydroxyl group that can be combined with the above functional group in the allyl compound, The polymer (A) can be obtained by reaction with a vinyl polymer having one or more functional groups selected from carboxyl groups, glycidyl groups, and carboxylic anhydride groups; Vinyl polymers having one or more functional groups selected from carboxylic acid groups include a polymerizable monomer containing any one of these functional groups and other monomers copolymerizable with these functional groups. It can be obtained by copolymerizing. Here, typical examples of hydroxyl group-containing monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and N- methylolated (meth)acrylamide,
Alternatively, it is a monoester of polyhydric alcohol such as glycerin or trimethylolpropane and (meth)acrylic acid, and the above-mentioned carboxyl group-containing or carboxylic anhydride group-containing monomers include (meth)acrylic acid, itacon, etc. Monoesters of acid, dibasic acids such as crotonic acid or maleic anhydride are typical examples, and glycidyl (meth)acrylate is a typical example of the glycidyl group-containing monomer. On the other hand, representative monomers that are copolymerizable with each of these monomers include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and (meth)acrylate. isobutyl acrylate,
These include 2-ethylhexyl (meth)acrylate, acrylonitrile, styrene, vinyltoluene, vinyl acetate, dibutyl fumarate or dibutyl itaconate, as well as oil-free alkyd resins with copolymerizable unsaturated double bonds. It will be done. Vinyl polymers having hydroxyl groups, carboxyl groups, glycidyl groups, and/or carboxylic anhydride groups in their side chains can be prepared using various monomers such as benzoyl peroxide, kyumene hydroperoxide, ditertiary butyl Most preferably, they are prepared by known solution polymerization methods using free radical catalysts such as peroxide, ditertiary butyl hydroperoxide, azobisisobutyronitrile or azobisisobutyramide. Solvents used in this solution polymerization include aromatic hydrocarbons such as benzene, toluene or xylene; ketones such as methyl ethyl ketone or methyl isobutyl ketone; esters such as ethyl acetate, butyl acetate or cellosolve acetate; butanol. or alcohols such as isobutanol; or cellosolves such as methyl cellosolve or butyl cellosolve are typical examples, and these may be used alone or in combination depending on the purpose. In this way, an allyl compound having an allyl group and at least one functional group selected from a hydroxyl group, a carboxyl group, and a glycidyl group in one molecule, and a vinyl polymer having a functional group that can react with each of these functional groups. The allyl group-containing vinyl polymer (A) can be obtained by reacting with the allyl group-containing vinyl polymer (A). In this case, the usage ratio of the functional group-containing allyl compound and the functional group-containing vinyl polymer is 1 to 40% by weight, preferably 4 to 30% by weight of the above compounds.
and 99-1% by weight of the latter resin, preferably 96-70%
The allyl group-containing vinyl polymer (A) within this range is particularly advantageous in terms of adhesion and gasoline resistance. If this allyl compound exceeds 40% by weight, the storage stability of the resin composition will be significantly deteriorated, which is not preferable. Here, the above-mentioned chlorinated polyolefin refers to a polyolefin with a chlorination rate of 50% or less, preferably 10 to 45%. Typical polyolefins include ethylene, propylene, 1-butene, -methyl-1-butene,
Homopolymers or copolymers of α-olefins such as 3-methyl-1-heptene or ethylene-
Vinyl acetate, ethylene-butadiene, ethylene-
There are copolymers of α-olefins such as acrylic acid esters and other vinyl monomers, and representative examples of the chlorinated polyolefins include chlorinated polyethylene, chlorinated polypropylene, and chlorinated ethylene. -Propylene copolymers or chlorinated ethylene-vinyl acetate copolymers. Regarding the chlorination rate of the chlorinated polyolefin, if the chlorination rate exceeds 50%, the adhesion to the polyolefin base material decreases, so the determination of the chlorination rate is based on the adhesion and flexibility. This should be done while taking into consideration various coating properties such as hardness and hardness, and preferably 10 to 45%, and in this way a resin composition with the most balanced coating properties can be obtained. The solid proportion (weight ratio) of the allyl group-containing vinyl polymer (A) and the chlorinated polyolefin (B) is such that the ratio of (A) to (B) is 90:10 to 10:90. , preferably within the range of 85:15 to 60:40. Since the allyl group-containing vinyl copolymer (A) contains a double bond that reacts with oxygen, it is necessary to use a curing catalyst to improve its curability and coating performance. . Here, typical examples of the curing catalyst (C) include so-called metal driers such as cobalt naphthenate, lead naphthenate, manganese naphthenate, etc., but the amount of these curing catalysts (C) used is Regarding the allyl group-containing vinyl polymer (A)
It is suitably within the range of 0.01 to 1% by weight. On the other hand, in order to effectively utilize the hydroxyl groups generated by the addition reaction between each of the above-mentioned functional group-containing allyl compounds and the functional group-containing vinyl polymer, the polyisocyanate compound (D) is used to Curing the composite (A) is extremely effective in further improving coating film performance, mainly solvent resistance, and especially gasoline resistance. Here, the polyisocyanate compound
Representative examples of (D) include tolylene diisocyanate, hexamethylene diisocyanate,
Examples include diisocyanates such as isophorone diisocyanate, and adducts of these diisocyanates with polyhydric alcohols, but more preferably derivatives of hexamethylene diisocyanate having a Biuret structure, such as duranate.
24A-100 (Asahi Kasei product), Desmodyur N (Bayer product), etc., and as an adduct of hexamethylene diisocyanate and cyanuric acid,
An example is Coronate EH (product of Nippon Polyurethane Co., Ltd.). Even when these polyisocyanate compounds (D) are not added, the composition of the present invention can guarantee and ensure sufficient performance, but if more stringent solvent resistance is not required, the above-mentioned ( It may be used in a range of 1 to 20 parts by weight based on 100 parts by weight of the total amount of component A) and component (B). If used in excess of 20 parts by weight, it may adversely affect the compatibility of the entire system. This is not desirable. The composition of the present invention thus obtained has excellent long-term adhesion and adhesion in a broad sense such as interlayer adhesion with the top coat, and is also a cured coating with excellent coating performance in solvent resistance. It provides a film and can be widely applied to various polyolefin materials and base materials such as various molded products such as films and sheets. For example, it can be used as a primer in coating polyolefin molded products. It can also be used as a top coat for various structures and structures, and it can also be used as a binder for printing inks, but it is especially useful for various molded products, structures, and structures made of polyolefin. Useful. Thus, the composition of the present invention can be used as a coating for molded articles, structures, or structures made of homopolymers or copolymers of α-olefins such as ethylene, propylene, 1-butene, or 3-methyl-1-heptene. It can be applied particularly to polyolefin molded products containing fillers such as titanium oxide, talc or silica, and can be used as a clear paint or as a well-known and commonly used additive such as pigments and leveling agents. Of course, the components may be mixed together and used as an enamel paint. Next, the present invention will be specifically explained using reference examples, examples, and comparative examples, and all parts and percentages are based on weight unless otherwise specified. Reference Example 1 [Preparation example of allyl group-containing vinyl polymer (A)] 90 parts of toluene was charged into a reactor equipped with a stirrer, a thermometer, a cooler, a dropping device, and a nitrogen gas inlet, and nitrogen gas was introduced into the reactor. While blowing, adjust the temperature inside the reactor.
48.75 parts of methyl methacrylate by raising the temperature to 110°C;
A monomer mixture consisting of 48.75 parts of isobutyl methacrylate and 22.5 parts of methacrylic acid, and toluene.
A solution prepared by dissolving 1.5 parts of azobisisobutyronitrile and 0.75 parts of t-butyl peroxybenzoate in 45 parts of the solution was added dropwise over 4 hours, and after keeping at the same temperature for 10 hours, toluene was added. 15
parts, allyl glycidyl ether 30 parts, α-methylstyrene 7.5 parts and 2-methylimidazole
0.25 part was charged and reacted at the same temperature for 3 hours. The allyl group-containing vinyl polymer thus obtained had a solid content of 51.3%, a viscosity (Gardner method at 25°C; hereinafter the same) of UV, and an acid value of 1.9.
The solution had a color number (Gardner method) of 1 to 2. Hereinafter, this will be abbreviated as polymer (A-1). Reference Example 2 [Preparation example of vinyl polymer for comparison] First, 105 parts of toluene was charged and the temperature was raised to 110° C. while blowing nitrogen gas. The composition of the monomer mixture to be added dropwise was then changed to 75 parts of methyl methacrylate and 75 parts of isobutyl methacrylate, and the use of allylglycidyl, α-methylstyrene and 2-methylimidazole was completely omitted. Except for this, a control vinyl polymer was obtained in the same manner as in Reference Example 1, but this solution had a solid content of 49.8%, a viscosity of XY, and a color number of 1 or less. Hereinafter, this will be abbreviated as polymer (A'-1). Reference Example 3 [Preparation example of allyl group-containing vinyl polymer (A)] The composition of the monomer mixture was changed to that of methyl methacrylate.
A target vinyl polymer solution was obtained in the same manner as in Reference Example 1, except that 72 parts, isobutyl methacrylate, 23.25 parts, and 22.25 parts of methacrylic acid had a solid content of 50.8%. , the viscosity was W-X, the acid value was 2.0, and the color number was 2. Hereinafter, this will be abbreviated as polymer (A-2). Reference Example 4 [Same as above] The composition of the monomer mixture was changed to methyl methacrylate.
A solution of the target vinyl polymer was obtained in the same manner as in Reference Example 1, except that 35.7 parts of isobutyl methacrylate, 35.55 parts of isobutyl methacrylate, and 33.9 parts of methacrylic acid were used. U, acid value was 1.6 and color number was 2. Hereinafter, this will be abbreviated as polymer (A-3). Example 1 200 parts of the polymer (A-1) was
166.7 parts of "14LLB" (chlorinated polypropylene manufactured by Toyo Kasei Kogyo Co., Ltd.; solid content 15%), 2 parts of 6% cobalt naphthenate and "Alpaste 1109-
After blending 13.6 parts of ``MA'' (a product of Toyo Aluminum Co., Ltd.) with a thinner of toluene/butyl acetate = 50/50 (weight ratio), it was adjusted to 12 seconds with an Iwata cup, and ``Noblen BC- 3B” (Mitsubishi Yuka
A molded plate made of chlorinated polypropylene (Co., Ltd.) was spray-painted and then force-dried at 60° C. for 30 minutes. The coating film obtained here has a metallic feel and has good adhesion (initial adhesion) to polypropylene molded products, and also has good adhesion after 6 months, that is, good durability. It was hot. Furthermore, the solvent resistance to various solvents was also good. Comparative Example 1 A control coating composition was obtained in the same manner as in Example 1, except that the same amount of polymer (A'-1) was used instead of polymer (A-1). Then, a coating film was obtained. Example 2 The same amount of polymer (A-1) was used instead of polymer (A-1).
Example 1 except that it was changed to use 2).
A coating composition was obtained in the same manner as above, and then a coating film was obtained. Example 3 The same amount of polymer (A-1) was used instead of polymer (A-1).
Example 1 except that it was changed to use 3)
A coating composition was obtained in the same manner as above, and a coating film was also obtained. Example 4 The same amount of polymer (A-1) was used instead of polymer (A-1).
2) and 33.3 instead of "Hardren 14LLB"
"Super Chron 814H" (Sanyo Kokusaku Pulp Co., Ltd.)
A coating composition was obtained in the same manner as in Example 1, except that chlorinated polypropylene (solid content = 60%) manufactured by Co., Ltd. was used, and a coating film was also obtained. Example 5 The same amount of polymer (A-1) was used instead of polymer (A-1).
2) and in addition 6.1 parts of "Coronate EH" (a polyisocyanate compound manufactured by Nippon Polyurethane Industries Co., Ltd.; solid content = 100%) was used, but the same as Example 1. A coating composition was obtained, and a coating film was also obtained. The performance tests for each of the coating films obtained in the above examples and comparative examples are described in the first section.
They are summarized in the table. However, the various tests were conducted 30 minutes after baking.

【table】

[Table] * Results from cellophane tape peeling.

Claims (1)

[Scope of Claims] 1 (A) An allyl compound having one or more functional groups selected from the group consisting of a hydroxyl group, a carboxyl group, and a glycidyl group, and a hydroxyl group, a carboxyl group that can react with each of the above-mentioned functional groups,
10-90 parts by weight of an allyl group-containing vinyl copolymer obtained by reacting a vinyl polymer having one or more functional groups selected from the group consisting of glycidyl groups and carboxylic anhydride groups, ) 90 to 10 parts by weight of a chlorinated polyolefin, (C) 0.01 to 1 part by weight of a curing catalyst, and (D) 0 to 20 parts by weight of a polyisocyanate compound in the above ranges. A resin composition for paint that has good adhesion to products.