JPH03292347A - Resin composition - Google Patents

Abstract

PURPOSE:To improve the adhesion to a metallic material and a workpiece by preparing a resin compsn. comprising a carboxylated, fluorinated vinyl copolymer and an org. solvent. CONSTITUTION:30-70wt.% fluorinated vinyl monomer (e.g. vinyl fluoride), 0.1-10wt.% carboxylated vinyl monomer (e.g. monobutyl maleate), and 30-70wt.% other copolymerizable monomer (e.g. methyl vinyl ether) are copolymerized in the presence of a radical polymn. initiator and 5-1000 pts.wt. (based on 100 pts.wt. the sum of the above three monomers) org. solvent (e.g. n-pentane) under 100kg/cm<2> or lower pressure at 0-140 deg.C to give a resin compsn. comprising a carboxylated, fluorinated vinyl copolymer and the org. solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel and useful resin composition, and more particularly, the present invention relates to a novel and useful resin composition, and more particularly, the present invention relates to a resin composition containing a carboxyl group-containing fluorine-containing vinyl copolymer as an essential component. A thermoplastic fluorine-containing resin composition comprising an aqueous solvent and having excellent weather resistance and adhesion to various metals such as copper, aluminum or iron, as well as alloys or plated materials. Regarding.

The thermoplastic fluorine-containing resin composition of the present invention can be used in a wide range of fields such as paints, sealants, and films, but it is especially desirable to use it in paints. .

[Conventional technology]

BACKGROUND ART Until now, resin compositions for paints that dry at room temperature, such as acrylic resin paints and acrylic urethane paints, have been used as exterior paints for buildings.

However, in recent years, as buildings have become taller and maintenance costs have soared, there has been a growing demand for even higher levels of weather resistance for exterior building materials. All paints have not been able to meet these demands because their weather resistance is insufficient.

For this reason, great efforts are being made in the industry to meet the demand for exterior paints with high weather resistance.

For example, Japanese Patent Application Laid-open No. 57-34107 discloses a solvent-soluble fluororesin, and also mentions that the resin and a curing agent can be used as a paint in combination.

If such a technique is followed, a coating film with a high degree of weather resistance can be obtained, but when used for drying at room temperature,
Since it has to be used as a two-component paint in combination with an isocyanate compound, there are restrictions on the pot life of the paint, making it difficult to put it to practical use.

Already, the inventors themselves have demonstrated that the thermoplastic type, namely -
It is clear from JP-A-61-113607 and Japanese Patent Application No. 63-182832 that it has been found that a corrugated solvent-soluble fluororesin has excellent performance.

However, it has since become clear that all of these resins have problems in adhesion to various metals such as stainless steel, aluminum, tinplate, and galvanized iron.

On the other hand, it has been known that in order to improve the adhesion of acrylic resins, a carboxyl group-containing vinyl monomer such as (meth)acrylic acid should be copolymerized.

However, when attempting to introduce carboxyl groups into a fluorine-containing vinyl polymer by reacting (meth)acrylic acid, the viscosity of the resulting copolymer inevitably becomes abnormally high, or conversely, the polymerization rate decreases. decrease or
It was not practical at all because it caused turbidity.

[Problem to be solved by the invention]

In this way, as long as conventional technology is followed, it is difficult to find a universal resin composition that can exhibit uniformly good adhesion to any metal material or processed product. The reality is that it is not possible.

To this end, the present inventors have investigated not only single metals such as copper, iron, and aluminum, and alloys such as brass and bronze, but also various plated materials such as galvanized iron and tinplate. In search of an extremely useful thermoplastic resin composition that has significantly improved adhesion to a wide variety of metal materials and processed products, such as (2), and therefore has a high degree of practicality, we have undertaken extensive research.

Therefore, the problem to be solved by the present invention is to provide a layer of practical thermoplastic resin that has good adhesion to a wide range of metal materials and processed products as mentioned above. and providing the composition.

[Means to solve the problem]

Therefore, the inventors of the present invention focused on the problems to be solved by the invention as described above, and as a result of repeated studies,
By introducing a specific functional group called a carboxyl group into a fluorine-containing vinyl copolymer, in other words, by using a specific resin called a fluorine-containing vinyl copolymer containing a carboxyl group, the adhesion to all kinds of metals is significantly improved. It was discovered that an improved thermoplastic fluorine-containing resin composition could be obtained, and the researchers went further by introducing the carboxyl group into a fluorine-containing vinyl copolymer according to the prior art. It has also been found that a carboxyl group-containing fluorine-containing vinyl polymer and, by extension, the desired thermoplastic fluorine-containing resin composition can be obtained with good reproducibility without abnormally high viscosity or turbidity. As a result, the present invention has been completed.

That is, the present invention aims to provide an extremely useful thermoplastic fluorine-containing resin composition comprising a carboxyl group-containing fluorine-containing vinyl copolymer and an organic solvent as essential components, respectively. In particular, the present invention uses, as essential components, fluorine-containing vinyl monomers, carboxyl group-containing vinyl monomers, and other copolymerizable monomers. An object of the present invention is to provide a thermoplastic fluorine-containing resin composition comprising a carboxyl group-containing fluorine-containing vinyl copolymer and an organic solvent.

Here, among the various raw materials used in preparing the carboxyl group-containing fluorine-containing vinyl copolymer, we will first exemplify only the most representative fluorine-containing vinyl monomers. Vinyl chloride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, promotrifluoroethylene, chlorotrifluoroethylene, pentafluoropropylene, hexafluoropropylene, or various types in which the (per)fluoroalkyl group has 1 to 18 carbon atoms. (bar)fluoroalkyl trifluorovinyl ether, etc.

Next, the carboxyl group-containing vinyl monomers to be copolymerized with the various fluorine-containing vinyl monomers listed above are particularly important comonomers. In other words, it is particularly important as an element that significantly improves adhesion to all kinds of metals, but only particularly representative examples of such carboxyl group-containing vinyl monomers are listed here. Ba,
Monoalkyl esters of unsaturated dicarboxylic acids, such as monobutyl fumarate and monobutyl maleate; monovinyl esters of aliphatic, cycloaliphatic or aromatic dibasic acids, such as monovinyl adipate and monovinyl phthalate. ; and at least one compound selected from the group consisting of crotonic acid.

Among them, monoalkyl esters of unsaturated dicarboxylic acids in which the alkyl group has 1 to 18 carbon atoms, such as monoethyl maleate or monobutyl fumarate, and aliphatic or aromatic compounds such as monovinyl adipate or monovinyl phthalate. monovinyl esters of group dibasic acids and chloro)7M.

In addition, in order to prepare the fluorine-containing vinyl copolymer used in the present invention, that is, the carboxyl group-containing fluorine-containing vinyl copolymer, in addition to the above-mentioned monomer components, these various monomer components must be used. Other monomers that can be copolymerized with can also be used, if necessary.

Examples of such copolymerizable monomers include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, ter t-butyl vinyl ether, n-pentyl vinyl ether, n-
Alkyl vinyl ethers such as hexyl vinyl ether, n-octyl vinyl ether or 2-ethylhexyl vinyl ether; cycloalkyl vinyl ethers such as cyclopentyl vinyl ether, cycloalkyl vinyl ether; cycloalkyl vinyl ethers such as cyclohamethylcyclohexyl vinyl ether; aralkyl vinyl ethers such as benzyl vinyl ether or phenethyl vinyl ether ;
2,2,3.3-tetrafluoropropyl vinyl ether, 2,2,3,3,4,45.5-octafluoropentyl vinyl ether, 2.2.3,3.4,4,5,
5,6.6,7.7.8,8,9.9-hexadecafluorononyl vinyl ether, perfluoromethyl vinyl ether, perfluoroethyl vinyl ether, perfluoropropyl vinyl ether, perfluorooctyl vinyl ether or perfluorohexyl vinyl ether (bar)fluoroalkyl vinyl ethers such as; or vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl persate, vinyl laurate, vinyl stearate, vinyl stearate, carboxylic acid vinyl esters such as vinyl benzoate, p-tert butyl vinyl benzoate, vinyl salicylate or vinyl cyclohexanecarboxylate, and also ethylene, vinyl chloride, vinylidene chloride or (meth)acrylonitrile or ethyl acrylate or methacrylate. Various (meth)acrylic acid esters such as methyl crotonate; or various crotonate esters such as methyl crotonate, ethyl crotonate, propyl crotonate, butyl crotonate or cyclohexyl crotonate.

Especially, from the viewpoint of sufficiently increasing the polymerization rate,
It is desirable to use alkyl vinyl ethers and/or cycloalkyl vinyl ethers, and on the other hand, when the resin composition of the present invention is used as an essential film-forming component for paints, especially from the viewpoint of coating film hardness, For example, vinyl esters of aliphatic monocarboxylic acids having a branched alkyl group having 4 to 17 carbon atoms; and vinyl benzoate, vinyl tert-butylbenzoate and vinyl cyclohexanecarpolate. The use of at least one compound is desirable.

When preparing the carboxyl group-containing fluorine-containing vinyl copolymer using each monomer component listed above, each of these should be considered from the viewpoint of adhesion to various metals and weather resistance. The usage ratio of the monomer components is 30 to 70% by weight of fluorine-containing vinyl monomers, 0.1 to 10% by weight of carboxyl group-containing vinyl monomers, and other copolymerizable monomers. 30 to 70% by weight, and the total of each of these monomer components is 100% by weight.
should be managed within a certain range.

The weight average molecular weight of the thermoplastic fluorine-containing vinyl copolymer, that is, the carboxyl group-containing fluorine-containing vinyl copolymer, is preferably in the range of 10,000 to 300,000.

If it is less than 10.000, the contamination resistance during outdoor exposure tends to deteriorate;
If it exceeds 00, the viscosity of the vinyl copolymer tends to increase, and as a result, the coating workability decreases, which is not preferable in either case.

As the polymerization initiator used in preparing the vinyl copolymer, of course, known and commonly used radical polymerization initiators are used, but among them, only the most representative ones are exemplified. Azo compounds such as bisisobutyronitrile or abbisisovaleronitrile; or tert-butylperoxypivalate, tert-butylperoxybenzoate, te
r t-butylperoxy-2-ethylhexanoate,
Benzoyl peroxide, lauroyl peroxide, acetyl peroxide, tert-butyl peroxide, dicumyl peroxide, tert-
Peroxides include butyl hydroperoxide, cumene hydroperoxide, methyl ethyl ketone peroxide or diisopropyl peroxycarbonate.

The amount of the radical polymerization initiator used is as follows:
It should be determined as appropriate depending on the type of polymerization initiator, polymerization temperature, and molecular weight of the resulting vinyl copolymer, but in general, 0.0 of the total amount of various monomer components.
Approximately 1 to 10% by weight is appropriate.

In order to prepare the vinyl copolymer using the various monomer components listed above, known polymerization methods such as emulsion polymerization, suspension polymerization, bulk polymerization, or solution polymerization can be applied, but bulk polymerization Alternatively, a solution polymerization method is preferred, and a solution polymerization method is particularly preferred from the standpoint that the obtained copolymer can be used as it is as a base resin component or a curable resin component for a solution-type paint. Typical solvents used for producing copolymers by solution polymerization include aromatic hydrocarbons such as benzene, toluene, or xylene; n-pentane, n-hexane, or n-hexane;
- aliphatic hydrocarbons such as octane; alicyclic hydrocarbons such as cyclobencune, cyclohexane, methylcyclohexane, ethylcyclohexane or mineral spirits; methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, te
rt-7"tanol, n-pentanol, isopentanol, n-hexanol, n-octatool, 2-ethylhexanol, cyclohexanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether,
Alcohols such as propylene glycol monomethyl ether or propylene glycol monoethyl ether; ethers such as dimethoxyethane, tetrahydrofuran, dioxane, diisopropyl ether or di-n-butyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, methyl amyl ketone, Ketones such as cyclohexanone or isophorone; methyl acetate, ethyl acetate, n-acetate
Esters such as propyl, isopropyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate or ethylene glycol monobuty, ether acetate; or Chlorinated hydrocarbons such as chloroform, methylene chloride, carbon tetrachloride, trichloroethane or tetrachloroethane;
N-methylpyrrolidone, dimethylformamide, dimethylacetamide or ethylene carbonate. These solvents may be used alone or as a mixture of two or more, but it goes without saying that a solvent that can dissolve the copolymer to be produced should be selected as appropriate. . The amount of solvent used as a polymerization solvent is 5 parts by weight per 100 parts by weight of the total amount of monomers used.
~1,000 severe penalties are appropriate.

Therefore, as an example, in order to prepare the vinyl copolymer by solution polymerization using each of the above-mentioned monomer components, all monomers, a solvent, and a polymerization initiator are charged at once and polymerized. Alternatively, the polymerization can be carried out by adding other monomers and a polymerization initiator continuously or in portions to a reactor containing the two solvents and fluorovinyl monomers. Alternatively, there is a method in which polymerization is carried out by adding monomers and a polymerization initiator, respectively, continuously or in portions to a reactor containing only the three solvents. There is also a method in which polymerization is carried out by adding a solvent, a polymerization initiator, and other monomers continuously or in portions to a reactor C charged with fluorine-containing vinyl monomers. There are various methods as described above, but it goes without saying that any of these methods can be applied to the present invention.

Conditions such as polymerization reaction temperature and pressure may be selected as appropriate depending on the type of polymerization initiator and polymerization solvent used, and the molecular weight of the vinyl copolymer to be obtained. , 0 to 140°C1, preferably 40
Temperatures within the range of ~100″C are suitable;
A pressure of 7 kg/cm 2 or less, preferably 40 kg/cm 2 or less is suitable.

For the vinyl copolymer obtained in this way, which is an essential film-forming component (base resin component) of the resin composition of the present invention, further, for the resin composition of the present invention,
If necessary, add pigments and various resins, flow regulators, color separation inhibitors, antioxidants, ultraviolet absorbers, etc.
Of course, various known and commonly used additive components such as a light stabilizer or a silane coupling agent can be incorporated.

Among them, the most representative pigments are inorganic pigments such as titanium oxide and carbon black; organic pigments such as xacrytone pigments and azo pigments; and aluminum powder and copper pigments. powder or metal powder such as zinc powder.

In addition, the various resins include cellulose resins such as nitrocellulose and cellulose acetate butyrate, vinyl chloride/vinyl acetate copolymer resins, ketone resins, and petroleum resins, to name just a few representative examples. Resins; further examples include (meth)acrylic resins that may contain styrene, oil-free alkyd resins, alkyd resins, and epoxy resins.

Next, the above-mentioned organic solvent, which is an essential component of the resin composition of the present invention, is one that is used in preparing the above-mentioned thermoplastic fluorine-containing resin, that is, the carboxyl group-containing fluorine-containing vinyl copolymer. Various kinds of solvents can be cited as representative examples.

The thermoplastic fluorine-containing resin composition of the present invention obtained by this process naturally has excellent weather resistance, and can be used with various metals such as copper, aluminum, and iron.
It has excellent adhesion to all kinds of metal materials and processed products, such as alloys and plated products, and is especially suitable for a wide range of applications such as paints, adhesives, sealants, and films. It can be used in various fields.

〔Example〕

Next, by using the present invention as a reference example, examples and comparative examples,
- Layers, specifically explained. In the following, all parts and percentages are based on weight unless otherwise specified.

Reference Examples 1 to 5 [Preparation example of carboxyl group-containing vinyl copolymer] 0, 5! sufficiently substituted with nitrogen! A portion of the solvent was charged into a stainless steel autoclave according to the recipe shown in Table 1, and the temperature was raised to 60°C while stirring, and then fluorine-containing vinyl monomers and other monomers were added. and a mixture of a polymerization initiator and the remaining solvent were added dropwise over a period of 3 hours, and among the fluorine-containing vinyl monomers, hexafluoropropylene and chlorotrifluoroethylene were liquefied. A method was adopted in which the material was collected and then injected under pressure.On the other hand, for tetrafluoroethylene, a method was adopted in which it was directly injected without being liquefied and collected.

After completion of the dropwise addition, the same temperature was maintained for 10 hours to continue the reaction.

The solution of the objective vinyl copolymer thus obtained was prepared using the same solvent as the respective polymerization solvent, with a non-volatile content of 5.
Each was diluted separately to 0%.

The Gardner viscosity at 25° C. of each copolymer solution is summarized in the same table.

Reference Examples 6 and 7 (Example of Preparation of Thermoplastic Fluorine-Containing Vinyl Copolymer for Control) A vinyl copolymer for control was prepared in the same manner as Reference Examples 1 to 5, except that the formulation was changed as shown in Table 1. A polymer solution was obtained.

The non-volatile content and viscosity of each copolymer solution are summarized in the same table.

In Table 1, the "amount of polymerization initiator used" means the number of parts based on the total amount of monomers, and the "amount of organic solvent used" for mixed solvents means the weight ratio. However, at the same time, it also represents the total amount used.

The product names and abbreviations in the same table have the following meanings.

"Beoha 9"...C8 manufactured by Shell in the Netherlands
Vinylnistyl ABNV...2,2'-azobis(2,4 dimethylvaleronitrile) [common name: azobisisohaleronitrile] TBP...ter t-Butyl peroxypivalate TBEH tert-butylperoxy-2-ethylhexanoneton/Examples 1 to 5 and Comparative Examples 1 and 2 Compounded according to the formulation shown in Table 2, and further mixed with toluene. /xylene/butyl acetate/cellosolve acetate = 30/30/3
Various thermoplastic fluororesin compositions were prepared by diluting with a mixed solvent having a polymerization ratio of 0/10 to a sprayable viscosity.

Next, each of the above-mentioned paints was air-sprayed onto various substrates as shown in the table, and heated at 25°C for 1 hour.
After drying at room temperature for 0 days, the film thickness was 3.
Various panels on which dry coating films of 0 to 40 μm were formed were obtained.

Then, for one of each panel,
The adhesion of the coating film was evaluated in accordance with the JIS K-5400 substrate test. These results are summarized as
Shown in the same table.

The other various panels were left in an atmosphere of 50° C. and 95% relative humidity for 240 hours, and then their adhesion was evaluated by the substrate test as described above. The results are summarized as secondary adhesion and are shown in the same table. In any case, the adhesion is determined by "X/100J" (where X is the number of substrates remaining without being peeled off). Effects of the Invention The thermoplastic fluorine-containing resin composition of the present invention has excellent adhesion to various metals and plated objects, and has inherently good weather resistance.

Therefore, it can be widely used for paints, adhesives, sealants, films, etc.

Claims (1)

[Scope of Claims] 1. A thermoplastic fluorine-containing resin composition, which contains a carboxyl group-containing fluorine-containing vinyl copolymer and an organic solvent as essential components. 2. The carboxyl group-containing fluorine-containing vinyl copolymer described above is obtained by copolymerizing fluorine-containing vinyl monomers and other monomers copolymerizable with the carboxyl group-containing vinyl monomers. The thermoplastic fluororesin composition according to claim 1, which is 3. The carboxyl group-containing fluorine-containing vinyl copolymer described above has vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, and the number of carbon atoms in the (per)fluoroalkyl group. becomes 1-18 (par)
The thermoplastic fluorine-containing resin composition according to claim 1, which is obtained using at least one fluorine-containing vinyl monomer selected from the group consisting of fluoroalkyl trifluorovinyl ethers. 4. The carboxyl group-containing fluorine-containing vinyl copolymer described above is a monoalkyl ester of an unsaturated dicarboxylic acid;
Claim 1: It is obtained using at least one carboxyl group-containing vinyl monomer selected from the group consisting of monovinyl esters of aliphatic, alicyclic or aromatic dibasic acids; and crotonic acid. The thermoplastic fluororesin composition described in . 5. The carboxyl group-containing fluorine-containing vinyl copolymer described above contains at least one other copolymerizable monomer selected from the group consisting of alkyl vinyl ethers, cycloalkyl vinyl ethers, and carboxylic acid vinyl esters. The thermoplastic fluororesin composition according to claim 1, which is obtained by using the thermoplastic fluororesin composition according to claim 1.