JPH03152119A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition, essentially containing a specific fluorine-containing copolymer, etc., as base resin components and capable of providing cured films excellent in adhesion to metal materials, etc., good in weather resistance and useful as coatings, etc. CONSTITUTION:The objective composition containing (A) a fluorine-containing copolymer having functional groups reactive with isocyanate group and (B) a compound having hydrolyzable silyl group and isocyanate group together in one molecular as essential base resin components. Furthermore, (C) a compound having reactivity with functional groups in the component (A) is preferably contained as a curing agent component and (D) an organic solvent is also preferably contained therein.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel and useful resin composition. More specifically, the present invention uses a specific fluorine-containing copolymer having a functional group (reactive polar group) capable of reacting with an isocyanate group as an essential base resin component, and a hydrolyzable silyl group and a hydrolyzable silyl group in one molecule. Regarding a resin composition consisting of a specific compound having an isocyanate group, in particular, a resin composition consisting of such a specific base resin component and a specific curing agent component.
This invention relates to a so-called curable resin composition.

The resin composition of the present invention is extremely useful as a paint, adhesive, sealant, etc., providing a cured product with excellent weather resistance and adhesion.

[Conventional technology]

By the way, the present inventors previously published Japanese Patent Application Laid-Open No. 62-25007.
A solution of a fluoroolefin copolymer containing a hydroxyl group, a curing agent reactive with the hydroxyl group, and a compound containing a 2,2゜6.6-tetra-substituted piperidinyl group, as disclosed in Publication No. 6. It has been discovered that a curable resin composition comprising As a result of an even longer exposure test using an accelerated weathering tester, some metal coatings showed
Gradually, it has become clear that there are some substances that reduce adhesion.

[Problem to be solved by the invention]

Therefore, the inventors of the present invention hastily embarked on research in order to solve the problems in the prior art as described above.

Therefore, the problem to be solved by the present invention is not only to improve weather resistance but also to maintain and ensure long-term adhesion to metal surfaces. Another object of the present invention is to provide an extremely useful resin composition, particularly a curable resin composition, which can maintain long-term weather resistance and adhesion properties.

[Means to solve the problem]

To this end, the present inventors have focused on the problems to be solved by the invention as described above, and as a result of extensive studies, we have developed a specific fluorine-containing copolymer having a functional group that can react with an isocyanate group. In layman's terms, a resin composition based on a compound having both a hydrolyzable silyl group and an isocyanate group in one molecule is, in particular, a solution of a fluorine-containing copolymer having such a specific functional group, In addition, a curable resin assembly in which a compound having both a hydrolyzable silyl group and an isocyanate group is added to a system consisting of the functional group and a reactive curing agent can be used not only on metal surfaces but also on metal surfaces. It was discovered that cured coatings and cured products with excellent adhesion can be formed even on inorganic substrates, etc., and further progress has been made to show that metal coatings using coatings obtained from such compositions can be used for a long period of time. The present invention was completed by finding that the adhesion to the surface of the substrate did not deteriorate at all even in the results of accelerated weathering tests over many years.

That is, the present invention first uses, as an essential base resin component, a fluorine-containing copolymer (A) having a functional group capable of reacting with an isocyanate group, and a compound having both a hydrolyzable silyl group and an isocyanate group in one molecule. (B) and each of the above-mentioned resin compositions.
It contains a fluorine-containing copolymer (A) and a compound (B) as essential resin components, and a curing agent component contains a compound (C) that is reactive with a functional group in the fluorine-containing copolymer (A). The curable resin composition further contains the above-mentioned fluorine-containing copolymer (A) and compound (B) as essential resin components, while compound (C) is a curing agent. It is an object of the present invention to generally provide a curable resin composition containing as a component, and further containing an organic solvent (D).

Here, first, the fluorine-containing copolymer (A) having a functional group capable of reacting with the isocyanate group mentioned above refers to fluorinated vinyl copolymer (A) as described in JP-A No. 62-250076 mentioned above. , vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, promotrifluoroethylene, chlorotrifluoroethylene, pentafluoropropylene, hexafluoropropylene, or (per)fluoroalkyl group having 1 to 18 carbon atoms, especially, The essential monomer components are various fluorine-containing vinyl monomers such as (per)fluoroalkyl trifluorovinyl ether of 1 to 4, and vinyl monomers having a functional group capable of reacting with an isocyanate group. It refers to copolymers.

To prepare the fluorine-containing copolymer (A), (1) a vinyl monomer having a functional group reactive with an isocyanate group and a fluorine-containing monomer as described above in an organic solvent as described below; Alternatively, (2) as mentioned above, fluorine-containing vinyl monomers and isocyanate group-reactive functional group-containing vinyl monomers may be copolymerized by emulsion polymerization or suspension polymerization. Copolymerize by turbidity polymerization method, then
Although known and commonly used methods are used, such as replacing water with the following organic solvents, the solution polymerization method (I) is particularly recommended because it is simple. .

That is, to mention only typical examples of such organic solvents, aromatic hydrocarbons such as toluene, xylene or benzene; aliphatic hydrocarbons such as n-pentane, n-hexane or n-octane; Class;
Alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane or ethylcyclohexane; ethers such as dimethoxyethane, tetrahydrofuran, dioxane, diisopropyl ether or di-n-butyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, Ketones such as methyl amyl ketone, cyclohexanone or isophorone; methyl acetate, ethyl acetate, n-acetate
Esters such as propyl, isopropyl acetate, n-butyl acetate, isobutyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate or ethylene glycol monobutyl ether acetate; or chloroform, methylene chloride, carbon tetrachloride, trichloroethane or tetra Examples include chlorinated hydrocarbons such as chloroethane, as well as N-methylpyrrolidone, dimethylformamide, dimethylacetamide, or ethylene carbonate. These solvents may be used alone or as a mixture of two or more.

By the method (1) described above, the fluorine-containing copolymer (A)
Typical examples of vinyl monomers having a functional group capable of reacting with the isocyanate group used in preparing the isocyanate group include 2-hydroxybutyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether,
6-hydroxybutyl vinyl ether, β-hydroxyethyl (meth)acrylate, β-hydroxypropyl (meth)acrylate, β-hydroxybutyl (meth)
Monomers containing hydroxyl groups such as acrylate or allyl alcohol; fumaric acid, maleic acid, (meth)
Monomers containing carboxyl groups such as half esters of acrylic acid, itaconic acid or crotonic acid, or maleic acid; or 2-aminoethyl vinyl ether, 3-aminopropyl vinyl ether, allylamine, N-methylaminoethyl vinyl ether , N-ethylaminoethyl vinyl ether, N-methylaminofucoropyl vinyl ether, N-methylaminobutyl vinyl ether or N-methylallylamine.

Among monomers containing such functional groups, monomers containing hydroxyl groups or amino groups are preferably used in terms of ease of reaction with isocyanate groups.

Further, in the present invention, when preparing the fluorine-containing copolymer (A) component from the above-described fluorine-containing vinyl monomers and vinyl monomers containing a functional group capable of reacting with an isocyanate group, Other copolymerizable monomers can also be used.

Such monomers include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isofurovir vinyl ether, n-butyl vinyl ether,
Alkyl vinyl ethers such as isobutyl vinyl ether, t-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether or 2-ethylhexyl vinyl ether; cycloalkyl vinyl ethers such as cyclopentyl vinyl ether, cyclohexyl vinyl ether or methylcyclohexyl vinyl ether; benzyl Aralkyl vinyl ethers such as vinyl ether or phenethyl vinyl ether; 2.2, 3.3-
Tetrafluoropropyl vinyl ether, 2.2,3.
3.4.4.5.5-octafluoropentyl vinyl ether, 2.2.3.3.4.4.5.5.6.6.7
7.8.8.9.9-(bar)fluoroalkyl such as hexadecafluorononyl vinyl ether, perfluoromethyl vinyl ether, perfluoroethyl vinyl ether, perfluoropropyl vinyl ether, perfluorooctyl vinyl ether or perfluorohexyl vinyl ether Vinyl ethers; or vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl persate, vinyl laurate, vinyl stearate, vinyl benzoate, pt-butylbenzoic acid Carboxylic acid vinyl esters such as vinyl, vinyl salicylate or vinyl cyclohexanecarboxylate are particularly representative, as well as ethylene, vinyl chloride, vinylidene chloride or (meth)acrylonitrile, or various (meth)acrylic acid esters. The types are particularly representative.

Among the copolymerizable monomers mentioned above, alkyl vinyl ethers and/or
It is desirable to use cycloalkyl vinyl ethers, and when the copolymer (A) is used as a base resin component for paints, from the viewpoint of coating hardness, the number of carbon atoms is 4 to 17. A monomer selected from the group consisting of vinyl esters of aliphatic monocarboxylic acids having a branched alkyl group, vinyl benzoate, vinyl pt-butylbenzoate, and vinyl cyclohexanecarboxylate. is particularly desirable.

The fluorine-containing copolymer (A
) may be prepared by copolymerization in the solvents listed above in the presence of a radical polymerization initiator.

The number average molecular weight of the fluorine-containing copolymer (A) having a functional group capable of reacting with an isocyanate group thus obtained is preferably within the range of 1,000 to 100,000.

Next, in the present invention, the above-mentioned compound (B) component having both a hydrolyzable silyl group and an isocyanate group in one molecule, which is mainly used under the name of an additive for improving adhesion, has the following definition. Any compound can be used as long as it complies with the above, but some of the most representative ones are γ-isocyanatepropyltrimethoxysilane, γ-isocyanatepropylethoxydimethoxysilane, T -Isocyanatepropyljethoxymethoxysilane, γ-isocyanatepropyltriethoxysilane, T-isocyanatepropyldimethoxymethylsilane, γ-isocyanatepropyldiethoxymethylsilane, γ-isocyanatepropylmethoxydimethylsilane or T-isocyanatepropylethoxydimethylsilane, etc. It is. Of course, these may be used alone or in combination of two or more.

Next, the above-mentioned curing agent (C
) components, as listed above, include a compound (B) having both a hydrolyzable silyl group and an isocyanate group in one molecule, and a fluorine-containing copolymer (B) having a functional group capable of reacting with the isocyanate group. It refers to a compound that performs a so-called curing reaction, in which it three-dimensionally crosslinks with a base resin component containing A) as an essential component to provide an insoluble and infusible cured coating film or cured product. Among them, it refers to a compound having a functional group that is reactive with a functional group in the grafted fluorine copolymer (A), such as a hydroxyl group, an amino group, and/or a carboxyl group.

Particularly representative compounds as the curing agent (C) component are listed below in the form of combinations corresponding to the respective functional groups of the fluorine-containing copolymer (A). It is something that can be done.

When the functional groups of the fluorine-containing copolymer (A) are hydroxyl, amino, and carboxyl groups, the curing agent (
Particularly typical examples of component C) include tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, methylcyclohexane-2,4-(or 2,6-) diisocyanate, 4.4'-methylenebis(cyclohexyl isocyanate) or 1
．． Diisocyanates such as 3-di(isocyanatomethyl)cyclohexane; triisocyanates such as 4-isocyanatomethyloctamethylene diisocyanate; the above diisocyanates and ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, or hydroxyl group-containing polyesters. Polyisocyanate resins obtained by reacting with a polyhydroxy compound; polyisocyanate resins having a billet bond obtained by reacting the above diisocyanates with water, or isocyanurate rings obtained by cyclopolymerizing the above isocyanates. Polyisocyanate resins having; methyl etherified methylol melamine, n
-Amino resins such as butyl etherified methylolmelamine and n-butyl etherified benzoguanamine; obtained by blocking the above polyisocyanates or polyisocyanate resins with a compound having active hydrogen such as alcohol, phenol, methyl ethyl ketoxime or ε-caprolactam. Blocked isocyanate; polyvalent metal alkoxides such as tetrabutoxytitanium, tributoxyaluminum or tetrabutoxyzirconium; or polyvalent metal chelates obtained by reacting the polyvalent metal alkoxides with chelating agents such as acetylacetone or ethyl acetoacetate. When the functional group of the fluorine-containing copolymer (A) is a hydroxyl group, polycarboxylic acid anhydrides such as trimellitic anhydride or pyromellitic anhydride can also be used. When the functional group of the copolymer (A) is an amino group or a carboxyl group, polyepoxy compounds such as glycidyl ethers of aliphatic polyhydric alcohols and glycidyl esters of aliphatic polyhydric carboxylic acids may also be used. Can be done.

The resin composition of the present invention having the above-described (A) and (B) as essential base resin components, and the curable resin of the present invention in which the curing agent (C) component is also added. To prepare the composition, in terms of solid content, 50 to 1 part by weight of component (C) is used for 50 to 99 parts by weight of fluorine-containing copolymer (A), and both of these components are used. It is desirable that the total solid content is 100 parts by weight, and the number of isocyanate groups in component (B) is 0.001 to 0 for each functional group in component (A). .8,
Preferably, they are blended in a ratio of o, oos to 0.5.

The thus obtained resin composition of the present invention may further contain a known and commonly used cellulose derivative, various other known and commonly used resins such as acrylic resin, polyester resin, or alkyd resin, solvents, pigments, or leveling agents. Agents and the like can be added, and in particular, the curable resin composition of the present invention can be put to practical use as it is.

In the resin composition of the present invention, as described above, pigments and solvents are blended as desired. First, such pigments include titanium oxide, iron oxide, copper-chrome black, or cobalt blue. Examples include inorganic pigments; organic pigments such as carbon black, phthalocyanine blue, phthalocyanine green, and quinacridone red; and metal powders such as aluminum powder, copper powder, and zinc powder.

Further, as such solvents, the solvents used in preparing the above-mentioned fluorine-containing copolymer (A) component, and mixtures thereof can be used, and they can dissolve or disperse this copolymer (A). For solvents, their use is -
On the other hand, there is no problem.

In that case, it goes without saying that the organic solvent (D) must be a solvent that does not have active hydrogen that reacts with the isocyanate group.

The curable resin composition of the present invention is applied by a known and commonly used method such as spray coating, brush coating, roll coater, etc., and depending on the type of curing agent (C) component,
It can be baked at room temperature or at a temperature of 60 to 250°C to form a cured coating film or cured product.

〔Effect of the invention〕

The resin composition of the present invention, in particular, the curable resin composition of the present invention can be made of metal materials such as aluminum and stainless steel,
It also provides cured coatings and cured products with good adhesion to inorganic substrates, etc. In addition, it can be used for accelerated weathering tests, etc.
Even after conducting severe and long-term exposure tests, the composition of the present invention can still provide cured coatings and cured products that can maintain good adhesion. has particularly remarkable effects in terms of weather resistance and adhesion.

Therefore, the present invention provides an extremely useful resin composition that can be used for various purposes such as paints, adhesives, sealants, and films.

〔Example〕

Next, the present invention will be explained by reference examples, examples, and comparative examples.
The layer will be explained in detail. In the following, all references to "1%" mean "wt%" unless otherwise specified.

Reference Examples 1 to 7 [Preparation example of fluorine-containing copolymer (A) having a functional group capable of reacting with an isocyanate group] 1! sufficiently substituted with nitrogen! A stainless steel autoclave was charged with 300 g of methyl isobutyl ketone, 6 g of t-butyl peroxypivalate, and monomers as shown in Table 1. At this time, reference example 1.2.5.6
and 7, bis(1,2°2
．． 6.6-bentamethyl-4-piperidinyl) sebacate was also charged.

Thereafter, while stirring, the mixture was kept at 60°C for 15 hours to carry out a polymerization reaction, and then the contents were taken out.
A required amount of xylene was added so that the misfortune ratio was 50% to obtain a solution of each desired copolymer (A). The number average molecular weight and Gardner color of each copolymer solution are also summarized in the same table.

Examples 1 to 7 Solutions of copolymers (A) prepared in Reference Examples 1 to 7 (A-
1) to (A-7) at the blending ratios listed in Table 2, a curing agent and a compound having both a hydrolyzable silyl group and an isocyanate group in one molecule, and if necessary. A curing catalyst was also added to form a paint. Then,
Untreated aluminum Fi (4105) degreased with toluene
0P), stainless steel plate (S115-304), slate plate, and glass plate using a doctor blade so that the dry film thickness is approximately 40 μm, and then baked under the conditions listed in Table 2. After doing this,
A cured coating film was obtained by leaving it at room temperature for 7 days.

Among the coated products thus obtained, those coated with untreated aluminum plates and stainless steel plates were subjected to ultraviolet irradiation at 70°C using a [Du-Panel Light Control Weather Meter] [accelerated weathering tester manufactured by Suga Test Instruments Co., Ltd.].
'C-8 hours, wet 50°C-4 hours as one cycle of repeated exposure for 3,000 hours, and as described in footnote 5 of the same table], each The adhesion of the coating film was evaluated. In addition, for coated slate plates and glass plates, adhesion was evaluated in the same manner as above without conducting an exposure test. These results are summarized in Table 2.

Comparative Examples 1 to 4 Solutions of copolymers (A) prepared in Reference Examples 1 to 4 (A-
Compound (C) using 1) to (A-4) and having both a hydrolyzable silyl group and an isocyanate group in one molecule
instead of a compound containing a 2,2,6,6-tetra-substituted piperidinyl group (1 hydroxyethyl-2,2,6
Adhesion was evaluated in the same manner as in Examples 1 to 4, except that 6-titramethylpiperidine) was used. The results are summarized in Table 2.

As is clear from Table 2, the composition of the present invention provides a cured coating film with good adhesion not only to various metal materials such as aluminum and stainless steel, but also to inorganic substrates. It can be seen that the adhesion after being subjected to the accelerated weathering test is still good.

Claims (1)

[Claims] 1. A fluorine-containing copolymer (A) having a functional group capable of reacting with an isocyanate group, and a compound (B) having both a hydrolyzable silyl group and an isocyanate group in one molecule. A resin composition comprising as a base resin component. 2. Contains a fluorine-containing copolymer (A) having a functional group capable of reacting with an isocyanate group and a compound (B) having both a hydrolyzable silyl group and an isocyanate group in one molecule as essential base resin components. , on the other hand, a compound (C
) as a curing agent component. 3. Contains a fluorine-containing copolymer (A) having a functional group capable of reacting with an isocyanate group and a compound (B) having both a hydrolyzable silyl group and an isocyanate group in one molecule as essential base resin components. , on the other hand, a compound (C
) as a curing agent component, and further comprising an organic solvent (D). 4. The fluorine-containing copolymer (A) having a functional group capable of reacting with the isocyanate group described above is vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, carbon At least one fluorine-containing vinyl monomer selected from the group consisting of fluoroalkyl trifluorovinylethers having 1 to 4 carbon atoms and perfluoroalkyl trifluorovinylethers having 1 to 4 carbon atoms, and a functional group capable of reacting with an isocyanate group. 4. The resin composition according to claim 1, wherein the resin composition has a vinyl monomer having a group as an essential monomer and is obtained by polymerizing a mixture of these monomers. 5. The functional group that can react with the isocyanate group described above is
The resin composition according to any one of claims 1 to 4, which is at least one member selected from the group consisting of a hydroxyl group, an amino group, and a carboxyl group. 6. The compound (B) having both a hydrolyzable silyl group and an isocyanate group in one molecule is γ-isocyanatepropyltrimethoxysilane, γ-isocyanatepropylethoxydimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-isocyanatepropyltriethoxysilane, - at least one compound selected from the group consisting of isocyanatepropyldimethoxymethylsilane and γ-isocyanatepropyldiethoxymethylsilane, claims 1 to 3.
The resin composition described in . 7. The ratio of the fluorine-containing copolymer (A) having a functional group capable of reacting with the isocyanate group described above and the compound (B) having both a hydrolyzable silyl group and an isocyanate group in one molecule is , wherein the ratio is 0.001 to 0.8 isocyanate groups in the compound (B) per one functional group in the copolymer (A). resin composition. 8. Usage ratio of the fluorine-containing copolymer (A) having a functional group capable of reacting with the isocyanate group described above and the compound (C) having reactivity with the functional group in this fluorine-containing copolymer (A) However, in terms of solid content, the above copolymer (A) has a content of 50 to
The resin composition according to claim 2 or 3, wherein the ratio of the compound (C) to 99 parts by weight is 50 to 1 part by weight.