JPH04222848A - Fluorine resin-containing resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition consisting essentially of a vinyl copolymer obtained by using a specific vinyl monomer having ultraviolet ray-absorbing properties and specific fluorine-containing copolymer and capable of forming a coating film having excellent weather resistance and ultraviolet ray-absorbing properties. CONSTITUTION:The objective fluorine resin composition containing (A) 1-50wt.% vinyl copolymer obtained by copolymerizing A1: ultraviolet ray-absorbing vinyl monomer (e.g. 4-acryloxy-benzophenone) having a structure expressed by the formula (X1 and X2 are H or 1-5C monovalent saturated hydrocarbon groups; Y1 and Y2 are H or OH and at least one of them is OH) with A2: copolymerizable other vinyl monomer (e.g. methyl acrylate) at a molar ratio of the component A1/the component A2 of 0.01-10 and (B) 50-99wt.% fluorine- containing copolymer obtained by copolymerizing B1: 15-70wt.% fluorine- containing monomer (preferably vinylidene fluoride or tetrafluoroethylene) with B2: copolymerizable monomer (e.g. methylvinyl ether) as essential film-forming components.

Description

[Detailed description of the invention]

0001

FIELD OF THE INVENTION The present invention relates to a new and useful fluororesin composition. More specifically, the present invention relates to a fluororesin composition that contains a specific vinyl copolymer and a specific fluorine-containing copolymer as essential film-forming components, and has the property of absorbing ultraviolet rays.

0002

BACKGROUND OF THE INVENTION Fluorine-containing copolymers themselves exhibit extremely high resistance to ultraviolet rays and are characterized by not deteriorating even when exposed to sunlight for a long period of time.

[0003] However, even when coated with a fluorine-containing copolymer, the coated substrate and undercoat film cannot be protected from photodeterioration. This is mainly because the fluorine-containing copolymer has ultraviolet resistance and extremely high ultraviolet transmittance.

Generally, the photodeterioration of materials coated with polymers with high UV transmittance can be improved by mixing UV absorbers into the polymers. It is well known.

However, fluorine-containing copolymers generally have high crystallinity and poor compatibility with other compounds. For this reason, even in the case of a combination of an ultraviolet absorber and a fluorine-containing copolymer, it is not possible to include a large amount of the ultraviolet absorber due to insufficient compatibility.
Even if it could be included, there were problems such as phase separation or volatilization during exposure.

[0006] Therefore, in order to block ultraviolet rays with a coating made of a fluorine-containing copolymer, the actual situation is that the coating must be thick.

[0007]

[Problems to be Solved by the Invention] However, the present inventors have earnestly undertaken research in order to solve the above-mentioned problems. Accordingly, it is an object of the present invention to provide a technique for protecting coated substrates and undercoats from photodegradation.

[0008] To solve this problem, the inventors of the present invention have conducted extensive research and found that by copolymerizing a monomer with ultraviolet absorbing properties and a specific vinyl monomer, It was discovered that a vinyl copolymer (A) having excellent compatibility with a fluorine-containing copolymer can be obtained, and the present invention was completed.

[0009]

Means for Solving the Invention That is, the present invention provides a fluorine-containing copolymer (B) containing a monomer having ultraviolet absorbing properties having the following structure as a part of its molecular structure, and a specific A vinyl copolymer obtained by copolymerizing vinyl monomers (A
), that is, a novel copolymer (A) and a fluorine-containing copolymer (B) are used as essential film-forming components. The present invention aims to provide a fluorine-containing resin composition with excellent ultraviolet absorbability that is useful in the field of ultraviolet light absorption.

0010

[Case 2]

(However, X1 and X2 in the formula may each be a hydrogen atom or a C
represents a monovalent saturated hydrocarbon group of 1 to C5,
Further, Y1 and Y2 each represent a hydrogen atom or a hydroxyl group, which may be the same or different, and at least one is a hydroxyl group. )

0012

[Structure] The structure of the present invention will be explained in detail below. First, a monomer (a-
Illustrating only particularly representative examples of 1) are 4-acryloxy-benzophenone, 4-methacryloxy-benzophenone, 4'-ethyl-4-methacryloxy-benzophenone, 2-hydroxy-4-acryloxy-benzophenone, and 2-hydroxy-4-acryloxy-benzophenone. -Hydroxy-4-(2-methacryloxyethoxy)-benzophenone, 2-hydroxy-4-(2-ethyl-2-methacryloxyethoxy)-benzophenone, 2-hydroxy-4-(2-hydroxy-3-methacryloxy) propoxy)-benzophenone, 2-hydroxy-4'-ethyl-4-(2-methyl-2-acryloxyethoxy)-benzophenone, 6
'-hydroxy-4-methacryloxy-benzophenone, 6'-hydroxy-4-(4-acryloxybutoxy)-benzophenone, 6'-hydroxy-4-(2-ethyl-3-acryloxypropoxy)-benzophenone or 6' -hydroxy-3-methyl-4-(3-hydroxy-4-methacryloxybutoxy)-benzophenone and the like.

On the other hand, methyl acrylate, methyl acrylate, , ethyl acrylate, 2-hydroxyethyl acrylate, propyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, n-butyl acrylate, iso-butyl acrylate, sec-butyl acrylate, ter
Acrylic acid esters such as t-butyl acrylate or 2-ethylhexyl acrylate; methyl methacrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate, propyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, n-butyl methacrylate, iso
- methacrylic acid esters such as butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate or n-octyl methacrylate; or such as methyl crotonate, ethyl crotonate, propyl crotonate or n-butyl crotonate. Crotonic acid esters, vinyl acetate, vinyl propionate, vinyl isobutyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, C9 branched aliphatic vinyl carboxylate, C10 branched aliphatic carboxylate Vinyl acid, C1
1 branched aliphatic vinyl carboxylates or aliphatic vinyl carboxylates such as vinyl stearate; having a cyclic structure such as vinyl cyclohexylcarboxylate, vinyl methylcyclohexylcarboxylate, vinyl benzoate, and vinyl p-tert-butylbenzoate. Carboxylic acid vinyl esters; α-olefins such as ethylene, propylene or butene-1; various halogenated olefins other than fluoroolefins such as vinyl chloride or vinylidene chloride; or styrene, α-methylstyrene or vinyltoluene. These include aromatic vinyl compounds.

The molar ratio of monomer (a-1) and monomer (a-2) is preferably controlled within the range of 0.01 to 10. If the molar ratio is less than 0.01, the fluororesin composition obtained by mixing with the fluorine-containing copolymer (A) will inevitably not have sufficient ultraviolet absorbency; , if it exceeds 10, the monomer (
Either case is preferable since the vinyl copolymer (A) obtained by copolymerizing a-1) with the monomer (a-2) will lose its compatibility with the fluorine-containing copolymer. do not have.

Furthermore, the proportion of the vinyl copolymer (A) in the fluororesin composition should be controlled within the range of 1 to 50% by weight. If it is less than 1% by weight, the fluororesin composition will not be provided with sufficient ultraviolet absorption, while if it is more than 50% by weight, the mechanical properties of the fluororesin composition will inevitably deteriorate. This is because it becomes like this.

The fluorine-containing vinyl monomer (b-1) used in the present invention includes only typical examples such as vinyl fluoride, vinylidene fluoride, trifluoroethylene, and tetrafluoroethylene. ethylene, chlorotrifluoroethylene, bromotrifluoroethylene, pentafluoropropylene, hexafluoropropylene or perfluoroalkyl perfluorocarbons such as trifluoromethyl trifluorovinyl ether, pentafluoroethyl trifluorovinyl ether or heptafluoropropyl trifluorovinyl ether; Fluorovinyl ether, etc., and in particular, use of tetrafluoroethylene, vinylidene fluoride, chlorotrifluoroethylene or hexafluoropropylene is preferred.

These fluorine-containing vinyl monomers may be used alone or in combination of two or more. The proportion of the fluorine-containing vinyl monomer should be controlled to be 15 to 70% by weight, preferably 30 to 60% by weight. If the proportion of the fluorine-containing vinyl monomer is less than 15% by weight, sufficient weather resistance cannot be obtained. On the other hand, if this proportion exceeds 70% by weight, the fluorine-containing vinyl monomer obtained by copolymerization will inevitably fail. This is because the solvent solubility of the polymer decreases.

The monomers (b-2) copolymerizable with the fluorine-containing vinyl monomer (b-1) include methyl vinyl ether, ethyl ethyl vinyl ether, n. -propyl vinyl ether,
Isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, 2-ethylhexyl vinyl ether, chloromethyl vinyl ether, chloroethyl vinyl ether, benzyl vinyl ether or phenylethyl vinyl ether Alkyl vinyl ethers or substituted alkyl vinyl ethers such as; cycloalkyl vinyl ethers such as cyclopentyl vinyl ether, cyclohexyl vinyl ether or methylcyclohexyl vinyl ether; or 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether ,
These include hydroxyalkyl vinyl ethers such as 3-hydroxybutyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 5-hydroxypentyl vinyl ether, and 6-hydroxyhexyl vinyl ether, as well as vinyl acetate, vinyl propionate, vinyl isobutyrate, and caproic acid. Aliphatic carboxylic acids such as vinyl, vinyl caprylate, vinyl caprate, vinyl laurate, C9 branched vinyl aliphatic carboxylate, C10 branched vinyl aliphatic carboxylate, C11 branched vinyl aliphatic carboxylate or vinyl stearate. Vinyls; vinyl cyclohexylcarboxylate, vinyl methylcyclohexylcarboxylate, vinyl benzoate or p-tert
-Carboxylic acid vinyl esters with a cyclic structure such as vinyl butylbenzoate; α-olefins such as ethylene, propylene or butene-1; various halogenated olefins other than fluoroolefins such as vinyl chloride or vinylidene chloride; styrene , aromatic vinyl compounds such as α-methylstyrene or vinyltoluene; methacrylic esters such as methyl methacrylate, ethyl methacrylate, butyl methacrylate or cyclohexyl methacrylate; or acrylic esters such as methyl acrylate, ethyl acrylate, butyl acrylate or cyclohexyl acrylate. etc.

In addition to the various copolymerizable monomers mentioned above, monomers containing silyl groups, monomers containing amino groups, or acid A variety of reactive polar group-containing monomers can be used, such as monomers containing groups.

Particularly typical examples of such monomers include vinyltrimethoxysilane, vinyltripropoxysilane, vinylmethyldiethoxysilane, vinyltris(β-methoxyethoxy)silane, allyltrimethoxysilane, and trimethoxysilane. Silylethyl vinyl ether, triethoxyethylsilyl vinyl ether, methyldimethoxysilylethyl vinyl ether, trimethoxysilylpropyl vinyl ether, triethoxysilylpropyl vinyl ether, methyldiethoxysilylpropyl vinyl ether, γ-(meth)acryloyloxypropyltrimethoxysilane, γ-( There are monomers containing hydrolyzable silyl groups such as meth)acryloyloxypropyltriethoxysilane or γ-(meth)acryloyloxypropylmethyldimethoxysilane;
N-dimethylaminoethyl (meth)acrylamide, N
-diethylaminoethyl (meth)acrylamide, N-
Amino group-containing amide unsaturated monomers such as dimethylaminopropyl (meth)acrylamide or N-diethylaminopropyl (meth)acrylamide; dialkylaminoalkyl (meth)acrylate such as dimethylaminoethyl (meth)acrylate or diethylaminoethyl (meth)acrylate; ) Acrylates; tert-butylaminoethyl (meth)acrylate, tert-butylaminopropyl (meth)acrylate, aziridinylethyl (meth)acrylate, pyrrolidinylethyl (meth)acrylate
Amino group-containing monomers such as acrylate or piperidinylethyl (meth)acrylate; or carboxyl group-containing monomers such as (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid or fumaric acid.

Among these copolymerizable monomers, it is particularly preferable to use at least one of (substituted) alkyl vinyl ethers, cycloalkyl vinyl ethers, and hydroxyalkyl vinyl ethers from the viewpoint of increasing the polymerization yield. desirable.

[0022] As a method for carrying out a copolymerization reaction using each of the monomer components described above, in the presence of a radical polymerization initiator,
Although known polymerization methods such as bulk polymerization, solution (pressure) polymerization, suspension polymerization, or emulsion polymerization can be applied, solution polymerization is the simplest method.

The radical polymerization initiators used in this case include acetyl peroxide, benzoyl peroxide, lauroyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, di- Peroxides such as tert-butyl peroxide, dicumyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyoctoate, tert-butyl peroxy acetate or tert-butyl peroxy pivalate; or azobisiso Particularly representative are azo compounds such as butyronitrile, dimethyl-2,2'azobis(2-methylpropionate) or azobisisovaleronitrile.

[0024] Furthermore, the solvent used during polymerization is as follows:
Toluene, xylene, cyclohexane, n-hexane,
Hydrocarbons such as octane or mineral spirits; esters such as methyl acetate, ethyl acetate, butyl acetate or ethylene glycol monoethyl ether acetate; or ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone or cyclohexanone; dimethyl Amides such as formamide, dimethylacetamide or N-methylpyrrolidone, methanol, ethanol, n
-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, ter
Alcohol solvents such as t-butanol or ethylene glycol monoalkyl ether, or
Particularly representative are mixtures of these.

Of course, the fluorine-containing copolymers thus prepared having hydroxyl groups can be formed into a film using a curing agent by a conventionally known method. As such a curing agent, any conventionally known curing agent can be used, and specifically, 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 1,3-di(
diisocyanates such as cyclohexane; triisocyanates such as 4-isocyanatomethyloctamethylene diisocyanate; or diisocyanates listed above and polyesters such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or hydroxyl group-containing polyesters. Polyisocyanate resins (isocyanate prepolymers) obtained by reacting with a hydroxy compound, as well as polyisocyanate resins having a buret bond obtained by reacting the above-mentioned diisocyanates with water; Or polyisocyanate resins having an isocyanurate ring obtained by cyclopolymerizing the diisocyanates listed above; or amino resins such as methyl etherified methylolmelamine, n-butyl etherified methylolmelamine, and n-butyl etherified benzoguanamine. In addition, various polyisocyanates or polyisocyanate resins such as those listed above are combined with alcohol, phenol,
Blocked isocyanates obtained by blocking with a compound having active hydrogen such as methyl ethyl ketoxime or ε-caprolactam; or polyvalent metal alkoxides such as tetrabutoxyethane, tributoxyaluminum or tetrabutoxyzirconium; the above-mentioned polyvalent metal alkoxides A polyvalent metal chelate compound obtained by reacting with a chelating agent such as acetylacetone or ethyl acetoacetate; or a polycarboxylic acid anhydride such as trimellitic anhydride or pyromellitic anhydride are particularly representative examples. .

When such a curing agent is blended, the amount to be blended is within a range of 1 to 100 parts by weight of the curing agent component per 100 parts by weight of the solid content of the fluorine-containing copolymer solution. Appropriate. If the amount of curing agent is small, it will inevitably be impossible to obtain a sufficiently cured coating film, and conversely, if the amount of curing agent is too large, the resulting coating film will inevitably become brittle. The case is also unfavorable.

The fluororesin composition thus obtained is
It is most effective to use it as it is as a clear coating, but if necessary, it is also possible to add a coloring agent and use it with various resins, solvents, etc. It goes without saying that various known and commonly used additives can be added, such as regulators, color separation inhibitors, antioxidants, ultraviolet absorbers, light stabilizers, or silane coupling agents.

Such coloring agents include dyes, organic pigments,
Examples of the resin include acrylic resin, fluorine-containing vinyl resin, cellulose resin such as nitrocellulose or cellulose acetate butyrate, vinyl chloride/vinyl acetate copolymer resin,
Examples include petroleum resins, ketone resins, oil-free alkyd resins, alkyd resins, and epoxy resins.

The resin composition of the present invention can be used as a clear paint for forming two-coat metallic coatings for automobiles, and can also be used for automobile repair, general building materials, architectural exteriors, slates, tiles, etc. It can also be used as a coating for metals or plastics.

[0030] As the coating method, conventionally commonly used methods such as air spray, airless spray, electrostatic spray, shower coating, dip coating, brush printing, or roll coating can be used as they are.

[0031] Furthermore, by selecting the curing agent mentioned above, the curing conditions can range from drying at room temperature to low-temperature baking at 130 to 150°C for 20 to 30 minutes, and then drying at 200 to 230°C.
Various conditions can be employed, ranging from high temperature short-time baking at 30 to 200 seconds at °C.

[0032]

[Examples] Next, the present invention will be specifically explained using reference examples, working examples, and comparative examples. In the following description, all references to % mean % by weight unless otherwise specified.

Reference Examples 1 to 3 Into a clean 1 liter stainless steel flask, add monomers and a solvent as shown in Table 1, and add 2% of the total amount of monomers as an initiator. tert-butylperoxy-2-ethylhexanoate. Thereafter, the mixture was maintained at 90° C. for 15 hours while stirring to carry out a polymerization reaction, thereby obtaining target solutions of vinyl copolymer (A): (A-1) to (A-3). .

[0034]

[Table 1]

Reference Examples 4 to 6 Monomers other than fluorine-containing vinyl monomers as shown in Table 2, a solvent, and polymerization were placed in a 1 liter stainless steel autoclave that was sufficiently purged with nitrogen. As initiators, 2% of tert-butylperoxypivalate and 0.5% of tert-butylperoxy-2-ethylhexanoate were charged based on the total amount of monomers.

Next, for Examples 3 and 4, 1% of bis(1,2,2,6,6-pentamethyl-4-
piperidinyl) sebacate was added.

Thereafter, the liquefied and collected fluorine-containing vinyl monomer was introduced under pressure and kept at 75°C for 15 hours while stirring to carry out a polymerization reaction, and then the temperature was raised to 80°C and the same temperature was maintained. The reaction was continued by holding for 4 hours to prepare a solution of the desired fluorine-containing copolymer (B): (B-1) ~
(B-3) was obtained.

[0038]

[Table 2]

Examples 1 and 2 A vinyl copolymer (A) solution, a fluorine-containing copolymer (B) solution, and a curing agent were mixed at the compounding ratios shown in Table 3, and cured to obtain a film with a thickness of A film having a diameter of about 25 μm was obtained.

[0040]

[Table 3]

Example 3 A vinyl copolymer (A) solution and a fluorine-containing copolymer (B) solution were mixed at the compounding ratio shown in Table 3 and cured to form a film having a thickness of about 25 μm. I got it.

Comparative Examples 1 and 2 Example 1 except that the vinyl copolymer (A) solution was not used.
In the same manner as in 2 and 2, a film having a thickness of about 25 μm was obtained.

Comparative Example 3 A film having a thickness of about 25 μm was obtained in the same manner as in Example 3, except that the vinyl copolymer (A) was not used.

Table 3 shows Examples 1 to 3 and Comparative Example 1.
The transmittance of visible light and ultraviolet rays for each film obtained in Steps 3 to 3 is also shown. In terms of visible light transmittance, there is almost no difference between the Examples and Comparative Examples, but in terms of UV transmittance, in the Examples, both films are completely different. While the films blocked ultraviolet rays, all films in the comparative examples showed high transmittance.

A lacquer-type acrylic white paint was applied onto a chromate-treated aluminum plate to form a coating film having a thickness of about 25 μm. Next, on this film, Examples 1-
The coatings were applied in the same manner as in Example 3 and Comparative Examples 1 to 3. These coating films were subjected to an accelerated weathering test using a Sunshine Weather-Ometer manufactured by Suga Test Instruments Co., Ltd. to examine changes in the gloss of the coating films over time, and the results are summarized in Table 3.

As is clear from the results in the same table, when coating is performed with a fluororesin composition to which vinyl copolymer (A) is added and mixed, coating is performed using only fluorine-containing copolymer (B). It is known that this method is more effective in preventing the deterioration of the paint film than when a coating is applied.

[0047]

【Effect of the invention】
The fluororesin composition of the present invention is
By coating on top of conventional coatings or directly on a substrate, a coating with extremely excellent weather resistance and ultraviolet absorption that is stable over time can be obtained. As a result, the internal base material can be protected from deterioration due to ultraviolet rays for a very long period of time, and the industrial effects thereof are extremely large.

Claims (3)

[Claims] Claim 1: Obtained by copolymerizing a vinyl monomer (a-1) having the following structure as a part of its molecular structure and another copolymerizable vinyl monomer (a-2). 1 to 50% by weight of vinyl copolymer (A) and fluorine-containing vinyl monomer (
50 to 50% of the fluorine-containing copolymer (B) obtained by copolymerizing 15 to 70% by weight of b-1) and 30 to 85% by weight of another copolymerizable monomer (b-2). A fluorine-containing resin composition, characterized in that it contains 99% by weight of 99% by weight as an essential component. [Formula 1] (However, X1 and X2 in the formula each represent a hydrogen atom or a monovalent saturated hydrocarbon group of C1 to C5, which may be the same or different, and Y1 and Y2 are , may be the same or different, respectively.
It shall represent a hydrogen atom or a hydroxyl group, and at least one shall be a hydroxyl group. ) [Claim 2] The above vinyl monomer (a-1)
and the vinyl monomer (a-2), the molar ratio is (a-1)/
The fluororesin composition according to claim 1, wherein (a-2) = 0.01 to 10. 3. The above-mentioned fluorine-containing vinyl monomer (b-
1) is vinylidene fluoride, tetrafluoroethylene,
The fluororesin composition according to claim 1 or 2, which is at least one selected from the group consisting of chlorotrifluoroethylene and hexafluoropropylene.