JPS5832183B2 - Hifuku Yoso Saibutsu - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a novel coating material containing a resin composition comprising a thermosetting copolymer having an N-alkoxyalkylamide group, a thermoplastic acrylic polymer, and polyvinylidene fluoride. Regarding the composition.

Coatings made from coating compositions containing polyvinylidene fluoride have excellent weather resistance, abrasion resistance, impact resistance and flexibility.

However, polyvinylidene fluoride coatings lack adhesion to substrates, making it difficult to make them into practical coatings.
It has drawbacks such as the high cost of polyvinylidene fluoride.

As a method for improving the adhesion of a polyvinylidene fluoride film to a substrate, for example, polyvinylidene fluoride 99-75
It is known to use a resin composition in which a thermoplastic acrylic polymer is mixed in a proportion of 1 to 25% by weight (see Japanese Patent Publication No. 4310363).

The coating created by this method has significantly improved adhesion to the substrate compared to polyvinylidene fluoride coatings, but on the other hand, this coating has poor coating properties such as solvent resistance, water resistance, and flexibility. This tendency increases as the mixing ratio of the thermoplastic acrylic polymer increases.

In order to improve the adhesion of polyvinylidene fluoride coatings to substrates without causing such deterioration in coating performance, hydroxyalkylated acrylic polymers and melamine resins, in particular, can be used instead of thermosetting polymers. It has also been proposed to use mixtures or melamine hydroxyalkylated acrylic resins (see said publication).

However, the film obtained by this method undergoes phase separation between the polyvinylidene fluoride and the hydroxyalkylated acrylic resin, and becomes rough and the film performance is significantly reduced, so it is not practical to use it as a protective film for substrates. above is impossible.

Therefore, the present inventors conducted research to develop a coating material containing a resin composition with a relatively low content of polyvinylidene fluoride. By using a resin composition made of a polymer having the following properties as a coating material, we succeeded in obtaining a coating film that eliminates the above-mentioned drawbacks.

However, the performance of this coating film, such as impact resistance, flexibility, and secondary physical properties after immersion in boiling water, is still insufficient, and the content of the polymer having an N-alkoxyalkylamide group in the resin composition is insufficient. This tendency increases as the number increases.

Therefore, the present inventors further conducted research to find a coating composition that could form a film with sufficiently excellent coating performance even if the content of polyvinylidene fluoride was small. It was discovered that a coating with extremely excellent performance could be obtained by using a resin composition containing a thermosetting polymer having an alkoxyalkylamide group and a thermoplastic acrylic polymer mixed in a specific ratio. invention has been achieved.

The present invention relates to N of monoethylenically unsaturated carboxylic acid amide.
- N from 2 to 50% by weight of alkoxyalkylated products, up to 15% by weight of monoethylenically unsaturated carboxylic acids, up to 50% by weight of methachronitrile and up to 98% by weight of other copolymerizable monoethylenically unsaturated monomers; - Thermosetting copolymer having an alkoxyalkylamide group (a) 80-2
0% by weight and a thermoplastic acrylic polymer from an alkyl ester of a monoethylenically unsaturated carboxylic acid having an alkyl group having 1 to 18 carbon atoms and optionally other copolymerizable monoethylenically unsaturated monomers. Coalescing b) A resin composition consisting of 20-80% by weight mA) 30-70% by weight and a resin composition consisting of 70-30% by weight of polyvinylidene fluoride (B).

In order to produce a copolymer having a thermosetting N-alkoxyalkylamide group used in the present invention, for example, an N-alkoxyalkylated product of monoethylenically unsaturated carboxylic acid amide*, a monoethylenically unsaturated carboxylic acid amide, An acid, methacrylonitrile, other copolymerizable unsaturated monomers, a solvent, a chain transfer agent, a catalyst, etc. are added, and the mixture is heated under reflux until a polymer with a desired degree of polymerization is obtained.

Polymerization is usually completed in about 1 to 16 hours.

It is desirable to add the catalyst sequentially as the polymerization progresses.

Since this polymerization reaction has an extremely high polymerization rate and is an exothermic reaction, it is necessary to thoroughly stir the reaction mixture to control the temperature.

As the catalyst, common catalysts such as peroxides such as cumene hydroperoxide, lauroyl peroxide, tertiary butyl peroxyisopropyl carbonate, benzoyl peroxide, α・αl azobisisobutyronitrile and other azo compounds are used. Examples of chain transfer agents include tertiary dodecyl mercaptan, 2-
Mercaptans such as mercaptoethanol are used.

Examples of N-alkoxyalkylated monoethylenically unsaturated carboxylic acid amides include acrylamide, methacrylamide, itaconic acid diamide, α-ethylacrylamide, crotonic acid amide, fumaric acid diamide, maleic acid diamide, etc., preferably acrylamide and methacrylamide. An N-alkoxyalkylated amide is used.

These N-alkoxyalkylated products are produced using, for example, the above-mentioned unsaturated carboxylic acid amide or its methylolated product as a starting material, as described in US Pat. No. 3,079,434 and US Pat.
It is produced by the method described in the specifications of No. 7965 and Japanese Patent Publications No. 47-27492 and No. 47-28765.

The reaction when acrylamide is used as a starting material is shown by the following formula.

In the formula, R1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
R2 represents an alkyl group (including a cycloalkyl group) having 8 or less carbon atoms.

Further, the reaction when N-alkylolacrylamide is used as a starting material is shown by the following formula.

The symbols in the formula have the above meanings.

Formula R1CHO used in producing N-alkoxyalkylated product of unsaturated carboxylic acid amide according to the above reaction
Examples of the aldehyde and its derivatives include formaldehyde, paraformaldehyde, trioxymethylene, hexamethylenetetramine, acetaldehyde, and butyraldehyde, with formaldehyde and its derivatives being particularly preferred.

Examples of the alcohol of formula R20H include monohydric alcohols such as methanol, ethanol, propatool, butanol, pentanol, cyclohexanol, and 3-chloropropatol.

Note that a part of this monohydric alcohol can be replaced by a polyhydric alcohol such as ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, or a derivative thereof.

The reaction is preferably carried out in the presence of an acidic catalyst.

As the acidic catalyst, for example, acetic anhydride, oxalic acid, phosphoric acid, phosphoric anhydride, acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, α-methylenegeltalic acid, etc. are used.

Note that in the reaction of Reaction Formula I, it is of course possible to use these reaction products instead of aldehyde and alcohol.

N- of unsaturated carboxylic acid amide in copolymer (a)
The proportion of the alkoxyalkylated compound is 2 to 50% by weight; if it is less than this, the resulting copolymer itself will not exhibit thermosetting properties, and polyvinylidene fluoride coating materials containing such a copolymer cannot be used. The resulting coatings lack water resistance, solvent resistance and impact resistance.

The proportion of methacrylonitrile in a) in the copolymerization is 50
It is not more than 2% by weight, preferably 2 to 30% by weight.

A copolymer containing an N-alkoxyalkylated product of an unsaturated carboxylic acid amide and methacrylonitrile within this range (2E(a) has an affinity for polyvinylidene fluoride due to the synergistic effect of the modified amide group and the methacrylate tolyl group. Coatings made from polyvinylidene fluoride coating compositions containing copolymer a) are extremely smooth and have excellent adhesion to substrates, weather resistance, and chemical resistance. It has properties such as durability and impact resistance.

Such excellent effects cannot be achieved by copolymers (a) obtained by using other unsaturated nitriles, such as acrylonitrile or α-methylene geltalonitrile, in place of methacrylatetrile.

Examples of monoethylenically unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, α-methylenegeltalic acid, crotonic acid, or hydroxyalkyl acrylate or methacrylate, maleic anhydride, succinic anhydride, phthalic anhydride, etc. An unsaturated acid obtained by an addition reaction with an acid anhydride is used.

The proportion of this unsaturated carboxylic acid in the copolymer (a) is 15% by weight or less, preferably 0.5 to 10% by weight.

By copolymerizing this unsaturated carboxylic acid, the thermosetting properties of the copolymer (ma) are further improved, and the copolymer (ma) has a higher thermosetting property than the polyvinylidene fluoride coating composition containing 't'(a). The produced coating further has improved adhesion to the substrate, and has extremely excellent solvent resistance, water resistance, and impact resistance.

If these unsaturated carboxylic acids are used in too large a quantity, the compatibility of the resulting copolymer with polyvinylidene fluoride tends to decrease.

Other copolymerizable ethylenically unsaturated monomers used in the copolymer (a) include, for example, acrylic acid or methacrylic acid and monohydric alcohols such as methanol, ethanol, propatool, n-butanol, secondary Butanol, tertiary butanol, pentanol, hexanol, cyclohexanol, 2-ethylhexanol, lauryl alcohol, decyl alcohol, dodecyl alcohol,
Acrylate or methacrylate obtained from stearyl alcohol etc., vinyl chloride, vinyl propionate,
vinyl acetate, acrylonitrile, methacrylonitrile,
Examples include 3-octenitrile, crotonitrile, oleonitrile, α-methylene geltalonitrile, and particularly preferred are acrylates or methacrylates having an alkyl group having 1 to 4 carbon atoms.

As the alkyl ester of a monoethylenically unsaturated carboxylic acid having an alkyl group having 1 to 18 carbon atoms (including a cycloalkyl group) used in the thermoplastic polymer b),
For example, monoethylenically unsaturated carboxylic acids such as acrylic acid and methacrylic acid, methanol, ethanol, propatool, isopropanol, n-butanol, secondary butanol, tertiary butanol, pentanol, hexanol, cyclohexanol, heptatool , 2-ethylhexanol, nonyl alcohol, tepyl alcohol, dodecyl alcohol, stearyl alcohol, lauryl alcohol and other monohydric alcohols, preferably acrylates or methacrylates having an alkyl group having 1 to 4 carbon atoms. can be given.

The content of these alkyl esters in the polymer (b) is 60% by weight or more.

Other copolymerizable ethylenically unsaturated phase monomers used in the thermoplastic polymer b) include, for example, vinyl chloride, vinyl acetate, vinyl propionate, acrylonitrile, methacrylatrile, α-methylenegeltalonitrile, crotonitrile, etc. Examples include nitrile.

The thermoplastic polymer (b) further improves the compatibility between polyvinylidene fluoride and the thermosetting copolymer a), and the uniformity of the coating formed from such a resin composition is extremely good. .

Furthermore, this coating has extremely good adhesion to substrates, solvent resistance, impact resistance, water resistance, and secondary physical properties after immersion in boiling water, and is particularly advantageous as an outdoor coating.

In order to improve the compatibility of the coating composition of the present invention with the pigment, or to improve the adhesion of the resulting coating to the substrate, 5% by weight of the following comonomer was added to the thermoplastic polymer: It is also advantageous to copolymerize in the following proportions:

2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine, 3ethyl-5-vinylpyridine, dimethylaminoethyl (meth)
Acrylate, diethylaminoethyl (meth)acrylate, dimethylamine propyl (meth)acrylate,
Zyl n-butylaminoethyl (meth)acrylate, N
-(β-[α(meth)acryloxyacetamidoto-ethyl)N-N/-ethyleneurea, N-(β-[α-(
meth)acryloxyacetamidotoethyl)N-N
/-)! Vinyl monomer general formula such as J dimethylene (in the formula, R3 is a hydrocarbon residue of a saturated or unsaturated fatty acid having 3 to 21 carbon atoms, R4 is a hydrogen atom, an alkyl group or group having 1 to 4 carbon atoms) CH2-()-C-23, R5 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R6 is a hydrocarbon residue of a saturated or unsaturated fatty acid having 2 to 20 carbon atoms) vinyl monomer.

The compound of formula (II) is produced, for example, by reacting 1 mole of tris-(hydroxymethyl)-aminomethane with 3 moles of tall oil fatty acid, and then reacting with formaldehyde. Commercially available products such as (manufactured by) are used.

More preferred thermoplastic polymerization (t'(b) includes 60% by weight or more of (meth)acrylate, 0.05 to 5% by weight of a monoethylenically unsaturated carboxylic acid such as acrylic acid, methacrylic acid, crotonic acid, etc., and optionally Another copolymerizable monoethylenically unsaturated monomer is copolymerized to produce a polymer having carboxyl groups, and then the carboxyl groups contained in this polymer are almost completely removed from the 2 rings in the ring.
Examples include copolymers obtained by reacting with alkylene imines having ~3 carbon atoms.

Examples of the alkyleneimine include 1,2-propyleneimine, ethyleneimine, 2-methylaziridine,
-ethylaziridine, 2-n-butylaziridine, 2.
3-dimethylaziridine, 2-ethyl-3-propylaziridine, 2-methylazetidine, 2-ethylacetidine, 2,4-dimethylacetidine, 2,4-di-n-octylacetidine, 2,3- Di(2-methylbutyl)
-Acetidine etc. are used.

The viscosity average molecular weight of the thermoplastic polymerization mb) is approximately 50,000~
It is desirable that it be in the range of 200,000.

As the thermoplastic polymer (b), commercially available ones such as acryloids A-10, A-11, A21, B-44 and B-62 (all manufactured by Rohm and Haas) may be used.

The content of thermoplastic polymerization mb) in resin composition 'I'1JA) is 20 to 80% by weight, particularly preferably 30 to 60% by weight.

A coating made from a polyvinylidene fluoride coating composition containing a resin composition mA) having a lower content of the thermoplastic polymer b) is characterized by the compatibility between the thermosetting resin and the polyvinylidene fluoride. Adhesion to the base material due to lack of
Flexibility, chemical resistance, etc. decrease.

Furthermore, a coating formed from a polyvinylidene fluoride coating composition containing a resin composition (A) containing a higher content of thermoplastic polymer b) has lower solvent resistance and water resistance.

It is particularly preferable to use the thermoplastic polymer (b) in a proportion such that the content thereof is 25% by weight or more based on the polyvinylidene fluoride.

The polyvinylidene fluoride (B) used in the present invention is a vinylidene fluoride homopolymer and 95 mol% or more of vinylidene fluoride and other monomers, such as dichlorofluoroethylene,
1.1.2-) It is a copolymer made by copolymerizing halogenated ethylene such as 1,1 fluoro-2-chloroethylene and tetrafluoroethylene, vinyl chloride, etc. in a proportion of 5 mol% or less.

Polyvinylidene fluoride (B) is disclosed in, for example, U.S. Pat.
It is manufactured by the method described in each specification of No. 5537 and No. 3102021.

The content of polyvinylidene fluoride (B) in the resin composition is 3
It is 0 to 70% by weight, preferably 40 to 70% by weight.

If the amount is less than this, the resulting film will have good adhesion to the substrate, but will lack weather resistance and flexibility.

On the other hand, if the content is higher than this, the adhesion of the resulting film to the base material will be poor and the smoothness of the surface of the film will be reduced.

When producing the coating composition of the present invention, for example, a solution of a thermosetting copolymer (Ea) having an N-alkoxyalkylamide group, a thermoplastic acrylic polymer or its solution, and a polyvinylidene fluoride powder or its Mix the dispersion.

As the solvent, suitable solvents capable of uniformly dissolving or dispersing the resin composition, such as n-butanol, xylene, cyclohexanone, r-butyrolactone,
Isophorone, diacetone alcohol, ethylene glycol monobutyl ether, cyethylene monophthyl ether, Tsurupez, etc. are used.

For example, the coating composition of the present invention may remain clear,
Alternatively, it is used in the form of pigmented enamel.

As the pigment, titanium dioxide, carbon black, talc, pallite, zinc sulfate, strontium chromate, barium chromate, iron oxide pigment, cadmium yellow, cadmium red, phthalocyanine blue, etc. are used.

These pigments may be used, for example, in a binder ratio of 0.
After dispersing in a thermosetting Kyoden polymer (a) or a thermoplastic polymer (b) or a solution thereof in a range of 5 to 1,
Mix with polyvinylidene fluoride.

In addition, the coating composition of the present invention includes stabilizers, flow agents,
Slip agents, plasticizers and other additives, other resins such as epoxy resins, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, aminoplasts, cellulose derivatives such as nitrocellulose, carboxyacetyl cellulose, polyesters, etc. Hydrocarbon resins and the like can also be added.

When applying the coating composition of the present invention, for example, brush coating, spray coating, roller coating,
Curtain 70 - Performed with a coater etc., then 20
A curing treatment is performed at 0 to 260°C for 1 to 30 minutes.

The coating composition of the present invention is significantly cheaper to produce than conventional polyvinylidene fluoride coating materials, and the resulting coating is hard, has a smooth surface, has good adhesion to substrates,
It has excellent flexibility and weather resistance.

The parts below mean parts by weight.

Example I Production of copolymer A: Into a reactor equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser, 1/3 of a solution having the following composition was added, and heated to reflux (approximately 93°C) for 1 hour. ) and kept under reflux until the polymerization reaction was completed.

n-Butanol 120 parts Xylene 20 parts N-butoxymethylacrylamide 100 parts Methacrylonitrile
225 parts ethyl acrylate
650 parts methacrylic acid
Part 25 Tertiary dodecyl mercaptan
2 parts Azobisisobutyronitrile 8
After adding the remainder of the solution to the reaction mixture for 2 hours, 20 parts of n-butanol, 12 parts of xylene, 150 parts of Tsurpets #150 (manufactured by Shell Chemical Co., Ltd.) and 5 parts of azobisisobutyronitrile were added for 3 hours. It was added under cover.

Then, after maintaining the reflux state for 2 hours, 6 parts of n-butanol, 40 parts of xylene and 300 parts of Tsurpetz #150 were added.
The reaction was terminated by adding 50% of the solution.

The obtained copolymer solution (A-1) had a resin solid content of 51.
0%, Gardner-Holdt viscosity z1, and acid value 7.8.

Preparation of copolymer B: 300 parts of xylene, 396 parts of methyl methacrylate, 4 parts of methacrylic acid and 1 part of azobisisobutyronitrile are placed in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, The temperature was raised to 75°C in 1 hour.

Two hours after the start of the reaction, a mixture consisting of 100 parts of cellosolve acetate, 200 parts of xylene and 3 parts of azobisisobutyronitrile was added over 5 hours, and the reaction mixture was added between 7 and 8.5 hours after the start of the reaction. 75℃ to 90℃
8.5 and 10 hours after the start of the reaction, one part each of azobisisobutyroniol (IJ) was added.

12 hours after the start of the reaction, 500 parts of xylene was added to terminate the reaction.

The copolymer solution thus obtained had a solid content of 30.4%, a Gardner-Holdt viscosity U, and an acid value of 2.1.

80 parts of the thermosetting copolymer solution (A-1) and 67 parts of the thermoplastic copolymer solution (B-1) obtained above were mixed with 40 parts of polyvinylidene fluoride and 63 parts of isophorone at room temperature. did.

The resin solid content ratio in this composition is (A-1)/(B-1
)/Polyvinylidene fluoride-40/2o/40
Met.

Titanium dioxide was mixed with this so that the ratio of pigment to binder was 0.6/1.

The polyvinylidene fluoride used here was 160 to 16
It has a melting point of 5°C, its plasticity number is 3020, and it has a high molecular weight.

Plasticity number is an empirical index of relative molecular weight that is used for polymers where it is difficult to obtain a true solution of the polymer to determine the absolute molecular weight.

The coating composition thus obtained was coated with Bonderite #330.
0 (manufactured by Parker Rising Co., Ltd.) treated zinc medium iron plate so that the dry film thickness is 20μ, and
A coating film was created by baking for 0 seconds.

The coating film thus obtained had a smooth surface, high hardness, and good impact resistance, chemical resistance, solvent resistance, and secondary physical properties after a boiling water immersion test.

Example 2 20 parts of N-butoxyacrylamide, 2 parts of methacrylic acid, 35 parts of ethyl acrylate, 4 parts of methyl methacrylate
5 parts and 18 parts of methacrylonitrile were polymerized in the same manner as in Example 1 in a mixed solvent consisting of 25 parts of n-butanol, 25 parts of xylene, 25 parts of Tsurpetz #15000, and 25 parts of diacetone alcohol, and the resin solid content concentration was 50.
A thermosetting copolymer solution (A-2) having a temperature of 2%, a Gardner-Holdt viscosity of Z3, and an acid value of 7.8 was obtained.

Separately, 64 parts of methyl methacrylate, 35 parts of ethyl acrylate and 1 part of acrylic acid were added to 110 parts of cellomelphacetate.
A thermoplastic copolymer solution (B- 2) was obtained.

32 parts of the thermosetting copolymer solution (A-2) and 80 parts of the thermoplastic copolymer solution (B-2) obtained above were mixed with 60 parts of polyvinylidene fluoride and 78 parts of isophorone at room temperature. .

The resin solid content ratio of this composition is (A-2)/(B-2)
)/polyvinylidene fluoride = 16/24/60.

Pigments were added to this composition in the same manner as in Example 1, and the coating was baked to form a coating film.

The resulting coating film had excellent coating performance, particularly in weather resistance and chemical resistance.

Example 3 Instead of thermoplastic copolymer solution (B-2), acryloid B-44 (thermoplastic acrylic copolymer containing methyl methacrylate and ethyl acrylate as main components) was mixed with 10 parts of n-butanol and toluene. Example 2 was prepared using a solution dissolved in 90 parts to give a solid content concentration of 30%.
A coating composition was prepared in the same manner as described above, and a coating film was created.

The resulting coating film had particularly excellent flexibility and adhesion to metals.

Example 4 The free carboxyl groups in the copolymer of the thermoplastic copolymer solution (B2) used in Example 2 were
An amino ester-modified thermoplastic copolymer solution (B-3) was prepared by completely esterifying with 1.2 propylene imine according to the method described in the above issue.

The resulting copolymer solution had a resin solid content concentration of 31.3% and a Gardner-Holdt viscosity of W.

This amino ester modified thermoplastic copolymer solution (B-3
) was used in place of the thermoplastic copolymer solution (B-2) of Example 2, a coating composition was produced in the same manner as in Example 2, and a coating film was created.

The resulting coating film had particularly excellent adhesion to metals and flexibility.

Example 5 20 parts of N-methoxyacrylamide, 2 parts of methacrylic acid, 35 parts of ethyl acrylate, 4 parts of methyl methacrylate
5 parts and 18 parts of methacrinitrile were polymerized in the same manner as in Example 1 in a mixed solvent consisting of 25 parts of n-butanol, 25 parts of xylene, 25 parts of Tsurpetz #150 and 25 parts of diacetone alcohol, Resin solid content concentration 50
．． 6%, Gardner-Holdt viscosity Z2Z3, acid value 7.0
A thermosetting copolymer solution (A-3) was obtained.

80 parts of this copolymer solution (A-3), 67 parts of thermoplastic copolymer solution (B-2), 40 parts of polyvinylidene fluoride, and 63 parts of isophorone were mixed at room temperature.

A coating composition was prepared by mixing this composition with titanium dioxide in the same manner as in Example 2, and the coating composition was baked onto an iron plate to form a coating film.

The resulting coating film was particularly excellent in flexibility and adhesion to metals.

Example 6 84 parts of methyl methacrylate, 15 parts of methacrylonitrile
1 part of cellosolve acetate and 1 part of methacrylic acid, 10 parts of cellosolve acetate
Example 1
Polymerization was carried out in the same manner as above to obtain a thermoplastic copolymer solution (B-4) having a resin solid content concentration of 30.1%, a Gardner-Holdt viscosity T, and an acid value of 2.2.

A coating composition was prepared in the same manner as in Example 1 except that this thermoplastic copolymer solution (B-4) was used in place of the thermoplastic copolymer solution (B-1). A paint film was created by baking the paint.

The resulting coating film had particularly excellent impact resistance and chemical resistance.

Comparative Example 1 Example 1 was added to a composition consisting of a thermosetting copolymer solution (A-1), polyvinylidene fluoride (solid content ratio 60:40), and isophorone, and containing no thermoplastic polymer.
Titanium dioxide was mixed in the same manner as above, and a paint film was created by baking the paint.

The obtained coating film had poor flexibility, and the secondary physical properties after immersion in boiling water were significantly deteriorated.

Comparative Example 2 Thermoplastic copolymer solution (B-1) and polyvinylidene fluoride (solid content ratio 60:40) and isophorone were excluded, and Example 1 and a composition containing no thermosetting copolymer were added. In the same manner, titanium dioxide was mixed and the coating was baked to create a coating film.

The resulting coating film had insufficient solvent resistance and had a significant deterioration in secondary physical properties after immersion in boiling water.

Comparative Example 3 A composition consisting of a thermosetting copolymer solution (A-2), polyvinylidene fluoride (solid content ratio 60:40), and isophorone and containing no thermoplastic copolymer was prepared in the same manner as in Example 1. A paint film was created by mixing titanium dioxide and baking the paint.

The resulting coating film had poor impact resistance, and the secondary physical properties after immersion in boiling water were significantly reduced.

Comparative Example 4 A composition consisting of a thermoplastic copolymer solution (B-2), polyvinylidene fluoride (solid content ratio 40:60), and isophorone and containing no thermoplastic copolymer was treated in the same manner as in Example 1. A paint film was created by blending titanium dioxide and baking the paint.

The resulting coating film had poor solvent resistance, and the secondary physical properties after immersion in boiling water significantly deteriorated.

Comparative Example 5 20 parts of N-butoxymethylacrylamide, 2 parts of methacrylic acid, 35 parts of ethyl acrylate, 45 parts of methyl methacrylate, and 18 parts of acrylonitrile were mixed with 25 parts of n-butanol, 25 parts of xylene, and 2 parts of Tsurpetz 8150.
Polymerization was carried out in the same manner as in Example 1 in a mixed solvent consisting of 5 parts of diacetone alcohol and 25 parts of diacetone alcohol to obtain a thermosetting copolymer having a resin solid content of 50.2%, a Gardner-Holdt viscosity of Z3, and an acid value of 72. A solution (A-4) was obtained.

This copolymer solution (A-4), thermoplastic copolymer solution (
A resin composition was prepared by mixing B-2), polyvinylidene fluoride, and isophorone in the same manner as in Example 2, and then titanium dioxide was added to obtain a coating composition.

Using this, paint baking was performed in the same manner as in Example 1, and a coating film was created on an iron plate.

The resulting coating film had poor flexibility, and its secondary physical properties after immersion in boiling water were significantly reduced.

Comparative Example 6 As a monomer component of the thermosetting copolymer solution (1-2),
A thermosetting copolymer solution (A-5) was obtained by polymerizing in the same manner as in Example 2 except that methyl methacrylate was used instead of methacrylate trile.

A coating composition was prepared in the same manner as in Example 2 except that this thermosetting copolymer solution (A-5) was used instead of the thermosetting copolymer solution (A-2), and a coating composition was prepared. It was created.

The resulting coating film had poor coating surface smoothness and lacked impact resistance and weather resistance.

Table 1 shows the performance of the coating films created in Examples 1 to 6 and Comparative Examples 1 to 6.

The test values 5 to 1 in the table are evaluated on a five-point scale, with 5 being excellent and 1 being bad, and MEK means methyl ethyl ketone.

A thermosetting copolymer solution (A-6) was obtained by polymerizing in the same manner as in Example 2 except that acrylonitrile was used instead of methacrylonitrile.

The properties of this solution (A-6) and the thermosetting copolymer solution (A-5) used in Comparative Example 6 are shown in Table 2.

40 parts of the thermosetting copolymer solution shown in Table 3, 100 parts of thermoplastic copolymer (B-2), 50 parts of polyvinylidene fluoride, and 60 parts of isophorone were mixed.

The resin solid content ratio of this composition is thermosetting copolymer/thermoplastic copolymer (B-2)/polyvinylidene fluoride-20.
/30150.

The composition was applied onto a glass plate to a dry film thickness of 25 μm, and dried at 260° C. for 5 minutes to form a film.

The properties of the obtained film are shown in Table 3.

Claims (1)

[Claims] 1 N-alkoxyalkylated product of monoethylenically unsaturated carboxylic acid amide 2 to 50% by weight, monoethylenically unsaturated carboxylic acid 15% or less by weight, methacrylonitrile 5
Thermosetting copolymer with N-alkoxyalkylamide groups from 0% by weight or less and from 98% by weight of other copolymerizable monoethylenically unsaturated monomers a) 80-20% by weight and carbon number Thermoplastic acrylic polymers from alkyl esters of monoethylenically unsaturated carboxylic acids having 1 to 18 alkyl groups and optionally other copolymerizable monoethylenically unsaturated monomers b) 20 to 80% by weight %
A coating composition comprising 30 to 70% by weight of a resin composition (4) consisting of and 70 to 30% by weight of polyvinylidene fluoride [F]).