JPS60228575A - Fluororesin paint - Google Patents

Abstract

PURPOSE:To provide the titled paint which has excellent weather resistance, etc. and does not require baking at a high temp., containing a fluorine-contg. block copolymer obtd. by copolymerizing a vinyl monomer and a specified copolymer contg. peroxy or azo linkages. CONSTITUTION:A vinyl monomer contg. no fluorine atom, such as methyl acrylate, is copolymerized with a copolymer contg. peroxy or azo linkages obtd. by copolymerizing a polymeric peroxide (e.g. a compd. of formula I wherein n is 2-30) or a polyazo compd. (e.g. a compd. of formula II wherein m is 1-100) and a fluorine-contg. vinyl monomer (e.g. a compd. of formula III). Alternatively, the polymeric peroxide or the polyazo compd. and a vinyl monomer contg. no fluorine atom are copolymerized and the resulting copolymer is then copolymerized with the fluorine-contg. vinyl monomer. The resulting fluorine-contg. block copolymer is incorporated to obtain the desired fluororesin paint.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a fluorine-containing resin coating that is curable at room temperature and contains a specific fluorine-containing block copolymer.

(Conventional technology and problems) In recent years, fluorine-containing resin paints, typically polytetrafluoroethylene, have been praised for their excellent water and oil repellency, non-stick properties, stain resistance, weather resistance, and chemical resistance. , its demand is increasing.

However, these fluorine-containing resin paints are made of polytetrafluoroethylene trapase, which is insoluble in organic solvents, so they must be heated to a temperature higher than the melting temperature of polytetrafluoroethylene, and cannot be used in places with high-temperature baking equipment. There is a restriction that it can only be painted. Furthermore, there is also a restriction that the object to be coated can only be coated if it can withstand the baking temperature.

To overcome these limitations, copolymers of fluoroolefins and vinyl ethers such as hyaloxyalkyl vinyl ethers have been proposed (Japanese Patent Application Laid-Open No. 1987-1999).
84107, Japanese Patent Publication No. 57-84108), but the coating films obtained from these materials do not have the important properties of fluorine-containing resin paints, such as non-adhesiveness and water and oil repellency.

The invention solves the above problems, eliminates the need for high-temperature baking, and has the excellent water and oil repellency, non-adhesiveness, stain resistance, weather resistance, and chemical resistance of conventional fluorine-containing resin paints. The purpose of the present invention is to provide a fluorine-containing resin paint having the following properties.

(Means and effects for solving the problems) The present invention combines a polymeric peroxide or a polyazo compound and a fluorine-containing vinyl/S/ type monomer or a fluorine-free vinyl type monomer forming a fluorine-containing polymer portion. A first step in which a copolymer containing a peroxy bond or an azo bond is obtained by copolymerizing the copolymer with a fluorine-free vinyl monomer and a copolymer containing a peroxy bond or an azo bond obtained in the first step. The second step of copolymerizing the fluorine-containing vinyl monomer and the fluorine-containing vinyl monomer forming the fluorine-containing vinyl monomer and the fluorine-containing vinyl monomer to form the fluorine-containing vinyl monomer and the fluorine-containing polymer portion. The fluorine-containing resin paint contains a fluorine-containing block copolymer with a vinyl monomer that does not contain the fluorine-containing block copolymer.

When the fluorine-containing block copolymer used in the invention is added to room-temperature curing paints such as acrylic resin paints and alkyd resin paints, it does not require high-temperature baking like conventional fluorine-containing resin paints. It cures at room temperature and exhibits the characteristics of a fluorine-containing resin paint. In addition, there are two-component reactive paints such as polyurethane resin paints and epoxy resin paints, and bake-curable paints such as melamine hardening paints and brick isocyanate hardening paints.
Even when a fluorine-containing block copolymer is added, the characteristics of a fluorine-containing resin coating are exhibited. Of course, coating compositions containing fluorine-containing block copolymers as a main component can also be used as room-temperature-curing coatings such as lacquer-type coatings and isocyanate-curing coatings, as well as bake-curing coatings such as melamine-curing coatings. It was discovered that this material exhibits the characteristics of a fluorine-containing resin paint.

The proportion of the fluorine-containing block polymer in the solid content of the resin constituting the paint of the present invention is 0.01% by weight or more. If it is less than 0.01% by weight, water and oil repellency, non-stick properties, stain resistance, etc. will be insufficient.

The fluorine-containing block copolymer used in the present invention can impart specific coating film performance to fluorine-containing resin paints even in small amounts, so it is extremely superior to conventional fluorine-containing resin paints. Not only can it be supplied at low cost, but it also makes effective use of fluorine raw materials that require a large amount of energy to manufacture, contributing to resource and energy savings.

In this way, adding a small amount of a fluorine-containing block copolymer imparts water and oil repellency, non-adhesiveness, and stain resistance, but this is because the intermolecular cohesive force is small and the surface tension is low. This is thought to be due to the orientation of normally small fluorine-containing polymer portions on the surface of the coating film.

The type of paint to which the fluorine-containing block copolymer used in the heather invention is added is not particularly limited as described above, but may include the resin components constituting the paint and the fluorine-containing block copolymer used in the present invention. It is preferable that the vinyl type monomer and the polymer portion of the vinyl monomer are compatible with each other or are miscible with each other.

By selecting the type of vinyl monomer in the fluorine-containing block copolymer, it is possible to mix it with various commonly used paint resins.

In addition, in cross-linking paints, by selecting a vinyl monomer containing a functional group that participates in the cross-linking reaction, the fluorine-containing block copolymer can be used as a resin for cross-linking paints. Crosslinking and bonding are also possible. For example, by selecting a vinyl monomer containing a hydroxyl group such as 2-hydroxyethyl methacrylate as a component of the polymer portion of the vinyl monomer of a fluorine-containing block copolymer, melamine-curing type When added to paints or isocyanate-curable paints, it can improve performance such as solvent resistance through a crosslinking reaction.

The constituent components of the fluorine-containing resin paint of the Moto invention include pigments such as coloring pigments, extender pigments, and rust-preventing pigments, as well as additives and organic solvents necessary for composing ordinary paints, depending on their use and purpose. It can be blended accordingly.

The polymerization process of the fluorine-containing block copolymer is carried out as follows.

First, in the first step, when a polymeric peroxide or a polyazo compound is polymerized with a fluorine-free vinyl monomer or a fluorine-containing vinyl monomer,
A peroxy bond or an azo bond is introduced into the chain,
A so-called peroxy bond-containing copolymer or azo bond-containing copolymer is obtained. Next, in the second step, a fluorine-containing vinyl monomer or a fluorine-free vinyl monomer is added to these copolymers for polymerization, resulting in a peroxy-bonded gold copolymer or an azo-bonded copolymer. The copolymer is cleaved at the peroxy bond or azo bond it contains, and a block copolymer is efficiently obtained.

At that time, if the peroxy bond-containing copolymer or azo bond-containing copolymer obtained in the first step is a fluorine-free copolymer, in the second step, a fluorine-containing polymer portion is formed. A fluorine-containing vinyl monomer is block copolymerized. In addition, when the copolymer obtained in the first step is a fluorine-containing copolymer, it is necessary to block copolymerize a vinyl monomer that does not contain fluorine in the second step. Polymeric peroxides used in the synthesis of block copolymers include those having the following structures represented by general formulas (I) to (■).

[In the formula, R represents an alkylene group having 1 to 18 carbon atoms, a substituted alkylene group, a cycloalkylene group having 8 to 15 carbon atoms, a substituted cycloalkylene group, a phenylene group, or a substituted phenylene or lene group; is an alkylene group having 2 to 1 carbon atoms or a substituted alkylene group, 8 −+ 0H−OH, OreR,− (wherein, R8 is a hydrogen atom or a methyl group, and R
6 is an alkylene group or substituted alkylene group having 2 to 10 carbon atoms. It also represents 1Q=l~18), or 0(O)I, 8-0C. Further, n=2 to 8o. ] [In the formula, Ro is the same group as Ro in the general formula (1). R8 represents an ethylene group, a phenylene group, or an acetylene group. Further, n=2 to 80. ] [In the formula, R□ is the same group as Ro in the above general formula (I). In addition, ('l=2 to 80) [wherein, R□ is the same group as R□ in the general formula (I) above. Also, n =
It is 2-80. [In the formula, R□ is the general formula (1) above]
It is the same group as R□ inside. Further, n=2 to 80. ] [In the formula, X represents a hydrogen atom, a methyl group, or a chlorine atom.

Further, n=2 to 30. ] ... (■) [In the formula, Ro is the same group as Ro in the general formula (1), and is alk. R2 represents an ethylene group, an acetylene group, or a phenylene group, and R, R6 represents a hydrogen atom or a methyl group. Further, n=2 to 30 and m-1 to 100. ] It is a compound shown by.

The polyazo compound used in the present invention has the following structure represented by the general formula (■).

Rf Rf... (■) [In the formula, Ro represents the same group as R□ in the general formula (I), and R9 represents a methyl group or a cyano group.

i Tam == O~1, N=2~80. Specific examples of the polymeric peroxy V of the general formula (I), which is a compound represented by the formula (I), include (n = 2 to 80 in all formulas). Specific examples of the polymeric peroxide (II) include υa8o1i.

U fl B U tl m (n = 2 to 80 in all formulas).

Specific examples of the polymeric peroxide of the general formula (fit) include (n = 2 to 80 in all formulas).

Specific examples of the polymeric peroxide of the general formula (■) include (n = 2 to 80 in all formulas).

Further, specific examples of the polymeric peroxide of the general formula (■) include (jl=g to 80 in all formulas).

Specific examples of the polymeric peroxide of the general formula (■) include IJH.

(In the formula, m=l~100.1l==2~80.)
and so on.

Further, the 1-lyazo compound of the general formula (■) is specifically: 8B''8 (wherein, 1fi=1 to 100, and n=2 to 80).
and so on.

Furthermore, examples of the fluorine-containing vinyl monomers used in the present invention include those having the following structural formulas represented by general formulas (■) to (XV): 0CtH,=
0R1000R,Rf...(IX) (wherein, Rf is CnF2n, a perfluoroalkyl group represented by 1,
RB is an alkyl group represented by -cm''gm-, -OR,)l-, -OH,0R8H- (wherein R3 is an alkyl group represented by Op Hwp+□, and p is a positive group of 1 to 10). ) R□ represents a hydrogen atom or a methyl group, n is a positive integer of 1 to 16, and m is a positive integer of 1 to 10.)OH,=
lR□000R, (OF,)qOR8--(X) [wherein, R8 is OmH2mC/F14+1 group, or -Cm
HzmC/Fi/H group, R2 is an alkylene group represented by -0pKsp-, -0H, OH, 0-1R0 is a methyl group or a hydrogen atom, m is a positive integer from 0 to 1o,
! is a positive integer from 0 to 16, p is a positive integer from 1 to 10, q
is a positive integer from 1 to 10. ] OH,=0R1000R,(OF,)nH---(X
I) [Wherein, Rs is an alkylene group represented by -Om"sm-, -OR,H-, -OH,0R2H- (wherein, R8 is an alkyl group represented by Op"2p+1, and p is 1 ~10 is a positive integer.) Ro represents a hydrogen atom or a methyl group, n is a positive integer of 1 to 16,
m is a positive integer from 1 to 10. ] [In the formula, Rf is Cn
F! Perfluoroalkyl group represented by n+□, R2
is an alkylene group represented by -CmH2m-, 10R8H-, -OH, (3R8H- (wherein, R8 represents an alkyl group represented by 0 pI (ip+□), and p is a positive integer of 1 to 10. )・R1 is an alkyl group represented by OqHs q+□, R4 is a hydrogen atom or a methyl group, n is a positive integer of 1 to 16,
m is a positive integer of 1 to 10, and q is a positive integer of 1 to 10. ] OH, = onlcooRsNso, Rf---(xm
) [In the formula, Rf is a perfluoroalkyl group represented by CnF□, R8 is an alkylene group represented by -OmH2m-, 10R8H--aH, aR, H- (In the formula, R8 is represented by 0pH2p+1 represents an alkyl group, p is a positive integer of 1 to 10.) R1 is Cp
An alkyl group represented by H2p+1, Ro is a hydrogen atom,
or represents a methyl group, n is a positive integer of 1 to 16, m is a positive integer of 1 to 10, and q is a positive integer of 1 to 10.

] 0) I2= (3R1000R2R8...(XI'/
) [In the middle, R1 is a fluorine atom, 0I (F2 group, 0H2F
group, OF8 group, 0000H2F group, or 0OOOHF
2 groups, R2 is an alkylene group represented by -CmH2I, 1-, -(3R8H--OH, ORH- 1 (wherein, R8 is an alkyl group represented by CpH2p+1, and p is a positive integer of 1 to 10) ), R8 is an alkyl group represented by 0qH33q+1, or 'r
A perfluoroalkyl group represented by F2r+1, or = (aH2)z)I, where m is a positive integer of 1 to 10, q is a positive integer of 0 to 16, r is a positive integer of 1 to 16,
l is a positive integer from 1 to 16. ]0RIR2= (3
R8R,---(XV) [wherein, Ri t R2# R
a t R4 represents a hydrogen atom, a chlorine atom, a fluorine atom, a phenyl group, a substituted phenyl group, or a perfluoroalkyl group represented by CnF2n+1, and at least one of R0 to R1 is a fluorine-containing substituent. Also, n is 1
It is a positive integer of ~6. ] Specifically, the fluorine-containing vinyl monomer of the general formula (IX) is, for example, 0F8(OF2)70H20H2000CH=0H2
0F8 (OF, ), 0H20H20000 (OH8)
= 0H2OF80H2000GH= OH2 etc.

Further, specific examples of the fluorine-containing vinyl monomer of the general formula (X) include 0F80H200I (20H,0OOOH: 0H2H
OF20F200H20H20000H= 0H202
F5(OH20H20)20H20000H=0H2
08F1700H20H20aOO(OH8) = O
H20F8 (OF2), 0OH2CH20000 (O
H8) = OH2, etc.

Further, the fluorine-containing vinyl monomer of the general formula (XI) is specifically, for example, 2H5 "H(OF2)60000G(OH8) = CH3I(
OF, )8 C! H20GOO[(= 0H2H(O
F2), C3H7000CjH=CjHQH(OF2
)60H,0000(CiH8) = 0H20F8(
CF2) 80FHCFQOH200H=aH2, etc.

Further, specific examples of the fluorine-containing vinyl monomer of the general formula (XI[) include 0,F,,0ON(0,H,)OH20000(OH8
”) = 0H202F, 0ON(02H,)OH,0
OOOH = 0H20F8 (CF2), 0ON (OH8
)OH2(OH8)OH20000H=OH.

0H8(OF2)7GON(OH20H20H8)CH
20H,0000(OH8)=CH2, etc.

Further, specific examples of the fluorine-containing vinyl monomer of the general formula (Xlll) include 0F8(OF, ), 802N(OH8)OH20H,
000G(OH8) = CH.

CFB (OF2)7302N(OH8)OH20H
20cOCH= 0H208F□7So, N(O)f8
)(OH,)□. 0OOOH= CH202F, So,
N (cQH,)OH2CtH20(:!00 (OH
3) = 0H208F□7So, N((7H8)((
jH2), 0COCjH= 0H202F5802N(
08H7) aH2an2ococ (OH,) = 0
H2G, F5So2N(02H5)C(02H,)HO
Examples include H2ococH=OH2.

Further, specific examples of the fluorine-containing vinyl monomer of the general formula (XIV) include 0H80000F == OH2, □0COF=OH2 C! 2, 000G(OH,F) = 0H20H,0
000(OHF2) = cH.

C3H70000(OF8) = 0H2on8oco
c (oco (3H2F) = 0H2C,H,0
000(OCOOH2F)=CH2C8F□70COG
(OF8) = 0H208F, 70000 (OH2
CtH20) = OH.

He F 0OOCF=OH.

6 and so on.

Further, specific examples of the fluorine-containing vinyl monomer of the general formula (XV) include CG! ,=CFGl, OFO! =OFO/ ,
0FQ=001. .

001F=OF,, OF,=OF2.0HO1=CF
Gl.

0HF=OC7, OHO/ =cp2.0HF=OCI
F.

0HF=OF,, CHF=CH0t, OH,=O
O! F.

0HF=CtHF, 0H2=CF2.0H2=CF
H.

0F2=0(OF8), t 0F8-OF=O
F, , OF8-C! H=OHF.

(3F, -OH= OH,e O,F7(OH8)O=
Oh,.

0FaOF90F = 0COFB>2 t (CF'
5) 20FOF = OF 0FaOH, = aH()
c, F□.

and so on.

Specific examples of the fluorine-containing vinyl monomers that form the fluorine-containing polymer portion are as shown above, and one or more of these may be used as the main component of the fluorine-containing vinyl monomer. However, fluorine-containing vinyl-type monomers or vinyl-type monomers other than the above-mentioned main components can also be added within a range that can exhibit the characteristics of the fluorine-containing resin coating.

Examples of the vinyl monomer used in the present invention include octyl (meth)acrylate [(meth)acrylated methyl refers to methyl methacrylate or acrylic methyl methacrylate. Same below. ], (meth)acrylic ethyl, (
Lower alkyl (meth)acrylates such as n-Flohil meth)acrylate, isopropyl (meth)acrylate, glycidyl (meth)acrylate; n-butyl (meth)acrylate, isobutyl (meth)acrylate, (
meth)acrylic p,y tert-butyl, (meth)acrylic n-hexyl, (meth)acrylic acid cyclohexyl, (meth)acrylic acid 2-ethylhexyl, (meth)acrylic acid octyl, (meth)acrylic acid lauryl,
Higher alkyl (meth)acrylates such as stearyl (meth)acrylate; lower fatty acid vinyl esters such as vinyl acetate and vinyl propionate; vinyl butyrate, vinyl cabrate, vinyl 2-ethylhexanoate, vinyl laurate, vinyl stearate, etc. higher fatty acid vinyl esters; aromatic vinyl monomers such as styrene, vinyltoluene, and vinylpyrrolidone; (meth)acrylamide,
Amide group-containing vinyl monomers such as N-methylol (meth)acrylamide and N-methoxymethyl (meth)acrylamide; hydroxyethyl (meth)acrylate,
Hydroxyl group-containing vinyl monomers such as hydroxypropyl (meth)acrylate and allyl alcohol; Carboxylic acid group-containing vinyl monomers such as (meth)acrylic acid, itaconic acid, crotonic acid, fumaric acid, and maleic acid; butadiene ;
Vinyl chloride; vinylidene chloride; (meth)acrylonitrile; diptyl fumarate; maleic anhydride; dodecyl anhydride; (meth)″allyl glycidyl ether/I/;
Alkali metal salts, ammonium salts, and organic amine salts of radically polymerizable unsaturated carboxylic acids such as (meth)acrylic acid and crotonic acid; radically polymerizable unsaturated monomers with sulfonic acid groups such as styrene sulfonic acid body,
and their alkali metal salts, ammonium salts, organic amine salts; quaternary ammonium salts derived from (meth)acrylic acid, such as 2-hydroxy-8-methacryloxybu-tetramethyltrimethylammonium salt; (
(Meth)acrylate/I/of an alcohol having 7 tertiary amide groups such as meth)acrylic acid diethylamino ester
These include acid esters and their quaternary ammonium salts. These vinyl type monomers are one or two of them.
More than one species is used as the main component of the vinyl monomer.

Furthermore, in order to improve the compatibility, miscibility, and crosslinking reactivity between the fluorine-containing block copolymer and the coating resin, vinyl monomers other than those mentioned above may be added.

The peroxy bond-containing copolymer or polyazo bond-containing gold copolymer used in the present invention has the above-mentioned general formulas (1) to (■...
) or the general formula (
It can be easily obtained by polymerizing a vinyl type monomer or a fluorine-containing vinyl type monomer using the polyazo compound shown in (2) by ordinary solution polymerization or non-aqueous dispersion polymerization.

In this case, the amount of polymeric peroxide or polyazo compound used is 0.5 to 20 parts by weight per 100 parts by weight of the vinyl monomer or fluorine-containing vinyl monomer, and the polymerization temperature is 60 to 180° C. Polymerization time is 2-10
It takes about an hour. In this case, the polymeric peroxide or polyazo compound used is one or two of them.
A mixture of more than one species can be used.

In addition, the polymerization temperature of block copolymerization reaction is 60 to 140°
The C1 polymerization time is about 8 to 15 hours, and the fluorine-containing block copolymer is obtained as a solution or a non-aqueous dispersion.

The preferred weight ratio of the fluorine-free polymer portion and the fluorine-containing polymer portion in the fluorine-containing block copolymer is 1/]9 to 19/1.

If the fluorine-containing polymer portion is less than 1/19, the characteristics of the fluorine-containing resin paint containing this fluorine-containing block co-coalescence will be reduced, and if it exceeds 19/l, the fluorine-containing polymer portion will be reduced. is too low, the compatibility or miscibility with the coating resin decreases.

(Effects of the Invention) The fluorine-containing resin paint of the present invention can produce various coating films with excellent weather resistance, water and oil repellency, non-stick properties, stain resistance, etc. using the same coating process as conventional solvent-based paints. Since it can be applied to objects to be coated, its utility value is recognized in various fields. In other words, it is possible to apply the coating not only on a line with baking drying or forced drying equipment, but also on-site, where normal temperature drying is required. In addition, the painting method is air spray painting,
Commonly used methods such as airless spray painting, dipping painting, and brush painting may be used, and no special painting method is required. It can also be easily applied as an aerosol type paint using a home appliance.The objects to be coated include not only inorganic materials that can withstand baking drying such as iron, zinc, aluminum, ceramics, concrete, and slate, but also wood, plastics, fibers, It can also be applied to organic materials such as cloth, and it is possible to produce plastic sheets, water-repellent clothing, and tents at a very low cost that are transparent, glossy, and have surface properties such as water-repellent, oil-repellent, and non-adhesive properties. In addition, the fluorine-containing resin paint of the present invention can be applied to fields such as highly weather-resistant paints, heavy anti-corrosion paints, waterproof paints, antifouling paints, non-adhesive paints, anti-icing paints, and anti-paper coatings. The uses are not limited to these.

Next, the present invention will be explained in further detail with reference to production examples, examples, and comparative examples. In addition, parts in the examples are parts by weight, %
is weight %.

(Example) Production Example 1 50 parts of methyl methacrylate and 125 parts of methyl ethyl ketone were charged into a reactor equipped with a thermometer, a stirrer, and a reflux condenser, heated to 70"C while blowing nitrogen gas, and polymerized for 8 hours. The reaction was carried out to obtain a transparent solution of the peroxy bond-containing copolymer.Then, while blowing nitrogen gas,
At 0”C, add 08F□, OH, OH, 0OoC to this solution.
A mixture of 250 parts of H=0H and 30 parts of methyl ethyl ketone was added dropwise over 0.5 hours, and further heated at 70"C for 5 minutes.
Polymerization reaction was carried out for a period of time, solid content 40.2%, viscosity (25°
C) A white polymer dispersion (A) with 2.5 voids was obtained.

Production Example 2 Into the same reactor as Production Example 1, 42 parts of methyl methacrylate, 8 parts of 2-hydroxyethyl methacrylate, 4 parts, and 125 parts of methyl ethyl ketone were charged, heated to 70°C without blowing nitrogen gas, and heated for 8 hours. A polymerization reaction was carried out to obtain a transparent solution of a peroxy bond-containing copolymer. Next, while blowing in nitrogen gas,
A mixture of 08F□70H, 0H20000H=OH, 250 parts, and 15 parts of methyl ethyl ketone was added dropwise to this solution over 0.5 hours, and the polymerization reaction was further carried out at 70°C for 5 hours, resulting in a solid content of 42.6% and a viscosity of (25 °C
) A white polymer dispersion (B) with a and a voids was obtained.

(Examples 1 to 10, Comparative Examples 1 to 6) Using the above dispersions (A) and (B), fluorine-containing resin paints were manufactured with the formulations shown in Table 1, and Examples 1 to 10 were prepared. Obtained. In addition, paints containing no dispersions (A) and (B) were produced with the formulations shown in Table 1, and Comparative Examples 1 to 6 were obtained.

However, titanium dioxide in Table 1 was dispersed in an acrylic resin varnish using a sand mill at 1500 revolutions per minute for 20 minutes. Other raw materials were mixed using a stirrer.

A mild steel plate (JIS G3141 (
Table 2 shows the results of various tests conducted using test plates that were applied to SPGO5B)) by air spray and cured under the curing conditions shown in Table 1.

In all of the comparative examples in Table 2, the contact angle with decane is unmeasurable and the contact angle with water is less than 1000, whereas in the examples, even with decane, the contact angle is 60° or more, and the contact angle with water is 1000 or less. It was observed that a coating film with excellent water and oil repellency was formed. In terms of stain resistance and non-adhesion, Examples 1 to 10 in which the fluorine-containing block copolymer was an essential component showed excellent results. In terms of acid resistance and alkali resistance, although a slight decrease in contact angle was observed in the examples, they maintained higher contact angles than the comparative examples in both water and decane.

As examples, lacquer type (Examples 1 to 2), isocyanate curable type (Examples 8 to 8), and melamine curable type (Examples 9 to 1o) are shown, but in all types, fluorine-containing It was confirmed that a coating film having characteristics as a resin coating composition was formed.

(Examples 11 to 80, Specifications 7 to 12) Fluorine-containing resin paints obtained by adding a fluorine-containing block copolymer dispersion to a commercially available paint were manufactured as follows.

That is, a fluorine-containing block copolymer dispersion 0-G having the composition shown in Table 3 was obtained by the same manufacturing method as in Manufacturing Example 1.

The obtained fluorine-containing block copolymer dispersions O to G were added to commercially available paints and mixed in a stirrer to obtain the fluorine-containing resin paints as Examples 11 to 80 in Tables 4 and 5. Comparative Examples 7 to 12 were commercially available paints containing no fluorine-containing block copolymer dispersion.

Next, test plates were prepared in the same manner as in Examples 1 to 10, and various tests were conducted. The results are shown in Tables 4 and 5.

The test method is as follows.

Appearance of paint film: JIS-K-54006, 160 degrees Specular gloss: JIS-K-54006, ? Pencil hit test: JIS-K + 5400 6, 14 Adhesiveness: Cut a 10 cm long piece of cellophane tape (manufactured by Chiban Co., Ltd.) with a width of 18 mm on the test plate, and approximately 5 crn from one side.
Using a spring meter, read the force required to place the part in close contact with the test plate and peel it off in a direction perpendicular to the test plate at a speed of 2 m/s. Data is i! Average value of 5 Tll constants.

Contact angle: Measure by dropping one drop of the test solution in the air onto a horizontal test plate and observing it with a microscope. Data are average values of two measurements.

Acid resistance = After soaking in 10% H2SO1 aqueous solution for 240 hours,
Wash with water, dry at room temperature for 1 hour, and measure the contact angle.

Alkali resistance: After immersing in 5% Mail aqueous solution for 240 hours, washing with water, drying at room temperature for 1 hour, and measuring the contact angle.

Stain resistance: Draw a line with red marker (lipstick) and apply 2
After 4 hours, the degree of contamination on the surface of the coating film after wiping with absorbent cotton soaked in xylene is determined.

Weather resistance: Sunshine type accelerated weather resistance test u L 15
00 hours 4F: Conducted a progressive test and measured the gloss retention rate (60 degree specular gloss after 1500 hours accelerated test and 60 degree specular gloss before V test).

As is clear from Tables 4 and 5, the high solid lacquer paint (4), polyester polyurethane resin coating (5), polyvinyl chloride resin paint (6), and polyamide hardening shown in Comparative Examples 7 to 11 Type epoxy resin paint (7),
Non-adhesive properties, water polishing properties, and oil repellency, which were not observed in melamine-curing alkyd resin-coated bonds 8),
In Examples 11 to 27, stain resistance,
It was also observed that the weather resistance was significantly improved.

In addition, Comparative Example 12 is a fluorine-containing resin paint (9) mainly composed of a copolymer of a fluoroolefin and a vinyl ether such as hyroxyalkyl vinyl ether.
High stickiness and no oil repellency.

On the other hand, Examples 28 to 30 for REM had a small degree of tackiness;
It can be seen that it exhibits good oil repellency, r:t3, and other excellent properties.

Patent issuer: Nippon Oil M Co., Ltd. 666-

Claims (1)

[Scope of Claims] t A polymeric peroxide or a polyazo compound is copolymerized with a fluorine-containing vinyl monomer or a fluorine-free vinyl monomer forming the fluorine-containing polymer portion to form a peroxy bond. Alternatively, the first step is to obtain an azo bond-containing copolymer, and then a fluorine-free vinyl monomer or fluorine-containing polymer portion is formed with the peroxy bond- or azo bond-containing copolymer obtained in the first step. The second step of copolymerizing the fluorine-containing vinyl monomer with the fluorine-containing vinyl monomer. A fluorine-containing resin paint containing a fluorine-containing block copolymer.