JPH04146945A - Polymer dispersion in organic solvent - Google Patents

Abstract

PURPOSE:To improve weather (light) resistance, oil repellency, stain resistance, and gloss by compounding a specific hydrocarbon solvent, a fluorocopolymer sol. in the solvent, and a (co)polymer insol. in the solvent. CONSTITUTION:A fluoroolefin and a vinyl ether are copolymerized in a hydrocarbon solvent having an anilin point of 40-70 deg.C and a flash point of 21 deg.C or higher (e.g. mineral spirit) to give a fluorocopolymer sol. in the solvent and having a fluorine content of 10-60wt.% and a wt.-average mol.wt. of 5000-250000. 65-100wt.% monomer of the formula (wherein R<1> is H or CH3; X is COOR<2>, CN, OCOR<3>, or 5-9C aryl; R<2> is a 1-15C linear or branched alkyl, a 5-9C cycloalkyl, or a 7-12C aralkyl group of which a part of H atoms may be substd. by F; and R<3> is 1-12C linear or branched alkyl) and 35-0wt.% monomer having a radical-polymerizable unsatd. group and at least one functional group are (co)polymerized in the presence of the fluorocopolymer to give an org. solvent- based polymer dispersion contg. 20-70wt.% resin component comprising the fluorocopolymer and a (co)polymer insol. in the solvent and having a wt.-average mol.wt. of 10000 or higher.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention has low air pollution, environmental hygiene problems, and low risk of fire, has high weather resistance even at relatively low temperatures such as 0°C, and has water repellency. It can form a film with excellent properties such as oil repellency, stain resistance, non-adhesiveness, and high gloss.It is also useful when used as a top coat or other paint that requires nine coats, or for repainting and repainting. Regarding polymer organic solvent dispersions that do not dissolve or swell base coatings or failed coatings even when used as paints, in detail, hydrocarbon organic solvents having a high aniline point and a high flash point,
A specific fluorine-containing copolymer soluble in the organic solvent, and
The present invention relates to a polymer organic solvent dispersion characterized in that it is a (co)polymer of a specific monomer and is insoluble in the organic solvent.

[Conventional technology]

Conventionally, organic solvent solutions of fluorine-containing copolymers containing fluoroolefin monomers and vinyl ether monomers as copolymerization components have been transparent, have high gloss, and have high weather resistance, especially when used as paints. (light) property, water repellency/oil repellency,
It is known to provide coating films with excellent properties such as stain resistance and non-stick properties. However, such organic solvent-soluble fluorine-containing copolymers tend to have insufficient solvent resistance when formed into a coating film, and may also lack thermal and mechanical properties. Another problem is that such fluorine-containing copolymers are significantly more expensive than acrylic resins that are generally used for paints.

Several proposals are known to solve the above problems, for example, in Japanese Patent Application Laid-Open No. 62-25103.

[In the presence of a dispersion stabilizer consisting of an organic solvent-soluble fluorine-containing polymer having a weight average molecular weight s, ooo~120.000 and a fluorine atom content of 1~60% by weight, the monomer is soluble but not formed. Discloses a method for producing a stable dispersion of a vinyl polymer insoluble in an organic liquid by dispersing and polymerizing at least one radically polymerizable monomer in an organic liquid in which the polymer is insoluble. ing.

However, in the above proposed embodiment, a fluorine-containing polymer (non-volatile content of 50 or 60% by weight) dissolved in an organic solvent mainly composed of an aromatic solvent such as xylene is used as a dispersion stabilizer, and heptane is mainly used as a dispersion stabilizer. As a component, acetic acid n-
In a solvent containing an ester-based polar solvent such as butyl,
A dispersion polymer liquid is synthesized by copolymerizing monomers such as (meth)acrylic acid ester, styrene, acrylonitrile, etc., but the resulting dispersion liquid contains a considerable amount of aromatic solvent and some polarity. Contains a solvent, so when used as a paint that requires multiple coats as described above, or as a paint for repainting or repair painting, there is a risk of dissolving or swelling the base coat. Moreover, it is difficult to say that it is sufficient in terms of air pollution and environmental hygiene, and also has a low flash point, so there are problems with fire safety during storage and use. Furthermore, the resulting coating film also lacks transparency and gloss.

[Problem that the invention seeks to solve]

The present inventors solved the above problems and developed a fluoropolymer that has high weather resistance (light) resistance, water repellency, oil repellency, stain resistance, non-adhesiveness, and high gloss when made into a coating film. It retains as much of the excellent properties as possible, has excellent solvent resistance, thermal and mechanical properties, and dissolves and swells the base coating even when used as a top coat or other paint that requires repeated coating. In order to obtain a polymer organic solvent dispersion that has excellent performance such as no water pollution, has less air pollution and environmental health problems, is fire safety safe, and is relatively inexpensive. As a result of research, for example, in the presence of a specific fluorine-containing copolymer solution that does not contain a low aniline point solvent and a low flash point solvent, in a hydrocarbon organic solvent having a specific aniline point and flash point, ( The inventors discovered that a polymer organic solvent dispersion obtained by (co)polymerizing specific monomers such as meth)acrylic acid ester and styrene could solve all of these problems, and thus completed the present invention.

[Means for solving problems]

The present invention includes the following (A) to (C).

(A) a hydrocarbon organic solvent having an aniline point of 40 to 70°C and a flash point of 21°C or higher; (B) a fluoroolefin monomer and a vinyl ether monomer as copolymerization components; A) a fluorine-containing copolymer soluble in A);

(C) (a) and (b) below [However, (a) and (
The total of b) is 100% by weight.

(a) 65 to 100% by weight of a monomer represented by the following general formula, and (b) 1
0 to 35% by weight of a monomer having at least one functional group in addition to these radically polymerizable unsaturated groups, and is insoluble in the solvent (A).
The object of the present invention is to provide a dispersion of a polymer in an organic solvent, characterized by comprising a co)polymer.

The present invention will be explained in detail below.

The hydrocarbon organic solvent (A) used in the polymer organic solvent dispersion of the present invention has an aniline point of 40 to 70°C and a bow defect of 2.
1°C or higher, preferably 35°C or higher, particularly preferably 40°C
The temperature must be above ℃. If the aniline point is too low (less than 40°C), air pollution and environmental health problems may occur.Furthermore, it may be used as a top coat or other paint that requires multiple coats, or as a paint for repainting or repair. If the temperature is too high, exceeding 70°C, the solubility of the fluorine-containing copolymer will decrease, resulting in a polymer dispersion. However, if the flash point is too low (less than 21°C), it may cause problems in terms of fire safety, which is undesirable. As the hydrogen-based organic solvent (A>, JIS industrial gasoline No. 4 and No. 5 such as 5 mineral spirits can be suitably used. For example, Mitsubishi mineral turpentine, diamond solvent [all of the above Mitsubishi Oil
], Pegasol AN-45, Pegasol 3040 [
Made by Mopil Oil ■], Exxon Naphtha No. 5,
It is coated with trade names such as Exxon Naphtha No. 6 and Exxon Naphtha No. 6 [manufactured by Exxon Chemical Co., Ltd.]. In addition, a mixed solvent obtained by mixing two or more of various petroleum hydrocarbon solvents can also be used as long as the flash point and aniline point conditions described above are satisfied.

In addition, in the present invention, a part of the hydrocarbon-based organic solvent (A) may be replaced with an organic solvent other than the hydrocarbon-based organic solvent (A) within a range that does not impair the excellent effects of the present invention. can.

Examples of such organic solvents for substitution include alcoholic solvents such as n-butyl alcohol, 1-butyl alcohol, n-hexyl alcohol, n-octyl alcohol, l-octyl alcohol, and 2-ethylhexyl alcohol. , the amount of these replacement solvents used is
Generally, the amount is preferably 30% by volume or less based on the total of the hydrocarbon organic solvent (A) and the replacement solvent.

The polymer organic solvent dispersion of the present invention contains a fluoroolefin monomer and a vinyl ether monomer as copolymerization components, and the fluorine-containing copolymer (B) is soluble in the organic solvent (A). It includes.

Examples of the above fluoroolefin monomers include:
Fluoroolefins of about C2 to C4 such as tetrafluoroethylene, chlorotrifluoroethylene, vinyl fluoride, vinylidene fluoride, and hexafluoropropylene are preferably used.

The amount of the fluoroolefin used is preferably selected so that the amount of fluorine atoms in the fluorine-containing copolymer (B) is generally about 10 to 60% by weight, preferably about 20 to 40% by weight. If the amount of fluoroolefin used is at least the lower limit, the physical properties of the film from the resulting polymer organic solvent dispersion will be high weather resistance (light) resistance, water repellency, oil repellency, stain resistance,
It is preferable because it maintains the excellent properties of a fluoropolymer such as non-adhesiveness and high gloss. On the other hand, if it is below the upper limit, the solubility in the hydrocarbon organic solvent (A) may decrease. It is preferable because there is no.

Examples of the vinyl ether monomer include methyl vinyl ether and ethyl vinyl ether.

Alkyl vinyl ethers such as 1-propyl vinyl ether, n-butyl vinyl ether, 1-butyl vinyl ether, n-amyl vinyl ether, i-amyl vinyl ether, 2-ethylhexyl vinyl ether, octadecyl vinyl ether; for example, cyclohexyl vinyl ether, 2-methylcyclohexyl vinyl ether,
Examples include cycloalkyl vinyl ethers such as 3,3.5-)limethylcyclohexyl vinyl ether; hydroxyalkyl vinyl ethers such as hydroxybutyl vinyl ether; and epoxy group-containing alkyl vinyl ethers such as glycidyl vinyl ether.

In addition to the fluoroolefin monomer and vinyl ether monomer, the fluorine-containing copolymer (B) may optionally contain olefins such as ethylene, propylene, and l-butylene; for example, vinyl chloride. , haloolefins other than fluoroolefins such as vinylidene chloride; for example, vinyl esters such as vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl versatate; for example, acrylic acid, methacrylic acid, maleic acid, crotonic acid, a, β-unsaturated mono- or di-carboxylic acids such as itaconic acid; for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, l-butyl acrylate, n-hexyl acrylate, n -Octyl acrylate C1-C1a straight chain or branched alkyl esters of acrylic acid such as 1-octyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate; (meth) such as cyclohexyl acrylate, cyclohexyl methacrylate, etc. 06-C8 cycloalkyl esters of acrylic acid; for example, C of (meth)acrylic acid such as benzyl acrylate and benzyl methacrylate
7-C1e Aralkyl esters 1 For example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, 1-propyl methacrylate, n-butyl methacrylate, 1-butyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, l
- C of methacrylic acid such as octyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, etc.
1-C4 linear or branched alkyl esters; for example, 02-C4 hydroxyalkyl of (meth)acrylic acid such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, etc. Esters; for example, N,N-dimethylaminoethyl acrylate), N,N-dimethylaminoethyl methacrylate,
Aminoalkyl esters of (meth)acrylic acid such as NN-diethylaminoethyl acrylate and N,N-diethylaminoethyl methacrylate; for example, styrene,
Aromatic vinyl compounds such as a-methylstyrene and vinyltoluene; For example, vinyl cyanide compounds such as acrylonitrile and methacrylaterile; For example, n-butyl (meth)allyl ether, 2-hydroxyethyl (meth)allyl ether, glycidyl ( Examples of copolymerization components include (meth)allyl ethers such as meth)allyl ether; (meth)allyl esters such as (meth)allyl caproate; and the like.

The fluorine-containing copolymer (B) used in the present invention is a combination of the fluoroolefin monomer, the vinyl ether monomer, and the monomer used as necessary with the hydrocarbon organic copolymer used in the present invention. It is produced by copolymerization using a commonly used radical polymerization initiator in an organic solvent similar to solvent (A). Examples of such radical polymerization initiators include azo polymerization initiators; peroxide polymerization initiators that can be used in the (co)polymerization of component (C) of the present invention, which will be described later.

In addition, as the fluorine-containing copolymer (B), in order to improve the solubility in the hydrocarbon organic solvent (A), if necessary, a macromonomer copolymer and/or an acrylic (copolymer) may be added. ) It is also possible to use polymers, polyesters, etc. that have been modified by grafting or blocking.

The weight average molecular weight (hereinafter sometimes abbreviated as Mw) measured by gel permeation chromatography (hereinafter sometimes abbreviated as GPC) of the fluorine-containing copolymer (B) used in the present invention is generally s, ooo~250.0
00, preferably about 10.000 to 200.000.If the molecular weight is at least the lower limit, it acts as a good dispersion of the (co)polymer of component (C) of the present invention, This is preferable because the resulting dispersion has good stability.On the other hand, if the dispersion is obtained below the upper limit, the fluorine-containing copolymer (
This is preferred because the solubility of B) in the hydrocarbon organic solvent (A) does not decrease and the viscosity of the resulting dispersion does not become too high.

Such a fluorine-containing copolymer CB) of the present invention includes:
For example, it is possible to use an appropriate selection from the Lumiflon series, such as Lumiflon LFI100J [trade name; manufactured by Asahi Glass ■], and organic solvents such as those manufactured by Daikin Industries, Central Glass, and Pennwalt can also be used. It can also be selected from soluble fluorine-containing copolymers.

The polymer organic solvent dispersion of the present invention contains the following (a) and (b) [ However, (a
) and (b), the total of which is 100% by weight], which is substantially insoluble in the solvent (A).
It contains a polymer (C).

(a) 65 to 100% by weight of a monomer represented by the following general formula ■, and (b) 1
0 to 35% by weight of a monomer having at least one functional group in addition to these radically polymerizable unsaturated groups;
HaH Mataha CH3,xHaC00R2,CN,0COR'
Maf, -HaC.

~C9 aryl group, R? is a linear or branched alkyl group of C1 to C11l, in which some of the hydrogen atoms may be substituted with fluorine atoms, a cycloalkyl group of 06 to C8, or an aralkyl group of 07 to CI2, R' is C, to C
12 straight chain or branched alkyl groups.

As the monomer component (a), in the general formula (1), X is COOR2, and R2 is a C1 to C11l straight-chain or branched alkyl in which some of the hydrogen atoms may be substituted with fluorine atoms. A monomer which is a cycloalkyl group of C, to C1I or an aralkyl group of 07 to C12, that is, a (meth)acrylic acid ester monomer, can be used. Examples of R2 in this case include methyl group, ethyl group, n-propyl group, n-butyl group, l-butyl group,
n-hexyl group, n-octyl group, 1-octyl group, 2
-ethylhexyl group, l-nonyl group, n-dodecyl group,
Alkyl groups such as stearyl group, cyclohexyl group, methylcyclohexyl group, benzyl group, cycloalkyl group or aralkyl group can be avoided, and specific examples thereof include methyl acrylate, ethyl acrylate, n-propyl acrylate, etc. 3n-butyl acrylate, l-butyl acrylate, dobutyl acrylate, n
-hexyl acrylate n-octyl acrylate, l
- Acrylic acid ester monomers such as octyl acrylate, 2-ethylhexyl acrylate, l-nonyl acrylate, stearyl acrylate, cyclohexyl acrylate, benzyl acrylate; for example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, l- -Butyl methacrylate, 7-butyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, 1-octyl methacrylate, 2-ethylhexyl methacrylate, l-nonyl methacrylate, n-dodecyl methacrylate, l-dodecyl methacrylate, stearyl methacrylate, cyclo Examples include methacrylic acid ester monomers such as hexyl methacrylate and benzyl methacrylate. Examples of R2 include a C1-C11l linear or branched alkyl group in which a portion of hydrogen atoms are substituted with fluorine atoms, such as a (per)fluoroalkyl group, or a 06-C, cycloalkyl group. Examples of such monomers include "Viscoat 8FJ, rViscoat 8FMJ"
, rViscoat 3FMJ [manufactured by Osaka Organic Chemical Industry Co., Ltd.] and other fluorine-containing (meth)acrylic acid ester monomers can also be used.

In addition, as the monomer component (a), according to the general formula (2),
Monomers that are - group can be used. Examples of such monomers include vinyl cyanide monomers in which X is CN, such as acrylonitrile, methacrylateryl;
COR-r! R'' is a saturated fatty acid vinyl ester monomer which is a linear or branched alkyl group of C1 to Ctp, such as vinyl acetate 11, vinyl propionate, vinyl versatate, etc.; X is an aryl group of 06 to C, Aromatic vinyl monomers such as styrene, a-methylstyrene, vinyltoluene, ethylvinylbenzene, etc. can also be suitably used.

The amount of such monomer component (a) to be used is the same as that of the monomer (
65-10 based on 100% by weight of a) and (b)
0% by weight, preferably 75-99.5% by weight. If the amount of monomer component (a) used is too small, below the lower limit, the transparency of the resulting film from the polymer organic solvent dispersion and the film formability at low temperatures may decrease. Not preferable, but also preferable because a stable dispersion can be obtained by setting the amount to 99.5% by weight or less, and when this is used as a coating material, adhesion to various surfaces to be coated tends to be improved. .

In the present invention, the (co)polymer (C) that is insoluble in the hydrocarbon organic solvent (A) includes, in addition to the monomer (a), if necessary, one radically polymerizable unsaturated Monomers (b) which have at least one functional group in addition to the groups can be copolymerized.

Such a monomer component (b) includes a functional group such as a carboxyl group, an amide group or a substituted amide group, an amino group or a substituted amino group, a hydroxyl group, an epoxy group, a mercapto group, or a radically polymerizable unsaturated group. Examples include monomers having groups, etc., and in the present invention, one or more monomers can be appropriately selected and used from these.

Specific examples of these monomers include acrylic acid,
Carboxyl group-containing monomers such as methacrylic acid, itaconic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, citraconic acid (preferably acrylic acid, methacrylic acid); for example, acrylamide, methacrylamide, N, N - an amide group- or substituted amide group-containing monomer such as dimethylacrylamide, N-methylacrylamide, N-n-butoxymethylacrylamide (preferably acrylamide, methacrylamide); for example, 2
-Hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, allyl alcohol, methallyl alcohol (preferably 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate) ,2
-hydroxypropyl methacrylate); for example, aminoethyl acrylate, N, N
Dimethylaminoethyl acrylate, N,N-diethylaminoethyl acrylate, N,N-dimethylaminoethyl methacrylate, N,N-diethylaminoethyl methacrylate, (preferably N,N-dimethylaminoethyl methacrylate, N,N-diethylaminoethyl methacrylate) Monomers containing amino groups or substituted amine groups such as Mercapto group-containing monomers: For example, (poly)ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, allyl(meth)acrylate, triallyl cyanurate, tri Examples include monomers having two or more radically polymerizable unsaturated groups in one molecule, such as allyl isocyanurate, diallyl phthalate, and divinylbenzene. Among these monomers (b), it is preferable to use carboxy group-containing monomers, amide group-containing monomers, hydroxyl group-containing monomers, and substituted amino group-containing monomers.

The amount of the monomer (b) used is the amount of the monomer (a) and (
For example, from 0 to 35% by weight, preferably from 0.5 to 25% by weight, based on the total 100% by weight of b). If the amount of the monomer component (a) exceeds the upper limit, the resulting film from the polymer organic solvent dispersion will have insufficient transparency and film formability at low temperatures. Moreover, by copolymerizing 0.5% by weight or more, a stable dispersion can be obtained, and when this is used as a coating material, the adhesion to various surfaces to be coated is improved. Furthermore, crosslinking properties are improved when a crosslinking agent such as an isocyanate compound is used, which is preferable.

The Mw of the (co)polymer (C) in the present invention is preferably 10,000 or more, particularly 50,000 or more. If the Mw of the copolymer (C) is not less than the lower limit, the obtained When a polymer organic solvent dispersion is used as a paint, weather resistance (light) of the paint film
This is preferable because various physical properties such as water repellency, water repellency, oil repellency, and stain resistance do not deteriorate.

The amount of the fluorine-containing copolymer CB) used in the polymer organic solvent dispersion of the present invention is the same as that of the fluorine-containing copolymer (B) and the (
The amount of the fluorine-containing copolymer (B) is 20 to 8% by weight of the total 100% by weight of the resin component consisting of the co)polymer (C).
The amount of the fluorine-containing copolymer (B) used is preferably 0% by weight, more preferably 30 to 70% by weight, and particularly preferably 40 to 60% by weight. If the dispersion is present, it is preferable because the dispersion can be used to create a paint that is relatively inexpensive and has excellent workability and coating properties.On the other hand, if the dispersion is greater than or equal to the lower limit, the stability of the dispersion is It also has excellent weather resistance (light) when used as a paint.
It is preferable because it does not impair the excellent physical properties of the coating film, such as water repellency, water repellency, oil repellency, stain resistance, and tack resistance.

The method for producing the polymer organic solvent dispersion of the present invention includes dispersing the monomers (a) and ( b) using an appropriate polymerization initiator and a chain transfer agent used as necessary in a nitrogen stream or at the reflux temperature of an organic solvent,
It is preferable to heat the reaction for several hours while stirring. In this case, at least a portion of the organic solvent, monomer, polymerization initiator and/or chain transfer agent may be added sequentially.

In one polymerization, if necessary, in addition to the above-mentioned hydrocarbon-based organic solvent (A), the solvent (A) and an appropriate organic solvent with a lower boiling point are used in combination, and after the completion of the polymerization, the combined solvent Methods such as distilling off can also be adopted.

Examples of organic solvents that can be used in combination include aromatic hydrocarbons such as benzene, toluene, and xylene;
Aliphatic or alicyclic hydrocarbons such as hexane and n-hebutane; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; alcohols such as methyl alcohol, ethyl alcohol and n-propyl alcohol; etc. can be discouraged. These organic solvents can be used alone or in a mixture of two or more.

Examples of the polymerization initiator include penzoyl peroxide, lauroyl peroxide, caproyl peroxide, di-l-propyl peroxydicarbonate, di-2
-Organic peroxides such as ethylhexyl peroxydicarbonate, t-butyl peroxybivalate, etc.2, e.g.
, 2°-azobis-1-butyronitrile, 2.2-azobis-2,4-dimethylvaleronitrile, 2.2-azobis-4-methoxy-24-dimethylvaleronitrile, etc. alone or in combination. can be used. The amount of the polymerization initiator used is the total amount of monomers 1
Generally, about 0.01 to 1.0 parts by weight, preferably about 0.02 to 05 parts by weight are used.

Further, as the chain transfer agent, for example, cyanoacetic acid;
Cyanoacetic acid alkyl esters of alkyl groups C1 to C8; bromoacetic acid; bromoacetic acid esters of alkyl groups C1 to C, anthracene, phenanthrenefluorene, 9
- Aromatic compounds such as phenylfluorene: p-nitroaniline, nitrobenzene, dinitrobenzene, p-
Aromatic nitro compounds such as nitrobenzoic M, p-nitrophenol, p-nitrotoluene: benzoquinone, 2
．． 3.5. Benzoquinone derivatives such as 6-tetramethyl-p-benzoquinone; poran derivatives such as tributylborane; carbon tetrabromide, carbon tetrachloride, 1,1,2,2-tetrabromoethane, tribromoethylene, Trichlorethylene, promotrichloromethane, tribromomethane, 3-
Halogenated hydrocarbons such as chloro-1-flopen; aldehydes such as chloral and furaldehyde; C1 to C1,
Alkyl mercaptans: aromatic mercaptans such as thiophenol and toluene mercaptan; mercaptoacetic acid; C1-C1° alkyl esters of mercaptoacetic acid; hydroxylalkyl mercaptans of C1-CI2;
Examples include terpenes such as pinene and terpirucin.

When the above-mentioned chain transfer agent is used, it is preferably used in an amount of about 0.00 to 3.0 parts by weight per 100 parts by weight of the total amount of monomers.

The polymerization temperature is generally about 30 to 180°C, preferably about 60 to 150°C.

The polymer organic solvent dispersion of the present invention thus obtained usually contains a resin component consisting of the component (B) and the component (C) in an amount of generally 20 to 70% by weight, preferably 40 to 60% by weight.
Contains a viscosity of approximately 100-20.0OOcps
(using a BH-type rotational viscometer, 25°C, IORPM, the same applies hereinafter), and the flash point of the dispersion is preferably 21°C or higher, more preferably 35°C or higher, particularly preferably 40°C or higher. It is good to be.

The polymer organic solvent dispersion of the present invention can be used as is, or
If necessary, organic or inorganic colorants such as titanium oxide, carbon blank, and phthalocyanine blue may be added to the organic solvent dispersion; for example, inorganic substances such as calcium carbonate, silica, clay, talc, aluminum hydroxide, glass powder, etc. Fillers; anti-aging agents; preservatives and anti-mold agents; ultraviolet absorbers; antistatic agents; and the like can be added and mixed to be used as various paints.

In addition, the polymer organic solvent dispersion of the present invention may be crosslinked by blending a crosslinking agent such as an epoxy resin, an amino resin, an isocyanate compound, or a metal chelate, if desired, within a usage range that does not impede the excellent effects of the present invention. It can also be used as

The coating material containing the polymer organic solvent dispersion of the present invention can be diluted with an appropriate organic solvent as necessary and applied to various substrates by various methods such as impregnation, spraying, coating, and printing. be able to.

Substrates to which the paint containing the polymer organic solvent dispersion of the present invention can be suitably applied include, for example, metal plates such as aluminum plates, zinc plates, iron plates, and stainless steel plates; for example, vinyl chloride resins, chlorinated Molded products of thermoplastic synthetic resins such as vinylidene resin, vinyl acetate resin, styrene resin, acrylic resin, polyester resin, polycarbonate resin, ABS resin, AS resin, urethane resin, SBR; for example, phenol resin, melamine resin, urea resin, Examples include base materials such as molded products of thermosetting synthetic resins such as epoxy resins, unsaturated polyester resins, and polyimide resins; for example, inorganic materials such as glass, ceramics, slate plates, rocks, silicon plates, and ores; can.

〔Example〕

The present invention will be explained in more detail below by giving Examples and Comparative Examples. In addition, various tests in the present examples and comparative examples are as follows.

(1) Flash Point Measure the flash point of the polymer organic solvent dispersion according to ASTM D3278.

(2) Film transparency A polymer organic solvent dispersion was applied onto a glass plate with a thickness of about 2 mm using a doctor blade, and dried at 20°C for 3 days to create a film with a thickness of about 100μ.
C-Hm DP [The turbidity of the film is measured using a model manufactured by Tokyo Denshoku ■.

(3) Preparation of white paint A white paint with a PWo of 40% is prepared by blending TCP~30 [rutile type titanium oxide di-Tohoku Chemical Co., Ltd.] into the polymer organic solvent dispersion.

(4) Sagging property of paint The white paint prepared in the previous section (3) has a viscosity of approximately 1,000C.
ps, after diluting with mineral turpentine if necessary, onto a glass plate approximately 2 mm thick using an 8 mil doctor blade, and then holding the glass plate vertically. Observe the state of paint sagging and evaluate it according to the following criteria.

◎...No sagging at all, and no bulging at the bottom edge of the paint film.

○... The sagging is 0mm, but the lower edge of the coating film is slightly swollen.

■...Sag 1-2 mm.

△...Sagging 2-5 mm.

×・・・・Sagging 10mm or more.

(5) Approximately 150 g/m of medium-oil alkyd resin-based rust-preventing paint was applied to the lifting zinc phosphate treated steel plate. It was applied with a brush so that
Apply the white paint prepared in section 3) using a brush to approximately 150 g/m2, dry at 20°C and 70% RH for 24 hours, observe the condition, and evaluate according to the following criteria. .

○...No shrinkage, wrinkles, etc.

△　・Partial shrinkage and wrinkles appear.

×・Shrinking and wrinkles appeared on the entire surface.

(6) On the glossy flexible board, use a brush to apply the white paint prepared in the previous item (3) twice at a rate of about 150 g/m2,
Dry at 20°C, 70% RH or 0°C for 7 days each, and use a variable angle gloss meter TC-1080 [manufactured by Tokyo Denshoku ■] for 6 days.
Measure 0° gloss.

(7) Weather resistance The painted slate board prepared by drying at 20°C and 70% RH for 7 days in the previous section (6) was rated according to JIS B 7753.
5. of JIS A 1415. 1.0 according to
After conducting the test for 00 hours, perform the 60 hour test in the same manner as in the previous section (6).
゜Measure the gloss and determine the gloss retention rate.

Example 1 A fluorine-containing copolymer (B), Lumiflon PL-1100 [trade name: manufactured by Asahi Glass Company:
Fluorine-containing copolymer with Mw 180,000 and fluorine atom content 27% by weight; flash point 41°C, aniline point 44°C
hydrocarbon-based organic solvent solution, solids approximately 40% by weight] 25
0 parts by weight and 130 parts by weight of mineral tapene (flash point 41°C or higher, aniline point 44°C) as a hydrocarbon-based organic solvent were charged, the temperature was raised to 100°C, and while maintaining the same temperature, ethyl acrylate (EA ) 34.4% by weight, 45% by weight of methyl methacrylate (MA), 20% by weight of n-butyl methacrylate (BMA) and 6% by weight of methacrylic acid (MAAlo) 15
0 parts by weight, 30 parts by weight of mineral turpentine, and 3 parts by weight of t-butylperoxy-2-ethylhexanoate as a polymerization initiator were sequentially added over 2 hours with a flow force t] L, and further aged for 2 hours at the same temperature. did.

The resulting organic solvent dispersion of the copolymer was white with a solid content of 44.
It was a stable dispersion with a concentration of 5% by weight, a viscosity of 5.500 cps, and an average diameter of dispersed particles (according to the Horiba centrifugal sedimentation method) of about 0.31 μm, and no sedimentation was observed even after it was left at room temperature for 3 months. Moreover, the flash point was 41°C.

Using this copolymer organic solvent dispersion, a white paint was prepared according to the test method described above, and various paint tests were conducted. The test results are shown in Table 1.

Examples 2 to 6 An organic solvent dispersion of a copolymer was produced in the same manner as in Example 1 except that the composition of the monomer mixture was changed. Table 1 shows the composition of the monomer mixture, the solid content, viscosity, average particle size, and flash point of the resulting dispersion, as well as the results of various paint tests.

Example 7.8 An organic solvent dispersion of a copolymer was produced in the same manner as in Example 1, except that the amount of Lumiflon LF1100 and the amount of mineral turpentine used were changed.

The composition of the monomer mixture, the solid content of the resulting dispersion, the viscosity,
The average particle size, flash point, and various paint test results are shown in Table 1.

Comparative Example Using the same equipment as in Example 1, Lumiflon P was added to this equipment.
L-200 [Product name: Asahi Glass ■Made by: Mw 50000,
A fluorine-containing copolymer with a fluorine atom content of 30% by weight: 162 parts by weight of a xylene solution, approximately 60% by weight of solids and 153 parts by weight of heptane were charged, and while heating under reflux, M
MA 40% by weight, acrylonitrile (AN) 30% by weight
, 150 parts by weight of a monomer mixture consisting of 15% by weight of 5t and 15% by weight of 2-hydroxyethyl methacrylate (2HEMA), and 2.25 parts by weight of t-butylperoxy-2-ethylhexanoate as a polymerization initiator. The mixture was added sequentially over a period of 3 hours, and after further aging at the same temperature for 2 hours, 39 parts by weight of butyl acetate was post-added.

The obtained organic solvent dispersion of the copolymer was white and had a solid content of 47.
．． It was a stable dispersion liquid of 3% by weight, a viscosity of 95 cps, and an average particle size of dispersed particles (according to the Horiba centrifugal sedimentation method) of approximately 0.19 μm, and no sedimentation was observed even after being left at room temperature for 3 months. Moreover, the flash point was 2°C.

Using this copolymer organic solvent dispersion, a white paint was prepared according to the test method described above, and various paint tests were conducted. The test results are shown in Table 1.

Claims (1)

[Claims] (1) The following (A) to (C), (A) a hydrocarbon organic solvent having an aniline point of 40 to 70°C and a flash point of 21°C or higher, (B) a fluoroolefin monomer and a vinyl ether monomer as a copolymerization component, and the above solvent (A
), and (C) the following (a) and (b) [however, (a) and (b)
100% by weight], (a) the following general formula {1
｝▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
......{1} [However, R^1 is H or CH_
3.X is COOR^2, CN, OCOR^3 or C_
It is an aryl group of 6 to C_8, and R^2 is a linear or branched alkyl group of C_1 to C_1_0 in which some of the hydrogen atoms may be substituted with fluorine atoms, a cycloalkyl group of C_6 to C_8, or a cycloalkyl group of C_7 to C_1_2 aralkyl group, R^3 is C_1 to C_1_2 linear or branched alkyl group] 65 to 100% by weight of a monomer represented by: and (b) one radically polymerizable unsaturated group 0 to 35% by weight of a monomer having at least one functional group in addition to
A polymer organic solvent dispersion comprising a co)polymer.