JPS5959749A - Paint composition - Google Patents

Abstract

PURPOSE:To provide a paint compsn. having excellent mechanical characteristics, resistance to heat, oils and solvents, etc., containing a thermoplastic fluororubber and a liquid vehicle. CONSTITUTION:A thermoplastic fluororubber (pref. composd of 40-95pts.wt. elastomeric polymer chain segment and 60-5pts.wt. non-elastomeric polymer chain segment), a liquid vehicle (a liquid capable of dissolving or dispersing the above rubber, such as alcohol or ketone), a coupling agent such as gamma-aminopropyltriethoxysilane, a filler such as magnesium oxide, a film-forming stabilizer such as ethylamine, etc. are blended together to obtain a paint compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a fluorine-containing thermoplastic rubber concentrate composition, more specifically, it is composed of a solution or dispersion of a fluorine-containing thermoplastic rubber, and has properties such as heat resistance, oil resistance, solvent resistance, This invention relates to a fluorine-containing thermoplastic fluororubber coating composition that has poor acid resistance, steam resistance, weather resistance, oxidation resistance (ozone resistance), mechanical properties, etc.

ζ, Fluororubber paints, fluororesin paints, etc. have been known as materials that satisfy these requirements, but in the case of fluororubber, a vulcanizing agent is essential, and there are no vulcanizing agents available. The durability of the paint film is poor under harsh conditions.

On the other hand, fluororesins are known to have excellent coating film durability, but as the coating film lacks rubber elasticity, it should not be used in cases where a sealing effect is required or where a soft coating film is required. It doesn't add up. Also, the adhesiveness is poor.

In the case of other hydrocarbon polymers, it is difficult to satisfy the above requirements.

The inventors of the present invention have discovered that by using a fluorine-containing thermoplastic rubber, a coating film satisfying each of the above properties can be obtained, and have completed the present invention.

That is, the gist of the present invention is that the comb contains a fluorine-containing thermoplastic comb and a liquid carrier, and that the comb contains at least one of a camplinking agent, a filler, and a film-forming stabilizer. Characteristic coating compositions (exist).

In the present invention, the fluorine-containing thermal pJ plastic rubber refers to a rubber that has vulcanized rubber elasticity at a relatively low temperature (for example, around normal/Q) and exhibits plastic flow upon heating.

The fluorine-containing thermoplastic rubber preferably consists of at least one elastomeric polymer chain segment and at least one non-elastomeric polymer chain segment, at least one of which is a fluorine-containing polymer chain segment. Particularly preferred is one in which the weight ratio of the elastomeric polymer chain segment to the di-1 elastomeric polymer chain segment is 40-95:5-60.

A particularly preferred example of the fluorine-containing thermoplastic rubber is a chain consisting of two or three polymer chain segments, an iodine atom present at one end of the chain, and a small amount of iodide compound present at the bent end of the nuclear chain. and one of the polymer chain segments (if the chain consists of two polymer chain segments) or one or two (if the chain consists of three polymer chain segments) (1) vinylidene fluoride/hexafluoropropylene or pentafluoropropylene/tetrafluoroethylene (molar ratio 45-90:5-50:0-35) polymer and (2) perfluoro(01-C3 Alkyl vinyl ether) [Includes those containing multiple ether bonds. Same below. ]/tetrafluoroethylene/vinyritine fluoride (molar ratio 15-75:0-85:
0-85) selected from polymers, molecular weight 30,00
0-1,200. ooo elastomeric polymer chain segments, and the remainder of the polymer chain segments are (3) vinylidene fluoride/tetrafluoroethylene (cell ratio 0 to 10).
0:0-100) polymer and (4) ethylene/tetrafluoroethylene/hexafluoropropylene, 3.
3.3-Trifluoropropylene-12-trifluoromethyl-3,3,3-)trifluoropropylene-it or perfluoro(C1-C3 alkyl vinyl ether)
(Mole ratio 4O-60 = 60-4020-30) Molecular weight 3.000-400,00, J Tatsumi 1 shaku from polymer
0 non-elastomeric polymer chain segments, and the weight ratio of elastomeric polymer chain segments to non-elastomeric polymer chain segments is 40-95:5-6.
Examples include fluorine-containing ρS plastic rubbers in which ρS is 0.

A preferable fluorine-containing thermoplastic resin for use in the present invention is described in JP-A-53-3495.

Contains fluorine! ii The typical structure of J plastic rubber is as follows: QC(A-J3-...)IL.

[In the formula, Q is a residue obtained by removing an iodine atom from an iodide compound, and A, B, ... are each a polymer chain segment (at least one of which is a fluorine-containing polymer) ), ■ represents an iodine atom of 1n) L from the iodide compound, and n represents the number of bonds in Q. ], basically a chain consisting of at least two types of polymer chain segments, and the iodine atoms bonded to both ends thereof, as well as the residues from which at least one iodine atom has been removed from the iodide compound. The above-mentioned at least two types of polymer chain segments are different from the adjacent polymer chain segments (for example, the structure or composition of the polymer chain unit that constitutes them is different). ), at least one of which is a fluoropolymer chain segnont, consisting of at least one hard segment and at least one soft segment. Preferably one, each polymer chain segment are each a molecule @3,000U.”
However, at least one polymer chain has a molecular weight of more than 30,000. In addition, 1) at least 1 iodine from the η iotide compound;
! Residues other than l T-, if a polymerizable double bond exists in the imedidized product,
It may have some kind of substituent derived from the compound or the iotide compound constituting the i'l segment. These fluorine-containing thermoplastic rubbers are usually o, oo
Contains i to lo weight percent iodine atoms. However, after synthesis of fluorine-containing thermoplastic rubber, the iodine atom is removed by reaction,
Alternatively, substitutions with functional residues are also included.

The liquid carrier is selected from liquids that can dissolve or disperse the fluorine-containing thermoplastic comb used in the present invention, and specifically includes alcohols such as methanol, propanol-butanol, acetone, methyl ethyl ketone, etc. Ethyl acetate, dimethylformamide, dimethylacetamide,
N-methyl-2-pyrrolidone, dimethyl sulfoxide,
Triethyl phosphate, tetrahydrofuran, methyl isophthyl ketone, cyclohexanone, 1,4-cyclohexane, methyl cellosolve acetate, 2-2L-ropropane, methylisoamylketone/4-methoxy-4-methylbentanone-2,4-methoxy- Examples include 4-methylpenzenol-2' or a mixture of two or more of these.

As another component, a coupling agent can be used in combination to improve adhesion.

In the present invention, the coupling agent refers to a compound that acts on the interface between an organic material and an inorganic material and forms a strong bridge between the image materials through chemical or physical bonding.
It is usually a compound of silicon, titanium, zirconium, hafnium, thorium, tin, aluminum, or magnesium, and is a compound having a group capable of bonding an organic material and an inorganic material. Among these coupling agents, preferred are silane coupling agents and h+
Group transition elements (such as titanium or zirconium)
and its derivatives, among which aminosilane compounds are most preferred.

An example of a silane coupling agent is the general formula: [In the formula, 1 is "AA = l?i IjK, amino group,
At least one functional atom or group selected from aminoargyl group, ureido group, crisitooxy group, eboxycyclohegycyl M:, acryloyloxy group, mecryloyloxy group, mercapto group, and vinyl group. Alkyl group or vinyl group having 1 to 10 carbon atoms, 1
and l (3 is each a chlorine atom, a hydroxyl group, and a carbon number of 1 to
Ijj r- or group selected from 10 alkoxy groups, alkoxy-substituted alkoxy groups having 2 to 15 carbon atoms, hydroxyalkyloxy groups having 2 to 4 carbon atoms, and acyloxy groups having 2 to 15 carbon atoms, a is 0,1 or 2. ] Examples include silane compounds represented by the following.

R1 is an alkyl group having a functional substituent, and preferable examples include β-aminoethyl group, γ-aminopropyl group, N-(β-aminoethyl)-I-amino Propyl group, r-ureidopropyl group, γ-glycidoxypropyl/14, β-(3,4-evogycyclohegycyl)ethyl group, γ-acryloyloxyglopyl group,
Examples include γ-methacryloyloxypropyl group, β-chloroethyl group, r-chlorophoenyl group, and t-vinylpropyl group.

Alternatively, 1 may be a vinyl group.

Specific examples of the above-mentioned silane compounds that are preferably used include I-aminopropyltriethoxysilane, N-β
-Aminoethyl-γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, l-glycidoxyglopyltrimethoxysilane, β-(3.4
-epoxycinclohexyl)ethyltrimedelsilane,
γ-methacryloxypropyltrimethoxine, r-
Mercaptopropyltrimethoxysilane, f-chloropropyltrimethoxysilane, vinyltris(β,-methoxyethoxy)silane, vinyltriethoxysilane, vinyltrichlorosilane, vinylylz l-lyacetoxysilane, N-(1-rimethoxysilylpropyl) Mention may be made of ethylenediamine, N-β-aminoethyl-I-aminopropylmethyldimethoxysilane, and β-aminoethyl-β-aminoethyl-γ-aminoethyltrimethoxysilane. Among these silane coupling agents, aminosilane compounds such as I-aminoflovir l-IJ: l-xysilane, N-β-aminoethyl-γ-aminoglobil trimethoxysilone, N
-(+-IJ methoxysilylpropy/L/) ethyleneamine, N-β-aminoethyl-r-amitube[1-bimethyldimethoxysilane, γ-ureidopropyltriethoxysilane, β-aminoethyl-β-aminoethyl-γ - Compounds such as aminopropyltrimethoxysilane function as vulcanizing agents or vulcanization accelerators for fluororubber, and also greatly contribute to improving adhesiveness with substrates.
Furthermore, it is particularly preferable because it can be safely used with liquid carriers.

As a compound of titanium, zirconium, hafnium, yohytrium, etc., for example, the general formula: % formula %) In the formula C, ]" hachitanium, zirconium, hafnium, thorium, 1 (represents an alkyl group, a cycloalkyl group, or an aryl group. .] Compounds having at least one functional group can be mentioned. Compounds having at least one functional group Examples include glycerin, ethylene glycol, 1,3-butanediol, 2,3
-Butanediol, hexylene glycol, octylene glycol natonopolyhydric alcohols, oxyaldehydes such as salicylaldehyde and glycose, diacetonal: ]・-oxy'71- such as Az, fructose, etc.
Oxycarboxylic acids such as glycolic acid, lactic acid, dioxymaleic acid, and citric acid, diketones such as diacetylacetone, ketone acids such as acetoacetic acid, and nistillyl chloride acids such as ethyl acetoacetate. Oxyamines such as ethanolamine and jetanolamine, oxyphenols such as catechol and pyrogallol1
A compound etc. can be used.

Examples of specific compounds for 1) are trialkyl titanate (for example, tetraethyl titanate, triisopropyl titanate, trabutyl titanate), and tetraethylene glycol titanate. Ditamine acedylacetonate, isopropyltrioctanoyltitanate, cryltitanate, isopropyltriacryltichnate, isopropyltos(butyl, medirpa, ylophosphate) titanate, tetraisoprobyl di(dilaurylphosphite)titanate, dimeccrylogythiacetate Titanate, diacryloxyacetate titanate, di(dioctylphosphate-1-)ethylene titanate, etc. are included.

As the zirconium compound, a chemical compound similar to the titanium compound mentioned above can be used. As a specific example,
Examples include tetraalkyl zirconate such as tetraethyl zirconate and trabutyl zirconate, n-propyl zirconate, isopropyl zirconate, 11-butyl zirconate, imbutyl zirconate, zirconium acetylacetonate, etc. It will be done.

As the hafnium and thorium compounds, compounds similar to titanium and zirconium can be used.

As the tin compound, it is possible to use organic or inorganic compounds, such as S n C I 4 and the like. Examples of aluminum compounds include aluminum isopropylate, monopropylene aluminum diisopropylate, aluminum enriched butyrate, ethyl acetoacetate aluminum diisopropylate, and aluminum tris (ethylacetoacetate).

Examples of magnesium compounds include magnesium alcoholates such as magnesium methylate and magnesium ethylene.

The amine compound which is optionally added to the fluorine-containing thermoplastic rubber of the present invention functions as a vulcanizing agent for the fluorine-containing raw rubber, and also serves as a vulcanizing agent for the raw rubber; The mechanical properties of this compound are improved, and examples of typical compounds include ethylamine,
Monoamines such as propylamine, butylamine, benzylamine, allylamine, n-amylamine, ethanolamine, ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, 3.1-bis(3-aminopropyl)-2, 4, 8
, 10-TetraogyzaspiroC5+ 5] Diamines such as undecane, diethylenetriamine, triethylene 17'tolamine, tetraethylenebentamine, and polyamines such as rylene and \xamine, among others, 2 An amine compound having the above 7 wood end groups is preferred.

The coating composition of the present invention can be prepared in accordance with the conventional method for preparing fluororubber coatings.

The coupling agent to be added is usually 1 to 50 parts by weight, preferably 1 to 2 parts by weight, per 100 parts by weight of fluorine-containing thermoplastic rubber.
It is 0 parts by weight. When an amine compound is added as desired, the coupling agent and the amine compound are mixed in such a way that the total sum of the coupling agent and the amine compound takes the same ratio as above. In this case, the ratio of the coupling agent and the amine compound is 1:99 to The film-forming stabilizer is selected from the range of 99:l.
Since rack sometimes occurs under the desired conditions, it is added to prevent this, for example, by coating a solution or dispersion with a compatible vinylidene fluoride/hexafluoride propylene fluorine column. If it is blended to the extent that it does not adversely affect the physical properties, a coating film without cracking can be obtained. Addition of fluororubber to be used, first measure is molecular weight,
It is determined by the composition ratio, but the average molecular weight of IL is 500
~20,000, the ternary copolymer of hnylidene fluoride/hexafluoroglopyrene/tetrafluoroethylene has preferable coating properties.

As a filler, for example, 2
One or more of the metal oxides or hydroxides may be used. Specifically, the oxide size or ll (acid fj
Your physical strength will be used to your advantage. Also silica, clay, diatom 18,
Talc, carbon, etc. can be used for a long time.

The coating composition of the present invention is coated on a substrate by a conventional method and dried. te/'7': 1 model.

Further, if necessary, a good coating can be obtained by cooling the melt by % and applying it.The coating film thus obtained can be coated as needed. Alternatively, crosslinking can also be achieved by irradiation with radiation.

The paint iM1 composition of the present invention is a coating material with excellent heat resistance, oil resistance, solvent resistance, acid resistance, steam resistance, weather resistance, oxidation resistance (onion resistance), and mechanical properties. It is processed into coatings and is widely used as an industrial material.

Next, Examples, 15 and Comparative Examples will be shown to explain the present invention.

Example [~5] The false ingredients shown in Table 1 were mixed with dimethylacetamide/methyl ethyl ketone/methyl isopropyl ketone (weight ratio 4:l:
1) A coating composition was obtained by adding to the mixed solvent and stirring in a ball mill for half a day.

This coating composition was applied to a degreased aluminum plate and baked at 150° C. for 30 minutes to obtain a coating film, and the surface condition of the coating film (whether or not cracking occurred) was observed.

The results are shown in Table 2.

On the other hand, 1. to obtain a coating film, J
A No. 1 dumbbell was punched out in accordance with IS K 63Ql, and its tensile strength was measured. The results are shown in Table 2ζ.

Table 1 0propylene/tetrafluoroethylene (molar ratio 50
/30/20) Polymer segment 88% by weight
and a fluorine-containing thermoplastic rubber consisting of 12% by weight of polyvinylidene fluoride sedamenobuty.

3) Medium the -mal carhon 4) a
: I) = 4 : 1 mixture a : N
112 (CI(2)35i(OCH2CH3)35)
Solvent dimethylacetamide/methyl ethyl ketone/
Acetone (weight ratio 2:3:l) Example 6 and uSS
Rust prevention method 1 using the paint composition used in Example 1 and Example 5
A similar coating film was formed on the steel plate 55-41, and hydrochloric acid of I-12 to I-3 was sprayed on both sides of the steel plate. No rust was observed on the coating surface even after 30 minutes. - After 20 to 30 minutes, a coating film was formed (7) No rust was observed on the entire surface.

Patent Holder: Daikin Industries, Ltd. Agent: Patent Attorney: Written Amendment (1)
・1. .

January 1939] 911 Japan Patent Office Akiyoshi 1 Indication of the case Patent application No. 1939] 7 ] -□I 44
No. 2 Name of the invention Item 11 Product 3 Relationship with the case of the person making the amendment Representative piece of patent applicant Mountain 1) Date of order for amendment by Minoru 4, attorney 5: (voluntary) 6. Subject of amendment 7. Of the amendments, the following parts were amended in the details: q - first.

■Claims column As per attached sheet.

■2 Column for detailed explanation of the invention (Monday, page 17, line 3, next to “carbon”
Insert your finger.

+21119 page Table 2 bottom row, “NPa Jfe “Ml
'a J and i Jl three.

Above (separate Aut: ) Claims (]) 1i including a fluorine-containing thermoplastic rubber liquid carrier
V), additionally required are a coupling agent, a curing agent, and filler 11.
1. A coating composition comprising at least one stabilizer.

(2) The fluorine-containing thermoplastic comb consists of at least one elastomeric polymer chain segment and at least one non-elastomeric polymer 6'I segment, at least one of which is a fluorine-containing polymer chain. The segment is a thermoplastic comb according to claim 1. ) Of course.

[31 The fluorine-containing thermoplastic rubber contains 40 to 95 parts by weight of elastomeric polymer chain segments and non-elastomeric J! The paint according to claim 2 consisting of 5 to 60 remer chain segments + M11! proboscis

Claims (3)

[Claims] (1) A coating composition comprising a fluorine-containing cumulative heat IRJ plastic rubber and a liquid phase, and further comprising at least one of a coupling agent, a filler, and a film-forming stabilizer. thing. (2) The fluorine-containing thermoplastic rubber is composed of at least one elastomeric polymer chain segment and at least one non-elastomeric polymer chain segment, at least one of which is a fluorine-containing polymer chain segment. ft')', + l'1 plastic clover rubber special Y1 - claim as described in paragraph 1 *1 +1. L acid. (3) Contains fluorine! Il: The coating composition according to claim 2, wherein the plasticized raw rubber comprises 40 to 95 parts by weight of elastomeric polymer chain segments and 5 to 60 parts by weight of non-elastomeric polymer chain segments.