JPS62275174A - Curable composition - Google Patents

Abstract

PURPOSE:To obtain a curable compsn. which forms a coating film having excellent applicability, water and oil repellency, non-tackiness and antifouling properties, by blending a compd. having a curing moiety with a curing agent and a compd. having a polyfluorinated carbon chain. CONSTITUTION:A curable compsn. is obtd. by blending a compd. having a curing moiety with a curing agent and a compd. having a polyfluorinated chain and a functional group capable of reacting with said compd. and/or said curing agent. As the compd. having a curing moiety, compds. soluble in solvents are preferred from the viewpoint of good workability in forming a coating film. Said compd. can be chosen from among those which are conventionally used as principal ingredients for paints. A perfluoroalkyl group is preferred as the polyfluorinated carbon chain from the viewpoint of forming a cured film having improved water and oil repellency, antifouling properties, non-tackiness, etc. It is desirable that the compd. having a polyfluorinated chain is a non-poymeric compd. from the viewpoint of compatibility with the coating film base.

Description

Detailed Description of the Invention 3. Detailed Description of the Invention "Field of Industrial Application" The present invention relates to a curable composition, and more specifically,
A compound having a curing site, a curing agent, and a specific polyfluorinated carbon chain-containing compound are blended. The present invention relates to a curable composition that is useful for forming a coating that has excellent workability and exhibits solid water and oil repellency, non-adhesive properties, antifouling properties, etc. over a long period of time.

[Prior Art and Problems] Conventionally, a method has been proposed in which a compound or a regular polymer having a perfluoroalkyl group is blended for the purpose of modifying the surface 4v properties of a coating film. For example, JP-A No. 51-84824,
No. 52-8034, No. 52-47030, etc., disclose that the smoothness of the coating film can be improved by blending a fluorine-containing urethane compound, fluorinated acrylic resin, fluorinated silicone, etc. with the 8-curing resin. It is stated that. However, in these coatings, additives tend to dissipate due to lack of compatibility with the coating film, for example due to bleed-out phenomena, and therefore there are problems in maintaining good surface properties of the coating film over a long period of time. is recognized.

[Problems to be Solved by the Invention] It is an object of the present invention to solve the above-mentioned difficulties recognized in the prior art, and to (1) form a coating film with excellent weather resistance, excellent workability, and repellency. The object of the present invention is to provide a curable composition useful for forming a coating film that can exhibit water and oil repellency, non-adhesive properties, antifouling properties, etc. over a long period of time. .

[Means for solving the problem] According to the research of the wood inventor, there are 11 coatings with excellent weather resistance, water and oil repellency, non-adhesion, and stain resistance! In order to be able to form J, it is advantageous to incorporate a compound containing a perfluoroalkyl group. As a result of extensive research and consideration, the present inventors discovered that fluorinated alcohol,
Non-polymeric polyfluorinated carbon chain-containing compounds such as glycols or their derivatives are advantageous in terms of compatibility with the coating base, and the hydration of such polyfluorinated carbon chain-containing compounds (such as Due to the functional group,
It has been found that the compound can react with and bond to either the base compound having a curable site or the curing agent, or both. By blending a polyfluorinated carbon chain-containing compound having a functional group that can react with a coating film-forming composition based on a curing-reactive compound,
A curable composition useful for forming a weather-resistant coating film that exhibits excellent water and oil repellency, antifouling properties, non-adhesive properties, etc. over a long period of time can be obtained.

Thus, the present invention was completed based on the above findings, and contains a compound having a curable site, a curing agent, and a polyfluorinated carbon chain-containing compound that can react with the compound and/or the curing agent. The present invention provides a novel curable composition characterized by the following.

The compound having a curable site in the present invention may be any compound that can form a coating film or the like by curing, and may be either a non-polymer compound or a polymer compound. Further, as the compound having such a curable site, a compound soluble in a solvent is preferable because it has excellent workability in forming a coating film, and compounds that are generally used as a main component of curable paints are preferably employed. A compound having a curable site usually has two or more curable sites. As a hardening part,
Examples include hydroxy group, epoxy group, carboxyl group, amide group, amide group, incyanato group, methylol group, etherified methylol group, unsaturated bond, and halogen.

Examples of compounds having such a curable site include polyols, polyisocyanates, polyepoxies, polyamines, polyamides, and polycarboxylic acid compounds. Preferably polyhydric alcohol, polyether polyol,
These are polyols such as polyester polyols and acrylic polyols (acrylic polyols are preferably used because of their excellent weather resistance and water resistance. Such acrylic polyols are polyols such as hydroxyargyl (meth)acrylates and alkyl (meth)acrylates. It is a copolymer with a polymerizable monomer.In particular, the intrinsic viscosity measured in an uncured state in tetrahydrofuran at 30°C is 0.
It is preferably about 0.05 to 2.0 dl/g.

Various curing agents can be used as the curing agent in the present invention depending on the curable site of the compound. For example, when the curable site is a hydroxy group, a methylol group, a carboxyl group, an incyanate group, etc. can be used as the curing agent. Alternatively, a curing agent having an epoxy group or the like is used. Also, Canada
etc., functional groups that generate these functional groups, such as etherified methylol groups and blocked incyanatos (
It is also possible to use curing agents with As mentioned above, the compound having a preferred curing site in the present invention is a polyol, and therefore the curing agent preferably has a functional group as described above. In particular, melamine type, urea resin type, which is used in ordinary thermosetting acrylic paint,
Various curing agents such as polybasic acid-based, silicone-based, isocyanate-based, and block polyvalent incyanate-based curing agents are effective. Of course, in addition to these curing agents, it is also possible to use curing accelerators and the like. The curing agent is determined depending on the content of the curable part of the compound having a curable part, the blending ratio of the specific polyfluorinated carbon chain-containing compound described below, the desired cured density of the cured coating film, the type of the curing agent, etc. Therefore, the amount used can be adopted as appropriate, but usually 100 parts by weight of the compound having a curable site, 1 to 70 parts by weight of the curing agent,
Preferably, the amount is selected from a range of 2 to 55 parts by weight.

In the present invention, it is important that a compound having a curable site as described above and/or a polyfluorinated carbon chain-containing compound having a functional group capable of reacting with a curing agent is blended. Examples of polyfluorinated carbons include perfluoroalkyl groups and perfluoroalkylene groups, but they usually improve the water and oil repellency, stain resistance, non-viscous properties, etc. of the cured coating film. In the case of IJII in which a perfluoroalkyl group is preferable in terms of obtaining a perfluoroalkyl group, a compound having a perfluoroalkyl group having about 1 to 20 carbon atoms is preferably employed. Compounds having a fluoroalkyl group are preferred. Of course, a compound having a perfluoroalkylene group of 6 to 20 carbon atoms may also be employed. In addition, as the functional group, those capable of reacting with the compound having a curable site and/or the curing agent can be used as appropriate, and functional groups similar to those exemplified for the curable site of the compound having a curable site mentioned above can be used. can be mentioned. Among these, polyfluorinated carbon chain-containing compounds having a hydroxyl group as a functional group are preferably employed in the present invention.

The polyfluorinated carbon chain-containing compound is preferably a non-polymerizable compound from the viewpoint of compatibility with the coating film base.

Specific examples of the specific polyfluorinated carbon chain-containing compound in the present invention include the following. That is, CF3 (CF2)n C120H20H (n is 0
or an integer from 1 to 19), a perfluoroalkyl group-containing alcohol, HOCH? CH2(CF2)*
-CH7CH20H (m is an integer from 1 to 20), CF3
Glycols such as (CF2)nCON-(CH2CH20H)2, CF3(CF2)nCH2-
CH2CISi(OCH3)y or silicone compounds such as (i) R3-so and y is O-3).

In addition, polyfluoroalkyl group-containing carboxylic acids and carboxylic acid anhydrides, epoxy compounds, incyanate compounds, and amine compounds.

Also included are melamine compounds and phenol compounds.

In the present invention, the amount of the specific polyfluorinated carbon chain-containing compound is variously selected depending on the intended purpose;
- usually per 100 parts by weight of a compound having a curable site,
It is selected from the range of about 0.1 to 100 parts by weight or about 5 to 50 parts by weight of the polyfluorinated carbon chain-containing compound.

If the amount of the polyfluorinated carbon chain-containing compound is too small, the desired effect of improving the surface properties of the cured coating film will decrease, and if it is too large, the effect of the compound will be saturated, and It also impairs the properties of the cured coating film itself, which is based on fluoroolefin polymers.

Various solvents can be used in preparing the curable composition of the present invention, including aromatic hydrocarbons such as xylene and toluene, alcohols such as n-butanol, esters such as butyl acetate, and methyl isobutyl ketone. In addition to natones such as , glycol ethers such as ethylseronulp, various thinners for reprinting can also be used.

Such formulations include ball mills, paint shakers, sand mills, JYH mills, and Miki rolls.

This can be carried out using various equipment commonly used for forming paints, such as a kneader. At this time, add 1/1 pigment stabilizing agent, viscosity: A moderating agent, and leveling agent.

Anti-gelling agent, ′? , an external radiation absorber, etc. can also be added.

The composition of the present invention may also contain additives such as pigments, colorants, fillers, stabilizers, etc., as appropriate, for purposes such as 2g distinctiveness, mechanical strength, adhesion, and durability. be. Typical such additives include phthalocyanine green, titanium oxide, 7lumina, tarri, calcium carbonate,
Examples include silica.

When coating with the composition of the present invention, the three components, a compound having a curable site, a curing agent, and a compound containing polyfluorinated carbon particles, are usually mixed and dissolved using a predetermined solvent. , to paint. Also, if necessary,
The polyfluorinated carbon chain-containing compound and the compound having a curable site or a curing agent may be reacted in advance, and then the remaining component may be mixed and dissolved, and the mixture may be coated.

The composition of the present invention has excellent weather resistance, water and oil repellency, non-stick properties, antifouling properties, etc., and therefore exhibits various advantages in the field of coatings such as paints and fiber treatment agents. The composition of the present invention can also be used as a modifying compound for various synthetic resins, synthetic rubber, etc., and as a binder for magnetic recording materials, taking advantage of the above-mentioned excellent properties. First, in the field of paints, it has become possible to create coatings that have excellent stain resistance over a long period of time, including office equipment, various electrical equipment, kitchen equipment, roofing materials, road signs, soundproof walls, building exteriors, building interiors, automobiles, etc.
It is useful for painting areas that get dirty easily, such as vehicle painting and chemical plant exteriors. It can also be used as a fiber treatment agent, etc.
Can be applied thickly, is strong, and has excellent water and oil repellency.
It has the advantage of being able to form a durable coating film. In addition, it is useful as a stain-resistant coating for various parts of electronic 5-page equipment, as well as as a moisture-proof coating or modifying agent for toners and carriers, as a lubricating coating for magnetic recording media, as a binder, and as a modifying agent. It is also useful as an agent.

The curable composition of the present invention is not limited to metals such as iron, aluminum, copper, or their alloys (for example, stainless steel, brass), but also inorganic materials such as glass, cement, concrete, FRP, polyethylene, polypropylene, It can be applied to organic materials or base materials such as plastics such as ethylene-vinyl acetate copolymer, nylon, acrylic, polyester, ethylene-polyvinyl alcohol copolymer, vinyl chloride, vinylidene chloride, and polycarbonate, rubber, wood, and fiber. Moreover, the shape of the base material is not limited to a flat plate, and it is also possible to easily construct a base material with a complex shape. Furthermore, since it can be constructed on-site, it can also be applied to large structures such as the inner walls of tunnels.

[Examples] Next, Examples of the present invention will be described in more detail, but it goes without saying that the present invention is not limited by such explanations.

In addition, in the following Examples and Comparative Examples, part particularly refers to l.
jJ] Unless otherwise indicated, all parts are by weight.

Example 1 Units based on methyl methacrylate and hydroxyethyl methacrylate are each contained in the L';'II combination of i30/20 (mol %),
100 parts of an acrylic copolymer with an intrinsic viscosity of 0.30 dl/g measured at °C, CF3 (C:F2)n
CH2 (J20H (n = 6 to +4, mixed alcohol with an average molecular weight of about 514) 3.5 parts, dibutyltin silaurylate 7 x 10-" parts, polyisocyanate ("Coronate EH": product name 1 Roki Polyurethane) 20
A coating composition was prepared by mixing and dissolving 1 part in 240 parts of methyl imbutyl ketone.

The above composition was applied to an aluminum plate (J'
Using a film applicator, 2iT was applied onto the film (V 0.8 mm) to give a thickness of about 25≠ after drying, and the film was cured at room temperature for one week. The physical properties of various coatings 11A were determined for the coated aluminum plates obtained by peeling. Regarding adhesion tests, base cant and tape tests were conducted. For solvent resistance of the paint film, impregnate it with xylene case.

After rubbing the coating 200 times, it was confirmed that no abnormalities such as flaking or dissolution occurred in the coating. In addition, as a measure of water and oil repellency, the contact angle for water and Nujol was 311
It was fixed at 1.

Furthermore, as a measure of stain resistance, a marker ink test and a carbon black stain test were conducted.

In the magic ink test, a line was drawn on the surface using a black marker, and the repellency of the drawn line drawing was checked.Then, it was gently wiped with ethanol-impregnated gauze to check how well the written line drawing was wiped off.

Carbon black stain test is carbon black 0.1
After spraying the weight% distilled water dispersion onto the coating surface, 6
After repeating the cycle of drying for 20 minutes in a dryer at 0°C 10 times, the coating surface was washed with water and the amount of carbon stain remaining was checked.

(O: Dirt is not noticeable, Δ: Looks slightly darkened, ×: Significant darkening) In addition, as a measure of slipperiness, the dynamic friction coefficient was measured using a Hayton type surface property measuring machine. did.

The above various results are summarized in Table 1.

Example 2 CF3 (CF2)ncH2cH20H (n=6~+4
, mixed alcohol with an average molecular weight of about 514) 1.8 parts,
Polyisocyanate (“Coronate EH”: Product name 1
(manufactured by Nippon Polyurethane) and 4 parts of dibutyltin silaurylate, 4 parts of methyl isobutyl ketone,
The mixture was mixed and dissolved at 0fS and reacted in a flask at 50°C for 3 hours.

On the other hand, the molar ratio of methyl acrylate/hydroxybutyl acrylate/n-butyl acrylate was (20/
20/80) was dissolved in 200 parts of xylene/methyl isobutyl ketone (weight ratio 1/1), and 45 parts of titanium white ("0R-50": trade name 1 Ishihara Sangyo ■) was dissolved. The mixture was mixed and sufficiently dispersed in a ball mill to obtain a white paint. This paint was mixed and dissolved in the reaction product of the fluorinated alcohol and polyisocyanate to prepare a coating composition.

The composition described above was applied to the same 7 mil board as in Example 1 and cured in the same manner. After one week of room temperature curing, the same coating test as in Example 1 was conducted on the coated aluminum plate. The results are shown in Table 1.

Comparative Example 1 In Example 1, fluorinated alcohol CF3 (CF2
) A coating composition was prepared in the same manner as in Example 1, except that nc82c820H (n = 6 to +4, mixed alcohol with an average molecular weight of about 514) was not added, and the coating and coating film physical properties were tested under the same conditions as in Example 1. I did it. The results are shown in Table 1.

Example 3 100 parts of a copolymer containing methyl methacrylate and a molar ratio of rylate/hydroxyethyl methacrylate of 80/20 was dissolved in 300 parts of ethyl acetate, and then titanium white CR-50 (trade name 9 Ishihara Sangyorin) was dissolved in 300 parts of ethyl acetate. 80 parts were added and dispersed in a ball mill until the particle size was 10 mm or less.

Additionally, metaphenylenediamine 108'Il and HOC
One composition was prepared by adding and mixing 30 parts of H2CH2(CF2)6-GH2CH20H.

The composition thus obtained was applied with a film applicator onto a 0.3 mm thick zinc steel plate (6240 sandpaper polished product) and cured at 150° C. for 40 minutes to form a coating film with a thickness of 20 AL. A painted test piece was obtained, and the same coating film test as in Example 1 was conducted. The results are shown in Table 1.

Example 4 An acrylic material based on methyl methacrylate and hydroxyethyl methacrylate, each containing a proportion of 80,120 (mol 2) units and having an intrinsic viscosity of 0.30 dl/g, measured at 30°C in tetrahydrofradiate. 100 parts of copolymer, (CH:+0hSiCH2-CH2(
CF2 )6 CH7C1h S i (OCHx h
A composition was prepared consisting of 20 parts of xylene/n-butyl alcohol (ball ratio: 2171) as a solvent. This composition was applied onto a glass plate (thickness: 2.5 cm) and cured at 210°OX for 1 hour.
A similar coating test was conducted. The results are shown in Table 1.

Comparative Example 2 In actual bfi example 4, fluorosilane (CHzOh-
S ICH2GH2(CF2)6 CH2CH2(OC
A similar test was conducted on the results of coating with the same formulation except that H3)3 was not added. The results are shown in Table 1.

Example 5 An acrylic copolymer containing units based on methyl methacrylate and hydroxyethyl methacrylate in a proportion of 8Q/2Q (mol %) and having an intrinsic viscosity of 0.30 dl/g, measured at 30°C in tetrahydrofuran. 100 parts of polymer, CF3 (CF2). C0N(C2
H40H)2 [CF3 (CF2)n groupc7)n=
6-14. average molecular weight 470], 10 parts of methylated melamine resin ("Cynol 303": trade name, Mitsui Toatsu), acidic catalyst ("Catalys heooo": trade name).

A composition consisting of 1 part of Mitsui Toatsu) and 300 parts of xylene/n-butyl alcohol (weight ratio: 1/1) as a solvent was prepared, and after coating on an FRP flat plate (thickness 1.1 mm) by spraying. After baking and drying at 130°C for 40 minutes, the same coating test as in Example 1 was conducted. The results are shown in Table 1.

Synthesis Example 1 10 parts of methylated melamine resin ("Cynol 303": trade name, Mitsui Toatsu) were mixed with 5 parts of methyl isobutyl ketone.
The P)I of the solution was adjusted to 2 or less by adding a small amount of sulfuric acid. This is then added to the fluorinated alkyl CF3
(CF2)nC: 82GHzOH (n = 6~14
2.2 parts of a mixed alcohol having an average molecular weight of 514 was mixed and dissolved in 2 parts of acetone and reacted under reduced pressure at 60°C for 4 hours to obtain a fluorine-containing melamine resin solution (A).

Synthesis Example 2 7-Al: I-ru cF3(CF2)ncH2cH
10 parts of 20H (mixed alcohol with n = 6-14. average molecular weight 514) were dissolved in 10 parts of methyl isobutyl ketone, 10-4 parts of dibutyltin silaurylate IX and 5 parts of isophorone diincyanate were added, and the mixture was heated at 60°C.
The mixture was allowed to react for 4 hours. Next, this reaction mixture was added dropwise to a solution prepared by adding 5 parts of methyl isobutyl ketone to 15 parts of methylated melamine resin (Cymel 350: trade name, Mitsui Toatsu), and 2XlO of dibutyltin silaurylate was added thereto. , 811 parts were reacted at 60°C to obtain a fluorine-containing melamine resin solution (B).

Synthesis example 3 Fluorinated alcohol CF3 (CF2)n C82C
10 parts of H20+4 (n = 6 to 14. mixed alcohol with an average molecular weight of 514) was added to 10 parts of methyl isobutyl ketone.
dimethylsilyldiincyanate (CH3
25 parts of hSi(NGO) was added and reacted at room temperature for 20 minutes. Next, this reaction mixture was mixed with methylated melamine resin ('Cymel 350'°: trade name, Mitsui Toatsu) 1
5 parts of methyl isobutyl ketone was added, 2 x 1 O-3 parts of dibutyltin silaurylate was added, and the mixture was reacted at 60°C for 8 hours to obtain a fluorine-containing melamine resin solution (C). .

Example 6 Acrylic copolymer 100i used in Example 1.

Fluorine-containing melamine resin solution (A) 1 obtained in Synthesis Example 1
1 part, acidic catalyst (“Catalyst 6000”: trade name,
A composition consisting of 1 part of Mitsui Toatsu) and 100 parts of xylene/n-butyl alcohol (weight ratio: 8/2) as a solvent was prepared. The above composition was applied in the same manner as in Example 1 and cured by heating at 180° C. for 30 minutes. The coating film thus obtained was subjected to the same coating test as in Example 1. The results are shown in Table 2.

Example 7 The same formulation as in Example 6 was used, except that 20 parts of the fluorine-containing melamine resin solution (B) obtained in Synthesis Example 2 was added instead of the fluorine-containing melamine resin solution (A). Coating No. 11 was prepared and tested. The results are shown in Table 2.

Example 8 The same formulation as in Example 6 was used, except that 20 parts of the fluorine-containing melamine resin solution (C) prepared by 11P in Synthesis Example 3 was added instead of the fluorine-containing melamine resin solution (A). 411 minutes was created and tested. Second result
Shown in the table.

[Effects of the Invention] The curable composition of the present invention has the characteristics of being able to form a cured coating film with excellent workability and excellent long-term weather resistance. The combination has the excellent effect of forming a cured coating film that exhibits water and oil repellency, non-adhesiveness, stain resistance, etc. over a long period of time without impairing the above-mentioned properties.

Claims (4)

[Claims] (1) A curable composition comprising a compound having a curable site, a curing agent, and a polyfluorinated carbon chain-containing compound having a functional group capable of reacting with the compound and/or the curing agent. (2) The curable composition according to claim 1, wherein the compound having a curable site is soluble in a solvent. (3) The curable composition according to claim 1, wherein the polyfluorinated carbon chain-containing compound is a non-polymer. (4) per 100 parts by weight of the compound having a curable site,
The curable composition according to claim 1, which contains 1 to 70 parts by weight of a curing agent and 0.1 to 100 parts by weight of a polyfluorinated carbon chain-containing compound.