JPH04222805A - Surfactant, antifouling treatment agent and polishing agent - Google Patents

Abstract

PURPOSE:To provide a surfactant, antifouling treatment agent or polishing agent good in leveling nature, water-repellent durability and antifouling nature, to be applied on automotive bodies, etc., comprising a copolymer made up of, as the essential components, fluorine-contg. unsaturated monomer and crosslink-contg. unsaturated monomer. CONSTITUTION:A copolymerization is made between, as the essential components, (A) a fluorine-contg. unsaturated monomer [e.g. beta-acryloxyethyl(N- propylperfluoroctylsulfonamide)] and (B) a crosslink-contg. ethylenic unsaturated monomer (e.g. dicyclopentadienyloxyethyl methacrylate), and, where appropriate, (C) a crosslinkable ethylenic unsaturated monomer (e.g. dicyclopentenyl acrylate) and (D) a polyorganosiloxyl group-contg. ethylenic unsaturated monomer (e.g. polydimethylmonovinylsiloxane), thus giving a copolymer for use as the objective surfactant or antifouling treatment agent. The other objective polishing agent can be obtained by incorporating this copolymer with e.g. wax.

Description

[Detailed description of the invention]

0001

FIELD OF THE INVENTION The present invention relates to surfactants, antifouling agents and polishing agents.

0002

[Prior Art] JP-A No. 63-54410 describes an ethylenically unsaturated monomer containing a fluorine atom and an ethylenically unsaturated monomer containing a linear or branched alkyl group having 8 or more carbon atoms. JP-A No. 63-54411 describes a copolymer with a fluorine atom-containing ethylenically unsaturated monomer and an ethylenically unsaturated monomer containing an alkyl group having 16 or more carbon atoms. A surface modifier for wax formed by copolymerizing with a monomer is described.

0003

However, the above-mentioned surface modifiers have poor leveling properties and are insufficiently effective in applications requiring high leveling performance, such as automotive wax.

[0004] Also, there was a problem that the water repellent durability and stain resistance were insufficient.

[0005]

[Means for Solving the Problems] Therefore, the present invention, etc. has been intensively studied in view of the above circumstances, and has been developed to provide an alternative to ethylenically unsaturated monomers containing linear or branched alkyl groups having 8 or more carbon atoms. Introducing an ethylenically unsaturated monomer containing a bridge bond improves leveling properties, water-repellent durability, and stain resistance, and furthermore, introducing a cross-linking ethylenically unsaturated monomer there improves the leveling property, water repellency durability, and stain resistance. Water repellency, water repellency durability, and oil repellency are improved, and when an ethylenically unsaturated monomer containing a polyorganosiloxyl group is introduced as a copolymerization monomer, leveling property, water repellency, and oil repellency are further improved. They discovered this and completed the present invention.

That is, the present invention provides a copolymer obtained by polymerizing a fluorine atom-containing ethylenically unsaturated monomer (A) and a bridge bond-containing ethylenically unsaturated monomer (B) as essential components. A copolymer obtained by further polymerizing a crosslinkable ethylenically unsaturated monomer (C) and/or a polyorganosiloxyl group-containing ethylenically unsaturated monomer (D) therein. The present invention relates to a surfactant comprising the above, an antifouling agent comprising the copolymer, and a polishing agent comprising the copolymer.

As the fluorine atom-containing ethylenically unsaturated monomer (A) used in the present invention, any known and commonly used monomer can be used, but for example, (meth) having a polyfluoroalkyl group or a perfluoroalkyl group can be used. Acrylates, vinyl esters, vinyl ethers, malates, fumarates, α-olefins and the like can be mentioned.

Among them, having a perfluoroalkyl group,
Fluorine atom content is 5 to 80% by weight, especially 10 to 70%
Perfluoroalkyl group-containing ethylenically unsaturated weight percent is preferred.

[0009] Fluorine atom-containing ethylenically unsaturated heavy body (
A) can be represented by the following general formula.

0010

[Chemical formula 1]

[However, R1 represents a perfluoroalkyl group or polyfluoroalkyl group having 4 to 21 carbon atoms, R represents a hydrogen atom or a methyl group, and R' represents an alkyl group having 1 to 10 carbon atoms. and R'' represents a hydrogen atom or an alkylene group having 1 to 10 carbon atoms.
), specifically, the following can be used:

0012

[Case 2]

Hereinafter, acrylate and methacrylate compounds will be collectively referred to as (meth)acrylate compounds. A bridge-like bond refers to a bond that spans a single ring, such as in camphor (see Kyoritsu Publishing Co., Ltd. Chemistry Dictionary 2).

Examples of the ethylenically unsaturated monomer (B) containing a bridge bond according to the present invention include dicyclopentanyloxyethyl (meth)acrylate, isobornyloxyethyl (meth)acrylate, isobornyl ( Examples include meth)acrylate, adamantyl(meth)acrylate, dimethyladamantyl(meth)acrylate, dicyclopentanyl(meth)acrylate, and the like. Among the monomers (B), particularly preferred are those having a cyclic structure in the molecule, such as isobornyl (meth)acrylate, adamantyl (meth)acrylate, dimethyladamantyl (meth)acrylate, and dicyclopentanyl (meth)acrylate. Examples include (meth)acrylic esters having a homopolymer glass transition temperature of over 100°C.

The polymerization ratio of monomers (A) and (B) of the copolymer in the surfactant of the present invention is not particularly limited, but
Usually 2 parts of monomer (B) per 100 parts by weight of monomer (A)
5 to 400 parts by weight, particularly preferably 45 to 100 parts by weight, since the resulting copolymer has excellent water and oil repellency and antifouling properties.

The surfactant of the present invention may be a copolymer of only monomers (A) and (B), but it may also be a copolymer of (A) and (B). In order to obtain a coating film having higher water- and oil-repellency and water-repellent durability than the coating film, a crosslinkable ethylenically unsaturated monomer (C ) is preferred. Although the copolymerization ratio of monomer (C) is not particularly limited,
Usually 1.25 to 100 per 100 parts by weight of monomer (A)
Parts by weight, especially 6.25 to 50 parts by weight, are preferably used in terms of good oil repellency and excellent antifouling durability.

Furthermore, in order to obtain a coating film having higher leveling properties and water and oil repellency than a coating film made of a copolymer of only (A) and (B), it is necessary to combine the monomers (A) and monomers. A copolymer obtained by polymerizing the polyorganosiloxyl group-containing ethylenically unsaturated monomer (D) together with the polymer (B) is preferred. Although the copolymerization ratio of monomer (D) is not particularly limited,
It is usually 1.25 to 50 parts by weight per 100 parts by weight of monomer (A), and preferably 2.5 to 35 parts by weight in order to obtain a coating film with excellent slipperiness and sufficient hardness. .

[0018] In order to obtain a surfactant that exhibits extremely excellent effects in all respects, a quaternary copolymer polymerized using all of these monomers (A) to (D) is preferred. The crosslinkable ethylenically unsaturated monomer (C) according to the present invention is, for example, a monomer having a functional group capable of forming a covalent bond with the object to be treated through an addition or condensation reaction, or a curing catalyst. There are a wide range of monomers having functional groups that can three-dimensionally cure copolymers, such as N-methylol (meth)acrylamide, glycidyl (meth)acrylate, aziridinyl (
meth)acrylate, diacetone (meth)acrylamide, methylolated diacetone (meth)acrylamide,
Ethylene di(meth)acrylate, hydroxyalkyl (meth)acrylate, urethane di(meth)acrylate, polyester polyfunctional ) acrylate, neopentyl glycol di(meth)acrylate, polypropylene oxide di(meth)acrylate, dicyclopentenyloxyethylene(meth)acrylate, trimethylolpropane triacrylate, dicyclopentenyl(meth)acrylate
Examples include acrylate. Among them, dicyclopentenyl (meth) is a crosslinkable ethylenically unsaturated monomer suitable for obtaining a coating film with leveling properties and gloss.
Examples include acrylate and dicyclopentenyloxyethyl (meth)acrylate.

Further, as the polyorganosiloxyl group-containing ethylenically unsaturated monomer (D), any known and commonly used monomers can be used, and examples thereof include the following.

[0020]

[Chemical 3]

As mentioned above, the polyorganosiloxyl group-containing ethylenically unsaturated monomer (D) is particularly effective in providing stain resistance and durability. The copolymer used as the surfactant of the present invention may further contain monomers other than the above monomers (A), (B), (C), and (D), if necessary. May be manufactured. Monomers that can be used in combination include (meth)acrylate monomers such as methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, styrene, Examples include vinyl compounds such as p-methoxystyrene, γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, acrylic acid, and methacrylic acid.

As a method for producing the surfactant of the present invention, general methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization can be applied, and the polymerization method is not particularly limited. Various polymerization initiators such as organic peroxides and azo compounds can be employed as the polymerization initiation source. The surfactant, antifouling treatment agent, and polishing agent of the present invention are prepared by dissolving the raw material polymerizable compound in a suitable organic solvent and applying the action of a polymerization initiation source (organic peroxide, azo compound, etc. soluble in the solvent used). Among the manufacturing methods, the solution polymerization method, in which the desired surfactant can be directly manufactured, is particularly preferable. Any dispersion medium may be used as long as it can dissolve the monomer, but hydrocarbon solvents such as turpentine, mineral spirit, kerosene, and solvent naphtha that do not damage the painted surface are particularly preferred. The compound obtained by the solution polymerization method can be adjusted to an appropriate concentration depending on the intended use and used directly as an antifouling agent.

The surfactant of the present invention provides a homogeneous coating film with few defects, so it can be used as it is as a moisture-proofing agent, an oil infiltration inhibitor, a rust preventive, and an electrical insulating agent. It can also be used as an internal additive in paints, as a mold release agent between molds and molded products during FRP molding, as an additive for fire extinguishers, for bags, shoes, clothing, and car seats made of natural leather or synthetic leather sheets. For antifouling treatment, floor polishing, ships, etc.
It can also be used for aircraft bodies, surfboards, and skis.

Furthermore, the surfactant of the present invention can be suitably used as an emulsifier for emulsion polymerization and suspension polymerization. In particular, emulsion polymerization or suspension polymerization in a non-aqueous solvent can provide resin particles with finer and more uniform particle diameters than when conventional emulsifiers are used.

The surfactant of the present invention can also be used as a polishing agent, for example, in combination with wax. Among the waxes that can be used at this time, natural waxes include, for example, carnauba wax, candelilla wax, rice wax, palm wax, vegetable waxes such as wood wax, animal waxes such as beeswax, spermaceti wax, tallow, montan wax, and ceresin wax. Examples of mineral waxes such as , ozokerite, petroleum waxes such as paraffin, microcrystalline wax, and vaseline, and synthetic waxes include polyethylene and polypropylene. Silicone compounds such as dimethyl silicone oil (dimethylsiloxane), diethyl silicone oil, methylphenyl silicone oil, methylhydrogen silicone oil, polysiloxane amino, carboxy,
Other modified silicone oils such as modified products such as epoxy, polyester, and phenol, resin varnishes such as petroleum resins, terpene resins, rosin gum, acrylic resins, silicone resins, and tetrafluoroethylene resins, and wax substitutes such as fluorinated graphite. Substances can also be used.

As a combination of waxes, a combination of tetrafluoroethylene resin and fluorinated graphite is preferred. The mixing ratio of the surfactant of the present invention and wax is not particularly limited, but it is usually 0.5 to 20 parts by weight, preferably 2 to 8 parts by weight, per 100 parts by weight of wax solid content.

The surfactant of the present invention can be used as it is as an antifouling agent or as a polishing agent in combination with wax, but there are no particular restrictions on the method of applying these to the painted surface. It can be applied by a conventionally known method. For example, it can be applied to the surface of the article using a roll coater, bar coater, spin coater, spray, sponge, rag, etc. When polishing agents are used in combination with wax, polishing is generally performed after application.

The surfactant, antifouling treatment agent, and polishing agent of the present invention can be applied directly to the surfaces of metals, glass, plastics, fibers, wood, bamboo, etc., but are preferably applied to these substrates. applied to painted surfaces.

The polishing agent of the present invention is particularly excellent in water and oil repellency, stain resistance, and durability, and is therefore preferable for use in automobile bodies, aircraft bodies, furniture, and office equipment. In particular, liquid wax for automobile bodies, which has become popular in recent years, has better miscibility with other components than conventional solid fluorine-based surface modifiers.
Not only does it make it possible to reduce the time involved in preparation, but the uniform dispersion within the wax is much better than before, which reduces uneven coating and provides a coating film with excellent leveling properties. It can be suitably used in this respect.

[0030]

[Examples] Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples. However, the scope of the present invention is not limited in any way by the following examples.

[Reference Example] In this example, a typical method for producing the copolymer of the present invention will be explained using a specific example of a binary copolymer of a perfluoroalkyl compound and dicyclopentanyl acrylate. .

CH2=CHCOOCH2CH2-CnF2n+1 (
72 g of n=6 to 12, average 8), 48 g of dicyclopentanyl acrylate, and 280 g of turpentine are added, and the temperature is raised to 50° C. while stirring under a nitrogen atmosphere to make the inside of the system uniform. Next, add 1.2 g of azobisisobutyronitrile,
The temperature was raised to 85° C. over 30 minutes, and the copolymerization reaction was carried out at the same temperature for 7 hours. The obtained surfactant has a solid content concentration of 3
It was 0.2% by weight.

Copolymers were obtained in the same manner as described above using the monomers shown in Tables 1 and 2 in predetermined amounts. Furthermore, in Tables 1 and 2, FA is C.
F3(CF2)7CH2CH2OOCCH=CH2,F
SA is CF3(CF2)7SO2N(C3H7)CH2
CH2OOCCH=CH2, IBA is isobornyl acrylate, ADA is adamantyl acrylate, AMA
is adamantyl methacrylate, DCPA is dicyclopentanyl acrylate, StA is stearyl acrylate, EHA is 2-ethylhexyl acrylate, i-B
A is isobutyl acrylate, CHMA is cyclohexyl methacrylate, N-MAM is N-methylolacrylamide, DCPEA is dicyclopentenyl acrylate, and SiA is polydimethylmonovinylsiloxane [the first exemplified monomer (D)]. shall be indicated.

[Examples 1 to 8 and Comparative Examples 1 to 4] The following tests A to E were conducted using the copolymers obtained in the above reference examples, and the results are also shown in Tables 1 to 2. .

Test A: Leveling test size 300m
An acrylic melamine resin white painted iron plate for general automobiles in accordance with JIS K 5400, measuring m x 450 mm, was used, and each surfactant shown in Tables 1 and 2 was applied with a sponge, and after air-drying, it was dried. I wiped it dry with a cloth. The degree of uneven coating on the surface of this iron plate was visually observed, and the surfactant of the present invention was evaluated in terms of leveling property, which is one of the indicators of surfactant ability. The results are shown in Tables 1 and 2.

Evaluation criteria ◎: Excellent leveling properties. ○: Good.

△: Slightly good. ×: 〃 Defective. Test B: Water repellency test After the above Test A, the contact angle of water on the surface of the iron plate was measured using a goniometer (manufactured by Elmer Optical Co., Ltd., a microscope for measuring contact angles). The results are shown in Tables 1 and 2. Note that the larger the value of the contact angle, the better the water repellency.

Test C: Water repellency durability test The iron plate after completing Test B above was immersed in water at 25°C for 72 hours, air-dried, and the water repellency of the surface was measured in the same manner as Test B. Compared with water repellency. Table 1 shows the results.
It is shown in Table 2.

Evaluation criteria ◎: 90-100% of the water repellency before immersion in water was maintained. ○: 〃 80-9
Maintained below 0%.

△: 〃 60-8
Maintained below 0%. ×: 〃 60% or less. Test D: Oil repellency test The contact angle of n-dodecane on the surface of the iron plate after the completion of Test A above was measured in the same manner as Test B above. The results are shown in Tables 1 and 2. The larger the value of the contact angle, the better the oil repellency.

Test E: Antifouling property test 1 part by weight of carbon black powder was impregnated with 0.1 part by weight of lubricating oil, and this was poured into 99 parts by weight of water that was being vigorously stirred and dispersed. After Test D, 1 ml of this dispersion was placed on the surface of the iron plate, air-dried overnight, and then gently wiped off with a dry cloth, and the amount of remaining dirt was visually observed. The results are shown in Tables 1 and 2.

Evaluation criteria ◎: No dirt remains at all. ○: Slight stain remains.

[0043] △: Some dirt remains. ×: Considerable dirt remains.

[0044]

[Table 1]

[0045]

[Table 2]

After thoroughly washing the white-painted surface of an ordinary automobile with a detergent, 1 part by weight of the surfactant (solid content) of Example 7, 5 parts by weight of carnauba wax, 14 parts by weight of polytetrafluoroethylene, and 80 parts by weight of turpentine were added. and the surfactant 1 of Example 7.
The polishing agent excluding the weight part was applied to the right side and the left side respectively, air-dried, and then wiped off. After driving for one month, the vehicle was washed with water and visually observed for the amount of dirt remaining and the extent of limescale. I drove this car for another month, washed it with water, and checked how much dirt remained.
The degree of limescale formation was visually observed. These observation results were combined to evaluate the antifouling durability.

[0047] The right side coated with the polishing agent obtained by blending the surfactant of Example 7 of the present invention had extremely excellent antifouling durability, while the left side had extremely poor durability. It was something.

[0048]

[Effects of the Invention] The surfactant of the present invention has superior leveling property, which is one of the surfactant abilities, compared to conventional fluorine-based copolymer surfactants. Therefore, for example, the polishing agent made of a surfactant and wax of the present invention has remarkable effects such as excellent stain resistance, water and oil repellency, and durability of these properties, as well as excellent leveling properties that can reduce uneven coating. have.

The surfactant of the present invention is particularly useful not only for conventional uses but also as an additive for automobile body waxes and aircraft body waxes, which require a high degree of stain resistance, water and oil repellency.

Claims (8)

[Claims] [Claim 1] Consisting of a copolymer obtained by polymerizing a fluorine atom-containing ethylenically unsaturated monomer (A) and a bridge bond-containing ethylenically unsaturated monomer (B) as essential components. surfactant. [Claim 2]Claim 1, wherein the ethylenically unsaturated monomer (B) is dicycloalkanyl (meth)acrylate.
Surfactants as described. [Claim 3] The copolymer comprises monomer (A) and monomer (
The surfactant according to claim 1 or 2, which is a copolymer of B) and a crosslinkable ethylenically unsaturated monomer (C). 4. The copolymer comprises monomer (A) and monomer (
The surfactant according to claim 1 or 2, which is a copolymer of B) and an ethylenically unsaturated monomer (D) containing a polyorganosiloxyl group. 5. The copolymer comprises monomer (A) and monomer (
The surfactant according to claim 1 or 2, which is a copolymer of B), a crosslinkable ethylenically unsaturated monomer (C), and a polyorganosiloxyl group-containing ethylenically unsaturated monomer (D). . 6. An antifouling agent comprising the copolymer according to claim 1. 7. A polishing agent comprising the copolymer according to claim 1. 8. A polishing agent comprising the copolymer according to claim 1 and a wax.