JPH0330825A - Fluorine based surfactant having low foaming characteristic - Google Patents

Abstract

PURPOSE:To obtain a fluorine surfactant outstandingly reduced in foaming characteristics for use in coating material by introducing silicone group to the polymer having perfluoroalkyl group and polyoxyalkylene group. CONSTITUTION:At least one kind of ethylenic unsaturated monomer, fluoroalkyl group contg. ethylenic unsaturated monomer and silicone group contg. ethylene unsaturated monomer (preferably, alkyl group contg. monoethylene unsaturated monomer is included) selected from nonionic group contg. ethylenic unsaturated monomers, anionic group contg. ethylenic unsaturated monomers and cationic group contg. ethylenic unsaturated monomers are copolymerized by a known method. Preferably, radical polymerization initiator, photosensitizer and chain- transfer agent are used, as required, in an org. solvent. Since the fluorine surfactant obtained by this method is outstandingly lower in foaming characteristics than the conventional one, it is usable in various applications such as for preventing coating foaming and as leveling agent.

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to a low foaming fluorosurfactant and a leveling agent.

"Prior Art" As a fluorosurfactant made of a polymer having a fluoroalkyl group, a polymer having a fluoroalkyl group and a polyoxyalkylene group is known.

Such fluorine-based surfactants have extremely low intermolecular cohesive force and when added to aqueous media, organic solvents, resins, etc., they selectively adsorb to these surfaces and have the effect of lowering the surface tension. It is used as a leveling agent for paints, inks, and resins.

``Problems to be Solved by the Invention'' However, such conventional surfactants made of fluorine-based polymers have extremely high foaming properties, and have the disadvantage that the foam that forms a skin does not disappear quickly. Therefore, for example, when used to smooth the surface of a paint film, it is necessary to leave it for a long time after adding it to the paint and wait for the foam to disappear before applying. Conversely, the smoothness of the coating film surface had to be sacrificed.

"Means for Solving the Problems" As a result of intensive studies to solve the above problems, the present inventors found that when a silicone group is introduced into a conventional polymer having a perfluoroalkyl group and a polyoxyalkylene group, foaming occurs. The present inventors have discovered that this reduces the irradiance and have completed the present invention.

That is, the present invention provides a surfactant made of a polymer containing at least one group selected from a nonionic group, an anionic group, and a cationic group, a fluoroalkyl group, and a silicone group, and a leveling agent made of the surfactant. It provides:

The polymer according to the present invention usually comprises a nonionic group-containing ethylenically unsaturated monomer (a3), an anionic group-containing ethylenically unsaturated monomer (a2), and a cationic group-containing ethylenically unsaturated monomer. At least one ethylenically unsaturated monomer (A) selected from (a3), a fluoroalkyl group-containing ethylenically unsaturated monomer (B), and a silicone group-containing ethylenically unsaturated monomer (C); Obtained by polymerization.

The nonionic group-containing monoethylenically unsaturated monomer (a3) according to the present invention is a monomer having both a nonionic group and one ethylenically unsaturated double bond, such as polyoxyalkylene A monomer having both a group and one ethylenically unsaturated double bond is exemplified.

a, -1: CHz=CHCOOCHzCIhO(
CHzCH,O), Hn=5~20 abi2: CHz=CHCOOC1bCHzO(CH2(,If(
CH3)O), % (CHzGHz) I, Hm,
n=5~20 a, -3: CHz=CHCOO(CHzCHzO)e (CH2
Cl(CH3)0) 1I(CI(,C11Z)fiH
l,, m, n=5~20 a, -4: CH2=CHC00CH2CH2O(CII2CH2O
)-CH3n=10~20a, -5: Cl1z=CHCOOCHzCHzO(C)1zcHz
O). (CH2C1l(C)13)O) , 11m,
n=5-20 a, 5: CHz=C(CH3)COOCHzCHzO(Ctl□
CH20), Hn=10-20 a +-7: CHz = C”(CH3)C00C)lzcHz.

(CI, C old ℃H3)0) -(CHzCFIzO)
I, Hm, n=5-20 a, -8: 1, m, n=5-20 a, -9: CUt・C(CHz)COOCIIzCII□0(CI
l□CHzO) -CH1n=10~20 aji10: CHz□CHCOO(CHzCHzO) 1%C4H9
n = 5-20aji11: C1,, CHCOO(CIhCH(CH+)O), H
m = 5~20a+-12: CIIx□ClIC0OCHzCHzO(C)IzCH
zCHzCHzO), IHn=5~20 a +-13: C3t=C(CHt)Coo(CI, CHzO)nC,
H, n=5~20a+-14: CHz・C(CH3)COO(CHzCH(CHs)0
) -Hm=5~20 abi'5: 1, m, n=5~20 a +-16: CHz:C(CHz)COOCtlzCIhO(CHz
CHzCHzCHzO) -Hn=5-20 The anionic group-containing monoethylenically unsaturated monomer (a2) according to the present invention is an anionic group typified by a carboxyl group, a sulfonic acid group, a sulfuric acid group, and a phosphoric acid group. It is a monomer having one ethylenically unsaturated double bond, and its anionic group may be neutralized with a metal ion or ammonium ion. Examples include the following.

a z-1: CHz=CHCOOHa z-2:
C11z=CHCOOC'AtCHtCOONHaa
t4: CHt=CIICOOCHzCHzCII
zSOsNaa t-4: CHz=CHCOOCH
zCHzOSOJat-5: CHz・CHCOOC
ToCHzOP(0)(OH)za z-6: CH
z=C(CHs)COOHa z-7: CJ=C(
CL) COOCHzC1hCOONt14a z-8:
C)lz=c(CHs)COOCHzCHzCHt
SOJaa! -9: CHz=C(CHs)COO
C1bCHzOSOJa z-10: C1h=C(
C1h) COOC1lzCHzOP(0) (OH)
za z-11: Cth・C(CHi)COOCH
zCOON (CIri) zCationic group-containing monoethylenically unsaturated monomer (aZ) is a monomer that has both a cationic group represented by an amino group and one ethylenically unsaturated double bond. The cationic group may be quaternized, and examples include the following.

a:+-1: C) Iz=CHCOOCHzCHJ
(CL)za :l-2: CHz□CHCOOC
HzCHzCHJ (CH3) ic I! , -a3-
4: CHz2C(CHz)COOCHzCHJ(
CH+)za z-5: CHz=C(C13)C
OOC1hCHzCHJ(CHz):lCl-(C
sP+? ) It may be zNChCh-.

Examples of such monomers CB) include the following.

B-1: CsP+tCHzCHzOCOCH=C)
ItB-2: C7F+5cON(CHs)Ctlz
CHzOCOC1l=CI□B-3: C? F, 5C
ON(C2H4)CHIC)l! 0COCH=CI□B
-4: (,F+zCHzCHzSO□N■CIbC
) IzOCOCH=CHz The fluoroalkyl group-containing monoethylenically unsaturated monomer (B) according to the present invention is a monomer having one fluorinated aliphatic group and an ethylenically unsaturated double bond; Examples of the fluorinated aliphatic group include perfluoroalkyl groups or perfluoroalkenyl groups having 3 to 20 carbon atoms, and may be linear, branched, cyclic, or a combination thereof. Furthermore, fluorinated aliphatic groups have oxygen or nitrogen atoms combined in their main chains, such as CFiChCFzO (CF (
Ch) Ch3) n-CF (CF3) -B-6: C, P, O(CF (CF3)CFzO) zcP (
CF3) CONH (CI+□), 0COC1l=C1h
B-7: CsP+tCHzCIhOCOC(C)h
)・C112B-8: C, Pl? 502N(C)1
1) C) IZcH2OcOc(CHff)=C11□B
-9: C7F+5cON (CJs) C1l□CHz
OCOC (CHz) = Ctl□B-10: C, F, 3
CH2CH2SO□N11CHICH,0COC(C1
13)・CI+2B-12: C3F? O(CF (CF 3) CF 2o) 3CF
(CF ri C0N)l (CH2) 30COCI
I=C1l□C-3: 0H B-14: Ch(Cth)vcllzcHc)lzO
cOcll□cllzB-15: 1((CF2)as
OZN(CH,)C)12c)I! 0COC(CH3)
=CH2B-16: H(CFriac112cI(!0
COC(CH3)=CHz These monomers (B) are preferably monoethylenically unsaturated monomers containing a perfluoroalkyl group as the fluoroalkyl group.

The silicone group-containing monoethylenically unsaturated monomer (C) according to the present invention is a monomer having both a silicone group and one ethylenically unsaturated double bond, and examples thereof include the following: .

C-1: Cl2=CHCOO(CHz) y(Si(CHs)
Zo -h-st (CH3) 3n=5-500 C-2: L m, n=5-500! , mS n=5~500 C-4: Hz・C(CH,)Coo(CI+□) ding(St (
CH:l) zOsudingSi (C113) ]n=5~
500 1, mSn = 5~500 C-6: n-5~500 C-7: CHz=C'(CHs)Coo (COz) 3-fs
i (C82CHz) zo+-1-si (CH:
l) 3n=5-500 These monomers (C) are preferably monoethylenically unsaturated monomers containing polydimethylsiloxyl groups as silicone chains.

The surfactant of the present invention can be obtained by copolymerizing the monomers (A), (B), and (C) by a known and commonly used method, preferably in an organic solvent with a radical initiator as necessary. , the monomer (A) using a photosensitizer and a chain transfer agent,
It can be obtained by copolymerizing (B) and (C). The copolymer obtained in this way usually has a polystyrene equivalent of 1,000 or more, especially 5,000 to 10
Preferably, it has a weight average molecular weight of 0,000.

The copolymerization ratio of the polymer obtained from the monomers (A) to (C) is not particularly limited, but the commonly used copolymers are, when the total monomer is 100 parts by weight, It is a copolymer of the monomers (A) 16 to 70 parts by weight, (B) 2 to 65 parts by weight, and (C) 2 to 55 parts by weight.

The copolymer used in the fluorosurfactant of the present invention is composed of the monomers (A) to (C) and an alkyl group-containing monoethylenically unsaturated monomer (I). This is particularly preferred since it results in lower foaming properties.

The alkyl group-containing monoethylenically unsaturated monomer (D) here is a monomer having both an alkyl group and an ethylenically unsaturated double bond, and the alkyl group is linear, branched, It may have a cyclic structure or a combination thereof.

Examples of such monomers include the following alkyl (meth)acrylates having 1 to 30 carbon atoms.

D4: CH2=CHC00CH: ID-2: C
Hz=CIICOOCII□C1l□CH3D-3:
Cl2=CHCOOCI(CHs1h D-4: Cl2=CHCOO(CH2)SCH3D
-6:・CH1C41COOC1l□CH(CHz)s
cHzCLC)13 D-7: C1l□・CHCOO(CHz) l I
CH3D-3: CH,・CHCOO(CHz) 1
tcHzD-9: CH3CH3CH.

D-10: CH2=C(CH3)C00CR3CI
.

D-11: CHz=C(C1h)COOCCH3C
l.

D-12: CHz=C(CH3)COO(CI□)
scHiD-13: C12・C(CTo)COOC
IIzCH(CHz)+CH+CR□CH.

D-14: CHz=C(CHz)COO(CHz)
++C1hD-15: CHz=C(CHs)COO
(CHz)+tCH* As these monomers (D), monoethylenically unsaturated monomers containing an alkyl group having 8 to 12 carbon atoms are preferred.

In particular, a copolymer consisting of the monomers (A) to (D) having a low foaming property includes 20 to 50 parts by weight of the monomer (A) when the total monomer is 100 parts by weight, (B) 5 to 50 parts by weight, (
It is preferable to copolymerize 5 to 40 parts by weight of C) and 10 to 50 parts by weight of (D).

Radical initiators used as necessary during copolymerization include azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, methyl ethyl ketone peroxide, potassium persulfate, ammonium persulfate, etc. Examples of the chain transfer agent include benzophenone, acetophenone, benzoin, l-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-one, etc.; examples of the chain transfer agent include lauryl mercaptan, dodecyl mercaptan,
Examples include octyl thioglycolate and perfluorooctylethyl mercaptan.

As a solvent, methyl alcohol, ethyl alcohol,
Alcohols such as isopropyl alcohol, butyl alcohol, ethylene glycol monoethyl ether, ethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol diethyl ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dimethyl ether, methyl ethyl ether ethers such as methyl acetate, ethyl acetate, butyl acetate, chlorinated solvents such as chloroform, dichloroethane, perchloroethylene, carbon tetrachloride, aliphatic hydrocarbons such as hexane, heptane, octane, turpentine, etc. Examples include aromatic hydrocarbons such as toluene, xylene, and benzene.

The copolymer used as the surfactant of the present invention can be made water-soluble or oil-soluble by appropriately selecting the copolymerization ratio based on the hydrophilicity of the monomer (A). Either a water-soluble surfactant or an oil-soluble surfactant can be designed as required.

Next, the present invention will be explained in more detail with reference to Examples.

Hereinafter, "part" means "part by weight" and "%" means "% by weight."

Examples 1 to 2 and Comparative Example 1 400 parts of isopropyl alcohol and each 7-mer were added to birch at a copolymerization ratio shown in Table 1 in a flask, and 0.5 part of azobisisobutyronitrile was added. , using 1 part of octyl mercaptan at 65°C under nitrogen gas atmosphere.
Polymerization was carried out for 24 hours.

All of the obtained copolymers (solid content 20%) had a polystyrene equivalent weight average molecular weight of about 10,000.

The following tests were conducted using these copolymers. The test results are also shown in Table-1.

Surface Tension of Copolymer 0.1% Aqueous Solution A 20% isopropyl alcohol solution of crab copolymer was diluted with water, and a 0.1% aqueous solution was prepared using a platinum plate.
The surface tension of the aqueous solution was measured using the Mie method. (25°C
) Canvas disk swellability of 0.1% copolymer aqueous solution: To evaluate wettability, a disk-shaped canvas with a diameter of 1 inch (standard 1
No. 0) was gently floated on the surface of the aqueous solution, and the time it took for it to become naturally wetted by the aqueous solution and settle was measured (2
5°C).

Solubility of 1% copolymer aqueous solution: A 20% copolymer isopropyl alcohol solution was diluted with water to make a 1% aqueous solution, and the dissolution state was visually observed (2
5°C). The results were indicated as completely transparent: ◎, slightly cloudy: O1 was hardly dissolved: ×.

Foaming property of 1% copolymer aqueous solution: Pour 5IIll of 1% aqueous solution into a glass test tube with an inner diameter of 10 mm, tightly stopper it, shake vertically 50 times, and after 1 minute of standing, foam height (
mm) was measured (25°C).

Defoaming time of 1% copolymer aqueous solution: Put 50g of 1% copolymer aqueous solution into a 100mf wide sample bottle, tightly stopper it, shake it vertically 50 times, and let it stand for 1 minute until the bubbles completely disappear. was measured (25°C).

Leveling property for resin for water-based paints: Resin for water-based paints (Watersol S-74 manufactured by Dainippon Ink & Chemicals)
4) Add a 1% aqueous copolymer solution in an amount equivalent to the solid content of 0.1% in solid terms, add water in an amount equivalent to 25% of the resin, and stir well with a brush. It was painted on a flat plate, and the appearance of the paint film was observed after air drying.

The paint film is homogeneous and smooth: ◎, Brush marks remain on the paint film surface: △, The paint film surface has roughness:〉
Indicated by <.

Examples 3 to 7 and Comparative Example 2 Polymerization was carried out in exactly the same manner as in Example 1, except that 400 parts of butyl cellosolve was used as a solvent and each monomer was used at the copolymerization ratio shown in Table 1.

All of the obtained copolymers (solid content 20%) had a polystyrene equivalent weight average molecular weight of about 10,000.

Tests were conducted in the same manner as in Example 1 using these copolymers. The test results are also shown in Table-1.

Examples 8 to 10 and Comparative Example 2 400 parts of toluene and each monomer were placed in a flask in Table 2.
0.5 part of azobisisobutyronitrile, 1 part of octyl mercaptan were charged in bulk so that the copolymerization ratio shown in
Polymerization was carried out at 65°C for 24 hours under a nitrogen gas atmosphere.

All of the obtained copolymers (solid content 20%) had an average molecular weight of about 10,000 in terms of polystyrene. The following tests were conducted using these copolymers. Table 2 shows the test results.
It was shown to.

Solubility of 1% copolymer toluene solution: Dilute 20% copolymer solution in toluene with toluene,
% toluene solution, and the dissolution state was visually observed (2
5°C).

Surface tension of copolymer 1% toluene solution Above copolymer 1
% toluene solution was measured by the Wilhelmy method using a platinum plate (25''C).

Foaming properties of a 1% copolymer solution in toluene: The foaming properties of a 1% copolymer aqueous solution were tested according to the method.

Defoaming time of 1% copolymer toluene solution: Put 50g of 1% copolymer toluene solution into a 100mj2 wide mouth sample bottle, shake it vertically 30 times after sealing it, and measure the time until the foam disappears completely after standing still. (25°C).

Defoaming time of 1 part copolymer solution in organic solvent: 20% copolymer
The toluene solution was diluted with turpentine, perchlorene, or butyl acetate to obtain a 1% solution, and the defoaming time was measured in the same manner as above.

Leveling property for paint resin: ■ 1 part by weight (solid content) was added per 100 parts by weight of resin solid content of an acrylic air-drying paint (white), and the mixture was coated on a steel plate while stirring well. After being left at room temperature for one day, the appearance of the coating film surface was observed.

■ 1 part by weight (solid content) per 100 parts by weight of resin solid content of a baking clear paint (acrylic-melamine) was added and coated on a steel plate while stirring well. 3 at 140°C
After curing for 0 minutes, the appearance of the coating film surface was observed.

■ 1 part by weight (solid content) per resin solid content of baking white paint (alkyd-melamine) was added, and the paint was applied onto a steel plate while stirring well. Cure at 140°C for 25 minutes,
The appearance of the coating film surface was observed.

Examples 11 to 15 and Comparative Examples Polymerization was carried out in exactly the same manner as in Example 8, except that 400 parts of methyl isobutyl ketone was used as a solvent and each monomer was used at the copolymerization ratio shown in Table 2.

All of the obtained copolymers (solid content 20%) had an average molecular weight of about 10,000 in terms of polystyrene.

Tests were conducted in the same manner as in Example 7 using these copolymers. The test results are also shown in Table-2.

(Evaluation criteria for each test are based on Example 1.) "Effects of the Invention J The surfactant of the present invention has extremely low foaming properties compared to conventional fluorosurfactants, so it can prevent foaming of paints, In addition to being used as an antifoaming agent and leveling agent for paint that significantly prevents film roughness, it is also used as a polishing wax, cleaner, anti-fog, cleaning agent, metal surface treatment, corrosion prevention, rust prevention oil, solder flux, and plating bath addition. agents, emulsifiers, lubricating oil additives, internal additions to plastics, surface treatment of plastics, glass fiber treatment agents, mold release agents, anti-blocking agents, additives for wet film formation of urethane, penetrants for fiber processing, fibers It can be used for various purposes such as oil agents, oil-repellent treatments for paper, penetration enhancers for paper processing, surface treatment agents for pigments, and control of painting operations.

Claims (1)

[Scope of Claims] 1. A surfactant comprising a polymer containing at least one group selected from nonionic, anionic, and cationic groups, a fluoroalkyl group, and a silicone group. 2. The polymer contains a nonionic group-containing monoethylenically unsaturated monomer (a_1), an anionic group-containing monoethylenically unsaturated monomer (a_2), and a cationic group-containing monoethylenically unsaturated monomer At least one monoethylenically unsaturated monomer (A) selected from the group consisting of (a_3), a fluoroalkyl group-containing monoethylenically unsaturated monomer (B), and a silicone group-containing monoethylenically unsaturated monomer ( The surfactant according to claim 1, consisting of C). 3. The polymer contains a nonionic group-containing monoethylenically unsaturated monomer (a_1), an anionic group-containing monoethylenically unsaturated monomer (a_2), and a cationic group-containing monoethylenically unsaturated monomer At least one monoethylenically unsaturated monomer (A) selected from the group consisting of (a_3), a fluoroalkyl group-containing monoethylenically unsaturated monomer (B), and a silicone group-containing monoethylenically unsaturated monomer ( The surfactant according to claim 1, comprising C) and an alkyl group-containing monoethylenically unsaturated monomer (D). 4. The surfactant according to claim 2 or 3, wherein the silicone group-containing monoethylenically unsaturated monomer (C) is a polydimethylsiloxane group-containing monoethylenically unsaturated monomer. 5. Alkyl group-containing monoethylenically unsaturated monomer (D)
The surfactant according to claim 2, 3 or 4, wherein is an alkyl (meth)acrylate having 8 to 12 carbon atoms. 6. The monomers (a_1), (a_2) and (a_3)
is a monoethylenically unsaturated monomer containing a polyoxyalkylene group, a monoethylenically unsaturated monomer containing an acid residue, or a monoethylenically unsaturated monomer containing an optionally quaternized amino group. The surfactant according to claim 5, which is a surfactant. 7. A leveling agent comprising the surfactant according to claim 1.