JPH06116340A - Novel copolymer and stain-proof processing agent - Google Patents

Abstract

PURPOSE:To provide a novel copolymer containing structural units such as (meth)acrylate ester having fluoroalkyl group, having a prescribed mol.wt., excellent in durable stain-releasing property, and useful as stain-proof processing agents, etc. CONSTITUTION:This new copolymer comprises structural units derived from (A) a (meth)acrylate ester having a fluoroalkyl group preferably in an amount of 30-70wt.%, (B) a polyalkylene glycol (meth)acrylate preferably in an amount of 20-60wt.%, (C) 3-chloro-2-hydroxypropyl (meth)acrylate preferably in an amount of 0.5-30wt.%, and (D) glycerol mono(meth)acrylate preferably in an amount of 0.5-30wt.%, and has a mol.wt. of 1000-500000.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel copolymer and an antifouling agent containing the same.

[0002]

2. Description of the Related Art (meth) acrylic acid ester containing a fluoroalkyl group (as a stainproofing agent for imparting water and oil repellency to textile fabrics, etc., and facilitating removal of stains attached to fibers by washing etc. Hereinafter, a copolymer of a fluorine-containing compound) and a hydrophilic group-containing compound is known (JP-A-53-134786, 59-204).
980 and 62-7782).

Among the polymers of fluorine-containing compounds,
In order to improve the water-repellent and oil-repellent durability against washing, a copolymer comprising a fluorine-containing compound, a (meth) acrylic acid ester containing a hydroxyl group, and optionally an alkyl (meth) acrylate has been developed (for example, Japanese Patent Publication No. 50-3798, U.S. Pat. No. 3,356,628.
No.).

However, the copolymer of a (meth) acrylic acid ester having a hydrophilic group such as a hydroxyl group or a polyethylene glycol group and a (meth) acrylic acid ester having a fluoroalkyl group has an initial stain releasability and repellency. The water and oil repellency are slightly good, but the stain releasability and the water repellency durability are slight, and they are not at a satisfactory level. To solve these problems, we
Previously (a) fluoroalkyl group-containing (meth) acrylic acid ester, (b) polyalkylene glycol (meth) acrylate, (c) hydroxyl group-containing (meth) acrylic acid ester, and (d) alkyl (meth) acrylate Alternatively, a copolymer containing a constitutional unit derived from butadiene was found, and a tentative solution was found (JP-A-3-
No. 103411). However, unfortunately, there is still room for improvement regarding durability, not always
I can't say I'm completely satisfied.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide an antifouling finishing agent having improved initial durability, while having an initial stain release property.

[0006]

The gist of the present invention is (a) an acrylic ester or methacrylic ester having a fluoroalkyl group, (b) a polyalkylene glycol acrylate or a polyalkylene glycol methacrylate, and (c) 3-chloro. 2-hydroxypropyl acrylate or 3-chloro-2-hydroxypropyl methacrylate, and (d) a copolymer having a molecular weight of 1,000 to 500,000 containing constitutional units derived from glycerol monoacrylate or glycerol monomethacrylate. Another subject matter of the present invention lies in an antifouling agent containing the copolymer as an active ingredient.

The monomers that give each structural unit will be described below. The monomer (a) is generally represented by the formula: RfROCOR ¹ C═CH ₂ [wherein Rf is a linear or branched perfluoroalkyl group having 3 to 20 carbon atoms, and R ¹ is a hydrogen atom. or a methyl radical, R is a linear or branched alkylene group having 1 to 10 carbon ^{_{atoms, -SO 2 N (R 2)}} R 3
A group (R ² is an alkyl group having 1 to 10 carbon atoms,
R ³ represents a linear or branched alkylene group having 1 to 10 carbon atoms. ) Or —CH ₂ CH (OR ⁴ ) C
H ₂ - represents a group (R ⁴ represents an acyl group having a hydrogen atom or 1 to 10 carbon atoms.). ] It is a compound shown by these.

Specific examples of the monomer (a) are listed below. CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₁₀ OCOCH = CH ₂ CF ₃ (CF ₂ ) ₆ CH ₂ OCOC (CH ₃ ) = CH ₂ (CF ₃ ) ₂ CF (CF ₂ ) ₈ (CH ₂ ) ₂ OCOCH = CH ₂ CF ₃ CF ₂ (CF ₂ ) ₆ (CH ₂ ) ₂ OCOC (CH ₃ ) = CH ₂ CF ₃ CF ₂ (CF ₂ ) ₆ (CH ₂ ) ₂ OCOCH = CH ₂ CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) (CH ₂ ) ₂ OCOCH = CH ₂ CF ₃ (CF ₂ ) ₇ SO ₂ N (C ₂ H ₅ ) (CH ₂ ) ₂ OCOC (CH ₃ ) = CH ₂ (CF ₃ ) ₂ CF (CF ₂ ) ₈ CH ₂ CH (OCOCH ₃ ) CH ₂ OCOC (CH ₃ ) = CH ₂ (CF ₃ ) ₂ CF (CF ₂ ) ₈ CH ₂ CH (OH) CH ₂ OCOCH = CH ₂

The monomer (b) has the formula: CH ₂ = CR ⁵ COO- (R ⁶ O) _n -R ⁷ [wherein R ⁵ and R ⁷ are hydrogen atoms or methyl groups, R ⁶
Represents an alkylene group having 2 to 6 carbon atoms, and n represents an integer of 3 to 50. ] It is preferable that it is a compound shown by these.

Usually, --CH ₂ CH ₂ --is preferred as R ⁶ , but --CH (CH ₃ ) CH _2- , --CH (C ₂ H ₅ ) CH
It may be _2-, etc. That is, in the present invention, polyethylene glycol acrylate or methacrylate in which R ⁶ is —CH ₂ CH ₂ — can be particularly preferably used. Further, n is selected from an integer of 3 to 50, but usually n
Particularly good results are obtained when is selected from the integers from 9 to 25. Of course, it may be in the form of a mixture of two or more kinds in which R ⁶ is different and n is different.

Specific examples of the monomer (b) are listed below. CH ₂ ＝ C (CH ₃ ) COO (CH ₂ CH ₂ O) _3-9 H CH ₂ ＝ C (CH ₃ ) COO (CH ₂ CH ₂ O) ₉ H CH ₂ ＝ C (CH ₃ ) COO (CH ₂ CH ₂ O) ₆ H CH ₂ ＝ CHCOO (CH ₂ CH (CH ₃ ) O) ₁₁ CH ₃ CH ₂ ＝ C (CH ₃ ) COO (CH ₂ CH ₂ O) ₉ H CH ₂ ＝ C (CH ₃ ) COO (CH ₂ CH ₂ O) ₅ (CH ₂ CH (CH ₃ ) O) ₃ H CH ₂ ＝ C (CH ₃ ) COO (CH ₂ CH ₂ O) ₉ CH ₃ CH ₂ ＝ C (CH ₃ ) COO (CH ₂ CH ₂ O) ₂₃ CH ₃ CH ₂ = C (CH ₃ ) COO (CH ₂ CH ₂ O) ₄₀ H

The monomer (c), 3-chloro-2-hydroxypropyl (meth) acrylate, has the formula:

[Chemical 1] [In the formula, R ⁸ is a hydrogen atom or a methyl group. ] Is shown.

The monomer (d) glycerol mono (meth) acrylate has the formula:

[Chemical 2] [In the formula, R ⁹ is a hydrogen atom or a methyl group. ] Is shown.

In the copolymer of the present invention, a (meth) acrylic acid ester having a fluoroalkyl group (monomer
The copolymerization ratio of (a)) is at least 25% by weight, preferably 30 to 70% by weight. If it is less than 25% by weight, the water and oil repellency is not sufficient.

The copolymerization ratio of polyalkylene glycol (meth) acrylate (monomer (b)) is at least 15% by weight, preferably 20 to 60% by weight. 15% by weight
If it is less than 1, the dispersibility in water is not good and the durability is not sufficient.

The copolymerization ratio of 3-chloro-2-hydroxypropyl (meth) acrylate (monomer (c)) is at least 0.5% by weight, preferably 0.5 to 30% by weight. Glycerol mono (meth) acrylate (monomer
The copolymerization ratio of (d)) is at least 0.5% by weight, preferably 0.5 to 30% by weight.

The total copolymerization ratio of 3-chloro-2-hydroxypropyl (meth) acrylate (monomer (c)) and glycerol mono (meth) acrylate (monomer (d)) is at least 5% by weight. , Preferably 8 to 30% by weight
Is preferred. If it is less than 5% by weight, stain releasability and durability are not sufficient. Moreover, the ratio of 3-chloro-2-hydroxypropyl (meth) acrylate to the total of the monomer (c) and the monomer (d) is 10 to 90.
It is preferable that the content is wt%, more preferably 20 to 80 wt%. If the content is less than 10% by weight or more than 90% by weight, the durability is insufficient.

The molecular weight of the copolymer of the present invention is from 1,000 to
It is 500000, preferably 5000-200000. If it is less than 1000, the durability is not sufficient,
If it is 0 or more, the viscosity of the treatment liquid is too high and the workability is deteriorated.
The molecular weight is a value determined by gel permeation chromatography in terms of polystyrene. The copolymer of the present invention may be a random copolymer or a block copolymer.

The copolymer of the present invention comprises the monomer (a),
In addition to (b), (c) and (d), ethylene, vinyl chloride, vinylidene halide, styrene, acrylic acid and its alkyl ester, methacrylic acid and its alkyl ester, benzyl methacrylate, vinyl alkyl ketone, vinyl alkyl ether. In addition to water and oil repellency, durability, flexibility, and cost-effective co-polymerization by copolymerizing polymerizable compounds that do not contain fluoroalkyl groups, such as ethylene, isoprene, chloroprene, maleic anhydride, and butadiene. They can be made into a coalescence, or solubility, water pressure resistance and various other properties can be appropriately improved. The amount of these copolymerizable compounds containing no fluoroalkyl group is 0 to 40% by weight, preferably 0 to 20%.
% By weight.

In order to obtain the copolymer of the present invention, various polymerization reaction systems and conditions can be arbitrarily selected, and any of various polymerization systems such as bulk polymerization, solution polymerization, emulsion polymerization and radiation polymerization can be selected. Can also be adopted. For example, a method in which a mixture of compounds to be copolymerized is emulsified in water in the presence of a surfactant and copolymerized with stirring can be adopted.

As the polymerization initiator of the reaction system, various compounds of peroxide, azo type or persulfate type can be used. When the surfactant contains polyethylene glycol acrylate or methacrylate as a constituent unit,
It does not have to be added separately as it serves its function, but various anionic, cationic or nonionic emulsifiers may optionally be added. It is also possible to dissolve the raw material polymerizable compound in an appropriate organic solvent and perform solution polymerization by the action of a polymerization initiation source (a peroxide, an azo compound or ionizing radiation, which is soluble in the organic solvent used).

The copolymer thus obtained can be prepared into an arbitrary form such as an emulsion, a solvent solution or an aerosol according to a conventional method, and can be used as an antifouling agent. The copolymer of the present invention can be applied to the article to be treated as an antifouling agent by an arbitrary method depending on the type of the article to be treated and the form of preparation (solvent solution type, aerosol type, etc.). For example, in the case of an aqueous emulsion or a solvent solution type, a method of adhering to the surface of the object to be treated and drying by a known method of coating such as dip coating can be adopted. If necessary, curing may be carried out by applying it together with a suitable crosslinking agent. The aerosol-type antifouling agent may be simply sprayed and sprayed on the object to be treated, and can exhibit sufficient water and oil repellency and stain releasability after being immediately dried. Further, the copolymer of the present invention may be mixed with another polymer blender to be used as an antifouling agent. It is of course possible to obtain an antifouling agent by appropriately using other water repellents, oil repellents, insect repellents, flame retardants, antistatic agents, dye stabilizers and anti-wrinkle agents as additives.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to Examples, Comparative Examples and Test Examples. However,%
"%" Means "% by weight" unless otherwise specified.

The water repellency and oil repellency shown in the following Examples and Comparative Examples are represented by the following scales. That is, the water repellency is determined by the spray method of JIS L-1005. (Refer to Table 1) and the oil repellency is shown in Table 2
A few drops (diameter about 4 mm) of the test solution shown in 2 are placed on the test cloth at two locations, and the penetration state after 30 seconds is judged (AATCC
-TM118-1966).

[0025]

TABLE 1 Wet over the entire 50 surface shows a wet water repellent No. state 100 having no adhesion wetting the surface shows a partially wet 80 surface shows a slightly adhering wetting 90 surface 70 surface What 0 indicates that the front and back surfaces are completely wet

[0026]

Table 2 Oil repellent test solution surface tension (dyne / cm 25 ° C.) 8 n-heptane 20.0 7 n-octane 21.8 6 n-decane 23.5 5 n-dodecane 25.0 4 n-tetradecane 26 .7 3 n-Hexadecane 27.3 2 Hexadecane 35 / nu 29.6 Jol 65 mixed solution 1 Nujol 31.2 0 1-

The dirt release performance (SR property) was tested as follows. That is, spread the test cloth on the horizontally spread blotter paper and use the dirty motor oil (SAE20W-4
0, put it in the engine of a small passenger car and drop 5 drops of it discharged after traveling 4000 km), put a polyethylene sheet on it, put a weight of 2 kg, and after 60 seconds remove the weight and polyethylene sheet, and remove the excess oil After leaving it for 1 hour at room temperature, add ballast cloth to the test cloth to make it 1 kg, and then add 25 g of detergent (Super Zab: trade name).
Using an electric washing machine, bath volume 35 liters, liquid temperature 40
Treat at 10 ° C for 10 minutes, rinse and air dry. The state of residual stains on the dried test cloth is compared with a judgment standard photographic plate, and the stain release performance is expressed by the corresponding judgment grade (see Table 3). The judgment standard photographic plate is AATCC-Test method 13
0-1970 was used.

[0028]

[Table 3] Judgment grade Judgment standard 1.0 Significant stain remaining 2.0 2.0 Stain remaining equivalent 3.0 Slight stain remaining 4.0 Inconspicuous stain 5. 0 No stain remains

Example 1 CF ₃ CF ₂ (CF ₂ CF ₂ ) _n CH ₂ CH ₂ OCOC (CH ₃ ) =
CH ₂ a compound represented by (n = 3, 4, 5 the weight ratio of the compound of the 5: 3: 1 _{mixture) 20g, CH 2 = C (} CH 3) COO
_{(CH 2 CH 2 O) 9} CH 3 10g, CH 2 = C (CH 3) COO
(CH ₂ CH (CH ₃ ) O) ₁₂ H 5 g, CH ₂ ═C (CH ₃ ) CO
OCH ₂ CH (OH) CH ₂ Cl 4 g, CH ₂ ═C (CH ₃ ) C
1 g of OOCH ₂ CH (OH) CH ₂ OH and 60 g of isopropanol were placed in a four-necked flask, and oxygen in the system was sufficiently replaced with nitrogen, and then azobisisobutyronitrile 0.1 g was added.
g was added and a copolymerization reaction was carried out while stirring at 70 ° C. for 10 hours. It was shown by gas chromatography that the conversion of the copolymerization reaction was 97% or more. From this conversion rate, it was found that the ratio of each structural unit in the obtained copolymer was almost the same as the ratio of the charged monomers. At the end of the polymerization reaction, 40 g of isopropanol,
60 g of deionized water was charged and diluted. The resulting copolymer solution contained 19.5% copolymer solids. The molecular weight of the copolymer was 12000 (in terms of styrene) according to gel permeation chromatography.

Test Example 1 The copolymer dispersion of Example 1 was used to give a copolymer solid content of 0.6.
It was diluted and adjusted with water so that it would be weight%. A PET pongy cloth was dipped in this, and squeezed with a roll to obtain a wet pickup of 80%. Then, it was dried at 110 ° C. for 2 minutes and further heat-treated at 180 ° C. for 30 seconds to complete the water / oil repellent / fouling prevention treatment. For the cloth treated in this way,
The water repellency, the oil repellency and the stain release property were measured at the initial stage and after the same washing as in the stain release performance test 5 times. The results are shown in Table 4.

Example 2 In the same manner as in Example 1, CF ₃ CF ₂ (CF ₂ CF ₂ ) nCH ₂
CH ₂ OOCCH = CH ₂ (20 g of a compound represented by a mixture of n = 3, 4, and 5 in a weight ratio of 5: 3: 1), CH ₂ =
C (CH ₃ ) COO (CH ₂ CH ₂ O) ₆ H 8 g, CH ₂ = C (C
H ₃ ) COO (CH ₂ CH (CH ₃ ) O) ₁₂ H 7 g, CH ₂ = C
_{(CH 3) COOCH 2 CH (} OH) CH 2 Cl4g, CH 2 = C
(CH ₃ ) COOCH ₂ CH (OH) CH ₂ OH 1 g was copolymerized. The resulting dispersion contained 19.5% copolymer solids. Table 4 shows the composition and molecular weight of the copolymer.

Examples 3 to 7 The procedure of Example 1 was repeated except that the monomers shown in Table 4 were used to obtain copolymer dispersions. Table 4 shows the composition and molecular weight of the copolymer.

Test Examples 2 to 7 The dispersions prepared in Examples 2 to 7 had a copolymer solid content of 0.6.
It was diluted and adjusted with water so that it would be weight%. A PET pongie cloth was treated in the same manner as in Test Example 1 using these diluted solutions. The treated fabric had the performance shown in Table 4.

Comparative Examples 1 to 4 The procedure of Example 1 was repeated except that the monomers shown in Table 4 were used to obtain copolymer dispersions. Table 4 shows the results of evaluating the dispersion liquid in the same manner as in Example 1.

Example 8 CF ₃ CF ₂ (CF ₂ CF ₂ ) _n CH ₂ CH ₂ OCOC (CH ₃ ) =
CH ₂ a compound represented by (n = 3, 4, 5 the weight ratio of the compound of the 5: 3: 1 _{mixture) 18g, CH 2 = C (} CH 3) COO
_{(CH 2 CH 2 O) 9} CH 3 10g, CH 2 = C (CH 3) COO
(CH ₂ CH (CH ₃ ) O) ₉ H 7 g, CH ₂ ═C (CH ₃ ) CO
OCH ₂ CH (OH) CH ₂ Cl 4 g, CH ₂ ═C (CH ₃ ) C
OOCH ₂ CH (OH) CH ₂ OH 1g, deoxygenated pure water 7
0 g, 80 g of isopropanol and 0.04 g of n-lauryl mercaptan were placed in a glass four-necked flask equipped with a mercury thermometer and a stirrer of polytetrafluoroethylene crescent-shaped blade, and stirred under a nitrogen stream. Dispersed well. Furthermore, after bubbling nitrogen for about 1 hour, 0.4 g of azobisisobutylamidine hydrochloride
Was added to 10 g of water, and the solution was further stirred at 60 ° C. for 10 hours under a nitrogen stream to carry out a copolymerization reaction. Conversion rate of copolymerization reaction is 99% by gas chromatography
It was shown that it was above. From this conversion rate, it was found that the ratio of each structural unit in the obtained copolymer was almost the same as the ratio of the charged monomers. The resulting dispersion contained 20% copolymer solids. The composition and molecular weight of the copolymer are shown in Table 5.

Test Example 8 The copolymer dispersion prepared in Example 7 was used to obtain a copolymer solid content of 0.6.
It was diluted and adjusted with water so that it would be weight%. 35 cotton on this
%, 65% polyester mixed fabric was dipped and squeezed with a roll to obtain a wet pickup of 80%. Then 1
The antifouling treatment was completed by drying at 05 ° C for 3 minutes and further heat-treating at 150 ° C for 3 minutes. With respect to the cloth thus treated, water repellency, oil repellency and stain release property were measured at the initial stage and after 5 times of washing as in the stain release performance test. The results are shown in Table 5.

Example 9 In the same manner as in Example 8, CF ₃ CF ₂ (CF ₂ CF ₂ ) _n CH ₂ C
14 g of a compound represented by H ₂ OCOCH═CH ₂ (a mixture of n = 3, 4, and 5 in a weight ratio of 5: 3: 1), CH ₂ ═C
(CH ₃ ) COO (CH ₂ CH ₂ O) ₉ H 11 g, CH ₂ ═C (C
H ₃ ) COO (CH ₂ CH (CH ₃ ) O) ₁₂ H 10 g, CH ₂ =
C (CH ₃ ) COOCH ₂ CH (OH) CH ₂ Cl ₄ g, CH ₂ =
1 g of C (CH ₃ ) COOCH ₂ CH (OH) CH ₂ OH was copolymerized. The resulting dispersion contained 19.8% copolymer solids. The composition and molecular weight of the copolymer are shown in Table 5.

Examples 10 to 13 The same procedure as in Example 8 was repeated except that the monomers shown in Table 5 were used to obtain copolymer dispersions. The composition and molecular weight of the copolymer are shown in Table 5.

Test Examples 9 to 13 The copolymer dispersions prepared in Examples 9 to 13 were diluted with water so that the solid content of the copolymer was 0.6% by weight. Using these diluents, 35% cotton, as in Test Example 8,
A mixed fabric of 65% polyester was treated. The treated fabric had the performance shown in Table 5.

Comparative Examples 5 to 10 The same procedure as in Example 8 was repeated except that the monomers shown in Table 5 were used to obtain copolymer dispersions. Table 5 shows the results of evaluating the dispersion liquid in the same manner as in Example 8.

[0041]

[Table 4]

[0042]

[Table 5]

In Tables 4 and 5, the abbreviations have the following meanings. SFA _{is, CF 3 CF 2 (CF 2} CF 2) n CH 2 CH 2 OCO
CH = CH ₂ (mixture of n = 3, 4, and 5 in a weight ratio of 5: 3: 1) SFMA is CF ₃ CF ₂ (CF ₂ CF ₂ ) _n CH ₂ CH ₂ OC.
_{OC (CH 3) = CH 2} (n = 3,4,5 weight ratio of the compound of 5: 3: mixture of 1) brFA _{is, (CF 3) 2 CF 2} (CF 2 CF 2) n CH 2 CH 2 O
COCH = CH ₂ (a mixture of n = 3, 4, and 5 in a weight ratio of 5: 3: 1) PE-200 has CH ₂ = C (CH ₃ ) COO (CH ₂ CH ₂
O) ₆ H

PE-350 is CH ₂ = C (CH ₃ ) COO
_{(CH 2 CH 2 O) 9} H M-90G _{is, CH 2 = C (CH 3} ) COO (CH 2 CH 2 O)
₉ CH ₃ PP-500 _{is, CH 2 = C (CH 3} ) COO (CH 2 CH
_{(CH 3) O) 8 H} PP-700 _{is, CH 2 = C (CH 3} ) COO (CH 2 CH
_{(CH 3) O) 9 H} PP-800 _{is, CH 2 = C (CH 3} ) COO (CH 2 CH
(CH ₃ ) O) ₁₂ H HCPMA is 3-chloro-2-hydroxypropyl methacrylate GLM is glycerol monomethacrylate N-MAM is N-methylol acrylamide BAMA is CH ₂ ═C (CH ₃ ) —CO—NH. -CH ₂ O
-C ₄ H ₉ THFA is tetrahydrofurfuryl acrylate

[0045]

The antifouling agent using the copolymer of the present invention is very excellent in stain releasability as compared with the conventional antifouling agents.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshitaka Saito 4-23-1, Bunkyo, Fukui City, Fukui Prefecture Nikka Kagaku Co., Ltd. (72) Inventor Akio Tsujimoto 4-23-1, Bunkyo, Fukui City, Fukui Prefecture Nichika Kagaku Co., Ltd. (72) Inventor Motonobu Kubo 1-1, Nishiichitsuya, Settsu-shi, Osaka Daikin Industries, Ltd. Yodogawa Works (72) Inventor Norimasa Uesugi 1-1, Nishiichitsuya, Settsu-shi, Osaka Daikin Yodogawa Manufacturing Co., Ltd.

Claims (2)

[Claims] 1. (a) Acrylic ester or methacrylic acid ester having a fluoroalkyl group, (b) Polyalkylene glycol acrylate or polyalkylene glycol methacrylate, (c) 3-chloro-2-hydroxypropyl acrylate or 3-chloro. 2-hydroxypropyl methacrylate, and (d) a molecular weight of 100 containing a constitutional unit derived from glycerol monoacrylate or glycerol monomethacrylate
0-500000 copolymers. 2. An antifouling agent containing the copolymer according to claim 1 as an active ingredient.