JPH0355515B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a water- and oil-repellent stain-proofing agent, and more specifically, to a water- and oil-repellent stain-proofing agent comprising a specific urethane compound base material containing a polyfluoroalkyl group and a specific blender copolymer. Conventionally, various polyfluoroalkyl group-containing urethane compounds have been proposed as substances useful for antifouling treatment of interior products such as carpets. For example, see US Pat. No. 3,398,182, US Pat. No. 3,484,281, JP-A-53-112855, JP-A-54-74,000, and the like. and,
In JP-A-47-7600, etc., it has been proposed to antifouling carpets by using a polyfluoroalkyl group-containing main agent in combination with a water-insoluble addition polymer blender having a specific main transition temperature and solubility parameter. There is. The present inventor has identified a polyfluoroalkyl group (hereinafter referred to as
As a result of various studies and studies on antifouling treatment using urethane compounds containing urethane compounds (sometimes abbreviated as R _f groups), we have found that carpets can be treated by using specific R _f group-containing urethane compounds together with R _f group-containing acrylate compounds. In addition to improving stain resistance against dry stains in treatments such as
It has been found that oil repellency can be imparted. In particular, good results can be obtained with an antifouling agent in which a specific R _f group-containing urethane compound is dispersed in an aqueous medium in the coexistence of a specific hydrophilic group-containing urethane compound. Thus, the present invention provides the general formula R _f ¹ −X ¹ −A ¹ −
A repellent comprising a polymer or copolymer containing a urethane compound represented by CONH-Y ¹ -NHCO-A ² -Z and an acrylate represented by the general formula R _f ROCOCR'=CH ₂ as constituent units. This product provides a new water-oil-repellent and stain-proofing agent. A particularly preferred embodiment of the antifouling agent of the present invention is in the form of an aqueous dispersion dispersed in a medium mainly consisting of water. In the case of such an aqueous dispersion, it is desirable to perform the dispersion in the coexistence of a specific hydrophilic group-containing urethane compound. That is, the general formula R _f ² −
The urethane compound is dispersed in a medium mainly consisting of water in the presence of a hydrophilic group-containing urethane compound represented by X ² -A ³ -CONH-Y ² -NHCO-W. Therefore, R _f ¹ and R _f ² of the urethane compound and
are each a linear or branched polyfluoroalkyl group having 4 to 16 carbon atoms, and those in which the terminal end is a perfluoroalkyl group are usually used,
Those containing a hydrogen atom or a chlorine atom at the end,
Alternatively, an oxyperfluoroalkylene-containing group can also be used. A preferred embodiment of R _f ¹ and R _f ² is a perfluoroalkyl group, which has 6 to 12 carbon atoms.
Particularly preferred are X ¹ and X ² are each −R ¹
−, −CON(R ² )−Q ¹ −, and −SO ₂ N(R ² )−Q ¹
- (However, -R ¹ - represents an alkylene group, R ² represents a hydrogen atom or lower alkyl group, and Q ¹ represents a divalent organic group)
It is one of the alkylene groups, especially those with 1 to 20 carbon atoms.
preferably. Also, A ¹ , A ² , and A ³
are respectively -O-, -S-, or -N(R ³ )- (however,
R ³ represents a hydrogen atom or a lower alkyl group)
From the viewpoint of availability, -O- is preferred. Next, Y ¹ and Y ² are divalent organic groups, and those with carbon numbers of 24 or less, especially 6 to 15, are selected to stiffen the urethane molecule and improve the durability of its antifouling performance. Those containing at least one aromatic ring or aliphatic ring are preferably employed.
Z in the urethane compound is a non-hydrophilic monovalent organic group, and examples include those containing an alkyl group, an aryl group, a hetero atom, and -X ¹ -R _f ¹ . From the viewpoint of oil and stain resistance, a lower alkyl group having 1 to 4 carbon atoms is preferably employed. W in the urethane compound is a hydrophilic group, -(CH ₂ CH ₂ O) _n -R ⁴ (where m is an integer of 1 to 50, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) ) and other nonionic groups,
−(CH ₂ CH ₂ O) _n −SO ₃ M (where M is a hydrogen atom,
alkali metal, one of the ammonium groups), -
(CH ₂ CH ₂ O) _n −PO ₃ M, −CH ₂ CH ₂ SO ₃ M, −
Anionic groups such as CH ₂ CH ₂ COOM, and -CH ₂ CH ₂ NR′R″RX (where R′, R″, R are alkyl groups, aryl groups, and X is Cl, Br, I, OCOCH ₃ Various examples include cationic groups such as -(CH ₂ CH ₂ O) ₂₀ -CH ₃ from the viewpoint of compatibility with other processing agents. etc. can be preferably adopted. In the present invention, R _f ¹ and R _f ² , X ¹ and X ² , A ¹ and
A ³ , Y ¹ and Y ² do not necessarily have to match. Moreover, the urethane compound and may each be a mixture. For example, it is also possible to use a mixture of a plurality of urethane compounds having different numbers of carbon atoms, R _f ¹ and R _f ² , respectively. In the present invention, when dispersing the urethane compound in a medium mainly composed of water, it is important to allow the urethane compound to coexist. When a urethane compound is not coexisting, that is, when the urethane compound is used alone for dispersion, or when the urethane compound is replaced by a common surfactant, such as sodium lauryl sulfate, alkylphenol polyglycol ether, ammonium perfluorooctanoate, etc. dispersion may be difficult or water repellent, oil repellent,
There is a tendency for dry soil resistance to decrease. The coexistence ratio (weight ratio) of urethane compound/urethane compound is not particularly limited, but if the ratio is too small, the stability of the dispersion will decrease, and if it is too large, the water repellency will tend to decrease. Usually, it can be selected from the range of 99/1 to 25/75, preferably 95/5 to 50/50. In the present invention, the medium mainly composed of water includes the case of water alone, but it is a more preferable embodiment that a water-soluble organic solvent coexists. Addition of a water-soluble organic solvent lowers the interfacial tension of the medium, lowers the melting point of the urethane compound, and increases the solubility, making dispersion easier. Various organic solvents can be used, including dioxane, tetrahydrofuran, ethylpropyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether,
Ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, etc. Water-soluble ethers, formamide, dimethylformamide, acetamide, and other water-soluble amides can be preferably employed. The amount of the water-soluble organic solvent added is usually 10 to 300 parts by weight, preferably 20 to 150 parts by weight, based on 100 parts by weight of the total amount of the urethane compound.
It can be selected from a range of parts by weight. In the present invention, the urethane compound is usually a diisocyanate (CON-Y ¹ -NCO), a fluorine-containing compound R _f ¹ -X ¹ -A ¹ -H (for example, 2-perfluoroalkylethanol), and a compound Z- ^A2 -H
(for example, methanol). Similarly, urethane compounds are made by combining diisocyanate (OCN-Y ² -NCO) with a fluorine-containing compound R _f ² -X ² -A ³ -H (e.g. 2-perfluoroalkylethanol) and a compound W-H (e.g. polyoxy It can be produced by addition reaction with ethylene glycol monomethyl ether). In the present invention, the dispersion of the urethane compound and the water-based medium can be carried out in various ways. For example, the mixture of the urethane compound and the aqueous medium is stirred at high speed under heating, and then cooled to room temperature. method, a method in which a solution of a water-soluble organic solvent of a urethane compound is dropped into an aqueous solution of a urethane compound under stirring, or a method in which an aqueous solution of a urethane compound is dropped into a solution of a urethane compound in a water-soluble organic solvent while stirring; Possible methods include dropping a water-soluble organic solvent solution into water while stirring, or conversely dropping water dropwise. The water-repellent, oil-repellent and antifouling agent of the present invention has the above-mentioned urethane compound combined with the general formula RfROCOCR′=CH ₂
(However, Rf in the formula is a linear or branched perfluoroalkyl group having 4 to 16 carbon atoms, and R is a linear or branched divalent group having 1 to 10 carbon atoms. A polymer or copolymer containing as a constituent unit an acrylate represented by an alkylene group (R' is a hydrogen atom or a methyl group) is added and mixed as a blender. In the present invention, the polymer or copolymer containing the acrylates as a constituent unit may include various conventionally known or well-known polymers without particular limitation. for example,
CF ₃ (CF ₂ ) ₈ (CH ₂ ) ₂ OCOCH=CH ₂ , CF ₃ (CF ₂ ) ₇
(CH ₂ ) ₁₁ OCOCH=CH ₂ , CF ₃ (CF ₂ ) ₈
(CH ₂ ) ₂ OCOC (CH ₃ )=CH ₂ , CF ₃
(CF ₂ ) ₄ CH ₂ OCOC (CH ₃ )=CH ₂ , CF ₃ (CF ₂ ) ₆ (CH ₂ ) ₂ OCOC (CH ₅ )=CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ ) ₂ OCOCH=CH ₂ ,
CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) (CH ₂ ) ₂ OCOC (CH ₃ )=
CH ₂ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₃ COOCH=CH ₂ , Polymers of unsaturated esters represented by acrylates or methacrylates containing perfluoroalkyl groups having 3 to 20 carbon atoms, preferably 4 to 16 carbon atoms, or containing such unsaturated esters and fluoroalkyl groups. Examples include copolymers with one or more polymerizable compounds.
In this case, the polymerizable compounds that do not contain a fluoroalkyl group include ethylene, vinyl acetate, vinyl fluoride, vinyl chloride, vinylidene halide,
Acrylonitrile, styrene, α-methylstyrene, p-methylstyrene, acrylic acid and its alkyl esters, methacrylic acid and its alkyl esters, acrylamide, methacrylamide,
Examples include diacetoacrylamide, methylolated diacetone acrylamide or methacrylamide, vinyl alkyl ethers, vinyl alkyl ketones, butadiene, isoprene, chlorobrene, glycidyl acrylate, and maleic anhydride. By copolymerizing these polymerizable compounds that do not contain fluoroalkyl groups, it is possible to impart high water and oil repellency in addition to stain resistance against dry stains. In the present invention, CF ₂ Cl (CF ₂ ) ₁₀ CH ₂ OCOC (CH ₃ )=CH ₂ , H
Water and oil repellents made of polymers or copolymers of fluoroalkyl group-containing polymerizable compounds such as (CF ₂ ) ₁₀ CH ₂ OCOCH=CH ₂ can also be mentioned. However, as the water and oil repellent, it is preferable to use a polymer or copolymer containing a perfluoroalkyl group as described above. Therefore, if we consider availability and other factors, the general formula R _f ROCOCR′=
CH ₂ (However, R _f in the formula is a linear or branched perfluoroalkyl group having 4 to 16 carbon atoms,
R is a linear or branched divalent alkylene group having 1 to 10 carbon atoms, and R' is a hydrogen atom or a methyl group). It can be said that the use of water and oil repellents made of polymers or copolymers containing esters as constituent units is particularly advantageous for a wide range of commercial applications. In order to obtain the polymer or copolymer for water and oil repellent used in the method of the present invention, various polymerization reaction methods and conditions can be arbitrarily selected, including bulk polymerization,
Any of various polymerization methods such as solution polymerization, suspension polymerization, emulsion polymerization, radiation polymerization, and photopolymerization can be employed. For example, a method in which a compound to be polymerized is emulsified in water in the presence of a surfactant and the polymerization is carried out while stirring, or a method in which a compound capable of polymerizing as a raw material is dissolved in an appropriate organic solvent and a polymerization initiating source (superposition A method of solution polymerization using the action of a polymerization initiator such as an oxide or an azo compound, or ionizing radiation, etc. may be employed. The ratio (weight ratio) of urethane compound/specific blender copolymer can be varied, but is usually 1/100 to 100/1, preferably 1/10 to 10/1.
1, particularly from 1/2 to 2/1. By using such a mixture, dry soil resistance is improved compared to when each is used alone. If the amount of the specific blender copolymer is too large, the water repellency and oil repellency will be impaired, and if the amount is too small, the effect of improving dry soil resistance will not be recognized. When adding and mixing the specific blender copolymer, an aqueous dispersion of the urethane compound is employed in a preferred embodiment of the present invention, so it is preferable to use the blender in the form of an aqueous dispersion. . The aqueous dispersion of the specific blender copolymer can be mixed well with the aqueous dispersion of the urethane compound in a wide range of proportions, and can be mixed within the above-mentioned urethane compound/specific blender copolymer ratio range. In the aqueous dispersion, which is a preferred embodiment of the water- and oil-repellent stain-proofing agent of the present invention, the solid content (urethane compound + urethane compound + specific blender copolymer) concentration is not particularly limited, but is usually 5 to 5.
60% by weight, preferably 15-50% by weight,
For antifouling treatment, remove the solid content with water.
It is used diluted to about 0.1 to 4% by weight.
Aqueous dispersions have advantages over organic solvent-based ones, such as a higher flash point of the stock solution and the possibility of increasing the solid content concentration, and are also less likely to pollute the working environment during antifouling processing. Advantages such as being able to reduce The water-repellent, oil-repellent and antifouling agent of the present invention is made of polyamide,
It can be advantageously applied to various articles made of polyester, leather, wood, etc., such as interior products such as carpets, reception sets, curtains, wallpaper, and vehicle interior items, as well as outdoor tents. The stain-proofing method for carpets, etc. using the water- and oil-repellent stain-proofing agent of the present invention is not particularly limited, and various well-known or publicly known means can be adopted, such as coating such as dipping, spraying, and coating. Examples of known processing methods include attaching the material to the surface of the object to be processed and drying it. In addition, for antifouling processing, we use antistatic agents, insect repellents, flame retardants, dye stabilizers,
It is also possible to appropriately use various treatment agents such as anti-wrinkle agents, additives, and the like. 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 description. In addition, in the following Examples and Comparative Examples, water repellency, oil repellency, and dry soil resistance were measured as follows. That is, water repellency is determined by using a mixed solution consisting of 20 parts by volume of isopropanol and 80 parts by volume of water.
A few drops are placed on two locations on the sample carpet, and the time taken for the solution to penetrate is also expressed. Oil repellency was determined by placing a few drops (approximately 4 mm in diameter) of the test solution shown in Table 1 below on the sample carpet in two places.
Judgment is made based on the penetration state after seconds (AATCC-
TM118−1966).

[Table] Dry soil resistance is measured using 5x7 sample carpets.
Cut into cm pieces, place in a container with the dry soil shown in Table 2 below (twice the weight of the sample), and mix and stir vigorously for 3 minutes to contaminate. After contamination, remove excess dirt with a vacuum cleaner, measure reflectance, and evaluate the degree of contamination. The degree of contamination is calculated using the following formula. Contamination degree (%) = [(R _p − R _p ) ÷ R _p ] × 100 R _p : Reflectance of uncontaminated sample R _p : Reflectance of contaminated sample

[Table] Examples 1 to 3 and Comparative Examples 1 to 3 72.0g (0.1 mol) of 14.4 g (0.009 mol), 80 g deionized water, and 20 g ethylene glycol monomethyl ether,
Pour into a three-necked flask with an internal volume of 300ml equipped with a thermometer, cooling tube, and vacuum stirrer, and bring the temperature to approx.
Raise to 100℃. After high shear stirring for 30 minutes, the mixture was cooled to room temperature to obtain a dispersion. CH ₂ = CHCOO (CH ₂ ) ₃ (CF ₂ ) ₇ CF ₃ 150 g, deoxygenated pure water 600 g, acetone 100 g, n-hexadecyl mercaptan 2 g, azobisisobutyramidine dihydrochloride 4 g, C ₁₇ H ₃₃ COO
(CH ₂ CH ₂ O) ₁₄ By placing 1.0 g of H into a SUS-27 pressure-resistant container (inner volume 2) equipped with a thermocouple thermometer and an electromagnetic stirrer, and stirring under a nitrogen stream. Emulsify and disperse thoroughly. Furthermore, after cleaning by nitrogen blowing for about 1 hour, 50g of vinyl chloride with a purity of 99.9% was added, and the mixture was heated to 50°C while stirring gently.
A stable emulsified latex solution was obtained by polymerizing for 7 hours. The resulting stable emulsion latex contained 21.3% copolymer solids. The elemental analysis value of the copolymer is F46.8%, and the calculated value from the reaction raw material is F46.5%. In addition, this copolymer in benzotrifluoride at 30°C, 0.50g/100ml.
The intrinsic viscosity of the solution was 0.58. / were mixed in the proportions shown in Table 3 below, and the mixture was diluted with deionized water so that the solid content was 0.5% by weight. This diluted solution was evenly sprayed onto a nylon rubber tuffed carpet (wet pick-up 50%) and dried at 130 DEG C. for 20 minutes. The water repellency, oil repellency, and dry soil resistance of the thus obtained treated carpet were measured. Similar measurements were also carried out on carpets treated with a solution diluted to a solids content of 0.5% by weight (Comparative Examples 2 to 3) and untreated carpets (Comparative Example 1). These measurement results are shown in Section 3 below.
They are summarized in the table.

[Table] Example 4 CH ₂ =C (CH 3 ) COOCH 2 CH ₂ Co in _a glass autoclave (inner volume 1) equipped _{with a} stirrer
F _2o+1 (n=6-12, average 9) 140g, vinylidene chloride 56g, N-methylolacrylamide 4g,
2.5 g of t-dodecyl mercaptan, 400 g of deoxygenated pure water, 100 g of acetone, C _o H _2o+1 NH
(CH ₃ ) ₂・CH ₃ COO (n=8-16, average 13) 6
g, C ₁₃ H ₃₇ NH ₂ .CH ₃ COO 6 g, and azobissuisobutyramidine-dihydrochloride 3 g were added, and the mixture was thoroughly emulsified and dispersed by stirring under a nitrogen stream. Next, the temperature of the reaction vessel was gradually raised, and a copolymerization reaction was carried out at 60° C. for 15 hours while stirring to obtain an emulsified dispersion. The obtained latex has a solid content concentration of 26.5%.
It was hot. When the polymer was separated from this latex and dissolved in benzotrifluoride,
[η] at °C was 0.070. / were mixed at a ratio of 1/1 (weight ratio), and dilution and treatment were performed in the same manner as in Example 1. The resulting treated carpet had a water repellency of 3 minutes or more, an oil repellency of 6, and a dry soil resistance of 6. Example 5 CH ₂ =CHCOOCH ₂ CH ₂ C _o F _2o+ 1 in a glass autoclave (inner volume 1) equipped with a stirrer
(n=6-12, average 9) 112 g, stearyl methacrylate 44 g, N-methylol acrylamide 4 g, deoxygenated pure water 280 g, acetone 120 g, azobisisobutyramidine dihydrochloride 3.2 g,

[Formula] 16g, C _o H _2o+1 NH(CH ₃ ) ₂・CH ₃ COO (n=8~
16, average 13) 2g is added and thoroughly emulsified and dispersed by stirring under a nitrogen stream. Next, vinyl chloride
40 g was press-fitted, the temperature of the reaction vessel was gradually raised, and a copolymerization reaction was carried out at 50° C. for 20 hours with stirring to obtain an emulsified dispersion. The obtained latex had a solid content concentration of 34.5%. / were mixed at a ratio of 1/1 (weight ratio), and dilution and treatment were performed in the same manner as in Example 1. The resulting treated carpet had a water repellency of 3 minutes or more, an oil repellency of 6, and a dry soil resistance of 5. Example 6 72.0g _{( 0.1} ^mol ₎ of 14.4 g (0.009 mol) of ethylene glycol monomethyl ether, 80.0 g of deionized water, and 20.0 g of ethylene glycol monomethyl ether
g into a three-necked flask with an internal volume of 300 ml equipped with a thermometer, condenser, and vacuum stirrer, and raise the temperature to approximately 100°C. After stirring under high shear for 30 minutes, the mixture was cooled to room temperature to obtain a dispersion. The dispersion liquid and the emulsified latex solution were mixed at a ratio of 1/1 (weight ratio) to prepare a sample. Dilution and processing were performed in the same manner as in Example 1. The resulting treated carpet has a water repellency of 3 minutes or more, an oil repellency of 6, and a dry soil resistance of 7.
It was hot. Example 7 Example 6 Instead of 85.5g (0.1 mol) of Instead of A dispersion was obtained in the same manner as in Example 4, except for using 15.4 g (0.009 mol) of . A sample was prepared by mixing the dispersion liquid and emulsified latex at a ratio of 1/1 (weight ratio). Dilution and processing were performed in the same manner as in Example 1. The water repellency of the resulting treated carpet was 3.
The oil repellency was 6 and the dry soil resistance was 6. Example 8 Example 6 Instead of 73.2g (0.1 mol) of Instead of A dispersion was obtained in the same manner as in Example 4, except that 13.9 g (0.009 mol) was used. The dispersion liquid and the emulsified latex solution were mixed at a ratio of 1/1 (weight ratio) to prepare a sample. Dilution and processing were performed in the same manner as in Example 1. The resulting treated carpet had a water repellency of 3 minutes or more, an oil repellency of 6, and a dry soil resistance of 6. Example 9 25.0g (0.35mol) 75.0 g (0.05 mol) of water, 80.0 g of deionized water, and 20.0 g of ethylene glycol monomethyl ether were placed in a three-necked flask with an internal volume of 300 ml equipped with a thermometer, cooling tube, and vacuum stirrer, and the temperature was adjusted to about 100 ml.
Raise to ℃. After stirring under high shear for 30 minutes, the mixture was cooled to room temperature to obtain a dispersion. The dispersion liquid and the emulsified latex solution were mixed at a ratio of 1/1 (weight ratio) to prepare a sample. Dilution and processing were performed in the same manner as in Example 1. The resulting treated carpet had a water repellency of 3 minutes or more, an oil repellency of 5, and a dry soil resistance of 5.

Claims (1)

[Claims] 1 General formula Rf ¹ −X ¹ −A ¹ −CONH−Y ¹ −NHCO
-A ² -Z (However, Rf ¹ is a polyfluoroalkyl group having 4 to 16 carbon atoms, and X ¹ is -R ¹ -, -CON
( ^R2 ) ^-Q1- , or _-SO2N ( ^R2 ) ^-Q1- , where ^R1 is an alkylene group, ^R2 is a hydrogen atom or a lower alkyl group, and ^Q1 is an alkylene group. , A ¹ and A ² are each -O-, -S-, or -N(R ² )-
, R ² is a hydrogen atom or a lower alkyl group, Y ¹ is a residue obtained by removing the isocyanate from an aromatic or alicyclic diisocyanate, and Z is an alkyl group, an aryl group, or -X ¹ −Rf ¹ ), a urethane compound represented by the general formula Rf ² −X ² −
A ³ -CONH-Y ² -NHCO-W (however, Rf ² is a polyfluoroalkyl group having 4 to 16 carbon atoms,
X ² is −R ¹ −, −CON(R ² )−Q ¹ −, or −SO ₂ N
(R ² )-Q ¹ -, R ¹ is an alkylene group,
R ² is a hydrogen atom or a lower alkyl group, Q ¹ is an alkylene group, and A ³ is -O-, -S-, or -N
(R ³ )-, R ³ is a hydrogen atom or a lower alkyl group, Y ² is a residue obtained by removing the isocyanate from an aromatic or alicyclic diisocyanate, and W is a hydrophilic group. ) and the general formula RfROCOCR'=CH ₂
(However, Rf in the formula is a linear or branched perfluoroalkyl group having 4 to 16 carbon atoms, and R is a linear or branched divalent group having 1 to 10 carbon atoms. A water/oil repellent/antifouling agent comprising a polymer or copolymer containing as a constituent unit an acrylate represented by the following alkylene group and R' is a hydrogen atom or a methyl group. 2. The processing agent according to claim 1, which is employed in the form of an aqueous dispersion in which the urethane compound and the urethane compound are dispersed in a medium mainly consisting of water. 3. The processing agent according to claim 2, wherein the urethane compound/urethane compound ratio (weight ratio) is from 99/1 to 25/75. 4. The processing agent according to claim 1, wherein the ratio (polymerization ratio) of urethane compound/acrylate polymer or copolymer is 1/100 to 100/1.