JPH02132125A - Copolymer with its molecular chain end blocked with hydrolyzable silyl group, its production and room temperature-curable composition containing thereof - Google Patents

Abstract

PURPOSE:To provide the title composition of good workability, capable of giving rubbery cured products of both high mechanical strength and extension rate, with the molecular chain end blocked with hydrolyzable silyl group. CONSTITUTION:The objective copolymer with the molecular chain end blocked with hydrolyzable silyl group, 100-50000 in molecular weight of formula I (R<1> is monovalent hydrocarbon group; R<2>-R<6> are each divalent hydrocarbon group; A is residue of compound containing in one molecule one or more primary amines, two or more secondary amines or two or more thiol groups; Y is hydrolyzable group; a is 1-3; m and n are each 10-500; s and t are each >=1). This copolymer can be obtained by reaction between (1) polyoxyethylene or polyoxypropylene, (2) polybutadiene with the molecular chain end blocked with epoxy group, (3) butylamine or allylamine, etc., and (4) an organosilicon compound having both hydrolyzable group and epoxy group.

Description

Detailed Description of the Invention [Technical Field of the Invention] The present invention relates to a copolymer in which the molecular chain ends are blocked with hydrolyzable silyl groups, which can be used to obtain a rubber-like cured product with particularly high strength and high elongation. The present invention relates to a copolymer useful as a base polymer for room temperature curable compositions and a method for producing the copolymer, and further relates to a copolymer useful as a base polymer for a room temperature curable composition, which is suitable as a sealant composition, and which transforms into a rubber-like elastic body when exposed to moisture at room temperature. The present invention relates to a curable composition, particularly a room temperature curable composition which yields a rubber-like cured product having high strength, high elongation, essentially adhesive properties, and has good workability.

[Technical background of the invention and its problems]

As a liquid organic polymer having a hydrolyzable silyl group at the end, a polymer whose main chain is polyether is known (Japanese Unexamined Patent Publication No. 156599/1982), and room temperature curable polymers based on this are known. In recent years, compositions have begun to be used as sealing materials for joints of buildings, joints of transportation machines, etc. (Japanese Patent Application Laid-open No. 73998/1983, etc.). However, this type of material does not inherently have adhesive properties, and
Since the strength after curing is low, it has the disadvantage that it cannot be used in areas where large forces are applied.

[Purpose of the invention]

The present invention is intended to solve these problems, and is intended to be used as a base polymer for a room-temperature curable composition that yields a rubber-like cured product that inherently has adhesive properties, has high strength, and has a high elongation rate. The object of the present invention is to provide a useful copolymer, a method for producing the copolymer, and a room-temperature-curable silk composition.

[Structure of the invention]

That is, the present invention provides a general formula; R'3-a A- CllJliR'OR2SiYaOH (wherein R1 is a monovalent hydrocarbon group,
4Rs, R6 is a divalent hydrocarbon group, A is 1 in 1 molecule
Compounds containing one or more secondary amines or secondary amines
or a residue of a compound containing two or more thiol groups, Y is a hydrolyzable group, a is a number from 1 to 3, m,
n represents a number from 10 to 500, and S and t represent a number of 1 or more.

), the molecular chain end of which is blocked with a hydrolyzable silyl group having a molecular weight of 1,000 to 50,000; -CHR'-0-{-R'-0}--R'-CH
-CH. ＼0″゛ゝ0/ ?In the formula, R4, R5, m are as described above) A polyether whose molecular chain terminal is blocked with an epoxy group, (mouth) General formula; CH2-CHR6-0{- C112C11=Cll(:
H2→Ma0-R6CH-CIl■\0/
A polybutadiene whose molecular chain end is blocked with an epoxy group represented by \0/ (in the formula, R'' and n are as described above), (c) a compound containing one or more primary amine groups in one molecule, or The above-mentioned copolymer is characterized by reacting a compound containing two or more secondary amino groups or a compound containing two or more thiol groups, and (ii) an organosilicon compound having an epoxy group and a hydrolyzable group. The present invention relates to a method for producing a copolymer, and a room-temperature curable composition containing at least one of the above copolymers as a main component.

In the copolymer of the present invention in which the molecular chain ends are blocked with hydrolyzable silyl groups represented by the above general formula, m and n are each selected within the range of 10 to 500.

When m and n are smaller than 10, it is difficult to obtain a rubber-like cured product with a high elongation rate, which is a feature of the present invention; on the other hand, when m and n are 50
When it is larger than 0, the workability as a sealing material decreases.

The monovalent hydrocarbon group for R1 is selected from alkyl groups such as methyl, ethyl, and probyl groups, aryl groups such as phenyl, and aralkyl groups such as β-phenylethyl and β-phenylbrobyl groups. However, a methyl group or a phenyl group is preferred from the viewpoint of ease of synthesis and availability of raw materials, and a methyl group is particularly preferred. Examples of the divalent hydrocarbon for R2 include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a phenylene group, and a cyclohexylene group. to tri and methylene groups are preferred. R
The divalent hydrocarbon groups of 3, R4, R', and R6 are exemplified by the same ones as R2, but methylene groups are preferred from the viewpoint of easy availability of raw materials and ease of synthesis.

The hydrolyzable group of Y is an alkoxy group, an alkoxyalkoxy group, an acyloxy group, an N,N-dialkylalkoxy group, an N-alkylamide group, an N,N-dialkylaminoxy group, a ketoxime group, and an alkyl group. Carbon groups such as methoxy, ethoxy, proboxy, isoproboxy, hexyloxy groups etc. Alkoxy group of number 1 to 6 and 2-
A methoxyethoxy group is suitable, and a methoxy group and an ethoxy group are particularly preferred from the viewpoint of fast curing reactivity. The number of hydrolyzable groups a is selected within the range of 1 to 3, but preferably 3 is 2 in order to obtain a composition that provides a rubber-like cured product with a high elongation rate.

A is a residue obtained by reacting a compound containing one or more primary amines, a compound containing two or more secondary amines, or a compound containing two or more thiol groups.

Further, s and t are each a number of 1 or more, and must be selected within a range such that the copolymer of the present invention has a molecular weight of 1,000 to 50,000. If the molecular weight is less than 1,000, a cured rubber product with a high elongation rate, which is a feature of the present invention, cannot be obtained;
Conversely, if the molecular weight is greater than 50,000, the viscosity will be high and workability will be poor.

The copolymer of the present invention has, for example, the general formula (a); In the formula, R4. R S , m is as described above) A polyether whose molecular chain terminal is blocked with an epoxy group, (input) General formula: CH2-CI{R6-0{-CIl, C to CIICI■
-}-;-0-R'fll-CI+2\0''゛~1]' (in the formula, R6 and n are as described above), a polybutadiene whose molecular chain terminal is blocked with an epoxy group, (c) A compound containing one or more primary amine groups, a compound containing two or more secondary amine groups, or a compound containing two or more thiol groups in one molecule, and (2) an epoxy group and a hydrolyzable group. It can be synthesized by reacting with an organosilicon compound having

Typical examples of component (a) include those obtained by condensing shrimp chlorohydrin with polyoxyethylene, polyoxypropylene, or copolymers thereof, each of which is blocked at both ends with hydroxyl groups.

The polybutadiene of the component (portion) may be any of the cis form, trans form, and 1.2 adduct, and may also be a copolymer.

A typical example of the (oral) component is one obtained by condensing shrimp chlorohydrin with polybutadiene whose both ends are blocked with hydroxyl groups.

The compound (c) is (a). A compound having an amino group or a thiol group that reacts with (1) and (2) epoxy groups, and contains a primary amine in one molecule for the purpose of obtaining a cured rubber product with a high elongation rate, which is a feature of the present invention. It is necessary to be a compound containing one or more secondary amines, a compound containing two or more secondary amines, or a compound containing two or more thiol groups.

As such component (c), butylamine, allylamine, pentylamine, hexylamine, aniline, aminophenol, ethylenediamine, hexamethylenediamine, diaminobenzene, P, P' are used due to the ease of obtaining raw materials and ease of reaction. -diaminodiphenylmethane, P
, P'-diaminodiphenylsulfone, piperazine,
1,3-di-4-piperidylpropane, hexamethylene dithiol, phenylene dithiol, 2,5-dimercapto-1. 3. 4-thiadiazole is preferred, and piperazine and 2,5-dimercap}-1.3.4-thiadiazole are particularly preferred because of their high reactivity and ease of reaction control.

The organosilicon compound (2) has an epoxy group and a hydrolyzable group in one molecule.

These (2) components are preferably r-glycidoxybutyltrimethoxysilane, r-glycidoxybutyltrimethoxysilane, T-glycidoxybutyltriethoxysilane, T-glycidoxybutyltriethoxysilane, methyl ( T-glycidoxypropyl)dimethoxysilane, methyl(γ-glycidoxybutyl)dimethoxysilane, methyl(T-glycidoxybutyl)diethoxysilane, methyl(r-glycidoxybutyl)diethoxysilane, phenyl(T -glycidoxyprovir)
Dimethoxysilane, phenyl (T-glycidoxybutyl) dimethoxysilane, dimethyl (γ-glycidoxyprobyl) methoxysilane, dimethyl (r-”lysidoxybutyl) methoxysilane and these alkoxy groups can be converted into alkyl alkoxy groups, acyloxy groups, Examples include compounds substituted with an N,N-dialkylamino group, an N-alkylamino group, an N,N-diallylaminoxy group, a ketoxime group, an alkenoxy group, and the like.

The copolymer of the present invention has the following characteristics (a) and (b) as described above.
and (2) by reacting the epoxy group with the amine group or thiol group (c).

Reactions (a), (c), (c) and (ii) are preferably carried out at a temperature higher than the ambient temperature, for example at a temperature of 50 to 150°C. In this case, compounds such as methanol, ethanol, phenol, salicylic acid and tris(dimethylaminemethyl)phenol are preferably used as reaction accelerators. Methanol is one of the preferred
It is one. Although it is not necessary to use a solvent when carrying out this reaction, a hydrocarbon-based, ether-based, or ester-based solvent may be used.

(b), (mouth). The amount of (c) and (2) to be blended is theoretically the molar ratio (a): (l): (c): (2) = s:
t: (s+t+l):2.

However, in reality, there is no problem even if (c) and (2) are used in amounts slightly exceeding the theoretical amounts.

The reaction procedure is (a). (1), (3) and (2) may be added at the same time and reacted, but first, (1), (3) and the copolymer in an amount exceeding their equivalents and in the above molecular weight range are obtained. It is easier to control the degree of polymerization, and it is easier to control the degree of polymerization by reacting an appropriate amount of (c) to extend the chain, and then adding the required amount or a slightly larger amount of (ii). Hydrolyzable groups can be introduced at the chain ends.

The present invention further relates to a room temperature curable composition containing at least one of the above copolymers as a main component.

A representative example of this composition is (A) 100 parts by weight of at least one of the above copolymers (B) 3 to 300 parts by weight of an inorganic filler (C
) A composition comprising 0.001 to 20 parts by weight of a curing catalyst is exemplified.

Each component will be explained below.

Component (B) is a component for imparting appropriate non-fluidity and reinforcing properties to the composition. Examples of these components (B) include fumed silica, precipitated silica, ground silica, diatomaceous earth, calcium carbonate, titanium oxide, alumina, aluminum hydroxide, iron oxide, talc, and clay. The amount of component (B) used is in the range of 3 to 300 parts by weight, preferably 5 to 200 parts by weight, per 100 parts by weight of component (A). If the amount of component (B) is less than 3 parts by weight, non-fluidity and reinforcing properties cannot be obtained, and if it is more than 300 parts by weight, the viscosity of the composition increases and workability decreases.

The curing catalyst (C) used in the present invention includes tin carboxylates such as tin octylate; organic tin carboxylates such as dibutyltin dilaurate, dibutyltin dimaleate, and dibutyltin phthalate; organic tin oxides and their esters; Reactants; organic titanate esters such as tetrabutyl titanate; amines; amine salts; quaternary ammonium salts; guanidine compounds and the like. These curing catalysts were chopped into 100 parts by weight of component (A) to give 0.00 parts by weight.
It is preferable to use it in a range of 0.001 to 20 parts by weight. If the amount of component (C) is less than this, the curing speed will be too slow and it will be unsuitable for use, while if it is more than this, it will not only be meaningless but also undesirable as there is a risk of oozing or precipitation.

Since the composition of the present invention inherently has adhesive properties, it is not necessary to use commonly used silane coupling agents to impart adhesive properties, but they may be used to further enhance adhesive properties. Alternatively, hydrolyzable silanes including these may be added for the purpose of enabling long-term storage in one package. These hydrolyzable silanes include H2N (CH2) 3S1 (DC}13) z,}
12N (CH2) ,Si (OCH2CI{,)
,j}12N (CL) ,NH ([:Hz) ss
i (0[:}I-) −. C]13 CH2=C C-O fCL)TSl (OCtl2C
}I3) ,,[1 CL"CllSi (OCH2CH3) 3, (CH3
) 2Si (OCI{3) 2,C}13si (D
I:l{3) s. CH3Si (OCH2CH3)
An example is 3+St (OCLCt{,) s.

In order to obtain long-term storage stability in a single package, it is also effective to add a monohydric primary alcohol such as methanol or ethanol.

The composition of the present invention may also contain a thixotropic agent such as hydrogenated castor oil, and a plasticizer such as dioctyl phthalate, butylbenzyl phthalate, or chlorinated paraffin.

The composition of the present invention can be used in a single package as described above, or it can be stored separately, for example, into two components: a component consisting of components (A) and (B), and a component (C). It is also possible to prepare two packages in which the two are mixed together before use.

〔Effect of the invention〕

A sealing material can be obtained by adding a curing catalyst such as an organotin compound, a filler, and the like to the copolymer of the present invention. By using the copolymer of the present invention as a base polymer, a sealing material that has a high elongation rate, high strength, and can exhibit adhesive properties can be obtained.

〔Example〕

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

In addition, parts in Examples and Comparative Examples are parts by weight.
% is by weight.

Example 1 2 moles of glycidyl group-end-blocked polyoxypropylene having an average degree of polymerization of 32, a molecular weight of about 2.000, and a viscosity of 550 cSt at 25°C, and a polyoxypropylene having an average degree of polymerization of 20, a molecular weight of about i, 100, and a viscosity of 550 cSt at 25°C. Viscosity is 2,400
6 moles of n-butylamine and methanol corresponding to 10% of the total amount of polyoxypropylene and polybutadiene were added to 3 moles of cSt glycidyl group-terminated polybutadiene, and heating and stirring was started at 60° C. under a nitrogen atmosphere. A portion of the sample was extracted at 2 hour intervals after the start of heating and stirring, and the total amount of epoxy groups and amino groups in the sample was determined by potentiometric titration, and the peak due to protons of epoxide methylene (2.67 pprn based on TMS) was observed by NMR. Viscosity measurements were made at 25°C. 18 from heating stirring
After a period of time, the titration of epoxy groups and amine groups decreased by approximately the theoretical m, the peak due to epoxide methylene protons disappeared, and the viscosity at 25°C became constant at 3,400 cSt. −
2.2 mol of dimethoxysilane (glycidoxybrobyl) was added, and heating and stirring were continued under the same conditions. A portion of the silane was extracted at 2 hour intervals after the addition of the silane, and the total amount of epoxy groups and amine groups in the sample was determined by potentiometric titration, and the peak due to protons of epoxide notylene was observed using NMH. Since they almost disappeared 18 hours later, the reaction was concluded to be complete, and methanol was distilled off. The obtained reaction product has a viscosity of 28,200 CSt at 25°C, a specific gravity of 1.02 at the same temperature, and a number average molecular weight of 7.0 as measured by GPC.
500 was a pale yellow viscous liquid, which was confirmed to be a copolymer (P1) whose terminals were blocked with hydrolyzable silyl groups represented by the following formula.

CI+, (CH,0) 2Si (CH2)J[H2CH(:I
I210H C1{3? Cl+■),01-I C113 Example 2 Average degree of polymerization 50, molecular weight approximately 3. QOO, 2 moles of glycidyl group-end-blocked polyoxybrobylene with a viscosity of 970 cSt at 25°C, average degree of polymerization 20, molecular droplets of about 1,100, and a viscosity at 25°C of 2. 400c
5 moles of piperazine and methanol in an amount corresponding to 10% of [1] of polyoxypropylene and polybutadiene were added to 2 moles of St glycidyl group-terminated polybutadiene, and heating and stirring was started at 60° C. under a nitrogen atmosphere. p1
Similar to the synthesis of , a portion was taken out at 2 hour intervals and potentiometric titration, NMR measurement and viscosity measurement were performed, and it was found that the titration of epoxy groups and imino groups decreased by approximately the theoretical amount 8 hours after the start of heating and stirring. At the same time, the peak due to protons of epoxide methylene disappeared, and the viscosity at 25°C became constant at 3,900 cSt.
2.2 mol of T-glycidoxybrobyl>dimethoxysilane was added and the reaction was continued. Eight hours after the addition of the silane, the total amount of epoxy groups and imino groups was quantified and the proton peak of epoxide methylene was observed by NMR, and their disappearance was confirmed, indicating the completion of the reaction, and methanol was distilled off. The obtained reaction product has a viscosity of 35, OOOcSt at 25°C, a specific gravity of 1.02, and a GP
[The number average molecular weight measured by 8. 500 was a pale yellow viscous liquid, which was confirmed to be a copolymer (P-2) whose terminals were blocked with hydrolyzable silyl groups represented by the following formula.

C113 ([LO) zsi (CH2) 30CH2CHCI
+20H 1 River Example 3 2 moles of glycidyl group-end-blocked polyoxypropylene with an average degree of polymerization of 50, a molecular weight of about 3.000, and a viscosity of 970 cSt at 25°C and an average degree of polymerization of 56, a molecular weight of about 3,000, and a viscosity of 970 cSt at 25°C. The viscosity at 12,000c
To 1 mol of St glycidyl end-blocked polybutadiene,
2,5-dimerkabuto i. 3.4-thiadiazole 4
mol and 8 of polybutadiene and polybutadiene
f. Ethanol in an amount equivalent to 10% of ffi was added, and heating and stirring was started at 80° C. under a nitrogen atmosphere. P-1
Similar to the synthesis of , a portion was taken out at 2 hour intervals and subjected to potentiometric titration, NMR measurement, and viscosity measurement. After heating and stirring, titration 1 of mercapto groups and epoxy groups decreased by almost the theoretical amount in 10 hours. At the same time, the proton peak of epoxide methylene disappeared, and the viscosity at 25°C decreased to 7. Since it became constant at 600 cSt, methyl (T
2.2 mol of diethylsilane (glycidodibrovir) was added and the reaction was continued. Six hours after the addition of the silane, the total amount of mercabuto groups and epoxy groups was determined, and the peak of epoxide methylene was observed by NMR, and the disappearance of these groups was confirmed, indicating the completion of the reaction, and the ethanol was distilled off.

The resulting reaction product had a viscosity of 42.0 at 25°C.
00CSt, a pale yellow viscous liquid with a specific gravity of 1.02 and a number average molecular droplet of 9,800 as measured by GPC. It was confirmed that it was polymer (P-3).

CH, (C2+1SO) 2S l (CI+2) 30[L
cllcL Example 4 3 moles of glycidyl group-end-blocked polyoxypropylene having an average degree of polymerization of 32, a molecular weight of about 2,000, and a viscosity of 550 cSt at 25°C, and an average degree of polymerization of 56, a molecular weight of about 3,000, and a viscosity of 550 cSt at 25°C. The viscosity at 12,00
Add 5 moles of P, P'-diaminodiphenylmethane, ethanol equivalent to 10% of the polyoxybrobylene, and phenol equivalent to 2% of the polybutadiene to 1 mole of glycidyl group-end-capped polybutadiene of 0 cSt.
Heating and stirring was started at 80°C. Similar to the synthesis of P-1, 2
Aliquots were taken out at time intervals and subjected to potentiometric titration and NMR
The measurement and viscosity measurement revealed that after 14 hours, the [t of the amine group and the epoxy group decreased by almost the theoretical amount, and the proton peak due to epoxide methylene in NMR disappeared, and the viscosity at 25°C became 6. 300cS
Since the temperature became constant at t, 2.2 mol of phenyl(T-glycidoxyprobyl)jethoxysilane was added to continue the reaction. 14 hours after adding the silane, the total layer of amino groups and epoxy groups was quantified by potentiometric titration, and the peak of epoxide methylene was observed by NMR. When these disappeared, the reaction was confirmed to be complete, and ethanol was distilled off. did. The resulting reaction product had a viscosity of 48 at 25°C.
, 300 cSt, a pale yellow viscous liquid with a specific gravity of 1.02 and a number average molecular weight of 9,400 by GPC. It was confirmed that it was a combination (P-4).

Examples 5 to 8 Fillers shown in Table 1 were added to 100 parts of the copolymers (P-1 to 4) whose molecular chain ends were blocked with hydrolyzable silyl groups obtained in Examples 1 to 4. , an inorganic pigment and a thixotropic agent were added and uniformly dispersed using a triple roll, and the tin compounds shown in Table 1 were further added and mixed to form samples 1 to 4.
was prepared. These samples were cured into a 2 mm thick sheet, cured at room temperature for 14 days, punched into JI3 No. 2 dumbbells, and subjected to a tensile test. In addition, these samples 1 to 4
A shear adhesion test specimen shown in FIG. 1 was prepared using the same method, and after curing at room temperature for 28 days, a tensile test was conducted. These results are also shown in Table 1.

Comparative Example 1 Molecular weight approximately 8,000, C113 (Cll=0) 2S+-Ct12[tl2[:tl2] as the terminal group
For 100 parts of polyoxypropylene having 0-,
After adding the filler, inorganic pigment, and thixotropic agent shown in Table 1 and uniformly dividing the mixture with a Miki roll,
The organic tin compounds shown in Table 1 were also added and mixed to obtain Sample-5. Tests similar to Examples 5 to 8 were conducted using Sample-5. The results are also shown in Table 1.

Comparative Example 2 A dilane coupling agent shown in Table 1 was added as an adhesion imparting agent to Sample-5 prepared in Comparative Example 1 to obtain Sample-6. Using this sample, tests similar to those in Examples 5 to 8 were conducted, and the results are also shown in Table 1.

As shown by the above results, the copolymer of the present invention is useful as a base polymer for room-temperature curable compositions, and in particular, the cured product of the composition has high strength and high elongation.
It is clear that even systems containing no silane coupling agent have good adhesion.

[Brief explanation of drawings]

FIG. 1 shows a perspective view of a specimen subjected to a shear adhesion test. Note that the unit in the figure is mm. 1... Sample

Claims (1)

[Claims] 1 General formula; ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 is a monovalent hydrocarbon group, R^2, R^3,
R^4, R^5, and R^6 are divalent hydrocarbon groups, and A is a compound containing one or more primary amines or two or more secondary amines in one molecule, or two thiol groups. In the residue of the compound containing the above, Y is a hydrolyzable group, a is a number of 1 to 3, m and n are numbers of 10 to 500, and s and t are numbers of 1 or more. ), and the molecular weight is 1,000 to 50,00
A copolymer in which the molecular chain ends are blocked with a hydrolyzable silyl group. 2 (a) General formula; ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Polyether whose molecular chain terminals are blocked with epoxy groups, represented by (in the formula, R^4, R^5, m are as above) , (b) General formula; ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^6, n is as described above) Polybutadiene whose molecular chain terminal is blocked with an epoxy group, (c) 1 A compound containing one or more primary amino groups, a compound containing two or more secondary amino groups, or a compound containing two or more thiol groups in the molecule, and (d) having an epoxy group and a hydrolyzable group. 2. The method for producing a copolymer according to claim 1, which comprises reacting the copolymer with an organosilicon compound. 3. The method according to claim 2, wherein component 3(a) is polyoxyethylene, polyoxypropylene, or a copolymer thereof. Component 4 (c) is butylamine, allylamine, pentylamine, hexylamine, aniline, aminophenol, ethylenediamine, hexamethylenediamine, diaminobenzene, P,P'-diaminodiphenylmethane,
A claim that the compound is selected from P,P'-diaminodiphenylsulfone, piperazine, 1,3-di-4-piperidylpropane, hexamethylene dithiol, phenylene dithiol, and 2,5-dimercapto-1,3,4-thiadiazole. The method described in 2. 3. The method according to claim 2, wherein component 5 (d) is an organosilicon compound represented by the general formula: ▲A mathematical formula, a chemical formula, a table, etc.▼ (wherein R^1, Y, and a are as described above). 6. A room-temperature curable composition containing at least one copolymer according to claim 1 as a main component.