JP4596151B2 - Heat curable silicone rubber adhesive composition - Google Patents

Description

  The present invention relates to an addition-curable silicone rubber adhesive composition having good adhesion to various substrates such as resins and metals.

In order to obtain an addition-curable silicone adhesive having adhesiveness to various substrates, studies have been conventionally made to add an adhesion-imparting component to a curable silicone resin to develop adhesiveness. For example, an addition-curable silicone rubber composition containing a hydrogensiloxane containing an alkoxysilyl group (Japanese Patent Publication No. 53-21026: Patent Document 1) or an addition-curable type containing a hydrogensiloxane containing an epoxy group Silicone rubber compositions (Japanese Patent Publication No. 53-13508: Patent Document 2) have been proposed.
Through these conventional studies, addition-curable silicone adhesives having adhesiveness have been put on the market for various types of substrates.

  However, these adhesives are difficult to self-adhere to some base materials, particularly resins, and may not exhibit adhesive properties unless a primer component is used. Polycarbonate, polyphenylene sulfite, and the like are listed as difficult-to-adhere resins, and there is an increasing need for addition-curable silicone adhesives that can easily adhere to such resins.

  On the other hand, as an addition-curable silicone adhesive that self-adheres to a hard-to-adhere resin, a technique of adding a nitrogen compound (Japanese Patent Publication No. 52-147963: Patent Document 3) and an alkoxysilane added as an adhesion-imparting material A technique of adding an organotin compound, an organotitanium compound, an organoaluminum compound, or a zirconium compound as a hydrolysis catalyst has been developed and is publicly known.

  However, these techniques can affect the curability of the addition curable silicone adhesive. When a nitrogen compound is added to the addition-curable silicone adhesive, the catalytic ability of platinum atoms that are addition reaction catalysts is significantly hindered, and the curability becomes very unstable. Moreover, when an organotin compound, an organotitanium compound, an organoaluminum compound, a zirconium compound, etc. are added similarly, the organohydrogensiloxane in the addition-curable silicone adhesive is deactivated. Moreover, since the siloxane bond in the silicone polymer is cleaved when heated, it also causes a decrease in the heat resistance of the cured product.

Japanese Patent Publication No.53-21026 Japanese Patent Publication No.53-13508 Japanese Patent Publication No. 52-147963

  The present invention has been made in view of the above circumstances, and maintains thermosetting stability after storage, heat stability of the cured product, and heat-curable silicone rubber bonding that exhibits good adhesion even to difficult-to-adhere resins. An object is to provide an agent composition.

  As a result of intensive studies to achieve the above object, the present inventor has (A) an organopolysiloxane containing at least two alkenyl groups bonded to silicon atoms in one molecule represented by the following average composition formula: (B) Organohydrogenpolysiloxane represented by the following average composition formula, (C) platinum-based metal compound, (D) curing controller, (E) addition functional group-containing alkoxysilane, addition functional group and alkoxy group-containing organosiloxane And a thermosetting silicone rubber adhesive composition comprising at least one organic silicon compound selected from an addition functional group and an alkoxysilyl group-containing isocyanurate compound, and (G) a carboxylic acid anhydride. Knowing that it also exhibits good adhesion to resin, and is excellent in the storage stability of the material and the thermal stability of the cured product, the present invention Which has led to be.

Therefore, the present invention
(A) The following average composition formula R ¹ _a R ² _b SiO _{(4-ab) / 2}
Wherein R ¹ is an unsubstituted or substituted monovalent hydrocarbon group not containing an aliphatic unsaturated bond, R ² is an alkenyl group, a is 0.96 to 2.00, and b is 0.001 to 0.00. 5, a + b = 1.00 to 2.04.)
An organopolysiloxane containing at least two alkenyl groups bonded to silicon atoms in one molecule represented by: 100 parts by mass
(B) The following average composition formula R ³ _c H _d SiO _{(4-cd) / 2}
(Wherein R ³ is an unsubstituted or substituted monovalent hydrocarbon group not containing an aliphatic unsaturated bond, c is 0.70 to 2.0, d is 0.01 to 1.2, and c + d = 0.0. 8 to 3.0.)
The amount of silicon atom-bonded hydrogen atoms from 0.4 to 10 per alkenyl group in the composition,
(C) platinum-based metal compound: 1 to 2,000 ppm as a metal element-containing mass with respect to the total amount of the composition,
(D) a necessary amount of curing control agent,
(E) at least one organic silicon compound selected from an addition functional group-containing alkoxysilane, an addition functional group and an alkoxy group-containing organosiloxane, an addition functional group and an alkoxysilyl group-containing isocyanurate compound,
(F) Zirconium compound: 0.001 to 10 parts by mass,
(G) Carboxylic anhydride: A thermosetting silicone rubber adhesive composition comprising 0.001 to 10 parts by mass is provided.

  The heat-curable silicone rubber adhesive composition of the present invention maintains the curing stability after storage, the thermal stability of the cured product, and exhibits good adhesion even to difficult-to-adhere resins. It is useful as an adhesive for peripheral and in-vehicle components.

The heat-curable silicone rubber adhesive composition of the present invention is
(A) an organopolysiloxane containing at least two alkenyl groups bonded to silicon atoms in one molecule represented by the following average composition formula:
R ¹ _a R ² _b SiO _{(4-ab) / 2}
Wherein R ¹ is an unsubstituted or substituted monovalent hydrocarbon group not containing an aliphatic unsaturated bond, R ² is an alkenyl group, a is 0.96 to 2.00, and b is 0.001 to 0.00. 5, a + b = 1.00 to 2.04.)
(B) an organohydrogenpolysiloxane represented by the following average composition formula:
R ³ _c H _d SiO _{(4-cd) / 2}
(Wherein R ³ is an unsubstituted or substituted monovalent hydrocarbon group not containing an aliphatic unsaturated bond, c is 0.70 to 2.0, d is 0.01 to 1.2, and c + d = 0.0. 8 to 3.0.)
(C) a platinum-based metal compound,
(D) a curing control agent,
(E) at least one organic silicon compound selected from an addition functional group-containing alkoxysilane, an addition functional group and an alkoxy group-containing organosiloxane, an addition functional group and an alkoxysilyl group-containing isocyanurate compound,
(F) zirconium compound,
(G) It contains a carboxylic acid anhydride.

The organopolysiloxane of component (A) has the following average composition formula R ¹ _a R ² _b SiO _{(4-ab) / 2}
Wherein R ¹ is an unsubstituted or substituted monovalent hydrocarbon group not containing an aliphatic unsaturated bond, R ² is an alkenyl group, a is 0.96 to 2.00, and b is 0.001 to 0.00. 5, a + b = 1.00 to 2.04, preferably a is 1.80 to 2.00, b is 0.001 to 0.1, and a + b is 1.90 to 2.04.
It contains at least two alkenyl groups bonded to a silicon atom in one molecule, but the molecular structure is not particularly limited and may be linear, branched, cyclic or three-dimensional network It may be a polymer consisting of a single siloxane unit or a copolymer consisting of two or more siloxane units, but the main chain usually consists of repeating diorganosiloxane units. Generally, it is a linear diorganopolysiloxane in which both ends of the molecular chain are blocked with a triorganosiloxy group.

Here, as the unsubstituted or substituted monovalent hydrocarbon group represented by R ¹ in the above formula, methyl group, ethyl group, propyl group, isopropyl group, butyl group, hexyl group, octyl group, dodecyl group, etc. Alkyl groups, cyclopentyl groups, cyclohexyl groups, cycloalkyl groups such as cycloheptyl groups, aryl groups such as phenyl groups, tolyl groups, xylyl groups, naphthyl groups, aralkyl groups such as benzyl groups, phenylethyl groups, phenylpropyl groups, etc. Or a substituted hydrocarbon group in which some or all of the hydrogen atoms of these hydrocarbon groups are substituted with fluorine atoms, chlorine atoms, nitrile groups, etc., such as trifluoropropyl groups, chloromethyl groups, cyanoethyl groups, etc. The R ¹ may be the same or different from each other, but in these, all of them are preferably methyl groups in view of their chemical stability and ease of synthesis. If necessary for characteristics, a part of the methyl group may be substituted with a phenyl group or a trifluoropropyl group.

On the other hand, examples of the alkenyl group represented by R ² include a vinyl group, an allyl group, an isopropenyl group, a butenyl group, and a pentenyl group. R ² is preferably a vinyl group or an allyl group, and is most preferably a vinyl group from the viewpoint of ease of synthesis and chemical stability. This alkenyl group may be bonded to the silicon atom at the end of the molecular chain, or may be bonded to the silicon atom at the non-terminal end of the molecular chain (in the middle of the molecular chain), or may be bonded to both of these, A diorganopolysiloxane containing alkenyl groups bonded to silicon atoms at both ends of the molecular chain is preferred.

  The viscosity at 25 ° C. of the organopolysiloxane as the component (A) is preferably 10 mPa · s or more, and more preferably selected from the range of 50 to 500,000 mPa · s. If this viscosity is lower than 10 mPa · s, the cured product becomes brittle and may not be able to cope with the deformation of the substrate. On the other hand, if the viscosity is too high, the viscosity of the composition before curing increases and the workability decreases. There is a risk. These organopolysiloxanes may be used in combination of two or more if the viscosity is in the above range. Here, in the present invention, the viscosity can be measured by a rotational viscometer or the like.

The component (B) organohydrogenpolysiloxane has at least two hydrogen atoms (that is, SiH groups) bonded to silicon atoms in the molecule (usually 2 to 200), preferably 3 or more (for example 3 to 3). About 150) and the following average composition formula R ³ _c H _d SiO _{(4-cd) / 2}
(Wherein R ³ is an unsubstituted or substituted monovalent hydrocarbon group not containing an aliphatic unsaturated bond, c is 0.70 to 2.0, d is 0.01 to 1.2, and c + d = 0.0. 8 to 3.0, preferably c is 1.0 to 2.0, d is 0.01 to 1.0, and c + d is 1.1 to 2.2.
In which hydrogen atoms (SiH groups) bonded to silicon atoms in the component (B) are contained in the component (A) in the presence of the component (D) platinum-based catalyst described later. It acts as a crosslinking agent that reacts with an alkenyl group bonded to a silicon atom to give a three-dimensional network structure.

Here, examples of the unsubstituted or substituted monovalent hydrocarbon group represented by R ³ in the above formula include the same groups as those described above for R ¹ , which may be the same or different from each other. From the standpoint of ease and chemical stability, all are preferably methyl groups. If necessary for characteristics, a part of the methyl group may be substituted with a phenyl group or a trifluoropropyl group. In addition, you may use these organohydrogenpolysiloxane individually by 1 type or in combination of 2 or more types.

Further, the molecular structure of the organohydrogenpolysiloxane is not particularly limited, and may be any of linear, branched, cyclic and three-dimensional network, and a polymer composed only of siloxane units having a silicon-hydrogen bond. However, it may be a copolymer of one or two or more of these with triorganosiloxy units, diorganosiloxy units, monoorganosiloxy units and SiO ₂ units. Further, the position of the SiH group in the molecule is not particularly limited, and may be located at either the molecular chain end or the molecular chain non-terminal (in the middle of the molecular chain), or may be located in both of them.

  Further, the degree of polymerization (or the number of silicon atoms in the molecule) is not particularly limited, but the number of silicon atoms is preferably 2 to 200 in terms of compatibility with the component (A) and ease of synthesis. 4 to 150 are preferred.

  The blending amount of component (B) is in the entire composition (for example, in the case where component (E) described later contains an alkenyl group, in the total of components (A), (D), (E)). In particular, for one alkenyl group contained in component (A), in this component (B) or when component (E) described later contains an SiH group, component (B), The number of hydrogen atoms (SiH groups) bonded to silicon atoms contained in the total organohydrogenpolysiloxane of (E) is in the range of 0.4 to 10, preferably 1.2 to 5. It is. If it is less than 0.4, the curing becomes insufficient and the required strength of the cured product cannot be obtained, and if it exceeds 10, the foaming occurs at the time of curing or the physical properties change over time.

  The platinum-based metal compound of component (C) is used as a catalyst for promoting the addition curing reaction (hydrosilation) of the above-described aliphatic unsaturated group-containing organopolysiloxane and organohydrogenpolysiloxane. However, this can use a well-known thing.

  Specific examples of platinum-based metal compounds include platinum black, chloroplatinic acid, alcohol-modified products of chloroplatinic acid, complexes of chloroplatinic acid and olefins, aldehydes, vinyl siloxanes or acetylene alcohols, and rhodium. The

  Furthermore, in the present invention, when the use of the composition is taken into consideration, mixing of corrosive components is not desirable. For this reason, it is preferable that the platinum-based metal compound is also free of chlorine ions. Therefore, as the platinum-based metal compound, a zero-valent platinum complex having a chlorine ion of 5 ppm or less is preferably used. Specifically, US Pat. No. 3,715,334, US Pat. No. 3,775,452, Examples thereof include vinyl siloxane / platinum complexes described in US Pat. No. 3,814,730.

  The addition amount may be appropriately increased or decreased depending on the desired curing rate, but is usually in the range of 1 to 2,000 ppm, preferably 1 to 200 ppm in terms of platinum metal mass based on the total amount of the composition.

The component (D) curing control agent functions to adjust the curing time in order to use the material of the present invention in practical use, and those conventionally known as control agents are used. Specifically, from the group consisting of vinylmethylcyclotetrasiloxane, triallyl isocyanurate, alkyl maleate, acetylene alcohols and their silanes, siloxane modified products, hydroperoxides, tetramethylethylenediamine, benzotriazole and mixtures thereof. Examples include selected compounds.
Although the addition amount of a component (D) is a required amount and it is not specifically limited, Usually, 0.001-10 mass parts with respect to 100 mass parts of a component (A), Preferably you may be about 0.1-5 mass parts. be able to.

Component (E), an addition functional group-containing alkoxysilane, an addition functional group and an alkoxy group-containing organosiloxane, at least one organosilicon compound selected from an addition functional group and an alkoxysilyl group-containing isocyanurate compound, It is an adhesion-imparting component for functioning as an adhesive. The additional functional group refers to an alkenyl group bonded to a silicon atom typified by a vinyl group or an allyl group, and a hydrogen atom bonded to a silicon atom.
Specific examples of the additional functional group-containing alkoxysilane, the additional functional group and the alkoxy group-containing organosiloxane include vinyl alkoxysilanes such as vinyltrimethoxysilane and vinyltriethoxysilane, and / or vinyl groups as partial hydrolysis condensates thereof. Examples thereof include an alkoxy group-containing siloxane, a hydrosilyl group (SiH group) and an alkoxy group-containing organopolysiloxane as a hydrosilylation addition reaction product of vinyl alkoxysilane and organohydrogenpolysiloxane. In addition, as an isocyanurate compound containing an additional functional group and an alkoxysilyl group, alkoxysilyl obtained by hydrosilylation addition reaction of one or two allyl groups of triallyl isocyanurate with one or two allyl groups Examples include modified triallyl isocyanurate and / or a partial hydrolysis condensate thereof. The alkoxy group preferably has 1 to 6 carbon atoms, particularly 1, 2 or 3 carbon atoms.

  The amount of component (E) to be added is not particularly limited, and an appropriate amount is selected from the expression of effects and the effect on the properties of the cured product, but usually 0.01 to 20 masses per 100 parts by mass of component (A). Parts, preferably 0.1 to 10 parts by mass.

The zirconium compound of component (F) has a function of enhancing the effect as an adhesiveness-imparting agent of the alkoxysilane containing additional functional group of component (E). The structure is preferably a substituted product such as alkoxide, acetylacetone, and fatty acid, and an organic zirconium compound having a ligand. The substituted product may be either single or complex, and the following compositional formula can be given. .
Zr (OC ₂ H ₅ ) ₄ ,
Zr (OC ₃ H ₇ ) ₄ ,
Zr (OC ₄ H ₉ ) ₄ ,
Zr (OC ₈ H ₁₇ ) ₄ ,
Zr (OC ₃ H ₇ ) ₂ (ACAC) ₂ ,
Zr (ACAC) ₄ ,
Zr (OC ₃ H ₇ ) ₃ (OCOC ₁₂ H ₂₅ )
(In the formula, ACAC represents acetylacetone.)
Among these, when Zr (ACAC) ₄ is used, it is preferable because the storage stability of the composition is excellent.

  The addition amount of the zirconium compound needs to be added in a necessary and sufficient amount to obtain an adhesion promoting effect, and is 0.001 to 10 parts by mass, preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the component (A). Add parts. If the addition amount is too small, the adhesion promoting effect is insufficient, and if it is too much, there are adverse effects such as the physical properties of the cured product becoming unstable.

  The component (G) carboxylic anhydride is added for the purpose of reducing the adverse effects of deterioration of the storage stability of the composition due to the zirconium compound of component (F) and deterioration of the thermal properties of the cured product.

  As described above, when tin, titanium, aluminum, and zirconium compounds are added in anticipation of an adhesion promoting effect, the storage stability of the material is poor due to hydrolysis of alkoxysilanes in the composition or deterioration of hydrogensiloxane. Problems such as deterioration of properties of cured products due to siloxane cleavage at the time occur. The present inventor can control the activity of these metal compounds by adding the zirconium compound and the carboxylic acid anhydride together, and the storage stability and cured product of the resulting silicone rubber adhesive composition It has been found that this is useful when the heat resistance of the material is improved, in particular, when the storage stability of the material becomes a problem, such as when it is a one-component material.

  The structure of the carboxylic anhydride may be either an intermolecular or intramolecular anhydride, but if the boiling point after hydrolysis is low, problems such as odor and ambient contamination may occur. It is preferable that the boiling point is equal to or higher than the heat curing temperature, for example, a long-chain aliphatic carboxylic acid anhydride having about 10 to 30 carbon atoms or a molecule containing about 1 to 4, especially 1 to 2 aromatic rings. An aromatic carboxylic acid anhydride etc. are mentioned. The following compounds can be mentioned as typical examples.

（Ｃ₁₂Ｈ₂₅ＣＯ）₂Ｏ、（Ｃ₆Ｈ₅ＣＯ）₂Ｏ

(C ₁₂ H ₂₅ CO) ₂ O, (C ₆ H ₅ CO) ₂ O

  The addition amount of carboxylic acid anhydride is 0.001-10 mass parts with respect to 100 mass parts of component (A), Preferably it is 0.01-5 mass parts. If the addition amount is too small, the zirconium compound of component (F) is deactivated, and if it is too much, there are adverse effects such as the physical properties of the cured product becoming unstable.

  Further, a reinforcing silica filler in an amount that does not interfere with the effect of the present invention, or a non-reinforcing filler such as quartz powder, diatomaceous earth, calcium carbonate, an inorganic pigment such as cobalt blue, a colorant such as an organic dye, cerium oxide It is also possible to add heat resistance and flame retardancy improvers such as zinc carbonate, manganese carbonate, bengara, titanium oxide, and carbon black. Furthermore, it is optional to add powdery, whisker-like, carbon black having a developed structure, graphite or the like to these compositions for the purpose of improving the conductive stability.

The silicone rubber adhesive composition of the present invention can be produced by mixing the above-mentioned components according to a conventional method, and can be made into two or more components used after mixing immediately before use. Since stability is good, it can be made into one liquid property.
The silicone rubber adhesive composition of the present invention is cured by heating. The curing conditions are 60 to 250 ° C., particularly 70 to 150 ° C., 30 seconds to 5 hours, particularly 1 minute to 2 hours. It can be.

  The heat-curable silicone rubber adhesive composition of the present invention thus obtained can be applied to a substrate such as a resin or metal, particularly to a poorly adhesive resin such as polyphenylene sulfite or polycarbonate. Since it exhibits excellent adhesiveness and is excellent in the storage stability of materials and the thermal stability of cured products, it is useful as an adhesive for use in the vicinity of electrical and electronic parts and in-vehicle parts.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, “part” means “part by mass”, “viscosity” indicates a value measured at 25 ° C. measured by a rotational viscometer, “Me” represents a methyl group, “Vi” represents a vinyl group, “iPr” represents an isopropyl group, and “ACAC” represents acetylacetone. Show.

[Examples 1-6, Comparative Examples 1-4]
A silicone rubber adhesive composition was prepared by mixing the components and amounts shown in Table 1. Using the obtained composition, the viscosity, hardness, and shear adhesive strength were evaluated by the methods shown below. The results are also shown in Table 1.
"viscosity"
The viscosity of the silicone rubber adhesive composition was measured with a rotational viscometer. Similarly, the viscosity after storage at 40 ° C. for 7 days was measured.
"Hardness"
The value immediately after curing at 120 ° C. for 60 minutes as the initial mixing value, the value after heating the cured product at 150 ° C. for 100 hours as the value after heat resistance of the cured product, after storage of the liquid composition The values when the uncured composition was stored at 40 ° C. for 7 days under curing conditions at 120 ° C. for 60 minutes were measured with a type A hardness meter in accordance with JIS K 6301.
<Shear adhesive strength>
A plate-like (width 25 mm) glass plate, stainless steel (SUS) plate, polyphenylene sulfide (PPS) plate is used as a base material, and the two base materials are bonded to each other with a cured silicone rubber (adhesive surface: length 10 mm). X width 25 mm x rubber thickness 2 mm) Adhesion between the base material and the cured silicone rubber when the two base materials are pulled in opposite directions (perpendicular to the rubber thickness) at a pulling speed of 50 mm / min. The stress until the interface peeled was measured with an autograph, and the shear adhesive force was calculated as the stress per unit area. The cured silicone rubber is obtained by curing the silicone rubber adhesive composition at 120 ° C. for 60 minutes.
Further, for the purpose of confirming the storage stability as a liquid composition, the shear adhesive strength was measured in the same manner as described above for those cured under conditions of 120 ° C. and 60 minutes after storage at 40 ° C. for 7 days.

V-Sx: Vinyl group-containing organopolysiloxane represented by the following formula, viscosity 4,990 mPa · s
ViMe ₂ Si—O— (SiMe ₂ —O) ₄₀₀ —SiMe ₂ Vi
H-Sx: hydrogen polysiloxane represented by the following formula, viscosity: 50 mPa · s
Me ₃ Si—O— (SiMe ₂ —O) ₁₅ — (SiMeH—O) ₂₀ —SiMe ₃
Platinum catalyst: 1,2-divinyl-1,1,2,2-tetramethyl-disiloxane complex of platinum / toluene solution (Pt = 0.5% by mass)
Control agent: Ethynyl-cyclohexanol / toluene solution (50% by mass)

Adhesive aid

Hydrolysis catalyst a: Zr (ACAC) ₄
b: Zr (O-iPr) ₄
c: Zr (O-iPr) ₃ (OCOC ₁₂ H ₂₅ )
d: Ti (O-iPr) ₄

Acid anhydride

As is apparent from the results in Table 1, the heat-curable silicone rubber adhesive composition of the present invention not only exhibits good adhesion to difficult-to-adhere materials but also has excellent storage properties and physical properties after curing. It can be a material with small change and excellent stability.

Claims (3)

(A) The following average composition formula R ¹ _a R ² _b SiO _{(4-ab) / 2}
Wherein R ¹ is an unsubstituted or substituted monovalent hydrocarbon group not containing an aliphatic unsaturated bond, R ² is an alkenyl group, a is 0.96 to 2.00, and b is 0.001 to 0.00. 5, a + b = 1.00 to 2.04.)
An organopolysiloxane containing at least two alkenyl groups bonded to silicon atoms in one molecule represented by: 100 parts by mass
(B) The following average composition formula R ³ _c H _d SiO _{(4-cd) / 2}
(Wherein R ³ is an unsubstituted or substituted monovalent hydrocarbon group not containing an aliphatic unsaturated bond, c is 0.70 to 2.0, d is 0.01 to 1.2, and c + d = 0.0. 8 to 3.0.)
The amount of silicon atom-bonded hydrogen atoms from 0.4 to 10 per alkenyl group in the composition,
(C) platinum-based metal compound: 1 to 2,000 ppm as a metal element-containing mass with respect to the total amount of the composition,
(D) a necessary amount of curing control agent,
(E) at least one organic silicon compound selected from an addition functional group-containing alkoxysilane, an addition functional group and an alkoxy group-containing organosiloxane, an addition functional group and an alkoxysilyl group-containing isocyanurate compound,
(F) Zirconium compound: 0.001 to 10 parts by mass,
(G) Carboxylic anhydride: A heat-curable silicone rubber adhesive composition comprising 0.001 to 10 parts by mass. The thermosetting silicone rubber adhesive composition according to claim 1, wherein the component (F) is a zirconium compound represented by the following formula.
Zr (ACAC) ₄
(In the formula, ACAC represents acetylacetone.) The heat-curable silicone rubber adhesive composition according to claim 1 or 2, wherein the composition is one-component.