JP2535986B2 - Paint composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a coating composition.

[Prior Art] A coating composition containing a fluorine-containing polymer as a main component is compared with a general coating composition using an acrylic resin,
It is known that the durability is remarkably excellent. However, the coating composition containing a fluoropolymer as a main component has a problem in workability because it is difficult to dissolve in a solvent. Fluorine-containing copolymers that have solved these problems have already been proposed. (JP-A-53-96088, etc.). Paint compositions using these fluorine-containing copolymers are also known. (JP-A-55-25318, JP-A-56-21686, etc.).

A polyisocyanate or melamine-based curing agent is used in a coating composition using these fluorine-containing copolymers.

When polyisocyanate is used, a room temperature curing type coating can be obtained, but the coating becomes a two-part type and there is a disadvantage that the two parts must be mixed at the time of use.
Further, when the melamine type is used, the above-mentioned inconvenience is solved, but a high temperature baking work is required, and there is a problem that it cannot be coated at a coating site or the like. Since the heat resistance of the conventionally used curing agent is inferior to that of the fluorine-containing copolymer, the cured product may not exhibit the heat resistance of the fluorine-containing copolymer sufficiently.

Further, the conventional coating composition containing a fluorine-containing copolymer as a main component is subjected to a primer treatment on the surface of the base material in advance in order to obtain good adhesion to an inorganic base material such as glass or stainless steel. I needed it.

[Problems to be Solved by the Invention] The present invention solves the aforementioned drawbacks of the prior art. It can be used in either one-component or two-component type,
It is possible to obtain a cured coating film without the need for baking even if it is used as a one-component type, and for an inorganic substrate such as glass or stainless steel, without any primer treatment, giving excellent adhesion, and It is an object of the present invention to provide a coating composition which gives excellent weather resistance.

[Means for Solving Problems] The present invention has been made to solve the above problems, and has a fluorine content of 10 based on a fluoroolefin unit.
An acidic phosphoric acid ester containing a fluorine-containing copolymer having a curing-reactive site, which is more than wt% and soluble in a solvent, and a polyfunctional organosilicon compound containing an isocyanate group directly bonded to a silicon atom. A coating composition comprising no compound and no phosphonic acid compound.

In the present invention, a fluorine-containing copolymer containing 10% by weight or more of a fluorine atom based on a fluoroolefin unit and having good compatibility or solubility with a specific organic silicon compound and a solvent for a coating material which is usually used is used. It is important to. If the fluorine content is too small, the advantages as a base for weather-resistant coatings are reduced, and the effect of improving the workability of the composition becomes poor, and it is not preferable in terms of the properties of the cured coating film. . In addition, the fluorine atom
Even if it is a fluoropolymer containing 10% by weight or more, polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer, polychlorotrifluoroethylene , Such as tetrafluoroethylene-ethylene copolymer, which is insoluble in various solvents, is difficult to be compatible with a specific organosilicon compound, and it is difficult to entangle molecular chains or form a network structure. Can not. Usually, the fluorine content of the specific fluorocopolymer in the present invention can be selected from the range of about 10 to 70% by weight, preferably about 15 to 50% by weight.

As the fluorinated copolymer in the present invention, those of addition polymerization type can be preferably adopted from the viewpoints of easiness of operation in the composition application step, mechanical properties of the cured coating film, and the like, and a specific organosilicon Functionality such as hydroxyl group, epoxy group, carboxyl group, amino group, acid amide group, ester group, unsaturated bond, active hydrogen, halogen, mercapto group, silanol group, and alkoxysilyl group from the aspect of reactivity with compounds. Those containing a group are adopted. Particularly, those containing a hydroxyl group, an epoxy group, a carboxyl group, an amino group, an acid amide group, or active hydrogen are preferable.

In the present invention, typical examples of suitable addition polymers include polyvinylidene fluoride, tetrafluoroethylene-propylene copolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, and further tetrafluoroethylene. Examples include copolymers of fluoroolefins such as chlorotrifluoroethylene or hexafluoropropylene, and vinyl ethers, vinyl esters, allyl ethers, allyl esters, ethylenically unsaturated compounds such as acryloyl compounds or methacryloyl compounds, and the like. A fluoroolefin-vinyl ether copolymer can be preferably used from the viewpoint of a solvent-soluble addition polymer having a fluorine content.

The fluoroolefin-ethylenically unsaturated compound-based copolymer that can be preferably used in the present invention contains a unit based on a fluoroolefin and an ethylenically unsaturated compound in an amount of 30 to 70% and 70 to 30 mol%, respectively, Those having an intrinsic viscosity of about 0.05 to 2.0 dl / g measured at 30 ° C. in tetrahydrofuran in the cured state are exemplified. Vinyl ether is preferred as the ethylenically unsaturated compound. Preferred fluoroolefin components include tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, vinylidene fluoride, hexafluoropropylene, pentafluoropropylene and the like having 2 carbon atoms.
Approximately 4 fluoroolefins are employed, and tetrafluoroethylene, chlorotrifluoroethylene, and hexafluoropropylene are particularly preferable. Such fluoroolefins may be used alone or in combination of two or more. Further, as a preferable ethylenically unsaturated compound,
Vinyl ether, vinyl ester, allyl ether, and allyl ester are adopted because of their excellent copolymerizability with fluoroolefins. Among them, carbon number 2
Alkyl vinyl ethers, alkyl vinyl esters, alkyl allyl ethers and alkyl allyl esters containing about 15 linear, branched or alicyclic alkyl groups are preferred. These ethylenically unsaturated compounds may be those in which part or all of the hydrogen bonded to carbon has been replaced by fluorine. The ethylenically unsaturated monomer may be used alone or in combination of two or more kinds.

The fluorocopolymer in the present invention has the curing reactive site as described above. Such a curing reactive site can be introduced by the method described below. Hydroxyalkyl vinyl ether, hydroxyalkyl allyl ether,
A method of copolymerizing a curing reactive site-containing ethylenically unsaturated compound such as glycidyl vinyl ether, glycidyl allyl ether, aminoalkyl vinyl ether, aminoalkyl allyl ether, carboxyalkyl allyl ether, acrylic acid, methacrylic acid, and vinylsilane derivative, after polymerization A method in which an ethylenically unsaturated compound having a hydrolyzable ester bond is copolymerized and then hydrolyzed to form a hydroxyl group or a carboxyl group, and a hydroxyl group-containing fluorine-containing copolymer is polybasic such as succinic anhydride. A method of introducing a curing reactive site through a polymer reaction such as reacting an acid anhydride to form a carboxyl group or reacting a hydroxyl group-containing fluorocopolymer with an isocyanate alkyl acrylate to form an unsaturated bond. Etc. are exemplified.

The content ratio of the curing reactive site in the specific fluorine-containing copolymer can be appropriately changed, but if it is too small, the crosslinking reaction does not proceed sufficiently and the crosslinking density is difficult to increase, so a tough coating film. It becomes difficult to obtain, and if it is too large, the crosslinking density becomes too large, the resulting coating film becomes brittle, and the shrinkage stress accompanying the curing reaction also becomes large, so the adhesion to the substrate is Get smaller. Therefore, usually, as the content of the curing reactive site-containing unit,
It can be selected from the range of about 0.5 to 40 mol%, preferably about 1 to 30 mol%. When the curing-reactive site is a hydroxyl group, the fluorine-containing copolymer has a hydroxyl value of 2 to
About 200, preferably in the range of about 5-150,
The content ratio of the curing reactive site may be selected.

Such a fluorinated copolymer is obtained by causing a polymerization initiator or a polymerization initiation source such as ionizing radiation to act on a monomer mixture in a predetermined ratio in the presence or absence of a polymerization medium to carry out a copolymerization reaction. It can be manufactured.

As the polyfunctional organosilicon compound in the present invention,
A compound generally called silyl sissoanato is adopted. It is essential that such an organosilicon compound has at least one isocyanate group directly bonded to silicon in one molecule. This isocyanate group is one of the functional groups referred to in the present invention. In addition to such a group, it may have a functional group capable of reacting with the curing reactive site or a group capable of being converted into a functional group capable of reacting with the curing reactive site by hydrolysis or the like. Examples of such a functional group include a hydrolyzable group directly bonded to silicon, such as an alkoxy group. The polyfunctional organosilicon compound is required to have at least two functional groups including the above isocyanate group. That is, when it has at least two isocyanate groups, it may have no other functional group, and when it has one isocyanate group, it has at least one other functional group. . Such a polyfunctional organosilicon compound has the general formula R _4-p Si
A compound represented by (-N = C = O) _p is preferably adopted. p is an integer of 1 to 4, and when a plurality of Rs are present (when p is 1 or 2), a plurality of Rs may be different. R is a hydrolyzable group such as an alkoxy group or represents an organic group other than that. When p is 1, at least one of the three R's must be a hydrolyzable group. When R is a hydrolyzable group, it is preferably an alkoxy group, but is not limited to this and may be another hydrolyzable group such as an acyloxy group. As the alkoxy group, an alkoxy group having 4 or less carbon atoms, particularly a methoxy group or an ethoxy group is preferable. When R is not a hydrolyzable group, it is an organic group having a carbon atom bonded to a silicon atom, such as an alkyl group, an alkenyl group,
A cycloalkyl group, an aryl group, an arylalkyl group and the like are preferable. Preferably, an alkyl group or alkenyl group having 18 or less carbon atoms, or a phenyl group or benzyl group which may have a substituent is used. Most preferably, an alkyl group having 4 or less carbon atoms or a phenyl group is used. Specifically, for example, silyl tetra isocyanates: Si (N = C = O ) 4, methyl silyl _{triisocyanate: CH 3 Si (N = C} = O) 3, butyl silyl triisocyanate: C ₄ H ₉ Si _{(N = C = O) 3} , octylsilyl _{triisocyanate: C 8 H 17 Si (N} = C = O) 3, silyl _{triisocyanate: CH 3 OSi (N = C} = O) 3, triethoxysilyl tri Isocyanate: C ₂ H ₅ OSi (N = C = O) ₃ , Phenylsilyltriisocyanate: Vinylsilyl triisocyanate: CH ₂ = CHSi (N = C =
O) ₃ , dimethylsilyl diisoanato: (CH ₃ ) ₂ Si (N
= C = O) ₂ , methylphenylsilyl diisocyanate: Dimethoxysilyldiisoanato: (CH ₃ O) ₂ Si (N =
C = O) ₂ , dibutoxysilyl diisocyanate: (C ₄ H ₉
O) ₂ Si (N = C = O) _{2 and the} like are exemplified.

As such a polyfunctional organosilicon compound, a compound having 2 or more of p, that is, having 2 or more isocyanate groups directly bonded to a silicon atom is preferably used because of its excellent reactivity. Further, a polyfunctional organosilicon compound having p = 4, that is, having four isocyanate groups directly bonded to a silicon atom, has an extremely short curing time, and therefore the workability may be extremely poor depending on the coating method. .
From the viewpoint of curing rate and coating workability, p is 3, that is, only a compound having three isocyanate groups directly bonded to a silicon atom is used, or p is 2 to 4, that is, directly bonded to a silicon atom. 2 to 2 isocyanate groups
Preference is given to using a mixture of compounds having four.

In addition, compounds in which the isocyanate group of these polyfunctional organosilicon compounds is blocked by a suitable organic group,
Although it has excellent heat resistance and adhesion to the substrate, it cannot be said to be preferable because it requires a baking operation when forming a coating film. That is, as the above-mentioned isocyanate group, an unblocked free isocyanate group is preferable.

In the present invention, the polyfunctional organosilicon compound may be used alone or in combination of two or more kinds, and may be partially condensed.

In the composition of the present invention, the polyfunctional organosilicon compound is blended in an excess equivalent amount with respect to the fluorine-containing copolymer having a curing reactive site. That is, the polyfunctional organosilicon compound having n functional groups is blended in an amount exceeding N / n mol with respect to 1 mol of the fluorocopolymer having N curing reactive sites. Preferably, the polyfunctional organosilicon compound having n'isocyanato groups is blended in an amount exceeding N / n 'mole. However, since the isocyanate group easily reacts with the curing reactive site, the crosslinking of the fluorocopolymer progresses as the blending amount approaches N / n'mol, resulting in the formation of a highly viscous product and the final product. The number of reactive groups required for the curing of such a coating composition is reduced. Therefore, the more preferable lower limit of the compounding amount of the polyfunctional organosilicon compound is N / (n-
1) mol, and particularly preferably N / (n'-1) mol.
When N moles of the polyfunctional organosilicon compound are blended, an average of one molecule of the polyfunctional organosilicon compound reacts per one curing reactive site of the fluorine-containing copolymer, and (n-
1) functional groups remain. Further, when a large amount of N-mol or more polyfunctional organosilicon compound is blended, the excess thereof remains unreacted. Although it is preferable that the amount of the unreacted component is small, the presence of the unreacted component is not particularly inconvenient because moisture or the like reacts with the curing agent during curing of the paint. Preferably, the compounding amount of the polyfunctional organosilicon compound is about 10 mol% or less in excess. When a usual fluorine-containing copolymer and a polyfunctional organosilicon compound are used, the amount of the latter compounded with respect to the former is 1/100 to 1 by weight.
00/1 is preferable. Particularly preferably, 5/100 to 40/100
(That is, 5 to 40 parts by weight of the polyfunctional organosilicon compound per 100 parts by weight of the fluorocopolymer) is desirable from the viewpoint of adhesion to the substrate and weather resistance.

When a polyfunctional organosilicon compound is blended with the fluorine-containing copolymer having a curing reactive site, the isocyanate group reacts with the curing reactive site even by simple mixing due to the high reactivity of the isocyanate group. The reaction of the isocyanate group to the curing reactive site may be more positively performed by heating or using a catalyst. The reaction product has a functional group (isocyanate group or hydrolyzable group) derived from a polyfunctional organosilicon compound. Therefore, this functional group becomes a new curing reactive site. The cure reactive site can react with water. For example, 2
The individual isocyanate groups react with water to form a urea bond. The hydrolyzable group reacts with water to form a silanol group, and two silanol groups react with each other to form a siloxane bond. Therefore, the coating composition of the present invention can be cured by moisture in the air. This type of paint is a so-called one-component curing type paint. Further, a curing agent other than water, such as a polyol or polyamine, can be used for curing. In particular, the composition of the present invention is preferably used for a one-component curing type paint as described above. Further, in the case of a one-component curing type coating material, it is preferable that the fluorine-containing copolymer and the polyfunctional organosilicon compound are sufficiently reacted in advance so that the change in the viscosity of the coating composition is small. , When N moles or more of a polyfunctional organosilicon compound is mixed with 1 mole of a fluorine-containing copolymer having N curing reactive sites, gelation does not occur even if simply mixed. .
When the polyfunctional organosilicon compound has a blocked isocyanate group, it is not necessary to react this with the fluorocopolymer in advance, and it may be a simple mixture.

It is preferable that the composition of the present invention contains a solvent for reasons such as ease of coating work. As such a solvent, various solvents can be used, such as xylene, aromatic hydrocarbons such as toluene, esters such as butyl acetate, ketones such as methyl isobutyl ketone, glycol diethers such as diethyl cellosolve, etc. In addition, various commercially available thinners can be adopted, and these can be mixed and used at various ratios. It is desirable to appropriately select such an organic solvent in consideration of the condition of the article to be coated, the evaporation rate, the working environment, and the like.

In preparing the coating composition of the present invention, a ball mill, a paint shaker, a sand mill, a jet mill,
Various equipment used for ordinary coating such as three rolls and kneaders can be used. At this time, a pigment, a dispersion stabilizer, a viscosity modifier, a leveling agent, an anti-gelling agent, an ultraviolet absorber, a synthetic resin or a precursor thereof may be added. In addition, it is preferable to avoid the presence of water such as humidity as much as possible during the preparation. When compounded in the presence of water, gelation proceeds, which may make it difficult to use as a paint.

The coating composition of the present invention has a high curing rate even when dried at room temperature and forms a coating film in a short time. However, heat drying may be used in order to remove the solvent and cure in a shorter time.

Further, the coating composition of the present invention can be applied not only to an inorganic substrate such as glass and metal, but also to an organic substrate, and can provide a coated article having excellent weather resistance.

[Action] Although the curing mechanism of the composition of the present invention is not necessarily clear, it is considered that the curing agent causes a reaction such as hydrolysis due to the action of moisture in the air to promote crosslinking. Therefore, it is considered that the composition of the present invention maintains the one-pack curability. Further, the cured product obtained from the composition of the present invention is considered to have extremely excellent heat resistance and weather resistance because the crosslinked structure is stable. Further, since such a crosslinked structure has a high affinity for a substrate such as glass or enamel which has SiO as a main component, it is considered that the adhesion with the substrate is enhanced. Further, the curing mechanism of the composition of the present invention is that which chemically bonds with the --OH group present in the oxide layer on the surface of the glass or the surface of the metal, and therefore is extremely excellent for substrates such as glass and metal. It is thought that good adhesion can be obtained.

[Examples] The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

The tests conducted in the following examples and comparative examples were conducted as follows.

[Heat resistance test] The test piece was heated at 180 ° C for 8 hours. The yellow index after heating was measured with a 3M color computer manufactured by Suga Test Instruments Co., Ltd., and the difference from that before heating was defined as ΔY.

[Adhesion test I] After the test piece was boiled for 20 hours, a gourd-shaped cut line (1 mm square x 100 pieces) was put in the coating film with a cutter knife, and then a cellophane tape was strongly pressed. After that, the cellophane tape was peeled off, and the number X of the remaining pieces of the coating film was counted to be X / 100.

[Adhesion test II] After inserting a scoring cut line (1 mm square x 100 pieces) with a cutter knife into the coating film of the test piece, the cellophane tape was strongly pressed. After that, the cellophane tape was peeled off, and the number X of the remaining pieces of the coating film was counted to be X / 100.

[Solvent resistance test] The coating film of the test piece was strongly rubbed with a gauze containing xylene, and the state of the coating film was observed. It was repeated until the coating film dissolved, and the number of times was counted. This test was conducted up to 200 times, and when dissolution of the coating film was not observed yet, it was set to> 200.

[Storage stability] A mixture of a fluorine-containing copolymer, a curing agent, a solvent and, in some cases, a curing catalyst is left in a sealed state at room temperature,
The time to cure such a mixture was measured.

[Weather resistance test] The gloss retention (%) was measured after irradiation for 4000 hours on a sunshine weather ometer.

Example 1 Units based on chlorotrifluoroethylene / cyclohexyl vinyl ether / ethyl vinyl ether / hydroxybutyl vinyl ether 52.5 / 19.5 / 16.3 / 1 respectively
100 parts by weight of a fluorine-containing copolymer containing 1.7 (wt%) and an intrinsic viscosity of 0.20 dl / g measured in tetrahydrofuran at 30 ° C, and 15 parts by weight of methylsilyltriisocyanate as a curing agent in toluene. Mixed to 250 parts. The mixture was applied onto a glass plate having a thickness of 2.5 mm by a film applicator so as to have a dry film thickness of 25 μ,
It was left to stand for a day and cured to obtain a test piece. The results of each of the above-mentioned tests using the test piece are shown in Table 1.

Comparative Examples 1 to 2 Test pieces were obtained in the same manner as in Example 1 except that the curing agent and its amount and curing conditions shown in Table 1 were used. The test results using this test piece are shown in Table 1.

Example 2 Carboxyethyl vinyl ether was used in place of hydroxybutyl vinyl ether as a fluorine-containing copolymer component (copolymer composition was adjusted to have the same molar ratio as that of the fluorine-containing copolymer used in Example 1). A test piece was obtained in the same manner as in Example 1 except for the above. The test results using the test piece are shown in Table 1.

Example 3 Same as Example 1 except that glycidyl vinyl ether (copolymer composition was equivalent to the molar ratio of the fluorocopolymer of Example 1) was used as the fluorocopolymer component instead of hydroxybutyl vinyl ether. A test piece was obtained.
The test results using the test piece are shown in Table 1.

Example 4 As Example 1 except that aminobutyl vinyl ether (copolymer composition was equivalent to the molar ratio of the fluorine-containing copolymer of Example 1) was used as the fluorine-containing copolymer component instead of hydroxybutyl vinyl ether. A test piece was obtained in the same manner.
The test results using the test piece are shown in Table 1.

Example 5 As Example 1 except that ethylvinylsilanediol (copolymer composition was equivalent to the molar ratio of the fluorine-containing copolymer of Example 1) was used as the fluorine-containing copolymer component instead of hydroxybutyl vinyl ether. A test piece was obtained in the same manner.
The test results using the test piece are shown in Table 1.

Example 6 As Example 1 except that trimethoxyvinylsilane (copolymer composition was equivalent to the molar ratio of the fluorine-containing copolymer of Example 1) was used as the fluorine-containing copolymer component instead of hydroxybutyl vinyl ether. A test piece was obtained in the same manner.
The test results using the test piece are shown in Table 1.

Examples 7 to 10 Test pieces were obtained in the same manner as in Example 1 except that the curing agents shown in Table 2 were used. The test results using this test piece are shown in Table 2.

Example 11 As the fluorine-containing copolymer, a fluorine-containing copolymer containing units based on chlorotrifluoroethylene / cyclohexyl vinyl ether / ethyl vinyl ether / hydroxybutyl vinyl ether at 56/10/10/24 (wt%), respectively, A test piece was obtained in the same manner as in Example 1 except that xylene was reacted with succinic anhydride in the presence of triethylamine, and 10 mol% of the hydroxyl group of the unit based on hydroxybutyl vinyl ether was modified to a carboxy group. It was The test results using this test piece are shown in Table 2.

Example 12 Tetrafluoroethylene / as a fluorine-containing copolymer
A test piece was obtained in the same manner as in Example 1 except that a fluorine-containing copolymer containing units based on hydroxyethylene allyl ether / ethylene vinyl ester at 62/12/26 (% by weight) was used. The test results using this test piece are shown in Table 2.

Example 13 The same procedure as in Example 1 was carried out except that a fluorine-containing copolymer containing units of hexafluoropropylene / glycidyl vinyl ether / propylene of 70/12/18 (% by weight) was used as the fluorine-containing copolymer. A test piece was obtained. The test results using this test piece are shown in Table 2.

Example 14 100 parts by weight of the fluorinated copolymer of Example 1, 15 parts by weight of methylsilyltriisocyanate and 100 parts by weight of xylene were evenly mixed and applied on a degreased stainless steel plate, and at room temperature for 1 day. A test piece was obtained by curing. The result of the adhesion test II using this test piece was 100/100. Further, the result of the adhesion test II after boiling this test piece for 2 hours was 100/100.

Comparative Example 3 100 parts by weight of the fluorine-containing copolymer of Example 1, an isocyanate curing agent (Coronate EH, manufactured by Nippon Polyurethane Co.) 1
8.5 parts by weight, 7 × 10 ⁻³ parts by weight of dibutyltin dilaurate and 150 parts by weight of xylene were uniformly mixed, applied on a degreased stainless steel plate, and cured at room temperature for 7 days to obtain a test piece. The result of adhesion test II using this test piece is 20/1
It was 00, and it was 0/100 after boiling for 2 hours.

[Effects of the Invention] The composition of the present invention has the effect of making the coating work extremely easy because it cures with one liquid and does not require baking at high temperature. Further, it has an effect that it exhibits extremely excellent adhesion to a substrate such as glass or metal, and has sufficient weather resistance and extremely excellent heat resistance. Further, it has an effect that the curing time is short.

Further, the coated article of the present invention does not have a peeling between the coating film and the article, and retains gloss for a long period of time.

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Claims (3)

(57) [Claims] 1. A fluorine-containing copolymer having a curing reactive site, which has a fluorine content of 10% by weight or more based on a fluoroolefin unit and is soluble in a solvent, and an isocyanate group directly bonded to a silicon atom. A coating composition containing a polyfunctional organosilicon compound, containing no acidic phosphoric acid ester compound, and containing no phosphonic acid compound. 2. A fluorinated copolymer containing a polymer unit based on a fluoroolefin and a polymer unit based on a vinyl ether, and having an intrinsic viscosity of 0.05 to 2 dl / g measured in tetrahydrofuran at 30 ° C. The composition according to claim 1, which is a soluble fluorine-containing copolymer. 3. The composition according to claim 1, wherein the curing reactive site is a hydroxyl group, an amino group, a carboxyl group, an epoxy group, a silanol group or an alkoxysilyl group.