JP2021109900A - Additive composition containing organoalkoxysilane - Google Patents

Abstract

To provide an additive for a coating material that is capable of improving workability, decreasing the content of an organic solvent, and suppressing generation of cracks in a coating film thus formed.SOLUTION: The additive composition according to the present invention is an additive composition to be added to a coating material, containing an organoalkoxysilane represented by the following general formula (1): R1SiR23-x(OL)x ...(1) (in the foregoing general formula (1), R1 is an unsubstituted or halogen-substituted, linear, branched, or cyclic hydrocarbon group having 4 to 20 carbon atoms, R2 is an unsubstituted or halogen-substituted hydrocarbon group having 1 to 3 carbon atoms or a hydrocarbon group having 2 to 20 carbon atoms in total and interrupted by an oxygen atom that is not adjacent, L is an unsubstituted or halogen-substituted, linear, branched, or cyclic hydrocarbon group having 1 to 4 carbon atoms, and x is 1, 2, or 3).SELECTED DRAWING: None

Description

The present invention relates to an additive composition containing an organoalkoxysilane to be added to a coating material, a method for forming a coating film including a step of adding a silane crosslinking rate adjusting agent, and the use of a silane crosslinking rate adjusting agent.

Many organic polymer-based paints are known as paints for painting floors and walls. For example, epoxy resin-based and polyurethane-based paints are often used for painting concrete surfaces, and organic lacquer-based paints are also used for painting wood surfaces.
Since these paints have high viscosity and poor workability, they are used by blending an organic solvent to adjust the viscosity. When painting with these paints containing an organic solvent, the organic solvent volatilizes when the coating film is formed, so that the coating film shrinks. If the coating film has poor followability to the base material, the adhesion of the coating film to the base material after the solvent is volatilized may decrease, or the coating film may peel off from the base material.
In addition, when diluted with a large amount of organic solvent, the organic solvent volatilizes during the coating work, and the organic solvent remaining in the coating film gradually volatilizes even after coating. It is not preferable from the viewpoint of human health.

Therefore, as a coating material having a small amount of volatile components, a coating agent that crosslinks with silane has also been developed (for example, Patent Document 1).

Japanese Patent Publication No. 2014-521819

However, the silane-crosslinked coating agent as disclosed in Patent Document 1 has a drawback that cracks are likely to occur in the formed coating film. Further, when the viscosity of such a silane cross-linking coating agent is high, it is necessary to add a diluent in order to improve workability, but what kind of diluent is used to obtain a high-quality coating film. There was no knowledge as to whether it was suitable.
Therefore, an object of the present invention is to provide an additive for a coating material, which can improve workability, reduce the content of an organic solvent, and suppress the occurrence of cracks in the formed coating film. ..

The additive composition according to the present invention is an additive composition to be added to a coating material, and contains an organoalkoxysilane represented by the following general (1).
R ¹ SiR ² _3-x (OL) _x ... (1)
(In the above general formula (1), R ¹ is an unsubstituted or halogen-substituted linear, branched or cyclic hydrocarbon group having 4 to 20 carbon atoms, and R ² is An unsubstituted or halogen-substituted hydrocarbon group having 1 to 3 carbon atoms, or a hydrocarbon group interrupted by a non-adjacent oxygen atom having a total of 2 to 20 carbon atoms. L is an unsubstituted or halogen-substituted, linear, branched or cyclic hydrocarbon group having 1 to 4 carbon atoms, where x is 1, 2 or 3).

Organoalkoxysilanes have reactivity with paints by having an alkoxy group. The coating material having reactivity with an alkoxy group is not particularly limited, and is, for example, a coating material having a reactive group with an alkoxysilyl group, an alkoxy group, an epoxy group, or the like.
The additive composition can be added not only to paints but also to adhesives, sealing materials, coating agents, waterproof materials and the like.

When applying the paint to the base material, it is necessary to reduce the viscosity of the paint to improve workability. When applying paint using a roller or the like, if the viscosity of the paint is too high, it will be difficult to apply the paint evenly, and the work of impregnating the roller with the paint and the work of spreading the paint on the coated surface with the roller. This is because it becomes difficult to do.
Therefore, the viscosity of the coating material was lowered by adding the additive composition having a low viscosity according to the present invention to the coating material. Further, the additive composition of the present invention has a −SiOL group (alkoxysilyl group), and this portion contributes to the cross-linking reaction. The additive composition component cured by the cross-linking reaction remains in the coating film, and since it is not necessary to use an organic solvent, less volatile products are generated. Therefore, the burden on the environment and the health concerns of the coating operator and the user of the coating film are reduced. Moreover, since the additive composition does not volatilize, shrinkage of the coating film at the time of forming the coating film is unlikely to occur.

In addition, having a −SiOL group makes it possible to maintain the cross-linking reaction at an appropriate rate.
Regarding organoalkoxysilane as a reactive diluent, the relationship between its reactivity and the properties of the obtained coating film is not known, and conventionally, a large number of paints and a large number of diluents have been combined one by one. , The optimum combination was selected by observing the morphology of the obtained coating film.
On the other hand, the inventors can appropriately adjust the cross-linking rate by having an alkoxy group having 1 to 4 carbon atoms in the molecule of the organoalkoxysilane, and as a result, cracks occur. It has been found that a small amount of coating film can be formed.

In the organoalkoxysilane according to the present invention, the number of alkoxy groups bonded to the Si atom can be selected according to the desired crosslinking rate and the desired crosslinking density, and the number may be one, but two. Alternatively, the number may be three.
It is considered that by having an alkoxy group, the cross-linking rate of silane can be adjusted and the phenomenon of rapid curing of the coating film when the coating film is formed can be suppressed, so that the occurrence of cracks can be suppressed. Be done. The larger the number of alkoxy groups (for example, when x is 3 in the general formula (1)), the slower the crosslinking rate, and the more cracks can be suppressed.
When the number of alkoxy groups is small (for example, when x is 1 in the general formula (1)), the contribution to slowing the cross-linking rate is lower than when the number of alkoxy groups is large, but the cross-linking density is high. Since it is lowered, the flexibility of the coating film is improved, and the occurrence of cracks can be suppressed.
The alkoxy group may have 1 to 4 carbon atoms, but can be selected according to the desired coating film characteristics and the type of coating material, and is an organoorgan having an alkoxy group having 1 to 3 carbon atoms. Alkoxysilane is preferred. Organoalkoxysilanes having an ethoxy group having 2 carbon atoms are more preferable because they exhibit an appropriate cross-linking rate and can obtain a coating film in which cracks are less likely to occur.
Organoalkoxysilanes having a triethoxysilyl group (x is 3 in the general formula (1)) show an appropriate crosslinking rate, and therefore cracks are particularly less likely to occur in the formed coating film. Further, the crosslink density is higher than that of the organoalkoxysilane having a monoethoxysilyl group or a diethoxysilyl group, and a coating film having excellent strength can be formed.

In the organoalkoxysilane according to the present invention, R ² bonded to a Si atom has an unsubstituted or halogen-substituted hydrocarbon group having 1 to 3 carbon atoms, or a total of 2 to 20 carbon atoms. Hydrocarbon groups interrupted by non-adjacent oxygen atoms.
R ² is not particularly limited, for example a methyl group, an ethyl group, an isopropyl group, may be straight-chain or branched aliphatic hydrocarbon groups such as n-isopropyl group, which is interrupted by oxygen atom which is not adjacent carbonized It may be a hydrogen group.
In the organoalkoxysilanes of the present invention, R ¹ is an unsubstituted or halogen-substituted linear, branched or cyclic alkyl group, alkenyl group or arylalkyl group having 4 to 20 carbon atoms. Is. R ¹ is not particularly limited, and may be, for example, an isooctyl group, a normal octyl group, a decyl group, a dodecyl group, or the like.

Examples of preferred organoalkoxysilanes are isooctylrimethoxysilane, isooctyl (methyl) dimethoxysilane, isooctyl (dimethyl) methoxysilane, n-octylrimethoxysilane, n-octyl (methyl) dimethoxysilane, n-octyl (dimethyl). Methoxysilane, decyltrimethoxysilane, decyl (methyl) dimethoxysilane, decyl (dimethyl) methoxysilane, dodecyl (methyl) dimethoxysilane, dodecyl (dimethyl) methoxysilane, dodecyltrimethoxysilane, dodecyl (methyl) dimethoxysilane, dodecyl ( These are dimethyl) methoxysilane, tetradecyltrimethoxysilane, tetradecyl (methyl) dimethoxysilane, tetradecyl (dimethyl) methoxysilane, hexadecyltrimethoxysilane, hexadecyl (methyl) dimethoxysilane, and hexadecyl (dimethyl) methoxysilane.

Examples of preferred organoalkoxysilanes are also isooctyltriethoxysilane, isooctyl (methyl) diethoxysilane, isooctyl (dimethyl) ethoxysilane, n-octyltriethoxysilane, n-octyl (methyl) diethoxysilane, n-octyl. (Dimethyl) ethoxysilane, decyltriethoxysilane, decyl (methyl) diethoxysilane, decyl (dimethyl) ethoxysilane, dodecyl (methyl) diethoxysilane, dodecyl (dimethyl) ethoxysilane, dodecyltriethoxysilane, dodecyl (methyl) Diethoxysilane, dodecyl (dimethyl) ethoxysilane, tetradecyltriethoxysilane, tetradecyl (methyl) diethoxysilane, tetradecyl (dimethyl) ethoxysilane, hexadecyltriethoxysilane, hexadecyl (methyl) diethoxysilane, hexadecyl (dimethyl) It is ethoxysilane.

Examples of preferred organoalkoxysilanes are also isooctyl lipoxysilane, isooctyl (methyl) dipropoxysilane, isooctyl (dimethyl) propoxysilane, n-octyl lipopoxysilane, n-octyl (methyl) dipropoxysilane, n-octyl. (Dimethyl) propoxysilane, decyltripropoxysilane, decyl (methyl) dipropoxysilane, decyl (dimethyl) propoxysilane, dodecyl (methyl) dipropoxysilane, dodecyl (dimethyl) propoxysilane, dodecyltripropoxysilane, dodecyl (methyl) Dipropoxysilane, dodecyl (dimethyl) propoxysilane, tetradecyltripropoxysilane, tetradecyl (methyl) dipropoxysilane, tetradecyl (dimethyl) propoxysilane, hexadecyltripropoxysilane, hexadecyl (methyl) dipropoxysilane, hexadecyl (dimethyl) It is a propoxysilane.

Examples of preferred organoalkoxysilanes are also isooctyl ribtoxisilanes, isooctyl (methyl) dibutoxysilanes, isooctyl (dimethyl) butoxysilanes, n-octylribtoxisilanes, n-octyl (methyl) dibutoxysilanes, n-octyls. (Dimethyl) butoxysilane, decyltributoxysilane, decyl (methyl) dibutoxysilane, decyl (dimethyl) butoxysilane, dodecyl (methyl) dibutoxysilane, dodecyl (dimethyl) butoxysilane, dodecyltributoxysilane, dodecyl (methyl) Dibutoxysilane, dodecyl (dimethyl) butoxysilane, tetradecyltributoxysilane, tetradecyl (methyl) dibutoxysilane, tetradecyl (dimethyl) butoxysilane, hexadecyltributoxysilane, hexadecyl (methyl) dibutoxysilane, hexadecyl (dimethyl) Butoxysilane.

In the present invention, when the total amount of the additive composition is 100%, the organoalkoxysilane is preferably contained in an amount of 30% by weight or more, and particularly preferably 50% by weight or more.
The content of the organoalkoxysilane can be selected according to the desired crosslinking rate, the desired degree of crack suppression, and the like, and the higher the content, the greater the contribution to the suppression of crack generation.
The additive composition may optionally contain (A) a nitrogen-containing organosilicon compound, (B) a catalyst, (C) an adhesion promoter, (D) a water scavenger, (E) a filler, and the like. Can include.

(A) The nitrogen-containing organosilicon compound may have the function of a curable catalyst or a co-catalyst.

(B) The catalyst is a catalyst for a composition that can be cured by silane condensation, and may be a catalyst containing a metal such as an organic titanium compound or a tin catalyst, or a catalyst containing no metal such as triethylamine. It may be an acidic compound such as phosphoric acid or acetic acid.

(C) The adhesion accelerator may be an adhesion accelerator used for a system that can be cured by silane condensation, and may be, for example, epoxysilane and a hydrolyzate thereof.

The water supplement (D) is, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, tetraethoxysilane, O-methylcarbamatemethylmethyl-dimethoxysilane, O-methylcarbamatemethyl-trimethoxysilane, O-. It may be a silane such as ethylcarbamate methylmethyl-diethoxysilane, O-ethyl-carbamate-methyltriethoxysilane, and / or a partial condensate thereof.

(E) The filler is an unreinforced filler, that is, a filler having a BET surface area of preferably up to 50 m ² / g, for example, quartz, particularly quartz powder, diatomaceous earth, calcium silicate, zirconium silicate, talc, kaolin, zeolite. , Metal oxide powders such as aluminum oxides, titanium oxides, iron oxides or zinc oxides and / or mixed oxides thereof, barium sulfate, calcium carbonate, gypsum, silicon nitride, silicon carbide, boron nitride, glass. Powders and plastic powders, such as polyacrylonitrile powders; reinforced fillers, ie fillers with a BET surface area ^{greater than 50 m 2} / g, such as fumed silica, precipitated silica, precipitated lime, carbon black, such as furnace carbon black and acetylene black. , A silicon-aluminum mixed oxide with a large BET surface area, or aluminum trihydroxide. The fillers cited may be in a hydrophobized state, eg, as a result of treatment with organic silanes and / or organic siloxanes, or with stearic acid, or ethers from hydroxyl groups to alkoxy groups. It may be in a hydrophobic state as a result of silicate. The composition according to the present invention may contain only one kind of filler, or may contain a mixture of a plurality of different fillers (H).

The additive composition of the present invention can contain 0.01 parts by weight or more and 20 parts by weight or less of an organic solvent with respect to 100 parts by weight of organoalkoxysilane. The amount of the organic solvent is more preferably 1 part by weight or more and 5 parts by weight or less. The organic solvent contained may be one kind or a mixed solvent of two or more kinds.

In the present invention, an organic solvent may also be a solubility parameter (SP value) 6cal / cm ³ or more 15 cal / cm ³ or more, and more preferably 8cal / cm ³ or more 11cal / cm ³ or more.
An organic solvent having an SP value in the above range is oriented toward the interface of bubbles generated when the coating composition is applied to the base material and bursts, or destroys the liquid phase on the lamella on the coating film surface. It bursts.

In the present invention, the organic solvent can include acetic acid ester and at least one selected from the group consisting of linear or cyclic ketones.

By blending a linear or cyclic ketone, foam biting during coating is particularly reduced, and a coating film having a high finish can be formed.
By blending an acetic acid ester, the leveling property of the obtained coating film is enhanced. It is also possible to simultaneously contain a linear or cyclic ketone and an acetic acid ester, and it is possible to obtain a coating film having less foam biting and higher leveling property.

The coating material to which the additive composition according to the present invention is added may contain a polymer having one or more alkoxysilyl groups in the molecule and / or a silicone resin having one or more alkoxysilyl groups in the molecule. ..

The polymer according to the present invention may be a polymer represented by the following general formula (2).
^{_{Y - [(CR 3 2)}} b -SiR 4 a (OR 5) 3-a] y (2)
(During the ceremony,
Y is a y-valent polymer group bonded via nitrogen, oxygen, sulfur, or carbon.
R ⁴ may be the same or different, monovalent, hydrocarbon groups SiC- bonded being optionally substituted,
R ³ may be the same or different, and is a monovalent, optionally substituted hydrocarbon group to which a nitrogen, phosphorus, oxygen, sulfur or carbonyl group can be attached to a hydrogen or carbon atom. And
R ⁵ is a hydrogen atom, or a monovalent, optionally substituted hydrocarbon group, which may be the same or different.
y is an integer from 1 to 10, preferably 1, 2, or 3, more preferably 1 or 2.
a may be the same or different, 0, 1 or 2, preferably 0 or 1, and b may be the same or different, an integer from 1 to 10, preferably. 1, 3, or 4, more preferably 1 or 3, more specifically 1. )

Examples of radicals ^{R 4} are alkyl groups such as methyl, ethyl, n- propyl, isopropyl, 1-n-butyl, 2-n-butyl, isobutyl, tert- butyl, n- pentyl, isopentyl, neopentyl, tert- Pentyl group; hexyl group, eg n-hexyl group; heptyl group, eg n-heptyl group; octyl group, eg n-octyl group, isooctyl group and 2,2,4-trimethylpentyl group; nonyl group, eg n -Nonyl group; decyl group, eg n-decyl group; dodecyl group, eg n-dodecyl group; octadecyl group, eg n-octadecyl group; cycloalkyl group, eg cyclopentyl, cyclohexyl, cycloheptyl group and methylcyclohexyl Groups; alkenyl groups such as vinyl, 1-propenyl and 2-propenyl groups; aryl groups such as phenyl, naphthyl, anthryl and phenanthryl groups; alkaline groups such as o-, m-, p-tolyl groups, xylyl groups. Groups and ethylphenyl groups, as well as aralkyl groups, such as benzyl groups, α- and β-phenylethyl groups.

Examples of substituted radicals ^{R 4} are haloalkyl groups such as 3,3,3-trifluoro -n- propyl group, 2,2,2,2 ', 2', 2'-hexafluoroisopropyl radical and hepta Fluoroisopropyl groups and haloaryl groups, such as o-, m- and p-chlorophenyl groups.

The group R ⁴ is preferably a monovalent hydrocarbon group optionally substituted with a halogen atom and having 1 to 6 carbon atoms, more preferably an alkyl having 1 or 2 carbon atoms. It contains a group, more specifically a methyl group.

Examples of group R ³ are hydrogen atoms, groups identified for R, and optionally substituted hydrocarbons attached to carbon atoms by nitrogen, phosphorus, oxygen, sulfur, carbon, or carbonyl groups. It is a group.

Preferably, R ³ is a hydrocarbon group having a hydrogen atom and 1 to 20 carbon atoms, more specifically a hydrogen atom.

Examples of radicals R ⁵ is an example in which the specified for hydrogen atom or a group R.

Group R ⁵ is preferably an alkyl group substituted with a hydrogen atom or optionally a halogen atom and having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. , More specifically, methyl and ethyl groups.

In the present invention, the polymer on which the polymer group Y is based is carbon-carbon, carbon-nitrogen, or carbon-carbon at least 50%, preferably at least 70%, more preferably at least 90% of all bonds in the main chain. It should be understood that all polymers are oxygen-bonded.

The polymer group Y preferably comprises an organic polymer group, which, as the polymer chain, is a polyoxyalkylene, such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer. And polyoxypropylene-polyoxybutylene copolymers; hydrocarbon polymers such as polyisobutylene, polyethylene, or copolymers of polypropylene and polyisobutylene with isoprene; polyisoprene; polyurethane; polyester, polyamide; polyacrylate; polymethacrylate; and polycarbonate. Including, they are preferably -OC (= O) -NH-, -NH-C (= O) O-, -NH-C (= O) -NH-, -NR'-C (= O) -NH-, NH-C (= O) -NR'-, -NH-C (= O)-, -C (= O) -NH-, -C (= O) -O-, -O -C (= O)-, -OC (= O) -O-, -SC (= O) -NH-, -NH-C (= O) -S-, -C (= O) One group by -S-, -SC (= O)-, -SC (= O) -S-, -C (= O)-, -S-, -O- and -NR'- or more groups ^{_{- [(CR 1 2) b}} -SiR a (oR 2) 3-a] is coupled to the proviso, R ', which may be the same or different, given for R Has a definition, or is a group-CH (COOR ")-CH _2- COOR", where R "may be the same or different, and has a given definition for R.

Examples of group R'are various steric isomers of cyclohexyl, cyclopentyl, n-propyl and isopropyl, n-butyl, isobutyl and tert-butyl, pentyl, hexyl, or heptyl groups, and also phenyl groups.

The group R'is preferably a group-CH (COOR ")-CH _2- COOR" or optionally substituted hydrocarbon group having 1 to 20 carbon atoms, more preferably 1 to 20. A linear group having up to carbon atoms, a branched group or a cycloalkyl group,
Alternatively, it is an aryl group having 6 to 20 carbon atoms and optionally substituted with a halogen atom.

The group R "is preferably an alkyl group having 1 to 10 carbon atoms, more preferably a methyl group, an ethyl group, or a propyl group.

More preferably, the group Y in the formula (2) contains a polyurethane group and a polyoxyalkylene group, and more preferably a polyoxypropylene-containing polyurethane group or a polyoxypropylene group.

The polymers of the present invention are groups that are attached at any desired position in the polymer, eg, in and / or at the ends of the chain, preferably at the ends of the chain, more preferably at the ends, in the manner described. ^{_{[(CR 1 2) b -SiR}} a (OR 2) 3-a] can have.

End groups of the polymers used according to the present invention preferably has the general formula ^{_{-O-C (= O) -NH-}} (CR 1 2) b -SiR a (OR 2) 3-a (3)
And -NH-C (= O) -NR '- (CR 1 2) b -SiR a (OR 2) 3-a (4)
(In formulas, groups and subscripts have one of the definitions specified above for them.)
Is.

In one particularly preferred embodiment of the present invention, compound (A), in any case, -O-C (= O) -NH- (CR 1 2) b group or a -NH-C (= O) - ^{_{NR '- (CR 1 2)}} b group (R'., ^{R 1} and b, having one of the definitions specified above) dimethoxymethylsilyl coupled by, trimethoxysilyl, diethoxymethylsilyl, Alternatively, it comprises a silane-terminated polyether having a triethoxysilyl-terminated group and a silane-terminated polyurethane, more specifically a silane-terminated polypropylene glycol and a silane-terminated polyurethane.

The average molecular weight _Mn of the polymer is preferably at least 400 g / mol, more preferably at least 600 g / mol, more specifically at least 800 g / mol, preferably less than 30,000 g / mol, more preferably 19,000 g. Less than / mol, more specifically less than 13,000 g / mol.

The viscosity of the polymer, measured at 20 ° C. in each case, is preferably at least 0.2 Pas, more preferably at least 1 Pas, very preferably at least 5 Pas, preferably 1,000 Pas or less, more preferably 700 Pas. It is as follows.

The polymers used in accordance with the present invention can be commercial products or prepared by methods common in chemistry.

Suitable manufacturing methods for preparing polymers and examples of polymers are also known and are included in the disclosures herein EP 1 535 940 B1 (paragraphs [0005]-[0025] and similarly of the invention. It is described in publications including Examples 1-3 and Comparative Examples 1-4) or EP 1 896 523 B1 (paragraphs [0008]-[0047]). Corresponding polymers are also commercially available, for example, from Wacker Chemie under the name GENIOSIL® STP-E.

The silicone resin according to the present invention may be a silicone resin containing a unit represented by the following general formula (3).
R ⁶ _c (R ⁷ O) _d R ⁸ _e SiO _{(4-c-d-e) / 2} (3)
(During the ceremony,
R ⁶ may be the same or different, bridging two units of hydrogen atom, monovalent, SiC-bonded, optionally substituted aliphatic hydrocarbon group, or formula (3). It is a divalent, optionally substituted aliphatic hydrocarbon group,
R ⁷ is a hydrogen atom or a monovalent, optionally substituted hydrocarbon group, which may be the same or different.
R ⁸ is a monovalent, SiC-linked, optionally substituted aromatic hydrocarbon group that may be the same or different.
c is 0, 1, 2, or 3 and
d is 0, 1, 2, or 3, preferably 0, 1, or 2, more preferably 0 or 1.
e is 0, 1, or 2, preferably 0 or 1.
However, the total of c + d + e is 3 or less, and the total of c + e is 0 or 1 in at least 40% of the units of the formula (3). )

The paint of the present invention is based on 10 parts by weight of polymer and preferably contains at least 60 parts by weight, more preferably at least 80 parts by weight of silicone resin.

The silicone resin preferably comprises at least 90% by weight of the unit of the formula (3). Particularly preferably, the silicone resin comprises only the unit of the formula (3).

The example of group R ^{6 is} an example of the aliphatic identified above for R. However, group ^{R 6} is,
Further, for example, a divalent aliphatic such as an alkylene group having 1 to 10 carbon atoms such as a methylene, ethylene, propylene, or butylene group in which two silyl groups of the formula (II) are linked to each other. It can also contain groups. One particular current example of a divalent aliphatic group is the ethylene group.

However, the group R ⁶ is preferably optionally substituted with halogen atoms and is a monovalent SiC-linked aliphatic hydrocarbon atom group having 1 to 18 carbon atoms, more preferably 1 to 6. It contains an aliphatic hydrocarbon group having up to a carbon atom, more specifically a methyl group.

The example of the group R ^{7 is} an example specified for a hydrogen atom or a group R.

The group R ⁷ is substituted with a hydrogen atom, or optionally a halogen atom, and is an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, more specific. It contains methyl and ethyl groups.

An example of group R ⁸ is the aromatic group identified above for R.

The group R ⁸ is preferably a SiC-linked aromatic hydrocarbon group optionally substituted with a halogen atom and having a carbon atom from 1 to 18, such as ethylphenyl, trill, xsilyl, chlorophenyl, naphthyl, or. It contains a styryl group, more preferably a phenyl group.

Examples of silicone resins used in accordance with the present invention are substantially, preferably exclusively, (Q) formula SiO _4/2, Si (OR ⁷ ) O _3/2 , Si (OR ⁷ ) ₂ O _{2 /. 2} and Si (OR ⁷ ) ₃ O _1/2 unit, (T) formula PhSiO _3/2 , PhSi (OR ⁷ ) O _2/2 and PhSi (OR ⁷ ) ₂ O _1/2 unit, (D) It consists of the units of the formula Me ₂ SiO _2/2 and Me ₂ Si (OR ⁷ ) O _1/2 , and the unit of the formula (M) Me ₃ SiO _1/2 (in the formula, Me is a methyl group and Ph is A phenyl group, R ⁷ is an alkyl group substituted with a hydrogen atom or optionally a halogen atom and having 1 to 10 carbon atoms, more preferably a hydrogen atom or 1 to 4 carbon atoms. Is an organopolysiloxane resin, the resin is preferably 0-2 mol (Q) units, 0-2 mol (D) units per molar (T) unit. , 0-2 mol (M) units.

Silicone resins used according to the present invention preferably have an average molar mass (number average) Mn of at least 400 g / mol, more preferably at least 600 g / mol. The average molar mass _Mn is preferably 400,000 g / mol or less, more preferably 100,000 g / mol or less, and more specifically 50,000 g / mol or less.

The silicone resin used according to the present invention can be either solid or liquid at 23 ° C. and 1,000 hPa, and the silicone resin is preferably liquid. The silicone resin preferably has a viscosity of 10 to 100,000 mPas, preferably 50 to 50,000 mPas, more specifically 100 to 20,000 mPas. _{This silicone resin has a polydispersity (M w} / M _n ) of preferably 5 or less, more preferably 3 or less.

In the present invention, the alkoxysilyl group of the coating material and the ethoxy group of the organoalkoxysilane are crosslinked by a condensation reaction to form a coating film. Ethanol is the only substance that volatilizes by the condensation reaction and evaporates to the outside of the system, and the shrinkage of the coating film during condensation is small. Further, by having a desired crosslinking reaction rate, a coating film is formed while gradually curing, so that a coating film having few cracks can be obtained. According to the present invention, there is little evaporation of harmful organic solvents during the coating operation, and the burden on the operator is light. In addition, since the amount of ethanol remaining in the coating film is small, there is little damage to the user and the environment even when the obtained coating film is used.

The present invention is also an additive composition added to a coating material containing a polymer having one or more alkoxysilyl groups in the molecule and / or a silicone resin having one or more alkoxysilyl groups in the molecule, wherein the silane. It is an additive composition containing 30% by weight or more of a cross-linking rate adjusting agent in the additive composition.

Alkoxysilyl groups in the coating material are crosslinked to form a coating film, and the crosslinking rate can be adjusted by containing 30% by weight or more of a silane crosslinking rate adjusting agent. If the cross-linking speed is too fast, the coating film shrinks rapidly and hardens. Here, cracks occur and the finish is deteriorated. However, if the cross-linking rate is adjusted by introducing the silane cross-linking rate adjusting agent of the present invention, the shrinkage rate becomes slow and cracks are less likely to occur.

The silane cross-linking rate adjusting agent of the present invention may be an organoalkoxysilane represented by the following general (1).
R ¹ SiR ² _3-x (OL) _x ... (1)
(In the above general formula (1), R ¹ is an unsubstituted or halogen-substituted linear, branched or cyclic hydrocarbon group having 4 to 20 carbon atoms, and R ² is An unsubstituted or halogen-substituted hydrocarbon group having 1 to 3 carbon atoms, or a hydrocarbon group interrupted by a non-adjacent oxygen atom having a total of 2 to 20 carbon atoms. L is an unsubstituted or halogen-substituted, linear, branched or cyclic hydrocarbon group having 1 to 4 carbon atoms, where x is 1, 2 or 3).

In particular, for a coating material containing a polymer having one or more alkoxysilyl groups in the molecule and / or a silicone resin having one or more alkoxysilyl groups in the molecule, a cross-linking rate adjusting agent having an alkoxy group should be used. Is preferable. The reaction rate when the alkoxy group in the cross-linking rate adjusting agent and the alkoxysilyl group in the coating material undergo a cross-linking reaction can be appropriately adjusted, and as a result, the shrinkage rate of the coating film is controlled. Then, the coating film is gradually cured while releasing alcohol, and the degree of shrinkage is not high, so that the occurrence of cracks is suppressed.
The alkoxy group contained in the organoalkoxysilane may have 1 to 4 carbon atoms, but preferably has 1 to 3 carbon atoms, and more preferably 2 carbon atoms.

The present invention is also a method of forming a coating film on a substrate.
A step of adding a silane cross-linking rate modifier to a coating material containing a polymer having one or more alkoxysilyl groups in the molecule and / or a silicone resin having one or more alkoxysilyl groups in the molecule to obtain a coating composition. When,
The step of applying the coating composition to the base material and
Includes a step of cross-linking the coating composition.

The base material is not particularly limited as long as it has a surface on which the above coating composition is applied, and may have a surface such as concrete, marble, wood, polyurethane resin, epoxy resin, or acrylic resin.
When a coating composition obtained by adding a silane crosslinking rate adjusting agent to a coating material is applied to a substrate, the alkoxysilyl group in the coating material and the triethoxysilyl group in the silane crosslinking rate adjusting agent gradually react and crosslink. Occurs and hardens. The coating film shrinks with curing, but since the cross-linking rate is adjusted to a desired rate, rapid curing and shrinkage are suppressed, and the occurrence of cracks is suppressed. Therefore, according to the coating film forming method according to the present invention, it is possible to obtain a coating film having high finishability. Further, only ethanol generated by the silane cross-linking rate adjusting agent is generated at the time of cross-linking, and a large amount of organic solvent harmful to the environment and health is not evaporated.
Further, the silane cross-linking rate adjusting agent of the present invention has a low viscosity, and when added to a coating material, the viscosity of the coating material composition can be lowered, and workability is improved.

The present invention also adjusts the silane cross-linking rate as a crack generation inhibitor for a coating material containing a polymer having one or more alkoxysilyl groups in the molecule and / or a silicone resin having one or more alkoxysilyl groups in the molecule. Regarding the use of agents.

Here, the silane crosslinking rate adjusting agent used may be organoalkoxysilane represented by the following general (1).
R ¹ SiR ² _3-x (OL) _x ... (1)
(In the above general formula (1), R ¹ is an unsubstituted or halogen-substituted linear, branched or cyclic hydrocarbon group having 4 to 20 carbon atoms, and R ² is An unsubstituted or halogen-substituted hydrocarbon group having 1 to 3 carbon atoms, or a hydrocarbon group interrupted by a non-adjacent oxygen atom having a total of 2 to 20 carbon atoms. L is an unsubstituted or halogen-substituted, linear, branched or cyclic hydrocarbon group having 1 to 4 carbon atoms, where x is 1, 2 or 3).

When a silane cross-linking rate modifier is used in a paint containing a polymer having one or more alkoxysilyl groups in the molecule and / or a silicone resin having one or more alkoxysilyl groups in the molecule, the alkoxysilyl group in the paint can be used. , The trialkoxysilyl group in the silane crosslinking rate adjuster gradually reacts to cause crosslinking and cure. The coating film shrinks with curing, but since the cross-linking rate is adjusted to a desired rate, rapid curing and shrinkage are suppressed, and the occurrence of cracks is suppressed. Therefore, according to the coating film forming method according to the present invention, it is possible to obtain a coating film having high finishability. Further, only alcohol generated by the silane cross-linking rate adjusting agent is generated at the time of cross-linking, and a large amount of organic solvent harmful to the environment and health is not evaporated.
Further, the silane cross-linking rate adjusting agent of the present invention has a low viscosity, and when added to a coating material, the viscosity of the coating material composition can be lowered, and workability is improved.

In the examples described below, all reported viscosities were measured at a temperature of 23 ° C. Unless otherwise stated, the following examples bring the reactants to room temperature at about 50% relative humidity without ambient pressure (ie about 1000 hPa), room temperature (ie about 23 ° C.) or further heating or cooling. It is done at the temperature achieved when combined in. In addition, all reported parts and percentages are weight-based, unless otherwise stated.

The following examples used the following substances:
(Polymer having one or more alkoxysilyl groups in the molecule)
GENIOSIL (R) STP-E2: having an average molar mass (M _n ) of 4000 g / mol and having a terminal group of formula-OC (= O) -NH-CH _{2- SiCH 3} (OCH ₃ ) _2. Polypropylene glycol having a silane at the end (commercially available from Wacker Chemie AG (Munich, Germany)).

(Silicone resin having one or more alkoxysilyl groups in the molecule)
Phenylsilicone resin: A hydrolyzate condensate of trimethoxyphenylsilane, which has ^{a kinematic viscosity of 280 mm 2} / s at 25 ° C. and an average composition (MeSiO _{3 /)} having a molecular weight of M _w = 2800 _{g / mol and M n = 1000 g / mol. 2) 0.38 (MeSi (OEt)} O 2/2) 0.46 (MeSi (OEt) 2 O 1/2) 0.15 (Me 2 SiO 2/2) T -functional low molecular weight is _0.01 A methoxyfunctional methyl-phenylpolysiloxane having a methylsiloxane.

(Organoalkoxysilane _{having 3 OCH 2} CH groups in the molecule)
SILRES BS1701: Octiltriethoxysilane _{having 3 OCH 2} CH groups (commercially available from Wacker Chemie AG (Munich, Germany)).

(Organoalkoxysilane _{having 3} OCH groups in the molecule)
SILRES BS1316: Isooctyltrimethoxysilane _{having 3} OCH groups (commercially available from Wacker Chemie AG (Munich, Germany)).

(Alkoxysilane _{having 3 OCH 2} CH groups in the molecule)
TES28: _{Tetraethoxysisilane having 3 OCH 2} CH groups (commercially available from Wacker Chemie AG (Munich, Germany)).

(Siloxane, which is a hydrolyzate of alkoxysilane having _{3 OCH 2} CH groups in the molecule)
TES40: 20 ° C. (DIN 51757) density 1.06 to 1.07 g / cm ³ , flash point (DIN 51755) 62 ° C., SiO ₂ content of about 41% oligomeric tetraethoxysilane hydrolyzate (Wacker Chemie AG) Commercially available from Munich, Germany).

( _{Alcohol having 3 OCH 2} CH groups in the molecule)
Ethanol: HOCH ₂ CH ₃

GENIOSIL (R) GF 9: N- (2-amino-ethyl) -3-aminopropyltrimethoxysilane (commercially available from Wacker Chemie AG (Munich, Germany)). Functions as a cross-linking agent.

(Organic solvent (cyclic ketone))
Cyclohexanone: C ₆ H ₁₀ O

(Organic solvent (acetate))
Methoxypropyl acetate: C ₄ H ₉ OCH ₃ CO ₂ H

Example 1: A coating composition is obtained by adding SILRES BS1701 which is an organoalkoxysilane to a coating material obtained by mixing GENIOSIL (R) STP-E2 which is a polymer and a phenyl silicone resin. The blending amount of each component is as shown in Table 1, and 9% and 81% of the total amount of GENIOSIL (R) STP-E2 and phenylsilicone resin are blended so as to have a ratio of 1: 9, respectively, and SILRES BS1701 And GENOSIL (R) GF9 were blended in an amount of 5% each.
This coating composition is applied to the mortar panel using a roll. After application once, store in standard climatic conditions (23 ° C./50% air humidity) for 24 hours, then apply the second layer again using the same roll and the same amount of material. The total amount applied in the two applications is about 100 g / m ² , which is the same in Examples 1-5 and Comparative Examples 1-12.
The obtained coating film was stored under standard climatic conditions (23 ° C./50% atmospheric humidity) for 7 days, and then the finishability was visually confirmed. Regarding the occurrence of cracks, visually ^{check the amount of cracks generated per unit area (1 m 2} ), level 1 for those with no cracks, level 2 for those with slight fine cracks, and 1 for clear cracks. Level 3 for those confirmed in more than one place, level 4 for those with many clear cracks, level 5 for those with very many clear cracks,
Those with numerous cracks were evaluated on a 6-point scale with level 6. If the crack generation level is 1 and 2, the quality of the coating film is a pass level, and if the crack generation level is 3 or more, the quality cannot withstand use and is determined to be a reject level.
Regarding the generation of bubbles, the presence or absence of bubbles in the coating film was visually confirmed. Regarding the leveling property, it was visually confirmed whether or not there was a step between the base material to be coated and the formed coating film.
The evaluation methods for crack generation, bubble generation, and step generation are the same in Examples 1 to 9 and Comparative Examples 1 to 7.
In Example 1, a coating film in which no crack was generated was formed (crack generation level 1). On the other hand, since bubbles and steps were observed, the leveling property evaluation result was "poor".

The blending amount of each component in Examples 1 to 5 and the evaluation result of the obtained coating film are shown in Table 1. Table 2 shows the blending amounts of each component in Comparative Examples 1 to 12 and the evaluation results of the obtained coating film.

Example 2: The same as in Example 1 except that the amount of SILRES BS1701 to be blended was set to 10%, and the blending amounts of GENIOSIL (R) STP-E2 and phenylsilicone resin were adjusted accordingly. The mixing ratio of GENIOSIL (R) STP-E2 and the phenylsilicone resin to 1: 9 is the same in Examples 2 to 5 and Comparative Examples 1 to 12.
Also in Example 2, a coating film in which no cracks were generated was formed (crack generation level 1). On the other hand, bubbles and steps were observed. The leveling property evaluation result is "poor".

Example 3: The same as in Example 1 except that 0.1% cyclohexanone was blended as an organic solvent.
Also in Example 3, a coating film in which no cracks were generated was formed (crack generation level 1). No foaming was observed, and the defoaming effect of cyclohexanone was observed. The occurrence of steps was observed. The leveling property evaluation result is "poor".

Example 4: The same as in Example 1 except that 0.2% methoxypropyl acetate was blended as an organic solvent.
Also in Example 4, a coating film in which no cracks were generated was formed (crack generation level 1). Although bubbles were observed, no steps were observed, and it can be said that the leveling effect of methoxypropyl acetate was observed. The leveling property evaluation result is "good".

Example 5: The same as in Example 1 except that 0.1% cyclohexanone and 0.2% methoxypropyl acetate were blended as an organic solvent.
Also in Example 5, a coating film without cracks was formed. No bubbles or steps were observed, and it can be said that the defoaming effect of cyclohexanone and the leveling effect of methoxypropyl acetate were observed.

Example 6: The same as in Example 1 except that 10% of SILRES BS1316 having a methoxy group in the molecule was blended as an additive composition.
In Example 6, a small amount of fine cracks were observed, and the crack generation level was determined to be 2. Even in the additive composition having a methoxy group, a certain effect of suppressing the occurrence of cracks was observed. Bubbles and steps were also observed. The leveling property evaluation result is "good".

Example 7: The same as in Example 6 except that 0.1% cyclohexanone was blended as an organic solvent.
In Example 7, a small amount of fine cracks were observed as in Example 6, and the crack generation level was determined to be 2. In Example 7, it was confirmed that the additive composition having a methoxy group showed a certain effect of suppressing the occurrence of cracks. No foaming was observed, and the defoaming effect of cyclohexanone was observed. The occurrence of steps was observed. The leveling property evaluation result is "poor".

Example 8: The same as in Example 6 except that 0.2% methoxypropyl acetate was blended as an organic solvent.
In Example 8, fine cracks were slightly observed as in Example 6, and the crack generation level was determined to be 2. In Example 8, it was confirmed that the additive composition having a methoxy group showed a certain effect of suppressing the occurrence of cracks. Although bubbles were observed, no steps were observed, and the leveling property evaluation result was "good". It can be said that the leveling effect of methoxypropyl acetate was recognized.

Example 9: The same as in Example 6 except that 0.1% cyclohexanone and 0.2% methoxypropyl acetate were blended as an organic solvent.
In Example 9, a small amount of fine cracks were observed as in Example 6, and the crack generation level was determined to be 2. In Example 9, it was confirmed that the additive composition having a methoxy group showed a certain effect of suppressing the occurrence of cracks. No bubbles or steps were observed, and the leveling property evaluation result was "good". It can be said that the defoaming effect of cyclohexanone and the leveling effect of methoxypropyl acetate were observed.

Comparative Example 1: The same as in Example 1 except that the additive composition is not blended.
In Comparative Example 1, one or more clear cracks were confirmed, and the crack generation level was determined to be 3. Bubbles and steps were also observed. The leveling property evaluation result is "poor".

Comparative Example 2: Comparative Example 2 except that 5% of tetraethoxysilane (TES28) having an ethoxy group in the molecule but not having R ¹ or R ^{2 represented in the general formula (1) was blended as an additive composition.} Is similar to.
In Comparative Example 2, one or more clear cracks were confirmed, and the crack generation level was determined to be 3. It is considered that the composition having no R ¹ or R ² has an insufficient effect of suppressing the occurrence of cracks. Bubbles and steps were also observed. The leveling property evaluation result is "poor".

Comparative Example 3: The same as in Comparative Example 2 except that 10% of tetraethoxysilane (TES28) was blended as an additive composition.
In Comparative Example 8, many clear cracks were generated, and the degree of occurrence was certified as level 4. Bubbles and steps were also observed. The leveling property evaluation result is "poor".

Comparative Example 4: As an additive composition, 5 is a siloxane (TES40) which is a hydrolyzate of an alkoxysilane _{having 3 OCH 2} CH ^{groups in the molecule but not having R 1} or R ² represented in the general formula (1). % Is the same as in Comparative Example 2.
In Comparative Example 4, one or more clear cracks were confirmed, and the crack generation level was determined to be 3. Bubbles and steps were also observed. The leveling property evaluation result is "poor".

Comparative Example 5: The same as in Comparative Example 2 except that 10% of siloxane (TES40) was blended as an additive composition.
In Comparative Example 5, one or more clear cracks were confirmed, and the crack generation level was determined to be 3. Bubbles and steps were also observed. The leveling property evaluation result is "poor".

Comparative Example 6: Similar to Comparative Example 2 except that 5% of ethanol _{having 3 OCH 2} CH ^{groups in the molecule but not R 1} or R ² represented in the general formula (1) was blended as an additive composition. Is.
In Comparative Example 6, many clear cracks were generated, and the degree of occurrence was certified as level 4. Bubbles and steps were also observed. The leveling property evaluation result is "poor".

Comparative Example 7: Similar to Comparative Example 2 except that 5% of ethanol _{having 3 OCH 2} CH ^{groups in the molecule but not R 1} or R ² represented in the general formula (1) was blended as an additive composition. Is.
In Comparative Example 7, a large number of clear cracks were generated, and the crack generation level was determined to be 5. Bubbles and steps were also observed. The leveling property evaluation result is "poor".

Claims (11)

An additive composition to be added to paints.
An additive composition containing an organoalkoxysilane represented by the following general (1).
R ¹ SiR ² _3-x (OL) _x ... (1)
(In the above general formula (1), R ¹ is an unsubstituted or halogen-substituted linear, branched or cyclic hydrocarbon group having 4 to 20 carbon atoms, and R ² is An unsubstituted or halogen-substituted hydrocarbon group having 1 to 3 carbon atoms, or a hydrocarbon group interrupted by a non-adjacent oxygen atom having a total of 2 to 20 carbon atoms. L is an unsubstituted or halogen-substituted, linear, branched or cyclic hydrocarbon group having 1 to 4 carbon atoms, where x is 1, 2 or 3). The additive composition according to claim 1, wherein the organoalkoxysilane is contained in an amount of 30% by weight or more. The additive composition according to claim 1 or 2, wherein the organic solvent is further contained in an amount of 0.01 part by weight or more and 20 parts by weight or less with respect to 100 parts by weight of the organoalkoxysilane. The additive composition according to claim 3, wherein the organic solvent has a solubility parameter (SP value) of 6 cal / cm ³ or more and 15 cal / cm ^{3 or more.} The additive composition according to claim 3 or 4, wherein the organic solvent contains at least one selected from the group consisting of an acetate ester and a linear or cyclic ketone. The coating according to any one of claims 1 to 5, wherein the coating material contains a polymer having one or more alkoxysilyl groups in the molecule and / or a silicone resin having one or more alkoxysilyl groups in the molecule. The additive composition according to the above. An additive composition to be added to a paint containing a polymer having one or more alkoxysilyl groups in the molecule and / or a silicone resin having one or more alkoxysilyl groups in the molecule, wherein a silane cross-linking rate adjusting agent is used. An additive composition containing 30% by weight or more in the additive composition. The additive composition according to claim 7, wherein the silane cross-linking rate adjusting agent is an organoalkoxysilane represented by the following general (1).
R ¹ SiR ² _3-x (OL) _x ... (1)
(In the above general formula (1), R ¹ is an unsubstituted or halogen-substituted linear, branched or cyclic hydrocarbon group having 4 to 20 carbon atoms, and R ² is An unsubstituted or halogen-substituted hydrocarbon group having 1 to 3 carbon atoms, or a hydrocarbon group interrupted by a non-adjacent oxygen atom having a total of 2 to 20 carbon atoms. L is an unsubstituted or halogen-substituted, linear, branched or cyclic hydrocarbon group having 1 to 4 carbon atoms, where x is 1, 2 or 3). It is a method of forming a coating film on a base material.
A step of adding a silane cross-linking rate modifier to a coating material containing a polymer having one or more alkoxysilyl groups in the molecule and / or a silicone resin having one or more alkoxysilyl groups in the molecule to obtain a coating composition. When,
The step of applying the coating composition to the base material and
A method comprising a step of cross-linking the coating composition. Use of a silane cross-linking rate modifier as a crack formation inhibitor for paints containing polymers having one or more alkoxysilyl groups in the molecule and / or silicone resins having one or more alkoxysilyl groups in the molecule. The use according to claim 10, wherein the silane cross-linking rate adjusting agent is an organoalkoxysilane represented by the following general (1).
R ¹ SiR ² _3-x (OCH ₂ CH ₃ ) _x ... (1)
(In the above general formula (1), R ¹ is an unsubstituted or halogen-substituted linear, branched or cyclic alkyl group, alkenyl group or arylalkyl group having at least 7 carbon atoms. Yes, R ² is an unsubstituted or halogen-substituted hydrocarbon group having 1 to 6 carbon atoms, or a hydrocarbon interrupted by a non-adjacent oxygen atom having a total of 2 to 20 carbon atoms. It is a hydrogen group and x is 1, 2 or 3)