WO2022058136A1

WO2022058136A1 - Moisture-curable composition and method for producing coating film using the same

Info

Publication number: WO2022058136A1
Application number: PCT/EP2021/073658
Authority: WO
Inventors: Takuya TABATA
Original assignee: Wacker Chemie Ag
Priority date: 2020-09-17
Filing date: 2021-08-26
Publication date: 2022-03-24
Also published as: JP6919147B1; JP2022050157A

Abstract

An object of the present invention is to propose a moisture-curable composition which is a coating film waterproof material composition and includes a polymer containing a hydrolyzable silyl group as a non-isocyanate binder, has a low viscosity, achieves the maximum mechanical properties of a cured coating film after application at an early stage, and has a small coating film shrinkage. The moisture-curable composition includes a silane-modified polymer (A), a silicone resin (B), and a material having reactivity (C). Specifically, regarding the material having reactivity (C), when a time required for hydrolyzing half the quantity of silane-containing groups of the silane modified polymer (A) (a half-life of the silane-containing groups) is defined as 1.0, a time required for hydrolyzing half the quantity of reactive groups of the material having reactivity (C) (a half-life of the reactive groups) under the same condition is 0.1 to 20 times.

Description

DESCRIPTION

MOISTURE-CURABLE COMPOSITION AND METHOD FOR PRODUCING COATING

FILM USING THE SAME

TECHNICAL FIELD

[0001]

The present invention relates to a moisture-curable composition that includes a specific polymer undergoing silane cross-linking, a silicone resin, and a material having specific reactivity, and a method for producing a coating film using the moisture-curable composition.

BACKGROUND ART

[0002]

General coating film waterproof materials include urethane, acryl, chloroprene rubber, asphalt, silicone, or the like as a binder component and are classified into a one- component type and a two-component type according to their product forms. Mineral fillers such as calcium carbonate, clay, carbon black, and fine powder silica, and other components such as a pigment, a thickener, a surfactant, a stabilizer, and a diluent are added to these binder components.

In particular, urethane can satisfy various required properties including high elongation and high strength and has a very high degree of freedom in their formulation design. Thus, urethane is used not only as a coating film waterproof material but also has various applications such as for sealing materials, adhesives, and coating materials such as paint. Urethane is known as a proven binder practically used for many years.

However, since urethane contains highly reactive isocyanate, isocyanate-free materials tend to be preferred from the standpoint of ecological and environmental hazardousness.

[0003]

On the other hand, a polymer containing a hydrolyzable silyl group is known as an isocyanate-free moisture-curable polymer and has many applications, such as for adhesives, sealing materials, coating film waterproof materials, and coating materials such as paint, in a wide range of fields including industries, architecture, civil engineering, and electrical and electronic engineering.

However, it has been difficult for the polymer containing the hydrolyzable silyl group to achieve mechanical properties required for coating film waterproof materials, such as high elongation and high strength.

[0004] Regarding this, Patent Literature 1 achieves an adhesive that satisfies durability class D4 in the European Standard DIN EN 204 by using a silicone resin in a cross-linkable adhesive containing urethane bonds with a low contained amount of isocyanate. However, such an adhesive has a high viscosity during application and thus causes a problem in workability and finished appearance.

It is conceivable that an organic solvent can be used for reducing the viscosity and improving workability and finished appearance. However, a solventless or a water-based type adhesive tends to be preferred from the standpoint of ecological and environmental hazardousness. Furthermore, an organic solvent is evaporated from the cured coating film over time, resulting in an increase in the coating film shrinkage ratio. Consequently, poor followability to a base material such as concrete poses problems including a crack of the coating film and poor adhesion to the base material.

[0005]

Using a reactive material having reactivity with the base polymer which forms an organic matrix (a coating film active component) after curing can reduce the viscosity as well as the shrinkage ratio. However, there is a problem in which mechanical properties such as modulus change over time, requiring a longer time to achieve the maximum mechanical properties of the cured product.

CITATION LIST

PATENT LITERATURE

[0006]

Patent Literature 1 : Japanese Translation of PCT Patent Application Publication No. 2014-521819 (WO2013/026654 corresponding thereto) SUMMARY OF INVENTION

TECHNICAL PROBLEM

[0007]

In view of the foregoing circumstances, an object of the present invention is to propose a coating film waterproof material composition which includes a polymer containing a hydrolyzable silyl group as a non-isocyanate binder, has a low viscosity, achieves the maximum mechanical properties of a cured coating film after application at an early stage, and has a small coating film shrinkage.

SOLUTION TO PROBLEM

[0008]

As a result of intensive studies, the present inventors have found a moisture-curable composition capable of producing a coating film which achieves the maximum mechanical properties of the coating film after application at an early stage and has a small shrinkage by blending a specific material having reactivity (C) with a compound which includes a silicone resin (B) and, as a main component, a silane modified polymer (A), thereby completing the present invention.

[0009]

The moisture-curable composition of the present invention makes it possible to achieve the maximum mechanical properties of the cured coating film at an early stage by using a material having a similar degree of reactivity to the silane modified polymer.

Specifically, when a time required for hydrolyzing half the quantity of silane- containing groups of the silane modified polymer (A) (a half-life of the silane-containing groups) under a prescribed condition (e.g., under a condition of pH 9) is defined as 1.0, if the time required for hydrolyzing half the quantity of reactive groups of the material having reactivity (C) (a half-life of the reactive groups) under the same condition is 0.1 to 20 times, a moisture-curable composition obtained by mixing (A), (B), and (C) can achieve the maximum mechanical properties at an early stage about one week after application and curing. The temperature for measuring the half-life may be any temperature at which (A) and (B) are in a liquid form. For example, the temperature may be in the range of 20°C or higher and 30°C or lower. The temperature for measuring the half-life of the silane-containing groups of (A) is preferably the same as the temperature for measuring the half-life of the reactive groups of (C). However, the difference between these temperatures may be within ±5°C. [0010]

The maximum mechanical properties described herein refer to the maximum value of the mechanical properties (50% modulus) obtained within four weeks after (A), (B), and (C) are mixed and cured.

More specifically, in a case where the silane modified polymer (A) is a polymer containing an alkoxy silyl group, when the time required for hydrolyzing half the quantity of the alkoxysilane to a silanol (a half-life) is defined as 1.0, using a material having reactivity with a half-life of 0.1 to 20 times that of the silane modified polymer (A) makes it possible to produce a moisture-curable composition which causes a small change in the mechanical properties such as modulus over time. [0011]

The material having reactivity refers to a reactive diluent which has a reactive group that reacts with the silane modified polymer and is used for diluting the moisture-curable composition containing the silane modified polymer. The material having reactivity is classified roughly into alcohol, oxime, acetone, acetic acid, amine, amide, or the like in accordance with by-product substances in the reaction. An alkoxysilane with a methoxy group or an ethoxy group is particularly preferable.

[0012]

In a case where the half-life of the material having reactivity exceeds 20 times that of the silane modified polymer, first, silanols of the hydrolyzed silane modified polymer form a silane modified polymer matrix (a cross-linked structure) through a dehydration condensation reaction. Subsequently, silanol groups of the material having reactivity being gradually hydrolyzed undergo a dehydration condensation reaction to form a matrix of the material having reactivity. This tends to cause the mechanical properties such as modulus to significantly change over time.

[0013]

On the other hand, in a case where the half-life of the material having reactivity is from 0.5 times or more to 20 times or less that of the silane modified polymer, the dehydration condensation reaction occurs between the silane modified polymer and the material having reactivity. In this manner, the matrix is formed between the silane modified polymer and the material having reactivity. It is inferred that this makes it possible to achieve the maximum mechanical properties, such as with respect to the modulus, at an early stage and prevent a significant change in the mechanical properties over time.

[0014]

Furthermore, the material having reactivity forms the matrix by reacting with the silane modified polymer. In this manner, the shrinkage of the coating film is hardly caused by evaporation of the diluent as compared with a case where an organic solvent is used as the diluent.

As long as the material having reactivity has a reactive group that reacts with the silane modified polymer, the contained amount of the reactive group is not limited. However, it is particularly preferable that the amount of the reactive group included in the material having reactivity be a predetermined amount or less (e.g., 10% by weight or less) from the standpoint of the effect of reducing the shrinkage of the coating film. When the amount of the reactive group is within this range, less of the substance by-produced by the reaction of the reactive group (e.g. alcohol) is evaporated from the coating film. As a result, the shrinkage of the coating film is further reduced.

[0015]

The lower limit value for the amount of the reactive group is not particularly defined. However, when the material having reactivity contains a predetermined amount or more (e.g., 0.5% by weight or more) of the reactive group, the material having reactivity is sufficiently incorporated in the coating film by reacting with the silane modified polymer, which is further preferable.

[0016]

Thus, when the material that includes the reactive group with a half-life of 0.1 to 20 times that of the silane modified polymer is used in combination with the silane modified polymer and the silicone resin, it becomes possible to provide the sufficient mechanical properties to a coating film waterproof material and achieve the maximum mechanical properties of the cured coating film after application at an early stage.

Furthermore, when the contained amount of the reactive group in the material having reactivity is 0.5% by weight or more and 10% by weight or less, it becomes possible to achieve the moisture-curable composition causing the smaller coating film shrinkage.

Furthermore, reducing the viscosity of the entire moisture-curable composition through the material having reactivity preferably improves the workability of the moisture- curable composition in the application step and also the finished appearance of the coating film.

DESCRIPTION OF EMBODIMENTS

[0017]

The present invention will be described in detail below.

[0018]

A moisture-curable composition of the present invention may be provided in any mode, form, and composition as long as it is in a form of at least one liquid or more and cured by moisture to yield a cured product of the composition as a final product. The moisture- curable composition is represented by a coating material containing a polymer with an alkoxysilyl group, which is hydrolyzed by moisture and cured by formation of siloxane bonds.

[0019]

The moisture-curable composition is not particularly limited to a particular one as long as it contains a silane modified polymer (A), a silicone resin (B), and a material having reactivity (C) that has a predetermined reactivity.

[0020]

The silane modified polymer (A) in the present invention contains at least one moisture-reactive organosilyl group. This group may be a terminal organosilyl group bonded to one end of the polymer backbone. The silane modified polymer (A) is preferably a silane modified polymer including at least one polyoxyalkylene constitutional unit. The silane modified polymer (A) is not particularly limited to particular ones as long as it is an organic polymer. Examples thereof may include a polyoxypropylene polymer, a polyoxybutylene polymer, a polyisobutylene polymer, a (meth)acrylic acid ester-based polymer, and organic polymers using a plurality of these polymers.

[0021]

The silane modified polymer (A) may be a silane modified polymer represented by the following general formula (1):

Y-[(CR¹ ₂)b-SiR_a(OR²)3-_a]x (1)

(In the formula (1), Y is an x-valent organic polymer group bonded thereto via a nitrogen, oxygen, sulfur or carbon atom, the x-valent organic polymer group containing a polyoxyalkylene or a polyurethane as a polymer chain,

R may be the same as or different from each other and is a monovalent, optionally substituted, SiC-bonded hydrocarbon group,

R¹ may be the same as or different from each other and is a hydrogen atom or a monovalent, optionally substituted hydrocarbon group of which a carbon atom can be bonded to a nitrogen, phosphorus, oxygen, or sulfur atom or a carbonyl group,

R² may be the same as or different from each other and is a hydrogen atom or a monovalent, optionally substituted hydrocarbon group, x is an integer of 1 to 10, a is 0, 1, or 2, and b is an integer of 1 to 10).

[0022]

The silane modified polymer (A) has terminal groups, where at least one of them may be a group represented by the following general formula (2) or general formula (3):

-O-C(=O)-NH-(CR¹ ₂)b-SiR_a(OR²)3-a (2),

-NH-C(=O)-NR’-(CR¹ ₂)b-SiR_a(OR²)₃-a (3)

(in the formulas (2) and (3), the groups and subscripts each have corresponding one of the definitions defined above for them, and

R’ may be the same as or different from each other and has the definition given for R).

[0023]

For example, the silane modified polymer that has a terminal group represented by the above-mentioned general formula (2) or (3) and is represented by the general formula (1) has a half-life (the time required for hydrolyzing half the quantity of the alkoxy silane to silanol under the condition of pH 9) of less than 1 hour. Furthermore, the silane modified polymer forms a matrix of the moisture-curable composition through a dehydration condensation reaction between these silanols.

[0024]

The polymer (A) serving as the silane modified polymer is a main component of the moisture-curable composition, and serves as a component for forming a film by moisture after application.

The silane modified polymer (A) can be purchased as a commercial product or can also be prepared by common chemical methods. The polymer (A) may be used alone or as a mixture of two or more thereof.

A so-called a-silane terminated polymer having a reactive alkoxysilyl group bonded to an adjacent urethane unit via a methylene spacer is particularly suitable as the silane modified polymer (A). This is because the reactivity thereof is high and the polymer achieves a higher cure rate upon contact with air, and thus, requires no co-use of any toxic tin catalysts. Examples of commercially available a-silane terminated polymers may include GENIOSIL (registered trademark) STP-E10 and STP-E30 available from Wacker — Chemie AG. [0025]

Examples of the group R may include an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a hexyl group, e.g., an n-hexyl group, a heptyl group, e.g., an n-heptyl group, an octyl group, e.g., an n-octyl group, an isooctyl group, and a 2,2,4-trimethylpentyl group, a nonyl group, e.g., an n-nonyl group, a decyl group, e.g., an n-decyl group, a dodecyl group, e.g., an n-dodecyl group, and an octadecyl group, e.g. an n-octadecyl group; a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a methylcyclohexyl group; an alkenyl group such as a vinyl group, a 1 -propenyl group, and a 2- propenyl group; an aryl group such as a phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group; an alkaryl group such as o-, m-, and p-tolyl groups, a xylyl group, and an ethylphenyl group; and an aralkyl group such as a benzyl group, and a- and P-phenylethyl groups. [0026]

Examples of the substituted group R may include a haloalkyl group such as a 3,3,3- trifluoro-n-propyl group, a 2,2,2,2',2',2'-hexafluoroisopropyl group, and a heptafluoroisopropyl group, and a haloaryl group such as o-, m- and p-chlorophenyl groups.

The group R may preferably contain a monovalent hydrocarbon group which is optionally substituted with a halogen atom and has 1 to 6 carbon atoms. The group R may more preferably contain an alkyl group with 1 or 2 carbon atoms, and more particularly a methyl group.

[0027]

Examples of the group R¹ may include a hydrogen atom, groups defined for R, and a hydrocarbon group of which a carbon atom can be bonded to a nitrogen, phosphorus, oxygen, or sulfur atom or a carbonyl group and which may optionally be substituted with a substituent.

R¹ is preferably a hydrogen atom or a hydrocarbon group with 1 to 20 carbon atoms, and more particularly a hydrogen atom.

[0028]

Examples of the group R² may include a hydrogen atom, and those defined for the group R.

The group R² is preferably a hydrogen atom or an alkyl group which is optionally substituted with a hydrogen atoms and has 1 to 10 carbon atoms, more preferably an alkyl group with 1 to 4 carbon atoms, and more particularly a methyl group or an ethyl group. [0029]

It should be understood that the polymer which becomes the base of the polymer group Y in the present invention includes all polymers in which at least 50%, preferably at least 70%, and more preferably at least 90% of the total bonds in the main chain are carboncarbon, carbon-nitrogen, or carbon-oxygen bonds. [0030]

The polymer group Y preferably includes an organic polymer group. The organic polymer group contains, as a polymer chain, a polyoxyalkylene such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, a polyoxyethylenepolyoxypropylene copolymer, and a polyoxypropylene-polyoxybutylene copolymer; a hydrocarbon polymer such as polyisobutylene, polyethylene, a polypropylene-isoprene copolymer, and a polyisobutylene-isoprene copolymer; a polyisoprene; a polyurethane; a polyester; a polyamide; a polyacrylate; a polymethacrylate; and a polycarbonate. They are preferably bonded to one or more groups of -[(CR¹2)b-SiR_a(OR2)3-a] via -O-C(=O)-NH-, -NH- C(=O)O-, -NH-C(=O)-NH-, -NR’-C(=O)-NH-, NH-C(=O)-NR’-, -NHC(=O)-, -C(=O)-NH-, - C(=O)-O-, -O-C(=O)-, -O-C(=O)-O-, -S-C(=O)-NH-, -NH-C(=O)-S-, -C(=O)-S-, -S-C(=O)-, -S-C(=O)-S-, -C(=O)-, -S-, -O-, or -NR'-, provided that R' may be the same as or different from each other and has the definition defined for R, or is the group of -CH(COOR")-CH2- COOR", where R" may be the same as or different from each other and has the definition defined for R. [0031]

Examples of the group R' may include a cyclohexyl group, a cyclopentyl group, an n- propyl group, an isopropyl group, an n-butyl group, an isobutyl group , a tert-butyl group, various stereoisomers of pentyl groups, hexyl groups, and heptyl groups, and a phenyl group.

The group R' is preferably a group of -CH (COOR")-CH2-COOR" or a hydrocarbon group that has 1 to 20 carbon atoms and is optionally substituted with a substituent, more preferably a straight chain group, a branched group or a cycloalkyl group with 1 to 20 carbon atoms, or an aryl group that has 6 to 20 carbon atoms and is optionally substituted with a halogen atom.

[0032]

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

[0033]

The group Y in the formula (1) more preferably contains a urethane group and a polyoxyalkylene group, and more preferably a polyoxypropylene-containing urethane group or a polyoxypropylene group.

[0034]

Here, the polymer (A) can have a group of -[(CR¹2)b-SiR_a(OR²)3-_a)] bonded in the manner described herein at any desired position in the polymer, e.g., within the chain and/or at the terminal thereof, preferably within the chain and also at the terminal, and more preferably at the terminal.

[0035]

The terminal group of the polymer (A) is preferably a group represented by the general formula (2) or (3):

-O-C(=O)-NH-(CR¹ ₂)b-SiR_a(OR²)3-a (2)

-NH-C(=O)-NR’-(CR¹2)b-SiR_a(OR²)₃-a (3)

(In the formulas (2) and (3), the groups and subscripts each have corresponding one of the definitions defined above for them,

R may be the same as or different from each other and is a monovalent, optionally substituted, SiC-bonded hydrocarbon group, and

R' may be the same as or different from each other and has the definition given for R).

[0036]

In a particularly preferable embodiment according to the present invention, the silane modified polymer (A), in any case, contains a silane-terminated polyether and a silane- terminated polyurethane with a dimethoxymethylsilyl, trimethoxysilyl, diethoxymethylsilyl, or triethoxysilyl terminal group that is bonded by a -O-C(=O)-NH-(CR¹2)b or -NH-C(=O)- NR'-(CR¹2)b group (where R', Rl, and b each have corresponding one of the definitions specified above), and more particularly contains a silane-terminated polypropylene glycol and a silane-terminated polyurethane.

[0037]

The number-average molar mass Mn of the silane modified polymer (A) is preferably at least 400 g/mol, more preferably at least 600 g/mol, and more particularly at least 800 g/mol, and is preferably less than 30,000 g/mol, and more preferably less than 19,000 g/mol.

[0038]

The viscosity of the silane modified polymer (A) is preferably at least 0.2 Pa-s, more preferably at least 1 Pa-s, and very preferably at least 5 Pa-s, and is preferably 1,000 Pa-s or lower, and more preferably 700 Pa-s or lower, measured at 20°C, in any case.

[0039]

In a first particularly preferred embodiment of the present invention, the silane modified polymer (A) contains, as a polymer group Y, a linear or branched polyoxyalkylene group, more preferably, a polyoxypropylene group in which chain terminals of the polyoxyalkylene groups are bonded to one or more groups of -[(CR¹2)b-SiR_a(OR²)3-_a] preferably through -O-C(=O)-NH-. In this embodiment, preferably at least 85%, more preferably at least 90%, and more specifically at least 95%, of the all chain terminals are bonded to the groups of -[(CR¹2)b-SiR_a(OR²)3-_a] through -O-C(=O)-NH-.

This polyoxyalkylene group Y has the number-average molecular weight (Mn) of 200 to 30,000, preferably 1,000 to 20,000. An appropriate production method for preparing such a silane modified polymer (A) as well as examples of the silane modified polymer itself are known and described in the publications including EP1535940B1 or EP1896523B1 which are incorporated into the disclosure of the present specification by reference. The corresponding silane-terminated polymer is commercially available, for example, under the name of GENIOSIL (registered trademark) STP-E from Wacker Chemie AG.

[0040]

In a case where the silane modified polymer (A) is chemically synthesized, it can be synthesized by various known production methods including, for example, an addition reaction such as hydrosilylation, Michael addition, or Diels- Alder addition, or a reaction between an isocyanate functional compound and a compound including an isocyanate reactive group. [0041]

The contained amount of the silane modified polymer (A) relative to the entire composition is not particularly limited. For example, the range of 5 to 90 parts by mass is preferable. When it is 5 parts by mass or more, components other than the components forming the polymer matrix do not remain in large amounts in the composition, and sufficient performance as a composition is exhibited. Then, the amount of the polymer matrix to be formed is sufficient, and the required mechanical properties such as tensile strength, elongation, and tear strength become sufficient. Thus, there is little occurrence of defects in a cured product such as adhesion failure and cracking of the coating film, and there is a low possibility that adverse effects due to other components are caused. The range of 10 to 60 parts by mass is more preferable.

[0042]

The silicone resin (B) is used together with the silane modified polymer (A) so as to be incorporated into the matrix of the coating film waterproof material and to achieve mechanical properties such as high strength.

The form of the silicone resin (B) is not limited to a particular one, and may be, for example, a liquid, powder, dispersion, sol, or the like. The silicone resin (B) may be covered by a powder.

Examples of the above-mentioned silicone resin (B) typically include those represented by the following general formula (4):

R³c(R⁴O)dR⁵ _eSiO(4-c-d-e)/2 (4)

(In the formula (4),

R³ may be the same as or different from each other and is a hydrogen atom, a monovalent, SiC-bonded, optionally substituted aliphatic hydrocarbon group, or a divalent, optionally substituted aliphatic hydrocarbon group obtained by bridging two units represented by the formula (4),

R⁴ may be the same as or different from each other and is a methyl group or an ethyl group,

R⁵ may be the same as or different from each other and is a monovalent, SiC-bonded, optionally substituted aromatic hydrocarbon group, c is 0, 1, 2, or 3, d is 0, 1, 2, 3, or 4, e is 0, 1, or 2, and c + d + e 0). [0043]

Examples of the group R³ may include the examples of the aliphatic groups specified above for R. However, the group R³ may also include, for example, a divalent aliphatic group such as an alkylene group which has 1 to 10 carbon atoms and bonds two silyl groups represented by the formula (4) together. Examples of such an alkylene group may include a methylene group, an ethylene group, a propylene group, and a butylene group. An ethylene group is a particularly preferable example of the divalent aliphatic group.

However, the group R³ preferably includes a monovalent, SiC-bonded aliphatic hydrocarbon atom group which is optionally substituted with a halogen atom and has 1 to 18 carbon atoms, more preferably an aliphatic hydrocarbon group with 1 to 8 carbon atoms, and more particularly a methyl group.

[0044]

Examples of the group R⁴ may include a hydrogen atom, and the examples specified for the group R. The group R⁴ includes a hydrogen atom, or an alkyl group which is optionally substituted with a halogen atom and has 1 to 10 carbon atoms, more preferably an alkyl group with 1 to 4 carbon atoms, and more particularly a methyl group or an ethyl group. [0045]

Examples of the group R⁵ may include the aromatic group specified above for R.

The group R⁵ preferably includes a SiC-bonded aromatic hydrocarbon group which is optionally substituted with a halogen atom and has 1 to 18 carbon atoms. Specific examples thereof may include a phenyl group, an ethylphenyl group, a tolyl group, a xylyl group, a chlorophenyl group, a naphthyl group, and a styryl group. A phenyl group is more preferable.

[0046]

The silicone resin (B) that is particularly preferrable for use is a silicone resin in which at least 90% of all the group(s) R³ is a methyl group, at least 90% of all the group(s) R⁴ is a methyl, ethyl, propyl or isopropyl group, and at least 90% of all the group(s) R⁵ is a phenyl group.

[0047]

In each case according to the present invention, it is further preferable to use a silicone resin having the unit represented by the formula (4), in which c is 0, in an amount of at least 20%, more preferably at least 40%, relative to the total number of units represented by the formula (4).

[0048]

In each case according to the present invention, it is further preferable to use a silicone resin having the unit represented by the formula (4), in which c is a value of 2, in an amount of at least 10%, more preferably at least 20%, and 80% or less, more preferably 60% or less, relative to the total number of units represented by the formula (4).

[0049]

In each case, the preferentially used silicone resin is one having the unit represented by the formula (4), in which d is a value of 0 or 1, in an amount of at least 80%, more preferably at least 95%, relative to the total number of units represented by the formula (4). [0050]

In each case, it is preferential to use a silicone resin having the unit represented by the formula (4), in which d is a value of 0, in an amount of at least 60%, more preferably at least 70%, and preferably 99% or less, more preferably 97% or less, relative to the total number of units represented by the formula (4). [0051]

In each case, more preferentially used as the component (B) is a silicone resin having the unit represented by the formula (4), in which e is a value other than 0, in an amount of at least 1%, preferably at least 10%, and more particularly at least 20%, relative to the total number of units represented by the formula (4). Although the silicone resin (B) having only the unit represented by the formula (4), in which e is other than 0, may be used, a silicone resin (B) having the unit represented by the formula (4), in which e is 0, in an amount of at least 10%, very preferably at least 20%, and preferably 80% or less, more preferably 60% or less, is more preferable.

[0052]

In each case, it is preferential to use a silicone resin (B) having the unit represented by the formula (4), in which e is a value of 1, in an amount of at least 20%, more preferably at least 40%, relative to the total number of units represented by the formula (4). Although a silicone resin (B) having only a unit represented by the formula (4), in which e is 1, may be used, it is more preferable to use a silicone resin (B) having the unit represented by the formula (4), in which e is 0, in an amount of at least 10%, very preferably at least 20%, and preferably 80% or less, and more preferably 60% or less.

[0053]

In each case, preferentially used is a silicone resin (B) having the unit represented by the formula (4), in which the sum of c + e is 0 or 1, in an amount of at least 50% relative to the total number of units represented by the formula (4). [0054]

In a particularly preferred embodiment of the present invention, in each case, a silicone resin is used as a base surface-adjusting agent where the silicone resin has its unit represented by the formula (4), in which e is 1 and c is 0, in an amount of at least 20%, more preferably at least 40%, relative to the total number of units of formula (4). In this case, 70% or less, more preferably 40% or less, of the total number of units represented by the formula (4) preferably has d other than 0.

[0055]

In another particularly preferable embodiment of the present invention, the silicone resin used as the component (B) is a resin having, in each case, the unit represented by the formula (4) in which e is 1 and c is 0, in an amount of at least 20%, more preferably at least 40%, relative to the total number of units represented by the formula (4), and further having at least 1%, preferably at least 10%, of units represented by the formula (4) in which c is 1 or 2, preferably 2. In this case, preferably 70% or less, more preferably 40% or less, of all units represented by the formula (4), has d other than 0, and in at least 1% of all units represented by the formula (4), d is 0.

[0056]

Examples of the silicone resins (B) used in accordance with the present invention may substantially, preferably exclusively, include organopolysiloxane resins including units represented by the formula (Q) of SiO4/2, Si(ORⁿ)O3/2, Si(ORⁿ)2O2/2, and Si(ORⁿ)3Oi/2, units represented by the formula (T) of PhSiO3/2, PhSi(ORⁿ)O2/2, and PhSi(ORⁿ)2Oi/2, units represented by the formula (D) of Me2SiO2/2 and Me2Si(ORⁿ)Oi/2, and units represented by the formula (M) of Me3SiOi/2 (in the formulas, Me is a methyl group, Ph is a phenyl group, R¹¹ is a hydrogen atom or an alkyl group which is optionally substituted with a halogen atom and has 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group with 1 to 4 carbon atoms). The resin preferably includes per unit mole of the (T) unit: 0 to 2 mol of the (Q) unit, 0 to 2 mol of the (D) unit, and 0 to 2 mol of the (M) unit.

[0057]

Preferable examples of the silicone resins (B) used in accordance with the present invention may substantially, preferably exclusively, include organopolysiloxane resins including a T unit of PhSiO3/2, PhSi(ORⁿ)O2/2, and PhSi(ORⁿ)2Oi/2, and/or a D unit of Me2SiO2/2 and Me2Si(ORⁿ)Oi/2 (in the formulas, Me is a methyl group, Ph is a phenyl group, R¹¹ is a hydrogen atom or an alkyl group which is optionally substituted with a halogen atom and has 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, and a molar ratio of the (T) unit to the (D) unit is 0.5:2.0). [0058]

More preferable examples of the silicone resins (B) used in accordance with the present invention may substantially, preferably exclusively, include organopolysiloxane resins including a T unit of PhSiO3/2, PhSi(ORⁿ)O2/2, and PhSi(ORⁿ)2Oi/2, a T unit of MeSiOs/2, MeSi(ORⁿ)O2/2, and MeSi(ORⁿ)2Oi/2, and, as needed, a D unit of Me2SiO2/2 and Me2Si(ORⁿ)Oi/2 (in the formulas, Me is a methyl group, Ph is a phenyl group, R¹¹ is a hydrogen atom or an alkyl group which is optionally substituted with a halogen atom and has 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, and a molar ratio of a phenyl silicone unit to a methyl silicone unit is 0.5:4.0). The amount of the D units in the silicone resin (B) is preferably less than 10% by weight.

[0059]

More preferable examples of the silicone resins (B) used in accordance with the present invention may substantially, preferably exclusively, include organopolysiloxane resins including a T unit of PhSiO3/2, PhSi(ORⁿ)O2/2, and PhSi(ORⁿ)2Oi/2 (in the formulas, Ph is a phenyl group, R¹¹ is a hydrogen atom or an alkyl group which is optionally substituted with a halogen atom and has 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group with 1 to 4 carbon atoms). The amount of the D units in the silicone resin (B) is preferably less than 10% by weight.

[0060]

The silicone resin (B) used in accordance with the present invention preferably has Mn (number average molecular weight) of at least 400, more preferably at least 600. This Mn is preferably 400,000 or less, more preferably 10,000 or less, and more specifically 50,000 or less.

[0061]

The silicone resin (B) used in accordance with the present invention may be either solid or liquid at 23°C and 1,000 hPa, and the silicone resin (B) is preferably liquid. This silicone resin preferably has a viscosity of 10 to 100,000 mPa-s, preferably 50 to 50,000 mPa-s, and more specifically 100 to 20,000 mPa-s. This silicone resin (B) has a poly dispersity (Mw/Mn) of preferably 5 or less, and more preferably 3 or less.

[0062]

This silicone resin (B) may be used either in pure form or in the form of a solution in a suitable solvent.

[0063]

Examples of the solvents which can be used in this case may include an ether (e.g., diethyl ether, methyl tert-butyl ether, ether derivatives of glycols, and tetrahydrofuran (THF)), an ester (e.g., ethyl acetate, butyl acetate, and glycol esters), a hydrocarbon (e.g., pentane, cyclopentane, hexane, heptane, octane, and other long-chain, branched and unbranched alkanes), a ketone (e.g., acetone and methyl ethyl ketone), an aromatic (e.g., toluene, xylene, ethylbenzene, and chlorobenzene), and an alcohol (e.g., methanol, ethanol, glycol, propanol, isopropanol, glycerol, butanol, isobutanol, and tert-butanol).

[0064]

However, it is preferable to use the silicone resin (B) containing no organic solvent. [0065]

The contained amount of the silicone resin (B) relative to the silane modified polymer (A) is not particularly limited, and for example, the ratio of the silane modified polymer (A) to the silicone resin (B) is preferably 5: 100 to 100:5 in terms of parts by mass, more preferably 50:50 to 50:200, and still more preferably, the contained amount of the silicone resin (B) relative to the silane modified polymer (A) is less than 2.5 times.

Within the above-mentioned range, components other than the components forming the polymer matrix do not remain in a large amount in the composition, and sufficient performance as the composition is exhibited. Then, the amount of the polymer matrix to be formed is sufficient, and required mechanical properties such as tensile strength, elongation, and tear strength become sufficient, so that there is little occurrence of defects in a cured product such as adhesion failure and cracking of the coating film, and there is a low possibility that adverse effects due to other components are caused.

[0066]

The material having reactivity (C) is not particularly limited to a particular one as long as it contains a reactive group which has a predetermined half-life and reacts with the silane modified polymer (A). The material (C) may be an alcohol-based material, an oxime- based material, a carboxylic acid-based material, an amine-based material, or an amide-based material. These materials having reactivity react with the silane modified polymer (A) in the presence of a catalyst such as a tin compound.

In terms of dilution of the silane modified polymer (A), it is desirable that the viscosity of the material having reactivity (C) be lower than that of the silane modified polymer (A). It is further preferable that the viscosity of the material having reactivity (C) be lower than 2,200 mPa-s.

[0067]

The material having reactivity (C) is not particularly limited to a particular one as long as it has a reactive group with a predetermined half-life, and may be, for example, a silane compound represented by the following general formula (4):

R³c(R⁴O)dR%SiO(4-c-d-e)/2 (4) (In the formula (4),

R⁵ may be the same as or different from each other and is a monovalent, SiC-bonded, optionally substituted aromatic hydrocarbon group, c is 0, 1, 2, or 3, d is 0, 1, 2, 3, or 4, e is 0, 1, or 2, and c + d + e 0).

[0068]

The silane compound which is the material having reactivity (C) may be a single monomer or an oligomer obtained by polymerizing the same or different monomers, but has a time (half-life), required for hydrolyzing half the quantity of the alkoxy silanes to silanols under pH 9 conditions, of less than 20 hours, and forms a matrix of the moisture-curable composition through a dehydration condensation reaction between these silanols and the polymer (A) and/or between the silanols of one terminal-modified silicone (C) serving as the material having reactivity.

[0069]

The material having reactivity (C) may also be, for example, a compound represented by the following general formula (5):

Y-[(CR⁵¹2)_g-SiR⁵⁰f(OR⁵²)3-f]w (5)

(In the formula (5), Y is a w-valent organic polymer group bonded thereto via a nitrogen, oxygen, sulfur or carbon atom, the w-valent organic polymer group containing a polyoxyalkylene or a polyurethane as a polymer chain,

R⁵⁰ may be the same as or different from each other and is a monovalent, optionally substituted, SiC-bonded hydrocarbon group,

R⁵¹ may be the same as or different from each other and is a hydrogen atom or a monovalent, optionally substituted hydrocarbon group of which a carbon atom can be bonded to a nitrogen, phosphorus, oxygen, or sulfur atom or a carbonyl group,

R⁵² may be the same as or different from each other and is a hydrogen atom or a monovalent, optionally substituted hydrocarbon group, w is 1, f is 0, 1, or 2, and g is an integer of 1 to 10).

The material having reactivity (C) in the above-mentioned formula (5) has, on average, one silane-modified group in one molecule of the material having reactivity (C). In the case where a one terminal-modified type with the silane-modified group only at one terminal is used, a part of the terminal may remain unreacted in some cases.

[0070]

The material having reactivity (C) may be, for example, a silane cross-linked polymer represented by any one selected from the following general formulas (6) and (7):

R22.O-Z¹-O-CO-NH-(CH₂)-SiR²⁰ _v(OR²¹)3-v (6)

R24._O-Z²-O-CO-NH-(CH₂)3-Si(OR²³)3 (7)

(In the formulas (6) and (7),

Z¹ is a divalent polymer group that does not contain a C-bonded hydroxyl group,

Z² is a divalent polymer group that does not contain a C-bonded hydroxyl group,

R²⁰ may be the same as or different from each other and is a monovalent SiC- bonded, optionally substituted hydrocarbyl group,

R²¹ may be the same as or different from each other and is a hydrogen atom or a monovalent, optionally substituted hydrocarbyl group,

R²³ may be the same as or different from each other and is a hydrogen atom or a monovalent, optionally substituted hydrocarbyl group,

R²² is a monovalent, optionally substituted hydrocarbyl group,

R²⁴ is a monovalent, optionally substituted hydrocarbyl group, and v is 0 or 1, preferably 0).

[0071]

The material having reactivity (C) represented by the above-described general formulas (6) and (7) is a one terminal-modified type, and forms a matrix of a moisture-curable composition through a dehydration condensation reaction of these silanols and the polymer (A) in which these silanols have a time (half-life), required for hydrolyzing half the quantity of alkoxysilanes to silanols under pH 9 conditions, of less than 1 hour.

[0072]

Examples of the group R²⁰ in the formulas (6) and (7) may include an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a hexyl group, e.g., an n-hexyl group, a heptyl group, e.g., an n-heptyl group, an octyl group, e.g., an n-octyl group, an isooctyl group, and a 2,2,4-trimethylpentyl group, a nonyl group, e.g., an n-nonyl group, a decyl group, e.g., an n- decyl group, a dodecyl group, e.g., an n-dodecyl group, and an octadecyl group, e.g., an n- octadecyl group; a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a methylcyclohexyl group; an alkenyl group such as a vinyl group, a 1 -propenyl group, and a 2-propenyl group; an aryl group such as a phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group; an alkaryl group such as o-, m-, and p-tolyl groups, a xylyl group, and an ethylphenyl group; and an aralkyl group such as a benzyl group, and a- and 0-phenylethyl groups.

[0073]

Examples of the substituted group R²⁰ may include a haloalkyl group such as a 3,3,3- trifluoro-n-propyl group, a 2,2,2,2',2',2'-hexafluoroisopropyl group, and a heptafluoroisopropyl group; and a haloaryl group such as o-, m- and p-chlorophenyl groups. [0074]

The group R²⁰ is preferably a monovalent hydrocarbyl group which may be optionally substituted with a halogen atom and has 1 to 6 carbon atoms. The group R²⁰ is more preferably an alkyl group with 1 or 2 carbon atoms, and more particularly a methyl group.

[0075]

Examples of the groups R²¹ and R²³ in the general formulas (6) and (7), which are independently of each other, may include a hydrogen atom and the examples specified for the group R²⁰ in the general formulas (6) and (7).

[0076]

The groups R²¹ and R²³, which are independently of each other, may preferably be a hydrogen atom or an alkyl group which may be substituted with a halogen atom and has 1 to 10 carbon atoms, more preferably an alkyl group with 1 to 4 carbon atoms, and more particularly a methyl group or an ethyl group.

[0077]

Examples of the groups R²² and R²⁴ in the general formulas (6) and (7), which are independently of each other, may include the examples specified for the group R²⁰ in the general formulas (6) and (7).

[0078]

The groups R²² and R²⁴, which are independently of each other, are an alkyl group which may be optionally substituted with a halogen atom and has 1 to 10 carbon atoms, more preferably an alkyl group with 1 to 6 carbon atoms, and more particularly a methyl group, an ethyl group, an n-propyl group or an n-butyl group.

[0079]

Examples of the polymer groups Z¹ and Z² in the general formulas (6) and (7), which are independently of each other, may include a polyester group, a polyether group, a polyurethane group, a polyalkylene group, and a polyacrylate group, which do not contain a C -bonded hydroxyl group.

[0080]

The polymer groups Z¹ and Z², which are independently of each other, are preferably an organic polymer group including a polyoxyalkylene, e.g., a polyoxyethylene, a polyoxypropylene, a polyoxybutylene, a polyoxytetramethylene, a polyoxyethylenepolyoxypropylene copolymer, and a polyoxypropylene-polyoxybutylene copolymer; a hydrocarbon polymer, e.g., a polyisobutylene and a polyisobutylene-isoprene copolymer; a polychloroprene; a polyisoprene; a polyurethane; a polyester; a polyamide; a polyacrylate; a polymethacrylate; a vinyl polymer and/or a polycarbonate, which do not contain a C-bonded hydroxyl group, as a polymer chain.

[0081]

Particularly preferably, the groups Z¹ and Z² are a linear polyoxyalkylene group which does not contain a C-bonded hydroxyl group.

[0082]

The groups Z¹ and Z² have a number-average molar mass (number-average Mn) of preferably at least 2,000 g/mol, more preferably at least 3,000 g/mol, and particularly preferably at least 4,000 g/mol. They have a number-average molar mass Mn of preferably up to 11,000 g/mol, more preferably up to 9,000 g/mol, and particularly preferably up to 7,000 g/mol.

[0083]

Herein, a number-average molar mass Mn may be determined in relation to the present invention by size-exclusion chromatography (SEC) on a Styragel HR3-HR4-HR5- HR5 column available from Waters (Waters Corp.) at an injection volume of 100 pL with an RI detector (refractive index detector) in THF at 60°C and at a flow rate of 1.2 ml/min with reference to a polystyrene standard.

[0084]

The polymer represented by the formula (6) which can be used as the material having reactivity (C) is preferably prepared by reacting a polymer represented by the formula (8) with a silane represented by the formula (9):

R²²-O-Z¹-OH (8), and OCN-(CH₂)-SiRv(OR²¹)₃-v (9), wherein all groups and subscripts in these formulas have corresponding ones of the definitions defined above for those in the general formulas (6) and (7). [0085]

The polymer represented by the formula (7) which can be used as the material having reactivity (C) is preferably prepared by reacting a polymer represented by the formula (10) with a silane represented by the formula (11):

R24__O-Z²-OH (10), and

OCN-(CH₂)₃-Si(OR²³)₃ (11), wherein all groups and subscripts in these formulas have corresponding ones of the definitions defined above.

[0086]

The reaction in this case is preferably carried out so that there are mainly complete silane terminals, i.e., there are the silane terminals in an amount of at least 90%, more preferably at least 95%, and more particularly at least 98%, among the total OH functional chain terminals present in the molecule.

[0087]

Preferably, the non-silane functional polymers of the formulas (8) and (10) may be included in an amount of up to 15 parts by mass, more preferably up to 10 parts by mass, and more particularly up to 5 parts by mass, relative to 100 parts by mass of the material having reactivity (C).

[0088]

Herein, the polymers represented by the formulas (6) and (7) can be prepared by methods described in EP15356940B1 or EP1896523B1 in principle, and these methods differ only in that the monofunctional polymers of the formula (8) or the formula (10) are used as a reactant, respectively, and the stoichiometry of each of the reactants is adapted accordingly. Suitable preparation methods are further described in DE-A102013216852.

[0089]

The polymers represented by the formulas (6) and (7) are preferably prepared in the presence of a catalyst (KB). Examples of the catalysts (KBs) optionally used may include a bismuth-containing catalyst, e.g., catalysts with trade names Borchi (R) Kat 22, Borchi (R) Kat VP 0243, and Borchi (R) Kat VP 0244 available from Borchers GmbH, and other catalysts described in Japanese Translation of PCT Patent Application Publication No. 2016- 534192 (WO2015/024773 corresponding thereto).

[0090] When a catalyst (KB) is used for the preparation of the polymer represented by the formula (6), the contained amount thereof is preferably 0.001 to 5 parts by mass, more particularly 0.05 to 1 part by mass, relative to 100 parts by mass of the OH-functional polymer represented by the formula (8) in any case.

[0091]

When a catalyst (KB) is used for the preparation of the polymer represented by the formula (7), the contained amount thereof is preferably 0.001 to 5 parts by mass, more particularly 0.05 to 1 part by mass, relative to 100 parts by mass of the OH-functional polymer represented by the formula (10) in any case.

[0092]

In the preparation of the polymer represented by the formula (6) used in accordance with the present invention, the reactants represented by the formulas (8) and (9) are preferably used in quantitative ratios so that preferably 0.9 to 2.0 mol, more preferably 0.95 to 1.6 mol, still more preferably 1.0 to 1.4 mol, of isocyanate groups are used per 1 mol of the hydroxyl functional group.

[0093]

In the preparation of the polymer represented by the formula (7) used in accordance with the present invention, the reactants represented by the formulas (10) and (11) are preferably used in quantitative ratios so that preferably 0.9 to 2.0 mol, more preferably 0.95 to 1.6 mol, still more preferably 1.0 to 1.4 mol, of isocyanate groups are used per 1 mol of the hydroxyl functional group.

[0094]

The average molecular masses Mn of the polymers represented by the formulas (6) and (7) are each preferably at least 3,000 g/mol, preferably up to 8,000 g/mol, and more preferably up to 7,000 g/mol.

[0095]

The viscosities of the polymers represented by the formulas (6) and (7), which are independently of each other, are preferably at least 0.2 Pa-s, more preferably at least 0.5 Pa-s, and particularly preferably at least 1 Pa-s, and are preferably up to 10 Pa-s, more preferably up to 8 Pa-s, and more particularly up to 5 Pa-s, as measured at 20°C, in any case.

[0096]

The polymer represented by the formula (6) which can be used as the material having reactivity (C) preferably includes a linear polyoxypropylene terminated at one chain end with the group represented by the formula of -O-CO-NH-(CH2)-Si(CH3)(OCH3)2 in any case. At the other end, the polymer includes an alkyl group in a very preferably aspect. Examples thereof may include those available from Wacker Chemie (Munich, Germany) as a product name GENIOSIL (registered trademark) XM 20 in any case.

[0097]

The polymer represented by the formula (7) which can be used as the material having reactivity (C) preferably includes a linear polyoxypropylene terminated at one chain end with the group represented by the formula of -O-CO-NH-(CH2)3-Si(OCH3)3 in any case. At the other end, the polymer includes an alkyl group in a very preferably aspect. Examples thereof may include those available from Wacker Chemie (Munich, Germany) as a product name GENIOSIL (registered trademark) XM 25 in any case.

[0098]

The material having reactivity (C) may be only the polymer represented by the formula (6), only the polymer represented by the formula (7), or a mixture of the polymers represented by the formulas (6) and (7). The polymers represented by the formulas (6) and (7) may contain only respective one types of the compounds represented by the formulas (6) and (7), but may also include multiple compounds represented by the formula (6) and multiple compounds represented by the formula (7).

[0099]

The moisture-curable composition of the present invention includes the material having reactivity (C) at a concentration of preferably up to 80 parts by mass, more preferably up to 70 parts by mass, and preferably at least 5 parts by mass, and more preferably at least 10 parts by mass, relative to the entire moisture-curable composition.

[0100]

When the moisture curable composition including the silane modified polymer (A) represented by the above-described general formula (1) is applied to various base materials in various uses, a form as the coating material composition and a composition content thereof are not limited to a particular one.

In a case where the moisture-curable composition including the silane modified polymer is applied to base materials of construction materials, industrial structures, and the like as a typical use, the following composition is preferable.

Silane modified polymer (A): 5 to 90 parts by mass

Silicone resin (B): 5 to 90 parts by mass

Material having reactivity (C): 5 to 80 parts by mass

Inorganic particle (D): 0 to 20 parts by mass

Thixotropic agent (E): 0 to 10 parts by mass Amine compound (F): 0.01 to 10 parts by mass

Dehydrating agent (G): 0 to 10 parts by mass

Stabilizer (H): 0.01 to 5 parts by mass

Filler (I): 0 to 80 parts by mass

Curing catalyst (J): 0 to 5 parts by mass

The amount in parts by mass of each component represents the amount in parts by mass of each component relative to 100 parts by mass of the entire moisture-curable composition.

[0101]

The optionally formulated inorganic particles (D) form a network in the system by van der Waals force acting between the particles and thicken the entire system, thereby imparting a certain level or higher of thixotropy to the moisture-curable composition of the present invention.

[0102]

Examples of inorganic particles used as a raw material of the inorganic particles (D) may include inorganic particles of silica, titanium dioxide, bentonite, zinc oxide, talc, kaolin, mica, vermiculite, magnesium carbonate, calcium carbonate, aluminum silicate, barium silicate, calcium silicate, magnesium silicate, strontium silicate, tungstic acid metal salts, magnesium, zeolite, barium sulfate, calcined calcium sulfate, calcium phosphate, fluorapatite, hydroxyapatite, and metal soaps. Further, composite particles obtained by coating particles with metal oxides or the like or reformed particles in which particle surface is processed by compounds or the like may be used.

[0103]

The surface of these particles usually includes two portions where one is covered with silanol groups, carbinol groups, or other hydrophilic groups such as hydroxyl groups and another is covered with groups obtained by hydrophobizing these groups by alkyl groups or the like, or other hydrophobic groups.

Aggregation properties and solubility of the inorganic particles in the system can be controlled by adjusting the ratio between the hydrophilic groups and the hydrophobic groups. [0104]

Among the above-described inorganic particles, silica is preferably used. Exemplary types of silicas may include fumed silica, wet silica, colloidal silica, and the like. In any type of silica particles, hydrophilic silanols are present on their surface and these silanol groups can be subjected to a hydrophobization treatment by alkyl groups or the like at any ratio, making it easy to adjust the molar ratio between the hydrophilic groups and the hydrophobic groups on the surface. Further, from the viewpoints of taking an aggregation structure and having a high affinity towards various oil components, easy availability and economic efficiency, silica allows for wide use applications, and thus, is preferable.

[0105]

In the present invention, the most preferable silica is fumed silica.

Fumed silica particles take a multidimensional aggregation structure. This makes it possible to, for example, control the balance between the hydrophilic groups and the hydrophobic groups on the surface according to aggregation levels and rearrange aggregation units.

Further, fumed silica particles with a porous structure have a larger surface area and improved association and adsorption functions, causing the system to be formed more stably and uniformly.

[0106]

The size of primary particles of the fumed silica particles as a minimum single unit is usually about 5 to 30 nanometers, and the primary particles are aggregated to form primary aggregates, which are also referred to as secondary particles. The size of the primary aggregates is usually about 100 to 400 nanometers. The primary particles are fused to each other by chemical bonds, and it is usually difficult to separate the primary aggregates. Further, the primary aggregates are aggregated to each other to form an aggregation structure called secondary aggregates, which are also referred to as tertiary particles. The size of the secondary aggregates is about 10 pm. The aggregated form between the primary aggregates in the secondary aggregates is usually caused not by the chemical bonds but by hydrogen bonds and van der Waals forces.

[0107]

Among the fumed silica particles, when in a powder state, the secondary aggregates represent the largest aggregate state in many cases. However, the secondary aggregates can be further aggregated in the moisture curable composition. Specifically, one example thereof is provided by the case where, in the present invention, the hydrophobized silica effectively forms a network with the hydrophobic portions of the silane terminal-modified polymer and the material having reactivity (the reactive diluent) by van der Waals force. Such aggregates can be separated by a force weaker than that for separating the secondary aggregates. Specifically, one example thereof is provided by the case where the abovedescribed aggregates can be separated during application of the moisture-curable composition of the present invention using a comb trowel or the like, resulting in a reduction in the viscosity of the composition caused by such aggregation. [0108]

The above-described fumed silica particles are preferably hydrophobized, and the component used for hydrophobization is not limited to a particular one. Examples of the component used for hydrophobization may include halogenated organic silicon such as methyltrichlorosilane, alkoxysilanes such as dimethyldialkoxysilane, silazane, and low molecular weight methylpolysiloxane. The hydrophobization can be performed using a known method of treating the fumed silica particles with these components. [0109]

The contained amount of the inorganic particle (D) relative to the entire composition is desirably from 0.1 to 20 parts by mass. When the contained amount exceeds 20 parts by mass, the viscosity in the entire system increases and this could cause nonuniformity due to an agitation failure during the production of the moisture-curable composition, and a significant reduction in workability during application. The contained amount is more preferably in the range of 1 to 10 parts by mass, and further preferably in the range of 2 to 5 parts by mass. [0110]

For the optionally formulated component (E) serving as the thixotropic agent, examples of organic components may include a hydrogenated castor oil-based agent, an amide-based agent, a polyethylene oxide-based agent, a polymerized plant oil-based agent, and a surfactant-based agent. The component (E) may be used alone or in combination of two or more thereof.

[0111]

The amine compound (F) is a component which has a function of a curing catalyst or a curing cocatalyst for the moisture curable composition of the present invention, and which can further act as an adhesion promoter.

The amine compound (F) is not particularly limited in structure and molecular weight, and can be purchased as a commercial product or can be prepared by a common chemical method.

The amine compound (F) may be used alone or as a mixture of two or more thereof. [0112]

The amine compound (F) may be, for example, an organosilicon compound containing a unit represented by the general formula (12). Examples of the units represented by the general formula (12) may include an aminopropyltrimethoxysilyl group.

DhSi(OR³¹)iR³²jO₍₄-i-j-h)/2 (12)

(In the formula (12), R³¹ may be the same as or different from each other and is a hydrogen atom or an optionally substituted hydrocarbon group, D may be the same as or different from each other and is a monovalent SiC-bonded group, including basic nitrogen,

R³² may be the same as or different from each other and is a monovalent SiC-bonded organic group which includes no basic nitrogen and is optionally substituted with a substituent, i is 0, 1, 2, or 3, preferably 1 or 0, j is 0, 1, 2, or 3, preferably 1, 2, or 3, more preferably 2 or 3, and h is 1, 2, 3, or 4, preferably 1, provided that the sum of f + g + h is not more than 4 and at least one group D is present per molecule). [0113]

The amine compound (F) may include not only a silane, that is, a compound represented by the general formula (11) in which i + j + h = 4 but also a siloxane, that is, a unit represented by the formula (12) in which i + j + h < 3, although a silane is preferential. [0114]

The contained amount of the amine compound (F) relative to the entire composition is preferably in the range of 0.01 to 10 parts by mass.

When the contained amount is less than 0.01 parts by mass, a curing failure and/or an adhesion failure may occur. When the contained amount exceeds 10 parts by mass, adverse effects such as unnecessary reactions, wrinkles on the surface of the coating film, and deterioration of surrounding materials after formation of the coating film may arise. Further, an application failure may occur due to a shorter usable time. Further, in terms of storage stability, adverse effects such as thickening, gelation, and hardening may occur. The contained amount is thus more preferably in the range of 0.5 to 3.0 parts by mass. [0115]

The dehydrating agent (G) is a component for dehydrating the moisture-curable composition of the present invention by capturing water.

The dehydrating agent (G) can be purchased as a commercial product or prepared by common chemical methods.

The component (G) may be used alone or as a mixture of two or more thereof. [0116]

Examples of the dehydrating agent (G) may include a silane such as vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, O- methylcarbamatemethyl-methyldimethoxysilane, O-methylcarbamatemethyl- trimethoxysilane, O-ethylcarbamatemethyl-methyldiethoxysilane, O-ethylcarbamatemethyl- tri ethoxy silane, and a partial condensation product thereof, and orthoesters such as 1,1,1- trimethoxy ethane, 1,1,1 -tri ethoxy ethane, trimethoxymethane, and tri ethoxymethane. [0117]

The contained amount of the dehydrating agent (G) relative to the entire composition is preferably in the range of 0.01 to 10 parts by mass, although the dehydrating agent (G) may be omitted. When the contained amount is less than 0.01 parts by mass, an insufficient dehydration effect may cause adverse effects such as thickening, gelation, and hardening during the production and the storage. The contained amount exceeding 10 parts by mass may cause adverse effects such as deterioration in the physical properties of the coating film as well as a curing failure and uneven curing after application. The contained amount is more preferably in the range of 0.5 to 3.0 parts by mass.

[0118]

The stabilizer (H) is a component that functions as an ultraviolet absorber, an antioxidant, a thermal stabilizer, or a light stabilizer in the moisture curable composition of the present invention and can also act as a stabilizer against polymer deterioration.

The stabilizer (H) can be purchased as a commercial product or prepared by common chemical methods.

The stabilizer (H) may be used alone or as a mixture of two or more thereof. [0119]

The stabilizer (H) is not limited to a particular one as long as it can exhibit the abovedescribed functions and actions. However, the stabilizer (H) is preferably an antioxidant, an ultraviolet stabilizer, or a HALS.

[0120]

The contained amount of the stabilizer (H) relative to the entire composition is preferably in the range of 0.01 to 5 parts by mass. When the contained amount is less than 0.01 parts by mass, ultraviolet rays, heat, oxidization, or the like may cause coating film deterioration. The contained amount exceeding 5 parts by mass may cause unexpected adverse effects such as a color tone change in a case where a product is transparent. The contained amount is more preferably in the range of 0.5 to 2.0 parts by mass. [0121]

The optionally formulated filler (I) is a component that functions as an extender, a viscosity modifier, or an adjuster for physical properties such as tensile strength and elongation in the moisture-curable composition of the present invention and can also act as a curing promoter of the coating material with moisture that is contained in the filler. This component is not an essential component in the coating material composition of the present invention in a case where the above-described functions and actions are not required. The filler (I) can be purchased as a commercial product or prepared by common chemical methods.

The filler (I) may be used alone or as a mixture of two or more thereof. [0122]

The filler (I) is not limited to a particular one as long as it can exhibit the abovedescribed functions and actions. However, examples of the filler (I) may include a nonreinforcing filler, preferably a filler having a BET surface area of a maximum of 50m²/g, such as quartz, silica sands, diatomaceous earth, calcium silicate, zirconium silicate, talc, kaolin, zeolite, a powder of a metal oxide such as aluminum oxide, titanium oxide, iron oxide, zinc oxide, or a mixed oxide thereof, barium sulfate, calcium carbonate, gypsum, silicon nitride, silicon carbide, boron nitride, a glass powder, and a polymer powder such as a polyacrylonitrile powder; a reinforcing filler, a filler having a BET surface area of more than 50m²/g, such as silica prepared by thermal decomposition, precipitated silica, precipitated calcium carbonate, carbon black such as furnace black and acetylene black, and a mixed silicon-aluminum oxide having a high BET surface area; a filler in a form of hollow bead made of aluminum trihydroxide such as a magnetic microbead available from, for example, 3M Deutschland GmbH (Neuss, Germany) under the trade name of Zeeospheres (trademark) and an elastic polymer bead available from, for example, Akzo Nobel N. V. (Sundsvall, Sweden) under the trade name of EXPANCEL (registered trademark), and a glass bead; and a fibrous filler such as asbestos and a polymer fiber.

The above-described fillers may be hydrophobized by, for example, a treatment with organosilane and/or organosiloxane, or stearic acid, or etherification of alkoxy groups by hydroxyl groups. [0123]

The filler (I) is preferably calcium carbonate, talc, aluminum hydroxide, or silica, particularly preferably aluminum hydroxide. As a grade of calcium carbonate, it is preferably crushed or precipitated and, in some cases, subjected to a surface treatment with fatty acids such as stearic acid or salts thereof. Preferable silica is thermally decomposed (fumed) silica. [0124]

The water content of the filler (I) is preferably less than 1 part by mass, more preferably less than 0.5 parts by mass. [0125]

The contained amount of the filler (I) relative to the entire composition is preferably in the range of 0 to 80 parts by mass, more preferably in the range of 0 to 60 parts by mass. Within the above-described ranges, defects of the coating material such as an adhesion failure and a crack of the coating film are less likely to occur, and the appropriate viscosity enables uniform stirring during production.

[0126]

The curing catalyst (J) is a component that functions as a curing catalyst in the moisture-curable composition of the present invention. This component is not an essential component in the moisture-curable composition of the present invention in a case where the above-described functions and actions are not required. However, this component becomes effective in a case where the reactivity of the silane terminal-modified polymer (A) is low.

The curing catalyst (J) can be purchased as a commercial product or prepared by common chemical methods.

The curing catalyst (J) may be used alone or as a mixture of two or more thereof. [0127]

The curing catalyst (J) is not limited to a particular one as long as it can exhibit the above-mentioned functions and actions. Examples of the component (J) containing a metal may include an organotitanium compound and an organotin compound. Specific examples thereof may include a titanate ester, e.g., tetrabutyl titanate, tetrapropyl titanate, tetraisopropyl titanate, and titanium tetraacetylacetonate; a tin compound, e.g., dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin dioctanoate, dibutyltin acetyl acetonate, dibutyltin oxide and dioctyltin compounds corresponding to the above-described compounds. [0128]

Examples of the metal-free curing catalyst (J) may include a basic compound such as triethylamine, tributylamine, l,4-diazabicyclo[2.2.2]octane, l,5-diazabicyclo[4.3.0]non-5-ene, l,8-diazabicyclo[5.4.0]undeca-7-ene, N,N-bis-(N,N-dimethyl-2-aminoethyl)methylamine, N,N-dimethylcyclohexylamine, N,N-dimethylphenylamine, and N-ethylmorpholinine. [0129]

As the curing catalyst (J), it is likewise possible to use an acidic compound such as phosphoric acid and an ester thereof, toluenesulfonic acid, sulfuric acid, nitric acid, or other organic carboxylic acids such as acetic acid or benzoic acid. [0130]

The contained amount of the curing catalyst (J) relative to the entire composition is preferably in the range of 0 to 5 parts by mass. When the contained amount exceeds 5 parts by mass, there is a possibility that a wrinkle may occur on the surface of the coating film due to application failure by a shorter usable time, and defects such as thickening, gelation, and curing may occur during storage. More preferably, the contained amount thereof is in the range of 0 to 0.2 parts by mass.

[0131]

The moisture-curable composition of the present invention may include an optional component in addition to the above-described components as long as the object of the present invention is achieved. For example, the composition may include any other substance such as a defoaming agent, a curing rate adjuster, an additive, an adhesion promoter, or an auxiliary agent. In some cases, a component for improving adhesion such as epoxysilane may be added.

[Examples]

[0132]

The present invention will be specifically described by using Examples, Comparative examples, and results shown in Table 1. However, the present invention is not limited to the following Examples.

[0133]

The half-life of the silane modified polymer (A) and the material having reactivity (C) was measured as follows: a substance to be measured ((A) or (C)) was added to a commercially available NMR solvent containing a buffer and the resulting mixed solution was stirred to initiate a hydrolysis reaction. 'H-NMR spectra of these mixed solutions were measured at a predetermined time after the start of the stirring.

For example, both the silane modified polymer (A) and the material having reactivity (C) used in Example 1 and Example 2 have a structure of -Si-O-CHs. In this case, the ratio between -Si-O-CHs (before hydrolysis) and CH3OH (after hydrolysis) is measured, and a time required for the amount of the substance before hydrolysis to become half is defined as the half-life.

[0134]

As an example for the buffer, any of the following three buffers may be used. pH 4.0: buffer solution Certipur (registered trademark) (citric acid / sodium hydroxide / hydrochloric acid) available from Merck KGaA pH 7.0: buffer (potassium dihydrogenphosphate / sodium hydrogenphosphate) manufactured by J.T.Baker pH 9.0: buffer solution Certipur (registered trademark) pH 9.0 (boric acid / potassium chloride / sodium hydroxide) available from Merck KGaA

To 2,250 pL of the buffer, 450 pL of heavy water containing 3- (trimethylsilyl)propionic-2,2,3,3-d4 acid sodium (Na-TSP-d4) serving as a shift reagent and an internal standard and 5 pL of the substance to be measured are added. The resulting mixture is put in a 5mm NMR sample tube.

'H-NMR measurements were performed every 5 minutes at 25°C using NMR Avance DPX400 manufactured by Bruker.

[0135]

The viscosity of the moisture-curable compositions obtained in Examples and Comparative examples was set to the measurement values obtained using a viscoelasticity measuring device (Physica MCR 301 manufactured by Anton Paar GmbH) at a shear rate (10 (1/s)) after 60 seconds.

[0136]

When the viscosity is less than 30,000 mPa-s, workability and finished appearance are excellent.

[0137]

The moisture-curable compositions in Examples 1 to 3 and Comparative examples 1 to 5 were poured into a mold, smoothened by a spatula, and cured under conditions of 23°C±2°C and a humidity of 50%±5% to produce a cured sheet with a size of 150 mm x 150 mm x 2 mm. The linear shrinkage ratio (the ratio of shrinkage in the the 150mm linear direction) of the coating film (cured product) was evaluated after a 28-day curing.

[0138]

When the linear shrinkage ratio is less than 2%, the shrinkage ratio of the coating film is particularly excellent.

[0139]

The tensile strength and elongation of the coating films in Examples 1 to 3 and Comparative examples 1 to 5 were each evaluated by the method described in JIS K6249 (No. 3 dumbbell) after a 1, 2, and 4-week curing.

[0140]

When the tensile strength is 2.3 or more and the elongation is 450 or more, the mechanical properties of the coating films were evaluated to be particularly excellent. [0141] <Change ratio of mechanical properties>

The 50% modulus (the tensile stress at 50% elongation of the test pieces) of the coating films in Examples 1 to 3 and Comparative examples 1 to 5 were evaluated by the method described in JIS K6249 (No. 3 dumbbell) after curing for a predetermined period. [0142] <Evaluation standard of change ratio of mechanical properties>

In the coating films in Examples 1 to 3 and Comparative examples 1 to 5, if the ratio of the difference between the maximum value and the minimum value of the 50% modulus within 28 days with respect to the 50% modulus after 7-day curing is less than 20%, the maximum mechanical properties were determined to be achieved at an early stage and the change ratio of the mechanical properties was evaluated to be excellent. [0143] <Overall evaluation of moisture-curable compositions and coating films>

The object of the present invention is to achieve a coating film having maximum mechanical properties after application at an early stage and a small shrinkage. The standard for solving such a problem was set as follows: the viscosity of the moisture-curable composition was low, the linear shrinkage ratio of the obtained coating film was less than 2% after 28 days, and the change ratio of the 50% modulus was less than ±20%.

Obtaining a coating film with the larger tensile strength and elongation is further preferable.

[0144]

The following components were used for the moisture-curable composition.

As the silane modified polymer (A), 25.0 parts by mass of GENIOSIL (registered trademark) STP-E30 (the viscosity is 30,000 mPa-s at 25°C, in the above-described general formula (1), Y is a divalent organic polymer group which includes an oxyalkylene group as the polymer chain and is bonded through a urethane group, R, R¹, and R² each are a methyl group, and a = 1, b = 1, and x = 2) manufactured by Wacker Chemie AG and 10.0 parts by mass of GENIOSIL (registered trademark) STP-E10 (the viscosity is 10,000 mPa-s at 25°C, in the above-described general formula (1), Y is a divalent organic polymer group which includes an oxyalkylene group as the polymer chain and is bonded through a urethane group, R, R¹, and R² each are a methyl group, and a = 1, b = 1, and x = 2) manufactured by Wacker Chemie AG; as the silicone resin (B), 15.0 parts by mass of SILRES (registered trademark) IC 678 (a liquid phenyl silicon resin composed of only a phenyl-functional T unit, the methoxy content of 15% by weight, the average molar mass of 900 g/mol) manufactured by Wacker Chemie AG; as the material having reactivity (C), 20.0 parts by mass of GENIOSIL XM20 (the contained amount of the reactive group of 1.2% by weight) manufactured by Wacker Chemie AG, as the vinyl silane-based dehydrating agent (G), 0.7 parts by mass of GENIOSIL (registered trademark) XL 10 (vinyltrimethoxysilane) manufactured by Wacker Chemie AG; and, as the stabilizer (H), 2.50 parts by mass of GENIOSIL (registered trademark) Stabilizer F manufactured by Wacker Chemie AG were added together and uniformly stirred.

Y-[(CR¹2)b-SiR_a(OR²)3-a]x (1)

[0145]

As the inorganic particle (D), 1.50 parts by mass of HDK (registered trademark) 2000 manufactured by Wacker Chemie AG and, as synthetic calcium carbonate of the filler component (I), 43.3 parts by mass of LIGHTON-BS-O manufactured by Shiraishi Group were added and mixed together, and uniformly kneaded.

Further, as the amine compound (F), 2.00 parts by mass of GENIOSIL (registered trademark) GF96 (3-aminopropyltrimethoxysilane) manufactured by Wacker Chemie AG was added, and the resulting mixture was uniformly stirred to prepare a moisture-curable composition 1.

[0146]

The moisture-curable composition thus obtained was poured into a mold, smoothened by a spatula, and cured under conditions of 23°C±2°C and a humidity of 50%±5% to cause a reaction with moisture in the air for curing, thereby obtaining a coating film.

[0147]

Both the silane-containing groups of GENIOSIL (registered trademark) STP-E30 and STP-E10 as the silane modified polymer (A) and the reactive groups of GENIOSIL (registered trademark) XM20 as the material having reactivity (C) had the half-life of 1 hour.

Thus, the half-life of the reactive groups of the material having reactivity (C) was equal to that of the silane-containing groups of the silane modified polymer (A).

[0148]

As a result of the viscosity measurement of the moisture-curable composition 1, the viscosity was 22,700 mPa-s, which was lower than the standard value of 30,000 mPa-s.

Thus, a favorable result was obtained. As a result, the workability and finished appearance were excellent.

The obtained coating film had a linear shrinkage ratio of 0.3% after four weeks, and thus, the obtained coating film had the particularly small shrinkage.

The coating film had a tensile strength of 3.1 MPa after one week and 3.3 MPa after four weeks, both of which were greater than 2.3 MPa. Thus, the coating film had the particularly sufficient tensile strength.

The coating film had an elongation of greater than 450 in all cases after one week, two weeks, and four weeks. Thus, the coating film exhibited the particularly excellent properties.

As a result of measuring the 50% modulus of the coating film, it was 0.8 after one week, and the maximum value and the minimum value within 28 days were 0.8 and 0.7, respectively. This gave rise to the change ratio of 12.5%, which was less than the standard value of 20%. Thus, it can be concluded that the excellent mechanical properties were achieved from an early stage.

[0149]

The above-described results showed that the moisture-curable composition 1 had the low viscosity, the coating film had the small shrinkage, and the mechanical properties (50% modulus) were achieved at an early stage. Thus, it can be concluded that the physical properties of the coating film were excellent.

[0150]

Except for 20.0 parts by mass of SILRES (registered trademark) BS1316 (isooctyltrimethoxy silane, the contained amount of the reactive groups of 40% by weight) manufactured by Wacker Chemie AG being used as the material having reactivity (C), a moisture-curable composition 2 was obtained using the same components with the same amounts (parts by mass) and the same preparation methods as those in Example 1. The evaluation was also performed in the same manner.

[0151]

While the half-life of the silane-containing groups of GENIOSIL (registered trademark) STP-E30 and STP-E10 as the silane modified polymer (A) was 1 hour, the halflife of the reactive groups of SILRES (registered trademark) BS1316 as the material having reactivity (C) was 17 hours.

Thus, the half-life of the reactive groups of the material having reactivity (C) was 17 times that of the silane-containing groups of the silane modified polymer (A).

[0152]

As a result of the viscosity measurement of the moisture-curable composition 2, the viscosity was 7,800 mPa-s, which was lower than the standard value of 30,000 mPa-s. Thus, a favorable result was obtained. As a result, the workability and finished appearance were excellent. The obtained coating film had a linear shrinkage ratio of 1.9% after four weeks, and thus, the obtained coating film had the particularly small shrinkage. The contained amount of the reactive groups of SILRES (registered trademark) BS1316 used as the material having reactivity (C) was greater than 10%, and thus, it is speculated that the shrinkage ratio slightly increased due to the reduced portion of alcohols produced through hydrolysis as compared with Example 1.

The coating film had a tensile strength of 4.3 MPa after one week and 4.3 MPa after four weeks, both of which were greater than 2.3 MPa. Thus, the coating film had the particularly sufficient tensile strength.

The coating film had an elongation of greater than 450 in all cases of after one week, two weeks, and four weeks. Thus, the coating film exhibited the particularly excellent properties.

As a result of measuring the 50% modulus of the coating film, it was 1.3 after one week, and the maximum value and the minimum value within 28 days were 1.3 and 1.1, respectively. This gave rise to the change ratio of 15.4%, which was less than the standard value of 20%. Thus, it can be concluded that the excellent mechanical properties were achieved even at an early stage. [0153]

The above-described results showed that the moisture-curable composition 2 had the low viscosity, the coating film had the small shrinkage, and the mechanical properties (50% modulus) were achieved at an early stage. Thus, it can be concluded that the physical properties of the coating film were excellent. [0154] <Example 3>

As the silane modified polymer (A), 25.0 parts by mass of GENIOSIL (registered trademark) STP-E35 (the viscosity is 30,000 mPa-s at 25°C, in the above-described general formula (1), Y is a divalent organic polymer group which includes an oxyalkylene group as the polymer chain and is bonded through a urethane group, R¹ and R² each are a methyl group, and a = 0, b = 3, and x = 2) manufactured by Wacker Chemie AG and 10.0 parts by mass of GENIOSIL (registered trademark) STP-E15 (the viscosity is 10,000 mPa-s at 25°C, in the above-described general formula (1), Y is a divalent organic polymer group which includes an oxyalkylene group as the polymer chain and is bonded through a urethane group, R¹ and R² each are a methyl group, and a = 0, b = 3, and x = 2) manufactured by Wacker Chemie AG were used.

As the material having reactivity (C), 20.0 parts by mass of GENIOSIL (registered trademark) XM25 manufactured by Wacker Chemie AG was used. The contained amount of the reactive groups of XM25 is 1.9% by weight.

Except for the above-mentioned matters, a moisture-curable composition 3 was obtained using the same components with the same amounts (parts by mass) and the same preparation methods as those in Example 1. The evaluation was also performed in the same manner.

[0155]

The half-life of the silane-containing groups of GENIOSIL (registered trademark) STP-E35 and STP-E15 as the silane modified polymer (A) was 1 hour, and the half-life of the reactive groups of GENIOSIL (registered trademark) XM25 as the material having reactivity (C) was also 1 hour.

Thus, the half-life of the reactive groups of the material having reactivity (C) was 1 time that of the silane-containing groups of the silane modified polymer (A).

[0156]

As a result of the viscosity measurement of the moisture-curable composition 3, the viscosity was 23,000 mPa-s, which was lower than the standard value of 30,000 mPa-s. Thus, a favorable result was obtained. As a result, the workability and finished appearance were excellent.

The obtained coating film had a linear shrinkage ratio of 0.3% after four weeks, thus, the obtained coating film had the particularly small shrinkage.

The coating film had a tensile strength of 4.0 MPa after one week and 4.3 MPa after four weeks, both of which were greater than 2.3 MPa. Thus, the coating film had the particularly sufficient tensile strength.

The coating film had an elongation of greater than 450, exhibiting the particularly excellent properties.

As a result of measuring the 50% modulus of the coating film, it was 1.0 after one week, and the maximum value and the minimum value within 28 days were 1.1 and 1.0, respectively. This gave rise to the change ratio of 10%, which was less than the standard value of 20%. Thus, it can be concluded that the excellent mechanical properties were achieved even at an early stage.

[0157]

The above-described results showed that the moisture-curable composition 3 had the low viscosity, the coating film had the small shrinkage, and the mechanical properties (50% modulus) were achieved at an early stage. Thus, it can be concluded that the physical properties of the coating film were excellent. [0158]

Comparative example 1>

Except for the material having reactivity (C) not being used, the same components with the same amounts (parts by mass), and the same preparation methods as those in Example 1 were used. The evaluation was also performed in the same manner. [0159]

As a result of the viscosity measurement of a moisture-curable composition, the viscosity was 59,000mPa-s, which was greater than the standard value. The reduction in the viscosity could not be achieved because no material having reactivity (C) functioning as a diluent was added. As a result, the workability and the finished appearance were poor.

The physical properties of the coating film in terms of the linear shrinkage ratio, the tensile strength, and the elongation were all excellent. However, the moisture-curable composition was not preferable in that the viscosity was too high.

[0160]

Comparative example 2>

Except for 20.0 parts by mass of ShellSol MC421 (a hydrocarbon-based solvent without reactive groups) manufactured by Shell Chemicals Japan Ltd. being used as a diluent, the same components with the same amounts (parts by mass) and the same preparation methods as those in Example 1 were used. The evaluation was also performed in the same manner.

[0161]

As a result of the viscosity measurement, the viscosity was 6,400 mPa-s, and the workability and finished appearance were excellent.

On the other hand, the result of the linear shrinkage ratio measurement was 2.0, which was greater than the standard value. It is speculated that ShellSol MC421, used as a diluent, was not incorporated in the matrix of the coating film due to a lack of reactive groups and evaporated over time, resulting in an increase in the shrinkage ratio due to the reduced portion.

As a result of measuring the tensile strength and the elongation, the coating film physical properties of both were excellent.

As a result of measuring 50% modulus, it was greater than the standard value and the result was poor. That is, it was 2.8 after one week, and the maximum and minimum values within 28 days were 3.5 and 2.8, respectively. This gave rise to a change ratio of 25%, which was greater than the standard value of 20%. Thus, it can be concluded that the excellent mechanical properties could not be achieved even at an early stage. It is speculated that ShellSol MC421 used as a diluent was not incorporated in the matrix of the coating film due to a lack of reactive groups and evaporated over time, also causing a change in 50% modulus over time. [0162]

The above-described results showed that, although the moisture-curable composition in Comparative example 2 had the low viscosity, the obtained coating film had the large shrinkage and failed to achieve the mechanical properties (50% modulus) at an early stage. [0163] Comparative example 3>

Except for 20.0 parts by mass of SILRES (registered trademark) BS1701 (isooctyltriethoxysilane, the contained amount of reactive groups of 49%) manufactured by Wacker Chemie AG being used as the material having reactivity (C), the same components with the same amounts (parts by mass) and the same preparation methods as those in Example 1 were used. The evaluation was also performed in the same manner.

[0164]

While the half-life of the silane-containing groups of GENIOSIL (registered trademark) STP-E30 and STP-E10 as the silane modified polymer (A) was 1 hour, the halflife of the reactive groups of SILRES (registered trademark) BS1701 as the material having reactivity (C) was 46 hours.

Thus, the half-life of the reactive groups of the material having reactivity (C) was 46 times that of the silane-containing groups of the silane modified polymer (A).

[0165]

As a result of the viscosity measurement of the moisture-curable composition of Comparative example 3, the viscosity was 6,300 mPa-s, which was lower than the standard value of 30,000 mPa-s. Thus, a favorable result was obtained. As a result, the workability and finished appearance were excellent.

The obtained coating film had a linear shrinkage ratio of 3.0% after four weeks, which was greater than the standard value.

The amount of the reactive groups of SILRES (registered trademark) BS1701 used as the material having reactivity (C) was greater than 10%, and thus, it is speculated that the shrinkage ratio increased due to the reduced portion of alcohols produced through hydrolysis.

As a result of measuring the tensile strength and the elongation, both coating film physical properties were excellent.

As a result of measuring 50% modulus, it was greater than the standard value and the result was poor. That is, it was 1.3 after one week, and the maximum value and the minimum value within 28 days were 2.7 and 1.3, respectively. This gave rise to the change ratio of 108%, which was greater than the standard value of 20%.

It is speculated that slow hydrolysis of SILRES (registered trademark) BS1701 used as the material having reactivity (C) delayed the subsequent condensation reactions of silanols and caused a change in 50% modulus over time.

[0166]

The above-described results showed that, although the moisture-curable composition in Comparative example 3 had the low viscosity, the obtained coating film had the large shrinkage and the mechanical properties (50% modulus) could not be achieved at an early stage.

[0167]

Comparative example 4>

Except for 20.0 parts by mass of SILRES (registered trademark) IC678 (a silicone resin, the contained amount of reactive groups of 15% by weight) manufactured by Wacker Chemie AG being used as the material having reactivity (C), the same components with the same amounts (parts by mass) and the same preparation methods as those in Example 1 were used. The evaluation was also performed in the same manner.

[0168]

While the half-life of the silane-containing groups of GENIOSIL (registered trademark) STP-E30 and STP-E10 as the silane modified polymer (A) was 1 hour, the halflife of the reactive groups of SILRES (registered trademark) IC678 as the material having reactivity (C) was 50 hours.

Thus, the half-life of the reactive groups of the material having reactivity (C) was 50 times that of the silane-containing groups of the silane modified polymer (A).

[0169]

As a result of the viscosity measurement, the viscosity was 26,500 mPa-s, which was lower than the standard value of 30,000 mPa-s. Thus, a favorable result was obtained. As a result, the workability and finished appearance were excellent.

As a result of measuring the linear shrinkage ratio, the linear shrinkage ratio after 4 weeks was 1.3.

The contained amount of the reactive groups of SILRES (registered trademark) IC678 used as the material having reactivity (C) was greater than 10%, and thus, it is speculated that the shrinkage ratio increased due to the reduced portion of alcohols produced through hydrolysis as compared with Example 1.

Although the tensile strength was excellent, the elongation was lower than the standard value of 450 in all cases of after one week, two weeks, and four weeks. It is speculated that SILRES (registered trademark) IC678 used as the material having reactivity (C) significantly increased cross-linking points.

On the other hand, as a result of measuring 50%, it was greater than the standard value and the result was poor. That is, it was 5.3 after one week, and the maximum value and the minimum value within 28 days were 14.0 and 5.3, respectively. This gave rise to the change ratio of 164%, which was greater than 20%. It is speculated that slow hydrolysis of SILRES (registered trademark) IC678 used as the material having reactivity (C) delayed the subsequent condensation reactions of silanols, causing a change in 50% modulus over time. [0170]

The above-described results showed that, although the moisture-curable composition in Comparative example 4 had the low viscosity and the obtained coating film had the small shrinkage, the mechanical properties (50% modulus) could not be achieved at an early stage. [0171] Comparative example 5>

Except for 20.0 parts by mass of SILRES (registered trademark) IC368 (a silicone resin, the contained amount of reactive groups of 15% by weight) manufactured by Wacker Chemie AG being used as the material having reactivity (C), the same components with the same amounts (parts by mass) and the same preparation methods as those in Example 1 were used. The evaluation was also performed in the same manner.

[0172]

While the half-life of the silane-containing groups of GENIOSIL (registered trademark) STP-E30 and STP-E10 as the silane modified polymer (A) was 1 hour, the halflife of the reactive groups of SILRES (registered trademark) IC368 as the material having reactivity (C) was 50 hours.

[0173]

As a result of the viscosity measurement of the moisture-curable composition, the viscosity was 30,400 mPa-s, which was greater than the standard value.

The contained amount of the reactive groups of SILRES (registered trademark) IC368 used as the material having reactivity (C) was greater than 10%, and thus, it is speculated that the shrinkage ratio increased due to the reduced portion of alcohols produced through hydrolysis.

Although the tensile strength was excellent, the elongation was less than the standard value. It is speculated that SILRES (registered trademark) IC368 used as the material having reactivity (C) increased cross-linking points. As a result of measuring 50% modulus, since the elongation of less than 50% was achieved after 4 weeks, relevant data could not be obtained. When a comparison was made with the 50% modulus after two weeks as it was measurable, the change ratio was greater than 20%. It is speculated that the slow hydrolysis of SILRES (registered trademark) IC368 used as the material having reactivity (C) delayed the subsequent condensation reactions of silanols, causing a change in 50% modulus over time, and significantly increasing crosslinking points.

[0174]

The above-described results showed that the moisture-curable composition in Comparative example 5 had the high viscosity and the mechanical properties (50% modulus) could not be achieved at an early stage.

[0175]

[Table 1]

Claims

1. A moisture-curable composition comprising: a silane modified polymer (A); a silicone resin (B); and a material having reactivity (C), wherein the silane modified polymer (A) is represented by the following general formula (1), the silicone resin (B) is an organopolysiloxane resin including a unit represented by the formula (Q) of SiO4/2, Si(ORⁿ)O₃/2, Si(ORⁿ)2O2/2, and Si(ORⁿ)₃Oi/2, a unit represented by the formula (T) of PhSiO₃/2, PhSi(ORⁿ)O2/2, and PhSi(OR¹¹)₂Oi/₂, a unit represented by the formula (D) of Me2SiO2/2 and Me2Si(ORⁿ)Oi/2, and a unit represented by the formula (M) of Me₃SiOi/2 (in the formulas, Me is a methyl group, Ph is a phenyl group, R¹¹ is a hydrogen atom, an alkyl group which is optionally substituted with a halogen atom and has 1 to 10 carbon atoms, or an alkyl group with 1 to 4 carbon atoms), where the resin includes per unit mole of the (T) unit: 0 to 2 mol of the (Q) unit, 0 to 2 mol of the (D) unit, and 0 to 2 mol of the (M) unit, the material having reactivity (C) is a one terminal-modified silicone represented by the following general formula (5) with a reactive group that reacts with the silane modified polymer (A), and a half-life of the reactive group is 0.1 to 20 times a half-life of a silane-containing group of the silane modified polymer (A), so that the silane modified polymer (A) and the material having reactivity (C) react with each other to form a matrix, causing a small change in mechanical properties over time:

Y-[(CR¹2)b-SiR_a(OR²)_3-a]x (1)

R¹ may be the same as or different from each other and is a hydrogen atom or a monovalent, optionally substituted hydrocarbon group of which a carbon atom can be bonded to a nitrogen, phosphorus, oxygen, or sulfur atom or a carbonyl group, R² may be the same as or different from each other and is a hydrogen atom or a monovalent, optionally substituted hydrocarbon group,

45 a is 0, 1, or 2, and b is an integer of 1 to 10), and Y-[(CR⁵¹2)_g-SiR⁵⁰f(OR⁵²)3-f]w (5)

(in the formula (5), Y is a w-valent organic polymer group bonded thereto via a nitrogen, oxygen, sulfur or carbon atom, the w-valent organic polymer group containing a polyoxyalkylene or a polyurethane as a polymer chain, R⁵⁰ may be the same as or different from each other and is a monovalent, optionally substituted, SiC-bonded hydrocarbon group,

R⁵¹ may be the same as or different from each other and is a hydrogen atom or a monovalent, optionally substituted hydrocarbon group of which a carbon atom can be bonded to a nitrogen, phosphorus, oxygen, or sulfur atom or a carbonyl group, R⁵² may be the same as or different from each other and is a hydrogen atom or a monovalent, optionally substituted hydrocarbon group, w is 1, f is 0, 1, or 2, and g is an integer of 1 to 10). The moisture-curable composition according to claim 1, wherein a contained amount of the reactive group in the material having reactivity (C) is 0.5% by weight or more and 10% by weight or less. The moisture-curable composition according to claim 1 or 2, wherein the silane modified polymer (A) has terminal groups, where at least one of them is a group represented by the following general formula (2) or general formula (3): -O-C(=O)-NH-(CR¹ ₂)b-SiR_a(OR²)3-a (2), -NH-C(=O)-NR’-(CR¹2)b-SiR_a(OR²)₃-a (3)

R’ may be the same as or different from each other and has the definition given for R). The moisture-curable composition according to claim 3, wherein a is 1 and b is 1 in the general formula (2) or the general formula (3). The moisture-curable composition according to any one of claims 1 to 4, wherein a

46 contained amount of the silicone resin (B) relative to the silane modified polymer (A) is less than 2.5 times. A method for producing a coating film, comprising curing the moisture-curable composition according to any one of claims 1 to 5 that contains a curing catalyst to form a coating film. The method for producing a coating film according to claim 6, wherein the coating film has a tensile strength of 2.0 N/mm² or greater, and an elongation at break of 450% or greater.

47