WO2020239334A1

WO2020239334A1 - Method for forming moisture curing-type coating material

Info

Publication number: WO2020239334A1
Application number: PCT/EP2020/061384
Authority: WO
Inventors: Takuya TABATA; Hiroshi Kanzawa
Original assignee: Wacker Chemie Ag
Priority date: 2019-05-31
Filing date: 2020-04-23
Publication date: 2020-12-03
Also published as: JP2020195942A

Abstract

An object is to propose a method for forming a moisture curing-type coating material by which curing inside a coating film is sufficiently achieved even when the surface curing speed is high, blistering, peeling, or cracking is not caused to the coating film by moisture originating from water vapor from a substrate or the like, and good adhesiveness is maintained for a long period of time. The method for forming a moisture curing-type coating material includes: forming a substrate adjusting agent on a substrate; further applying a moisture curing-type coating material thereonto; and, when curing is caused by moisture, acquiring water vapor required for the curing by using water vapor present in the substrate, and/or water vapor arising from the substrate adjusting agent, in addition to water vapor present in outside air.

Description

METHOD FOR FORMING MOISTURE CURING-TYPE COATING MATERIAL

TECHNICAL FIELD

[0001]

The present invention relates to a method for forming a moisture curing-type coating material including a moisture curable resin having a silyl group crosslinkable by

hydrolysis. More specifically, the present invention relates to a method for forming a moisture curing-type coating

material, including forming a substrate adjusting agent including silane on a substrate, further applying a moisture curing-type coating material thereonto, and curing it by moisture .

BACKGROUND ART

[0002]

A polymer having a hydrolyzable silyl group, which is known as a moisture curable coating material, is easily handled, excellent in coating properties, and also excellent in various performances. Thus, such a polymer is included in many industrial products such as an adhesive, a sealing material, a coating film waterproof material, or a coating material such as a paint, and used over a wide range of fields .

[0003]

The moisture curing-type coating material including a polymer having a hydrolyzable silyl group is required to have good adhesiveness with plastic such as FRP or an ABS resin, metal such as aluminum or stainless steel, a building material such as porous autoclaved lightweight concrete (ALC) or concrete, and various substrates in an industrial building in the aforementioned fields.

[0004]

In particular, a film-forming urethane-based primer or an acrylic primer is sometimes used to ensure adhesion to a cement-based porous substrate such as concrete. In a case where the moisture curing-type coating material is applied and cured on this primer, if the surface curing speed of the moisture curing-type coating material is too high, moisture necessary for curing is not supplied from the atmosphere, causing a problem of curing being inhibited inside the coating film. On the other hand, there is a different problem in that moisture originating from water vapor from the substrate or the like causes a defect such as blistering, peeling, or cracking to the coating film.

[0005]

Patent Literature 1 discloses that, regarding a polymer having a hydrolyzable silyl group, the moisture curable coating material is formed on a substrate such as wood.

However, there is no mention of the problem in that, if the surface curing speed of the moisture curing-type coating material is too high, the moisture necessary for curing is not supplied from the atmosphere and the curing inside the coating film is inhibited. Further, there is no mention of the problem in that the moisture originating from the water vapor from the substrate or the like causes a defect such as blistering, peeling, or cracking to the coating film.

[0006]

Further, Patent Literature 2 discloses that blistering in the coating film is prevented by applying a specific water permeation inhibitor to the surface of a concrete plate and then applying, successively, a specific solvent-type epoxy- based substrate adjusting agent including a monoepoxy compound and an epoxy resin and a specific urethane-based curable filler. However, there is no mention of the moisture curing- type coating material or the curing inside the coating film.

[0007]

As such, as yet, there has been no method for forming the moisture curing-type coating material by which the curing inside the coating film is sufficiently achieved even when the surface curing speed is high, a defect such as blistering, peeling, or cracking is not caused to the coating film by the moisture originating from the water vapor from the substrate or the like, and good adhesiveness is maintained for a long period of time. Citation List

Patent Literature

[0008]

Patent Literature 1: Japanese Translation of PCT Patent Application Publication No. 2014-521819

Patent Literature 2: Japanese Patent Application Laid- Open No. 2008-088018

SUMMARY OF INVENTION TECHNICAL PROBLEM

[0009]

The present invention has been made in the above

circumstances, and an object of the present invention is to propose a method for forming a moisture curing-type coating material by which curing inside a coating film is sufficiently achieved even when the surface curing speed is high,

blistering, peeling, or cracking is not caused to the coating film by moisture originating from water vapor from a substrate or the like, and good adhesiveness is maintained for a long period of time.

SOLUTION TO PROBLEM

[0010]

As a result of extensive studies, the present inventors have found that the problem of not achieving sufficient curing inside the coating film when the surface curing speed is high can be solved by making it possible to supply the moisture necessary for the curing inside the coating film of the moisture curable coating material from the substrate. Further, the present inventors have found that the problem of the occurrence of blistering, peeling, or cracking in the coating film caused by the moisture originating from the water vapor from the substrate or the like can be solved by applying a substrate adjusting agent on a porous substrate, not in a manner of forming a film on the porous substrate so as to clog a hole part, but in a manner of forming a hydrophobized coating film to a deep part along a surface having

irregularities. Further, the present inventors have found that these make it possible to maintain good adhesiveness for a long period of time.

The foregoing finding has led to the completion of the present invention.

[0011]

That is, the method for forming a moisture curing-type coating material of the present invention is characterized by forming a substrate adjusting agent on a substrate, further applying a moisture curing-type coating material thereonto, and, when curing is caused by moisture, acquiring water vapor required for the curing by using water vapor present in the substrate, and/or water vapor arising from the substrate adjusting agent, in addition to water vapor present in outside air .

Further, the method for forming a moisture curing-type coating material of the present invention is characterized in that the substrate adjusting agent is applied on a porous substrate, not in a manner of forming a film on the porous substrate so as to clog a hole part, but in a manner of forming a hydrophobized coating film to a deep part along a surface having irregularities and the moisture curing-type coating material is further applied thereonto, and, when the curing is caused by moisture, the water vapor required for the curing is acquired by using water vapor present in the porous substrate in addition to the water vapor present in the outside air.

ADVANTAGEOUS EFFECTS OF INVENTION

[0012]

The method for forming a moisture curing-type coating material of the present invention, which makes it possible to supply the moisture necessary for the curing inside the coating film of the moisture curing-type polymer from the substrate, has an advantageous effect of achieving the

sufficient curing inside the coating film by supplying a sufficient amount of the water vapor to the inside of the coating film even when the surface curing speed is high.

Further, the method for forming a moisture curing-type coating material of the present invention, in which the substrate adjusting agent is applied on the porous substrate, not in a manner of forming a film on the porous substrate so as to clog a hole part, but in a manner of forming the

hydrophobized coating film to a deep part along a surface having irregularities, has an advantageous effect of causing no blistering, peeling, or cracking to the cured coating film of the moisture curing-type coating material as the moisture originating from the water vapor from the substrate or the like does not stay at the interface between the substrate and the moisture curing-type coating material.

Further, owing to the foregoing advantageous effects, there is another advantageous effect of maintaining good adhesiveness between the coating film and the substrate for a long period of time.

DESCRIPTION OF EMBODIMENTS

[0013]

Hereinafter, the present invention will be described in detail .

[0014]

A moisture curing-type coating material as an object of the method for forming the moisture curing-type coating material of the present invention may be in any mode and in any form, and have any composition so long as the coating material is in the form of at least one liquid or more and a cured product of a composition can be finally obtained by curing by moisture. Further, the coating material may be composed of a single component or a mixture of two or more components. The moisture curing-type coating material is represented by a coating material including a polymer having an alkoxysilyl group which is hydrolyzed by moisture and produces a siloxane bond, thereby causing curing.

[0015]

Typically, a moisture curing-type coating material including a silane terminal-modified polymer represented by the following general formula (1) exhibits various excellent performances as a coating material and is industrially easily available, and thus this material is an object of the moisture curing-type coating material of the present invention.

(Chemical formula 1) Y- [ (CR¹2) _b-SiR_a (OR²) 3-alx (1)

(In the formula,

Y is an x-valent organic polymer group bonded via

nitrogen, oxygen, sulfur, or carbon, having a polyoxyalkylene or a polyurethane as a polymer chain;

R, which may be the same or different, is a monovalent, optionally substituted, SiC-bonded hydrocarbon group;

R¹, which may be the same or different, is a hydrogen atom or a monovalent, optionally substituted, hydrocarbon group in which a carbon atom can be bonded to nitrogen, phosphorus, oxygen, sulfur, or a carbonyl group;

R², which may be the same or different, is a hydrogen atom or a monovalent, optionally substituted, hydrocarbon group;

x is an integer of 1 to 10;

a, which may be the same or different, is 0, 1, or 2; and b, which may be the same or different, is an integer of 1 to 10. )

[0016]

When the moisture curing-type coating material including the silane terminal-modified polymer represented by the above general formula (1) is applied to various substrates in

various use applications, a form of the coating material composition and the composition content are not limited.

In a case where the moisture curing-type coating material including the silane terminal-modified polymer is applied to a typical use, that is, a substrate such as a building material or an industrial building, in particular, a porous substrate, the moisture curing-type coating material is preferably the following composition:

(A) the silane terminal-modified polymer represented by the above-mentioned general formula (1) : 5 to 100 parts by mass ;

(B) an amine compound: 0.01 to 10 parts by mass;

(C) a dehydrating agent: 0.01 to 10 parts by mass;

(D) a stabilizer: 0.01 to 5 parts by mass;

(E) a plasticizer: 0 to 95 parts by mass;

(F) a filler: 0 to 80 parts by mass; and (G) a catalyst: 0 to 5 parts by mass,

provided that part(s) by mass of each component is based on 100 parts by mass of the entire composition of the moisture curing-type coating material.

[0017]

The component (A) , which is a main agent of the coating material composition, is a component for forming a coating film using moisture after application.

The component (A) may be purchased as a commercial product or may be prepared by any general chemical method. The component (A) may be a single substance or a mixture of two or more kinds of substances.

[0018]

Examples of the group R may include an alkyl group, e.g., a methyl group, an ethyl group, an n-propyl group, an

isopropyl group, a 1-n-butyl group, a 2-n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, and a tert-pentyl group; a hexyl group, e.g., an n-hexyl 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; an octadecyl group, e.g., an n-octadecyl group; a cycloalkyl group, e.g., a cyclohexyl group, a cycloheptyl group, and a methylcyclohexyl group; an alkenyl group, e.g., a vinyl group, a 1-propenyl group, and a 2-propenyl group; an aryl group, e.g., a phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group; an alkaryl group, e.g., o-, m-, p-tolyl groups, a xylyl group, and an ethylphenyl group; and an aralkyl group, e.g., a benzyl group, and a- and b- phenylethyl groups.

[0019]

Examples of substituted groups R may include a haloalkyl group, e.g., 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, e.g., o-, m- and p-chlorophenyl groups.

The group R may preferably include a monovalent hydrocarbon group optionally substituted by a halogen atom and having 1 to 6 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms, and more particularly a methyl group .

[0020]

R¹, which may be the same or different, is a hydrogen atom or a monovalent, optionally substituted, hydrocarbon group in which a carbon atom can be bonded to nitrogen, phosphorus, oxygen, sulfur, or a carbonyl group.

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

[0021]

R², which may be the same or different, is a hydrogen atom or a monovalent, optionally substituted, hydrocarbon group .

The group R² is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms and optionally substituted by a halogen atom, more preferably an alkyl group having 1 to 4 carbon atoms, and more particularly a methyl group or an ethyl group.

[0022]

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

[0023]

The polymer group Y preferably includes an organic polymer group, which includes as a polymer chain a

polyoxyalkylene, e.g., a polyoxyethylene, a polyoxypropylene, a polyoxybutylene, a polyoxytetramethylene, a polyoxyethylene- polyoxypropylene copolymer, and a polyoxypropylene- polyoxybutylene copolymer; a hydrocarbon polymer, e.g. a polyisobutylene, a polyethylene or a copolymer of a

polypropylene and a polyisobutylene with isoprene; a

polyisoprene ; a polyurethane; a polyester, a polyamide; a polyacrylate; a polymethacrylate; and a polycarbonate. The polymer group Y is preferably bonded to one or more -[(CR¹2)_b ^_ SiR_{a (}OR²) 3 _a) ] groups by at least one of -O-C (=0) -NH-, -NH- C(=0)0-, -NH-C (=0) -NH-, -NR’ -C (=0) -NH-, NH-C (=0) -NR' -NH- C (=0) - , -C (=0) -NH- , -C (=0) -0- , -0-C (=0) - , -0-C(=0)-0-, -S- C (=0) -NH- , -NH-C (=0) -S-, -C(=0)-S-, -S-C(=0)-, -S-C(=0)-S-, - C(=0)-, —S— , -0-, and -NR’-, provided that R’ may be the same or different, has the definition given for R, or may be a group of -CH (COOR" ) -CH2-COOR" in which R" may be the same or different and has the definition given for R.

[0024]

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, hexyl and heptyl groups, and a phenyl group .

The group R’ is preferably a group of -CH (COOR" ) -C¾- COOR" or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, more preferably a straight chain group, a branched group or a cycloalkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms and

optionally substituted by a halogen atom.

[0025]

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

[0026]

More preferably, the group Y in the formula (1) includes a polyurethane group and a polyoxyalkylene group, more

preferably a polyoxypropylene-containing polyurethane group or a polyoxypropylene group.

[0027]

The component (A) herein may have groups- [ (CR^) _b- SiR_a (OR²) _3-a) ] bonded in the described manner at any desired position in the polymer, e.g., in the chain and/or at the terminal, preferably in the chain and at the terminal, more preferably at the terminal.

[0028]

The terminal groups of the component (A) are preferably those represented by the general formula (3) and the general formula ( 4 ) .

(Chemical formula 3)

-o-c (=0) -NH- (CR¹2) _b-SiR_a (OR²) _3-a (3)

(Chemical formula 4)

-NH-C (=0) -NR' - (CR ) _b-SiR_a (OR²) _3-a (4)

(In the formula, the groups and subscripts have one of the definitions specified above for them. )

[0029]

In one particularly preferred embodiment of the present invention, the component (A) includes in each case a silane- terminated polyether and a silane-terminated polyurethane having a dimethoxymethylsilyl , trimethoxysilyl ,

diethoxymethylsilyl , or triethoxysilyl terminal group, and more particularly a silane-terminated polypropylene glycol and a silane-terminated polyurethane, which are bonded by a group of -O-C (=0) -NH- (CR ) _b or a group of -NH-C (=0) -NR’ - (CR ) _b (R', R¹, and b have one of the definitions specified above) .

[0030]

The average molecular weight Mn of the component (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, more preferably less than 19,000 g/mol, and more particularly less than 13,000 g/mol.

[0031]

The viscosity of the component (A) as measured at 20°C in each case is preferably at least 0.2 Pas, more preferably at least 1 Pas, and particularly preferably at least 5 Pas, and is preferably 1,000 Pas or less, and more preferably 700 Pas or less.

[0032]

In a first particularly preferred embodiment of the present invention, the component (A) includes, as the polymer group Y, a linear or branched polyoxyalkylene group, more preferably a polyoxypropylene group of which the chain

terminals are preferably bonded to one or more -[ (CR¹ ₂)_b ^_

SiR_a (OR²) 3-_a) ] groups by -O-C (=0) -NH- . Herein, preferably at least 85%, more preferably at least 90%, and more particularly at least 95% of the total chain terminals are bonded to the - [ (CR¹ _{2) b} ^_SiR_{a (}OR²) 3 _a) ] group by -O-C (=0) -NH- . The

polyoxyalkylene group Y preferably has a number-average molecular weight Mn of 4,000 to 30,000, preferably 8,000 to 20,000. The appropriate producing methods of preparing such components (A) and examples of the component (A) themselves are also known, and described in publications, including

EP1535940B1 or EP1896523B1, which are hereby incorporated in their entireties by reference. Corresponding silane-terminated polymers are also commercially available, for example, under the name GENIOSIL (registered trademark) STP-E available from Wacker Chemie AG.

[0033]

Second, as in the particularly preferred embodiment of the present invention, the compound (A) includes a linear or branched polyurethane group, as the polymer group Y, prepared by starting from a polyether polyol and/or a polyester polyol Yl, preferably having Mn of 200 to 20,000. The polyol used herein is more preferably a polyether polyol, more

particularly a polypropylene glycol having an Mn of 300 to 10,000, more particularly 400 to 5,000. The polyol Yl may be branched or not. The particularly preferred Yl is an

unbranched polyol or a polyol having one branching moiety. A mixture of branched and unbranched polyols may also be used.

[0034]

When the component (A) is chemically synthesized, various known producing methods including, for example, an addition reaction such as hydrosilylation, Michael addition, and Diels- Alder addition, or reactions between an isocyanate functional compound and a compound containing an isocyanate-reactive group may be adopted for chemical synthesis.

[0035]

The content of the component (A) relative to the entire composition is preferably within the range of 5 to 100 parts by mass. This is because the content of less than 5 parts by mass may cause a large amount of components other than the main agent to remain in the coating film, so that sufficient performances as the coating film are not exhibited. In addition, the amount of the resin matrix to be formed becomes insufficient, and defects as the coating material such as poor adhesion and cracking of the film occur in addition to a possibility of causing adverse effects due to other

components. The content thereof is more preferably within the range of 10 to 60 parts by mass.

[0036]

The component (B) , which is an amine compound, is a component that can have a function of a curing catalyst or a curing cocatalyst for the coating material composition of the present invention, and can also serve as an adhesion promoter.

The component (B) may be purchased as a commercial product or may be prepared by any general chemical method.

The component (B) may be a single substance or a mixture of two or more kinds of substances.

[0037]

The component (B) may have any structure and molecular weight so long as it is an amine compound.

The component (B) preferably includes an organosilicon compound including a unit represented by the general formula (5) .

(Chemical formula 5)

D_hSi (OR⁶) _gR⁷ _fO_{(4-f-g-h) /2} (5)

(In the formula,

R⁶, which may be the same or different, represents a hydrogen atom or an optionally substituted hydrocarbon group,

D, which may be the same or different, represents a monovalent SiC-bonded group including a basic nitrogen atom, R⁷, which may be the same or different, represents an optionally

substituted, monovalent, SiC-bonded organic group including no basic nitrogen atom,

f is 0, 1, 2, or 3, preferably 1 or 0,

g is 0, 1, 2, or 3, preferably 1, 2, or 3, more

preferably 2 or 3,

h is 0, 1, 2, 3, or 4, preferably 1,

provided that the sum of f + g + h is 4 or less and there is at least one group D per molecule.)

[0038] The component (B) may include, not only silane, that is, a compound represented by the general formula (5) satisfying f + g + h = 4, but also siloxane, that is, a unit of the formula (5) satisfying f + g + h < 3. However, silane is given

preference .

[0039]

The content of the component (B) relative to the entire composition is preferably within the range of 0.01 to 10 parts by mass. This is because the content of less than 0.01 parts by mass may cause a curing failure and/or an adhesion failure. The content of more than 10 parts by mass may cause an adverse effect such as inducing an unnecessary reaction or

deteriorating a surrounding material after formation of the coating film, which may cause an application failure due to a short pot life and the occurrence of wrinkles on the film surface. Further, this is because a defect such as thickening, gelling, or hardening in terms of preservation stability may be caused. The content thereof is more preferably within the range of 0.5 to 2.5 parts by mass.

[0040]

The component (C) , which is a dehydrating agent, is a component that can cause dehydration by capturing water in the system.

The component (C) may be purchased as a commercial product or may be prepared by any general chemical method.

The component (C) may be a single substance or a mixture of two or more kinds of substances.

[0041]

Examples of the component (C) may include silanes, e.g., vinyltrimethoxysilane, vinyltriethoxysilane,

vinylmethyldimethoxysilane, methyl O-methylcarbamate- methyldimethoxysilane, methyl O-methylcarbamate- trimethoxysilane, methyl O-ethylcarbamate- methyldiethoxysilane, and methyl O-ethylcarbamate- triethoxysilane, and/or their partial condensates, and

orthoesters, e.g., 1 , 1 , 1-trimethoxyethane, 1,1,1- triethoxyethane, trimethoxymethane, and triethoxymethane .

[0042] The content of the component (C) relative to the entire composition is preferably within the range of 0.01 to 10 parts by mass. This is because the content of less than 0.01 parts by mass may cause a defect such as thickening, gelling, or hardening during the production and the storage due to an insufficient dehydration effect, while the content of more than 10 parts by mass may cause an adverse effect such as deteriorating physical properties of the coating film and may also cause a curing failure and uncured state after the application. The content thereof is more preferably within the range of 0.5 to 2.0 parts by mass.

[0043]

The component (D) , which is a stabilizer, is a component that can have functions of an ultraviolet absorber, an

antioxidant, a thermal stabilizer, and a light stabilizer for the coating material composition of the present invention, and can also serve as a stabilizer for polymer degradation.

The component (D) may be purchased as a commercial product or may be prepared by any general chemical method.

The component (D) may be a single substance or a mixture of two or more kinds of substances.

[0044]

The component (D) may be any substance so long as it can exhibit the functions and actions described above, and is preferably, but not limited to, an antioxidant, a UV

stabilizer, or a HALS.

[0045]

The content of the component (D) relative to the entire composition is preferably within the range of 0.01 to 5 parts by weight. This is because the content of less than 0.01 part by mass may cause deterioration of the coating film due to ultraviolet rays, heat, oxidation, or the like, and the content of more than 5 parts by mass may cause an unexpected defect, for example, a color tone change or the like to occur in the case of a transparent product. The content thereof is more preferably within the range of 0.5 to 2.0 parts by mass.

[0046]

The component (E) , which is a plasticizer, is a component that can have a function of adjusting viscosity and viscous properties in the coating material composition of the present invention and can also serve as an agent for adjusting

physical properties such as tensile strength and elongation or as an additive for improving flexibility and weather

resistance of the cured product thereof. This component is not an essential component for the coating material composition of the present invention when the above-mentioned functions or actions are not required.

The component (E) may be purchased as a commercial product or may be prepared by any general chemical method.

The component (E) may be a single substance or a mixture of two or more kinds of substances.

[0047]

The component (E) may be any substance so long as it can exhibit the functions and actions described above, and

examples thereof may preferably include, but not limited to, a tetraalkoxysilane such as tetraethoxysilane and/or a partial condensate thereof, a plasticizer including a reactive

plasticizer, a rheological additive, a flame retardant, and an organic solvent.

[0048]

Examples of the component (E) may include a phthalic acid ester (e.g., dioctyl phthalate, diisooctyl phthalate, and diundecyl phthalate) , a perhydrogenated phthalic acid ester (e.g., 1 , 2-cyclohexanedicarboxylic acid diisononyl ester and 1 , 2-cyclohexanedicarboxylic acid dioctyl ester), a non- phthalic plasticizer, an adipic acid ester (e.g., dioctyl adipate) , a benzoic acid ester, a glycol ester, an ester of saturated alkanediol (e.g., 2 , 2 , 4-trimethyl-l , 3-pentanediol monoisobutyrate and 2 , 2 , 4-trimethyl-l , 3-pentanediol

diisobutyrate) , a phosphoric acid ester, a sulfuric acid ester, a polyester, a polyether (e.g., polyethylene glycol and polypropylene glycol, preferably having an Mn of 1,000 to 10,000), polystyrene, polybutadiene, polyisobutylene, a paraffinic hydrocarbon, and a branched macromolecular

hydrocarbon .

[0049] Examples of the above-mentioned component (E) may typically include substances represented by the following general formula (2) .

(Chemical formula 2)

R³c(R⁴0)_dR⁵eSi0(4-c-d-e)/2 (2)

(in the formula,

R³, which may be the same or different, is a hydrogen atom, a monovalent, SiC-bonded, optionally substituted

aliphatic hydrocarbon group, or a divalent, optionally

substituted aliphatic hydrocarbon group bridging two units of the formula ( 2 ) ,

R⁴, which may be the same or different, is a methyl group or an ethyl group,

R⁵, which may be the same or different, 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, and

e is 0 , 1 , or 2. )

[0050]

Examples of the group R³ may include the examples of the aliphatic group specified above for R. However, the group R³ may also include a divalent aliphatic group, e.g., an alkylene group having 1 to 10 carbon atoms, e.g., a methylene group, an ethylene group, a propylene group, or a butylene group, which bonds the two silyl groups in the formula (2) to each other, for example. One particular current example of the divalent aliphatic group is an ethylene group.

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

[0051]

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 having 1 to 10 carbon atoms optionally substituted by a halogen atom, more preferably an alkyl group having 1 to 4 carbon atoms, and more particularly a methyl group or an ethyl group .

[0052]

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

The group R⁵ preferably includes an SiC-bonded aromatic hydrocarbon group having 1 to 18 carbon atoms optionally substituted by a halogen atom, e.g., an ethylphenyl group, a tolyl group, a xylyl group, a chlorophenyl group, a naphthyl group or a styryl group, more preferably a phenyl group.

[0053]

The component (E) that is preferably used is a silicone resin in which at least 90% of all the group R³ is a methyl group, at least 90% of all the group R⁴ is a methyl group, an ethyl group, a propyl group, or an isopropyl group, and at least 90% of all the group R⁵ is a phenyl group.

[0054]

According to the present invention, preference is given in each case to using a silicone resin having the units represented by the formula (2) in which at least 20%, more preferably at least 40% of the total number of units

represented by the formula (2) is the unit represented by the formula (2) in which c is 0.

[0055]

An embodiment of the present invention employs in each case a silicone resin having the units represented by the formula (2) in which at least 10%, more preferably at least 20%, and 80% or less, more preferably 60% or less of the total number of units represented by the formula (2) is the unit represented by the formula (2) in which c is 2.

[0056]

A preferentially used silicone resin is one having the units represented by the formula (2) in which at least 80%, more preferably at least 95% of the total number of units represented by the formula (2) is the unit represented by the formula (2) in which d is 0 or 1, in each case.

[0057]

In each case, preference is given to using a silicone resin having the units represented by the formula (2) in which at least 60%, more preferably at least 70%, and preferably 99% or less, more preferably 97% or less of the total number of units represented by the formula (2) is the unit represented by the formula (2) in which d is 0.

[0058]

The component (E) more preferentially used in each case is a silicone resin having the units represented by the formula (2) in which at least 1%, preferably at least 10%, more particularly at least 20% of the total number of units represented by the formula (2) is the unit represented by the formula (2) in which e is a value other than 0.

A silicone resin (E) having only the units represented by the formula (2) in which e is a value other than 0 may be used, and more preferably at least 10%, particularly preferably at least 20%, and preferably 80% or less, more preferably 60% or less of the units represented by formula (2) has e which is 0.

[0059]

In each case, preference is given to using a silicone resin (E) having the units represented by the formula (2) in which at least 20%, more preferably at least 40% of the total number of units represented by the formula (2) is the unit represented by the formula (2) in which e is 1. A silicone resin (E) having only the units represented by the formula (2) in which e is 1 may be used, and more preferably at least 10%, particularly preferably at least 20%, and preferably 80% or less, more preferably 60% or less of the units represented by the formula (2) has e which is 0.

[0060]

Preference is given to using, in each case, a silicone resin (E) having the units represented by the formula (2) in which at least 50% of the total number of the units

represented by the formula (2) are the units represented by the formula (2) in which the sum of c + e is 0 or 1.

[0061]

In one particularly preferred embodiment of the present invention, used as a substrate adjusting agent, in each case, is a silicone resin having the units represented by the formula (2) in which at least 20%, more preferably at least 40% of the total number of the units represented by the formula (2) is the unit represented by the formula (2) in which e is 1 and c is 0. In this case, preferably 70% or less, more preferably 40% or less of the total number of the units represented by the formula (2) have d other than 0.

[0062]

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

[0063]

An example of the silicone resin used in accordance with the present invention is substantially, preferably

exclusively, an organopolysiloxane resin composed of a (Q) unit of formulas S1O4_/2, Si (OR¹¹) O3_/2, Si (OR¹¹) 2O2_/2_/ and

Si (OR¹¹) 3O1_/2, a (T) unit of formulas PhSi0_3/2, PhSi (OR¹¹) Q212, and PhSi (OR¹¹) 2O1_/2, a (D) unit of formulas Me2Si02/2 and

Me2Si (OR¹¹) O1_/2, and an (M) unit of formula Me₃SiOi/2 (in the formulas, Me is a methyl group, Ph is a phenyl group, and R¹¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms optionally substituted by a halogen atom, and more preferably a hydrogen atom or an alkyl having 1 to 4 carbon atoms) . The resin preferably includes the (Q) unit of 0 to 2 mols, the (D) unit of 0 to 2 mols, and the (M) unit of 0 to 2 mols per (T) unit.

[0064]

A preferred example of the silicone resin used in accordance with the present invention is substantially, preferably exclusively, an organopolysiloxane resin composed of a T unit of formulas PhSi0_3/2, PhSi (OR¹¹) Q₂1₂₁ and

PhSi (OR¹¹) 2O1_/2, and/or a D unit of formulas Me2SiC>2/2 and

Me2Si (OR¹¹) O1/2 (in the formulas, Me is a methyl group, Ph is a phenyl group, and R¹¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms optionally substituted by a halogen atom, and more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, having a molar ratio of the (T) unit to the (D) unit of 0.5 to 2.0) .

[0065]

A more preferred example of the silicone resin used in accordance with the present invention is substantially, preferably exclusively, an organopolysiloxane resin composed of a T unit of formulas PhSi0_3/2, PhSi (OR¹¹) Q₂1₂₁ and

PhSi (OR¹¹) 2O1_/2, and/or a T unit of formulas MeSi0_3/2,

MeSi (OR¹¹) O2_/2_/ and MeSi (OR¹¹) 2O1/2 and/or a D unit of formulas Me₂Si0_2/2 and Me₃Si (OR¹¹) O1/2 (in the formulas, Me is a methyl group, Ph is a phenyl group, and R¹¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms optionally substituted by a halogen atom, and more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, having a molar ratio of a phenyl silicone unit to a methyl silicone unit of 0.5 to 4.0) . The amount of the D unit in these silicone resins is preferably less than 10% by weight.

[0066]

An even more preferred example of the silicone resin used in accordance with the present invention is substantially, preferably exclusively, an organopolysiloxane resin composed of the T unit of formulas PhSi0_3/2, PhSi (OR¹¹) Q₂1₂, and

PhSi (OR¹¹) 2O1_/2, (in the formulas, Ph is a phenyl group, and R¹¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms optionally substituted by a halogen atom, and more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) . The amount of the D unit in these silicone resins is preferably less than 10% by weight.

[0067]

The silicone resins used in accordance with the present invention preferably has a number-average molecular weight Mn of at least 400, more preferably at least 600. Mn is

preferably 400,000 or less, more preferably 10,000 or less, and more particularly 50,000 or less.

[0068]

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

[0069]

The silicone resin may be used either in a pure form or in the form of a solution in a suitable solvent.

[0070]

In this case, examples of the solvents that may be used may include ethers (e.g., diethyl ether, methyl tert-butyl ether, ether derivatives of glycols, and THF) , esters (e.g., ethyl acetate, butyl acetate, and glycol ester) , hydrocarbons (e.g., pentane, cyclopentane, hexane, cyclohexane, heptane, octane, or other long chain, branched and unbranched alkanes), ketones (e.g., acetone and methyl ethyl ketone), aromatics (e.g., toluene, xylene, ethylbenzene, and chlorobenzene), and other alcohols (e.g., methanol, ethanol, glycol, propanol, isopropanol, glycerol, butanol, isobutanol, and tert-butanol ) .

[0071]

However, it is preferable to use a silicone resin that does not contain an organic solvent.

[0072]

The component (E) as a rheological additive is preferably a polyamide wax, a hydrogenated castor oil or a stearate. An aqueous dispersion of silica may also be mentioned.

[0073]

The content of the component (E) relative to the entire composition is preferably in the range of 0 to 95 parts by mass. If the amount exceeds 95 parts by mass, the amount of the resin matrix to be formed becomes insufficient, and defects as a coating material such as poor adhesion, cracking of a coating film, and the like may occur, resulting in curing failure or uncured state after the application. The content thereof is more preferably within the range of 0 to 80 parts by mass .

[0074]

The component (F), which is a filler, is a component that can have functions of a weighting agent and of adjusting physical properties such as viscosity and viscous properties, tensile strength and elongation of the coating material composition of the present invention, and can also serve as a curing accelerator for the coating material by moisture contained therein. This component is not an essential

component for the coating material composition of the present invention when the above-mentioned functions or actions are not required.

The component (F) may be purchased as a commercial product or may be prepared by any general chemical method.

The component (F) may be a single substance or a mixture of two or more kinds of substances.

[0075]

The component (F) may be any substance so long as it can exhibit the functions and actions described above, and

examples thereof may include, but not limited to, a non reinforcing filler, preferably a filler having a BET surface area of up to 50 m²/g, e.g., quartz, diatomaceous earth, calcium silicate, zirconium silicate, talc, kaolin, and zeolite, metal oxide powders, e.g., aluminum oxide, titanium oxide, iron oxide, or zinc oxide, and/or mixed oxides thereof, barium sulfate, calcium carbonate, gypsum, silicon nitride, silicon carbide, boron nitride, glass powder and polymer powder, e.g., polyacrylonitrile powder; a reinforcing filler, a filler having a BET surface area of greater than 50 m²/g, e.g., silica prepared by thermal decomposition, precipitated silica, precipitated calcium carbonate, carbon black, e.g., furnace black and acetylene black, and mixed silicon/aluminum oxide of high BET surface area; fillers in the form of hollow beads of aluminum trihydroxide, e.g., magnetic microbeads, examples of which are available under the trade name Zeeospheres (trademark) available from 3M Deutschland GmbH of Neuss, Germany, elastic polymer beads of the kind available under the trade name EXPANCEL (trademark) available from

AKZONOBEL, Expancel of Sundsvall, Sweden, or glass beads; and fillers in fiber form, e.g., asbestos and also polymer fibers. The fillers described above may be hydrophobized, for example, by treatment with an organosilane and/or organosiloxane, or with stearic acid, or by etherification of hydroxyl groups to alkoxy groups.

[0076]

The component (F) is preferably calcium carbonate, talc, aluminum hydroxide or silica, with aluminum hydroxide being particularly preferred. A preferred calcium carbonate grade is ground or precipitated, optionally surface treated with a fatty acid such as stearic acid or salts thereof. A preferred silica is preferably pyrolytic (fumed) silica.

[0077]

The component (F) preferably has a moisture content of less than 1 part by mass, more preferably less than 0.5 parts by mass .

[0078]

The content of the component (F) relative to the entire composition is preferably within the range of 0 to 80 parts by mass. This is because, if the amount exceeds 80 parts by mass, the amount of the resin matrix to be formed becomes

insufficient, and defects as a coating material such as poor adhesion, cracking of a film, and the like may occur, and there is a possibility that poor stirring may occur due to high viscosity at the time of producing. The content thereof is more preferably within the range of 0 to 60 parts by mass. When the component (F) is silica, the content thereof is preferably within the range of 0 to 10 parts by mass.

[0079]

In a specific embodiment of the present invention, the composition of the present invention includes, as the filler (F) ,

a) silica, more particularly fumed silica, and b) calcium carbonate, aluminum trihydroxide and/or talc, in combination.

[0080]

The component (G) , which is a catalyst, is a component that can have a function of a curing catalyst for the coating material composition of the present invention. This component is not an essential component for the coating material composition of the present invention when the above-mentioned functions or actions are not required.

The component (G) may be purchased as a commercial product or may be prepared by any general chemical method.

The component (G) may be a single substance or a mixture of two or more kinds of substances.

[0081]

The component (G) may be any substance so long as it can exhibit the functions and actions described above, and

examples of the component (G) containing metal may include an organotitanium compound and an organotin compound. Specific examples thereof may include: titanate esters, e.g.,

tetrabutyl titanate, tetrapropyl titanate, tetraisopropyl titanate, and titanium tetraacetylacetonate ; and tin

compounds, e.g., dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin dioctanoate, dibutyltin acetylacetonate, dibutyltin oxide, and corresponding

dioctyltin compounds.

[0082]

Examples of the component (G) containing no metal may include basic compounds, e.g., triethylamine, tributylamine, l,4-diazabicyclo[2.2.2] octane, l,5-diazabicyclo[4.3.0] none-5- ene, 1 , 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 ( ethylmorpholinine ) .

[0083]

It is likewise possible to use acidic compounds as the component (G) , e.g., phosphoric acid and esters thereof, toluene sulfonic acid, sulfuric acid, nitric acid or other organic carboxylic acids, e.g., acetic acid and benzoic acid. [0084]

The content of the component (G) relative to the entire composition is preferably within the range of 0 to 5 parts by mass. This is because the content of more than 5 parts by mass may cause an application failure due to a short pot life and the occurrence of wrinkles on the film surface and may also cause a defect such as thickening, gelling, or hardening during the storage. The content thereof is more preferably within the range of 0 to 0.2 parts by mass.

[0085]

The moisture curing-type coating material composition of the present invention may include an optional component in addition to the above-described components so long as the object of the present invention is achieved. For example, all other substances such as a defoaming agent, an additive, and an auxiliary agent may be included. If necessary, a component for improving the adhesiveness after immersion in water, for example, epoxysilane or the like, may be included.

[0086]

Any mode, form, and composition may be employed for the substrate adjusting agent used in the method for forming the moisture curing-type coating material of the present invention so long as the substrate adjusting agent is in the form of at least one liquid or more and finally cured by the moisture, not in a manner of forming a film so as to clog a fine hole on the porous substrate, but in a manner of forming a

hydrophobized coating film to a deep part along a surface having irregularities. Further, the substrate adjusting agent may be composed of a single component or a mixture of two or more kinds of components. The substrate adjusting agent is represented by a coating material including a silane monomer or an oligomer, a silicone oil, or a silicone resin, having an alkoxysilyl group which is hydrolyzed by the moisture and produces a siloxane bond, thereby causing curing.

When the substrate adjusting agent is applied to the porous substrate, not in a manner of forming a film on the porous substrate so as to clog a hole part, but in a manner of forming a hydrophobized coating film to a deep part along a surface having irregularities, it is preferable to hydrolyze a coating liquid including a compound composed mainly of a silane compound having a molecular weight as small as

possible .

[0087]

Typically, the silane represented by the following general formula (2) easily achieves the above-mentioned obj ect .

(Chemical formula 2)

R³c(R⁴0)_dR⁵eSi0(4-c-d-e)/2 (2)

(In the formula,

aliphatic hydrocarbon group, or a divalent, optionally

R⁴, which may be the same or different, is a methyl group or an ethyl group,

d is 0, 1, 2, 3, or 4 and

e is 0 , 1 , or 2 ) .

[0088]

Examples of the group R³ may include the examples of the aliphatic group specified above for R. However, the group R³ may also include a divalent aliphatic group, such as an alkylene group having 1 to 10 carbon atoms, e.g., a methylene group, an ethylene group, a propylene group, or a butylene group, which bonds the two silyl groups in the formula (2) to each other, for example. One particular current example of the divalent aliphatic group is an ethylene group.

However, the group R³ preferably includes a monovalent, SiC-bonded, aliphatic hydrocarbon atom group having 1 to 18 carbon atoms optionally substituted by a halogen atom, more preferably an aliphatic hydrocarbon group having 1 to 8 carbon atoms .

[0089] Examples of the group R⁴ may include a hydrogen atom and the examples specified for the group R.

[0090]

The group R⁵ preferably includes an SiC-bonded aromatic hydrocarbon group having 1 to 18 carbon atoms optionally substituted by a halogen atom, e.g., an ethylphenyl group, a tolyl group, a xylyl group, a chlorophenyl group, a naphthyl group or a styryl group, or a phenyl group.

[0091]

The long chain alkyl group bonded to the silicon atom in the silane maintains its high hydrophobicity even if the siloxane bond is cut by an alkali component. Thus, it is considered that it does not flow together with water and remains in the substrate, so that siloxane bonds are formed again. In addition, the alkoxy group bonded to the silicon atom in the silane forms a monomolecular layer on the

substrate by a condensation reaction with the hydroxyl group of the substrate, so that the group enters deep into the substrate, but does not clog the fine holes of the substrate.

[0092]

The silane, oligomer, silicone oil, or silicone resin may be used either in a pure form or in the form of a solution in a suitable solvent.

However, it is preferable to use a silicone resin

containing no organic solvent.

[0093]

The silane, oligomer, silicone oil, or silicone resin used in accordance with the present invention may be a

commercially available product or prepared by conventional methods in silicon chemistry.

[0094] When the silane monomer or oligomer, silicone oil, silicone resin, or a mixture thereof, containing the unit represented by the aforementioned general formula (2), is applied to various substrates in various use applications as the substrate adjusting agent, there is no limitation to a form of the coating agent composition and the composition content .

In a case where the application is performed to a typical use application, that is, a substrate such as a building material or an industrial building, in particular, a porous substrate, the following composition is preferable:

(H) the silane monomer or oligomer, silicone oil, silicone resin, or a mixture thereof, containing the unit represented by the aforementioned general formula (2) : 5 to 100 parts by mass;

(I) a surfactant: 0 to 40 parts by mass;

(J) a filler: 0 to 50 parts by mass; and

(K) an organic solvent or water: 0 to 95 parts by mass, provided that part(s) by mass of each component is based on 100 parts by mass of the entire composition of the moisture curing-type coating material.

[0095]

The component (H) , which is a main agent of the substrate adjusting agent composition, is a component for forming a coating film using the moisture after application.

The component (H) may be purchased as a commercial product or may be prepared by any general chemical method.

The component (H) may be a single substance or a mixture of two or more kinds of substances.

[0096]

The content of the component (H) relative to the entire composition is preferably within the range of 5 to 100 parts by mass. This is because the content of less than 5 parts by mass may cause blistering or an adhesion failure to the coating film caused by a water drop inside the substrate due to poor hydrophobization . The content thereof is more

preferably within the range of 10 to 100 parts by mass.

[0097] The component (I), which is a surfactant, is a component that can emulsify an oil component in a case where the

substrate adjusting agent composition of the present invention is formed by emulsion or a water dispersion. This component is not an essential component for the coating material

composition of the present invention when the above-mentioned functions or actions are not required.

The component (I) may be purchased as a commercial product or may be prepared by any general chemical method.

The component (I) may be a single substance or a mixture of two or more kinds of substances. The component (I) may also include a resin structure.

[0098]

A variety of known surfactants may be used for the component (I) . Specific examples of anionic surfactants may include alkyl sulfates having a chain length of 8 to 18 carbon atoms, alkyl and alkaryl ether sulfates having 8 to 18 carbon atoms in a hydrophobic group and having 1 to 40 ethylene oxides (EO) or propylene oxides (PO) units, alkyl sulfonates having 8 to 18 carbon atoms, alkylaryl sulfonates, esters and half esters of sulfosuccinic acids with monohydric alcohols or alkylphenols .

[0099]

Examples of nonionic surfactants may include polyvinyl alcohol, alkyl polyglycol ethers consisting of 3 to 40

ethylene oxide (EO) units and an alkyl having 8 to 20 carbon atoms, ethylene oxide/propylene oxide (EO/PO) block

copolymers, and alkylamine addition products with ethylene oxide or propylene oxide.

[0100]

Examples of cationic surfactants may include salts of primary, secondary and tertiary fatty amines having 8 to 24 carbon atoms, quaternary alkyl and alkylbenzole ammonium salts, alkylpyridinium salts, alkylimidazolinium and

alkyloxazolinium salts, long chain substituted amino acids, and betaines.

[0101]

Preferred examples of the surfactants may include nonionic surfactants, in particular, alkyl polyglycol ethers, alkylamine addition products with ethylene oxide or propylene oxide, and polyvinyl alcohol. Polyvinyl alcohol preferably contains 5 to 20% vinyl acetate units and has a degree of polymerization of 500 to 3000.

[0102]

The content of the component (I) relative to the entire composition is preferably within the range of 0 to 40 parts by mass. This is because the content of more than 40 parts by mass may cause peeling or an adhesion failure to the coating film due to absorption of the moisture to a hydrophilic group of the surfactant. The content thereof is more preferably within the range of 0 to 30 parts by mass.

[0103]

The component (J), which is a filler, is a component that exhibits the same function and action as those of the filler of the component (F) in the moisture curing-type coating material composition. This component is not an essential component for the coating material composition of the present invention when the above-mentioned function or actions are not required .

[0104]

The descriptions as above for the component (F) may apply to illustrations, procurement methods, adjustment methods, and the like of the component (J) .

[0105]

In a case where the component (J) is silica or includes silica, silica has a significant influence on viscosity and a thixotropic property of the composition.

The substrate adjusting agent composition needs to be applied to the porous substrate, not in a manner of forming a coating film as a continuous film (in a manner of not clogging a fine hole) , but in a manner of forming a hydrophobized coating film so as to cover the surface of the fine pore at an appropriate depth, and thus, the kind, the amount, and the like of the silica of the component (J) are optimized for each case to achieve the purpose.

[0106] The content of the component (J) relative to the entire composition is preferably within the range of 0 to 50 parts by mass. This is because the content of more than 50 parts by mass may cause an application failure due to high viscosity, inhibition of permeation of the silane component into the substrate, and the like. The content thereof is more

preferably within the range of 0 to 5 parts by mass.

[0107]

The component (K) , which is an organic solvent or water, is a component serving as a medium in a case where the

substrate adjusting agent composition of the present invention is formed by an organic solvent dispersion, emulsion, or a water dispersion. This component is not an essential component for the coating material composition of the present invention when the above-mentioned functions or actions are not

required .

[0108]

It is normally advantageous to prepare the substrate adjusting agent composition into a dispersion or emulsion for thinly and uniformly applying the desired substrate adjusting agent onto the substrate. Water is environmentally more advantageous than an organic solvent. However, in an

environment where an organic solvent does not cause a problem, applying an organic solvent dispersion is sometimes more advantageous .

[0109]

The component (K) may be purchased as a commercial product .

The component (K) may be a single substance or a mixture of two or more kinds of substances.

[0110]

When the component (K) is an organic solvent, examples thereof may include ethers (e.g., diethyl ether, methyl tert- butyl ether, ether derivatives of glycols, and THF) , esters (e.g., ethyl acetate, butyl acetate, and glycol ester), hydrocarbons (e.g., pentane, cyclopentane, hexane,

cyclohexane, heptane, octane, or other long chain, branched and unbranched alkanes), ketones (e.g., acetone and methyl ethyl ketone), aromatics (e.g., toluene, xylene, ethylbenzene, and chlorobenzene), and other alcohols (e.g., methanol, ethanol, glycol, propanol, isopropanol, glycerol, butanol, isobutanol, and tert-butanol ) .

[0111]

In a case where the component (K) is water, it is preferable to use ion exchange water preferably at pH 2 to 12, particularly preferably at pH 4 to 10, without being

particularly limited thereto. Using mineral water is not recommended. However, when used, the mineral water is

preferably used in combination with a metal deactivator or the like .

[0112]

The content of the component (K) relative to the entire composition is preferably within the range of 0 to 95 parts by mass. This is because the content of more than 95 parts by mass may cause blistering or an adhesion failure to the coating film due to a water drop inside the substrate, which is caused by poor hydrophobization due to the insufficient amount of the silane component. The content thereof is more preferably within the range of 0 to 60 parts by mass.

[0113]

The substrate adjusting agent composition of the present invention may include an optional component in addition to the above-described components so long as the object of the present invention is achieved. Examples of the optional component may include amino-modified silane and amino-modified oil for facilitating the curing of the composition, various acid/alkali catalysts for facilitating hydrolysis and

condensation polymerization, a preservative or the stabilizer described as the aforementioned component (D) in consideration of preservation stability, and a tin catalyst.

[0114]

The substrate used in the method for forming the moisture curing-type coating material of the present invention may be any substrate so long as the substrate adjusting agent can be applied thereto and the object of the present invention is achieved. However, in a case where the water vapor for curing the moisture curing-type coating material needs to be supplied from the substrate, a water-containing substrate needs to be selected. Further, in a case where the curing of the moisture curing-type coating material needs the water vapor from the substrate, a porous substrate needs to be selected.

Examples of the substrate include a cement-based

substrate, a mineral substrate, metal, glass, and ceramic.

Further, surfaces of these substrates may be coated.

[0115]

The preferable substrate is a cement-based substrate. Examples of the cement-based substrate may include concrete, concrete, mortar, a siding board (cement fiber board) ,

autoclaved lightweight concrete (ALC) , a slate board, and a calcium silicate plate. Of these, concrete is preferable.

[0116]

Examples of the porous substrate may include concrete, mortar, a siding board, autoclaved lightweight concrete (ALC) , a slate board, a calcium silicate plate, a plasterboard, a building stone, a brick, and ceramic such as a clay tile. Of these, a porous cement-based substrate is preferable. When the normal cement-based substrate is produced by a general method, the resulting cement-based substrate has the porous surface. Examples of the porous cement-based substrate may include concrete, mortar, a siding board, autoclaved lightweight concrete (ALC), a slate board, and a calcium silicate plate.

Of these, concrete is preferable.

[0117]

In the method for forming the moisture curing-type coating material of the present invention, when the substrate adjusting agent is formed on the substrate, the moisture curing-type coating material is further applied thereto, and the curing is caused by moisture, the water vapor required for the curing can be acquired by using the water vapor present in the substrate, and/or the water vapor arising from the

substrate adjusting agent, in addition to the water vapor present in the outside air.

This makes it possible to ensure the sufficient curing inside the coating film even when the surface curing speed is high .

With this being satisfied, concretely, any method may be employed .

[0118]

However, when the water vapor present in the substrate is used, the water vapor is required to pass through a layer of the substrate adjusting agent and reach a layer of the coating film of the moisture curing-type coating material.

In this case, if the substrate adjusting agent is formed on the substrate as a film, that is, as a continuous phase, the film thickness needs to be sufficiently thin so as to allow the passage of the water vapor, or the substrate

adjusting agent needs to be applied without forming a film. Detailed conditions of such a case are determined by a

combination of the kind of the substrate adjusting agent and the kind of the substrate and need to be adjusted for each case .

In a case where the substrate adjusting agent is used without forming a film, it is required to be functional enough to prevent peeling of the coating film of the moisture curing- type coating material and other problems.

[0119]

In a case where the water vapor arising from the

substrate adjusting agent is used, the water vapor may be used in combination with the water vapor present in the substrate or singly used.

In a case of using both water vapor, the above conditions for using the water vapor present in the substrate are

applied. Additionally, the selection and the application method of the substrate adjusting agent are appropriately optimized according to the purpose.

In a case of singly using the water vapor of the

substrate adjusting agent, the substrate adjusting agent may be applied on the substrate with or without forming a film, and the selection and the application method of the substrate adjusting agent are optimized according to the purpose.

[0120]

In the method for forming the moisture curing-type coating material of the present invention, it is preferable that the porous substrate is used and the substrate adjusting agent is applied, not in a manner of forming a film on the porous substrate so as to clog a hole part, but in a manner of forming the hydrophobized coating film to a deep part along a surface having irregularities. This makes it possible to use the water vapor present in the porous substrate in addition to the water vapor present in the outside air as the water vapor required for curing the moisture curing-type coating material.

In this manner, the sufficient curing inside the coating film can be ensured even when the surface curing speed is high. Further, the hydrophobized substrate, while allowing permeation of the water vapor, can prevent blistering,

peeling, or cracking caused to the coating film by the

moisture resulting from the water vapor or the like. Further, for the above reasons, good adhesiveness can be maintained for a long period of time.

With this being satisfied, concretely, any method may be employed .

[0121]

Further, in this case, if the water vapor present in the substrate can be supplied in an amount necessary and

sufficient for sufficiently curing the inside, that is, the lower part, of the moisture curing-type coating material coating film, peeling or cracking of the film, or other problems are not caused by the moisture.

The necessary and sufficient amount of the water vapor to be supplied is determined by a combination of conditions such as the kind of the substrate, the water content of the

substrate, a porous state and an irregularity state of the surface, the coating method of the substrate adjusting agent, and the coating method and the film thickness of the moisture curing-type coating material coating film. The optimum

conditions thereof are adjusted for each case.

[0122]

The method for forming the moisture curing-type coating material described above can exhibit a remarkable effect even in the porous substrate, in particular, a cement-based substrate such as concrete.

In particular, the more excellent effect can be exhibited when the surface of concrete for construction/building

material and civil engineering is provided with coating for bonding, sealing, waterproofing, and the like, measures for preventing detachment of concrete pieces, and imparting aesthetic appearance.

[0123]

In the coating method of the substrate adjusting agent, in general, dilution is performed using an appropriate diluent such as water or an organic solvent so as to have a proper concentration of an active component after dilution, and application is performed onto the substrate using a brush, a roller, an airless spray, an air spray, or the like.

Examples of the water arising from the substrate

adjusting agent may be considered to include water used in the emulsion-based substrate adjusting agent and water used as the diluent when the moisture curing-type coating material is applied and formed possibly before the moisture of such water is completely evaporated.

[0124]

In a case where the moisture curing-type coating material is used as an adhesive of a building member, in particular, in a case, for example, where a large panel or a film for

preventing detachment of concrete pieces is adhered to a porous substrate, the moisture required for curing is not supplied to the center part not in contact with the outside air. In such a case, the present forming method becomes effective .

[0125]

The method for forming the moisture curing-type coating material of the present invention can be used in various use applications without limitation. Examples thereof may include a coating material for building finishing and the like, a coating film waterproof material for a veranda, a rooftop, and the like, a floor material for a factory, a building, and the like, measures for preventing detachment of concrete pieces for a highway and an elevated railroad, an adhesive and a sealing material for a building structure, a vehicle and a ship, and various concrete secondary products.

EXAMPLES

[0126]

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

[0127]

As a test substrate, mortar (in conformance with JIS A5201) (20 x 270 x 70 mm) was used. A substrate adjusting agent was applied onto this substrate in a predetermined coating amount per unit area with a brush. After 24 hours, a moisture curing-type coating material was applied in a

predetermined thickness with an applicator, followed by curing under conditions of 23°C and 50%RH for a predetermined time, thereby producing a test product.

Note that the formation of the substrate adjusting agent was omitted in some cases.

[0128]

The test substrate and the production method of the coating film for test/evaluation described above were

employed .

The substrate adjusting agent was applied in an amount of 100 g/m². The moisture curing-type coating material was applied thereonto in a thickness of 2 to 3 mm, and the surface of the coating material coating film was further covered with an aluminum film on the top to shield the water vapor from the outside air. The resulting test product was half-immersed in water for curing for a predetermined time.

The internal curing was evaluated by confirming the curing of the moisture curing-type coating material in the center part on the side of the aluminum film.

[0129] <Evaluation method of blistering resistance of coating film>

employed .

The test product produced in each Example and Comparative Example was half-immersed in a calcium hydroxide saturated solution for a predetermined period of time to examine the presence of blistering in the moisture curing-type coating material coating film, thereby confirming forming properties thereof .

[0130]

The following respective components were used as the moisture curing-type coating material composition. As a silane terminal-modified polymer of the component (A) , GENIOSIL

(registered trademark) STP-E30 manufactured by Wacker Chemie AG in an amount of 92.8 parts by mass, as an amine compound of the component (B) , GENIOSIL (registered trademark) GF96 manufactured by Wacker Chemie AG in an amount of 2.0 parts by mass, as a dehydrating agent of the component (C) , GENIOSIL (registered trademark) XL10 manufactured by Wacker Chemie AG in an amount of 0.70 parts by mass, as a stabilizer of the component (D) , GENIOSIL (registered trademark) Stabilizer F manufactured by Wacker Chemie AG in an amount of 2.5 g, and as a filler (silica) of the component (F), HDK (registered trademark) H18 manufactured by Wacker Chemie AG in an amount of 2.0 parts by mass were used. These components were stirred and mixed for preparation.

As the substrate adjusting agent, SILRES (registered trademark) BS CREME C manufactured by Wacker Chemie AG, which was an aqueous silane/siloxane primer not forming a film in a coating film, was used.

A test product was produced using the above test

substrate according to the above production method of the coating film for test/evaluation .

The test product was evaluated according to the above measurement method and evaluation method of the internal curing of the moisture curing-type coating material curable coating film to find that the internal curing was good.

The test product was evaluated according to a test method and evaluation method of the blistering resistance of the coating film to find that the blistering resistance was good with no blistering.

[0131]

A test product was produced with all the same components as those in Example 1 in the same amounts by parts by mass using the same substrate adjusting agent except that, as a silane terminal-modified polymer of the component (A) ,

GENIOSIL (registered trademark) XT-50 manufactured by Wacker Chemie AG in an amount of 92.8 parts by mass was used,

followed by evaluation in the same manner.

The internal curing was good and the blistering

resistance was good with no blistering.

[0132]

A test product was produced with all the same components as those in Example 1 in the same amounts by parts by mass except that, as the substrate adjusting agent, WACKER

(registered trademark) PRIMER G790 manufactured by Wacker Chemie AG, which was a solvent-based silicone resin primer not forming a film in a coating film, followed by evaluation in the same manner.

Here, WACKER (registered trademark) PRIMER G790 was diluted with mineral spirits (paraffin) to have a

concentration of 50 mass%.

The internal curing was good and the blistering

resistance was good with no blistering.

[0133]

A test product was produced with all the same components as those in Example 2 in the same amounts by parts by mass except that, as the substrate adjusting agent, WACKER

concentration of 50 mass%.

The internal curing was good and the blistering

resistance was good with no blistering.

[0134]

A test product was produced with all the same components as those in Example 1 in the same amounts by parts by mass except that the substrate adjusting agent was not used

(blank), followed by evaluation in the same manner.

The internal curing was good. The blistering resistance was poor with the occurrence of blistering.

[0135]

A test product was produced with all the same components as those in Example 2 in the same amounts by parts by mass except that the substrate adjusting agent was not used

(blank), followed by evaluation in the same manner.

[0136]

A test product was produced with all the same components as those in Example 1 in the same amounts by parts by mass except that, as the substrate adjusting agent, floneOl primer manufactured by HIGASHI NIPPON TORYO Co., Ltd., which was an one liquid solvent-based urethane primer not forming a film in a coating film, was used, followed by evaluation in the same manner .

The internal curing was poor. Further, the blistering resistance was poor with the occurrence of blistering.

[0137]

A test product was produced with all the same components as those in Example 2 in the same amounts by parts by mass except that, as the substrate adjusting agent, floneOl primer manufactured by HIGASHI NIPPON TORYO Co., Ltd., which was an one liquid solvent-based urethane primer not forming a film in a coating film, was used, followed by evaluation in the same manner.

The contents of the compositions and evaluation results in Examples 1 to 4 and Comparative Examples 1 to 4 are shown in Table 1.

WA11930S

[0138]

[Table 1]

[0139]

Conclusions and speculation obtained from Examples 1 to 4 and Comparative examples 1 to 4 are as follows.

When the substrate adjusting agent not forming a film in a coating film was used (Examples 1 to 4) and when the

substrate adjusting agent was not used (blank) (Comparative Examples 1 and 2), the internal curing of the coating film of the moisture curing-type coating material was good. It is speculated that the water vapor supplied from the substrate was sufficiently supplied to the coating film of the moisture curing-type coating material. In contrast, the internal curing was insufficient when the substrate adjusting agent forming a film in a coating film was used (Comparative Examples 3 and 4) . It is speculated that the water vapor from the substrate was blocked by the continuous film of the substrate adjusting agent .

No blistering of the coating film of the moisture curing- type coating material occurred in any of Examples 1 to 4. It is speculated that the water vapor from the substrate was appropriately consumed for curing the coating film of the moisture curing-type coating material and/or the substrate adjusting agent prevented formation of the moisture at the interface between the mortar substrate and the moisture curing-type coating material caused by excessive supply of the water vapor from the substrate to the coating film of the moisture curing-type coating material. In contrast, the blistering occurred in all of Comparative examples 1 to 4. It is speculated that, in Comparative Examples 1 and 2, the non- hydrophobized substrate caused the formation of the moisture by excessively supplying the water vapor from the substrate to the coating film of the moisture curing-type coating material, resulting in the occurrence of the blistering. It is

speculated that, similarly in Comparative Examples 3 and 4, the non-hydrophobized substrate caused the formation of the moisture by excessively supplying the water vapor from the substrate, and, further, the moisture thus formed was

prevented from escaping to the outside by the presence of the film of the substrate adjusting agent, thereby resulting in the occurrence of the blistering.

INDUSTRIAL APPLICABILITY

[0140]

The method for forming the moisture curing-type coating material of the present invention can be applied to a coating material for building finishing and the like, a coating film waterproof material for a veranda, a rooftop, and the like, a floor material for a factory, a building, and the like, measures for preventing detachment of concrete pieces for a highway and an elevated railroad, an adhesive/sealing material for a vehicle and a ship, and a building structure, various concrete secondary products, and the like, as well as other various uses.

Claims

1. A method for forming a moisture curing-type coating material, comprising: forming a substrate adjusting agent on a substrate; further applying a moisture curing-type coating material thereonto; and, when curing is caused by moisture, acquiring water vapor required for the curing by using water vapor present in the substrate, and/or water vapor arising from the substrate adjusting agent, in addition to water vapor present in outside air.

2. The method for forming a moisture curing-type coating material according to claim 1, wherein the substrate is a porous substrate, the substrate adjusting agent is not to form a film on the porous substrate so as to clog a hole part, but to form a hydrophobized coating film to a deep part along a surface having irregularities, and the water vapor required for the curing of the moisture curing-type coating material is acquired by using water vapor present in the porous substrate in addition to the water vapor present in the outside air.

3. The method for forming a moisture curing-type coating material according to claim 1 or 2, wherein the moisture curing-type coating material includes a silane terminal- modified polymer represented by the following general formula (1), and the substrate adjusting agent includes a silane monomer or an oligomer, a silicone oil, a silicone resin or a mixture thereof, containing a unit represented by the

following general formula (2) :

(Chemical formula 1)

Y- [ (CR¹ _{2) b}-SiR_{a (}OR²) _3-a] x (1)

(in the formula,

Y is an x-valent organic polymer group bonded via nitrogen, oxygen, sulfur, or carbon, having a

polyoxyalkylene or a polyurethane as a polymer chain;

x is an integer of 1 to 10;

(Chemical formula 2)

R³c(R⁴0)_dR⁵eSi0(4-c-d-e)/2 (2)

(in the formula,

R³, which may be the same or different, is a hydrogen atom, a monovalent, SiC-bonded, optionally substituted aliphatic hydrocarbon group, or a divalent, optionally substituted aliphatic hydrocarbon group bridging two units of the formula (2),

R⁴, which may be the same or different, is a methyl group or an ethyl group,

R⁵, which may be the same or different, 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, and

e is 0 , 1 , or 2 ) .

4. The method for forming a moisture curing-type coating material according to any one of claims 1 to 3, wherein the moisture curing-type coating material is a composition

including the following components:

(A) a silane terminal-modified polymer represented by the following general formula (1) : 5 to 100 parts by mass (Chemical formula 1)

Y- [ (CR¹ _2)b-SiR_{a (}OR²) _3-al_x (D

(in the formula,

Y is an x-valent organic polymer group bonded via

nitrogen, oxygen, sulfur, or carbon, having a

polyoxyalkylene or a polyurethane as a polymer chain; R, which may be the same or different, is a monovalent, optionally substituted, SiC-bonded hydrocarbon group;

x is an integer of 1 to 10;

a, which may be the same or different, is 0, 1, or 2; and b, which may be the same or different, is an integer of 1 to 10.);

(B) an amine compound: 0.01 to 10 parts by mass;

(C) a dehydrating agent: 0.01 to 10 parts by mass;

(D) a stabilizer: 0.01 to 5 parts by mass;

(E) a plasticizer: 0 to 95 parts by mass;

(F) a filler: 0 to 80 parts by mass; and

(G) a catalyst: 0 to 5 parts by mass,

5. The method for forming a moisture curing-type coating material according to any one of claims 1 to 4, wherein the substrate adjusting agent is a composition including the following components:

(H) a silane monomer or an oligomer, a silicone oil, a silicone resin or a mixture thereof, containing a unit represented by the following general formula (2) :

(Chemical formula 2)

R³c(R⁴0)_dR⁵eSi0(4-c-d-e)/2 (2)

(in the formula,

R³, which may be the same or different, is a hydrogen atom, a monovalent, SiC-bonded, optionally substituted aliphatic hydrocarbon group, or a divalent, optionally substituted aliphatic hydrocarbon group bridging two units of the formula (2), R⁴, which may be the same or different, is a methyl group or an ethyl group,

c is 0, 1, 2, or 3,

d is 0, 1, 2, 3, or 4, and

e is 0 , 1 , or 2 ) ;

(I) a surfactant: 0 to 40 parts by mass;

(J) a filler: 0 to 50 parts by mass; and

6. The method for forming a moisture curing-type coating material according to any one of claims 1 to 5, wherein the substrate is a cement-based substrate.

7. The method for forming a moisture curing-type coating material according to any one of claims 1 to 6, wherein the moisture curing-type coating material is used for any one or combination of purposes including protection and modification of the substrate, imparting aesthetic appearance to the substrate, bonding between the substrate and another material, sealing, and waterproof coating material.