JP6919147B1 - A moisture-curable composition and a method for producing a coating film using the moisture-curable composition. - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer having a hydrolyzable silyl group as a non-isocyanate-based binder, to have a low viscosity, to exhibit the maximum mechanical properties of a cured coating film after construction at an initial stage, and to provide a coating film. It is an object of the present invention to propose a coating film waterproof material composition having a small shrinkage. SOLUTION: A reactive material (C) having a predetermined reactivity is blended with a silane-modified polymer (A) and a silicone resin (B). Specifically, when the time (half-life of the silane-containing group) at which half the amount of the silane-containing group of the silane-modified polymer (A) is hydrolyzed is 1.0, the material (C) having reactivity under the same conditions. ) Is blended with the reactive material (C) having a time (half-life of the reactive group) in which half of the reactive group is hydrolyzed by 0.1 to 20 times. [Selection diagram] None

Description

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

A general coating film waterproofing material contains urethane, acrylic, chloroprene rubber, asphalt, silicone, etc. as a binder component, and is classified into a one-component type and a two-component type as product forms. Calcium carbonate, clay, carbon black, fine powdered silica, other pigments, thickeners, surfactants, stabilizers, diluents and the like are added to these binder components as mineral fillers.
In particular, urethane can satisfy various required characteristics such as high elongation and high strength, and has a very high degree of freedom in formulation design. It is used for various purposes such as materials, and is known as a binder that has been put into practical use and has a long track record.
However, since urethane contains highly reactive isocyanate, deisocyanate tends to be preferred from the viewpoint of harmfulness to the ecosystem and the environment.

On the other hand, polymers having a hydrolyzable silyl group are known as isocyanate-free moisture-curable polymers, and are used in industries such as adhesives, sealants, coating materials such as coating waterproofing materials and paints, construction, and civil engineering. , Electrical and electronic, etc. are used in a wide range of fields.
However, it has been difficult for a polymer having a hydrolyzable silyl group to exhibit mechanical properties such as high elongation and high strength required for a waterproof coating film.

Therefore, in Patent Document 1, by using a silicone resin as a crosslinkable adhesive having a urethane bond and having a low isocyanate content, an adhesive satisfying the European DIN EN 204 standard and durability class D4 is realized. However, since the viscosity is high during construction, problems remain in workability and finishability.
It is conceivable to use an organic solvent for the purpose of reducing the viscosity to improve the workability and finish, but from the viewpoint of harmfulness to the ecosystem and the environment, a solvent-free or water-based type tends to be required. In addition, since the organic solvent has a large coating film shrinkage rate due to volatilization from the cured coating film over time, there are problems such as cracks in the coating film and poor adhesion of the base material when the followability to a base material such as concrete is poor. there were.

By using a material having a reactivity that reacts with the base polymer that forms the organic matrix (coating active ingredient) after curing, it is possible to reduce the viscosity and shrinkage, but it is modulus over time. There is a problem that it takes time to develop the maximum mechanical properties of the cured product due to changes in the mechanical properties such as.

Japanese Patent Publication No. 2014-521819

The present invention has been made in view of the above circumstances, contains a polymer having a hydrolyzable silyl group as a non-isocyanate-based binder, has a low viscosity, and initially initializes the maximum mechanical properties of the cured coating film after construction. It is an object of the present invention to propose a coating film waterproofing material composition which is developed at the above stage and has a small coating film shrinkage.

As a result of diligent studies, the present inventors have added a material having a predetermined reactivity to a compound containing a silicone resin and containing a silane-modified polymer as a main component, thereby maximizing the machine for coating a coating film after construction. We have found a moisture-curable composition that develops physical properties at an early stage and gives a coating film with small shrinkage, and have completed the present invention.

In the moisture-curable composition of the present invention, the maximum mechanical properties of the cured coating film can be exhibited at an initial stage by using a material having the same degree of reactivity with the silane-modified polymer.
Specifically, the time (half-life of the silane-containing group) at which half the amount of the silane-containing group of the silane-modified polymer (A) is hydrolyzed under a predetermined condition (for example, the condition of pH 9) is set to 1.0. If the time (half-life of the reactive group) at which half the amount of the reactive group of the reactive material (C) under the same conditions is hydrolyzed is 0.1 to 20 times, then (A), The moisture-curable composition obtained by mixing (B) and (C) is applied, and the maximum mechanical properties can be exhibited at an initial stage of about one week after curing. The temperature for measuring the half-life may be any temperature as long as (A) and (B) are liquids, and may be, for example, a temperature of 20 ° C. or higher and 30 ° C. or lower. It is preferable that the temperature at which the half-life of the silane-containing group (A) is measured and the temperature at which the half-life of the reactive group (C) is measured are the same, but there may be a difference within ± 5 ° C. ..

Here, the maximum mechanical property is the maximum value of the mechanical property (50% modulus) obtained within 4 weeks after mixing (A), (B), and (C) and curing.
More specifically, when the silane-modified polymer (A) is a polymer having an alkoxysilyl group, the time (half-life) at which half the amount of alkoxysilane is hydrolyzed to silanol is set to 1.0, which is 0. By using a reactive material having a half-life of 1 to 20 times, it is possible to provide a moisture-curable composition in which changes in mechanical properties such as modulus are small with time.

The reactive material is a reactive diluent that has a reactive group that reacts with the silane-modified polymer and dilutes the moisture-curable composition containing the silane-modified polymer. , Oxim, acetone, acetic acid, amine, amide, etc. In particular, an alkoxysilane having a methoxy group or an ethoxy group is preferable.

When the half-life of the reactive material exceeds 20 times that of the silane-modified polymer, silanols of the hydrolyzed silane-modified polymer first form a silane-modified polymer matrix (crosslinked structure) by a dehydration condensation reaction. After that, the silanol groups of the reactive material that is gradually hydrolyzed undergo a dehydration condensation reaction to form a reactive material matrix, so that mechanical properties such as modulus tend to change significantly over time.

On the other hand, when the half-life of the reactive material is 0.5 times or more and 20 times or less with respect to the silane-modified polymer, the silane-modified polymer and the reactive material undergo a dehydration condensation reaction with each other. This allows the silane-modified polymer and the reactive material to form a matrix with each other. Therefore, it is possible to develop the maximum mechanical properties such as modulus at an early stage, and it is considered that the mechanical properties such as modulus do not change significantly with time.

Further, since the reactive material forms a matrix by reacting with the silane-modified polymer, shrinkage of the coating film due to volatilization of the diluent is less likely to occur as compared with the case where an organic solvent is used as the diluent.
The reactive material may be any material having a reactive group that reacts with the silane-modified polymer, and the content of the reactive group does not matter, but the effect of reducing the shrinkage of the coating film is the reactive material. It is particularly preferable that the amount of the reactive group contained in is not more than a predetermined amount (for example, 10% by weight or less). If the amount of the reactive groups is within this range, the amount of substances by-produced by the reaction of the reactive groups (for example, alcohol) evaporates from the coating film is small, so that the shrinkage of the coating film is further reduced. Is.

The lower limit of the amount of the reactive group is not particularly specified, but any reactive material having a predetermined amount or more (for example, 0.5% by weight or more) of the reactive group can be reacted with the silane-modified polymer. , It is more suitable because a sufficient amount is taken into the coating film.

Therefore, by using a material having a reactive group having a half-life of 0.1 to 20 times that of the silane-modified polymer in combination with the silane-modified polymer and the silicone resin, the silane-modified polymer and the silicone resin have sufficient mechanical properties as a coating film waterproofing material. The maximum mechanical properties of the cured coating after construction can be expressed at an early stage.
Further, when the content of the reactive group in the reactive material is 0.5% by weight or more and 10% by weight or less, a moisture-curable composition having a smaller coating film shrinkage can be realized.
Further, if the viscosity of the entire moisture-curable composition is lowered by a reactive material, the workability of the coating process of the moisture-curable composition is improved and the finish of the coating film is improved, which is preferable. ..

Hereinafter, the present invention will be described in detail.

The moisture-curable composition of the present invention may be in any form, form, and composition as long as it is in the form of at least one liquid and is cured by moisture to finally obtain a cured product of the composition. May be good. A typical coating material contains a polymer having an alkoxysilyl group, which is hydrolyzed by moisture and cured by the formation of a siloxane bond.

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

<About silane-modified polymer (A)>
The silane-modified polymer (A) in the present invention contains at least one moisture-reactive organosilyl group. This may be a terminal organosilyl group linked to one end of the polymer backbone. Preferably, it is a silane-modified polymer containing at least one polyoxyalkylene structural unit.
The silane-modified polymer (A) is not particularly limited as long as it is an organic polymer, and is, for example, a polyoxypropylene polymer, a polyoxybutylene polymer, a polyisobutylene polymer, a (meth) acrylic acid ester-based polymer, or a polymer thereof. It may be an organic polymer or the like using a plurality of.

The silane-modified polymer (A) may be a silane-modified polymer represented by the following general formula (1).
Y-[(CR ¹ ₂ ) _b- SiR _a (OR ² ) _3-a ] _x (1)
(In the formula (1), Y is an x-valent organic polymer group bonded via nitrogen, oxygen, sulfur or carbon, and the x-valent organic polymer containing polyoxyalkylene or polyurethane as a polymer chain. Is the basis and
R is a monovalent, optionally substituted SiC-linked hydrocarbon group that may be the same or different.
R ¹ may be the same or different, and is a monovalent, optionally substituted hydrocarbon group to which a nitrogen, phosphorus, oxygen, sulfur or carbonyl group can be attached to a hydrogen atom or carbon atom. And
R ² is a hydrogen atom, or a monovalent, optionally substituted hydrocarbon group, which may be the same or different.
x is an integer from 1 to 10
a is 0, 1, or 2,
b is an integer from 1 to 10. )

At least one of the terminal groups of the silane-modified polymer (A) may be a group represented by the following general formula (2) or general formula (3).
^{_{-O-C (= O) -NH-}} (CR 1 2) b -SiR a (OR 2) 3-a (2)
-NH-C (= O) -NR '- (CR 1 2) b -SiR a (OR 2) 3-a (3)
(In equations (2), (3), groups and subscripts have one of the definitions specified above for them.
R'may be the same or different and has a given definition for R. )

For example, in the silane-modified polymer represented by the general formula (1) having the terminal group represented by the general formula (2) or the general formula (3), half of the alkoxysilane is hydrolyzed to silanol under the condition of pH 9. The time (half-life) is less than 1 hour, and a matrix of moisture-curable compositions is formed by a dehydration condensation reaction between these silanols.

The polymer (A) as the silane-modified polymer is the main component of the moisture-curable composition and
It is a component that forms a film due to moisture after application.
The silane-modified polymer (A) can be purchased as a commercial product or can be prepared by common chemical methods. The polymer (A) may be a simple substance or a mixture of two or more kinds.
A so-called α-silane-terminated polymer having a reactive alkoxysilyl group bonded to adjacent urethane units via a methylene spacer is particularly suitable as the silane-modified polymer (A). This is because it is highly reactive and achieves a high curing rate when in contact with air, so there is no need to formulate a toxic tin catalyst. Commercially available α-silane terminal polymers are GENIOSIL® STP-E10 or STP-E30 from Wacker-Chemie AG.

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

Examples of substituted groups R are haloalkyl groups such as 3,3,3-trifluoro-n-propyl group, 2,2,2,2', 2', 2'-hexafluoroisopropyl group and heptafluoro. An isopropyl group and a haloaryl group, such as an o-, m- and p-chlorophenyl group.
The group R is preferably a monovalent hydrocarbon group optionally substituted with a halogen atom and having 1 to 6 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms. , More specifically, it contains a methyl group.

Examples of group R ¹ are hydrogen atoms, groups identified for R, and optionally substituted hydrocarbons attached to carbon atoms by nitrogen, phosphorus, oxygen, sulfur, carbon, or carbonyl groups. It is a group.
Preferably, R ¹ is a hydrocarbon group having a hydrogen atom and 1 to 20 carbon atoms, more specifically a hydrogen atom.

The example of group R ^{2 is} an example specified for a hydrogen atom or group R.
The group R ² is preferably substituted with a hydrogen atom or optionally a halogen atom and has an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. , More specifically, methyl and ethyl groups.

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

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

Examples of group R'are various steric isomers of cyclohexyl, cyclopentyl, n-propyl and isopropyl, n-butyl, isobutyl and tert-butyl, pentyl, hexyl, or heptyl groups, and also phenyl groups.
The group R'is preferably a group-CH (COOR ")-CH2-COOR" or optionally substituted hydrocarbon group having 1 to 20 carbon atoms, more preferably 1 to 20 groups. A linear group having a carbon atom, a branched group or a cycloalkyl group, or an aryl group having 6 to 20 carbon atoms and optionally substituted with a halogen atom.

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

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

Here, the polymer (A) is attached at any desired position in the polymer, eg, within and / or at the end of the chain, preferably within and at the end of the chain, more preferably at the end, in the manner described. group ^- can have a _{[(CR 1 2) b -SiR} a (OR 2) 3-a].

The terminal group of the polymer (A) is preferably the general formula (2) or the general formula (3).
^{_{-O-C (= O) -NH-}} (CR 1 2) b -SiR a (OR 2) 3-a (2)
-NH-C (= O) -NR '- (CR 1 2) b -SiR a (OR 2) 3-a (3)
(In equations (2), (3), groups and subscripts have one of the definitions specified above for them.
R is a monovalent, optionally substituted SiC-linked hydrocarbon group that may be the same or different.
R'may be the same or different and has a given definition for R. )

In one particularly preferred embodiment of the present invention, silane-modified polymer (A), in any case, -O-C (= O) -NH- (CR 1 2) b group or a -NH-C (= O _{^{) -NR. '- (CR 1}} 2) b group (R', R1 and b dimethoxymethylsilyl coupled by having) one of the definitions specified above, trimethoxysilyl, diethoxymethylsilyl Also included are silane-terminated polyethers and silane-terminated polyurethanes with triethoxysilyl-terminated groups, and more specifically silane-terminated polypropylene glycols and silane-terminated polyurethanes.

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

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

In the case of the first particularly preferable embodiment of the present invention, the silane-modified polymer (A) preferably has a linear or branched polyoxyalkylene group as the polymer group Y, more preferably their chain ends. by -O-C (= O) -NH- , 1 one group or more groups ^- containing _{[(CR 1 2) b -SiR} a (oR 2) 3-a] is coupled to a polyoxypropylene group .. Here, preferably at least 85% of the total chain ends, more preferably at least 90%, more particularly at least 95%, -O-C (= O) -NH- by a group - ^[(CR ₁ 2) _{b −} SiR _a (OR ² ) _3-a ] is bound.
The polyoxyalkylene group Y has a Mn (number average molecular weight) of 200 to 30,000, preferably 1,000 to 20,000. Suitable manufacturing methods for preparing such silane-modified polymers (A) and examples of silane-modified polymers (A) themselves are also known and include EP1535940B1 or EP1896523B1 which are included in the disclosures herein. It is mentioned in the publication. Corresponding silane-terminated polymers are also commercially available, for example, from Wacker Chemie AG under the name GENIOSIL® STP-E.

When chemically synthesizing the silane-modified polymer (A), for example, an addition reaction such as hydrosilylation, Michael addition, deal-alder addition, or between an isocyanate-functional compound and a compound containing an isocyanate-reactive group. It can be synthesized by various known production methods such as the reaction of.

The content of the silane-modified polymer (A) in the entire composition is not particularly limited, and is preferably in the range of 5 to 90 parts by mass, for example. When it is 5 parts by mass or more, a large amount of components other than the components forming the polymer matrix do not remain in the composition, sufficient performance as a composition is exhibited, and the amount of the polymer matrix to be formed is sufficient. This is because the required mechanical properties such as tensile strength, elongation, and tear strength are sufficient, defects such as poor adhesion and film cracking are less likely to occur as a cured product, and the possibility of causing harmful effects due to other components is reduced. Is. More preferably, it is in the range of 10 to 60 parts by mass.

<About silicone resin (B)>
When the silicone resin (B) is used together with the silicone resin (A), it is incorporated into a matrix of a coating film waterproofing material to exhibit high-strength mechanical properties.
The form of the silicone resin (B) is not particularly limited, and may be, for example, a liquid, a powder, a dispersion liquid, a sol, or the like, or may be coated with a powder.
The example of the silicone resin (B) typically contains the following general formula (4).
R ³ _c (R ⁴ O) _d R ⁵ _e SiO _{(4-c-d-e) / 2} (4)
(In equation (4),
R ³ may be the same or different, bridging two units of hydrogen atom, monovalent, SiC-bonded, optionally substituted aliphatic hydrocarbon group, or formula (4). It is a divalent, optionally substituted aliphatic hydrocarbon group,
R ⁴ may be the same or different, a methyl group or an ethyl group,
R ⁵ is a monovalent, SiC-linked, optionally substituted aromatic hydrocarbon group that may be the same or different.
c is 0, 1, 2, or 3 and
d is 0, 1, 2, 3 or 4 and
e is 0, 1, or 2,
c + d + e ≠ 0)

An example of a group R ^{3 is} an example of the aliphatic identified above for R. However, radicals R ³ may also, for example, links the two silyl groups of the formula (4) to each other, for example, an alkylene group having methylene, ethylene, propylene, or 1 to 10 carbon atoms, such as butylene It can also contain divalent aliphatic groups such as. One particular current example of a divalent aliphatic group is the ethylene group.
However, the group R3 is preferably optionally substituted with halogen atoms and is a monovalent SiC-linked aliphatic hydrocarbon atom group having 1 to 18 carbon atoms, more preferably 1 to 8 atoms. It contains an aliphatic hydrocarbon group having up to carbon atoms, more specifically a methyl group.

Examples of radicals R ⁴ is a hydrogen atom, or an example that is specified for radical R. Group R ⁴ is a hydrogen atom or is substituted by halogen atoms, an alkyl group having carbon atoms of from 1 to 10, alkyl group having carbon atoms of more preferably from 1 to 4, more specific It contains methyl and ethyl groups.

An example of group R ⁵ is the aromatic group identified above for R.
The radicals R ⁵ are preferably, optionally aromatic hydrocarbon radicals SiC- bonded with carbon atoms of 1 are substituted by halogen atoms up to 18, e.g., ethyl phenyl, tolyl, xylyl, chlorophenyl, naphthyl or, It contains a styryl group, more preferably a phenyl group.

Particularly preferred for use as the silicone resin (B) is that ^{at least 90% of all groups R 3} are methyl groups and at least 90% of all groups R ⁴ are methyl, ethyl, propyl or isopropyl groups. at least 90% is a silicone resin which is a phenyl group of all radicals R ^5.

According to the present invention, in each case, a silicone resin having at least 20%, more preferably at least 40% of the units of formula (4) where c is 0 is used based on the total number of units of formula (4). It is more preferable to do so.

In one embodiment of the invention, in each case, at least 10%, more preferably at least 20%, of the units of formula (4) where c represents a value of 2, based on the total number of units of formula (4). Yes, a silicone resin having 80% or less, more preferably 60% or less is used.

The preferentially used silicone resin, in each case, contains at least 80%, more preferably at least, at least 80% of the units of formula (4) where d represents a value of 0 or 1, based on the total number of units of formula (4). It has 95%.

In each case, based on the total number of units in equation (4), the units in equation (4) where d represents a value of 0 are at least 60%, more preferably at least 70%, preferably 99% or less, more. It is preferable to use a silicone resin having 97% or less.

More preferentially used as component (B) is, in each case, at least 1% of the units of equation (4) where e represents a non-zero value, based on the total number of units of equation (4). , Preferably at least 10%, more specifically at least 20% silicone resin. A silicone resin (B) having only the unit of formula (4) in which e is non-zero can be used, but more preferably at least 10%, very preferably at least 20% of the unit of formula (4). Preferably, 80% or less, more preferably 60% or less, is a silicone resin (B) in which e is 0.

In each case, use a silicone resin (B) having at least 20%, more preferably at least 40% of the units of formula (4) where e represents a value of 1, based on the total number of units of formula (4). Is prioritized. A silicone resin (B) having only the unit of the formula (4) in which e is 1, can be used, but more preferably at least 10%, very preferably at least 20% of the unit of the formula (4), and is preferable. Is 80% or less, more preferably 60% or less, is a silicone resin (B) in which e is 0.

Preferred is the silicone resin (B) which, in each case, has at least 50% of the units of formula (4) where the sum of c + e is 0 or 1 based on the total number of units of formula (4). ).

In one particularly preferred embodiment of the invention, in each case, at least 20% of the units of formula (4) where e is 1 and c is 0, based on the total number of units of formula (4). More preferably, a silicone resin having at least 40% is used as the base conditioner. In this case, preferably 70% or less, more preferably 40% or less of the total unit of the formula (4) has d other than 0.

In another particularly preferred embodiment of the present invention, the silicone resin used as component (B) is 1 in e and 0 in c, based on the total number of units of formula (4) in each case. The unit of the formula (4) is at least 20%, more preferably at least 40%, and the unit of the formula (4) in which c is 1 or 2, preferably 2, and e is 0 is at least 1. %, Preferably at least 10% of the resin. In this case, preferably 70% or less, more preferably 40% or less of all the units of the formula (4) have d other than 0, and at least 1% of all the units of the formula (4) have d. It is 0.

Examples of the silicone resin (B) used in accordance with the present invention are substantially, preferably exclusively, (Q) formula SiO _4/2 , Si (OR ¹¹ ) O _3/2 , Si (OR ¹¹ ) ₂ O _2/2 and Si (OR ¹¹ ) ₃ O _1/2 unit, (T) formula PhSiO _3/2 , PhSi (OR ¹¹ ) O _2/2 and PhSi (OR ¹¹ ) ₂ O _1/2 unit, It consists of the units of formula (D) Me ₂ SiO _2/2 and Me ₂ Si (OR ¹¹ ) O _1/2 , and the unit of formula (M) Me ₃ SiO _1/2 (Me is a methyl group in the formula). , Ph is a phenyl group and R ¹¹ is an alkyl group substituted with a hydrogen atom or optionally a halogen atom and having 1 to 10 carbon atoms, more preferably a hydrogen atom or 1 to 4 atoms. It is an alkylopolysiloxane resin having a carbon atom of (), which is preferably 0-2 mol (Q) units and 0-2 mol (0-2 mol) per mol of (T) units. Includes D) units, 0-2 mol (M) units.

Preferred examples of the silicone resin (B) used in accordance with the present invention are substantially, preferably exclusively, of the formula PhSiO _3/2 , PhSi (OR ¹¹ ) O _2/2 and PhSi (OR ¹¹ ) ₂ O ₁ It consists of a T unit of _{/ 2 and a D unit of the formula Me 2} SiO _2/2 and Me ₂ Si (OR ¹¹ ) O _1/2 (in the formula, Me is a methyl group and Ph is a phenyl group). , R ¹¹ is substituted with a hydrogen atom or optionally a halogen atom and has an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or 1 to 4 carbon atoms. It is an alkyl group and has a molar ratio of (T) units to (D) units of 0.5: 2.0.) Organopolysiloxane resin.

Further preferred examples of the silicone resin (B) used in accordance with the present invention are substantially, preferably exclusively, of the formula PhSiO _3/2 , PhSi (OR ¹¹ ) O _2/2 and PhSi (OR ¹¹ ) ₂ O. _1/2 of T units, and also the formula ^{_{MeSiO 3/2, MeSi (oR 11)}} O 2/2 and ^MeSi _{(oR 11) 2 O 1/2} of T units, and also, optionally, wherein _Me 2 SiO _Consists of D units of 2/2 and Me ₂ Si (OR ¹¹ ) O _1/2 (in the formula, Me is a methyl group, Ph is a phenyl group, and R ¹¹ is by a hydrogen atom or optionally a halogen atom. Substituted alkyl groups having 1 to 10 carbon atoms, more preferably alkyl groups having hydrogen atoms or 1 to 4 carbon atoms, 0.5 to 4. It has a molar ratio of 0 phenylsilicone units to methylsilicone units.) Organopolysiloxane resin. The amount of D units in these silicone resins (B) is preferably less than 10% by weight.

Further preferred examples of the silicone resin (B) used in accordance with the present invention are substantially, preferably exclusively, of the formula PhSiO _3/2 , PhSi (OR ¹¹ ) O _2/2 and PhSi (OR ¹¹ ) ₂ O. _It consists of 1/2 T units (in the formula, Ph is a phenyl group and R ¹¹ is an alkyl group substituted with a hydrogen atom or optionally a halogen atom and having 1 to 10 carbon atoms. , More preferably an alkyl group having a hydrogen atom or 1 to 4 carbon atoms.) Organopolysiloxane resin. The amount of D units in these silicone resins (B) is preferably less than 10% by weight.

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

The silicone resin (B) used according to the present invention can be either solid or liquid at 23 ° C. and 1,000 hPa, and the silicone resin (B) is preferably liquid. The silicone resin preferably has a viscosity of 10 to 100,000 mPa · s, preferably 50 to 50,000 mPa · s, more specifically 100 to 20,000 mPa · s. The silicone resin (B) has a polydispersity (Mw / Mn) of preferably 5 or less, more preferably 3 or less.

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

Solvents that can be used in this case include ethers (eg, diethyl ether, methyl tert-butyl ether, ether derivatives of glycol, THF), esters (eg, ethyl acetate, butyl acetate, glycol esters), hydrocarbons (eg, pentane). , Cyclopentane, hexane, cyclohexane, heptane, octane, or other long chain, branched and unbranched alkanes), ketones (eg acetone, methyl ethyl ketone), aromatics (eg toluene, xylene, ethylbenzene) , Chlorobenzene), or other alcohols (eg, methanol, ethanol, glycol, propanol, isopropanol, glycerol, butanol, isobutanol, tert-butanol).

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

The content of the silicone resin (B) with respect to the silane-modified polymer (A) is not particularly limited, and for example, the silane-modified polymer (A): the silicone resin (B) is preferably in the range of 5: 100 to 100: 5 parts by mass, and is 50. : 50 to 50: 200 is even more preferable, and the content of the silicone resin (B) with respect to the silane-modified polymer (A) is even more preferably less than 2.5 times.
Within the above range, a large amount of components other than the components forming the polymer matrix do not remain in the composition, sufficient performance as the composition is exhibited, and the amount of the polymer matrix to be formed is sufficient and is required. This is because mechanical properties such as tensile strength, elongation, and tear strength are sufficient, defects such as poor adhesion and film cracking are less likely to occur as a cured product, and the possibility of causing harmful effects due to other components is reduced. ..

<About reactive material (C)>
The reactive material (C) is not particularly limited as long as it contains a reactive group that has a predetermined half-life and reacts with the silane-modified polymer (A). It may be alcohol-based, oxime-based, carboxylic acid-based, amine-based, amide-based, or the like. These reactive materials react with the silane-modified polymer (A) in the presence of a catalyst such as a tin compound.
In the sense of diluting the silane-modified polymer (A), it is desirable that the viscosity of the reactive material (C) is lower than that of the silane-modified polymer (A). It is more preferable if the viscosity of the reactive material (C) is lower than 2,200 mPa · s.

The reactive material (C) is not particularly limited as long as it has a reactive group having a predetermined half-life, and may be, for example, a silane compound containing the following general formula (4).
R ³ _c (R ⁴ O) _d R ⁵ _e SiO _{(4-c-d-e) / 2} (4)
(In equation (4),
R ³ may be the same or different, bridging two units of hydrogen atom, monovalent, SiC-bonded, optionally substituted aliphatic hydrocarbon group, or formula (4). It is a divalent, optionally substituted aliphatic hydrocarbon group,
R ⁴ may be the same or different, a methyl group or an ethyl group,
R ⁵ is a monovalent, SiC-linked, optionally substituted aromatic hydrocarbon group that may be the same or different.
c is 0, 1, 2, or 3 and
d is 0, 1, 2, 3 or 4 and
e is 0, 1, or 2,
c + d + e ≠ 0)

The silane compound which is the reactive material (C) may be a single monomer or an oligomer obtained by polymerizing the same or different monomers, but the time required for half the amount of alkoxysilane to be hydrolyzed to silanol under the condition of pH 9. Matrix of moisture-curable composition by dehydration condensation reaction between silanols having a (half-life) of less than 20 hours and silanols of these silanols and the polymer (A) and / or silanols of one-ended modified silicone (C) as a material having the reactivity. To form.

The reactive material (C) may also be, for example, a compound containing the following general formula (5).
^{_{Y - [(CR 51 2)}} g -SiR 50 f (OR 52) 3-f] w (5)
(In formula (5), Y is an organic polymer group containing polyoxyalkylene or polyurethane as a w-valent polymer chain bonded via nitrogen, oxygen, sulfur or carbon.
R ⁵⁰ is a monovalent, optionally substituted SiC-linked hydrocarbon group that may be the same or different.
R ⁵¹ may be the same or different, and may be a monovalent, optionally substituted hydrocarbon group to which a nitrogen, phosphorus, oxygen, sulfur or carbonyl group can be attached to a hydrogen atom or carbon atom. And
R ⁵² is a hydrogen atom, or a monovalent, optionally substituted hydrocarbon group, which may be the same or different.
w is 1
f is 0, 1, or 2,
g is an integer from 1 to 10. )
The reactive material (C) in the above formula (5) has an average of one silane modifying group in one molecule of the reactive material (C). In the case of a one-ended modified type having a silane-modified group at only one terminal, a part of the terminal may remain unreacted.

The reactive material (C) may be, for example, a silane crosslinked polymer selected from the following general formulas (6) and (7).
R ^22- O-Z ^1- O-CO-NH- (CH ₂ ) -SiR ²⁰ _v (OR ²¹ ) _3-v (6)
R ^24- O-Z ^2- O-CO-NH- (CH ₂ ) _3- Si (OR ²³ ) ₃ (7)
^{(Z 1} in the formulas (6) and (7) represents a divalent polymer group containing no C-bonded hydroxyl group.
Z ² represents a divalent polymeric group containing no C-bonded hydroxyl groups,
R ²⁰ represents a monovalent, SiC-bonded, substituted hydrocarbyl group that may be the same or different.
R ²¹ represents a hydrogen atom or a monovalently substituted hydrocarbyl group which may be the same or different.
R ²³ represents a hydrogen atom or a monovalently substituted hydrocarbyl group which may be the same or different.
R ²² represents a monovalently substituted hydrocarbyl group.
R ²⁴ represents a monovalently substituted hydrocarbyl group.
v is 0 or 1, preferably 0)

The reactive material (C) of the general formulas (6) and (7) is a one-ended modified type, and the time (half-life) at which half the amount of alkoxysilane is hydrolyzed to silanol under the condition of pH 9 is long. A matrix of moisture-curable compositions is formed by the dehydration condensation reaction of these silanols with the silanols of the polymer (A) for less than 1 hour.

Examples of the general formula (6), group ^{R 20} in (7) are alkyl groups such as methyl group, ethyl group, n - propyl group, an isopropyl group, 1 - n - butyl group, 2 - n - butyl group, Isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group; hexyl group, eg n-hexyl group; heptyl group, eg n-heptyl group; Octyl group, eg n-octyl group, isooctyl group and 2, 2, 4-trimethylpentyl group; nonyl group, eg n-nonyl group; decyl group, eg n-decyl group; dodecyl group, eg n- Dodecyl group; octadecyl group, eg n-octadecyl group; cycloalkyl group, eg cyclopentyl group, cyclohexyl group, cycloheptyl group and methylcyclohexyl group; alkenyl group, eg vinyl group, 1-propenyl group and 2-propenyl group Aryl groups such as phenyl, naphthyl, anthryl and phenanthryl groups; alkaline groups such as o −, m −, p − tolyl groups; xsilyl and ethylphenyl groups; and aralkyl groups such as benzyl groups. , Α − and β − phenylethyl groups.

Examples of substituted radicals ^{R 20} is a haloalkyl group, e.g., 3,3,3-trifluoro -n- propyl group, 2,2,2,2 ', 2', 2'-hexafluoroisopropyl radical and hepta Fluoroisopropyl group, haloaryl group, for example o-, m- and p-chlorophenyl group.

The group R ²⁰ is preferably a monovalent hydrocarbyl group having 1 to 6 carbon atoms optionally substituted with a halogen atom, more preferably an alkyl group having 1 or 2 carbon atoms. More specifically, it is a methyl group.

^{The examples of the groups R 21} and R ^{23 in} the general formulas (6) and (7) are ^{examples in which a hydrogen atom or the group R 20} in the general formulas (6) and (7) is specified independently of each other.

The groups R ²¹ and R ²³ are independent of each other, preferably an alkyl group having 1 to 10 carbon atoms which may be substituted with a hydrogen atom or a halogen atom, more preferably 1 or 4 carbon atoms. Alkyl group having, more specifically, a methyl group or an ethyl group.

The examples of groups R ²² and R ^{24 in} the general formulas (6) and (7) are examples specified for the general formulas (6) and (7) groups R ^{20 independently of each other.}

The groups R ²² and R ²⁴ are independent of each other, preferably an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, and more preferably an alkyl having 1 to 6 carbon atoms. A group, more specifically a methyl group, an ethyl group, an n-propyl group or an n-butyl group.

In the examples of the general formulas (6) and (7) polymer groups Z ¹ and Z ² , independent of each other, a C-bonded hydroxyl group-free polyester group, a polyether group, a polyurethane group, a polyalkylene group or a polyacrylate group Is.

The polymer groups Z ¹ and Z ² are independent of each other, preferably as polymer chains of polyoxyalkylenes such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene. Copolymers and polyoxypropylene-polyoxybutylene copolymers; hydrocarbon polymers such as polyisobutylene or copolymers of polyisobutylene and isoprene; polychloroprene; polyisoprene; polyurethane; polyester; polyamide; polyacrylate; polymethacrylate; vinyl polymer and / Alternatively, it is an organic polymer group containing a polycarbonate (these do not contain a C-bonded hydroxyl group).

Particularly preferably the group Z ¹ and Z ² is a linear polyoxyalkylene groups that do not contain C-bonded hydroxyl groups.

The groups Z ¹ and Z ² are preferably at least 2 0 0 0 g / mol, more preferably at least 3 0 0 0 g / mol, and very preferably at least 4 0 0 0 g / mol. It has a number average molar mass (number average M n). They are preferably a maximum of 1100 g / mol, more preferably a maximum of 900 0 g / mol, and very preferably a maximum of 700 0 g / mol. Has n.

Here, the number average molar mass M n is detected by RI (refractive index detector) at 60 ° C. in THF and 1.2 ml / min with respect to the polystyrene standard in relation to the present invention. Determined by size exclusion chromatography (SEC) on an injection volume of 100 μl on polystyrene HR3-HR4-HR5-HR5 columns from Waters.

The polymer of formula (6) that can be used as the reactive material (C) is preferably of the following formula R ^22- O-Z ^1- OH (8).
Polymer and the following formula OCN- (CH ₂ ) -SiR _v (OR ²¹ ) _3-v (9)
It is prepared by reacting with silane of the above, and all the groups and subscripts in the formula have one of the definitions of the above general formulas (6) and (7).

The polymer of formula (7) that can be used as the reactive material (C) is preferably of the following formula R ^24- O-Z ^2- OH (10).
Polymer and the following formula OCN- (CH ₂ ) _3- Si (OR ²³ ) ₃ (11)
Prepared by reacting with silane in the formula, all groups and subscripts in the formula have one of the above definitions.

The reaction in this case is preferably predominantly a complete silane end, i.e. at least 90% of all OH functional chain ends present, more preferably at least 95%, more specifically at least 98%. This is done so that the silane end is present.

Preferably, the non-silane functional polymer of the formulas (8) and (10) has a maximum of 15 parts by mass, more preferably a maximum, when the reactive material (C) is 100 parts by mass. It can be contained in an amount of 10 parts by mass, more specifically up to 5 parts by mass.

Here, the polymers of the formulas (6) and (7) are, in principle, by the method described in EP 1 5 3 5 6 9 4 0 B 1 or EP 1 8 9 6 5 2 3 B 1. These methods can be prepared only in that the monofunctional polymers of formula (8) or formula (10) are used as the reactants and the stoichiometry of each of the reactants is adapted accordingly. It's different. Suitable preparation methods are further described in DE-A 1 0 2 0 1 3 2 1 6 8 52.

The polymers of formulas (6) and (7) are preferably prepared in the presence of a catalyst (KB). An example of an optionally used catalyst (KB) is a bismuth-containing catalyst, eg, trade name B or cy (R) from Bolchers Co., Ltd. (Bor cher s G mb H). Cat 2 2, B or c hi (R) K at V P 0 2 4 3 or B or c hi (R) K at V P 0 244, and other catalysts Is further described in Special Table 2016-534192.

When the catalyst (KB) is used for the preparation of the polymer of formula (6), the amount contained is based on 100 parts by mass of the OH functional polymer of formula (8) in each case. , Preferably 0. 0 0 1 to 5 parts by mass, more specifically 0. 0 5 to 1 parts by mass.

When a catalyst (KB) is used for the preparation of the polymer of formula (7), the amount contained is in each case relative to 100 parts by weight of the OH functional polymer of formula (10). Preferably 0. 0 0 1 to 5 parts by mass, more specifically 0. 0 5 to 1 parts by mass.

In the preparation of the polymer of formula (6) used according to the present invention, the reactants of formulas (8) and (9) are preferably 0. 9 ~ 2. 0 mol, preferably 0. 9 5 to 1. 6 moles, more preferably 1. 0 to 1. 4 moles of isocyanate groups are used in a quantitative ratio such that they are used per mole of hydroxyl functional groups.

In the preparation of the polymer of formula (7) used according to the present invention, the reactants of formulas (10) and (11) are preferably 0. 9 ~ 2. 0 mol, preferably 0. 9 5 to 1. 6 moles, more preferably 1. 0 to 1. 4 moles of isocyanate groups are used in a quantitative ratio such that they are used per mole of hydroxyl functional groups.

The average molecular weight M n of the polymers of formulas (6) and (7) is preferably at least 300 0 g / mol, preferably at most 800 g / mol, more preferably at maximum. It is 70 0 g / mol.

The viscosities of the polymers of formulas (6) and (7) were measured independently of each other at 20 ° C., preferably at least 0. 2 Pa · s, more preferably at least 0. 5 Pa · s, very preferably at least 1 Pa · s, preferably at most 10 Pa · s, more preferably at most 8 Pa · s, more specifically at most 5 Pa · s Is.

Polymers of formula that can be used as the material (C) having a reactive (6) is preferably of formula in one strand end in any case - O - C O - N H - (C H 2) - S i ( _{CH 3} ) (OCH ₃ ) Includes linear polyoxypropylene stopped at _2. At the other end, very preferably, these polymers have an alkyl group and are available, for example, from Wacker Chemie (Munich, Germany) for sale, GENIOSIL® X M. 20 can be mentioned.

Polymers of formula that can be used as the material (C) having a reactive (7), preferably in both cases the formula at one chain end - O - C O - N H - (C H 2) 3 - Includes linear polyoxypropylene stopped at Si (OCH ₃ ) _3. At the other end, very preferably, these polymers have an alkyl group and are available, for example, from Wacker Chemie (Munich, Germany). 25 can be mentioned.

The reactive material (C) may be a polymer of formula (6) only, a polymer of formula (7) only, or a mixture of polymers of formulas (6) and (7). The polymer represented by the formulas (6) and (7) may contain only one compound represented by the formulas (6) and (7), respectively, but is represented by the formulas (6) and (7). It can also contain multiple compounds.

The moisture-curable composition of the present invention preferably has a maximum of 80 parts by mass, more preferably a maximum of 70 parts by mass, preferably at least 5 parts by mass, and more preferably at least 5 parts by mass with respect to the entire moisture-curable composition. Contains material (C) that is reactive at a concentration of 10 parts by weight.

<Composition of waterproof coating film and each raw material>
The form and content of the coating material composition when the moisture-curable composition containing the silane-modified polymer (A) represented by the general formula (1) is coated on various substrates in various applications are not limited.
When a moisture-curable composition containing a silane-modified polymer is applied to a base material such as a building material or an industrial structure, which is a typical application, the following composition is preferable.
Silane-modified polymer (A): 5 to 90 parts by mass Silicone resin (B): 5 to 90 parts by mass Reactive material (C): 5 to 80 parts by mass Inorganic particles (D): 0 to 20 parts by mass Shaking Agent (E): 0 to 10 parts by mass Amin 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 Filling agent (I): 0 to 80 parts by mass Curing catalyst (J): 0 to 5 parts by mass However, the mass part of each component is a mass part when the entire moisture-curable composition is 100 parts by mass.

Inorganic particles (D), which are optionally blended, form a network in the system by their van der Waals force with respect to the moisture-curable composition of the present invention to thicken the entire system to a certain level or more. It gives the chixiness of.

Examples of the inorganic particles used as raw materials for the inorganic particles (D) include silica, titanium dioxide, bentonite, zinc oxide, talc, kaolin, mica, permiculite, magnesium carbonate, calcium carbonate, aluminum silicate, barium silicate, and silicic acid. Examples thereof include inorganic particles such as calcium, magnesium silicate, strontium silicate, metal tungstate, magnesium, zeolite, barium sulfate, calcined calcium sulfate, calcium phosphate, fluoroapatite, hydroxyapatite, and metal soap. Further, composite particles obtained by coating particles with a metal oxide or the like, or modified particles whose surface is treated with a compound or the like may be used.

Usually, the surface of these particles is a portion covered with a hydrophilic group such as a silanol group, a carbinol group, or another hydroxyl group, and a group obtained by hydrophobizing these groups with an alkyl group or the like, or another hydrophobic group. There is a part covered by the base of.
By adjusting the ratio of the hydrophilic group to the hydrophobic group, the cohesiveness and solubility of the inorganic particles in the system can be controlled.

Among the inorganic particles, it is preferable to use silica. There are various types of silica such as fumed silica, wet silica, colloidal silica, etc. In all types of silica particles, hydrophilic silanol is present on the surface and the silanol group is alkylated at an arbitrary ratio. Since the hydrophobic treatment with a group or the like can be performed, it is easy to set the molar ratio of the hydrophilic group to the hydrophobic group on the surface. Further, silica is preferable because it has a cohesive structure, has a high affinity with various oils, and can be used for a wide range of purposes from the viewpoints of availability, economy, and the like.

The most preferred silica in the present invention is fumed silica.
The fumed silica particles have a multi-order aggregated structure. Therefore, the balance between the hydrophilic group and the hydrophobic group on the surface can be controlled or the aggregation unit can be recombined according to the aggregation level.
Further, since the fumed silica particles have a porous structure, the surface area is increased and the functions of association and adsorption are further increased, so that the system can be produced more stably and uniformly.

The primary particles, which are the smallest units of fumed silica particles, usually have a size of about 5 to 30 nanometers, and the primary particles aggregate to form primary aggregates, that is, secondary particles. ..
The size of the primary aggregate is usually about 100 to 400 nanometers. Since the primary particles are fused by chemical bonds, it is usually difficult to separate the primary aggregates. Further, the primary aggregates form an aggregated structure, which is referred to as a secondary aggregate, that is, a tertiary particle. The size of the secondary aggregate is about 10 μm. The agglutination morphology between the primary agglomerates in the secondary agglomerates is usually due to hydrogen bonds or van der Waals forces rather than chemical bonds.

In powder form, fumed silica particles are often the largest agglomerated state of secondary agglomerates. However, secondary agglomerates can further agglomerate in the moisture-curable composition. That is, in the present invention, one of the cases is that the hydrophobic silica effectively forms a network with respect to the hydrophobic portion of the silane terminal-modified polymer and the reactive material (reactive diluent) by van der Waals force. This is an example. The force for separating the agglomerates can be separated with a force weaker than the force for separating the secondary agglomerates. That is, in the moisture-curable composition of the present invention, when it is applied with a comb iron or the like at the time of application, the viscosity at the time of action is reduced by separating the agglomerates, which is one example.

The fumed silica particles are preferably hydrophobized, and the components used for hydrophobization are not particularly limited. The components used for hydrophobization are, for example, organosilicon halides such as methyltrichlorosilane, alkoxysilanes such as dimethyldialkoxysilane, silazane, and low molecular weight methylpolysiloxane, which are hydrophobized by known methods of treatment. be able to.

The content of the inorganic particles (D) with respect to the entire composition is preferably 0.1 to 20 parts by mass, and if it exceeds 20 parts by mass, the viscosity of the entire system increases due to poor stirring during the production of the moisture-curable composition. This is because there is a possibility that non-uniformity and workability during construction will be significantly reduced. It is more preferably in the range of 1 to 10 parts by mass, still more preferably in the range of 2 to 5 parts by mass.

The component (E) as a rocking agent to be optionally blended is, for example, a hydrogenated castor oil type, an amide type, a polyethylene oxide type, a vegetable oil polymerized oil type, a surfactant type or the like in the organic system. The component (E) may be a single component, or two or more of these may be used in combination.

The amine compound (F) is a component that has the function of a curing catalyst or a curing co-catalyst with respect to the moisture-curable composition of the present invention, and can also act as an adhesion accelerator.
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 general chemical method.
The amine compound (F) may be a simple substance or a mixture of two or more kinds.

The amine compound (F) may be, for example, an organosilicon compound containing the unit of the general formula (12). An aminopropyltrimethoxysilyl group is mentioned as an example of the unit of the general formula (12).
D _h Si (OR ³¹ ) _i R ³² _j O _{(4-i-j-h) / 2} (12)
(In formula (12), R ³¹ represents a hydrogen atom or optionally substituted hydrocarbon group, which may be the same or different.
D represents a monovalent SiC-linked group containing basic nitrogen, which may be the same or different.
R ³² represents a monovalent SiC-linked organic group that may be the same or different and may be substituted if it does not contain basic nitrogen.
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.
h is 1, 2, 3, or 4, preferably 1, where the sum of f + g + h is 4 or less and there is at least one group D per molecule. )

The amine compound (F) can include not only silane, that is, the compound of the general formula (11) of i + j + h = 4, but also siloxane, that is, the unit of the formula (12) of i + j + h ≦ 3. Silane has priority.

The content of the amine compound (F) in the entire composition is preferably in the range of 0.01 to 10 parts by mass.
This is because if it is less than 0.01 parts by mass, poor curing and / or poor adhesion may occur. If it exceeds 10 parts by mass, it may cause unnecessary reactions, wrinkles on the film surface, deterioration of surrounding materials after the coating film is formed, and the pot life is shortened. This may cause construction defects. In addition, there is a possibility that problems such as thickening, gelation, and hardening may occur due to storage stability. More preferably, it is in the range of 0.5 to 3.0 parts by mass.

The dehydrating agent (G) is a component that dehydrates the moisture-curable composition of the present invention by trapping water.
The dehydrating agent (G) can be purchased as a commercial product or can be prepared by common chemical methods.
The component (G) may be a simple substance or a mixture of two or more kinds.

Examples of dehydrating agent (G) include silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, O-methylcarbamatemethyl-methyldimethoxysilane, O-methylcarbamatemethyl-trimethoxysilane, O-. Ethyl carbamate methyl-methyl diethoxysilane, O-ethyl carbamate methyl-triethoxysilane and / or a partial condensate thereof, and also orthoesters such as 1,1,1-trimethoxyethane, 1,1,1 -Triethoxyethane, trimethoxymethane and triethoxymethane.

The content of the dehydrating agent (G) in the entire composition may not be included, but is preferably in the range of 0.01 to 10 parts by mass. If it is less than 0.01 parts by mass, the dehydration effect is not sufficient, and problems such as thickening, gelling, and hardening may occur during manufacturing and storage. If it exceeds 10 parts by mass, the coating film may have problems. This is because it may cause harmful effects such as deterioration of physical properties, and it may cause poor curing or uncured after construction. More preferably, it is in the range of 0.5 to 3.0 parts by mass.

The stabilizer (H) has the functions of an ultraviolet absorber, an antioxidant, a heat stabilizer and a light stabilizer with respect to the moisture-curable composition of the present invention, and acts as a stabilizer for polymer deterioration. It is an ingredient that can also be used.
Stabilizer (H) can be purchased as a commercial product or can be prepared by common chemical methods.
The stabilizer (H) may be a simple substance or a mixture of two or more kinds.

The stabilizer (H) may be any one that exhibits the above-mentioned functions and actions, and is not limited, but is preferably an antioxidant, an ultraviolet stabilizer, and HALS.

The content of the stabilizer (H) in the entire composition is preferably in the range of 0.01 to 5 parts by mass. If it is less than 0.01 parts by mass, the coating film may be deteriorated due to ultraviolet rays, heat, oxidation, etc., and if it exceeds 5 parts by mass, unexpected defects such as color change in a transparent product may occur. Because there is a possibility of causing it. More preferably, it is in the range of 0.5 to 2.0 parts by mass.

The optional filler (I) has the functions of a bulking material, viscosity / viscosity adjustment, and physical property adjustment such as tensile strength and elongation with respect to the moisture-curable composition of the present invention, and is coated with the contained moisture. It is a component that can also act as a curing accelerator for the material. This component is not an essential component for the coating material composition of the present invention if the above functions and actions are not required.
Filler (I) can be purchased as a commercial product or can be prepared by common chemical methods.
The filler (I) may be a single substance or a mixture of two or more kinds.

The filler (I) may be any one exhibiting the above-mentioned functions and actions, and is not limited, but examples thereof include non-reinforcing fillers, preferably fillers having a BET surface area of up to 50 m2 / g, for example. Quartz, silica sand, diatomaceous soil, calcium silicate, zirconium silicate, talc, kaolin, zeolite, metal oxide powders such as aluminum oxide, titanium oxide, iron oxide, or zinc oxide and / or a mixture of them, barium sulfate. , Calcium carbonate, sucrose, silicon nitride, silicon carbide, boron nitride, glass powder and polymer powder, eg, polyacrylonitrile powder; reinforcing filler, filler with BET surface area greater than 50 m2 / g, eg prepared by thermal decomposition. Silica, precipitated silica, precipitated calcium carbonate, carbon black, eg furnace black and acetylene black and mixed silicon / aluminum oxide with high BET surface area; filler in the form of hollow beads of aluminum trihydroxide, eg Neuss, Germany. Magnetic microbeads, such as those available under the trade name Zeeospheres ™ from 3M Deutschland Polymers, eg, AKZONOBEL, Expancel, Sweden, of that type available under the trade name EXPANCEL®. Elastic polymer beads, or glass beads; fiber-shaped fillers, such as asbestos and also polymer fibers.
The filler may be hydrophobized, for example, with organosilanes and / or organosiloxanes, by treatment with stearic acid, or by etherification of hydroxyl groups to alkoxy groups.

The filler (I) is preferably calcium carbonate, talc, aluminum hydroxide and silica, with aluminum hydroxide being particularly preferred. The preferred grade of calcium carbonate is ground or precipitated and is optionally surface treated with fatty acids such as stearic acid or salts thereof. The preferred silica is preferably pyrolyzed (fumed) silica.

The filler (I) preferably has a water content of less than 1 part by mass, more preferably less than 0.5 parts by mass.

The content of the filler (I) in the entire composition is preferably in the range of 0 to 80 parts by mass. More preferably, it is in the range of 0 to 60 parts by mass. Within the above range, defects such as poor adhesion and cracking of the film are unlikely to occur, and the viscosity at the time of production is suitable, so that the mixture can be uniformly stirred.

The curing catalyst (J) is a component having a function of a curing catalyst with respect to the moisture-curable composition of the present invention. This component is not an essential component for the moisture-curable composition of the present invention when the above functions and actions are not required, but is effective when the reactivity of the silane terminal-modified polymer (A) is low. It is an ingredient.
The curing catalyst (J) can be purchased as a commercial product or can be prepared by common chemical methods.
The curing catalyst (J) may be a simple substance or a mixture of two or more kinds.

The curing catalyst (J) may have the above-mentioned functions and actions, and is not limited, but examples of the component (J) containing a metal are organic titanium and an organic tin compound, and examples are titanium acid esters. For example, tetrabutyl titanate, tetrapropyl titanate, tetraisopropyl titanate and tetraacetylacetonate titanium; tin compounds such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin dioctanoate, dibutyltin acetylacetonate, dibutyltin Oxides and corresponding dioctyltin compounds.

Examples of metal-free curing catalysts (J) include basic compounds such as triethylamine, tributylamine, 1,4-diazabicyclo [2.2.2] octane, 1,5-diazabicyclo [4.3.0]. Non-5-ene, 1,8-diazabicyclo [5.4.0] Undec-7-ene, N, N-bis- (N, N-dimethyl-2-aminoethyl) methylamine, N, N-dimethyl Cyclohexylamine, N, N-dimethylphenylamine and N-ethylmorpholinine.

It is similarly possible to use acidic compounds such as phosphoric acid and its esters, toluenesulfonic acid, sulfuric acid, nitric acid, or other organic carboxylic acids such as acetic acid and benzoic acid as the curing catalyst (J).

The content of the curing catalyst (J) in the entire composition is preferably in the range of 0 to 5 parts by mass. If it exceeds 5 parts by mass, construction defects may occur due to shortened pot life, wrinkles may occur on the film surface, and defects such as thickening, gelation, and hardening may occur during storage. Because. More preferably, it is in the range of 0 to 0.2 parts by mass.

The moisture-curable composition of the present invention may contain any component other than the above-mentioned components as long as the object of the present invention is achieved. For example, all other substances such as defoaming agents, curing rate modifiers, additives, adhesion improvers and auxiliaries can be included. In some cases, a component that improves adhesiveness, such as epoxysilane, can be added.

Examples and comparative examples will be shown, and the results will be described in Table 1 to explain the present invention in detail. However, the present invention is not limited to the following examples.

<Measurement of half-life>
For the half-life of the silane-modified polymer (A) and the reactive material (C), the substance to be measured ((A) or (C)) is added to an NMR solvent containing a commercially available buffer solution, and a mixed solution thereof is added. The hydrolysis reaction was started by stirring the mixture, and the measurement was carried out by measuring ^{the 1} H-NMR spectrum of these mixed solutions at a predetermined time immediately after the stirring.
For example, the silane-modified polymer (A) and the reactive material (C) used in Examples 1 and 2 all have a structure of _{−Si—O—CH 3.} In this case, the ratio between before hydrolysis (-Si-O-CH ₃ ) and after hydrolysis (CH ₃ OH) is measured, and the time until the amount of the substance before hydrolysis is halved is taken as the half-life.

As an example of the buffer solution, any one of the following three types may be used.
pH 4.0: Merck & Co. Buffer Solution Certipure® (citric acid / sodium hydroxide / hydrochloric acid)
pH 7.0: JT Baker's buffer solution (potassium dihydrogen phosphate / sodium hydrogen phosphate)
pH 9.0: Merck Buffer Solution Certipure® pH 9.0 (boric acid / potassium chloride / sodium hydroxide)
To 2250 μL of the buffer solution, 450 μL of heavy water containing sodium 3- (trimethylsilyl) propionate-2,2,3,3-d4 (Na-TSP-d4), which is a shift reagent and an internal standard, and 5 μL of the substance to be measured are added. Introduce into a 5 mm NMR sample tube.
¹ H-NMR was measured every 5 minutes at 25 ° C. using Bruker's NMR Avance DPX400.

<Viscosity measurement of moisture-curable composition>
The moisture-curable compositions obtained in Examples and Comparative Examples were measured after 60 seconds at a shear rate (10 (1 / s)) using a viscoelasticity measuring device (Physica MCR 301 / manufactured by Anton Pearl Co., Ltd.). The value was taken as viscosity.

<Viscosity evaluation criteria>
When the viscosity is less than 30,000 mPa · s, workability and finish are good.

<Line shrinkage rate>
The moisture-curable compositions of Examples 1 to 3 and Comparative Examples 1 to 5 are poured into a mold, smoothed with a spatula, and cured under the conditions of 23 ° C. ± 2 ° C. and humidity of 50% ± 5%. A cured sheet having a size of 150 mm × 150 mm × 2 mm was prepared, and the linear shrinkage rate (ratio of shrinkage with respect to the linear direction of 150 mm) of the coating film (cured product) after curing for 28 days was evaluated.

<Line shrinkage evaluation criteria>
When the linear shrinkage rate is less than 2%, the shrinkage rate of the coating film is particularly good.

<Tensile strength and elongation>
The tensile strength and elongation after curing for 1 week, 2 weeks, and 4 weeks were evaluated by the method (No. 3 dumbbell) described in JIS K6249 for the coating films of Examples 1 to 3 and Comparative Examples 1 to 5, respectively.

<Tensile strength and elongation evaluation criteria>
When the tensile strength was 2.3 or more and the elongation was 450 or more, the mechanical properties of the coating film were evaluated to be particularly good.

<Rate of change in mechanical properties>
Evaluate the 50% modulus (tensile stress when the test piece is stretched by 50%) cured for a predetermined period by the method (No. 3 dumbbell) described in JIS K6249 for the coating films of Examples 1 to 3 and Comparative Examples 1 to 5. bottom.

<Evaluation criteria for rate of change in mechanical properties>
When the ratio of the difference between the maximum value and the minimum value of the 50% modulus within 28 days to the 50% modulus after curing for 7 days is less than 20% for the coating films of Examples 1 to 3 and Comparative Examples 1 to 5. , It was judged that the maximum mechanical properties were expressed at the initial stage, and the rate of change in mechanical properties was evaluated to be good.

<Comprehensive evaluation of moisture-curable composition and coating film>
The coating film after construction has a low viscosity of the moisture-curable composition, the linear shrinkage rate of the obtained coating film after 28 days is less than 2%, and the rate of change of 50% modulus is less than ± 20%. It was used as a reference for solving the problems of the present invention of obtaining a coating film having a small shrinkage and manifestation of the maximum mechanical properties of the film at an initial stage.
It is more suitable if a coating film having high tensile strength and elongation can be obtained.

<Example 1>
The following components were used as the moisture-curable composition.
As the silane-modified polymer (A), GENIOSIL (registered trademark) STP-E30 manufactured by Wacker Chemie AG (viscosity is 30,000 mPa · s at 25 ° C., Y in the above general formula (1) is oxyalkylene as a polymer chain. It is a divalent organic polymer group bonded via a urethane group containing a group, and R, R ¹ and R ² are all methyl groups, a = 1, b = 1, and x =. 2) with respect to 25.0 parts by mass of the company's GENIOSIL® STP-E10 (10,000 mPa · s at a viscosity of 25 ° C., Y in the above general formula (1) is a polymer chain. It is a divalent organic polymer group bonded via a urethane group containing an oxyalkylene group, and R, R ¹ and R ² are all methyl groups, a = 1 and b = 1. , X = 2) as 10.0 parts by mass, silicone resin (B), SILRES® IC 678 (consisting of only phenyl functional T units, 15 wt% methoxy group content and 900 g). 15.0 parts by mass of liquid phenyl silicone resin having an average molar mass of / mol), and MENIOSIL XM20 manufactured by the same company as the reactive material (C) (content of reactive group is 1.2% by weight). 20.0 parts by mass, using the company's GENIOSIL (registered trademark) XL10 (vinyltrimethoxysilane) as 0.7 parts by mass as a vinylsilane-based dehydrating agent (G), and using the company's GENIOSIL as a stabilizer (H). 2.50 parts by mass of Stabilizer F (registered trademark) is added and stirred uniformly.
_{^{Y - [(CR 1 2)}} b -SiR a (OR 2) 3-a] x (1)

As inorganic particles (D), HDK (registered trademark) 2000 manufactured by the same company is 1.50 parts by mass, and as synthetic calcium carbonate as a filler of component (I), Ryton BS-O manufactured by Shiraishi Kogyo Co., Ltd. is 43.3 mass by mass. Partially add and mix and knead uniformly.
Further, as an amine compound (F), 2.00 parts of GENIOSIL (registered trademark) GF96 (3-aminopropyltrimethoxysilane) manufactured by Wacker Chemie AG was added, and the mixture was uniformly stirred to prepare a moisture-curable composition 1. Prepared.

The obtained moisture-curable composition is poured into a mold, smoothed with a spatula, and cured under the conditions of 23 ° C ± 2 ° C and humidity 50% ± 5% to react and cure with moisture in the air. , A coating film was obtained.

The half-life of the silane-containing groups of GENIOSIL® STP-E30, STP-E10, which is a silane-modified polymer (A), and the reactive groups of GENIOSIL® XM20, which is a reactive material (C), will be any. Was also one hour.
Therefore, the reactive group half-life of the reactive material (C) was one times the half-life of the silane-containing group of the silane-modified polymer (A).

As a result of measuring the viscosity of the moisture-curable composition 1, it was 22,700 mPa · s, which was lower than the reference value of 30,000 mPa · s, and good results were obtained. Therefore, workability and finish were good.
The linear shrinkage rate of the obtained coating film after 4 weeks was 0.3%, and the shrinkage of the obtained coating film was particularly small.
The tensile strength of the coating film was 3.1 MPa after 1 week and 3.3 MPa after 4 weeks, both of which exceeded 2.3 MPa, and had particularly sufficient tensile strength.
The elongation of the coating film exceeded 450 at all of the lapses of 1 week, 2 weeks, and 4 weeks, showing particularly good characteristics.
As a result of measuring the 50% modulus of the coating film, it was 0.8 after 1 week, the maximum value within 28 days was 0.8, and the minimum value was 0.7. Then, the rate of change was 12.5%, which was less than the reference value of 20%. Therefore, it can be said that good mechanical properties were exhibited from the initial stage.

From the above, it can be said that the moisture-curable composition 1 had a low viscosity, the shrinkage of the coating film was small, and the mechanical properties (50% modulus) were exhibited at the initial stage, so that the physical properties of the coating film were good.

<Example 2>
Other than using 20.0 parts by mass of SILRES® BS1316 (isooctyltrimethoxysilane, the content of reactive groups is 40% by mass) manufactured by the same company as the reactive material (C). The same components, the same number of parts by mass, and the same preparation method as in Example 1 were used to obtain a moisture-curable composition 2, and the same evaluation was performed.

The half-life of the silane-containing groups of GENIOSIL (registered trademark) STP-E30 and STP-E10, which are silane-modified polymers (A), is 1 hour, whereas SILRES (registered trademark), which is a reactive material (C), has a half-life of 1 hour. The half-life of the reactive group of BS1316 was 17 hours.
Therefore, the reactive group half-life of the reactive material (C) was 17 times the half-life of the silane-containing group of the silane-modified polymer (A).

As a result of measuring the viscosity of the moisture-curable composition 2, it was 7,800 mPa · s, which was lower than the standard value of 30,000 mPa · s, and good results were obtained. Therefore, workability and finish were good.
The linear shrinkage rate of the obtained coating film after 4 weeks was 1.9%, and the shrinkage of the obtained coating film was particularly small. The reactive group content of SILRES (registered trademark) BS1316 used as the reactive material (C) exceeded 10%, and the shrinkage rate was slightly increased as compared with Example 1 with respect to the decrease in alcohol produced by hydrolysis. It is probable that it was done.
The tensile strength of the coating film was 4.3 MPa after 1 week and 4.3 MPa even after 4 weeks, both of which exceeded 2.3 MPa, and had a particularly sufficient tensile strength.
The elongation of the coating film exceeded 450 at all of the lapses of 1 week, 2 weeks, and 4 weeks, showing particularly good characteristics.
As a result of measuring the 50% modulus of the coating film, it was 1.3 after 1 week, the maximum value within 28 days was 1.3, and the minimum value was 1.1. Then, the rate of change was 15.4%, which was less than the reference value of 20%. Therefore, it can be said that good mechanical properties were exhibited from the initial stage.

From the above, it can be said that the moisture-curable composition 2 had a low viscosity, the shrinkage of the coating film was small, and the mechanical properties (50% modulus) were exhibited at the initial stage, so that the physical properties of the coating film were good.

<Example 3>
As a silane-modified polymer (A), GENIOSIL (registered trademark) STP-E35 (viscosity is 30,000 mPa · s at 25 ° C., Y in the above general formula (1) is a urethane containing an oxyalkylene group as a polymer chain. It is a divalent organic polymer group bonded via a group, and R ¹ and R ² are both methyl groups, and a = 0, b = 3, and x = 2) are 25. With respect to 0.0 parts by mass, GENIOSIL® STP-E15 (viscosity of 10,000 mPa · s at 25 ° C., Y in the above general formula (1) contains an oxyalkylene group as a polymer chain. It is a divalent organic polymer group bonded via a urethane group, and R ¹ and R ² are both methyl groups, a = 0, b = 3, and x = 2). 10.0 parts by mass was used.
As the reactive material (C), 20.0 parts by mass of GENIOSIL® XM25 manufactured by the same company was used. The content of the reactive group of XM25 is 1.9% by weight.
Other than that, the same components as in Example 1, the same number of parts by mass and the preparation method were used to obtain a moisture-curable composition 3, and the same evaluation was performed.

The half-life of the silane-containing groups of GENIOSIL® STP-E35 and STP-E15, which are silane-modified polymers (A), is 1 hour, and that of GENIOSIL® XM25, which is a reactive material (C). The half-life of the reactive group was also 1 hour.
Therefore, the reactive group half-life of the reactive material (C) was one times the half-life of the silane-containing group of the silane-modified polymer (A).

As a result of measuring the viscosity of the moisture-curable composition 3, it was 23,000 mPa · s, which was lower than the reference value of 30,000 mPa · s, and good results were obtained. Therefore, workability and finish were good.
The linear shrinkage rate of the obtained coating film after 4 weeks was 0.3%, and the shrinkage of the obtained coating film was particularly small.
The tensile strength of the coating film was 4.0 MPa after 1 week and 4.3 MPa after 4 weeks, both exceeding 2.3 MPa, and had particularly sufficient tensile strength.
The elongation of the coating film exceeded 450, showing particularly good characteristics.
As a result of measuring the 50% modulus of the coating film, it was 1.0 after 1 week, the maximum value within 28 days was 1.1, and the minimum value was 1.0. Then, the rate of change was 10%, which was less than the reference value of 20%. Therefore, it can be said that good mechanical properties were exhibited from the initial stage.

From the above, it can be said that the moisture-curable composition 3 had a low viscosity, the shrinkage of the coating film was small, and the mechanical properties (50% modulus) were exhibited at the initial stage, so that the physical properties of the coating film were good.

<Comparative example 1>
The same evaluation was performed using the same components, the same number of parts by mass, and the preparation method as in Example 1 except that the reactive material (C) was not added.

As a result of measuring the viscosity of the moisture-curable composition, it was 59,000 mPa · s, which exceeded the standard value. Since the reactive material (C) that functions as a diluent is not contained, the viscosity cannot be reduced. Therefore, workability and finish were poor.
Although the linear shrinkage, tensile strength, and elongation were all good in the physical properties of the coating film, they are not preferable in that the viscosity of the moisture-curable composition is too high.

<Comparative example 2>
The same components and the same number of parts as in Example 1 except that 20.0 parts by mass of Shellzol MC421 (hydrocarbon solvent, which does not contain reactive groups) manufactured by Shell Chemicals Japan Co., Ltd. was used as a diluent. And the preparation method was used, and the same evaluation was performed.

As a result of viscosity measurement, it was 6,400 mPa · s, and workability and finish were good.
On the other hand, the result of the linear contraction rate measurement was 2.0, which exceeded the standard value. Since Shelsol MC421 used as a diluent does not have a reactive group, it is not incorporated into the matrix of the coating film, so it is considered that it volatilized over time and the shrinkage rate increased with respect to the decrease.
As a result of the tensile strength and elongation measurement, the physical characteristics of the coating film were all good.
As a result of 50% modulus measurement, it exceeded the standard value and was poor. That is, it was 2.8 after one week, the maximum value within 28 days was 3.5, and the minimum value was 2.8. Then, the rate of change was 25%, which exceeded the standard value of 20%. Therefore, it can be said that good mechanical properties could not be exhibited from the initial stage.
Since Shelsol MC421 used as a diluent does not have a reactive group, it is not incorporated into the matrix of the coating film. Therefore, it is considered that it volatilized with time and the 50% modulus changed with time.

As described above, although the moisture-curable composition of Comparative Example 2 had a low viscosity, the obtained coating film had a large shrinkage, and mechanical properties (50% modulus) could not be exhibited at an initial stage.

<Comparative example 3>
Other than using 20.0 parts by mass of SILRES (registered trademark) BS1701 (isooctyltriethoxysilane, content of reactive group is 49%) manufactured by Wacker Chemie AG as the reactive material (C). , All using the same components as in Example 1, the same number of parts by mass and the preparation method, and the same evaluation was performed.

The half-life of the silane-containing groups of GENIOSIL (registered trademark) STP-E30 and STP-E10, which are silane-modified polymers (A), is 1 hour, whereas SILRES (registered trademark), which is a reactive material (C), has a half-life of 1 hour. The half-life of the reactive group of BS1701 was 46 hours.
Therefore, the reactive group half-life of the reactive material (C) was 46 times the half-life of the silane-containing group of the silane-modified polymer (A).

As a result of measuring the viscosity of the moisture-curable composition 1, it was 6,300 mPa · s, which was lower than the standard value of 30,000 mPa · s, and good results were obtained. Therefore, workability and finish were good.
The linear shrinkage rate of the obtained coating film after 4 weeks was 3.0%, which exceeded the standard value.
It is considered that the reactive group content of SILRES (registered trademark) BS1701 used as the reactive material (C) exceeded 10%, and the shrinkage rate increased with respect to the decrease in alcohol produced by hydrolysis.
As a result of the tensile strength and elongation measurement, the physical characteristics of the coating film were all good.
As a result of 50% modulus measurement, it exceeded the standard value and was poor. That is, after 1 week, the maximum value was 1.3 and the maximum value within 28 days was 2.7, and the minimum value was 1.3. Then, the rate of change was 108%, which exceeded the standard value of 20%.
It is considered that the hydrolysis of SILRES (registered trademark) BS1701 used as the reactive material (C) was slow, the subsequent condensation reaction of silanol was also slow, and the 50% modulus changed with time.

As described above, although the moisture-curable composition of Comparative Example 3 had a low viscosity, the obtained coating film had a large shrinkage, and mechanical properties (50% modulus) could not be exhibited at an initial stage.

<Comparative example 4>
Other than using 20.0 parts by mass of SILRES (registered trademark) IC678 (silicone resin, content of reactive group is 15% by mass) manufactured by Wacker Chemie AG as the reactive material (C). , All using the same components as in Example 1, the same number of parts by mass and the preparation method, and the same evaluation was performed.

The half-life of the silane-containing groups of GENIOSIL (registered trademark) STP-E30 and STP-E10, which are silane-modified polymers (A), is 1 hour, whereas SILRES (registered trademark), which is a reactive material (C), has a half-life of 1 hour. The half-life of the reactive group of IC678 was 50 hours.
Therefore, the reactive group half-life of the reactive material (C) was 50 times the half-life of the silane-containing group of the silane-modified polymer (A).

As a result of the viscosity measurement, it was 26.5 mPa · s, which was lower than the standard value of 30,000 mPa · s, and good results were obtained. Therefore, workability and finish were good.
As a result of the linear contraction rate measurement, the linear contraction rate after 4 weeks was 1.3.
The reactive group content of SILRES® IC678 used as the reactive material (C) exceeded 10%, and the shrinkage rate increased with respect to the decrease in alcohol produced by hydrolysis as compared with Example 1. Conceivable.
The tensile strength was good, but the elongation was below the reference value of 450 at all of 1 week, 2 weeks, and 4 weeks. It is considered that the cross-linking point was significantly increased by SILRES® IC678 used as the reactive material (C).
On the other hand, as a result of 50% modulus measurement, it exceeded the reference value and was poor. That is, after 1 week, the maximum value was 5.3, the maximum value within 28 days was 14.0, and the minimum value was 5.3. Then, the rate of change was 164%, and the rate of change exceeded 20%. It is considered that the hydrolysis of SILRES® IC678 used as the reactive material (C) was slow, the subsequent condensation reaction of silanol was also slow, and the 50% modulus changed with time.

As described above, the moisture-curable composition of Comparative Example 4 had a low viscosity, and although the shrinkage of the obtained coating film was small, mechanical characteristics (50% modulus) could not be exhibited at an initial stage.

<Comparative example 5>
Other than using 20.0 parts by mass of SILRES (registered trademark) IC368 (silicone resin, content of reactive group is 15% by mass) manufactured by Wacker Chemie AG as the reactive material (C). , All using the same components as in Example 1, the same number of parts by mass and the preparation method, and the same evaluation was performed.

The half-life of the silane-containing groups of GENIOSIL (registered trademark) STP-E30 and STP-E10, which are silane-modified polymers (A), is 1 hour, whereas SILRES (registered trademark), which is a reactive material (C), has a half-life of 1 hour. The half-life of the reactive group of IC368 was 50 hours.
Therefore, the reactive group half-life of the reactive material (C) was 50 times the half-life of the silane-containing group of the silane-modified polymer (A).

As a result of measuring the viscosity of the moisture-curable composition, it was 30,400 mPa · s, which exceeded the standard value.
As a result of the linear contraction rate measurement, the linear contraction rate after 4 weeks was 1.3.
It is considered that the reactive group content of SILRES® IC368 used as the reactive material (C) exceeded 10%, and the shrinkage rate increased with respect to the decrease in alcohol produced by hydrolysis.
The tensile strength was good, but the elongation was below the standard value. It is considered that the cross-linking point was increased by SILRES® IC368 used as the reactive material (C).
As a result of 50% modulus measurement, the elongation was less than 50% after 4 weeks, and the data was not obtained. The rate of change was more than 20% when compared with the 50% modulus after 2 weeks when the measurement was possible. The hydrolysis of SILRES® IC368 used as the reactive material (C) was slow, the subsequent condensation reaction of silanol was slow, the 50% modulus changed over time, and the cross-linking points increased significantly. Conceivable.

As described above, the moisture-curable composition of Comparative Example 5 had a high viscosity and could not exhibit mechanical characteristics (50% modulus) at an initial stage.

Claims (7)

Silane-modified polymer (A) and
Silicone resin (B) and
Including the reactive material (C)
The silane-modified polymer (A) is represented by the following general formula (1).
The silicone resin (B) is
(Q) Equation SiO _4/2 , Si (OR ¹¹ ) O _3/2 , Si (OR ¹¹ ) ₂ O _2/2 and Si (OR ¹¹ ) ₃ O _1/2 units,
Unit (T) PhSiO _3/2 , PhSi (OR ¹¹ ) O _2/2 and PhSi (OR ¹¹ ) ₂ O _1/2,
(D) formula _Me 2 _{SiO 2/2} and _Me 2 ^{Si (OR} ₁₁₎ units _{O 1/2,} and
(M) _{Consists of units of formula Me 3} SiO 1/2 (in the formula, Me is a methyl group, Ph is a phenyl group, R ¹¹ is substituted with a hydrogen atom or a halogen atom, and 1 to 10 Alkyl group having 1 carbon atom, hydrogen atom or alkyl having 1 to 4 carbon atoms.) Organopolysiloxane resin, 0-2 per mole (T). Includes (Q) units of mol, (D) units of 0-2 mol, (M) units of 0-2 mol,
The reactive material (C) is a one-ended modified silicone represented by the following general formula (5), and has a reactive group that reacts with the silane-modified polymer (A).
Since the half-life of the reactive group is 0.1 to 20 times the half-life of the silane-containing group of the silane-modified polymer (A), the silane-modified polymer (A) and the material having the reactivity (C). ) Form a matrix with each other, and the change in mechanical properties over time is small.
Moisture curable composition.
^{_{Y - [(CR 1 2)}} b -SiR a (OR 2) 3-a] x (1)
(In formula (1), Y is an organic polymer group containing polyoxyalkylene or polyurethane as an x-valent polymer chain bonded via nitrogen, oxygen, sulfur or carbon.
R is a monovalent, unsubstituted or substituted SiC-linked hydrocarbon group, which may be the same or different.
R ¹ may be the same or different, and is a monovalent, unsubstituted or substituted hydrocarbon capable of attaching a nitrogen, phosphorus, oxygen, sulfur or carbonyl group to a hydrogen atom or a carbon atom. Is the basis and
R ² may be the same or different, a hydrogen atom or a monovalent, is a hydrocarbon radical which is unsubstituted or substituted,
x is 2,
a is 0, 1, or 2,
b is an integer from 1 to 10. )
^{_{Y - [(CR 51 2)}} g -SiR 50 f (OR 52) 3-f] w (5)
(In formula (5), Y is an organic polymer group containing polyoxyalkylene or polyurethane as a w-valent polymer chain bonded via nitrogen, oxygen, sulfur or carbon.
R ⁵⁰ is may be the same or different, monovalent, an unsubstituted or substituted SiC- bonded hydrocarbon radical,
R ⁵¹ may be the same or different, and is a monovalent, unsubstituted or substituted hydrocarbon capable of attaching a nitrogen, phosphorus, oxygen, sulfur or carbonyl group to a hydrogen atom or a carbon atom. Is the basis and
R ⁵² is a hydrogen atom, or a monovalent, unsubstituted or substituted hydrocarbon group, which may be the same or different.
w is 1
f is 0, 1, or 2,
g is an integer from 1 to 10. ) The moisture-curable composition according to claim 1, wherein the content of the reactive group in the reactive material (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 at least one of the terminal groups of the silane-modified polymer (A) is the following general formula (2) or general formula (3).
^{_{-O-C (= O) -NH-}} (CR 1 2) b -SiR a (OR 2) 3-a (2)
-NH-C (= O) -NR '- (CR 1 2) b -SiR a (OR 2) 3-a (3)
(In equations (2), (3), groups and subscripts have one of the definitions specified above for them.
R'may be the same or different and has a given definition 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 type according to any one of claims 1 to 4 , wherein the content of the silicone resin (B) with respect to the silane-modified polymer (A) is less than 2.5 times. Composition. A method for producing a coating film, which comprises curing the moisture-curing composition according to any one of claims 1 to 5 , which comprises 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 more and an elongation at break of 450% or more.