JP2024106825A - Composition set used in one-component curing composition - Google Patents

Abstract

[Problem] To provide a composition set for one-component curing compositions with good storage stability. [Solution] In one embodiment of the present invention, there is provided a composition set for use in one-component curing compositions, comprising a first composition and a second composition, wherein the first composition contains at least (A) a silicone having hydroxyl groups at both ends, (B) a crosslinking agent having a hydrolyzable group capable of undergoing a condensation reaction with the terminal hydroxyl groups of the silicone having hydroxyl groups at both ends, and (C) an adhesive aid having a hydrolyzable group, and the second composition contains at least (D) a catalyst for promoting the condensation reaction, and the hydrolysis rate of the component (C) is faster than that of the component (B). [Selected Figure] None

Description

The present invention relates to a composition set used in a one-component curing composition and a method for producing the same.

Polymers having hydrolyzable groups are known to be used as moisture-curing compositions, and because of their ease of handling, coatability, and various good functions, they are widely used as adhesives, sealants, waterproof coating materials, etc.

Known moisture-curing compositions include one-component curing compositions in which all components are filled in a mixed state, and two-component curing compositions in which two compositions with some of the components mixed are packaged separately and mixed at the time of use. Among these, one-component curing compositions are preferably used because they do not require complicated operations such as mixing when used.

Even if all the components of a one-component curing composition are mixed and stored in a sealed container, the curing reaction will proceed gradually due to small amounts of moisture (e.g., moisture in the air) that gets mixed in, so the expiration date is generally set based on the time when all the components are mixed. Therefore, if it takes time from manufacturing to supplying a one-component curing composition, there are cases where a sufficient expiration date cannot be guaranteed for sellers and users of the one-component curing composition.

In addition, in light of the recent risk of difficulties in procuring raw materials due to rising transportation costs and supply chain disruptions, concentrating all raw materials at a specific manufacturing site and manufacturing one-component curing compositions may be irrational from the economic perspective and from the perspective of ensuring a stable supply of products that include one-component curing compositions.

Therefore, from the viewpoint of ensuring the expiration date, economic aspects, and/or stable supply, there is a social need to produce an intermediate composition containing only some of the components, and then mix the other components at a desired time and/or place to produce a one-component curing composition.

Patent Document 1 discloses a set of moisture-curable compositions (i.e., two-component curing compositions) that are mixed at the time of use, but does not disclose a composition set intended to be used as a one-component curing composition.

JP 2001-1070023 A

It is known that one-component curing compositions do not normally cure or bond as desired with only a base polymer (e.g., silicone with hydroxyl groups at both ends) and a crosslinker, but cure and bond as desired with the presence of a catalyst and an adhesive assistant. In view of the properties of such one-component curing compositions and the above-mentioned social needs, the inventors have attempted to obtain a one-component curing composition by separately producing an intermediate composition containing silicone with hydroxyl groups at both ends and a crosslinker, and an intermediate composition containing an adhesive assistant and a catalyst, forming a composition set, storing them for a certain period of time, and then mixing them. When the physical properties of the obtained one-component curing composition were evaluated, the curing speed was sometimes significantly delayed depending on the timing of addition of each component, compared to a conventional one-component curing composition in which all components were mixed at once. In addition, a new problem was found in which the intermediate composition was denatured depending on the combination of each component constituting the one-component curing composition. Such a significant delay in the curing speed and denaturation problem leads to a decrease in work efficiency for consumers who use the one-component curing composition, and is a serious problem that cannot be tolerated in the market.

Therefore, the present invention provides a composition set of one-part curing compositions with good storage stability.

In view of the above problems, the present inventors conducted extensive research and unexpectedly discovered that a composition set of one-component curing compositions with good storage stability can be obtained by selecting an adhesive aid having a hydrolyzable group that has a faster hydrolysis rate than the crosslinking agent in a composition set consisting of a first composition containing a silicone with hydroxyl groups at both ends, a crosslinking agent, and an adhesive aid having a hydrolyzable group, and a second composition containing a catalyst, and thus completed the present invention.

Therefore, the present invention provides the following in summary.
[1] A composition set for use in a one-component curing composition, comprising a first composition and a second composition,
The first composition is
(A) a silicone having hydroxyl groups at both ends,
(B) a crosslinking agent having a hydrolyzable group capable of undergoing a condensation reaction with the terminal hydroxyl groups of the silicone having hydroxyl groups at both ends, and (C) an adhesive aid having a hydrolyzable group.
At least
The second composition is
(D) at least a catalyst that promotes a condensation reaction;
and wherein the component (C) has a faster hydrolysis rate than the component (B).
[2] The composition set according to [1], wherein the first composition and/or the second composition contains a silicone oil.
[3] The composition set according to [1] or [2], wherein the component (B) is an oxime silane crosslinking agent.
[4] The component (B) is represented by the following general formula (III):
(Wherein,
n is 1 to 4;
R ² and R ³ are independently hydrogen or a C ₁ -C ₁₀ alkyl group, a C 2 -C 10 alkenyl group, a C ₂ -C _{10 alkynyl} group, a C ₃ -C ₁₀ cycloalkyl group or a C ₃ -C ₁₀ cycloalkenyl group, each of which may be substituted _with one or more substituents;
R ⁴ , R ⁵ and R ⁶ are independently hydrogen or a C ₁ -C _{10 alkyl group, a C 2 -C 10} alkenyl group, a C ₂ -C ₁₀ alkynyl group, a C ₃ -C ₁₀ cycloalkyl group, a C ₃ -C ₁₀ cycloalkenyl group, a C ₆ -C ₁₀ aryl group or a C _{3 -C 10} heteroaryl group, each of which may be substituted with one or more _substituents ;
However, when n is 2, R ⁶ is not present, when n is 3, R ⁵ and R ⁶ are not present, and when n is 4, R ⁴ , R ⁵ and R ⁶ are not present.
The composition set according to any one of [1] to [3], having the structure:
[5] The composition set according to [4], wherein R ² is a C ₁ -C ₁₀ alkyl group optionally substituted with one or more substituents, and R ³ is a C ₁ -C ₁₀ alkyl group optionally substituted with one or more substituents.
[6] The component (B) is any one of the following:
The composition set according to any one of [1] to [5], comprising at least one selected from the group consisting of methyltris(methylethylketoxime)silane, vinyltris(methylethylketoxime)silane, tetra(methylethylketoxime)silane, phenyl(methylethylketoxime)silane, methyltris(methylisobutylketoxime)silane, vinyltris(methylisobutylketoxime)silane, tetra(methylisobutylketoxime)silane, methyltris(acetoxime)silane, vinyltris(acetoxime)silane, methyltris(2-pentanoxime)silane, and vinyltris(2-pentanoxime)silane.
[7] The composition set according to any one of [1] to [6], wherein the component (B) includes at least one selected from the group consisting of methyltris(methylethylketoxime)silane and vinyltris(methylethylketoxime)silane.
[8] The composition set according to any one of [1] to [7], wherein the component (C) is a silane coupling agent that does not have an oxime group bonded to a silicon atom.
[9] The component (C) is represented by the following general formula (IV):

(Wherein,
m is 1 to 3;
R ⁷ is a C ₁ -C ₆ alkyl group, a C _{2 -C 6 alkenyl group, a C 2} -C ₆ alkynyl group, a C ₃ -C ₆ cycloalkyl group or a C ₃ -C ₆ cycloalkenyl group, each of which may be substituted with one _{or more} substituents;
R ⁸ and R ⁹ are independently hydrogen or a C ₁ -C ₁₀ alkyl group, a C 2 -C 10 alkenyl group, a C ₂ -C 10 alkynyl group, a C 3 -C ₁₀ cycloalkyl group, a C ₃ -C ₁₀ cycloalkenyl group, a C ₆ -C ₁₀ aryl group, or a C _{3 -C 10} heteroaryl group, each of which may be _{substituted with} one or more _substituents ;
R ¹⁰ is a C ₁ -C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, or a C ₂ -C ₆ alkynyl group, optionally substituted with one or more substituents;
R ¹¹ and R ¹² are independently hydrogen or a C ₁ -C ₁₀ alkyl group, a C 2 -C 10 alkenyl group, a C ₂ -C 10 alkynyl group, a C ₃ -C ₁₀ cycloalkyl group, a C ₃ -C ₁₀ cycloalkenyl group, a C ₆ -C ₁₀ aryl group, or a C _{3 -C 10} heteroaryl group, each of which may be substituted _with one or more _substituents ;
provided that when m is 2, R ⁹ is absent, and when m is 3, R ⁸ and R ⁹ are absent.
The composition set according to any one of [1] to [8], having the structure:
[10] The composition set according to [9], wherein R ⁷ is a C ₁ -C ₆ alkyl group optionally substituted with one or more substituents.
[11] The component (C) is any one of the following:
The composition set according to any one of [1] to [10], comprising at least one member selected from the group consisting of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, and N-cyclohexyl-3-aminopropyltrimethoxysilane.
[12] The composition set according to any one of [1] to [11], wherein the component (D) is a tin-based catalyst.
[13] The composition set according to any one of [1] to [12], wherein the first composition contains 0.01 to 30 parts by mass of the component (B) relative to 100 parts by mass of the total amount of the first composition and the second composition.
[14] The composition set according to any one of [1] to [13], wherein the first composition contains 0.01 to 30 parts by mass of the component (C) relative to 100 parts by mass of the total amount of the first composition and the second composition.
[15] A one-component curing composition comprising the first composition and the second composition according to any one of [1] to [14].
[16] A method for producing a one-component curing composition comprising at least (A) a silicone having hydroxyl groups at both ends, (B) a crosslinking agent having a hydrolyzable group capable of undergoing a condensation reaction with the terminal hydroxyl groups of the silicone having hydroxyl groups at both ends, (C) an adhesion aid having a hydrolyzable group, and (D) a catalyst for promoting the condensation reaction, comprising:
A first composition including the component (A), the component (B), and the component (C);
a step of mixing the second composition containing the component (D),
The method, wherein the component (C) has a faster hydrolysis rate than the component (B).
[17] A first composition for use in combination with a second composition as a composition set of a one-component curing composition, comprising:
The first composition is
(A) a silicone having hydroxyl groups at both ends,
(B) a crosslinking agent having a hydrolyzable group capable of undergoing a condensation reaction with the terminal hydroxyl groups of the silicone having hydroxyl groups at both ends, and (C) an adhesive aid having a hydrolyzable group.
At least
The second composition is
(D) at least a catalyst that promotes a condensation reaction;
The first composition, wherein the component (C) has a faster hydrolysis rate than the component (B).
[18] A second composition for use in combination with a first composition as a composition set of a one-component curing composition, comprising:
The first composition is
(A) a silicone having hydroxyl groups at both ends,
(B) a crosslinking agent having a hydrolyzable group capable of undergoing a condensation reaction with the terminal hydroxyl groups of the silicone having hydroxyl groups at both ends, and (C) an adhesive aid having a hydrolyzable group.
At least
The second composition is
(D) at least a catalyst that promotes a condensation reaction;
The second composition, wherein the component (C) has a faster hydrolysis rate than the component (B).

According to one embodiment of the present invention, it is possible to provide a composition set of one-component curing compositions having good storage stability. Furthermore, according to one embodiment of the present invention, the first composition and the second composition can be mixed at a desired timing to obtain a one-component curing composition, so that by simply changing the type of catalyst contained in the second composition, a wide range of one-component curing compositions can be provided according to the desired application and curing speed.

[Definition]
As used herein, the term "C ₁ -C ₁₀ hydrocarbon group" refers to a group containing 1 to 10 carbon atoms and a hydrogen atom. The C ₁ -C ₁₀ hydrocarbon group may be linear, branched, or cyclic, and may be saturated or unsaturated. The C 1 -C 10 hydrocarbon group may contain one or more ring structures. The C ₁ -C ₁₀ hydrocarbon group may have one or more nitrogen atoms, oxygen atoms, sulfur atoms, etc. at its terminals or in the molecular chain. Examples of the C ₁ -C ₁₀ hydrocarbon group include, but are not limited to, a C ₁ -C ₁₀ alkyl group, a C _{2 -C 10} alkenyl group, a _{C 2} -C ₁₀ alkynyl group, a C ₃ -C ₁₀ cycloalkyl group, a C ₃ -C ₁₀ cycloalkenyl group, a C ₆ -C ₁₀ aryl group, and a C ₃ -C ₁₀ heteroaryl group.

As used herein, a "C ₁ -C ₁₀ alkyl group" refers to a saturated linear or branched chain hydrocarbon group containing from 1 to 10 carbon atoms, including, but not limited to, for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl (e.g., n-hexyl), heptyl (e.g., n-heptyl), octyl (n-octyl, isooctyl, 2,2,4-trimethylpentyl), nonyl (e.g., n-nonyl), decyl (e.g., n-decyl), and the like. As used herein, a "C ₁ -C ₆ alkyl group" refers to a saturated linear or branched chain hydrocarbon group containing from 1 to 6 carbon atoms. As used herein, a "C ₁ -C ₃ alkyl group" refers to a saturated linear or branched chain hydrocarbon group containing from 1 to 3 carbon atoms.

As used herein, a " _C2 - _C10 alkenyl group" refers to a linear or branched hydrocarbon group containing from 2 to 10 carbon atoms and having at least one unsaturated double bond, including, but not limited to, for example, ethenyl (vinyl), propenyl, isopropenyl, butenyl, pentenyl, hexenyl, etc. As used herein, a " _C2 - _C6 alkenyl group" refers to a linear or branched hydrocarbon group containing from 2 to 6 carbon atoms and having at least one unsaturated double bond.

As used herein, a " _C2 - _C10 alkynyl group" means a linear or branched hydrocarbon group containing from 2 to 10 carbon atoms and having at least one unsaturated triple bond, including, but not limited to, for example, acetynyl, propargyl, etc. As used herein, a " _C2 - _C6 alkynyl group" means a linear or branched hydrocarbon group containing from 2 to 6 carbon atoms and having at least one unsaturated triple bond,

As used herein, " _C3 - _C10 cycloalkyl group" means a saturated monocyclic or bicyclic hydrocarbon group containing from 3 to 10 carbon atoms, including, but not limited to, for example, cyclopropyl, cyclobutyl, cyclohexyl, cycloheptyl, and the like.

As used herein, a " _C3 - _C10 cycloalkenyl group" means a monocyclic or bicyclic hydrocarbon group containing from 3 to 10 carbon atoms and having at least one unsaturated double bond, including, but not limited to, for example, cyclopropenyl, cyclobutenyl, cyclohexenyl, and the like.

As used herein, a " _C6 - _C10 aryl group" may be either monocyclic or polycyclic (e.g., bicyclic or tricyclic) containing from 6 to 10 carbon atoms in the ring structure, and examples include, but are not limited to, phenyl, naphthyl, and the like.

As used herein, a " _C3 - _C10 heteroaryl group" is a group that contains 3 to 10 carbon atoms in the ring structure and one or more oxygen atoms, nitrogen atoms and/or sulfur atoms in the ring structure and may be either monocyclic or polycyclic (e.g., bicyclic or tricyclic), and examples thereof include, but are not limited to, phenyl, naphthyl, furyl, thienyl, pyridyl, indolyl, quinolyl, isoquinolyl, imidazolyl, etc.

As used herein, "hydroxyl group" refers to a group represented by "-OH."

As used herein, "C ₁ -C ₁₀ alkoxy group" means a group having the structure of the formula "-O-C ₁ -C ₁₀ alkyl group", including, but not limited to, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, and the like.

As used herein, "aldehyde group" refers to a group having the structure "-C(=O)H."

As used herein, "carboxyl group" refers to a group having the structure "-C(=O)OH."

As used herein, "ester group" refers to a group having the structure "-C(=O)O-R" (where R represents a hydrocarbon group).

As used herein, "acyloxy group" refers to a group having the structure "-O-C(=O)-R" (where R represents a hydrocarbon group).

As used herein, an "amide group" refers to a group having the structure "-C(=O)NR(R')" (wherein R and R' are independently hydrogen or a hydrocarbon group). Thus, the amide group includes a carbamoyl group (-C(=O)NH ₂ ), a monoalkylcarbamoyl group (e.g., a methylcarbamoyl group), a dialkylcarbamoyl group (e.g., a dimethylcarbamoyl group), and the like.

As used herein, an "amino group" refers to a group represented by "-NR ₂ ", where each R independently represents hydrogen or a hydrocarbon group. When all R are hydrogen, the group is a primary amino group, when one R is hydrogen, the group is a secondary amino group, and when neither of the two R are hydrogen, the group is a tertiary amino group.

As used herein, "halogen group" refers to, for example, fluorine, chlorine, bromine, and iodine.

As used herein, "thiol group" refers to a group represented by "-SH."

As used herein, "imino group" refers to a group having the structure "RN=C(R')-" (wherein R and R' independently represent any substituent).

As used herein, an "oxime group" refers to a group having the structure "R ₂ C═N—O—" (wherein each R independently represents an optional substituent).

The term "substituent" as used herein means a substituent including a hydrocarbon group, a hydroxyl group, a _C1 - _C10 alkoxy group, an aldehyde group, a carboxyl group, an ester group, an acyloxy group, an amide group, an amino group, a halogen group, a thiol group, an imino group, an oxime group, and the like, as defined herein.

The term "hydrolyzable group" as used herein is not particularly limited as long as it is a group that can be hydrolyzed. Examples of hydrolyzable groups include, but are not limited to, carboxyl groups, ester groups, alkoxy groups, amide groups, imino groups, halogen groups, oxime groups, and acyloxy groups.

The term "hydrolysis rate" used in this specification refers to the rate at which a hydrolyzable group is hydrolyzed. The hydrolysis rate may be, for example, based on literature values, or may be calculated or estimated thermochemically (for example, by a thermochemical equation) with reference to these literature values, or may be experimentally measured or calculated by a known method, a method described in this specification, or a method similar thereto. In addition, as a simple method for evaluating the hydrolysis rate, for example, a mixture of a crosslinking agent (component (B)) and/or an adhesive aid (component (C)) and water is left at a predetermined temperature, and the state of the mixture after a certain time is confirmed, and it can be visually judged whether the mixture has separated into two phases, whether there is a sudden change in the viscosity of the mixture, etc. Details will be described later.

[Configuration of composition set]
In one embodiment of the present invention, there is provided a composition set for use in a one-component curing type composition, comprising a first composition and a second composition,
The first composition is
(A) a silicone having hydroxyl groups at both ends,
(B) a crosslinking agent having a hydrolyzable group capable of undergoing a condensation reaction with the terminal hydroxyl groups of the silicone having hydroxyl groups at both ends, and (C) an adhesive aid having a hydrolyzable group.
At least
The second composition is
(D) at least a catalyst that promotes a condensation reaction;
The present invention provides a composition set in which the component (C) has a faster hydrolysis rate than the component (B).

The "first composition" used in this specification is not particularly limited as long as it contains at least (A) a silicone having hydroxyl groups at both ends, (B) a crosslinking agent having a hydrolyzable group capable of undergoing a condensation reaction with the terminal hydroxyl group of the silicone having hydroxyl groups at both ends, and (C) an adhesive aid having a hydrolyzable group, the hydrolysis rate of the component (C) being faster than that of the component (B), and a one-component curing composition can be obtained by mixing with the second composition described in this specification.

[Component (A)]
The "silicone having hydroxyl groups at both ends" (also referred to as "component (A)" in the present specification) is not particularly limited as long as it is a silicone having hydroxyl groups at both ends and capable of undergoing a condensation reaction in the presence of a crosslinking agent. Silicone having hydroxyl groups at both ends is typically a siloxane-based polymer having hydroxyl groups at both ends.

The silicone having hydroxyl groups at both ends is, for example, represented by the following general formula (I):
(wherein A is a siloxane-containing polymer chain).
A may have the following structure: A is not particularly limited as long as it is a siloxane-containing polymer chain, and may be either linear or branched.

A is preferably represented by the following general formula (II):
(wherein each R ¹ is independently a C ₁ -C ₁₀ hydrocarbon group optionally substituted with one or more substituents, and s is 0, 1, or 2.)
The siloxane unit has the structure:

When the silicone having hydroxyl groups at both ends contains siloxane units having the structure of general formula (II), it may be composed of a single type of main chain (i.e., only one type of siloxane unit having the structure of general formula (II)) or may be composed of two or more types of main chains (i.e., two or more types of siloxane units having the structure of general formula (II)). When two or more types of main chains are contained, the number of repetitions of each siloxane unit may be the same or different. When the silicone having hydroxyl groups at both ends contains siloxane units having the structure of general formula (II), it is preferable that it is composed of a single type of main chain (i.e., only one type of siloxane unit having the structure of general formula (II)).

When the silicone having hydroxyl groups at both ends contains a siloxane unit having the structure of general formula (II), it may be linear, or it may be branched including a trifunctional type (R ¹ SiO _2/3 ) and/or a tetrafunctional type (R ¹ SiO ₂ ), or it may be a combination of a difunctional type (R ¹ ₂ SiO) and/or a monofunctional type (R ¹ ₃ SiO _1/2 ).

In one embodiment of the present invention, each R ¹ is independently a C ₁ -C ₁₀ alkyl group, a C ₃ -C ₁₀ cycloalkyl group or a C ₆ -C ₁₀ aryl group, each optionally substituted with one or more substituents, preferably a C ₁ -C ₁₀ alkyl group, each optionally substituted with one or more substituents, more preferably a C ₁ -C ₆ alkyl group, each optionally substituted with one or more substituents, even more preferably a methyl, ethyl, propyl or butyl, each optionally substituted with one or more substituents, and even more preferably methyl.

In one embodiment of the present invention, s is 2.

In one embodiment of the present invention, each R ¹ is independently a C ₁ -C ₁₀ alkyl group, a C ₃ -C ₁₀ cycloalkyl group or a C ₆ -C ₁₀ aryl group, optionally substituted with one or more substituents, and s is 2; preferably, each R ¹ is independently a C ₁ -C ₁₀ alkyl group, optionally substituted with one or more substituents, and s is 2; more preferably, each R ¹ is independently a C ₁ -C ₆ alkyl group, optionally substituted with one or more substituents, and s is 2; even more preferably, each R ¹ is independently methyl, ethyl, propyl or butyl, optionally substituted with one or more substituents, and s is 2; even more preferably, each R ¹ is methyl and s is 2.

In one embodiment of the present invention, the silicone having hydroxyl groups at both ends is α,ω-dihydroxypolydimethylsiloxane.

The number average molecular weight (Mn) of the silicone with hydroxyl groups at both ends is not particularly limited, but is, for example, about 5,000 to about 150,000 g/mol, preferably about 25,000 to about 120,000 g/mol, and more preferably about 60,000 to about 100,000 g/mol.

The viscosity of the silicone having hydroxyl groups at both ends is not particularly limited, but is, for example, about 100 to about 500,000 mPa·s, preferably about 1,000 to about 200,000 mPa·s, more preferably about 10,000 to about 100,000 mPa·s, and even more preferably about 40,000 to about 60,000 mPa·s at 23°C. The viscosity may be measured, for example, with a rotational viscometer (e.g., BL type, BH type, BS type, cone-plate type, rheometer) or the like.

In a preferred embodiment of the present invention, the silicone having hydroxyl groups at both ends is an α,ω-dihydroxypolydimethylsiloxane having a viscosity of about 100 to about 500,000 mPa·s (preferably about 1,000 to about 200,000 mPa·s, more preferably about 10,000 to about 100,000 mPa·s, and even more preferably about 40,000 to about 60,000 mPa·s).

The content of silicone with hydroxyl groups at both ends is not particularly limited as long as the object of the present invention can be achieved. The content of silicone with hydroxyl groups at both ends is, for example, about 10 to about 95 parts by mass, preferably about 15 to about 90 parts by mass, more preferably about 20 to about 80 parts by mass, and even more preferably about 30 to about 75 parts by mass, per 100 parts by mass of the first composition and the second composition combined. Alternatively, the content of silicone with hydroxyl groups at both ends is, for example, about 10 to about 95 parts by mass, preferably about 15 to about 90 parts by mass, more preferably about 20 to about 80 parts by mass, and even more preferably about 30 to about 75 parts by mass, per 100 parts by mass of the first composition.

[Component (B)]
The "crosslinking agent having a hydrolyzable group capable of undergoing a condensation reaction with the terminal hydroxyl groups of the silicone having hydroxyl groups at both ends" (also referred to as the "crosslinking agent" or "component (B)" in the present specification) is not particularly limited as long as it is a crosslinking agent that contains one or more hydrolyzable groups in the molecule capable of undergoing a condensation reaction with the terminal hydroxyl groups of the silicone having hydroxyl groups at both ends. Typical examples of crosslinking agents include those containing silicon atoms.

The crosslinking agent may be a compound having one silicon atom (e.g., a silane derivative) or a compound having two or more silicon atoms. When the crosslinking agent is a compound having two or more silicon atoms, the crosslinking agent may have a structure in which the silicon atoms are linked by siloxane bonds crosslinked with oxygen, and the molecular skeleton may be linear, branched, or cyclic.

The crosslinking agent may have a reactive functional group (e.g., a primary amino group, an epoxy group, a (meth)acryloyl group, a (meth)acryloxy group, a mercapto group, an isocyanato group, etc.) in addition to the hydrolyzable group. In this case, the crosslinking agent having such a reactive functional group not only contributes to the condensation reaction but can also function as an adhesion promoter, etc.

The crosslinking agent preferably has a hydrolyzable group bonded to a silicon atom. When the crosslinking agent contains multiple silicon atoms in the molecule, each hydrolyzable group may be bonded to the same silicon atom or to different silicon atoms.

Examples of crosslinking agents in which a hydrolyzable group is bonded to a silicon atom include those in which an oxime group is bonded as a hydrolyzable group (also called oxime silane crosslinking agents, for example, those having the structure of general formula (IIII) described later); those in which an alkoxy group is bonded as a hydrolyzable group (also called alkoxy silane crosslinking agents, for example, tetramethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, tetraethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, silane, phenyltriethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, dimethyldimethoxysilane, vinylmethyldimethoxysilane, dimethyldiethoxysilane, 3-chloropropyltrimethoxysilane, tetrakis(2-ethoxyethoxy)silane, methyltris(2-methoxyethoxy)silane, vinyl(2-ethoxyethoxy)silane, phenyltris(2-methoxyethoxy)silane, partial hydrolysis condensates thereof, etc.); ₂ " (wherein each R is independently hydrogen or a hydrocarbon group) is bonded (also called an enoxysilane-based crosslinking agent, for example, methyltripropenoxysilane, methyltriisopropenoxysilane, vinyltriisopropenoxysilane, phenyltriisopropenoxysilane, dimethyldiisopropenoxysilane, methylvinyldiisopropenoxysilane, and partial hydrolysis condensation products thereof); those having an acyloxy group bonded as a hydrolyzable group (also called an acyloxysilane-based crosslinking agent, for example, methyltriacetoxysilane and partial hydrolysis condensation products thereof); and the like, which may be used alone or in combination of two or more. As the crosslinking agent in which a hydrolyzable group is bonded to a silicon atom, an oxime silane-based crosslinking agent or an alkoxy silane-based crosslinking agent is preferred, and an oxime silane-based crosslinking agent is more preferred.

In one embodiment of the present invention, the crosslinking agent has the following general formula (III):
(Wherein,
n is 1 to 4;
R ² and R ³ are independently hydrogen or a C ₁ -C ₁₀ alkyl group, a C 2 -C 10 alkenyl group, a C ₂ -C _{10 alkynyl} group, a C ₃ -C ₁₀ cycloalkyl group or a C ₃ -C ₁₀ cycloalkenyl group, each of which may be substituted _with one or more substituents;
R ⁴ , R ⁵ and R ⁶ are independently hydrogen or a C ₁ -C _{10 alkyl group, a C 2 -C 10} alkenyl group, a C ₂ -C ₁₀ alkynyl group, a C ₃ -C ₁₀ cycloalkyl group, a C ₃ -C ₁₀ cycloalkenyl group, a C ₆ -C ₁₀ aryl group or a C _{3 -C 10} heteroaryl group, each of which may be substituted with one or more _substituents ;
However, when n is 2, R ⁶ is not present, when n is 3, R ⁵ and R ⁶ are not present, and when n is 4, R ⁴ , R ⁵ and R ⁶ are not present.
It has the structure:

In one embodiment of the present invention, ^R2 is a _C1 - _C10 alkyl group optionally substituted with one or more substituents, preferably a _C1 - _C6 alkyl group optionally substituted with one or more substituents, more preferably methyl, ethyl or isobutyl.

In one embodiment of the present invention, ^R3 is a _C1 - _C10 alkyl group optionally substituted with one or more substituents, preferably a _C1 - _C6 alkyl group optionally substituted with one or more substituents, more preferably methyl, ethyl or isobutyl.

In one embodiment of the present invention, R ² is a C ₁ -C 10 alkyl group optionally substituted with one or more substituents and R ³ is a C ₁ -C ₁₀ alkyl group optionally substituted with one or more substituents, preferably R ² is a C ₁ -C ₆ alkyl group optionally substituted with one or more substituents and R ³ is a C ₁ -C ₆ alkyl group optionally substituted with one or _more substituents, more preferably R ² is methyl, ethyl or isobutyl and R ³ is methyl, ethyl or isobutyl.

In one embodiment of the present invention, n is 2, 3 or 4, preferably 3 or 4.

In one embodiment of the present invention, ^R4 is a _C1 -C10 alkyl group, a C2- _C10 alkenyl group or a _C6 - _C10 aryl group, optionally substituted with _one or more substituents, preferably a _C1 - _C6 alkyl group, _{a C2} - _C6 alkenyl group or a _C6 aryl group, optionally substituted with one or more substituents, more preferably methyl, ethenyl or phenyl.

In one embodiment of the invention, the crosslinking agent is:
The compound includes at least one selected from the group consisting of methyltris(methylethylketoxime)silane, vinyltris(methylethylketoxime)silane, tetra(methylethylketoxime)silane, phenyl(methylethylketoxime)silane, methyltris(methylisobutylketoxime)silane, vinyltris(methylisobutylketoxime)silane, tetra(methylisobutylketoxime)silane, methyltris(acetoxime)silane, vinyltris(acetoxime)silane, methyltris(2-pentanoxime)silane, and vinyltris(2-pentanoxime)silane.

In one embodiment of the present invention, the crosslinking agent includes at least one selected from the group consisting of methyltris(methylethylketoxime)silane and vinyltris(methylethylketoxime)silane.

The content of the crosslinking agent is not particularly limited as long as the object of the present invention can be achieved. The content of the crosslinking agent is, for example, about 0.01 to about 30 parts by mass, preferably about 0.1 to about 20 parts by mass, more preferably about 1 to about 15 parts by mass, and even more preferably about 3 to about 10 parts by mass, relative to 100 parts by mass of the total amount of the first composition and the second composition described below. Alternatively, the content of the crosslinking agent is, for example, about 0.01 to about 30 parts by mass, preferably about 0.1 to about 20 parts by mass, more preferably about 1 to about 15 parts by mass, and even more preferably about 3 to about 10 parts by mass, relative to 100 parts by mass of the first composition.

The ratio of the silicone with hydroxyl groups at both ends (component (A)) and the crosslinking agent (component (B)) is not particularly limited as long as the object of the present invention can be achieved, but for example, the ratio of component (B) is about 0.01 to about 50 parts by mass, preferably about 0.1 to about 40 parts by mass, more preferably about 0.5 to about 30 parts by mass, even more preferably about 1 to about 25 parts by mass, and even more preferably about 5 to about 15 parts by mass, per 100 parts by mass of component (A).

[Component (C)]
The term "adhesive aid having a hydrolyzable group" used in this specification (also referred to simply as "adhesive aid" or "component (C)" in this specification) is not particularly limited as long as it has one or more hydrolyzable groups and can aid adhesion to an adherend. It is preferable that the hydrolyzable group of the adhesive aid does not have an oxime group, since an oxime compound that can be generated by hydrolysis of the adhesive aid may affect the appearance (e.g., color tone).

As the adhesive aid, a silane coupling agent is preferred from the viewpoint of adhesive strength, etc. Silane coupling agents usually have an organic functional group and a hydrolyzable group bonded to a silicon atom. Depending on the type of organic functional group, the silane coupling agent may be, for example, an amino group-containing silane coupling agent (e.g., N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane); a vinyl group-containing silane coupling agent (e.g., vinyltrimethoxysilane, vinyltriethoxysilane, diethoxymethylvinylsilane); a (meth)acrylic group-containing silane coupling agent (e.g., 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane); an isocyanate group-containing Examples of suitable coupling agents include silane coupling agents (e.g., 3-isocyanatepropyltriethoxysilane); epoxy group-containing silane coupling agents (e.g., 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane); ureido group-containing silane coupling agents (e.g., 3-ureidopropyltriethoxysilane); mercapto group-containing silane coupling agents (e.g., 3-mercaptopropyltrimethoxysilane); and the like. These may be used alone or in combination of two or more.

As the adhesion aid, an amino group-containing silane coupling agent or a vinyl group-containing silane coupling agent is preferred, and an amino group-containing silane coupling agent is more preferred. As the adhesion aid, a silane coupling agent that does not have an oxime group as a hydrolyzable group bonded to a silicon atom is preferred. As the adhesion aid, an amino group-containing silane coupling agent that does not have an oxime group bonded to a silicon atom is more preferred.

In one embodiment of the present invention, the adhesive aid has the following general formula (IV):
(Wherein,
m is 1 to 3;
R ⁷ is a C ₁ -C ₆ alkyl group, a C _{2 -C 6 alkenyl group, a C 2} -C ₆ alkynyl group, a C ₃ -C ₆ cycloalkyl group or a C ₃ -C ₆ cycloalkenyl group, each of which may be substituted with one _{or more} substituents;
R ⁸ and R ⁹ are independently hydrogen or a C ₁ -C ₁₀ alkyl group, a C 2 -C 10 alkenyl group, a C ₂ -C 10 alkynyl group, a C 3 -C ₁₀ cycloalkyl group, a C ₃ -C ₁₀ cycloalkenyl group, a C ₆ -C ₁₀ aryl group, or a C _{3 -C 10} heteroaryl group, each of which may be _{substituted with} one or more _substituents ;
R ¹⁰ is a C ₁ -C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, or a C ₂ -C ₆ alkynyl group, optionally substituted with one or more substituents;
R ¹¹ and R ¹² are independently hydrogen or a C ₁ -C ₁₀ alkyl group, a C 2 -C 10 alkenyl group, a C ₂ -C 10 alkynyl group, a C ₃ -C ₁₀ cycloalkyl group, a C ₃ -C ₁₀ cycloalkenyl group, a C ₆ -C ₁₀ aryl group, or a C _{3 -C 10} heteroaryl group, each of which may be substituted _with one or more _substituents ;
provided that when m is 2, R ⁹ is absent, and when m is 3, R ⁸ and R ⁹ are absent.
It has the structure:

In one embodiment of the present invention, m is 2 or 3.

In one embodiment of the invention, R ⁷ is a C ₁ -C ₆ alkyl group optionally substituted with one or more substituents, preferably a C ₁ -C ₃ alkyl group optionally substituted with one or more substituents, more preferably methyl or ethyl.

In one embodiment of the invention, R ⁸ is a C ₁ -C ₆ alkyl group optionally substituted with one or more substituents, preferably methyl or ethyl, more preferably methyl.

In one embodiment of the present invention, R ¹⁰ is a C ₁ -C ₆ alkyl group optionally substituted with one or more substituents, preferably a C ₁ -C ₃ alkyl group optionally substituted with one or more substituents, more preferably methyl, ethyl, propyl or isopropyl, and even more preferably propyl.

In one embodiment of the invention, R ¹¹ is hydrogen.

In one embodiment of the present invention, R ¹² is hydrogen or a C ₁ -C ₁₀ alkyl group or a C 3 -C 10 cycloalkyl group optionally substituted with one or more substituents, preferably hydrogen or a C ₁ -C ₁₀ alkyl group or a C ₃ -C ₁₀ cycloalkyl group optionally substituted with one or more amino groups, more preferably hydrogen, aminomethyl, diaminomethyl, triaminomethyl, ₁ -aminoethyl, 2-aminoethyl, 1,2-diaminoethyl, cyclopentyl, cyclohexyl or cycloheptyl, and even more preferably ₂ -aminoethyl or cyclohexyl.

In one embodiment of the invention, the adhesion promoter is:
The compound includes at least one member selected from the group consisting of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, and N-cyclohexyl-3-aminopropyltrimethoxysilane.

The content of the adhesive aid is not particularly limited as long as the object of the present invention can be achieved. The content of the adhesive aid is, for example, about 0.01 to about 30 parts by mass, preferably about 0.05 to about 20 parts by mass, more preferably about 0.1 to about 10 parts by mass, and even more preferably about 0.5 to about 5 parts by mass, per 100 parts by mass of the total amount of the first composition and the second composition described below. Alternatively, the content of the adhesive aid is, for example, about 0.01 to about 30 parts by mass, preferably about 0.05 to about 20 parts by mass, more preferably about 0.1 to about 10 parts by mass, and even more preferably about 0.5 to about 5 parts by mass, per 100 parts by mass of the first composition.

The ratio of the crosslinking agent (component (B)) to the adhesive aid (component (C)) is not particularly limited as long as the object of the present invention can be achieved, but for example, the amount of the (C) component is about 0.01 to about 300 parts by mass, preferably about 0.1 to about 100 parts by mass, more preferably about 0.5 to about 50 parts by mass, even more preferably about 5 to about 30 parts by mass, and even more preferably about 10 to about 20 parts by mass, per 100 parts by mass of the (B) component. Alternatively, the ratio of the (B) component to the (C) component is, for example, about 0.001 to about 100 mol, preferably about 0.01 to about 30 mol, more preferably about 0.05 to about 10 mol, and even more preferably about 0.1 to about 3 mol, per 1 mol of the (B) component. Alternatively, the ratio of the (B) component to the (C) component is, for example, about 0.001 to about 30 mol, preferably about 0.003 to about 10 mol, more preferably about 0.01 to about 3 mol, and even more preferably about 0.03 to about 1 mol of the hydrolyzable group of the (C) component per 1 mol of the hydrolyzable group of the (B) component.

In the invention described herein, it is important that the adhesive aid (component (C)) has a faster hydrolysis rate than the crosslinking agent (component (B)). By having these two components (component (B) and component (C)) coexist in the same composition (first composition), coloring and denaturation that are thought to be caused by hydrolysis of the crosslinking agent can be suppressed. When the hydrolyzable groups are exemplified by amide groups, acyloxy groups, oxime groups, and alkoxy groups, it is generally believed that the hydrolysis rate is faster in the order of amide groups > acyloxy groups > oxime groups > alkoxy groups. Therefore, for example, when both components (B) and (C) have hydrolyzable groups bonded to silicon atoms, the following combinations of hydrolyzable groups in component (B) and component (C) are exemplified.

On the other hand, it is generally believed that hydrolyzable groups become less susceptible to hydrolysis as the number of carbon atoms increases and/or the structure becomes bulkier. Therefore, a person skilled in the art will understand that there may be cases where the combinations shown in the above table are not achieved. And, since a person skilled in the art can naturally imagine such cases, he or she will also understand that it is possible to evaluate which of the desired crosslinking agent and the desired adhesive aid has a faster (or slower) hydrolysis rate by using experimental scientific techniques, etc., which will be described later.

When the crosslinking agent and the adhesive aid have the same type of hydrolyzable group (for example, when the crosslinking agent and the adhesive aid have an alkoxy group as a hydrolyzable group), it is possible to confirm or estimate which of the crosslinking agent and the adhesive aid has a faster (slower) hydrolysis rate, taking into account the number of carbon atoms and bulkiness of the hydrolyzable group. Even in such a case, it is possible to evaluate which of the desired crosslinking agent and the desired adhesive aid has a faster (slower) hydrolysis rate, using the experimental science techniques described below.

The hydrolysis rate may be affected by other components present in the reaction system (e.g., components that have catalytic activity for the hydrolysis reaction) and the pH and temperature of the reaction system. Therefore, a person skilled in the art can confirm or estimate which of the crosslinking agent and the adhesive aid has a faster (or slower) hydrolysis rate, taking into account the composition of the components contained in the first composition, the pH and temperature of the first composition, etc. Even in such a case, it may be possible to evaluate which of the desired crosslinking agent and the desired adhesive aid has a faster (or slower) hydrolysis rate, using the experimental science techniques described below.

The hydrolysis rate can be evaluated by, for example, calculating the reaction rate constant using the Arrhenius equation or an Arrhenius plot, and determining whether the hydrolysis rate of the crosslinking agent or the adhesive aid is faster (or slower) based on the calculated reaction rate constant.

Alternatively, the hydrolysis rate may be calculated or evaluated experimentally, for example, by mixing a desired crosslinker and/or a desired adhesive aid with water under desired conditions (e.g., room temperature), measuring the amount of the crosslinker and/or adhesive aid in the mixture after a predetermined time has elapsed using a known method (e.g., mass spectrometry, nuclear magnetic resonance spectroscopy, infrared spectroscopy or Fourier transform infrared spectroscopy, ultraviolet-visible spectroscopy, chromatography such as gas chromatography, liquid chromatography or size exclusion chromatography, or a combination thereof), and comparing the amount of the crosslinker and/or adhesive aid before mixing with water to measure the amount of the product in the mixture using a known method, or by evaluating the physical properties of the mixture (e.g., pH, viscosity, color tone, turbidity, presence or absence of precipitates such as crystals, absorbance, transmittance, reflectance, temperature, miscibility with water, or a combination thereof) visually or with a desired device. If it is difficult or inappropriate to calculate, evaluate, etc. the hydrolysis rate based on the physical properties of the resulting mixture, the hydrolysis rate may be calculated, evaluated, etc. by further measuring the amount of the crosslinker and/or the amount of the crosslinker in the mixture and/or the amount of the product.

In general, it is believed that the hydrolysis rate and the activation energy have an inverse correlation. Therefore, when it is not possible to directly calculate the hydrolysis rate, the activation energy can be calculated with reference to the method disclosed in the literature (e.g., T. Ozawa, Bull. Chem. Soc. Jpn., 38, 1881 (1965)), and it can be estimated based on the calculated activation energy whether the hydrolysis rate of the crosslinking agent or the adhesive assistant is faster (or slower).

In addition to components (A), (B), and (C), the first composition may contain various additives such as plasticizers, fillers, thixotropic regulators, solvents, anti-sagging agents, antioxidants, antioxidants, pigments (dyes), flame retardants, dehydrating agents, antistatic agents, UV absorbers, surfactants (including leveling agents), and dispersants, as necessary, within the scope of the object of the present invention.

The "second composition" used in this specification is not particularly limited as long as it contains at least a catalyst (D) that promotes a condensation reaction and can give a one-component curing composition by mixing with the first composition.
[Component (D)]

The term "catalyst for promoting condensation reaction" used in this specification (also referred to simply as "catalyst" or "component (D)") is not particularly limited as long as it is capable of promoting the condensation reaction between the silicone having hydroxyl groups at both ends (component (A)) and the crosslinking agent (component (B)), and/or the condensation reaction between the products obtained by the condensation reaction. The catalyst for promoting the condensation reaction is preferably one that is capable of promoting at least the condensation reaction between the silicone having hydroxyl groups at both ends (component (A)) and the crosslinking agent (component (B)). The catalyst for promoting the condensation reaction is preferably a metal-containing catalyst.

Examples of metal-containing catalysts include, but are not limited to, tin-based catalysts (e.g., dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin dioctanoate, dibutyltin acetylacetonate, dibutyltin bismaleic acid monobutyl ester, dioctyl bismaleic acid monobutyl ester, dibutyltin oxides (e.g., bis(acetoxydibutyltin)oxide, bis(lauroxydibutyltin)oxide), and the corresponding dioctyltin compounds); titanium. Examples of catalysts include: titanium tetraacetylacetonate, titanium diisopropoxy bis(acetylacetonate), titanium dioctanoxy dioctanate, titanium dioctanoxy bis(ethylacetoacetate), titanium tetraisopropylate, titanium tetrabutylate, etc.; zirconium catalysts (zirconium tetra-n-butoxide, etc.); and the like. These may be used alone or in combination of two or more.

The catalyst preferably includes a tin-based catalyst, and more preferably includes dibutyltin dilaurate.

The content of the catalyst is not particularly limited as long as the object of the present invention can be achieved. The content of the catalyst is, for example, about 0.001 to about 20 parts by mass, preferably about 0.005 to about 5 parts by mass, and more preferably about 0.01 to about 1 part by mass, per 100 parts by mass of the total amount of the first composition and the second composition. Alternatively, the content of the catalyst that promotes the condensation reaction is, for example, about 0.001 to about 100 parts by mass, preferably about 0.01 to about 50 parts by mass, more preferably about 0.1 to about 25 parts by mass, and even more preferably about 1 to about 10 parts by mass, per 100 parts by mass of the second composition.

In addition to component (D), the second composition may contain various additives such as plasticizers, fillers, thixotropic regulators, solvents, anti-sagging agents, anti-aging agents, antioxidants, pigments (dyes), flame retardants, dehydrating agents, antistatic agents, UV absorbers, surfactants (including leveling agents), and dispersants, as necessary, within the scope of the object of the present invention.

[Other ingredients]
Plasticizers that may be optionally included in the first composition and/or the second composition include, but are not limited to, non-functional silicone oils; phthalates (e.g., dioctyl phthalate, diisooctyl phthalate, diundecyl phthalate); perhydrogenated phthalates (e.g., diisononyl 1,2-cyclohexanedicarboxylate, dioctyl 1,2-cyclohexanedicarboxylate); adipate esters (e.g., dioctyl adipate); benzoate esters; glycol esters; esters of saturated alkanediols (e.g., 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate); phosphate esters; sulfonate esters; polyesters; polyethers (e.g., polyethylene glycol or polypropylene glycol having a molar mass of 1000 to 10000 g/mol; polystyrene; polybutadiene; polyisobutylene; paraffinic hydrocarbons; high molecular weight branched hydrocarbons; and the like, which may be used alone or in combination of two or more.

As the plasticizer, non-functional silicone oil is preferred. Non-functional silicone oil means a silicone oil that is hardly or not involved at all in the condensation reaction, and is usually a silicone oil that does not contain reactive functional groups (e.g., alkenyl groups or hydrogen atoms bonded to silicon atoms) capable of crosslinking with the silicone (component (A)) at both ends of the hydroxyl groups, or other reactive functional groups in the molecule. Non-functional silicone oil is preferably a linear or branched diorganopolysiloxane whose molecular chain ends are blocked with triorganosiloxy groups and which is not involved in the condensation reaction, or a cyclic diorganopolysiloxane that does not have reactive functional groups in the molecule, and more preferably a polydimethylsiloxane.

When the first composition and/or the second composition contains a plasticizer, the content of the plasticizer is, for example, about 0.1 to about 50 parts by mass, preferably about 1 to about 40 parts by mass, more preferably about 10 to about 35 parts by mass, and even more preferably about 15 to about 30 parts by mass, relative to 100 parts by mass of the total amount of the first composition and the second composition. Alternatively, when the first composition contains a plasticizer, the content of the plasticizer is, for example, about 0.1 to about 50 parts by mass, preferably about 1 to about 40 parts by mass, more preferably about 10 to about 35 parts by mass, and even more preferably about 20 to about 30 parts by mass, relative to 100 parts by mass of the first composition. Alternatively, when the second composition contains a plasticizer, the content of the plasticizer is, for example, about 1 to about 99 parts by mass, preferably about 10 to about 99 parts by mass, more preferably about 50 to about 99 parts by mass, and even more preferably about 80 to about 99 parts by mass, relative to 100 parts by mass of the second composition.

Examples of fillers that may be included in the first composition and/or the second composition as necessary include, but are not limited to, carbon black, calcium carbonate, heavy calcium carbonate, precipitated calcium carbonate (light calcium carbonate), colloidal calcium carbonate, magnesium carbonate, zinc carbonate, metal oxide powders (e.g., aluminum oxide, titanium oxide, iron oxide, zinc oxide, and mixed oxides thereof), barium sulfate, magnesium oxide, silica (e.g., fumed silica, calcined silica, precipitated silica, ground silica, and fused silica), gypsum, quartz, silicon nitride, silicon carbide, diatomaceous earth, silica sand, calcium silicate, zirconium silicate, talc, kaolin, zeolite, boron nitride, glass powder, polymer powder (e.g., polyacrylonitrile powder), barium oxide, rosewood clay, kaolin clay, calcined clay, magnetic microbeads, elastic polymer beads, glass beads, and fibrous fillers (e.g., asbestos and/or polymer fibers). These may be used alone or in combination of two or more.

The fillers may be hydrophobized, for example, by treatment with organosilanes and/or organosiloxanes or stearic acid, or by etherification of hydroxyl groups to alkoxy groups.

When the first composition and/or the second composition contain a filler, the content of the filler is, for example, about 0.1 to about 70 parts by mass, preferably about 1 to about 60 parts by mass, more preferably about 3 to about 55 parts by mass, and even more preferably about 5 to about 50 parts by mass, per 100 parts by mass of the total amount of the first composition and the second composition.

Examples of thixotropic regulators that may be included in the first composition and/or the second composition as necessary include, but are not limited to, inorganic particles such as silica, titanium dioxide, bentonite, zinc oxide, talc, kaolin, mica, vermiculite, magnesium carbonate, calcium carbonate, aluminum silicate, barium silicate, calcium silicate, magnesium silicate, strontium silicate, metal tungstate, magnesium, zeolite, barium sulfate, calcined calcium sulfate, calcium phosphate, fluoroapatite, hydroxyapatite, and metal soaps; composite particles obtained by coating these inorganic particles with metal oxides; modified particles in which the surface of inorganic particles is treated with a compound; organic substances such as hydrogenated castor oil, amide, oxidized polyethylene, vegetable oil polymerized oil, and surfactants; and the like. These may be used alone or in combination of two or more.

As a thixotropic agent, taking into consideration the aggregate structure and affinity with other components, inorganic particles are preferred, inorganic particles containing silica are more preferred, fumed silica, wet silica, and colloidal silica are even more preferred, and fumed silica is even more preferred.

Examples of solvents that may be included in the first composition and/or the second composition as necessary include, but are not limited to, aromatic hydrocarbons such as benzene, xylene, and toluene; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as methyl acetate, ethyl acetate, and butyl acetate; ethers such as diethyl ether, tetrahydrofuran, and dioxane; and the like. These may be used alone or in combination of two or more.

Anti-sagging agents that may be included in the first composition and/or the second composition as necessary include, but are not limited to, acetylene black, ketjen black, colloidal silica, etc., which may be used alone or in combination of two or more.

Antiaging agents that may be included in the first composition and/or the second composition as necessary include, but are not limited to, hindered phenols, etc., which may be used alone or in combination of two or more.

Antioxidants that may be included in the first composition and/or the second composition as necessary include, but are not limited to, butylhydroxytoluene (BHT), butylhydroxyanisole (BHA), etc., which may be used alone or in combination of two or more.

Pigments (dyes) that may be included in the first composition and/or the second composition as necessary include, but are not limited to, inorganic pigments such as titanium oxide, zinc oxide, ultramarine, red iron oxide, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride, and sulfate; organic pigments such as azo pigments, phthalocyanine pigments, quinacridone pigments, quinacridonequinone pigments, dioxazine pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, flavanthrone pigments, perylene pigments, perinone pigments, diketopyrrolopyrrole pigments, quinonaphthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, isoindoline pigments, and carbon black; and the like. These may be used alone or in combination of two or more.

Flame retardants that may be included in the first composition and/or the second composition as necessary include, but are not limited to, chloroalkyl phosphates, dimethyl methyl phosphonates, bromine compounds, phosphorus compounds, ammonium polyphosphates, neopentyl bromide polyethers, brominated polyethers, etc., which may be used alone or in combination of two or more.

Examples of dehydrating agents that may be included in the first composition and/or the second composition as necessary include, but are not limited to, 1,1,1-trimethoxyethane, 1,1,1-triethoxyethane, trimethoxymethane, triethoxymethane, etc., which may be used alone or in combination of two or more. In one embodiment of the present invention, component (C) can also function as a dehydrating agent, so that the first composition does not require the additional dehydrating agent described above.

Antistatic agents that may be included in the first composition and/or the second composition as necessary include, but are not limited to, quaternary ammonium salts; hydrophilic compounds such as polyglycols and ethylene oxide derivatives; and the like. These may be used alone or in combination of two or more.

The amounts of the first composition and the second composition used are not particularly limited, but for example, the amount of the second composition is about 0.001 to about 500 parts by mass, preferably about 0.01 to about 100 parts by mass, more preferably about 0.05 to about 50 parts by mass, and even more preferably about 0.1 to about 10 parts by mass, per 100 parts by mass of the first composition.

[Method of producing composition set and one-component curing composition]
The method for producing the composition set and one-component curing type composition described in this specification is not particularly limited, and may be, for example, the method described below.

The composition set described herein may be produced from a first composition obtained by mixing the components (A), (B), and (C), and, if necessary, other components such as a thixotropic regulator and a plasticizer, under desired conditions (e.g., under dry conditions), and a second composition obtained by mixing the component (D), and, if necessary, other components such as a thixotropic regulator and a plasticizer, under desired conditions (e.g., under dry conditions).

The one-component curing composition described herein can be produced by mixing the first and second compositions obtained above under desired conditions (e.g., dry conditions).

In one embodiment of the present invention, there is provided a method for producing a one-component curable composition comprising at least (A) a silicone having hydroxyl groups at both ends, (B) a crosslinking agent having a hydrolyzable group capable of undergoing a condensation reaction with the terminal hydroxyl groups of the silicone having hydroxyl groups at both ends, (C) an adhesive aid having a hydrolyzable group, and (D) a catalyst for promoting the condensation reaction, the method comprising the steps of:
A first composition including the component (A), the component (B), and the component (C);
a step of mixing the second composition containing the component (D),
The method further comprises the steps of: (a) hydrolyzing the component (C) at a rate faster than that of the component (B);

In one embodiment of the present invention, there is provided a method for producing a one-component curable composition comprising at least (A) a silicone having hydroxyl groups at both ends, (B) a crosslinking agent having a hydrolyzable group capable of undergoing a condensation reaction with the terminal hydroxyl groups of the silicone having hydroxyl groups at both ends, (C) an adhesive aid having a hydrolyzable group, and (D) a catalyst for promoting the condensation reaction, the method comprising the steps of:
preparing a first composition comprising the component (A), the component (B), and the component (C);
preparing a second composition containing the component (D); and mixing the first composition and the second composition,
The method further comprises the steps of: (a) hydrolyzing the component (C) at a rate faster than that of the component (B);

[Use of composition sets, etc.]
The composition set described in this specification can be used as a composition set for producing a one-component curing composition. The use of the one-component curing composition is not particularly limited, and may be, for example, a sealant, adhesive, sealant, potting agent, elastic adhesive, coating material, lining material, structural adhesive in concrete or mortar, crack injection material, etc. for civil engineering and construction, concrete, wood, metal, glass, plastic, etc.

In another embodiment of the present invention, a sealant is provided that includes the first composition and the second composition described herein.

In another embodiment of the present invention, there is provided a first composition for use in combination with a second composition as a one-part curable composition set, comprising:
The first composition is
(A) a silicone having hydroxyl groups at both ends,
(B) a crosslinking agent having a hydrolyzable group capable of undergoing a condensation reaction with the terminal hydroxyl groups of the silicone having hydroxyl groups at both ends, and (C) an adhesive aid having a hydrolyzable group.
At least
The second composition is
(D) at least a catalyst that promotes a condensation reaction;
A first composition is provided, in which the component (C) has a faster hydrolysis rate than the component (B).

In another embodiment of the present invention, there is provided a second composition for use in combination with the first composition as a composition set of one-part curable compositions, comprising:
The first composition is
(A) a silicone having hydroxyl groups at both ends,
(B) a crosslinking agent having a hydrolyzable group capable of undergoing a condensation reaction with the terminal hydroxyl groups of the silicone having hydroxyl groups at both ends, and (C) an adhesive aid having a hydrolyzable group.
At least
The second composition is
(D) at least a catalyst that promotes a condensation reaction;
A second composition is provided in which the component (C) has a faster hydrolysis rate than the component (B).

The composition set described in this specification will be described in more detail below using examples. However, the following examples are not intended to limit the composition set described in this specification in any way.

[Example 1]
30.5 parts by weight of polydimethylsiloxane having hydroxyl groups at both ends (viscosity: about 50,000 mPa·s (23°C), product name: POLYMER FD 50, manufactured by Wacker Chemie AG), 20 parts by weight of non-functional polydimethylsiloxane (product name: WACKER (registered trademark) AK 100, manufactured by Wacker Chemie AG), 3.8 parts by weight of methyltris(methylethylketoxime)silane (product name: MOS, manufactured by KOREA BIO-GEN), 0.2 parts by weight of vinyltris(methylethylketoxime)silane (product name: VOS, manufactured by KOREA BIO-GEN), Example 1 was prepared by mixing 4.45 parts by mass of silica (product name: KONASIL (registered trademark) K-150D, manufactured by OCI), 39 parts by mass of heavy calcium carbonate (product name: SOFTON 2200, manufactured by Bihoku Funka Kogyo Co., Ltd.), and 1 part by mass of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (product name: GENIOSIL (registered trademark) GF 91, manufactured by Wacker Chemie AG). Furthermore, 1 part by mass of non-functional polydimethylsiloxane (product name: WACKER (registered trademark) AK 100, manufactured by Wacker Chemie AG) and 0.05 part by mass of dibutyltin dilaurate (product name: DABCO T-12 Catalyst, manufactured by EVONIC Industries AG) were mixed to obtain a second composition of Example 1. The appearance of the first composition and the second composition of Example 1 immediately after preparation was white.

[Example 2]
Except for changing the amounts of the polydimethylsiloxane having hydroxyl groups at both ends to 48.5 parts by mass, the non-functional polydimethylsiloxane to 21 parts by mass, the methyltris(methylethylketoxime)silane to 4.8 parts by mass, the silica to 6.45 parts by mass, and the heavy calcium carbonate to 17 parts by mass in the first composition, the same method as in Example 1 was repeated to obtain the first composition and the second composition of Example 2. The appearance of the first composition and the second composition of Example 2 immediately after preparation was white.

[Example 3]
The first composition was prepared in the same manner as in Example 1, except that the first composition contained 59.5 parts by mass of polydimethylsiloxane having hydroxyl groups at both ends, 23.5 parts by mass of non-functional polydimethylsiloxane, 5.88 parts by mass of methyltris(methylethylketoxime)silane, 0.12 parts by mass of vinyltris(methylethylketoxime)silane, 8.45 parts by mass of silica, 0 parts by mass of heavy calcium carbonate, and 1.5 parts by mass of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, to obtain the first composition and the second composition of Example 3. The appearance of the first composition and the second composition of Example 3 immediately after preparation was translucent.

[Example 4]
In the first composition, the polydimethylsiloxane having hydroxyl groups at both ends was 64.5 parts by mass, the methyltris(methylethylketoxime)silane was 5.88 parts by mass, the vinyltris(methylethylketoxime)silane was 0.12 parts by mass, the silica was 7.45 parts by mass, and the heavy calcium carbonate was 0 parts by mass. The same method as in Example 1 was repeated to obtain the first composition and the second composition of Example 4. The appearance of the first composition and the second composition of Example 4 immediately after preparation was translucent.

[Example 5]
In the first composition, the polydimethylsiloxane having hydroxyl groups at both ends is 72.5 parts by mass, the non-functional polydimethylsiloxane is 13 parts by mass, the methyltris(methylethylketoxime)silane is 6.37 parts by mass, the vinyltris(methylethylketoxime)silane is 0.13 parts by mass, the silica is 5.95 parts by mass, and the heavy calcium carbonate is 0 parts by mass. Except for this, the same method as in Example 1 is repeated to obtain the first composition and the second composition of Example 5. The appearance of the first composition and the second composition of Example 5 immediately after preparation is translucent.

[Example 6]
In the first composition, the polydimethylsiloxane with hydroxyl groups at both ends is 64.5 parts by mass, methyltris(methylethylketoxime)silane is 5.88 parts by mass, tetra(methylethylketoxime)silane is 0.12 parts by mass instead of vinyltris(methylethylketoxime)silane, silica is 7.45 parts by mass, and heavy calcium carbonate is 0 parts by mass. Except for this, the same method as in Example 1 is repeated to obtain the first composition and the second composition of Example 6. The appearance of the first composition and the second composition of Example 6 immediately after preparation is translucent.

[Example 7]
In the first composition, the polydimethylsiloxane with both terminal hydroxyl groups is 64.5 parts by mass, methyltris(methylethylketoxime)silane is replaced with 5.88 parts by mass, vinyltris(methylisobutylketoxime)silane is replaced with 0.12 parts by mass, silica is 7.45 parts by mass, and heavy calcium carbonate is 0 parts by mass. Except for this, the same method as in Example 1 is repeated to obtain the first composition and the second composition of Example 7. The appearance of the first composition and the second composition of Example 7 immediately after preparation is translucent.

[Example 8]
In the first composition, 64.5 parts by mass of polydimethylsiloxane having hydroxyl groups at both ends, 5.88 parts by mass of methyltris(methylethylketoxime)silane, 0.12 parts by mass of vinyltris(methylethylketoxime)silane, 7.45 parts by mass of silica, 0 parts by mass of heavy calcium carbonate, and 1 part by mass of 3-aminopropyltriethoxysilane (product name: GENIOSIL (registered trademark) GF 93, manufactured by Wacker Chemie AG) instead of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane were used, and the same method as in Example 1 was repeated to obtain the first composition and the second composition of Example 8. The appearance of the first composition and the second composition of Example 8 immediately after preparation was translucent.

[Example 9]
In the first composition, 64.5 parts by mass of polydimethylsiloxane having hydroxyl groups at both ends, 5.88 parts by mass of methyltris(methylethylketoxime)silane, 0.12 parts by mass of vinyltris(methylethylketoxime)silane, 7.45 parts by mass of silica, 0 parts by mass of heavy calcium carbonate, and 1 part by mass of vinyltrimethoxysilane (product name: GENIOSIL (registered trademark) XL 10, manufactured by Wacker Chemie AG) instead of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane were used, and the same method as in Example 1 was repeated to obtain the first composition and the second composition of Example 9. The appearance of the first composition and the second composition of Example 9 immediately after preparation was translucent.

[Reference Example]
The first composition and the second composition obtained in Example 4 were mixed to obtain a one-component curing type composition of the Reference Example.

[Comparative Example 1]
Except for mixing 0 part by mass of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane in the first composition and 1 part by mass of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane in the second composition, the same method as in Example 1 was repeated to obtain the first composition and the second composition of Comparative Example 1. The appearance of the first composition and the second composition of Comparative Example 1 immediately after preparation was white.

[Comparative Example 2]
In the first composition, 64.5 parts by mass of polydimethylsiloxane having hydroxyl groups at both ends, 5.88 parts by mass of methyltris(methylethylketoxime)silane, 0.12 parts by mass of vinyltris(methylethylketoxime)silane, 7.45 parts by mass of silica, 0 parts by mass of heavy calcium carbonate, and 0 parts by mass of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane were used, and in the second composition, 1 part by mass of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane was mixed. The same method as in Example 1 was repeated to obtain the first composition and the second composition of Comparative Example 2. The appearance of the first composition and the second composition of Comparative Example 2 immediately after preparation was translucent.

[Comparative Example 3]
In the first composition, 64.5 parts by mass of polydimethylsiloxane having hydroxyl groups at both ends, 5.88 parts by mass of methyltris(methylethylketoxime)silane instead of methyltris(methylisobutylketoxime)silane, 0.12 parts by mass of vinyltris(methylethylketoxime)silane instead of vinyltris(methylisobutylketoxime)silane, 7.45 parts by mass of silica, 0 parts by mass of heavy calcium carbonate, 0 parts by mass of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, and in the second composition, 1 part by mass of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane was mixed, and the same method as in Example 1 was repeated to obtain the first composition and the second composition of Comparative Example 3. The appearance of the first composition and the second composition of Comparative Example 3 immediately after preparation was translucent.

[Comparative Example 4]
The first composition contained 64.5 parts by mass of polydimethylsiloxane having hydroxyl groups at both ends, 5.88 parts by mass of methyltris(methylethylketoxime)silane, 0.12 parts by mass of vinyltris(methylethylketoxime)silane, 7.45 parts by mass of silica, 0 parts by mass of heavy calcium carbonate, and 0 parts by mass of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, and the second composition contained 1 part by mass of 3-aminopropyltriethoxysilane. The same method as in Example 1 was repeated to obtain the first composition and the second composition of Comparative Example 4. The appearance of the first composition and the second composition of Comparative Example 4 immediately after preparation was translucent.

[Comparative Example 5]
In the first composition, 64.5 parts by mass of polydimethylsiloxane having hydroxyl groups at both ends, 5.88 parts by mass of methyltris(methylethylketoxime)silane, 0.12 parts by mass of vinyltris(methylethylketoxime)silane, 7.45 parts by mass of silica, 0 parts by mass of heavy calcium carbonate, and 0 parts by mass of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane were used, and in the second composition, 1 part by mass of vinyltrimethoxysilane was mixed. The same method as in Example 1 was repeated to obtain the first composition and the second composition of Comparative Example 5. The appearance of the first composition and the second composition of Comparative Example 5 immediately after preparation was translucent.

[Test Example 1: Evaluation of hydrolysis rate]
The hydrolysis rates of the following crosslinking agents and adhesive aids were evaluated by the following test methods.
At 23° C. and 50% relative humidity, 2 g of the crosslinking agent or adhesive assistant and 0.1 g of purified water were mixed and stirred. After about 10 minutes, about 20 minutes, and about 30 minutes, the state of the resulting mixture was visually evaluated. The results are shown in Table 2.
<Crosslinking Agent>
・Methyl tris (methyl ethyl ketoxime) silane ・Vinyl tris (methyl ethyl ketoxime) silane ・Tetra (methyl ethyl ketoxime) silane ・Methyl tris (methyl isobutyl ketoxime) silane ・Vinyl tris (methyl isobutyl ketoxime) silane <Adhesion aid>
・N-(2-aminoethyl)-3-aminopropyltrimethoxysilane ・3-aminopropyltriethoxysilane ・3-aminopropyltrimethoxysilane

[Test Example 2: Evaluation of storage stability 1 (evaluation of touch-free time)]
The first and second compositions of Examples 1 to 9, the one-component curing type composition of the Reference Example, and the first and second compositions of Comparative Examples 1 to 5 were used to evaluate the tack-free time by the following test method.
The first compositions of Examples 1 to 9, the one-component curing composition of the Reference Example, and the first compositions of Comparative Examples 1 to 5 were each filled into a container and stored at 50° C. for 4 weeks. Thereafter, the first compositions of Examples 1 to 9 and the second compositions of Examples 1 to 9 prepared immediately before were mixed, respectively, to obtain the one-component curing compositions of Examples 1 to 9. Similarly, the first compositions of Comparative Examples 1 to 5 and the second compositions of Comparative Examples 1 to 5 prepared immediately before were mixed, respectively, to obtain the one-component curing compositions of Comparative Examples 1 to 5.
The tack-free time of the thus obtained one-component curing compositions of Examples 1 to 9, the one-component curing compositions of Comparative Examples 1 to 5, and the one-component curing composition of Reference Example was evaluated according to the method of JIS K 6249 10 (b). The results are shown in Tables 3 to 5.

[Test Example 3: Evaluation of storage stability 2 (evaluation of appearance)]
The first compositions of Examples 1 to 9, the one-component curing type composition of Reference Example, and the first compositions of Comparative Examples 1 to 5 were used to evaluate the appearance by the following test method.
The first compositions of Examples 1 to 9, the one-component curing composition of Reference Example, and the first compositions of Comparative Examples 1 to 5 were each filled into a container and stored at 50° C. for 4 weeks. After storage, the appearance (color tone) of each composition was visually evaluated. The results are shown in Tables 3 to 5.

From the results of Test Example 1, the crosslinking agent such as methyltris(methylethylketoxime)silane remained separated from the water even 30 minutes after mixing with water. From this, it was considered that the hydrolysis reaction of the crosslinking agent such as methyltris(methylethylketoxime)silane hardly progressed or did not progress at all. On the other hand, the adhesive assistant such as N-(2-aminoethyl)-3-aminopropyltrimethoxysilane produced a viscous liquid within 30 minutes after mixing with water. From this, it was considered that the hydrolysis reaction of the adhesive assistant such as N-(2-aminoethyl)-3-aminopropyltrimethoxysilane progressed to a certain degree.
Therefore, it is believed that the hydrolysis rate of an adhesion promoter such as N-(2-aminoethyl)-3-aminopropyltrimethoxysilane is faster than that of a crosslinking agent such as methyltris(methylethylketoxime)silane.

As is clear from the results of Test Example 2, the first compositions of Examples 1 to 9 had a tack-free time comparable to that of the one-component curing composition of Reference Example, even when mixed with the second composition after storage at 50° C. for 4 weeks. On the other hand, the first compositions of Comparative Examples 1 to 5 had a significantly delayed tack-free time when mixed with the second composition after storage at 50° C. for 4 weeks, compared to Examples 1 to 9 and Reference Examples.
Therefore, the composition set described herein has good storage stability with no significant delay in curing speed.
In Comparative Example 1, the crosslinking agent is hydrolyzed by the moisture (including unintentionally contained moisture) present in the first composition to produce a hydrolyzate. Then, the hydrolyzates dehydrate and condense with each other, consuming the crosslinking agent. As a result, it is considered that the crosslinking reaction did not proceed to the desired extent when the first composition and the second composition were mixed, and the touch-free time was significantly delayed. On the other hand, in Example 1, the crosslinking agent and an adhesive aid having a hydrolyzable group with a faster hydrolysis rate than the crosslinking agent coexist in the first composition, and the moisture (including unintentionally contained moisture) present in the first composition reacts preferentially with the adhesive aid, suppressing the hydrolysis of the crosslinking agent, and it is considered that the crosslinking reaction proceeded to the desired extent when the first composition and the second composition were mixed, and the touch-free time was not significantly delayed.

As is clear from the results of Test Example 3, the first compositions of Examples 1 to 9 were translucent or white even after four weeks of storage at 50° C. On the other hand, the first compositions of Comparative Examples 1 to 5 clearly turned yellow after four weeks of storage at 50° C.
Therefore, the composition set described herein has good storage stability without impairing the appearance (e.g., color tone).
In particular, the oxime silane crosslinking agent may be hydrolyzed by moisture (including unintentionally contained moisture) present in the first composition to generate an oxime, which is considered to further impair the appearance (e.g., color tone) of the first composition or a one-component curing composition obtained by mixing the first composition with the second composition.
Therefore, when an oxime silane-based crosslinking agent is used, it is believed that by coexisting in the first composition an adhesive aid having a hydrolyzable group that has a faster hydrolysis rate than the crosslinking agent, changes in appearance (e.g., color tone) can be more easily suppressed.

The present invention relates to a composition set of one-part curable compositions with good storage stability, and is therefore fully applicable in industry.

Claims (18)

A composition set for use in a one-component curing type composition, comprising a first composition and a second composition,
The first composition is
(A) a silicone having hydroxyl groups at both ends,
(B) a crosslinking agent having a hydrolyzable group capable of undergoing a condensation reaction with the terminal hydroxyl groups of the silicone having hydroxyl groups at both ends, and (C) an adhesive aid having a hydrolyzable group.
At least
The second composition is
(D) at least a catalyst that promotes a condensation reaction;
and wherein the component (C) has a faster hydrolysis rate than the component (B). The composition set according to claim 1, wherein the first composition and/or the second composition contains a silicone oil. The composition set according to claim 1, wherein the component (B) is an oxime silane crosslinking agent. The component (B) is represented by the following general formula (III):
(Wherein,
n is 1 to 4;
R ² and R ³ are independently hydrogen or a C ₁ -C ₁₀ alkyl group, a C 2 -C 10 alkenyl group, a C ₂ -C _{10 alkynyl} group, a C ₃ -C ₁₀ cycloalkyl group or a C ₃ -C ₁₀ cycloalkenyl group, each of which may be substituted _with one or more substituents;
R ⁴ , R ⁵ and R ⁶ are independently hydrogen or a C ₁ -C _{10 alkyl group, a C 2 -C 10} alkenyl group, a C ₂ -C ₁₀ alkynyl group, a C ₃ -C ₁₀ cycloalkyl group, a C ₃ -C ₁₀ cycloalkenyl group, a C ₆ -C ₁₀ aryl group or a C _{3 -C 10} heteroaryl group, each of which may be substituted with one or more _substituents ;
However, when n is 2, R ⁶ is not present, when n is 3, R ⁵ and R ⁶ are not present, and when n is 4, R ⁴ , R ⁵ and R ⁶ are not present.
The set of compositions according to claim 1 having the structure: 5. The composition set forth in claim 4, wherein R ² is a C ₁ -C ₁₀ alkyl group optionally substituted with one or more substituents, and R ³ is a C ₁ -C ₁₀ alkyl group optionally substituted with one or more substituents. The component (B) is any one of the following:
The composition set according to claim 1, comprising at least one selected from the group consisting of methyltris(methylethylketoxime)silane, vinyltris(methylethylketoxime)silane, tetra(methylethylketoxime)silane, phenyl(methylethylketoxime)silane, methyltris(methylisobutylketoxime)silane, vinyltris(methylisobutylketoxime)silane, tetra(methylisobutylketoxime)silane, methyltris(acetoxime)silane, vinyltris(acetoxime)silane, methyltris(2-pentanoxime)silane, and vinyltris(2-pentanoxime)silane. The composition set according to claim 1, wherein the component (B) includes at least one selected from the group consisting of methyltris(methylethylketoxime)silane and vinyltris(methylethylketoxime)silane. The composition set according to claim 1, wherein the component (C) is a silane coupling agent that does not have an oxime group bonded to a silicon atom. The component (C) is represented by the following general formula (IV):

(Wherein,
m is 1 to 3;
R ⁷ is a C ₁ -C ₆ alkyl group, a C _{2 -C 6 alkenyl group, a C 2} -C ₆ alkynyl group, a C ₃ -C ₆ cycloalkyl group or a C ₃ -C ₆ cycloalkenyl group, each of which may be substituted with one _{or more} substituents;
R ⁸ and R ⁹ are independently hydrogen or a C ₁ -C ₁₀ alkyl group, a C 2 -C 10 alkenyl group, a C ₂ -C 10 alkynyl group, a C 3 -C ₁₀ cycloalkyl group, a C ₃ -C ₁₀ cycloalkenyl group, a C ₆ -C ₁₀ aryl group, or a C _{3 -C 10} heteroaryl group, each of which may be _{substituted with} one or more _substituents ;
R ¹⁰ is a C ₁ -C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, or a C ₂ -C ₆ alkynyl group, optionally substituted with one or more substituents;
R ¹¹ and R ¹² are independently hydrogen or a C ₁ -C ₁₀ alkyl group, a C 2 -C 10 alkenyl group, a C ₂ -C 10 alkynyl group, a C ₃ -C ₁₀ cycloalkyl group, a C ₃ -C ₁₀ cycloalkenyl group, a C ₆ -C ₁₀ aryl group, or a C _{3 -C 10} heteroaryl group, each of which may be substituted _with one or more _substituents ;
provided that when m is 2, R ⁹ is absent, and when m is 3, R ⁸ and R ⁹ are absent.
The set of compositions according to claim 1 having the structure: 10. The composition set forth in claim 9, wherein ^R7 is a _C1 - _C6 alkyl group optionally substituted with one or more substituents. The component (C) is any one of the following:
The composition set according to claim 1, comprising at least one member selected from the group consisting of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, and N-cyclohexyl-3-aminopropyltrimethoxysilane. The composition set according to claim 1, wherein the component (D) is a tin-based catalyst. The composition set according to claim 1, wherein the first composition contains 0.01 to 30 parts by mass of the (B) component per 100 parts by mass of the total amount of the first composition and the second composition. The composition set according to claim 1, wherein the first composition contains 0.01 to 30 parts by mass of the (C) component per 100 parts by mass of the total amount of the first composition and the second composition. A one-component curing composition comprising the first composition and the second composition according to claim 1. A method for producing a one-component curing composition comprising at least (A) a silicone having hydroxyl groups at both ends, (B) a crosslinking agent having a hydrolyzable group capable of undergoing a condensation reaction with the terminal hydroxyl groups of the silicone having hydroxyl groups at both ends, (C) an adhesive aid having a hydrolyzable group, and (D) a catalyst for promoting the condensation reaction,
A first composition including the component (A), the component (B), and the component (C);
a step of mixing the second composition containing the component (D),
The method, wherein the component (C) has a faster hydrolysis rate than the component (B). A first composition for use in combination with a second composition as a composition set of one-component curable compositions, comprising:
The first composition is
(A) a silicone having hydroxyl groups at both ends,
(B) a crosslinking agent having a hydrolyzable group capable of undergoing a condensation reaction with the terminal hydroxyl groups of the silicone having hydroxyl groups at both ends, and (C) an adhesive aid having a hydrolyzable group.
At least
The second composition is
(D) at least a catalyst that promotes a condensation reaction;
The first composition, wherein the component (C) has a faster hydrolysis rate than the component (B). A second composition for use in combination with the first composition as a composition set of one-component curable compositions,
The first composition is
(A) a silicone having hydroxyl groups at both ends,
(B) a crosslinking agent having a hydrolyzable group capable of undergoing a condensation reaction with the terminal hydroxyl groups of the silicone having hydroxyl groups at both ends, and (C) an adhesive aid having a hydrolyzable group.
At least
The second composition is
(D) at least a catalyst that promotes a condensation reaction;
The second composition, wherein the component (C) has a faster hydrolysis rate than the component (B).