KR20170016433A - Primer composition - Google Patents

Abstract

The present invention provides a primer composition which is excellent in various durability, exhibits good adhesion to various adherends in a short time after application, and has high storage stability. The primer composition of the present invention comprises (A) an acrylic copolymer obtained by copolymerizing (A1) a monomer component comprising a (meth) acrylic acid ester containing an alkoxysilyl group and a (meth) acrylic acid ester containing (B) a titanium compound in an amount of 0.3 to 10 parts by mass, and (B) a titanium compound in an amount of 0.3 to 10 parts by mass based on 100 parts by mass of the acrylic copolymer (A), (B) C) the solvent is 100 to 5000 parts by mass.
_{Ti (iC 3 H 7 O)} a (C 5 H 7 O 2) b (C 6 H 9 O 3) c (1)
(a, b, and c are any integers from 0 to 4, provided that a + b + c = 4)

Description

PRIMER COMPOSITION [0002]

The present invention relates to a primer composition useful for bonding a room temperature curable organopolysiloxane composition to various adherends, to a primer composition characterized by having a short time until an adhesive property is obtained and excellent storage stability.

In the adhesion of the room temperature curable organopolysiloxane composition used as a sealing material for architectural use, a general industrial sealant, and an adhesive to various adherends, a silane-based primer containing a silane coupling agent, a titanic acid ester or a solvent as a main component, Quot; urethane-based primer " containing an isocyanate compound as a main component, a silane-modified acrylic resin, and an " acrylic primer " containing a solvent as a main component have been used (see Patent Documents 1 to 4).

As the silane coupling agent for the silane-based primer, those having an amino group, an epoxy group, a mercapto group or an isocyanate group are generally used. It is also known that the polyisocyanate compound of the urethane base primer is obtained by the addition reaction of an isocyanate compound with a polyol such as polyethylene glycol.

The silane-based primer is useful for an inorganic adherend such as metal or glass, and has good heat resistance, weather resistance, and durability. However, the silane-based primer often shows insufficient adhesiveness to organic adherends such as various resins. Especially in recent years, a coating material containing an acrylic resin as a main component, which is mostly used in aluminum sashes, An acrylic electrodeposited coating is insufficient in adhesion to a fluorine resin coating painted with aluminum on a paint mainly composed of aluminum or a fluorine resin.

On the other hand, although the urethane-based primer has adhesiveness that can be satisfactorily satisfactory to a wide range of adherends including metal and organic adherends, due to the characteristics of the urethane resin, durability such as heat resistance, weather resistance, Which is unsuitable for the use of a silicone-curable composition requiring long-term durability. Further, even when a silane-based or polyisocyanate-based blend primer is used, it is difficult to achieve both adhesion and durability.

However, a silane-based or acrylic-based primer is often used as a silicone-based curable composition. The acrylic primer is composed mainly of an acrylic resin having an alkoxysilyl group and a solvent. As such acrylic primers, many of those which exhibit good adhesiveness to various resins such as acrylic resins and polystyrene resins, which are difficult to bond without a primer, to the room temperature-curable organopolysiloxane composition, are commercially available. Among these, there are those which adhere well to acrylic electrodeposition-coated aluminum and fluorine resin-coated aluminum and have higher heat resistance, weather resistance and water resistance than urethane type primers. In view of this, acrylic primers have been suitably used as primers for use on resin-coated surfaces or metal-coated surfaces.

Japan Patent Office 53-005043 Japanese Patent No. 2522856 Japanese Patent Application Laid-Open No. 4-224879 Japanese Patent Application Laid-Open No. 8-295852

However, the acrylic primer having good adhesiveness has a delayed appearance of the adhesive force with the room temperature curable organopolysiloxane composition (room temperature curable silicone rubber composition), so that the room temperature curable organopolysiloxane composition can be easily moved after curing, There is a problem that peeling occurs when a force is applied to the substrate.

Therefore, in recent years, in order to increase the production efficiency in various industrial fields, it has become essential to shorten the time of the bonding process by the room temperature curable silicone rubber composition, and it is possible to provide a silicone rubber composition which is excellent in various durability, Development of a primer capable of exhibiting adhesiveness has been desired. In addition, a primer composition having high storage stability, which does not deteriorate adhesiveness even for long-term storage, is also demanded.

Accordingly, it is an object of the present invention to provide a primer composition which is excellent in various durability, exhibits good adhesion to various adherends in a short time after application, and has high storage stability.

The inventors of the present invention have conducted various studies on the primer composition according to the present invention. As a result, it has been found that the above primer composition can solve the above problems by mixing an acrylic copolymer having a specific structure and a titanium compound having a specific structure at a predetermined ratio And reached the present invention.

That is,

(1) a cured product of a room temperature curable organopolysiloxane composition (typically, a condensation reaction curing type room temperature curable silicone rubber composition) and a cured product of an organic resin, a metal and a painted metal surface (for example, acrylic resin or fluorine resin as a main component (A1) a (meth) acrylate ester containing an alkoxysilyl group, and (A2) an alkoxysilyl group in an amount of from 0.01 to 10 parts by weight based on 100 parts by weight of the total of (B) 0.4 to 10 parts by mass of a titanium compound represented by the formula (1), (C) 100 to 200 parts by mass of a solvent, and (C) 100 to 200 parts by mass of a (meth) acrylic acid ester- And 5,000 parts by mass of the polymer.

_{Ti (iC 3 H 7 O)} a (C 5 H 7 O 2) b (C 6 H 9 O 3) c (1)

(a, b, and c are any integers from 0 to 4, provided that a + b + c = 4)

(2) The component (A) is prepared by mixing (A1) 1 to 20 mass% of at least one (meth) acrylic acid ester containing an alkoxysilyl group with (meth) acrylic acid ester having a total of 100 mass% (A2) a monomer component containing 50 to 99 mass% of at least one (meth) acrylic acid ester containing no alkoxysilyl group.

(3) the proportion of (A1) at least one (meth) acrylate ester containing an alkoxysilyl group is 1 to 10% by mass when the entire monomer component of the component (A) is 100% (2).

(4) In the case where the total amount of the monomer components of the component (A) is 100 mass%, the proportion of the at least one (meth) acrylic acid ester containing no alkoxysilyl group in the component (A2) is 50% by mass or more and 99% (2) or (3). ≪ / RTI >

(5) The component (B) is at least one selected from the group consisting of (B1) a titanium tetraalkoxide and / or an alkoxy group-containing titanium chelate compound, (B2) acetylacetone, (B2) acetyl acetone in an amount of 0.8 (1) to (4), wherein the primer composition is produced by mixing at a molar ratio of not more than 2.0 mol.

(6) The primer composition according to any one of (1) to (5), further comprising 1 to 100 parts by mass of (D) alkyltrialkoxysilane.

(7) The primer composition according to any one of (1) to (6), wherein the titanium compound of the component (B) is an integer wherein a = 2 and b + c = 2 in the formula (1).

According to the present invention, it is possible to provide a primer composition which exhibits good adhesiveness in a short period of time after application and exhibits various durability and storage stability, for various adherends such as acrylic electrodeposited coated aluminum and fluorine resin coated aluminum.

Hereinafter, the present invention will be described in more detail. In addition, the present invention is not limited to the following embodiments, but the present invention encompasses any combination of the following components. In the present specification, (meth) acrylic acid means acrylic acid and / or methacrylic acid, and the same applies to other compounds.

The primer composition of the present invention comprises

(A) a monomer component containing an alkoxysilyl group-containing acrylic copolymer (i.e., (A1) a (meth) acrylic acid ester containing an alkoxysilyl group and (A2) a (meth) acrylic acid ester not containing an alkoxysilyl group, Acrylic copolymer obtained by the above-mentioned method)

(B) a titanium compound represented by the formula (1)

_{Ti (iC 3 H 7 O)} a (C 5 H 7 O 2) b (C 6 H 9 O 3) c (1)

(a, b, and c are any integers from 0 to 4, provided that a + b + c = 4)

(C) Solvent

(A) 0.3 to 10 parts by mass of the titanium compound (B) and 100 to 5000 parts by mass of the solvent (C) relative to 100 parts by mass of the acrylic copolymer.

Hereinafter, each component contained in the primer composition of the present invention will be described in detail.

<(A) Acrylic Copolymer>

The alkoxysilyl group-containing acrylic copolymer of the component (A) is a component which becomes the main component of the primer composition of the present invention after drying and is a component that determines the adhesion between the base material and the primer composition.

The acrylic copolymer contained in the primer composition of the present invention can be obtained by copolymerizing at least one kind of (meth) acrylic acid ester (hereinafter referred to as an alkoxysilyl group-containing component (A1)) containing an alkoxysilyl group in the molecule and an alkoxysilyl group (Hereinafter referred to as &quot; alkoxysilyl group-free component (A2) &quot;) containing at least one kind of a (meth) acrylic acid ester. In the present invention, (meth) acrylic acid means methacrylic acid or acrylic acid, or a mixture thereof (mixed acid). Similarly, (meth) acrylate refers to methacrylate or acrylate, or a mixture thereof (mixed ester). Further, (meth) acrylate refers to methacrylate or acrylate, or a mixture thereof.

The polymerization reaction method for copolymerizing the above monomer components is not particularly limited, and examples thereof include radical polymerization, cationic polymerization, and anionic polymerization. Among them, random radical polymerization using an organic peroxide or an organic azo compound as an initiator is effective as a simple method.

[Alkoxysilyl group-containing component (A1)]

The alkoxysilyl group-containing component (A1) is a monomer component comprising at least one of (meth) acrylic acid esters containing an alkoxysilyl group in the molecule. Among these monomers, the (meth) acrylic acid ester (A1) containing an alkoxysilyl group may be used alone or in combination of two or more. Further, the (meth) acrylic acid ester (A1) containing an alkoxysilyl group has at least one, preferably two or three alkoxysilyl groups in one molecule.

The content of the alkoxysilyl group-containing component (A1) is preferably from 1 to 20% by mass, more preferably from 1 to 15% by mass, based on 100% by mass of the whole monomer component of the component (A) Is 1 to 10% by mass. In the present invention, it is preferable to contain a methacrylate ester containing an alkoxysilyl group as the component (A1), more preferably a methacrylate ester containing an alkoxysilyl group in an amount of 1 to 10 % By mass is most preferable. When the content of the component (A1) is less than 1% by mass based on the whole monomer component of the component (A), adhesion development is not obtained. When the content of the component (A1) is more than 20 mass% of the total monomer components of the component (A), the adhesion to the adherend is deteriorated.

Examples of the (meth) acrylic acid ester containing an alkoxysilyl group in the molecule include 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- Acryloxypropylmethyldimethoxysilane, and 3- (meth) acryloxypropylmethyldiethoxysilane. Particularly preferred is 3- (meth) acryloxypropyltrimethoxysilane.

[Alkoxysilyl group-free component (A2)]

The alkoxysilyl group-free component (A2) is a monomer component containing at least one of (meth) acrylic esters having no alkoxysilyl group in the molecule. Among these monomers, the (meth) acrylic ester (A2) containing no alkoxysilyl group may be used alone or in combination of two or more.

The content of the alkoxysilyl group-free component (A2) is preferably 50 to 99 mass%, more preferably 70 to less than 99 mass%, based on 100 mass% , And more preferably 80 mass% or more and less than 99 mass%. Outside this range, adhesiveness to an adherend is deteriorated. Further, in the present invention, it is preferable to contain a methacrylate ester containing no alkoxysilyl group as the component (A2).

Examples of the (meth) acrylic acid ester containing no alkoxysilyl group in the molecule include aliphatic hydrocarbon esters of (meth) acrylic acid, alicyclic hydrocarbon esters of (meth) acrylic acid, aromatic hydrocarbon esters of (meth) acrylic acid, And esters of (meth) acrylic acid with an alcohol.

Examples of the aliphatic hydrocarbon ester of (meth) acrylic acid include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (Meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (Meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, Meth) acrylate.

Examples of alicyclic hydrocarbon esters of (meth) acrylic acid include cyclohexyl (meth) acrylate and isobornyl (meth) acrylate.

Examples of the aromatic hydrocarbon ester of (meth) acrylic acid include phenyl (meth) acrylate, benzyl (meth) acrylate and tolylmeth (meth) acrylate.

Examples of esters of (meth) acrylic acid with an alcohol containing an ether bond include alkoxyalkyl (meth) acrylates such as 2-methoxyethyl (meth) acrylate and 2-methoxybutyl (meth) acrylate; (Meth) acrylates such as glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate.

The (meth) acrylic acid ester which does not contain an alkoxysilyl group is preferably an aliphatic hydrocarbon ester of (meth) acrylic acid, more preferably a (meth) acrylic acid alkyl ester having an alkyl group of 1 to 20 carbon atoms, (Meth) acrylic acid alkyl ester having an alkyl group having 1 to 10 carbon atoms. Particularly preferable examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate and tert-butyl (meth) acrylate. Further, in the present invention, it is particularly preferable that the content of methyl (meth) acrylate is less than 99% by mass and less than 99% by mass when the entire monomer component is 100% by mass. And it is most preferable to contain methyl methacrylate at 30 mass% or more and less than 99 mass%.

[Other ingredients]

The (A) acrylic copolymer may contain other monomer components other than the alkoxysilyl group-containing component (A1) and the alkoxysilyl group-free component (A2). Examples of other monomer components include N, N-dimethylacrylamide, N-methylol (meth) acrylamide, N-vinylpyrrolidone, vinyl propionate, vinyl stearate, vinyl chloride, vinylidene chloride, Vinyl monomers other than acrylic monomers, and the like. The content of the other monomer component is 49 mass% or less, preferably 20 mass% or less, and more preferably 0 mass%, based on 100 mass% of the entire monomer component of the component (A).

&Lt; (B) Titanium compound >

The titanium compound of the component (B) is an organic titanium compound represented by the following formula (1)

_{Ti (iC 3 H 7 O)} a (C 5 H 7 O 2) b (C 6 H 9 O 3) c (1)

(a, b, and c are any integers from 0 to 4, provided that a + b + c = 4)

The acetylacetonate containing at least one kind of _{(C 5 H 7 O 2)} , isopropoxide (iC ₃ H ₇ O) and ethyl acetoacetate _{(C 6 H 9 O 3)} . Preferably, acetylacetonate (C ₅ H ₇ O ₂₎ and isopropoxide (iC ₃ H ₇ O) in at least contains one (that is, formula (1) of, 1≤a + b≤ 4), and more preferably, acetylacetonate (C ₅ H ₇ O ₂ ) (that is, in formula (1), b = 4).

In the above formula (1), a, b and c are each an integer of 0 to 4 and further satisfy a + b + c = 4, wherein a, b and c are preferably A combination of a = 0, b = 4, c = 0, a combination of a = 2, b = 2 and c = 0, a combination of a = 4, b = 0 and c = 0 , a combination of a = 2, b = 0, c = 2, a combination of a = 0, b = 0 and c = 4, a combination of a = 0, b = 2 and c = 2.

The component (B) plays a role as an adhesion promoter that improves the adhesion of the primer composition of the present invention to the base material and shortens the time for exhibiting the adhesion property between the curable composition and the primer composition.

The blending amount of the component (B) is 0.3 to 10 parts by mass based on 100 parts by mass of the component (A). Preferably 0.3 to 5 parts by mass, more preferably 0.4 to 3 parts by mass, and still more preferably 0.45 to 2.5 parts by mass. When the amount is less than 0.3 part by mass, the expression of the adhesiveness tends to be slow, and desired adhesion can not be obtained in a short time. On the other hand, if the amount exceeds 10 parts by mass, the storage stability of the primer composition is lowered, and the adhesive property of the primer composition to a substrate after a long period of time can not be obtained. There is a tendency to peel off together with the composition.

As commercially available products containing such titanium tetraacetylacetonate compounds, there can be mentioned, for example, organotin TC-401 (manufactured by Matsumoto Fine Chemical Co., Ltd.) (a = 0, b = 4, c = 0 in formula (1) (Isopropyl alcohol solution containing 65 mass% of titanium tetraacetylacetonate compound of Ti (C ₅ H ₇ O ₂ ) ₄ to be displayed), Orgatics TC-100 (manufactured by Matsumoto Fine Chemical Co., Ltd.) (Acetyl acetonate) compound of Ti (iC ₃ H ₇ O) ₂ (C ₅ H ₇ O ₂ ) ₂ represented by a = 2, b = 2, isopropyl alcohol solution containing by mass%), Organic ticks TA-10 in the (Matsumoto Fine Chemical whether or sikki manufactured claim) (wherein (1) a = 4, b = 0, c = 0 Ti (iC 3 represented by the H ₇ O) to titanium tetraisopropoxide compound of ₄₉₉ mass%), Organic ticks TC-750 (Matsumoto Fine Chemical whether or sikki Ltd.) IC ₃ H ₇ O (Ti) represented by a = 2, b = 0, c = 2 in the (Expression _{(1) 2 (C 6 H} 9 O 3) 2 of titanium di-isopropoxy bis (ethylacetoacetate ) Compound in an amount of 95% by mass). Among them, Orgatics TC-401 is suitable from the viewpoint of adhesiveness.

As the component (B), titanium oxide alkyl ester and / or alkoxy group-containing titanium chelate compound and acetylacetone are mixed with 0.8 mol or more and less than 2.0 mol of acetylacetone per mole of titanium atom in the titanium-containing compound May be used. When the component (B) thus produced is used, it may be mixed in advance before the preparation of the primer composition of the present invention, or may be separately prepared in the preparation of the primer composition of the present invention and mixed in the primer composition.

The component (B) is prepared by mixing a titanium tetraalkoxide and / or an alkoxy group-containing titanium chelate compound with acetylacetone in a proportion of from 0.8 mol or more to less than 2.0 mol of acetylacetone per mol of the alkoxy group in the titanium-containing compound You may.

&Lt; (C) Solvent >

The solvent of the component (C) is used for dissolving or dispersing the component (A) and the component (B) to facilitate the coating operation and impart fast drying properties. The type of the solvent of the component (C) is not particularly limited so long as the primer composition does not lose transparency and uniformity, but it is selected according to the solvent resistance of the object to be adhered and the brush working conditions.

Such solvents include ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and butyl acetate, and aromatic hydrocarbons such as toluene and xylene as positive solvents for the component (A). As the poor solvent for the component (A), alcohols and aliphatic hydrocarbons may be used. Examples of the alcohols include methanol, ethanol, isopropyl alcohol and 2-ethyl-1-hexanol. Examples of the aliphatic hydrocarbons include n-hexane, n-heptane, and isooctane (2,2,4-trimethylpentane).

The blending amount of the component (C) is 100 to 5000 parts by mass, preferably 200 to 3000 parts by mass, and more preferably 300 to 1000 parts by mass with respect to 100 parts by mass of the component (A). When the blending amount of the component (C) is less than 100 parts by mass, the film thickness of the alkoxysilyl group-containing acrylic copolymer remaining on the substrate surface after application and drying of the primer composition becomes too thick, The use fee of the acrylic copolymer is increased, resulting in a cost disadvantage. On the other hand, if the blending amount of the component (C) exceeds 5000 parts by mass, the layer of the primer composition after drying becomes too thin, and the function of improving the adhesiveness is lost.

<(D) Additive>

As an additive for the component (D), optionally, an alkyltrialkoxysilane, acetylacetone or the like may be contained as optional components in order to improve the storage stability and the like of the primer composition of the present invention. As the alkyltrialkoxysilane in the component (D), for example, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane and vinyltrimethoxysilane can be given Of these, methyltrimethoxysilane and acetylacetone are preferred.

The blending amount of the component (D) is 0.1 to 100 parts by mass with respect to 100 parts by mass of the component (A). Preferably 0.5 to 10 parts by mass, and more preferably 1 to 5 parts by mass. When the amount is less than 0.1 parts by mass, the primer composition thickens during storage, so that the period of time until gelation is accelerated. When the amount exceeds 100 parts by mass, there is no disadvantage in terms of performance, but there is a disadvantage in terms of cost.

<Other additives>

In the primer composition of the present invention, other optional components may be added within the range not to impair the performance thereof. Examples of the silane condensation catalyst include organotin compounds such as dibutyltin dimethoxide, dibutyltin diacetate, dibutyltin dioctanoate and dibutyltin dilaurate; Aluminum alkoxide such as aluminum acetylacetonate; Zirconium alkoxide such as zirconium acetylacetonate; And a silane coupling agent as an adhesion-imparting agent. The kind and amount thereof to be added are selected according to the use.

&Lt; Bonding method using primer composition >

In order to adhere and cure the cured product of the room temperature curable organopolysiloxane composition (typically, the condensation reaction curing type room temperature curable silicone rubber composition) to various substrates using the primer composition of the present invention, a metal, a coating metal A primer composition of the present invention is applied to the surface of various substrates such as an organic resin or the like such as a surface of a painted metal such as aluminum coated with a paint containing a fluorine resin as a main component and dried and then the curable composition is brought into contact with the coated surface Cure.

The drying time of the primer composition after application is preferably from 5 minutes to 480 minutes and more preferably from 10 minutes to 120 minutes at room temperature (25 DEG C). If the drying time is shorter than 5 minutes, drying of the solvent is insufficient and the strength of the primer layer after drying can not be obtained. In addition, if the drying time exceeds 480 minutes, there is a high possibility that contaminants such as dust or dust adhere to the surface of the surface, which may hinder adhesion.

Further, the primer composition of the present invention is effective as an adhesion-imparting agent, an adhesion-improving agent and an adhesion-improving agent for adhering a cured product (silicone rubber) of the room-temperature-curable organopolysiloxane composition to various substrates, But also to a curable composition having a silyl group capable of forming a siloxane bond with the primer composition, for example, a modified silicone-based curable composition or a silylated polyurethane system.

Example

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.

<Preparation of (A) Acrylic Copolymer>

Based on the components shown in Table 1, each of the copolymers of Synthesis Examples 1 to 4 was produced by the following preparation method.

[Synthesis Example 1]

150.0 g of ethyl acetate and 150.0 g of isopropyl alcohol were placed in a 5 L four-necked glass flask equipped with a reflux condenser, a rotary stirrer, a nitrogen inlet tube, and a thermometer. Next, 20.0 g of methyl methacrylate, 20.0 g of n-butyl methacrylate and 2.0 g of 3-trimethoxysilylpropyl methacrylate were added and mixed, and the temperature of the mixed solution in the flask was adjusted to 80 Lt; 0 &gt; C. Subsequently, 1.5 g of 2,2'-azobis (2-methylbutyronitrile) was added and mixed and dissolved. A mixed solution of 60.0 g of methyl methacrylate, 60.0 g of n-butyl methacrylate and 6.0 g of 3-trimethoxysilylpropyl methacrylate was added to the dropping funnel, and the mixture was added dropwise to the flask over 2 hours. At this time, the solution temperature in the flask was adjusted to 75 캜 to 80 캜. After completion of the dropwise addition, the mixture was further aged at 80 DEG C for 2 hours, and then the heating by the oil bath was terminated and cooling was continued until the temperature reached 40 DEG C. [ After cooling, 200.0 g of ethyl acetate and 300.0 g of isopropyl alcohol were added and mixed until homogeneous to obtain a colorless transparent acrylic copolymer solution.

[Synthesis Example 2]

150.0 g of ethyl acetate and 150.0 g of isopropyl alcohol were placed in a 5 L four-necked glass flask equipped with a reflux condenser, a rotary stirrer, a nitrogen inlet tube, and a thermometer. Next, 40.0 g of methyl methacrylate and 2.0 g of 3-trimethoxysilylpropyl methacrylate were added and mixed, and the temperature of the mixed solution in the flask was heated to 80 DEG C using an oil bath. Subsequently, 1.5 g of 2,2'-azobis (2-methylbutyronitrile) was added and mixed and dissolved. A mixed solution of 120.0 g of methyl methacrylate and 6.0 g of 3-trimethoxysilylpropyl methacrylate was added to the dropping funnel, and the mixture was dropped into the flask over 2 hours. At this time, the solution temperature in the flask was adjusted to 75 캜 to 80 캜. After completion of the dropwise addition, the mixture was further aged at 80 DEG C for 2 hours, and then the heating by the oil bath was terminated and cooling was continued until the temperature reached 40 DEG C. [ After cooling, 200.0 g of ethyl acetate and 300.0 g of isopropyl alcohol were added and mixed until homogeneous to obtain a colorless transparent acrylic copolymer solution.

[Synthesis Example 3] (Comparative synthesis example)

150.0 g of ethyl acetate and 150.0 g of isopropyl alcohol were placed in a 5 L four-necked glass flask equipped with a reflux condenser, a rotary stirrer, a nitrogen inlet tube, and a thermometer. Next, 15.0 g of methyl methacrylate, 15.0 g of n-butyl methacrylate and 12.0 g of 3-trimethoxysilylpropyl methacrylate were added and mixed, and the temperature of the mixed solution in the flask was adjusted to 80 Lt; 0 &gt; C. Subsequently, 1.5 g of 2,2'-azobis (2-methylbutyronitrile) was added and mixed and dissolved. A mixed solution of 45.0 g of methyl methacrylate, 45.0 g of n-butyl methacrylate and 36.0 g of 3-trimethoxysilylpropyl methacrylate was added to the dropping funnel, and the mixture was added dropwise to the flask over 2 hours. At this time, the solution temperature in the flask was adjusted to 75 캜 to 80 캜. After completion of the dropwise addition, the mixture was further aged at 80 DEG C for 2 hours, and then the heating by the oil bath was terminated and cooling was continued until the temperature reached 40 DEG C. [ After cooling, 200.0 g of ethyl acetate and 300.0 g of isopropyl alcohol were added and mixed until homogeneous to obtain a colorless transparent acrylic copolymer solution.

[Synthesis Example 4] (Comparative synthesis example)

A colorless transparent acrylic copolymer solution was synthesized in the same manner as in Synthesis Example 1 except that n-butyl methacrylate was changed to tert-butyl methacrylate.

&Lt; Examples and Comparative Examples &

On the basis of the components shown in Table 2, Examples 1 to 7 and Comparative Examples 1 to 3 were produced by the following methods.

[Example 1]

577 parts by mass of the acrylic copolymer solution obtained in Synthesis Example 1 (containing 100 parts by mass of the acrylic copolymer of component (A), 208 parts by mass of ethyl acetate and 268 parts by mass of isopropyl alcohol), 40 parts by mass of ethyl acetate, 30 parts by mass of alcohol, 4.8 parts by mass of 2-ethyl-1-hexanol, 40 parts by mass of isooctane, and 2.0 parts by mass of methyltrimethoxysilane were added. Subsequently, titanium tetraacetylacetate containing 65% by mass of titanium tetraacetylacetonate (0.78 parts by mass in terms of mass of titanium tetraacetylacetonate) of an isopropyl alcohol solution (Orgatics TC-401, manufactured by Matsumoto Fine Chemical Co., Ltd.) was added and mixed to obtain a pale yellow transparent primer A composition was obtained.

[Example 2]

Instead of 1.2 parts by mass of an isopropyl alcohol solution of titanium tetraacetylacetonate containing 65% by mass of titanium tetraacetylacetonate of Example 1 (manufactured by Matsumoto Fine Chemical Co., Ltd., Orgatics TC-401) 0.84 parts by mass of an isopropyl alcohol solution of diisopropoxy titanium bis (acetylacetonate) containing 75% by mass of titanium oxide bis (acetylacetonate) (manufactured by Matsumoto Fine Chemical Co., Ltd., Orgatics TC-100) (0.63 parts by mass in terms of mass of diisopropoxy titanium bis (acetylacetonate)) and 0.36 parts by mass of acetylacetone, thereby obtaining a light yellow transparent primer composition.

[Example 3]

Instead of 1.2 parts by mass of an isopropyl alcohol solution of titanium tetraacetylacetonate containing 65% by mass of titanium tetraacetylacetonate of Example 1 (manufactured by Matsumoto Fine Chemical Co., Ltd., Orgatics TC-401), tetraisopropyl 0.48 part by mass (that is, 0.48 parts by mass in terms of mass of tetraisopropyl titanate) of titanate (99 mass% active ingredient, Orgatics TA-10 manufactured by Matsumoto Fine Chemical Co., Ltd.) and 0.72 parts by mass of acetylacetone Thereby obtaining a light yellow transparent primer composition.

[Example 4]

A primer composition was obtained in the same manner as in Example 1 except that the acrylic copolymer solution of Synthesis Example 2 was used instead of the acrylic copolymer solution of Synthesis Example 1.

[Example 5]

Instead of 1.2 parts by mass of an isopropyl alcohol solution of titanium tetraacetylacetonate containing 65% by mass of titanium tetraacetylacetonate of Example 1 (manufactured by Matsumoto Fine Chemical Co., Ltd., Orgatics TC-401) 1.2 mass parts of titanium oxide bis (ethylacetoacetate) (95 mass% or more of active ingredient, manufactured by Matsumoto Fine Chemical Co., Ltd., Orgatics TC-750) (i.e., mass of diisopropoxy titanium bis (ethylacetoacetate) (1.14 parts by mass to 1.2 parts by mass in terms of equivalent amount) was added to the reaction mixture, to obtain a light yellow transparent primer composition.

[Example 6]

A primer composition was obtained in the same manner as in Example 2 except that 0.36 parts by mass of acetylacetone was not added.

[Example 7]

A primer composition was obtained in the same manner as in Example 3 except that 0.72 parts by mass of acetylacetone was not added.

[Comparative Example 1]

Except that 1.2 parts by mass of an isopropyl alcohol solution of titanium tetraacetylacetonate (Orgatics TC-401, manufactured by Matsumoto Fine Chemical Co., Ltd.) containing 65% by mass of titanium tetraacetylacetonate was not added To obtain a primer composition.

[Comparative Example 2]

A primer composition was obtained in the same manner as in Example 1, except that the acrylic copolymer solution of Synthesis Example 3 (Comparative Synthesis Example) was used instead of the acrylic copolymer solution of Synthesis Example 1.

[Comparative Example 3]

A primer composition was obtained in the same manner as in Example 1 except that the acrylic copolymer solution of Synthesis Example 4 (Comparative Synthesis Example) was used instead of the acrylic copolymer solution of Synthesis Example 1.

&Lt; Evaluation of adhesiveness >

With respect to each of the primer compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 3, the adhesion to an aluminum blackboard was evaluated by the following method.

[Preparation of Test Specimen]

Each primer composition was applied to a plate of acrylic electrodeposited aluminum by a brush and allowed to stand for 30 minutes under conditions of 23 ° C and relative humidity (RH) of 50%. Thereafter, a two-component silicone sealant (SEALANT-FC-295SG: A mixture of a main agent and a curing agent of Shin-Etsu Chemical Co., Ltd.) was applied to the coated surface of the aluminum plate coated with each primer composition, and the coating was applied to the surface of 10 mm width, 50 mm length and 2 mm thickness with a spatula And molded into test pieces.

[Adhesion test]

After curing the test piece under the following conditions, the cured product of the silicone-based sealing material was cut with a knife, the cut portion was manually peeled off (hand pulled and pulled), and its peeling state was observed (hand peel test by knife cut) To evaluate the state of the adhesion interface between the adherend and the primer composition.

[Adhesion Expression]

The adhesion development was evaluated by a hand detachment test using the knife cut after curing for 4 hours in an environment of a temperature of 23 캜 and a relative humidity of 50%. The evaluation showed that the ratio of the area of the coagulated and destroyed area of the sealing material was 100%, &quot;? &Quot;, that which was 80% or more and less than 100% Quot; x &quot;. Table 1 shows the test results of adhesion development when each primer composition was used. Further, the copper silicone sealant is a fast curing sealing material which is cured and rubberized after mixing with a base and a curing agent.

[Initial adhesive property]

The initial adhesiveness was evaluated by the same method as that of the test method of adhesion development after curing for 7 days under an environment of a temperature of 23 캜 and a relative humidity of 50%. Table 3 shows the results of initial adhesion test when each primer composition was used.

[Water Resistance Adhesion]

The water resistance was evaluated by the same method as in the test method for adhesion development after curing for 7 days in an environment of a temperature of 23 占 폚 and a relative humidity of 50% for 7 days in hot water at 50 占 폚. Table 3 shows the test results of the water-resistant adhesiveness when each primer composition was used.

&Lt; Evaluation of storage stability &

With respect to the respective primer compositions obtained in Examples 1 to 4, storage stability was evaluated by the following methods.

[Storage stability]

Each of the obtained primer compositions was sealed in a glass bottle and allowed to stand for 28 days in a drier adjusted to 50 DEG C and taken out. The resultant was air-cooled and returned to 23 DEG C, and the above (primer adhesion to acrylic electrodeposited aluminum, The state of the adhesion interface between the adherend and the primer composition was evaluated by the same conditions and methods as those of the adhesion test.

The results of the above tests (adhesion development to the electrodeposition coated aluminum, initial adhesion, and water resistance) were the same as those of the above test results, or when the ratio of the cohesive failure was increased, Quot; is &quot; when the ratio of &quot; The storage stability test results are shown in Table 4. This makes it possible to verify whether or not the performance of the primer composition can be exerted even when the primer composition is used after storage for a long time in the unused state.

As shown in the examples, the composition of the present invention has good adhesion to various adherends used in architectural sealing materials and excellent storage stability.

The present invention can be suitably used for bonding a room-temperature-curable organopolysiloxane composition used as a sealing material for construction, a sealing material for general industrial use, an adhesive, and various adherends.

Claims (7)

As a primer composition for improving adhesion between a cured product of a room temperature curable organopolysiloxane composition and a substrate selected from an organic resin, a metal, and a painted metal surface,
(A) 100 parts by mass of an acrylic copolymer obtained by copolymerizing a monomer component comprising (A1) a (meth) acrylic acid ester containing an alkoxysilyl group and (A2) a (meth) acrylic ester containing no alkoxysilyl group,
(B) 0.3 to 10 parts by mass of the titanium compound represented by the formula (1)
_{Ti (iC 3 H 7 O)} a (C 5 H 7 O 2) b (C 6 H 9 O 3) c (1)
(a, b, and c are any integers from 0 to 4, provided that a + b + c = 4)
(C) 100 to 5000 parts by mass of a solvent
Wherein the primer composition comprises at least a polyol. The composition according to claim 1, wherein the component (A) comprises 1 to 20 mass% of a (meth) acrylic acid ester containing (A1) an alkoxysilyl group, (A2) ) Alkoxysilyl group-containing (meth) acrylic acid ester, and 50 to 99 mass% of a (meth) acrylic acid ester containing no alkoxysilyl group. The positive resist composition according to claim 2, wherein the proportion of the (meth) acrylic acid ester containing at least one alkoxysilyl group in the (A1) is 1 to 10% by mass, &Lt; / RTI &gt; The method according to claim 2 or 3, wherein, when the total monomer component of the component (A) is 100 mass%, the ratio of the at least one alkoxysilyl group-free (meth) And 50% by mass or more and less than 99% by mass. The method according to any one of claims 1 to 4, wherein the component (B) is at least one compound selected from the group consisting of (B1) titanium tetraalkoxide and / or alkoxy group-containing titanium chelate compound and (B2) (B2) acetylacetone in a ratio of from 0.8 mol or more to less than 2.0 mol based on 1 mol of the alkoxy group in the reaction mixture. The primer composition according to any one of claims 1 to 5, further comprising 1 to 100 parts by mass of (D) alkyltrialkoxysilane. The primer composition according to any one of claims 1 to 6, wherein the titanium compound of the component (B) is an integer compound in which a = 2 and b + c = 2 in the formula (1).