JP2008143990A - Surface treating agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a surface treating agent which is applied to the surface of an adherend beforehand and can enhance the adhesion of a sealing material, an adhesive, paint, a coating material or the like to the adherend. <P>SOLUTION: The surface treating agent comprises at least a component (A) of a composite compound comprising a structure or a composition obtained by reacting or mixing a titanium compound oligomer (a1) with a silicon compound (a2) having one or more alkoxy groups in the molecule and a component (B) of a solvent. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a surface treatment agent, and more particularly, to a surface treatment agent containing a structure obtained by reacting a specific silicon compound with a titanium compound oligomer or having a mixed composition. It is related with the surface treating agent which improves the adhesiveness with respect to.

  In the field of surface treatment agents, various metal and resin-coated metals, films, etc. have been studied in various fields for the adhesion between organic resins and silicone resins, and those with high adhesiveness are required. Yes. In particular, sealing materials are widely used in buildings and the like to fill joints and gaps between various members and to improve water tightness and air tightness, and are required to have high adhesiveness.

  Typical sealing materials include silicone-based, polyurethane-based, polysulfide-based, and modified silicone-based materials, and there are one-pack type and two-pack type. In particular, silicone-based and modified silicone-based sealing materials are widely used because of their excellent durability and weather resistance, but two-pack type sealing materials have low adhesion to various substrates. There were many.

  Therefore, it is known to treat with a primer or the like in order to improve adhesion before applying a sealing material or the like to the adherend. Regarding the primer, adhesion is improved by combining a titanium compound monomer and a silane coupling agent, or by adding a titanium compound monomer, a silane coupling agent, a silicone resin, etc. Yes.

  However, in such a case, cracks are likely to occur during film formation, the adhesive strength is lowered, and the deformation followability to a soft adherend is poor, so that sufficient adhesiveness may not be obtained. In addition, with conventional technology, metal members coated with resin such as fluororesin coating, acrylic electrodeposited aluminum, etc., and stainless steel are easily repelled, and sufficient adhesion to adherends with poor surface wettability. In many cases, sex was not obtained.

JP-A-11-209702 JP-A-6-128553 JP 7-228800 A JP 2003-279117 A Sugiyama Iwayoshi, “Contained Metal Organic Compounds and Their Use”, M.M. R. Functional substance series No. 5 (Nippon CMI Co., Ltd.) p. 112-p. 116

  This invention is made | formed in view of the said background art, The subject is providing the surface treating agent which can remarkably improve the adhesiveness of various adherends and organic resins, such as a silicone resin.

  As a result of intensive studies to solve the above problems, the present inventor has found that a composite compound obtained by mixing or reacting a specific silicon compound in a solvent with respect to a titanium compound oligomer has a surface tension and stability of the titanium compound oligomer. The present invention has been completed by finding that the adhesion is remarkably improved by being dissolved or dispersed in an appropriate solvent selected in consideration of the above.

That is, the present invention includes at least the following component (A) and component (B):
(A) Containing a compound (B) solvent having a structure in which a silicon compound (a2) having one or more alkoxy groups in the molecule is reacted with or mixed with the titanium compound oligomer (a1). The surface treating agent characterized by these is provided.

  According to the surface treating agent of the present invention, adhesion between various adherends and organic resins can be enhanced. In particular, the adhesion of an organic resin such as a silicone resin can be enhanced on a metal; a metal coated with a resin; a glass; an adherend such as a plastic film such as PET or OPP. In addition, the surface treatment agent of the present invention is excellent in wettability to various adherends, film-forming properties, adhesion, surface modifying properties, etc., and more specifically, is represented by acrylic electrodeposition coated aluminum. High adhesiveness can be expressed with respect to a coated metal plate that is very difficult to bond, or an adherend such as stainless steel that is very difficult to bond. Furthermore, if the surface treating agent of the present invention is used, various sealing materials, adhesives, paints, coating materials and the like can be firmly bonded to an adherend which is extremely difficult to bond.

  Hereinafter, the present invention will be described. However, the present invention is not limited to the following embodiments, and can be arbitrarily modified and implemented.

The surface treating agent of the present invention contains at least the following component (A) and component (B).
(A) Complex compound (B) solvent having a structure in which a silicon compound (a2) having one or more alkoxy groups in the molecule is reacted with a titanium compound oligomer (a1) or a mixed composition

［式（１）中、Ｒ^１〜Ｒ^４は、それぞれ独立に炭素数１〜１８個のアルキル基を示す。］ The titanium compound oligomer (a1) that is a raw material of the component (A) is not particularly limited, but is a chelating agent to a titanium alkoxide represented by the following formula (1) or a titanium alkoxide represented by the following formula (1). Those having a structure in which a titanium chelate compound having a structure in which is coordinated are condensed.

Wherein ^(1), R 1 ~R ⁴ represents an alkyl group having 1 to 18 carbon atoms independently. ]

As the “titanium alkoxide represented by the formula (1)” which is the starting material before the condensation, R ^{1 to} R ⁴ in the formula (1) are each independently an alkyl group having 1 to 18 carbon atoms. More preferably, they are each independently an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 5 carbon atoms.

  The “titanium alkoxide represented by the formula (1)” is not limited to the following specific examples. For example, tetramethoxy titanate, tetraethoxy titanate, tetranormal propoxy titanate, tetraisopropoxy titanate, tetranormal butoxy titanate, Examples include tetraisobutoxy titanate, diisopropoxy dinormal butoxy titanate, ditertiary butoxy diisopropoxy titanate, tetratertiary butoxy titanate, tetraisooctyl titanate, and tetrastearyl alkoxy titanate. These can be used alone or in admixture of two or more.

  The starting material before the condensation has a structure in which a chelating agent is coordinated to “titanium alkoxide represented by formula (1)” in addition to the above “titanium alkoxide represented by formula (1)”. Titanium chelate compounds are also preferred. The chelating agent is not particularly limited, but it is at least one selected from the group consisting of β-diketone, β-ketoester, polyhydric alcohol, alkanolamine and oxycarboxylic acid, and component (A) composite compound It is preferable at the point which improves stability with respect to the hydrolysis of this.

  β-diketone compounds include 2,4-pentanedione, 2,4-hexanedione, 2,4-heptanedione, dibenzoylmethane, thenoyltrifluoroacetone, 1,3-cyclohexanedione, 1-phenyl1,3 Β-ketoesters include methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, butyl acetoacetate, methyl pivaloyl acetate, methyl isobutyroyl acetate, methyl caproyl acetate, methyl lauroyl acetate and the like. Examples of the polyhydric alcohol include 1,2-ethanediol, 1,2-propanediol, 1,2-butanediol, 1,2-pentanediol, 2,3-butanediol, and 2,3-pentanediol. , Glycerin, diethylene glycol, glycerin, hex Examples of the alkanolamine include N, N-diethylethanolamine, N- (β-aminoethyl) ethanolamine, N-methylethanolamine, N-methyldiethanolamine, N-ethylethanolamine, N- Examples thereof include normal butyl ethanolamine, N-normal butyl diethanol amine, N-tertiary butyl ethanol amine, N-tertiary butyl diethanol amine, triethanol amine, diethanol amine, monoethanol amine and the like. Examples of oxycarboxylic acids include glycolic acid, lactic acid, Examples include tartaric acid, citric acid, malic acid, and gluconic acid. These can be used alone or in combination of two or more.

  The above-mentioned “titanium alkoxide represented by the formula (1)” or “titanium chelate compound having a structure in which a chelating agent is coordinated to the titanium alkoxide” is condensed to obtain a titanium compound oligomer (a1). Although there is no limitation in particular as the method of condensing here, it is preferable to carry out by making water react with titanium alkoxide or a titanium chelate compound in an alcohol solution.

  About the quantity of the water used in order to condense and oligomerize, the mole number of water is 0.5-2 mol with respect to 1 mol of titanium alkoxide and / or a titanium chelate compound, ie, 1 mol of titanium atoms. It is preferable that it is 0.7-1.7 mol, and it is especially preferable that it is 1.0-1.5 mol.

At the time of condensation by hydrolysis, it is preferable to obtain a titanium compound oligomer (a1) using a solvent such as alcohol, and optionally through a heat treatment such as reflux. Although there is no particular limitation on the alcohol used in this case, the alcohol of the alkyl radicals R ¹ to R ⁴ to a hydroxyl group is bonded structure of the formula (1) is preferred in that it does not change the reactivity of the titanium compound oligomeric. Specific examples include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2-ethylhexanol and the like.

  The amount of alcohol used is not particularly limited, but it is preferable to dilute the amount of water used for condensation and oligomerization with alcohol so that the concentration is 0.5 to 20% by mass, more preferably. Is diluted to a concentration of 0.7 to 15% by mass, particularly preferably 1.0 to 10% by mass.

  The titanium compound oligomer (a1) obtained by condensing and hydrolyzing by hydrolysis is not particularly limited in molecular weight, degree of polymerization and the like, but is preferably 2 to 20 mer on average and more preferably 4 to 15 mer.

  It is also preferable that the titanium compound oligomer (a1) which is a raw material of the component (a) has a structure in which a chelating agent is further coordinated with the above-described titanium compound oligomer. That is, a structure obtained by further coordinating a chelating agent to a titanium alkoxide represented by the above formula (1) or a titanium chelate compound having a structure in which a chelating agent is coordinated thereto. Also preferred are those having That is, a structure in which a chelating agent is reacted before and / or after the condensation is preferable in terms of enhancing the stability of the component (A) composite compound against hydrolysis.

  Although there is no limitation in particular as a chelating agent used after condensation, the above-mentioned chelating agent can be used conveniently. Particularly preferred are β-diketone, β-ketoester or alkanolamine.

  The component (A) contained in the surface treatment agent of the present invention has a structure in which “a silicon compound (a2) having one or more alkoxy groups in the molecule” is reacted with the above-described titanium compound oligomer (a1). Or it has a mixed composition.

  The “silicon compound (a2) having one or more alkoxy groups in the molecule” is not particularly limited, and examples thereof include silane coupling agents and silicon compounds in which four alkoxy groups are bonded to silicon atoms. . Among these, those containing an amino group, a mercapto group, or an epoxy group are preferable from the viewpoint of improving the film forming property and adhesiveness. In addition, those having a structure in which an alkyl group is directly bonded to a silicon atom are preferable in terms of improving film forming property and adhesiveness. In this case, the alkyl group is preferably a methyl group. Moreover, the partial hydrolysis-condensation product of the said compound can also be used conveniently.

  The type of “silicon compound (a2) having one or more alkoxy groups in the molecule” is not limited to the following, but examples include tetramethoxysilane, tetraethoxysilane, tetranormalpropoxysilane, γ- Aminopropylaminoethyltrimethoxysilane, γ-aminopropylaminoethylmethyldimethoxysilane, γ-aminopropylaminoethyltriethoxysilane, γ-aminopropylaminoethylmethyldiethoxysilane, γ-aminopropyltrimethoxysilane, γ-amino Propyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxyp Propylmethyldimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ-mercaptopropyltriethoxysilane, Examples include γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, and γ-methacryloxypropyltrimethoxysilane. These can be used alone or in admixture of two or more.

  The component (A) preferably has a structure obtained by reacting the “titanium compound oligomer (a1)” with the “silicon compound (a2) having one or more alkoxy groups in the molecule”. Here, the reaction method is not particularly limited, but it is preferable that (a1), (a2) and the solvent are mixed and then refluxed at the boiling point of the solvent used to advance the reaction. There is no regulation in the order of blending.

  The ratio of use of “titanium compound oligomer (a1)” and “silicon compound (a2) having one or more alkoxy groups in the molecule” is not particularly limited, but the mass ratio of (a1) and (a2) is ( a1) / (a2) = 0.1 / 10 to 10 / 0.1, preferably (a1) / (a2) = 0.5 / 10 to 10 / 0.5 (mass ratio). The range is more preferable, and the range of 1/10 to 10/1 (mass ratio) is particularly preferable. In the ratio of (a1) / (a2), if the amount of (a1) used is too small relative to the amount of (a2) used, film-forming properties, adhesiveness, etc. may be reduced, while (a1) When there is too much usage-amount, film forming property, adhesiveness, etc. will be reduced and stability, such as a hydrolyzability, may be insufficient.

  About a component (A), if it has a structure which can be obtained with the said manufacturing method, it will not be limited to what was manufactured with the specific manufacturing method. As the structure of the component (A), the alkoxyl group at the terminal of the titanium compound oligomer (a1) and the alkoxyl group present in the silicon compound (a2) react with each other through moisture in the air or unreacted water, and Ti— Examples include a bonded structure such as O—Si and a structure in which a functional group such as an amino group or a mercapto group present in the silicon compound (a2) is coordinated to a titanium atom, and a structure having such a structure is preferable.

  Component (A) may have a composition in which silicon compound (a2) having one or more alkoxy groups in the molecule is mixed with titanium compound oligomer (a1). The “mixed composition” includes the case where the whole amount of the reaction does not proceed and the unreacted material remains mixed.

The “component (A) composite compound” includes the following five forms, and any of them may be used.
(A1) having a structure obtained by the reaction of (a2) (a1) having a structure obtained by the reaction of (a2) and (a1) a mixture of (a1) and (a2) And a mixture of (a2), a mixture of (a1) and (a2), a mixture of (a1) and (a2), and a mixture of (a1) and (a2). , “One having a structure obtained by the reaction of (a1) and (a2), a mixture of (a1) and (a2)” is preferable.

  The surface treating agent of the present invention contains the component (B) solvent as an essential component. The solvent is not particularly limited, but a solvent having high volatility and high wettability with respect to various adherends is preferable. Preferred solvents include hydrocarbon solvents, ester solvents, alcohol solvents and the like. Specifically, examples of the hydrocarbon solvent include hexane, heptane, toluene, etc., examples of the ester solvent include methyl acetate, ethyl acetate, and propyl acetate, and examples of the alcohol solvent include methanol, Examples include ethanol, normal propanol, isopropanol, normal butanol, isobutanol, and tertiary butanol. Solvents can be used alone or in combination of two or more in consideration of wettability to the adherend.

  Although the content rate of a component (A) in the surface treatment agent of this invention does not have limitation in particular, It is preferable that 1-40 mass parts of components (A) are contained in 100 mass parts of surface treatment agents. The content is more preferably 5 to 30 parts by mass, particularly preferably 2 to 20 parts by mass, and further preferably 2.5 to 10 parts by mass.

  The surface treatment agent of the present invention can be suitably used for sealing materials, adhesives, paints, coating materials and the like. That is, it is preferable to treat the adherend with the surface treatment agent of the present invention before applying the sealing material, adhesive, paint, coating material or the like to the adherend. The surface treatment agent of the present invention is particularly preferably used for treating the surface of an adherend to which a sealing material or an adhesive is applied in terms of wettability to the adherend.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples and comparative examples unless it exceeds the gist.

Manufacturing example 1
[Synthesis of titanium compound oligomer A (tetraisopropoxytitanium oligomer)]
After dissolving 28.4 g (0.10 mol) of tetraisopropyl titanium in 50.0 g of isopropanol, a mixed solution of 2.7 g (0.15 mol) of water and 50.0 g of isopropanol was added dropwise. After completion of dropping, the mixture was stirred for 1 hour to obtain a tetraisopropoxytitanium oligomer. This is designated as “titanium compound oligomer solution A”.

Manufacturing example 2
[Synthesis of titanium compound oligomer B (tetraisopropoxytitanium oligomer)]
A tetraisopropoxytitanium oligomer was obtained in the same manner as in Production Example 1 except that the amount of water relative to 28.4 g (0.10 mol) of tetraisopropyltitanium was changed to 2.2 g (0.12 mol) of water. This is designated as “titanium compound oligomer solution B”.

Manufacturing example 3
[Synthesis of Titanium Compound Oligomer C (Tetranormal Butoxy Titanium Oligomer)]
Tetranormal butoxytitanium (34.0 g, 0.10 mol) was dissolved in normal butal (30.0 g), and then a mixture of 2.7 g (0.15 mol) of water and normal butanol (60.0 g) was added dropwise. After completion of the dropwise addition, the mixture was stirred for 1 hour and further refluxed for 1 hour to obtain a tetranormal butoxytitanium oligomer. This is designated as “titanium compound oligomer solution C”.

Manufacturing example 4
[Synthesis of Titanium Compound Oligomer D (tetranormal butoxytitanium oligomer)]
A tetranormal butoxytitanium oligomer was obtained in the same manner as in Production Example 3 except that the amount of water relative to 34.0 g (0.10 mol) of tetranormalbutoxytitanium was changed to 2.2 g (0.12 mol) of water. . This is designated as “titanium compound oligomer solution D”.

Manufacturing example 5
[Synthesis of titanium compound oligomer E (diisopropoxybisacetylacetonate titanium oligomer)]
After dissolving 36.4 g (0.1 mol) of diisopropoxybisacetylacetonate titanium in 50.0 g of isopropanol, a mixed solution of 2.7 g (0.15 mol) of water and 100.0 g of isopropanol was added dropwise. After completion of dropping, the mixture was stirred for 1 hour and further refluxed for 1 hour to obtain a diisopropoxybisacetylacetonate titanium oligomer. This is designated as “titanium compound oligomer solution E”.

Manufacturing Example 6
[Titanium Compound Oligomer F (Synthesis of Titanium Diisopropoxybistriethanolate Oligomer]
After dissolving 46.2 g (0.1 mol) of titanium diisopropoxybistriethanolate in 50.0 g of isopropanol, a mixed solution of 2.2 g of water (0.12 mol) and 50.0 g of isopropanol was added dropwise. After completion of dropping, the mixture was stirred for 1 hour and further refluxed for 1 hour to obtain a titanium diisopropoxy bistriethanolate oligomer. This is designated as “titanium compound oligomer solution F”.

Example 1
After mixing 10 parts by mass of the titanium compound oligomer solution A (tetraisopropoxytitanium oligomer solution) produced in Production Example 1 and 2.5 parts by mass of γ-aminopropylaminoethyltrimethoxysilane, after refluxing for 1 hour, n- 67.5 parts by mass of hexane and 20 parts by mass of 2-propanol were added to obtain a surface treating agent.

Examples 2-12, Comparative Examples 1-2
In Example 1, except that the titanium compound oligomer (a1), the silicon compound (a2) having one or more alkoxy groups in the molecule, and the solvent were replaced with the types and amounts described in Tables 1 and 2. In the same manner as in Example 1, surface treatment agents (2) to (12) were obtained. Moreover, the surface treating agent of Table 1 and Table 2 was prepared as a comparison. In addition, the numerical value in Table 1 and Table 2 shows the mass%.

Evaluation example 1
[Adhesion evaluation with silicone sealant]
Using the surface treatment agents prepared in Examples 1 to 12 and Comparative Examples 1 and 2, "acrylic electrodeposited aluminum", "mirror-polished stainless steel plate SUS304 plate defined in JIS G4305 (in the table, The coating amount is 20 g / in the surface of each adherend of “mirror surface SUS304”) and “sealing material in which a silicone-based sealing material is previously cured (indicated as“ cured sealing material ”in the table)”. After coating with a brush so as to be m ² , the coating was dried at room temperature (25 ° C.) for 60 minutes.

  After drying at room temperature, “SE792 (manufactured by Dow Corning Toray)”, which is a silicone sealant, is applied as a sealant to a film thickness of 5 mm, and is subjected to an environment of 25 ° C. and 50% RH. A test piece was obtained by curing for one day.

  From these test pieces, the cured sealing material was pulled in the horizontal direction by hand, and the state of cohesive failure of the sealing material when peeled was observed, and the adhesiveness was evaluated from the state of cohesive failure and interface peeling. The results are shown in Table 3.

Evaluation example 2
[Adhesion evaluation with two-component modified silicone sealant]
The sealing material is changed from “SE792 (manufactured by Dow Corning Toray)” to “bond MS seal (manufactured by Konishi Co., Ltd.)” which is a two-component modified silicone sealing material. The adhesiveness was evaluated in the same manner as in Evaluation Example 1 except that the “mortar plate” was added. The results are shown in Table 4.

  When the surface was treated using the surface treating agents of Examples 1 to 12, the sealing material showed good adhesion to any of the evaluated adherends. On the other hand, in Comparative Examples 1 and 2 where surface treatment was performed using a silane coupling agent, peeling sometimes occurred at the interface, and good adhesion was not exhibited.

  The surface treatment agent of the present invention can remarkably improve wettability, film-forming property, adhesion, surface modifying property, etc., for adherends such as metal, resin-coated metal, glass and plastic film. Therefore, it is widely used in industrial fields where sealing materials, adhesives, paints, coating materials and the like are used.

Claims (10)

At least the following component (A) and component (B)
(A) Containing a compound (B) solvent having a structure in which a silicon compound (a2) having one or more alkoxy groups in the molecule is reacted with or mixed with the titanium compound oligomer (a1). A surface treatment agent characterized by The titanium compound oligomer (a1) is a titanium alkoxide represented by the following formula (1) or a titanium chelate compound having a structure in which a chelating agent is coordinated to a titanium alkoxide represented by the following formula (1): The surface treating agent according to claim 1, which has a condensed structure.

Wherein ^(1), R 1 ~R ⁴ represents an alkyl group having 1 to 18 carbon atoms independently. ] The titanium compound oligomer (a1) is condensed with a titanium alkoxide represented by the following formula (1) or a titanium chelate compound having a structure in which a chelating agent is coordinated to a titanium alkoxide represented by the following formula (1). The surface treating agent according to claim 1, which has a structure obtained by further coordinating a chelating agent to the one having the above structure.

Wherein ^(1), R 1 ~R ⁴ represents an alkyl group having 1 to 18 carbon atoms independently. ]   The surface treatment agent according to claim 2 or 3, wherein the condensation is performed by reacting titanium alkoxide or a titanium chelate compound with water in an alcohol solution.   5. The method according to claim 2, wherein the condensation is carried out by reacting 0.5 to 2 mol of water in an alcohol solution with respect to 1 mol of titanium alkoxide and / or titanium chelate compound. The surface treating agent according to claim 1.   6. The claim according to claim 2, wherein the chelating agent is at least one selected from the group consisting of β-diketone, β-ketoester, polyhydric alcohol, alkanolamine and oxycarboxylic acid. Surface treatment agent. The surface treating agent according to any one of claims 2 to 6, wherein R ^{1 to} R ⁴ in the formula (1) are each independently an alkyl group having 1 to 8 carbon atoms.   The surface treating agent according to any one of claims 1 to 7, wherein the silicon compound (a2) having one or more alkoxy groups in the molecule contains an amino group, a mercapto group, or an epoxy group. .   The surface treatment according to any one of claims 1 to 8, wherein the silicon compound (a2) having one or more alkoxy groups in the molecule has a structure in which an alkyl group is directly bonded to a silicon atom. Agent.   The surface treating agent according to any one of claims 1 to 9, wherein the surface treating agent is used for surface treatment of an adherend to which a sealing material or an adhesive is applied.