JP5554664B2 - Substrate treatment composition for metal substrate adhesion - Google Patents

Description

  The present invention relates to a base treatment composition capable of imparting good adhesion to a metal substrate.

  Conventionally, many metal substrates have been used for surface materials such as various sandwich panels used for building panels, marine panels and the like. However, there are hydroxides on the surface of the metal substrate due to adsorption of moisture in the atmosphere, etc., oxides are present due to heat during refining and rolling of the metal substrate, and processing oil that has been altered by heat. In many cases, such substances adhere to the adhesiveness.

  The methods for improving adhesion to such metal substrates include physical treatments such as cleaning and polishing, chemical chemical treatments using acids such as phosphoric acid, chromic acid, and sulfuric acid, and baking coating or coating with primers, etc. Methods such as processing are known (for example, Patent Documents 1 to 3).

JP-A-1-297482 JP-A-7-278499 JP 2000-154336 A

  However, in physical treatment, chemical treatment, and baking coating, facilities and processes are large and lack in simplicity. In particular, chemical treatment using an acid compound has a problem in terms of worker safety. Although the primer treatment is relatively simple, the effect of improving the adhesiveness is not sufficient.

  An object of the present invention is to provide a base treatment composition that can provide a metal substrate surface that can be easily dried at room temperature, has high safety, and has good adhesion, for the purpose of improving these problems. .

  As a result of diligent research, the inventors of the present invention have prepared a base treatment composition using a silane compound having a hydrolyzable silyl group and an epoxy group in a molecule and phosphoric acids or phosphonic acids at a specific mixing ratio. It has been found that a metal substrate surface with good adhesion can be obtained even at a low concentration, and the present invention has been completed. That is, this invention is comprised from the following 1st-4th invention.

The present invention will be described in detail below.
1st invention is the surface treatment agent composition containing the silane compound (A) which has a hydrolyzable silyl group and an epoxy group in a molecule | numerator, phosphoric acid or phosphonic acid (B), and an organic solvent (C). The total amount of the silane compound (A) and the phosphoric acid or phosphonic acid (B) is 0.1 to 15% by weight of the total amount of the base treatment composition, and the silane compound ( A base for bonding a metal substrate, wherein the weight ratio of A) to the phosphoric acid or phosphonic acid (B) is (A) :( B) = 1: 0.3-3 The present invention relates to a treatment agent composition.
When a silane compound having a hydrolyzable silyl group and an epoxy group in the molecule and phosphoric acids or phosphonic acids are used in a specific mixing ratio, a metal substrate surface with good adhesion can be obtained even at a low concentration. . As a result, it is possible to obtain an undercoat agent composition that can provide good adhesion to the surface of the metal substrate with a simple operation while ensuring the safety of the operator.

2nd invention is related with the base-treatment agent composition for metal base-material adhesion | attachment which concerns on 1st invention characterized by the said phosphoric acid or phosphonic acid (B) being phosphoric acid.
It is preferable that the phosphoric acid or phosphonic acid (B) is phosphoric acid because a metal substrate surface with good adhesion can be obtained more efficiently.

3rd invention is related with the base-treatment agent composition for metal base-material adhesion | attachment which concerns on the 1st or 2nd invention characterized by the said organic solvent (C) being C6 or less alcohol. Is.
It is preferable to use an alcohol having 6 or less carbon atoms as the organic solvent (C) because a ground treatment composition that is safer and can be dried at room temperature is obtained.

4th invention is related with the base-treatment agent composition concerning the invention in any one of the 1st-3rd characterized by the said metal base material being aluminum or stainless steel.
The surface treatment agent composition of the present invention can give good adhesion particularly to aluminum or stainless steel among metal substrates.

  The use of the base treatment composition according to the present invention provides an effect that a metal substrate surface having a good adhesion and a good safety can be obtained by drying at room temperature.

  Hereinafter, embodiments for carrying out the present invention will be described in detail. In addition, this invention is not limited only to these illustrations, Of course, a various change can be added in the range which does not deviate from the summary of this invention.

[Silane Compound (A)]
The silane compound (A) in the present invention is a compound having a hydrolyzable silyl group and an epoxy group represented by the following general formula (1) in the molecule.
-SiR ¹ _3-a (OR ² ) _a (1)
(However, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, R ² is one or more groups selected from a phenyl group or an alkyl group having 1 to 20 carbon atoms, a is 1, 2 or 3; Each)

As for the silicon atom of the hydrolyzable silyl group, 1 to 3 alkoxyl groups (OR ² ) are bonded as hydrolyzable groups in addition to the bond to the residue of the hydrolyzable silyl group, and the remaining bonds are bonded. 2 to 0 hydrocarbon groups (R ¹ ) are bonded.

Here, the alkoxyl group (OR ² ) is preferably a methoxy group, an ethoxy group, a propoxy group, or a butoxy group, and more preferably a methoxy group or an ethoxy group. The hydrocarbon group (R ¹ ) bonded to the remaining bond of the silicon atom is preferably a methyl group, an ethyl group, a propyl group, a butyl group, or a phenyl group, and is preferably a methyl group, an ethyl group, or a propyl group. A butyl group is more preferable, and a methyl group and an ethyl group are particularly preferable. The hydrolyzable silyl group is preferably an alkyldialkoxysilyl group (a = 2) or a trialkoxysilyl group (a = 3) from the viewpoint of easy availability.

  The silane compound (A) is not particularly limited as long as it satisfies the above conditions. 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycid Xylpropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylethyldiethoxysilane and the like can be used. These may be used alone or in combination of two or more.

  Moreover, the said silane compound (A) may use a commercial item. Examples of such commercially available products include KBM303, KBM402, KBM403, KBE402, KBE403 (trade names, all manufactured by Shin-Etsu Chemical Co., Ltd.), G0261, G0210, D2632 (trade names, all manufactured by Tokyo Chemical Industry Co., Ltd.), PP-40 (trade name, manufactured by Toray Dow Corning Co., Ltd.), SILQUEST A-186, A-187, A-1871 (trade name, manufactured by Momentive Performance Materials Japan GK) and the like.

[About phosphoric acids or phosphonic acids (B)]
The phosphoric acid or phosphonic acid (B) in the present invention is not particularly limited as long as it is represented by any one of the following general formulas (2) to (4).
R ³ O—P (═O) (OH) ₂ Formula (2)
^{HO-P (= O) (} OR 3) 2 ··· Equation (3)
R ³ —P (═O) (OH) ₂ Formula (4)
(However, in any formula, R ³ represents hydrogen or an organic group.)

  Specifically, phosphoric acid, methyl phosphoric acid, butyl phosphoric acid, isodecyl phosphoric acid, 2-ethylhexyl phosphoric acid, lauryl phosphoric acid, stearyl phosphoric acid, oleyl phosphoric acid, phosphonic acid, phenylphosphonic acid and the like can be used. These may be used alone or in combination of two or more. Among these, it is preferable to use phosphoric acid because a metal substrate surface with good adhesion can be obtained more efficiently. Moreover, the said phosphoric acid or phosphonic acid (B) may use a commercial item. As such commercially available products, AP-1, AP-4, DP-4, MP-4, AP-8, AP-10, MP-10 (trade names, all manufactured by Daihachi Chemical Industry Co., Ltd.), Examples include Phoslex A-8, Phoslex A-18D, Phoslex A-18 (trade names, all manufactured by Sakai Chemical Industry Co., Ltd.), and the like.

[Organic solvent (C)]
The organic solvent (C) in the present invention is not particularly limited as long as it is compatible with the silane compound (A) and the phosphoric acid or phosphonic acid (B) to form a uniform solution. Of these, alcohols having 6 or less carbon atoms are preferable in terms of toxicity to workers, odor, and drying properties. Specifically, methanol, ethanol, propanol, 2-propanol, butanol, pentanol, hexanol and the like can be used, and 2-propanol is particularly preferable.

[About the surface treatment agent composition]
The surface treatment agent composition of the present invention can be easily obtained by stirring and mixing at least the silane compound (A), the phosphoric acid or phosphonic acid (B), and the organic solvent (C). At this time, it is preferable to use an airtight container and mix under an inert atmosphere such as nitrogen gas so that the hydrolyzable silyl group of the silane compound (A) does not react with moisture in the air.

In the present invention, the mixing ratio of the silane compound (A) and the phosphoric acid or phosphonic acid (B) is important. The weight ratio of the silane compound (A) and the phosphoric acid or phosphonic acid (B) is (A) :( B) = 1: 0.3-3 (more preferably (A) :( B) = 1: When blended at 0.5 to 2), good adhesion to the metal substrate can be imparted.
The inventors efficiently interacted (or reacted) with the epoxy group contained in the molecule of the silane compound (A) and the hydroxyl group contained in the molecule of the phosphoric acid or phosphonic acid (B). It is assumed that the surface of the metal substrate can be modified. In particular, it is considered that the interaction (or reaction) between the silane compound (A) and the phosphoric acid or phosphonic acid (B) is efficient in the range of the above weight blending ratio, and that good adhesiveness is imparted.

  When it is out of the range of the above blending ratio, the effect of imparting adhesiveness to the surface of the metal substrate is reduced. This is because the interaction (or reaction) between the silane compound (A) and the phosphoric acid or phosphonic acid (B) is unlikely to proceed, or the interaction (or reaction product) between the two tends to be unstable. It is thought that this is because

The blending ratio of the organic solvent (C) in the ground treatment composition of the present invention is such that the total amount of the silane compound (A) and phosphoric acid or phosphonic acid (B) is 0.1 of the total amount of the ground treatment composition. To 15% by weight (preferably 0.2 to 10% by weight).
In the surface treatment agent composition of the present invention, the silane compound (A) and phosphoric acid or phosphonic acid (B) are active ingredients, but if the total amount of these is less than the blending amount, sufficient adhesion strength is obtained. I can't get it. Moreover, when the said mixture ratio is exceeded, since the drying property at normal temperature is bad and stickiness tends to remain on the surface of the metal substrate, the above-mentioned mixture ratio is preferable.

The surface treatment agent composition of the present invention gives a surface having improved adhesiveness to all metal substrates, but exhibits a more remarkable effect particularly on aluminum or stainless steel.
As a method of using the surface treatment agent composition of the present invention, it may be applied to the surface of a metal substrate using a brush or the like, dried at room temperature, and then used for the next process (bonding or painting). . The coating amount of the undercoating composition is not particularly limited is approximately 10 to 50 g / ^{m 2} (preferably 20~40g / ^{m 2).} In addition, the ground treatment composition of the present invention can be suitably used as a pre-process for an adhesion operation (that is, an adhesive application operation) or as a pre-process for a painting operation (that is, a paint application operation). In addition, the surface treatment agent composition of the present invention can be particularly preferably used for urethane resin-based or hydrolyzable silyl group-containing polymer-based adhesives or paints.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to an Example. The present invention should be construed as being based on the knowledge that a ground treatment composition in which a specific compound is mixed in a specific ratio can impart good adhesion to the surface of a metal substrate.

[Preparation of base treatment composition]
The following A liquid-L liquid were prepared as a base-treatment agent composition.
Solution A After dissolving 0.5 parts by weight of phosphoric acid (Kishida Chemical Co., Ltd. “special grade phosphoric acid”) in 99 parts by weight of 2-propanol (Kishida Chemical Co., Ltd. “2-propanol”), 3- 0.5 parts by weight of glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. “KBM403”) was dissolved to obtain a base treatment composition “Liquid A”.

-Liquid B After dissolving 2 parts by weight of phosphoric acid in 96.5 parts by weight of 2-propanol, 1.5 parts by weight of 3-glycidoxypropyltrimethoxysilane was dissolved to prepare a base treatment agent composition "Liquid B "

-Solution C After dissolving 2 parts by weight of phosphoric acid in 95 parts by weight of 2-propanol, 3 parts by weight of 3-glycidoxypropyltrimethoxysilane was dissolved to obtain a base treatment agent composition “C solution”. .

-Solution D After dissolving 5 parts by weight of phosphoric acid in 90 parts by weight of 2-propanol, 5 parts by weight of 3-glycidoxypropyltrimethoxysilane was dissolved to obtain a base treatment agent composition "D solution". .

-Solution E After dissolving 5 parts by weight of phosphoric acid in 90 parts by weight of methanol (Kishida Chemical Co., Ltd. "Methanol"), 5 parts by weight of 3-glycidoxypropyltrimethoxysilane was dissolved to prepare a base treatment composition. “Liquid E” was obtained.

-Solution F After dissolving 2 parts by weight of phosphonic acid (Kishida Chemical Co., Ltd., “phosphonic acid”) in 95 parts by weight of 2-propanol, 3 parts by weight of 3-glycidoxypropyltrimethoxysilane was dissolved to prepare a base. The agent composition “F solution” was obtained.

-Liquid G After dissolving 2 parts by weight of methyl phosphoric acid (Daihachi Chemical Industry Co., Ltd. “AP-1”) in 95 parts by weight of 2-propanol, 3 parts by weight of 3-glycidoxypropyltrimethoxysilane is dissolved. As a result, a surface treatment agent composition “G solution” was obtained.

-Solution H After dissolving 2 parts by weight of phosphoric acid in 95 parts by weight of 2-propanol, 3 parts by weight of 3-glycididoxypropylmethyldiethoxysilane (Shin-Etsu Chemical Co., Ltd. "KBE402") is dissolved as a silane compound. As a result, a base treating agent composition “H liquid” was obtained.

-Solution I 5 parts by weight of phosphoric acid was dissolved in 95 parts by weight of 2-propanol to obtain a base treatment composition "solution I".

-Liquid J 5 parts by weight of 3-glycidoxypropyltrimethoxysilane was dissolved in 95 parts by weight of 2-propanol to obtain a base treatment composition “liquid J”.

-Liquid K After dissolving 2 parts by weight of phosphoric acid in 88 parts by weight of 2-propanol, 10 parts by weight of 3-glycidoxypropyltrimethoxysilane was dissolved to obtain a base treating agent composition "K liquid". .

-Solution L After dissolving 2 parts by weight of phosphoric acid in 95 parts by weight of 2-propanol, 3 parts by weight of vinyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. "KBM1003") is dissolved as a silane compound, and the surface treatment agent A composition “Liquid L” was obtained.

-Solution M After dissolving 2 parts by weight of phosphoric acid in 95 parts by weight of 2-propanol, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. “KBM603”) was used as the silane compound. 3 parts by mass was added to try to prepare a surface treating agent composition. However, when the silane compound was added, it became cloudy and a precipitate was formed, so that a homogeneous surface treatment agent composition could not be obtained.

[Preparation of deposition materials and adhesives]
The following test pieces were prepared as adherend materials (that is, applied materials for the base treatment composition). The long side end 20 mm of each test piece was bent at 90 ° and subjected to a “T-peeling test” described later.
・ Aluminum (A3003) 100mm × 25mm × 0.5mm
・ Stainless steel (SUS304) 100mm x 25mm x 0.7mm
・ Painted aluminum 100mm × 25mm × 0.7mm
Furthermore, a two-component mixed curable urethane resin adhesive prepared by the following method was prepared as an adhesive.
・ Main agent Castor oil-based polyol (ITO SEIKI Co., Ltd. “URIC H-30”) 100 parts by mass, calcium carbonate (Nitto Flour & Chemical Co., Ltd. “NS # 2300”) 100 parts by mass, synthetic zeolite (Union Showa Co., Ltd. “Molecular sieve” 4A ") 10 parts by mass and 0.3 parts by mass of DBU (1,8-diazabicyclo (5,4,0) undecene-7) phenol salt (San Apro Co., Ltd." U-CAT SA-1 ") The mixture was put into a Lee mixer and stirred and mixed under reduced pressure for 30 minutes to obtain a main agent (agent A).
-Curing agent Polymethylene polyphenyl polyisocyanate (Sumika Bayer Urethane Co., Ltd. "Sumijour 44V20") was prepared as a curing agent (B agent) as it was.
In these main agents (agent A) and curing agent (agent B), the hydroxyl group (denoted as OH) in the main component and the isocyanate group (denoted as NCO) in the curing agent are NCO / OH = 1.25. Used as a mixture.

[Test method / T-peeling test]
Each surface treating agent composition (solutions A to L) was applied to the aluminum or stainless steel test piece using a brush (coating amount: 30 g / m ² ) and dried.
Then, the temperature was adjusted to 23 ° C., and the mixed two-component mixed urethane resin adhesive was applied to a test piece of aluminum or stainless steel with a glass rod (applying amount: about 150 g / m ² ), and each was attached to painted aluminum. Combined (bonding area: 25 mm × 15 mm). After curing this at 23 ° C. and 50% relative humidity for 3 days, a T-shaped peeling test (tensile speed: 200 mm / min) was performed to measure the adhesive strength and observe the fracture state. The results are shown in Table 1. Here, the symbol “AF” of the fracture state indicates separation at the aluminum or stainless steel interface, “CF” indicates cohesive failure of the adhesive layer, and “CF / AF” indicates a mixture of cohesive failure and interface failure. Represent.

[Example 1] The base treatment composition “Liquid A” was used.
[Example 2] A base treating agent composition “Liquid B” was used.
[Example 3] A base treating agent composition “C solution” was used.
[Example 4] A base treating agent composition “D solution” was used.
[Example 5] A base treatment composition “E solution” was used.
[Example 6] A base treatment composition “F solution” was used.
[Example 7] A base treatment composition “Liquid G” was used.
[Example 8] A base treatment composition “Liquid H” was used.
[Comparative Example 1] The test piece was subjected to the test as it was without using the base treatment composition.
[Comparative Example 2] The base treatment composition “Liquid I” was used.
[Comparative Example 3] A base treatment composition “Liquid J” was used.
[Comparative Example 4] A base treatment composition “Liquid K” was used.
[Comparative Example 5] The base treatment composition “Liquid L” was used.
[Reference Example] A commercially available wash primer: “Vinylex 110
Active primer "(trade name, epoxy-modified melamine alkyd resin,
Nippon Paint Co., Ltd.) was used.

  As shown in Table 1, the adhesion test of a metal substrate (aluminum, stainless steel) whose surface was treated by applying a pretreatment agent composition (Examples 1 to 7) having the constituent requirements of the present invention in advance. Then, good adhesive strength and fracture state were obtained. On the other hand, in the case of using no base treating agent composition (Comparative Example 1) or using the base treating agent composition lacking the constituent requirements of the present invention (Comparative Examples 2 to 5), the value of the adhesive strength as a whole. Was low, and the fracture state was also interface fracture. In addition, the surface treatment agent composition of the present invention exhibits better adhesive strength and fractured state than those using a commercially available wash primer (reference example) that is currently widely used as a metal substrate surface treatment agent. It was.

The surface treatment agent composition according to the present invention has an effect that a metal substrate surface that is more easily dried at room temperature and has high safety and good adhesion can be obtained, and is extremely useful industrially.

Claims (4)

A silane compound (A) having a hydrolyzable silyl group and an epoxy group in the molecule;
Phosphoric acids or phosphonic acids (B);
A surface treatment agent composition containing an organic solvent (C),
While the total amount of the silane compound (A) and the phosphoric acid or phosphonic acid (B) is 0.1 to 15% by weight of the total amount of the base treatment agent composition,
Metal substrate adhesion, wherein the weight part ratio of the silane compound (A) to the phosphoric acid or phosphonic acid (B) is (A) :( B) = 1: 0.3-3 Surface treatment agent composition for   The ground treatment composition for adhesion to a metal substrate according to claim 1, wherein the phosphoric acid or phosphonic acid (B) is phosphoric acid.   The said organic solvent (C) is C6 or less alcohol, The base-treatment agent composition for metal base-material adhesion | attachment of Claim 1 or 2 characterized by the above-mentioned. The said metal base material is aluminum or stainless steel, The base-treatment agent composition as described in any one of Claims 1-3 characterized by the above-mentioned.