JP6112067B2 - Primer composition and adhesive bonding or sealing method - Google Patents

Description

  The present invention relates to a primer composition containing an organosilicon compound having a hydrolyzable silyl group and an S—Si bond in the molecule, and an adhesive bonding or sealing method.

In recent years, adhesives and sealing materials have been widely used in buildings and automobiles. The sealing material is a material used for the purpose of filling the joints and gaps between various members to provide watertightness and airtightness. Therefore, it is necessary to exhibit good adhesion to various base materials constituting joints and window frames, that is, inorganic materials such as glass, ceramics, metal, cement, and mortar, and organic materials such as plastic. The self-adhesive property of the sealing material is insufficient, and the use of a primer is essential in many cases.
In addition, the following literature is mentioned as a prior art relevant to this invention.

JP 2000-86990 A JP 2002-265868 A

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a primer composition and an adhesive bonding or sealing method that provide excellent adhesion between a substrate and an adhesive or a sealing agent.

（式中、Ｒ¹は置換もしくは無置換の炭素数１〜１０のアルキル基、又は置換もしくは無置換の炭素数６〜１０のアリール基であり、Ｒ²はそれぞれ独立に置換もしくは無置換の炭素数１〜２０のアルキル基、置換もしくは無置換の炭素数６〜１０のアリール基、炭素数７〜１０のアラルキル基、置換もしくは無置換の炭素数２〜１０のアルケニル基、又は置換もしくは無置換の炭素数１〜２０のアルコキシ基であり、Ｒ³は置換もしくは無置換の炭素数１〜１０のアルキル基、又は置換もしくは無置換の炭素数６〜１０のアリール基であり、ｎは１〜３の整数であり、ｍは１〜１２の整数である。）
で表される有機ケイ素化合物を含有するプライマー組成物が高い密着性を与えることを知見し、本発明をなすに至った。 As a result of intensive studies to achieve the above object,
The following formula (1)

(In the formula, R ¹ is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, and R ² is independently substituted or unsubstituted carbon. An alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, or substituted or unsubstituted Wherein R ³ is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, and n is 1 to 3 is an integer of 3, and m is an integer of 1 to 12.)
It was discovered that the primer composition containing the organosilicon compound represented by the above gives high adhesion, and the present invention has been made.

（式中、Ｒ¹は置換もしくは無置換の炭素数１〜１０のアルキル基、又は置換もしくは無置換の炭素数６〜１０のアリール基であり、Ｒ²はそれぞれ独立に置換もしくは無置換の炭素数１〜２０のアルキル基、置換もしくは無置換の炭素数６〜１０のアリール基、炭素数７〜１０のアラルキル基、置換もしくは無置換の炭素数２〜１０のアルケニル基、又は置換もしくは無置換の炭素数１〜２０のアルコキシ基であり、Ｒ³は置換もしくは無置換の炭素数１〜１０のアルキル基、又は置換もしくは無置換の炭素数６〜１０のアリール基であり、ｎは１〜３の整数であり、ｍは１〜１２の整数である。）
〔２〕
前記有機ケイ素化合物が、下式（２）で表される有機ケイ素化合物を含有することを特徴とする〔１〕記載のプライマー組成物。

（式中、Ｒ¹，ｎ，Ｒ²は上記と同様であり、Ｒ⁴は置換もしくは無置換の炭素数１〜２０のアルキル基、置換もしくは無置換の炭素数６〜１０のアリール基、炭素数７〜１０のアラルキル基、又は置換もしくは無置換の炭素数２〜１０のアルケニル基であり、Ｍｅはメチル基である。）
〔３〕
前記有機ケイ素化合物が、下式（３）〜（８）で表される有機ケイ素化合物のうち１種又は２種以上であることを特徴とする〔１〕又は〔２〕記載のプライマー組成物。

（式中、Ｒ¹，ｎは上記と同様である。Ｍｅはメチル基、Ｅｔはエチル基である。）
〔４〕
（１）基材に〔１〕〜〔３〕のいずれかに記載のプライマー組成物を塗布する工程、
（２）前記プライマー組成物が塗布された基材に接着剤を塗布する工程
を含むことを特徴とする接着結合方法。
〔５〕
前記接着剤が、アクリル系接着剤、エポキシ系接着剤、ウレタン系接着剤、又はシリコーン系接着剤であることを特徴とする〔４〕記載の接着結合方法。
〔６〕
（１）基材に〔１〕〜〔３〕のいずれかに記載のプライマー組成物を塗布する工程、
（２）前記プライマー組成物が塗布された基材にシーリング剤を塗布する工程
を含むことを特徴とするシーリング方法。
〔７〕
前記シーリング剤が、アクリル系シーリング剤、エポキシ系シーリング剤、ウレタン系シーリング剤、又はシリコーン系シーリング剤であることを特徴とする〔６〕記載のシーリング方法。 Accordingly, the present invention provides the following primer composition and adhesive bonding method or sealing method.
[1]
A primer composition comprising an organosilicon compound represented by the following formula (1):

(In the formula, R ¹ is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, and R ² is independently substituted or unsubstituted carbon. An alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, or substituted or unsubstituted Wherein R ³ is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, and n is 1 to 3 is an integer of 3, and m is an integer of 1 to 12.)
[2]
[1] The primer composition according to [1], wherein the organosilicon compound contains an organosilicon compound represented by the following formula (2).

(Wherein R ¹ , n and R ² are the same as above, R ⁴ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, carbon (It is a 7 to 10 aralkyl group or a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, and Me is a methyl group.)
[3]
The primer composition according to [1] or [2], wherein the organosilicon compound is one or more of the organosilicon compounds represented by the following formulas (3) to (8).

(Wherein R ¹ and n are the same as above, Me is a methyl group, and Et is an ethyl group.)
[4]
(1) The process of apply | coating the primer composition in any one of [1]-[3] to a base material,
(2) An adhesive bonding method comprising a step of applying an adhesive to a substrate on which the primer composition is applied.
[5]
[4] The adhesive bonding method according to [4], wherein the adhesive is an acrylic adhesive, an epoxy adhesive, a urethane adhesive, or a silicone adhesive.
[6]
(1) The process of apply | coating the primer composition in any one of [1]-[3] to a base material,
(2) A sealing method comprising a step of applying a sealing agent to a substrate on which the primer composition is applied.
[7]
The sealing method according to [6], wherein the sealing agent is an acrylic sealing agent, an epoxy sealing agent, a urethane sealing agent, or a silicone sealing agent.

  The primer composition of the present invention contains an organosilicon compound having a hydrolyzable silyl group and an S-Si bond in the molecule. By using the primer composition of the present invention, a substrate and an adhesive or sealing are used. Provides excellent adhesion to the agent.

  Hereinafter, the present invention will be specifically described. In the present invention, the “silane coupling agent” is included in the “organosilicon compound”.

[Primer composition]
The primer composition of the present invention is characterized by containing an organosilicon compound (silane coupling agent) having both the following structures (i) and (ii).
(I) Hydrolyzable silyl group (ii) S-Si bond

（式中、Ｒ¹は置換もしくは無置換の炭素数１〜１０のアルキル基、又は置換もしくは無置換の炭素数６〜１０のアリール基であり、Ｒ²はそれぞれ独立に置換もしくは無置換の炭素数１〜２０のアルキル基、置換もしくは無置換の炭素数６〜１０のアリール基、炭素数７〜１０のアラルキル基、置換もしくは無置換の炭素数２〜１０のアルケニル基、又は置換もしくは無置換の炭素数１〜２０のアルコキシ基であり、Ｒ³は置換もしくは無置換の炭素数１〜１０のアルキル基、又は置換もしくは無置換の炭素数６〜１０のアリール基であり、ｎは１〜３の整数であり、ｍは１〜１２の整数である。） The organosilicon compound having both (i) and (ii) can be represented by the following formula (1).

(In the formula, R ¹ is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, and R ² is independently substituted or unsubstituted carbon. An alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, or substituted or unsubstituted Wherein R ³ is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, and n is 1 to 3 is an integer of 3, and m is an integer of 1 to 12.)

（式中、Ｒ¹，ｎ，Ｒ²は上記と同様であり、Ｒ⁴は置換もしくは無置換の炭素数１〜２０のアルキル基、置換もしくは無置換の炭素数６〜１０のアリール基、炭素数７〜１０のアラルキル基、又は置換もしくは無置換の炭素数２〜１０のアルケニル基であり、Ｍｅはメチル基である。） In this case, what is shown as the following formula (2) is preferable.

(Wherein R ¹ , n and R ² are the same as above, R ⁴ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, carbon (It is a 7 to 10 aralkyl group or a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, and Me is a methyl group.)

（式中、Ｒ¹，ｎは上記と同様である。Ｍｅはメチル基、Ｅｔはエチル基である。） Furthermore, what is shown as a following formula (3)-(8) is more preferable, and these 1 type (s) or 2 or more types can be used as an organosilicon compound.

(Wherein R ¹ and n are the same as above, Me is a methyl group, and Et is an ethyl group.)

Examples of the alkyl group and aryl group for R ¹ include a methyl group, an ethyl group, a propyl group, a butyl group, and a phenyl group. Among these, a methyl group and an ethyl group are preferable.

Examples of the alkyl group for R ² include a methyl group, an ethyl group, a tert-butyl group, an octyl group, a decyl group, a dodecyl group, and the like, and examples of the aryl group and aralkyl group include a phenyl group, a benzyl group, a xylyl group, and a tolyl group. Examples of the alkenyl group include a vinyl group, a propenyl group, and a pentenyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an octoxy group, and a dodecoxy group. Among them, a methyl group, an ethyl group, a methoxy group, and an ethoxy group are preferable, and at least one is more preferably a methoxy group or an ethoxy group.

Examples of the alkyl group and aryl group of R ³ include a methyl group, an ethyl group, a propyl group, a butyl group, and a phenyl group. Among these, a methyl group is preferable.

Examples of the alkyl group of R ⁴ include a methyl group, an ethyl group, a tert-butyl group, an octyl group, a decyl group, a dodecyl group, and the like, and examples of the aryl group and aralkyl group include a phenyl group, a benzyl group, a xylyl group, and a tolyl group. Examples of the alkenyl group include a vinyl group, a propenyl group, and a pentenyl group. Among them, a methyl group and an ethyl group are preferable.

  In addition, examples of the substituent in the substituted alkyl group, aryl group, alkenyl group, and alkoxy group include a halogen atom.

  Various additives can be added to the primer composition of the present invention as necessary. Examples of such additives include, for example, dilution solvents, curing catalysts, physical property modifiers that adjust the tensile properties of the resulting cured film, storage stability improvers, radical inhibitors, metal deactivators, ozone degradation. Examples thereof include an inhibitor, a lubricant, and a pigment.

  In this case, the diluent solvent includes alcohol solvents such as methanol, ethanol and isopropanol, aromatic hydrocarbon solvents such as benzene, toluene and xylene, aliphatic hydrocarbon solvents such as pentane, hexane, heptane and decane, diethyl Examples include ether solvents such as ether, tetrahydrofuran and 1,4-dioxane, ester solvents such as ethyl acetate and butyl acetate, and ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone. When these dilution solvents are used, it is preferable to use them so that the concentration of the organosilicon compound is 1 to 50% by mass, particularly 1 to 40% by mass.

  Further, the curing catalyst is not particularly limited. For example, stannous octoate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin oxide, dibutyltin dimethoxide, dibutyltin dimaleate, dibutyltin bisacetylacetonate, dibutyltin Metal catalysts such as silylate and bismuth octylate; divalent organotin compounds such as tin octoate, tin octylate, tin butanoate, tin naphthenate, tin caprylate, tin oleate and tin laurate; dibutyltin dioctoate Dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dimaleate, dibutyltin distearate, dibutyltin dioleate, dibutyltin benzoate, dioctyltin dilaurate, dioctyltin diversate, diphenyltin diacetate, diphenyl Tetravalent organotin compounds such as tiltin dimethoxide, dibutyltin oxide, dibutyltin bis (triethoxysilicate), a reaction product of dibutyltin oxide and phthalate; dibutyltin diacetylacetonate, dibutyltin bis (acetylacetonate) ), Etc .; primary amines such as butylamine, hexylamine, octylamine, dodecylamine, oleylamine, cyclohexylamine, benzylamine; secondary amines such as dibutylamine; diethylenetriamine, triethylenetetramine, Polyamines such as guanidine, diphenylguanidine, xylylenediamine; triethylenediamine and derivatives thereof, 2-methyltriethylenediamine, morpholine, N-methylmorpholine, 2-ethyl-4-methyli Cyclic amines such as dazole and 1,8-diazabicyclo [5.4.0] -7-undecene; aminoalcohol compounds such as monoethanolamine, diethanolamine and triethanolamine; 2,4,6-tris (dimethylaminomethyl) Amine compounds such as aminophenol compounds such as phenol and carboxylates thereof; quaternary ammonium salts such as benzyltriethylammonium acetate; low molecular weight amide resins obtained from excess polyamines and polybasic acids; excess polyamines and epoxies Examples include reaction products with compounds. Among these, a tin-based catalyst and an amine-based catalyst are preferable from the viewpoint of having a small amount and a large catalytic ability. These catalysts can be used singly or in combination of two or more. The blending amount is preferably 0.001 to 5 parts by mass, particularly 0.01 to 3 parts by mass with respect to 100 parts by mass of the organosilicon compound.

  The adhesive bonding method or sealing method of the present invention includes (1) a step of applying the primer composition of the present invention to a substrate, and (2) a step of applying an adhesive or a sealing agent to the substrate coated with the primer. It is characterized by becoming.

  Examples of the adhesive include acrylic adhesives, epoxy adhesives, urethane adhesives, and silicone adhesives.

  Examples of the sealing agent include acrylic sealing agents, epoxy sealing agents, urethane sealing agents, and silicone sealing agents.

  Examples of the base material include various metals such as iron, stainless steel, aluminum, nickel, zinc, and copper; acrylic resin, phenol resin, epoxy resin, polycarbonate resin, polybutylene terephthalate resin, alkali-treated fluorine resin, and the like. Synthetic resin materials; inorganic materials such as glass, ceramic, cement, mortar; and modified silicone, silicone, polyurethane, acrylic urethane, polysulfide, modified polysulfide, butyl rubber, acrylic, SBR, fluorine-containing Sealing materials such as styrene and isobutylene.

  The application method of the primer composition of the present invention is not particularly limited, and a commonly used coating method such as brush coating method, spray coating method, wire bar method, blade method, roll coating method, dipping method, etc. is used. The substrate can be coated. The primer composition of the present invention can usually form a film at room temperature, but the film may be formed under various temperature conditions in order to adjust the film formation rate.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated in more detail, this invention is not limited to these Examples.

[Examples 1 to 3, Comparative Example 1]
Preparation of primer composition ( Preparation of primer composition)
A primer composition was prepared by blending the following components in the amounts shown in Table 1 (unit: g).

有機ケイ素化合物（１０）・・・下式（１０）で表される有機ケイ素化合物

有機ケイ素化合物（１１）・・・下式（１１）で表される有機ケイ素化合物

有機ケイ素化合物（１２）・・・３−メルカプトプロピルトリメトキシシラン
硬化触媒（Ａ）・・・Ｔｉ（ＯⁱＰｒ）₄ Organosilicon compound (9): organosilicon compound represented by the following formula (9)

Organosilicon compound (10): organosilicon compound represented by the following formula (10)

Organosilicon compound (11): organosilicon compound represented by the following formula (11)

Organosilicon compound (12) ... 3-mercaptopropyltrimethoxysilane curing catalyst (A) ... Ti (O ⁱ Pr) ₄

(Adhesion test of primer composition)
In each example and comparative example, an adhesion test was performed as follows. As the adherend, a painted metal plate (Fuji Sashi Co., aluminum plate) coated with fluorine resin paint (Dainippon Paint Co., Ltd., trade name: Dick Flow) by spray, and acrylic resin electrodeposition coated metal A plate (metal plate: aluminum plate manufactured by Fuji Sash Co., Ltd., paint: aluminum plate weather resistance improving paint [Electron AG300, manufactured by Kansai Paint Co., Ltd.]) was used as two types of adherends. After the surface of the adherend was washed with toluene, the primer composition was applied to the surface by brushing and dried to form a primer coating film. Next, a condensation type room temperature curable silicone elastomer composition (Shinetsu Chemical Co., Ltd., Sealant New 70) that releases N, N-diethylhydroxyamine was applied to the primer coating surface and cured. The thickness was 5 mm. The adhesion between the silicone elastomer cured after 14 days and the adherend was examined according to the method of JIS-A-5758. The results are shown in Table 2. In addition, the cohesive failure rate in the table | surface was calculated | required as follows.

Cohesive failure rate [CF: (%)]
The two aluminum plates sandwiching the room temperature curable silicone elastomer were pulled apart in the opposite direction, and the fracture occurred at the rubbery part (cohesive failure area) and the fracture occurred at the interface between the rubbery part and the aluminum plate. The area (interfacial fracture area) was measured, and the cohesive failure rate (%) represented by the following formula was calculated.
Cohesive failure rate (%) = 100. Cohesive failure area / (interface fracture area + cohesive failure area)
In the table, a cohesive failure rate of 100% was described as 100% rubber failure, and a cohesive failure rate of 0% was described as interface failure 100%.

  The results of the above examples and comparative examples demonstrate that the primer composition of the present invention has a high adhesion effect between the coated metal plate and the silicone elastomer.

[Examples 4 to 6, Comparative Example 2]
Preparation of primer composition ( Preparation of primer composition)
A primer composition in which the following components were blended in the amounts shown in Table 3 (unit: g) was prepared.

硬化触媒（Ｂ）・・・ジブチル錫ジラウレート

Curing catalyst (B): Dibutyltin dilaurate

(Adhesion test of primer composition)
In each example and comparative example, an adhesion test was performed as follows. Float glass (50mm x 50mm x 3mm thickness), anodized aluminum plate (50mm x 50mm x 3mm thickness), acrylic resin plate (50mm x 50mm x 3mm thickness) and polyester plate (50mm x 50mm x 3mm thickness) ) The primer composition was applied on top by brushing and dried to form a primer coating film. Then, after applying urethane adhesive (UM700, manufactured by Cemedine Co., Ltd.), it was dried by heating at 120 ° C for 10 minutes, and then left to stand for 3 days at 23 ° C and 55 ° C RH for training. The agent layer was cut with a knife, and a manual peeling test was performed in which the cut portion was peeled off by hand. The state of destruction of the adhesive layer was visually observed. The thickness of the urethane adhesive was 3 mm. The results are shown in Table 4.

  The results of the above examples and comparative examples demonstrate that the primer composition of the present invention demonstrates a high adhesion effect between a glass substrate, an anodized aluminum substrate, an acrylic resin substrate, a polyester resin substrate and a urethane adhesive. It is.

Claims (7)

A primer composition comprising an organosilicon compound represented by the following formula (1):

(In the formula, R ¹ is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, and R ² is independently substituted or unsubstituted carbon. An alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, or substituted or unsubstituted Wherein R ³ is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, and n is 1 to 3 is an integer of 3, and m is an integer of 1 to 12.) The primer composition according to claim 1, wherein the organosilicon compound contains an organosilicon compound represented by the following formula (2).

(Wherein R ¹ , n and R ² are the same as above, R ⁴ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, carbon (It is a 7 to 10 aralkyl group or a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, and Me is a methyl group.) The primer composition according to claim 1 or 2, wherein the organosilicon compound is one or more of the organosilicon compounds represented by the following formulas (3) to (8).

(Wherein R ¹ and n are the same as above, Me is a methyl group, and Et is an ethyl group.) (1) The process of apply | coating the primer composition of any one of Claims 1-3 to a base material,
(2) An adhesive bonding method comprising a step of applying an adhesive to a substrate on which the primer composition is applied.   The adhesive bonding method according to claim 4, wherein the adhesive is an acrylic adhesive, an epoxy adhesive, a urethane adhesive, or a silicone adhesive. (1) The process of apply | coating the primer composition of any one of Claims 1-3 to a base material,
(2) A sealing method comprising a step of applying a sealing agent to a substrate on which the primer composition is applied.   The sealing method according to claim 6, wherein the sealing agent is an acrylic sealing agent, an epoxy sealing agent, a urethane sealing agent, or a silicone sealing agent.