JP2020026496A - Organopolysiloxane composition - Google Patents

Abstract

To provide an organopolysiloxane composition which is hardened at an ordinary temperature and provides a hardened silicone rubber product having an excellent adhesion property to a magnesium alloy and a resin by itself.SOLUTION: The present invention provides an organopolysiloxane composition containing (A) an organopolysiloxane represented by the following formula (1) and/or (2), HO(SiRO)H(1), where R is a monovalent hydrocarbon group, n is 10 or more and X is O or an alkylene group, m is 0 or 1, (B) an organosilicon compound and/or a partial hydrolytic condensate thereof having three or more hydrolyzable groups each bound to a silicon atom in one molecule, excluding (A), (C) and (D), (C) an ester group-containing silane coupling agent, and (D) an amino silane coupling agent and/or a partial hydrolytic condensate thereof.SELECTED DRAWING: None

Description

  The present invention relates to an organopolysiloxane composition which gives a cured silicone rubber exhibiting excellent magnesium alloy adhesiveness and resin adhesiveness when cured at room temperature.

  In recent years, magnesium alloys represented by AZ-91D have been characterized by their light weight, high strength, corrosion resistance, designability, and recyclability, and are characterized by cell phones, digital videos, digital cameras, liquid crystal projectors, plasma displays, personal computers, MD players, and DVDs. It is widely used in information equipment such as recorders, electrical components, automobile oil pans, intake manifolds, lock housing parts, steering upper brackets, steering wheels, and other transportation equipment components, and has good self-adhesive properties to these components. There is a need for an organopolysiloxane composition for bonding magnesium alloys having the same.

  However, since these magnesium alloys are very difficult to adhere, a chemical conversion treatment is indispensable for adhesion, and organopolysiloxane compositions that have self-adhesiveness to magnesium alloys without treatment have been used to date. Only example approaches have been proposed. Japanese Patent Application Publication No. 2003-535152 (Patent Document 1) proposes a composition using a curable silicone and an amino group-containing silane adhesion promoter as a filler. Japanese Patent No. 3818365 (Patent Document 2) proposes a composition using an inorganic compound containing a metal element having a smaller ionization tendency than magnesium as a silicone oil and a curing agent. Further, in Japanese Patent No. 4553110 (Patent Document 3), adhesion to a magnesium alloy is achieved by using an acidic silane coupling agent whose pH of a 5% by mass aqueous solution of the silane coupling agent is 7 or less. . Furthermore, Japanese Patent Application Laid-Open No. 2007-204575 (Patent Document 4) reports adhesion to a magnesium alloy by using a zinc compound and an organopolysiloxane having a terminal silethylene bond in a base oil as a filler. However, in Patent Document 1, the effectiveness of amino group-containing silane adhesion promoters such as γ-aminopropyl trialkoxysilane and trialkoxypropyl ethylenediamine is insufficient. And base oils, it lacks flexibility in material design. Patent Document 3 discloses that the use of the exemplified acidic silane coupling agent improves the adhesion of the magnesium alloy, but does not describe the adhesion to the resin.

  In recent years, attempts have been made to partially convert metal to resin from the viewpoint of weight reduction and recyclability. As a resin used as those members, a resin having a small change rate with respect to mechanical characteristics and various durability tests, that is, a resin that is extremely stable mechanically and chemically is generally selected. It is said that a chemically stable resin does not have an active group or has very few active groups, so that it is difficult to obtain good adhesiveness, and furthermore, it is difficult to stably maintain the adhesiveness. . As a method for improving the adhesiveness to a resin, a method of adding an oligomer of an aminosilane coupling agent to a room-temperature-curable organopolysiloxane composition (Japanese Patent No. 3714861: Patent Document 5) is known. No examples have been reported in which both magnesium alloy adhesion and resin adhesion are compatible.

  If both magnesium alloy adhesiveness and resin adhesiveness can be achieved, a single type of adhesive can be used for a variety of applications, eliminating the need to use multiple adhesives, eliminating the need for manufacturing processes and products. Management becomes simple.

JP 2003-535152 A Japanese Patent No. 3818365 Japanese Patent No. 4553110 JP 2007-204575 A Japanese Patent No. 3714861

  SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and provides an organopoly which cures at room temperature by atmospheric moisture (crosslinking by a condensation reaction) to provide a silicone rubber cured product having good self-adhesiveness to magnesium alloys and resins. An object of the present invention is to provide a siloxane composition, in particular, an organopolysiloxane composition for bonding a magnesium alloy and a resin.

  The present inventors have conducted intensive studies focusing on the specificity of the magnesium alloy adherend and the resin in order to achieve the above object. As a result, (A) general formulas (1) and / or (2) described later (B) an organosilicon compound other than the (A) component, the (C) component and the (D) component, which has at least three hydrolyzable groups bonded to a silicon atom in one molecule; And / or a partially hydrolyzed condensate thereof, (C) a silane coupling agent having a specific molecular structure having a carboxylic acid silyl ester bond, (D) a silane coupling agent having a functional group containing a nitrogen atom, and preferably (E) A) an organopolysiloxane composition containing at least one filler is cured at room temperature (23 ° C. ± 10 ° C.) by atmospheric moisture (crosslinking by a condensation reaction) to form a magnesium alloy and a resin; It found to give a silicone rubber cured product with good self adhesion to, the present invention has been accomplished.

（式中、Ｒ及びｎは上記の通りであり、Ｘは独立に酸素原子又は炭素数２〜５のアルキレン基であり、ｍは独立に０又は１である。）
（Ｂ）一分子中にケイ素原子に結合した加水分解可能な基を少なくとも３個有する、（Ａ）成分、（Ｃ）成分及び（Ｄ）成分以外の有機ケイ素化合物及び／又はその部分加水分解縮合物：０．１〜５０質量部、
（Ｃ）下記一般式（３）で示されるシランカップリング剤：０．１〜１５質量部、

（式中、Ｒ¹、Ｒ²、Ｒ³は同一又は異種の炭素数１〜１０の一価炭化水素基であり、ｋは３〜１４の整数であり、ａは０〜２の整数であり、ｂは０〜３の整数である。）
（Ｄ）下記一般式（４）で示されるシランカップリング剤及び／又はその部分加水分解縮合物 ０．１〜１５質量部
Ｒ⁴Ｓｉ（Ｒ⁶）_c（ＯＲ⁵）_3-c （４）
（式中、Ｒ⁴は少なくとも１個の１級アミノ基及び／又は２級アミノ基から選ばれる窒素原子を含む官能性基を有する炭素数１〜２０の一価炭化水素基である。Ｒ⁵、Ｒ⁶はそれぞれ独立に炭素数１〜１０の非置換又は置換一価炭化水素基であり、ｃは０、１又は２である。）
を含有してなるオルガノポリシロキサン組成物。
［２］
（Ｂ）成分が、下記一般式（５）で示される加水分解性オルガノシラン化合物及び／又はその部分加水分解縮合物である［１］に記載のオルガノポリシロキサン組成物。
Ｒ⁷ _dＳｉＲ⁸ _4-d （５）
（式中、Ｒ⁷は一価炭化水素基であり、Ｒ⁸は独立に加水分解性基である。ｄは０又は１である。）
［３］
（Ｄ）成分が、下記一般式（６）

（式中、Ｒ⁹、Ｒ¹⁰はそれぞれ独立に炭素数１〜１０の非置換一価炭化水素基であり、Ｒ¹¹は炭素数１〜１０の二価炭化水素基であり、Ｒ¹²は芳香環を含む炭素数７〜１０の二価炭化水素基であり、ｅは１〜３の整数である。但し、ＮＨ基及びＮＨ₂基の少なくとも一方はＲ¹²の芳香環に直結していない。）
で示されるシランカップリング剤及び／又はその部分加水分解縮合物である［１］又は［２］に記載のオルガノポリシロキサン組成物。
［４］
更に、（Ｅ）成分として少なくとも１種の充填剤を（Ａ）成分１００質量部に対して１〜５００質量部含有してなる［１］〜［３］のいずれかに記載のオルガノポリシロキサン組成物。
［５］
マグネシウム合金及び樹脂接着用である［１］〜［４］のいずれかに記載のオルガノポリシロキサン組成物。 Accordingly, the present invention provides the following organopolysiloxane composition.
[1]
(A) an organopolysiloxane represented by the following general formula (1) and / or (2): 100 parts by mass,
HO (SiR ₂ O) _n H (1)
(In the formula, R is the same or different and is an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 10 or more.)

(In the formula, R and n are as described above, X is independently an oxygen atom or an alkylene group having 2 to 5 carbon atoms, and m is independently 0 or 1.)
(B) an organosilicon compound other than the component (A), the component (C) and the component (D), which has at least three hydrolyzable groups bonded to a silicon atom in one molecule, and / or a partial hydrolytic condensation thereof. Product: 0.1 to 50 parts by mass,
(C) a silane coupling agent represented by the following general formula (3): 0.1 to 15 parts by mass,

(Wherein, R ¹ , R ² , and R ³ are the same or different monovalent hydrocarbon groups having 1 to 10 carbon atoms, k is an integer of 3 to 14, and a is an integer of 0 to 2 , B is an integer of 0 to 3.)
(D) A silane coupling agent represented by the following general formula (4) and / or a partially hydrolyzed condensate thereof 0.1 to 15 parts by mass R ⁴ Si (R ⁶ ) _c (OR ⁵ ) _3-c (4)
(Wherein, R ⁴ is a monovalent hydrocarbon group having 1 to 20 carbon atoms having a functional group containing at least one primary amino group and / or secondary nitrogen atom selected from an amino group .R ⁵ , R ⁶ are each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and c is 0, 1 or 2.)
An organopolysiloxane composition comprising:
[2]
The organopolysiloxane composition according to [1], wherein the component (B) is a hydrolyzable organosilane compound represented by the following general formula (5) and / or a partially hydrolyzed condensate thereof.
R ⁷ _d SiR ⁸ _4-d (5)
(In the formula, R ⁷ is a monovalent hydrocarbon group, and R ⁸ is independently a hydrolyzable group. D is 0 or 1.)
[3]
The component (D) has the following general formula (6)

(Wherein, R ⁹ and R ¹⁰ are each independently an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R ¹¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ¹² is an aromatic group. A divalent hydrocarbon group having 7 to 10 carbon atoms including a ring, and e is an integer of 1 to _3. However, at least one of the NH group and the NH ₂ group is not directly bonded to the aromatic ring of R ¹² . )
The organopolysiloxane composition according to [1] or [2], which is a silane coupling agent and / or a partially hydrolyzed condensate thereof.
[4]
The organopolysiloxane composition according to any one of [1] to [3], further comprising 1 to 500 parts by mass of at least one filler as component (E) based on 100 parts by mass of component (A). object.
[5]
The organopolysiloxane composition according to any one of [1] to [4], which is used for bonding a magnesium alloy and a resin.

  The organopolysiloxane composition of the present invention is intended to provide a cured silicone rubber exhibiting excellent magnesium alloy adhesiveness and resin adhesiveness by curing at room temperature, and in particular, an organopolysiloxane composition for bonding magnesium alloy and resin. Useful as

（式中、Ｒは同一又は異種の炭素数１〜１０の非置換もしくはハロゲン原子置換の一価炭化水素基であり、ｎは１０以上の整数であり、Ｘは独立に酸素原子又は炭素数２〜５のアルキレン基であり、ｍは独立に０又は１である。） [(A) component]
The organopolysiloxane of the component (A) used in the organopolysiloxane composition of the present invention acts as a main component (base polymer) of the composition of the present invention, and has the following general formula (1) and / or (2) It is shown by.
HO (SiR ₂ O) _n H (1)
(In the formula, R is the same or different and is an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 10 or more.)

(Wherein, R is the same or different and is an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 10 or more, and X is independently an oxygen atom or 2 carbon atoms. And m is independently 0 or 1.)

  In the general formulas (1) and (2), R is an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, for example, an alkyl group such as a methyl group, an ethyl group, or a propyl group; cyclohexyl A cycloalkyl group such as a group; an alkenyl group such as a vinyl group and an allyl group; an aryl group such as a phenyl group and a tolyl group; and a hydrogen atom bonded to a carbon atom of these groups is partially substituted with a halogen atom. Groups, for example, 3,3,3-trifluoropropyl group. Among these, a methyl group, a vinyl group, a phenyl group, and a 3,3,3-trifluoropropyl group are preferable, and a methyl group is particularly preferable. A plurality of Rs in the general formulas (1) and (2) may be the same or different groups.

  In addition, n is an integer of 10 or more, particularly an integer such that the viscosity at 25 ° C. of the organopolysiloxane is in the range of 25 to 500,000 mPa · s, and preferably in the range of 500 to 100,000 mPa · s. In the present invention, the viscosity is a value at 25 ° C. measured by a rotational viscometer (for example, BL type, BH type, BS type, cone plate type, rheometer, etc.). Specifically, the value of n for providing such a viscosity may be an integer of usually about 10 to 2,000, preferably about 20 to 1,500, and more preferably about 50 to 1,000.

In the general formula (2), X is independently an oxygen atom or an alkylene group having 2 to 5 carbon atoms, and examples of the alkylene group having 2 to 5 carbon atoms include an ethylene group, a propylene group, and a butylene group. Is exemplified. Among these, X is preferably an oxygen atom or an ethylene group.
m is independently 0 or 1.

[Component (B)]
The component (B) used in the organopolysiloxane composition of the present invention functions as a crosslinking agent (curing agent), and has at least three hydrolyzable groups bonded to silicon atoms in one molecule. It is a hydrolyzable organosilicon compound and / or a partially hydrolyzed condensate thereof other than the components (A), (C) and (D). The organosilicon compound of the component (B) is usually hydrolyzable. Other than the basic group, the compound does not contain a hetero atom such as a nitrogen atom, an oxygen atom, and a sulfur atom in the molecule. Examples of the organosilicon compound include a hydrolyzable organosilane compound represented by the following general formula (5) and / or a partially hydrolyzed condensate thereof (that is, a molecule formed by partially hydrolyzing and condensing the organosilane compound). Organosiloxane oligomers having at least two, preferably at least three, residual hydrolyzable groups therein are preferred.
R ⁷ _d SiR ⁸ _4-d (5)
(In the formula, R ⁷ is a monovalent hydrocarbon group, and R ⁸ is independently a hydrolyzable group. D is 0 or 1, and preferably 1.)

In Formula (5), examples of the hydrolyzable group R ⁸ include a ketoxime group, an alkoxy group, an acyloxy group, and an alkenyloxy group. Specifically, a ketoxime group having 3 to 8 carbon atoms such as a dimethyl ketoxime group, a methyl ethyl ketoxime group, a methyl isobutyl ketoxime group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, and sec. -Butoxy group, tert-butoxy group and the like having 1 to 4 carbon atoms, particularly 1 to 2 carbon atoms such as an alkoxy group, acetoxy group and propionoxy group having 2 to 4 carbon atoms, a vinyloxy group, an allyloxy group and a propenoxy group And an alkenyloxy group having 2 to 4 carbon atoms such as an isopropenoxy group.
The remaining group R ⁷ bonded to the silicon atom other than the hydrolyzable group is not particularly limited as long as it is a monovalent hydrocarbon group, and specifically, a methyl group, an ethyl group, a propyl group And monovalent hydrocarbon groups having 1 to 10 carbon atoms such as alkyl groups such as butyl group, alkenyl groups such as vinyl group, and aryl groups such as phenyl group. Among these, a methyl group, an ethyl group, a vinyl group, and a phenyl group are preferable.

  Specific examples of such component (B) include tetrakis (methylethylketoxime) silane, methyltris (dimethylketoxime) silane, methyltris (methylethylketoxime) silane, ethyltris (methylethylketoxime) silane, methyltris (methylisobutylketoxime) silane , Ketoxime silanes such as vinyltris (methylethylketoxime) silane [also known as vinyltributanoxime silane], methyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, tetramethoxysilane, vinyltriethoxysilane, tetraethoxysilane Such as alkoxysilanes, acetoxysilanes such as methyltriacetoxysilane and vinyltriacetoxysilane, and methyltriisoprope Kishishiran, vinyltriisopropenoxysilane, isopropenoxysilane silanes such as phenyltrimethoxysilane isopropenoxysilane silane, and the like partially hydrolyzed condensate of the silane. These may be used alone or in combination of two or more.

  Component (B) is used in an amount of 0.1 to 50 parts by mass, preferably 5 to 30 parts by mass, per 100 parts by mass of component (A). If the amount is less than 0.1 part by mass, sufficient crosslinking cannot be obtained, and it is difficult to obtain a desired composition having rubber elasticity. If the amount exceeds 50 parts by mass, the obtained cured product tends to have low mechanical properties.

The component (B) is clearly different from the component (A) in that the component (B) does not have a repeating structure of a bifunctional diorganosiloxane unit represented by (SiR ₂ O) _n in the molecule. The component (B) has a carboxylic acid silyl ester bond or a functional group containing at least one nitrogen atom selected from a primary amino group and / or a secondary amino group in the molecule. This is clearly different from the silane coupling agent of the component (C) and the component (D) described later in that it is not used.

[(C) component]
The silane coupling agent of the component (C) used in the organopolysiloxane composition of the present invention has one to four carboxylic acid silyl ester bonds in the molecule. This is essential for imparting good magnesium alloy adhesion to the obtained cured product (silicone rubber). As described in Patent Document 3, an acid-based silane coupling agent is effective for improving adhesion to a magnesium alloy. In the silane coupling agent having a carboxylic acid silyl ester group used in the present invention, the carboxyl group is protected by a silyl group when uncured, but the carboxyl group is expressed by the removal of the silyl group by hydrolysis during curing. By doing so, an improvement in the adhesive strength to the magnesium alloy is realized. Further, by protecting a highly active carboxyl group with a silyl group, it is possible to use a carboxyl group in combination with an amino group-containing silane coupling agent, which has been difficult with conventional acid-based silane coupling agents.

（式中、Ｒ¹、Ｒ²、Ｒ³は同一又は異種の炭素数１〜１０の一価炭化水素基であり、ｋは３〜１４の整数であり、ａは０〜２の整数であり、ｂは０〜３の整数である。） The carboxylic acid silyl ester group-containing silane coupling agent according to the present invention has a structure represented by the following general formula (3).

(Wherein, R ¹ , R ² , and R ³ are the same or different monovalent hydrocarbon groups having 1 to 10 carbon atoms, k is an integer of 3 to 14, and a is an integer of 0 to 2 , B is an integer of 0 to 3.)

In the general formula (3), OR ¹ is a hydrolyzable group in the silane coupling agent, and R ¹ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, for example, a methyl group Alkyl groups such as ethyl, propyl and the like; cycloalkyl groups such as cyclohexyl; saturated or unsaturated aliphatic hydrocarbon groups such as alkenyl such as vinyl and allyl; aryl groups such as phenyl and tolyl An aromatic hydrocarbon group such as an aralkyl group such as a benzyl group and a phenylethyl group; Among these, an alkyl group such as a methyl group, an ethyl group, and a propyl group is preferable, and a methyl group and an ethyl group are particularly preferable.
The value of a in the formula is an integer of 0 to 2, and is preferably 0.

In the general formula (3), R ² is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, for example, an alkyl group such as a methyl group, an ethyl group or a propyl group; a cycloalkyl group such as a cyclohexyl group. Alkyl group; saturated or unsaturated aliphatic hydrocarbon group such as alkenyl group such as vinyl group and allyl group; aryl group such as phenyl group and tolyl group; aromatic carbon group such as aralkyl group such as benzyl group and phenylethyl group. And a hydrogen group. Among these, an alkyl group such as a methyl group, an ethyl group and a propyl group, and an aryl group such as a phenyl group are preferable, and a methyl group and a phenyl group are particularly preferable.

In the general formula (3), R ³ is derived from a silyl group that protects a carboxyl group and is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, such as a methyl group and an ethyl group. Alkyl groups such as propyl and isopropyl groups; cycloalkyl groups such as cyclohexyl groups; saturated or unsaturated aliphatic hydrocarbon groups such as alkenyl groups such as vinyl and allyl groups; aryl groups such as phenyl and tolyl groups An aromatic hydrocarbon group such as an aralkyl group such as a benzyl group and a phenylethyl group; and a protecting group such as a tert-butyldimethyl group and a tert-butyldiphenyl group. Among these, protective groups such as an alkyl group such as a methyl group, an ethyl group, a propyl group, and an isopropyl group, an alkenyl group such as a vinyl group, an aryl group such as a phenyl group, a tert-butyldimethyl group, and a tert-butyldiphenyl group. Preferred are a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyldimethyl group and a tert-butyldiphenyl group.
In the formula, the value of b is an integer of 0 to 3, preferably an integer of 1 to 3, and more preferably 3. When the value of b is 2 or 3, even if the structures of R ³ are the same, It may be heterogeneous.

  In the general formula (3), k represents the number of repetitions of the saturated hydrocarbon group of the spacer connecting the hydrolyzable alkoxysilyl group of the silane coupling agent and the carboxylic acid silyl ester group. In the formula, the value of k is an integer of 3 to 14, preferably an integer of 5 to 13, and more preferably an integer of 8 to 11. When the value of k is less than 3, the synthesis becomes difficult. When the value of k is more than 14, the molecular weight becomes too large, and the adhesiveness may be reduced.

Specific examples of such a carboxylic acid silyl ester group-containing silane coupling agent include the following compounds. In the formula, ⁱ Pr represents an isopropyl group, ^t Bu represents a tert-butyl group, and Ph represents a phenyl group.

The component (C) is clearly different from the component (A) in that it does not have a repeating structure of a bifunctional diorganosiloxane unit represented by (SiR ₂ O) _n in the molecule. The component (C) is a component having a carboxylic acid silyl ester bond in the molecule, and a nitrogen atom selected from at least one primary amino group and / or secondary amino group. In that it has no functional group containing an atom, it is clearly different from the silane coupling agent of the component (B) and the component (D) described later.

[(D) component]
Next, the component (D) is a silane coupling agent represented by the following general formula (4) (that is, a hydrolyzable organosilane compound having a functional group-containing monovalent hydrocarbon group) and / or its partial hydrolysis. It is a condensate and is an essential component for developing good resin adhesion to the present composition.
R ⁴ Si (R ⁶ ) _c (OR ⁵ ) _3-c (4)
(Wherein, R ⁴ is a monovalent hydrocarbon group having 1 to 20 carbon atoms having a functional group containing at least one primary amino group and / or secondary nitrogen atom selected from an amino group .R ⁵ , R ⁶ are each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and c is 0, 1 or 2.)

In the above formula (4), R ⁴ is a functional group containing a nitrogen atom selected from at least one primary amino group and / or secondary amino group (for example, unsubstituted or substituted amino group, unsubstituted or substituted imino group). A monovalent hydrocarbon group having 1 to 20 carbon atoms having at least one group such as an N-β (aminoethyl) -γ-aminopropyl group and a γ-amino group. Monovalent carbonization having at least one of nitrogen atoms such as propyl group, N-phenyl-γ-aminopropyl group, γ-ureidopropyl group, γ-acetamidopropyl group and having 3 to 20 carbon atoms, particularly 8 to 14 carbon atoms. And a hydrogen group.

Also, R ^5, R ⁶ are each independently from 1 to 10 carbon atoms, in particular unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms, is the same as R ¹ of the above-mentioned formula (1) Examples include a methyl group, an ethyl group, a propyl group, and an isopropyl group.

（式中、Ｒ⁹、Ｒ¹⁰はそれぞれ独立に炭素数１〜１０の非置換一価炭化水素基であり、Ｒ¹¹は炭素数１〜１０の二価炭化水素基であり、Ｒ¹²は芳香環を含む炭素数７〜１０の二価炭化水素基であり、ｅは１〜３の整数である。但し、ＮＨ基及びＮＨ₂基の少なくとも一方はＲ¹²の芳香環に直結していない。） Further specific examples of the hydrolyzable silane coupling agent as the component (D) include a carbon atom having a functional group containing a nitrogen atom selected from at least one primary amino group and / or secondary amino group. Any one of silane compounds containing one monovalent hydrocarbon group and 1 to 3 organooxy groups can be used. Among them, silane compounds represented by the following general formula (6) can be used. When a coupling agent (hydrolyzable organosilane compound) and / or a partially hydrolyzed condensate thereof is used, the adhesiveness is further improved.

(Wherein, R ⁹ and R ¹⁰ are each independently an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R ¹¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ¹² is an aromatic group. A divalent hydrocarbon group having 7 to 10 carbon atoms including a ring, and e is an integer of 1 to _3. However, at least one of the NH group and the NH ₂ group is not directly bonded to the aromatic ring of R ¹² . )

The silane coupling agent represented by the above formula (6) has an NH group (imino group) and an NH ₂ group (amino group), contains an aromatic ring between the NH group and the NH ₂ group, and further has NH 4 This is an alkoxysilane compound in which at least one of the group and the NH ₂ group is not directly bonded to the carbon atom constituting the aromatic ring, and is described in detail in JP-A-5-105689.

In the above formula (6), examples of the unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms, of R ⁹ and R ¹⁰ include a methyl group, an ethyl group, a propyl group, a butyl group and a hexyl group. An alkyl group such as a cyclohexyl group; an alkenyl group such as a vinyl group, an allyl group, a propenyl group, a butenyl group, and a hexenyl group; an aryl group such as a phenyl group and a tolyl group; An aralkyl group and the like can be mentioned. As R ⁹ , a methyl group or an ethyl group is preferable, and as R ¹⁰ , a methyl group is preferable.

Examples of the divalent hydrocarbon group having 1 to 10 carbon atoms for R ¹¹ include a methylene group, an ethylene group, a propylene group, a tetramethylene group, a hexamethylene group, an octamethylene group, a decamethylene group, and a 2-methylpropylene group. Examples thereof include an arylene group such as an alkylene group and a phenylene group, and a group in which the alkylene group and the arylene group are bonded. A methylene group, an ethylene group, and a propylene group are preferable, and a propylene group is particularly preferable.

As the divalent hydrocarbon group having 7 to 10 carbon atoms and containing an aromatic ring represented by R ^12, a group in which a phenylene group and an alkylene group are bonded is preferable, and examples thereof include those represented by the following formula.
-C ₆ H ₄ -CH _{2-
-C 6 H 4 -CH 2 -CH 2} -
_{-C 6 H 4 -CH 2 -CH 2} -CH 2 -
-CH ₂ -C ₆ H ₄ -
_{-CH 2 -C 6 H 4 -CH 2} -
_{-CH 2 -C 6 H 4 -CH 2} -CH 2 -
_{-CH 2 -C 6 H 4 -CH 2} -CH 2 -CH 2 -
_{-CH 2 -CH 2 -C 6 H 4} -
_{-CH 2 -CH 2 -C 6 H 4} -CH 2 -
_{-CH 2 -CH 2 -C 6 H 4} -CH 2 -CH 2 -
_{-CH 2 -CH 2 -CH 2 -C 6} H 4 -
_{-CH 2 -CH 2 -CH 2 -C 6} H 4 -CH 2 -
Is - among these, particularly preferably _{-CH 2 -C 6 H 4 -CH 2} .

In this case, the alkylene group bonded to the right side of the phenylene group (on the NH ₂ side in the formula (6)) (in the case where there is no alkylene group, becomes —NH ₂ group) even if it is at the ortho, meta or para position Good.

Examples of the silane coupling agent represented by the general formula (6) include the following.

The silane coupling agent and / or the partially hydrolyzed condensate thereof of the component (D) may be used alone or in combination of two or more.
The compounding amount of the component (D) is 0.1 to 15 parts by mass, preferably 0.1 to 5 parts by mass, per 100 parts by mass of the component (A). If the amount is less than 0.1 part by mass, the cured product will not show sufficient adhesive performance. If the amount exceeds 15 parts by mass, the rubber strength after curing or the curability will decrease.

[(E) component]
In the organopolysiloxane composition of the present invention, (E) a filler can be blended, and as the filler, a reinforcing or non-reinforcing filler for imparting rubber properties to the present composition is used. be able to. As such a filler, specifically, surface-treated or untreated fumed silica, precipitated silica, wet silica, carbon powder, talc, bentonite, surface-treated or untreated calcium carbonate, zinc carbonate, magnesium carbonate And surface-treated or untreated calcium oxide, zinc oxide, magnesium oxide, aluminum oxide, aluminum hydroxide, and the like. These can be used alone or in combination of two or more.

  When compounding the filler of the component (E), the compounding amount is preferably in the range of 1 to 500 parts by mass, more preferably 5 to 450 parts by mass, per 100 parts by mass of the component (A). Range. If the amount is less than 1 part by mass, sufficient adhesive strength to the intended magnesium alloy and resin may not be obtained due to insufficient rubber strength, and if it exceeds 500 parts by mass, the viscosity of the material becomes high and the workability may be poor. .

[Other ingredients]
The organopolysiloxane composition of the present invention may contain, in addition to the above components, generally known additives and catalysts, as long as they do not adversely affect the curability at room temperature and the self-adhesion to magnesium alloys and resins. In particular, a condensation reaction catalyst) may be used. As additives, polyethers as thixotropy improvers, pigments, coloring agents such as dyes, heat resistance improvers such as red iron oxide and cerium oxide, cold resistance improvers, rust inhibitors, plasticizers, potassium methacrylate and the like Examples include oil resistance improvers and the like, and if necessary, fungicides, antibacterial agents and the like. Examples of the catalyst (condensation reaction catalyst) include organometallic compounds such as organic tin ester compounds, organic tin chelate compounds, alkoxytitanium compounds, and titanium chelate compounds, and silicon compounds having a guanidyl group.

  The organopolysiloxane composition of the present invention may contain components other than the components (B), (C), and (D) as long as the composition does not adversely affect the curability at room temperature and the self-adhesion to magnesium alloys and resins. In combination with a generally known silane coupling agent (ie, a so-called carbon functional silane compound having a functional group-containing monovalent hydrocarbon group and at least two hydrolyzable groups in the molecule). Is also good. Contains an epoxy group such as 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane Methacryloxy group-containing alkoxysilanes such as alkoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-mercapto Mercapto group-containing alkoxysilanes such as propyltrimethoxysilane and 3-mercaptopropylmethyldimethoxysilane; 3-isocyanatopropyltrimethoxysilane; Tokishishiran, 3-isocyanate propyl methyl dimethoxy silane, an isocyanate group-containing alkoxysilanes such as 3-isocyanate propyl methyl diethoxy silane can be cited.

[Preparation of organopolysiloxane composition]
The method for preparing the organopolysiloxane composition of the present invention is not particularly limited, and it can be obtained by mixing predetermined amounts of the above-mentioned components according to a conventional method.
When the organopolysiloxane composition of the present invention is used for bonding a magnesium alloy and a resin, the organopolysiloxane composition is cured (cross-linked) by a condensation reaction at room temperature (23 ° C. ± 10 ° C.) by moisture in the atmosphere, thereby obtaining a magnesium alloy and a resin. To give a cured silicone rubber exhibiting good self-adhesion to the silicone rubber.
The organopolysiloxane composition cures when left at room temperature (23 ° C. ± 10 ° C.), and its molding method, curing conditions, and the like employ known methods and conditions according to the type of the composition. can do.

  Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the following examples, the viscosity is a value at 25 ° C. measured by a rotational viscometer.

[Example 1]
(Component A) 100 parts by mass of dimethylpolysiloxane having a viscosity of 20,000 mPa · s and both ends of a molecular chain blocked with a hydroxyl group (silanol group) bonded to a silicon atom, and the surface of component (E) was treated with a fatty acid. After adding 100 parts by mass of heavy calcium carbonate (product name; MC Coat P-20, manufactured by Maruo Calcium) and mixing with a mixer, (B component) 10 parts by mass of vinyltributanoxime silane, 0.1 parts of dioctyltin dilaurate 1 part by mass of (C-1 component) 11-trimethoxysilylundecanoic acid trimethylsilyl ester, (D-1 component) 3-amino-propyltrimethoxysilane (product name; KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.) One part by mass was added and mixed completely under reduced pressure to obtain Composition 1.

[Example 2]
(Component A) 100 parts by mass of dimethylpolysiloxane having a viscosity of 20,000 mPa · s and both ends of a molecular chain blocked with a hydroxyl group (silanol group) bonded to a silicon atom, and the surface of component (E) was treated with a fatty acid. After adding 100 parts by mass of heavy calcium carbonate (product name; MC Coat P-20, manufactured by Maruo Calcium) and mixing with a mixer, (B component) 10 parts by mass of vinyltributanoxime silane, 0.1 parts of dioctyltin dilaurate 1 part by mass of (C-1 component) 11-trimethoxysilylundecanoic acid trimethylsilyl ester, (D-2 component) N-2- (aminoethyl) -3-aminopropyltrimethoxysilane (product name; KBM- 603, manufactured by Shin-Etsu Chemical Co., Ltd.) and thoroughly mixed under reduced pressure to obtain a composition 2.

[Example 3]
(Component A) 100 parts by mass of dimethylpolysiloxane having a viscosity of 20,000 mPa · s and both ends of a molecular chain blocked with a hydroxyl group (silanol group) bonded to a silicon atom, and the surface of component (E) was treated with a fatty acid. After adding 100 parts by mass of heavy calcium carbonate (product name; MC Coat P-20, manufactured by Maruo Calcium) and mixing with a mixer, (B component) 10 parts by mass of vinyltributanoxime silane, 0.1 parts of dioctyltin dilaurate 1 part by mass of (C-1 component) 11-trimethoxysilylundecanoic acid trimethylsilyl ester, (D-3 component) N- [3- (trimethoxysilyl) propyl] -1,3-benzenedimethamine ( 1 part by mass of a product name (CF-73, manufactured by Shin-Etsu Chemical Co., Ltd.) was added and mixed thoroughly under reduced pressure to obtain a composition 3.

[Example 4]
(Component A) 100 parts by mass of dimethylpolysiloxane having a viscosity of 20,000 mPa · s and both ends of a molecular chain blocked with a hydroxyl group (silanol group) bonded to a silicon atom, and the surface of component (E) was treated with a fatty acid. After adding 100 parts by mass of heavy calcium carbonate (product name; MC Coat P-20, manufactured by Maruo Calcium) and mixing with a mixer, (B component) 10 parts by mass of vinyltributanoxime silane, 0.1 parts of dioctyltin dilaurate Parts by mass, (C-2 component) 1.2 parts by mass of triethylsilyl 11-trimethoxysilylundecanoate, (D-3 component) N- [3- (trimethoxysilyl) propyl] -1,3-benzenediene 1 part by mass of methamine (product name: CF-73, manufactured by Shin-Etsu Chemical Co., Ltd.) was added and mixed thoroughly under reduced pressure to obtain Composition 4.

[Example 5]
(Component A) 100 parts by mass of dimethylpolysiloxane having a viscosity of 20,000 mPa · s and both ends of a molecular chain blocked with a hydroxyl group (silanol group) bonded to a silicon atom, and the surface of component (E) was treated with a fatty acid. After adding 100 parts by mass of heavy calcium carbonate (product name; MC Coat P-20, manufactured by Maruo Calcium) and mixing with a mixer, (B component) 10 parts by mass of vinyltributanoxime silane, 0.1 parts of dioctyltin dilaurate Parts by mass, (C-3 component) 1.2 parts by mass of tert-butyldimethylsilyl ester of 11-trimethoxysilylundecanoic acid, (D-3 component) N- [3- (trimethoxysilyl) propyl] -1,3 -1 part by mass of benzenedimethanamine (product name: CF-73, manufactured by Shin-Etsu Chemical Co., Ltd.) was added and mixed completely under reduced pressure to obtain a composition 5.

[Example 6]
(Component A) 100 parts by mass of dimethylpolysiloxane having a viscosity of 20,000 mPa · s and both ends of a molecular chain blocked with a hydroxyl group (silanol group) bonded to a silicon atom, and the surface of component (E) was treated with a fatty acid. After adding 100 parts by mass of heavy calcium carbonate (product name; MC Coat P-20, manufactured by Maruo Calcium) and mixing with a mixer, (B component) 10 parts by mass of vinyltributanoxime silane, 0.1 parts of dioctyltin dilaurate Parts by mass, (C-4 component) 1.4 parts by mass of triisopropylsilyl ester of 11-trimethoxysilylundecanoic acid, (D-3 component) N- [3- (trimethoxysilyl) propyl] -1,3-benzene 1 part by mass of dimethanamine (product name: CF-73, manufactured by Shin-Etsu Chemical Co., Ltd.) was added and completely mixed under reduced pressure to obtain a composition 6.

[Example 7]
(Component A) 100 parts by mass of dimethylpolysiloxane having a viscosity of 20,000 mPa · s and both ends of a molecular chain blocked with a hydroxyl group (silanol group) bonded to a silicon atom, and the surface of component (E) was treated with a fatty acid. After adding 100 parts by mass of heavy calcium carbonate (product name; MC Coat P-20, manufactured by Maruo Calcium) and mixing with a mixer, (B component) 10 parts by mass of vinyltributanoxime silane, 0.1 parts of dioctyltin dilaurate Parts by mass, (C-5 component) 1.7 parts by mass of tert-butyldiphenylsilyl ester of 11-trimethoxysilylundecanoic acid, (D-3 component) N- [3- (trimethoxysilyl) propyl] -1,3 -1 part by mass of benzenedimethanamine (product name; CF-73, manufactured by Shin-Etsu Chemical Co., Ltd.) was added and mixed thoroughly under reduced pressure to obtain a composition 7.

[Comparative Example 1]
(Component A) 100 parts by mass of dimethylpolysiloxane having a viscosity of 20,000 mPa · s and both ends of a molecular chain blocked with a hydroxyl group (silanol group) bonded to a silicon atom, and the surface of component (E) was treated with a fatty acid. After adding 100 parts by mass of heavy calcium carbonate (product name; MC Coat P-20, manufactured by Maruo Calcium) and mixing with a mixer, (B component) 10 parts by mass of vinyltributanoxime silane, 0.1 parts of dioctyltin dilaurate 1 part by mass of (C-1 component) 11-trimethoxysilylundecanoic acid trimethylsilyl ester was added and completely mixed under reduced pressure to obtain a composition 8.

[Comparative Example 2]
(Component A) 100 parts by mass of dimethylpolysiloxane having a viscosity of 20,000 mPa · s and both ends of a molecular chain blocked with a hydroxyl group (silanol group) bonded to a silicon atom, and the surface of component (E) was treated with a fatty acid. After adding 100 parts by mass of heavy calcium carbonate (product name; MC Coat P-20, manufactured by Maruo Calcium) and mixing with a mixer, (B component) 10 parts by mass of vinyltributanoxime silane, 0.1 parts of dioctyltin dilaurate Parts by mass, and 1 part by mass of (D-3 component) N- [3- (trimethoxysilyl) propyl] -1,3-benzenedimethanamine (product name: CF-73, manufactured by Shin-Etsu Chemical Co., Ltd.) Mixing was completed under reduced pressure to obtain composition 9.

[Comparative Example 3]
(Component A) 100 parts by mass of dimethylpolysiloxane having a viscosity of 20,000 mPa · s and both ends of a molecular chain blocked with a hydroxyl group (silanol group) bonded to a silicon atom, and the surface of component (E) was treated with a fatty acid. After adding 100 parts by mass of heavy calcium carbonate (product name; MC Coat P-20, manufactured by Maruo Calcium) and mixing with a mixer, (B component) 10 parts by mass of vinyltributanoxime silane, 0.1 parts of dioctyltin dilaurate 1 part by mass of 3-trimethoxysilylallyl succinic anhydride (product name; X-12-967C, manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and the mixture was thoroughly mixed under reduced pressure to obtain Composition 10.

[Comparative Example 4]
(Component A) 100 parts by mass of dimethylpolysiloxane having a viscosity of 20,000 mPa · s and both ends of a molecular chain blocked with a hydroxyl group (silanol group) bonded to a silicon atom, and the surface of component (E) was treated with a fatty acid. After adding 100 parts by mass of heavy calcium carbonate (product name; MC Coat P-20, manufactured by Maruo Calcium) and mixing with a mixer, (B component) 10 parts by mass of vinyltributanoxime silane, 0.1 parts of dioctyltin dilaurate Parts by mass, 1 part by mass of 3-trimethoxysilylallyl succinic anhydride (product name: X-12-967C, manufactured by Shin-Etsu Chemical Co., Ltd.), (D-3 component) N- [3- (trimethoxysilyl) propyl 1 part by mass of -1,3-benzenedimethanamine (product name; CF-73, manufactured by Shin-Etsu Chemical Co., Ltd.) was added and completely mixed under reduced pressure to obtain composition 11.

The compositions of these Examples and Comparative Examples were poured into a 2 mm formwork and cured at 23 ° C. and 50% RH for 7 days to obtain a 2 mm thick rubber sheet. Rubber properties (hardness (durometer A), elongation at break, tensile strength) were measured from a 2 mm thick sheet according to JIS K6249.
In addition, according to the compositions of these Examples and Comparative Examples, various test pieces of magnesium alloy plate (AZ-91D) having a width of 25 mm and a length of 50 mm, nylon 66, polybutylene terephthalate, polystyrene, acrylonitrile, butadiene, and styrene were used. Thus, a shear adhesion test specimen having an adhesion area of 2.5 mm ² and an adhesion thickness of 1 mm was prepared. After curing at 23 ° C. and 50% RH for 7 days, the shear bond strength and the cohesive failure rate were measured according to the method specified in JIS K6249, and the cohesive failure rates were compared.
Tables 1 and 2 show the above results.

The compositions of Examples 1 to 7 having the carboxylic acid silyl ester group-containing silane coupling agent and the amino group-containing silane coupling agent of the present invention are higher than AZ-91D (magnesium alloy plate) and general-purpose resins. It turns out that it has adhesiveness (cohesive failure). On the other hand, the composition of Comparative Example 1 using the carboxylic acid silyl ester group-containing silane coupling agent alone has high adhesion to AZ-91D, but low adhesion to resin. In addition, the composition of Comparative Example 2 using the amino group-containing silane coupling agent alone does not exhibit adhesiveness to AZ-91D. In the composition of Comparative Example 3 in which the carboxylic acid silyl ester group-containing silane coupling agent and the amino group-containing silane coupling agent were not used and the allylsuccinic anhydride silane coupling agent was used, although the composition adhered to AZ-91D, And the adhesiveness to the resin is not sufficient. Furthermore, in the composition of Comparative Example 4 in which an allyl succinic anhydride silane coupling agent was used instead of the carboxylic acid silyl ester group-containing silane coupling agent and the amino group-containing silane coupling agent was used, the adhesion was significantly reduced. have done.
From the above results, it was shown that the composition of the present invention has high adhesiveness to magnesium alloys and resins.

Claims (5)

(A) an organopolysiloxane represented by the following general formula (1) and / or (2): 100 parts by mass,
HO (SiR ₂ O) _n H (1)
(In the formula, R is the same or different and is an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 10 or more.)

(In the formula, R and n are as described above, X is independently an oxygen atom or an alkylene group having 2 to 5 carbon atoms, and m is independently 0 or 1.)
(B) an organosilicon compound other than the component (A), the component (C) and the component (D), which has at least three hydrolyzable groups bonded to a silicon atom in one molecule, and / or a partial hydrolytic condensation thereof. Product: 0.1 to 50 parts by mass,
(C) a silane coupling agent represented by the following general formula (3): 0.1 to 15 parts by mass,

(Wherein, R ¹ , R ² , and R ³ are the same or different monovalent hydrocarbon groups having 1 to 10 carbon atoms, k is an integer of 3 to 14, and a is an integer of 0 to 2 , B is an integer of 0 to 3.)
(D) A silane coupling agent represented by the following general formula (4) and / or a partially hydrolyzed condensate thereof 0.1 to 15 parts by mass R ⁴ Si (R ⁶ ) _c (OR ⁵ ) _3-c (4)
(Wherein, R ⁴ is a monovalent hydrocarbon group having 1 to 20 carbon atoms having a functional group containing at least one primary amino group and / or secondary nitrogen atom selected from an amino group .R ⁵ , R ⁶ are each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and c is 0, 1 or 2.)
An organopolysiloxane composition comprising: The organopolysiloxane composition according to claim 1, wherein the component (B) is a hydrolyzable organosilane compound represented by the following general formula (5) and / or a partially hydrolyzed condensate thereof.
R ⁷ _d SiR ⁸ _4-d (5)
(In the formula, R ⁷ is a monovalent hydrocarbon group, and R ⁸ is independently a hydrolyzable group. D is 0 or 1.) The component (D) has the following general formula (6)

(Wherein, R ⁹ and R ¹⁰ are each independently an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R ¹¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ¹² is an aromatic group. A divalent hydrocarbon group having 7 to 10 carbon atoms including a ring, and e is an integer of 1 to _3. However, at least one of the NH group and the NH ₂ group is not directly bonded to the aromatic ring of R ¹² . )
The organopolysiloxane composition according to claim 1 or 2, which is a silane coupling agent and / or a partially hydrolyzed condensate thereof.   The organopolysiloxane composition according to any one of claims 1 to 3, further comprising 1 to 500 parts by mass of at least one filler as component (E) based on 100 parts by mass of component (A). object.   The organopolysiloxane composition according to any one of claims 1 to 4, which is used for bonding a magnesium alloy and a resin.