JP6988736B2 - Organopolysiloxane composition - Google Patents

Description

The present invention relates to an organopolysiloxane composition that provides a cured silicone rubber product that exhibits excellent magnesium alloy adhesiveness and resin adhesiveness when cured at room temperature.

In recent years, magnesium alloys typified by AZ-91D have the characteristics of light weight, high strength, corrosion resistance, design, and recyclability, so that they are mobile phones, digital videos, digital cameras, liquid crystal projectors, plasma displays, personal computers, MD players, and DVDs. It is widely used in information electronic devices 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-adhesiveness to these components. There is a need for an organopolysiloxane composition for bonding magnesium alloys.

However, since these magnesium alloys are extremely difficult-to-adhere adherends, chemical conversion treatment is essential for adhesion, and there have been a number of organopolysiloxane compositions that have self-adhesiveness to magnesium alloys without treatment. Only example methods have been proposed. Japanese Patent Application Laid-Open No. 2003-535152 (Patent Document 1) proposes a composition using a curable silicone and an amino group-containing silane adhesion promoter as a filler. Further, Japanese Patent No. 3818365 (Patent Document 2) proposes a composition using a silicone oil and an inorganic compound containing a metal element having a lower ionization tendency than magnesium as 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 having a pH of 7 or less in a 5% by mass aqueous solution of the silane coupling agent. .. Further, Japanese Patent Application Laid-Open No. 2007-204575 (Patent Document 4) reports adhesion to a magnesium alloy by using an organopolysiloxane having a terminal silethylene bond in a base oil and a zinc compound as a filler. However, in Patent Document 1, the effectiveness of amino group-containing silane adhesion promoters such as γ-aminopropyltrialkoxysilane and trialkoxypropylethylenediamine is insufficient, and in Patent Documents 2 and 4, the filler used is used. Because it is limited to base oil and base oil, it lacks the degree of freedom in material design. In Patent Document 3, the magnesium alloy adhesiveness is improved by using the exemplified acidic silane coupling agent, but there is no description about the adhesiveness to the resin.

In recent years, attempts have been made to partially resinify metals from the viewpoint of weight reduction and recyclability. As the resin used as such a member, a resin having a small rate of change with respect to mechanical properties and various durability tests, that is, a resin having very stable mechanical and chemical stability is generally selected. Since a resin having high chemical stability does not have or has very few active groups, it is difficult to obtain good adhesiveness and to stably maintain the adhesiveness. .. As a method for improving the adhesiveness to the resin, a method of adding an oligomer of an aminosilane coupling agent to a room temperature curable organopolysiloxane composition (Patent No. 3714861: Patent Document 5) is known. , No examples of both magnesium alloy adhesiveness and resin adhesiveness have been reported.

If both magnesium alloy adhesiveness and resin adhesiveness can be achieved, one type of adhesive can be used for various purposes, eliminating the need to use multiple adhesives properly, eliminating the manufacturing process and products. Is easy to manage.

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

The present invention has been made in view of the above circumstances, and is an organopoly that is cured at room temperature by atmospheric moisture (crosslinking due to a condensation reaction) to give a silicone rubber cured product having good self-adhesiveness to magnesium alloys and resins. It is an object of the present invention to provide a siloxane composition, particularly an organopolysiloxane composition for bonding a magnesium alloy and a resin.

As a result of diligent studies focusing on the peculiarities of the magnesium alloy adherend and the resin in order to achieve the above object, the present inventors have (A) the general formulas (1) and / or (2) described later. Organopolysiloxane represented by (B), an organosilicon compound other than the components (A), (C) and (D) having at least three hydrolyzable groups bonded to a silicon atom in one molecule. / 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). ) Organopolysiloxane composition containing at least one filler is cured at room temperature (23 ° C ± 10 ° C) by atmospheric moisture (crosslinking by condensation reaction) and is good for magnesium alloys and resins. It has been found that a cured silicone rubber having adhesiveness is provided, and the present invention has been made.

（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］
（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］に記載のオルガノポリシロキサン組成物。
［３］
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］又は［２］に記載のオルガノポリシロキサン組成物。
［４］
マグネシウム合金及び樹脂接着用である［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。 Therefore, the present invention provides the following organopolysiloxane compositions.
[1]
(A) Organopolysiloxane represented by the following general formula (1 ) : 100 parts by mass,
HO (SiR ₂ O) _n H (1)
(In the formula, R is an unsubstituted or halogen atom substituted monovalent hydrocarbon group having the same or different carbon atoms 1 to 10, and n is an integer of 10 or more. )
(B) Water represented by the following general formula (5) other than the components (A), (C) and (D) having at least three hydrolyzable groups bonded to silicon atoms in one molecule. Degradable organosilane compound and / or its partially hydrolyzed condensate: 0.1 to 50 parts by mass,
R ⁷ _d SiR ⁸ _4-d (5)
(In the formula, R ⁷ is a monovalent hydrocarbon group and R ⁸ is an independently hydrolyzable group. D is 0 or 1.)
(C) Silane coupling agent represented by the following general formula (3): 0.1 to 15 parts by mass,

(In the formula, R ¹ , R ² , and R ³ are monovalent hydrocarbon groups having the same or different carbon atoms of 1 to 10, k is an integer of 3 to 14, and a is an integer of 0 to 2. , B is an integer from 0 to 3.)
(D) 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 independently unsubstituted or substituted monovalent hydrocarbon groups having 1 to 10 carbon atoms, and c is 0, 1 or 2).
An organopolysiloxane composition comprising.
[ 2 ]
The component (D) is the following general formula (6).

(In the formula, R ⁹ and R ¹⁰ are independently unsubstituted monovalent hydrocarbon groups ^{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. It is 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 connected to the aromatic ring of ^{R 12.} )
The organopolysiloxane composition according to [1], which is a silane coupling agent and / or a partially hydrolyzed condensate thereof represented by.
[ 3 ]
The organopolysiloxane composition according to [1] or [2], which further contains 1 to 500 parts by mass of at least one filler as the component (E) with respect to 100 parts by mass of the component (A).
[ 4 ]
The organopolysiloxane composition according to any one of [1] to [3 ] for bonding a magnesium alloy and a resin.

The organopolysiloxane composition of the present invention provides a cured silicone rubber product that exhibits excellent magnesium alloy adhesiveness and resin adhesiveness when cured at room temperature, and in particular, an organopolysiloxane composition for magnesium alloy and resin adhesion. It is 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 agent (base polymer) of the composition of the present invention, and has the following general formulas (1) and / or (2). It is indicated by.
HO (SiR ₂ O) _n H (1)
(In the formula, R is an unsubstituted or halogen atom substituted monovalent hydrocarbon group having the same or different carbon atoms 1 to 10, and n is an integer of 10 or more.)

(In the formula, R is an unsubstituted or halogen atom substituted monovalent hydrocarbon group having 1 to 10 carbon atoms of the same or different species, n is an integer of 10 or more, and X is an oxygen atom or 2 carbon atoms independently. ~ 5 alkylene groups, m is independently 0 or 1)

In the general formulas (1) and (2), R is an unsubstituted or halogen atom 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. Cycloalkyl groups such as groups; alkenyl groups such as vinyl and allyl groups; aryl groups such as phenyl and trill groups; and hydrogen atoms bonded to the carbon atoms of these groups are partially substituted with halogen atoms. Examples thereof include groups such as 3,3,3-trifluoropropyl groups. Among these, a methyl group, a vinyl group, a phenyl group, a 3,3,3-trifluoropropyl group are preferable, and a methyl group is particularly preferable. The plurality of Rs in the general formulas (1) and (2) may be the same group or different groups.

Further, n is an integer of 10 or more, and in particular, the viscosity of this organopolysiloxane at 25 ° C. is in the range of 25 to 500,000 mPa · s, 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 that gives such a viscosity may be an integer of usually 10 to 2,000, preferably 20 to 1,500, and more preferably about 50 to 1,000.

Further, 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. Illustrated. Among these, oxygen atom and ethylene group are preferable as X.
m is independently 0 or 1.

[(B) component]
The component (B) used in the organopolysiloxane composition of the present invention acts as a cross-linking agent (hardener) and has at least three hydrolyzable groups bonded to silicon atoms in one molecule (. A hydrolyzable organic silicon compound and / or a partially hydrolyzed condensate thereof other than the component A), the component (C) and the component (D), and the organic silicon compound of the component (B) is usually hydrolyzable. The molecule does not contain heteroatoms such as nitrogen atom, oxygen atom and sulfur atom. The organic silicon compound is a hydrolyzable organosilane compound represented by the following general formula (5) and / or a partially hydrolyzed condensate thereof (that is, a molecule produced by partially hydrolyzing and condensing the organosilane compound). An organosiloxane oligomer having at least two, preferably three or more residual hydrolyzable groups therein) is preferred.
R ⁷ _d SiR ⁸ _4-d (5)
(In the formula, R ⁷ is a monovalent hydrocarbon group and R ⁸ is an independently hydrolyzable group. D is 0 or 1, preferably 1.)

In the general formula (5) ^{, examples of the hydrolyzable group R 8} include a ketooxime group, an alkoxy group, an asyloxy group, an alkenyloxy group and the like. Specifically, a ketooxym group having 3 to 8 carbon atoms such as a dimethyl keto oxime group, a methyl ethyl keto oxime group, and a methyl isobutyl keto oxime group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, sec. -Acyloxy group, vinyloxy group, allyloxy group, propenoxy group having 1 to 4 carbon atoms such as butoxy group and tert-butoxy group, particularly 2 to 4 carbon atoms such as an alkoxy group having 1 or 2 carbon atoms, an acetoxy group and a propionoxy group. , An alkenyloxy group having 2 to 4 carbon atoms such as an isopropenoxy group can be exemplified.
^{Further, the residual group R 7} bonded to a silicon atom other than the hydrolyzable group is not particularly limited as long as it is a monovalent hydrocarbon group, but specifically, it is a methyl group, an ethyl group or a propyl group. , An alkyl group such as a butyl group, an alkenyl group such as a vinyl group, and a monovalent hydrocarbon group having 1 to 10 carbon atoms such as an aryl group such as a phenyl group are exemplified. 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 (methylethylketooxime) silane, methyltris (dimethylketooxime) silane, methyltris (methylethylketooxime) silane, ethyltris (methylethylketooxime) silane, and methyltris (methylisobutylketooxime) silane. , Ketooxime silanes such as vinyltris (methylethylketooxime) silane [also known as vinyltributanoximsilane], methyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, tetramethoxysilane, vinyltriethoxysilane, tetraethoxysilane Alkoxysilanes such as, methyltriacetoxysilanes, acetoxysilanes such as vinyltriacetoxysilanes, and isopropenoxysilanes such as methyltriisopropenoxysilanes, vinyltriisopropenoxysilanes, phenyltriisopropenoxysilanes, etc. In addition, partial hydrolysis condensates of these silanes and the like can be mentioned. These may be used alone or in combination of two or more.

The blending amount of the component (B) is in the range of 0.1 to 50 parts by mass, preferably 5 to 30 parts by mass with respect to 100 parts by mass of the component (A). If it is less than 0.1 part by mass, sufficient cross-linking cannot be obtained, it is difficult to obtain the desired composition having rubber elasticity, and if it exceeds 50 parts by mass, the obtained cured product tends to deteriorate in mechanical properties.

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

[(C) component]
The silane coupling agent of the component (C) used in the organopolysiloxane composition of the present invention has 1 to 4 carboxylic acid silyl ester bonds in the molecule, and the composition of the present invention is cured at room temperature. It is indispensable for imparting good magnesium alloy adhesiveness to the obtained cured product (silicone rubber). As described in Patent Document 3, an acid-based silane coupling agent is effective for improving the adhesiveness 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 the silyl group when uncured, but the carboxyl group is expressed by the desorption of the silyl group by hydrolysis during curing. By doing so, the adhesive strength to the magnesium alloy is improved. Further, by protecting the highly active carboxyl group with a silyl group, it is possible to use it in combination with an amino group-containing silane coupling agent, which was 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).

(In the formula, R ¹ , R ² , and R ³ are monovalent hydrocarbon groups having the same or different carbon atoms of 1 to 10, k is an integer of 3 to 14, and a is an integer of 0 to 2. , B is an integer from 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 group and propyl group; Cycloalkyl groups such as cyclohexyl group; Saturated or unsaturated aliphatic hydrocarbon groups such as alkenyl groups such as vinyl group and allyl group; aryl groups such as phenyl group and trill group Examples include aromatic hydrocarbon groups such as aralkyl groups such as benzyl group and phenylethyl group. Among these, an alkyl group such as a methyl group, an ethyl group or a propyl group is preferable, and a methyl group or an ethyl group is particularly preferable.
Further, the value of a in the equation is an integer of 0 to 2, preferably 0.

Further, 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 cyclo 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 trill group; Aromatic hydrocarbon such as aralkyl group such as benzyl group and phenylethyl group Hydrogen groups and the like can be mentioned. 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, for example, a methyl group or an ethyl group. Alkyl group such as propyl group and isopropyl group; Cycloalkyl group such as cyclohexyl 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 trill group Examples include aromatic hydrocarbon groups such as aralkyl groups such as benzyl group and phenylethyl group, and protective groups such as tert-butyldimethyl group and tert-butyldiphenyl group. Among these, 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, and a protective group such as a tert-butyldimethyl group and a tert-butyldiphenyl group are used. Particularly preferably, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyldimethyl group and a tert-butyldiphenyl group are preferable.
Further, the value of b in the equation is an integer of 0 to 3, preferably an integer of 1 to 3, more preferably 3, and when the values of b are 2 and 3, ^{the structures of R 3} may be the same as each other. It may be different.

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. The value of k in the equation is an integer of 3 to 14, preferably an integer of 5 to 13, and more preferably an integer of 8 to 11. If the value of k is less than 3, synthesis becomes difficult, and if the value of k is larger than 14, the molecular weight may become too large and the adhesiveness may decrease.

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 differentiated 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.} In addition, the component (C) essentially has a carboxylic acid silyl ester bond in the molecule, and nitrogen selected from at least one primary amino group and / or a secondary amino group. It is clearly differentiated from the silane coupling agent of the component (B) and the component (D) described later in that it does not have a functional group containing an atom.

[(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 a partial hydrolysis thereof. It is a condensate and is an essential component for exhibiting good resin adhesiveness in 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 independently unsubstituted or substituted monovalent hydrocarbon groups 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 a secondary amino group (for example, unsubstituted or substituted amino group, unsubstituted or substituted imino). A monovalent hydrocarbon group having 1 to 20 carbon atoms having at least one group (group, amide group, ureido group, etc.), specifically, N-β (aminoethyl) -γ-aminopropyl group, γ-amino. Monovalent carbonization of 3 to 20 carbon atoms, particularly 8 to 14 carbon atoms, containing at least one nitrogen atom such as a propyl group, an N-phenyl-γ-aminopropyl group, a γ-ureidopropyl group, a γ-acetamidopropyl group, etc. Propyl group can be mentioned.

Further, R ⁵ and R ⁶ are independently unsubstituted or substituted monovalent hydrocarbon groups having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms, and the same group as R ^{1 of} the above-mentioned formula (1) is used. It can be exemplified, and a methyl group, an ethyl group, a propyl group, and an isopropyl group are particularly preferable.

（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。） As a further specific example of the hydrolyzable silane coupling agent of the component (D), the number of carbon atoms having a functional group containing a nitrogen atom selected from at least one primary amino group and / or a secondary amino group is 1. Any silane compound containing 1 to 20 monovalent hydrocarbon groups and 1 to 3 organooxy groups can be used, and among them, the silane represented by the following general formula (6) can be used. Adhesion is further improved by the use of a coupling agent (hydrolytic organosilane compound) and / or a partially hydrolyzed condensate thereof.

(In the formula, R ⁹ and R ¹⁰ are independently unsubstituted monovalent hydrocarbon groups ^{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. It is 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 connected 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 contains an NH. It is an alkoxysilane compound in which at least one of the group and the NH ₂ group is not directly connected to the carbon atom constituting the aromatic ring, and the details are described in JP-A-5-105689.

In the above formula (6), the ^{unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms of R 9} and R ¹⁰ includes a methyl group, an ethyl group, a propyl group, a butyl group and a hexyl group. Alkyl groups such as: Cycloalkyl groups such as cyclohexyl groups; Alkyl groups such as vinyl groups, allyl groups, propenyl groups, butenyl groups and hexenyl groups; aryl groups such as phenyl groups and trill groups; benzyl groups, phenylethyl groups and the like Examples thereof include an aralkyl group, and R ⁹ is preferably a methyl group or an ethyl group, and R ¹⁰ is preferably a methyl group.

The ^{divalent hydrocarbon group having 1 to 10 carbon atoms of R 11} includes a methylene group, an ethylene group, a propylene group, a tetramethylene group, a hexamethylene group, an octamethylene group, a decamethylene group, a 2-methylpropylene group and the like. Examples thereof include an arylene group such as an alkylene group and a phenylene group, and a group in which these alkylene groups and an arylene group are bonded, but a methylene group, an ethylene group and a propylene group are preferable, and a propylene group is particularly preferable.

Further, ^{as the divalent hydrocarbon group having 7 to 10 carbon atoms containing the aromatic ring of 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 −
Of these, −CH ₂ −C ₆ H ₄ −CH ₂ − is particularly preferable.

In this case, the alkylene group bonded to the right side of the phenylene group (NH _{2 side in the formula (6)) (if there is no alkylene group, it becomes -NH 2} group) may be in the ortho-position, meta-position, 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 its partially hydrolyzed condensate of the component (D) may be used alone or in combination of two or more.
The blending amount of the component (D) is 0.1 to 15 parts by mass, preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the component (A). If it is less than 0.1 part by mass, the cured product does not exhibit sufficient adhesive performance, and if it is blended in excess of 15 parts by mass, the rubber strength after curing is lowered or the curability is lowered.

[(E) component]
In the organopolysiloxane composition of the present invention, the filler (E) can be blended, and as the filler, a reinforcing or non-reinforcing filler for imparting rubber physical characteristics to the composition is used. be able to. Specific examples of such fillers include surface-treated or untreated fumigant silica, precipitated silica, wet silica, carbon powder, talc, bentonite, surface-treated or untreated calcium carbonate, zinc carbonate, and magnesium carbonate. , Surface-treated or untreated calcium oxide, zinc oxide, magnesium oxide, aluminum oxide, aluminum hydroxide and the like are exemplified, and these can be used alone or in combination of two or more.

When the filler of the component (E) is blended, the blending amount thereof is preferably in the range of 1 to 500 parts by mass with respect to 100 parts by mass of the component (A), and more preferably 5 to 450 parts by mass. It is a range. If it is less than 1 part by mass, sufficient adhesive strength to the target 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 may be high and workability may be inferior. ..

[Other ingredients]
Further, the organopolysiloxane composition of the present invention contains additives and catalysts generally known in addition to the above components, as long as they do not adversely affect the curability at room temperature and the self-adhesiveness to magnesium alloys and resins. In particular, a condensation reaction catalyst) or the like may be used. Additives include polyethers as thixophilic improvers, colorants such as pigments and 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 improving agents, and if necessary, antifungal agents, antibacterial agents, and the like are added. Examples of the catalyst (condensation reaction catalyst) include organometallic compounds such as organotin ester compounds, organotin chelate compounds, alkoxytitanium compounds, and titanium chelate compounds, and silicon compounds having a guanidyl group.

Further, the organopolysiloxane composition of the present invention has components other than the above components (B), (C) and (D) as long as it does not adversely affect the curability at room temperature and the self-adhesiveness to magnesium alloys and resins. In combination with a commonly 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). May be good. Contains epoxy groups such as 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane Ekyloxy group-containing alkoxysilanes such as alkoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-mercapto Propyl group-containing alkoxysilanes such as propyltrimethoxysilane and 3-mercaptopropylmethyldimethoxysilane, 3-isocyanuppropyltrimethoxysilane, 3-isocyanuppropyltriethoxysilane, 3-isoxapropylmethyldimethoxysilane, 3-isocyanampropylmethyldi. Examples thereof include isocyanate group-containing alkoxysilanes such as ethoxysilane.

[Preparation of organopolysiloxane composition]
The method for preparing the organopolysiloxane composition of the present invention is not particularly limited, and can be obtained by mixing a predetermined amount of each of the above components according to a conventional method.
When the organopolysiloxane composition of the present invention is used for bonding magnesium alloys and resins, the magnesium alloys and resins are cured (crosslinked) by a condensation reaction with atmospheric moisture at room temperature (23 ° C ± 10 ° C). A silicone rubber cured product showing good self-adhesiveness is provided.
The organopolysiloxane composition is cured by being left at room temperature (23 ° C ± 10 ° C), but the molding method, curing conditions, etc. are known methods and conditions according to the type of composition. can do.

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

[Example 1]
The surface of (component E) was treated with a fatty acid on 100 parts by mass of dimethylpolysiloxane (component A) having a viscosity of 20,000 mPa · s and having both ends of the molecular chain sealed with a hydroxyl group (silanol group) bonded to a silicon atom. 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, (component B) vinyl tributanoximsilane 10 parts by mass, dioctyltin dilaurate 0.1 By mass, (C-1 component) 11-trimethoxysilyl undecanoic acid trimethylsilyl ester 1 part by mass, (D-1 component) 3-amino-propyltrimethoxysilane (product name; KBM-903, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 1 part by mass was added and mixed completely under reduced pressure to obtain composition 1.

[Example 2]
The surface of (component E) was treated with a fatty acid on 100 parts by mass of dimethylpolysiloxane (component A) having a viscosity of 20,000 mPa · s and having both ends of the molecular chain sealed with a hydroxyl group (silanol group) bonded to a silicon atom. 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, (component B) vinyl tributanoximsilane 10 parts by mass, dioctyltin dilaurate 0.1 By mass, (C-1 component) 11-trimethoxysilyl undecanoic acid trimethylsilyl ester 1 part by mass, (D-2 component) N-2- (aminoethyl) -3-aminopropyltrimethoxysilane (product name; KBM-) 603, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 1 part by mass was added and completely mixed under reduced pressure to obtain composition 2.

[Example 3]
The surface of (component E) was treated with a fatty acid on 100 parts by mass of dimethylpolysiloxane (component A) having a viscosity of 20,000 mPa · s and having both ends of the molecular chain sealed with a hydroxyl group (silanol group) bonded to a silicon atom. 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, (component B) vinyl tributanoximsilane 10 parts by mass, dioctyltin dilaurate 0.1 By mass, (C-1 component) 11-trimethoxysilyl undecanoic acid trimethylsilyl ester 1 part by mass, (D-3 component) N- [3- (trimethoxysilyl) propyl] -1,3-benzenedimethanamine ( Product name; CF-73, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 1 part by mass was added and completely mixed under reduced pressure to obtain Composition 3.

[Example 4]
The surface of (component E) was treated with a fatty acid on 100 parts by mass of dimethylpolysiloxane (component A) having a viscosity of 20,000 mPa · s and having both ends of the molecular chain sealed with a hydroxyl group (silanol group) bonded to a silicon atom. 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, (component B) vinyl tributanoximsilane 10 parts by mass, dioctyltin dilaurate 0.1 By mass, (C-2 component) 11-trimethoxysilyl undecanoic acid triethylsilyl ester 1.2 parts by mass, (D-3 component) N- [3- (trimethoxysilyl) propyl] -1,3-benzenedi 1 part by mass of metanamine (product name; CF-73, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) was added and completely mixed under reduced pressure to obtain Composition 4.

[Example 5]
The surface of (component E) was treated with a fatty acid on 100 parts by mass of dimethylpolysiloxane (component A) having a viscosity of 20,000 mPa · s and having both ends of the molecular chain sealed with a hydroxyl group (silanol group) bonded to a silicon atom. 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, (component B) vinyl tributanoximsilane 10 parts by mass, dioctyltin dilaurate 0.1 By mass, (C-3 component) 11-trimethoxysilyl undecanoic acid tert-butyldimethylsilyl ester 1.2 parts by mass, (D-3 component) N- [3- (trimethoxysilyl) propyl] -1,3 -Benzin dimethanamine (product name; CF-73, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) was added in an amount of 1 part by mass and completely mixed under reduced pressure to obtain the composition 5.

[Example 6]
The surface of (component E) was treated with a fatty acid on 100 parts by mass of dimethylpolysiloxane (component A) having a viscosity of 20,000 mPa · s and having both ends of the molecular chain sealed with a hydroxyl group (silanol group) bonded to a silicon atom. 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, (component B) vinyl tributanoximsilane 10 parts by mass, dioctyltin dilaurate 0.1 By mass, (C-4 component) 11-trimethoxysilyl undecanoic acid triisopropylsilyl ester 1.4 parts by mass, (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 Industry Co., Ltd.) was added and completely mixed under reduced pressure to obtain Composition 6.

[Example 7]
The surface of (component E) was treated with a fatty acid on 100 parts by mass of dimethylpolysiloxane (component A) having a viscosity of 20,000 mPa · s and having both ends of the molecular chain sealed with a hydroxyl group (silanol group) bonded to a silicon atom. 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, (component B) vinyl tributanoximsilane 10 parts by mass, dioctyltin dilaurate 0.1 By mass, (C-5 component) 11-trimethoxysilyl undecanoic acid tert-butyldiphenylsilyl ester 1.7 parts by mass, (D-3 component) N- [3- (trimethoxysilyl) propyl] -1,3 -Benzin dimethanamine (product name; CF-73, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) was added in an amount of 1 part by mass and completely mixed under reduced pressure to obtain the composition 7.

[Comparative Example 1]
The surface of (component E) was treated with a fatty acid on 100 parts by mass of dimethylpolysiloxane (component A) having a viscosity of 20,000 mPa · s and having both ends of the molecular chain sealed with a hydroxyl group (silanol group) bonded to a silicon atom. 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, (component B) vinyl tributanoximsilane 10 parts by mass, dioctyltin dilaurate 0.1 1 part by mass and 1 part by mass of (C-1 component) 11-trimethoxysilylundecanoic acid trimethylsilyl ester were added and completely mixed under reduced pressure to obtain Composition 8.

[Comparative Example 2]
The surface of (component E) was treated with fatty acid on 100 parts by mass of dimethylpolysiloxane (component A) having a viscosity of 20,000 mPa · s and having both ends of the molecular chain sealed with a hydroxyl group (silanol group) bonded to a silicon atom. 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, (component B) vinyl tributanoximsilane 10 parts by mass, dioctyltin dilaurate 0.1 Add 1 part by mass of (D-3 component) N- [3- (trimethoxysilyl) propyl] -1,3-benzenedimethanamine (product name; CF-73, manufactured by Shin-Etsu Chemical Industry Co., Ltd.). Completely mixed under reduced pressure to give composition 9.

[Comparative Example 3]
The surface of (component E) was treated with a fatty acid on 100 parts by mass of dimethylpolysiloxane having a viscosity (component A) of 20,000 mPa · s and having both ends of the molecular chain sealed with a hydroxyl group (silanol group) bonded to a silicon atom. 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, (component B) vinyltributanoximsilane 10 parts by mass, dioctyltin dilaurate 0.1 By weight, 1 part by mass of 3-trimethoxysilylallyl succinic anhydride (product name; X-12-967C, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) was added and completely mixed under reduced pressure to obtain composition 10.

[Comparative Example 4]
The surface of (component E) was treated with fatty acid on 100 parts by mass of dimethylpolysiloxane (component A) having a viscosity of 20,000 mPa · s and having both ends of the molecular chain sealed with a hydroxyl group (silanol group) bonded to a silicon atom. 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, (component B) vinyltributanoximsilane 10 parts by mass, dioctyltin dilaurate 0.1 By mass, 3-trimethoxysilylallyl succinic anhydride (product name; X-12-967C, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 1 part by mass, (D-3 component) N- [3- (trimethoxysilyl) propyl ] -1,3-benzenedimethanamine (product name; CF-73, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) was added by 1 part by mass and completely mixed under reduced pressure to obtain the composition 11.

The compositions of these Examples and Comparative Examples were poured into a 2 mm mold and cured at 23 ° C. and 50% RH for 7 days to obtain a 2 mm thick rubber sheet. The rubber physical characteristics (hardness (durometer A), elongation at cutting, tensile strength) were measured from a 2 mm thick sheet according to JIS K6249.
Further, depending on the compositions of these Examples and Comparative Examples, various test pieces of a magnesium alloy plate (AZ-91D) having a width of 25 mm and a length of 50 mm, nylon 66, polybutylene terephthalate, polystyrene, and acrylic nitrile butadiene styrene were used. A shear bond test piece having a bond area of 2.5 mm ² and a bond thickness of 1 mm was prepared. After curing at 23 ° C. and 50% RH for 7 days, the shear adhesion strength and the cohesive fracture rate were measured according to the method specified in JIS K6249, and the cohesive fracture rate was compared.
The above results are shown in Tables 1 and 2.

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 resin. It can be seen that it has adhesiveness (aggregation 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 adhesiveness to AZ-91D, but low adhesiveness to resin. Further, 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 silane coupling agent containing a carboxylic acid silyl ester group and the silane coupling agent containing an amino group were not used and the allylsuccinic anhydride silane coupling agent was used, the composition adhered to AZ-91D. , The adhesiveness to the resin is not sufficient. Further, 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 used in combination with the amino group-containing silane coupling agent, the adhesiveness 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 (4)

(A) Organopolysiloxane represented by the following general formula (1 ) : 100 parts by mass,
HO (SiR ₂ O) _n H (1)
(In the formula, R is an unsubstituted or halogen atom substituted monovalent hydrocarbon group having the same or different carbon atoms 1 to 10, and n is an integer of 10 or more. )
(B) Water represented by the following general formula (5) other than the components (A), (C) and (D) having at least three hydrolyzable groups bonded to silicon atoms in one molecule. Degradable organosilane compound and / or its partially hydrolyzed condensate: 0.1 to 50 parts by mass,
R ⁷ _d SiR ⁸ _4-d (5)
(In the formula, R ⁷ is a monovalent hydrocarbon group and R ⁸ is an independently hydrolyzable group. D is 0 or 1.)
(C) Silane coupling agent represented by the following general formula (3): 0.1 to 15 parts by mass,

(In the formula, R ¹ , R ² , and R ³ are monovalent hydrocarbon groups having the same or different carbon atoms of 1 to 10, k is an integer of 3 to 14, and a is an integer of 0 to 2. , B is an integer from 0 to 3.)
(D) 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 independently unsubstituted or substituted monovalent hydrocarbon groups having 1 to 10 carbon atoms, and c is 0, 1 or 2).
An organopolysiloxane composition comprising. The component (D) is the following general formula (6).

(In the formula, R ⁹ and R ¹⁰ are independently unsubstituted monovalent hydrocarbon groups ^{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. It is 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 connected to the aromatic ring of ^{R 12.} )
The organopolysiloxane composition according to claim 1, which is a silane coupling agent and / or a partially hydrolyzed condensate thereof. The organopolysiloxane composition according to claim 1 or 2 , further comprising at least one filler as the component (E) in an amount of 1 to 500 parts by mass with respect to 100 parts by mass of the component (A). The organopolysiloxane composition according to any one of claims 1 to 3 , which is used for bonding a magnesium alloy and a resin.