JPS62280279A - Primer composition - Google Patents

Abstract

PURPOSE:To provide the title compsn. having excellent adhesion between silicone rubber and substrates such as metal, plastics, etc., by mixing a specified org. titanic ester with an organosilicon compd. having alkoxy groups and an org. solvent. CONSTITUTION:100pts.wt. org. titanic ester (A) of formula I (wherein R<1> and R<2> are each H or an alkyl; R<3> and R<4> are each an alkyl or an aryl; 1<=l<4; 0<=m<4; 0<=n<4; l+m+n=4) (e.g., isopropyldiacrylisostearoyl titanate) is mixed with 1-10,000pts.wt. organosilicon compd. (B) having alkoxyl groups attached to the silicon atom, represented by formula II (wherein R<5> is a monovalent hydrocarbon; R<6> is a monovalent org. group having an addition-reactive or condensation-reactive functional group; R<7> is a member selected from the group consisting of an alkyl, an aryl, etc.; 0<=x<=3; 0<=y<=3; 0<=z<=4; 0<x+y+z<=4) (e.g., vinyltrimethoxysilane) and an appropriate amount of an org. solvent (C).

Description

Detailed Description of the Invention 3. Detailed Description of the Invention [Industrial Application Field 1] The present invention relates to a primer composition, and more particularly, to a primer composition effective for adhering silicone rubber and various substrates. .

[Prior art 1] Conventionally, a primer has been essential for adhering silicone rubber to various base materials such as plastics, glass, metal oxides, and metals. Primers are suggested.

[Problem to be Solved by the Invention 1] However, when the base material has an inert surface such as plastic, the adhesion of a primer based on ordinary organofunctional silane is insufficient and is not satisfactory. It wasn't.

As a result of studies to improve the above-mentioned drawbacks, the present inventors found that
We discovered that a primer based on a specific organic titanate ester is effective for adhering silicone rubber to plastic snacks, and have already proposed a primer based on this. However, this method was not completely satisfactory for adhering silicone rubber to metals.

Therefore, the present inventors investigated to solve the above problems and found that a composition consisting of a specific organic titanate ester, an alkoxy group-containing organosilicon compound, and a solvent can be used as a primer to treat silicone rubber as a primer. They discovered that it is effective for firmly adhering to various metals as well, and completed the present invention.

An object of the present invention is to provide a brimer composition that is effective for bonding silicone rubber to various substrates.

[Means for solving problems and their effects] The above objects are as follows: (a) General formula [wherein R' and R2 are hydrogen atoms or alkyl groups, R3
゜R4 represents an alkyl group or an aryl group, N ,
If.

n is 1≦N<4.0≦m<4.0≦4, di+m+n
"Organic titanate ester represented by the integer 1 of 4"
100 weight 1 part (b) average unit formula % formula % (wherein R5 is a substituted or unsubstituted monovalent hydrocarbon group excluding R6, R6 is a monovalent organic group having an addition-reactive or condensation-reactive functional group) group, R7 is an alkyl group, an aryl group,
A group selected from alkoxyalkyl groups, where X is 0≦X≦
3, y is )≦y≦3.2 is O<z≦4, but O<x
+y+z≦4. ) and (c) an arbitrary amount of an organic solvent.

To explain this, the organic titanate ester of component (a) used in the present invention is an essential component for imparting adhesion, and in the above formula, R' and R2 are hydrogen atoms, methyl groups, and ethyl groups. , is an alkyl group exemplified by a propyl group, and R3 and R4 are a methyl group, an ethyl group, a propyl group,
It is an alkyl group such as an isopropyl group or a butyl group, or an aryl group such as a phenyl group or a tolyl group.

1+ff1tn is an integer, which is 1≦Riku4, O≦
It is an integer satisfying m<4.0≦n<4, n+m+n=4. Examples of such organic titanate esters include isopropyl dimethacrylic isostearoyl titanate, isopropyl dimethacrylic isostearoyl titanate, cyphytyl diacryl titanate, and dibutyl isostearoyl titanate. These organic titanate esters can be used alone or as a mixture of two or more.

The organosilicon compound used in the present invention, which has at least two alkoxy groups bonded to silicon atoms in one molecule, is an important component for improving adhesion to metals. (b) Component is an average unit formula % formula % (wherein, R5 is a substituted or unsubstituted monovalent hydrocarbon group excluding R6, and this includes an alkyl group such as a methyl group, an ethyl group, a propyl group, an octyl group, etc.) 7 such as groups, phenyl groups, etc.
Replace the hydrogen atom of the lyl group and these groups with a halogen atom,
Examples include those substituted with a cyano group. R6 is a monovalent organic group having an addition-reactive or condensation-reactive functional group, and the functional groups include a vinyl group, an allyl group, an epoquine group, a methacryloxy group, a mercapto group, an amine 7 group, and an N-alkyl amine 7 group. The groups are exemplified, and the two functional groups are directly the main group, methylene group, ethylene group, 1. Propylene group, phenylene group, fluoroethylene group, -C1120CR2CH
2CH□-1-Cl]2C)120C)12C112-
1-C1120C112C1120CII2CH2-1
It is bonded to the silicon atom via a divalent organic group such as -(C112), (NHCII2CII2), ~, -. R7 is a group selected from alkyl groups such as methyl, ethyl and propyl groups, aryl groups such as phenyl, and flukoxyalkyl groups such as 2-methoxyethyl and 2-ethoxyethyl groups. X is O≦X≦3, y is 0≦
y≦3.2 is O<z≦4, but Q <x+y+z≦
It is 4. ) is an organosilicon compound represented by These include tetraalfoxysilane, organotri7ulfoxysilane, organodialkoxysilane, organopolysiloxane containing at least two alkoxy groups bonded to a silicon atom in one molecule, and partially hydrolyzed condensates thereof. .

As a component, from the viewpoint of adhesiveness and air drying properties, vfl preferably contains 3 to 4 flukoxyalkyl groups such as 2-methoxyethyl group or 2-ethoxyethyl group as R7 in one molecule. These are tetraalfoxyalfukidisilanes, organotrialkoxyalfuxidisilanes, and partially hydrolyzed condensates thereof. When used, one type of (oral) component is used, or two or more types are used in combination. This (mouth) component is an important component for significantly improving the adhesion of (a) r&. The blending ratio is 0.1 to 10 parts by weight per 100 parts by weight of component (A).
The amount is 0.000 parts by weight, preferably 5 to 2000 parts by weight.

(Example) Specific examples of ingredients include vinyltrimethoxysilane, methylvinylnomethoxysilane, vinyltriethoxysilane, methyltris(β-methoxyethoxy)silane, vinyltris(β-methoxyethoxy)silane,
γ-methacryloxypropyl(methyl)dimethoxysilane, γ-methacryloxypropyltriethoxysilane,
Allyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-glyndoxypropyl Yrimethoxysilane, β-(3.4-epoxycyclohexyl)
Ethyltrimethoxysilane, γ-7mi-7propyltriethoxysilane, N-β-7minoethyl-γ-aminopropyltrimethoxysilane, ethylorthosilicate, methylcello2solveorthosilicate, and one or two of these silanes and silicates. Partial hydrolysis condensates of more than one species are exemplified.

Component (c) used in the present invention includes component (a) and (
D) An organic solvent for dissolving T&, which is selected in consideration of the solubility of the (a) component and (b) component and the evaporability of the primer application process, for example:
Aromatic hydrocarbons such as toluene, xylene, benzene,
Examples include lower paraffins such as hexene and cyclohexane, ketones such as methyl ethyl ketone and acetone, alcohols such as ethanol and isopropyl alcohol, and chlorinated solvents such as trichlorethylene. These organic solvents can be used alone or as a mixed solvent of two or more.

The blending ratio of component (c) with (a) and (b) is not particularly limited, but may be selected as appropriate, taking into account the solubility of components (b) and (b), the viscosity of the dissolved product, and the ease of application. It's expensive. General 1 is (a) and (mouth) rfi. minute 100
It is preferable that the amount of the (no) component is within the range of 100 parts by weight to 2000 parts by weight.

The primer composition of the present invention can be easily obtained by simply making the components (a), (b), and (c) uniform. - Mainly, in the primer composition L of the present invention, various additives may be added as necessary, such as organosilicon compounds such as organopolysiloxane, 7-umed silica, precipitated silica, quartz powder, diatomaceous earth, and carbonic acid. Inorganic fillers such as calcium, red iron oxide, alumina, etc., various heat resistant agents, organic peroxides, and coloring agents may be added or blended as long as they do not impair the purpose of the present invention.

In use, the primer composition of the present invention is preferably applied to an adherend and air-dried for 30 minutes or more before applying the silicone rubber composition. It can also be dried under heat to ensure consistency.

When the brimer composition of the present invention is used as a primer for curing a silicone rubber composition and adhering it to a substrate in contact with the silicone rubber composition, it can be used as a primer for curing a silicone rubber composition and adhering it to a substrate that is in contact with the composition. Silicone rubber can be firmly adhered to the surfaces of synthetic resin materials such as polycarbonate resin, polyacetal resin, polyester resin, acrylic resin, and 717-l resin, and metal materials such as iron, stainless steel, nickel, aluminum, and phosphor bronze.

[Example 1] Next, the present invention will be explained with reference to an example. "Example Middle" indicates parts by weight.

Example 1 Isopropyl diacrylic isostearoyl titanate [
A primer composition was prepared by dissolving 11,110 parts of Ajinomoto Co., Ltd. (Plenac), 10 parts of ethyl orthosilicate, and 10 parts of vinyl)rimethoxysilane in 90 parts of toluene. This brimer composition was applied to nylon 6 resin, nylon 66 resin, polycarbonate resin and ABSi.
It is applied to four types of synthetic resin plates made of I-based resin and four types of metal plates made of iron, stainless steel, aluminum, and phosphor bronze.
It was left to stand at room temperature for 60 minutes to air dry. Next, the synthetic resin plate and metal plate coated with this primer are placed in a mold, and addition reaction liquid silicone rubber [Tomu
5E6706 manufactured by Silicone Co., Ltd.] was poured and heated under pressure of 25 kg/cm2 and temperature of 100°C for 10 minutes to harden the liquid silicone rubber.
A test plate in which the silicone rubber and the 1'&↑31 fat plate and the silicone rubber and the metal plate were firmly adhered was obtained. The obtained test plate was subjected to a 180 degree peel test according to the method of JIS-6744 to examine the adhesion state.
Both are completely adhered, and the state of the fractured surface after peeling II test is 100% cohesive failure (broken at the silicone rubber part)
Met.

Example 2 A brimer composition was prepared by dissolving 120 parts of isopropyl dimethacrylylisostearoyl titanate (Plenac, manufactured by Ajinomoto Co., Inc.) 7', 10 parts of n-propyl orthosilicate, and 10 parts of methyl cellosolve orthosilicate in 80 parts of toluene. This brimer composition was applied to four types of synthetic resin plates: nylon 6 resin, nylon 66U (fat), polycarbonate resin, and ABS resin, and four types of metal plates: iron, stainless steel, aluminum, and phosphor bronze. The synthetic resin plate was then air-dried.Then, the metal plate made from the synthetic resin plate was placed in a mold, and addition reaction liquid silicone rubber [5E6706 manufactured by Tomu Silicone Co., Ltd.] was poured over it under a pressure of 25 kg. /c
m2, heated under pressure for 10 minutes at a temperature of 100°C,
When the liquid silicone rubber was cured, test plates were obtained in which the silicone rubber and the synthetic resin plate and the silicone rubber and the metal plate were firmly adhered.

The obtained test plates were subjected to a 180 degree peel test according to the method of JIS-6744 to examine the adhesion state, and both were found to be completely adhered, and the state of the fractured surface after the peel test was 100% cohesive failure. (It broke at the silicone rubber part).

Example 3 The brimer composition obtained in Example 1 was applied to a nylon 6 resin plate and a metal plate of iron, stainless steel, or aluminum,
It was left to stand at room temperature for 60 minutes and air-dried. Next, a 4n+m thick unvulcanized molded product of a silicone rubber compound [5H52U manufactured by Tomu Silicone Co., Ltd.] to which 0.5% of 2°4') chlorobenzoyl peroxide was added as a crosslinking agent was placed on the primer-coated surface. in close contact with the pressure of 25k
When the silicone rubber was cured by heating under pressure for 10 minutes at a temperature of 170' g/cm2 and a temperature of 170'C, a test plate was obtained in which the silicone rubber and nylon 6 resin plate and the silicone rubber and metal plate were firmly adhered. It was done.

[Effect of the invention 1] The present invention provides a specific organic titanate ester as component (a), an organosilicon compound having at least two alkoxy groups bonded to a silicon atom in one molecule of component (b), and ) is a brimer composition consisting of an organic solvent, so when used as a primer for silicone rubber, it can strongly adhere to plastics and metals as well. has.

Patent Applicant Tou μ Silicone Co., Ltd. Procedural Amendment January 16, 1985 1. Indication of the Case 1988 Patent Application No. 122538 2. Name of the Invention Primer Composition 3. Person Making the Amendment Relationship with the Case Patent applicant 4. Date of amendment order Voluntary action 5. Subject of amendment' 6. Contents of the Amendment (1) In the 5th line of page 7, "bonded to a silicon atom" is amended to "bonded to a silicon atom is exemplified."

(2) As stated on page 10, line 3 Correct "make uniform" to "mix uniformly".

(3) As stated on page 10, line 12 Correct "not damaged" to "not damaged".

(4) 1-2.4 dichlorobenzoyl peroxide j described on page 13, lines 19-20 is corrected to "[2,5-methyl 2.5) (t-butyl peroxyhexane)".

Claims (1)

[Claims] 1 (a) General formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 and R^2 are hydrogen atoms or alkyl groups,
R^3 and R^4 represent an alkyl group or an aryl group,
l, m, n are 1≦l<4, 0≦m<4, 0≦n<4, l
+ m + n = integer of 4] 100 parts by weight of organic titanate ester (b) Average unit formula R^5_xR^6_y (OR^7)_zSiO_(_4
＿−＿x＿−＿y＿−＿z＿)＿/＿2(in the formula, R^5
is a substituted or unsubstituted monovalent hydrocarbon group excluding R^6, R
^6 is a monovalent organic group having an addition-reactive or condensation-reactive functional group, R^7 is a group selected from an alkyl group, an aryl group, and an alkoxyalkyl group, x is 0≦x≦3, y
is 0≦y≦3, z is 0<z≦4, but 0<x+y+
z≦4. ) A primer composition comprising 1 to 10,000 parts by weight of an organosilicon compound having at least two alkoxy groups bonded to silicon atoms in one molecule represented by (c) an arbitrary amount of an organic solvent. 2. The primer composition according to claim 1, wherein R^1 and R^2 of component (a) are hydrogen atoms. 3. The primer composition according to claim 1, wherein R^1 of component (a) is a hydrogen atom and R^2 is a methyl group.