JPH08217981A - Silane coupling agent composition and method of using it - Google Patents

Abstract

PURPOSE: To obtain a silane coupling agent composition improved in the adhesion of an inorganic material to an organic material by using as the constituents a silane coupling agent, a specified compound and an organopolysiloxane modified with an organic surfactant. CONSTITUTION: This composition is obtained by mixing 100 pts.wt. of at least one compound selected from a silane coupling agent and an organosilicon compound of formula I (wherein R<1> is H or a monovalent hydrocarbon group; X is a hydrolyzable group; and i is 1 to 4) with 1-100 pts.wt. organopolysiloxane modified with an organic surfactant and having in the molecule at least one substituent which comprises an organic surfactant of formula II (wherein R<2> and R<3> are each H, a monovalent hydrocarbon group or a hydrophilic group; A is a trivalent hydrocarbon group; j1 is 2 to 18; m is 2 to 6; and n is 1 to 50) and is directly bonded to an Si atom. This composition is used in an amount of 0.1-5 pts.wt. based on 100 pts.wt. inorganic material and 1-20 pts.wt. based on 100 pts.wt. organic material.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silane coupling agent composition and a method of using the same. More specifically, the present invention relates to a silane coupling agent composition that improves the adhesiveness of an inorganic material to an organic material, a composition of the composition and an organic material, and the silane coupling agent composition containing the inorganic material and the organic material. The present invention relates to a method for use in modifying a composite material with and a modified composite material thereof.

[0002]

BACKGROUND OF THE INVENTION Silane coupling agents begin with the surface treatment of glass fibers in fiber reinforced plastics, and then with organic materials such as elastomers, paints, adhesives, sealants, resin concrete and inorganic materials such as inorganic fillers or inorganic substrates. Is widely used as a modifier for the interface between organic and inorganic materials in composite materials that combine
It plays a major role in the design of composite materials by improving electrical properties, water resistance, weather resistance, adhesiveness, workability and acid resistance.

However, as the materials have become multifunctional and highly functional, the number of applications in which conventional silane coupling agents cannot meet the requirements is increasing. On the other hand, various modifications of organic materials and inorganic materials have been carried out, but in composite materials, deterioration often occurs at the interface where the modulus, expansion coefficient, and surface energy are different. Since the effect of the silane coupling agent, which is a modifier of the above, is greatly affected, the modification of the organic material or the inorganic material is often insufficient.

[0004]

Therefore, in order to improve the effect of modifying the interface between the inorganic material and the organic material, there is a demand for a silane coupling agent having characteristics superior to those of the conventional ones. The present invention, in order to meet such a demand,
It is an object of the present invention to provide a novel silane coupling agent composition having a markedly excellent coupling effect between an organic material and an inorganic material and a method of using the same.

[0005]

In order to solve the above-mentioned problems, the present inventors have conducted tests on many low-molecular compounds and high-molecular compounds and combinations thereof. As a result, the silane coupling agent and specific organic compounds have been tested. A composition comprising a surfactant-modified organopolysiloxane compound was found to improve the adhesiveness of an inorganic material to an organic material such as a thermosetting resin or a thermoplastic resin, and further studies were conducted to complete the present invention. It was

That is, the present invention relates to a silane coupling agent and the following formula I: R ¹ _4-i -Si-X _i (I) (wherein R ¹ is independently of each other a hydrogen atom or a monovalent hydrocarbon). At least 1 selected from the group consisting of organosilicon compounds represented by the formulas, X represents a hydrolyzable group independently of each other, and i represents an integer of 1 to 4).
100 parts by weight of a compound of the formula and the following formula II directly bonded to a silicon atom in one molecule:

Embedded image (In the formula, R ² and R ³ are independently of each other a hydrogen atom, 1
Represents a trivalent hydrocarbon group or a hydrophilic group, A represents a trivalent hydrocarbon group, j1 is an integer of 2 to 18, m is an integer of 2 to 6, and n is an integer of 1 to 500).
The present invention relates to a silane coupling agent composition comprising 1 to 1000 parts by weight of an organic surfactant-modified organopolysiloxane having at least one organic surfactant substituent represented by:

The present invention also relates to a silane coupling agent and the following formula I: R ¹ _4-i --Si--X _i (I) (wherein R ¹ is independently of each other a hydrogen atom or a monovalent hydrocarbon group). Wherein X represents a hydrolyzable group independently of each other, and i is an integer of 1 to 4).
100 parts by weight of the compound of the formula and the following formula III:

[Chemical 4] [In the formula, R's each independently represent a hydrogen atom or a monovalent hydrocarbon group, R ^a represents an organic surfactant substituent represented by the formula II according to claim 1, and R ^b represents the following formula: _{: - (CH 2) j2 O} (C 2 H 4 O) k (C 3 H 6 O) l R 4 ( wherein, R ⁴ is C 1 hydrogen or carbon atoms 19
Represents an alkyl group, k and l are 0 or a positive number, and k + 1 is 1 or more, and j2 is an integer of 1 to 18), and R ^c is R or R. ^a
Or the meaning of R ^b , and x, y and z are 0 or a positive number, provided that when y is 0, R ^c represents the meaning of R ^a ]. The present invention relates to a silane coupling agent composition comprising 1 to 1000 parts by weight of siloxane.

As the silane coupling agent used in the present invention, conventionally known compounds can be used. For example, the general formula:

Embedded image [Wherein n is 0, 1 or 2 and R ⁵ is an organic functional group, for example, an unsubstituted or substituted aminoalkyl group,
Isocyanatoalkyl group, glycidoxyalkyl group,
Epoxycyclohexyl alkyl group, vinyl group, methacryloxy group, mercapto group or the following _{formula: - (CH 2) j2 O} (C 2 H 4 O) k (C 3 H 6 O) l R 4 ( wherein, R ⁴ is a hydrogen atom, an acyl group or 1 carbon atom
To 19 in which k and l are 0 or a positive number and k + 1 ≧ 1, and j2 is an integer of 1 to 18), for example, a polyoxyalkylenealkyl group. Etc., R ⁶ represents an alkyl group, a phenyl group or an aryl group, and R ⁷ represents an unsubstituted or substituted alkyl group].

The following can be listed as specific examples of the silane coupling agent: N-γ- (aminoethyl)-
γ-aminopropyltriethoxysilane, N-γ- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylphenyldiethoxysilane, 2-amino-1-methylethyltriethoxysilane, N-methyl-γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane Ethoxysilane, N-butyl-γ-aminopropylmethyldiethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, N-β- (aminoethyl)
-N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane,
γ-glycidoxypropylmethyldimethoxysilane, β
-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane,
γ-isocyanatopropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, methacryloxypropyltrimethoxysilane, γ-polyoxyethylenepropyltrimethoxysilane and the like.

The specific organosilicon compound used in the present invention is a compound represented by the above formula I. The radical R ¹ in the formula I is a hydrogen atom or a monovalent hydrocarbon radical, for example having 1 to 20 carbon atoms, for example a methyl radical,
Alkyl groups such as ethyl group and hexyl group, cycloalkyl groups such as cyclohexyl group, aryl groups such as phenyl group,
Examples include araryl groups such as benzyl and phenethyl groups, and aralkyl groups such as tolyl groups. When i is 1 or 2 in the formula I, the 3 or 2 groups R ¹ present may be the same or different. Further, the group X in the above formula I is a hydrolyzable group, for example, an alkoxy group having 1 to 8 carbon atoms such as methoxy group and ethoxy group, an alkoxycarbonyl group such as acetoxy group, or a bromine atom, chlorine atom, iodine atom and the like. And halogen atoms. When i is 2, 3 or 4 in the formula I, a plurality of groups X may be the same or different.

Specific examples of the organosilicon compound represented by the formula I include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriacetoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, Ethyltriacetoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldiacetoxysilane, trimethylmethoxysilane,
Examples include, but are not limited to, trimethylethoxysilane, trimethylacetoxysilane, triethylmethoxysilane, triethylethoxysilane, triethylacetoxysilane, and the like.

The above-mentioned silane coupling agent and organosilicon compound may be used as a mixture of two or more kinds, and may be used as they are or as a hydrolyzate and / or a partial condensate.

The organic surfactant-modified organopolysiloxane in the present invention is represented by the following formula II in which one molecule is directly bonded to a silicon atom:

[Chemical 6] (In the formula, R ² and R ³ are independently of each other a hydrogen atom, 1
Represents a trivalent hydrocarbon group or a hydrophilic group, A represents a trivalent hydrocarbon group, j1 is an integer of 2 to 18, m is an integer of 2 to 6, and n is an integer of 1 to 500).
And an organic surfactant having at least one substituent.

A in the above formula II is a trivalent hydrocarbon group, for example, the following formula:

[Chemical 7]

Embedded image And the like. R ² is a hydrogen atom, a monovalent hydrocarbon group such as an alkyl group having 1 to 19 carbon atoms, a phenyl group, an alkylphenyl group, a naphthyl group, a cyclohexyl group, a polycaprolactone group, a trifluoropropyl group or chloropropyl. Group or the like, or a hydrophilic group, for example, a group selected from a polyether group, a glucose group, a sulfate group or an ammonium sulfonate group, but preferably a monovalent hydrocarbon group, especially a methyl group, an ethyl group, a propyl group. Group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group,
Decyl group, undecyl group, dodecyl group, tridecyl group,
It is a linear or branched alkyl group such as a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group and a nonadecyl group, and particularly an octyl group or a nonyl group. Further, R ³ is selected from the same groups as the above R ² , but is preferably a hydrogen atom or ammonium sulfate group.

Particularly preferred organic surfactant-modified organopolysiloxane compounds have the formula III:

[Chemical 9] [Wherein, R represents a hydrogen atom or a monovalent hydrocarbon radical independently of one another, R ^a represents an organic surfactant substituent represented by the formula II, R ^b is the formula: - (CH _{2) j2 O (C 2 H} 4 O) k (C 3 H 6 O) l R 4 ( wherein, R ⁴ is C 1 hydrogen or carbon atoms 19
Represents an alkyl group, k and l are 0 or a positive number, and k + 1 is 1 or more, and j2 is an integer of 1 to 18), and R ^c is R or R. ^a
Or the meaning of R ^b , and x, y and z are 0 or a positive number, provided that when y is 0, R ^c represents the meaning of R ^a ].

R in the above formula III is independently selected from a hydrogen atom or a monovalent hydrocarbon group similar to R ¹ in the above formula I, preferably a monovalent hydrocarbon group, especially a methyl group. , Ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group,
Decyl group, undecyl group, dodecyl group, tridecyl group,
It is a linear or branched alkyl group such as a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and particularly a methyl group.

Further, R ⁴ in the R ^b group is a hydrogen atom or an alkyl group having 1 to 19 carbon atoms, and examples of the latter include those described above for R ¹ .
R ⁴ is preferably a hydrogen atom. R ^c also represents any of the above R, R ^a or R ^b , and the groups described as being preferable for each are also preferable for R ^c .

In the above formula, k, l, j1 and j2 are respectively k of 5 to 70, l of 0 to 50, and j.
It is preferred that 1 and j2 are 2 to 10. Further, x, y and z are 0 or a positive number, and each is, for example, 0 to 100.

The above-mentioned organic surfactant-modified organopolysiloxane compound is a polysiloxane having a SiH group, as described in, for example, JP-A-6-65379, which is a known method for producing modified silicones. formula:

[Chemical 10] Where A, R ² , R ³ and m have the same meaning as defined in formula II above, and j3 is 0 to 16
It represents an integer of 4) and can be produced by a method of adding an allyl group-containing organic surfactant using a catalyst such as chloroplatinic acid.

In the present invention, the organic surfactant-modified organopolysiloxane compound is 1 to 1000 parts by weight, particularly preferably 5 to 100 parts by weight, based on 100 parts by weight of the silane coupling agent and / or the specific organosilicon compound. Used. This is because when the amount of the organic surfactant-modified organopolysiloxane compound is too small,
This is because the effect of using the compound is insufficient, and conversely, if the amount is too large, the strength of the organic material composition obtained using the silane coupling agent composition may decrease.

Further, the present invention relates to the following embodiments using the above silane coupling agent composition: an organic material composition obtained by reacting the above silane coupling agent composition with an organic material, an inorganic material and an organic material A method of using the above silane coupling agent composition for modifying a composite material including a material, and a modification obtained by blending the above silane coupling agent composition into a composite material including an inorganic material and an organic material. Quality composite material.

The organic material used in the present invention means
A resin, such as a thermosetting resin or a thermoplastic resin, means specifically an epoxy resin, a phenol resin, a melamine resin, a urethane resin, an acrylic resin, a nylon resin,
Examples thereof include, but are not limited to, polypropylene resins and the like, and raw material monomers of those resins.

The inorganic materials used in the present invention include inorganic fillers such as silica, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, ferrite, aluminum hydroxide, calcium hydroxide, calcium carbonate, carbonic acid. Zinc, talc, clay, mica, montmorillonite, glass beads, glass fiber, silica sand, etc.
Alternatively, an inorganic base material, for example, a metal plate such as stainless steel, aluminum, or copper, a glass plate, or the like can be given, but the material is not limited to these.

In producing the organic material composition and composite material of the present invention, coloring agents, antioxidants, and
Various additives such as an ultraviolet absorber, a light stabilizer and a flame retardant may be added in an appropriate amount as needed. In addition, the silane coupling agent composition of the present invention contains 1,4-dioxane, 1,3-
Dioxane, trioxane, tetrahydrofuran, 4-
When a cyclic ether compound such as crown-12, 5-crown-15 or dioxolane is mixed, the strength and water resistance of the composite material can be further increased.

The silane coupling agent composition of the present invention is
When used for an organic material or a composite material of an organic material and an inorganic material, a mixture of a silane coupling agent and / or a specific organic silicon compound and an organic surfactant-modified organopolysiloxane compound may be used in advance. However, the components of the silane coupling agent composition may be added separately and then mixed. When the silane coupling agent composition of the present invention is used as a composite material of an organic material and an inorganic material (for example, an inorganic filler), even if the inorganic material is previously treated with the silane coupling agent composition, the organic material A silane coupling agent composition may be added at the time of kneading with the inorganic material. In short, as long as each component of the silane coupling agent composition of the present invention is finally added to the organic material or the composite material in a predetermined amount, the addition method or order does not matter.

The amount of the silane coupling agent composition of the present invention used is not particularly limited, but is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the inorganic material. Further, when reacting with an organic material, it is 0.
1 to 20 parts by weight is preferred. This is because when the amount of the silane coupling agent composition used is less than the above ratio, the adhesiveness between the inorganic material and the organic material or the adhesiveness between the organic materials is insufficient, which is not preferable, and the silane coupling agent composition Even if the amount used is increased from the above ratio, the mechanical strength and water resistance of the composite material, or the characteristics of the organic material are not further improved, which is not preferable from the economical point of view and coloring by heating. This is not suitable because problems such as gelation of resin and resin may occur.

[0027]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples. Examples 1 to 13, Comparative Examples 1 to 13 Strontium ferrite 100 having an average particle size of 1.2 μm
After mixing with a Henschel mixer, 1.0 part by weight of a composition in which the silane coupling agent or the organosilicon compound and the organosurfactant-modified organopolysiloxane compound are mixed in parts by weight in the types and amounts shown in Tables 1 and 3. To the mixture, 13.4 parts by weight of powdered nylon-6 (polyamide 6, manufactured by Ube Industries, Ltd., trade name: P1011F) was added and mixed again with a Henschel mixer to prepare a plastic magnetic composition. The composition was extruded in a string shape by an uniaxial extruder at an extrusion temperature of 250 ° C. to produce pellets of the above composition.

The above pellets were fed to an injection molding machine having a three-piece mold, and the resin temperature was 290 ° C. and the mold temperature was 80.
° C., the molding conditions of injection pressure 850 kg / cm ^2, prescribed test pieces (ASTM D790, ASTM D256, A
Injection molding properties and mechanical properties of the test piece were measured according to ASTM D648.

The fluidity during molding of the above composition was evaluated by using an injection molding machine equipped with a horseshoe-shaped flow length measuring instrument having a width of 10 mm and a thickness of 1 mm, a resin temperature of 280 ° C. and a mold temperature of 80 ° C. , Injection pressure 800kg / cm ² or 1200
It was carried out by measuring the flow length under the molding condition of kg / cm ² .

The magnetic properties of the molded product of the above composition are measured by subjecting the pellets to a magnetic field of 150000e, a resin temperature of 280 ° C., a mold temperature of 80 ° C., and an injection pressure of 850 kg / c.
A cylindrical test piece (thickness: 10 mm, diameter: 20 mm) was produced by injection molding under m ² molding conditions, and the magnetic characteristics of the test piece were recorded by a DC magnetization characteristic automatic recording device (Yokogawa Kitatsuden Electric Co., Ltd.). It was carried out by measuring at.

The results of the above tests are summarized in Tables 2 and 4. From these results, each Example of the present invention using a composition comprising a silane coupling agent or an organosilicon compound and an organosurfactant-modified organopolysiloxane does not use the organosurfactant-modified organopolysiloxane, It is also understood that various resin properties, mechanical properties and processability are superior to those of Comparative Examples used in too small or too large amounts. this is,
It clearly shows that the silane coupling agent composition of the present invention improves the adhesiveness between the organic material (resin) and the inorganic material (inorganic filler).

[0032]

[Table 1] (Footnote of Table 1) * 1: Nippon Unicar Co., Ltd., trade name "A-1230" * 2: Compound of the following formula

[Chemical 11] * 3: Compound of the following formula

[Chemical 12] * 4: Compound of the following formula

[Chemical 13] * 5: Compound of the following formula

Embedded image

[0033]

[Table 2]

[0034]

[Table 3] (Footnote of Table 3) * 1: Nippon Unicar, trade name "A-1230" * 2: Compound of the following formula

[Chemical 15]

[0035]

[Table 4]

[0036]

As described in detail above, the silane coupling agent composition of the present invention improves the adhesiveness between an organic material and an inorganic material in a composite material as compared with a conventional silane coupling agent, Mechanical properties of materials, electrical properties,
It improves water resistance, weather resistance, acid resistance, heat resistance, workability and the like. Therefore, the silane coupling agent of the present invention is extremely effective in modifying a composite material, and in particular, F
RP, FRTP, elastomer, paint, adhesive, sealant, resin concrete, foundry, sealant, artificial marble, plastic magnet, rubber magnet,
Compounded in composite materials such as magnetic tapes and PCBs, it exhibits an extremely high coupling effect.

Claims (5)

[Claims] 1. A silane coupling agent and the following formula I: R ¹ _4-i —Si—X _i (I) (wherein, R ^1's independently of each other represent a hydrogen atom or a monovalent hydrocarbon group, X independently represents a hydrolyzable group, and i represents an integer of 1 to 4), and at least 1 selected from the group consisting of organosilicon compounds
100 parts by weight of the compound of the species and the following formula II directly bonded to a silicon atom in one molecule: (In the formula, R ² and R ³ are independently of each other a hydrogen atom, 1
Represents a trivalent hydrocarbon group or a hydrophilic group, A represents a trivalent hydrocarbon group, j1 is an integer of 2 to 18, m is an integer of 2 to 6, and n is an integer of 1 to 500).
A silane coupling agent composition comprising 1 to 1000 parts by weight of an organic surfactant-modified organopolysiloxane having at least one organic surfactant substituent represented by: 2. A silane coupling agent and the following formula I: R ¹ _4-i —Si—X _i (I) (wherein, R ^1's each independently represent a hydrogen atom or a monovalent hydrocarbon group, X independently of each other represents a hydrolyzable group, and i is an integer of 1 to 4).
100 parts by weight of a compound of the following formula III: [In the formula, R's each independently represent a hydrogen atom or a monovalent hydrocarbon group, R ^a represents an organic surfactant substituent represented by the formula II according to claim 1, and R ^b represents the following formula: _{: - (CH 2) j2 O} (C 2 H 4 O) k (C 3 H 6 O) l R 4 ( wherein, R ⁴ is C 1 hydrogen or carbon atoms 19
Represents an alkyl group, k and l are 0 or a positive number, and k + 1 is 1 or more, and j2 is an integer of 1 to 18), and R ^c is R or R. ^a
Or the meaning of R ^b , and x, y and z are 0 or a positive number, provided that when y is 0, R ^c represents the meaning of R ^a ]. A silane coupling agent composition comprising 1 to 1000 parts by weight of siloxane. 3. An organic material composition obtained by reacting the silane coupling agent composition according to claim 1 or 2 with an organic material. 4. A method of using the silane coupling agent composition according to claim 1 or 2 for modifying a composite material composed of an inorganic material and an organic material. 5. A modified composite material obtained by blending the silane coupling agent composition according to claim 1 with a composite material composed of an inorganic material and an organic material.