JPH06287198A - Silane coupling agent - Google Patents

Abstract

PURPOSE:To obtain a silane coupling agent composed of an onium salt of an halogenated alkylalkoxysilane with an imidazole, an imidazoline, a triazine, a triazole, etc., good in solubility in water and heat resistance and useful as an adhesion improver, a surface treating agent, etc. CONSTITUTION:A halogenated alkylalkoxysilane expressed by formula I [R is H or monovalent hydrocarbon; X is halogen; R' is H or 1-6C hydrocarbon; (a) is an integer of 0-2; (n) is an integer of 2-5] (e.g. y- chloropropyltrimethoxysilane) or its derivative is made to react with a compound such as an imidazole expressec by formula II (R<1> to R<3> are H, monovalent hydrocarbon, amino, etc.; R<4> is H, amino, etc.), an imidazoline expressed by formula III (R<5> to R<9> are the same species as that of R<1>; R<10> is the same species as that of R<4>), a triazine expressed by formula IV [R<11> to R<17> are the same species as that of R<1>; (m) is 1-5] or a triazole ring-containing compound expressed by formula V [R<18> to R<21> are the same species as that of R<1>; (p) is 0-5] to produce an onium salt. Thereby, the objective silane coupling agent having both high water solubility and heat resistance is obtained.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel silane coupling agent, and further to a composite material produced by using the silane coupling agent.

[0002]

2. Description of the Related Art A silane coupling agent is a compound having a portion having reactivity with an inorganic substance and a portion having high reactivity / solubility with respect to an organic substance in one molecule, and is an interface between the inorganic substance and the organic substance. It is widely used in the manufacture of many composite materials because it acts as an adhesion aid for Utilizing this property, silane coupling agents are widely used in glass cloth reinforced epoxy resin composite materials, but γ-aminopropyltriethoxysilane and γ-glycidoxypropyl which have been conventionally used for this application are used. Trimethoxysilane and the like have insufficient heat resistance and cannot be used for applications such as glass cloth reinforced epoxy resin laminates, which are electronic component materials required to have heat resistance. On the other hand, recently, a cationic silane coupling agent such as N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride has been widely used. Usually, the glass cloth treatment with a silane coupling agent is generally a method of treating with an aqueous solution of a silane coupling agent, and the water solubility of the silane coupling agent is important. However, these conventional cationic silanes are generally used. In order to prepare a stable aqueous solution or emulsion dispersion having low water solubility, only a silane coupling agent having a certain concentration or less could be used. Furthermore, in order to improve the stability of the aqueous solution or emulsion dispersion of the above-mentioned cationic silane, various additives must be used, but there is a problem that these additives adversely affect the glass cloth reinforced epoxy resin composite material. However, a silane coupling agent having high water solubility has been strongly demanded.

[0003]

SUMMARY OF THE INVENTION The present invention aims to solve the above-mentioned drawbacks of conventional silane coupling agents,
To provide a novel silane coupling agent capable of forming a stable aqueous solution without adding various additives, and capable of imparting high heat resistance to a glass cloth reinforced composite material such as an epoxy resin laminated plate To do.

[0004]

Means for Solving the Problems As polymerization catalysts for epoxy compounds, imidazole, imidazoline, triazine,
Triazole ring-containing compounds are well known, but it is considered that this is because the carbon-nitrogen unsaturated double bond in the above compound causes an epoxy ring opening reaction. Among the above compounds, those having a nitrogen-hydrogen bond form an onium salt with a halogenated alkyl compound. Therefore, the inventors of the present invention have earnestly studied and found that onium salts of these compounds and a halogenated alkylalkoxysilane or a derivative thereof are useful as a silane coupling agent, and in particular, the surface of glass cloth in a glass cloth-reinforced epoxy resin composite material. It was found that when it was used as a treatment agent, it exhibited extremely excellent heat resistance and water solubility, and further studies were conducted to complete the present invention.

That is, the present invention relates to a halogenated alkylalkoxysilane or a derivative thereof, an imidazole,
The present invention relates to a silane coupling agent comprising an onium salt with a compound selected from imidazoline, triazine, and a compound containing a triazole ring.

[Chemical 9] (In the formula, R represents a hydrogen atom or a monovalent hydrocarbon group,
X represents a halogen atom, R ′ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, a represents an integer of 0 to 2, and n represents an integer of 2 to 5). An organosilicon compound having the formula II:

[Chemical 10] (In the formula, R ¹ , R ² and R ³ are independently of each other a hydrogen atom, a monovalent hydrocarbon group, an amino group, a hydroxyalkyl group, a ureidoalkyl group, a cyanoalkylaminoalkyl group, a nitro group, a formal group or A phenyl group, and R ⁴ represents a hydrogen atom, an amino group, an aminoalkyl group or a cyanoalkylaminoalkyl group), and a silane coupling agent consisting of an onium salt with a compound represented by the above formula I An organosilicon compound and the following formula I
II:

[Chemical 11] (In the formula, R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are independently of each other a hydrogen atom, a monovalent hydrocarbon group, an amino group, an aminoalkyl group, a hydroxyalkyl group, a ureidoalkyl group, a cyanoalkyl group. A silane cup comprising an onium salt with a compound represented by an aminoalkyl group, a nitro group, a formal group or a phenyl group, and R ¹⁰ represents a hydrogen atom, an amino group, an aminoalkyl group or a cyanoalkylaminoalkyl group. A ring agent, an organosilicon compound represented by the above formula I, and the following formula IV:

[Chemical 12] (In the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R
¹⁷ independently represent a hydrogen atom, a monovalent hydrocarbon group, an amino group, an aminoalkyl group, a hydroxyalkyl group, a ureidoalkyl group, a cyanoalkylaminoalkyl group, a nitro group, a formal group or a phenyl group, At least one of R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ represents a hydrogen atom, an amino group, an aminoalkyl group or a cyanoalkylaminoalkyl group, and m is 1 to 5
A silane coupling agent consisting of an onium salt with a compound represented by the formula:

[Chemical 13] (In the formula, R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ are independently of each other a hydrogen atom, a monovalent hydrocarbon group, an amino group, an aminoalkyl group, a hydroxyalkyl group, a ureidoalkyl group, a cyanoalkylaminoalkyl group. , Nitro group, formal group or phenyl group, provided that at least one of R ¹⁹ , R ²⁰ and R ²¹ represents a hydrogen atom, an amino group, an aminoalkyl group or a cyanoalkylaminoalkyl group, and p is 0. To an integer of 5) and a silane coupling agent comprising an onium salt with a compound represented by the formula: Further, the present invention relates to a thermosetting resin composite material, particularly an epoxy resin composite material, produced by using at least one of the above silane coupling agents.

The silane coupling agent of the present invention is, for example, an organosilicon compound represented by the formula I with respect to the formula II,
One or two compounds represented by III, IV and V
It is produced by directly mixing and heating at least a temperature of 150 ° C. or lower in a nitrogen stream by using one or more kinds. In addition, formulas II and II
When the compounds represented by I, IV and V are used, an isocyanuric acid adduct, a benzotriazole adduct, a trimellitic acid adduct, a hydrochloride, a hydrate or the like of these compounds or an acid salt is used. You can also Further, using various solvents in which this mixture is compatible, for example, water, methanol, ethanol, isopropanol, ethylene glycol, propylene glycol, toluene, dimethylformamide, dimethylacetylamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, etc. It can also be produced by a method of mixing and heating after melting.

Specific examples of the organosilicon compound represented by the above formula I used for synthesizing the silane coupling agent of the present invention include, but are not limited to, the following. :

[Chemical 14]

The following are specific examples of the compound represented by the above formula II, III, IV or V which is reacted with the organosilicon compound represented by the above formula I in the synthesis of the silane coupling agent of the present invention. Examples thereof include, but are not limited to, of course. Specific examples of the compound represented by the formula II:

[Chemical 15] Specific examples of compounds of formula III:

[Chemical 16] Specific examples of compounds of formula IV:

[Chemical 17] Specific examples of the compound represented by the formula V:

[Chemical 18]

The silane coupling agent of the present invention alone
Alternatively, it can be used as a mixture of two or more kinds,
Other compounds such as various conventional silane coupling agents,
It can be used in combination with a nonionic surfactant, a nonionic surfactant, a cationic surfactant, an amphoteric surfactant, an antistatic agent, alcohols, aromatic hydrocarbons, other solvents and the like.

Examples of the thermosetting resin with which the silane coupling agent of the present invention exhibits excellent effects include epoxy resin, phenol resin, polyamide resin, polyimide resin, etc., among which epoxy resin is particularly preferable. Further, as the inorganic material used for the composite material of the present invention, glass,
Examples thereof include silica, calcium silicates, metals, metal oxides and metal hydroxides. In addition, these composite materials show excellent solder heat resistance and water resistance when a laminated plate is prepared by impregnating a glass cloth with a thermosetting resin, especially an epoxy resin, and curing it, so that it is useful as a printed wiring board. The sex is remarkable.

The silane coupling agent of the present invention is used in addition to the above-mentioned applications, and is also an adhesiveness improver between materials (especially between an organic material and an inorganic material such as an inorganic filler), a surface treatment agent, a resin modifier, and a paint. It can be widely used as a modifier, a fiber surface modifier, other additives, adhesives, etc.

Next, the present invention will be explained based on examples, but the present invention is not limited to these. In addition,
In the following description, all "parts" mean "parts by weight". Example 1 The inside was replaced with dry nitrogen in advance, and a stirring device, a nitrogen introducing tube,
A 1000 ml four-necked flask equipped with a thermometer and a condenser was charged with 154.06 parts (2.26 parts) of imidazole.
Mol) and γ-chloropropyltrimethoxysilane 34
5.94 parts (1.74 mol) are added and the contents are heated under a nitrogen atmosphere at 90 ° C. for 8 hours and then cooled. After separating the reaction product and the unreacted product by high-speed GPC, the content was confirmed to form an onium salt of the following structural formula by measurement of free chloride ion.

[Chemical 19] Free chloride ion Calculated value 13.8% Measured value 12.6%

Example 2 The inside was previously replaced with dry nitrogen, and a stirring device, a nitrogen introducing pipe,
To a 1000 ml four-necked flask equipped with a thermometer and a condenser, 177.32 parts (2.11 mol) of 2-methylimidazoline and 322.68 parts (1.62 mol) of γ-chloropropyltrimethoxysilane were added. The contents are heated under a nitrogen atmosphere at 90 ° C. for 8 hours and then cooled. After separating the reaction product and the unreacted product by high-speed GPC, it was confirmed from the measurement of free chloride ion that the contents formed an onium salt. Free chloride ion Calculated value 12.6% Measured value 12.0%

Example 3 The inside was previously replaced with dry nitrogen, and a stirring device, a nitrogen introducing pipe,
In a 1000 ml four-necked flask equipped with a thermometer and a condenser, 6- [2- (2-methylimidazole-
1-yl) ethyl-1,3,5-triazine-2,4-
Diamine / isocyanuric acid adduct / dihydrate 264.7
3 parts (0.77 mol), γ-chloropropyltrimethoxysilane 235.27 parts (1.18 mol) and dimethylformamide 150.00 parts (30 parts with respect to the raw material) were added and the contents were added under a nitrogen atmosphere. The product is heated at 90 ° C. for 8 hours and then cooled. After separating the reaction product from the unreacted product and the solvent by high-speed GPC, the content was confirmed to form an onium salt by measurement of free chloride ion. Free chloride ion Calculated value 9.6% Measured value 8.9%

Example 4 The inside was previously replaced with dry nitrogen, and a stirring device, a nitrogen introducing pipe,
In a 1000 ml four-necked flask equipped with a thermometer and a condenser, 68.90 parts (0.82 mol) of 3-amino-1,2,4-triazole and 181.10 parts of γ-chloropropyltrimethoxysilane (0. .91 mol) and 375.00 parts of ethylene glycol (150 with respect to the raw material)
Part) and the contents are heated under a nitrogen atmosphere at 90 ° C. for 8 hours and then cooled. After separating the reaction product from the unreacted product and the solvent by high-speed GPC, the content was confirmed to form an onium salt by measurement of free chloride ion. Free chloride ion Calculated value 12.6% Measured value 11.9%

Example 5 The water solubility of the silane coupling agent of the present invention obtained in Examples 1 to 4 and the heat resistance and water content of the epoxy resin laminate using these silane coupling agents were measured. The results are shown in Table 1. For comparison, the results of the same test using some known silane coupling agents are also shown.

[Table 1] The glass cloth surface treatment method, laminated plate test piece preparation method and evaluation method adopted in the above test are as follows. Surface treatment method for glass cloth The silane coupling agent obtained in Examples 1 to 4 was dissolved in distilled water whose pH was adjusted to 4 in advance with acetic acid to prepare a 0.5% solution as a solid content of the silane coupling agent. Prepare.
The γ-aminopropyltriethoxysilane of Comparative Compound 1 is dissolved in distilled water to prepare a solution having a solid content of 0.5%.
The γ-glycidoxypropyltrimethoxysilane of Comparative Compound 2 was dissolved in distilled water adjusted to pH 4 with acetic acid,
Prepare a 0.5% solids solution. The silane coupling agents of Comparative Compounds 3 and 4 are each dissolved in methanol to prepare a 0.5% solution as the solid content of the silane coupling agent. The respective solutions thus prepared were then deoiled with glass cloth (Nitto Boseki Co., Ltd., W
E-18K) is dipped and squeezed with a squeeze roll to 100
Dry at 10 ° C for 10 minutes. Method for producing laminated plate test piece FR-4 type epoxy resin (Yukaka Shell Epoxy Co., Ltd., Epicoat 104) was applied to surface-treated glass cloth.
5-A-70) is impregnated and dried at 140 ° C. for 10 minutes to obtain a prepreg. A copper aluminum foil was further laminated on both surfaces of a laminate in which eight prepregs were laminated, and 170 ° C, 4
Molding is performed under the conditions of 0 kg / cm and 70 minutes. The copper foil is removed by etching the entire surface and cut into a laminated plate test piece of 50 × 50 mm. Evaluation method (1) Water solubility test The amount dissolved in 100% by weight of distilled water adjusted to pH 4 with acetic acid in advance is measured (unit is% by weight). (2) Solder heat resistance test A test piece is treated with a pressure cooker at 133 ° C and then immersed in a solder bath at 260 ° C for 20 seconds. Determine the processing time in the pressure cooker where blistering or peeling of the test piece surface occurs. (3) Water Absorption Test After treating the test piece with a pressure cooker at 133 ° C. for 180 minutes, the test piece is immersed in distilled water at 23 ° C. for 24 hours to obtain the water absorption rate. (4) Adhesion Rate of Treatment Agent (Silane Coupling Agent) to Glass Cloth At the time of glass cloth treatment, the adhesion rate of the treatment agent is determined from the increased weight. (5) Laminated Resin Content The resin content is determined from the weight of the laminated test piece.

[0017]

As described in detail above, the silane coupling agent of the present invention has both excellent water solubility and heat resistance, which have been desired to be developed in the past. Therefore, the silane coupling agent of the present invention can form an aqueous solution without adding various additives, and can impart high heat resistance to a glass cloth reinforced composite material such as an epoxy resin laminate. It can also be suitably applied to a glass cloth reinforced epoxy resin laminate as a printed wiring board. Further, since the silane coupling agent of the present invention has excellent properties as described above, it is possible to improve adhesion between materials, surface treatment agent, resin modifier, paint modifier, surface modification of fiber. It can be widely used as a quality agent, other additives, an adhesive, etc.

Claims (7)

[Claims] 1. A silane coupling agent comprising an onium salt of a halogenated alkylalkoxysilane or a derivative thereof and a compound selected from imidazole, imidazoline, triazine and a triazole ring-containing compound. 2. The following formula I: (In the formula, R represents a hydrogen atom or a monovalent hydrocarbon group,
X represents a halogen atom, R ′ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, a represents an integer of 0 to 2, and n represents an integer of 2 to 5). And an organosilicon compound having the following formula II: (In the formula, R ¹ , R ² and R ³ are independently of each other a hydrogen atom, a monovalent hydrocarbon group, an amino group, a hydroxyalkyl group, a ureidoalkyl group, a cyanoalkylaminoalkyl group, a nitro group, a formal group or A phenyl group, and R ⁴ represents a hydrogen atom, an amino group, an aminoalkyl group or a cyanoalkylaminoalkyl group) and a compound represented by an onium salt. 3. The following formula I: (In the formula, R represents a hydrogen atom or a monovalent hydrocarbon group,
X represents a halogen atom, R ′ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, a represents an integer of 0 to 2, and n represents an integer of 2 to 5). And an organosilicon compound having the formula III: (In the formula, R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are independently of each other a hydrogen atom, a monovalent hydrocarbon group, an amino group, an aminoalkyl group, a hydroxyalkyl group, a ureidoalkyl group, a cyanoalkyl group. A silane cup comprising an onium salt with a compound represented by an aminoalkyl group, a nitro group, a formal group or a phenyl group, and R ¹⁰ represents a hydrogen atom, an amino group, an aminoalkyl group or a cyanoalkylaminoalkyl group. Ring agent. 4. The following formula I: (In the formula, R represents a hydrogen atom or a monovalent hydrocarbon group,
X represents a halogen atom, R ′ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, a represents an integer of 0 to 2, and n represents an integer of 2 to 5). An organosilicon compound having the formula IV: (In the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R
¹⁷ independently represent a hydrogen atom, a monovalent hydrocarbon group, an amino group, an aminoalkyl group, a hydroxyalkyl group, a ureidoalkyl group, a cyanoalkylaminoalkyl group, a nitro group, a formal group or a phenyl group, At least one of R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ represents a hydrogen atom, an amino group, an aminoalkyl group or a cyanoalkylaminoalkyl group, and m is 1 to 5
Represents an integer) and a silane coupling agent comprising an onium salt with a compound represented by. 5. The following formula I: (In the formula, R represents a hydrogen atom or a monovalent hydrocarbon group,
X represents a halogen atom, R ′ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, a represents an integer of 0 to 2, and n represents an integer of 2 to 5). And an organosilicon compound having the following formula V: (In the formula, R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ are independently of each other a hydrogen atom, a monovalent hydrocarbon group, an amino group, an aminoalkyl group, a hydroxyalkyl group, a ureidoalkyl group, a cyanoalkylaminoalkyl group. , Nitro group, formal group or phenyl group, provided that at least one of R ¹⁹ , R ²⁰ and R ²¹ represents a hydrogen atom, an amino group, an aminoalkyl group or a cyanoalkylaminoalkyl group, and p is 0. To an integer of 5), and a silane coupling agent comprising an onium salt with a compound represented by the formula: 6. A thermosetting resin composite material produced by using the silane coupling agent according to claim 1. Description: 7. An epoxy resin composite material produced by using the silane coupling agent according to claim 1. Description: