DE102004001368A1 - New alkyphenyl-amino-silane compounds, used as coupling agents on woven glass mat for production of reinforced epoxy resin laminates, e.g. printed circuit boards - Google Patents

Abstract

Arylamino-functional silanes and/or their hydrochloride salts in which the benzene ring is also substituted with a 1-6C alkyl group are new. Arylamino-functional silanes of formula (I) and/or their hydrochloride salts are new. R-C6H4-CH2NHCH2CH2NH(CH2)3Si(R1>)n(OR2>)3-n (I) R, R1>, R2>1-6C alkyl; n : 0 or 1 Independent claims are also included for (1) water-resistant substrates consisting of woven glass fabric coated with (I) (2) a method for the production of substrates by coating woven glass fabric with (I) and then applying the coated fabric to an epoxy laminate to reinforce the laminate.

Description

Background of the invention

Field of the invention

The The present invention relates to a group of amino-functional Silane coupling agents used as coatings for glass fiber fabrics in the manufacture of epoxy laminating composites, e.g. PCBs Find use and have a better performance than before known compounds. In particular, the present invention relates Invention on the synthesis and use of certain arylalkylaminofunktioneller Silanes that can be produced at a lower cost and which are non-styryl raw materials, the lighter available are as the currently used.

Description of the state of the technique

In the manufacture of glass fiber reinforced plastics, organofunctional alkoxysilanes (commonly referred to as "coupling agents") are applied to glass cloth to improve the bond strength of the glass-matrix interface while preventing moisture from entering the interface, which is of particular interest to printed circuit boards Industrial grade epoxy laminates include chlorosilated arylenes derived aminosilanes such as Z-6032 and Z-6224 from Dow Corning and A-1128 from OSi (now part of Crompton), which are the most widely used It is known that in the manufacture of glass fiber reinforced epoxy laminates, a process is used which comprises (1) treating glass fiber fabrics with a silane solution, (2) impregnating with epoxy resin, and (3) crosslinking at an elevated temperature Silane solution prepared in an aqueous system, which, due to its non-flammability, is considered to be highly desirable in terms of both cost and safety for fiberglass coating applications. U.S. Patent No. 3,819,675 discloses a wide variety of cationic, unsaturated amino-functional silane coupling agents for composite applications. One particular composition that has achieved extraordinary commercial success is a styrylamino-functional silane having the formula: CH ₂ = CHC ₆ H ₄ CH ₂ NH (CH ₂ ) ₂ NH (CN ₂ ) ₃ Si (OCH ₃ ) ₃ HCl (Z-6032) for applications covering a wide range of polymer composites. In this capacity, it has attained the status of a "universal" primer, ie a primer that is equally useful for bonding organic polymers (such as polyolefins, unsaturated polyesters, phenols, epoxies, etc.) and inorganic materials However, whether the styryl double bond in the silane is necessary for non-vinyl polymers such as epoxy resins is highly troubling, however, despite its high price, Z-6032 and its low HCl form Z-6224 have occupied a dominant position in epoxy laminate applications for the last 30 years. The high price is due to the raw material chloromethylstyrene (CH ₂ = CHC ₆ H ₄ CH ₂ Cl), due to the high costs associated with difficult production and product instability, cooling during transport and storage to prevent polymerization only available from very few sources Although simple chloromethylated arene-benzyl chloride-derived A-1128 having the formula C ₆ H ₅ CH ₂ NH (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ HCl is a lower cost product but has its drawback a lower water resistance a much lower market presence. The search for a viable alternative product is therefore essential.

Summary the invention

und/oder Salze davon bereitgestellt, worin R eine Alkylgruppe mit 1 bis 6 Kohlenstoffatomen ist, R¹ eine Alkylgruppe mit 1 bis 6 Kohlenstoffatomen ist, R² gleich oder verschieden sein kann und unabhängig aus Alkylgruppen mit 1 bis 6 Kohlenstoffatomen ausgewählt ist, und n einen Wert von 0 oder 1 hat. Bevorzugte Salze schließen HCl-Salze ein, sind jedoch nicht darauf beschränkt. In bestimmten bevorzugten Ausführungsformen ist R Methyl oder Ethyl, R¹ Methyl und R² Methyl oder Ethyl.In one embodiment, arylamino-functional silane compounds are prepared according to the following formula:

and / or salts thereof, wherein R is an alkyl group having 1 to 6 carbon atoms, R ^{1 is} an alkyl group having 1 to 6 carbon atoms, R ^{2 may be the} same or different and is independently selected from alkyl groups having 1 to 6 carbon atoms, and n has a value of 0 or 1. Preferred salts include, but are not limited to, HCl salts. In certain preferred embodiments R is methyl or ethyl, R ^{1 is} methyl and R ^{2 is} methyl or ethyl.

According to one another embodiment Fiberglass fabric substrates are provided with compounds according to the above Formula are coated.

detailed Description of the preferred embodiment

It It is known that serving as a primer silane coatings on glass their effect by means of bound to the glass surface silanol groups and an organofunctional group that easily bonds to chemicals with the resin binder, unfold. For effective grafting of the silane on the glass fiber surface are preferably two Steps required. First the alkoxysilane is hydrolyzed in a bath, so that more water-soluble Silanol is formed which absorbs the submerged glass fiber webs. Then a condensation reaction of the silanols takes place on the glass surface, at the siloxane bond is completed. The solution preferably remains aqueous System as long as soluble (recognizable by the clarity of the solution), how the contents of the bath remain in a production bath. A Lifespan of the solution bath about 2 days or more is for practical purposes preferred. In the meantime, during the Hydrolysis at the same time a condensation of the silanols, so that water-insoluble Siloxane is formed, which is generally ineffective for adhesion is. Therefore, the preparation of the silane solution is preferably under conditions carried out, the opposite to the hydrolysis favor condensation, typically at ambient temperatures and an acidic pH of about 4-5 to the reduce premature siloxane formation to a minimum.

The Water Although an important property of adhesion promoters according to the preferred embodiments, but the water resistance of the resulting composite may be even more important. There are many amino-functional silanes that the requirements regarding Water and solution stability, but the resulting siloxanes are in terms of water resistance see, for example, A-1100, A-1120 in Modern Plastics, 1962, P. 135). A good adhesion promoter according to the preferred embodiments should therefore have a good but difficult balance between Hydrophilicity (for hydrolysis) and hydrophobicity (of the resulting siloxane for moisture rejection) in the laminates made therefrom.

und ihre Salze ein, worin R eine Alkylgruppe mit 1 bis 6 Kohlenstoffatomen ist, R¹ eine Alkylgruppe mit 1 bis 6 Kohlenstoffatomen ist, R² gleich oder verschieden sein kann und unabhängig aus Alkylgruppen mit 1 bis 6 Kohlenstoffatomen ausgewählt ist, und n einen Wert von 0 oder 1 hat. Der Begriff „Alkylgruppe", wie er hierin verwendet wird, ist eine verzweigte oder unverzweigte Kette mit 1 bis 6 Kohlenstoffatomen. Bevorzugte Salze schließen HCl-Salze ein, sind jedoch nicht darauf beschränkt.A group of arylalkylamino functional silanes having improved waterfastness in accordance with the preferred embodiments of the present invention utilizes lower cost chloromethylated arylenes having selected alkyl substitutions. Preferred compounds include arylamino-functional silane compounds according to the following formula:

and their salts, wherein R is an alkyl group having 1 to 6 carbon atoms, R ^{1 is} an alkyl group having 1 to 6 carbon atoms, R ^{2 may be the} same or different and is independently selected from alkyl groups having 1 to 6 carbon atoms, and n is a value from 0 or 1 has. The term "alkyl group" as used herein is a branched or unbranched chain of 1 to 6 carbon atoms Preferred salts include, but are not limited to, HCl salts.

The compounds of the above composition prepared by a process according to the preferred embodiments give substantially the same, and in some respects even better results than the hitherto known products, without the need for expensive styryl raw materials. Since the products are non-vinyl products, they are also more stable and therefore easier to handle. The superiority of the silane composition according to the preferred embodiments when using the standard industrial test (121 ° C, +1 atm) and the more severe steam pressure cook test (132 ° C, +2 atm) and the subsequent solder bath test at 500 ° F with respect to the water solution stability Example 4 below, with respect to the adhesive strength of Example 5 below and with respect to the resistance to boiling water from Example 6 below clearly. The results of the tests solve the long-standing question of the styryl double bond puzzle, ie non-styrene silanes can be just as powerful with proper alkyl substitution on the arylenes in epoxy lamination, which was not previously known.

Law unexpected is also the higher one Hydrophobicity in some preferred embodiments, requiring a longer hydrolysis time than the standard product currently used (see example 4), but at resolution in water a longer one Solution stability upright receives - a seemingly incompatible, but most desirable Feature in the production and handling of an aqueous silane solution for the Coating of glass fibers.

worin X eine Austrittsgruppe, vorzugsweise ein Halid wie Chlorid ist, mit der entsprechenden Aminosilanverbindung umgesetzt wird. Die Reaktion erfolgt vorzugsweise durch langsame, z.B. tropfenweise Zugabe einer Lösung, die die Benzylverbindung in einem kompatiblen Lösungsmittel enthält, zu dem Aminosilan unter Erwärmung wie z.B. Rückfluss.Compounds according to the preferred embodiments can be prepared by a process in which a compound according to the following formula:

wherein X is a leaving group, preferably a halide such as chloride, is reacted with the corresponding Aminosilanverbindung. The reaction is preferably carried out by slow, eg dropwise, addition of a solution containing the benzyl compound in a compatible solvent to the aminosilane under heating such as reflux.

The Compositions in the following examples which are structurally represented and further characterized in terms of physical properties are intended to merely illustrate and apply the invention not as limiting.

example 1

Preparation of CH ₃ CH ₂ C ₆ H ₄ CH ₂ NH (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ HCl (I)

The preparation of the compound according to the above formula (I) is carried out as follows: CH ₃ CH ₂ C ₆ H ₄ CH ₂ Cl + H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ → (I)

To a 2 liter 3-necked round bottom flask equipped with an addition funnel, reflux condenser, thermometer, and stirrer is charged 226 g (1.02 mole) of commercially available 2-aminoethyl (3-aminopropyl) trimethoxysilane (A-1120 from OSi) and heated to 60 ° C. Over a period of one hour, 156 grams (1.0 mole) of ethylbenzyl chloride in 570 grams of anhydrous methanol are added dropwise to the container while stirring, with gentle reflux (65 ° -70 ° C) with occasional heating. By stirring at reflux for a further two and a half hours, the alkylation of the amino nitrogen of the silane is completed with the concomitant formation of the near theoretical (1.05 mol / kg) chloride ion by analysis of a recovered 40 wt% methanol solution. The starting material ethylbenzyl chloride, as used, was in accordance with NMR spectroscopic data of para and ortho isomers in a ratio of about 70:30. Due to the highly hygroscopic nature of the amine salt product and the hydrolysis-sensitive trimethoxysilane ester group, no attempt was made to isolate the product. The product obtained (950 grams) had the following physical properties: relative density at 25 ° C: 0.901; Refractive index n _D ²⁵ : 1.396; Cl ^- : 3.70%; ¹ H-NMR (CD ₃ OD, TMS) δ = 0.6 (2H, br m), 1.15 (3H, t, J = 7.26 Hz), 1.6 (2H, br m), 2 , 55 (2H, q, J = 7.55 Hz), 2.8 (6H, m), 3.3 (9H, s), 3.9 (2H, s), 7.16 (4H, m) (some signals were hidden in a broad peak of CH ₃ OH and CHOH (solvent) appearing at 6 = 3.4 and 5.0 ppm, respectively).

Example 2

Preparation of CH ₃ CH ₂ C ₆ H ₄ CH ₂ NH (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ (II)

Neutralization with alcoholic NaOH gave a low-chloride version. The preparation of the compound according to the above formula (II) is carried out as follows: CH ₃ CH ₂ C ₆ H ₄ CH ₂ NH (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ HCl + NaOH / CH ₃ OH → NaCl + (II)

The product obtained in Example 1 (940 grams of I) is neutralized with vigorous stirring by the stepwise addition of a solution containing 40 grams of NaOH dissolved in 150 grams of methanol and the resulting NaCl precipitate removed by filtration to give a clear solution of the product Product (1022 grams of II) is obtained which has the following properties: relative density at 25 ° C: 0.879; Refractive index at 25 ° C: 1.389; Cl ^- : 0.3%; ¹ H-NMR (CD ₃ OD, TMS) δ = 0.6 (2H, br s), 1.15 (3H, br t), 1.6 (2H, br m), 2.5 (8H, br overlapped m), 3.3 (9H, s), 7.1 (4H, m) (some signals were hidden in a broad peak of CH ₃ OH and CHOH (solvent), those at δ = 3.4 and 5, respectively , 0 ppm appeared).

Example 3

Preparation of CH ₃ CH ₂ C ₆ H ₄ CH ₂ NH (CH ₂ ) ₂ NH (CH ₂ ) ₃ SiCH ₃ (OCH ₃ ) ₂ HCl → (III)

The preparation of the compound according to the above formula (III) is carried out as follows: CH ₃ CH ₂ C ₆ H ₄ CH ₂ Cl + H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ SiCH ₃ (OCH ₃ ) ₂ → (III)

The procedure of Example 1 was followed using 156 grams (1.0 mole) of ethylbenzyl chloride in 550 grams of anhydrous methanol and 210 grams (1.02 mole) of 2-aminoethyl (3-aminopropyl) methyldimethoxysilane (KBM 602 ex Shin-Etsu) to produce 915 grams of a 40% by weight solution of ethylbenzylated aminoalkylmethyldimethoxysilane hydrochloride which is amber in color, has the expected chloride ion analysis of 1.09 mol / kg and has the following physical properties: relative density at 20 ° C: 0.890; Refractive index n _D ²⁵ : 1.4040; Cl ^- : 3.87%; ¹ H-NMR (CD ₃ OD, TMS) δ = 0.15 (3H, s), 0.55 (2H, br m), 1.15 (3H, t, J = 7.26 Hz), 1, 6 (2H, br m), 2.55 (2H, q, J = 7.55 Hz), 2.8 (6H, m), 3.3 (6H, s), 3.9 (2H, s) , 7.16 (4H, m) (some signals were hidden in a broad peak of CH ₃ OH and CHOH (solvent) appearing at δ = 3.4 and 5.0 ppm, respectively).

Example 4 - Water Solubility Test

100 ml of distilled water acidified with 1% glacial acetic acid was added Stirring gradually a 1.0 gram sample of Example 1 was added. The solution was slightly cloudy at the beginning, but became clear after 45 minutes while the commercial product Z-6032 (Dow Corning) under similar Conditions became clear in 20 minutes. The solution stayed for more than two weeks at ambient temperatures while the Z-6032 solution is in less than a week cloudy has been.

Example 5 - Adhesive strength

A. Preparation of a silane coating solution

By Add 10 g of acetic acid and subsequently 6.7 g of the silane product of Example 1 (the 40 percent active silane contains) to 1000 ml of distilled water, an aqueous silane solution was prepared, so that 0.67% (target concentration) or 0.27% (actual concentration) Concentration of the primer solution was created. The solution was stirred vigorously at ambient temperature for one hour, so that a clear silane coating solution was formed.

B. Treatment of the glass fiber fabric

Thermally-cleaned glass fiber cloth (type 7628) was immersed in the silane coating solution prepared in 5A at ambient temperature for 2.5 minutes. The silane treated fiberglass fabric was passed through a series of rollers to squeeze out excess silane solution and then dried at 115 ° C for 30 minutes. The dry treated 7628 glass fiber fabrics showed a silane uptake of 0.08 wt%, thinner 1080 fabrics showed a silane uptake of 0.12 wt%. The glass fiber fabric was cut into 5 × 25 cm ² sized pieces and subjected to a tensile test. The tensile test was performed using an Instron overhead speed of 10 cm / min. carried out. The results are shown in Table 1. The columns titled "Tensile Strength" represent the tear strength (kg / 5 cm) and the columns titled "RTS%" represent the relative tensile strength, with 128.7 kg / 5 cm (0.67% Z-6224 ) are considered 100.

TABLE 1 Tensile strength of silane-treated glass fiber fabrics 7628

Example 6 - Water resistance a multilayer laminate by FR-4 epoxy resin

A. Preparation of an Epoxy Lacquer Solution

 B. Preparation of the laminate

4-layer laminates: Strips of glass fiber fabrics (type 7628) treated with the silane coating prepared in 5B-1 were impregnated with the above-mentioned varnish (6A), precrosslinked at 150 ° C for 5 minutes with a gradual increase in temperature pressure-crosslinked to 190 ° C and 20 a pressure of 35 kg / cm ² in 15 minutes and held there for 2 hours.

C. Test for resistance across from boiling water

(I) Steam pressure cooker:

The Conditions for The standard test is a steam temperature of about 121 ° C (at a Pressure of 1 atm) and a time of one hour.

The Conditions for the aggravated Test were a steam temperature of about 132 ° C (at a pressure of 2 atm) and a time of either one or two hours.

The Laminate patterns were for one or two hours among the previously closer executed cooking Conditions immersed in the pressure cooker.

(II) solder bath:

To The samples were immersed in the pressure cooker according to the IPC-TM-650 test method into a solder bath for about 20 seconds a temperature of 500 ± 10 ° F (260 ± 5 ° C) dipped. The results are shown in Table 2 for samples in which the coating prepared by the method of Example 5A Example 1 was used.

Table 2 Resistance of multilayer laminate to boiling water by FR-4 epoxy resin

The various methods and techniques described above a number of possibilities to carry out the invention ready. Naturally It can be assumed that not necessarily all described Tasks or benefits according to a certain embodiments described herein can be achieved. Therefore recognizes e.g. the person skilled in the art that the methods can be carried out in a manner that an advantage or group of advantages as taught herein be achieved or optimized, without necessarily other tasks or benefits, as they may be taught or suggested herein to achieve.

Farther the expert recognizes the interchangeability of various features from different embodiments. In similar Way you can the various features and steps discussed above as well as other known equivalents such features or steps mixed by a person skilled in the art and be tuned to methods according to those described herein Perform principles.

Though The invention has been described in connection with certain embodiments however, those skilled in the art will understand that the invention over the specifically disclosed embodiments in addition to other alternative embodiments and / or uses and obvious modifications and equivalents thereof. Accordingly, the invention should not be limited by the specific disclosures preferred embodiments, but rather be limited by reference to the appended claims.

Claims (18)

Arylaminofunctional silane compound having the formula:

and / or HCl salts thereof wherein R is an alkyl group having 1 to 6 carbon atoms, R ^{1 is} an alkyl group having 1 to 6 carbon atoms, R ^{2 may be the} same or different and is independently selected from alkyl groups having 1 to 6 carbon atoms, and n has a value of 0 or 1. Arylaminofunctional silane compound according to claim 1, in which the compound is an HCl salt. An arylamino-functional silane compound according to claim 1 wherein R = CH ₃ , R ² = CH ₃ and n = 0

and the HCl salt thereof in which the methyl group is ortho, meta or para substituted, or mixtures thereof. An arylamino functional silane compound according to claim 1 wherein R = CH ₃ , R ² = C ₂ H ₅ and n = 0

and the HCl salt thereof in which the methyl group is ortho, meta or para substituted, or mixtures thereof. An arylamino functional silane compound according to claim 1 wherein R = C ₂ H ₅ , R ² = CH ₃ and n = 0

and the HCl salt thereof in which the methyl group is ortho, meta or para substituted, or mixtures thereof. An arylamino-functional silane compound according to claim 1, wherein R = C ₂ H ₅ , R ₂ = C ₂ H ₅ and n = 0

and the HCl salt thereof in which the methyl group is ortho, meta or para substituted, or mixtures thereof. An arylamino functional silane compound according to claim 1 wherein R = C ₃ H ₇ , R ² = CH ₃ and n = 0

and the HCl salt thereof in which the methyl group is ortho; meta- or para-substituted, or mixtures thereof. An arylamino functional silane compound according to claim 1, wherein R = C ₃ H ₇ , R ² = C ₂ H ₅ and n = 0

and the HCl salt thereof in which the methyl group is ortho, meta or para substituted, or mixtures thereof. An arylamino functional silane compound according to claim 1 wherein R = CH ₃ , R ¹ = CH ₃ , R ² = CH ₃ and n = 1

and the HCl salt thereof in which the methyl group is ortho, meta or para substituted, or mixtures thereof. An arylamino functional silane compound according to claim 1 wherein R = CH ₃ , R ¹ = CH ₃ , R ² = C ₂ H ₅ and n = 1

and the HCl salt thereof in which the methyl group is ortho, meta or para substituted, or mixtures thereof. An arylamino functional silane compound according to claim 1, wherein R = C ₂ H ₅ , R ¹ = CH ₃ , R ² = CH ₃ and n = 1

and the HCl salt thereof in which the methyl group is ortho, meta or para substituted, or mixtures thereof. An arylamino-functional silane compound according to claim 1, wherein R = C ₂ H ₅ , R ¹ = CH ₃ , R ² = C ₂ H ₅ and n = 1

and the HCl salt thereof in which the methyl group is ortho, meta or para substituted, or mixtures thereof. An arylamino functional silane compound according to claim 1 wherein R = C ₃ H ₇ , R ¹ = CH ₃ , R ² = CH ₃ and n = 1

and the HCl salt thereof in which the methyl group is ortho, meta or para substituted, or mixtures thereof. An arylamino-functional silane compound according to claim 1, wherein R = C ₃ H ₇ , R ¹ = CH ₃ , R ² = C ₂ H ₅ and n = 1

and the HCl salt thereof in which the methyl group is ortho, meta or para substituted, or mixtures thereof. Waterproof substrate, one with at least one A compound according to claim 1 coated glass fiber fabric comprises. A waterproof substrate according to claim 15, wherein the coating amount of the compound is about 0.05 to 0.2% by weight, based on the weight of the glass fiber fabric. A waterproof substrate according to claim 15, wherein the coating amount of the compound is about 0.065 to 0.15% by weight, based on the weight of the glass fiber fabric. A method of making a substrate, comprising: applying at least one compound of claim 1 to a glass fiber fabric to form a coated fiberglass fabric; and Applying the coated fabric to an epoxy laminate to reinforce the laminate.