Treatment agent for inorganic siliconaceous filler

A treatment agent for inorganic siliconaceous fillers has as its main ingredient an organosilicon compound of general fomrula (I): ##STR1## in which X represents a functional group selected from among H.sub.2 NCH.sub.2 CH.sub.2 --, H.sub.2 NCH.sub.2 CH.sub.2 CH.sub.2 --, ##STR2## Y.sup.1 is CH.sub.2 .dbd.CHCH.sub.2 -- or --CH.sub.2 CH.sub.2 CH.sub.2 SiR.sub.n.sup.1 Z.sub.3-n.sup.1, R.sup.1 is a substituted or nonsubstituted monovalent hydrocarbon group, Z.sup.1 is an alkoxy group having 1-6 carbon atoms and n is an integer from 0-2, or of general formula (II): ##STR3## in which Y.sup.2 is ##STR4## --CH.sub.2 CH.sub.2 CH.sub.2 SiR.sub.m.sup.2 Z.sub.3-m.sup.2 or a substitutent or nonsubstituted monovalent hydrocarbon group, Z.sup.2 is an alkoxy group having 1-6 carbon atoms and m is an integer from 0-2.

TECHNICAL FIELD OF THE INVENTION 
This invention relates to a treatment agent for inorganic siliconaceous 
filler and more specifically, relates to a treatment agent for inorganic 
siliconaceous filler which possesses effects which increase the 
compatibility, water resistance and adhesion with organic resins, of 
inorganic siliconaceous fillers which are used in various types of organic 
resins. 
Inorganic siliconaceous fillers such as glass cloth and glass fiber are 
commonly used as one of the ingredients of laminated plates and structural 
materials. Normally, these articles are manufactured by impregnating 
thermocuring or thermoplastic resin into glass cloth or glass fiber 
followed by curing by heating. 
For example, a thermocuring resin laminated plate may be manufactured by 
impregnating a thermocuring resin into a glass cloth, heating to form a 
prepreg in a semicured state and cutting to specified dimensions after 
which several plates are placed on top of each other and laminated by hot 
pressing. In addition, laminated copper plates which are used for printed 
wiring boards such as glass/epoxy laminated copper plates and 
glass/polyimide laminated copper plates, are manufactured by hot pressing 
superimposed sheets of copper foil on one or both sides. 
From among the numerous elements which define the characteristics of glass 
fiber/epoxy resin compounds, the fiber/matrix interface is believed to be 
the most highly sensitive region within said compound. If the adhesion of 
the fiber to the resin in this region is weak, it will cause such defects 
as layer peeling, blistering and plateback, and these defects tremendously 
impair the function, reliability and manufacturing yield of printed 
circuit boards. Therefore, in more advanced multilayer circuit boards, it 
is necessary to improve the adhesion between the glass fiber and epoxy 
resin in order to achieve the higher level of product quality which is 
required since the circuit dimensions are smaller and the operating 
temperature is higher in such boards. 
In order to improve the adhesion between the two phases of these materials 
and protect them from the effects of moisture, it is a common measure to 
use a bonding agent which improves the adhesion to the glass fiber surface 
of epoxy resins and other resins. Examples of commonly used bonding agents 
include 3-aminopropyltriethoxysilane and 
3-glycidoxypropyltrimethoxysilane. Although it is clear that there is a 
strong adhesion between the resin components when silanes, especially the 
amino-substituted silanes and glycidoxy-substituted silanes mentioned 
above are used, these silane compounds still remain inadequate with 
respect to improving the adhesion between the resin and the glass fiber 
plate. 
OBJECT OF THE PRESENT INVENTION 
An object of this invention is to provide a new treatment agent for 
inorganic siliconaceous filler which results in remarkably improved 
adhesion between the inorganic siliconaceous filler and the organic resin, 
thereby making it suitable for more advanced compound applications. 
SUMMARY OF THE INVENTION 
As a result of earnest studies in order to obtain a treatment agent for 
inorganic siliconaceous fillers as described above, the inventors were 
able to complete the present invention by discovering a treatment agent 
for inorganic siliconaceous fillers which has as its main ingredient an 
organosilicon compound of general formula (I): 
##STR5## 
in which X represents a functional group selected from among H.sub.2 
NCH.sub.2 CH.sub.2 --, H.sub.2 NCH.sub.2 CH.sub.2 CH.sub.2 --, 
##STR6## 
Y.sup.1 represents CH.sub.2 .dbd.CHCH.sub.2 -- or --CH.sub.2 CH.sub.2 
CH.sub.2 SiR.sub.n.sup.1 Z.sub.3-n.sup.1, R.sup.1 is a substituted or 
nonsubstituted monovalent hydrocarbon group, Z.sup.1 is an alkoxy group 
having 1-6 carbon atoms and n is an integer from 0-2, or general formula 
(II): 
##STR7## 
in which 
##STR8## 
--CH.sub.2 CH.sub.2 CH.sub.2 SiR.sub.m.sup.2 Z.sub.3-m.sup.2 or a 
substituted or nonsubstituted monovalent hydrocarbon group, R.sup.2 is a 
substituted or nonsubstituted monovalent hydrocarbon group, Z.sup.2 is an 
alkoxy group having 1-6 carbon atoms and m is an integer from 0-2. 
In other words, this invention relates to a treatment agent for inorganic 
siliconaceous fillers which yields tremendously improved properties for 
applications of more advanced compounds. 
DETAILED DESCRIPTION 
Examples of organosilicon compounds of general formula (I) or (II) of the 
present invention include 
N,N-bis{3-(methyldimethoxysilyl)propyl}ethylenediamine, 
N,N-bis{3-(trimethoxysilyl)propyl}propylenediamine, 
N-allyl-N-{3-(trimethoxysilyl)propyl}ethylenediamine, 
N-allyl-N-{3-(methyldimethoxysilyl)propyl}propylenediamine, 
N-glycidyl-N,N-bis{3-(methyldimethoxysilyl)propyl}amine, 
N-glycidyl-N,N-bis{3-(trimethoxysilyl)propyl}amine, 
N-glycidyl-N-allyl-N-{3-(dimethylethoxysilyl)propyl}amine, 
N-glycidyl-N-allyl-N-{3-(trimethoxysilyl)propyl}amine, 
N,N-diglycidyl-N-{3-(trimethoxysilyl)propyl}amine, 
N-glycidyl-N-ethyl-N-{3-(trimethoxysilyl)propyl}amine, 
N-glycidyl-N-phenyl-N-{3-(trimethoxysilyl)propyl}amine, 
N,N-bis{3-(methyldiethoxysilyl)propyl}methacrylamide, 
N,N-bis{3-(dimethylethoxysilyl)propyl}methacrylamide, 
N,N-bis{3-(trimethoxysilyl)propyl}methacrylamide, 
N-allyl-N-{3-methyldiethoxysilyl)propyl}methacrylamide, and 
N-allyl-N-(3-trimethoxysilyl)propylacrylamide. In addition, two or more 
types of these compounds can be used in a mixture. 
These compounds can be prepared according to the following reactions. 
##STR9## 
The following provides descriptions of the above reactions to produce the 
compounds of general formulas I and II. 
An explanation will first be given regarding the reaction of the 
nitrogen-containing compound and the silane compound in the first two 
reactions. The catalyst that is used in this reaction is a catalyst that 
is commonly used in so-called hydrosilation reactions. Although examples 
of this catalyst include transition metals such as platinum, palladium, 
nickel, cobalt and ruthenium, as well as their complexes, platinum metals 
and complexes such as platinum black and chloroplatinic acid are 
preferable as they are able to result in a reduction in the reaction time 
as well as resulting in a high yield. 
The amount of catalyst is preferably 0.001-5.0 parts by weight per 100 
parts by weight of the nitrogen-containing compound with 0.01-1.0 parts by 
weight being more preferable. When the amount of catalyst added is less 
than 0.001 parts by weight, the reaction speed is insufficient and even if 
the catalyst is added in excess of 5.0 parts by weight, not only will 
there not be any observed improvement in reaction speed, but this is also 
not preferable in economic terms. 
The prepared mole ratio of the silane compound with respect to the 
nitrogen-containing compound is roughly 2 moles, with a range of 2.0-3.0 
being preferable in terms of practicality. Although the reaction can be 
carried out within a hydrosilation reaction temperature range of 
-30.degree. to 150.degree. C., the reaction is normally carried out within 
a more preferable range of 10.degree. to 110.degree. C. Although the 
reaction is normally carried out at atmospheric pressure, the pressure may 
be increased or decreased if necessary. 
In addition, although the use of solvents at the time of reaction is not 
required, the use of a solvent to improve the solubility of the catalyst 
or control the temperature is allowable. Examples of such solvents include 
hydrocarbon-type solvents such as toluene, xylene, cyclohexane, n-hexane, 
n-heptane, naphtha, mineral spirit or petroleum benzine, halogenated 
hydrocarbon-type solvents such as chloroform, carbon tetrachloride, 
trichloroethylene, perchloroethylene or 1,1,1-trichloroethane, ether-type 
solvents such as ethyl ether, tetrahydrofuran or ethylene glycol diethyl 
ether, ester-type solvents such as ethyl acetate, butyl acetate or amyl 
acetate, ketone-type solvents such as acetone, methyl ethyl ketone or 
methyl isobutyl ketone, and aprotic polar solvents such as methylformamide 
or dimethylacetoamide. 
Since reaction time varies according to the raw materials used, catalyst as 
well as solvent and reaction temperature, there are no limitations on this 
parameter in particular. However, reaction conditions are normally set so 
that the reaction is completed within 0.5 to 6 hours. The reaction is 
carried out by ordinary methods. 
As an example, a method is employed in which a mixture of 
N,N-diallyl(meth)acrylamide and catalyst is heated to the specified 
temperature while stirring followed by dropping in the silane compound. 
Since the compound is obtained as the result of a reaction of high 
selectivity, purification of the compound can be performed with currently 
known methods such as distillation, gas chromatography separation, liquid 
chromatography separation or column chromatography. 
In order to increase the stability of the raw materials and products during 
the reaction and at the time of purification, the prior addition of known 
and suitable polymerization inhibitors and oxidation inhibitors is 
allowable as a routine procedure. 
The following provides an explanation of the third reaction between the 
chloride-containing compound and the silane compound. In this reaction, 
since hydrogen chloride is formed, a dehydrochlorination agent is 
required. Although the amino group-containing silane compound can be used 
in excess for this purpose, more typically, another amine which does not 
react with the chloride-containing compound is added to the system. 
Examples of such an amine include pyridine, triethylamine, tributylamine 
and N-methylmorpholine. The amount of this amine that is added must be 
equal to or greater than the amount required to neutralize the hydrogen 
chloride that is produced as a by-product of the reaction. Typically, 
1.0-1.5 equivalents of the amine is used with respect to the 
chloride-containing compound. If more than this amount is used, the 
reaction will be slowed and the reaction mixture will become too basic, 
resulting in the disadvantage of the stability of the products being 
decreased. 
The prepared mole amount of the silane compound with respect to the 
chloride-containing compound is roughly 1.0 equivalents, and more 
preferably, 0.95-1.05 equivalents. If less than 0.95 equivalents of the 
silane compound is used, there will be an excessive amount of the 
unreacted chloride-containing compound remaining. Conversely, if more than 
1.05 equivalents are added, a large amount of the silane compound will 
remain unreacted making this disadvantageous in economic terms. However, 
when using the silane compound as a dehydrochlorination agent as described 
above, it is only natural that the prepared mole ratio of silane to the 
chloride-containing compound be according to the amount of the amine added 
separately to function as the dehydrochlorination agent. In other words, 
since it is preferable that the total amount of amine in the reaction 
mixture be 2.0-2.5 equivalents with respect to the chloride-containing 
compound, it is preferable that the silane compound be prepared in an 
amount that results when the amount of amine that is actually added to 
serve as the dehydrochlorination agent is subtracted from the above 
amount. 
Although this reaction is typically achieved by dropping the 
chloride-containing compound into a solution of the silane compound 
indicated in formula (5) and the amine used for dehydrochlorination, the 
use of a solvent is allowed to facilitate temperature control or make 
stirring easier. Examples of this solvent include hydrocarbon-type 
solvents such as toluene, xylene, cyclohexane, n-hexane, n-heptane, 
naphtha, mineral spirit or petroleum benzine, halogenated hydrocarbon-type 
solvents such as chloroform, carbon tetrachloride, trichloroethylene, 
perchloroethylene or 1,1,1-trichloroethane, ether-type solvents such as 
ethyl ether, tetrahydrofuran or ethylene glycol diethyl ether, ester-type 
solvents such as ethyl acetate, butyl acetate or amyl acetate, and aprotic 
polar solvents such as dimethylformamide or dimethylacetoamide. 
Since the reaction time varies according to the raw materials used, 
catalyst, as well as the solvent and reaction temperature, there are no 
limitations on this parameter in particular. However, reaction conditions 
are typically set so that the reaction is completed within 0.5 to 6 hours. 
After the reaction is completed and the hydrochloride of the amine is 
removed using by filtration or washing, the compound can be purified into 
the target substance by using known purification procedures similar to 
those of the previous method. In addition, the prior addition of 
polymerization inhibitors and oxidation inhibitors similar to those of the 
previous method during the reaction and at the time of purification is 
allowed as a routine procedure. 
Further, it is also possible to use other alkoxysilanes such as 
methyltrimethoxysilane, -glycidoxypropyltrimethoxysilane and 
-aminopropyltrimethoxysilane as additives with the above-described 
organosilicon compounds as the main ingredient. 
The treatment agent for inorganic siliconaceous fillers of this invention 
has an organosilicon compound of general formulae (I) and/or (II) as its 
main ingredient. Although it may be used as is, it also may be used 
dissolved in an organic solvent such as water, hydrocarbon type solvents 
such as toluene, xylene, cyclohexane, n-hexane, n-heptane, naphtha, 
mineral spirit and petroleum benzine, halogenated hydrocarbon-type 
solvents such as chloroform, carbon tetrachloride, trichloroethylene, 
perchloroethylene and 1,1,1-trichloroethane, ether-type solvents such as 
ethyl ether, tetrahydrofuran and ethylene glycol diethyl ether, ester-type 
solvents such as ethyl acetate, butyl acetate and amyl acetate, 
ketone-type solvents such as acetone, methyl ethyl ketone and 
methylisopropyl ketone, alcohol-type solvents such as methanol, ethanol, 
isopropanol, butanol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 
ethylene glycol and propylene glycol, aprotic polar solvents such as 
dimethylformamide, dimethylacetoamide and dimethylsulfoxide, or 
organopolysiloxane-type solvents such as hexamethyldisiloxane and 
1,1,3,3,5,5,7,7,9,9,-decamethylcyclopentasiloxane. The solvent may be one 
type of solvent or a mixture of two or more types of solvents. 
In addition, the concentration of the organosilicon compound main 
ingredient of formulae (I) and (II) in the inorganic siliconaceous filler 
treatment agent varies according to the type of inorganic siliconaceous 
filler and its method of treatment and is adjusted in accordance with 
this. 
Examples of inorganic siliconaceous fillers which are treated with the 
inorganic siliconaceous filler treatment agent of the present invention 
include glass cloth, glass fiber, silica, glass beads, asbestos and 
wollastonite. Its application may be extended to any components of glass 
cloth and glass fiber. For example, E glass, C glass and S glass, etc., 
are preferable, and particularly in printed wiring board applications, 
nonalkaline glass such as E glass is preferable. The glass cloth used in 
this invention may be woven in any manner such as a flat weave, twilled 
weave, Shushi weave or triaxial weave. In addition, woven materials having 
other fibers in addition to glass fiber, such as a blend of glass fiber 
and carbon fiber, a blend of glass fiber and organic fiber or a blend of 
glass fiber and ceramic fiber, may also be used. 
The glass cloth used in this invention may be either glass cloth at the 
stage in which the binder required for scutching is adhered to the cloth, 
or glass cloth at the stage at which the binder has been removed. 
The binder mentioned here refers to the general type of binders which are 
added in the glass fiber spinning process (generally referred to as 
primary binders), and the binder which is added to the longitudinal glass 
fibers in the glass cloth gluing process (generally referred to as 
secondary binders. Specific examples include starch, surface activating 
agents, lubricants, synthetic oils and acrylic polymers. 
Although methods for removing the binder include burning (dry method) and 
washing (wet method), a dry method is normally employed in which the glass 
cloth is continuously treated in an oven at approximately 600.degree. C., 
or treated in several runs in an oven at 350.degree.-400.degree. C. 
Examples of the organic resin that are also used in this invention include 
thermocuring resins such as epoxy, phenol, melamine, unsaturated 
polyester, diallylphthalate, polyimide and furan resins, or thermoplastic 
resins such as polyethylene, polypropylene, polystyrene, polybutylene, 
polyvinyl chloride, polyvinylidene chloride, polytetrafluoroethylene, 
polytrifluoropropene, polyvinyl acetate, polyacrylonitrile, 
polymethylmethacrylate, polyamide, polycarbonate, polyethylene 
terephthalate, polybutylene terephthalate, cellulose acetate and 
polyformaldehyde resins. 
Commonly known methods may be used for applying the inorganic siliconaceous 
filler treatment agent of this invention to the inorganic siliconaceous 
filler. For example, in the case of applying the agent to glass cloth, any 
arbitrary method, such as immersion, spraying or gasification, can be 
employed. When using the immersion method, the glass cloth is immersed in 
the inorganic siliconaceous filler treatment agent for several seconds to 
one minute and, after air drying, the glass cloth is dried by heating at 
80.degree.-180.degree. C. 
When applying the agent to particulate inorganic siliconaceous fillers, 
such as silica or glass beads, any arbitrary method, such as a dry method, 
wet method or spraying, can be used. When using a dry method, the 
inorganic siliconaceous filler is forcibly stirred in a Henshell mixer or 
V blender and treated with the inorganic siliconaceous filler treatment 
agent which has been added. 
EXAMPLES

The following discussion provides a detailed description of the present 
invention through the use of examples. However, these examples do not 
limit the present invention in any manner. 
EXAMPLES 1-8 AND COMATIVE EXAMPLE 1 
Heat-cleaned glass cloth (205 g/m.sup.2) was immersed for 30 minutes in an 
adjusted aqueous solution of 1 wt. % of 
N,N-bis(3-trimethoxysilylpropyl)ethylenediamine. The glass cloth was air 
dried for 30 minutes followed by drying by heating in an oven at 
100.degree. C. for 30 minutes. After thoroughly impregnating the treated 
glass cloth with an epoxy resin blended liquid consisting of 100 parts by 
weight of Epicoat #1001 (Yuka Shell Co., Ltd.), 4 parts by weight of 
dicyandiamide, 0.2 part by weight of benzyldimethylamine and 100 parts by 
weight of methylcellusorb, the glass cloth was attached to a mold form and 
air dried for 30 minutes. Following this, the prepreg was made by heating 
the mold form for 5 minutes in a hot air drier at 160.degree. C. 10 of the 
prepregs were superimposed on each other and preheated in a 160.degree. C. 
press for 4 minutes with contact pressure. Treatment was continued by 
pressurizing the prepregs (40 kg/cm.sub.2) for 20 minutes at 160.degree. 
C. and followed by heat treatment for 60 minutes at 150.degree. C. for the 
after-curing process. The laminated plate that was thus obtained was cut 
into 10 cm.times.10 cm squares followed by the conducting of a pressure 
cooker test. In other words, the penetration of water into the interface 
regions of the test samples was accelerated by boiling the laminated 
plates for 30-60 minutes at 2 atm. This test is useful for confirming 
whether or not the completed laminated plates can withstand a humidity 
cycle. 
As a result of visual examination of the plates, the degree of damage was 
classified into 5 classes (1: zero, 5: all) with respect to the degree of 
peeling which was clear, referred to as blistering or measling, between 
the glass fiber and the epoxy resin. 
1.0 wt. % aqueous solutions were adjusted using the compounds indicated in 
Table 1 as the organosilicon compound. For the solution that did not use a 
treatment agent of the present invention, the glass fiber was treated, the 
epoxy resin laminated plate was made and the test was performed in the 
same manner as in Example 1 (Comparative Example 1). The results are 
summarized in Table 1. 
TABLE 1 
__________________________________________________________________________ 
Results 
Structural Formula of Compound 
1 2 3 4 5 
__________________________________________________________________________ 
Example 
1 H.sub.2 NCH.sub.2 CH.sub.2 N{ CH.sub.2 CH.sub.2 CH.sub.2 Si(OMe).su 
b.3 }.sub.2 .largecircle. 
##STR10## .largecircle. 
3 
##STR11## .largecircle. 
4 
##STR12## .largecircle. 
5 
##STR13## .largecircle. 
6 
##STR14## .largecircle. 
7 
##STR15## .largecircle. 
8 
##STR16## .largecircle. 
Comparative Example 1 
##STR17## .largecircle. 
__________________________________________________________________________ 
EXAMPLES 9-11 AND COMATIVE EXAMPLE 2 
The treated glass cloth prepared in Example 1 was impregnated with 
polyester resin (a blend of 100 parts by weight of Ester GA20 (Mitsui 
Toatsu Co., Ltd.) and 1.5 parts by weight of benzoylperoxide). 10 pieces 
of the impregnated glass cloth were superimposed on each other and cured 
for 1 hour with contact pressure at 100.degree. C. Then, the plates were 
after-cured for an additional 4 hours. A pressure cooker test as described 
previously was then conducted using these polyester resin laminated 
plates. The results are summarized in Table 2. 
In addition, a treated glass cloth, other than those which used the 
compounds indicated in Table 2 for the organosilicon compound, was 
prepared and polyester resin laminated plates were made using this cloth 
and tests were conducted in the same manner as in Examples 9-11. Those 
results are summarized in Table 2. 
TABLE 2 
__________________________________________________________________________ 
Results 
Structural Formula of Compound 
1 2 3 4 5 
__________________________________________________________________________ 
Example 
9 
##STR18## .largecircle. 
10 
##STR19## .largecircle. 
11 
##STR20## .largecircle. 
Comparative Example 2 
##STR21## .largecircle. 
__________________________________________________________________________ 
The inorganic siliconaceous filler treatment agent of this invention, which 
has an organosilicon compound of general formulae (I) and/or (II) for its 
main ingredient, strengthens the bonding of inorganic siliconaceous 
fillers with various types of organic resins, and exhibits improved water 
resistance and adhesion in comparison to conventionally used organosilicon 
compounds. 
Based on the above, the inorganic siliconaceous filler treatment agent of 
the present invention is effective as a treatment agent of organic 
siliconaceous materials which are used in various types of compound 
materials, and is able to be suitably used in these types of applications.