JPS5958031A - Silicone resin and manufacture of the same - Google Patents

Abstract

PURPOSE:To provide a silicone resin capable of giving films composed chiefly of close and purer SiOx after its heat decomposition, constituted by the main skeleton expressed by formula -(H2SiO)n. CONSTITUTION:The objective silicone resin can be obtained by reaction of a chlorinated silane of formula III (b is 1-3) with a polymer of formula II (R<4> is H or OH) formed by polycondensation between water and a bifunctional silane of formula I (R<3> is monovalent chain hydrocarbon; X is halogen; a is 0, 1, or 2). This silicone is represented by formula IV [R<1> are either all H or made up of more than half of H and the rest of -OSiH3, -OSiH2CH3, -OSiH(CH3)2, or -OSi(CH3)3; R<2> is -SiH3, -SiH2CH3, -SiH(CH3)2, or -Si(CH3)3; n is 2-200].

Description

[Detailed description of the invention]

(1) Technical field of the invention The present invention relates to a silicone resin, more specifically, a silicone resin that can be thermally decomposed into 5i
n) (Related to silicone (91 resin) that provides a film containing gold as a main component and its manufacturing method. (2) Prior art and problems Until now, there are many known methods for forming 5tox coatings71, but most of them are The method can be divided into two methods: a method based on vapor phase growth of silane monomer, and a method based on thermal growth of a siloxane/prepolymer coating film.The present invention relates to the latter method, and a typical method of the latter method is , polymethylsiloxane, such as (0113Si(')1.a).
(0□H,0)2810)□ is thermally decomposed, but since there are many organic groups that can be thermally decomposed in these prepolymers, the resulting silicon oxide film lacks density, and 1 The total film thickness of the coating is 0.3 to 0.5 because the strain during disassembly remains in the film.
If the thickness is greater than μm, there are drawbacks such as cracks. In the case of polymethylsiloxane with a heat content of 1'li, the 81-0 bond is not completely decomposed and remains in the 5iOX film even if it is heated to 700 °C or higher in the case of 7-methyl, and the residual film rate is low in dimethyl. It also has the disadvantage of being small. (3) Purpose of the invention In view of the current state of the prior art, the present invention has the following features:
It is an object of the present invention to provide a silicone prepolymer that provides a dense and purer SiOx film after thermal dedusting, and a method for producing the same. (4) The invention (・14 formation and above H[', To achieve the object, the present invention
General formula? R"0-(-1su5to(R2(in the formula, R1
teeth. )] or at least half are 11 and the rest are -081113+-08IH2ctJ3
゜-08IH(('!)Is) 2 + WakaL <
r,L-O8i(ra+3)3-ChD;It
ij, 81113. -8il120118. -8i
ll(O113)2° or -8i(OH3)3 f); 11 is a natural number from 2 to 20 (1)
According to the present invention, the timing of the licone (I11 fat) is -(-l).
The point is that l2S 109 is used as a living skeleton. Therefore, the main component that scatters during thermal decomposition after coating is hydrogen. Thermal decomposition is very easy, and the pinholes left in the 8i0X film are minute, and in a high-temperature oxidizing atmosphere, slo becomes 5i02 during or after decomposition, and the pinholes disappear. . The obtained 51(lx (X is 1 to
(Positive number 2) The film has extremely little strain and is very fine with no pinholes. The excellent characteristics of the silicone resin according to the present invention are as follows:
It is not lost even if it is replaced with line 29 (-< is 3.).The fewer the number of -' replacement pieces, the better.
o The length of the process should be less than one half at most. Conventionally, +11□SlO□te has not been created, and the reason for this is that the 1-1-Si bond is extremely unstable during polymerization. This is thought to be due to the fact that no suitable starting material was found. However, as a result of (Ai・1, the starting price of wealth is fully noted, by treating it in depth, [1
It has been found that the -81 bond can be made sufficiently stable. As a second form of invention, the general formula, H2
S4 (OR") (z-a)X" In the formula, as is a monovalent chain hydrocarbon group, and X is a halogen element. a is 0, 1. Represents Wakakake 2. ] By condensation polymerization of the trifunctional silane compound represented by r and water, the general formula: 1-10-
41 to Si09H [wherein R4 is 11 or OH]. ] to obtain the nh* compound, and then the general formula I (OH
a) 3-bHbSel C In the formula, b represents 1.2 or 3. )'L'5iO by reacting a chlorinated silane compound represented by
-)-rt"11 In the formula, ru is all "1, or t, at least half are IJ, and the rest is 108iH3+-0
8iH20113, -08i11(0113)2~.
JL<bar O8i (0■3) a-C6')
; R2i, -8] lja +-5in2a) r8
．． -5sn<ou8>, 'Fit,,<u-81
(0113), -Ch');nr,j:,2~2oo
is a natural number. ] The silicone resin is expressed as
;・The one with IJ1 blue, Shishi is 2'L with 4. A bath agent that only slightly dissolves the reaction water in the first half 8 For example, methyl isoptylgtone (MI Ji K
) or 1 old (mixture with benzene, 8 soap solution, etc.) and carry out slowly at a temperature of about 25 to 50°C. Monomer concentration at the time of polymerization is preferably 40ωt% or less (7 8~2oωt% 柘柘〔The higher the pressure is -Z, the easier it becomes to gel, and on the other hand, the lower the concentration -C, the reaction time is also longer, and it settles at 0be for solvent-based stitching;, 1° decreases. This is because when the polymerization rM11w exceeds 50°C, gelation tends to occur, and below 25°C); 1 reaction time becomes longer.When adding water to the solvent, a hood of 1u''Vj, 30'CμF is good; Preferably (-< is 10°C.) Bring the temperature below freezing and add water to the solvent. Ranolization tw
tr: is suppressed. However, in this case, the faster the heating rate to the 1st polymerization temperature, the better. This is because the silanolized monomer ■1□5t(0)J)2 moves from the solvent layer to the water layer, and at that time, the t+-si bond becomes silanolized, and as a result, 1~ becomes a trifunctional silane and gels. When it gets easier, it becomes easier to use. In addition, it should be avoided to allow alkali metals, alkaline earth metals, other general metals, dilute hydrochloric acid, and other acids such as sulfuric acid and sulfuric acid to be contained in or come into contact with the system. Evening. Therefore. The reaction vessel is made of glass, preferably V:1 quartz. Thoroughly clean at least all liquid contact parts. Additionally, the use of catalysts such as acids, alkalis or salts commonly used for siloxane synthesis is avoided. When using dialkoxysilane, the polymerization reaction time for one row is approximately 12 hours at a polymerization temperature of 35°C.
0 hours or more is good. There is no particular limit to the long reaction time, but considering the instability of the 1l-8i bond, 5
Preferably within 0 hours (~2 to 50 hours at a temperature of 2 to 50 hours, the average degree of polymerization is as large as the formula 0 formula %). 6 xlj combination 110 (-)
12s30941 MONI I HK solution is relatively stable and can be coated, but if stored at a temperature of 25°C, it will gel after 3 days. Also, add tW and regel. Next, obtain n/1 combination + 10,000F bow SiO-j and salt m'/U7 compound ((IHa) s-B 11b81
Ce Tono JX response & 31° After the above condensation polymerization reaction, the aqueous layer was separated and the water in the solvent layer was removed, resulting in chlorinated silanization @! Add 7.1 chloride to the nose at low temperature, and it will slowly react and rot. The main purpose of this reaction c1 city body 110 (-R
2S inch end of error (1-f (Oi13) 3-bI
IbSt-AljTifm-jl+KotoKYo) to form an unstable 5t-fJ bond with a stable Q. Immediately after the reaction, 110M and excess chlorinated silane compound were generated under reduced pressure F! Remove the snout or inactive 1 living gasle 11
For example, Ar, N2, etc. are bubbled to remove them from the system. The 2L silicone resin R204+t'28 io +nIt2 obtained in this way is oil-like when the degree of monopolymerization is small (n = 1 to 2 or 3);
When the degree of polymerization is high (n43), it is a powder, but
It is also stable even after the solvent is removed by evaporation, and does not generate hydrogen gas or gel. It is widely known that polydimethylsiloxa 7 ((01J3)2810)n remains oily even if the degree of polymerization is extremely increased.
Silicone resin R20+R1S 10) according to the present invention
[In the case of L2, n)2 in the na degree of polymerization formula
If n is 3 or 4 or more, it is treated as a powder (1 or n). This fact can be presumed to be due to a special molecular opening. In the case of the resin according to the present invention, it is also available in powder form. Oil 3B F% Si CL
It was found that both polymers before treatment showed the same interplanar spacing of 7.2±0.2 A in X-ray diffraction analysis. I considered hydrogen bonds as shown in Figure 1.

[12S
10) Theoretical 5i calculated by h1° from the crystal structure of n
The distance between -81 is 6.6λ, which is close to the tweets of 7.2±0.2 people. Historically, the ratio jJiii based on the crystal structure in Figure 1
The specific gravity of the above material was approximately 1.8, and the specific gravity of the above material was 2i, which was 1.64 when measured using a vicinometer. These and other infrared absorptions described below are according to the present invention / Reconha 1 fat is +)
1□5iO-), , is the main skeleton. Father, (5i- in -8□840+n)] Part of the bond changes to 5i-011 bond/Hi'JA fr, the rate of change V1゜For example, ((!H3) 2Its i O
This can be determined by reacting Q with the hydrogen of its ON group and performing all absorption measurements on Akatsuki 1. The molecular formula after the reaction is ((i113)2118i0+112., i((”!+
13) 2118i01. LSi(')U,,5ill(
When expressed as (II,)2, 1 absorption of the S 1-11 bond in -II□Si〇-, where the average value of 2 is less than 1, is approximately 2250...Tsuno L-11, (0113 )211si(1-S i-1 bond O
Ch1゛about 214 (l ChLK, then -H2
11 H in SiO- is (0113) 214Sio
When fL is substituted with f'c, the absorption of the remaining 5t-H bond appears at about 2180C#&. Assuming that these absorption coefficients are constant, the degree of polymerization and the degree of decomposition of the St-- bond in -[12Si0- can be determined from this absorption. In the range of actual measurements. zf of 0 to 0.92 is obtained, and most of the 1 and 0.
．． 1 or less The resin according to the present invention has a weight of 16 and a larger volume when heated in air or oxygen (7) than when heated in air or oxygen (compared to conventional silicone resins or other silicone resins). It has characteristics that are not seen in organic 1!1 fats.It is thought that (II□5in)n changes to SiO in nitrogen, and changes to 5i02 in the presence of oxygen, depending on γL and oxygen concentration. is considered to be 5iOx (x is a number between 1 and 2). (5) Embodiments of the Invention A) Example 1 108y of M I B K was stirred in a reflux condenser, and a thermometer and The flask was cooled to -30°C.Then, the jetoxy 7-run 12
After dropping II (0.1 mol) from the funnel, add 1 mol of water.
71 tJl of 8y (1 mol) was dropped from the funnel. Water was added at a rate of about 0.2γ1 for 7 seconds so that the liquid temperature did not rise above 110°C. The flask was then transferred to a 35°C water bath. When the water droplets dissolved, both the aqueous layer and the organic layer became slightly cloudy, but they became clear within 1 hour. After being kept at 35°C for 22 hours, the solution was transferred to a separatory funnel, washed three times with cold water, and the aqueous layer was separated. Transfer the organic layer to an eggplant-shaped flask and add 50111111
Moisture and evaporation were removed under pressure of 1+g. 3 coins 1
1 flask, add C, and bubble N2 gas.
Add 7 runs of dimethyl chloride for 5 years and release 10 minutes for 1 ifft.
,,Ta. Then, the liquid was poured into an eggplant-shaped flask and the 11-axis viscous liquid 4.IP was poured into an eggplant-shaped flask. ] Also, the precipitate was combusted to obtain a ladle-like polymer.Then, it was dissolved in toluene, and BB% in 30%
It was made into a bath liquid. This 11J1 fat liquid is converted into K 8 r crystal 4
to le. The results of spin coating at 2000 rpm for 30 seconds and measurement of infrared absorption showed that tl K in HR8iO was attributable to 22
50G no large absorption and tl ((+lIs) 2
A small absorption of 2 140-' attributed to H in siOo,s was observed. A slight absorption of 2140 particles = 1 in 1 μm was observed in the eyebrows. Tota 2 890 Shin and 1
#L VC, II (0113) 2St (011.
A large and broad absorption of 5t-O of ~1200G7+&-' was observed, indicating that this material was [1.(0)1. ), -si +H2S1o +-n8
1(C)]3)211, and n
The average value is 5, which is the second highest. Next, this K[lr crystal plate was heat-treated in air at 450°C for 60 minutes, and when the infrared absorption was measured, only the 5t-o bond was detected, and other absorptions disappeared, indicating that the 81(12) bond was present. Example 2 N2-dichlorosilane (10%) based gas was poured into a four-eye quartz flask in which an interface was formed between an organic layer consisting of 150 Y of methyl isobutyl ketone and 50 F of benzene and 20 F of water.
Introduced at a rate of λ/min. Bubbled in for 48 minutes. next. After blending at 30°C for 4 hours, wash with water and make a 50mm
Treat under reduced pressure of +p for 30 minutes to remove moisture [7. Furthermore, NZ-chlorosilane (10%) gas was introduced into the organic layer at a rate of if/min to effect silylation. Next, acetonitrile was added to about 15 cc of the resulting solution, and the resulting precipitate was dissolved in slightly dark benzene. Acetonitrile was added once again to remove the precipitate, and the mixture was dried at 40°C. After drying, one powder was coated with 3 yvcmhy of methyl isobutyl ketone and spin-coded on a crystal plate with a spin cord at 11,000 rpm. Cure (heat treatment I, !I) (7
However, only the absorption of the 5i-r) bond was observed by the infrared absorbance. father. The average degree of polymerization (n in the above formula)+j was 18 to 20. When applied in the same manner but at 200 (') rpm on a silicon wafer and cured, IIMJ! The diameter was 1.1 μn]. In addition, when the film was heat-treated at 350°C for 60 minutes instead of in oxygen, the film thickness was 0.84 μm. This is considered to have occurred and the volume increased by 1.C) Example 3 The same procedure as Example 1 was carried out, but the polymerization time was changed, and the polymerization time was increased by 0.6.
Polymerization was carried out in seven ways: 7 hours, 2 hours, 4 hours, 8 hours, 12 hours, 16 hours, and 32 hours. The table shows the relationship between the ocular degree n, shape, and one-size-fits-all time of the polymers. Data for Example 1 are also listed in the table. Table Example Same as Example 1, except that MIBK was mixed with 84y, one jetoxysilane was 36y (0.3 mol), and 6
After adding the water, raise the bath temperature to 30℃ and keep it for 2 hours.
Next, water was added for 48 y at a dropping rate of about 2 drops/sec, and the bath temperature was further raised to 45° C. and maintained for 42 hours. Further, dimethylchlorosilane zoy was used. The average value of n of the obtained n*heavy a product was 58±10. This method was attempted three times, one of which resulted in gelation during polymerization. e) Example 5 Same as Example 2 except that N2-dichlorosilane (
The IOL) system mixed gas was introduced for 120 hours, and the deposition temperature was set at 40°C. The polymerization time was 20 hours. The degree of loading n of the obtained polymer was 95 and 20. (6) Effects of the Invention As is clear from the above explanation, one aspect of the present invention is a prepolymer that provides a denser and purer SiOx film when forming a SiOx coating film by a pyrolysis method, and a method for producing the same. is provided.

[Brief explanation of drawings]

FIG. 1 is an atomic arrangement model diagram of a molecule having a main skeleton of +l-12SlO+-n. Figure 1: HO: SN○: 0 Hand-written stamp December 21, 1981 Kazuo Wakasugi, Commissioner of the Patent Office 1, Indication of the case Patent Application No. 167516 of 1982 2. Name of the invention Silicone resin and its manufacturing method 3. Relationship with the case of the person making the amendment Name of the patent applicant (522) Fujitsu Co., Ltd. 4. Agent address: 5-8-10 Toranomon-chome, Minato-ku, Tokyo 105
In column 6 of "Detailed Description of the Invention" of the specification to be amended, on page 8 of the specification of contents of the amendment, in lines 3 to 5, ``Furthermore...'' is deleted.

Claims (1)

[Claims] 1. General formula: rt2o (-n4sio+nrt2c
In the formula, Bl is all 11, or at least half of it is 1, and the remainder is 105il13. -08
iH□OH3゜-08ill (Ot13) 2, or 108i((]l5)a deli i I
t2 fj, -SiH3+ -8iH□OH
3, -8i11 (0113) 2 or mechanism 5t (Ct+
3), and n is a natural number from 2 to 200. ]
Silicone resin represented by 7'. 2 General formula: 11□St (OR”) (2-,)Xa(
In the formula, R'' is a -valent chain hydrocarbon group, X is a rogen element, and a represents (1, 1, or 2). By condensation polymerization of water, the general formula!
' is H or OH. ] A polymer represented by the formula '(01'a)x-bHb81(e
(wherein b represents 1.2 or 3) is reacted with a chlorinated silane compound represented by the general formula; R20 + where 5i
O-)-R" (in the formula, all It's)] are 1], or at least half are !1, and the remainder is 105il13, -08iH□('II3.-
08ilJ (0113) 2° or mechanism 08i (0IJ
s) a; It2) go, -81113°-8il120113. -8ill (Oi13)2.
Wakakake-81 (01ls,) 3; n is expressed as 2 to 2 (1 (l is a natural number); 7'
L silicone (171 made of fat gold: "('(How to do it.