JPS6086119A - Preparation of flame-retardant silicone modified epoxy resin - Google Patents

Abstract

PURPOSE:To obtain the titled resin useful as wiring plate, producing a small amount of smear during drill processing, by blending a specific epoxy resin, with tetrabromobisphenol A, a specified silicone intermediate, and a catalyst in a specific ratio, heating the blend at a specified temperature. CONSTITUTION:100pts.wt. epoxy resin (e.g., bisphenol A type epoxy resin, etc.) having 0-0.08 hydroxyl number is blended with 40-80pts.wt. tetrabromobisphenol A, 0.1-20pts.wt. silicone intermediate having 150-300 alkoxy group equivalent and 0.001-0.05pts.wt. catalyst (preferably quaternary ammonium salt), and heated at 120-200 deg.C, preferably at 150-170 deg.C (preferably 2-5hr) to give the desired resin. EFFECT:Since the reaction is carried out in one stage, shortening of process and uniformity of quality can be carried out.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is a flame retardant silicone epoxy resin which is widely used in wiring board manufacturing for RC! l! Concerns about force law.

In order to make the through-hole of the multi-NOc line wire the same as the above, it is necessary to reduce the order of Sumi-1 during drilling. The drill conditions are set by the multi-layer self-driving manufacturer (1), but even then, the lifting platform VCfi smear (1) of the epoxy multilayer #Il board is described. Therefore, multi-layer distribution board manufacturers use smear removal treatment or bamboo rope, but they use porcelain sulfur and hydrogen fluoride plates for treatment #L, which is dangerous. In addition, the through-hole material in paper cans may deteriorate due to insufficient processing solution or water washing. In order to reduce the occurrence of smears, it has been clear for a long time that 82L should be used in a 1g high lees tray.
l'gL/) In addition, +IH generally eliminates problems such as wear of the drill blade and small diameter (under 0.8φ) (1) H drill blade breakage.

The cause of smear is during drilling cL) I # rub psvc
Is it possible to prevent the softening of fallen fat due to further falling? One possible method is to reduce the frictional heat generated during drilling.

In other words, by reducing the friction of the resin, the M tension r
It is a method to reduce the amount of water and prevent softening of the resin, and is intended to prevent explosions.

The present invention relates to a manufacturing method VC of a flame-retardant silicone-modified epoxy resin that has been purified with low friction in order to reduce the occurrence of smear during drilling. Evo* Qi fat 100 ff1
iitJ, (bJ tetrabromobisphenol A40
~80 heavy jk, (C) alkoxy content is 150-50
0 silicone intermediate 0.1-2 (limit part and (
d) A mixture consisting of 21 parts of 0.001 to 0.05 l of catalyst is characterized in that it reacts in one go when heated to 120 to 200''C.

The busy IF+#rc of the present invention will be explained below.

The epoxy resin (a) should preferably have a small number of hydroxyl groups, with each hydroxyl having a value of 0 to 0.08, and each hydroxyl having a small f value. If it is larger than t'L, the n/ζ silicone-modified epoxy resin will form a polymer image, resulting in uneven curing.

The 0 hydroxyl Louis curve is hydroxyl, the base number of 400 sets multiplied by 100 violets, and the hydroxyl group equivalent was measured by the lumped acetyl method. The aI types of epoxy 1■ fats include hisphenol Am epoxy side fat, noenol novolak type epoxy side fat, cresol novolac type epoxy side fat, hydantoin voice epoxy side fat, tetraglycidyl isone annulate, and their halogens. The monster is used 1'L
Ru.

(b) 1/, I Tetrabromobisph-L-Nol A-1 7 (The purpose of imparting self-extinguishing properties to the oxyresin, the water spring of this compound, the epoxy group of the epoxy resin) It reacts with silicone intermediates, but with alkoxy, it cannot be used because of the annotation.
@E *: Epoxy side mlc/) which was done in two stages
Reaction of sieve molecule phosphization and reaction of epoxy tree Hbano/recone modification r can be carried out in one step. Ji capital is used, but
In the case of bisphenol A type epoxy IJ,
The ratio of hydroxyl group/epoxy group is preferably 1/4 to 1/2. Tetrabromobisphenol 8 is 40% by weight 1. J: If it is too small, the 1M flammability will not be satisfied, but if it is more than 1 part, the obtained silicone-modified epoxy resin will be vaporized through the sieve, and the cured product will be non-uniformly cured.

(c) c/,) The silicone intermediate is a mercanosiloxane with alkoxy JLf such as coalescence, but the alkoxy groups include methoxy, ethoxy, etc. According to Zeisel's Ashigura method, alkoxy is 1.
50~. If the silicone intermediate used is larger than 500 mm, the silicone intermediate will be sieved and pre-electrified.
-7 Gives sweet heterogeneous gentility r. In addition, if it is smaller than n, the alkoxy group of the silicone intermediate due to steric hindrance,
It is produced by reacting with resin or tetrabromobisphenol A, and the reaction with the base is sufficient to produce 0.
1-20 fl! However, if too little is used, there will be no effect on drillability, and if too much is used, undesirable alkoxy groups will remain.

(dJsu7!l! Mediums include 6th amine, quaternary ammonium salt, imitaneol, alkaline mN hydroxide (IJ'
Phosphonium halides, sulfonium salts, and 6th-class amines are commonly used. Examples of the tertiary amine include penzyldimenalamine, triethanolamine, and pyridine. Quaternary ammonium salts include Ojubenzyltrimenalammonium hydroxide, benflutrimethylammonium chloride, tetramethylammonium bromide, tetramethylammonium bromide, tetraethelammonium chloride, N-cetylpyridinium chloride, etc. There is. Imidazole includes 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-
2 Enyl Isedan'-l. Alkali metal paulownia hydroxides include c-cho, sodium hydroxide, potassium hydroxide, linium hydroxide, etc.

Halokenated phosphonium salts include t, ethyl tri-2-enyl phosphonium bromide, tetra-enyl phosphonium chloride, tetra-butyl phosphonium chloride,
Methyltriphenylphosphonium iodide, 1. Sulfonium items include triphenylsulfonium chloride, benzyldimethylsulfonium chloride, and dimethylglohilsulfonium promide. Examples of the g5-class phosphine include triphenylphosunine and tributylphosphine.
If less tp is used, the reaction time will be more than 10 hours, and if more V is used, impurities in the resin will affect the electrical properties of the cured product.

The formation reaction depth # is preferably 120 to 200℃, preferably 150 to 200℃.
It's 170℃. If the temperature is lower than 120°C, the reaction will be slow and will take more than 10 hours.

At temperatures above 200°C, the catalytic effect is lost (tetrabromobisphenol A begins to decompose again).

The sweet acid reaction time may be any number of hours, but is preferably 2 to 5 hours. The end point of the reaction is cetyltrimethylammonium bromide-i! The epoxy equivalent is calculated by adding the epoxy equivalent to the magazine by adding the epoxy equivalent.
90-110% of i'chi, afL is eel point and dingi.

It is not necessary to directly replace the inert waste.

Alcohol, which is a by-product of the reaction, is removed by distillation and must be removed by pressure distillation (thus, it is removed).

(a), <b), <d)'T: Mixing and cutting #Ding ξ is low molecular weight epoxy resin 2II! It is a general aid used to add l + molecular weight and to give τ, or at that time, a silicone intermediate such as K (c) is mixed with 7Jl] heated for seconds. There isn't. T B A to non-invention
Synthesis of 7CM silicone-modified epoxy resin, which was conventionally carried out in two stages, takes advantage of the selectivity of the OB. It is easy to make the quality uniform.It is easy to make VC and 1 quality flame retardant silicone injection epoxy tree 11Er in a short time. Zartb.

Hereinafter, the present invention will be practiced and congratulated based on υyc.

Example 7 Bisunenol AjJ Eho-at of epoxy BM175
Shi side fat 4300 g-Tetrabromobisphenol A
2650g, KR218 (part name: Meikoshi Kagakuto (ceramic methoxym210 lysilicon intermediate) 420g, tetramethylammonium chloride 0.25g busy mixture @
- Stirred and kept temperature at 160°C for 2 hours. During that time, volatile components in the system were removed under reduced pressure. Solid resin with epoxy equivalent of 584? Obtain'fcO Example 2 Epoxy equivalent 175v Bis-2 enol A type epoxy resin 43 Q Ogs Tetrabromobisphenol A26
50 g, KR213 (product name: Shikoshi Kagaku Koto W Kai Methoxy Togashi 157 C/) silicone intermediate) 315 g, tetramethylammonium chloride U, 25 g ff 1 Stir in a mixer and keep at 160°C VC for 2 hours 1 ko;f:
During this time, the volatile molecules of Poko were removed under reduced pressure. Epoxy equivalent weight 56
8 solid resin f*.

Comparative Example Epoxy II 175 bisphenol Aa epoxy resin 4500 g, tetrabromobisphenol A26
50g, tetramethylammonium chloride 0.25
Example 1, Example 2.gff1 Mixed stand was stirred and the mixture was kept at 160°C for 2 hours during which time kg of volatile matter in the system was removed. A varnish for Gripreg was prepared using the silicone-modified epoxy resin obtained in Example V. A 1vc is shown in the distribution.

Table 1 Distribution of varnish for Gripreg
'0. I stretched it out for 5 minutes and prayed for Pregregs. 170℃ using 15 sheets of prepreg and 6 sheets of 55μ thick τ.

After 1 hour of force-rotor thermoforming, a 6-layer, 1-piece powder plate was prepared and drilled.The drilling conditions were 6υ per revolution, 000 rpm
■, Feed speed jjl 3.000 fl1m/ 謔, Large diameter 1.0φmm.

I made 12,000 holes with 02 stacked sheets.

Table 2 shows the trial sales results of the 6-layer rice distribution board prototype.

Table 26 Layered IM Board Test 1' ``Product Test Destruction Yume Esu Through Pole Episode 1''j4-IWl Group Smear Occupancy of 102 (Average Dark Note 2) Dead! #I Spectrometer 2L shown in term table 2
ゐlike silicone modified 1 epoxy resin used 1ζ*1
．． #2 is blood, L/), :C Compared to #5 using boxy lateral bending, the focus on the drill bit mouth is 17J1, V is the same as above, 6o, and Tg is a little higher on the nurse, and it is 6 percoll. The bite and suction is just about the same. There are few broken drills or drill wear when drilling small diameter holes.

Claims (1)

[Claims] 1. (a) 100 lateral bends of epoxy with a hydroxyl value of 0 to 0.08 [, (Ill) Tetrabromobisphenol A40 to 8O
(cJ 150-500 silicone intermediates 0.1-20JfJ1), and (d)
uo o 1~o, o 5. mi part. It is time to heat the mixture to 120°C to 200°C and turn it into ash in one step. Manufacturability of the flame-retardant silicone epoxy resin described in item 1