JPS5855984B2 - Silicone resin composition for lamination - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silicone resin composition for lamination, particularly to a silicone resin composition for laminated molded products having excellent transparency.

Conventionally, laminated molded products mainly made of silicone resin and glass cloth have excellent properties such as heat resistance and electrical insulation, so they are used as class H heat-resistant and insulating materials for microwave ovens, electric motors, and various other electrical devices. Widely used.

However, the silicone resins used to manufacture this type of laminated molded product are usually condensation-type resins that are crosslinked and cured by dehydration or dealcoholization reactions. When manufacturing molded products, there were the following difficulties.

(a) High-pressure molding of 50 to 200 kg/cd is required.

(b) Requires long post-cure.

For example, a thin laminate requires about 12 to 24 hours, and a thick laminate of 10 mm or more requires 3 days to nearly a week.

(e) If a mold that is under pressure and heating is suddenly returned to normal pressure, the molded product will bulge or crack. It is then necessary to dismantle the mold.

(d) The molded product obtained by pressurizing and heating molding as described in (e) above has poor mechanical strength and remains slightly heat-softening, so it is necessary to convert it into a product with excellent physical properties. In order to do this, as mentioned in (b) above, it is necessary to complete the so-called post-cure process, in which the temperature is raised stepwise in a heating oven. opacity), making it impossible to obtain molded products with excellent transparency.

(e) In addition, condensation-curing silicone resins have poor compatibility with glass cloth and do not impregnate glass cloth well, so they are unsuitable as resin raw materials for producing laminates with excellent transparency. .

The present invention aims to solve such disadvantages and provide a silicone resin composition suitable for manufacturing laminate molded products with particularly excellent transparency and mechanical strength, which has the following characteristics: (a) average composition formula ( In the formula, R1 is a group selected from substituted or unsubstituted monovalent hydrocarbon groups having 1 to 10 carbon atoms, a, b, c, and d represent the mole fraction of each siloxane unit, and a = 0.5 to
0.9, b = 0.1~0.5, C-〇~0.05,
d=0 to 0.05)**, and the alkenyl group directly bonded to a silicon atom is 0.0% per silicon atom.
Organopolysiloxane resin containing 5 to 0.3 alkenyl groups, (b) average composition formula (R2 in the formula is a hydrogen atom, a group selected from a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms) , e, f and g represent the mole fraction of each siloxane unit, e=0.1
~0.7, f=0.2~0.5, g=o, i~0
．． It is 7.

), which has 0.05 to 0.3 hydrogen atoms per silicon atom directly bonded to silicon atoms, and () → platinum-based catalyst, the main components are ( A silicone resin for lamination in which the blending ratio of component (b) to component (b) is 0.6 to 1.7 hydrogen atoms in component (b) per vinyl group in component (a). It is a composition, and if it is applied to the production of laminated molded products by combining it with glass cloth etc., the following advantages will be brought about.

(2) The pressure during pressure molding may be as low as 5 to 50 kg/c4.

■ Even if the mold is dismantled without cooling after molding, the molded product will not bulge or crack.

■ Post-cure is not necessarily required.

(2) For example, it is easy to manufacture molded products with a thickness of 10 mm or more.

■ Molded products with excellent mechanical strength, electrical properties, heat resistance, and transparency can be obtained.

■ Molding conditions are simplified, thus reducing molding time.

The present invention will be explained in detail below.

First, component (A) constituting the composition of the present invention is represented by the average compositional formula (I), in which R1 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms. This includes alkyl groups such as methyl, ethyl and propyl groups, alkenyl groups such as vinyl, allyl and hexenyl groups, cycloalkyl groups such as cyclohexyl and cycloheptyl groups, phenyl groups and tolyl groups. , aralkyl groups such as xylyl group, natonoaryl group, benzyl group, phenylethyl group, chlorogen-substituted-valent hydrocarbon groups such as chlorophenyl group, tetrachlorophenyl group, chloromethyl group, pentafluorobutyl group, trifluoropropyl group, etc. For example, in this case, the alkenyl group directly bonded to a silicon atom is 0.05% per silicon atom.
It is essential to have ~0.3 pieces.

In addition, a, b, c, and d in the formula represent the mole fraction of each siloxane unit as described above, and these siloxane units are commonly referred to as T units, D units, M units, and Q units in order among those skilled in the art. In order to provide a molded product with excellent mechanical strength, heat resistance, etc. by heating and curing as a silicone resin for lamination, a, which indicates the molar fraction of T units, is required.
The value of is required to be between 0.5 and 0.9; if it is less than 0.5, the resin will be incompletely cured and will remain thermosoft, and if it is greater than 0 or 9, it will not harden. The resin becomes brittle and favorable results are not obtained in either case.

The presence of M units and Q units is optional, but if they are included, they must be kept in small amounts so that the values of C and d, which indicate their molar fractions, are 0.05 or less. .

Specific examples of the above T unit, D unit and M unit are:
CH35jO1,5, C6H55iO1,5, CH2=
CH81OCHCHCH2Si01.5.1・5)
2-CHSiO, CH5in1. ,．． 37 1-5 5+1 C6H115i01.5, CIC6H4S iol, 5
, CF3CH2CH2CH25iO1,5, (CH3)
25jO1(C2H5) 2S 1O1(C6H5)
2SiO1(CH3)(CH2=CH)SiOl (C6H5)(C2H5)SiOl (CF s CH2CH2CH2) (CHs ) S
1O1(CH3) 3S 100-5, (CH3)
(C6H5) 2 S iOo, 5, (CH2=CH
)(CH3)2SiOo,5,(CF3CH2CH2C
Examples include H2)(CH3)2SiO8,5.

Next, component (b) is represented by the average compositional formula (n), and is composed of siloxane units of T unit, D unit, and M unit, and R2 in the formula is a hydrogen atom, and the upper eyelid b) It represents a monovalent hydrocarbon group similar to R1 in component, but this group is required to have 0.05 to 0.3 hydrogen atoms per silicon atom directly bonded to silicon atoms. .

In addition, e, f, and g in the formula represent the mole fraction of each siloxane unit as described above, and component (B) reacts with component (A) to create a cured resin with excellent mechanical strength, heat resistance, etc. In order to give
．． 7. f, which indicates the molar fraction of D units, is 0.2 to 0.5, M
g, which indicates the molar fraction of units, must be within the range of 0.1 to 0.7.

Specific examples of each of these siloxane units include, in addition to those exemplified in component (a), siloxane units having a Si--H bond, i.e., (H) (CH3) SiOl (H) (C2H5) S 1O1 (H) (C6H5) sio, (H)(CF3CH2CH2CH2)SjOl(HX
CH3) 2 S iOo,s, (HXC6H3) 2
SiQ)-5, (H)(CH3)(C6H5)SiOo
, 5, etc.

This (b) # may contain an alkenyl group directly bonded to a silicon atom as long as it is in a small amount so as not to impair the purpose of the present invention.

For the above-mentioned components @) and (b), for example, after blending hydrolyzable silanes corresponding to the respective constituent siloxane units, they are hydrolyzed according to a conventional method, and then dehydrated by adding a suitable condensation catalyst such as an alkali or acid. It is produced by completing a condensation reaction or a dealcoholization condensation reaction.

In the present invention, these components (a) and (b) preferably do not have a hydroxyl group or an alkoxy group bonded to a silicon atom.

←→Acid component The platinum-based catalyst is a component required for the reaction (addition reaction) of the (1) component and (2) component,
Examples of this include chloroplatinic acids such as chloroplatinic acid and chlorinated platinic acid, coordination compounds of chloroplatinic acid and alcohols or aldehydes, and complexes of chloroplatinic acid and various olefins.

The amount of the platinum-based catalyst added is preferably at least 0.1 ppm, preferably in the range of 1 to 100 ppm, based on the total amount of components (a) and (b).

The silicone resin composition for lamination of the present invention has the above-mentioned components (a), (b), and ←→ as main components.
Even at room temperature, the addition reaction between component (a) and component (b) proceeds due to the catalytic action of the acid component, and this addition reaction proceeds extremely rapidly under heating. It may become difficult to work when making molded products.

In order to avoid such disadvantages, it is advantageous to include a reaction retarder in the composition of the present invention, which mainly includes acetylene alcohols, amine compounds and phosphorus compounds. Examples of layers include 3-methyl-3butyn-2-ol, 2-methyl-1-pentyn-3-ol, 3,5-dimethyl-1-
Hexyne-3-ol, 2,5-dimethyl-3-hexyne-2,5-diol, 3,6-dimethyl-4-octyne-
3,6-diol, 2,4,7,9-tetramethyl-5
-decyne-4,7-diol is used as an amine compound such as 2,2-piquinoline, 2-picoline, 4-picoline, 2-
6-lutidine, 22'-piperidine, pyridine, N-N
-Dimethylbormamide, N-N-diethylformamide, ethylenethiourea, N-N'-diethylthiourea, and phosphorus compounds include triethylphosphine, tributylphosphine, triamylphosphine, triphenylphosphine, tritolylphosphine, trimethylphosphite, triethylphosphine, Examples include phytophyte, tributyl phosphite, triphenyl phosphite, tribenzyl phosphite, and the like.

Also, the acetylene alcohols exemplified here and (a)
A condensate of the component and the siloxane unit constituting the component (b) can also be used.

The amount of these reaction retarders used is based on (a) component and (b)
The amount may be approximately 0.0001 to 0.01% by weight based on the total amount of the components.

The silicone resin composition of the present invention has the above-mentioned (a) and (
Obtained by mixing the components (b) and ()) and, if necessary, a predetermined amount of each of the above-mentioned reaction retarders,
When manufacturing a laminated molded product by combining this with glass cloth, etc., it is advantageous to prepare the composition in advance as a solution in an organic solvent. Examples of organic solvents include benzene, toluene, xylene, trichloroethylene, acetone, and methyl ethyl ketone. , ligroin, etc. are exemplified.

The amount of these organic solvents used is ((1) and (b))
The amount may be approximately 10 to 900% by weight based on the total amount of the components.

The silicone resin composition of the present invention obtained in this way can be obtained by, for example, impregnating a glass cloth with it, pre-drying it, stacking a large number of sheets of the same, and applying 9/crrt to 5 to 100.
By pressurizing and heating molding under conditions of 120 to 250°C, a laminate molded product with excellent transparency, mechanical strength, and electrical properties can be obtained.

Next, examples of the present invention will be given.

Example 1 Production of vinyl group-containing organopolysiloxane resin: 3044P of water and 11% of toluene in a flask with a stirrer.
522f, 228 g of acetone, and 228 g of isopropyl alcohol were charged and cooled to below 15°C. Then, while cooling and stirring, 149% of methyltrichlorosilane was added at a temperature of below 30°C. ! l (1 mol), phenyltrichlorosilane 951.1' (4.5 mol), hinyltrichlorosilane 161.5f? (1 mol), C1 (CH5)
A mixture of silicone oil 2591 (3.5 moles as siloxane units) having the molecular formula of 2SiOC8i(CH3)20]2oC1 and toluene 1522f was added dropwise over a period of 3 hours.

After the dropwise addition was completed, the mixture was stirred at a temperature of 20 to 30°C for 30 minutes, and then the organic layer was separated and washed with water until it became neutral.

After washing with water, the organic layer was dehydrated under reflux for 1 hour, then 0.5 f of potassium hydroxide was added, and dehydrated under reflux for 1 hour to remove remaining active groups such as silanol groups and alkoxy groups.

After cooling, add 2.01 g of acetic acid and stir at room temperature for 2 hours to neutralize, concentrate and filtrate to a resin concentration of 6.
It was adjusted to 0% (this is referred to as resin A).

This was a transparent liquid containing 0.057 mol of vinyl groups bonded to silicon atoms in organopolysiloxane 100P.

■ Production of organohydrodiene polysiloxane resin: 686 grams of water and 3 grams of acetone in a flask equipped with a stirrer.
43.2P,) Charge 172g of toluene, cool to below 15°C, then cool and stir, then add 211.5g of phenyltrichlorosilane. (1 mole), methylhydrodiene dichlorosilane 115P (1 mole) and toluene 172R were mixed at a temperature of 25
It was added dropwise at a temperature below ℃.

After the dropwise addition was completed, the organic layer was stirred for 1 hour at a temperature of 20 to 25°C, and immediately 16.7P (0,125 mol) of tetramethyldihydrodiene disiloxane was added, and after stirring for 15 minutes, the concentrated 5 (l) of hydrochloric acid was added and stirring continued for 15 hours at room temperature.

After stirring, the organic layer was washed with water until it became neutral, dehydrated and filtered, and the solvent was distilled off (this is referred to as resin B).

This was a transparent liquid containing 0.60 mol of hydrogen atoms bonded to silicon atoms in organohydrodiene polysiloxane 1001.

Resin A100I', resin 1395f! , 2 of chloroplatinic acid
- Ethylhexanol solution (platinum content 2% by weight) 0.5
A mixture of 0.5tiI of a condensate of P and 2-ethyl-3-butyn-2-ol and trimethylchlorosilane was diluted with 20oz of toluene, a glass cloth was impregnated with this solution, and after air-drying for 30 minutes, 10 molecules were prepared at 110°C. Dry.

The pickup at this time was between 35 and 40% by weight.

This material was cut into 31×31 CIrL, 15 sheets were stacked, heated from room temperature to 180° C. under a molding pressure of 10 kg/ca, and held at this temperature for 1 hour to produce a laminate.

When the properties of the thus obtained laminate were investigated, the properties were as shown in the table below (indicated as the present invention in the table).

Note that the comparative example shown in the same table is the data shown for a laminate obtained by pressure and heat molding using a conventional condensation type silicone resin in accordance with the above-mentioned example of the present invention. .

○Glass cloth: In the case of the present invention, Nittobo 18G-104
In the case of the comparative example, Nittobo 18G-104BN was used as BT.

Conditions for post-cure: The temperature of the laminate obtained by pressure and heat molding was raised stepwise to 200°C (total heating time up to 200°C: 40 hours), and then heated at 200°C for an additional 2 hours.

○Solvent resistance: Shown as weight increase rate (%) when immersed in toluene solution for 1 hour.

○Water resistance: Indicated by weight increase rate (%) when immersed in water at 50°C for 24 hours.

Claims (1)

[Claims] 1 (a) Average compositional formula [R15iO1,5]. (R45iO]b(RiSiOo, J. (5i02)d(R1 in the formula is a group selected from substituted or unsubstituted monovalent hydrocarbon groups having 1 to 10 carbon atoms, a,
b, c and d represent the mole fraction of each siloxane unit,
a = 0.5 to 0.9, b = 0.1 to 0.5, C-〇 to 0.05, d = 0 to 0.05), and an alkenyl group directly bonded to a silicon atom Alkenyl group-containing organopolysiloxane resin having 0.05 to 0.3 per silicon atom, (b) average compositional formula [R15jO1,
5]. [R25io]f[R23SiOo, 5] (R2 in the formula
is a hydrogen atom or a group selected from a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, e, f and g represent the mole fraction of each siloxane unit, and e = 0.1 to 0.
7, f = 0.2 to 0.5, g = 0.1 to 0.7), and the hydrogen atoms directly bonded to silicon atoms are 0.05 to 0.3 per silicon atom. Organohydrodiene polysiloxane resin, and () platinum-based catalyst are the main components, and the blending ratio of component (x) to component (a) is determined per one alkenyl group in component (b). A silicone resin composition for lamination having 0.6 to 1.7 hydrogen atoms in the composition.