JPH0125498B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing flame-retardant paper-phenolic resin laminates or copper-clad laminates. Recently, insulating materials, especially laminates or copper-clad laminates used in consumer electronic devices, have been developed to allow parts to be inserted at room temperature or slightly higher temperature from the viewpoint of automation of processing equipment, energy saving, and high dimensional accuracy. It is required that holes for gas removal, gas vent holes, etc. can be punched out. Therefore, phenolic resins plasticized with various natural drying vegetable oils such as tung oil are usually used as resins for low-temperature punchable laminates. However, laminates used for insulating materials,
There is an increasing demand for copper-clad laminates to be flame retardant from the viewpoint of safety. From the viewpoint of flame retardancy, plasticizers such as drying vegetable oils used to improve punching workability are themselves flammable, making flame retardation even more difficult and complicated. Halogen or phosphorus compounds are added to the resin to make the laminate flame retardant, and these compounds include additive flame retardants and reactive flame retardants that are chemically bonded to the resin. Each has its advantages and disadvantages; in the former case, the flame retardant remains unreacted in the product, causing a decline in properties such as heat resistance and solvent resistance. Therefore, reactive flame retardants are preferable in order to avoid deterioration of properties, but conventional glycidyl ether type reactive flame retardants with epoxy groups have some residual epoxy groups as reactive groups in varnish or resin-impregnated coated paper. If this occurs, this may cause poor mold release of the end plate or deterioration of the resin in the varnish or coated paper over time, causing problems in manufacturing workability. The present invention is aimed at improving the above-mentioned problems, and uses a halogen compound (a halogen compound ( This paper relates to a method for manufacturing laminates or copper-clad laminates using reactive flame-retardant plasticizers. In the present invention, a varnish is produced by adding a halogen compound to a phenolic resin, and then the varnish is impregnated into a paper base material and dried to create a prepreg, which is then pressure-heat molded with a predetermined number of prepreg copper foils stacked or not stacked. When manufacturing flame-retardant copper-clad laminates or laminates, the halogen compounds are (a) epoxidized vegetable oil and (b) two or more phenolic hydroxyl groups and one or more halogens in one molecule. A halogenated polyhydric phenol having an atom [] and (c) a halogenated epoxy resin having two or more epoxy groups and one or more halogen atom in one molecule [] are essential components, and the general formula [ ]

Halogenated phenols represented by the formula (where X represents Br or Cl and p = 1 to 5
It is. Further, R represents an alkyl group, and q=1 to 2,
p+q≦5. ) is characterized in that it uses a reaction product (reactive flame retardant plasticizer) obtained by carrying out a heating reaction in the presence of a basic catalyst with or without addition. The present invention has made it possible to provide a reactive flame-retardant plasticizer that can improve the flame retardancy and low-temperature punchability of copper-clad laminates or laminates. To explain the present invention in more detail, since the halogenated epoxy resin [] is used to impart reactivity to the epoxidized vegetable oil used for plasticizing the phenolic resin, first the epoxidized vegetable oil [] and the halogenated polyhydric phenol [] It is preferable to react [ ] after reacting the halogenated phenol [ ]. That is, epoxidized vegetable oil [], halogenated polyhydric phenols [], and primary, secondary, and tertiary amines, quaternary amines, with or without addition of halogenated phenols [] that act as reaction regulators. Adding substances that act as reaction catalysts between epoxy groups and phenolic hydroxyl groups, such as ammonium salts and alkali metal salts of alkoxides,
The reaction is carried out without a solvent or in a solvent, and the reaction is continued until the halogenated polyhydric phenols [] and the added halogenated phenols [] are no longer detected, and the halogenated epoxy resin [] is added to the reaction product. and continue the reaction. [],
The end point is when [] is no longer detected by liquid chromatography. This reaction product is used as a laminate resin as it is or by adding it to a phenolic resin in combination with a phosphorus-based, nitrogen-based, antimony-based, or boron-based flame retardant. The reaction temperature during synthesis of halogen compounds is 50~
The reaction is preferably carried out at 200°C, preferably 80 to 120°C, and the reaction solvent is preferably a solvent with a boiling point of 80°C or higher, such as toluene xylene, methyl ethyl ketone, methyl isobutyl ketone, or methyl glycol. Unreacted halogenated polyphenols [],
If unreacted phenols and halogenated phenols [] remain in the varnish and are applied to a paper-phenol laminate, it will cause a decrease in dielectric properties (tan8, ε), so unreacted [], [ ] is preferably not detected at all. Next, the compounding conditions for the synthesis of this reactive flame-retardant plasticizer will be described. Amount of epoxidized vegetable oil []; Q Epoxy equivalent; q Amount of halogenated polyphenol []; R, hydroxyl group equivalent; r Amount of halogenated phenol []; T, molecular weight; t, then halogen The blending amount of the halogenated phenols [ ] should be Q/q>R/r, but as the blending amount of the halogenated phenols increases, unreacted [ ] will remain [ ] and [ ]. ] The reaction product becomes easier to gel. Therefore R/r>Q/2q
It is preferable that Furthermore, unlike halogenated polyhydric phenols [ ], halogenated phenols [ ] do not undergo gelation even if the reaction continues due to their structure, so they can serve as reaction regulators for [ ] and [ ]. Moreover, it becomes possible to increase the halogen content of the reactive flame-retardant plastic, which is the object of the present invention. Halogenated polyvalent phenol []
The blending ratio of [] and halogenated phenol [] is preferably 100 to 20 mol%, and 0 to 80 mol% of [], and various halogen-containing compounds can be obtained by changing the blending ratio with epoxidized vegetable oil []. amount of flame retardant plasticizer is obtained. Considering the properties of the laminate, it is preferable to determine the blending amount of [ ] and [ ] so that the halogen content is 10% or more. The amount of the halogenated epoxy resin [ ] may be sufficient as long as it reacts with the free phenolic hydroxyl groups of the halogenated polyhydric phenols [ ] added to the epoxidized vegetable oil [ ]. Blending amount of halogenated epoxy resin; If U epoxy equivalent is u, then U/u<R/2r,
Since the halogenated epoxy resin itself is a reactive flame retardant, there is no problem with R/2r or more, but this will cause problems with the mold releasability of the end plate and the storage stability of varnish and coated paper as mentioned earlier. Therefore, it is preferable to suppress U/u<R/r or less. A simple explanation of the reactive flame retardant plasticizers mentioned above is that they are plasticized with epoxidized vegetable oil [ ] that is useful for improving the low-temperature punchability of laminates, and then halogenated polyhydric phenols and halogenated phenols are added to the plasticizer. The halogenated epoxy resin [] is added to the free hydroxyl group of the polyhydric phenol added to [] to impart flame retardancy due to halogen, and to further increase the reactivity, the flame retardance and reaction due to the epoxy group It has been given a certain gender. In the present invention, the epoxidized vegetable oil [ ] is an epoxidized vegetable oil obtained by oxidizing the double bonds of fatty acids in an unsaturated vegetable oil, such as epoxidized linseed oil, epoxidized soybean oil, epoxidized dehydrated castor oil, and epoxidized safflower oil. oil, epoxidized sunflower oil, and epoxidized corn oil. Examples of halogenated phenols include monobromo, dibromo, tribromo, tetrabromo of catechol, resorcinol, and hydroquinone, monobromo, dibromo, trifuro of pyrogallol, and phyllologlucinol, bisphenol-A, and bisphenol-A. There are monobromo, dibromo, tribromo, and tetrabromo compounds of bisphenol compounds such as S, bisphenol F, and polybromo compounds of novolac resins. Similarly, there is a chlor compound corresponding to the above-mentioned bromine compound in which Cl is bonded instead of Br. Examples of halogenated phenols include monobromo, dibromo, tribromo, tetrabromo, pentabromo, and corresponding chloro phenols in which Br is replaced with Cl. Furthermore, monobromo, dibromo, tribromo, tetrabromo and Br of cresols (o-, m-, p-) are Cl
There is a corresponding chlor form in place of . There are monobromo, dibromo, tribromo xylenols, and the corresponding chloride in which Br is replaced with Cl. As the halogenated epoxy resin, glycidyl ether of tetrabromobisphenol A (ESB
-400 (trade name of Sumitomo Chemical), Epicron 152 (trade name of Dainippon Ink)) and glycidyl ether of brominated novolac resin (BREN brand name of Nippon Kayaku). Next, the base resin to which this reactive flame-retardant plasticity is added can be any of those commonly used as phenolic resins for laminates, such as resol-type phenolic resins, dry vegetable oil-modified phenolic resins, and liquid polybutadiene-modified phenolic resins. be able to. The halogen content of the reactive flame retardant plasticizer according to the present invention can be freely designed up to about 55%. Considering the flame retardancy of the laminate, it is preferable to use a laminate with a halogen content of 20% or more. Those with low halogen content can plasticize simple resol type phenolic resins. Since those with a high halogen content can satisfy flame retardancy with a small amount added, it is preferable to use those modified with the above-mentioned vegetable oil or xylene resin or liquid polybutadiene resin. Examples of phosphorus flame retardants used in combination include triphenyl phosphate, cresin diphenyl phosphate,
Examples include xylyl diphenyl phosphate and red phosphorus. The phenolic resin to which the flame-retardant plasticizer obtained in the present invention is added can be any resin used in the production of laminates. Further, this flame retardant reactive plasticizer may be used by being added to a phenolic resin base varnish, or may be added to a phenolic resin base varnish. The amount added depends on the flame retardant grade, but in order to satisfy V-1 of UL-94, when the plasticizer of the present invention is used alone, the halogen atoms in the resin including the base range must be 10 to 10. 30% by weight
It is preferable to mix them so that When using phosphorus compounds together, the resin including the base range should contain 5 to 20% bromine atoms and 0.5% phosphorus atoms by weight.
It is preferable to mix it so that it becomes -3.0%. The following will be explained based on examples. (Hereinafter, % is weight %.) Synthesis Example 1 Epoxidized soybean oil (ADEKASIZER O-130PA
Adeka Argus product name, epoxy equivalent: approx.
230) 1000g Methyl Cellosolve 150g, Tetrabromobisphenol-A (TBA, Fireguard)
2000 Teijin Kasei products each hydroxyl equivalent 272) 381g, tribromophenol (TBP hydroxyl equivalent 331) 530
g and heated to 100℃ to dissolve TBA, then 60
The mixture was cooled to 0.degree. C., 28.7 g of diethylamine was added thereto, and the mixture was heated to react at 115.degree. After 8 hours, the reaction product was collected and the molecular weight distribution was measured using high performance liquid chromatography (HLC Toyo Soda product name U-801 model).
It was confirmed that there was 5% unreacted tetrapromobisphenol A and almost no unreacted TBP. Add glycidyl ether of TBA (ESB-
400 Sumitomo Chemical (trade name) Epoxy equivalent (approximately 330) After 2 hours of adding 660 g, HLC showed no reaction.
Confirmed that there was no TBA. Solid content with toluene
It was adjusted to 70% so that it could be added to the base resin. (Solid bromine content: approx. 30%) Synthesis Example 2 In a flask similar to Synthesis Example 1, add epoxidized soybean oil (ADEKASIZA-O-130PA, epoxy equivalent amount: approx.
230), 100 g of toluene, 272 g of TBA (Fire Guard 2000, hydroxyl equivalent: 272), and 504 g of dibromophenol (DBP, molecular weight 252) were added and heated to 100°C to dissolve the TBA. After cooling to 60°C, 35.5 g of benzyldimethylamine was added and heated to react at 105°C. After 8 hours, collect the reaction product.
The molecular weight distribution was measured by HLC, and unreacted TBA,
It was confirmed that there was almost no DBP. Next, brominated epoxy resin (ESB-400, epoxy equivalent
330) 231 g was added and the reaction was continued at 115°C. 3
After some time, it was confirmed by HLC that 40% of ESB-400 had reacted. The solid content was adjusted to 70% with toluene. (Solid bromine content: approx. 29%) Synthesis Example 3 Epoxidized linseed oil (Adekasizer O-180 epoxy equivalent: approx. 170) in the same flask as in Synthesis Example 1.
1000 g of xylene, 734 g of pentabromophenol (PBP molecular weight 489), and 67.5 g of tetramethylammonium chloride were added and reacted at 150°C.
After 10 hours, the reaction product was collected and HLC was measured. Approximately 10% of unreacted PBP remained. 516 g of tetrabromobisphenol F (TBF manufactured by Ube Industries, Ltd., hydroxyl equivalent: 258) was added to the reaction solution and reacted at 150° C. for 1 hour. From HLC, unreacted TBF was found to be 10%. 462 g of brominated epoxy resin (ESB-400 epoxy equivalent: 330) was added to this and reacted at 120°C for 6 hours.
No unreacted PBP, TBF from HLC, ESB
-400 was confirmed to be 60% responsive. After the reaction was completed, the solid content was adjusted to 70% with toluene. (Brome content: approx. 42%) Synthesis example 4 Epoxidized linseed oil (ADEKASIZA-O-180 epoxy equivalent: approx. 170) in the same flask as in synthesis example 1.
1000g, toluene 200g, TBA (Fireguard)
Add 544g of 2000 hydroxyl equivalent 272) and heat to 100℃ to dissolve TBA. After cooling to 50°C, 30g of benzyldimethylamine was added and reacted at 150°C for 2 hours. After cooling, add 497g of TBP (molecular weight 331).
React at 120°C for 8 hours. Collect the reaction solution
As a result of HLC measurement, unreacted TBA was 5% and unreacted TBP was almost nonexistent. 200 g of brominated novolac epoxy resin (BREN, Nippon Kayaku brand name epoxy equivalent weight 286) was added to this reaction solution.
The reaction was carried out at 120°C for 3 hours. After the reaction was completed, it was confirmed by HLC that no unreacted TBA remained. The solid content was adjusted to 70% with toluene.
(Bromide content: approx. 33%) Synthesis example of base resin: 1000g of tung oil and 1450g of cresol in a 20-synthesis pot.
g, and 3 g of paratoluenesulfonic acid were added and reacted at 110°C for 1 hour. Next, 2550 g of phenol, 1000 g of paraform, and 160 g of 25% ammonia water were added and the mixture was heated to 80°C.
The mixture was allowed to react for 3 hours. Next, it was concentrated under reduced pressure, and when the temperature of the liquid reached 85℃, the concentration was stopped, and the pressure was returned to normal, and 1200g of acetone was added to make a varnish.The solid content was 64%, and the gelation time was set on a hot plate at 160℃. was 220 seconds. Synthesis examples 1 to 4 using the base resin as shown in Table 1
Added reactive flame retardant plastic synthesized in . A prepreg was prepared by impregnating cotton linter paper (adhesive resin amount: 16%) pre-treated with a water-soluble phenol resin with the varnish containing the above flame-retardant plasticizer and drying it. A predetermined number of sheets of the prepreg are stacked, copper foil coated with adhesive is layered on one side, and the prepreg is stacked under a pressure of 100 kg/ ^cm2.
A copper-clad laminate was created by heat forming at 150°C for 60 minutes. The properties of the copper-clad laminate were measured according to JIS-C-6481, and the results are shown in Table 1.

【table】

[Table] From the data in Table 1, it is better to use tetrabromobisphenol A, a general-purpose flame retardant.
The reactive flame retardant plasticizer synthesized in the present invention has excellent soldering heat resistance, air heat resistance, dielectric properties, punching workability at low temperature measurements, and trichlene resistance. This is clearly an effect of the flame retardant plasticizer obtained in the present invention.

Claims (1)

[Claims] 1. After producing a varnish by adding a halogen compound to a phenolic resin, this is impregnated into a paper base material and dried to create a prepreg, and the prepreg is heated with or without overlaying a copper foil. When manufacturing flame-retardant copper-clad laminates or laminates by pressure molding, epoxidized vegetable oil [ ] is used as a halogen compound.One molecule contains two or more phenolic hydroxyl groups and one or more halogen A halogenated polyvalent phenol having an atom [] and a halogenated epoxy resin having two or more epoxy groups and one or more halogen atom in one molecule [] are essential components, and the general formula []
Halogenated phenols represented by the formula (where X represents Br or Cl and p = 1 to 5
It is. Further, R represents an alkyl group, and q=1 to 2,
p+q≦5. ) A method for producing a flame-retardant laminate, characterized by using a reactant obtained by carrying out a heating reaction in the presence of a basic catalyst with or without the addition of . 2. The method for producing a flame-retardant laminate according to claim 1, wherein the halogenated phenol [] is tetrabromobisphenol-A. 3. The method for producing a flame-retardant laminate according to claim 1, wherein the halogenated phenol [ ] is a brominated novolak resin. 4. The method for producing a flame-retardant laminate according to claim 1, 2 or 3, wherein the halogenated epoxy resin [] is glycidyl ether of tetrabromobisphenol-A. 5. The method for producing a flame-retardant laminate according to claim 1, 2, or 3, wherein the halogenated epoxy resin [] is a glycidyl ether of a brominated novolak resin.