JPH058220B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical Field of the Invention] The present invention relates to a heat-resistant resin composition for laminates that has excellent electrical properties and processability. [Technical background of the invention and its problems] In recent years, with the remarkable development of the electronics industry, the usage conditions for printed wiring boards have become harsher, and the characteristics required of the printed circuit boards that are the material for printed wiring boards have also become more severe. It's becoming commonplace. In other words, due to the chipping of mounted components, automatic insertion of mounted components, and higher density wiring patterns, there is a need for laminates with better electrical properties, physical properties, and workability. Due to the emphasis on fire safety, it has become essential to make laminates flame retardant. Satisfying these requirements means that the laminate has excellent low-temperature punchability, dimensional stability (low expansion, low shrinkage), electrical properties (tracking resistance, arc resistance, moisture resistance), heat resistance, and flame resistance. This means that it must be of excellent quality.
Conventional resins for flame-retardant laminates have had the following problems. Flame retardants traditionally added to resins to make laminates flame retardant can be roughly divided into additive and reactive types.
Each has its advantages and disadvantages. Additive flame retardants are those in which the flame retardant does not react with the resin, and phosphate esters such as triphenyl phosphate, a typical example, impart a plasticizing effect, but have the disadvantage of deteriorating electrical and mechanical properties. On the other hand, in the reactive type, the flame retardant reacts with the resin, and brominated epoxy resin, which is a typical example, provides excellent electrical properties but has the drawback of deteriorating processability. The disadvantages of these flame retardants become even greater when they are highly plasticized and require low-temperature punchability. Furthermore, the flame retardance of the laminate is achieved by the combined use of flame retardants such as nitrogen compounds, halogen compounds, phosphorus compounds, etc., but the type of flame retardant element has a great influence on the properties. For example, the introduction of halogen is highly effective in improving flame retardancy, but has the drawback of lowering arc resistance, tracking resistance, and heat resistance, and generating harmful gases such as hydrogen halides during combustion. Flame retardancy by introducing phosphorus improves arc resistance and tracking resistance, and there is no risk of generating harmful gases, but it has drawbacks such as the difficulty of achieving sufficient flame retardancy with phosphorus alone. [Object of the Invention] The present invention was made in order to eliminate the above-mentioned drawbacks, and an object of the present invention is to provide a heat-resistant resin composition for laminates that has excellent electrical properties and low-temperature punching workability. . [Summary of the Invention] As a result of intensive research to achieve the above object, the present invention has been developed by incorporating a reactive phosphoric acid ester into the skeleton of a melamine-modified phenolic resin and using a petroleum resin as a plasticizing aid. It was discovered that the above object can be achieved, and the present invention was completed. That is, the present invention provides (A) general formula (In the formula, R ¹ and R ² represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), (B) phenols, (C) melamines, ( A resin composition for a laminate, comprising D) formaldehyde and (E) petroleum resin. A preferred embodiment is a resin composition for a laminate in which the amount of reactive phosphoric acid ester is 20 to 60% by weight based on the total amount, and the amount of petroleum resin is also 2 to 20% by weight. According to the present invention, it is possible to convert the phosphorus-based flame retardant in the prior art to a reactive type that is incorporated into the skeleton, thereby preventing the deterioration of electrical properties, which is a drawback of additive flame retardants, and also to prevent the deterioration of electrical properties caused by conversion to the reactive type. Deterioration of processability can be prevented by compensating for the reduction in the plasticizing effect with petroleum resin and by not using reactive brominated epoxy resin or the like. (A) Reactive phosphoric acid esters used in the present invention include: These can be used alone or as a mixture of two or more of them. When these reactive phosphoric esters are produced by a conventional method for producing phosphoric esters, they become reactants with other phosphoric esters.
The content of reactive phosphate esters is preferably 70% or more. Examples of the phenols (B) used in the present invention include phenol, cresol, xylenol, butylphenol, nonylphenol, phenol adducts of tung oil, xylene resin/phenol mixtures, etc. One or a mixture of two or more of these used as a system. Melamines (C) used in the present invention include melamine, benzoguanamine, acetoguanamine, formguanamine, etc., and one or two of these may be used.
Used as a mixture of more than one species. Formaldehydes (D) used in the present invention include formalin, paraformaldehyde, and the like. Examples of the (E) petroleum resin used in the present invention include Quinton 1500 and Quinton 1700 (trade name, manufactured by Nippon Zeon Co., Ltd.). The method for producing the resin composition for laminates of the present invention is not particularly limited to the reaction order as it can be produced by reacting each of the above-mentioned components, but the reaction order is not particularly limited. It is desirable to add a petroleum resin and a petroleum resin to produce a resin composition for a laminate after adding and reacting a phosphoric acid ester and a formaldehyde. Next, regarding the blending ratio of each component, it is necessary that the amount of reactive phosphoric acid esters is 20 to 60% by weight based on the total weight. If it is less than 20% by weight, sufficient flame resistance cannot be obtained, and if it exceeds 60% by weight, electrical properties may deteriorate, which is not preferable. Further, the blending ratio of petroleum resin needs to be 2 to 20% by weight based on the total weight. If it is less than 2% by weight, it has no effect on plasticization, and if it exceeds 20% by weight, the electrical properties deteriorate, which is not preferable. The resin composition for laminates obtained in this way is dissolved and diluted in an organic solvent, and a paper base material such as kraft paper is impregnated with this to make a prepreg. After laminating a plurality of sheets of this prepreg, the prepreg is molded under heat and pressure. A laminate can be obtained. [Embodiments of the Invention] Examples of the present invention will be specifically described below. The present invention is not limited to these examples. Production of Reactive Phosphoric Acid Ester A reactive phosphoric acid ester containing 75% diphenyl resorcinol phosphate was produced by a conventional method for producing a phosphoric acid ester (hereinafter referred to as a phosphorus compound). Example 1 126g of melamine in a four-necked flask with a condenser.
188 g of phenol and 551 g of 37% formalin were charged and reacted at 90°C for 2 hours. Next, 239 g of phosphorus compound, 130 g of 37% formalin, and 6 g of dimethylamine were added and reacted under reflux for 2 hours.
After dehydration under reduced pressure, 35 g of Quinton 1500 (trade name of petroleum resin manufactured by Nippon Zeon Co., Ltd.) was added to obtain a resin composition for a laminate. This was diluted with a methyl ethyl ketone:methanol=1:1 solvent to prepare a varnish having a resin solid content of 55% by weight, a viscosity of 1.5 poise (25°C), and a gelation time of 3 minutes and 40 seconds (150°C). Example 2 Phenol 200 in a four-necked flask with a condenser
g, 100 g of tung oil, and para-toluenesulfonic acid
After charging 0.3g and reacting at 100℃ for 1 hour, 40
% aqueous ammonia. Next, 250 g of benzoguanamine, 400 g of phosphorus compound, and 37% formalin.
After adding 660 g and 8 g of dimethylamine and reacting under reflux for 2 hours and 30 minutes, dehydration was performed under reduced pressure, and Quinton 1500 (product name of petroleum resin manufactured by Nippon Zeon Co., Ltd.) 50
g was added to obtain a resin composition for a laminate. This was diluted with methyl ethyl ketone: methanol = 1:1 solvent, the resin solid content was 55% by weight, and the viscosity was 2.8 poise (25
A varnish with a gelation time of 3 minutes and 50 seconds (150°C) was prepared. Example 3 Nicanor H in a four-necked flask with a condenser
(Product name manufactured by Mitsubishi Gas Chemical Co., Ltd.) 75g, Phenol 125
g, 100 g of tung oil and para-toluenesulfonic acid
After charging 0.27g and reacting at 110℃ for 1 hour,
Neutralized with 40% ammonia water. Next, 250 g of benzoguanamine, 400 g of phosphorus compound, and 37% formalin.
After adding 550 g and 6 g of dimethylamine and reacting under reflux for 2 hours and dehydrating under reduced pressure, 50 g of Quinton 1500 (described above) was added to obtain a resin composition for a laminate. This was diluted with methyl ethyl ketone: methanol = 1:1 solvent, resin solid content 55% by weight, viscosity 3.2 poise (25℃), gelation time 3 minutes 10 seconds (150
℃) varnish was prepared. Comparative example 1 126g of melamine in a four-necked flask with a condenser.
188 g of phenol and 551 g of 37% formalin were charged and reacted at 90°C for 2 hours. Next, dehydration was performed under reduced pressure, diluted with toluene:methanol=1:9 solvent, and 209 g of triphenyl phosphate was added to this.
was added to prepare a varnish having a resin solid content of 55% by weight, a viscosity of 1.0 poise (25°C), and a gelation time of 6 minutes and 10 seconds (150°C). Comparative example 2 Phenol 200 in a four-necked flask with a condenser
g, 100 g of tung oil, and para-toluenesulfonic acid
After charging 0.3g and reacting at 100℃ for 1 hour, 40
% aqueous ammonia. Next, benzoguanamine 250g, phenol 12g, 37% formalin 460
g, and 5 g of dimethylamine were added and reacted under reflux for 2 hours, dehydrated under reduced pressure, diluted with toluene:methanol=1:1 solvent, and 341 g of triphenyl phosphate was added thereto to obtain a resin solid content of 55% by weight. Viscosity 1.8 poise (25℃), gel time 6 minutes20
A varnish was prepared in seconds (150 °C). Comparative example 3 Nicanol H in a four-necked flask with a condenser
(previously) 75g, phenol 125g, tung oil 100g and para-toluenesulfonic acid 0.27g, 110
After reacting at ℃ for 1 hour, it was neutralized with 40% aqueous ammonia. Next, 200 g of benzoguanamine, 12 g of phenol, 350 g of 37% formalin, and 4 g of dimethylamine were added and reacted under reflux for 2 hours.
After dehydration under reduced pressure, toluene:methanol=1:1
Dilute with solvent and add triphenyl phosphate to this
341 g was added to prepare a varnish having a resin solid content of 55% by weight, a viscosity of 1.5 poise (25°C), and a gelation time of 5 minutes and 30 seconds (150°C). The varnishes prepared in Examples 1 to 3 and Comparative Examples 1 to 3 above were impregnated and coated on 10 mils kraft paper to obtain prepregs with a resin content of 50% by weight and a resin flow of 8%. Eight sheets of this prepreg and one sheet of copper foil with adhesive were stacked together at 170℃ and 100Kg/cm ² to give a
A copper clad laminate with a thickness of 1.6 mm was manufactured by heating and press molding for 1 minute. The properties of the manufactured copper clad laminates were tested and the results are shown in Table 1.

【table】

[Table] [Effects of the invention] As is clear from the above explanation and Table 1,
The resin composition for laminates of the present invention has excellent electrical properties and low-temperature punching workability, and has flame resistance.
When used as a laminate or printed circuit board, it can withstand harsh usage conditions.

Claims (1)

[Claims] 1 (A) General formula (In the formula, R ¹ and R ² represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), (B) phenols, (C) melamines, ( A resin composition for a laminate, comprising D) formaldehyde and (E) petroleum resin. 2 (A) The amount of reactive phosphate ester is the total [(A) + (B)
+(C)+(D)+(E)] 20 to 60% by weight of the resin composition for a laminate according to claim 1. 3 (E) The total amount of petroleum resin [(A) + (B) + (C) + (D) +
(E)] 2 to 20% by weight based on the amount of the resin composition for a laminate according to claim 1 or 2.