JPS60248768A - Resin composition for laminated board - Google Patents

Abstract

PURPOSE:To provide a flame-retardant composition having excellent electrical properties and low-temperature punchability, by compounding a reactive phosphoric acid ester, phenolic compound, melamine compound, formaldehyde, and petroleum resin. CONSTITUTION:The objective composition is produced by compounding (A) a reactive phosphoric acid ester of formula (R<1> and R<2> are H or 1-20C alkyl), (B) a phenolic compound, (C) a melamine compound, (D) formaldehyde, and (E) a petroleum resin. The amount of the component A is 20-60wt%, and that of the component E is 2-20wt% based on the whole composition.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a flame-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 is becoming.

In other words, better electrical characteristics are achieved due to the use of chips for mounted components, automatic insertion of mounted components, higher density wiring patterns, etc.
At the same time as the need for laminates with excellent physical properties and workability increased, fire-retardant laminates became an indispensable condition due to the emphasis on fire safety. Satisfying these requirements means that the laminate has low-temperature punchability, dimensional stability (low expansion, low shrinkage), electrical properties (tracking resistance,
However, conventional resins for flame-retardant laminates have the following problems.

Flame retardants conventionally added to resins to make laminates flame retardant can be roughly divided into additive types and reactive types, each of which has its own length. Additive flame retardants are those in which the flame retardant does not react with the resin, and phosphoric acid esters such as triphenyl phosphate, a typical example, impart a plasticizing effect but have the drawback 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 of this, 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.

In addition, flame retardant laminates are achieved by using flame retardants such as nitrogen compounds, halogen compounds, and phosphorus compounds in combination, but the type of flame retardant element has a large effect on the properties. For example, the introduction of halogen Although it has a great effect on improving flame retardancy, it has the disadvantage of decreasing arc resistance, tracking resistance, and heat resistance, and generating harmful gases such as hydrogen halides when burned. Although it improves arc resistance and tracking resistance, and there is no risk of generating harmful gases, it has drawbacks such as the difficulty of achieving sufficient flame retardancy using 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 flame-resistant resin composition for laminates that has excellent electrical properties and low-temperature punching workability. .

[Summary of the Invention] As a result of extensive 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) reactive phosphoric esters represented by the general formula (wherein R' and R2 represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms); and (B) phenols. A resin composition for a laminate comprising: (C) melamines; (D) formaldehydes; and (E) petroleum resin. In a preferred embodiment, 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 the same.
This is a resin composition for a laminate containing 2 to 120% 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 type flame retardants. Deterioration in processability can be prevented by compensating for the reduction in plasticizing effect that occurs with petroleum resins and by not using reactive brominated epoxy resins.

Examples of the (A) reactive phosphoric acid esters used in the present invention include the following, and these are used alone or as a mixture of two or more. When these reactive phosphoric esters are produced by a conventional method for producing phosphoric esters, they become reactants with other phosphoric esters.

It is desirable that the content of the reactive phosphoric esters is 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, and mixtures of one or more of these. used.

Melamines (C) used in the present invention include melamine,
Examples include benzoguanamine, acetoguanamine, and formguanamine, and these may be used alone or as a mixture of two or more thereof.

Formaldehydes ([)) used in the present invention include:
Examples include formalin and paraformaldehyde.

As the petroleum resin (E) used in the present invention, for example, Finton 1500. Examples include Finton 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 since it can be produced by reacting each of the above-mentioned components. 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 layer 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.

Preparation of Reactive Phosphoric Acid Ester A reactive phosphoric acid ester containing 75% diphenylresorcinol phosphate was produced by a conventional method for producing a phosphoric acid ester (hereinafter referred to as a phosphorus compound).

Example 1 126 g of melamine, phenol 188 (), and 337% formalin 551 were placed in a four-loaf flask with a condenser.
was charged and reacted at 90°C for 2 hours. Next, 239G of phosphorus compound, 130g of 37% formalin, and 6g of dimethylamine were added and reacted under reflux for 2 hours.
After dehydration under reduced pressure, Finton 1500 (trade name of petroleum resin manufactured by Nippon Zeon Co., Ltd.) 35Q was added to obtain a resin composition for a laminate. This is methyl ethyl ketone:methanol-1=
A varnish having a resin solid content of 55% by weight, a viscosity of 1.5 poise (at 25°C), and a gelation time of 3 minutes and 40 seconds (at 150°C) was prepared by diluting with 1 solvent.

Example 2 Phenol 200Q, 100 g of tung oil, and 0.3 g of p-toluenesulfonic acid were charged into a four-hole flask with a condenser, and the mixture was reacted at 100° C. for 1 hour, and then neutralized with 40% aqueous ammonia. Then 250g of benzoguanamine
, phosphorus compound 400 (] , 337% formalin 660
1, and 8 g of dimethylamine were added and the reaction was carried out under reflux for 2 hours and 30 minutes, followed by dehydration under reduced pressure.
0 (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 methyl ethyl ketone:methanol-1:1 solvent, and the resin solid content was 55% by weight and the viscosity was 2.8 poise (2.
A varnish with a gelation time of 3 minutes and 50 seconds (150°C) was prepared.

Example 3 In a four-eye flask with a condenser, 15 g of dicanol H (trade name manufactured by Mitsubishi Gas Chemical Co., Ltd.), 100 g of phenol 125 iJ 1 tung oil, and 0.27 f of p-toluenesulfonic acid)
was charged, reacted at 110°C for 1 hour, and then neutralized with 40% aqueous ammonia. Then benzoguanamine 250
(], phosphorus compound 400 (), 337% formalin 550, and 6 g of dimethylamine were added and reacted under reflux for 2 hours. After dehydration under reduced pressure, Finton 1500
(mentioned above) 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 3.2 poise (2
A varnish with a gelation time of 3 minutes and 10 seconds (150°C) was prepared.

Comparative Example 1 126 g of melamine, 1881111 phenol and 551 g of 37% formalin in a four-loop flask with a condenser
was 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 to give a resin solid content of 55% by weight, a viscosity of 1.0 poise (25°C), and a gelation time of 6 minutes. A second (150°C) varnish was prepared.

Comparative Example 2 Phenol 2009, 100 g of tung oil, and 0.3 p-toluenesulfonic acid were placed in a four-loaf flask with a condenser.
was charged, reacted at 100°C for 1 hour, and then neutralized with 40% aqueous ammonia. Next, benzoguanamine 250Q
, phenol 127137% formalin 460 (1,
and 5 g of dimethylamine were added and reacted for 2 hours under reflux reaction. After dehydration under reduced pressure, toluene:methanol-1:1
Dilute with solvent and add triphenyl phosphate 341 to this.
g to give a resin solid content of 55% by weight and a viscosity of 1.8 poise (
A varnish with a gelation time of 6 minutes and 20 seconds (150°C) was prepared.

Comparative example 3 Two canol H in a four-loop flask with a condenser (described above)
75a, 125g of phenol, 100g of tung oil (+i) and 0.27i7 of para-toluenesulfonic acid,
After reacting at 0°C for 1 hour, the mixture was neutralized with 40% aqueous ammonia. Next, benzoguanamine 200Q, phenol 1217.37% formalin 350 (J), and dimethylamine 4g were added and reacted for 2 hours under reflux, dehydrated under reduced pressure, diluted with toluene:methanol-1=1 solvent, and triphenyl phosphate was added to this. 341g was added to give a resin solid content of 55% by weight, a viscosity of 1.5 poise (25°C),
A varnish with a gelation time of 5 minutes and 30 seconds (150°C) was prepared.

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 a prepreg with a resin content of 50% by weight and a resin flow of 8%.
Layer 8 sheets of this prepreg and 1 sheet of adhesive material-foil 1
A copper-clad laminate having a thickness of 1.6 mm was manufactured by heat-pressing molding at 70° C. and 100 kmcm2 for 75 minutes.
The properties of the manufactured copper-clad laminates were tested and the results are shown in Table 1.

[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 board or printed circuit board, it can withstand harsh usage conditions.

Claims (1)

[Scope of Claims] 1 (A) a reactive phosphoric acid ester represented by the general formula (wherein R' and R2 represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms); and (B) phenol. (C) melamines, (D) formaldehydes, and (E). A resin composition for a laminate, comprising a petroleum resin. 2 (A) The amount of reactive phosphate ester is the total [<A)+
20 for the amount of (B) + (C > + (D) + (E))
60% by weight of the resin composition for a laminate according to claim 1. 3 (E) The amount of petroleum resin is the whole [(A> +(B)+(
The resin composition for a laminate according to claim 1 or 2, wherein the amount is 2 to 20% by weight based on the amount of C) + (D) + (E)].