JPH0228241A - Phenolic resin composition for laminate - Google Patents

Abstract

PURPOSE:To obtain a composition having excellent heat resistance, dimensional stability and punchability in preparing a phenol resin composition for laminates from a polymer produced by condensing a phenol with an aldehyde by using a reaction product of a brominated epoxy resin and salicylic acid as the phenol. CONSTITUTION:A brominated epoxy resin is reacted with salicylic acid to give a reaction product wherein carboxyl groups of salicylic acid are added to both end epoxides of the brominated epoxy resin. The reaction product or the reaction product and a phenol such as cresol are reacted with an aldehyde such as formalin in the presence of a resol catalyst such as triethylamine to give a resol-type phenol resin. The resin is used as a main component to give the aimed composition providing print substrate having slight warpage, excellent flame retardance and standing surface packaging.

Description

[Detailed Description of the Invention] [Purpose of the Invention (Industrial Field of Application) The present invention provides a method for producing a material having excellent heat resistance, dimensional stability, and punching workability.
This invention relates to a phenolic resin composition for laminates with less warpage.

(Prior Art) In recent years, the technological trend of printed wiring boards used in electronic devices has been to make them lighter, thinner, and smaller, and rapid changes have also been seen in the mounting methods. In other words, in the past, the majority of methods were to drill holes in the printed circuit board, insert components with leads into them, and then attach the leads and the printed circuit board semi-Ifl to fix them. There is a shift towards surface mount methods, in which parts are mounted and reflow soldering is performed. Although some of the printed circuit boards used in this surface mount method are paper (base material) and phenol (resin) printed circuit boards, most are glass or epoxy printed circuit boards. The reason paper/phenol printed circuit boards are not used is that they have lower heat resistance, warpage, and poor dimensional stability than glass/epoxy printed circuit boards.

On the other hand, phenol printed circuit boards usually use resins containing flame retardants such as phosphoric acid esters and bromine compounds, or oil-modified resins with good punching force DI, so they are heat resistant. There was a drawback of low gender. These characteristics of flame retardancy, punching workability, and heat resistance are contradictory to each other, and it has been extremely difficult to obtain paper/phenol printed circuit boards that satisfy these characteristics.

(Problems to be Solved by the Invention) The present invention was made to solve the above-mentioned drawbacks, and provides a paper/phenol printed circuit board with excellent heat resistance, dimensional stability, punching workability, and less warping. The object of the present invention is to provide a phenolic resin composition for laminates.

[Structure of the Invention] (Means for Solving the Problems) As a result of extensive research in an attempt to achieve the above object, the present inventors have discovered that a reaction product of a brominated epoxy resin and salicylic acid is introduced into the resol skeleton. Specifically, the inventors have discovered that the above objects can be achieved, and have completed the present invention. That is, the present invention provides a resol type phenolic resin for laminates which is mainly composed of a polymer obtained by condensation of phenols and aldehydes, in which some or all of the phenols are 9, (a
) A phenol resin composition for a laminate, which is a reaction product obtained by reacting a brominated epoxy resin with (b) salicylic acid to add a carboxyl group as a component (b) to an epoxide as a component (a). It is.

(a) Brominated epoxy resin used in the present invention and (b)
The reaction product with salicylic acid and the resol type phenol resin into which it is introduced can be obtained as follows.

(a) (b) First, (a) a brominated epoxy resin (only the epoxides at both ends are shown) and (b) salicylic acid are reacted to introduce salicylic acid into the epoxides at both ends of the brominated epoxy resin, The reaction product Th(I) is then produced.The reaction product CI) is reacted alone or with other phenols with the addition of an aldehyde such as formalin and a resol catalyst such as triethylamine to form a resol-type phenolic resin (II). This reaction product (
The phenol resin (II) into which I) has been introduced can be mixed with or co-condensed with the phenol resin into which it has not been introduced. Also phenolic resin (II)
can also be modified with melamine, etc.

The brominated epoxy resin (a) used here is exemplified by the following structural formula.

Specifically, YDB-400E is commercially available.
K-60 (manufactured by Tobu Kasei Co., Ltd., trade name), Araldite XA
C-5019N-75 (manufactured by Ciba Kaigyi Co., Ltd., trade name), etc., and these may be used alone or in combination of two or more. The blending ratio of the brominated epoxy resin is preferably 20 to 40% by weight based on the total resin phenol component.

When this proportion is 20% by weight, sufficient heat resistance and flame retardance cannot be obtained, and when this proportion exceeds 40% by weight, electrical properties deteriorate, which is not preferable.

Moreover, (b) salicylic acid is 0-oxybenzoic acid.

The blending ratio of salicylic acid is preferably 1.1 to 1.5 equivalents to the epoxide of the brominated epoxy resin. If the blending ratio is less than 1.1 equivalents, it will not be possible to react sufficiently with the brominated epoxy resin, resulting in a decrease in heat resistance, which is not preferable. Moreover, if the amount exceeds 1.5 equivalents, salicylic acid becomes excessive and unreacted components adversely affect other properties, which is not preferable.

The phenolic resin used in the present invention is made by reacting phenols and formaldehydes, and
These modified resins include, for example, melamine-modified phenol resins. These can be used alone or in combination of two or more. Examples of the phenol include phenol, cresol, xylenol, punarphenol nonylphenol, etc., and all phenols commonly used for laminated boards are included.

These phenols can be used alone or in combination of two or more.
Use for historical purposes. Examples of aldehydes include formalin, paraformaldehyde, acetaldehyde, etc., and these may be used alone or in combination of two or more. Further, for modifying the phenol resin, for example, melamine is used, and examples of the melamine include melamine, benzoguanamine, acetoguanamine, pormuguanamine, etc., and these may be used alone or in combination of two or more kinds.

The phenolic resin composition for laminates of the present invention may contain components with functions such as flame retardants and fillers within limits that do not contradict the purpose of the present invention.

(Function) By introducing a reaction product of a linear and heat-resistant brominated epoxy resin and salicylic acid into the resol skeleton of phenol, it is possible to achieve the desired level of performance with or without the addition of a small amount of additive H fuel. It is possible to obtain a resin composition that has flame retardant properties, improves heat resistance and dimensional stability, and has less warpage without impairing the excellent punching workability that phenolic resin has.

(Example) Next, the present invention will be specifically explained using examples.

Example 1 Brominated epoxy resin YD in a four-loaf flask with a condenser
B-400EK-60 (manufactured by Kyoto Kasei Co., Ltd., product name) 13
0Q, 30 g of salicylic acid, and 2 g of triethylamine were added, and the mixture was refluxed for 2 hours to obtain a reaction product. Next, 100 g of phenol, 130 g of 37% formalin and 5 g of dimethylamine were added to this reaction product, and 2
After reacting under reflux for a period of time, it was dehydrated under reduced pressure and diluted with a mixed solvent of toluene:methanol (1:1), and 80 (1) i.liphenyl phosphate was added thereto, resulting in a resin solid content of 55!L.
! A varnish (A) having a viscosity of 2.3 poise (25°C) and a gelation time of 5 minutes and 10 seconds (150°C) was prepared.

Example 2 Brominated epoxy resin YD in a four-loaf flask with a condenser
130 g of B-400EK-60 (mentioned above), 30 l of salicylic acid, and 2 g of triethylamine were added, and the mixture was refluxed for 2 hours to obtain a reaction product. Next, to this reaction product, 70 g of melamine, 90 g of phenol, Add 130 g of 37% Polmarin and 5 g of dimethylamine,
After reacting under reflux for a period of time, it was dehydrated under reduced pressure and diluted with a mixed solvent of toluene:methanol=1:1, and 40 g of triphenyl phosphate was added thereto, resulting in a resin solid content of 60% by weight.
Viscosity 2.5 poise (25℃), gelation time 4 minutes 30 seconds (
Varnish (B) was prepared at a temperature of 150°C.

Comparative Example 1 200 g of phenol, 100 g of tung oil, and 0.3 (l) of p-toluenesulfonic acid were placed in a four-bottle flask with a condenser, and after reacting at 100°C for 1 hour, the mixture was neutralized with 40% aqueous ammonia. benzoguanamine 250
g, 1209.37% phenol, 460 g of Polmarin and 5 g of dimethylamine were added, and the mixture was refluxed for 2 hours, dehydrated under reduced pressure, diluted with a mixed solvent of toluene:methanol=1:1, and triphenyl phosphate 341
g and 100 g of tetrabromodiphenyl ether to give a resin solid content of 55% by weight and a viscosity of 1.8 poise (25
℃), gelation time 6 minutes 20 seconds (150℃) varnish (C
) was prepared.

Comparative Example 2 100 g of melamine, 250 g of phenol, 350 g of 37% formalin, and 4 g of dimethylamine were added to a four-bottle flask with a condenser, and the mixture was refluxed for 2 hours, dehydrated under reduced pressure, and diluted with a mixed solvent of toluene:methanol=1=1. To this, 341 g of triphenyl phosphate and 130 (l) of brominated epoxy resin YDB-400F and -60 (mentioned above) were added, resulting in a resin solid content of 55% by weight, a viscosity of 2.0 poise (at 25°C), and gelation. Time 5 minutes 30 seconds (15
Varnish (D) was prepared at 0°C.

Varnishes prepared in Examples 1-2 and Comparative Examples 1-2 (A
) to (D> were impregnated and coated on 10 mils Clara 1-paper to make a prepreg with a resin content of 50 Itf and 17-8% resin. Adhesive and copper foil were applied on both sides of 8 sheets of the prepreg. piled up, 170°C 1100kg/
A printed circuit board having a thickness of 1.611 IN was manufactured by integrally molding the product under heat and pressure for 75 minutes at cI 12.

Various tests were conducted on this printed circuit board, and the results are shown in Table 1.

The printed circuit board using the phenolic resin composition for laminates of the present invention had excellent mechanical properties, and the effects of the present invention were confirmed.

[Effects of the Invention] As is clear from the above explanation and Table 1, the printed circuit board using the phenolic resin composition for laminates of the present invention has excellent heat resistance, dimensional stability, and punching workability. It has low warpage, good flame retardancy, and can withstand surface mounting.

Patent applicant: Toshiba Chemical Corporation

Claims (1)

[Claims] 1. In a resol type phenolic resin for laminates which is mainly composed of a polymer obtained by condensation of phenols and aldehydes, some or all of the above phenols are (a
) A phenol resin composition for a laminate, which is a reaction product obtained by reacting a brominated epoxy resin and (b) salicylic acid to add a carboxyl group as a component (b) to an epoxide as a component (a). .