JPS604845B2 - laminate board - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is characterized in that monomers and/or oligomers of isoprobenylphenol, alone or in mixtures, are used as part of the phenol component and reacted with aldehydes in the presence or absence of tympani oil. This paper relates to a laminate using a new phenolic resin obtained by the above method.

The aim is to provide a laminate with excellent mechanical and electrical properties. Conventionally, laminates obtained by impregnating and curing base materials such as paper with phenolic resin obtained by reacting formaldehyde with phenol, cresol, alkylphenol, or amine compounds have been used for decorative boards, heat-resistant products, and electrical applications. Although it is widely used for insulation purposes, there has been a demand for laminates with advanced mechanical and electrical properties, especially with the development of communication equipment and electronic equipment in recent years. In particular, copper-clad laminates require not only high insulation properties, but also punching workability, surface resistance, volume resistance, soldering heat resistance, dimensional stability, dielectric constant, dielectric strength, bending strength, and water absorption. There is a need for something that satisfies all qualities such as: The present invention provides a laminate that has improved many of the properties required of these laminates, and in particular has significantly improved punching workability and insulation resistance.

Normally, the punching workability of laminates requires sufficient flexibility without cracking or chipping at or near room temperature. Alkylphenols such as phenol, butylphenol, octylphenol, and/nylphenol are widely used, and drying oils modified with phenols such as linseed oil, tung oil, or cashew nut oil are also used as plasticizers. . However, the use of these plasticizers to improve die-cutting properties has the disadvantage of compromising other physical properties. In addition, insulation resistance, especially insulation resistance after boiling, is related to the water absorption of the resin and is important, but the addition of a key flame agent in flame-retardant grades may lead to a decrease in insulation resistance after boiling. There is now. In view of the above-mentioned circumstances, the inventors of the present invention have conducted extensive studies regarding the establishment of improved technology for phenolic resins for laminates, and have determined that the total amount of the phenolic component is Alternatively, the base material is impregnated with a resol-type phenolic resin obtained by heating an aldehydic component in the presence of an acid or basic catalyst, especially by using baggage oil in combination during the reaction. The present invention has been completed based on the discovery that the laminate obtained by heating the laminate is improved in many properties, particularly in punching workability and insulation resistance. Isoprobenylphenol used in the present invention is represented by the general formula (1), or its oligomer is represented by the general formula (0) or (m) (in formulas b and m, n is 0 to 18). (representing an integer), and in each of the above formulas, the hydroxyl group may be located at any of the ortho, meta, or para positions.

Monomers, dimers, and trimers can be synthesized as pure compounds, but oligomers of tetramer or higher coexist as a mixture. These monomers, dimers, or trimers may be used alone, or a mixture of oligomers may be used to achieve the same effect. Typical manufacturing methods for isoprobenylphenol and its oligomers are as follows:
It is a seed. {1) A method of cleaving diphenylolpropane in the presence of an acid or alkali catalyst.

By this method p-isoprobenylphenol and its oligomers are obtained.

Further, by heating the obtained p-isoprobenylphenol, a dimer, a trimer, or a mixture of these oligomers can be obtained. '21 A method for obtaining hydroquinone or resorcinol as a created product by oxidizing and further decomposing diisopropylbenzene.

{3' A method of producing by dehydrogenating propylphenol.

Isobrobenylphenol and/or oligomers thereof obtained by any of these three methods can be used in the present invention.

{1}1 When the diphenylolpropane shown above is used as a starting material, the raw material is generally a p-p' unit called bisphenol-A, but it is also possible to use the p-p' unit which exists as an isomer. Similarly obtained.

In each of these cases, the product is p-isoprobenylphenol and its oligomers. The phase produced during cleavage may be removed, or the mixture may be used as is. When using diisopropylbenzene as the starting material, it is obtained as a by-product. The main purpose is to produce hydroquinosol or resorcinol, but as side reactions, the creation of m- or p-isoprobenylphenol and the creation of m- or p-isoprobenylphenol are It cannot be avoided. These created organisms can also be used as they are in the present invention without being separated. In the method of dehydrogenating propylphenol in [3},
Although it is possible to obtain ortho, para, and meta isomers singly or as a mixture, propenylphenol is generally obtained as a mixture of isomers in the method of propylating phenol with propylene. Similar effects can be obtained when these are used in the present invention.

An example of a method for producing oligomers from isoprobenylphenol monomers is as follows.

P-isoprobenylphenol is heated to 12,500 ℃ for 1 hour, then cooled to 110 to 120 qO and gradually solidified. It's a yellow lump. Next, it is dissolved in toluene and recrystallized by a conventional method to obtain white crystals.
Yield is 70%. This crystal is a dimer represented by the following formula.

Alternatively, if p-isoprobenylphenol is dissolved in acetic acid (50%), a catalytic amount of 37% HCI is added to maintain the solution at pH=1, and the mixture is heated at 2500 for 1 hour, white crystals will precipitate. .

These crystals are recrystallized from ethanol water. The crystals thus obtained are trimers of p-isoprobenylphenol. Although the same effect can be obtained even if only the isoprobenyl phenol monomer and/or oligomer used in the present invention is used as the raw material for the phenolic component, it is preferable to use other phenolic compounds in combination depending on the purpose.

Other phenolic compounds include conventionally known phenols, cresols, xylenols, ethylphenol, propylphenol, butylphenol, aminophenol, octylphenol, /nylphenol, dodecylphenol, and other C, ~C2o alkyls. Alkylphenols having a group, also bisphenol-
A, phenolic compounds having an alkylphenol-like structure such as phenylphenol, cumylphenol, and styrenated phenol, and polyhydric phenols such as catechol and resorcinol can be used in combination. Furthermore, resol-type initial condensates obtained by reacting phenols and aldehydes can also be used in combination. Moreover, any mixture of these can also be used in combination. In order to achieve the excellent effects of the present invention when other phenolic compounds are used in combination, isoprobenylphenol or its oligomer must account for 2% by weight or more of the total phenolic component raw materials. It is necessary to occupy. As the aldehyde component used in the present invention, formaldehyde, paraformaldehyde, or other compounds that release formaldehyde upon heating can be used.

The present invention provides a modified phenolic resin for impregnating a laminate by combining and reacting the above-mentioned phenolic component, aldehydic component, and drying oil, or without using a drying oil, and impregnating a base material with the modified phenolic resin. This is a laminate obtained by stacking a desired number of base materials and bonding them under heat.

In producing the phenolic resin for impregnation used in the present invention,
As the drying oil used in combination during the reaction, drying oils having unsaturated double bonds such as tung oil and linseed oil are preferred.

When these drying oils are used together, these drying oils should be used during normal phenolic resin production, that is, when producing a modified phenolic resin by reacting the phenolic component and aldehydic component in the presence of a basic catalyst. Alternatively, the drying oil and the above-mentioned feral component may be reacted in advance in the presence of an acidic catalyst, and then reacted with the aldehyde component to form a resin. .

When a resol-type modified phenolic resin is obtained by reacting a phenolic component and an aldehyde component in the presence or absence of string oil, caustic alkali, ammonia,
Alternatively, it is preferable to use a basic catalyst such as amines and carry out the reaction in the coexistence of water or an organic solvent, and as the organic solvent, aliphatic alcohol, acetone, dioxane, etc. are used. The reaction temperature is usually 50 pm to 100 q0, and the reaction time is 1 to 1 vowel, usually 2 to 6 hours. The aldehydic component is used at a molar ratio of 0.3 to 2.0 with respect to the above-mentioned self-phenolic component charged in advance, but a range of 0.7 to 1.4 is usually preferred.
The amount of drying oil used can be varied over a wide range in order to impart the desired flexibility to the resulting cured resin product, but a range of 10 to 10% by weight based on the phenolic component is suitable. After the reaction, the catalyst is neutralized if necessary to obtain a resin layer. Furthermore, in order to obtain a resol type modified phenolic resin, phenol-bag oil cooking, which is commonly used as a method for producing phenolic resin for laminates, can be applied. For example, as described in Tokkan Sho 50 34341, the phenolic component and drying oil are reacted at a temperature of 50° C. to 100° C. in the presence of a strong acid such as sulfuric acid, hydrochloric acid, or para-toluenesulfonic acid; Next, the reaction product is cooled to room temperature to 50C0, the acid is neutralized, and an aldehydic component and a basic catalyst are added and reacted to obtain a resin layer. After dehydrating or removing solvent from the resin layer thus obtained under reduced pressure, alcohol, ketone, benzene, toluene,
A resol-type impregnating resin varnish is obtained by adding a solvent such as xylene, and a fibrous base material such as linter paper or kraft paper is impregnated with this to obtain an impregnated base material for a laminate. The base material is impregnated and dried so that the impregnated base material can contain 30 to 7% by weight of the resin on a dry basis, and the desired number of sheets are stacked, and the temperature is usually 130°C to 180°C and the pressure is 20°C. ~
A laminate is obtained by heating and curing under the molding conditions of 150k9/base. This will be explained below using examples.

Example 1 p-isoprobenylphenol 400 g, phenol 1
00 minutes, 427 hours of 37% formalin water, 16.8 hours of 30% methylamine water, and 2.4 hours of ethylenediamine were reacted for 3 hours and 30 minutes at 98 degrees to 10,000 degrees while stirring.

Water was removed under reduced pressure. A methanol solvent was added to obtain a varnish with a resin concentration of 60%. or more resin varnish to a thickness of 1
Impregnated with 0 mils linter paper, resin content 45% after drying
prepreg was obtained.

Nine sheets of this prepreg were stacked and laminated and molded (90k9/c style, 16000, 50 minutes) to obtain a laminate (thickness grade 1.6). In addition, separately from this, a copper-clad laminate (thickness 1.6 side) with 35 mm copper foil attached was also created. Example 2 P having a composition of 3% by weight of p-isoprobenylphenol, 85% by weight of dimer, 7% by weight of trimer, and 5% by weight of tetramer
-isop.

Benylphenol and its oligomer mixture 200 times, phenol 300 times, 37% formalin water 494 times,
The mixture was reacted for 3 hours at 980 to 10 and 0 while adding 19.4 hours of 30% methylamino water and 2.8 hours of ethylenediamine. Water was removed under reduced pressure, and when the content reached 9 to 960 g, the pressure was returned to normal pressure to complete dehydration. A methanol solvent was added to obtain a varnish with a resin concentration of 60%. Thereafter, a laminate was produced in the same manner as in Example 1. Example 3 p6 with a composition of 3% by weight of isoprobenylphenol, 85% by weight of dimer, 7% by weight of trimer, and 5% by weight of tetramer
- Isoprobenylphenol and its oligomer mixture 62.2 hours, phenol 308 hours, tung oil 130 hours, 3
7% formalin water 395 minutes, 25.0% ammonia water
o. 98 for 2 days and ethylenediamine 2.2 days.

The reaction was carried out at ~100q0 for 4 hours while keeping the lights on. Water was removed under reduced pressure. The obtained resin was dissolved in a mixed solvent of methanol and toluene (1:1) to obtain a varnish with a resin concentration of 60%. Thereafter, a laminate was produced in the same manner as in Example 1.

Example 4 p-Isoprobenylphenol 51.8 pm, phenol 225.5 pm, nonylphenol 92.9 pm, linseed oil 130 pm, 37% formalin water 338 pm, 25.0% ammonia water 8.7 pm and ethylenediamine 1.9 to 9
8.

The reaction was carried out for 4 hours and 30 minutes at a temperature of ~10,000.
Water was removed under reduced pressure. The obtained resin was dissolved in a mixed solvent of methanol and toluene (1:1) to give a resin concentration of 60%.
got the varnish. Thereafter, a laminate was produced in the same manner as in Example 1.

Example 5 p having a composition of 3% by weight p-isoprobenylphenol, 85% by weight dimer, 7% by weight trimer, and 5% by weight tetramer
- A mixture of isobrobenylphenol and its oligomer 62%, phenol 62%, tung oil 130% and 40% p
-Add 0.19 g of toluenesulfonic acid aqueous solution to 650 ml.
The reaction was carried out at ~70°C for 10 minutes.

Then, after neutralizing with 25% ammonia water, phenol 2
After 46 days, 395 minutes of 37% formalin water and 12.8 hours of 25% ammonia water were added, and the mixture was allowed to react for 5 hours at 9~looo. Remove water under reduced pressure until the contents are 900~95o
When the pressure reached 0, the pressure was returned to normal and dehydration was stopped.

The obtained resin was mixed with a mixed solvent of methanol and toluene (1:
1) to obtain a varnish with a resin concentration of 60%. below,
A laminate was produced in the same manner as in Example 1.

Comparative example 1 Phenol 500 hours, 37% formalin water 561 hours, 3
0% methylamine water 22.0% and ethylenediamine 3.
The reaction was carried out at 98°C to 100°C for 2 hours and 30 minutes while holding a rope for 2 nights.

Water was removed under reduced pressure and then methanol solvent was added to obtain a varnish with a resin concentration of 60%. Thereafter, a laminate was produced as a trial by the same operation as in Example 1. Comparative Example 2 370 hours of phenol, 130 hours of tung oil, 416 hours of 37% formalin water, 10.7 hours of 25.0% ammonia water, and 2.4 hours of ethylenediamine were reacted for 3 hours and 30 minutes at 9 to 10 degrees while holding a candle. I let it happen.

Next, water was removed under reduced pressure, and the resulting resin was dissolved in a mixed solvent of methanol and toluene (1:1) to a resin concentration of 6.
A 0% varnish was obtained. Thereafter, a laminate was produced in the same manner as in Example 1.

Comparative Example 3 Phenol 262 days, nonylphenol 108 days, linseed oil 130 days, 37% formalin water 346 days, 25.0
Aqueous ammonia (8.9%) and ethylenediamine (2.0%) were reacted for 4 hours and 30 minutes at a temperature of 980-10%.

Next, water was removed, and the resulting resin was dissolved in a mixed solvent of methanol and toluene (1:1) to obtain a varnish with a resin concentration of 60%. Thereafter, a laminate was produced in the same manner as in Example 1.

Comparative Example 4 124 parts of phenol, 130 parts of tung oil and 0.19 parts of 40% p-toluenesulfonic acid were added and reacted at 650 to 70 qo for 10 minutes.

Next, after neutralizing with 25% aqueous ammonia, 246 ml of phenol, 395 ml of 37% formalin water, and 12.8 ml of 25% aqueous ammonia were added to give 98 ml. The reaction was carried out at ~100oo for 5 hours. Water was removed under reduced pressure, and the resulting resin was dissolved in a mixed solvent of methanol and toluene (1:1) to obtain a varnish with a resin concentration of 60%.

A laminate was produced in the same manner as in Example 1.

Physical property tests were conducted on the laminates obtained in the above Examples and Comparative Examples, and the results shown in Table 1 were obtained. Meanwhile, the method of the above characteristic test was as follows.

・{1} Water absorption, insulation resistance, volume resistivity, soldering heat resistance, trickle cleaning resistance, and bending strength are in accordance with JISC64
81.

'2} Punching workability was in accordance with ASTM D-614-44.

・Table-1

Claims (1)

[Scope of Claims] 1 (a) Isopropenylphenol and/or an oligomer of isopropenylphenol (b) An impregnated base material impregnated with a modified phenolic resin obtained by reaction with formaldehyde and/or a compound that generates formaldehyde. Laminated board with multiple layers bonded by heat and pressure. 2 (a) Isopropenylphenol and/or oligomers of isopropenylphenol (b) Formaldehyde and/or compounds that generate formaldehyde (
c) A laminate made of multiple layers of impregnated base material impregnated with a modified phenolic resin obtained by reaction with drying oil and bonded by thermocompression.