JPH04358826A - Phenol resin laminated sheet and manufacture thereof - Google Patents

Abstract

PURPOSE:To obtain a tough phenol resin laminated sheet with excellent punchability, water resistance, electric characteristics and mechanical characteristics by manufacturing a laminated sheet with a resol-type modified phenol resin obtd. by reacting a reaction product of one of phenols and a linear compd. of a specified formula with formaldehyde and a base material. CONSTITUTION:In a laminated sheet consisting of a resin ingredient and a base material, the resin ingredient is a resol-type modified phenol resin obtd. by reacting a reaction product of one of phenols and a linear compd. of formula I (wherein n is an integer of 3-16; R is a hydrogen atom or a methyl group) having an unsatd. group and an aldehyde group at the molecular terminals at a ratio of 0.1-0.5 mole of the linear compd. per 1 mole of hydroxyl group of the phenol with formaldehyde. The base material is impregnated with this resol-type modified phenol resin, dried, laminated and heat-pressed to obtain a laminated sheet.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention is a resol-type modified product obtained by reacting formaldehyde with a reaction product of a linear compound having one unsaturated group and one aldehyde group at the end of the molecule and phenol. This article relates to a phenolic resin laminate consisting of a phenolic resin composition and a base material, and a method for producing the same, and further relates to a phenolic resin laminate suitable for printed wiring boards with excellent punching workability, moisture resistance, electrical properties, and mechanical properties. The present invention relates to a plate and a method for manufacturing the same.

0002

[Prior art] Phenolic resin has heat resistance, electrical properties,
It has excellent mechanical properties and is used in laminates for printed wiring boards. However, since phenolic resins generally have the disadvantage of being hard and brittle, when used in laminates, they have the disadvantage of poor punching workability. As a method for improving this drawback, a method is known in which a flexible phenolic resin modified with vegetable oils such as tung oil, dehydrated castor oil, cashew nut kernel oil, urushiols, or alkylphenols is used. However, as printed wiring boards have recently become more dense, there has been a need for laminates with better punching workability and toughness, and conventional methods have the disadvantage of lacking these properties.

0003

[Problems to be Solved by the Invention] The present invention was made with the aim of obtaining a phenolic resin laminate with punching workability and toughness that cannot be obtained by conventional methods.
A laminate consisting of a base material and a resol-type modified phenolic resin obtained by reacting formaldehyde with a reaction product of phenol and a linear compound having 1 unsaturated group and 1 aldehyde group has excellent punching workability and toughness. Based on this knowledge, we conducted various studies and completed the present invention. The purpose is to provide an extremely tough phenolic resin laminate with excellent punching workability, water resistance, electrical properties, and mechanical properties, and a method for producing the same.

0004

[Means for Solving the Problems] The present invention provides a laminate consisting of a resin component and a base material, in which the resin component has phenols and one unsaturated group and one unsaturated group at the end of the molecule represented by the general formula (1). 0.1 to 0.5 of the linear compound per mole of hydroxyl group of the phenol with a linear compound having an aldehyde group of
The present invention relates to a phenol resin laminate, characterized in that it is a resol type modified phenol resin obtained by reacting a molar amount of a reactant with formaldehyde, and a method for producing the same.

Examples of the linear compound having one unsaturated group and one aldehyde group at the molecular end represented by the general formula (1) used in the present invention include 5-heptanal, 6-heptanal, and 9-heptanal. -Methyl-8-nonenal, 10-undecenal, 14-pentadecenal, etc. can be mentioned.

The phenols used in the present invention include phenol, cresol, xylenol, pt-butylphenol, bisphenol A, and resorcinol.
1 of valent and divalent phenols and their substituted products
Phenols containing 50 mol% or more of at least trifunctional or higher functional phenols are used. Preferred phenols are phenol and cresol.

[0007] The formaldehydes used in the present invention include formalin and paraformaldehyde.

An example of the chemical structure of the resol-type modified phenol resin composition of the present invention is shown by general formula (2).

[0009]

[Case 2]

General formula (2) is a linear compound having one unsaturated group and one aldehyde group at the end of the molecule.
phenols are linked, a part of the phenol nucleus is methylolated with formaldehyde, and it is also bonded to other phenol nuclei through methylene bonds, and further bonded to other phenol nuclei through linear compounds. represents. That is, ortho, meta,
The unsaturated group of the linear compound and the aldehyde group bond to the reactive position at the para position, and formaldehyde reacts with the reactive positions at the ortho, meta, and para positions on the nucleus of the phenol to form a methylol group and a methylene bond. do. Curing of the resin proceeds by the formation of methylene bonds through a condensation reaction between methylol groups and reactive sites on the phenol nucleus.

As can be seen from the structural example of general formula (2),
A linear hydrocarbon group that plays a role in imparting flexibility is present in the main chain of the phenolic resin. This resin structure is considered to be the reason why the phenolic resin laminate of the present invention has excellent punching workability and toughness. For this reason,
In the reaction between a phenol and a linear compound having one unsaturated group and one aldehyde group at the end of the molecule, it is an essential condition in the present invention that the reaction is sufficiently completed. If the reaction is insufficient, there will be many pendant-shaped compounds in which only one side of the linear compound is bonded to the phenol nucleus, resulting in a brittle resin, which will affect the punching workability and toughness of laminates using this. This is because the quality is significantly inferior.

In the present invention, the phenol and the linear compound having one unsaturated group and one aldehyde group at the end of the molecule are defined as 0.1 to 0.0% of the linear compound per mole of hydroxyl group of phenol. The reaction is carried out at a ratio of 5 moles. This is because if the amount of the linear compound is too small, the flexibility effect will be insufficient, whereas if it is too large, the resin will polymerize and gel.

Catalysts used in the reaction of phenols and linear compounds in the present invention include para-toluenesulfonic acid, methanesulfonic acid, boron trifluoride, tin chloride, ferric chloride and the like. Examples include acidic catalysts such as Friedel-Crafts type catalysts. The amount of the catalyst used is not particularly limited, but is preferably 0.01 to 2% by weight based on the total amount of phenols and linear compounds. Further, the reaction is preferably carried out at a temperature of 80 to 160°C. If necessary, the reaction may be carried out in a solvent such as toluene.

The proportion of formaldehyde reacted with the reaction product of phenol and linear compound is in the range of 0.5 to 2.0 moles of formaldehyde per mole of hydroxyl group of phenol. Catalysts used in this reaction include basic catalysts such as ammonia, triethylamine, ethylenediamine, hexamethylenetetramine, triethanolamine, barium hydroxide, and the like. The reaction is preferably carried out in a solvent such as toluene at a temperature of 80-100°C.

[0015] In the present invention, after reacting phenols and linear compounds under an acidic catalyst, part or most of the unreacted phenols are removed, and then reacting with formaldehydes under a basic catalyst. A more preferable resol type modified phenol resin can be obtained by this method. Since linear compounds are trifunctional compounds, for example, when phenol and 6-heptanal are reacted, the molar ratio of 6-heptanal/phenol is 0.26 or more, 6-
If the modification rate expressed by heptanal/(phenol + 6-heptanal) is 20% by weight or more, gelation will occur, so 2
It is difficult to obtain a resin with a modification rate of 0% or more. In such cases, phenols and linear compounds are reacted under an acidic catalyst, some or most of the unreacted phenols are removed to achieve a desired modification rate, and then formaldehyde is reacted under a basic catalyst. A more preferable resol-type modified phenol resin can be obtained by reacting with.

The substrate used in the present invention may be paper containing cellulose as a main component, glass cloth, glass nonwoven fabric, synthetic fiber cloth such as polyester fiber cloth or aramid fiber cloth, or canvas. In the case of paper materials whose main component is cellulose, such as kraft paper and linter paper, those that have been treated with resin in advance can also be used.
For example, a resin treated with a water-soluble low molecular weight phenol resin containing a large amount of mononuclear methylol obtained by reacting phenol, cresol, etc. with formaldehyde at a relatively low temperature in the presence of a tertiary amine is used.

[0017] The laminate of the present invention is obtained by impregnating a base material with a solution of the resol-type modified phenolic resin, drying it, stacking 3 to 10 sheets, heating and pressurizing, and curing the resin to form a plate-like body. It can be obtained by The amount of resin to be impregnated is 30 to 70% by weight on a dry basis based on the total amount of resin and base material. The heating and pressurizing conditions are a temperature of 120 to 180° C. and a pressure of 50 to 150 kg/cm 2 .

In the present invention, other phenolic resins can be appropriately used in combination with up to 50% by weight of the total resin as the resin to be impregnated into the base material.

[0019]

EXAMPLES The present invention will be illustrated by the following examples.

(Example 1) 1400 g of phenol, 600 g of 14-pentadecenal and 20 g of p-toluenesulfonic acid were placed in a 5 liter flask equipped with a stirrer and reacted at 120° C. for 6 hours. This intermediate product had a viscosity of 270 mmPa·s/25° C., an unreacted phenol content of 36.1% by weight, and an average molecular weight of 216 by vapor pressure method. The remaining double bond and remaining aldehyde group of 14-pentadecenal were not observed in the infrared absorption spectrum and nuclear magnetic resonance spectrum, indicating that the reaction was complete.

[0021] Next, 800 g of toluene and 20 g of triethanolamine were added to dilute and neutralize, and then 500 g of paraformaldehyde and 30 g of 25% ammonia aqueous solution were added, reacted at 90 to 100°C for 4 hours, and then heated under reduced pressure. Below, dehydration and toluene removal were performed to obtain toluene 10
00g and 1000g of methanol were added to dilute the solution to obtain a solution (A) of 14-pentadecenal modified resol type phenolic resin having a resin content of 52% by weight. In addition, 1000 g of phenol, 9800 g of 37% formalin, and 20 g of triethylamine were mixed and reacted at 60°C for 2 hours, then concentrated under reduced pressure, and mixed with methanol/water = 80/20.
A water-soluble low molecular weight phenol resin solution (B) having a resin content of 50% by weight was obtained by diluting with a mixed solvent.

Kraft paper was impregnated with the resin solution (B) and dried to obtain a treated substrate having a resin content of 10.5%. Next, this treated base material was impregnated with the resin solution (A) and dried to obtain a prepreg with a total resin content of 56%. Laminated 8 sheets of this, overlapped 35μm copper foil on one side, 160℃, 80-90k
The mixture was heated and pressed at g/cm2 for 60 minutes to obtain a phenolic resin laminate having a thickness of 1.6 mm.

(Example 2) In a 5 liter flask with a stirrer, 1600 g of phenol and 10-undecenal 4 were added.
00g and 20g of para-toluenesulfonic acid were charged and reacted at 120°C for 6 hours. The viscosity of this intermediate product is 195 mmPa・s/25°C, and the unreacted phenol content is 4
8.7% by weight, and the average molecular weight by vapor pressure method was 166.Residual double bonds and residual aldehyde groups of 10-undecanal were not observed in infrared absorption spectra and nuclear magnetic resonance spectra, indicating that the reaction was complete. .

Next, unreacted phenol was removed while heating under reduced pressure until the residual phenol content became 15% by weight. After diluting and neutralizing by adding 700 g of toluene and 20 g of triethanolamine, 400 g of paraformaldehyde and 25 g of a 25 g ammonia aqueous solution were added, and the mixture was reacted at 90 to 100°C for 4 hours, followed by dehydration and dehydration under reduced pressure. Perform toluene and mix 1/1 of toluene and methanol.
Diluted by adding a mixed solvent of 1 to give a resin content of 52% by weight.
A solution (C) of a 10-undecenal-modified resol type phenol resin was obtained.

Next, the treated base material obtained in the same manner as in Example 1 was impregnated with the resin solution (C) and dried in the same manner as in Example 1. A laminate was obtained.

(Comparative Example 1) A 5-liter flask equipped with a stirrer was charged with 1200 g of phenol, 800 g of tung oil, and 5 g of p-toluenesulfonic acid, and reacted at 80° C. for 3 hours. Next, 800 g of toluene and 20 g of triethanolamine were added to dilute and neutralize, and then 500 g of paraformaldehyde and 30 g of a 25% ammonia aqueous solution were added and reacted at 90 to 100°C for 4 hours, followed by dehydration under reduced pressure. Then, toluene was removed, and 1,000 g of toluene and 1,000 g of methanol were added to dilute the solution to obtain a tung oil-modified resol type phenol resin solution (D) with a resin content of 50% by weight.

Next, the treated base material obtained in the same manner as in Example 1 was impregnated with the resin solution (D) and dried, and then in the same manner as in Example 1, a 1.6 mm thick phenol resin was impregnated with the resin solution (D). A laminate was obtained.

(Comparative Example 2) 1200 g of cresol (a mixture of 60% m-cresol and 40% p-cresol) and 50% formalin were placed in a 5 liter flask equipped with a stirrer.
50g, prepare 40g of 25% ammonia, 90~10
React at 0°C for 3 hours, then dehydrate under reduced pressure, dilute by adding 600 g of toluene and 600 g of methanol to obtain a resol type phenol resin solution (E) with a resin content of 51% by weight.
I got it.

Next, the treated base material obtained in Example 1 was impregnated with the resin solution (E) and dried in the same manner as in Example 1, and a 1.6 mm thick phenolic resin laminate was formed in the same manner. Obtained.

Table 1 shows the properties of the resins obtained in Examples 1 and 2 and Comparative Examples 1 and 2. The gelation time in Table 1 is 150℃
It represents the gel time on a hot plate. The cured product torque indicates the torque after 3 hours at 150° C. using a Curelastometer manufactured by Orientech (JSR Curelastometer Model IIIS, SRIS3105 die B type). As the resin hardens, the torque increases and reaches a constant value. The value after 3 hours is this constant value. The smaller the torque, the more flexible the cured product is. Table 2 shows the characteristics of the laminates obtained in Examples 1 and 2 and Comparative Examples 1 and 2. The deflection in Table 2 represents the amount of deflection deformation of the laminate until it breaks during bending strength measurement.
The larger the deflection, the stronger the laminate. The laminates obtained in Examples 1 and 2 were used in Comparative Examples 1 and 2.
It can be seen that the punching workability, toughness, water/moisture resistance, and electrical properties are superior to the laminate obtained in the above.

[0031]

[Table 1]

[0032]

[Table 2]

[0033]

[Effects of the Invention] The phenolic resin laminate of the present invention has excellent punching workability, water resistance, electrical properties, and mechanical properties, and can be suitably used for printed wiring boards. The reason why the phenolic resin laminate of the present invention has excellent punching workability, water resistance, electrical properties, and mechanical properties that could not be obtained by conventional methods is not fully clear, but the present invention This is thought to be because the phenol cores of the modified phenol resin used are bonded by flexible linear saturated hydrocarbon main chains.

Claims (3)

[Claims] Claim 1: A laminate consisting of a resin component and a base material, wherein the resin component is a phenol and a straight chain having one unsaturated group and one aldehyde group at the molecular end represented by the general formula (1). Linear compound 0 per mole of hydroxyl group of phenol with [Chemical formula 1]
．． A phenol resin laminate, characterized in that it is a resol type modified phenol resin prepared by reacting a reactant with formaldehyde in a proportion of 1 to 0.5 mole. [Claim 2] A linear compound per mole of hydroxyl group of the phenol consisting of a phenol and a linear compound having one unsaturated group and one aldehyde group at the end of the molecule represented by the general formula (1). A base material is impregnated with a resol type modified phenolic resin obtained by reacting the compound at a ratio of 0.1 to 0.5 mole under an acidic catalyst and then reacting with formaldehyde under a basic catalyst, and dried. A method for producing a phenolic resin laminate, which is obtained by laminating layers and heating and pressurizing them. [Claim 3] After reacting phenols and linear compounds under an acidic catalyst, removing a part or most of the unreacted phenols, and then reacting with formaldehydes under a basic catalyst. The method for producing a phenolic resin laminate according to claim 2.