JPS6121122A - Preparation of oil-modified phenol formaldehyde resin for laminated board - Google Patents

Abstract

PURPOSE:To obtain the titled resin giving a laminated board having excellent heat-resistance, solvent-resistance and punchability and useful as an electronic material, etc., by reacting a phenolic compound and formaldehyde to the addition reaction product of tung oil and catechol having a specific structure. CONSTITUTION:The objective resin can be produced by reacting (A) the addition reaction product of tung oil and catechol and having the structure of formula I (one of -X- is formula II or III, and the other two -O- groups are formula II-IV) with (B) a phenolic compound, (C) formaldehyde and (D) a resol condensation catalyst (e.g. ammonia), preferably at 50-120 deg.C for 2-15hr. The amount of the component B is e.g. 0.5-9pts.wt. per 1pt.wt. of tung oil, and the amounts of the components C and D are e.g. 1.0-2.0mol and 0.01-0.5mol per 1mol of the component B, respectively. The component A can be prepared by reacting 1mol of catechol with e.g. 0.005-0.1mol of tung oil in a solvent such as methanol, in the presence of an acid catalyst (e.g. p-toluenesulfonic acid).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing an oil-modified phenol-formaldehyde resin for laminates.

[Conventional technology]

Recently, phenolic resin laminates or copper-clad horizontal laminates for electronic materials are required to have excellent punching properties at room temperature or relatively low temperatures near room temperature, from the perspective of automating processing equipment and saving labor. .

For this purpose, phenol formaldehyde resin compositions modified with drying oil, particularly tung oil, are used.

However, since the reaction rate of phenol added to tung oil etc. with formaldehyde is slower than that of phenol, a part of the tung oil-phenol addition reaction product tends to remain unreacted during the resolization reaction and curing reaction (heat resistance, solvent resistance,
Properties such as dimensional stability deteriorate. Furthermore, during punching, the unreacted tung oil-)2-nyl addition reaction product lowers the resin crosslinking density, which tends to cause interlayer separation and a decrease in mechanical strength. A common method for producing an unreacted tung oil-phenol addition reaction product is to add phenols to tung oil to increase the active sites for reaction with formaldehyde. However, even with this method, the reaction does not occur. Since plasticizers with few active sites cannot be completely eliminated, dramatic improvements in properties cannot be expected.

[Problem that the invention seeks to solve]

The present invention was made in order to improve the various drawbacks mentioned above, and by modifying phenol formaldehyde resin using a new substance, a laminate with excellent heat resistance, solvent resistance, and punching workability is produced. The aim is to obtain a resin for use in laminates.

[Means for solving problems]

Invention 1 CH2COO(CH2)7 X (CH2)+1
CHsCH-COO(CH2)7X-(CH2)
a CH3CH2-C00(CH2)7-X (CH
2) An addition reaction product of tung oil and catechol represented by the chemical formula sCHs is reacted with phenols and formaldehyde.

CH2Co0(CHz)7X (CH2)3 CHs of the present invention
CH-COO(CH2)7X(CH2)3CH
3CI(z C,00(CHII)7
The plasticizer represented by the chemical formula Hz)s CHa can be obtained by adding tung oil to catechol dissolved in a reaction bath and reacting it under an acid catalyst.

Reaction bath agents include methyl alcohol, FK alcohol, propyl alcohol, acetone, methyl ethyl ketone, benzene, toluene, xylene, cyclohexanone,
Organic solvents such as dioxane are used.

As the acid catalyst, acids such as sulfuric acid, phosphoric acid, p-toluenesulfonic acid, and hydrofluoric acid, and Lewis acids such as aluminum chloride and zinc chloride can be used alone or in combination.

Catechol is dissolved in a reaction solvent such as methyl alcohol in an amount of 15 to 2 times its weight, and then 0.0% per mole of catechol/'io """'/0.0% per mole of tung oil per 200 moles of tung oil.
05-2'! jk,% of an acid catalyst such as para-toluenesulfonic acid is added, and the mixture is reacted at 60 to 100°C for 2 to 20 hours.

Since the obtained reaction product is a mixture of the tung oil-catechol addition reaction product and unreacted catechol, the reaction solvent is distilled off under reduced pressure and then washed several times with distilled water to remove unreacted catechol. The water is then removed by vacuum drying to produce oily tung oil.
A catechol addition reaction product is obtained.

The structure of this addition reactant was determined by liquid chromatography, nuclear magnetic resonance, and infrared absorption instrumental analysis.

Since this tung oil-catechol addition reaction product has high reactivity with formaldehyde, it can be used as a reactive plasticizer rather than performing a resolization reaction together with ordinary phenols.

Tung oil-catechol addition reaction product is 1/1 to tung oil! ~9
1.0 to 2.0 times the weight of phenols and phenols
Formaldehyde is added in an amount of 0.01 to 0.5 times the mole of the phenol, and a resolization catalyst is added in an amount of 0.01 to 0.5 times the amount of the phenol to react.

As the phenols, commonly used phenols such as phenol, cresol 6-ol, ethylphenol, flobylphenol, butylphenol, octylphenol, and nonylphenol are used.

As the formaldehyde source, paraform, formalin, etc. are used alone or in combination.

As the resolization catalyst, amines such as ammonia, monomethylamine, dimethylamine, trimethylamine, triethylamine, and ethylenediamine, and alkalis such as sodium hydroxide, potassium hydroxide, and magnesium hydroxide are used alone or in combination.

Although the reaction conditions are not particularly specified, 50
Preferably, the reaction is carried out at ~120°C for 2 to 15 hours.

The addition reaction product of catechol and tung oil, which is used as a plasticizer without invention, is an addition reaction product of catechol and tung oil, which has high reactivity with formaldehyde among phenols, and has excellent heat resistance, solvent resistance, dimensional stability, and mechanical strength. The decline in is suppressed.

Moreover, since the amount of catechol added to tung oil is relatively small at 2 moles, there are few crosslinking points between the tung oil plasticizer and the phenolic resin, which impairs the plasticizing effect and improves the punching workability at low temperatures.

The present invention will be explained in more detail with reference to examples 1.
-ru.

〔Example〕

Example 1 Catechol 600g, paratoluenesulfone [0.2g
, 250g of methyl alcohol are mixed and heated to 60°C to form catechol. 120 g of tung oil was added to this mixture, and the reaction was carried out at 80° C. for 5 hours. Since the obtained reaction product was a mixture of the tung oil-catechol reaction product and unreacted catechol, it was washed several times with distilled water to remove unreacted catechol. Next, add acetone and water mixture (mixing ratio 5/1~
1/2) several times to remove heavy metals from tung oil.

Next, acetone and water were distilled off by drying under reduced pressure to obtain a tung oil-catechol addition reaction product.

The results of liquid chromatography, nuclear magnetic resonance, and infrared spectroscopy measurements of the compound thus obtained are shown in FIGS. 1, 2, and 3. Fourth
The figure is a liquid chromatography chart of the decomposed product obtained by ester decomposition of this compound with methyl alcohol.

The explanation about the symbols is as follows.

1 Catechol peak 2 Tung oil peak 6 Tung oil -
Peak 4 of catechol addition reaction product Nuclear magnetic resonance chart of tung oil-catechol addition reaction product 5 Nuclear magnetic resonance chart of acetylated tung oil-catechol addition reaction product 6 Signal of -OH proton of catechol 7 Signal of catechol 10COCH, proton 8 Tung oil-
CHa proton signal 9 Tetramethylsilane signal 10 Infrared absorption spectrum of tung oil 11 Infrared absorption spectrum of tung oil-catechol addition reaction product = 9- 12 Peak due to double bond of tung oil 13 Absorption due to benzene ring hydrogen 14 Eleostearin Peak 15 of methyl acid A peak of the adduct of methyl eleostearate and 1 mole of catechol From the liquid chromatography chart in Figure 1, it was found that this was a single peak and the molecular weight was about 1100. Also,
The molecular weight of this compound was measured by vapor pressure equilibrium method and was found to be 1090. The theoretical molecule when 2 moles of catechol (molecular weight 110) reacted with tung oil (molecular weight 872) [10
92 (good agreement). This compound was also acetylated by a conventional method and the nuclear magnetic resonance before and after acetylation was compared.
Figure 2) Phenolic -OH was observed before acetylation, but after acetylation, the -OH group signal disappeared and a new 10COCR3 proton signal was generated, which caused the -OH group to interact with tung oil. It was confirmed that it was not involved in the reaction. Furthermore, the proton of the methyl group of tung oil (tung oil 1
The integral ratio of the protons of the -0CCR3 group of catechol ~10- after acetylation (there are 6 in catechol) is 3:4, and 2 moles of catechol are added to 1 mole of tung oil. It was confirmed that Furthermore, infrared spectroscopy revealed that the number of conjugated double bonds in tung oil had been reduced to 74, and that substitution had occurred in the catechol ring. In addition, when this compound was decomposed into esters in methyl alcohol in the presence of IJ and analyzed by liquid chromatography, a peak of eleostearic acid and a peak of an addition reaction product of 1 mole of catechol to eleostearic acid were detected. was confirmed. (Figure 4) From the above analysis results, it was confirmed that the structure of the compound obtained here is as follows.

Note that the measurement conditions for liquid chromatography, nuclear magnetic resonance, and infrared absorption are as follows.

Liquid chromatography: using Toyo Soda HLC-801 model, 6
The measurement was carried out using a column arrangement of two 3000 columns and four G20 00 columns using tetrahydrofuran as the mobile phase. The sample concentration was 2% and the measurement was performed at a flow rate of 1.5 ml/m.

Nuclear magnetic resonance: Measurement was carried out using a Hitachi NR-24 model using deuterated chloroform as a solvent at a sample concentration of 30%, a sweep rate of 2 Hz/sec, and tetramethylsilane as a standard spectrometer.

Infrared spectroscopy: Measured by coating method using Hitachi Model 285.

200 g of this compound, 210 g of phenol.

80% paraform 150g, 25% ammonia water 33g
was placed in a flask and reacted at 70° C. for 5 hours with stirring.

The gelation time of the reaction product was 183 seconds on a 160°C hot plate. Acetone was added to this to make the resin content 52%.

Example 2 Catechol 700g, para-toluenesulfonic acid 0.37
g and 250 g of isopropyl alcohol were mixed and heated to 60°C to dissolve catechol. Add 37% of tung oil to this mixture.
g was added thereto, and the reaction was carried out at 80° C. for 16 hours. After removing propyl alcohol from the reaction solution under reduced pressure, it is washed several times with steamed water to remove unreacted catechol. Next, water was removed by vacuum drying to obtain an oily tung oil-catechol addition reaction product. The main product of this addition reaction product was isolated by a fractional dissolution method using a mixed solvent of acetone and water (mixing ratio 1/4 to 1/1).

The results of liquid chromatography, nuclear magnetic resonance, and infrared spectroscopy of the compound thus obtained are shown in FIGS. 5, 6, and 7. 8th
The figure is a liquid chromatography chart of the decomposed product obtained by ester decomposition of this compound with methyl alcohol.

The explanation about the symbols is as follows.

16 Tung oil-catechol addition reaction product peak 17 Tung oil-
Nuclear magnetic resonance chart of catechol addition reaction product 18 Nuclear magnetic resonance chart of acetylated tung oil-catechol addition reaction product 19 Catechol-OH proton signal 20
Catechol 10COCI1. proton signal 21
Signal 22 of -CH5 proton of tung oil Signal 23 of tetramethylsilane Absorption due to double bond of tung oil 24 Absorption due to benzene ring hydrogen 25 Peak of adduct of methyl eleostearate and 2 moles of catechol From the liquid chromatography chart in Figure 5, It was found that the molecular weight was about 1,500 since it was one peak. In addition, the molecular weight of this compound was measured using a vapor pressure equilibrium molecular weight measuring device and was found to be 1510, compared to tung oil (molecular weight 872).
It was in good agreement with the theoretical molecule -15-1532 when 6 moles of catechol (molecular weight 110) were reacted with. Next, this product was acetylated by a conventional method, and the nuclear magnetic resonance before and after acetylation was compared. (Figure 6) As in Example 1, after acetylation, the -OH signal disappears and a new 1000 CH
3 proton signals were observed.

Furthermore, the integral ratio of -CH3 protons of tung oil (9 protons exist in 1 mole of tung oil) and protons of 10COCH3 of catechol after acetylation (6 protons exist in 1 mole of acetylated catechol) is 1/4, and tung oil 1 It was confirmed that 6 moles of catechol were added per mole.

In addition, infrared spectroscopy shows that the conjugated 2M bonds in tung oil are about 1/2% after the reaction.
It was found that substitution had occurred in the catechol nucleus. Furthermore, when this compound was deesterified in methyl alcohol in the presence of sodium hydroxide and the decomposed products were analyzed by liquid chromatography, only the peak of the addition reaction product, in which 2 moles of catechol was added to methyl eleostearate, was detected. . (FIG. 8) From the analysis results shown below, it was confirmed that the structure of the compound obtained here was as follows.

267 g of the obtained addition reaction product, 143 g of phenol,
80% paraform 150g, 25% ammonia water 33g
was placed in a flask and reacted at 70° C. for 5 hours with stirring. The gelation time of the reaction product was 129 seconds on a 160°C hot plate.

Acetone was added to this to make the fat content 52%.

Comparative Example 160 g of tung oil, 192 g of metacresol, 0.1 g of para-toluenesulfonic acid were mixed and reacted at 1109C for 1 hour. The obtained reaction product is a tung oil-metacresol adduct;
It was confirmed that the reaction product was a mixture of tung oil polymer and unreacted metacresol, with an average of 64 moles of metacresol added to 1 mole of tung oil (Figure 2).
To this reaction product, 58 g of phenol and 15 g of 80% paraform were added.
0 g and 33 g of 25% ammonia water were added thereto, and the mixture was reacted at 70° C. for 7 hours with stirring. Gelation time of reaction product is 160℃
It was 170 seconds on a hot plate. Acetone was added to this to make the resin content 52%.

Synthesis of Shimoori varnish (water-soluble phenolic resin) 400 g of phenol, 800 g of 37% formalin and 5 g of magnesium hydroxide were reacted at 55°C for 8 hours, and after dehydration under reduced pressure, methanol was added to reduce the resin content to 15% (Fl).
I arranged it.

A resin-impregnated paper was produced by impregnating cotton linter paper with the above-mentioned undercoat resin and drying to adjust the resin content to 15%.

This resin-impregnated paper was further impregnated with the varnishes of Examples and Comparative Examples, dried, and adjusted to a resin content of 50% to produce resin-impregnated paper.

Eight sheets of the resin-impregnated paper and one sheet of copper foil coated with adhesive were stacked at 17° and pressed together at 160° C. and 1 kg rad for 50 minutes to obtain a copper-clad laminate with a thickness of 1.6 mm.

Various properties of this copper-clad laminate are shown in the table for comparison.

As described above, the laminate produced using the tung oil-catechol addition reaction product of the present invention has excellent heat resistance and solvent resistance, and good dimensional stability. Furthermore, it has excellent machinability and does not crack or bulge at room temperature (it can be punched), and has significant characteristics compared to conventional laminating machines.

[Brief explanation of drawings]

FIG. 1 is a liquid chromatography chart of the tung oil-catechol addition reaction product of Example 1, the raw material catechol, and tung oil, and the horizontal axis indicates the molecular weight. The molecular weight scale is determined by determining the relationship between the elution area (count number) and the molecular weight from liquid chromatography charts of various standard substances known for molecule 1. FIG. 2 is a nuclear magnetic resonance measurement chart of the tung oil-catechol addition reaction product of Example 1 and the tung oil-catechol addition reaction product acetylated by a conventional method. FIG. 5 is an infrared spectroscopy chart of tung oil and the tung oil-catechol addition reaction product of Example 1. FIG. 4 is an oil body chromatography chart of the decomposed product obtained by ester decomposition of the tung oil-tecol addition reaction product of Example 1 with methyl alcohol. FIG. 5 is a liquid chromatography chart of the tung oil-catechol addition reaction product of Example 2. FIG. 6 is a nuclear magnetic resonance measurement chart of the tung oil-catechol addition reaction product and the acetylated tung oil-catechol addition reaction product of Example 2. FIG. 7 is an infrared spectroscopic measurement chart of the oil-catechol addition reaction product of Example 20. FIG. 8 is a liquid chromatography chart of the decomposed product obtained by ester decomposing the tung oil-catechol addition reaction product of Example 2 with methyl alcohol. Figure 9 shows the liquid chromatography of the addition reaction product of Comparative Example 1.
It is. =21-

Claims (1)

[Claims] 1. ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [However, one of the three (-X-) is (A) or (B) of the following formula, and the other two are ( Selected from A), (B), and (C) in combination or in combination. (A) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (B) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (C) Tung oil, which is represented by the chemical formula -CH=CH-CH=CH-CH=CH-] A method for producing an oil-modified phenol/formaldehyde resin for laminates, which comprises reacting an addition reaction product of catechol, phenols, and formaldehyde.