CN1068361C - Drying oil-modified phenolic resin composition for laminate, and phenolic resin laminate using the drying oil-modified phenolic resin composition - Google Patents

Abstract

The present invention provides a phenolic resin laminated board with good moisture resistance, punching processability and flame retardance. A drying oil-modified phenol resin composition for a laminate, which comprises a drying oil-modified phenol resin obtained by reacting a drying oil, a phenol and formaldehyde as the main components, wherein the phenol is a cresol mixture of phenol, m-cresol and p-cresol, the molar ratio of phenol to the cresol mixture is 9: 1 to 5: 5, the drying oil-modified phenol resin is a drying oil-modified phenol resin composition for a laminate obtained by reacting a drying oil with the phenol and formaldehyde in the presence of an alkaline catalyst, a paper base material is impregnated with a melamine resin-modified water-soluble phenol resin, and the mixture is dried to prepare a prepreg, and a plurality of sheets of the prepreg are stacked, and the prepreg is heated and pressurized together with or without a copper foil to form a phenol resin laminate.

Description

Drying oil-modified phenolic resin composition for laminate, and phenolic resin laminate using the drying oil-modified phenolic resin composition

The present invention relates to a drying oil-modified phenolic resin composition for laminates and a phenolic resin laminate made using the drying oil-modified phenolic resin composition for laminates.

Paper-based phenolic resin laminates have good processability, so they are mostly used for punching. Phenolic resins synthesized only with phenols and formaldehyde are strong and have no plasticity. Even if they are used to manufacture paper-based phenolic resin laminates, they cannot obtain the punching processability required for laminates today. Therefore, attempts have been made to improve the punching processability by using low elastic modulus paper substrates such as kraft paper and cotton linter paper. Another method is to impart flexibility to the phenolic resin itself. As a method of imparting flexibility to the phenolic resin itself, a method of modifying the phenolic resin with drying oil is widely used.

On the other hand, there is also known a method of impregnating a paper substrate with a water-soluble melamine resin or a water-soluble phenolic resin and then impregnating it with a drying oil-modified phenolic resin to improve flame retardancy, moisture resistance, and the like.

Conventional drying oil-modified phenolic resins are resins synthesized using only phenol as a raw material phenol. Such drying oil-modified phenolic resins have problems such as low crosslink density after curing, poor moisture resistance, and poor punching processability. Furthermore, after the paper substrate is treated with a water-soluble phenolic resin, although the moisture resistance is improved, the flame retardancy and the punching processability are deteriorated, and it is very difficult to achieve a balanced improvement of each characteristic.

The object of the present invention is to provide a phenolic resin composition for laminates which can produce a laminate having a high crosslinking density in a hardened product and excellent moisture resistance, flame retardancy and punching processability when the laminate is manufactured. The present invention also aims to provide a phenolic resin laminate made from such a phenolic resin composition for a laminate.

The dry oil-modified phenolic resin composition for laminates provided by the invention is characterized in that: dry oil modified phenolic resins obtained from the reaction of dry oil, phenols and formaldehyde as the main component of dry oil for laminates In the modified phenolic resin composition, the phenols are composed of a cresol mixture formed by phenol, m-cresol and p-cresol, and the molar ratio of phenol to the cresol mixture is phenol:cresol mixture=9:1～5: 5. The drying oil-modified phenolic resin is a substance obtained by reacting drying oil with the phenols and then reacting with formaldehyde in the presence of a basic catalyst.

The present invention also provides such a phenolic resin laminate, which is impregnated with the above-mentioned drying oil-modified phenolic resin composition for laminates of the present invention by a paper base material and dried, and several sheets of the obtained preforms are stacked, together with copper foil, Or without copper foil, heating and pressing.

The present invention also provides such a phenolic resin laminate, which is impregnated with a water-soluble phenolic resin modified with a melamine resin by a paper substrate and dried, then impregnated with the above-mentioned laminate of the present invention for the oil-modified phenolic resin composition and After drying, the obtained preforms are stacked, together with copper foil or without copper foil, heated and pressurized.

The present invention also provides such a phenolic resin laminate, which is impregnated with a mixture of the above-mentioned drying oil-modified phenolic resin composition for laminates of the present invention and a water-soluble phenolic resin modified with a melamine resin by a paper substrate and dried, The obtained preforms are stacked, together with copper foil or without copper foil, heated and pressurized.

The present invention also provides such a phenolic resin laminate, which is impregnated with a water-soluble phenolic resin modified by a melamine resin by a paper substrate and dried, and then impregnated with the above-mentioned dry oil-modified phenolic resin composition for a laminate of the present invention and The mixture of water-soluble phenolic resin modified with melamine resin is dried, and the obtained preforms are stacked, together with copper foil or without copper foil, heated and pressurized.

First, the drying oil-modified phenolic resin, which is the main component of the drying oil-modified phenolic resin composition for laminates of the present invention, will be described.

Regarding the manufacture of the above-mentioned drying oil-modified phenolic resin, the drying oil is first reacted with phenols.

Drying oils used in the production of drying oil-modified phenolic resins include, for example, tung oil, dehydrated castor oil, linseed oil, ortica oil. These drying oils can be used alone or in combination of two or more.

The phenols can be composed of a cresol mixture formed by phenol, m-cresol and p-cresol, and the molar ratio of phenol to the cresol mixture, that is, phenol:cresol mixture, is a mixture of 9:1-5:5. If the molar ratio of the cresol mixture is less than 1, the galvanic corrosion resistance and punching workability cannot be improved in the production of phenolic resin laminates, and if the molar ratio of the cresol mixture exceeds 5, the punching workability cannot be improved. The ratio of m-cresol and p-cresol in the cresol mixture is usually 60±5% by weight of m-cresol and 40±5% by weight of p-cresol.

The amount of drying oil reacted with phenols is usually 20 to 50% by weight, preferably 25 to 40% by weight, based on the total amount of phenols and drying oil. If the amount of the drying oil is less than 20% by weight, the punchability and the galvanic corrosion resistance will decrease, and if it exceeds 50% by weight, the punchability will decrease and the strength will also decrease.

The reaction temperature of the reaction between phenols and drying oil is generally 65 to 120°C, preferably 70 to 100°C, and the reaction time is usually 30 to 200 minutes, preferably 30 to 150 minutes. This reaction usually proceeds well under normal pressure. The reaction between the drying oil and phenols is preferably carried out in the presence of an acidic catalyst such as p-toluenesulfonic acid. When an acidic catalyst is used, the amount thereof is usually 0.05 to 0.4% by weight, preferably 0.05 to 0.3% by weight, based on the total amount of phenols and dry oil (such as tung oil).

After the above reaction is completed, add formaldehyde and a basic catalyst to the reaction solution, usually at 60-90°C, preferably at 65-85°C, and react for 30-240 minutes, preferably 30-180 minutes, to obtain the layer of the present invention The main component of the drying oil-modified phenolic resin composition for pressing boards is the drying oil-modified phenolic resin. In addition, this reaction usually proceeds sufficiently under normal pressure.

As the formaldehyde source, formalin, paraformaldehyde and the like can be used. The amount of formaldehyde used is usually 1.0-1.7 moles per mole of phenols, preferably 1.0-1.5 moles.

As the basic catalyst, there can be used, for example, ammonia, hexamethylenetetramine, trimethylamine, triethylamine and the like. The amount of the basic catalyst used is usually 0.01-0.05 mol, preferably 0.01-0.04 mol, per mol of phenol.

In the dry oil-modified phenol resin obtained in this way, as a structure derived from phenols, it is a product containing only phenol in the skeleton, a product containing both phenol and m-cresol and/or p-cresol in the skeleton, and a product containing only phenol in the skeleton. Mixtures of products containing m-cresol and/or p-cresol.

In the cresol mixture used in the present invention, m-cresol has a meta-position methyl group, and p-cresol has a p-position methyl group. Therefore, the above-mentioned drying oil-modified phenolic resin as a whole has a large ortho-position activity. Therefore, when the drying oil-modified phenolic resin composition for laminates of the present invention containing the drying oil-modified phenolic resin as the main component is used for the production of laminates, the crosslinking density increases and the properties such as moisture resistance are good. , There is no brittleness, so the punching processability is also improved.

The dry oil-modified phenolic resin for laminates of the present invention is mainly composed of the above-mentioned dry oil-modified phenolic resins, but if necessary, brominated epoxy resins, four Flame retardant components such as brominated compounds such as bromobisphenol A diglycidyl ether, phosphate esters such as triphenyl phosphate and cresyl diphenyl phosphate. The blending amount of the flame retardant component is usually 25 to 60% by weight, preferably 25 to 50% by weight, based on the total amount of the drying oil-modified phenolic resin and the flame retardant component.

When using the dry oil-modified phenolic resin composition for laminates of the present invention to manufacture phenolic resin laminates, this dry oil-modified phenolic resin composition for laminates is dissolved in methanol, toluene, a mixed solvent of methanol and toluene Make varnish in an organic solvent, impregnate paper and other substrates, and make a preform after drying. Several preforms are stacked, heated and pressurized, and the phenolic resin laminate of the present invention is obtained. At this time, in order to improve the adhesion between the base material and the drying oil-modified phenolic resin composition for laminates, the base material can also be treated with water-soluble phenolic resin, water-soluble melamine resin, etc. alone or in combination.

In the case of paper substrates, the present inventors have found that instead of using water-soluble phenolic resins, water-soluble melamine resins, etc. alone or in combination, it is better to treat paper substrates with water-soluble phenolic resins modified with melamine resins. A phenolic resin laminate excellent in each characteristic was obtained, and the phenolic resin laminate of the present invention was completed. That is, the water-soluble phenolic resin modified with melamine resin is blended in the above-mentioned drying oil-modified phenolic resin composition for laminates, so that the affinity of the drying oil-modified phenolic resin to the paper substrate is improved, and the resin and The adhesiveness of the base material is improved, and the moisture resistance and punching processability are improved. Moreover, the water-soluble phenolic resin modified with melamine resin has a flame-retardant effect, and the compatibility with the dry oil-modified phenolic resin is also good, so the flame retardancy and heat resistance of the obtained phenolic resin laminate are improved. Peel strength is also improved in the case of copper-clad laminates.

The water-soluble phenolic resin modified with melamine resin used in the present invention can be prepared like this: for example, in the presence of an alkaline catalyst, melamine and formaldehyde are reacted at 60-80°C (preferably at 65-75°C) for 90-150 Minutes (preferably 100-140 minutes), then add phenols, formaldehyde and basic catalyst to the reaction mixture, react at 70-100°C (preferably 80-95°C) for 20-45 minutes (preferably 25 ~45 minutes is preferred), this reaction can usually be fully carried out under normal pressure.

As the formaldehyde source, formalin, paraformaldehyde and the like can be used. In the reaction with melamine, the amount of formaldehyde is usually 0.5 to 0.8 times the weight of melamine, preferably 0.55 to 0.75 times the weight, and the amount of formaldehyde added at the same time as phenols is usually 0.25 to 0.45 times the weight of phenols The weight is preferably 0.3 to 0.4 times the weight.

As the above-mentioned basic catalyst, there can be used, for example, ammonia, hexamethylenetetramine, trimethylamine, sodium hydroxide, calcium hydroxide and the like. In the reaction of melamine and formaldehyde, the consumption of basic catalyst is usually 0.5～3% by weight of melamine, preferably 0.7～2.5% by weight, and the amount of basic catalyst added simultaneously with phenols and formaldehyde is usually 2% of phenols ~10% by weight, preferably 3-7% by weight.

As the phenols, phenol is generally used, but various other alkylphenols and the like can also be used. These phenols may be used alone or in combination of two or more.

The ratio of melamine to phenols is usually 0.25-0.5 times by weight of melamine, preferably 0.3-0.4 times by weight of phenols.

In this way, the phenolic resin laminated board of the present invention obtained by combining the dry oil-modified phenolic resin for the laminated board of the present invention with the water-soluble phenolic resin modified with melamine resin is impregnated with melamine on the paper substrate. Resin-modified water-soluble phenolic resin is dried and then impregnated with the above-mentioned dry oil-modified phenolic resin composition for laminates of the present invention and dried. Copper foil, phenolic resin laminate made by heating and pressing.

As the paper base material, linter paper, kraft paper, etc. can be used.

When the drying oil-modified phenolic resin composition for laminates and the water-soluble phenolic resin modified with melamine resin are impregnated into the paper substrate, varnishes which are respectively soluble in solvents can be used. The solvent that can be used for the preparation paint of the dry oil-modified phenolic resin composition for laminates is as described above, and can be used for the solvent of the water-soluble phenolic resin preparation paint modified with melamine resin, which can be organic solvents such as methanol, water or organic solvents. Mixed solvents of water, etc.

The adhesion amount of the dry oil-modified phenolic resin composition for laminates in the preform is usually 40-65% by weight, preferably 40-60% by weight. The adhesion amount of the water-soluble phenolic resin modified with melamine resin in the preform is usually 10-30% by weight, preferably 10-25% by weight.

Stack several preforms, heat and press to obtain the phenolic resin laminate of the present invention, and heat and press without adding copper foil, or laminate copper foil on one or both sides of the preform laminate , heated and pressed to make single-sided or double-sided copper-clad laminates.

The heating and pressurizing conditions are generally, the heating temperature is 150-200°C, preferably 160-190°C, the pressure is 5-20MPa, preferably 9-15MPa; the time is 30-180 minutes, preferably 60-120 minutes .

The phenolic resin laminate of the present invention is a mixture of the above-mentioned drying oil-modified phenolic resin composition for laminates of the present invention and water-soluble phenolic resin modified with melamine resin, preferably containing drying oil. A mixture of 100 parts by weight of modified phenolic resin and 3 to 20 parts by weight (more preferably 3 to 15 parts by weight) of water-soluble phenolic resin modified by melamine resin is impregnated and dried, and several sheets of the obtained preform are overlapped, and A phenolic resin laminate made by heating and pressing with or without copper foil. If the amount of water-soluble phenolic resin modified with melamine resin in the mixture is less than 3 parts by weight, the effect of improving the moisture resistance of the phenolic resin laminate will be small, and if it exceeds 20 parts by weight, there will be compatibility with paint, punching processing, etc. The problem of reduced sex.

The solid content in the lacquer (the total concentration of components other than the solvent dissolved in the solvent) is usually preferably 50 to 80% by weight.

The adhesion amount of the mixture of dry oil-modified phenolic resin composition for laminates and water-soluble phenolic resin modified with melamine resin in the preform is usually 40-65% by weight, preferably 45-60% by weight.

Other conditions are the same as above.

In the phenolic resin laminate of the present invention, after the paper substrate is impregnated and dried with a water-soluble phenolic resin modified with a melamine resin, the above-mentioned dry oil-modified phenolic resin composition for a laminate of the present invention and modified with a melamine resin are used. A mixture of water-soluble phenolic resins (preferably containing 100 parts by weight of dry oil-modified phenolic resin, 3 to 20 parts by weight of water-soluble phenolic resin modified with melamine resin, more preferably a mixture of 3 to 15 parts by weight ) impregnated and dried, and the obtained preforms are laminated with several sheets, together with copper foil or without copper foil, a phenolic resin laminate made by heating and pressing.

The solid content concentration (the total concentration of non-solvent components dissolved in the solvent) of the varnish used when the paper substrate is impregnated with the melamine resin-modified water-soluble phenolic resin is usually 10 to 20% by weight.

The adhesion amount of the dry oil-modified phenolic resin composition for laminates in the preform is usually 40-65% by weight, preferably 45-60% by weight. The water-soluble phenolic resin modified with melamine resin in the preform The total adhesion amount is usually 10-30% by weight, preferably 10-25% by weight.

Other conditions are the same as above.

The present invention will be described more specifically below with examples of the present invention and comparative examples thereof, but the present invention is not limited by these examples.

Example 1

After tung oil 35g, phenol 57.6g, cresol mixture (m-cresol 60% by weight, p-cresol 40% by weight) 7.4g and p-toluenesulfonic acid 0.1g were reacted at 80° C. for 60 minutes, added paraformaldehyde 30g and ammoniacal liquor ( Ammonia content 25% by weight) 5 g, reacted at 70° C. for 120 minutes. After concentrating the reaction solution under reduced pressure, methanol was added to obtain a tung oil-modified phenolic resin varnish with a solid content of 70% by weight (35% by weight of tung oil modification rate). 100 parts by weight of the solid content of this lacquer, blend 30 parts by weight of triphenyl phosphate, 20 parts by weight of tetrabromobisphenol A diglycidyl ether (epoxy equivalent 400), add the mixed solvent (toluene/methanol) of methyl alcohol and toluene =1/1 weight ratio) to prepare a top coating paint 1 having a solid content of 60% by weight.

240g of formalin, 125g of melamine, and 1.5g of trimethylamine were reacted at 70°C for 120 minutes, then 370g of phenol, 140g of paraformaldehyde, and 20g of trimethylamine were added, and reacted at 90°C for 30 minutes. Thereafter, the reaction solution was concentrated under reduced pressure to remove condensed water, unreacted substances, and the like. Methanol was added thereto to obtain a melamine resin-modified water-soluble phenolic resin (20% by weight of melamine) primer for a solid content of 60% by weight.

On kraft paper with a paper weight of 125g/ ^m2 , the water-soluble phenolic resin base coating varnish modified with melamine resin is dipped, dried, and the resin adhesion amount is 17 to 20% by weight, and then the top coating varnish 1 is dipped on the top, Drying, so that the adhesion of the whole resin (solid content) is 50-54% by weight, to obtain a preform.

Stack 8 sheets of this preform, and then stack copper foil with adhesive on it (copper foil thickness 35 μm, adhesive thickness 30 μm), heat at 160 ° C and 9.8 MPa for 80 minutes, and obtain a thickness of 1.6 mm. Single-clad copper laminate.

Example 2

After tung oil 35g, phenol 30.2g, cresol mixture (m-cresol 60% by weight, p-cresol 40% by weight) 34.8g and p-toluenesulfonic acid 0.1g were reacted at 80° C. for 60 minutes, added paraformaldehyde 30g and ammoniacal liquor ( Ammonia content 25% by weight) 5 g, reacted at 70° C. for 120 minutes. The reaction solution was concentrated under reduced pressure, and then methanol was added to obtain a tung oil-modified phenolic resin varnish with a solid content of 70% by weight (35% by weight of tung oil modification rate).

100 parts by weight of the solid content of this lacquer, blend 30 parts by weight of triphenyl phosphate, 20 parts by weight of tetrabromobisphenol A diglycidyl ether (epoxy equivalent 400), add the mixed solvent (toluene/methanol) of methyl alcohol and toluene =1/1 weight ratio) to prepare a top coating paint 2 having a solid content of 60% by weight.

Except having changed the top coating varnish 1 of Example 1 into the top coating varnish 2, it carried out similarly to Example 1, and obtained the single copper-clad laminated board of thickness 1.6mm.

Example 3

100 weight parts of tung oil modified phenolic resin varnish solid components synthesized in embodiment 1, the water-soluble phenolic resin lacquer that mixes embodiment 1 with the melamine resin modification by solid component 5 weight parts, and triphenyl phosphate 30 Parts by weight, 20 parts by weight of tetrabromobisphenol A diglycidyl ether (epoxy equivalent 400), add the mixed solvent (toluene/methanol=1/1 weight ratio) of methyl alcohol and toluene, make the surface of solid content 60 weight % Apply lacquer3.

Except changing the top coating paint 1 of Example 1 into the top coating paint 3, it carried out similarly to Example 1, and obtained the single copper-clad laminated board of thickness 1.6mm.

Example 4

100 weight parts of tung oil modified phenolic resin varnish solid components synthesized in embodiment 2, the water-soluble phenolic resin lacquer that mixes embodiment 1 with the melamine resin modification by solid component 10 weight parts, and triphenyl phosphate 30 Parts by weight, 20 parts by weight of tetrabromobisphenol A diglycidyl ether (epoxy equivalent 400), add the mixed solvent (toluene/methanol=1/1 weight ratio) of methyl alcohol and toluene, make the surface of solid content 60 weight % Apply lacquer4.

On kraft paper with a paper weight of 125 g/m ² which is not treated with primer, the topcoat paint 4 is dipped and dried to obtain a preform with a resin adhesion of 50 to 54% by weight.

Stack 8 of these preforms, and then put copper foil with adhesive on it (copper foil thickness 35μm, adhesive thickness 30μm), heat at 160°C and 9.8MPa for 80 minutes to obtain a thickness of 1.6mm single-sided copper-clad laminates.

Example 5

On kraft paper with a paper weight of 120 g/m ² without primer treatment, the top coating paint 1 of Example 1 was directly impregnated and dried to obtain a preform with a resin adhesion of 50 to 54% by weight.

Example 6

Except that the water-soluble phenolic resin varnish modified with melamine resin in embodiment 3 is added 5 weight parts and changed into 2 weight parts in terms of solid components, operate in the same way as embodiment 3 to obtain a single copper-coated layer with a thickness of 1.6mm platen. Example 7

Except that the water-soluble phenolic resin varnish modified with melamine resin in embodiment 3 is added 5 weight parts and changed into 25 weight parts in terms of solid components, operate in the same way as embodiment 3 to obtain a single-sided copper-clad layer with a thickness of 1.6mm platen. Comparative example 1

After reacting 35 g of tung oil, 65 g of phenol and 0.1 g of p-toluenesulfonic acid at 80° C. for 6 hours, add 30 g of paraformaldehyde and 5 g of ammonia water (ammonia content 25% by weight), and react at 70° C. for 120 minutes. After concentrating the obtained reaction solution under reduced pressure, methanol was added to prepare a tung oil-modified phenolic resin varnish with a solid content of 70% by weight (tung oil modification ratio: 35% by weight).

100 parts by weight of solid components of tung oil modified phenolic resin paint, 30 parts by weight of triphenyl phosphate, 20 parts by weight of tetrabromobisphenol A diglycidyl ether (epoxy equivalent 400), add a mixture of methanol and toluene Solvent (toluene/methanol = 1/1 weight ratio) was used to prepare top coating paint 5 having a solid content of 60% by weight.

Except having changed the top coating varnish 1 of Example 1 into the top coating varnish 5, it carried out similarly to Example 1, and obtained the single copper-clad laminated board of thickness 1.6mm. Comparative example 2

On kraft paper with a paper weight of 120 g/m ² without primer treatment, the topcoat paint 5 of Comparative Example 1 was directly dipped and dried to obtain a preform with a resin adhesion of 50 to 54% by weight.

Stack 8 of these preforms, and then stack the copper foil with adhesive (copper foil thickness 35μm, adhesive thickness 30μm), heat at 160°C and 9.8MPa for 80 minutes, and obtain a single sheet with a thickness of 1.6mm. Clad copper laminate.

For the single copper-clad laminates obtained in the above examples and comparative examples, flame retardancy, punching workability, and moisture resistance were studied, and the results are shown in Table 1.

The test method is as follows:

Flame retardancy (UL94): Place the test piece whose copper foil is completely removed by etching method vertically, touch the lower end of the burner flame for 10 seconds, leave the flame, and measure the time required for the fire to extinguish. After the fire is extinguished, touch the flame for another 10 seconds, leave the flame, and measure the time required for the fire to extinguish. The total average value of 10 measured values of 5 test pieces was calculated. The appearance range means the maximum and minimum values of the respective measured values.

Moisture resistance (water absorption rate): The test piece was subjected to a treatment of holding at 2128 hPa for 8 hours at a saturated vapor pressure of 121° C. in an autoclave, and the weight change before and after the treatment was measured to calculate the water absorption rate.

Punching processability: Use an 80-ton punch to punch out holes with a hole spacing of 1.78mm at a temperature of 40°C, and check for peeling and parallel holes (mebai). In Table 1, ○ indicates that peeling and double holes, which are the evaluation criteria of punching workability, did not occur, △ indicates slightly, and × indicates quite a lot.

Table 1 project Example comparative example 1 2 3 4 5 6 7 1 2 Flame Retardancy (seconds) Average Appearance Range Evaluation Moisture Resistance (%) Punching Processability 2.40～7V-03.3 2.40～6V-03.2 1.70～4V-03.1 4.73～8V-04.7 4.93～8V-04.7 2.40～6V-03.4 1.10～3V-02.7 2.50～8V-03.5 4.93～8V-05.0 stripped and holed ○○ ○○ ○○ ○○ ○○ ○○ ×△ △△ ○○

From the comparison of Examples 1 to 7 and Comparative Examples 1 and 2, it can be seen that the punching processability of laminates can be improved by using the drying oil-modified phenolic resin composition for laminates of the present invention.

From the comparison of Comparative Example 2 and Example 5, it can be seen that the dry oil-modified phenolic resin composition for laminates of the present invention has better effect of giving laminates moisture resistance than existing dry oil-modified phenolic resins, And has the same punching processability.

As shown in the comparison between Comparative Example 1 and Comparative Example 2, when the conventional tung oil-modified phenolic resin is used in combination with the water-soluble phenolic resin modified with melamine resin, the punching property is deteriorated, while the flame retardancy and moisture resistance are improved. . However, as shown in the comparison between Examples 1-7 and Comparative Examples, when the dry oil-modified phenolic resin composition for laminates of the present invention is used in combination with water-soluble phenolic resins modified with melamine resins, the flame retardancy of the laminates Improved performance and moisture resistance.

Example 3 and Examples 6 and 7 show that when using the dry oil-modified phenolic resin composition for laminates of the present invention and the mixture of water-soluble phenolic resin modified with melamine resin, the mixture corresponds to dry 100 parts by weight of oil-modified phenolic resin, when the water-soluble phenolic resin modified with melamine is less than 3 parts by weight, the effect produced by mixing with dry oil-modified phenolic resin is small, and when it exceeds 20 parts by weight, punching processing reduced sex.

The above results show that for the manufacture of phenolic resin laminates, moisture resistance, punching processability, resistance A phenolic resin laminate with improved flammability and balanced improvements in these properties.

In addition to phenol, the dry oil-modified phenolic resin composition for laminates of the present invention is also made of m-cresol and p-cresol. The high crosslink density, as a result, has the effect of imparting excellent moisture resistance and punching processability to the phenolic resin laminate. Combining the dry oil-modified phenolic resin composition for laminates of the present invention and the phenolic resin laminate of the present invention made with the water-soluble phenolic resin modified with melamine resin, due to the water-soluble phenolic resin modified with melamine resin The effect of combining resins has good moisture resistance and punching processability, etc., and also has good flame retardancy.

Claims (4)

1. veneer sheet dry oil modified phenolic resin composition, it is characterized in that: at the dry oil modified phenolic resin with siccative oil, phenols and formaldehyde reaction gained is in the veneer sheet usefulness dry oil modified phenolic resin composition of principal constituent, this phenols is made up of the cresols mixture that phenol and meta-cresol and p-cresol form, phenol is phenol to the mol ratio of this cresols mixture: cresols mixture=9: 1～5: 5, this dry oil modified phenolic resin be after the reaction of siccative oil and this phenols again in the presence of basic catalyst with formaldehyde reaction gained material.

2. by the described veneer sheet dry oil modified phenolic resin composition of claim 1, wherein said cresols mixture is made up of meta-cresol 60 ± 5 weight % and p-cresol 40 ± 5 weight %.

3. by the described veneer sheet dry oil modified phenolic resin composition of claim 2, its feature also is: with described dry oil modified phenolic resin is principal constituent, also contain at least a flame retardant resistance composition that is selected from brominated epoxy resin, bromo diphenyl ether and phosphoric acid ester, its amount is 25～60 weight % of described dry oil modified phenolic resin and described flame retardant resistance composition total amount.

4. phenolic sheet, it is characterized in that: the described veneer sheet of one of paper base material dipping claim 1～3 with dry oil modified phenolic resin composition also after drying, with several overlappings of gained preforming material, with Copper Foil or do not add Copper Foil, heating and pressurizing forms.