JPS5948051B2 - Manufacturing method of modified phenolic resin - Google Patents

Description

[Detailed Description of the Invention] The present invention provides electrical performance, heat resistance, chemical resistance, dimensional stability,
The present invention relates to a method for producing a modified phenolic resin that has good warpage and is highly flexible and is useful as an electrical insulating material, a laminate, and a decorative board.

Conventionally, a base material is impregnated with a resol-type phenolic resin obtained by reacting phenols such as phenol, cresol, and xylenol with formaldehyde and dried, and the resin-impregnated base material is used as a laminated material with a predetermined composition. It is well known to obtain a laminate by heating and pressing. These laminates are widely used industrially as electrical insulating materials, structural materials, etc., but in recent years, with the development of electrical equipment and electronic equipment, various laminates have been used, and they have been used for communication, consumer use, etc. Simplified mounting method for equipment parts, small size, high performance, good electrical insulation, heat resistance, and mechanical performance.
There has been an increasing demand for laminates with uniform properties such as punchability. Among these, there is a great demand for printed wiring materials, and in this field they are used after being punched into a desired shape. However, since phenolic resin is generally hard and brittle, it must be heated to ~150°C during punching, which causes dimensional changes due to expansion and contraction, and warping due to changes in residual stress. There are disadvantages in that a phenomenon occurs, and the heating operation is complicated. For this reason, various methods have been proposed in which plasticization is imparted by using various modifiers to improve punching workability or formability.
It is well known that rubber-based substances and drying oils are generally used as modifiers in such cases; however, rubber-based substances generally have poor compatibility with phenolic resins, which limits the types of rubber that can be used. .

Nitrile rubber is compatible with phenolic resin, and when used in laminates, it either improves punching workability or deteriorates electrical performance such as high frequency characteristics due to polar bending of the nitrile group. Although the use of other rubber-based materials does not reduce electrical performance such as high frequency characteristics, the compatibility with the phenol resin is insufficient and the layers separate, making it impossible to obtain a laminate. Furthermore, it is known to use tung oil as a drying oil, which contains a large amount of conjugated double bonds and is highly reactive with substances such as phenols.

However, tung oil has poor mechanical performance and punching workability. Although it is possible to obtain a well-balanced laminate in such cases, it has the disadvantage of deteriorating high frequency characteristics. In order to improve these properties, the method of Japanese Patent Publication No. 47-4331.2 is 1.
A method that utilizes a phenol-added butadiene-based polymer to which phenols have been added by using a Friedel-Crafts catalyst on the pendant double bonds of polybutadiene or styrene-butadiene copolymer containing at least 20% of the 2-structure. However, a large amount of catalyst must be used and the compatibility with the phenolic resin is not satisfactory.

Therefore, the obtained laminate has poor moisture resistance, water resistance, and chemical resistance, and it is difficult to put the obtained laminate into practical use. As a result of intensive research aimed at solving the above-mentioned drawbacks, the present inventors have discovered a method for extremely effectively modifying polybutadiene.

That is, the method of the present invention involves reacting polybutadiene with isopropenylphenol or isopropenylphenol oligomers represented by formula (4) or formula (4) alone or in a mixture in the presence of an acidic catalyst, and then reacting with phenol. Provided is a method for producing a modified phenolic resin, in which the reaction product is reacted with formaldehyde as part of the phenol component, with or without adding an acid catalyst as necessary. By applying this method to the production method of phenolic resin, the compatibility with the phenolic resin was improved and we succeeded in producing a phenolic resin with excellent properties such as high frequency properties, chemical resistance, and punching workability. The method of the present invention was then achieved. The characteristics of the reaction between polybutadiene and isopropenylphenol or its oligomer will be explained in more detail.

Conventionally, various methods for modifying polybutadiene with phenols have been reported, but generally the method described in British Patent No. 11062
As disclosed in No. 67, the conditions for modifying polybutadiene with phenols include sulfuric acid, hydrochloric acid, and zinc chloride;
1 to 6 strong acid catalysts such as Lewis acids such as titanium tetrachloride.
% by weight and heated at 150 to 180°C to react.

In other words, the conventional modification method is a reaction in which phenols are added to the double bonds of polybutadiene under extremely severe conditions using a large amount of catalyst and heating at high temperatures. However, the reaction constant of phenols to polybutadiene is small, and Only 1 mole of phenols is added per mole. Modified polybutadiene of this level has poor properties when compared with phenolic resin, and phase separation occurs. Furthermore, even if a laminate can be manufactured, the layers may peel off or
It has poor trichloride resistance and is difficult to put into practical use. On the other hand, isopropenylphenol or its oligomer is a much more reactive substance than phenols, and therefore easily reacts with α-methylene adjacent to the double bond of polybutadiene. Therefore, since double bonds remain in polybutadiene modified with isopropenylphenol or its oligomer, it is possible to further add phenols to the polybutadiene. In other words, in the conventional modification method, approximately 1 mole of phenol was added per mole of polybutadiene, but in the modification method of the present invention, 2.0 to 3.0 mole of isopropenylphenol or its oligomer was added per mole of polybutadiene. About 1.0 mole of phenols react. That is, compared to the conventional polybutadiene modification method, 3 to 4 times as much phenol is reacted, so the ratio of phenyl nuclei introduced per molecule of polybutadiene increases. According to the conventional modification method, the crosslinking reaction of the resin is achieved only by methylolation of the phenols added to the modified polybutadiene, but in the method of the present invention, it is further achieved by the methylolation of the isopropenylphenol nucleus. As a result, the rate of introduction of methylol groups is increased, the effect of impregnating the resulting phenolic resin into the laminate is improved, and the performance of the laminate is improved. The polybutadiene used in the present invention is a polybutadiene homopolymer or a polybutadiene copolymer, and the butadiene component may have a 1,2 structure or a 1,4 structure alone or in a mixture.

There are polybutadienes with different terminal groups, such as polybutadiene glycol, polybutadiene dicarboxylic acid, epoxidized polybutadiene, and urethanized polybutadiene, but the polybutadiene used in the present invention is not limited by terminal groups, etc., and all polybutadienes are Available for use. For example, the product name, Sumika Oil Φ5
0 (Sumitomo Oil), Polyoil Φ110 (Nippon Zeon)
, New Poly Oil NX-5 (Nippon Zeon), NISS
Examples include OPBG-1000 (Nippon Soda). As the polybutadiene copolymer, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, etc. are used, and the number average molecular weight is usually in the range of 200 to 8,000. In the present invention, isopropenylphenol or formula () in the presence or absence of phenols
The acidic catalyst used in the reaction (first stage modification) of isopropenylphenol oligomers represented by formula (l) alone or in a mixture with polybutadiene includes mineral acids such as sulfuric acid, phosphoric acid, and hydrochloric acid; There are organic acids such as p-toluenesulfonic acid and methanesulfonic acid, and the amount used is 100 to 5000 - especially 500 to 200% based on the reactants.
A range of 0- is preferred. 80 for reaction temperature and time
~200°C for 0.5-5 hours, preferably 100-13
The temperature is 0° C. and the time is in the range of 1.5 to 4 hours. The reaction of polybutadiene with isopropenylphenol or its oligomers gives very favorable results in the coexistence of other phenols that have low reactivity with isopropenylphenol or its oligomers.

Phenols used in the present invention include phenol, cresol, xylenol, butylphenol, octylphenol, nonylphenol, alkylphenols such as dodecylphenol, bisphenol Ae phenylphenol, cumylphenol, styrenated phenol, catechol, These include polyvalent phenols such as resorcinol.

In the present invention, the catalyst used for the reaction of the reaction product of polybutadiene and isopropenylphenol or its oligomer with phenols (second stage modification) is p-
Strong acids such as toluenesulfonic acid, methanesulfonic acid, and sulfuric acid are used, and the amount of catalyst used is 100 to 50% based on the reactants.
000 PFI, particularly preferably in the range of 500 to 2000 PL. The reaction temperature and time are 120-180℃.
~5 hours is appropriate, especially at 150-170℃, 1
．． A range of 5 to 3 hours is preferred. In order to effectively achieve the method of the present invention, polybutadiene modification (first stage modification)
At this time, 0.1 to 2 times the weight ratio of isopropenylphenol or its oligomer to polybutadiene,
Preferably, 0.5 to 1.5 times the amount is used.

The isopropenylphenol or oligomer thereof used in the method of the present invention is a compound represented by the general formula I, (wherein, n in □ represents an integer of 0 to 18.

) In each of the above formulas, the hydroxyl group may be located at any of the ortho, meta, and para positions, or a mixture thereof.

Monomers, dimers, and trimers can be synthesized as pure compounds, but oligomers of one or more tetramers coexist as a mixture. These monomers and oligomers can be used either singly or as a mixture. In the method of the present invention, the phenolic resin is produced by reacting it with formaldehyde under acidic or alkaline conditions after the modification reaction is completed.

A method of obtaining a novolak-type resin by reacting with formaldehyde under acidic conditions, a method of obtaining a novolak-type to resol-type resin by partially reacting with formaldehyde under an acidic condition, or a method of obtaining a novolak-type to resol-type resin by reacting partially with formaldehyde under an acidic condition, or alkaline after a modification reaction. Any method of obtaining a resol type resin is possible.

In order to obtain a resol type resin, the acidic catalyst used for modification is neutralized with ammonia, organic amines, etc., and then subjected to a reaction with formaldehyde. The formaldehyde/phenol (mole ratio) between the formaldehyde used in the reaction with formaldehyde and all the phenols in the raw materials is generally 0.7 to 2.0, preferably 0.8 to 1.
The range is 6. 90-11 for reaction temperature and time
A range of 2 to 6 hours at 0°C is preferred. As a catalyst, hydrochloric acid, oxalic acid, p-toluenesulfonic acid, sulfuric acid, etc. are used in the production of novolac type resin, and ammonia, methylamine, dimethylamine, triethylamine, ethylenediamine, diethylamine, caustic soda, etc. are used in the production of resol type resin. Caustic potash etc. are used.

The amount of polybutadiene used in order to exhibit excellent effects in the method of the present invention is 5 to 100% by weight, preferably 15 to 60% by weight, based on the total phenols in the phenolic resin raw material.
% by weight.

As formaldehydes, formalin aqueous solution, paraformaldehyde, etc. are generally used. After the reaction is completed, the phenolic resin is dehydrated and dissolved in aromatic hydrocarbons, ketones, or alcohols to obtain a varnish. A comparison of the conventional method of modifying polybutadiene with phenols, the reactivity of the modified polybutadiene with formaldehyde, and the physical properties of the resulting resin with those obtained by the method of the present invention is as follows.

By the method of the present invention, in which phenols are further introduced into polybutadiene into which isopropenyl phenol or its oligomer (1) is introduced (first stage modification) (second stage modification), a large amount of phenyl nuclei can be introduced into polybutadiene. can increase the crosslinking density of

2. Polybutadiene modified by the method of the present invention reacts more quickly with formaldehyde than in conventional modification methods using phenols.

3. The modified phenolic resin varnish obtained by the method of the present invention has excellent uniformity and stability.

(4) The laminate obtained by impregnating a base material with the modified phenolic resin obtained by the method of the present invention and heating and pressurizing it has high interlayer bonding strength, so moisture resistance, water resistance, heat resistance, chemical resistance, etc. are improved. . According to the modification method of the present invention, however, polybutadiene homopolymer or polybutadiene copolymer, which until now has been difficult to use as a plasticizer due to phase separation, is skillfully modified to obtain a modified phenolic resin having the above-mentioned characteristics. be able to.

When this resin is made into a laminated product according to the usual method, the above advantages are summarized, so electrical and mechanical performance centered on high frequency characteristics, moisture resistance, water resistance, heat resistance dimensional change rate, warpage and room temperature Punching workability is significantly improved. The method of the invention will be better understood by, but is not limited to, the following examples.

Example 1 Isopropenylphenol oligomer having a composition of 90% by weight of p-isopropenylphenol dimer and 10% by weight of trimer and tetramer - 102tPolybutadiene having a number average molecular weight of 650 (Sumika Oil +50 manufactured by Sumika Oil Co., Ltd.) ) 102t and nonylphenol 1
03r was kept under stirring at 115°C, 0.31r of p-toluenesulfonic acid was charged, and the mixture was stirred for 3 hours.

Furthermore, phenol 147r was added, and the mixture was reacted at 170°C for 2 hours. After the reaction, 195 tons of 37% formalin and 9.1 tons of 25% ammonia were added, and the mixture was reacted at 95° C. for 6 hours.

Water was removed under reduced pressure and when the content reached 90°C, dehydration was stopped and the content was cooled and dissolved in a mixed solvent of methanol and toluene in a ratio of 1:1 to obtain a varnish with a resin concentration of 50%. A 10 mils thick linter paper was impregnated with the obtained resin varnish and dried to obtain a prepreg with a resin content of 45%.

Laminate molding by stacking 9 sheets of this prepreg (90k9/1,
(160° C., 50 minutes) to obtain a laminate. Thickness is 1.6mm
It was hot. Example 2 An isopropenylphenol oligomer having a composition of 90% by weight of p-isopropenylphenol dimer and 10% by weight of trimer and tetramer - 103V Polybutadiene having a number average molecular weight of 1300 (Nippon Zeon Co., Ltd.'s New Polymer) Oil NX-5) 109V and Nonylphenol II
The OV was kept under stirring at 115°C, and 0.31v of p-toluenesulfonic acid was charged, followed by stirring for 3 hours.

Further, 150V of phenol was added and the mixture was reacted at 165°C for 2.5 hours. After reaction, 37% formalin 203V125%
Ammonia 8.21V and ethylene diamine 0.96
v was added and reacted at 95°C for 4.5 hours. Water was removed under reduced pressure and when the content reached 90°C, dehydration was stopped and the content was cooled and dissolved in a 1:1 mixed solvent of methanol and toluene to obtain a varnish with a resin concentration of 50%. A laminate with a thickness of 1.6 mm was obtained according to the same treatment as in Example 1. Example 3 Isopropenylphenol oligomer 102y having a composition of 90% by weight of p-isopropenylphenol dimer, 10% by weight of trimer and tetramer, and a number average molecular weight of 1600
Polybutadiene (polyoil Φ110 manufactured by Nippon Zeon Co., Ltd.) 102V having a p-
0.30y of toluenesulfonic acid was charged and stirred for 3 hours.

Furthermore, 103 V of nonylphenol and 149 V of phenol were added and reacted at 167° C. for 2.5 hours. After reaction, 37%
Formalin 203V, 25thia. Ammonia 9.2V was added and the mixture was reacted at 95°C for 5 hours. Water was removed under reduced pressure, and when the contents reached 90°C, dehydration was stopped and the mixture was cooled and dissolved in a mixed solvent of methanol and toluene (1:1) with a l-resin concentration of 50.
% varnish was obtained. Thickness 1 according to the same treatment as in Example 1
．． A 6 mwL laminate was obtained.

Comparative Example 1 Polybutadiene having a number average molecular weight of 1300 (New Pono Oil NX-5 manufactured by Nippon Zeon Co., Ltd.) 100y,
1 of phenol 253V and nonylphenol 1109
p-Toluenesulfonic acid 0.37 kept under stirring at 15°C
y was charged and stirred for 3 hours.

After reaction 37% formalin 195y 125% ammonia 9
．． 0y was added and the mixture was reacted at 95°C for 5 hours.

Water was removed under reduced pressure, and when the contents reached 90°C, dehydration was stopped and cooled, and dissolved in a 1:1 mixed solvent of methanol and toluene to obtain a varnish with a resin concentration of 50%. A laminate plate having a thickness of 1.6 mwL was obtained by processing in the same manner as in Example 1.

Comparative Example 2 An isopropenylphenol oligomer having a composition of 90% by weight of p-isopropenylphenol dimer and 10% by weight of trimer and tetramer - 253V and a number average molecular weight of 1300
Polybutadiene (New Polyoil NX-5, manufactured by Nippon Zeon Co., Ltd.) having 100 V and nonylphenol IIOV were kept under stirring at 115° C., and 0.37 V of p-toluenesulfonic acid was charged and stirred for 3 hours.

After the reaction, 195 y of 37% formalin and 9.0 y of 25% ammonia were added and reacted at 95° C. for 5 hours.

Water was removed under reduced pressure, and when the contents reached 90°C, dehydration was stopped and cooled, and dissolved in a 1:1 mixed solvent of methanol and toluene to obtain a varnish with a resin concentration of 50%. A laminated plate having a thickness of 1.6 nm was obtained by processing in the same manner as in Example 1.

Comparative Example 3 Polybutadiene having a number average molecular weight of 1300 (Nippon Zeon Co., Ltd. New Polyoil NX-5) 100
y) Phenol 300V was kept under stirring at 170 to 180°C, 4.0y of anhydrous aluminum chloride was charged, and the mixture was stirred for 6 hours.

After the reaction was cooled and neutralized with ammonia, 37% formalin 195y and 25% ammonia 9.0% were added, and the mixture was heated at 95°C for 50 minutes.
Allowed time to react. Water was removed under reduced pressure, and when the contents reached 90°C, dehydration was stopped and cooled, and methanol and toluene were added.
: A varnish with a resin concentration of 50% was prepared by dissolving it in a mixed solvent of 1:1. The modified polybutadiene resin obtained by this method lacks compatibility with the phenolic resin, making it impossible to produce a laminate.

Comparative Example 4 Polybutadiene having a number average molecular weight of 650 (manufactured by Sumika Oil Co., Ltd., Sumika Oil Fathom 50) 200 tons of 100V phenol was mixed with 4.5 tons of concentrated sulfuric acid while stirring at 160 lc.
was charged and stirred for 6 hours.

After the reaction, cool and neutralize with ammonia. 37% formalin 130V, 25% ammonia 5.5f and ethylenediamine 0.64? was added and reacted at 95t for 5 hours.
Water was removed under reduced pressure and when the contents reached 90'C, dehydration was stopped and the contents were cooled. The obtained modified phenolic resin became cloudy during gelation and could not be used as a phenolic resin for laminates. Examples 1 to 3 and Comparative Example 1 above
Table 1 shows the properties of the laminates obtained in 2 to 2.

The method for the above special ratio test is as follows. (1
) Water absorption rate, insulation resistance, soldering heat resistance, and trichloride resistance are JIS
According to C-6481.

(2) Dielectric loss tangent and dielectric constant are based on JISK-6911.

(3) The punching method is based on ASTM D-617.

(4) Dimensional change rate is 140111><13 in length and width
A test piece of No. n was heated at 100 tons for 24 hours, then cooled to room temperature, and dimensional changes were determined.

(5) The warpage is 100' for a 14011x13mm test piece.
After heating at C for 24 hours, the mixture was cooled to room temperature.

Claims (1)

[Scope of Claims] 1. In the presence or absence of phenols, isopropenylphenol or isopropenylphenol oligomers represented by formula (II) or formula (III) alone or as a mixture and polybutadiene in the presence of an acidic catalyst. 1. A method for producing a modified phenol resin, which comprises reacting the resin with a phenol in the presence of an acidic catalyst, and then reacting the reaction product with formaldehyde as part of a phenol component. ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) [In formulas (II) and (III), n represents an integer from 0 to 18. ]