JP2003176398A - Phenolic resin composition, prepreg and paper substrate phenolic resin laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a paper substrate phenolic resin laminate which scarcely releases unreacted phenol and formaldehyde and is thereby low odorous. <P>SOLUTION: This phenolic resin composition used for producing the paper substrate phenolic resin laminate is characterized by comprising a resol type phenolic resin and a novolak type phenolic resin. The prepreg for the paper substrate phenolic resin laminate is characterized by impregnating a paper substrate with the phenolic resin composition. The paper substrate phenolic resin laminate contains at least one prepreg. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a phenol resin composition, a prepreg, and a paper-based phenol resin laminate.

[0002]

2. Description of the Related Art Paper-based phenolic resin laminates are often used as printed circuit boards mounted in electronic devices and the like. Resol-type phenolic resin is used as the phenolic resin impregnated in the paper base material for producing the paper-based phenolic resin laminate. However, unreacted phenol and formaldehyde remain when synthesizing the resol-type phenol resin. For this reason, the paper-based phenolic resin laminate has a peculiar odor, and its use has been shunned especially in the United States and the like due to its odor. Also, if you use electronic equipment for a long time, the temperature of the equipment will rise,
There is a problem that phenol and formaldehyde are more easily released.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a phenol resin composition having low odor and low unreacted phenol and formaldehyde when a paper-based phenol resin laminate is manufactured. . Another object of the present invention is to provide a prepreg for a paper-based phenolic resin laminate and a paper-based phenolic resin laminate, which has low unreacted phenol and formaldehyde and has a low odor.

[0004]

These objects are achieved by the present invention described in (1) to (6) below. (1) A phenol resin composition used for producing a paper-based phenol resin laminate, comprising a resol-type phenol resin and a novolac-type phenol resin. (2) The phenol resin composition according to (1), wherein the resol-type phenol resin contains an oil-modified resol-type phenol resin. (3) The phenol resin composition according to (1) or (2) above, wherein the content of the resol-type phenol resin is 20 to 80% by weight of the whole phenol resin composition. (4) The phenol resin composition according to any one of (1) to (3) above, wherein the content of the novolac type phenol resin is 20 to 80% by weight based on the whole phenol resin composition. (5) A prepreg for a paper-based phenol resin laminate, which is obtained by impregnating a paper substrate with the phenol resin composition according to any one of (1) to (4). (6) A paper-based phenol resin laminate comprising at least one prepreg according to (5) above.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The phenol resin composition, prepreg and paper-based phenol resin laminate of the present invention will be described in detail below. The phenolic resin composition of the present invention is a phenolic resin composition used for producing a paper-based phenolic resin laminate, and contains a resol type phenolic resin and a novolac type phenolic resin. The paper base phenol resin prepreg of the present invention is obtained by impregnating a paper base with the above-mentioned phenol resin composition. Further, the paper-based phenolic resin laminate of the present invention contains at least one prepreg described above.

First, the phenol resin composition of the present invention will be described. The phenol resin composition of the present invention is used for producing a paper-based phenol resin laminate. The phenol resin composition of the present invention contains a resol type phenol resin. Thereby, the impregnating property with respect to the paper base material can be improved. Moreover, the cost of the paper-based phenolic resin laminate can be reduced. The resol-type phenol resin is not particularly limited, and those commonly used can be used.

In the present invention, the content of the resol type phenol resin is not particularly limited, but it is preferably 20 to 80% by weight, particularly 30 to 60% by weight based on the whole phenol resin composition.
Is preferred. If the content of the resol-type phenol resin is less than the lower limit value, the curing of the novolac-type phenol resin described below may be insufficient. When the novolac resin is insufficiently cured, heat resistance, chemical resistance, etc. may be deteriorated. Further, if the content of the resol-type phenol resin exceeds the upper limit value, the effect of reducing odor may decrease.

The resole type phenolic resin of the present invention is not particularly limited, but preferably contains an oil-modified resole type phenolic resin. As a result, the punchability of the printed board from the phenol resin laminated board can be improved. Examples of the oil-modified resol-type phenol resin include dry oil-modified resol-type phenol resin such as tung oil, linseed oil and walnut oil, and semi-dry oil-modified resol-type phenol resin such as soybean oil, cottonseed oil and safflower oil. Of these, tung oil-modified resol type phenol resin is preferable. This makes it possible to further improve punchability. The content of the oil-modified resol-type phenol resin is not particularly limited, but is preferably 5 to 40% by weight, and particularly 10 to 30% by weight of the total phenol resin composition.
Is preferred. This makes it possible to further improve the punchability of the phenol resin laminate.

The phenolic resin composition of the present invention contains a novolac type phenolic resin. Thereby, unreacted phenol and formaldehyde can be reduced. Novolak type phenolic resin has less residual unreacted phenol and formaldehyde during synthesis than resol type phenolic resin.Therefore, a phenolic resin composition prepared by mixing resol type phenolic resin and novolac type phenolic resin on a paper substrate is used. By impregnating and drying, a prepreg containing less unreacted phenol and formaldehyde can be obtained. As a method for removing unreacted phenol of the resol-type phenol resin, a method of steam distillation of the phenol resin is known, but it is not preferable because the number of processing steps increases. On the other hand, in the present invention, the unreacted substances are reduced by blending the phenol resin composition which is usually practiced. Therefore, unreacted phenol and formaldehyde can be reduced without increasing the number of steps.

Further, when used in combination with the above-mentioned resol type phenol resin, it can be cured without using a crosslinking agent other than the phenol resin. Furthermore, the combination of the above-mentioned resol-type phenol resin and novolac-type phenol resin can reduce powder generated when punching a printed board. When a printed board is punched from a paper-based phenolic resin laminate made of a conventional resin composition, powder of the resin composition or the like is generated from the punched cross section. Such powder affects the wettability of solder and the connection reliability.

Examples of the novolac type phenolic resin include phenol novolac type resin, bisphenol A novolac type phenolic resin, bisphenol F novolac type phenolic resin, cresol novolac type phenolic resin and alkylphenol novolac type phenolic resin. Among these, phenol novolac type resin, bisphenol F novolac type phenol resin, and cresol novolac type phenol resin are preferable. As a result, it is possible to further reduce the powder generated when punching the printed board.

The content of the novolac type phenol resin is not particularly limited, but is preferably 20 to 80% by weight, and particularly preferably 30 to 60% by weight based on the whole phenol resin composition. When the content of the novolac type phenol resin is within the above range, odor and the like can be reduced and powder generated when punching the printed board can be further reduced.

Further, a flame-retardant compound such as a halogen compound, a phosphorus compound or an amino resin may be blended within a range not deviating from the object of the present invention. The content of the flame-retardant compound is not particularly limited, but is preferably 5 to 30% by weight, and particularly preferably 10 to 20% by weight based on the whole phenol resin composition. This makes it possible to improve the flame retardancy without impairing the properties of the paper-based phenolic resin laminate. Examples of the halogen compound include tetrabromobisphenol A (TBBA) and TBBA-epoxy oligomer.

Examples of the phosphorus compound include phosphoric acid ester, condensed phosphoric acid ester, phosphine oxide and the like. Examples of the phosphoric acid ester include triethyl phosphate, tributyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, resorcyl diphenyl phosphate, triisopropyl phenyl phosphate, and the like. Are used as one kind or as a mixed system of two or more kinds. Among these, one or more phosphorus compounds selected from triphenyl phosphate, tricresyl phosphate and cresyl diphenyl phosphate are preferable in terms of availability.

The amino resin is, for example, a melamine resin or a guanamine resin, but a melamine resin is preferable in order to enhance the flame retarding effect. An amino resin is an initial reaction product of an amino compound such as melamine or guanamine and an aldehyde such as formaldehyde, and includes those obtained by etherifying a part or all of their methylol groups with a lower alcohol such as methanol or butanol. .

Next, the prepreg will be described. The prepreg of the present invention is obtained by impregnating a paper base material with the above-mentioned phenol resin composition. As a result, it is possible to obtain a paper-based phenol resin laminate having a small amount of unreacted phenol and formaldehyde. Examples of the paper base material include kraft paper and linter paper. Also,
The paper substrate previously treated with a water-soluble phenolic resin, a methylol melamine resin or the like is also included in the present invention.
As a method of impregnating the paper base material with the phenol resin composition, a method which is usually used can be used. For example, a method of impregnating a paper base material with a resin varnish, a method of applying it with various coaters, a spraying method with a spray, and the like can be mentioned.

Next, the paper base phenolic resin laminate will be described. The paper-based phenolic resin laminate of the present invention,
At least one prepreg is included.
The paper-based phenolic resin laminated plate can be obtained by laminating a metal foil on one side or both sides of the prepreg when it is one sheet. When the number of prepregs is 2 or more,
It can be obtained by laminating a metal foil on one or both outermost sides of the prepreg. Examples of the metal forming the metal foil include copper or a copper-based alloy, aluminum or an aluminum-based alloy, and the like.

In the present invention, in order to obtain a particularly flame-retardant paper-based phenol resin laminate, the compounding ratio of the phenol resin composition is such that the unmodified resol type phenol resin 100 is used.
20 to 150 parts by weight of a dry oil-modified resol type phenolic resin, 20 parts by weight of novolac type phenolic resin, relative to parts by weight.
To 200 parts by weight, halogen compounds 0 to 100 parts by weight, phosphoric acid ester 10 to 100 parts by weight, and amino resin 10
-100 parts by weight is preferred.

[0019]

EXAMPLES The present invention will now be described in detail with reference to examples and comparative examples, but the present invention is not limited thereto. In the description, “%” indicates “% by weight”.

(Example 1) [Production of unmodified resol-type phenol resin] 1000 g of phenol, 980 g of 37% aqueous formaldehyde solution,
A mixture of 20 g of triethylamine was reacted at 60 ° C. for 2 hours, then concentrated under reduced pressure and diluted with methanol to obtain a resol type phenol resin varnish having a resin content of 50%.

[Production of oil-modified resol type phenolic resin] 1600 g of phenol and 1000 g of tung oil were reacted at 95 ° C for 2 hours in the presence of paratoluenesulfonic acid, and 650 g of paraformaldehyde, 30 g of hexamethylenetetramine and 2000 g of toluene were added. 2 at 90 ° C
After the reaction for time, the mixture was concentrated under reduced pressure, and this was diluted with a mixed solvent of toluene and methanol to obtain an oil-modified phenol resin varnish having a resin content of 50%.

[Production of Unmodified Novolac-Type Phenolic Resin] The novolac-type phenolic resin is a phenol 10
It was obtained by reacting 00 g with 600 g of 37% aqueous formaldehyde solution using 10 g of oxalic acid as a catalyst. This was diluted with methanol to obtain a novolac type phenol resin varnish having a resin content of 50%.

(Preparation of resin varnish for impregnating paper base material) 100 parts by weight (30.3%) of the above-mentioned unmodified resol-type phenol resin varnish and 40 parts by weight (12.1%) of oil-modified resol-type phenol resin varnish. ), And 100 parts by weight (30.3%) of an unmodified novolac-type phenol resin varnish,
TBBA-epoxy oligomer (GX-153 manufactured by Dainippon Ink and Chemicals, Inc.) 10 parts by weight (6.1%) and triphenyl phosphate (TPP, manufactured by Daihachi Chemical Co., Ltd.) 20 parts by weight (12.1%). , Methylol melamine resin (resin content 50%) (Phenolite TD-2538, Dainippon Ink and Chemicals, Inc.) 30 parts by weight (9.1%), and water 50.
And 5 parts by weight (in this case, the amount of resin is 58% and the amount of water is 11%) to obtain a resin varnish for impregnating a paper base material.

(Production of Laminated Plate) Next, the above-mentioned resin varnish for impregnating the paper base material was impregnated with the paper base material so that the resin impregnation rate was 55% (ratio to the whole prepreg) to obtain a prepreg. Eight sheets of this prepreg and copper foil with adhesive (made by FSM Nippon Denryoku Co., Ltd.) were overlaid on both the front and back sides, and 150
The laminated plate A having a thickness of 1.6 mm was obtained by heat-press molding at 100 ° C. and 100 kg / cm ² for 10 minutes.

Example 2 In a resin varnish for impregnating a paper substrate, the amounts of unmodified resol-type phenol resin varnish, oil-modified resol-type phenol resin varnish and unmodified novolac-type phenol resin varnish were set as follows. Except for the above, the same procedure as in Example 1 was performed. The unmodified resol-type phenol resin varnish was 100 parts by weight, the oil-modified resol-type phenol resin varnish was 80 parts by weight, and the unmodified novolac-type phenol resin varnish was 100 parts by weight.

Example 3 A resin varnish for impregnating a paper substrate was prepared in the same manner as in Example 1 except that the amount of the oil-modified resol type phenolic resin was changed to 150 parts by weight.

Example 4 The procedure of Example 1 was repeated, except that the resin varnish for impregnating the paper base material contained 20 parts by weight of the oil-modified resol type phenol resin.

(Example 5) The procedure of Example 1 was repeated, except that the nonylphenol novolac type phenol resin was prepared by using 4-nonylphenol instead of phenol in the production of the novolac type phenol resin.

Example 6 A resin varnish for impregnating a paper substrate was prepared in the same manner as in Example 1 except that the oil-modified resol type phenolic resin was not used.

Comparative Example 1 A resin varnish for impregnating a paper substrate was prepared in the same manner as in Example 1 except that the resol type phenol resin was not used.

(Comparative Example 2) A resin varnish for impregnating a paper substrate was prepared in the same manner as in Example 1 except that novolac type phenol resin was not used.

The characteristics of the laminates obtained in the above-mentioned examples and comparative examples were evaluated. Each property was evaluated by the following methods. The results obtained are shown in Table 1.

Flame retardancy Measured by the vertical method based on UL standard. The thickness of the sample was 2 mm. Solder heat resistance It was measured based on JIS C 6481. Punching Workability Measured according to ASTM D617-44. Each symbol is as follows. ⊚: No resin chipping or peeling of the copper foil on the end faces of the laminated plate, and little generation of resin powder. ◯: No resin chipping or peeling of copper foil on the end surface of the laminated plate. However, many resin powders are generated. Δ: There was resin chipping and copper foil peeling on the end faces of the laminate. However, the generation of resin powder is small. X: Resin chipping and copper foil peeling occurred on the end faces of the laminate, and resin powder was often generated.

Bending Strength Measured according to JIS C 6481. Formaldehyde emission amount Measured based on the JAS desiccator method. Phenol elution amount It was measured based on JIS K 0102.

[0035]

[Table 1]

As is apparent from the table, Examples 1 to 6 are
It had excellent flame retardancy and punching processability. Moreover, especially Examples 1, 4, and 6 were excellent in bending strength. Also, especially in Examples 1, 4, 5 and 6, the amount of formaldehyde emission was small. From this, it was shown that the odor was low.

[0037]

According to the present invention, it is possible to obtain a paper-based phenol resin laminate having a small amount of unreacted phenol and formaldehyde emission, low odor, and good punching processability.

Continued front page    F term (reference) 4F072 AA07 AB03 AB31 AD15 AD16                       AD17 AG03 AH25 AH31                 4F100 AB01B AB01C AB17B AB17C                       AB33B AB33C AK33A AL05A                       BA03 BA06 BA10B BA10C                       CA23A DG10A DH01A EJ82                       GB41 JD20 YY00A                 4J002 CC04W CC04X CC06W CC06X                       CC08W CC08X GF00

Claims (6)

[Claims] 1. A phenol resin composition used for producing a paper-based phenol resin laminate, comprising a resol-type phenol resin and a novolac-type phenol resin. 2. The resol type phenolic resin contains an oil-modified resol type phenolic resin.
The phenolic resin composition described in 1. 3. The phenol resin composition according to claim 1, wherein the content of the resol-type phenol resin is 20 to 80% by weight based on the whole phenol resin composition. 4. The phenol resin composition according to claim 1, wherein the content of the novolac type phenol resin is 20 to 80% by weight based on the whole phenol resin composition. 5. A prepreg for a paper-based phenolic resin laminate, comprising a paper base material impregnated with the phenolic resin composition according to any one of claims 1 to 4. 6. A paper-based phenolic resin laminate comprising at least one prepreg according to claim 5.