JP2003165899A - Resin composition, prepreg and laminated plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition that can develop flame retardancy without a halogen compound and has light shielding properties. <P>SOLUTION: This resin composition is for impregnating base materials to form sheet prepregs. The resin composition comprises (A) a tetrakishydroxyphenylethane type epoxy resin, (B) a halogen atom-free epoxy resin (wherein the resin (A) is excluded), (C) a novolac type phenol resin and (D) a halogen atom-free phosphorus compound. Base materials are impregnated with the resin composition to obtain the prepreg. A metal foil layer is laminated on the prepreg, pressed with heat to obtain the laminated plate. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition, a prepreg and a laminated board.

[0002]

2. Description of the Related Art Thermosetting resins typified by epoxy resins are widely used in electric and electronic equipment parts and the like, and are often provided with flame retardancy from the viewpoint of ensuring safety against fire. A halogen-containing compound is generally used to make these resins flame-retardant, but various problems such as generation of carcinogenic toxic substances such as dioxin have been pointed out when incinerated. For these reasons, various flame retardants have been investigated as alternatives to halogen-containing compounds.

As a flame retardant which replaces the halogen-containing compound, one using an inorganic filler such as a metal hydroxide has been put into practical use. However, in the various chemical liquid processes used in the laminated plate manufacturing process (basic compounds in the desmear process, oxide compounds in the blackening process, etc.), many of the common inorganic fillers react and cause defects. there were. Further, as compared with the case where only the resin without the addition of the inorganic filler is used, it becomes brittle and easily broken, so that the drill workability also tends to be deteriorated as compared with the conventional FR-4 material. For this reason, it is not preferable as a flame retardant for this application, and phosphorus compounds and nitrogen compounds have been investigated as other flame retardants.

On the other hand, conventionally, a method of adding a fluorescent absorber or a fluorescent dye to a resin has been widely used for a laminated board material suitable for forming a circuit using a photolithography method. This is because the effect of preventing the ultraviolet ray transmission of the fluorescent absorber or the fluorescent dye prevents the circuit reflection on the opposite surface side due to the transmission of ultraviolet and visible light (wavelength 300 to 450 nm). However, on the other hand, there is a demerit that the migration resistance of the laminated plate is deteriorated. Furthermore, many of these compounds are halogen-containing compounds and are not suitable for halogen-free materials. Therefore, no halogen-free material has a light shielding property.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin composition, a prepreg and a laminate which have flame retardancy and light-shielding properties without using a halogen-containing compound. is there.

[0006]

Such an object is achieved by the present invention described in (1) to (9) below. (1) A resin composition used for forming a sheet-like prepreg by impregnating a base material, comprising (A) a tetrakishydroxyphenylethane type epoxy resin and (B) an epoxy containing substantially no halogen atom. Resin (However,
(Excluding the component (A)), (C) phenolic resin,
(D) A resin composition comprising: a phosphorus compound that does not substantially contain a halogen atom. (2) The content of the tetrakishydroxyphenylethane type epoxy resin is 1 to 20% by weight of the entire resin composition.
The resin composition according to (1) above, which is (3) The resin composition according to the above (1) or (2), wherein the substantially halogen-free epoxy resin has a novolac type epoxy resin. (4) The resin composition according to any one of (1) to (3) above, wherein the novolac type phenolic resin has a triazine-modified novolac type phenolic resin. (5) Any of the above (1) to (4), wherein the phosphorus compound containing substantially no halogen atom has 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide. The resin composition according to claim 1. (6) The resin composition according to any one of (1) to (5) above, wherein the phosphorus compound containing substantially no halogen atom contains triphenylphosphine oxide. (7) The above 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and triphenylphosphine oxide are blended in a weight ratio of 1: 1 to 1: 5. The resin composition according to (6). (8) A prepreg obtained by impregnating a substrate with the resin composition according to any one of (1) to (7). (9) A laminated board, which is obtained by laminating a metal foil on the prepreg according to the above (8), and applying heat and pressure.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The resin composition, prepreg and laminate of the present invention will be described in detail below. The resin composition of the present invention is a resin composition used for forming a sheet-like prepreg by impregnating a base material with (A) a tetrakishydroxyphenylethane type epoxy resin,
(B) Epoxy resin containing substantially no halogen atom (excluding the above component (A)), (C) phenol resin, and (D) a phosphorus compound containing substantially no halogen atom. It is characterized by. Also,
The prepreg of the present invention is characterized in that it is obtained by impregnating a base material with the above resin composition. The laminated plate of the present invention is characterized in that a metal foil is laminated on the above-mentioned prepreg and heated and pressed.

The resin composition of the present invention will be described below. The resin composition of the present invention has a tetrakishydroxyphenylethane type epoxy resin. Thereby, when the resin composition of the present invention is used as a prepreg, the ultraviolet ray resistance can be improved. That is, it is preferable to use a resin that absorbs a wavelength (300 to 450 nm) in the visible region from the ultraviolet. The content of the tetrakis hydroxyphenylethane type epoxy resin is not particularly limited, but is preferably 1.0 to 20% by weight, and particularly preferably 2 to 15% by weight, based on the entire resin composition. If the content of the tetrakishydroxyphenylethane type epoxy resin is less than the lower limit value, the effect of improving the ultraviolet ray resistance may be lowered, and if it exceeds the upper limit value, the heat resistance may be lowered.

The resin composition of the present invention has an epoxy resin containing substantially no halogen atom. Examples of the epoxy resin which constitutes the epoxy resin containing substantially no halogen atom include bisphenol A type epoxy resin, bisphenol F type epoxy resin and other bisphenol type epoxy resin, bisphenol A novolac type epoxy resin, cresol type novolac epoxy resin, etc. Novolak type epoxy resin and the like. Among these, the novolac type epoxy resin containing substantially no halogen atom is preferable.

The content of the epoxy resin containing substantially no halogen atom is not particularly limited, but is preferably 20 to 70% by weight, and particularly preferably 40 to 50% by weight of the entire resin composition.
Is preferred. If the content of the epoxy resin is out of the above range, the resin may not be sufficiently cured, and the resin may cause curing failure. Further, in the resin composition of the present invention, although not particularly limited, it is preferable to use a bisphenol type epoxy resin and a novolac type epoxy resin in combination as the component (B). Thereby, it can have sufficient heat resistance and toughness as a laminated board use. The combination ratio of the bisphenol type epoxy resin and the novolac type epoxy resin is not particularly limited, but the weight ratio is preferably 1: 2 to 1: 5,
In particular, 1: 4 is preferable. When the combination ratio is within the above range, the adhesion between the metal foil and the resin can be further improved. In addition, it means that the content of halogen atoms in the epoxy resin is 0.1
It means less than wt%.

The resin composition of the present invention contains a phenol resin. As a result, excellent heat resistance can be obtained by curing the epoxy resin used. Examples of the phenol resin include phenol novolac resin, cresol novolac resin, phenol aralkyl resin, biphenyl aralkyl resin, and naphthalene aralkyl resin. Among these, phenol aralkyl resin, biphenyl aralkyl resin,
One or more resins selected from naphthalene aralkyl resins are preferred. Thereby, flame retardancy can be further improved. The content of the phenolic resin is
Although not particularly limited, 20 to 50% by weight, preferably 30 to 40% by weight, of the entire resin composition is preferable. When the content of the phenol resin is within the above range, the heat resistance of the cured resin product can be improved.

The resin composition of the present invention contains a phosphorus compound containing substantially no halogen atom. Thereby, flame retardancy can be further improved. Examples of the phosphorus compound containing substantially no halogen atom include, for example, trimethyl phosphate, triethyl phosphate,
Tributyl phosphate, tri-2-ethylhexyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, tris (2, Phosphate esters such as 6-dimethylphenyl) phosphate and resorcindiphenylphosphate, condensed phosphate esters such as dialkylhydroxymethylphosphonate, phosphine oxides such as triphenylphosphine oxide, and 9,10-dihydro-9-oxa-10-phosphine. Examples thereof include faphenanthrene-10-oxide. Among these, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is preferable. This makes it possible to impart flame retardancy to a resin cured product using the epoxy resin without impairing the properties of the epoxy resin. Further, triphenylphosphine oxide is preferable. Thereby, the flame retardancy of the resin cured product can be further improved. The phrase "substantially free of halogen atoms" means, for example, a phosphorus compound having a halogen atom content of less than 0.1% by weight.

Further, it is preferable to use the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and triphenylphosphine oxide (HCA) in combination. The combination ratio is not particularly limited, but 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and triphenylphosphine oxide are in a weight ratio of 1: 1 to 1: 4. Is preferable, and 1: 2 to 1: 3 is particularly preferable. When the combined ratio is within the above range, the water absorption can be reduced while having sufficient flame retardancy.

The content of the phosphorus compound containing substantially no halogen atom is not particularly limited, but is preferably 0.5 to 5.0% by weight, and particularly 1 to 5.0% by weight based on the entire resin composition.
3% by weight is preferred. In order not to impair the excellent properties of the epoxy resin, those that react with the epoxy resin are preferable, and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and triphenylphosphine oxide are particularly preferable. .

In the present invention, the above-mentioned tetrakishydroxyphenylethane type epoxy resin and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- are used.
By using oxide, triphenylphosphine oxide, and triphenylphosphine oxide in combination, in the state where the V-0 level is maintained in non-halogen flame retardancy, ultraviolet ray absorption resistance, which is a drawback of conventional epoxy resin compositions, is maintained. It is possible to improve the characteristics. Further, by the above combination, in addition to the above effects, the long-term storage stability of the resin varnish can be improved. Conventionally, the long-term storability of resin varnish is about one week, and if it is longer than that, the quality of the product may be impaired. On the other hand, in the present invention, the long-term storability of the resin varnish is about 2 weeks, the product quality is not impaired, and the above-mentioned problems can be greatly improved.

The flame-retardant resin composition of the present invention comprises the above-mentioned tetrakishydroxyphenylethane type epoxy resin,
An epoxy resin containing substantially no halogen atom, a novolak type phenol resin, and a phosphorus compound containing substantially no halogen atom as essential components, but other curing agents within the range not deviating from the object of the present invention. The curing accelerator, coupling agent, and other components may be added. Phenol aralkyl resin as a curing agent,
When a novolak resin having a large hydroxyl equivalent such as a biphenylaralkyl resin or a naphthalenearalkyl resin is used in combination, flame retardancy and solder heat resistance can be improved.

Next, the prepreg will be described. The prepreg of the present invention is obtained by impregnating a base material with the above resin composition. This makes it possible to obtain a prepreg excellent in flame retardancy and ultraviolet absorption resistance. Examples of the base material include glass fiber cloth such as glass woven cloth, glass non-woven cloth, and glass paper, woven cloth and nonwoven cloth made of organic fibers such as paper (pulp), aramid, polyester, and fluororesin, metal fiber, and carbon. Examples thereof include woven fabrics, non-woven fabrics and mats made of fibers, mineral fibers and the like. You may use these base materials individually or in mixture.

Examples of the method of impregnating the base material with the resin composition include a method of immersing the base material in a resin varnish, a method of coating with a coater, and a method of spraying. Among these, the method of immersing the base material in the resin varnish is preferable. Thereby, the impregnation property of the resin composition on the substrate can be improved. In addition,
When dipping the base material in the resin varnish, ordinary impregnation coating equipment can be used.

The solvent used for the resin varnish preferably has good solubility in the resin composition, but a poor solvent may be used within a range that does not have an adverse effect. Examples of the solvent exhibiting good solubility include methyl ethyl ketone and cyclohexanone. The solid content of the resin varnish is not particularly limited, but the solid content of the resin composition is preferably 40 to 80% by weight, and particularly 50.
˜65 wt% is preferred. This can further improve the impregnation property of the resin varnish into the base material.

Next, the laminated plate will be described. The laminated plate of the present invention is obtained by laminating a metal foil on the prepreg and heating and pressing the same. This makes it possible to obtain a laminate having excellent flame retardancy and ultraviolet absorption resistance. In the case of one prepreg, metal foil or film is laminated on both upper and lower surfaces or one surface. Also, two or more prepregs can be laminated. When laminating two or more prepregs, metal foils or films are laminated on the outermost upper and lower surfaces or one surface of the laminated prepregs. Next, a laminated plate can be obtained by heating and pressing a laminate of the prepreg and the metal foil. The heating temperature is not particularly limited, but is preferably 120 to 220 ° C, and particularly preferably 150 to 200 ° C. The pressure to be applied is not particularly limited, but is preferably 2 to 5 MPa, and particularly preferably 2.5 to 4 MPa.

Hereinafter, the present invention will be described in detail based on Examples and Comparative Examples, but the present invention is not limited thereto.

Example 1 Preparation of varnish 42% by weight of cresol novolak type epoxy resin (Epiclon N-690 manufactured by Dainippon Ink and Chemicals, Inc.), tetrakis hydroxyphenylethane type epoxy resin (Epicoat 1031S manufactured by Japan Epoxy Resins Co., Ltd.) 7% by weight, bisphenol A type epoxy resin (Epicoat 1016 manufactured by Japan Epoxy Resins Co., Ltd.) 12% by weight, phenol aralkyl resin (Mirex XL manufactured by Mitsui Chemicals, Inc.)
C-LL) to 37% by weight, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (1% by weight), triphenylphosphine oxide (1% by weight), and methylcellosolve to add non-volatile components. The varnish was adjusted so that the concentration was 60%. At this time epoxy resin,
The phosphorus component is 0.24 with respect to 100 parts by weight of the total of the curing agent.
It became%.

Preparation of prepreg Using the above varnish, glass cloth (thickness 0.10 m
m, manufactured by Asahi Schebel Co., Ltd.), 80 parts of the resin composition was impregnated with the solid content of the varnish, and dried in a dryer oven at 150 ° C. for 5 minutes to prepare a prepreg A having a resin content of 50%. In the same manner, glass cloth (thickness 0.18
mm, manufactured by Asahi Schebel Co., Ltd., resin content 46
% Prepreg was created.

Preparation of Laminated Plate A thickness of 1 mm above and below one prepreg of 0.10 mm thickness as described above.
8μm electrolytic copper foil is overlaid, pressure 25kgf / cm2,
Heat and pressure molding was performed at a temperature of 190 ° C. for 120 minutes to obtain a thickness of 0.
A 1 mm double-sided copper clad laminate A was obtained. Similarly, the thickness is 0.
A double-sided copper-clad laminate B having a thickness of 0.40 mm was obtained by using two 20 mm prepregs.

Example 2 The same as Example 1 except that the compounding amount was changed as shown in Table 1.

(Example 3) The addition amount of the tetrakishydroxyphenylethane type epoxy resin as the component (A) was changed to
The same procedure was performed as in Example 1 except that the amount of the cresol novolac epoxy resin added was 47% by weight, which was 2% by weight.

(Example 4) The same as in Example 1 except that 2% by weight of triphenylphosphine oxide was used without using 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide. did.

(Example 5) The same procedure as in Example 1 was carried out except that 2% by weight of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was used and triphenylphosphine oxide was not used. .

Comparative Example 1 The procedure of Example 1 was repeated except that the tetrakishydroxyphenylethane type epoxy resin was not used and the cresol novolac type epoxy resin was 49% by weight.

Comparative Example 2 The procedure of Example 1 was repeated except that 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and triphenylphosphine oxide were not used.

With respect to the obtained laminated plate, the ultraviolet transmittance,
The flame retardancy, solder heat resistance, and peel strength were evaluated. The results are shown in Table 1. Each evaluation was performed as follows. UV transmissivity The copper foil of the obtained double-sided copper clad laminate A was removed by etching and used as a sample. Using the UV illuminance meter (UV LIGHT MEASURE UV-MO2) manufactured by Oak Manufacturing Co., Ltd. evaluated.

Flame-retardant The obtained double-sided copper-clad laminate B having the copper foil removed by etching was used as a sample and evaluated by the vertical method according to UL-94 standard.

Solder heat resistance Using the obtained double-sided copper clad laminate B, JIS C 64
It evaluated according to 81. Regarding the solder heat resistance, after conducting a moisture absorption treatment for 2 hours of boiling, it was immersed in a solder bath at 260 ° C. for 120 seconds, and then examined for abnormal appearance. Each symbol is as follows. ⊚: No abnormality. ○: Some measling is available, but it is practical. Δ: Measling is present and not practical. ×: swelling

Peel strength Using the obtained double-sided copper-clad laminate B, JIS C 64
It evaluated according to 81.

[0034]

[Table 1]

.. As is clear from the table, Examples 1-5
Had excellent flame retardancy and low UV transmittance. From this, it was shown that Examples 1 to 5 are both halogen-free and have both flame retardancy and light shielding properties. In addition, Examples 1 and 2
Had a particularly low ultraviolet transmittance.

[0036]

EFFECTS OF THE INVENTION According to the present invention, a highly advanced resin composition which exhibits flame retardancy without using a halogen-containing flame retardant and imparts light shielding properties in the ultraviolet and visible regions (wavelength 300 to 450 nm). An article, a prepreg, and a laminate obtained from the prepreg can be obtained.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08K 5/5397 C08K 5/5397 F-term (reference) 4F072 AA04 AA07 AB09 AB28 AD27 AE07 AF16 AG03 AG19 AH02 AH22 AJ04 AK14 AL12 4F100 AB01B AB33B AG00 AH10A AK33A AK53A AL05A BA02 BA03 BA06 BA13 DG11 DH01A EJ17 EJ42 EJ82A GB43 JD09 JJ07 JL00 YY00A 4J002 CD041 CD051 CD061 EW046 EW146 FD136 GF00 GQ00 4J036 AA01 AB03 AD08 AF06 AF08 AF19 FA12 FB08 JA08 JA11

Claims (9)

[Claims] 1. A resin composition used for forming a sheet-like prepreg by impregnating a base material, comprising: (A) a tetrakishydroxyphenylethane type epoxy resin; and (B) a substantially halogen atom. A resin composition comprising: a non-epoxy resin (excluding the above component (A)), (C) a phenol resin, and (D) a phosphorus compound containing substantially no halogen atom. 2. The content of the tetrakishydroxyphenylethane type epoxy resin is 1 to 2 based on the total amount of the resin composition.
The resin composition according to claim 1, which is 0% by weight. 3. The resin composition according to claim 1, wherein the epoxy resin containing substantially no halogen atom is a novolac type epoxy resin. 4. The resin composition according to claim 1, wherein the novolac-type phenol resin has a triazine-modified novolac-type phenol resin. 5. The phosphorus compound containing substantially no halogen atom is 9,10-dihydro-9-oxa-10-.
The resin composition according to any one of claims 1 to 4, which comprises phosphaphenanthrene-10-oxide. 6. The resin composition according to claim 1, wherein the phosphorus compound containing substantially no halogen atom contains triphenylphosphine oxide. 7. The 9,10-dihydro-9-oxa-
The weight ratio of 10-phosphaphenanthrene-10-oxide and triphenylphosphine oxide is 1: 1 to 1: 1.
The resin composition according to claim 6, which is blended in a ratio of 1: 5. 8. A prepreg obtained by impregnating a base material with the resin composition according to any one of claims 1 to 7. 9. A laminated board, characterized in that a metal foil is laminated on the prepreg according to claim 8 and heated and pressed.