JPH11158349A - Thermosetting resin composition and molded product using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermosetting resin composition having dihydrobenzoxazing ring in the molecule and satisfying both low-water absorptivity and curability. SOLUTION: This thermosetting resin composition comprises a dihydrobenzoxazine ring-bearing resin with the number ratio: the phenolic hydroxyl group/nitrogen atom (OH/N) in the whole composition of 0.4 to 1.5, and further, pref. contains one or both of phenolic resin and epoxy resin, and/or elastomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a resin-containing composition having a dihydrobenzoxazine ring, wherein the ratio of phenolic hydroxyl groups to nitrogen atoms in the composition is in a specific range.

[0002]

2. Description of the Related Art Conventionally, as a thermosetting resin system having a dihydrobenzoxazine ring, JP-B-49-47378 is known.
JP-A-2-69567 or JP-A-4-227
It is known that a resin having a dihydrobenzoxazine ring as disclosed in JP-A-922-92 is used alone or in combination with an epoxy resin. Also, J.I. Or
g. Chem. , 3423 (1965), Polm. S
ci. Technol. , 27 (1985);
JP-A--24292 and 8-183855 show that it is effective to add a compound having a phenolic hydroxyl group and a resin in order to improve the curability of the resin having a dihydrobenzoxazine ring.

[0003]

In the case of a cured thermosetting resin having a dihydrobenzoxazine ring, it is considered that the phenolic hydroxyl group in the cured product is immobilized by ionic bonds between molecules and intramolecularly by nitrogen atoms. It exhibits excellent low water absorption. On the other hand, as described above, it is known that the addition of a compound having a phenolic hydroxyl group or a resin is effective in improving the curability. However, if the amount of the compound having a phenolic hydroxyl group or the resin is excessively increased, the phenolic hydroxyl group is not fixed by an ionic bond due to a nitrogen atom derived from the dihydrobenzoxazine ring. However, the low water absorption characteristic of the cured product is greatly impaired. The present invention has been made in view of such circumstances, and has as its object to provide a thermosetting resin composition that satisfies both characteristics of low water absorption and curability, and a molded article using the composition.

[0004]

That is, the present invention relates to a resin composition containing a resin having a dihydrobenzoxazine ring, wherein the ratio of the number of phenolic hydroxyl groups to the number of nitrogen atoms (OH / N) in all the compositions is 0. The present invention relates to a thermosetting resin composition characterized in that the composition is set to 0.4 to 1.5, and a molded article using the composition.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The resin having a dihydrobenzoxazine ring used in the present resin composition can be synthesized from the corresponding compound having a phenolic hydroxyl group, formalin and a primary amine according to the following formula. This resin is
As shown in U.S. Pat. No. 5,152,939, a ring-opening polymerization reaction is caused by heating to form a phenolic hydroxyl group without generating volatile components, and to form a crosslinked structure having excellent properties.

Embedded image The characteristics of these resins are described in JP-A-7-188364.
As described in Japanese Patent Application Laid-Open Publication No. H10-260, there is a point that voids hardly remain in a cured product due to crosslinking and curing by a ring opening reaction. The cured product has characteristics such as low water absorption, relatively high glass transition temperature, high strength, and excellent flame retardancy. Examples of the compound having a phenolic hydroxyl group as a raw material include a phenol novolak resin, a resole resin, a phenol-modified xylene resin, an alkylphenol resin,
Phenol resins such as melamine-modified phenolic resin and polybutadiene-modified phenolic resin, or bis (2-hydroxyphenyl) methane, bis (4-hydroxyphenyl) methane, 4,4′-dihydroxydiphenylsulfone, 1,1-bis (4-hydroxy Phenyl) ethane,
P, P'-isopropylidene biphenol (bisphenol A), tetrafluorobisphenol A, 2,2-
Biphenol compounds such as bis [4- (4-hydroxyphenoxy) phenyl] propane, biphenol compounds such as 4,4'-biphenol, tris (4-hydroxyphenyl) methane, 1,1,1-tris (4-hydroxyphenyl ) Trisphenol compounds such as ethane, and tetraphenol compounds. These are not particularly limited, but those in which the ortho position of the hydroxy group serving as a crosslinking point is unsubstituted are preferable from the viewpoint of curing properties. Specific examples of the primary amine include methylamine, cyclohexylamine, aniline, and substituted aniline. When an aliphatic amine is used, the resulting thermosetting resin cures quickly, and the heat resistance of the cured product is slightly inferior. When an aromatic amine such as aniline is used, the obtained cured product has improved heat resistance, but is cured. Sex slows down.

The resin having a dihydrobenzoxazine ring in the present invention is prepared by adding a mixture of a compound having a phenolic hydroxyl group and a primary amine to an aldehyde heated to 70 ° C. or more, preferably at 70 to 110 ° C., 70
Reaction at -100 ° C for 20-120 minutes, then 120 ° C
It can be synthesized by drying under reduced pressure at the following temperature. In the synthesis of the resin, a compound that promotes the ring opening reaction of the dihydrobenzoxazine ring can be used. These compounds include amine compounds such as benzylmethylamine, imidazole and its derivatives, phosphorus-containing compounds,
Boron trifluoride amine complex, dicyandiamide and derivatives thereof, a compound having a phenolic hydroxyl group,
That is, a modified phenol resin such as a phenol novolak resin, a resol resin or a xylene-modified phenol resin, a xylylene-modified resin, and a low-molecular phenol compound such as bisphenol A can be mentioned. In particular, when a compound having a phenolic hydroxyl group is added and used, the amount of the compound used significantly increases the water absorption of the cured product, which is a great feature of the cured product of the resin having a dihydrobenzoxazine ring. Will be impaired. In order to prevent these, if the ratio of the number of phenolic hydroxyl groups and nitrogen atoms in the resin composition is controlled within a certain range,
It has been found that curability can be improved while suppressing an increase in water absorption. When a resin having a dihydrobenzoxazine ring and a compound having a phenolic hydroxyl group or a resin are used in combination, the ratio (OH / N) of the phenolic hydroxyl group to the number of nitrogen atoms in the resin composition is 1.5 to 0.4. It is necessary to Outside this range, the water absorption rate will increase significantly.

Further, an epoxy resin can be used in combination.
For example, bisphenol epoxy resin, novolak epoxy resin, cresol novolak epoxy resin,
Polyphenol-based epoxy resin, polyglycol-based epoxy resin, alicyclic epoxy resin, halogenated bisphenol A, halogenated bisphenol F, especially chlorosidyl ether of tetrabromobisphenol A or tetrabromobisphenol F and glycidyl ether of brominated novolak can do. By these modifications, it is possible to obtain a cured resin having a wide range of resin properties. These can be used in combination of two or more. For example, when a novolak-type epoxy resin or a cresol novolak-type epoxy resin is used, the crosslinking density can be improved, and when an alicyclic epoxy resin is used, tracking resistance can be improved. it can. As a curing agent for the epoxy resin, a compound such as benzylmethylamine, imidazole and its derivatives, a phosphorus compound, a boron trifluoride amine complex, dicyandiamide and its derivatives can be used as necessary.

In the present invention, the toughness is improved by blending an elastomer as required. The elastomer to be compounded is not particularly limited, but the elastomer in which a part of the main chain structural unit is crosslinked by the structural unit and the thermosetting resin having a dihydrobenzoxazine ring and the dihydrobenzoxazine ring are opened. A liquid elastomer having a functional group capable of reacting with the resulting phenolic hydroxyl group is preferably used. In the case of an elastomer in which a part of the main chain structural units are cross-linked with each other, an acrylonitrile-butadiene copolymer elastomer is particularly preferably used. Further, a thermosetting resin having a dihydrobenzoxazine ring in the elastomer and a phenolic hydroxyl group generated by opening of the dihydrobenzoxazine ring can react with a functional group such as an epoxy group,
Those having a functional group having a high solubility parameter such as a hydroxyl group or a carboxyl group are particularly preferred. In the case of a solid elastomer, the particle diameter is preferably 0.2 mm or less. When the elastomer having these crosslinked structures is mixed and cured with a thermosetting resin having a dihydrobenzoxazine ring, it is easy to obtain a sea-island type dispersion structure in which the selected particle size is maintained as long as particle aggregation does not occur. And toughness is improved. On the other hand, in a method of depositing and dispersing an elastomer in a thermosetting resin composition such as spinodal decomposition when an elastomer having no crosslinked structure is used,
It is difficult to control the particle size of the elastomer, and a uniform sea-island structure may not be obtained. Examples of the functional group of the liquid elastomer having a functional group capable of reacting with a thermosetting resin having a dihydrobenzoxazine ring and a phenolic hydroxyl group generated by opening the dihydrobenzoxazine ring include an amino group, an epoxy group, a carboxyl group, Phenolic hydroxyl groups are mentioned. The proportion of the elastomer is preferably 1 to 50 parts by weight, more preferably 2 to 40 parts by weight, based on 100 parts by weight of the thermosetting resin composition. When the amount is less than 1 part by weight, it is difficult to improve the toughness, and when the amount exceeds 50 parts by weight, the mechanical properties may be deteriorated.

Further, the resin composition of the present invention comprises a reinforcing agent,
Usable as fillers are ordinary inorganic and organic fillers and reinforcing fibers. For example, staple fiber, thread, cotton cloth, glass cloth, glass mat, glass fiber, carbon fiber, quartz fiber, flame-retardant synthetic fiber, silica powder, calcium carbonate, magnesium hydroxide and the like. Pretreatment of these with a coupling agent is also effective in improving the affinity of the interface with the resin. There is no particular limitation on the method, order, etc., for mixing these resins and curing agents.
The use of a coupling agent at this time is also effective for improving the affinity of the interface with the resin. Mold release agent if necessary,
It is also possible to use a coloring agent together. The method for producing a copper-clad laminate, a prepreg, a sealing material, and a molding material from these resin compositions is not particularly limited. Usually, these resin compositions are formed into a solution by using an organic solvent, and then applied to a substrate and dried.
The thus-prepared prepregs are laminated, copper foils are formed on both sides thereof, and then pressed, whereby a copper-clad laminate can be manufactured. In addition, a sealing material, a molding material, and the like can be manufactured by melt-kneading the resin composition and the filler. Since the thermosetting composition of the present invention does not generate volatile by-products during curing, it does not have an odor or the like and does not cause deterioration of the working environment.

[0010]

EXAMPLES Specific examples of the present invention will be shown below, but the present invention is not limited to these. Synthesis of Dihydrobenzoxazine Resin Two kinds of resins were synthesized by the following method. (Resin A) (1) Synthesis of phenol novolak resin 1.9 kg of phenol, formalin (37% aqueous solution)
1.0 kg and 4 g of oxalic acid were charged into a 5-liter flask and reacted at a reflux temperature for 6 hours. Continue with 6 inside
The pressure was reduced to 666.1 Pa or less to remove unreacted phenol and water. The obtained resin had a softening point of 84 ° C. (ring and ball method), and a 3 to polynuclear / binuclear ratio of 82/18 (peak area ratio by gel permeation chromatography). (2) Introduction of dihydrobenzoxazine ring 1.70 phenol novolak resin synthesized as above
kg (equivalent to 16 mol of hydroxyl groups) to aniline 1.
The mixture was mixed with 49 kg (corresponding to 16 mol) and stirred at 80 ° C. for 5 hours to prepare a uniform mixed solution. 1.62 kg of formalin was charged into a 5-liter flask, heated to 90 ° C., and a novolak / aniline mixed solution was gradually added thereto over 30 minutes. At the end of the addition, the mixture was kept at the reflux temperature for 30 minutes and then reduced to 6666.1 Pa or less at 100 ° C. for 2 hours to remove the condensed water. A thermosetting compound was obtained. (Resin B) A thermosetting compound having a dihydrobenzoxazine ring introduced therein was obtained in the same manner as in Resin A, except that a mixture of 0.93 kg of aniline and 0.64 kg of toluidine was used instead of aniline. The resulting thermosetting compound had a dihydrobenzoxazine ring introduced into 71% (by NMR analysis) of a reactive hydroxyl group of the phenol novolak resin. Further, as a phenol novolak resin used as a curing agent used for accelerating the curing of the resin having a dihydrobenzoxazine ring, HP-850N manufactured by Hitachi Chemical Co., Ltd. was used. Furthermore, a brominated epoxy resin manufactured by Toto Kasei Kogyo Co., Ltd., YDB-400T, was used as a flame retardant. Crosslinked NBR manufactured by Nippon Synthetic Rubber Co., Ltd.
XER-91 was used.

Examples 1 to 6 and Comparative Examples 1 to 4 Resin compositions having the formulations shown in Table 1 were prepared, and the gel time at 160 ° C. was measured. After curing at 185 ° C. for 90 minutes, the bending strength, the elastic modulus, the water absorption (after PCT for 20 hours), and the glass transition temperature by TMA were measured. The amount of the phenolic hydroxyl group was calculated by NMR analysis, and the number of nitrogen atoms in the resin having a dihydrobenzoxazine ring was calculated by elemental analysis.

[0012]

[Table 1] HP-850N: Phenol novolak resin manufactured by Hitachi Chemical Co., Ltd. YDB-400T: Brominated epoxy resin manufactured by Toto Kasei Kogyo Co., Ltd. XER-91: Crosslinked NBR manufactured by Nippon Synthetic Rubber Co., Ltd.

[0013]

[Table 2]

Examples 7 and 8 and Comparative Example 5 The resin compositions shown in Examples 1 and 2 and Comparative Example 1 were dissolved in MEK to prepare 55% varnish. Table 3 shows the results. This varnish was coated on a glass cloth to prepare a coated cloth and a prepreg. Coating conditions: 140 ° C / 1.5 minutes + 170
C./2 minutes + 175.degree. C./2 minutes + 150.degree. C./1.5 minutes. A copper foil (18 μm) was placed on both sides of the eight coated cloths obtained, the pressure was 30 kg / cm ² , and the temperature was 30 ° C. from room temperature to 185 ° C.
After heating at 185 ° C. for 60 minutes, the laminate was heated and pressed at 185 ° C. for 60 minutes to obtain a copper-clad laminate. The obtained copper-clad laminate was subjected to a water absorption treatment for a predetermined time by the Presher-Cooker method, and was immersed in a solder bath to measure the time for blistering.

[0015]

[Table 3]

Examples 9 to 10 and Comparative Example 6 Carnauba wax, anilinosilane, carbon black and fusible silicon dioxide powder were added to the resin formulations shown in Examples 1 and 2 and Comparative Example 1 in amounts of 1, 2, 2, and 320 parts, respectively. The resulting mixture was mixed with a hot roll (front roll temperature: 120 ° C., post-roll cooling) to form a sealing material composition. This resin composition was pulverized, a semiconductor element was placed in a metal cavity of a transfer molding machine, and resin molding was performed at 180 ° C., 70 kgf / cm ² for 180 seconds. Thereafter, post-curing is performed at 180 ° C. for 6 hours, and a predetermined time is set at 85 ° C. and 85% RH for 2 hours.
After absorbing water for 4 hours, heat treatment was performed at 215 ° C. for 90 seconds (reflow crack test) to evaluate the incidence of package cracks. Table 4 shows the results.

[0017]

[Table 4]

[0018]

According to the present invention, the dihydrobenzoxazine ring is formed by adjusting the ratio of the number of phenolic hydroxyl groups to the number of nitrogen atoms in the resin composition containing the resin containing the dihydrobenzoxazine ring to a specific range. The curability could be improved without impairing the low water absorption characteristic of the cured resin product. When these cured products are used as electronic materials for wiring boards and semiconductor encapsulating materials, it is possible to simultaneously improve the curing speed and the reliability derived from low water absorption.

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[Procedure amendment]

[Submission date] January 20, 1998

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0006

[Correction method] Change

[Correction contents]

The resin having a dihydrobenzoxazine ring according to the present invention is prepared by adding a mixture of a compound having a phenolic hydroxyl group and a primary amine to an aldehyde heated to 70 ° C. or higher, preferably at 70 to 110 ° C., 70
Reaction at -100 ° C for 20-120 minutes, then 120 ° C
It can be synthesized by drying under reduced pressure at the following temperature. In the synthesis of the resin, a compound that promotes the ring opening reaction of the dihydrobenzoxazine ring can be used. These compounds include amine compounds such as benzylmethylamine, imidazole and its derivatives, phosphorus-containing compounds,
Boron trifluoride amine complex, dicyandiamide and derivatives thereof, a compound having a phenolic hydroxyl group,
That is, a modified phenol resin such as a phenol novolak resin, a resole resin or a xylene-modified phenol resin, a xylylene-modified resin, and a low-molecular phenol compound such as bisphenol A can be mentioned. In particular, when a compound having a phenolic hydroxyl group is added and used, the amount of the compound used significantly increases the water absorption of the cured product, which is a great feature of the cured product of the resin having a dihydrobenzoxazine ring. Will be impaired. In order to prevent these, if the ratio of the number of phenolic hydroxyl groups and nitrogen atoms in the resin composition is controlled within a certain range,
It has been found that curability can be improved while suppressing an increase in water absorption. When a resin having a dihydrobenzoxazine ring and a compound having a phenolic hydroxyl group or a resin are used in combination, the ratio (OH / N) of the phenolic hydroxyl group to the number of nitrogen atoms in the resin composition is 1.5 to 0.4. It is necessary to If it exceeds 1.5, the water absorption rate will increase significantly, and if it is less than 0.4, the curability will be improved.
I can't do that .

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0013

[Correction method] Change

[Correction contents]

[0013]

[Table 2]

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0014

[Correction method] Change

[Correction contents]

The resin compositions shown in Examples 1 and 2 and Comparative Example 3 were dissolved in MEK to prepare a 55% varnish. Table 3 shows the results. This varnish was coated on a glass cloth to prepare a coated cloth and a prepreg. The coating conditions are 140 ° C /
1.5 minutes + 170 ° C / 2 minutes + 175 ° C / 2 minutes + 150 ° C
/1.5 minutes. The copper foil (1
8 μm), a pressure of 30 kg / cm ² ,
After the temperature was raised to 85 ° C. in 30 minutes, heating and pressure lamination was performed at 185 ° C. for 60 minutes to obtain a copper-clad laminate. The obtained copper-clad laminate was subjected to a water absorption treatment for a predetermined time by the Presher-Cooker method, and was immersed in a solder bath to measure the time for blistering.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0015

[Correction method] Change

[Correction contents]

[0015]

[Table 3]

[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0016

[Correction method] Change

[Correction contents]

Examples 9 to 10 and Comparative Example 6 Carnauba wax, anilinosilane, carbon black and fusible silicon dioxide powder were added to the resin formulations shown in Examples 1, 2 and 3 in amounts of 1, 2, 2, and 320 parts, respectively. The resulting mixture was mixed with a hot roll (front roll temperature: 120 ° C., post-roll cooling) to form a sealing material composition. This resin composition was pulverized, a semiconductor element was placed in a metal cavity of a transfer molding machine, and resin molding was performed at 180 ° C., 70 kgf / cm ² for 180 seconds. Thereafter, post-curing is performed at 180 ° C. for 6 hours, and a predetermined time is set at 85 ° C. and 85% RH for 2 hours.
After absorbing water for 4 hours, heat treatment was performed at 215 ° C. for 90 seconds (reflow crack test) to evaluate the incidence of package cracks. Table 4 shows the results.

[Procedure amendment 6]

[Document name to be amended] Statement

[Correction target item name] 0017

[Correction method] Change

[Correction contents]

[0017]

[Table 4]

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C08L 63/00 C08L 63/00 A H05K 1/03 610 H05K 1/03 610K 610L (72) Inventor Yoshinori Sato Shimodate, Ibaraki 1500 Ogawa, Hitachi Chemical Industry Co., Ltd., Shimodate Plant (72) Inventor Shinichi Kamoshida, Oji 1500, Shimodate City, Ibaraki Prefecture Hitachi Chemical Industry Co., Ltd. (72) Inventor Shunichi Numata 1500, Oji Ogawa, Shimodate City, Ibaraki Prefecture Inside the Shimodate Plant of Hitachi Chemical Co., Ltd.

Claims (6)

[Claims] In a resin composition containing a resin having a dihydrobenzoxazine ring, the ratio of the number of phenolic hydroxyl groups to the number of nitrogen atoms (OH / N) in the whole composition is from 0.4 to 1.
5. A thermosetting resin composition, wherein the composition is set to 5. 2. The thermosetting resin composition according to claim 1, wherein the resin composition contains at least one of a phenol resin and an epoxy resin. 3. The thermosetting resin composition according to claim 1, wherein the resin composition contains an elastomer. 4. A cured product obtained by curing the resin composition according to claim 1. 5. A composite molding material comprising the resin composition according to claim 1 and a reinforcing material. 6. A laminated board, a wiring board or a resin-sealed semiconductor device obtained by molding the composite molding material according to claim 5.