JPH09216994A - Thermosetting resin composition and cured product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermosetting resin compsn. which can improve the adhesion between a resin and a reinforcement to provide a cured product having excellent low moisture absorption and mechanical properties by incorporating a specified coupling agent into a resin compsn. comprising a thermosetting resin having a dihydrobenzoxazine ring. SOLUTION: This resin compsn. comprises a thermosetting resin having a dihydrobenzoxazine ring, a reinforcement selected among org. fillers and fiber materials, and a coupling agent. The coupling agent is a compd. represented by formula I (wherein R<1> represents N2 -CONH-, C6 H5 NH-, NH2 - CH2 -CH2 -NH- or a group of formula II; R<2> represents CH3 or C2 H5 ; a is 1 to 10; b is 0 to 2; and c is 1 to 3) or formula III (wherein R<3> represents a group of formula IV; and a, b, and c are each as defined above). This resin compsn. is excellent in the adhesion between the resin and the reinforcement and can provide a cured product possessing good mechanical properties and low moisture absorption. Therefore, it is useful as a raw material for the preparation of a highly functional molding material, a paint, an adhesive, a metal foil-clad laminate sheet, a semiconductor device, FRP and the like.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermosetting resin composition which is preferably used as a raw material for manufacturing prepregs, metal-clad laminates, encapsulants, wiring boards, semiconductor devices and the like, and a cured product thereof.

[0002]

2. Description of the Related Art Thermosetting resins having a dihydrobenzoxazine ring are known to give cured products excellent in low water absorption, heat resistance and mechanical strength (JP-A-49-47).
No. 387). This resin is cured by using a ring-opening polymerization reaction of a dihydrobenzoxazine ring, and is thermoset with almost no generation of volatile components (US Pat.
No. 152930), which is an excellent resin without deterioration of characteristics due to volatile matter.

However, when the thermosetting resin is mixed with various fillers, fibers, etc. to form a resin composition, the adhesiveness between the resin and the fillers, fibers, etc. is insufficient, and dihydrobenzoxazine is present. The properties such as low hygroscopicity and high strength of the resin having a ring could not be sufficiently exhibited.

[0004]

DISCLOSURE OF THE INVENTION The present invention improves the adhesion between a thermosetting resin having a dihydrobenzoxazine ring and a reinforcing agent such as a filler or a fibrous agent, and improves the adhesion between the resin and the reinforcing agent. Contains a thermosetting resin having a dihydrobenzoxazine ring, which has excellent hygroscopicity and mechanical properties.
An object is to provide a composition having excellent mechanical properties and a cured product thereof.

[0005]

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that a resin composition containing a thermosetting resin having a dihydrobenzoxazine ring has a specific chemical structure. By adding a coupling agent, it was found that the adhesion between the resin and the reinforcing agent was improved and the above-mentioned object was achieved, and the present invention was completed based on this finding.

That is, the present invention provides a thermosetting resin composition containing a thermosetting resin having a dihydrobenzoxazine ring, a reinforcing agent selected from organic fillers, inorganic fillers and fibers, and a coupling agent. The present invention provides a thermosetting resin composition characterized by using a compound represented by the following formula (1) or (2) as a ring agent.

[0007]

Embedded image

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The thermosetting resin having a dihydrobenzoxazine ring used in the resin composition of the present invention is a resin having a dihydrobenzoxazine ring and cured by a ring-opening polymerization reaction of the dihydrobenzoxazine ring. It is not particularly limited as long as it is. Specifically, as shown in the following reaction formula,

[0009]

Embedded image (R in the formula is a methyl group, a phenyl group, or a phenyl group substituted with at least one alkyl group or alkoxyl group having 1 to 3 carbon atoms.) At least one of the ortho positions of the polyphenol or the hydroxyl group is hydrogen. A compound having two or more hydroxyphenyl groups or hydroxyphenylene groups in one molecule in combination (hereinafter referred to as a polyfunctional phenol compound).
And a primary amine are added to formaldehyde such as formalin heated to 70 ° C. or higher to give 70-
110 ° C., preferably 90 to 100 ° C., 20 minutes to 2
It is obtained by reacting for a time and then drying under reduced pressure at a temperature of 120 ° C. or lower.

Examples of polyfunctional phenol compounds include catechol, hydroquinone, resorcinol, bis (2-hydroxyphenyl) methane, bis (4-hydroxyphenyl) methane, 4,4'-dihydroxydiphenylsulfone, 1,1-bis (4). -Hydroxyphenyl) ethane,
p, p'-isopropylidene biphenol (bisphenol A), tetrafluorobisphenol A, 2,2-
Bis [4- (4'-hydroxyphenoxy) phenyl]
Propane, tris (4-hydroxyphenyl) methane,
1,1,1-tris (4-hydroxyphenyl) ethane, 4,4'-biphenol, phenol novolac resin, resole resin, phenol-modified xylene resin, alkylphenol resin, melamine phenol resin, phenol-modified polybutadiene, etc. may be mentioned. These are not particularly limited, but those in which the ortho position of the hydroxyl group serving as a crosslinking point is unsubstituted are desirable in terms of curing properties.For example, in the case of a phenol novolak resin, the ortho ratio is small and the molecular weight is relatively small. It is preferred to use small so-called random novolaks.

Specific examples of the primary amine include methylamine, substituted anilines such as aniline, toluidine and anisidine. When it is an aliphatic amine, the obtained thermosetting resin cures quickly but has poor heat resistance. When an aromatic amine such as aniline is used, the cured product obtained by curing the obtained thermosetting resin has good heat resistance, but cures slowly.

Among the thermosetting resins having a dihydrobenzoxazine ring, preferably, the structural unit (A) represented by the following formula (A) and the structural unit represented by the following formula (B) in one molecule. (B), each structural unit is bonded directly or via an organic group, and the molar ratio of (A) / (B) is 1 / 0.25 to 1/9, and 1 molecule When the number of structural units (A) therein is m and the number of structural units (B) is n,
A thermosetting resin having m ≧ 1, n ≧ 1 and 10 ≧ m + n ≧ 2 is used.

[0013]

Embedded image (Wherein R is a methyl group, a cyclohexyl group, a phenyl group or a phenyl group substituted with at least one alkyl group or alkoxyl group having 1 to 3 carbon atoms,
Hydrogen in the aromatic ring of (A) and (B), except for one of the ortho positions of the hydroxyl group of (A), may be substituted with an alkyl group or alkoxyl group having 1 to 3 carbon atoms or a halogen atom. M and n are within the above ranges, and the structural units (A) and (B)
If the space is previously bound by a stable bond via a group having an appropriate chain length, the properties of the cured product will be good.

The structural unit (A) and the structural unit (B) are bonded directly or through an organic group. Examples of the organic group include an alkylene group and a divalent aromatic group. Examples of the alkylene group include an alkylene group having 5 or more carbon atoms,-
And an alkylidene group represented by CR'H- (wherein R 'is a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a phenyl group or a substituted phenyl group). Examples of the substituent of the substituted phenyl group include a methyl group, a methoxy group, and a carboxyl group. Further, examples of the divalent aromatic group include a phenylene group, a xylylene group, and a tolylene group. Two or more of the above organic groups may be inserted between each structural unit.

The thermosetting resin used in the present invention is
The molar ratio of (A) / (B) is preferably 1 / 0.25 to
1/9, more preferably 1 / 0.67 to 1/9.
Outside this range, curability, mechanical strength, and heat resistance may decrease.

The above-mentioned thermosetting resin having a dihydrobenzoxazine ring is a compound having two or more hydroxyphenylene groups in which at least one ortho-position of a hydroxyl group is hydrogen in one molecule (hereinafter referred to as reactable hydroxyphenylene group). A compound having a group) and a primary amine are added to formaldehyde such as formalin heated to 70 ° C. or higher, and the mixture is heated at 70 to 110 ° C., preferably 90 to 100 ° C. for 20 minutes. It is obtained by reacting for ˜2 hours and then drying under reduced pressure at a temperature of 120 ° C. or lower. In this reaction, the hydroxyl group 1 of the compound having a reactive hydroxyphenylene group
It is important to use the primary amine in a ratio of 0.2 to 0.9 mol per mol.

As the compound having a reactive hydroxyphenylene group, various compounds partially having a phenol nucleus can be used. Specific examples thereof include phenol novolac resin, resol resin, phenol-modified xylene resin, alkylphenol resin, melamine phenol resin, and phenol-modified polybutadiene.

The thermosetting resin having a dihydrobenzoxazine ring has a temperature of 150 ° C. or higher, preferably 170 to 2 ° C.
By heating to 20 ° C., curing is performed without using a catalyst or a curing agent and without generating by-products.

The thermosetting resin having a dihydrobenzoxazine ring used in the present invention can be used in combination of two or more kinds. In addition, by preliminarily treating these thermosetting resins at 80 to 180 ° C., preferably 120 to 160 ° C., a part of them can be pre-polymerized to control the curing rate and melt viscosity during molding.

Examples of the reinforcing agent to be blended with the thermosetting resin having a dihydrobenzoxazine ring include various organic fillers, inorganic fillers and fibrous agents, which are not particularly limited, and they may be used alone or in combination of two or more. Used as a mixture.

As the organic filler, cotton floc, α-
Examples thereof include cellulose, pulp, wood flour and the like. Examples of the inorganic filler include zircon powder, quartz glass powder, talc powder, calcium carbonate powder, magnesia powder, calcium silicate powder, silica powder, zeolite, clay and mica. The particle size of the inorganic filler can be appropriately selected. Examples of the fiber agent include glass fiber and glass cloth. The mixing ratio of these reinforcing agents is preferably 1 with respect to 100 parts by weight of the thermosetting resin.
0 to 300 parts by weight.

As the coupling agent to be added to the thermosetting resin composition of the present invention, the compounds represented by the above (1) and (2) are used. By incorporating this coupling agent, the adhesiveness between the resin and the reinforcing agent is remarkably improved as compared with other coupling agents, and a thermosetting resin composition giving a cured product excellent in mechanical properties and hygroscopicity is obtained. can get. Specific examples of the coupling agent used in the present invention include γ-ureidopropyltriethoxysilane, γ-anilinopropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltriethoxy. Examples thereof include silane hydrochloride.

The mixing ratio of the coupling agent is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the thermosetting resin. If the amount is less than 0.1 parts by weight, the effect of incorporating the coupling agent is small, and if the amount is more than 10 parts by weight, the components that do not contribute to the adhesion between the resin and the reinforcing agent are increased, so that they become volatile components during curing, and It may cause a decrease.

In the thermosetting resin composition of the present invention, in addition to the above-mentioned components, if necessary, a compound having a phenolic hydroxyl group which has an effect of opening the dihydrobenzoxazine ring, such as bisphenol A or novolac. A resin, a resole resin, a compound having an amino group, or the like, or a curing agent such as an epoxy resin having reactivity with a phenolic hydroxyl group formed by ring opening of a dihydrobenzoxazine ring can be added. The mixing ratio of the curing agent is preferably 1 to 30 parts by weight with respect to 100 parts by weight of the thermosetting resin. Further, a curing accelerator that accelerates the reaction between the thermosetting resin and the curing agent can be added. As a curing accelerator,
For example, conventionally known compounds such as imidazole compounds, dicyandiamide compounds and phosphorus compounds can be mentioned. The preferred mixing ratio of the curing accelerator is 0.1 to 5 parts by weight with respect to 100 parts by weight of the thermosetting resin.

After the thermosetting resin having a dihydrobenzoxazine ring, the reinforcing agent and the coupling agent are finely pulverized,
The powders may be mixed, but it is preferable to melt-mix with a heating roll, a kneader, an extruder or the like.

If desired, a releasing agent, a coloring agent or the like may be added to the above composition.

The thermosetting resin composition of the present invention is kneaded with a heating roll or the like, and then 180 to 220 ° C., molding pressure 2
Cured by compression molding or transfer molding at 0 to 70 kgf / cm ² for 3 to 10 minutes to obtain a cured product having good mechanical properties and low hygroscopicity utilizing the properties of the thermosetting resin having a dihydrobenzoxazine ring. be able to.

The cured product is further heated at 180 to 220 ° C.
By post-curing for 5 to 120 minutes, a cured product having better properties can be obtained.

[0029]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples of the present invention and Comparative Examples thereof, but the present invention is not limited to these Examples.

Examples 1-5, Comparative Examples 1-3 Synthesis of thermosetting resin having dihydrobenzoxazine ring (I) -Resin A (1) Synthesis of phenol novolac 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 novolac resin synthesized as described above
kg (corresponding to 16 mol of hydroxyl groups) to 0.1 kg of aniline.
The mixture was mixed with 93 kg (corresponding to 10 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. After the addition was completed, the mixture was kept at a reflux temperature for 30 minutes, and after that, the condensation water was removed by reducing the pressure to 6666.1 Pa or less at 100 ° C. for 2 hours, and 71% of the reactive hydroxyl groups were dihydrobenzoxazinized. Resin was obtained (m = 1, n = 2.2).

1.70 kg (corresponding to 16 mol of hydroxyl groups) of phenol novolac resin synthesized according to the above (1) was reacted in the same manner as 1.4 kg (corresponding to 16 mol) of aniline and 2.59 kg of formalin (37% aqueous solution),
A thermosetting resin in which a dihydrobenzoxazine ring was introduced into all the reactive hydroxyl groups was synthesized. Excess aniline and formalin were removed during drying, and the yield of this thermosetting resin was 3.34 kg. This indicates that 14 mol out of 14 mol of the hydroxyl group of the phenol novolac resin reacted to be dihydrobenzoxazinized.

From the above, the thermosetting resin thus obtained had 10 mol out of 14 mol of hydroxyl groups capable of reacting.
(= 71%) is presumed to be dihydrobenzoxazinated.

Synthesis of thermosetting resin having dihydrobenzoxazine ring (II) -Resin B 2.28 kg of bisphenol A and 1.86 k of aniline
g and formalin (37% aqueous solution) 3.24 kg were used, and a thermosetting resin was synthesized in the same manner as in the above (2).

Resin A or Resin B50 obtained as described above
A predetermined amount of a coupling agent is added to and mixed with a resin composition composed of 50% by weight and glass fiber (manufactured by Nitto Boseki Co., Ltd., microfiber NHX, glass fiber length 100 μm).
After kneading with a biaxial heating roll, this was crushed to prepare a powdery molding material.

Next, the mold temperature is 200 ° C. and the molding pressure is 50.
Molding was performed at kgf / cm ² for 8 minutes. The mechanical properties of the obtained molded product were measured according to JIS K 6911.
Table 1 shows the measurement results.

In the examples, SZ, manufactured by Toray Dow Corning Silicone Co., Ltd., was used as the coupling agent.
6032, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride;
AY43-031, γ-ureidopropyltrimethoxysilane, manufactured by Nippon Unicar Co., Ltd., Y9669 (γ-
(Anilinopropyltrimethoxysilane), and in the comparative example, Toray Dow Corning Silicone Co., Ltd.
AY43-043, trimethylmethoxysilane; manufactured by Shin-Etsu Silicone Co., Ltd., KBE903, γ-aminopropyltriethoxysilane was used.

[0038]

[Table 1]

[0039]

The thermosetting resin composition containing the thermosetting resin having a dihydrobenzoxazine ring of the present invention has excellent adhesion between the resin and the reinforcing agent, and the cured product has good mechanical properties and low hygroscopicity. Is equipped with. Therefore, the thermosetting resin composition of the present invention is a highly functional molding material, paint, coating agent, adhesive, sealant, prepreg, metal foil-clad laminate,
It is useful as a raw material for manufacturing semiconductor devices and FRP.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshinori Sato 1500 Ogawa, Shimodate-shi, Ibaraki Hitachi Chemical Co., Ltd. Shimodate factory (72) Inventor Shinichi Kamoshida 1500 Ogawa, Shimodate, Ibaraki Hitachi Chemical Co., Ltd. Inside the Shimodate Factory (72) Minor Kakitani Minato 1500 Ogawa, Shimodate City, Ibaraki Hitachi Chemical Co., Ltd.Shimodate Factory (72) Hideo Nagase 1500 Ogawa, Shimodate City, Ibaraki Hitachi Chemical Co., Ltd.Shimodate Factory

Claims (5)

[Claims] 1. A thermosetting resin composition containing a thermosetting resin having a dihydrobenzoxazine ring, a reinforcing agent selected from organic fillers, inorganic fillers and fiber agents, and a coupling agent. A thermosetting resin composition comprising a compound represented by the following formula (1) or (2) as Embedded image 2. The thermosetting resin composition according to claim 1, wherein the coupling agent is γ-ureidopropyltriethoxysilane or γ-anilinopropyltrimethoxysilane. 3. The thermosetting resin composition according to claim 1, wherein the coupling agent is N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltriethoxysilane hydrochloride. 4. A thermosetting resin 10 containing an amount of coupling agent.
The thermosetting resin composition according to claim 1, which is 0.1 to 10.0 parts by weight with respect to 0 parts by weight. 5. A cured product obtained by curing the thermosetting resin composition according to claim 1.