JPH07126351A - Diallyl phthalate resin compoistion excellent in adhesion to copper foil - Google Patents

Abstract

PURPOSE:To obtain a diallyl phthalate resin compsn. which is excellent in adhesion to a copper foil and gives a molding hardly degradable at high temp. and humidity. CONSTITUTION:This diallyl phthalate resin compsn. contains 50-90wt.% diallyl plithalate resin, 3-15wt.% maleic anhydride. and 7-35wt.% cresole novolak epoxy resin.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel diallyl phthalate resin composition. More specifically, the present invention relates to a resin composition having excellent adhesiveness to a metal, particularly to a copper foil useful for applications such as a copper clad laminate for a printed circuit of an electronic device.

[0002]

2. Description of the Related Art Conventionally, diallyl phthalate resins mainly composed of prepolymers derived from diallyl orthophthalate, diallyl isophthalate and diallyl terephthalate are excellent in retaining electric properties at high temperature and high humidity. , Has been used for many years as a molding material for electric and electronic parts that require high reliability, or as a casting resin, and has a track record of many years. Further, the diallyl phthalate resin has excellent dimensional stability, heat resistance, moisture resistance and water resistance,
It is also used as a resin for laminates. However, its application is the adhesion of diallyl phthalate resin to metal,
It was limited because copper, which is mainly used among others, has poor adhesion.

However, in recent years, with the miniaturization of electric and electronic devices, miniaturization of each component and surface mounting technology on a substrate have been rapidly advanced, and the required characteristics such as heat resistance are inevitably severe. Under such a trend, the heat resistance of the diallyl phthalate resin is re-evaluated, and it is required to improve the adhesiveness with a metal, which is a drawback of this resin.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a diallyl phthalate resin composition having excellent adhesiveness to metals and copper, while maintaining the excellent properties of conventional diallyl phthalate resins. To do.

[0005]

Means for Solving the Problems As a result of earnest research, the present inventor has improved the peel strength of a copper-clad molded article by melting and mixing a specific epoxy resin and a specific curing agent with a diallyl phthalate resin, thereby improving the high temperature. The present invention has been completed by finding that a resin composition with little deterioration in a high humidity atmosphere can be obtained.

According to the present invention, (a) diallyl phthalate resin is 50 to 90% by weight, and (b) maleic anhydride is 3 to
A diallyl phthalate resin composition having excellent adhesiveness to a copper foil, which comprises 15% by weight and (c) 7 to 35% by weight of a cresol novolac type epoxy resin.

Conventionally, an epoxy resin is often used in a copper-clad laminate because of its good adhesiveness. However, in order to impart the characteristics to the diallyl phthalate resin, the epoxy resin is melt-mixed with the diallyl phthalate prepolymer. Then, it has no effect on the adhesiveness. That is, it is essential to add a considerable amount of a curing agent, and even if an epoxy resin that does not contain a curing agent is mixed with a diallyl phthalate-based resin, the epoxy resin does not cure due to heating, and the mechanical strength of the entire system is extremely high. It becomes weak. Further, in this case, the peel strength is not expressed. Further, as the curing agent for the commercially available epoxy resin, it is general to use mainly amine compounds from the viewpoint of room temperature curability and price, but if the amine curing agent is the main component, the curing of diallyl phthalate resin is It is unfavorable because it is hindered and the heat resistance and water resistance of the cured product deteriorate. As a result of various studies by the present inventor, maleic anhydride, which is classified as an acid anhydride-based curing agent, does not inhibit the curing of diallyl phthalate resin due to its excellent copolymerizability with an allyl group, and the heat resistance of the cured product. It was found that it is particularly preferable in that it does not deteriorate the water resistance. The amount of this maleic anhydride compounded is 3 to 15% by weight, preferably 3 to 10% by weight, based on the total amount of (a), (b) and (c) of the resin composition. When it is less than this range, the function as an epoxy resin curing agent is weak, and as a result, it takes time to cure the entire composition, and the improvement of the peel strength with the copper foil is small. Further, if it exceeds this range, the heat resistance and the moisture resistance are adversely affected, and the peel strength with the copper foil is also lowered, which is not preferable.

Among acid anhydrides other than maleic anhydride, phthalic anhydride, pyromellitic dianhydride and the like are known, but these have a high melting point and do not dissolve or disperse at a roll kneading temperature of 80 to 100 ° C. Further, the liquid acid anhydride at room temperature is not a general commercial product that copolymerizes with an allyl group like maleic anhydride, and in the diallyl phthalate resin composition containing them, mechanical strength, electrical properties, etc. This leads to deterioration of the physical properties as a whole.

As the epoxy resin, a cresol novolac type epoxy resin is used. This resin is used for encapsulant applications by taking advantage of its heat resistance. By using this resin in the composition of the present invention, the peel strength is improved, and a molded product with little deterioration in heat resistance and water resistance can be obtained. . It should be noted that the diallyl phthalate resin composition using a bisphenol type epoxy resin, which is widely used for paints, adhesives and the like due to its low price, does not show improved adhesiveness.

The amount of the epoxy resin compounded is 7 to 35% by weight, preferably 12 to 25% by weight, based on the total amount of (a), (b) and (c) of the above resin composition. Outside this range, there is little improvement in peel strength with the copper foil. If this range is exceeded,
Since the curing speed of the epoxy resin is slower than that of the diallyl phthalate resin, the molding cycle is inevitably long and not practical. The cresol novolac type epoxy resin used in the composition of the present invention has a softening point of 11
It is preferably 0 ° C. or less and an epoxy equivalent of 250 or less.

The composition of the present invention may further contain an epoxy resin curing accelerator. Since the reaction of the acid anhydride with the epoxy resin is accelerated by the anionic polymerization type curing agent, it can be used as a so-called curing accelerator. As anionic polymerization type curing agents, tertiary amines, part of secondary amines, imidazoles, metal salts of carboxylic acids and the like are known, and benzyldimethylamine as an aromatic tertiary amine and imidazoles as an aromatic tertiary amine are known. 2-Methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole and the like can be used. The suitable amount of the compound is 0.01 to 0.5 parts by weight based on 100 parts by weight of the total amount of the epoxy resin and maleic anhydride. When the compounding amount of the curing accelerator is small, the curing promoting effect is small, and when the compounding amount is too large, the curing rate of the composition becomes too fast and the workability is affected.

The dialphtalate resin referred to in the present invention is a homopolymer obtained by polymerizing at least one selected from ortho, iso and tere dialphthalate monomers,
Post-curable diallyl phthalate prepolymer which is a mixture of copolymers or homopolymers, or at least one selected from the diallyl phthalate prepolymer and a reactive monomer having an unsaturated group such as an allyl group or a vinyl group. Or a mixture of at least one diallyl phthalate monomer selected from the above isomer monomers and a post-curable copolymerizable prepolymer provided by at least one polymerization selected from the above reactive monomers, and further the above diallyl phthalate A mixture of two or more kinds selected from a prepolymer, a copolymer prepolymer and unsaturated polyesters, or a mixture of the mixture with at least one kind of the reactive monomer is collectively referred to.

Examples of the reactive monomer having an unsaturated group include styrene-based monomers such as styrene and α-chlorostyrene, methyl (meth) acrylate and butyl (meth).
Acrylate, n-octyl (meth) acrylate, 2
-Ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, ethyleneglycolyl (meth) acrylate, propylene Acrylic monomers such as glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, vinyl ester monomers such as vinyl acetate and vinyl benzoate, Acrylic acetate, allyl benzoate, allyl (meth) acrylate, diallyl oxalate, diallyl adipate,
Examples include allyl ester monomers such as diethylene glycol bis (allyl carbonate), diethylene glycol bis (allyl phthalate), polyethylene glycol bis (allyl phthalate), diallyl maleate, diallyl fumarate, diallyl citrate, diallyl phthalate and the like.

The compounding amount thereof may be, for example, about 70% by weight or less, preferably about 50% by weight or less in the diallyl phthalate resin. The proportion of the reactive monomer in the copolymerized prepolymer is usually 50% by weight or less, and the copolymerized prepolymer is further selected from the blended amount of the reactive monomer. Can also be added.

As the curing agent for the diallyl phthalate resin used in the present invention, di-tert-butyl peroxide, 2,5-
Dimethyl-2,5-di- (tert-butylperoxy)-
Hexane, 1,3-bis- (tert-butylperoxy-
Isopropyl) -benzene, 2,5-dimethyl-2,5
-Di- (tert-butylperoxy) -hexyne-3, dialkyl peroxides such as dicumyl peroxide and diaryl peroxides; ketone peroxides such as methylethylketone peroxide and cyclohexanoneperoxide; 1,1-
Peroxyketals such as bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane; hydroperoxides such as cumene hydroperoxide; peroxidation such as lauroyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide. Diaroyl and diacyl peroxide; peroxycarbonates such as diisopropylperoxycarbonate; peroxyesters such as tert-butylperoxyacetate, tert-butylperoxypivalate, tert-butylperoxyoctoate, tert-butylperoxybenzoate, tert-butylperoxyisopropylcarbonate. Other than the above organic peroxides, azo compounds such as azobisisobutyronitrile can be used as well.

Practically, the peroxides usually used for diallyl phthalate resins such as dicumyl peroxide, tert-butyl peroxybenzoate, benzoyl peroxide and the like are directly applied. It is suitable that the compounding amount is 0.1 to 6% by weight based on the diallyl phthalate resin content.
The composition of the present invention, as in the case of the conventional diallyl phthalate-based resin composition, if desired, for example, a filler, a polymerization accelerator, a polymerization inhibitor, an internal mold release agent, a coupling agent, a pigment, a flame retardant, etc. The additive (1) can be blended within a range that does not impair the properties of the present composition to improve the molding processability or the physical properties of the molded article.

Epoxy resin, acid anhydride, aromatic dicarboxylic acid diallyl ester and / or its prepolymer,
The curable resin composition comprising an organic peroxide is described in JP-A-50-109299. The content is such that a bisphenol type resin is used as an epoxy resin and maleic anhydride is not used as an acid anhydride, and as described above, the composition specified by the present invention has excellent adhesiveness to a copper foil. Is not disclosed.

As the molding method of the composition of the present invention, the known molding methods and molding conditions similar to those of the conventional diallyl phthalate resin can be applied as they are. That is, a casting method of injecting the composition of the present invention into a mold and curing it, an injection molding method or a transfer molding method of heating the composition into a fluid state and then curing the composition in a mold and heating the composition. A compression molding method in which a material is heated and pressed to be cured in a mold, the composition is dissolved in an appropriate solvent, impregnated into a fibrous sheet, dried, and optionally, under a pressure condition, the fibrous sheet Laminating method for curing resin in, coating method for applying fine powder or solution of the composition to a substrate and curing on the substrate, impregnating the composition solution into printing paper etc., and drying substrate A forming method such as a decorative board forming method in which the material is heated and pressed to be cured can be exemplified.

Next, the molding method in the case of adhering copper foil will be explained. In the compression molding method, an amount of the molded product after molding the composition is placed in the lower mold of the mold so as to give a desired thickness. ,
A copper foil is placed on it, and then the mold is closed to mold. This composition may be in the form of powder, granules, pellets or tablets, and may or may not be preheated.

In the casting method, a copper foil is placed or hung so as to come into contact with the inner surface of the mold, and 50 parts of the composition is placed thereon.
Heat to ~ 150 ° C to cure and inject. In the transfer molding method, a copper foil is sandwiched and fixed between the fixed side and the movable side of the mold, and then the composition placed in a pot is transferred by a plunger with a pressure of about 10 to 200 kgf / cm ^2. Mold. In the injection molding method, a copper foil is sandwiched and fixed between the fixed side and the movable side of the mold, and then the composition melted in a plasticizing cylinder is melted to about 100 to 2000 kgf / c.
Injection molding is performed at a pressure of m ² .

In the method for forming a laminated plate, the composition is prepared by using an aliphatic ketone such as acetone, methyl ethyl ketone or methyl isobutyl ketone, an aromatic hydrocarbon such as benzene, toluene, xylene or chlorobenzene, and an acetic acid ester of diethylene glycol monoalkyl ether. Dissolve in a solvent such as. The amount of solvent is usually 2 per 100 parts by weight of the composition.
It may be up to 00 parts by weight. A fibrous reinforcing material is impregnated with this solution and dried to obtain a prepreg. Examples of the fibrous reinforcing material include natural fiber, synthetic fiber, woven fabric made of synthetic resin, non-woven fabric, paper, mat, etc., and these materials include natural fiber such as cellulose, cotton, asbestos, ceramic, and glass fiber. Examples of such inorganic fibers include synthetic fibers such as polyamide, polyimide, polyimide amide, and polyester. The amount of the composition loaded on the fibrous reinforcing material is not particularly limited. The amount may be such that the reinforcing material portion does not have scratches during molding and can sufficiently adhere to the copper foil. Usually, the supported amount is such that the weight fraction of the resin composition excluding the weight of the solvent is 0.4 to 0.85 in the total weight of the prepreg excluding the weight of the solvent.
The range is good. As a method for supporting the resin composition on the reinforcing material, a coating method using an applicator, a comma coater, a bar coater, a gravure coater, a flow coater, a spray coater or the like can be used in addition to the impregnation. The prepreg impregnated or coated with the composition removes volatile components in the drying step. In the case of batchwise drying, for example, at room temperature for about 0.2 to 1 hour, then at 40 to 120 ° C. for about 3 to 30.
Dry for a minute. However, when a curing agent having a low decomposition temperature such as benzoyl peroxide is used, the drying conditions should be high and not long. The coating or impregnation step and the drying step can be continuously performed, and a commercially available impregnation machine, coating machine, dryer or the like can be used. One to several sheets of the prepreg thus prepared are stacked so as to obtain a desired thickness, copper foil is further stacked thereon, and compression molding is performed by a mold.

In the decorative board molding method, the composition solution is applied to a particle board, a plywood board, a slate board or an aluminum board or an iron board, and dried as in the case of forming a laminated board.
A copper foil is overlaid on it and compression-molded with a mold.

In the above molding, the mold temperature is about 6
An example is 0 to 220 ° C. The pressure for compression molding may be about 5 to 100 kgf / cm ² .

[0024]

EXAMPLES The present invention will be described more specifically below with reference to examples and comparative examples.

Examples 1 to 3 and 10, Comparative Examples 1 to 4 The compositions having the compositions shown in Examples 1 to 10 and Comparative Examples 1 to 4 of Tables 1 and 2 were mixed with a mixing roll having a diameter of 9 inches at a roll temperature. The mixture was kneaded at 80 to 100 ° C. for 5 minutes, taken out, cooled, and coarsely crushed in a mortar. The composition obtained is molded in a mold at 170 ° C. under a pressure of 30 kgf / cm ² and a curing time of 5 minutes. First, copper foil (CF-T manufactured by Fukuda Metal Foil & Powder Co., Ltd.
What was cut into a 12 cm × 12 cm square having a thickness of 9, 35 μm) was placed in the lower mold of the mold so that the rough surface was in contact with the composition surface and the glossy surface was in contact with the mold surface. Next, the composition is placed on a copper foil in an amount such that the thickness of the molded product after molding is 2 mm, and finally another copper foil of the same shape is put through the composition, with the rough surface being the composition surface and the glossy surface being The mold was placed in contact with the upper mold and pressure-molded as described above to obtain a double-sided copper-clad molded plate. 2 from this molded plate
Four 5 mm × 100 mm samples were cut out and used as molded samples.

The copper foil on the surface of the sample, which was molded and cut out in the same manner as above, was molded by the lower mold of the mold, and was completely peeled off.
Leave the copper foil on the other side as it is and use a pressure cooker tester (abbreviated as PCT below) at 122 ° C and relative humidity of 1
It was exposed for 100 hours in a 00% environment, and this was used as a sample after PCT treatment. In addition, a sample molded and cut out in the same way,
The sample was baked in an oven at 180 ° C. for 3 hours and used as a sample after the after-baking treatment. In addition, the after-baked sample was completely peeled off the copper foil on the surface formed by the lower mold of the mold, leaving the copper foil on the other surface as it was. The sample was subjected to time exposure (after-baking + PCT) and treatment.

Regarding each of the above samples, JIS C6481
The peel strength was measured by the copper-clad laminate test method for printed circuits. The results are shown in Tables 1 and 2.

Next, in order to measure the volume resistivity of the above composition, a mold having a diameter of 10 cm and a thickness of 2 mm to obtain a disk-shaped molded product was used at a mold temperature of 170 ° C. and a pressure of 50 kgf / c.
It was molded into a disk at m ² and a curing time of 5 minutes to obtain a sample in a molded state. A disk obtained by molding in the same manner was used for PCT 12
Exposed for 100 hours in an environment of 2 ° C and 100% relative humidity,
The sample was treated with PCT. Further, a disk obtained by similarly molding was fired in an oven at 180 ° C. for 3 hours to obtain a sample after the after-baking treatment. In addition, the sample after the post-baking treatment was put in an environment of 122 ° C and 100% relative humidity by PCT.
It was exposed for 00 hours and used as a sample after (after-baking + PCT) treatment.

Regarding the above disk-shaped sample, JIS K6
The volume resistivity was measured by the general test method for 911 thermosetting plastics. The results are also shown in Tables 1 and 2.

Example 4 The composition shown in Example 4 in Table 1 was used for the above-mentioned double-sided copper-clad molding plate and a disk having a diameter of 10 cm and a thickness of 2 mm at a mold temperature of 180 ° C. and after-baking. Condition 18
Peel strength and volume resistivity were measured by performing molding and post-treatment in the same manner as in Examples 1 to 3 except that the temperature was 0 ° C. for 3 hours. The results are also shown in Table 1.

Examples 5 and 7 to 9 The compositions shown in Examples 5 and 7 to 9 of Tables 1 and 2 were used for molding the above-mentioned double-sided copper-clad molded plate and a disk having a diameter of 10 cm and a thickness of 2 mm. Molding was performed in the same manner as in Examples 1 to 3 except that the mold temperature was 150 ° C. and the after-baking condition was 150 ° C. for 5 hours, and post-treatments were performed to measure the peel strength and the volume resistivity. The results are also shown in Tables 1 and 2.

Example 6 The composition shown in Example 6 of Table 1 was used for molding the above double-sided copper-clad laminate and a circular plate having a diameter of 10 cm and a thickness of 2 mm at a mold temperature of 190 ° C. and after-baking. Condition 190
Molded in the same manner as in Examples 1 to 3 except that the temperature was 2 hours,
After the post-treatment, the peel strength and volume resistivity were measured.
The results are also shown in Table 1.

[0033]

[Table 1]

[0034]

[Table 2]

In Tables 1 and 2, (1) diallyl orthophthalate prepolymer (trade name "Daiso Dup" manufactured by Daiso) (2) diallyl isophthalate prepolymer (trade name "Daiso Isodup" manufactured by Daiso) (3) Diallyl Orthophthalate Monomer (4) Diallyl Isophthalate Monomer (5) Diallyl Terephthalate Monomer (6) Pentaerythritol Tetraacrylate (7) Dicumyl Peroxide (Brand name “Park Mill D” manufactured by NOF Corporation) (8) tert-Butylperoxyisopropyl Carbonate (Brand name "KayaCarbon Bic-75" manufactured by Akzo, purity 75%) (9) 2,5-Dimethyl-2,5-di (tert-butylperoxy) -hexane (Brand name "Kayahexa AD" (Yaku Akzo) (10) 2,5-dimethyl-2, - di (tert- butylperoxy) - hexyne-3 (trade name "Pahekishin 25
B ”manufactured by NOF CORPORATION (11) Orthocresol novolac type I (trade name“ YD
CN704 "manufactured by Tohto Kasei Co., epoxy equivalent 220g / e
q, softening point 90 ° C) (12) Orthocresol novolac type II (trade name "A.
E. R. ECN280 "made by Asahi Kasei Corporation, epoxy equivalent 220g / eq, softening point 85 ° C (13) Bisphenol A type (trade name" AERR66 "
4 "Asahi Kasei Kogyo Co., Ltd., epoxy equivalent 950g / eq, softening point 102 ° C) (14) Benzyldimethylamine (15) 2-Methylimidazole

As shown in Tables 1 and 2, the molded product of the composition of the present invention was a composition containing no epoxy resin (Comparative Example 2) and a composition containing no maleic anhydride in terms of copper foil peel strength and volume resistivity. (Comparative Example 3) and a molded article made of a composition using a bisphenol type epoxy resin (Comparative Example 4) are clearly superior. In the case of the composition containing only diallyl phthalate resin (Comparative Example 1), the volume resistivity was almost the same as that of the product of the present invention, but the copper foil peel strength was clearly inferior.

[0037]

EFFECTS OF THE INVENTION The resin composition according to the present invention has a significantly improved adhesive strength with a copper foil as compared with a conventional diallyl phthalate resin composition, and has little deterioration under high temperature and high humidity. It is useful as a molding material for electronic parts.

Claims (1)

[Claims] 1. (a) Diallyl phthalate resin 50-9
0% by weight, (b) 3 to 15% by weight of maleic anhydride, and (c) 7 to 35% by weight of a cresol novolac type epoxy resin, and a diallyl phthalate resin composition having excellent adhesion to a copper foil. object.