KR100722814B1 - High dielectric constant and low dielectric loss resin composition for copper foil laminate - Google Patents

Abstract

The present invention provides a resin composition for a copper foil with resin and a copper clad laminate, wherein the composition has a structure in which a ferroelectric inorganic filler is evenly dispersed in a mixture of a benzoxazine resin, a phenol curing agent, and a thermoplastic resin. This composition reinforces elasticity by introducing thermoplastic resin instead of glass fiber reinforcement, and lowers dielectric loss by introducing benzoxazine resin instead of epoxy resin, and uses dicyanic diamide. Instead, by using a phenol curing agent has the effect of improving the heat resistance.

The copper foil laminate prepared using the composition has a thinner thickness and a higher dielectric constant than the conventional copper foil laminate for built-in capacitors, and thus can not only significantly increase capacitance, but also have high glass transition temperature and lead heat resistance. Dielectric loss characteristics are effective.

Description

RESIN COMPOSITION FOR COPPER CLAD LAMINATE OF HIGH DIELECTRIC CONSTANT AND LOW DIELECTRIC LOSS}             

1 is a schematic view of the state formed by patterning the main electrode, ground electrode and the secondary electrode on the copper foil laminate in order to measure the dielectric constant and dielectric loss of the copper foil laminate in the embodiment of the present invention.

The present invention relates to a resin composition for a copper foil laminate having high dielectric constant and low dielectric loss used in an embedded printed circuit board (Embedded PCB).

In recent years, as the proportion of small terminals such as mobile phones and PDAs increases in electronic products, there is an increasing demand for smaller and lighter terminals. Embedded printed circuit board technology, which inserts components inside the PCB, can shorten the wiring distance and shorten the PCB area, increase mounting reliability by reducing the number of surface-mount components, and reduce component assembly costs. Due to this, it is one of the technologies that are attracting attention recently.

BACKGROUND ART Copper foil laminates for embedded printed circuit boards, which are conventionally used, are used by impregnating epoxy fibers in glass fiber reinforcing agents, and methods of reducing thickness or introducing ferroelectric inorganic fillers have been proposed to increase capacitance. However, when the glass fiber reinforcing agent is used, there is a limit to thin thickness, and because the dielectric loss of the epoxy resin composition itself is high, it may be used in a decoupling capacitor, but it has a problem in that it is difficult to use in high frequency components.

For this reason, a method of using a compound having a dihydro benzooxadine ring containing a large amount of nitrogen atoms in a molecule instead of an epoxy composition has been proposed as a component of the resin composition.

U.S. Patent No. 5,162,977 describes a prepreg in which a glass fiber reinforcing material is impregnated into a resin composition in which a ferroelectric filler is dispersed in an existing FR-4 epoxy resin composition, and the prepreg is sandwiched between copper foils to pressurize embedded printing. Disclosed is a technique for producing a copper foil laminate for a circuit board. In this case, the dielectric constant of the copper-clad laminate could be increased by using the ferroelectric filler, but since the epoxy resin was used in the resin composition, the dielectric loss was high and the dicyane diamide curing agent was used, resulting in a poor heat resistance. Moreover, also in the manufacturing method of a copper foil laminated board, since the glass fiber reinforcement material was used, there exists a limit to thin thickness, and there exists a problem that it is difficult to obtain a preferable capacitance.

In addition, US Pat. No. 6,274,224 discloses a technique of coating a composition obtained by dispersing barium titanate in an epoxy resin on a copper foil, laminating two coated copper foils, and then pressing to manufacture a copper foil laminate for an embedded printed circuit board. Is disclosed. In this case, the ferroelectric filler is contained, so that the high dielectric constant and high dielectric constant can be exhibited, and since the coating is directly on the copper foil without using the glass fiber reinforcement material, the thickness can be made thin, thereby obtaining a desirable capacitance, but instead of the glass fiber reinforcement material It was found that copper foil laminates were brittle and difficult to handle because they did not contain an elastic thermoplastic resin that could play a role.

In addition, US Patent No. 6,150,456 discloses a composition obtained by dispersing a ferroelectric filler such as barium titanate in a thermosetting or thermoplastic polyimide on a copper foil, and then bonding two coated copper foils by press or laminate, and then curing the embedded printing. The technique which manufactures the technique which manufactures the copper foil laminated board for circuit boards is disclosed. In this case, the dielectric constant could be increased by using a ferroelectric filler, and since the polyimide itself has high mechanical strength and good elasticity, it is possible to manufacture a copper foil laminate without a glass fiber reinforcement. However, polyimide has a problem in that it is difficult to be easily applied to a PCB process because of the disadvantage of curing at a temperature of 350 ° C. or higher because the curing temperature is considerably higher than that of a thermosetting resin such as an epoxy resin.

As such, the conventional resin composition does not provide a good balance of various dielectric properties required for high dielectric constant and low dielectric loss and copper foil laminate.

 Therefore, an object of the present invention is to solve the problems of the prior art as described above and the technical problem that has been requested from the past.

After extensive research and various experiments, the inventors have developed a resin composition for copper clad laminates comprising benzoxazine resins, phenol curing agents, thermoplastic resins, and ferroelectric inorganic fillers. Introduced thermoplastic resin to reinforce elasticity, benzoxazine resin is introduced instead of epoxy resin to lower the dielectric loss, and phenolic curing agent can be used to improve heat resistance instead of using dicyandiamide. Found. In addition, it has been found that various physical properties required for the composition for copper foil laminated plates can be obtained in a balanced manner by the above composition, and have completed the present invention.

Specifically, the first object of the present invention is to provide a resin composition in which various physical properties such as high dielectric constant, low dielectric loss, high glass transition temperature (Tg), excellent copper foil peel strength, flame retardancy, and lead heat resistance are obtained in a balanced manner. .

A second object of the present invention is to provide a copper foil with a resin produced using the composition.

A third object of the present invention is to provide a copper foil laminated sheet produced using the resin-clad copper foil.

The resin composition according to the present invention for achieving this object is composed of (A) benzoxazine resin, (B) phenol curing agent, (C) thermoplastic resin and (D) ferroelectric inorganic filler.

In general, it is very difficult to balance various physical properties in the resin composition for copper foil laminate. On the other hand, the present invention provides a resin composition for a copper foil laminate that can express desired properties by a combination of the above specific components.

Moreover, this invention provides the copper foil with resin which coat | covered the said resin composition to copper foil in thickness of 5-20 micrometers.

Moreover, this invention provides the copper foil laminated board integrated by the method of heating and pressurizing two said copper foils with resin, or heating and pressurizing the copper foil with resin and copper foil.

Hereinafter, the present invention will be described in detail.

In the composition of the present invention, benzoxazine resin is used instead of the epoxy resin. When using an epoxy resin, it is difficult to lower the dielectric loss to 0.03 or less without glass fiber, but when using a benzoxazine resin, it is possible to lower the dielectric loss to 0.02 or less and further to 0.01 or less. In addition, although the flame retardancy of the benzoxazine resin itself is V-1 level, in the composition of the present invention, since the excess ferroelectric filler is used together, the flame retardancy of the copper foil laminate may reach V-0 level without a separate flame retardant.

The benzoxazine resin (A) is not particularly limited as long as it is a resin having a dihydro benzooxadine ring and cured by a ring opening reaction of dihydrobenzoxadine, for example, a compound having a phenolic hydroxyl group. And primary amines and formaldehyde.

Preferred examples of such compounds include the structure of Formula 1 below.

[Formula 1]

In the formula, R ₁ is an alkyl group, a cyclohexyl group, a phenyl group, or a phenyl group substituted from an alkyl group or an alkoxy group.

Examples of the compound having a phenolic hydroxyl group, polyfunctional phenols (bifunctional compounds), biphenol compounds (biphenol compounds), bisphenol compounds (bisphenol compounds), trisphenol compounds (trisphenol compounds), tetraphenol compounds (tetraphenol compounds) And phenolic resins. Here, examples of the polyfunctional phenol include catechol, hydroquinone, resorcinol, and the like, and bisphenol compounds such as bisphenol A, bisphenol F, and their positions Isomers, bisphenol S, and the like, and the phenol resins include phenol novolak resins, resol phenol resins, phenol-modified xylene resins, alkyl phenol resins, melamine phenol resins, and phenol-modified polybutadiene resins.                     

Examples of the primary amine include methylamine, cyclohexylamine, aniline, substituted aniline, and the like. When the aliphatic amine is used among the primary amines, the curing rate of the cured product is increased but the heat resistance is poor. When the aromatic amine such as aniline is used, the heat resistance is improved, but the curing rate is slowed.

The benzoxazine resin (A) is 0.5 to 1.5 mol, preferably 0.6 to 1.0 mol of a primary amine per 1 mol of a compound having a phenolic hydroxyl group, and the mixture is heated to 50 to 60 ℃, formaldehyde Is added in an amount of 1.5 mol to 2.5 mol, preferably 1.9 mol to 2.1 mol, based on 1 mol of the primary amine, and then heated to 60 to 120 캜, preferably 90 to 110 캜, and heated for 60 to 120 minutes. After drying, it may be produced by drying under reduced pressure at a temperature of 100 ° C. or higher.

The preferred content of the benzoxazine resin (A) is 40 to 90 parts by weight, more preferably 60 to 80 parts by weight based on 100 parts by weight of the total resin composition. When the content of the benzoxazine resin is less than 40 parts by weight, it is difficult to provide the desired flame retardancy, and when it exceeds 90 parts by weight, the adhesive strength is lowered, and the problem that the brittleness of the resin composition may increase may be undesirable.

The phenol curing agent (B) serves to promote the curing reaction of the benzoxazine, and does not degrade heat resistance unlike dicyandiamide (Dicy) widely used as a conventional epoxy resin curing agent. As the phenol curing agent (B), a phenol novolak resin, a bisphenol A novolak resin, a cresol novolak resin, a phenol-modified xylene resin, an alkyl phenol resin, melamine-modified resin and the like may be used.

It is suitable that the said phenol hardener (B) is 110 or more, Preferably it is 120 or more, The number average molecular weight is 1000, It is good to use the high molecular type phenol resin which is preferably 1500 or more. The content of the phenol curing agent (B) is 1 to 50 parts by weight based on 100 parts by weight of the benzoxazine resin (A), preferably 5 to 20 parts by weight. When the phenol curing agent (B) is used in less than 1 part by weight based on 100 parts by weight of benzoxazine resin, there is a disadvantage in that the curing reaction is slow and takes a long time, and when used in excess of 50 parts by weight, an excessive amount of uncured phenol is also used. There is a disadvantage that the heat resistance is generated.

The resin composition of the present invention may further include a curing accelerator in order to promote the curing reaction, and such a curing accelerator is preferably an imidazole series curing accelerator. Examples of the imidazole series curing accelerators include 1-methylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole (2-Ethyl-4 -methylimidazole), 2-Phenylimidazole, 2-cyclohexyl-4-methylimidazole, 4-butyl-5-ethylimidazole (4- Butyl-5-ethyl imidazole), 2-Methyl-5-ethylimidazole, 2-octyl-4-hexylimidazole, 2, Imidazoles, such as 5-chloro-4-ethylimidazole, 2-butoxy-4-allylimidazole, imidazole Derivatives and the like, and 2-methylimidazole and 2-phenylimidazole are particularly preferred due to excellent reaction stability and low cost. At this time, the content of imidazole is used in an amount of 0.01 to 0.1 parts by weight, and more preferably 0.03 to 0.06 parts by weight, based on 100 parts by weight of the total resin component. If the content of the imidazole is used less than 0.01 parts by weight, the curing time is long and the glass transition temperature does not come out enough, when used in excess of 0.1 parts by weight of varnish varnish (varnish) storage stability is poor.

In some cases, in addition to the imidazole, a curing retardant may be further included in the composition of the present invention for controlling the curing rate and improving the glass transition temperature (Tg). Such curing retardants include boric acid, salicylic acid, hydrochloric acid, sulfuric acid, oxalic acid, terephthalic acid, isophthalic acid, and phosphoric acid. (phophoric acid), lactic acid, and the like, and the content thereof is preferably 0.1 to 10 molar equivalents, more preferably 0.5 to 5 molar equivalents, based on the molar equivalent of the imidazole cure accelerator.

The thermoplastic resin (C) serves to provide elasticity and support to the resin composition instead of the glass fiber reinforcement, and at the same time, the resin is easily broken due to the excessive inorganic filler added to increase the dielectric constant, and the adhesion to the copper foil is poor. It serves to reduce. Examples of the thermoplastic resin (C) include polyether sulfone (PES), polyphenylene oxide (PPO), acrylonitrile butadiene rubber (NBR), carboxyl terminated acrylonitrile butadiene rubber (CTBN), carboxyl terminated butadiene Rubber (CTB), acrylic acid, acrylate-ester, acryl rubber in combination with acrylamide, vanyl-terminated polybutadiene rubber (VTBN), styrene butadiene rubber (SBR), styrene butadiene ethylene (SBE), polyester And polystyrene (PS) polyvinyl acetal (PVA), polyamide, phenoxy, and the like, and these may be used alone or in combination of two or more thereof. The content of the thermoplastic resin (C) is preferably 5 to 30% by weight based on the total weight of the resin composition. If the thermoplastic resin is used at less than 5% by weight, the elasticity and brittleness of the thermoplastic resin may not be sufficient. Therefore, when used in excess of 30% by weight, the phase transition phenomenon between the high molecular weight thermoplastic resin and the thermosetting resin is used. May occur, and the minimum viscosity of the composition may be increased to reduce resin flowability, and thus, bonding may not occur properly between the copper foil with resin and the copper foil with resin and / or between the copper foil with resin and copper foil during press bonding. .

As the ferroelectric inorganic filler (D) added to the composition of the present invention, for example, barium titanium oxide (barium titanium oxide), barium strontium titanate, titanium oxide (Titanium oxide), lead zir Lead zirconium titanate, lead lanthanum zirconate titanate, lead magnesium niobate-lead titanate, silver, nickel, nickel-coated Nickel coated Polymer sphere, Gold coated Polymer sphere, Tin solder, Graffite, Tantalum nitides, Metal silicon nitride Nitride, Carbon black and Aluminum borate can be optionally used, and these can be used alone or in combination of two or more. have. In some cases, although the dielectric constant is slightly lower, silica, cray, or the like may be used. The particle diameter of the ferroelectric inorganic filler (D) is preferably 0.1 to 10 ㎛.

The content of the ferroelectric inorganic filler (D) is preferably 10 to 700 parts by weight based on 100 parts by weight of the total resin composition. If the content of the inorganic filler (D) is less than 10 parts by weight, it is difficult to exert the effect of the addition, on the contrary, if it exceeds 700 parts by weight, the resin flow is too small, which is not preferable because the press bonding occurs.

In some cases, it may further comprise an appropriate dispersant to evenly disperse the ferroelectric inorganic filler (D) in the composition and prevent its settling, which dispersant may be carboxylate, sulfonate, and phosphate. You can choose from the group consisting of. When the dispersant is added, its content is preferably 0.005 to 0.05 parts by weight, more preferably 0.01 to 0.03 parts by weight based on 1 part by weight of the ferroelectric inorganic filler (D).

This invention also provides the copper foil with resin which coat | covered the said resin composition to copper foil in thickness of 5-20 micrometers. Moreover, this invention provides the copper foil laminated board integrated by the method of heating and pressurizing two such copper foils with resin, and integrated, or the method of heating and pressurizing the copper foil with resin and copper foil.

Since the manufacturing method of these copper foil with resin and copper foil laminated board is known in the art, the detailed description is abbreviate | omitted.

Hereinafter, the content of the present invention will be described in detail through Examples and Comparative Examples, but the scope of the present invention is not limited thereto.

Example 1

A resin composition was prepared in the composition shown in Table 1 below.

(1) slurry production

After completely dissolving 3 g of a dispersant (BYK-Chemi BYK W9010) in 30 g of methyl ethyl ketone (MEK) and 30 g of dimethyl formaldehyde (DMF), it was placed in a ball mill container and barium titanium oxide as a ferroelectric filler. (Sakai BT05) 300 g of the ball was added for 24 hours to prepare a slurry.

(2) varnish manufacturing

First, in a 500 ml beaker, 90 g of methyl ethyl ketone (MEK), 150 g of dimethyl formaldehyde (DMF), 40 g of polyvinyl acetal (Sekisui KS-5z), 20 g of epoxy modified polyphenylene oxide (Asahi Kasei P412) After completely dissolved, 250 g of benzoxazine resin (Huntsman, XTW8291, methyl ethyl ketone dissolved 80%), phenol novolak resin (Huntsman, XTW8293, methyl ethyl ketone 68% dissolved), 58.84 g, and 2-phenylimida 0.06 g of sol was added and completely dissolved. Then, the slurry prepared in (1) was added thereto, followed by mixing for 10 hours to prepare a varnish.

(3) Copper Clad Laminate Manufacturing

The varnish prepared in (2) was coated on a copper foil (Furukawa Co., F2-WS) having a thickness of 18 μm so as to have a final thickness of 10 μm, and then dried at 170 ° C. for 6 minutes to prepare a copper foil with resin. The two copper foils with the resin were faced together and heated and pressed for 90 minutes at a temperature of 200 ° C. and a pressure of 35 kg / cm 2 using a press to prepare a copper foil laminate having a dielectric thickness of 20 μm.

Example 2

A composition was prepared with the composition shown in Table 1 below.

In preparing the slurry, 60 g instead of 30 g of methyl ethyl ketone (MEK), 60 g instead of 30 g of dimethylformaldehyde (DMF), 6 g instead of 3 g of a dispersant (BYK-Chemi BYK W9010), barium titanium oxide (Sakai BT05) A copper foil laminate was manufactured in the same manner as in Example 1, except that 600 g was used instead of 300 g.

Example 3

A non-halogen resin composition was prepared with the composition shown in Table 1 below.

In preparing the slurry, 90 g instead of 30 g of methyl ethyl ketone (MEK), 90 g instead of 30 g of dimethylformaldehyde (DMF), 9 g instead of 3 g of a dispersant (BYK-Chemi, BYK W9010), barium titanium oxide (Sakai BT05) Copper foil laminate was manufactured in the same manner as in Example 1, except that 900 g was used instead of 300 g.

Example 4

A non-halogen resin composition was prepared with the composition shown in Table 1 below.

In preparing the slurry, 120 g instead of 30 g of methyl ethyl ketone (MEK), 120 g instead of 30 g of dimethylformaldehyde (DMF), 12 g instead of 3 g of a dispersant (BYK-Chemi BYK W9010), barium titanium as a ferroelectric filler A copper foil laminate was manufactured in the same manner as in Example 1, except that 1200 g was used instead of 300 g of oxide (Sakai BT05).

Example 5

A non-halogen resin composition was prepared with the composition shown in Table 1 below.

In preparing varnish, instead of 90 g of methyl ethyl ketone (MEK), 110 g, 20 g of epoxy modified polyphenylene oxide (Asahi Kasei P412), 20 g of polystyrene (GPPS 15NFE, LG Chemical), phenol novolac Except that 58.84 g of the resin (Huntsman, XTW8293, 68% methylethyl ketone dissolved) was used, the same as in Example 2 except that 40 g of the polymer type phenol novolak resin (Gifu Shellac GPX-41) was used. The copper foil laminated board was manufactured by the method.

Example 6

A non-halogen resin composition was prepared with the composition shown in Table 1 below.                     

In preparing the slurry, a slurry was prepared in the same manner as in Example 2, except that 120 g of dimethylformaldehyde was used instead of 60 g of methyl ethyl ketone (MEK) and 60 g of dimethyl formaldehyde (DMF). .

In preparing varnish, instead of using 90 g of methyl ethyl ketone (MEK) and 150 g of dimethyl formaldehyde (DMF), instead of using 240 g of dimethyl formaldehyde and 40 g of polyvinyl acetal (Sekisui KS-5z) Instead of using 30 g of polyvinyl acetal (Sekisui KS-23Z), 30 g of epoxy modified polyphenylene oxide (Asahi Kasei P412), 30 g of polyethersulfone (Smitomo Chemical 5003PS), phenol novolac resin (Huntsman Copper foil laminates were prepared in the same manner as in Example 2, except that 40 g of a polymeric phenol novolak resin (Gifu Shellac GPX-41) was used instead of 58.84 g of XTW8293, 68% dissolved in methyl ethyl ketone. Prepared.

Comparative Example 1

A resin composition was prepared with the composition shown in Table 2 below.

First, 115 g of methyl ethyl ketone (MEK), 150 g of dimethylformaldehyde (DMF), and 6.1 g of dicyandiamide (Dicy), an amine curing agent, were completely dissolved in a 500 ml beaker, followed by complete dissolution. Then, polyvinyl acetal (Sekisui KS- 5z) 40 g and 20 g of epoxy-modified polyphenylene oxide (Asahi Kasei Co., P412) were added to dissolve completely. Then, 175 g of bisphenol A type epoxy resin (Bakelite, LER1222, methyl ethyl ketone dissolved in 80%), 60 g of cresol novolac epoxy resin (BAKELITE, LER N690) and 0.3 g of 2-phenylimidazole were added. It was put in a mixed solution and completely dissolved, to prepare a copper foil laminate in the same manner as in Example 1.

Comparative Example 2

A resin composition was prepared with the composition shown in Table 2 below.

A copper foil laminate was produced in the same manner as in Comparative Example 1 except that the slurry was prepared in the same manner as in Example 2.

Comparative Example 3

A resin composition was prepared with the composition shown in Table 2 below.

A copper foil laminate was manufactured in the same manner as in Comparative Example 1 except that the slurry was prepared in the same manner as in Example 3.

[Comparative Example 4]

A resin composition was prepared with the composition shown in Table 2 below.

A copper foil laminate was produced in the same manner as in Comparative Example 1 except that the slurry was prepared in the same manner as in Example 4.

[Comparative Example 5]

A resin composition was prepared with the composition shown in Table 2 below.                     

In preparing the slurry, the slurry was prepared in the same manner as in Example 2, except that 120 g of dimethylformaldehyde was used instead of 60 g of methyl ethyl ketone (MEK) and 60 g of dimethyl formaldehyde (DMF). Prepared.

In preparing varnish, instead of using 115 g of methyl ethyl ketone (MEK) and 150 g of dimethyl formaldehyde (DMF), instead of using 265 g of dimethylformaldehyde and 6.1 g of dicyandiamide (Dicy), an amine curing agent, 70 g of polyphenol acetal (Gifu Shellac, GPX-41), 40 g of polyvinyl acetal (KS-5z, Sekisui), 30 g of reactive polyvinyl acetal (KS-23Z, Sekisui), epoxy modified polyphenylene Instead of using 30 g of oxide (Asahi Kasei P412), instead of using 30 g of polyether sulfone (Smitomo Chemical Co., Ltd. 5003PS) and 6.1 g of dicyanic diamide diamide, an amine-based curing agent, polymer type phenol novolak resin (Gifu Shellac) A copper foil laminate was manufactured in the same manner as in Comparative Example 2, except that GPX-41) was used.

Comparative Example 6

A resin composition was prepared in the composition shown in Table 3 below.

In preparing the slurry, 50 g instead of 30 g of methyl ethyl ketone (MEK), 50 g instead of 30 g of dimethylformaldehyde (DMF), 5 g instead of 3 g of a dispersant (BYK-Chemi BYK W9010), barium titanium oxide (Sakai BT05) Slurry was prepared in the same manner as in Example 1, except that 500 g was used instead of 300 g.

In preparing the varnish, Example 1 and 10 except that 10 g of dicyan diamide was used instead of 58.84 g of phenol novolak resin (Huntsman, XTW8293, methyl ketone 68% dissolved in methyl). The copper foil laminated sheet was manufactured by the same method.

Comparative Example 7

A resin composition was prepared in the composition shown in Table 3 below.

(1) slurry production

In preparing the slurry, 120 g instead of 30 g of methyl ethyl ketone (MEK), 120 g instead of 30 g of dimethylformaldehyde (DMF), 12 g instead of 3 g of a dispersant (BYK-Chemi, BYK W9010), barium titanium oxide (Sakai BT05) Slurry was prepared in the same manner as in Example 1, except that 1200 g was used instead of 300 g.

(2) varnish manufacturing

In preparing the varnish, 10 g of methyl ethyl ketone, 160 g of dimethylformaldehyde, 500 g of benzoxazine resin (soluble in Huntsman, XTW8291, methyl ethyl ketone 80%), phenol novolac resin (Huntsman, XTW8293) 147.06 g of methyl ethyl ketone (68% dissolved) and 0.12 g of 2-phenylimidazole were completely dissolved, and then varnish was prepared in the same manner as in Example 1.

(2) Copper Foil Laminate Manufacturing

The glass (Nittibo, 106) was impregnated into the varnish prepared in the above (1), and then dried at 170 ° C. for 6 minutes to prepare a prepreg. One sheet of the prepreg prepared above was sandwiched between copper foils and heated and pressed for 90 minutes at a temperature of 200 ° C. and a pressure of 35 kg / cm 2 to prepare a copper foil laminate having a dielectric thickness of 50 μm.

Comparative Example 8

A resin composition was prepared in the composition shown in Table 3 below.

A copper foil laminate was produced in the same manner as in Example 1 except that no slurry was added.

Experimental Example

(1) Copper foil laminated sheet evaluation

The physical properties of the copper foil laminate were evaluated by the following methods, and the results are shown in Tables 1 and 2 below.

(Iii) Dielectric constant and dielectric loss: After the copper foil laminate was formed into a pattern with a main electrode (a) diameter of 3 cm, a negative electrode (c) diameter of 4 cm, and a main electrode and ground electrode gap of 1 cm as shown in FIG. After removing the remaining copper foil except the etching, and cut the specimen size to 5 × 5 cm, 1 MHz dielectric constant and dielectric loss were measured by using L, C, R measuring instruments (HP4194A, Hewlett Packard). In FIG. 1, a is a main electrode, b is a ground electrode, and c is a negative electrode.

(Ii) Glass transition temperature: The copper foil layer of the copper foil laminated sheet was removed by etching, and the glass transition temperature was measured by DSC (differential scanning calorimeter, TA, Q100).

(Iii) Copper foil peeling strength: After peeling the copper foil of width 1cm from the copper foil laminated board surface, the peeling strength of copper foil was measured using the tensile strength analyzer (Texture Analyzer).                     

(Iii) Lead heat resistance: The time taken to bear after placing a sample cut into a size of 5 cm × 5 cm in a lead bath at 288 ℃.

(Iii) Flame retardancy: Copper foil laminates for flame retardancy measurement are always unclad (LG Chemical, LG-E451) of 0.4 mm thickness between two sheets of copper foil with resin in Examples 1-6, Comparative Examples 1-6, and Comparative Example 8. Copper foil laminated plate was manufactured by heating and pressing for 90 minutes at a temperature of 200 ° C. and a pressure of 35 kg / cm 2. In Comparative Example 7, a prepreg and an 18 μm copper foil were placed on both sides of 0.4 mm Unclad, and in the same manner. It pressed and manufactured the copper foil laminated board. After the copper foil laminated plate prepared above was etched to completely remove the copper foil, the flame retardance of dividing the sample cut into 125 mm × 13 mm size into V-0, V-1 and V-2 grades by the vertical combustion test method Measurement was performed by performing the UL94 test method, an evaluation standard method.                     

As shown in Table 1, the dielectric constant increased according to the barium titanium oxide (BT05) content in Examples 1 to 4 according to the present invention, the epoxy modified polyphenylene oxide used as benzoxazine resin itself and thermoplastic resin The low dielectric loss resulted in low dielectric loss of less than 0.02. In addition, it exhibits a high glass transition temperature characteristic of 175 ℃, and excellent heat resistance withstand 600 seconds or more in the lead heat characteristics. In Example 5 using the polymer type phenol novolak resin and polystyrene, the glass transition temperature was lowered by about 20 ° C., but the barium titanium oxide content was the same as in Example 2, showing the same dielectric constant and capacitance as in Example 2. As in Examples 1 to 4, excellent lead heat resistance was shown, and in particular, the dielectric loss value was significantly lowered to 0.009. In Example 6 using the polymer type phenol novolak resin, reactive polyvinyl acetal, and polyether sulfone, the glass transition temperature was lowered by about 10 ° C. compared with Examples 1 to 4, but barium titanium oxide was used as Example 2 Containing the same, in this case, too, the dielectric loss could be much lowered to 0.01. In Examples 2 to 6, the benzoxazine resin itself exhibited flame retardancy of V-1, and when the inorganic filler was added at 60% or more, the flame retardancy of the benzoxazine resin itself was V-0 without using a flame retardant.                     

As shown in Table 2, in Comparative Examples 1 to 4, instead of using a benzoxazine resin, bisphenol A type epoxy resin LER1222 and cresol novolac epoxy resin N690 were used together, and phenol novolac resin was used. Instead, diamine diamide (Dicy), which is an amine curing agent, was used, and the varnish was prepared by changing the barium titanium oxide content as in Examples 1 to 4. As shown in Comparative Examples 1 to 4, the dielectric constant was determined by the barium titanium oxide content rather than the resin composition, and when using the same barium titanium oxide, the dielectric constant showed similar values regardless of the resin composition. The glass transition temperature was about 40 ° C. lower than that of Examples 1 to 4 according to the present invention using a benzoxazine resin. Instead of using a phenol curing agent, the glass transition temperature used a low heat resistance dicyan diamide curing agent. Because of this, the lead heat resistance was much lowered, and the dielectric loss of the epoxy resin itself was high, resulting in a much higher dielectric loss than when the benzoxazine resin was used. In Comparative Example 5, unlike in Comparative Examples 1 to 4 using dicyan diamide curing agent, GPX-41, which is a polymer type phenol novolak resin, was used. As in Example 6, a reactive polyvinyl acetal was used as the thermoplastic resin. KS-23z and polyethersulfone (5003PS) were used. In this case, the glass transition temperature was increased by about 10 ° C. compared with Comparative Examples 1 to 4, and the lead heat resistance and dielectric loss were slightly improved, but still exhibited poor physical properties than those shown in Examples 1 to 6. In Comparative Examples 2 to 5, since the flame retardancy of the epoxy resin itself was inferior to that of the benzoxazine resin, the flame retardancy did not show V-0 even when 60% or more of the ferroelectric filler was added, unlike in Examples 2 to 6.                     

As shown in Table 3, in Comparative Example 6, instead of the phenol novolak resin, dicyandiamide (Dicy) curing agent was used, but in this case, dielectric loss was higher and glass transition temperature and lead heat resistance were significantly lower than those of Example 2. . In Comparative Example 7, since the thermoplastic resin was not added, the viscosity was low, the brittleness was increased, and the resin-bonded copper foil could not be manufactured. Since the copper foil laminated plate was manufactured using glass fiber, the dielectric constant decreased, and the thickness of the copper foil laminated plate was thick. This greatly decreased. In Comparative Example 8, since the ferroelectric filler was not added, the capacitance was also greatly reduced, and the flame retardancy did not show V-0.

Those skilled in the art to which the present invention pertains will be able to perform various applications and modifications within the scope of the present invention based on the above contents.

The resin composition of the present invention is characterized by being composed of a benzoxazine resin, a phenol curing agent, a thermoplastic resin, and a ferroelectric inorganic filler, and this composition reinforces elasticity by introducing a thermoplastic resin instead of using a glass fiber reinforcing agent, and epoxy Dielectric loss was reduced by introducing benzoxazine resin instead of resin, and benzoxazine resin itself and excess inorganic filler showed excellent flame retardancy without a separate flame retardant. As a curing agent, a phenol curing agent is used instead of dicyanide (Dicy) to increase heat resistance.

In addition, the copper foil laminate of the present invention using the above-mentioned composition is thinner and has a higher dielectric constant than the conventional copper foil laminate for built-in capacitors, and thus can not only significantly increase capacitance, but also have high glass transition temperature and excellent lead heat resistance and flame resistance. Has an effect of exhibiting low dielectric loss characteristics.

Claims (15)

A resin composition for producing a copper foil with resin or a copper foil laminated plate, the resin composition comprising (A) a benzoxazine resin, (B) a phenol curing agent, (C) a thermoplastic resin, and (D) a ferroelectric inorganic filler. The benzoxazine resin (A) according to claim 1, wherein 0.5 to 1.5 mol of the primary amine is reacted with respect to 1 mol of the compound having a phenolic hydroxyl group, and formaldehyde is 1.5 to 2.5 mol with respect to 1 mol of the primary amine. It is added by the ratio of and obtained by ring-opening reaction of dihydro benzooxadine, The resin composition characterized by the above-mentioned. The resin composition according to claim 1, wherein the benzoxazine resin (A) is a compound represented by the following formula (1).

(One) In the formula, R ₁ is an alkyl group, a cyclohexyl group, a phenyl group, or a phenyl group substituted from an alkyl group or an alkoxy group. The resin composition according to claim 1, wherein the benzoxazine resin (A) is included in an amount of 40 to 90 parts by weight based on 100 parts by weight of the total resin composition. The phenol curing agent (B) is one selected from the group consisting of a phenol novolak resin, a bisphenol A novolak resin, a cresol novolak resin, a phenol-modified xylene resin, an alkyl phenol resin, and a melamine-modified resin. Resin composition, characterized in that two or more. The resin composition according to claim 1, wherein the phenol curing agent (B) has a phenol resin equivalent of 110 or more and a number average molecular weight of 1000 or more. The resin composition according to claim 1, wherein the phenol curing agent (B) is contained in an amount of 1 to 50 parts by weight based on 100 parts by weight of the benzoxazine resin (A). The method of claim 1, wherein the thermoplastic resin (C) is polyether sulfone (PES), polyphenylene oxide (PPO), acrylonitrile butadiene rubber (NBR), carboxyl terminal acrylonitrile butadiene rubber (CTBN), Compound Terminated Butadiene Rubber (CTB) Acrylic Acid, Acrylate-ester, Acrylamide Combination Acrylic Rubber, Vanyl Terminated Poly Butadiene Rubber (VTBN), Styrene Butadiene Rubber (SBR), Styrene Butadiene Ethylene (SBE), Poly Resin composition, characterized in that one or more selected from the group consisting of esters, polystyrene (PS) polyvinyl acetal (PVA), polyamide (polyamide), and phenoxy (phenoxy). The resin composition of claim 1, wherein the thermoplastic resin (C) is included in an amount of 5 to 30% by weight based on the total weight of the resin composition. The method of claim 1, wherein the ferroelectric inorganic filler (D) is a barium titanium oxide, barium strontium titanate, titanium oxide, lead zirconium titanate, lead lentium zirconate titanate, lead magnesium niboate-lead One or two or more selected from the group consisting of titanate, silver, nickel, nickel-coated polymer spares, gold-coated polymer spares, tin soles, grafts, tantalum nitides, metal silicon nitride, carbon black and aluminum borate Resin composition, characterized in that. The resin composition according to claim 1, wherein the ferroelectric inorganic filler (D) has a particle diameter of 0.1 to 10 µm. The resin composition of claim 1, wherein the ferroelectric inorganic filler (D) is included in an amount of 10 to 700 based on 100 weights of the total resin composition. The resin composition according to claim 1, wherein the ferroelectric inorganic filler (D) contains a dispersant in an amount of 0.005 to 0.05 parts by weight based on 1 part by weight of the ferroelectric filler (D). Copper foil with resin which coated the resin composition of any one of Claims 1-13 to copper foil with a thickness of 5-20 micrometers. The copper foil laminated board which integrated the copper foil with resin of Claim 14, and pressurized, or the copper foil with resin of Claim 14, and copper foil were integrated by heating and pressurizing.

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