KR20070035179A - Halogen free epoxy resin composition and resin coated copper foil manufactured by using the same - Google Patents

Abstract

The present invention relates to a non-halogen flame-retardant epoxy resin composition and a copper foil with a resin produced using the same.

The non-halogen flame-retardant epoxy resin composition of the present invention has a flame retardancy that satisfies UL's 94V-0 flame retardant grade without using a halogen-based flame retardant, has excellent toughness and excellent impact resistance, and at the same time has excellent copper foil adhesive strength and heat resistance, In addition to the problem, cracks and breaks are not easily generated in the thermal shock or drop test, which has become more stringent in the recent component mounting, so that problems such as poor connection reliability can be solved at the same time.

Description

Halogen free epoxy resin composition and resin coated copper foil manufactured by using the same

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 according to the present invention.

It is a schematic diagram of the state formed in order to measure the copper foil adhesive strength of the copper foil laminated board which concerns on this invention.

The present invention relates to a non-halogen flame-retardant epoxy resin composition and a copper foil with a resin produced using the same.

In recent years, as environmental concerns and safety for the human body have increased, not only it is difficult to burn in the production of electric and electronic products, but also it is required to generate less harmful gases or fumes.

In general, legislation prohibiting the use of halogen-based flame retardants has been passed since incineration of halogen-based flame retardants can lead to toxic dioxins. Therefore, in the build-up printed wiring board material, efforts have been made to introduce non-halogen flame retardants such as phosphorus flame retardants, nitrogen flame retardants, and metal hydrate-based flame retardants instead of halogen flame retardants.

In addition, as the demand for miniaturization and high functionalization of electronic devices increases, the width of circuit wiring narrows, and as the number of component mounting increases, mechanical and thermal stresses tend to be concentrated, and even though defects can be easily generated by heat and mechanical shock, they are more stringent. Since a test such as a thermal shock or drop test that has been made must be passed, a material having excellent heat resistance and toughness is required.

Japanese Patent Laid-Open No. 2003-147171 discloses an epoxy resin, a curing agent, a polyvinyl acetal resin, an electrically insulating whisker, a metal hydrate, and a coupling in the production of a copper foil with a resin for a non-halogen build-up printed wiring board. ), And a resin composition using a phosphorus compound is described, but such a composition is difficult to disperse fillers due to the addition of inorganic fillers such as washers and metal hydrates, and the copper foil adhesive strength is lowered and brittle ( Brittleness was increased, making it difficult to show the desired copper foil adhesive strength and toughness.

Japanese Patent Laid-Open No. 2002-80377 discloses a resin composition using an epoxy resin, a nitrogen-containing curing agent, a thermosetting maleimide, and a reactive polymer in the production of a copper foil with a non-halogen resin for a build-up printed wiring board. The compositions showed that the flame retardancy was not only difficult to achieve UL's 94V-0, but also difficult to exhibit the desired copper foil adhesive strength and toughness.

Korean Patent Laid-Open Publication No. 2004-0056169 discloses a bisphenol A epoxy resin, a self-extinguishing biphenyl structure-containing novolak epoxy resin, and a functional group per molecule of 3 or more in the production of a copper foil with a resin for a non-halogen build-up printed wiring board. Although a rubber-modified epoxy resin, a novolak curing agent and an imidazole-based curing accelerator, and a phosphorus flame retardant, in which a polyfunctional epoxy and aliphatic polyglycidyl ether epoxy resin is reacted with rubber, have been described, the same also applies to these compositions. It did not exhibit the desired toughness.

In order to solve the above problems, the present inventors have studied the resin composition which is excellent in heat resistance, toughness and copper foil adhesive strength without containing halogen, and the flame retardancy of UL 94V-0 flame retardant grade without the use of a halogen-based flame retardant. In the present invention, a non-halogen epoxy resin composition having excellent toughness and excellent impact resistance and excellent copper foil adhesive strength and heat resistance was found and completed the present invention.

The present invention is to provide a non-halogen flame-retardant epoxy resin composition and a copper foil with a resin prepared using the same.

The present invention is (A) a novolac epoxy resin comprising a biphenyl structure, a novolac epoxy resin comprising a dicyclodipentadiene structure and a mixture of one of them. Non-halogen flame-retardant epoxy resins including resins, (B) phosphorus-containing epoxy resins, (C) amine-based curing agents, (D) polyvinyl acetal resins, and (E) acrylonitrile butadiene rubbers To provide a composition.

Moreover, this invention provides the copper foil with resin manufactured using the said resin composition.

Hereinafter, the present invention will be described in detail.

In the non-halogen flame-retardant epoxy resin composition of the present invention, the novolac epoxy resin including the biphenyl structure as the component (A) is represented by the following general formula (1), and the novolak epoxy resin including the dicyclodipentadiene structure is represented by the following general formula (2). It is represented by, can be used alone or mixed.

In the case of using the epoxy resin having the above structure, since the polarity between molecules is small, it shows low dielectric constant and dielectric loss, so that the signal transmission speed can be increased. In particular, when using a novolak epoxy resin containing a biphenyl structure of the formula (1) it was found that the resin itself is self-extinguishing, which contributes to the improvement of flame retardancy.

The content of the novolak epoxy resin containing the (A) biphenyl structure or the novolak epoxy resin containing the dicyclodipentadiene structure is 10 to 90% by weight in the total weight of the component (A + B), preferably 20 to 80% by weight. If the content of the novolac epoxy resin containing a biphenyl structure or the novolac epoxy resin containing a dicyclodipentadiene structure is less than 10% by weight, the dielectric constant and dielectric loss may be increased, resulting in a delay in signal transmission speed. And, if it is more than 90% by weight is not preferred because the phosphorus content is not sufficient enough may cause a problem of poor flame retardancy.

In the non-halogen flame-retardant epoxy resin composition of this invention , phosphorus containing epoxy resin which is (B) component introduce | transduced phosphorus in an epoxy resin frame | skeleton, and is represented by General formula (3).

In Chemical Formula 3, R and R 'are each independently a part of a bifunctional epoxy resin or a polyfunctional epoxy resin, and an epoxy group in the epoxy resin is ring-opened and connected through a hydroxyl group reaction, for example, a bisphenol A epoxy Resins, bisphenol S type epoxy resins, tetraphenyl ethane epoxy resins and phenol novolac type epoxy resins.

Phosphorus contained in the phosphorus-containing epoxy resin imparts flame retardancy by blocking heat and oxygen because phosphorus decomposes at a lower temperature than the resin to form a char when burned.

The content of the phosphorus-containing epoxy resin (B) is 10 to 90% by weight, and preferably 20 to 80% by weight in the total weight of the component (A + B). If the content of the phosphorus-containing epoxy resin is less than 10% by weight, the flame retardancy of the resin is not sufficient, if the content of more than 90% by weight it is not preferable because the problem that the signal transmission speed may be delayed due to the high dielectric constant and dielectric loss.

In addition, the present invention may further include a polymer type bisphenol A epoxy resin or a rubber-modified epoxy resin represented by the following general formula (4) in the component (A) and (B). By doing so, the adhesive force and elasticity can be further improved.

As for the polymeric bisphenol A epoxy resin represented by the said Formula (4), the thing of epoxy equivalent 1000-10,000 is used, More preferably, the thing of 1500-3000 is used. If the epoxy resin equivalent is less than 1000, it does not show sufficient adhesive strength and elasticity. If the epoxy resin equivalent is 10,000 or more, the solubility is easily dropped in the varnish state, and phase separation with the epoxy resin is generated, thereby increasing adhesion and elasticity. It is not preferable because it can drop. In addition, the content of the polymer bisphenol A epoxy resin is less than 30% by weight, more preferably less than 20% by weight of the total weight of the component (A + B). When the content of the polymer type bisphenol A epoxy resin is more than 30% by weight, the curing reaction is delayed, and an excessive thickness deviation occurs at the time of pressing, the dielectric constant and dielectric loss are increased, and the flame retardancy is also not preferable.

Rubber modified epoxy resins include acrylic rubber, acrylonitrile butadiene rubber, carboxyl-terminated acrylonitrile butadiene rubber having a carboxyl group at the end, and butadiene rubber. The epoxy resin is reacted with a rubber selected from the group consisting of. The content of the rubber modified epoxy resin is less than 30% by weight, more preferably less than 20% by weight of the total weight of the component (A + B). If the content of the rubber-modified epoxy resin is more than 30% by weight, the dielectric constant and dielectric loss are high, and the flame retardancy is also lowered, which is not preferable.

In the non-halogen flame-retardant epoxy resin composition of the present invention , the amine-based curing agent (C) component is used as a crosslinking agent of the epoxy resin, has excellent copper foil adhesion, and has the advantage of exhibiting a flame retardant effect by the nitrogen component.

The amine-based curing agent includes at least one member selected from the group consisting of polyamine, polyamide, diaminodiphenyl methane, and dicyandiamide, and in particular, copper with resin Dicyandiamide is the most widely used and most preferred curing agent for gourds. Dicyandiamide is represented by the following formula (5).

In order for dicyanamide to cure the resin component, 0.4 to 0.6 equivalents are used per 1 equivalent of the epoxy resin, and preferably 0.45 to 0.55 parts by weight. If the amine curing agent is used in less than 0.4 equivalent to 1 equivalent of epoxy resin, the curing reaction is slow and takes a long time to cure, and when used in excess of 0.6 equivalents, it tends to deteriorate moisture resistance and heat resistance.

The non-halogen flame-retardant epoxy resin composition of the present invention may further include a curing accelerator, and the curing accelerator is preferably an imidazole series curing accelerator. For example, 1-Methyl Imidazole, 2-Methyl Imidazole, 2-Ethyl 4-Methyl Imidazole, 2-Phenyl Imidazole 2-Phenyl Imidazole, 2-Cyclohexyl 4-Methyl Imidazole, 4-Butyl 5-Ethyl Imidazole, 2-Methyl 5- 2-Methyl 5-Ethyl Imidazole, 2-Octhyl 4-hexyl Imidazole, 2,5-Chloro-4-ethyl imidazole (2,5-Chloro-4 -Ethyl Imidazole) and 2-Butoxy 4-Allyl Imidazole, in particular 2-methyl imidazole or 2-phenyl imidazole with good reaction stability desirable. In this case, the content of the curing accelerator includes 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 component (A + B). If the content of the curing accelerator is used less than 0.01 parts by weight, it takes a long time to cure, there is a problem that the glass transition temperature does not come out sufficiently, when used in excess of 0.1 parts by weight of varnish (Varnish) storage stability is poor.

In the non-halogen flame-retardant epoxy resin composition of the present invention , the polyvinyl acetal (D) component (D) component serves to control the viscosity and to provide coating properties and elasticity by controlling the viscosity to the resin composition. Examples of the polyvinyl acetal resin include BX-1, BX-2, BX-5, BX-55, BX-7, BH-S, KS-1, KS-2, KS-3Z and KS manufactured by Sekisui. -5, KS-5Z, KS-8, KS-23Z, KS-10, etc., and can be used alone or in combination of two or more. At this time, the content of the polyvinyl acetal resin includes 5 to 30 parts by weight, more preferably 10 to 20 parts by weight based on 100 parts by weight of the component (A + B + C). If the content of the polyvinyl acetal resin is less than 5 parts by weight, the flowability of the copper foil with the resin is increased, an excessive thickness deviation may occur, and the coating property and elasticity are deteriorated. Via filling becomes difficult, and since the resin on the hole wall surface is etched during the desmear process, plating voids are easily generated during plating, which is not preferable.

In the non-halogen flame-retardant epoxy resin composition of the present invention, (E) component acrylonitrile butadiene rubber (Acrylonitrile Butadiene Rubber) serves to impart the adhesiveness and elasticity of the resin composition, the acrylonitrile group content of acrylonitrile butadiene It is preferable to use 15 to 30% by weight of the total weight of the rubber, and 30 to 70 Moony Viscosity. It is also preferable to use the acrylonitrile butadiene rubber (Carboxyl-Terminated Acrylonitrile Butadiene Rubber) which has a carboxyl group at the terminal. If the acrylonitrile group content is less than 15% by weight, it is difficult to dissolve in the dimethylformamide (DMF) solvent used as the solvent of the resin composition, and when it exceeds 30% by weight, the dielectric constant and dielectric loss are increased. In addition, when the pattern viscosity is 30 or less, stickiness may be generated. When the pattern viscosity is 70 or more, the phase transition with the epoxy resin may occur, so the elasticity may be lowered, which is not preferable. In this case, the content of acrylonitrile butadiene rubber includes 1 to 15 parts by weight, more preferably 3 to 12 parts by weight, based on 100 parts by weight of the component (A + B + C). If the content of acrylonitrile butadiene rubber is less than 1 part by weight, the elasticity of the copper foil with resin is not sufficient, and if it exceeds 15 parts by weight, the dielectric constant and the dielectric loss become high, which is not preferable.

The non-halogen flame-retardant epoxy resin composition of the present invention may further include one compound selected from the group consisting of (F) phosphazene compounds, condensed phosphate esters, and mixtures thereof.

The phosphazene compound (Phosphazene), or the condensed phosphate ester, which is the (F) component, increases flame retardancy, and serves to lower dielectric constant and dielectric loss. Since the phosphazene compound or the condensed phosphate ester is well soluble in dimethylformamide (DMF) used as a solvent of the resin composition, it is easy to use as an additive flame retardant, and has an effect of lowering the dielectric constant and dielectric loss, in particular of the phosphazene compound. In the case of elasticity is effective at the same time. In this case, the content of the phosphazene compound or the condensed phosphate ester is 20 parts by weight or less, more preferably 15 parts by weight or less based on 100 parts by weight of the component (A + B + C + D + E). If the content of the phosphazene compound or the condensed phosphate ester is 20 parts by weight or more, the adhesive strength and heat resistance are lowered, the hygroscopicity is lowered, the curing reaction is delayed, the flowability is increased, and the thickness variation occurs after pressing. Not desirable

After coating the non-halogen flame-retardant epoxy resin composition which concerns on this invention on the copper foil whose thickness is 10-15 micrometers so that final thickness may be 30-100 micrometers, it dries in oven at 150-200 degreeC for 3 to 10 minutes, and copper foil with resin To prepare.

As the coating method, roll coating, curtain coating, spin coating, slot die coating, various printing, deposition, and the like known in the art may be used.

Non-halogen flame-retardant epoxy resin composition according to the present invention, the flame retardancy satisfies UL's 94V-0 flame retardant grade without using a halogen-based flame retardant, excellent toughness and excellent impact resistance, and at the same time excellent copper foil adhesive strength and heat resistance Therefore, not only environmental problems but also thermal shock and drop tests, which have recently become more stringent in component mounting, can easily solve the problem of poor connection reliability because cracks or breaks are not easily generated.

Hereinafter, preferred examples are provided to aid in understanding the present invention. However, the following examples are merely provided to more easily understand the present invention, and the contents of the present invention are not limited thereto.

Example  One  :

(1) Preparation of Resin Composition

180 g of dimethylformamide (DMF) was placed in a 500 ml beaker, 3 g of dicyanamide, 0.15 g of 2-phenyl imidazole, 8 g of phosphazene compound (SPB100 from Otsuka Chemical, 13% of phosphorus), and polyvinyl acetal resin (Sekisui) KS-5Z) 16g, 9g of acrylonitrile butadiene rubber (Nippon Zeon Nipol1072) having a carboxyl group at the end and completely dissolved, 50g of a novolak epoxy resin (NC3000H) containing a biphenyl structure, epoxy containing phosphorus 50 g of a resin (KDP550, phosphorus content 3%) was added thereto, and stirred until completely dissolved and mixed to prepare a resin composition.

(2) Production of Copper Foil with Resin

The resin composition prepared in (1) was coated on a copper foil having a thickness of 12 μm (JTC of Nikko Japan Co., Ltd.) so as to have a final thickness of 80 μm, and then dried in an oven at 170 ° C. for 6 minutes to prepare a copper foil with resin. .

Example  2 ~ 8  :

The resin composition and the copper foil with resin were manufactured by the method similar to Example 1 with the composition of the component shown in following Table 1.

 ingredient Example (unit: g) One 2 3 4 5 6 7 8 Novolac Epoxy Resin With Biphenyl Structure (NC3000H) 50 - 35 50 35 60 20 30 Novolac epoxy resin (XD1000L) containing a dicyclodipentadiene structure - 30 - - - - - 30 Phosphorus-containing epoxy resin (KDP550) 50 70 35 20 35 20 60 20 Polymer Bisphenol A Epoxy Resin (YD109K) - - 15 15 15 10 10 10 Acrylic rubber modified epoxy resin (KR628) - - 15 15 15 10 10 10 Dicyanamide 3 2.5 2.5 3 2.5 3 2.5 3 2-phenyl imidazole 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 Phosphazene compound (SPB100) 8 3 11 15 - 15 5 15 Condensed Phosphate Ester (Nonfla500) 16 - - - Polyvinyl Acetal Resin (KS-5Z) 16 16 16 16 16 10 10 10 Polyvinyl Acetal Resin (KS-23Z) 6 6 6 Acrylonitrile Butadiene Rubber (Nipol 1072) 9 9 9 9 9 9 - 9 Acrylonitrile Butadiene Rubber (PNR-1H) - - - - - - 9 -

Comparative example  One  :

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

In preparing the resin composition, Example 1 and 3.5g were used instead of 3 g of dicyandiamide, and 100 g of a novolak epoxy resin (Japanese Chemical Co., Ltd. NC3000H) containing a biphenyl structure was used instead of a phosphorus-containing epoxy resin. The resin composition and the copper foil with resin were manufactured by the same method.

Comparative example  2 ~ 6  :

The resin composition and the copper foil with resin were manufactured by the method similar to Example 1 with the composition of the component shown in following Table 2.

 ingredient Comparative Example (Unit: g) One 2 3 4 5 6 Novolac Epoxy Resin With Biphenyl Structure (NC3000H) 100 - 50 50 35 35 Phosphorus-containing epoxy resin (KDP550) - 100 50 50 35 35 Polymer Bisphenol A Epoxy Resin (YD109K) - - - - 15 15 Acrylic rubber modified epoxy resin (KR628) - - - - 15 15 Dicyanamide 3.5 2 - 3 2.5 2.5 Cresol Novolac Phenolic Curing Agent (GPX-41) - - 31 - - - 2-phenyl imidazole 0.15 0.15 0.15 0.15 0.15 0.15 Phosphazene compound (SPB100) 8 8 8 8 11 - Polyvinyl Acetal Resin (KS-5Z) 16 16 16 - 16 16 Phenoxy Resin (YP-50) - - - 16 - - Acrylonitrile Butadiene Rubber (Nipol 1072) 9 9 9 9 - 9 Acrylic Rubber (AR51) - - - - 9 -

Experimental Example  :

The physical properties were measured after manufacturing the copper foil laminated board for evaluation by the copper foil with resin manufactured by the said Examples 1-8 and Comparative Examples 1-6.

(1) permittivity, dielectric loss, Tensile rate (Tensile Elongation), for evaluating the properties of glass transition temperature Copper clad laminate  Produce

Two copper foils with the resin prepared in Examples 1 to 8 and Comparative Examples 1 to 6 were faced to each other, and heated and pressed for 90 minutes at a temperature of 195 ° C. and a pressure of 35 kg / cm 2 using a press to press the copper foil laminate for evaluation. Prepared.

(2) Evaluation for measuring physical properties of copper foil adhesive strength, lead heat resistance and flame retardancy Compulsive Manufacture of Laminates

Two sheets of copper foil with resins prepared in Examples 1 to 8 and Comparative Examples 1 to 6 were faced to a 0.1 mm thick laminated sheet (LG Chem. LGE481) removed by etching the copper foil, using a press and a temperature of 195 ° C. and 35 kg. The copper foil laminated sheet for evaluation was produced by heating and pressurizing for 90 minutes by the pressure of / cm <2>.

The physical properties of the evaluation copper foil laminate prepared above were evaluated by the following method, and the results are shown in Table 3 below.

(Iii) permittivity and dielectric loss

In order to measure the dielectric constant and dielectric loss, the fabricated copper clad laminate specimens were formed in a pattern having a main electrode (a) diameter of 3 cm, a secondary electrode (c) diameter of 4 cm, and a main electrode and ground electrode spacing of 1 cm as shown in FIG. After that, the remaining copper foil except for the pattern was removed by etching, and the specimen size was cut into 5 × 5 cm, and then the 1 MHz dielectric constant and the dielectric loss were measured using L, C, and R measuring instruments (HP4194A manufactured by Hewlett-Packard). It was.

In FIG. 1, a is a main electrode, b is a ground electrode, and c is a negative electrode.

(Ii) Tensile rate (Tensile Elongation)

In order to evaluate the elasticity and toughness, the copper foil layer of the copper-clad laminate specimens was removed by etching, the specimen size was cut into 12 cm x 1.3 cm, and the specimen was cut by pulling at a speed of 5 mm / min with a tensile strength (Zwick). The percentage of length elongated was measured.

(Iii) glass transition temperature

In order to measure the glass transition temperature, the copper foil layer of the prepared copper-clad laminate specimen was removed by etching, and the glass transition temperature (Tg) was measured by heating at a rate of 10 ° C./min with a differential scanning calorimeter (DSC).

(Iii) copper foil adhesive strength

In order to measure the copper foil adhesion strength, the manufactured copper foil laminated specimens were removed by etching as shown in FIG. 2, and a part of the copper foil was peeled off from the test piece, and then the end of the copper foil was fixed to a tensioner (Texture Analyer). After making it peel, peeling strength was measured in the 90 degree direction.

(Iii) lead heat resistance

In order to measure the heat resistance of the lead, the prepared copper foil laminate specimens were placed in a lead bath at 288 ° C., and the samples were cut to a size of 5 cm × 5 cm, and then the time at which the copper foil began to swell was measured.

(Ⅵ) flame retardant

In order to measure the flame retardancy, the prepared copper foil laminated specimens were removed by etching the copper foil layer, the specimen cut into 12.5 cm × 1.3 cm size was burned for 10 seconds with a flame, the flame was removed, and the time for the flame to be extinguished was measured. (t ₁ ). The same method was repeated twice (t ₂ ). The same test is carried out on five specimens, where t ₁ and t ₂ are each 10 seconds or less, and when t ₁ + t ₂ is 50 seconds or less, a UL 94V-0 rating is obtained, and t ₁ and t ₂ are If each is 30 seconds or less and t ₁ + t ₂ is 250 seconds or less, then a UL 94 V-1 rating is obtained.

Permittivity (1MHz) Dielectric Loss (1MHz) Tensile rate (%) Glass transition temperature (℃) Copper foil adhesive strength (Kgf / cm) Lead heat resistance (seconds) Flame Retardant (UL94) Example One 3.9 0.029 24 146 1.4 > 180 V-0 2 3.9 0.033 24 153 1.4 > 180 V-0 3 3.9 0.034 30 146 1.4 > 180 V-0 4 3.9 0.030 29 145 1.4 > 180 V-0 5 3.8 0.029 26 135 1.4 > 180 V-0 6 3.5 0.026 28 141 1.4 > 180 V-0 7 3.9 0.035 26 151 1.5 > 180 V-0 8 3.5 0.026 25 149 1.4 > 180 V-0 Comparative example One 3.5 0.024 20 146 1.5 > 180 V-1 2 3.9 0.041 24 145 1.3 > 180 V-0 3 4.1 0.032 10 146 1.4 > 180 V-1 4 3.9 0.032 12 146 1.5 100 V-0 5 3.9 0.027 10 146 1.3 120 V-0 6 3.9 0.036 21 153 1.5 > 180 V-1

As shown in Table 3, in Examples 1 and 2, a novolac epoxy resin (NC3000H) containing a biphenyl structure, or a novolac epoxy resin (XD1000L) containing a dicyclodipentadiene structure, and a phosphorus-containing epoxy resin ( KDP550), dicyandiamide, polyvinyl acetal resin (KS-5Z), acrylonitrile butadiene rubber (Nipol1072), and phosphazene compound (SPB100) were used to exhibit excellent tensile modulus, copper foil adhesion, and lead heat resistance. In Examples 3 to 7, it was found that the tensile modulus can be further improved by adding a polymer type epoxy resin (YD019K) or an acrylic rubber modified epoxy resin (KR628). In Example 5, instead of using the phosphazene compound (SPB100) in Example 3, a condensed phosphate ester (Nonfla500) was applied, and exhibited an effect of further improving the dielectric constant and dielectric loss instead of a slight drop in tensile rate. In Example 6, instead of reducing the ratio of phosphorus-containing epoxy resin (KDP550), the ratio of novolac epoxy resin (NC3000H) containing a biphenyl structure was increased, and the ratio of phosphazene compound (SPB100) was increased to enhance flame retardancy, thereby increasing the dielectric constant and dielectric constant. It has been found that the loss characteristics can be further improved.

In the case of reducing the phosphazene compound (SPB100) ratio instead of increasing the phosphorus-containing epoxy resin (KDP550) ratio as in Example 2 and Example 7, the dielectric loss is increased, but may exhibit a high glass transition temperature of 150 ° C or higher. It can be seen.

In Comparative Example 1, only the novolac epoxy resin (NC3000H) containing a biphenyl structure was used alone, but the flame retardancy was not sufficient. In Comparative Example 2, only the phosphorus-containing epoxy resin (KDP550) was used alone, but the dielectric loss was high. Was generated. In comparison 3, cresol novolac phenol curing agent (GPX-41) was used instead of dicyandiamide as an epoxy curing agent, but the tensile strength was lowered and the flame retardancy was lowered. In Comparative Example 4, polyvinyl acetal ( Phenoxy resin (YP-50) was used instead of KS-5Z), but the viscosity was lowered, so that not only the resin flow was difficult to control, but also the tensile rate and heat resistance were poor. In Comparative Example 5, acrylic rubber (AR51) was used instead of acrylonitrile butadiene rubber (Nipol1072) in Example 3, and in Example 6, except for the phosphazene compound (SPB100) in Example 3, instead of acrylonitrile butadiene rubber When the acrylic rubber is used, a problem in which the tensile modulus falls a lot is generated, and in the case where the phosphazene compound is not used, the flame retardancy is decreased, the dielectric loss is increased, and the tensile strength is deteriorated.

The non-halogen flame-retardant epoxy resin composition of the present invention has a flame retardancy that satisfies UL's 94V-0 flame retardant grade without using a halogen-based flame retardant, has excellent toughness and excellent impact resistance, and at the same time has an excellent copper foil adhesive strength and heat resistance. . Therefore, not only environmental problems but also thermal shock and drop tests, which have recently become more stringent in component mounting, can easily solve the problem of poor connection reliability due to no cracking or breaking.

Claims (21)

(A) a novolac epoxy resin comprising a biphenyl structure, a novolac epoxy resin comprising a dicyclodipentadiene structure and a mixture thereof, and a novolak epoxy resin selected from the group consisting of B) A non-halogen flame-retardant epoxy resin composition comprising a phosphorus-containing epoxy resin, (C) an amine curing agent, (D) a polyvinyl acetal resin, and (E) an acrylonitrile butadiene rubber. The novolac epoxy resin of claim 1, wherein the novolac epoxy resin including the biphenyl structure as the component (A) is represented by the following formula (1), and the novolak epoxy resin including the dicyclodipentadiene structure is represented by the following formula Non-halogen flame-retardant epoxy resin composition, characterized in that. <Formula 1>

<Formula 2>

The content of the novolak epoxy resin containing the biphenyl structure which is the said (A) component, or the novolak epoxy resin containing the dicyclodipentadiene structure is 10-out of the total weight of a component (A + B). Non-halogen flame-retardant epoxy resin composition comprising 90% by weight. The non-halogen flame-retardant epoxy resin composition according to claim 1, wherein the phosphorus-containing epoxy resin (B) is represented by the formula (3). <Formula 3>

In Formula 3, R and R 'are each independently a part of a bifunctional epoxy resin or a polyfunctional epoxy resin, and an epoxy group in the epoxy resin is ring-opened and connected through a hydroxyl group reaction. The bifunctional epoxy resin or the polyfunctional epoxy resin is selected from the group consisting of bisphenol A type epoxy resin, bisphenol S type epoxy resin, tetraphenyl ethane epoxy resin and phenol novolac type epoxy resin. Non-halogen flame retardant epoxy resin composition. The non-halogen flame-retardant epoxy resin composition according to claim 1, wherein the content of the phosphorus-containing epoxy resin (B) is 10 to 90% by weight in the total weight of the component (A + B). The method according to claim 1, wherein the component (C) Amine-based curing agent is a non-halogen flame-retardant epoxy, characterized in that it comprises at least one selected from the group consisting of polyamine, polyamide, diaminodiphenyl methane and dicyandiamide Resin composition. The method according to claim 1, wherein the component (C) A non-halogen flame-retardant epoxy resin composition, characterized in that an amine curing agent is used in an amount of 0.4 to 0.6 equivalents based on 1 equivalent of the epoxy resin. The non-halogen flame retardant epoxy resin composition according to claim 1, wherein the content of the polyvinyl acetal as the component (D) is 5 to 30 parts by weight based on 100 parts by weight of the component (A + B + C). The acrylonitrile butadiene rubber of the component (E) has an acrylonitrile group content of 15 to 30% by weight in the total weight of the acrylonitrile butadiene rubber, and the Molecular Viscosity is Non-halogen flame-retardant epoxy resin composition, characterized in that 30 to 70. The non-halogen flame-retardant epoxy resin composition according to claim 1, wherein the content of acrylonitrile butadiene rubber (E) is 1 to 15 parts by weight based on 100 parts by weight of component (A + B + C). . The non-halogen flame retardant epoxy resin according to claim 1, further comprising (F) at least one compound selected from the group consisting of phosphazene compounds, condensed phosphate esters, and mixtures thereof. Composition. The non-halogen according to claim 12, wherein the content of the phosphazene compound or the condensed phosphate ester as the component (F) is 20 parts by weight or less based on 100 parts by weight of the component (A + B + C + D + E). Flame retardant epoxy resin composition. The non-halogen flame-retardant epoxy resin composition according to claim 1, further comprising a polymer type bisphenol A epoxy resin or a rubber-modified epoxy resin represented by Formula 4 below. <Formula 4>

15. The method according to claim 14, wherein the bisphenol A epoxy resin has an epoxy equivalent of 1000 to 10,000, and the content of the polymer bisphenol A epoxy resin is less than 30% by weight of the total weight of the component (A + B). Non-halogen flame retardant epoxy resin composition. 15. The method of claim 14, wherein the rubber-modified epoxy resin is acrylic rubber (Acryl Rubber), Acrylonitrile Butadiene Rubber (Acrylonitrile Butadiene Rubber), Carboxyl-Terminated Acrylonitrile Butadiene Rubber having a carboxyl group at the end Non-halogen flame-retardant epoxy resin composition characterized in that the epoxy resin is reacted with a rubber selected from the group consisting of butadiene rubber. 15. The non-halogen flame-retardant epoxy resin composition according to claim 14, wherein the content of the rubber-modified epoxy resin is less than 30% by weight of the total weight of the component (A + B). The non-halogen flame retardant epoxy resin composition according to claim 1, further comprising a curing accelerator in the resin composition. 19. The method of claim 18, wherein the curing accelerator is 1-methyl imidazole, 2-methyl imidazole, 2-ethyl 4-methyl imidazole. ), 2-Phenyl Imidazole, 2-Cyclohexyl 4-Methyl Imidazole, 4-Butyl 5-Ethyl Imidazole 2-Methyl 5-Ethyl Imidazole, 2-Octyl 4-hexyl Imidazole, 2,5-Chloro-4-ethyl Imidazole (2 , 5-Chloro-4-Ethyl Imidazole) and non-halogen flame-retardant epoxy resin composition, characterized in that it is selected from the group consisting of 2-butoxy 4-allyl imidazole. The non-halogen flame retardant epoxy resin composition according to claim 18, wherein the content of the curing accelerator comprises 0.01 to 0.1 parts by weight based on 100 parts by weight of the component (A + B). Copper foil with resin which coated the resin composition of any one of Claims 1-20 to copper foil.

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