KR101249479B1 - Resin composition and copper foil with resin obtained by using the resin composition - Google Patents

Abstract

It aims at providing the resin composition which can provide formation of the insulated resin layer which has favorable adhesiveness with the copper foil for printed wiring board manufactures, and is equipped with a flame-retardant, copper foil with resin, etc. In order to achieve this object, a resin composition for forming an insulating layer of a printed wiring board, comprising: a bisphenol-based epoxy resin which is an epoxy equivalent of 200 or less as an A component, a liquid at 25 ° C, a crosslinkable functional group as a B component, Crosslinking agent as C component, 4,4'-diaminodiphenylsulfone or 2,2-bis (4- (4-aminophenoxy) phenyl) propane as D component, flame-retardant epoxy resin as E component, polyfunctional as F component An epoxy resin and a resin composition characterized by having each of these components as a basic composition are employed.

Description

Copper foil with resin obtained using the resin composition and this resin composition RESIN COMPOSITION AND COPPER FOIL WITH RESIN OBTAINED BY USING THE RESIN COMPOSITION

This invention relates to the resin composition for insulating layer constitution of a printed wiring board, the manufacturing method of copper foil with resin, copper foil with resin, etc.

Resin-clad copper foil has been used for various purposes in the manufacture of printed wiring boards. For example, Patent Literature 1 employs a resin-clad copper foil in which resin is formed on the surface of the copper foil with a marginal portion where the surrounding copper foil is exposed to prevent occurrence of scars on the back surface of the resin-clad copper foil. It discloses and uses the form of the resin foil copper foil for prevention of the damage at the time of a press working.

In addition, Patent Document 2 discloses a method for laminating a resin-clad copper foil to a core layer in order to form a build-up layer in a build-up printed wiring board, wherein the adhesion of the dry film for resist is suppressed by suppressing copper foil depression near the core layer IVH during lamination. This is satisfactory, and there is no bubble, and consequently, a fine pattern can be obtained with high accuracy, and the resin component of the resin layer of the resin-clad copper foil is introduced into the core layer IVH to suppress depressions that are not affected. The use of the copper foil with resin of copper foil is disclosed.

In addition, since the copper foil with resin does not use a skeleton material for the resin layer, it has excellent migration resistance, and unlike the prepreg that uses a glass cloth as a skeleton material, the eyes of the cloth are draped on the substrate surface. It has been used for the purpose of preventing losing. For example, Patent Document 3 is provided between a glass fiber substrate material, a wiring layer, and a wiring pattern for the purpose of providing a printed wiring board which has no fear of insulation deterioration even when used at a high voltage, and which can increase the cost sufficiently. The insulating film which does not contain glass fiber is provided, and the wiring layer and wiring pattern do not contact the glass fiber in a glass fiber substrate material, and the insulating film which does not contain the said glass fiber is formed in the insulating resin part of copper foil with insulating resin. It is disclosed that the copper foil layer in which the said wiring pattern was formed is formed in the copper foil part of this insulated resin copper foil, and employ | adopts the printed wiring board characterized by the above-mentioned. As a result, migration resistance improves, the adhesive strength of an insulating layer, a wiring layer, and a wiring pattern improves, and high reliability and a long lifetime can be obtained.

As can be understood from the above, the resin-clad copper foil has been used for the purpose of supplementing the disadvantage caused by the shape of a printed wiring board. By the way, the low profile of the copper foil which comprises this resin foil with resin has been calculated | required in recent years. That is, the product with the low surface roughness of the copper foil of the side which forms the resin layer of copper foil has been calculated | required. It is because the etching precision at the time of etching a copper foil and forming a circuit can be improved, and formation of a fine pitch circuit can be made easy. It is also possible to provide a printed wiring board with less transmission loss when transmitting high frequency signals.

In response to such a demand, an unharmonized copper foil which has not been subjected to a roughening treatment on the bonding surface of the copper foil has been used. Initially, this unharmonized copper foil was heated, pressed, and bonded to insulating layer constituent materials such as FR-4 grade prepreg, and then processed into a copper clad laminate. When manufacturing a copper clad laminated board by such a general method, there existed a problem regarding adhesive stability between insulation layer component materials, such as an unharmonized copper foil and a prepreg.

Therefore, as disclosed in Patent Literature 4, it has been suggested to use an uncoated copper foil in the form of a resin-clad copper foil. In this patent document 4, an adhesive layer of two or more layers is provided on an uncoated copper foil for the purpose of providing a copper foil for copper-clad laminates excellent in circuit formation in which copper particles do not remain in the resin after etching treatment and comparable peeling strength when a roughened copper foil is used. In the copper foil for copper clad laminated board which provides a WHEREIN, 1 layer of the said contact bonding layers contains 1-50 weight part of epoxy resins in 100 weight part of polyvinyl acetal resins, The copper foil for copper clad laminated boards is disclosed.

Moreover, about the resin foil copper foil, the request | requirement of the flame retardance to the resin layer has also been performed. In order to meet this demand, the present applicant has proposed the invention disclosed in Patent Document 5 as a preferred resin-clad copper foil. Patent Document 5 contains 5 to 25 weights of nitrogen for the purpose of providing a resin-containing copper foil that does not contain a halogen element and has high flame retardancy and has excellent water resistance, heat resistance, and good peel strength between the substrate and the copper foil. The resin compound containing the epoxy resin containing the epoxy resin hardening | curing agent which is%, and the maleimide compound which has thermosetting, and does not contain a halogen element was used for the resin layer structure of the resin foil copper foil. .

Moreover, even if it does not carry out the roughening process of the copper foil which causes an etching residue and a halo phenomenon, patent document 6 adhere | attaches firmly to the copper foil surface, high adhesiveness of copper foil and a base material is attained, and also handleability This outstanding adhesive agent and an adhesive copper foil with an adhesive are disclosed. The adhesive agent mentioned in patent document 6 contains 40-70 weight% of epoxy resins, 20-50 weight% of polyvinyl acetal resins, melamine resin or urethane resin 0.1-20 weight% with respect to the resin component total amount, and 5 of this epoxy resin ~ 80% by weight is characterized in that the rubber-modified epoxy resin.

Patent Document 1: Japanese Patent Application Laid-Open No. 11-348177

Patent Document 2: Japanese Patent Application Laid-Open No. 2001-24324

Patent Document 3: Japanese Patent Laid-Open No. 2001-244589

Patent Document 4: Japanese Patent Application Laid-Open No. 11-10794

Patent Document 5: Japanese Unexamined Patent Publication No. 2002-179772

Patent Document 6: Japanese Patent Application Laid-Open No. 08-193188

[Problems to be solved by the invention]

However, in the invention disclosed in Patent Document 4, it is necessary to provide an adhesive layer of two or more layers on an uncoated copper foil, and to form a resin layer of the first layer and to form a resin layer of the second layer. This increases production costs and lowers productivity.

In addition, in the invention disclosed in Patent Document 5, when the roughness of the resin layer forming surface of the copper foil is lowered, the peeling strength between the cured resin layer and the copper foil becomes insufficient, and it is used as a copper clad laminate for forming a fine pitch circuit. Dissatisfaction left, and the resin composition which can improve the peeling strength and can use the low roughness copper foil further was calculated | required.

Moreover, in recent years, using a non-harmonic copper foil is common and it is used also as copper foil of a copper foil with resin. In such a case, it has been said that it can be used if the peeling strength of an unharmonized copper foil and a resin layer is 0.6 kgf / cm or more, but the improvement of adhesiveness with an insulated resin base material is calculated | required further. Considering only from this viewpoint, the resin composition disclosed in patent document 6 mentioned above is firmly adhered also to the copper foil surface which has not performed roughening process, and the adhesive agent and adhesive bond copper foil which high adhesiveness of copper foil and a base material are aimed at are disclosed. However, since the resin composition used as an adhesive agent disclosed in Patent Document 6 is poor in flame retardancy, its use as a printed wiring board was difficult.

As mentioned above, an object of this invention is to provide the resin composition which can respond to the request | requirement of this adhesive improvement, and the formation of the cured resin layer excellent in the characteristics, such as flame retardance and hygroscopic resistance, and a copper foil with resin. .

[Means for solving the problem]

Therefore, the inventors of the present invention have repeatedly studied, and have come to a resin composition that can solve the problems described above. Hereinafter, the outline | summary of this invention is described.

Resin composition concerning this invention: The resin composition for printed wiring board manufacture which concerns on this invention is a resin composition used in order to form the insulating layer of a printed wiring board, It is characterized by including each component of the following A component-F component.

A component: 1 type (s) or 2 or more types selected from the group which consists of bisphenol-A epoxy resin, bisphenol F-type epoxy resin, and bisphenol AD-type epoxy resin which are liquid equivalent at 25 degreeC and are liquid at 25 degreeC.

Component B: Linear polymer having a crosslinkable functional group.

C component: Crosslinking agent (However, if A component functions as a crosslinking agent of B component, it can be omitted.)

D-component: 4,4'-diaminodiphenylsulfone or 2,2-bis (4- (4-aminophenoxy) phenyl) propane.

E component: Flame-retardant epoxy resin.

F component: Multifunctional epoxy resin.

It is preferable that the resin composition for printed wiring board manufacture which concerns on this invention uses polyvinyl acetal resin and polyamideimide resin as a linear polymer which has a crosslinkable functional group which is said B component.

It is preferable that urethane resin is used for the resin composition for printed wiring board manufacture which concerns on this invention as a crosslinking agent which is said C component.

The resin composition for printed wiring board manufacture which concerns on this invention is a flame-retardant epoxy resin which is the said E component, The brominated epoxy resin provided with the structural formula shown in General formula (7) obtained as a derivative from tetrabromobisphenol A which has two or more epoxy groups in a molecule | numerator, It is preferable to mix and use 1 type or 2 types of brominated epoxy resin which has a structural formula shown in General formula (8).

The resin composition for manufacturing a printed wiring board according to the present invention is a flame-retardant epoxy resin which is the E component, and has 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 having two or more epoxy groups in a molecule thereof. It is preferable to use the phosphorus containing epoxy resin which is an oxide derivative.

The resin composition for printed wiring board manufacture which concerns on this invention is a flame-retardant epoxy resin which is said E component, It is preferable to mix and use 1 type or 2 types of the phosphorus containing epoxy resin which has a structural formula shown in any one of general formula (10)-(12). Do.

It is preferable that the resin composition for printed wiring board manufacture which concerns on this invention uses an ortho cresol novolak-type epoxy resin as a multifunctional epoxy resin of F component.

When the resin composition for printed wiring board manufacture which concerns on this invention makes the weight of a resin composition 100 weight part, A component 3 weight part-20 weight part, B component 3 weight part-30 weight part, C component 3 weight part- 10 parts by weight (can be omitted when component A functions as a crosslinking agent of component B), 5 parts by weight to 20 parts by weight of D component, 3 parts by weight to 20 parts by weight of F component, and a bromine atom derived from E component. It is preferable to determine the addition amount of E component so that it may contain in the range of 12 weight%-18 weight%.

When the resin composition for printed wiring board manufacture which concerns on this invention makes the weight of a resin composition 100 weight part, A component 3 weight part-20 weight part, B component 3 weight part-30 weight part, C component 3 weight part- 10 parts by weight (can be omitted when A component functions as a crosslinking agent of B component), 5 parts by weight to 20 parts by weight of D component, 3 parts by weight to 20 parts by weight of F component, and 100% by weight of the resin composition It is preferable to determine the addition amount of E component so that the phosphorus atom derived from E component may be contained in 0.5 weight%-3.0 weight% when it is set to.

Moreover, it is also preferable that the resin composition for printed wiring board manufacture which concerns on this invention adds a hardening accelerator as G component.

The manufacturing method of the copper foil with resin which concerns on this invention: In the manufacturing method of the copper foil with resin which concerns on this invention, the resin varnish used for formation of a resin layer is prepared in the order of the following process a and the process b, and the said resin varnish is prepared. It is a manufacturing method of the resin foil copper foil for printed wiring board manufacture which apply | coats to the surface of copper foil, and makes it the resin foil copper foil as a semi-hardened resin film of average thickness of 5 micrometers-100 micrometers.

Process a: The said A component, B component, C component (it can omit when A component functions as a crosslinking agent of B component), D component, E component, F component, G component, A component-F component are essential components When the weight of the resin composition is 100% by weight, each component is mixed so as to contain a bromine atom derived from E component in a range of 12% to 18% by weight or a phosphorus atom in a range of 0.5% to 3.0% by weight. It is set as the resin composition.

Process b: The said resin composition is melt | dissolved using an organic solvent, and it is set as the resin varnish whose resin solid content is 25 weight%-50 weight%.

And it is also preferable to add a hardening accelerator to the resin composition of the said process a as G component.

And as for the said copper foil used here, it is preferable to use what has the low roughness surface whose surface roughness Rzjis is 3.0 micrometers or less in the formation surface of the semi-hardened resin layer.

Moreover, it is preferable to provide a silane coupling process layer in the surface which forms the semi-hardened resin layer of the said copper foil.

Printed wiring board which concerns on this invention: The printed wiring board which concerns on this invention comprised the insulating layer using the resin composition mentioned above, It is characterized by the above-mentioned.

[Effects of the Invention]

The resin composition which concerns on this invention is A component, B component, C component (can be omitted when A component functions as a crosslinking agent of B component), D component, E component, F component, and G component among A component. It is equipped with the composition which made F-component as an essential component and added G component as needed. And as each component at this time, the component of a characteristic and the appropriate compounding quantity are employ | adopted. In particular, it is characterized by using 4,4'-diaminodiphenylsulfone or 2,2-bis (4- (4-aminophenoxy) phenyl) propane which is a D component. By employing such a resin composition, when the uncoated copper foil and the resin layer composed of this resin composition are pressed and cured, the adhesion is improved to a level of 0.8 kgf / cm or more as peel strength between the uncoated copper foil and the cured resin layer, and at the same time, flame retardant properties are achieved. The cured resin layer excellent in the agent characteristics, such as moisture absorption and the like, is obtained. Therefore, when manufacturing the resin-clad copper foil which formed the semi-hardened resin layer on the surface of copper foil using the resin composition which concerns on this invention, use of the low roughness copper foil used for formation of a fine pitch circuit is possible, and high quality resin adhesion is carried out. Copper foil can be obtained.

Best Mode for Carrying Out the Invention Hereinafter, the best mode for carrying out the present invention will be described item by item.

<Form of Resin Composition>

The resin composition which concerns on this invention is used for the insulation layer structure of a printed wiring board, and is excellent in adhesiveness with copper foil, and the cured resin layer after hardening becomes excellent in the characteristics, such as flame retardance and moisture absorption resistance. Hereinafter, the adhesiveness of the insulated resin layer formed from the resin composition concerning this invention, and copper foil is described mainly. And this resin composition is characterized by including each component of the following A component-F component. Hereinafter, each component is demonstrated.

A component: This A component is what is called a bisphenol-type epoxy resin. And it is preferable to mix and use 1 type (s) or 2 or more types chosen from the group which consists of a bisphenol-A epoxy resin, a bisphenol F-type epoxy resin, and a bisphenol AD-type epoxy resin. Here, the use of the bisphenol-based epoxy resin is easy to handle with a liquid epoxy resin at 25 ° C., and when the resin-clad copper foil having a semi-cured resin layer is produced, the warpage of the resin-clad copper foil (Curl) This is because the effect of suppressing the phenomenon) is remarkably obtained. Moreover, it is because it is possible to obtain favorable adhesiveness of the resin film after hardening, and copper foil. On the other hand, in the case where the liquid epoxy is of high purity, the crystallization state is maintained even when the liquid epoxy is returned to normal temperature, and the appearance may appear to be solid. In this case, it is possible to use the liquid back. It is contained in the liquid epoxy resin here. In addition, the temperature of 25 degreeC was specified here in order to clarify the meaning in the vicinity of room temperature.

And when epoxy equivalent is 200 or less, since a liquid state can be maintained at the temperature of 25 degreeC, preparation of a resin composition is easy and it can contribute also to suppression of the curl phenomenon at the time of manufacturing copper foil with resin. Although the lower limit of epoxy equivalent is not specified here, when considering that the epoxy equivalent of the minimum unit of bisphenol F type is the smallest, a lower limit is about 150. In addition, the epoxy equivalent here is the number of grams (g / eq) of resin containing a 1-gram equivalent epoxy group. In addition, as long as it is a bisphenol-type epoxy resin mentioned above, you may use individually by 1 type, or may mix and use 2 or more types. In addition, when mixing 2 or more types and using it, there is no restriction | limiting in particular also about the mixing ratio.

This bisphenol-type epoxy resin is used in the compounding ratio of 3 weight part-20 weight part when the resin composition used by this invention is 100 weight part. When the said epoxy resin is less than 3 weight part, the cured resin layer after hardening becomes weak and it will become easy to produce resin splitting. On the other hand, when it exceeds 20 weight part, since adhesiveness will generate | occur | produce on the resin surface which is semi-hardened at room temperature, handling property will fall and contamination will also become large, and it is unpreferable.

B component: This B component is a linear polymer which has a crosslinkable functional group. Here, it is preferable that the linear polymer which has a crosslinkable functional group is equipped with the functional group which contributes to hardening reaction of epoxy resins, such as a hydroxyl group and a carboxyl group. And it is more preferable that the linear polymer which has this crosslinkable functional group is soluble in the organic solvent whose boiling point is 50 degreeC-200 degreeC. As a linear polymer which has a functional group here, a polyvinyl acetal resin, a phenoxy resin, a polyether sulfone resin, a polyamideimide resin, etc. can be used. Especially, use of polyvinyl acetal resin and polyamide-imide resin is preferable. This is because the viscosity adjustment when processed with a resin varnish is easy.

It is preferable to use this linear polymer which has a crosslinkable functional group at the compounding ratio of 3 weight part-30 weight part when making a resin composition 100 weight part. When the said linear polymer is less than 3 weight part, resin flow will become large at the time of hot press, and it will become difficult to control the thickness of an insulated resin layer. As a result, generation | occurrence | production of resin powder is observed a lot from the edge part of the manufactured copper clad laminated board, and it is undesirable from a viewpoint of dust generation prevention. On the other hand, when it exceeds 30 weight part, resin flow will become small, but it becomes easy to produce defects, such as a void, in the insulating layer of the manufactured copper clad laminated board.

Moreover, although it is said that it is preferable to be soluble in the organic solvent whose boiling point here is 50 degreeC-200 degreeC, The organic solvent here is methanol, ethanol, methyl ethyl ketone, toluene, propylene glycol monomethyl ether, and dimethylformamide. , Dimethylacetamide, cyclohexanone, ethyl cellosolve, and the like. One kind of single solvent or two or more kinds of mixed solvents. When boiling point is less than 50 degreeC, the base acid of a solvent by heating becomes remarkable, and when it is set as semi-hardened resin from a resin varnish state, it becomes difficult to obtain a favorable semi-hardened resin layer. On the other hand, when a boiling point exceeds 200 degreeC, the amount of residual solvent in a semi-hardened state will become large and it will not satisfy | fill the required volatilization rate normally, and will not satisfy industrial productivity.

C component: This C component is a crosslinking agent for causing crosslinking reaction with B component. It is preferable to use a urethane type resin as this crosslinking agent. When this crosslinking agent is added, it is added according to the mixing amount of A component and B component, and it is thought that there is no need to specify the compounding ratio strictly strictly originally. However, when using a resin composition as 100 weight part, it is preferable to use with the compounding ratio of 10 weight part or less. It is because the hygroscopic resistance of the resin layer in a semi-cured state will deteriorate when C component which is a urethane type resin exceeding 10 weight part becomes weak, and the resin layer after hardening becomes weak. On the other hand, when this C component is used in a blending ratio of less than 3 parts by weight, the effect as a crosslinking agent will not be sufficiently exhibited in consideration of the mixing amount of the A component and the B component. Therefore, it is preferable to mix | blend 3 weight part or more.

However, in some cases, the C component may be omitted, and the C component is not an essential component. That is, when A component functions as a crosslinking agent of B component, addition of C component can be abbreviate | omitted. More specifically, the polyamideimide resin has a property of crosslinking with an epoxy resin, and when the polyamideimide resin is used as the B component, since the amine portion of the polyamideimide crosslinks with the epoxy resin, the addition of a crosslinking agent is unnecessary. There is. And even if A component functions as a crosslinking agent of B component, when B component of quantity sufficient for reaction does not exist, it is also possible to use C component together. In such a case, the amount of the component C added can be used in the range of 0 parts by weight to 10 parts by weight based on 100 parts by weight of the resin composition. If it is this range, it will not adversely affect the characteristics, such as moisture resistance of the resin layer in a semi-hardened state, the flexibility of the resin layer after hardening. Moreover, More preferably, C component when A component functions as a crosslinking agent of B component is used by the compounding ratio of 0 weight part-less than 3 weight part. It is because remarkable improvement of the resin characteristic is not acquired even if C component exceeds 3 weight part judged from the compounding quantity of A component and B component mentioned above.

D component: This D component is an epoxy resin hardening | curing agent and uses 4,4'- diamino diphenyl sulfone or 2, 2-bis (4- (4-amino phenoxy) phenyl) propane. In the resin composition which concerns on this invention, the hardened resin surface at the time of bonding the resin layer of the said copper foil with a resin to the inner-layer core material provided with the adhesiveness to the joint surface of the non-harmonic copper foil of the semi-hardened resin layer, and an inner layer circuit. And 4,4'-diaminodiphenylsulfone or 2,2-bis (4- (4-aminophenoxy) phenyl) propane is important to improve the adhesion to the inner circuit surface. On the other hand, it is preferable that the addition amount of the epoxy resin hardening | curing agent with respect to an epoxy resin employ | adopts calculation amount from reaction equivalent or the optimal amount obtained experimentally. It is preferable to make this epoxy resin hardening | curing agent into the range of 5 weight part-20 weight part using the resin composition which concerns on this invention as 100 weight part. When an epoxy resin hardener is less than 5 weight part, even if it uses the minimum amount of the said epoxy resin, it will become difficult to obtain the fully hardened resin layer. On the other hand, when an epoxy resin hardening | curing agent is added exceeding 20 weight part, the quantity as a hardening | curing agent becomes excessive, and the hardening rate is too fast, and it becomes a weak hardened resin layer.

E component: This E component is a flame-retardant epoxy resin, and can use both a halogen-type flame-retardant epoxy resin and a halogen-free flame-retardant epoxy resin. Hereinafter, these will be classified and described.

As the halogen flame-retardant epoxy resin, it is preferable to use a so-called brominated epoxy resin. A brominated epoxy resin is generically the epoxy resin containing bromine in an epoxy skeleton. And if the bromine atom content of the resin composition concerning this invention makes the weight of a resin composition 100 weight%, any bromine epoxy resin which can make bromine atom derived from E component be 12 to 18 weight% range. Can be used In particular, it is preferable to use the epoxy resin obtained as tetrabromobisphenol A which has two or more epoxy groups in a molecule | numerator, or derivative of this tetrabromobisphenol A. Among brominated epoxy resins, it is preferable because it is excellent in stability of resin quality in a semi-cured state, a flame retardant effect is high even after curing, and the mechanical properties of the cured resin obtained are improved. For reference, the structural formula of tetrabromobisphenol A is exemplified by the formula (6). In addition, the structural formula of the bisphenol-type brominated epoxy resin obtained as a derivative from tetrabromobisphenol A is illustrated in General formula (7).

Moreover, as the brominated epoxy resin of E component, the compound provided with the structural formula shown in General formula (8) is also preferable. Similar to the bisphenol-based brominated epoxy resin represented by the formula (7), it is preferable because it is excellent in the stability of the resin quality in the semi-cured state and at the same time can impart high flame retardancy.

And the E component which comprises the resin composition which concerns on this invention may be used individually by 1 type of brominated epoxy resin, or may mix and use 2 or more types of brominated epoxy resins. However, when the weight of the resin composition is 100% by weight in consideration of the total amount of the E component, it is preferable to determine the addition amount so that the bromine atom derived from the E component is in the range of 12% by weight to 18% by weight.

Herein, when the resin composition in the case of using a brominated epoxy resin contains a bromine atom derived from the E component in the range of 12% by weight to 18% by weight when the weight of the resin composition is 100% by weight, the flame retardance as the resin layer after curing In terms of securing. When the content of the bromine atom is less than 12% by weight, it is difficult to obtain good flame retardancy. On the other hand, even if content of the said bromine atom exceeds 18 weight%, the flame retardance of the resin layer after hardening does not improve and it is a waste of resources. Since the amount of bromine atoms contained in an epoxy skeleton differs according to the kind, brominated epoxy resin replaced the addition amount of E component by describing content of a bromine atom as mentioned above.

Subsequently, it is preferable to use what is called a phosphorus containing epoxy resin as a halogen-free flame-retardant epoxy resin. Phosphorus containing epoxy resin is a generic term of the epoxy resin containing phosphorus in an epoxy skeleton. And any phosphorus containing epoxy resin which can make the phosphorus atom derived from E component into 0.5 weight%-3.0 weight% when the phosphorus atom content of the resin composition which concerns on this invention is made into 100 weight% Can be used However, the use of a phosphorus-containing epoxy resin, which is a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative having two or more epoxy groups in a molecule, stabilizes the resin quality in a semi-cured state. This is preferable because of its excellent and high flame retardant effect. For reference, the structural formula of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is shown in Chemical Formula 9.

And when a phosphorus containing epoxy resin which is a 9,10- dihydro-9-oxa-10- phosphapefenthren-10-oxide derivative is concretely illustrated, use of the compound which has a structural formula shown in General formula (10) is preferable. It is preferable because it is excellent in the stability of resin quality in a semi-hardened state, and at the same time, a flame retardant effect is high.

Moreover, as a phosphorus containing epoxy resin of E component, the compound provided with the structural formula shown in General formula (11) is also preferable. Like the phosphorus containing epoxy resin shown by General formula (10), since it is excellent in stability of the resin quality in a semi-hardened state, and at the same time, provision of high flame retardance is possible, it is preferable.

Moreover, as a phosphorus containing epoxy resin of E component, the compound provided with the structural formula shown in General formula (12) is also preferable. Similar to the phosphorus-containing epoxy resins shown in the formulas (10) and (11), the resin is preferable because it is excellent in stability of the resin quality in the semi-cured state and at the same time, imparting high flame retardancy.

The epoxy resin obtained as a derivative from this 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- Naphthoquinone or hydroquinone was reacted with an oxide to give a compound represented by Formula 13 (HCA-NQ) or Formula 14 (HCA-HQ), and then an epoxy resin was reacted with a portion of the OH group to obtain a phosphorus-containing epoxy resin. Can be mentioned.

The resin composition in the case of using a phosphorus containing epoxy resin here may be used individually by 1 type of phosphorus containing epoxy resin as E component, or may mix and use two or more types of phosphorus containing epoxy resin. However, when the weight of the resin composition is 100% by weight in consideration of the total amount of the phosphorus-containing epoxy resin as the E component, the amount of the phosphorus atom derived from the E component is preferably set to be 0.5% by weight to 3.0% by weight. Since the amount of phosphorus atoms contained in an epoxy skeleton differs in the phosphorus containing epoxy resin according to the kind, the content of phosphorus atoms was described as above and the addition amount of E component was replaced.

F component: This F component is a polyfunctional epoxy resin. Polyfunctional epoxy resin here is a trishydroxyphenylmethane type epoxy resin, a phenol novolak-type epoxy resin, an ortho cresol novolak-type epoxy resin, etc., for example. And when it makes 100 weight part of resin compositions about this F component, it is preferable to use it at the compounding ratio of 3 weight part-20 weight part. When the F component is less than 3 parts by weight, it is difficult to improve the heat resistance characteristics. On the other hand, when F component exceeds 20 weight part, cured resin becomes weak.

The resin composition comprised from the above-mentioned A component-F component can be classified into a halogen-type flame-retardant resin composition and a halogen-free flame-retardant resin composition. Hereinafter, these are shown with a specific composition.

The halogen-based flame retardant resin composition for manufacturing a printed wiring board according to the present invention, when the weight of the resin composition is 100 parts by weight, A component 3 parts by weight to 20 parts by weight, B component 3 parts by weight to 30 parts by weight, C component 3 parts by weight to 10 parts by weight (when component A functions as a crosslinking agent of component B, it may also be 0 parts by weight to 10 parts by weight), 5 parts by weight to 20 parts by weight of D component, and 3 parts by weight of F component It is-20 weight part and the addition amount of E component is determined so that the bromine atom derived from E component may be contained in 12 weight%-18 weight%.

And when the halogen-free flame-retardant resin composition for printed wiring board manufacture which concerns on this invention makes the weight of a resin composition 100 weight part, A component is 3 weight part-20 weight part, B component is 3 weight part-30 weight part, 3 parts by weight to 10 parts by weight of C component (if the component A functions as a crosslinking agent of B component, it can also be 0 parts by weight to 10 parts by weight), 5 parts by weight to 20 parts by weight of D component, F component It is this 3 weight part-20 weight part, and the addition amount of E component is decided so that the phosphorus atom derived from E component may be contained in 0.5 weight%-3.0 weight%.

Moreover, it is also preferable that the resin composition for printed wiring board manufacture which concerns on this invention adds a hardening accelerator as G component. Therefore, this G component is an arbitrary addition component. And all compounds which function as a curing accelerator can be used as long as it merely promotes resin curing, but from the viewpoint of proceeding smoothly to cure the present resin system using general heat press conditions, it is an imidazole series curing accelerator. Preference is given to using 2-methylimidazole or 2-ethyl-4-methylimidazole.

As mentioned above, although the resin composition for printed wiring board manufacture which concerns on this invention was described, it adds for the case that addition and addition of another component are possible, unless deviating from the meaning of the technical idea of this invention.

<Form of copper foil with resin>

The resin foil with resin for printed wiring board manufacture which concerns on this invention is equipped with the resin layer of the semi-hardened state on the single side | surface of copper foil. And this resin layer is formed as a semi-hardened resin film with an average thickness of 5 micrometers-100 micrometers using the resin composition mentioned above. Thus, the resin layer formed using the resin composition mentioned above is excellent in adhesiveness with copper foil, and also excellent in heat resistance characteristics.

Here, when the average thickness of the said resin layer is less than 5 micrometers, joining with the uneven | corrugated shape which an inner layer circuit forms when joining the said copper foil with resin with respect to the outer layer of the inner core material provided with an inner layer circuit becomes impossible. On the other hand, even if the average thickness of the said resin layer exceeds 100 micrometers, there is no problem, but it is difficult to apply | coat and form a thick resin film, and productivity falls. In addition, when the resin layer is thickened, there is no difference in comparison with the prepreg, and the significance of adopting a product in the form of a copper foil with resin disappears.

And copper foil can be used for all manufacturing methods, regardless of the manufacturing method, such as an electrolytic method or a rolling method. And there is no special limitation also regarding the thickness. In addition, it is not necessary to necessarily give a roughening process to the surface which forms the resin layer of this copper foil. It is because the said resin composition is suitable for manufacture of the resin bonding copper foil which used the unharmonic copper foil. Therefore, although roughening process improves the adhesiveness of copper foil and a resin layer, there is no problem even if it does not provide a roughening process to the surface of copper foil. Since the joining surface of an unharmonized copper foil is a flat surface, the formation ability of a fine pitch circuit improves. In addition, you may perform a rust prevention process on the surface of the said copper foil. Concerning the rust prevention treatment, it is possible to employ inorganic rust prevention using known zinc, zinc-based alloys, or the like, or organic rust prevention by organic monomolecular coatings such as benzoimidazole and triazole. Moreover, it is preferable to provide a silane coupling process layer in the outermost surface which forms the resin layer of the said copper foil.

And when the formation surface of the semi-hardened resin layer of the said copper foil used here shows numerical value of surface roughness, it is preferable to use what has a low roughness surface whose value of Rzjis is 3.0 micrometers or less. When the value of Rzjis becomes 3.0 micrometers or less, the formation ability of the fine pitch circuit excellent in the etching factor will increase remarkably.

Moreover, in the case of the copper foil which is not especially roughening process, in order to improve the wettability of the joining surface and a resin layer, and to improve the adhesiveness at the time of press-processing to base resin, it is to provide a silane coupling agent layer in the joining surface. More preferred. For example, without roughening copper foil, antirust treatment is performed, and an epoxy functional silane coupling agent, an olefin functional silane, an acrylic functional silane, an amino functional silane coupling agent or a mercapto is applied to the silane coupling agent treatment. It is possible to use various kinds, such as a functional silane coupling agent, and peeling strength improves further by selecting and using a suitable silane coupling agent according to a use.

The silane coupling agent which can be used here is specified more specifically. Vinyltrimethoxysilane, vinylphenyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyl tree mainly on the coupling agent used for the glass cloth of prepreg for a printed wiring board Methoxysilane, 4-glycidylbutyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-3- (4- (3- Amino propoxy) propyl) propyl-3-aminopropyl trimethoxysilane, imidazole silane, triazine silane, (gamma)-mercaptopropyl trimethoxysilane, etc. can be used.

Formation of this silane coupling agent layer is not particularly limited in particular the immersion method, the showering method, the spraying method and the like. What is necessary is just to employ | adopt the method which can contact and adsorb | suck the solution containing copper foil and a silane coupling agent most uniformly according to process design. These silane coupling agents are dissolved in water at about 25 ° C as 0.5 to 10 g / 1 as a solvent. A silane coupling agent forms a film by condensation-bonding the OH group which protruded on the surface of copper foil, and the effect does not remarkably increase even if it uses the solution of thick concentration unnecessarily. Therefore, it should be originally determined according to the processing speed of the process or the like. However, when it is less than 0.5g / 1, adsorption rate of a silane coupling agent will be slow and it will not meet general commercial profit, and adsorption will also become nonuniform. In addition, even if the concentration is more than 10g / 1 is not economical because the adsorption rate is not particularly fast.

It is preferable that the semi-hardened resin layer of the above-mentioned copper foil with a resin has a storage elastic modulus of less than 3.0 GPa, and has low elasticity property, when it measures as follows after hardening reaction. The storage elastic modulus at this time is the resin surface of each copper foil with resin using two sheets of the same kind of resin foil with resin, and abuts, and makes it a copper clad laminated board by carrying out hot press molding on predetermined conditions, and is made of copper foil on both sides of the said copper clad laminated board. The layer is etched away to obtain a resin film, and the resin film is a storage modulus at 30 ° C. obtained by measuring dynamic viscoelasticity with a dynamic viscoelasticity measuring device (DMA). The hot press conditions here will be described later in Examples. When the storage modulus is less than 3.0 GPa, the cured resin layer has good flexibility and elasticity. As a result, a printed wiring board manufactured using the resin-clad copper foil according to the present invention is applied to a cured resin layer even after being inserted into an electronic product or the like, even when an impact due to unintentional drop of the product or vibration during transportation is received. It is hard to generate cracks, it is hard to cause damage to electronic components and circuits, and it is a product excellent in impact resistance and vibration resistance.

<The form of the manufacturing method of the copper foil with resin>

In the method for producing a resin-clad copper foil according to the present invention, first, a resin varnish is prepared in the order of the following steps a and b.

In process a, A component, B component, C component (can be omitted when A component functions as a crosslinking agent of B component), D component, E component, F component, A component-F component among G components are essential. When the weight of the resin composition containing the component is 100% by weight, each component is mixed so as to contain the bromine atom derived from the E component in the range of 12% to 18% by weight or the phosphorus atom in the range of 0.5% to 3.0% by weight. To a resin composition. There is no particular limitation on the mixing order, mixing means, and the like of each component at this time. Thus, it is possible to employ all known mixing methods. In addition, since each of these components was mentioned above, the description here is abbreviate | omitted.

Moreover, in said process a, it is also preferable to mix and use a suitable amount of G component (hardening accelerator) as needed. As a hardening accelerator here, 2-methylimidazole which is a hardening accelerator of imidazole series is used. Although the curing accelerator is to be determined by the manufacturer optionally in consideration of the production conditions, such as hot pressing conditions of copper-clad laminate production, if it is stated that the G component 0.1 parts by weight to 1.5 to 100 parts by weight of the resin composition according to the present invention It is about a weight part. This is because when the G component is less than 0.1 part by weight, the curing rate cannot be accelerated and there is no meaning to add. On the other hand, when G component exceeds 1.5 weight part, hardening is accelerated | stimulated too much and it becomes difficult to hold | maintain for a long time with stable quality in a semi-hardened state.

In the process b, the said resin composition is melt | dissolved using the organic solvent, and it is set as the resin varnish whose resin solid content is 25 weight%-50 weight%. The organic solvent at this time is preferably a solvent having a boiling point in the range of 50 ° C. to 200 ° C. as described above. For example, methanol, ethanol, methyl ethyl ketone, toluene, propylene glycol monomethyl ether, dimethylformamide, It is preferable to use one single solvent or two or more mixed solvents selected from the group consisting of dimethylacetamide, cyclohexanone, ethyl cellosolve and the like. It is for the same reason as mentioned above. In addition, let resin solid content be 25 to 50 weight% of resin varnish here. In addition, resin solid content means solid content which remains when a resin varnish is heated and volatile matter is removed. The range of resin solid content shown here is a range which can control a film thickness with the highest precision, when apply | coating to the surface of copper foil. In the case where the resin solid content is less than 25% by weight, the viscosity is too low to flow immediately after the application to the copper foil surface, making it difficult to ensure film thickness uniformity. On the other hand, when resin solid content exceeds 50 weight%, a viscosity will become high and thin film formation on the copper foil surface will become difficult. In addition, it can use if it can melt | dissolve all the resin components used by this invention other than the solvent specifically mentioned here.

When apply | coating the resin varnish obtained by the above to the single side | surface of copper foil, it does not specifically limit about a coating method. However, considering that the target thickness should be applied with high precision, the coating method and the coating device according to the film thickness to be formed may be appropriately selected and used. In addition, what is necessary is just to employ | adopt the heating conditions which can be made into the semi-hardened state suitably according to the property of the resin solution for drying after forming a resin film on the surface of copper foil. And after this drying, it becomes a semi-hardened resin layer of 5 micrometers-100 micrometers in average thickness, and becomes the resin foil with resin which concerns on this invention.

Form of printed wiring board: The printed wiring board which concerns on this invention comprised the insulating layer using the resin composition mentioned above. It is characterized by the above-mentioned. That is, the resin composition which concerns on this invention is made into the resin varnish, and a resin foil copper foil is manufactured using this resin varnish. And it can be processed into a multilayer printed wiring board as the copper clad laminated board laminated | stacked using this resin foil copper foil with resin by bonding to an inner layer core wiring board, and multilayered. Further, the resin composition according to the present invention is used as a resin varnish, and the resin varnish is impregnated into a skeleton such as a glass cloth or a glass nonwoven fabric to form a prepreg, a copper clad laminate is produced by a known method, and processed into a printed wiring board. It may be. That is, by using the said resin composition, manufacture of a printed wiring board is attained by all the well-known manufacturing methods. In addition, the printed wiring board as used in this invention includes what is called a single-sided board, a double-sided board, and a multilayer board of three or more layers. Hereinafter, an Example is described.

Example l

In this Example, the resin composition described below was prepared, it was set as the resin varnish, the resin foil copper foil with a resin was manufactured using this resin varnish, and it evaluated.

Preparation of resin composition: The resin composition whose ratio of bromine atom is 15.1 weight% when the following A component-F component are mixed and the resin composition is 100 weight% is obtained, Furthermore, G component is added and halogen-type resin composition Was prepared. Here, two types of brominated epoxy resins are used as the flame-retardant epoxy resin which is an E component. In addition, the compounding quantity of G component makes 100 weight part of resin compositions which mixed A component-F component, and shows the addition amount to this.

A component: Bisphenol-A epoxy resin which is liquid at 25 degreeC, and has an epoxy equivalent of 188 (brand name: Efototo YD-128, manufactured by Totokasei Co., Ltd.) / 15 parts by weight

B component: Polyvinyl acetal resin as a linear polymer having a crosslinkable functional group (brand name: Denka Butyral 5000A, manufactured by Denki Kagaku Co., Ltd.) / 10 parts by weight

C component: Urethane resin as a crosslinking agent (brand name: Coronate AP Stable, the product made by Nippon Polyurethane Co., Ltd.) / 4 weight part

D component: 4,4'- diamino diphenyl sulfone (brand name: Seikacure S, Wakayama Seika Co., Ltd.) / 15 parts by weight

E component: Brominated epoxy resin 1 (brand name: epicron 1121N-80M, product made by Nippon Ink Chemical Co., Ltd.) / 30 weight part as a flame-retardant epoxy resin

Brominated epoxy resin 2 (trade name: BREN-304, manufactured by Nippon Kayaku Co., Ltd.) / 20 parts by weight as a flame-retardant epoxy resin

F component: Ortho cresol novolak-type epoxy resin as a multifunctional epoxy resin (brand name: epicron N-680, the Japan Ink Chemical Co., Ltd.) / 6 weight part

G component: 2-methylimidazole (brand name: 2MZ, product of Shikoku Kasei Kogyo Co., Ltd.) /0.4 weight part as a hardening accelerator

Preparation of Resin Varnish: The resin composition of the above composition was dissolved in a mixed solvent of methyl ethyl ketone and dimethyl formamide (mixing ratio (volume ratio): methyl ethyl ketone / dimethylformamide = 1/1) to give a resin solid content of 35% by weight The varnish was prepared.

Production of Resin Copper Foil: The above-described resin varnish was uniformly applied to the rough surface (Rzjis = 2.8 μm) of an electrolytic copper foil having a nominal thickness of 18 μm, and then subjected to heat treatment at 140 ° C. for 5 minutes after air drying to give a number of semi-cured states. Copper foil with resin provided with a stratified layer was obtained. The average thickness of the resin layer at this time was 85 micrometers. Hereinafter, the content of the evaluation will be described in detail.

Adhesion evaluation: The resin layer of the said copper foil with resin was made to contact the surface of the prepreg of FR-4 grade of 100 micrometers thick, and hot press molding of pressure 20kgf / cm <2> and temperature 180 degreeC * 1 hour was performed, and the copper clad laminated board was manufactured. . And this copper clad laminated board was cut into the work size, and the linear circuit for peeling strength measurement of 10 mm width was formed by the etching method. Then, peeling strength was measured using the test linear circuit. The result is shown in Table 1 in contrast with the comparative example 1 mentioned later.

Measurement of elastic modulus as cured resin: Using two sheets of the said resin foil copper foil, the resin surface of each resin foil copper resin was made to contact each other, and hot press molding was performed on the conditions of 20 kgf / cm <2> and temperature 180 degreeC * 1 hour, and a copper clad laminated board was manufactured. It was. Then, the resin film was obtained by etching and melt | dissolving the copper foil layer in both surfaces of this copper clad laminated board. And using this resin film, dynamic viscoelasticity is measured with a dynamic viscoelasticity measuring apparatus (DMA), and it is called storage elastic modulus (Young's modulus in 30 degreeC. In some cases, it will only be called "elasticity."). Was obtained.

Example 2

In this Example, the resin composition described below was prepared, it was set as the resin varnish, the resin foil copper foil with a resin was manufactured using this resin varnish, and it evaluated.

Preparation of Resin Composition: The following A component to F component were mixed to obtain a resin composition having a bromine atom ratio of 15.3% by weight when the resin composition was 100% by weight, and a G component was added to the halogen-based resin composition. Was prepared. Here, two types of brominated epoxy resins are used as the flame-retardant epoxy resin which is an E component. In addition, the compounding quantity of G component makes 100 weight part of resin compositions which mixed A component-F component, and shows the addition amount to this.

A component: Bisphenol-A epoxy resin which is liquid at 25 degreeC, and has an epoxy equivalent of 188 (brand name: Efototo YD-128, manufactured by Totokasei Co., Ltd.) / 15 parts by weight

B component: Polyvinyl acetal resin as a linear polymer having a crosslinkable functional group (brand name: Denka Butyral 5000A, manufactured by Denki Kagaku Co., Ltd.) / 10 parts by weight

C component: Urethane resin as a crosslinking agent (brand name: Coronate AP Stable, the product made by Nippon Polyurethane Co., Ltd.) / 4 weight part

D-component: 2,2-bis (4- (4-aminophenoxy) phenyl) propane (brand name: BAPP, Wakayama Seika Co., Ltd.) / 24 parts by weight

E component: Brominated epoxy resin 1 (brand name: epicron 1121N-80M, product made by Nippon Ink Chemical Co., Ltd.) / 10 weight part as a flame-retardant epoxy resin

Brominated epoxy resin 2 (brand name: BREN-304, Japan Chemicals Co., Ltd.) / 30 weight part as a flame-retardant epoxy resin

F component: Ortho cresol novolak-type epoxy resin as a multifunctional epoxy resin (brand name: epicron N-680, the Japan ink chemical company make) / 7 weight part

G component: 2-ethyl-4-methylimidazole (brand name: 2E4MZ, product of Shikoku Kasei Kogyo Co., Ltd.) / 0.2 weight part as a hardening accelerator

Hereinafter, the resin varnish was prepared like Example 1, the copper foil with resin was manufactured, and the copper clad laminated board was manufactured using the said copper foil with resin. And this copper clad laminated board was cut into the work size, and the linear circuit for peeling strength measurement was formed. Then, peeling strength was measured using the test linear circuit. The result is shown in Table 1 in contrast with the comparative example 1 mentioned later.

Example 3

In this Example, the resin composition described below was prepared, it was set as the resin varnish, the resin foil copper foil with a resin was manufactured using this resin varnish, and it evaluated.

Preparation of resin composition: The resin composition whose ratio of the phosphorus atom when the following A component-F component were mixed to make a resin composition 100 weight% is 1.0 weight%, The G component was added, and halogen-free resin was added. The composition was prepared. Here, the phosphorus containing epoxy resin obtained by the synthesis method described below is used as a flame-retardant epoxy resin which is E component. In addition, the compounding quantity of G component makes 100 weight part of resin compositions which mixed A component-F component, and shows the addition amount to this.

Synthesis of phosphorus containing epoxy resin: Here, with reference to the synthesis example 6 of Unexamined-Japanese-Patent No. 11-279258, the phosphorus containing epoxy resin (E component) was synthesize | combined as follows. That is, 141 parts by weight of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 in a four-neck glass-separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device. -An oxide (trade name HCA manufactured by Sanko Co., Ltd.) and 300 parts by weight of ethyl cellosolve were added thereto, and heated to dissolve. Thereafter, 96.3 parts by weight of 1,4-naphthoquinone (reagent) was added in portions while paying attention to the temperature rise due to the heat of reaction. In this case, the molar ratio of 1,4-naphthoquinone and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is [1,4-naphthoquinone] / '9,10-dihydro. -9-oxa-10-phosphaphenanthrene-10-oxide '= 0.93. After the reaction, 262.7 parts by weight of Efototo YDPN-638 (phenol novolac type epoxy resin manufactured by Totokasei Co., Ltd.) and 409.6 parts by weight of YDF-170 (bisphenol F type epoxy resin manufactured by Totokasei Co., Ltd.) were added and stirred while introducing nitrogen gas. It melt | dissolved by heating to 120 degreeC. And 0.24 weight part of triphenylphosphines were added, and reaction of 130 degreeC * 4 hours was carried out. The epoxy equivalent of the obtained phosphorus containing epoxy resin was 327.Og / eq, and phosphorus content rate was 2.0 weight%. The following resin composition was prepared using the phosphorus containing epoxy resin obtained here.

A component: Bisphenol-A epoxy resin which is liquid at 25 degreeC, and has an epoxy equivalent of 188 (brand name: Efototo YD-128, manufactured by Totokasei Co., Ltd.) / 15 parts by weight

B component: Polyvinyl acetal resin as a linear polymer having a crosslinkable functional group (brand name: Denka Butyral 5000A, manufactured by Denki Kagaku Co., Ltd.) / 10 parts by weight

C component: Urethane resin as a crosslinking agent (brand name: Coronate AP Stable, the product made by Nippon Polyurethane Co., Ltd.) / 4 weight part

D component: 4,4'- diamino diphenyl sulfone (brand name: Seikacure S, Wakayama Seika Co., Ltd.) / 16 parts by weight

E component: Phosphorus containing epoxy resin synthesize | combined by said method as flame-retardant epoxy resin / 50 weight part

F component: Ortho cresol novolak-type epoxy resin as a multifunctional epoxy resin (brand name: epicron N-680, the Japan Ink Chemical Co., Ltd. product) / 5 weight part

G component: 2-methylimidazole (brand name: 2MZ, product of Shikoku Kasei Kogyo Co., Ltd.) /0.4 weight part as a hardening accelerator

Hereinafter, the resin varnish was prepared like Example 1, the copper foil with resin was manufactured, and the copper clad laminated board was manufactured using the said copper foil with resin. And this copper clad laminated board was cut into the work size, and the linear circuit for peeling strength measurement was formed. Then, peeling strength was measured using the test linear circuit. The result is shown in Table 2 compared with the comparative example 2 mentioned later.

Example 4

In this Example, the resin composition described below was prepared, it was set as the resin varnish, the resin foil copper foil with a resin was manufactured using this resin varnish, and it evaluated.

Preparation of resin composition: The resin composition whose ratio of the phosphorus atom when the following A component-F component were mixed to make a resin composition 100 weight% is 1.0 weight%, The G component was added, and halogen-free resin was added. The composition was prepared. Here, the polyamideimide resin synthesize | combined by the method described below was used as a linear polymer which has a crosslinkable functional group of B component. Therefore, since polyamideimide resin crosslinks with the epoxy resin of A component, C component (crosslinking agent) was abbreviate | omitted. Moreover, the phosphorus containing epoxy resin obtained by the synthesis | combining method described in Example 3 is used as a flame-retardant epoxy resin which is E component. In addition, the compounding quantity of G component makes 100 weight part of resin compositions which mixed A component-F component, and shows the addition amount to this.

The polyamideimide resin used in this Example was manufactured by the following method. In other words, 192 g of trimellitic anhydride, 211 g of o-tolidedine diisocyanate, 50 g of 4,4'-diphenylmethane diisocyanate, 365 g of N-methyl-2-pyrrolidone (distilled) 1L of N, N-dimethylacetamide was added and mixed, and the mixture was reacted at 70 ° C. for about 2 hours and at 100 ° C. for about 3 hours with stirring under a nitrogen atmosphere. Then, 1 L of N, N-dimethylacetamide was added, the temperature was raised to 160 degreeC over about 2 hours, and it stirred at 160 degreeC for about 1 hour, and stopped the reaction, and the polyamide-imide solution was obtained. The following resin composition was employ | adopted using this polyamideimide solution.

A component: Bisphenol-A epoxy resin which is liquid at 25 degreeC, and has an epoxy equivalent of 188 (brand name: Efototo YD-128, manufactured by Totokasei Co., Ltd.) / 15 parts by weight

B component: The above-mentioned polyamideimide resin as a linear polymer having a crosslinkable functional group / 15 parts by weight

D component: 4,4'- diamino diphenyl sulfone (brand name: Seikacure S, Wakayama Seika Co., Ltd.) / 16 parts by weight

E component: Phosphorus containing epoxy resin synthesize | combined similarly to Example 3 as a flame-retardant epoxy resin / 50 weight part

F component: Ortho cresol novolak-type epoxy resin as a multifunctional epoxy resin (brand name: epicron N-680, the Japan Ink Chemical Co., Ltd.) / 4 weight part

G component: 2-methylimidazole (brand name: 2MZ, product of Shikoku Kasei Kogyo Co., Ltd.) /0.4 weight part as a hardening accelerator

Hereinafter, the resin varnish was prepared like Example 1, the copper foil with resin was manufactured, and the copper clad laminated board was manufactured using the said copper foil with resin. And this copper clad laminated board was cut into the work size, and the linear circuit for peeling strength measurement was formed. Then, peeling strength was measured using the test linear circuit. The result is shown in Table 2 compared with the comparative example 2 mentioned later.

Example 5

In this Example, the resin composition described below was prepared, it was set as the resin varnish, the resin foil copper foil with a resin was manufactured using this resin varnish, and it evaluated. On the other hand, since the resin composition of Example 5 corresponds to the case where A component functions as a crosslinking agent of B component, the resin composition which does not use C component is employ | adopted.

Preparation of resin composition: When the following A component-F component (except C component) were mixed and the resin composition made 100 weight%, the ratio of the phosphorus atom is 1.0 weight%, the resin composition is obtained, and G component is further It added and prepared the halogen-free resin composition. Here, polyamideimide resin synthesized by the method described in Example 4 was used as the linear polymer having a crosslinkable functional group of B component. Therefore, since polyamideimide resin crosslinks with the epoxy resin of A component, C component (crosslinking agent) was abbreviate | omitted. Moreover, the phosphorus containing epoxy resin obtained by the synthesis | combining method described in Example 3 is used as a flame-retardant epoxy resin which is E component. In addition, the compounding quantity of G component makes 100 weight part of resin compositions which mixed A component-F component, and shows the addition amount to this.

A component: Bisphenol F-type epoxy resin (brand name: Efototo YDF-170, Totokasei Co., Ltd.) / 10 weight part which is liquid at 25 degreeC, and has an epoxy equivalent of 165.

Component B: Polyamide-imide resin synthesized in Example 4 as a linear polymer having a crosslinkable functional group / 14 parts by weight

D-component: 2,2-bis (4- (4-aminophenoxy) phenyl) propane (brand name: BAPP, Wakayama Seika Co., Ltd.) / 22 parts by weight

E component: Phosphorus containing epoxy resin synthesize | combined in Example 3 as a flame-retardant epoxy resin / 50 weight part

F component: Ortho cresol novolak-type epoxy resin as a multifunctional epoxy resin (brand name: epicron N-680, the Japan Ink Chemical Co., Ltd.) / 4 weight part

G component: 2-ethyl-4-methylimidazole (brand name: 2E4MZ, product of Shikoku Kasei Kogyo Co., Ltd.) / 0.2 weight part as a hardening accelerator

Hereinafter, the resin varnish was prepared like Example 1, the copper foil with resin was manufactured, and the copper clad laminated board was manufactured using the said copper foil with resin. And this copper clad laminated board was cut into the work size, and the linear circuit for peeling strength measurement was formed. Then, peeling strength was measured using the test linear circuit. The result is shown in Table 2 compared with the comparative example 2 mentioned later.

Comparative example

Comparative Example 1

This comparative example 1 is for contrast with the said Example 1 and Example 2 using a halogen-type resin composition. Therefore, only the composition of the resin composition used in Example 1 differs, and preparation of the other resin varnish, manufacture of the resin foil copper foil, and manufacture of the copper clad laminated board using the said resin foil copper foil are the same. Therefore, only the composition of the different resin composition is described.

A component: Bisphenol-A epoxy resin which is liquid at 25 degreeC, and has an epoxy equivalent of 188 (brand name: Efototo YD-128, manufactured by Totokasei Co., Ltd.) / 15 parts by weight

B component: Polyvinyl acetal resin as a linear polymer having a crosslinkable functional group (brand name: Denka Butyral 5000A, manufactured by Denki Kagaku Co., Ltd.) / 10 parts by weight

C component: Urethane resin as a crosslinking agent (brand name: Coronate AP Stable, the product made by Nippon Polyurethane Co., Ltd.) / 4 weight part

D component: Novolak-type phenol resin as a epoxy resin hardener (brand name: phenorite TD-2131, product made by Nippon Ink Chemical Co., Ltd.) / 24 weight part

E component: Brominated epoxy resin 1 (brand name: epicron 1121N-80M, product made by Nippon Ink Chemical Co., Ltd.) / 10 parts by weight

Brominated epoxy resin 2 (trade name: BREN-304, manufactured by Nippon Chemical Industries, Ltd.) / 30 parts by weight

F component: Ortho cresol novolak-type epoxy resin as a multifunctional epoxy resin (brand name: epicron N-680, the Japan ink chemical company make) / 7 weight part

G component: 2-ethyl-4-methylimidazole (brand name: 2E4MZ, product of Shikoku Kasei Kogyo Co., Ltd.) / 0.2 weight part as a hardening accelerator

Hereinafter, the resin varnish was prepared like Example 1, the copper foil with resin was manufactured, and the copper clad laminated board was manufactured using the said copper foil with resin. And this copper clad laminated board was cut into the work size, and the linear circuit for peeling strength measurement was formed. Then, peeling strength was measured using the test linear circuit. The results are shown in Table 1 to enable comparison with Example 1 and Example 2 above.

Comparative Example 2

This comparative example 2 is for contrast with the said Example 3-Example 5 using a halogen free resin composition. Therefore, only the composition of the resin composition used in Example 3 differs, and preparation of another resin varnish, manufacture of resin foil copper foil, and manufacture of the copper clad laminated board using the said resin foil copper foil are the same. Therefore, only the composition of the different resin composition is described.

A component: Bisphenol-A epoxy resin which is liquid at 25 degreeC, and has an epoxy equivalent of 188 (brand name: Efototo YD-128, manufactured by Totokasei Co., Ltd.) / 15 parts by weight

B component: Polyvinyl acetal resin as a linear polymer having a crosslinkable functional group (brand name: Denka Butyral 5000A, manufactured by Denki Kagaku Co., Ltd.) / 10 parts by weight

C component: Urethane resin as a crosslinking agent (brand name: Coronate AP Stable, the product made by Nippon Polyurethane Co., Ltd.) / 4 weight part

D component: Epoxy resin hardener (Dicyandiamide (reagent) / 4 weight part (solid content conversion) prepared as a 25% dimethylformamide solution)

E component: 50 weight part of phosphorus containing epoxy resin synthesize | combined by the method similar to Example 3

F component: Ortho cresol novolak-type epoxy resin as a multifunctional epoxy resin (brand name: epicron N-680, the Japan ink chemical company make) / 17 weight part

G component: 2-ethyl-4-methylimidazole (brand name: 2E4MZ, product of Shikoku Kasei Kogyo Co., Ltd.) / 0.2 weight part as a hardening accelerator

Hereinafter, the resin varnish was prepared like Example 1, the copper foil with resin was manufactured, and the copper clad laminated board was manufactured using the said copper foil with resin. And this copper clad laminated board was cut into the work size, and the linear circuit for peeling strength measurement was formed. Then, peeling strength was measured using the test linear circuit. The result is shown in Table 2 so that contrast with Example 3-Example 5 is possible.

<Contrast of Example and Comparative Example>

Compared with Example 1 and Example 2 and Comparative Example 1 using a halogen-based resin composition, as can be seen from Table 1, in the case of Example 1 and Example 2, the peel strength exceeds 0.9kgf / cm In addition, it turns out that adhesiveness without inferiority is exhibited even compared with the case of using the copper foil which performed the roughening process. On the other hand, in the case of the comparative example 1, it is understood that peeling strength is 0.4 kgf / cm and it does not satisfy the adhesiveness required practically.

Similarly, in comparison with Examples 3 to 5 and Comparative Example 2 using a halogen-free resin composition, as can be seen from Table 2, the peel strength of Example 3 is 0.8 kgf / cm, It turns out that peeling strength is 1.0 kgf / cm and the peeling strength of Example 5 is 1.0 kgf / cm, and the adhesiveness without any inferiority is exhibited even compared with the case of using the copper foil which performed the roughening process. On the other hand, in the case of the comparative example 2, peeling strength is 0.5 kgf / cm and it falls clearly compared with an Example.

Moreover, the elasticity modulus (Young's modulus) of the insulated resin layer comprised from the resin composition of Examples 1-5, Comparative Example 1, and Comparative Example 2 is compared. These elastic modulus are shown in Table 3.

As can be seen from Table 3, the modulus of elasticity of Examples 1 to 5 is less than 3.0 GPa in the range of 2.6 GPa to 2.8 GPa. On the other hand, the elasticity modulus of the comparative example 1 and the comparative example 2 is 3.0 GPa or more. Therefore, compared with the comparative example, it can be understood that the insulated resin layer comprised from the resin composition of the Example is low elasticity. The printed wiring board provided with the insulated resin layer which has such a low elasticity performance is excellent in impact resistance. Therefore, even after being inserted into an electronic product or the like, even if the printed wiring board is impacted by an unintentional fall of the product or the like, damage to the electronic components and circuits is small, thereby providing excellent impact resistance.

As can be understood from the above, in the case of entering the composition range of the resin composition according to the present invention, the composition exhibits good adhesion between the copper foil and the resin layer having cured flame retardancy, and is a composition deviating from the concept of the technical idea according to the present invention. In the case of, it is understood that good adhesion between the copper foil and the cured resin layer is not obtained.

The resin composition which concerns on this invention is equipped with flame retardance, and is equipped with favorable adhesiveness with the copper foil joined here. Therefore, it is suitable as an insulating layer constitution material of a copper clad laminated board and a printed wiring board. In addition, even if it is an uncoated copper foil, copper foil at this time can fully be used. Therefore, it is suitable for manufacture of the copper clad laminated board for forming the fine pitch circuit which is excellent in an etching factor. Moreover, provision of the resin foil with resin of favorable quality is attained by forming a resin layer on the surface of copper foil using this resin composition. Therefore, by using this resin foil with resin, it is possible to provide a high quality build-up printed wiring board which is excellent in migration resistance, is provided with a fine pitch circuit, and has high reliability.

Claims (19)

The resin composition used for forming the insulating layer of a printed wiring board, Comprising: Each component of the following A component, B component, and D component-F component is contained, The resin composition for manufacturing a printed wiring board. A component: 1 type (s) or 2 or more types selected from the group which consists of bisphenol-A epoxy resin, bisphenol F-type epoxy resin, and bisphenol AD-type epoxy resin which are liquid equivalent at 25 degreeC and are liquid at 25 degreeC. B component: Linear polymer which has a crosslinkable functional group which contributes to hardening reaction of at least 1 or more epoxy resin of A component, E component, or F component. D-component: 4,4'-diaminodiphenylsulfone or 2,2-bis (4- (4-aminophenoxy) phenyl) propane. E component: Brominated epoxy resin or phosphorus containing epoxy resin. F component: Multifunctional epoxy resin. The method of claim 1, The linear polymer which has a crosslinkable functional group which is said B component uses polyvinyl acetal resin or a polyamide-imide resin, The resin composition for printed wiring board manufacture. The method of claim 1, The composition further comprises a component B, a component C, which is a crosslinking agent for the crosslinking reaction of at least one epoxy resin among the component A, the component E or the component F. The resin composition for producing a printed wiring board. delete The method of claim 1, The said E component uses the phosphorus containing epoxy resin which is a 9,10- dihydro-9-oxa-10- phosphaphenanthrene-10-oxide derivative which has two or more epoxy groups in a molecule | numerator. Resin composition for wiring board manufacture. The method of claim 1, The said E component mixes and uses 1 type or 2 types of the phosphorus containing epoxy resin which has a structural formula shown in any one of following formula (3)-(5), The resin composition for printed wiring board manufacture characterized by the above-mentioned. (3)

[Formula 4]

[Chemical Formula 5]

Where n is an integer of 0-10. The method of claim 1, The ortho cresol novolak-type epoxy resin was added as a multifunctional epoxy resin of F component, The resin composition for printed wiring board manufacture characterized by the above-mentioned. The method according to claim 1 or 3, When the weight of the resin composition is 100 parts by weight, the A component is 3 parts by weight to 20 parts by weight, the B component is 3 parts by weight to 30 parts by weight, and the C component is 3 parts by weight to 10 parts by weight (the A component is a crosslinking agent of the B component). In case of functioning as 0 to 10 parts by weight), D component is 5 parts by weight to 20 parts by weight, and F component is 3 parts by weight to 20 parts by weight, When the weight of a resin composition is 100 weight%, the weight part of E component is determined so that the bromine atom derived from E component may be contained in the range of 12 weight%-18 weight%, The resin composition for printed wiring board manufacture characterized by the above-mentioned. The method according to claim 1 or 3, When the weight of the resin composition is 100 parts by weight, the A component is 3 parts by weight to 20 parts by weight, the B component is 3 parts by weight to 30 parts by weight, and the C component is 3 parts by weight to 10 parts by weight (the A component is a crosslinking agent of the B component). In case of functioning as 0 to 10 parts by weight), D component is 5 parts by weight to 20 parts by weight, and F component is 3 parts by weight to 20 parts by weight, When the weight of a resin composition is 100 weight%, the weight part of E component is determined so that the phosphorus atom derived from E component may be contained in the range of 0.5 weight%-3.0 weight%, The resin composition for printed wiring board manufacture characterized by the above-mentioned. The method according to claim 1 or 3, When the weight of the resin composition is 100 parts by weight, the A component is 3 parts by weight to 20 parts by weight, the B component is 3 parts by weight to 30 parts by weight, and the C component is 3 parts by weight to 10 parts by weight (the A component is a crosslinking agent of the B component). When it functions as 0 parts by weight to less than 3 parts by weight), D component is 5 parts by weight to 20 parts by weight, F component is 3 parts by weight to 20 parts by weight, When the weight of a resin composition is 100 weight%, the weight part of E component is determined so that the phosphorus atom derived from E component may be contained in the range of 0.5 weight%-3.0 weight%, The resin composition for printed wiring board manufacture characterized by the above-mentioned. The method of claim 1, The hardening accelerator was added as G component, The resin composition for printed wiring board manufacture. In the copper foil with resin provided with the semi-hardened resin layer on the single side | surface of copper foil, The said semi-hardened resin layer was formed with the average thickness of 5 micrometers-100 micrometers using the resin composition of Claim 1, The copper foil with resin for printed wiring board manufacture characterized by the above-mentioned. The method of claim 12, The said copper foil uses that the formation surface of the semi-hardened resin layer has the low roughness surface whose surface roughness (Rzjis) is 3.0 micrometers or less, The copper foil with resin for printed wiring board manufacture characterized by the above-mentioned. The method of claim 12, The copper foil with resin for printed wiring board manufacture characterized by including a silane coupling process layer in the surface which forms the semi-hardened resin layer of the said copper foil. The method of claim 12, One surface of each of the resin-clad copper foils was brought into contact with each other using one type of the above-described resin-clad copper foils, and hot pressing was formed under a condition of a pressure of 20 kgf / cm 2 and a temperature of 180 ° C. × 1 hour to obtain a copper-clad laminate. Semi-hardened resin layer whose storage elastic modulus in 30 degreeC obtained by etching dynamic copper viscoelasticity measuring apparatus (DMA) by etching and removing the copper foil layers on both surfaces of a laminated board to this resin film is less than 3.0 GPa. Copper foil with resin for manufacture of printed wiring boards characterized by including the above. As a manufacturing method of the copper foil with resin for manufacturing a printed wiring board of Claim 12, The resin varnish used for formation of a resin layer is prepared in the following process a and the process b, and the semi-hardened resin film of the average thickness of 5 micrometers-100 micrometers is formed by apply | coating this resin varnish to the surface of copper foil, and resin The copper foil with resin for printed wiring board manufacture characterized by using an attached copper foil. Process a: When the weight of the resin composition which made the said A component-F component into an essential component is 100 weight%, the range of 12 weight%-18 weight% of the bromine atom derived from E component, or 0.5 weight%-of the phosphorus atom- Each component is mixed so as to contain in a range of 3.0 wt% to obtain a resin composition. Process b: The said resin composition is melt | dissolved using an organic solvent, and it is set as the resin varnish whose resin solid content is 25 weight%-50 weight%. 17. The method of claim 16, The hardening accelerator is added as a G component to the resin composition of the said process a, The manufacturing method of the resin foil copper foil for printed wiring board manufacture characterized by the above-mentioned. The insulating layer was comprised using the resin composition of Claim 1, The printed wiring board characterized by the above-mentioned. The method of claim 3, Said C component uses urethane type resin, The resin composition for printed wiring board manufacture characterized by the above-mentioned.