JP5650908B2 - Resin composition and copper foil with resin obtained using the resin composition - Google Patents

Description

  The invention according to the present application relates to a resin composition for forming an insulating layer of a printed wiring board, a copper foil with resin, a method for producing a copper foil with resin, and the like.

  Resin-coated copper foil has been used for various purposes in the field of printed wiring board manufacture. For example, Patent Document 1 adopts a resin-attached copper foil in which a resin is formed on the surface of the copper foil so that there is a blank portion where the surrounding copper foil is exposed, It is disclosed to prevent the occurrence. The form of resin-coated copper foil is used to prevent dents during press working.

  Patent Document 2 discloses a method for laminating a resin-coated copper foil on a core layer in order to form a build-up layer with a build-up printed wiring board. The resin component of the resin layer of the copper foil with resin is caused to flow into the core layer IVH for the purpose of obtaining a fine pattern with good accuracy as a result of good adhesion of the dry film and no generation of bubbles, resulting in a dent without any influence. In order to suppress, it is disclosed to use a copper foil with resin of a copper foil having a necessary thickness.

  In addition, resin-coated copper foil is excellent in migration resistance because it does not use a skeleton material in its resin layer, and it is used to prevent cross eyes from being raised on the substrate surface unlike a prepreg using a glass cloth as a skeleton material. Has been used. For example, Patent Document 3 discloses that a glass fiber substrate material and a wiring are provided for the purpose of providing a printed wiring board or the like that can be prevented from insulation deterioration even when used at a high voltage and that can sufficiently suppress an increase in cost. An insulating film not containing glass fiber is provided between the layer and the wiring pattern, and the glass fiber is included in order to prevent the wiring layer and the wiring pattern from coming into contact with the glass fiber in the glass fiber substrate material. A non-insulating film is formed of an insulating resin portion of a copper foil with an insulating resin, and the copper foil layer on which the wiring pattern is formed is formed of a copper foil portion of the copper foil with an insulating resin. Employing a printed wiring board is disclosed. As a result, the migration resistance is improved, the adhesive strength between the insulating layer, the wiring layer and the wiring pattern is improved, and high reliability and long life can be obtained.

  As can be understood from the above, copper foils with resin have been used for applications that compensate for defects due to the shape of the printed wiring board. However, in recent years, there has been a demand for a low profile copper foil constituting the resin-coated copper foil. That is, a product having a low surface roughness of the copper foil on the side where the resin layer of the copper foil is formed has been desired. This is because the etching accuracy when forming a circuit by etching the copper foil can be improved, and a fine pitch circuit can be easily formed. In addition, when a high frequency signal is transmitted, a printed wiring board with less transmission loss can be provided.

  In response to such a demand, use of a non-roughened copper foil in which the roughening treatment is not performed on the bonding surface of the copper foil has been performed. Initially, this non-roughened copper foil was used by heating and pressing the insulating layer constituting material such as FR-4 grade prepreg to form a copper-clad laminate. When a copper clad laminate was produced by such a general method, there was a problem regarding adhesion stability between the non-roughened copper foil and the insulating layer constituting material such as prepreg.

  Therefore, as disclosed in Patent Document 4, it has been proposed to use a non-roughened copper foil in the form of a copper foil with resin. This Patent Document 4 aims to provide a copper foil for a copper clad laminate excellent in peel strength comparable to that obtained when a roughened copper foil is used and in circuit formation in which copper particles do not remain in the resin after etching treatment. As the copper foil for copper clad laminates, in which two or more adhesive layers are provided on the non-roughened copper foil, the first layer of the adhesive layer is 100 parts by weight of polyvinyl acetal resin and less than 1 to 50 parts by weight of epoxy resin The copper foil for copper clad laminated boards characterized by containing is disclosed.

  Moreover, the request | requirement of the flame retardance with respect to the resin layer has also been performed with respect to the copper foil with resin. In order to meet this requirement, the present applicant has proposed the invention disclosed in Patent Document 5 as a suitable copper foil with resin. In this patent document 5, copper with a resin that does not contain a halogen element, has high flame retardancy, has excellent water resistance, heat resistance, and good peel strength between the substrate and the copper foil. For the purpose of providing a foil, the composition contains an epoxy resin containing an epoxy resin curing agent having a nitrogen content of 5 to 25% by weight and a thermosetting maleimide compound, and does not contain a halogen element. A resin compound characterized in that it was used for the resin layer construction of a resin-coated copper foil.

  Furthermore, Patent Document 6 shows that the copper foil is firmly adhered to the surface without roughening the copper foil, which causes etching residue and haloing phenomenon, and the high adhesion between the copper foil and the substrate is shown. And an adhesive and a copper foil with adhesive are disclosed. The adhesive referred to in Patent Document 6 contains 40 to 70% by weight of an epoxy resin, 20 to 50% by weight of a polyvinyl acetal resin, and 0.1 to 20% by weight of a melamine resin or a urethane resin with respect to the total resin component, 5 to 80% by weight of the epoxy resin is a rubber-modified epoxy resin.

JP-A-11-348177 JP 2001-24324 A JP 2001-244589 A Japanese Patent Laid-Open No. 11-10794 JP 2002-179772 A Japanese Patent Laid-Open No. 08-193188

  However, in the invention disclosed in Patent Document 4, it is necessary to provide two or more adhesive layers on the non-roughened copper foil, and the first resin layer is formed, and the second resin layer is further formed. Therefore, the manufacturing process of the resin layer is lengthened, the production cost is increased, and the productivity is lowered.

  Further, in the invention disclosed in Patent Document 5, when the roughness of the formation surface of the resin layer of the copper foil is low, the peel strength between the cured resin layer and the copper foil becomes insufficient, and the fine pitch circuit There remains dissatisfaction with the use of the copper clad laminate for forming, and there has been a demand for a resin composition that can further improve the peel strength and use a low-roughness copper foil.

  Furthermore, in recent years, the use of non-roughened copper foil has become common, and it is also used as a copper foil for resin-coated copper foil. In such a case, it has been said that it can be used if the peel strength between the non-roughened copper foil and the resin layer is 0.6 kgf / cm or more, but further improvement in adhesion to the insulating resin substrate is desired. It is rare. Considering only from this viewpoint, the resin composition disclosed in Patent Document 6 described above is an adhesive that firmly adheres even to the surface of the copper foil that has not been subjected to roughening treatment, and achieves high adhesion between the copper foil and the base material. And an adhesive-attached copper foil. However, since the resin composition used as the adhesive disclosed in Patent Document 6 has poor flame retardancy, it has been difficult to use it for printed wiring boards.

  From the above, the present invention is a resin composition and a copper foil with a resin that can form a cured resin layer that meets the demand for improved adhesion and is excellent in various properties such as flame retardancy and moisture absorption resistance. The purpose is to provide.

  Accordingly, as a result of intensive studies, the present inventors have come up with a resin composition that can solve the above-described problems. The outline of the present invention will be described below.

Resin composition according to the present invention: The resin composition for producing a printed wiring board according to the present invention is a resin composition used for forming an insulating layer of a printed wiring board, and comprises the following components A to F: Each component is contained in a content in the following range (described as parts by weight when the weight of the resin composition is 100 parts by weight).

Component A: 3 parts by weight to 20 parts by weight of one or more selected from the group of bisphenol A type epoxy resin, bisphenol F type epoxy resin and bisphenol AD type epoxy resin having an epoxy equivalent of 200 or less and liquid at 25 ° C. Department.
Component B: 3 to 30 parts by weight of a linear polymer having at least one crosslinkable functional group among hydroxyl groups or carboxyl groups contributing to the curing reaction of the epoxy resin.
Component C: 3 parts by weight to 10 parts by weight of a crosslinking agent (provided that 0 part by weight to 10 parts by weight when the component A functions as a crosslinking agent for the component B).
Component D: 5 to 20 parts by weight of 4,4′-diaminodiphenylsulfone or 2,2-bis (4- (4-aminophenoxy) phenyl) propane.
Component E: parts by weight of brominated epoxy resin determined so that bromine atoms derived from the brominated epoxy resin contain in the range of 12% by weight to 18% by weight when the weight of the resin composition is 100% by weight.
F component: 3 parts by weight to 20 parts by weight of at least one selected from the group consisting of trishydroxyphenylmethane type epoxy resin, phenol novolac type epoxy resin, and ortho cresol novolac type epoxy resin.

Or
Component A: 3 parts by weight to 20 parts by weight of one or more selected from the group of bisphenol A type epoxy resin, bisphenol F type epoxy resin and bisphenol AD type epoxy resin having an epoxy equivalent of 200 or less and liquid at 25 ° C. Department.
Component B: 3 to 30 parts by weight of a linear polymer having at least one crosslinkable functional group among hydroxyl groups or carboxyl groups contributing to the curing reaction of the epoxy resin.
Component C: 3 parts by weight to 10 parts by weight of a crosslinking agent (provided that 0 part by weight to 10 parts by weight when the component A functions as a crosslinking agent for the component B).
Component D: 5 to 20 parts by weight of 4,4′-diaminodiphenylsulfone or 2,2-bis (4- (4-aminophenoxy) phenyl) propane.
Component E: Weight determined to contain the phosphorus-containing epoxy resin in the range of 0.5 to 3.0% by weight when the phosphorus atom derived from the phosphorus-containing epoxy resin is 100% by weight of the resin composition Department.
F component: 3 parts by weight to 20 parts by weight of at least one selected from the group consisting of trishydroxyphenylmethane type epoxy resin, phenol novolac type epoxy resin, and ortho cresol novolac type epoxy resin.

  The phosphorus-containing epoxy resin which is the above-mentioned E component is preferably a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative having two or more epoxy groups in the molecule.

  In the resin composition for producing a printed wiring board according to the present invention, it is preferable to use a polyvinyl acetal resin or a polyamide-imide resin for the linear polymer having a crosslinkable functional group as the component B.

  In the resin composition for producing a printed wiring board according to the present invention, it is preferable to use a urethane-based resin for the crosslinking agent which is the C component.

  In the resin composition for producing a printed wiring board according to the present invention, an ortho-cresol novolac type epoxy resin is preferably used as the F component polyfunctional epoxy resin.

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

Manufacturing method of resin-coated copper foil according to the present invention: In the manufacturing method of resin-coated copper foil according to the present application, a resin varnish used for forming a resin layer is prepared by the following steps a and b, and the resin varnish A method for producing a resin-coated copper foil for producing a printed wiring board, characterized in that a resin-coated copper foil is obtained as a semi-cured resin film having an average thickness of 5 μm to 100 μm by applying to the surface of the copper foil and drying. is there.

Step a: A component to F component among the A component, B component, C component (may be omitted when the A component functions as a crosslinking agent for the B component), D component, E component, F component, G component When the weight of the resin composition containing as an essential component is 100% by weight, the bromine atom derived from the E component is in the range of 12% to 18% by weight or the phosphorus atom is 0.5% to 3.0% by weight. Each component is mixed so that it may be contained in a range 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 to 50 weight%.

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

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

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

Printed wiring board according to the present invention: The printed wiring board according to the present application is characterized in that an insulating layer is formed using the above-described resin composition.

  The resin composition according to the present application includes the above-mentioned A component, B component, C component (can be omitted when the A component functions as a crosslinking agent for the B component), D component, E component, F component, and G component. Among them, the A component to the F component are essential components, and the G component is added as necessary. And as a component at this time, a characteristic component and an appropriate blending amount are adopted. In particular, it is characterized in that 4,4'-diaminodiphenylsulfone or 2,2-bis (4- (4-aminophenoxy) phenyl) propane, which is component D, is used. By adopting such a resin composition, when the non-roughened copper foil and the resin layer composed of this resin composition are pressed and cured, the non-roughened copper foil and the cured resin layer are between Thus, the adhesiveness is improved to a level of 0.8 kgf / cm or more as the peel strength, and at the same time, a cured resin layer excellent in various properties such as flame retardancy and moisture absorption resistance can be obtained. Accordingly, when a resin-coated copper foil having a semi-cured resin layer formed on the surface of the copper foil is produced using the resin composition according to the present invention, the use of the low-roughness copper foil used for forming the fine pitch circuit is positively used. It is possible to obtain a high-quality copper foil with resin.

  Hereinafter, the best mode for carrying out the present invention will be described for each item.

<Form of resin composition>
The resin composition according to the present application is used for forming an insulating layer of a printed wiring board, has excellent adhesion to a copper foil, and a cured resin layer after curing has various properties such as flame retardancy and moisture absorption resistance. Excellent characteristics. Hereinafter, the adhesion between the insulating resin layer formed of the resin composition according to the present application and the copper foil will be mainly described. And this resin composition is characterized by including each component of the following A component-F component. Hereinafter, each component will be described.

A component: This A component is what is called a bisphenol-type epoxy resin. And it is preferable to mix and use 1 type, or 2 or more types chosen from the group of bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol AD type epoxy resin. Here, the bisphenol-based epoxy resin is selectively used because it is easy to handle with a liquid epoxy resin at 25 ° C., and a resin-coated copper foil provided with a semi-cured resin layer is produced. This is because the effect of suppressing the warpage (curling phenomenon) is remarkably obtained. Moreover, it is because the favorable adhesiveness of the resin film after hardening and copper foil can be obtained. When the liquid epoxy is highly pure, if it is supercooled, the crystallized state is maintained even when the liquid epoxy is returned to room temperature, and the appearance may be solid. In this case, it is possible to return to liquid and use it. It considers including in the liquid epoxy resin said here. Furthermore, the temperature of 25 ° C. is specified here in order to clarify the meaning of around room temperature.

  And when an 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 when manufacturing copper foil with resin. Here, the lower limit value of the epoxy equivalent is not specified, but considering that the epoxy equivalent of the smallest unit of the bisphenol F type is the smallest, the lower limit value is about 150. In addition, the epoxy equivalent said here is the gram number (g / eq) of resin containing 1 gram equivalent of epoxy groups. Furthermore, if it is the above-mentioned bisphenol-type epoxy resin, 1 type may be used independently or 2 or more types may be used in mixture. In addition, when two or more kinds are mixed and used, there is no particular limitation with respect to the mixing ratio.

  This bisphenol-based epoxy resin is used in a blending ratio of 3 parts by weight to 20 parts by weight when the resin composition referred to in the present invention is 100 parts by weight. When the said epoxy resin is less than 3 weight part, the cured resin layer after hardening becomes weak and it becomes easy to produce a resin crack. On the other hand, if it exceeds 20 parts by weight, the resin surface in a semi-cured state at room temperature will be sticky, so that handling properties will be lacking and contamination will be increased.

Component B: Component B is a linear polymer having a crosslinkable functional group. Here, the linear polymer which has a crosslinkable functional group is provided with the functional group which contributes to the curing reaction of epoxy resins, such as a hydroxyl group and a carboxyl group. And it is preferable that the linear polymer which has this crosslinkable functional group is soluble in the organic solvent of the temperature of 50 to 200 degreeC of boiling points. As the linear polymer having a functional group, a polyvinyl acetal resin, a phenoxy resin, a polyethersulfone resin, a polyamideimide resin, or the like can be used. Among these, the use of polyvinyl acetal resin and polyamideimide resin is preferable. This is because it is easy to adjust the viscosity when processed into a resin varnish.

  The linear polymer having a crosslinkable functional group is used in a blending ratio of 3 to 30 parts by weight when the resin composition is 100 parts by weight. When the linear polymer is less than 3 parts by weight, the resin flow becomes large during hot pressing, making it difficult to control the thickness of the insulating resin layer. As a result, a large amount of resin powder is generated from the end of the produced copper-clad laminate, which is not preferable from the viewpoint of preventing dust generation. On the other hand, if it exceeds 30 parts by weight, the resin flow becomes small, but defects such as voids are likely to occur in the insulating layer of the produced copper-clad laminate.

  Moreover, although it is said that it is desirable that the boiling point here is soluble in an organic solvent having a temperature of 50 ° C. to 200 ° C., the organic solvent referred to here is methanol, ethanol, methyl ethyl ketone, toluene, propylene glycol monomethyl ether, One kind of single solvent or two or more kinds of mixed solvents selected from the group of dimethylformamide, dimethylacetamide, cyclohexanone, ethyl cellosolve and the like. When the boiling point is less than 50 ° C., the solvent is greatly diffused by heating, and when the resin varnish is changed to a semi-cured resin, it is difficult to obtain a good semi-cured resin layer. On the other hand, when the boiling point exceeds 200 ° C., the amount of residual solvent in the semi-cured state increases, so that the normally required volatilization rate is not satisfied and industrial productivity is not satisfied.

C component: This C component is a crosslinking agent for causing a crosslinking reaction with the B component. As this crosslinking agent, it is preferable to use a urethane-based resin. When this crosslinking agent is added, it is added according to the mixing amount of the component A and the component B, and it is considered that there is no need to specify the blending ratio strictly strictly. However, when the resin composition is 100 parts by weight, it is preferably used at a blending ratio of 10 parts by weight or less. If the C component which is a urethane-based resin is present exceeding 10 parts by weight, the moisture absorption resistance of the resin layer in the semi-cured state is deteriorated, and the cured resin layer becomes brittle. On the other hand, if this C component is used in a blending ratio of less than 3 parts by weight, the effect as a cross-linking agent will not be sufficiently exerted in consideration of the mixing amount of the A component and B component. Therefore, it is preferable to blend 3 parts by weight or more.

  However, the C component may be omitted, and the C component is not an essential component. That is, when the A component functions as a crosslinking agent for the B component, the addition of the C component can be omitted. More specifically, the polyamide-imide resin has a property of cross-linking with the epoxy resin. When the polyamide-imide resin is used for the B component, the amine part of the polyamide-imide cross-links with the epoxy resin, so that a cross-linking agent is added. May be unnecessary. And even if A component functions as a crosslinking agent of B component, C component can also be used together, when B component of a sufficient quantity for reaction does not exist. In such a case, the amount of component C added can be in the range of 0 to 10 parts by weight when the resin composition is 100 parts by weight. This is because, within this range, the moisture absorption resistance of the resin layer in the semi-cured state and the properties such as the flexibility of the resin layer after curing are not adversely affected. More preferably, the component C in the case where the component A functions as a crosslinking agent for the component B is used in a blending ratio of 0 to less than 3 parts by weight. Judging from the blending amounts of the A component and the B component described above, even if the C component exceeds 3 parts by weight, a remarkable improvement in the resin properties cannot be obtained.

D component: This D component is an epoxy resin curing agent, and 4,4'-diaminodiphenyl sulfone or 2,2-bis (4- (4-aminophenoxy) phenyl) propane is used. In the resin composition according to the present invention, when the resin layer of the resin-coated copper foil is bonded to the inner layer core material provided with the inner layer circuit, the adhesiveness of the semi-cured resin layer to the bonding surface of the non-roughened copper foil 4,4′-diaminodiphenylsulfone or 2,2-bis (4- (4-aminophenoxy) phenyl) propane is selectively used from the viewpoint of improving the adhesion to the cured resin surface and inner layer circuit surface. It is important to use it. In addition, it is preferable to employ | adopt the optimal amount obtained from the calculation amount from a reaction equivalent, or experiment, as the addition amount of the epoxy resin hardening | curing agent with respect to an epoxy resin. The epoxy resin curing agent is contained in the range of 5 to 20 parts by weight based on 100 parts by weight of the resin composition according to the present invention. When the epoxy resin curing agent is less than 5 parts by weight, it becomes difficult to obtain a sufficiently cured resin layer even if the minimum amount of the epoxy resin is used. On the other hand, when the epoxy resin curing agent is added in excess of 20 parts by weight, the amount as a curing agent becomes excessive, and the curing rate is too high, resulting in a brittle cured resin layer.

E component: This E component is a flame retardant epoxy resin, and both a halogen-based flame retardant epoxy resin and a halogen-free flame retardant epoxy resin can be used. Hereinafter, these will be described separately.

As the halogen-based flame retardant epoxy resin, a so-called brominated epoxy resin is preferably used. The brominated epoxy resin is a general term for epoxy resins containing bromine in the epoxy skeleton. And when the bromine atom content of the resin composition according to the present application is 100% by weight of the resin composition, the bromine atom derived from component E is in the range of 12% by weight to 18% by weight. Any brominated epoxy resin can be used. In particular, it is preferable to use an epoxy resin obtained as a tetrabromobisphenol A having two or more epoxy groups in the molecule or a derivative of the tetrabromobisphenol A. Among brominated epoxy resins, the resin quality is excellent in the semi-cured state, and after curing, the flame retardancy effect is high, and the mechanical properties of the resulting cured resin are improved, which is preferable. For reference, the structural formula of tetrabromobisphenol A is exemplified as Chemical Formula 1 . Chemical formula 2 illustrates the structural formula of a bisphenol brominated epoxy resin obtained as a derivative from tetrabromobisphenol A.

A compound having the structural formula shown in Chemical formula 3 is also preferred as the brominated epoxy resin of component E. Like the bisphenol brominated epoxy resin shown in Chemical Formula 2 , it is preferable because it is excellent in the stability of the resin quality in a semi-cured state and at the same time can impart high flame retardancy.

  And as E component which comprises the resin composition which concerns on this application, one type of brominated epoxy resin may be used independently, or two or more types of brominated epoxy resins may be mixed and used. However, in consideration of the total amount of the E component, when the resin composition weight is 100% by weight, the addition amount is determined so that the bromine atom derived from the E component is in the range of 12% by weight to 18% by weight.

  Here, the resin composition in the case of using a brominated epoxy resin contains bromine atoms derived from the component E in the range of 12 to 18% by weight when the weight of the resin composition is 100% by weight. From the viewpoint of ensuring flame retardancy as a cured resin layer. When the bromine atom content is less than 12% by weight, it becomes difficult to obtain good flame retardancy. On the other hand, even if the bromine atom content exceeds 18% by weight, the flame retardancy of the cured resin layer is not improved, and resources are wasted. Since brominated epoxy resins differ in the amount of bromine atoms contained in the epoxy skeleton depending on the type thereof, the bromine atom content is described as described above and replaced with the added amount of the E component.

Next, it is preferable to use a so-called phosphorus-containing epoxy resin as the halogen-free flame-retardant epoxy resin. The phosphorus-containing epoxy resin is a general term for epoxy resins containing phosphorus in an epoxy skeleton. And when the phosphorus atom content of the resin composition according to the present application is 100% by weight of the resin composition, the phosphorus atom derived from the E component can be in the range of 0.5% to 3.0% by weight. Any phosphorus-containing epoxy resin can be used. However, it is possible to use 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 the molecule, so that the resin quality in a semi-cured state It is preferable because of its excellent stability and high flame retardancy effect. For reference, the structural formula of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is shown in Chemical Formula 4 .

And when the phosphorus containing epoxy resin which is a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative is illustrated concretely, use of the compound provided with the structural formula shown in Chemical formula 5 is preferable. It is preferable because it is excellent in stability of the resin quality in a semi-cured state and at the same time has a high flame retardant effect.

Further, as the E component phosphorus-containing epoxy resin, a compound having the structural formula shown in Chemical Formula 6 is also preferable. Like the phosphorus-containing epoxy resin shown in Chemical formula 5 , it is preferable because it is excellent in the stability of the resin quality in the semi-cured state and at the same time it is possible to impart high flame resistance.

Furthermore, as the E component phosphorus-containing epoxy resin, a compound having the structural formula shown in Chemical Formula 7 is also preferable. Similar to the phosphorus-containing epoxy resins shown in Chemical Formula 5 and Chemical Formula 6 , it is preferable because it is excellent in the stability of the resin quality in a semi-cured state and at the same time can impart high flame retardancy.

The epoxy resin obtained as a derivative from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is converted to 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide. After reacting naphthoquinone or hydroquinone to obtain a compound represented by Chemical Formula 8 (HCA-NQ) or Chemical Formula 9 (HCA-HQ), an epoxy resin is reacted with the OH group portion to obtain a phosphorus-containing epoxy resin. Can be mentioned.

  Here, the resin composition in the case of using the phosphorus-containing epoxy resin may be used alone or in combination of two or more phosphorus-containing epoxy resins as the E component. . However, considering the total amount of the phosphorus-containing epoxy resin as the E component, when the resin composition weight is 100% by weight, the phosphorus atom derived from the E component is in the range of 0.5% to 3.0% by weight. The addition amount is determined so that Since the phosphorus-containing epoxy resin has different amounts of phosphorus atoms contained in the epoxy skeleton depending on the type, the phosphorus atom content is described as described above, and the amount added is changed to the addition amount of the E component.

F component: This F component is a polyfunctional epoxy resin. The polyfunctional epoxy resin referred to here is, for example, a trishydroxyphenylmethane type epoxy resin, a phenol novolac type epoxy resin, an orthocresol novolak type epoxy resin, or the like. And about this F component, when a resin composition is 100 weight part, it is used by the mixture 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. On the other hand, when the F component exceeds 20 parts by weight, the cured resin becomes brittle.

  The resin composition composed of the A component to the F component described above can be classified into a halogen-based flame retardant resin composition and a halogen-free flame retardant resin composition. Hereinafter, these are shown as specific compositions.

  In the halogen-based flame retardant resin composition for producing a printed wiring board according to the present invention, the component A is 3 to 20 parts by weight and the component B is 3 parts by weight when the weight of the resin composition is 100 parts by weight. -30 parts by weight, C component is 3 parts by weight to 10 parts by weight (in the case where A component functions as a crosslinking agent for B component, it can be 0 to 10 parts by weight), D component is 5 parts by weight Part to 20 parts by weight, F component is 3 parts by weight to 20 parts by weight, and the addition amount of the E component is determined so as to contain bromine atoms derived from the E component in the range of 12 to 18% by weight. is there.

  The halogen-free flame-retardant resin composition for producing a printed wiring board according to the present invention has a component A of 3 parts by weight to 20 parts by weight and a component B of 100 parts by weight when the resin composition weight is 100 parts by weight. 3 parts by weight to 30 parts by weight, 3 parts by weight to 10 parts by weight of the C component (in the case where the A component functions as a crosslinking agent for the B component, it can be 0 to 10 parts by weight), the D component Is 5 parts by weight to 20 parts by weight, the F component is 3 parts by weight to 20 parts by weight, and contains the phosphorus atom derived from the E component in the range of 0.5% by weight to 3.0% by weight. The amount to be added is determined.

  Furthermore, the resin composition for producing a printed wiring board according to the present invention preferably includes a curing accelerator as a G component. Therefore, this G component is an optional additive component. Any compound that functions as a curing accelerator can be used if it only accelerates resin curing, but it proceeds smoothly to cure the resin system using general hot press conditions. From the viewpoint of making it, it is preferable to use 2-methylimidazole or 2-ethyl-4-methylimidazole which is an imidazole-based curing accelerator.

  As mentioned above, the resin composition for producing a printed wiring board according to the present invention has been described, but other components can be added and added without departing from the spirit of the technical idea of the present invention. It is clearly stated just in case.

<Form of copper foil with resin>
The resin-coated copper foil for producing a printed wiring board according to the present application is provided with a semi-cured resin layer on one side of the copper foil. Then, this resin layer is formed as a semi-cured resin film having an average thickness of 5 μm to 100 μm using the above resin composition. Thus, the resin layer formed using the above-mentioned resin composition is excellent in adhesiveness with copper foil, and is excellent in heat resistance.

  Here, when the average thickness of the resin layer is less than 5 μm, when the resin-coated copper foil is bonded to the outer layer of the inner layer core material including the inner layer circuit, the uneven shape formed by the inner layer circuit Bonding becomes impossible. On the other hand, there is no problem even if the average thickness of the resin layer exceeds 100 μm, but it is difficult to apply and form a thick resin film, and productivity is lacking. In addition, if the resin layer is thickened, there is no difference compared to the prepreg, and the significance of adopting a product in the form of a resin-coated copper foil is lost.

  In addition, the copper foil can be used in any manufacturing method, such as an electrolytic method or a rolling method, regardless of its manufacturing method. And there is no special limitation also about the thickness. Further, it is not always necessary to subject the surface of the copper foil resin layer to the roughening treatment. This is because the resin composition is suitable for producing a resin-coated copper foil using a non-roughened copper foil. Therefore, if there is a roughening treatment, the adhesion between the copper foil and the resin layer is improved, but there is no problem even if the surface of the copper foil is not roughened. Since the bonding surface of the non-roughened copper foil is a flat surface, the ability to form a fine pitch circuit is improved. Furthermore, the surface of the copper foil may be subjected to rust prevention treatment. Regarding 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 using an organic monomolecular film such as benzimidazole or triazole. Furthermore, it is preferable to provide a silane coupling treatment layer on the outermost surface that forms the resin layer of the copper foil.

  And if the formation surface of the semi-hardened resin layer of the said copper foil used here expresses surface roughness with a numerical value, it is preferable to use what has a low roughness surface whose Rzjis value is 3.0 micrometers or less. This is because when the value of Rzjis is 3.0 μm or less, the ability to form a fine pitch circuit having an excellent etching factor is dramatically increased.

  In addition, in the case of copper foil that has not been particularly roughened, in order to improve the wettability between the bonded surface and the resin layer, and to improve the adhesion when pressed to the base resin, It is more preferable to provide a ring agent layer. For example, without roughening the copper foil, rust prevention treatment is performed, and silane coupling agent treatment is performed with epoxy functional silane coupling agent, olefin functional silane, acrylic functional silane, amino functional silane coupling agent. Or various things, such as a mercapto functional silane coupling agent, can be used, and peeling strength improves further by selecting and using a suitable silane coupling agent according to a use.

  The silane coupling agent that can be used here will be described more specifically. Vinyltrimethoxysilane, vinylphenyltrimethoxylane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, mainly for coupling agents similar to those used for prepreg glass cloth for printed wiring boards 4-glycidylbutyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) ptoxy) propyl-3 -Aminopropyltrimethoxysilane, imidazolesilane, triazinesilane, γ-mercaptopropyltrimethoxysilane, etc. can be used.

  The formation of the silane coupling agent layer is not particularly limited, such as a commonly used dipping method, showering method, spraying method, or the like. In accordance with the process design, a method that can contact and adsorb the solution containing the copper foil and the silane coupling agent most uniformly can be arbitrarily employed. These silane coupling agents are dissolved in water at a temperature of 25 ° C. as a solvent so as to be 0.5 to 10 g / l. The silane coupling agent forms a film by condensation bonding with OH groups protruding from the surface of the copper foil, and the effect is not significantly increased even if a solution having a very high concentration is used. Therefore, it should be originally determined according to the processing speed of the process. However, if it is less than 0.5 g / l, the adsorption rate of the silane coupling agent is slow, which is not suitable for general commercial profit, and the adsorption is not uniform. Moreover, even if the concentration exceeds 10 g / l, the adsorption rate is not particularly increased, which is uneconomical.

  The semi-cured resin layer of the resin-coated copper foil described above preferably has a storage elastic modulus of less than 3.0 GPa and a low elastic property when measured as follows after the curing reaction. The storage elastic modulus at this time is the same kind of resin-coated copper foil, the resin surfaces of the respective resin-coated copper foils are brought into contact with each other, hot press-molded under predetermined conditions, and subjected to hot press molding. It is obtained by measuring the dynamic viscoelasticity with a dynamic viscoelasticity measuring device (DMA) as a resin laminate by etching and removing the copper foil layers on both sides of the copper clad laminate. The storage elastic modulus at 30 ° C. The hot pressing conditions here will be described later in the examples. When this storage elastic modulus is less than 3.0 GPa, the cured resin layer has good flexibility and elastic properties. As a result, the printed wiring board manufactured using the resin-coated copper foil according to the present invention, after being incorporated into an electronic product, etc., may be subjected to an impact caused by unintentional dropping of the product, vibration during transportation, etc. Thus, cracks in the cured resin layer hardly occur, electronic components and circuits are hardly damaged, and the product has excellent impact resistance and vibration resistance.

<Form of manufacturing method of copper foil with resin>
In the method for producing a resin-coated copper foil according to the present application, first, a resin varnish is prepared by the following steps a and b.

  In step a, among A component, B component, C component (can be omitted when A component functions as a crosslinking agent for B component), D component, E component, F component, G component, A component to F component When the weight of the resin composition containing the component as an essential component is 100% by weight, the bromine atom derived from the component E is in the range of 12% to 18% by weight or the phosphorus atom is 0.5% to 3.0% by weight. Each component is mixed so that it may be contained in the range of to make a resin composition. There is no particular limitation on the mixing order of each component, mixing means, and the like at this time. Therefore, any known mixing technique can be employed. And since each of these components has already been described, description here is abbreviate | omitted.

  In the step a, it is also preferable to mix and use an appropriate amount of the G component (curing accelerator) as necessary. As the curing accelerator here, 2-methylimidazole, which is an imidazole-based curing accelerator, is used. The curing accelerator should be determined arbitrarily by the manufacturer in consideration of production conditions such as hot press conditions for the production of copper-clad laminates. The G component is about 0.1 to 1.5 parts by weight with respect to 100 parts by weight of the resin composition. This is because if the G component is less than 0.1 part by weight, the curing rate cannot be accelerated and there is no significance to add it. On the other hand, when the component G exceeds 1.5 parts by weight, curing is promoted too much, and it becomes difficult to store for a long period of time with a stable quality in a semi-cured state.

  In step b, the resin composition is dissolved using an organic solvent to obtain a resin varnish having a resin solid content of 25 wt% to 50 wt%. 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, dimethylacetamide It is preferable to use one kind of single solvent or two or more kinds of mixed solvents selected from the group of cyclohexanone, ethyl cellosolve and the like. This is because of the same reason as described above. And let resin solid content be a resin varnish of 25 to 50 weight% here. In addition, resin solid content is solid content which remains when a resin varnish is heated and a volatile matter is removed. The range of the resin solid content shown here is the range in which the film thickness can be controlled to the highest accuracy when applied to the surface of the copper foil. When the resin solid content is less than 25% by weight, the viscosity is too low and it flows immediately after application to the copper foil surface, making it difficult to ensure film thickness uniformity. On the other hand, when the resin solid content exceeds 50% by weight, the viscosity increases and it becomes difficult to form a thin film on the surface of the copper foil. Other than the solvents specifically mentioned here, any solvent can be used as long as it can dissolve all the resin components used in the present invention.

  When the resin varnish obtained as described above is applied to one side of a copper foil, the application method is not particularly limited. However, considering that the target thickness must be applied with high accuracy, a coating method and a coating apparatus corresponding to the film thickness to be formed may be appropriately selected and used. Moreover, what is necessary is just to employ | adopt suitably the heating conditions which can be made into a semi-hardened state according to the property of the resin solution for the drying after forming the resin film on the surface of copper foil. And after this drying, it becomes a semi-cured resin layer having an average thickness of 5 μm to 100 μm, and becomes a resin-coated copper foil according to the present invention.

Form of Printed Wiring Board: The printed wiring board according to the present application is characterized in that an insulating layer is configured by using the above resin composition. That is, using the resin composition according to the present invention as a resin varnish, a resin-coated copper foil is produced using the resin varnish. And it can process into a multilayer printed wiring board as a copper clad laminated board laminated | stacked on the inner-layer core wiring board using this resin-coated copper foil. In addition, the resin composition according to the present invention is used as a resin varnish, and the resin varnish is impregnated into a skeleton material such as glass cloth and glass nonwoven fabric to produce a copper-clad laminate by a known method and processed into a printed wiring board. You can also That is, by using the resin composition, a printed wiring board can be manufactured by any known manufacturing method. The printed wiring board referred to in the present invention includes a so-called single-sided board, a double-sided board, and a multilayer board having three or more layers. Hereinafter, examples will be described.

  In this example, the resin composition described below was prepared, and as the resin varnish, a resin-coated copper foil was produced and 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 15.1% by weight when the resin composition was 100% by weight. Components were added to prepare a halogen-based resin composition. Here, two types of brominated epoxy resins are used as the flame retardant epoxy resin which is the E component. Moreover, the compounding quantity of G component represents the addition amount with respect to 100 weight part of resin compositions which mixed A component-F component.

Component A: Bisphenol A type epoxy resin (trade name: Epotot YD-128, manufactured by Tohto Kasei Co., Ltd.) / 15 parts by weight in liquid form at 25 ° C. and having an epoxy equivalent of 188 Component B: As a linear polymer having crosslinkable functional groups Polyvinyl acetal resin (trade name: Denkabutyral 5000A, manufactured by Denki Kagaku Kogyo Co., Ltd.) / 10 parts by weight C component: urethane resin as a cross-linking agent (trade name: Coronate AP stable, manufactured by Nippon Polyurethane Industry Co., Ltd.) / 4 parts by weight Component D: 4,4′-diaminodiphenylsulfone (trade name: Seika Cure S, Wakayama Seika Kogyo Co., Ltd.) / 15 parts by weight E component: Brominated epoxy resin 1 (trade name: Epicron 1121N as flame retardant epoxy resin) -80M, manufactured by Dainippon Ink & Chemicals, Inc.) / 30 parts by weight
Brominated epoxy resin 2 as a flame retardant epoxy resin (trade name: BREN-304, manufactured by Nippon Kayaku Co., Ltd.) / 20 parts by weight F component: Ortho-cresol novolac type epoxy resin as a multifunctional epoxy resin (trade name: Epicron) N-680, manufactured by Dainippon Ink & Chemicals, Inc.) / 6 parts by weight G component: 2-methylimidazole (trade name: 2MZ, manufactured by Shikoku Chemicals) /0.4 parts by weight as a curing accelerator

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

Production of resin-coated copper foil: The above-mentioned resin varnish is uniformly applied to the roughened surface of an electrolytic copper foil having a nominal thickness of 18 μm (Rz = 2.8 μm), air-dried, and then subjected to heat treatment at 140 ° C. for 5 minutes. It performed and obtained copper foil with resin provided with the resin layer of the semi-hardened state. The average thickness of the resin layer at this time was 85 μm. The details of the evaluation contents will be described below.

Evaluation of adhesion: The resin layer of the copper foil with resin is brought into contact with the surface of an FR-4 grade prepreg having a thickness of 100 μm, and hot press molding is performed at a pressure of 20 kgf / cm ² and a temperature of 180 ° C. × 1 hour. A copper clad laminate was produced. And this copper clad laminated board was cut to the workpiece size, and the linear circuit for 10-mm width peeling strength measurement was formed by the etching method. Thereafter, the peel strength was measured using the test linear circuit. The results are shown in Table 1 so that they can be compared with Comparative Example 1 described later.

Measurement of elastic modulus as cured resin: Using the two resin-coated copper foils, the resin surfaces of the respective resin-coated copper foils are brought into contact with each other, pressure 20 kgf / cm ² , temperature 180 ° C. × 1 hour condition Was subjected to hot press forming to produce a copper clad laminate. Then, the resin film was obtained by etching and removing 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 device (DMA), and the storage elastic modulus at 30 ° C. (sometimes referred to as Young's modulus. Hereinafter, simply referred to as “elastic modulus”. Called).

  In this example, the resin composition described below was prepared, and as the resin varnish, a resin-coated copper foil was produced and 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 with respect to 100% by weight of the resin composition. Components were added to prepare a halogen-based resin composition. Here, two types of brominated epoxy resins are used as the flame retardant epoxy resin which is the E component. Moreover, the compounding quantity of G component represents the addition amount with respect to 100 weight part of resin compositions which mixed A component-F component.

Component A: Bisphenol A type epoxy resin (trade name: Epotot YD-128, manufactured by Tohto Kasei Co., Ltd.) / 15 parts by weight in liquid form at 25 ° C. and having an epoxy equivalent of 188 Component B: As a linear polymer having crosslinkable functional groups Polyvinyl acetal resin (trade name: Denkabutyral 5000A, manufactured by Denki Kagaku Kogyo Co., Ltd.) / 10 parts by weight C component: urethane resin as a cross-linking agent (trade name: Coronate AP stable, manufactured by Nippon Polyurethane Industry Co., Ltd.) / 4 parts by weight D component: 2,2-bis (4- (4-aminophenoxy) phenyl) propane (trade name: BAPP, Wakayama Seika Kogyo Co., Ltd.) / 24 parts by weight E component: brominated epoxy as flame retardant epoxy resin Resin 1 (trade name: Epicron 1121N-80M, manufactured by Dainippon Ink & Chemicals, Inc.) / 10 parts by weight
Brominated epoxy resin 2 as a flame retardant epoxy resin (trade name: BREN-304, manufactured by Nippon Kayaku Co., Ltd.) / 30 parts by weight F component: Orthocresol novolak type epoxy resin (trade name: Epicron) as a polyfunctional epoxy resin N-680, manufactured by Dainippon Ink & Chemicals, Inc.) / 7 parts by weight G component: 2-ethyl-4-methylimidazole (trade name: 2E4MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd.) / 0.2 parts by weight as a curing accelerator

  Hereinafter, in the same manner as in Example 1, a resin varnish was prepared, a resin-coated copper foil was manufactured, and a copper-clad laminate was manufactured using the resin-coated copper foil. And this copper clad laminated board was cut to the workpiece size, and the linear circuit for peeling strength measurement was formed. Thereafter, the peel strength was measured using the test linear circuit. The results are shown in Table 1 so that they can be compared with Comparative Example 1 described later.

  In this example, the resin composition described below was prepared, and as the resin varnish, a resin-coated copper foil was produced and evaluated.

Preparation of resin composition: The following components A to F were mixed to obtain a resin composition having a phosphorus atom ratio of 1.0% by weight when the resin composition was 100% by weight. Components were added to prepare a halogen-free resin composition. Here, the phosphorus-containing epoxy resin obtained by the synthesis method described below is used as the flame retardant epoxy resin which is the E component. Moreover, the compounding quantity of G component represents the addition amount with respect to 100 weight part of resin compositions which mixed A component-F component.

Synthesis of Phosphorus-Containing Epoxy Resin: Here, a phosphorous-containing epoxy resin (E component) was synthesized as follows with reference to Synthesis Example 6 of JP-A-11-279258. That is, 141 parts by weight of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 was added to a four-necked glass separable flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas introducing device. -Oxide (trade name HCA manufactured by Sanko Co., Ltd.) and 300 parts by weight of ethyl cellosolve were added and dissolved by heating. Then, 96.3 parts by weight of 1,4-naphthoquinone (reagent) was added in portions while paying attention to the temperature rise by reaction heat. At this time, the molar ratio of 1,4-naphthoquinone to 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was [1,4-naphthoquinone] / “9,10-dihydro-9. -Oxa-10-phosphaphenanthrene-10-oxide "= 0.93. After the reaction, 262.7 parts by weight of Epototo YDPN-638 (Tohto Kasei Co., Ltd., phenol novolac type epoxy resin) and 409.6 parts by weight of YDF-170 (Toto Kasei Co., Ltd., bisphenol F type epoxy resin) are added, and nitrogen gas is added. While stirring, the mixture was stirred and heated to 120 ° C. to dissolve. Then, 0.24 parts by weight of triphenylphosphine was added to carry out the reaction at 130 ° C. for 4 hours. The epoxy equivalent of the phosphorus-containing epoxy resin obtained at this time was 327.0 g / eq, and the phosphorus content was 2.0% by weight. The following resin composition was prepared using the phosphorus-containing epoxy resin obtained here.

Component A: Bisphenol A type epoxy resin (trade name: Epotot YD-128, manufactured by Tohto Kasei Co., Ltd.) / 15 parts by weight in liquid form at 25 ° C. and having an epoxy equivalent of 188 Component B: As a linear polymer having crosslinkable functional groups Polyvinyl acetal resin (trade name: Denkabutyral 5000A, manufactured by Denki Kagaku Kogyo Co., Ltd.) / 10 parts by weight C component: urethane resin as a cross-linking agent (trade name: Coronate AP stable, manufactured by Nippon Polyurethane Industry Co., Ltd.) / 4 parts by weight D component: 4,4'-diaminodiphenyl sulfone (trade name: Seika Cure S, Wakayama Seika Kogyo Co., Ltd.) / 16 parts by weight E component: Phosphorus-containing epoxy resin synthesized by the above method as a flame-retardant epoxy resin / 50 parts by weight component F: Orthocresol novolac type epoxy resin as a polyfunctional epoxy resin (trade name: Epi Ron N-680, manufactured by Dainippon Ink and Chemicals, Inc.) / 5 parts by weight G component: 2-methylimidazole (trade name as a curing accelerator: 2MZ, manufactured by Shikoku Chemicals Corporation) /0.4 parts

  Hereinafter, in the same manner as in Example 1, a resin varnish was prepared, a resin-coated copper foil was manufactured, and a copper-clad laminate was manufactured using the resin-coated copper foil. And this copper clad laminated board was cut to the workpiece size, and the linear circuit for peeling strength measurement was formed. Thereafter, the peel strength was measured using the test linear circuit. The results are shown in Table 2 so that they can be compared with Comparative Example 2 described later.

  In this example, the resin composition described below was prepared, and as the resin varnish, a resin-coated copper foil was produced and evaluated.

Preparation of resin composition: The following components A to F were mixed to obtain a resin composition having a phosphorus atom ratio of 1.0% by weight when the resin composition was 100% by weight. Components were added to prepare a halogen-free resin composition. Here, as a linear polymer having a crosslinkable functional group of component B, a polyamideimide resin synthesized by the method described below was used. Therefore, since the polyamideimide resin crosslinks with the A component epoxy resin, the C component (crosslinking agent) is omitted. Furthermore, the phosphorus-containing epoxy resin obtained by the synthesis method described in Example 3 is used as the flame retardant epoxy resin which is the E component. Moreover, the compounding quantity of G component represents the addition amount with respect to 100 weight part of resin compositions which mixed A component-F component.

  The polyamideimide resin used in this example was produced by the following method. That is, 192 g of trimellitic anhydride, 211 g of o-tolidine diisocyanate, 50 g of 4,4′-diphenylmethane diisocyanate, 365 g of N-methyl-2-pyrrolidone (distilled) was placed in a reaction vessel and mixed. Further, 1 L of N, N-dimethylacetamide was added and mixed, and the mixture was reacted at 70 ° C. for about 2 hours and further at 100 ° C. for about 3 hours with stirring under a nitrogen atmosphere. Thereafter, 1 L of N, N-dimethylacetamide was added, the temperature was raised to 160 ° C. over about 2 hours, and the reaction was stopped by stirring at 160 ° C. for about 1 hour to obtain a polyamideimide solution. The following resin composition was employ | adopted using this polyamideimide solution.

Component A: Bisphenol A type epoxy resin (trade name: Epotot YD-128, manufactured by Tohto Kasei Co., Ltd.) / 15 parts by weight in liquid form at 25 ° C. and having an epoxy equivalent of 188 Component B: As a linear polymer having crosslinkable functional groups The above-mentioned polyamideimide resin / 15 parts by weight D component: 4,4′-diaminodiphenyl sulfone (trade name: Seika Cure S, Wakayama Seika Kogyo Co., Ltd.) / 16 parts by weight E component: Implemented as a flame-retardant epoxy resin Phosphorus-containing epoxy resin synthesized in the same manner as in Example 3/50 parts by weight F component: Orthocresol novolac type epoxy resin (trade name: Epicron N-680, manufactured by Dainippon Ink & Chemicals, Inc.) as polyfunctional epoxy resin / 4 weight Part G component: 2-methylimidazole (trade name: 2MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd.) / 0.4 parts by weight as a curing accelerator

  Hereinafter, in the same manner as in Example 1, a resin varnish was prepared, a resin-coated copper foil was manufactured, and a copper-clad laminate was manufactured using the resin-coated copper foil. And this copper clad laminated board was cut to the workpiece size, and the linear circuit for peeling strength measurement was formed. Thereafter, the peel strength was measured using the test linear circuit. The results are shown in Table 2 so that they can be compared with Comparative Example 2 described later.

  In this example, the resin composition described below was prepared, and as the resin varnish, a resin-coated copper foil was produced and evaluated. In addition, since the resin composition of Example 5 corresponds to the case where the A component functions as a crosslinking agent for the B component, a resin composition that does not use the C component is employed.

Preparation of resin composition: The following A component-F component (except C component) are mixed, The resin composition whose ratio of a phosphorus atom when a resin composition is 100 weight% is 1.0 weight% The component G was further added to prepare a halogen-free resin composition. Here, the polyamideimide resin synthesized by the method described in Example 4 was used as the linear polymer having a crosslinkable functional group of component B. Therefore, since the polyamideimide resin crosslinks with the A component epoxy resin, the C component (crosslinking agent) is omitted. Furthermore, the phosphorus-containing epoxy resin obtained by the synthesis method described in Example 3 is used as the flame retardant epoxy resin which is the E component. Moreover, the compounding quantity of G component represents the addition amount with respect to 100 weight part of resin compositions which mixed A component-F component.

Component A: Bisphenol F type epoxy resin (trade name: Epototo YDF-170, manufactured by Tohto Kasei Co., Ltd.) / 10 parts by weight in liquid form at 25 ° C. and having an epoxy equivalent of 165 Component B: As a linear polymer having a crosslinkable functional group Polyamideimide resin synthesized in Example 4/14 parts by weight D component: 2,2-bis (4- (4-aminophenoxy) phenyl) propane (trade name: BAPP, Wakayama Seika Kogyo Co., Ltd.) / 22 weights Part E component: As flame-retardant epoxy resin, phosphorus-containing epoxy resin synthesized in Example 3/50 parts by weight F component: Orthocresol novolak type epoxy resin as a polyfunctional epoxy resin (trade name: Epicron N-680, large Nippon Ink Chemical Co., Ltd.) / 4 parts by weight G component: 2-ethyl-4-methylimidazole (trade name: 2E4M) as a curing accelerator Z, manufactured by Shikoku Kasei Kogyo Co., Ltd.) / 0.2 parts by weight

Hereinafter, in the same manner as in Example 1, a resin varnish was prepared, a resin-coated copper foil was manufactured, and a copper-clad laminate was manufactured using the resin-coated copper foil. And this copper clad laminated board was cut to the workpiece size, and the linear circuit for peeling strength measurement was formed. Thereafter, the peel strength was measured using the test linear circuit. The results are shown in Table 2 so that they can be compared with Comparative Example 2 described later.

Comparative example

[Comparative Example 1]
Comparative Example 1 is for comparison with Example 1 and Example 2 using a halogen-based resin composition. Therefore, only the composition of the resin composition used in Example 1 is different, and the other resin varnish preparation, the production of a resin-coated copper foil, and the production of a copper-clad laminate using the resin-coated copper foil are the same. Therefore, only the composition of the different resin compositions will be described.

A component: Bisphenol A type epoxy resin (trade name: Epototo YD-128, manufactured by Tohto Kasei Co., Ltd.) / 15 parts by weight in liquid form at 25 ° C. and having an epoxy equivalent of 188
Component B : Polyvinyl acetal resin as a linear polymer having a crosslinkable functional group (trade name: Denka Butyral 5000A, manufactured by Denki Kagaku Kogyo Co., Ltd.) / 10 parts by weight
Component C : Urethane resin as a crosslinking agent (trade name: Coronate AP stable, manufactured by Nippon Polyurethane Industry Co., Ltd.) / 4 parts by weight
Component D : Novolac-type phenolic resin as epoxy resin curing agent (trade name: Phenolite TD-2131, manufactured by Dainippon Ink & Chemicals, Inc.) / 24 parts by weight
E component: Brominated epoxy resin 1 (trade name: Epicron 1121N-80M, manufactured by Dainippon Ink & Chemicals, Inc.) / 10 parts by weight
Brominated epoxy resin 2 (trade name: BREN-304, manufactured by Nippon Kayaku Co., Ltd.) / 30 parts by weight
F component: Orthocresol novolak type epoxy resin as a polyfunctional epoxy resin (trade name: Epicron N-680, manufactured by Dainippon Ink & Chemicals, Inc.) / 7 parts by weight
G component: 2-ethyl-4-methylimidazole (trade name: 2E4MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd.) / 0.2 parts by weight as a curing accelerator

  Hereinafter, in the same manner as in Example 1, a resin varnish was prepared, a resin-coated copper foil was manufactured, and a copper-clad laminate was manufactured using the resin-coated copper foil. And this copper clad laminated board was cut to the workpiece size, and the linear circuit for peeling strength measurement was formed. Thereafter, the peel strength was measured using the test linear circuit. The results are shown in Table 1 so that the comparison with Example 1 and Example 2 is possible.

［比較例２］
この比較例２は、ハロゲンフリー系樹脂組成物を用いた上記実施例３〜実施例５との対比を行うためのものである。従って、実施例３で用いる樹脂組成物の組成が異なるのみであり、その他の樹脂ワニス調製、樹脂付銅箔の製造、当該樹脂付銅箔を用いた銅張積層板製造は同様である。従って、異なる樹脂組成物の組成に関してのみ述べる。

[Comparative Example 2]
Comparative Example 2 is for comparison with Examples 3 to 5 using a halogen-free resin composition. Therefore, only the composition of the resin composition used in Example 3 is different, and the other resin varnish preparation, the production of a resin-coated copper foil, and the production of a copper-clad laminate using the resin-coated copper foil are the same. Therefore, only the composition of the different resin compositions will be described.

Component A: Bisphenol A type epoxy resin (trade name: Epotot YD-128, manufactured by Tohto Kasei Co., Ltd.) / 15 parts by weight in liquid form at 25 ° C. and having an epoxy equivalent of 188 Component B: As a linear polymer having a crosslinkable functional group Polyvinyl acetal resin (trade name: Denkabutyral 5000A, manufactured by Denki Kagaku Kogyo Co., Ltd.) / 10 parts by weight C component: urethane resin as a cross-linking agent (trade name: Coronate AP stable, manufactured by Nippon Polyurethane Industry Co., Ltd.) / 4 parts by weight Component D: Epoxy resin curing agent (dicyandiamide (reagent) prepared as a 25% dimethylformamide solution) / 4 parts by weight (in terms of solid content)
E component: Phosphorus-containing epoxy resin synthesized by the same method as in Example 3/50 parts by weight F component: Orthocresol novolac type epoxy resin as a polyfunctional epoxy resin (trade name: Epicron N-680, Dainippon Ink and Chemicals, Inc. 17 parts by weight G component: 2-ethyl-4-methylimidazole (trade name: 2E4MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd.) / 0.2 parts by weight as a curing accelerator

  Hereinafter, in the same manner as in Example 1, a resin varnish was prepared, a resin-coated copper foil was manufactured, and a copper-clad laminate was manufactured using the resin-coated copper foil. And this copper clad laminated board was cut to the workpiece size, and the linear circuit for peeling strength measurement was formed. Thereafter, the peel strength was measured using the test linear circuit. The results are shown in Table 2 so that the comparison with Examples 3 to 5 can be made.

<Contrast between Example and Comparative Example>
When Example 1 and Example 2 using the halogen-based resin composition were compared with Comparative Example 1, as is clear from Table 1, in the case of Example 1 and Example 2, the peel strength was 0. It exceeds .9 kgf / cm, and it can be seen that even when compared with the case of using a roughened copper foil, the adhesiveness is inferior. On the other hand, in the case of the comparative example 1, it can be understood that the peel strength is 0.4 kgf / cm, which does not satisfy the practically required adhesion.

  Similarly, when Examples 3 to 5 and Comparative Example 2 using the halogen-free resin composition were compared, as can be seen from Table 2, the peel strength of Example 3 was 0.8 kgf / cm, the peel strength of Example 4 is 1.0 kgf / cm, and the peel strength of Example 5 is 1.0 kgf / cm, even compared to the case of using a roughened copper foil. It can be seen that the adhesiveness is not inferior. On the other hand, in the case of Comparative Example 2, the peel strength is 0.5 kgf / cm, which is clearly inferior to the Example.

  Furthermore, the elastic modulus (Young's modulus) of the insulating resin layers composed of the resin compositions of Examples 1 to 5, Comparative Example 1 and Comparative Example 2 is compared. These elastic moduli are shown in Table 3.

  As can be understood from Table 3, the elastic modulus of Examples 1 to 5 is in the range of 2.6 GPa to 2.8 GPa, and the elastic modulus is less than 3.0 GPa. On the other hand, the elastic modulus of Comparative Example 1 and Comparative Example 2 is 3.0 GPa or more. Therefore, it can be understood that the insulating resin layer made of the resin composition of the example is less elastic than the comparative example. A printed wiring board including an insulating resin layer having such low elasticity performance is excellent in impact resistance. Therefore, even if this printed wiring board is incorporated in an electronic product or the like, or is subjected to an impact due to an unintended drop or the like of the product, the electronic component and circuit are less damaged and excellent in impact resistance.

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

  The resin composition according to the present invention has flame retardancy and good adhesiveness with the copper foil bonded to the resin composition. Therefore, it is suitable as an insulating layer constituent material for copper-clad laminates and printed wiring boards. Moreover, the copper foil at this time can be sufficiently used even if it is a non-roughened copper foil. Therefore, it is suitable for the manufacture of a copper clad laminate for forming a fine pitch circuit having an excellent etching factor. In addition, by using this resin composition to form a resin layer on the surface of the copper foil, it is possible to provide a copper foil with resin of good quality. Therefore, by using this resin-coated copper foil, it is possible to provide a high-quality build-up printed wiring board having excellent migration resistance, a fine pitch circuit, and high reliability.

Claims (14)

A resin composition used for forming an insulating layer of a printed wiring board, wherein each of the following components A to F is contained in the following range (when the weight of the resin composition is 100 parts by weight): A resin composition for producing a printed wiring board, comprising:
Component A: 3 parts by weight to 20 parts by weight of one or more selected from the group of bisphenol A type epoxy resin, bisphenol F type epoxy resin and bisphenol AD type epoxy resin having an epoxy equivalent of 200 or less and liquid at 25 ° C. Department.
Component B: 3 to 30 parts by weight of a linear polymer having at least one crosslinkable functional group among hydroxyl groups or carboxyl groups contributing to the curing reaction of the epoxy resin.
Component C: 3 parts by weight to 10 parts by weight of a crosslinking agent (provided that 0 part by weight to 10 parts by weight when the component A functions as a crosslinking agent for the component B).
Component D: 5 to 20 parts by weight of 4,4′-diaminodiphenylsulfone or 2,2-bis (4- (4-aminophenoxy) phenyl) propane.
Component E: parts by weight of brominated epoxy resin determined so that bromine atoms derived from the brominated epoxy resin contain in the range of 12% by weight to 18% by weight when the weight of the resin composition is 100% by weight.
F component: 3 parts by weight to 20 parts by weight of at least one selected from the group consisting of trishydroxyphenylmethane type epoxy resin, phenol novolac type epoxy resin, and ortho cresol novolac type epoxy resin. A resin composition used for forming an insulating layer of a printed wiring board, wherein each of the following components A to F is contained in the following range (when the weight of the resin composition is 100 parts by weight): A resin composition for producing a printed wiring board, comprising:
Component A: 3 parts by weight to 20 parts by weight of one or more selected from the group of bisphenol A type epoxy resin, bisphenol F type epoxy resin and bisphenol AD type epoxy resin having an epoxy equivalent of 200 or less and liquid at 25 ° C. Department.
Component B: 3 to 30 parts by weight of a linear polymer having at least one crosslinkable functional group among hydroxyl groups or carboxyl groups contributing to the curing reaction of the epoxy resin.
Component C: 3 parts by weight to 10 parts by weight of a crosslinking agent (provided that 0 part by weight to 10 parts by weight when the component A functions as a crosslinking agent for the component B).
Component D: 5 to 20 parts by weight of 4,4′-diaminodiphenylsulfone or 2,2-bis (4- (4-aminophenoxy) phenyl) propane.
Component E: Weight determined to contain the phosphorus-containing epoxy resin in the range of 0.5 to 3.0% by weight when the phosphorus atom derived from the phosphorus-containing epoxy resin is 100% by weight of the resin composition Department.
F component: 3 parts by weight to 20 parts by weight of at least one selected from the group consisting of trishydroxyphenylmethane type epoxy resin, phenol novolac type epoxy resin, and ortho cresol novolac type epoxy resin. The print according to claim 2, wherein the phosphorus-containing epoxy resin as the E component is a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative having two or more epoxy groups in the molecule. A resin composition for producing a wiring board. The resin composition for producing a printed wiring board according to any one of claims 1 to 3 , wherein the linear polymer having a crosslinkable functional group as the component B uses a polyvinyl acetal resin or a polyamideimide resin. The resin composition for manufacturing a printed wiring board according to any one of claims 1 to 4 , wherein a urethane-based resin is used as the crosslinking agent as the component C. The resin composition for printed wiring board manufacture in any one of Claims 1-5 which added the ortho cresol novolak type epoxy resin as a polyfunctional epoxy resin of F component. The resin composition for manufacturing a printed wiring board according to any one of claims 1 to 6, wherein a curing accelerator is added as a G component. In resin-coated copper foil with a semi-cured resin layer on one side of the copper foil,
The semi-cured resin layer is formed with an average thickness of 5 μm to 100 μm using the resin composition according to any one of claims 1 to 7 . Copper foil. The said copper foil uses the resin-coated copper for printed wiring board manufacture of the printed wiring board of Claim 8 using the surface where the formation surface of the semi-hardened resin layer has a low-roughness surface whose surface roughness (Rzjis) is 3.0 micrometers or less. Foil. The copper foil with resin for printed wiring board manufacture of Claim 8 or Claim 9 provided with the silane coupling process layer in the surface which forms the semi-hardened resin layer of the said copper foil. Using one of the two resin-coated copper foils, the resin surfaces of the respective resin-coated copper foils are brought into contact with each other and hot pressed under conditions of a pressure of 20 kgf / cm ² and a temperature of 180 ° C. × 1 hour. Forming a copper-clad laminate, etching the copper foil layers on both sides of the copper-clad laminate into a resin film, and measuring the dynamic viscoelasticity of this resin film with a dynamic viscoelasticity measuring device (DMA) The resin-coated copper foil for printed wiring board production according to any one of claims 8 to 10 , further comprising a semi-cured resin layer having a storage elastic modulus at 30 ° C of less than 3.0 GPa. It is a manufacturing method of the resin-coated copper foil for printed wiring board manufacture in any one of Claims 8-11 ,
A semi-cured resin film having an average thickness of 5 μm to 100 μm is prepared by preparing a resin varnish to be used for forming a resin layer in the following steps a and b, applying the resin varnish to the surface of the copper foil, and drying it. A method for producing a resin-coated copper foil for producing a printed wiring board, comprising forming a resin-coated copper foil.
Step a: A component to F component among the A component, B component, C component (may be omitted when the A component functions as a crosslinking agent for the B component), D component, E component, F component, G component When the weight of the resin composition containing as an essential component is 100% by weight, the bromine atom derived from the E component is in the range of 12% to 18% by weight or the phosphorus atom is 0.5% to 3.0% by weight. Each component is mixed so that it may be contained in a range 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 to 50 weight%. The manufacturing method of the resin-coated copper foil for printed wiring board manufacture of Claim 12 which adds a hardening accelerator as G component to the resin composition of the said process a. The printed wiring board characterized by comprising the insulating layer using the resin composition in any one of Claims 1-7.