JP4741352B2 - LAMINATE FOR PRINTED WIRING BOARD AND METHOD FOR PRODUCING PRINTED WIRING BOARD USING SAME - Google Patents

Description

  The present invention relates to a laminate that can be suitably used for the production of a printed wiring board, and a method for producing a printed wiring board using the laminate, and more specifically, a printed wiring board having a high-density wiring used in the field of electronic materials, or The present invention relates to a laminate for a printed wiring board that can easily produce a copper-clad laminate used for the formation, a printed wiring board that can be used for high-density mounting, and a method for manufacturing a printed wiring board that can be mounted.

In recent years, along with demands for higher functionality of electronic devices, electronic components have been densely integrated and further mounted with high density. Is becoming more and more dense. Various methods such as realization of high-definition and stable wiring and adoption of a build-up multilayer wiring board have been studied as measures for increasing the density of printed wiring boards and the like. However, when the build-up multilayer wiring board is subjected to thermocompression bonding for the lamination between the multilayers, there is a concern that the connection strength between the layers connected by the fine vias may be reduced.
In forming fine wiring, a “subtractive method” is known as a metal pattern forming method useful in the field of conventional conductive patterns, particularly printed wiring boards. In the subtractive method, a metal layer formed on a substrate is provided with a photosensitive layer that is exposed to irradiation with actinic rays, and this photosensitive layer is imagewise exposed and developed to form a resist image. Is a method of forming a metal pattern by etching and finally removing the resist. In the metal substrate used in this method, in order to provide adhesion between the substrate and the metal layer, the substrate interface has been subjected to uneven treatment to develop adhesion by the anchor effect. As a result, the substrate interface portion of the resulting metal pattern becomes uneven, and there is a problem in that the high frequency characteristics deteriorate when used as an electrical wiring. Further, when forming the metal substrate, there is a problem that a complicated process of treating the substrate with a strong acid such as chromic acid is necessary in order to process the substrate.

  In order to solve this problem, a method has been proposed in which a radically polymerizable compound is grafted on the surface of the substrate to modify the surface, thereby minimizing the unevenness of the substrate and simplifying the substrate processing process. However, this method requires an expensive device (γ ray generator, electron beam generator). In addition, since the substrate used is an ordinary commercially available plastic substrate, the graft polymer is not sufficiently generated to attach the electroless plating catalyst or the like firmly there, and the substrate and the conductive layer There was a problem that the adhesion to the surface did not reach the practical strength.

A metal pattern formed on a smooth substrate is useful for a semiconductor device as a wiring (conductive film) of a printed wiring board. In recent years, there has been an increasing demand for electronic devices to process large amounts of data at high speed, and semiconductor devices used for image processing, communication control, etc., have increased internal clock frequency and external clock frequency year by year, and are connected. The number of pins is also increasing. For high-speed conduction, it is important to suppress signal delay and attenuation. To suppress signal propagation delay, it is effective to lower the dielectric constant, and to suppress dielectric loss, it is effective to reduce the dielectric constant and dielectric loss tangent, respectively. Since it is involved as the square root of the dielectric constant, the contribution of the dielectric loss tangent is substantial. For this reason, from the viewpoint of material characteristics, it is advantageous from the viewpoint of speeding up to employ an insulating material having a low dielectric loss tangent characteristic. In particular, in recent years, the frequency of semiconductor devices has entered the giga band, and as a property of the insulating film, a low dielectric constant and a low dielectric loss tangent in a region of 1 GHz or higher have been demanded.
That is, it is effective to lower the dielectric constant to suppress the signal propagation delay, and it is effective to reduce the dielectric constant and the dielectric loss tangent to suppress the dielectric loss. Is involved as the square root of the dielectric constant, and therefore the dielectric loss tangent is substantially involved. For this reason, from the viewpoint of material characteristics, it is advantageous from the viewpoint of speeding up to employ an insulating material having a low dielectric loss tangent characteristic.
In addition, smoothing the surface of the conductor greatly contributes to higher density. In the conventional built-up printed wiring board, the surface roughening treatment is performed in order to ensure the peel strength. However, the present situation is that the unevenness of several microns prevents further fine wiring.
Therefore, from the viewpoint of forming a printed wiring board useful for a semiconductor device, a means for forming a fine and highly adherent metal pattern on a smooth insulating substrate is eagerly desired.

As a method of forming a conductive metal pattern by forming a pattern on a substrate without giving irregularities to the substrate, a method of patterning with photosensitive silicon, applying a catalyst, and then forming a metal pattern by plating (For example, refer to Patent Document 2). However, it cannot be said that the adhesiveness between the silicone resin and the polyimide resin or the epoxy resin that is generally used as an insulating printed wiring board is sufficient, and a method having further excellent adhesiveness is desired.
Accordingly, the applicant of the present application has proposed a method for forming a metal pattern in which metal particles are attached to a fine pattern formed by a graft polymer that is directly bonded to a substrate (see, for example, Patent Document 3). According to this method, a desired fine pattern according to the exposure accuracy can be formed. However, from the practical point of view, the current situation is that further improvement in conductivity is desired by means such as increasing the thickness of the metal layer while maintaining the accuracy of the metal pattern in the line width direction.
JP 58-196238 A JP 2000-349417 A JP 2003-114525 A

The object of the present invention, which has been made in consideration of the above-mentioned conventional technical problems, is excellent in adhesiveness with an insulating film, has small irregularities at the interface with the insulating film, has a sufficient thickness, and has a giga band. It is an object of the present invention to provide a laminate useful for the production of a printed wiring board, in which a conductive layer with suppressed signal propagation delay can be easily formed on an arbitrary solid surface.
Another object of the present invention is to provide a method for producing a printed wiring board having high-definition wiring excellent in adhesion to an insulating film on a substrate using the laminate for printed wiring board of the present invention. It is to provide.

As a result of intensive studies, the present inventors have found that the above problems can be solved by a laminate having a specific insulating resin composition layer and a photosensitive composition layer capable of forming a plating resist, and the present invention has been completed. did.
That is, the configuration of the present invention is as follows .

<1> For producing a printed wiring board comprising an insulating resin composition layer containing a polymerizable compound and a polymerization initiator and a photosensitive composition layer that is cured or decomposed by exposure on a support . Using the laminate, laminating the insulating resin composition layer and the photosensitive composition layer on the substrate in this order, applying energy from the photosensitive composition layer side in a pattern, and developing A pattern forming step for forming a pattern composed of a photosensitive composition layer, and an unsaturated double bond capable of radical polymerization and a functional group capable of interacting with an electroless plating catalyst or a precursor thereof on the surface of the laminate. contacting a composition containing a reactive polymer precursor having, by performing the application of energy, the insulating resin composition layer, to have a electroless plating catalyst or its precursor and a functional group capable of interacting High A polymer compound producing step of producing a child compounds, conductive layer to form the catalyst adhering step of adhering an electroless plating catalyst or a precursor thereof in the generation region of the polymer compound, a circuit pattern by performing electroless plating A method for producing a printed wiring board, comprising a forming step and a photosensitive composition layer removing step for removing a remaining photosensitive composition layer in this order .
<2> After the conductive layer forming step of forming the circuit pattern by performing the electroless plating , and further before the photosensitive composition layer removing step , further comprising a step of performing electroplating. The method for producing a printed wiring board according to <1>, which is characterized.
<3> The energy application in the pattern formation step and the energy application in the polymer compound generation step are both exposure, and the exposure wavelength in the pattern formation step and the exposure wavelength in the polymer compound generation step are different from each other < The manufacturing method of the printed wiring board as described in 1> or <2> .
<4> The step of laminating the insulating resin composition layer and the photosensitive composition layer on the substrate in this order has the photosensitive resin layer and the insulating resin composition layer on the support in this order. The printed wiring board according to any one of <1> to <3>, which is a step of laminating the laminate for producing a printed wiring board so that the substrate and the insulating resin composition layer are in close contact with each other, and then peeling the support. A method for producing a plate.
<5> Unsaturated double bond and electroless plating capable of radical polymerization on the surface of the exposed insulating resin composition layer in the non-existing region of the pattern comprising the photosensitive resin composition layer in the polymer compound generation step A reactive polymer precursor having a functional group capable of interacting with the catalyst or its precursor is bonded to the insulating resin composition layer so that it can interact with the electroless plating catalyst or its precursor. a method for manufacturing such a step of producing a graft polymer that have a functional group <1> to the printed wiring board according to any one of <4>.
<6> The insulating resin composition layer in the laminate for a printed wiring board is made of a resin having a dielectric constant at 1 GHz of 5 or less and a dielectric loss tangent of 0.5 or less, and the energy application is exposure or heating, and The laminate for a printed wiring board has a protective film on the surface of the uppermost layer, and the support or the protective film is peeled off and the exposed layer is laminated on a substrate <1> to <5> The manufacturing method of the printed wiring board in any one of.
<7> The substrate is a printed wiring board on which a conductive layer is formed, and a circuit pattern is formed on the printed wiring board on which the conductive layer is formed using the laminate for producing a printed wiring board. <1> The manufacturing method of the multilayer printed wiring board in any one of <6> .

By using the laminate for producing a printed wiring board of the present invention, a high-definition conductive layer having excellent adhesion with an insulating film and having a sufficient thickness was formed on an arbitrary substrate or insulating film. It can be easily formed on the wiring.
The laminate for a printed wiring board according to the present invention is any one of a lamination process in which the laminate is adhered to an arbitrary solid surface such as a substrate, a region where a conductive layer is to be formed, or a region where an insulating region is to be formed. A resist pattern forming step of forming a resin layer as a patterned plating resist on the insulating film, radically polymerizable unsaturated double bonds capable of forming a graft polymer on the surface of the laminate, and no A composition containing a polymer precursor having a functional group capable of interacting with an electroplating catalyst or its precursor is brought into contact, and energy is applied by exposure or the like to generate a graft polymer in a region where there is no plating resist. A graft polymer forming step, and further, an electroless plating catalyst precursor is attached to the graft polymer formation region, and then the electroless · The can final printed circuit board by passing through the conductive layer forming step of forming a conductive layer by performing.
Here, the exposure wavelength used for graft polymer formation and the exposure wavelength for patterning the photosensitive composition may be the same when the photosensitive composition is positive, but in the case of the negative type Are preferably different from each other.

Further, according to the method of the present invention, the plating resist is not present on the surface of the graft polymer generation region, and the plating resist is present on the non-grafted region of the graft polymer. For this reason, when an electroless plating catalyst or its precursor is adhered to the graft polymer and electroless plating is performed, the formation of the plating film is hindered by the presence of the plating resist in the non-generated region of the graft polymer. The plated film by electroplating is selectively grown only in the thickness direction where there is no resist, and even if the formed conductive film has a sufficient thickness, the growth of the metal film in the lateral direction is hindered. Thus, a high-definition circuit can be formed.
After the formation of the conductive layer, the unreacted polymer composition layer and polymer precursor layer can be removed. The removal can be performed by a known method such as development.

According to the present invention, the signal propagation delay in the giga band is suppressed, the adhesiveness with the insulating film is excellent, the unevenness at the interface with the insulating film is small, and the high-resolution conductive layer is sufficient even if the thickness is sufficient. Can be easily formed on an arbitrary solid surface, and a laminate useful for the production of a printed wiring board can be provided.
Moreover, by using the laminate for a printed wiring board of the present invention, a method for producing a printed wiring board having a high-definition wiring excellent in adhesion to an insulating film on a substrate can be provided.
The printed wiring board obtained by the present invention has a fine wiring pattern excellent in high-frequency characteristics, and can be suitably used for a multilayer wiring board.

The laminate for a printed wiring board of the present invention contains a support for holding this laminate, (A) a polymerizable compound and a polymerization initiator, and can generate reactive active species by applying energy. It has two layers of a photosensitive resin composition layer and a photosensitive composition layer (B) that can be a plating resist.
In this specification, “(A) insulating resin composition layer” is referred to as “(A) layer” or “insulating film”, and “(B) photosensitive composition layer that is cured or decomposed by exposure” as “( B) layer ”or“ photosensitive layer ”, respectively.
A protective layer is provided on the surface of the laminate in order to protect various functions of the laminate including the support and the (A) layer and (B) layer formed thereon until use. It is preferable.
The order of formation of these (A) insulating resin composition layer and (B) photosensitive composition layer layer that is cured or decomposed by exposure is arbitrary. For example, the (A) layer, (B ) Layer may be sequentially provided, or (B) layer and (A) layer may be sequentially provided on the support.
In the present invention, “sequentially” means that these layers exist on the support in the order described, but other layers provided as desired, for example, an adhesive layer, a cushion layer, etc. It does not deny existence.
Hereinafter, each layer which comprises the laminated body useful for formation of the printed wiring board of this invention is demonstrated one by one.

[(A) Insulating resin composition layer]
For the formation of the insulating resin composition layer in the present invention, a known insulating resin that has been used as a conventional multilayer laminate, build-up substrate, or flexible substrate can be used. These resins are made of a thermosetting resin, thermoplastic resin, or their resin mixture, it contains a polymerization initiator.
These resins in the present invention, from the viewpoint of further improving the effect of suppressing the propagation delay of the signal at Giga band, the resin composition layer, dielectric constant at 1GHz is 5 or less and a dielectric loss tangent It is preferable that it is 0.5 or less. If the dielectric constant and the dielectric loss tangent are more than these values, the effect of suppressing signal delay due to smoothing when forming fine wiring is reduced, which is not preferable. In addition, after forming the pattern of the layer (A) , a reactive polymer precursor having an unsaturated double bond capable of radical polymerization and an electroless plating catalyst or a functional group capable of interacting with the precursor is contacted. from the viewpoint of easily performing the grafting reaction, Ru with one containing a polymerizable initiator as a material for generating the active species by applying exposure in these insulating resins, or heating, etc., energy. Also for the purpose of increasing the strength of the graft reactive or insulator layer, a polymerizable double bond-containing compound capable of reacting with the active species, such as, for example, polyfunctional acrylate monomers Ru added. In addition, inorganic or organic particles may be added as other components in order to increase the strength of the insulator layer or improve the electrical characteristics. In addition, the “insulating resin” in the present invention means a resin having an insulating property to the extent that it can be used for a known insulating film. Any resin having an insulating property corresponding to the above can be applied to the present invention.
Hereinafter, each component used for the insulating resin composition layer which can be used for this invention is demonstrated in order.

Specific examples of the thermosetting resin that can be used in the (A) insulating resin composition layer according to the present invention include, for example, epoxy resins, phenol resins, polyimide resins, polyester resins, bismaleimide resins, polyolefin resins, and isocyanate resins. Examples thereof include resins.
Examples of the epoxy resin include cresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, alkylphenol novolac type epoxy resin, biphenol F type epoxy resin, naphthalene type epoxy resin, dicyclo Examples include pentadiene type epoxy resins, epoxidized products of condensates of phenols and aromatic aldehydes having a phenolic hydroxyl group, triglycidyl isocyanurate, and alicyclic epoxy resins. These may be used alone or in combination of two or more. Thereby, it will be excellent in heat resistance.

  Examples of the polyolefin resin include polyethylene, polystyrene, polypropylene, polyisobutylene, polybutadiene, polyisoprene, cycloolefin resin, and copolymers of these resins.

Further, the epoxy resin will be described in detail.
In the present invention, (A) the epoxy resin constituting the insulating resin composition layer is composed of (a) an epoxy compound having two or more epoxy groups in one molecule and (b) a functional group that reacts with the epoxy group in one molecule. It consists of a reaction product with a compound having two or more. The functional group in (b) is selected from functional groups such as a carboxyl group, a hydroxyl group, an amino group, and a thiol group.

(A) As an epoxy compound (including what is called an epoxy resin) having two or more epoxy groups in one molecule, an epoxy compound having 2 to 50 epoxy groups in one molecule is preferable. More preferably, the epoxy compound has 2 to 20 epoxy groups in one molecule. Here, the epoxy group should just be a structure which has an oxirane ring structure, For example, a glycidyl group, an oxyethylene group, an epoxy cyclohexyl group etc. can be shown. Such polyvalent epoxy compounds are widely disclosed in, for example, published by Masaki Shinbo “Epoxy Resin Handbook” published by Nikkan Kogyo Shimbun (1987), and these can be used.
Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol S type epoxy resin, diphenyl ether type epoxy resin, hydroquinone type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin , Fluorene type epoxy resin, phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, trifunctional type epoxy resin, tetraphenylolethane type epoxy resin, dicyclopentadiene phenol type epoxy resin, water Bisphenol A type epoxy resin, bisphenol A nucleated polyol type epoxy resin, polypropylene glycol type epoxy resin, glycidyl ester type epoxy Shi resin, glycidyl amine type epoxy resins, glyoxal type epoxy resins, alicyclic epoxy resins, and the like heterocyclic epoxy resin.

(B) As a compound having two or more functional groups that react with an epoxy group in one molecule, a polyfunctional carboxylic acid compound such as terephthalic acid, a polyfunctional hydroxyl compound such as a phenol resin, an amino resin, 1, 3, 5 -Polyfunctional amino compounds such as triaminotriazine can be mentioned.
The resin composition of the present invention may contain an epoxy resin curing agent. For example, polyfunctional phenols, amine louis, imidazole compounds, acid anhydrides, organic phosphorus compounds, and halides thereof may be used, but those that do not inhibit the chemical reaction with the polymer precursor layer are preferably used. Moreover, you may mix | blend a hardening accelerator with the insulating resin composition of this invention as needed. Typical curing accelerators include, but are not limited to, tertiary amines, imidazoles, and quaternary ammonium salts.

Examples of the thermoplastic resin include phenoxy resin, polyether sulfone, polysulfone, polyphenylene sulfone, polyphenylene sulfide, polyphenyl ether, polyether imide, and the like. Other thermoplastic resins include (1) 1,2-bis (vinylphenylene) ethane resin (1,2-Bis (vinylphenyl) ethane) or a modified resin of this with a polyphenylene ether resin (Satoru Ama et al., Journal of Applied). Polymer Science Vol. 92, 1252-1258 (2004)). (2) Liquid crystalline polymers, specifically Kuraray Bexter. (3) Fluororesin (PTFE).
When placing a circuit board using a thermoplastic resin in a high-temperature environment such as a reflow process, select a material having heat resistance that does not cause deformation in the set high-temperature environment, for example, reducing the thermal expansion coefficient. In addition, deformation can be suppressed by increasing the glass transition temperature.

(Mixing of thermoplastic resin and thermosetting resin)
The thermoplastic resin and the thermosetting resin may be used alone or in combination of two or more. This is performed for the purpose of compensating for each defect and producing a superior effect. For example, thermoplastic resins such as polyphenylene ether (PPE) have a low resistance to heat, and are therefore alloyed with thermosetting resins. For example, it is used for alloying PPE with epoxy and triallyl isocyanate, or alloying PPE resin into which a polymerizable functional group is introduced and other thermosetting resins. Cyanate ester is a resin having the most excellent dielectric properties among thermosetting, but it is rarely used alone, and is used as a modified resin such as epoxy resin, maleimide resin, and thermoplastic resin. Details of these are described in Electronic Technology No. 2002/9, P35. A thermosetting resin containing an epoxy resin and / or a phenol resin and a thermoplastic resin containing a phenoxy resin and / or polyether sulfone (PES) are also used to improve dielectric properties.

  When the conductive pattern obtained by the means according to the present invention is used as the wiring (conductive film) of the printed wiring board, signal delay and attenuation are suppressed from the viewpoint of processing large-capacity data at high speed. For this purpose, it is effective to lower both the dielectric constant and the dielectric loss tangent. The use of low dielectric loss tangent material is as described in detail in "Journal of Electronics Packaging Society" Vol. 7, No. 5, P397 (2004), and in particular, an insulating material having low dielectric loss tangent characteristics is adopted. It is preferable to increase the speed. Specifically, the substrate is preferably made of an insulating resin whose dielectric constant (relative dielectric constant) at 1 GHz is 5 or less, and made of an insulating resin whose dielectric loss tangent at 1 GHz is 0.5 or less. Is more preferable. More preferably, an insulating material made of an insulating resin having a dielectric constant of 4.0 or less and a dielectric loss tangent of 0.1 or less is employed. The dielectric constant and dielectric loss tangent of the insulating resin are measured using a cavity resonator perturbation method based on the conventional method, for example, the method described in “18th Annual Meeting of the Japan Institute of Electronics Packaging”, p189. It can be measured using a device (εr for ultra-thin sheet, tan δ measuring device / system, manufactured by Keycom Corporation). Thus, in the present invention, it is also useful to select an insulating resin material from the viewpoint of dielectric constant and dielectric loss tangent. Typical insulating resins having a dielectric constant of 5 or less and a dielectric loss tangent of 0.5 or less include epoxy resin, liquid crystal polymer, polyimide resin, fluororesin, polyphenylene ether resin, cyanate ester resin, bis (bisphenylene ) Ethane resins and the like, and further their modified resins.

(Compound having a polymerizable double bond)
A necessary compound can be added to the insulating film according to the purpose of use. In the present invention, a compound having a radical polymerizable double bond is contained. The compound having a radical polymerizable double bond is an acrylate or methacrylate compound. The acrylate compound [(meth) acrylate] that can be used in the present invention is not particularly limited as long as it has an acryloyl group that is an ethylenically unsaturated group in the molecule, but is curable and the hardness of the formed intermediate layer. From the viewpoint of improving the strength, a polyfunctional monomer is preferable.

  The polyfunctional monomer that can be suitably used in the present invention is preferably an ester of a polyhydric alcohol and acrylic acid or methacrylic acid. Examples of polyhydric alcohols include ethylene glycol, 1,4-cyclohexanol, pentaerythritol, trimethylolpropane, trimethylolethane, dipentaerythritol, 1,2,4-cyclohexanol, polyurethane polyol and polyester polyol. . Of these, trimethylolpropane, pentaerythritol, dipentaerythritol and polyurethane polyol are preferable. The intermediate layer may contain two or more types of polyfunctional monomers. The polyfunctional monomer is one containing at least two ethylenically unsaturated groups in the molecule, and more preferably containing three or more. Specific examples include polyfunctional acrylate monomers having 3 to 6 acrylate groups in the molecule, and several acrylic acids in the molecule called urethane acrylate, polyester acrylate, and epoxy acrylate. An oligomer having an ester group and having a molecular weight of several hundred to several thousand can be preferably used as a component of the intermediate layer of the present invention.

Specific examples of acrylates having three or more acrylic groups in the molecule include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol. Examples thereof include polyol polyacrylates such as hexaacrylate, and urethane acrylates obtained by reaction of polyisocyanates with hydroxyl group-containing acrylates such as hydroxyethyl acrylate. In addition, as a compound having a polymerizable double bond, methacrylic acid or acrylic acid is used for a thermosetting resin or a thermoplastic resin, for example, an epoxy resin, a phenol resin, a polyimide resin, a polyolefin resin, a fluorine resin, A resin obtained by subjecting a part of the resin to a (meth) acrylation reaction may be used. Specific examples include (meth) acrylate compounds of epoxy resins.
It is preferable that these insulating resins are 5-100 mass% in conversion of solid content in the composition which forms an insulating resin composition layer.

(Type of polymerization initiator added to the insulating resin composition layer)
As the polymerization initiator that can be used in the insulating resin composition layer (A) in the present invention, either a thermal polymerization initiator or a photopolymerization initiator can be used. As the thermal polymerization initiator, peroxide initiators such as benzoyl peroxide and azoisobutyronitrile, and azo initiators can be used. Further, the photopolymerization initiator may be a low molecule or a polymer, and generally known ones are used.
Examples of the low-molecular photopolymerization initiator include known radicals such as acetophenones, benzophenones, Michler's ketone, benzoylbenzoate, benzoins, α-acyloxime ester, tetramethylthiuram monosulfide, trichloromethyltriazine, and thioxanthone. Generators can be used. Usually, sulfonium salts and iodonium salts used as photoacid generators also act as radical generators upon irradiation with light, and these may be used in the present invention. Further, for the purpose of increasing sensitivity, a sensitizer may be used in addition to the radical photopolymerization initiator. Examples of the sensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, and thioxanthone derivatives.
As the polymer photoradical generator, polymer compounds having an active carbonyl group in the side chain described in JP-A-9-77891 and JP-A-10-45927 can be used.
The amount of the polymerization initiator to be contained in the insulating resin is selected according to the use of the surface graft material to be used, but generally it is about 0.1 to 50% by mass in solid content in the insulator layer. It is preferable that it is about 1.0 to 30.0% by mass.

(Other additives contained in the insulating resin composition layer)
In the layer (A) of the present invention, a composite (composite) of a resin and other components is used to enhance the mechanical strength, heat resistance, weather resistance, flame retardancy, water resistance, electrical characteristics and the like of the resin coating. Material) can also be used. Examples of the material used for the composite include paper, glass fiber, silica particles, phenol resin, polyimide resin, bismaleimide triazine resin, fluorine resin, polyphenylene oxide resin, and the like.
Further, this insulating resin composition may be filled with a filler used for general wiring board resin materials as necessary, for example, inorganic fillers such as silica, alumina, clay, talc, aluminum hydroxide, calcium carbonate, and cured epoxy. You may mix | blend 1 type, or 2 or more types of organic fillers, such as resin, crosslinked benzoguanamine resin, and a crosslinked acrylic polymer.
Further, the insulating resin composition may contain one or more various additives such as a colorant, a flame retardant, an adhesion imparting agent, a silane coupling agent, an antioxidant, and an ultraviolet absorber as necessary. It may be added.
When these materials are added, it is preferable to add them in the range of 1 to 200% by mass, and more preferably in the range of 10 to 80% by mass with respect to the resin. When this addition amount is less than 1% by mass, there is no effect of strengthening the above-mentioned properties, and when it exceeds 200% by mass, properties such as strength peculiar to the resin are reduced. The graft polymerization reaction also does not proceed.

(Insulating resin composition layer shape)
The thickness of the (A) insulating film in the present invention is generally in the range of 1 μm to 200 μm, and preferably in the range of 10 μm to 150 μm.
From the viewpoint of improving the physical properties of the formed conductive layer, the insulating film made of an insulating resin has an average roughness (Rz) measured by JIS B 0601 (1994), 10-point average height method of 3 μm or less. It is preferable to use a certain material, and it is more preferable that Rz is 1 μm or less. If the surface smoothness of the substrate is within the above value range, that is, if there is substantially no unevenness, the circuit is extremely fine (for example, a circuit pattern with a line / space value of 25/25 μm or less). It is used suitably when manufacturing.
From the same viewpoint, when the wiring is formed on the substrate using the laminate of the present invention, the smoothness of the substrate used is preferably in the above range.

(A) Formation of Insulating Resin Composition Layer (A) The layer supports the coating liquid prepared so as to improve the coating property by dissolving the above-described components in an appropriate solvent or varnishing. The film for insulating film formation is formed by apply | coating and drying on the body or the (B) photosensitive composition layer mentioned later. By forming a film for forming an insulating film into a film, the thickness accuracy is high, handling properties, alignment accuracy, and the like are improved, and the film can be suitably used as an insulating film for various electronic parts, an adhesive film, and the like.
A general organic solvent is used as the solvent. As the organic solvent, either a hydrophilic solvent or a hydrophobic solvent can be used, but a thermosetting resin and a thermoplastic resin that form an insulating resin composition layer, and a polymer that forms those resins after the reaction. Solvents that dissolve the precursor are useful. Specifically, alcohol solvents such as methanol, ethanol and 1-methoxy-2-propanol, ketone solvents such as acetone and methyl ethyl ketone, ether solvents such as tetrahydrofuran, and nitrile solvents such as acetonitrile are preferable. Furthermore, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, ethylene glycol monomethyl ether, tetrahydrofuran and the like can be used.

From the viewpoint of the coating liquid or varnish viscosity and workability, coating properties, and drying time and work efficiency with respect to 100 parts by weight of the insulating resin composition. It is preferably 5 parts by weight or more and 2000 parts by weight or less, and more preferably 10 to 900 parts by weight.
As a method for preparing the varnish of the resin composition, it can be prepared by using a known method such as a mixer, a bead mill, a pearl mill, a kneader, or a three roll. All of the various blending components may be added simultaneously, the order of addition may be set as appropriate, and if necessary, some blending components may be added after preliminary kneading in advance. .

Coating on the support for film formation is performed by a conventional method, for example, blade coating method, rod coating method, squeeze coating method, reverse roll coating method, transfer coal coating method, spin coating method, bar coating method, Known application methods such as an air knife method, a gravure printing method, and a spray coating method may be used.
The method for removing the solvent is not particularly limited, but it is preferably carried out by evaporation of the solvent. As a method for evaporating the solvent, methods such as heating, decompression and ventilation are conceivable. Among these, it is preferable to evaporate by heating from the viewpoint of production efficiency and handleability, and it is more preferable to evaporate by heating with ventilation. For example, by coating on one side of the support described below, and heating and drying at 80 ° C. to 200 ° C. for 0.5 to 10 minutes to remove the solvent, the film is in a semi-cured and non-sticky state It is preferable to do.

[(B) Photosensitive composition layer cured or decomposed by exposure]
The layer (B) contains a photodegradable polymer compound, the solubility of the region is improved by exposure, and the layer is a positive photosensitive composition that is removed by development, or a photopolymerization initiator and a polymer A negative photosensitive composition in which an exposed portion is polymerized and cured, and an unexposed portion is removed by development, and is useful for forming a patterned plating resist layer. .
First, the positive photosensitive composition that can be used for the layer (B) will be described.
A positive photosensitive composition is a photoacid generator that easily decomposes upon irradiation with light to generate an acid, and an alkali-insoluble or hardly alkali-soluble resin having an acid-decomposable group. The acid-decomposable group is decomposed by the action of the acid generated from the resin, and contains an alkali-soluble resin, or the photoacid generator, the alkali-soluble resin, and the alkali solubility of the alkali-soluble resin. A photosensitive composition comprising a compound having a function of inhibiting and a compound having a function of reducing or eliminating the alkali solubility-inhibiting ability by the action of an acid or promoting the alkali solubility of the alkali-soluble resin. It is preferable.

(Photoacid generator)
As the photoacid generator that can be used in the layer (B) in the present invention, known ones can be mentioned without limitation.
For example, diazonium salts described in SI Schlesinger, Photogr. Sci. Eng., 18, 387 (1974), TSBal etal, Polymer, 21, 423 (1980), U.S. Pat. -140140 ammonium salt, DCNecker etal, Macromolecules, 17, 2468 (1984), CS Wen etal, Teh, Proc. Conf. Rad. Curing ASIA, p. 478 Tokyo, Oct (1988), U.S. Patent No. Phosphonium salts described in 4,069,055, 4,069,056, etc., JV Crivello etal, Macromorecules, 10 (6), 1307 (1977), Chem. & Eng. U.S. Pat.Nos. 339,049, 410,201, JP-A-2-150848, JP-A-2-965514, etc., JV Crivello etal, Polymer J. 17, 73 (1985), JV Crivello etal. J. Org. Chem., 43, 3055 (1978), WR Wattetal, J. Polymer Sci., Polymer Chem. Ed., 22, 1789 (1984), JV Crivelloetal, Polymer Bull., 14, 279 (1985), JV Crivello etal, Macromorecules, 14 (5), 1141 (1981), JV Crivello etal, J. Polymer Sci., Pol ymer Chem. Ed., 17, 2877 (1979), European Patent 370,693, US Patent 3,902,114, European Patents 233,567, 297,443, 297,442, US Patents 4,933,377, 410,201, 339,049 No. 4,760,013, No. 4,734,444, No. 2,833,827, Korean Patent No. 2,904,626, No. 3,604,580, No. 3,604,581, etc.,

Selenonium salts described in JV Crivello etal, Macromorecules, 10 (6), 1307 (1977), JV Crivelloetal, J. Polymer Sci., Polymer Chem. Ed., 17, 1047 (1979), CS Wen etal, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988) and other onium salts such as arsonium salts, U.S. Pat.No. 3,905,815, Japanese Patent Publication No. 46-4605, Japanese Patent Publication No. 48-36281 JP 55-32070, JP 60-239736, JP 61-169835, JP 61-169837, JP 62-58241, JP 62-212401, JP 63 Organohalogen compounds described in JP-A-70243, JP-A-63-298339, etc., K. Meier etal, J. Rad. Curing, 13 (4), 26 (1986), TP Gill etal, Inorg. Chem., 19 , 3007 (1980), D. Astruc, Acc. Chem. Res., 19 (12), 377 (1896), JP-A-2-16145, and the like,

S. Hayase etal, J. Polymer Sci., 25, 753 (1987), E. Reichmanis etal, J. PholymerSci., Polymer Chem. Ed., 23, 1 (1985), QQ Zhu etal, J. Photochem., 36, 85, 39, 317 (1987), B. Amit etal, Tetrahedron Lett., (24), 2205 (1973), DHR Barton etal, J. Chem Soc., 3571 (1965), PM Collins etal, J. Chem. SoC., Perkin I, 1695 (1975), M. Rudinstein etal, Tetrahedron Lett., (17), 1445 (1975), JW Walker etal J. Am. Chem. Soc., 110, 7170 (1988), SCBusman etal, J. Imaging Technol., 11 (4), 191 (1985), HMHoulihan etal, Macormolecules, 21, 2001 (1988), PMCollinsetal, J. Chem. Soc., Chem. Commun., 532 ( 1972), S. Hayasetal, Macromolecules, 18, 1799 (1985), E. Reichmanis etal, J. Electrochem. Soc., Solid State Sci. Technol., 130 (6), FM Houlihan etal, Macromolcules, 21, 2001 ( 1988), European Patent Nos. 0290,750, 046,083, 156,535, 271,851, 0,388,343, U.S. Pat.Nos. 3,901,710, 4,181,531, JP-A-60-198538, JP-A-53- O-Nitrobenzyl described in No. 133022, etc. A photoacid generator having a type protecting group,

M. TUNOOKA etal, Polymer Preprints Japan, 35 (8), G. Berner etal, J. Rad. Curing, 13 (4), WJ Mijs etal, Coating Technol., 55 (697), 45 (1983), Akzo, H. Adachi etal, Polymer Preprints, Japan, 37 (3), European Patent Nos. 0199,672, 84515, 199,672, 044,115, 0101,122, U.S. Patent Nos. 4,618,564, 4,371,605 4,431,774, JP-A-64-18143, JP-A-2-245756, Japanese Patent Application No. 3-140109, etc., and compounds that generate sulfonic acid by photolysis, such as iminosulfonate And disulfone compounds described in JP-A-61-166544.

  As content in the reactive polymer composition layer of the photoacid generator which decomposes | disassembles by said exposure and generate | occur | produces an acid, it is 0.001-40 mass% normally in conversion of solid content, Preferably 0.01 -20% by mass, more preferably 0.1-5% by mass.

  In the present invention, when a layer made of a positive photosensitive composition is used as the photosensitive resin composition layer, examples of the alkali-soluble binder used in the layer (B) include phenol / formaldehyde resins and cresol / formaldehyde. Resin, phenol / cresol / formaldehyde co-condensation resin, phenol-modified xylene resin, polyhydroxystyrene, polyhalogenated hydroxystyrene, N- (4-hydroxyphenyl) methacrylamide copolymer, hydroquinone monomethacrylate copolymer, Examples thereof include sulfonylimide polymers described in JP-A-7-28244, carboxyl group-containing polymers described in JP-A-7-36184, and the like. In addition, an acrylic resin containing a phenolic hydroxyl group described in JP-A No. 51-34711, an acrylic resin having a sulfonamide group described in JP-A No. 2-866, a urethane resin, etc. Alkali-soluble polymer compounds can also be used. These alkali-soluble binders may be used singly or in combination of two or more.

In addition, a resin in which an alkali-soluble group is protected with an acid-decomposable group can be used in combination with the photoacid generator. This resin is a compound having a —C—O—C— or —C—O—Si— bond, and examples thereof include the following compounds.
(A) including those selected from the group consisting of at least one orthocarboxylic acid ester and carboxylic acid amide acetal, the compound of which can have polymerizability, the above group as a bridging element in the main chain or on the side A compound which can occur as a side substituent,
(B) an oligomeric compound or a polymer compound containing in the main chain a compound selected from the group of repeating acetals and ketals;
(C) a compound comprising at least one enol ester or N-acylamino carbonate group,
(D) β-ketoester or β-ketoamide cyclic acetal or ketal,

(E) a compound containing a silyl ether group,
(F) a compound containing a silyl enol ether group,
(G) a monoacetal or monoketal in which the aldehyde or ketone component has a solubility of 0.1 to 100 g / liter with respect to the developer;
(H) tertiary alcohol ethers, and
(I) Carboxylic acid esters and carbonates of tertiary allylic or benzylic alcohols.

The compounds (a) that can be cleaved by the above acids are described in German Patent Publication Nos. 2,610,842 and 2,928,636. Mixtures containing the compound (b) are described in German Patents 2,306,248 and 2,718,254. The compound (c) is described in European Patent Publication Nos. 0,006,626 and 0,006,627. The compound (d) is described in European Patent Publication No. 0,202,196, and the compound used as (e) is described in German Patent Publication Nos. 3,544,165 and 3,601. , 264. The compound (f) is described in German Patent Publication Nos. 3,730,785 and 3,730,783, and the compound (g) is described in German Patent Publication No. 3,730,783. In the issue. The compound (h) is described in, for example, US Pat. No. 4,603,101, and the compound (i) is described in, for example, US Pat. No. 4,491,628 and JM Frechet et al. Imaging Sci. 30, 59-64 (1986)).
The content of the compound protected with these acid-decomposable groups in the layer (B) is usually 1 to 60% by mass, more preferably 5 to 40% by mass, based on the total solid content of the composition. is there.

  Among these various binders, from the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable, acrylic resins, polyhydroxystyrene resins More preferred are resins and polysiloxane resins. Further, from the viewpoint of developing property control, an acrylic resin, an acrylamide resin, and an acrylic / acrylamide copolymer resin are preferable.

  In particular, acrylic resins (binders that may contain a polymerizable group) are preferable. Examples of the acrylic resins include benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like. Copolymers comprising monomers selected from: Cyclomer P series, Plaxel CF200 series (all manufactured by Daicel Chemical Industries, Ltd.), Ebecryl 3800 (manufactured by Daicel UCB), and Dial NR series (Mitsubishi Rayon) Manufactured by Co., Ltd.), Biscoat R264, KS resist 106 (both manufactured by Osaka Organic Chemical Industry Co., Ltd.) and the like are preferable.

The alkali-soluble binder is preferably a polymer having a weight average molecular weight (polystyrene equivalent value measured by GPC method) of 1000 to 2 × 10 ⁵ , more preferably 2000 to 1 × 10 ⁵ , and 5000 to ⁵ ×. 10 ⁴ polymers are particularly preferred.
Moreover, as content in the (B) layer of an alkali-soluble binder, 10-90 mass% is preferable with respect to the total solid of this composition, 20-80 mass% is more preferable, 30-70 mass% is especially preferable. preferable.

Next, the negative photosensitive composition will be described.
The negative photosensitive composition applicable to the present invention is a photosensitive composition containing a binder polymer, a photopolymerizable compound having an ethylenically unsaturated bond, and a photopolymerization initiator.
Examples of the binder polymer include acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, and phenol resins. From the viewpoint of alkali developability, an acrylic resin is preferable. These can be used alone or in combination of two or more.

  The binder polymer can be produced, for example, by radical polymerization of a polymerizable monomer. Examples of the polymerizable monomer include polymerizable styrene derivatives such as styrene, vinyl toluene, α-methyl styrene, p-methyl styrene, and p-ethyl styrene, vinyl such as acrylamide, acrylonitrile, and vinyl-n-butyl ether. Esters of alcohol, (meth) acrylic acid alkyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, (meth) acrylic acid, α-bromo (meth) acrylic acid, α-chloro (meth) ) Acrylic acid, β-furyl (meth) ) Acrylic acid, β-styryl (meth) acrylic acid, maleic acid, maleic anhydride, monoester maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanosilicic acid Cinnamic acid, itaconic acid, crotonic acid, propiolic acid. These may be used alone or in combination of two or more.

  Examples of the (meth) acrylic acid alkyl ester include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, (meth) Examples include hexyl acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and structural isomers thereof. These can be used alone or in combination of two or more.

  The binder polymer preferably contains a carboxy group from the viewpoint of improving alkali developability, and can be produced, for example, by radical polymerization of a polymerizable monomer having a carboxy group and another polymerizable monomer. it can. As the polymerizable monomer having a carboxy group, methacrylic acid is preferable.

  Moreover, when styrene or a styrene derivative is contained as a polymerizable monomer, both adhesiveness and peeling properties are improved, which is preferable. The content of styrene or a styrene derivative as a copolymerization component is preferably 3 to 30% by weight, more preferably 4 to 28% by weight, and particularly preferably 5 to 27% by weight in the binder polymer.

  Among the polymerizable monomers, it is preferable to use a combination of (meth) acrylic acid, (meth) acrylic acid alkyl ester, and a copolymerized vinyl polymer such as styrene or a styrene derivative.

The acid value of the binder polymer is preferably 30 to 200 mgKOH / g, and more preferably 45 to 150 mgKOH / g. When the acid value is less than 30 mg KOH / g, the development time tends to be long. On the other hand, when it exceeds 200 mg KOH / g, the developer resistance of the photocured resist tends to be lowered. Moreover, when performing solvent image development as a image development process, it is preferable to prepare the polymerizable monomer which has a carboxy group in a small quantity.
The polymer dispersity (weight average molecular weight / number average molecular weight) is preferably 1.0 to 3.0, and more preferably 1.0 to 2.0. When the degree of dispersion exceeds 3.0, the adhesiveness and resolution tend to decrease. However, the weight average molecular weight and the number average molecular weight in the present embodiment are values measured by gel permeation chromatography and converted by a calibration curve using standard polystyrene.

The weight average molecular weight of the binder polymer is preferably 5,000 to 300,000, more preferably 40,000 to 150,000, and still more preferably 25,000 to 150,000. When the weight average molecular weight is less than 5,000, the developer resistance tends to decrease, and when it exceeds 300,000, the development time tends to be long.
If necessary, it may have a photosensitive functional group.

  These binder polymers are used alone or in combination of two or more. As a binder polymer in the case of using two or more types in combination, for example, two or more types of binder polymers comprising different copolymerization components, two or more types of binder polymers having different weight average molecular weights, and two or more types of binder polymers having different degrees of dispersion are used. A binder polymer is mentioned. A polymer having a multimode molecular weight distribution described in JP-A-11-327137 can also be used.

The polymerizable compound contained in the photosensitive composition is a polymerizable unsaturated compound having an ethylenically unsaturated bond. Specifically, for example, a polyhydric alcohol is reacted with an α, β-unsaturated carboxylic acid. Urethane monomers such as compounds obtained, bisphenol A-based (meth) acrylate compounds, compounds obtained by reacting glycidyl group-containing compounds with α, β-unsaturated carboxylic acids, and (meth) acrylate compounds having a urethane bond in the molecule , Nonylphenoxypolyethyleneoxyacrylate, phthalic acid compounds, and (meth) acrylic acid alkyl esters.
The polymerizable compound described in detail below contained in the photosensitive composition may be used alone or in combination of two or more according to the purpose.

  Among these, a bisphenol A (meth) acrylate compound or a (meth) acrylate compound having a urethane bond in the molecule is preferable because it can improve plating resistance and adhesion. Further, it is possible to use a combination of a polymerizable compound having one polymerizable ethylenically unsaturated bond in the molecule and a polymerizable compound having two or more polymerizable ethylenically unsaturated bonds in the molecule, Sensitivity and resolution can be improved, which is preferable.

Specific examples of the compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid include, for example, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups, propylene group Polypropylene glycol di (meth) acrylate having a number of 2 to 14, polyethylene polypropylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups, trimethylolpropane di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, EO, PO-modified trimethylolpropane tri (meth) acrylate, tetramethylol Methanate Examples include li (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.
Here, EO represents ethylene oxide, the EO-modified compound refers to a compound having a block structure of an ethylene oxide group, and similarly PO represents propylene oxide, and the PO-modified compound refers to a propylene oxide group. It means a compound having a block structure.

  Examples of bisphenol A-based (meth) acrylate compounds include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxypolypropoxy) phenyl. ) Propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane and the like. . Examples of the 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxy) phenyl) propane, 2,2 -Bis (4-((meth) acryloxytriethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetraethoxy) phenyl) propane, 2,2-bis (4-((meta ) Acryloxypentaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptaethoxy) phenyl) Propane, 2,2-bis (4-((meth) acryloxyoctaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxynonane) Xyl) phenyl) propane, 2,2-bis (4-((meth) acryloxydecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecaethoxy) phenyl) propane, 2 , 2-bis (4-((meth) acryloxydodecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecaethoxy) phenyl) propane, 2,2-bis (4- ((Meth) acryloxytetradecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxy) Hexadecaethoxy) phenyl) propane and the like, and 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is BPE- 00 (made by Shin-Nakamura Chemical Co., Ltd., product name) and 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane is BPE-1300 (Shin-Nakamura Chemical) It is commercially available as a product name manufactured by Kogyo Co., Ltd. The number of ethylene oxide groups in one molecule of the 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane is preferably 4-20, and more preferably 8-15. .

  As the (meth) acrylate compound having a urethane bond in the molecule that can be used as the polymerizable compound, for example, a (meth) acryl monomer having an OH group at the β-position and a diisocyanate compound (isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, 1,6-hexamethylene diisocyanate and the like), tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, EO, PO Examples thereof include modified urethane di (meth) acrylate. Examples of the EO-modified urethane di (meth) acrylate include UA-11 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name). Examples of the EO and PO-modified urethane di (meth) acrylate include UA-13 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name).

  Nonylphenoxypolyethyleneoxyacrylate includes, for example, nonylphenoxytetraethyleneoxyacrylate, nonylphenoxypentaethyleneoxyacrylate, nonylphenoxyhexaethyleneoxyacrylate, nonylphenoxyheptaethyleneoxyacrylate, nonylphenoxyoctaethyleneoxyacrylate, nonylphenoxynonaethyleneoxy Examples include acrylate, nonylphenoxydecaethyleneoxyacrylate, and nonylphenoxyundecaethyleneoxyacrylate.

  Examples of the phthalic acid compounds include γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyalkyl-β ′-(meth) acryloloxyalkyl-o-phthalate, and the like. Is mentioned. These may be used alone or in combination of two or more.

The photosensitive composition in the present invention contains a polymerization initiator capable of generating an initiating species such as a radical by exposure for the purpose of causing and promoting the polymerization reaction of the polymerizable compound.
Examples of the photopolymerization initiator used here include benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl, ] Aromatic ketones such as 2-morpholino-propanone-1, quinones such as alkylanthraquinones, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkylbenzoin, benzyl derivatives such as benzyldimethyl ketal, 2- (O-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5 -Diphenylimidazole dimer, 2- (o-methoxyphenyl) 2,4,5-diarylimidazole dimer, 2,4,5-triarylimidazole dimer such as 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 9-phenylacridine, 1 , 7-bis (9,9′-acridinyl) heptane, acridine derivatives, N-phenylglycine, and N-phenylglycine derivatives. Further, 2,4,5-triarylimidazole dimer is preferable because it can improve adhesion and sensitivity.
These may be used alone or in combination of two or more.

In the negative photosensitive composition, when the total amount of the binder polymer and the polymerizable compound is 100 parts by weight, the content of the binder polymer is preferably 40 to 80 parts by weight, and 45 to 70 parts by weight. More preferably. The polymerizable compound is preferably 20 to 60 parts by weight, and more preferably 30 to 55 parts by weight. Within this range, both sensitivity and film properties are achieved.
Moreover, it is preferable that it is 0.1-20 weight part with respect to 100 weight part of total amounts of a binder polymer and a polymeric compound, and, as for content of a polymerization initiator, it is 0.2-10 weight part. More preferred.

  In the negative photosensitive composition, if necessary, a photopolymerizable compound (such as an oxetane compound) having at least one cationically polymerizable cyclic ether group in the molecule, a cationic polymerization initiator, a dye such as malachite green , Photochromic agents such as tribromophenylsulfone and leucocrystal violet, thermochromic inhibitors, plasticizers such as p-toluenesulfonamide, pigments, fillers, antifoaming agents, flame retardants, stabilizers, adhesion-imparting agents, A leveling agent, a peeling accelerator, an antioxidant, a fragrance, an imaging agent, a thermal crosslinking agent, and the like can be contained in an amount of about 0.01 to 20 parts by weight with respect to 100 parts by weight of the total amount of the binder polymer and the polymerizable compound. .

In the layer (B), in addition to the above-described components that can impart a negative or positive function, for example, the purpose of improving alkali solubility and the glass transition temperature of the composition are adjusted to make the film brittle. An appropriate alkali-soluble low molecular weight compound may be added for the purpose of preventing the heat resistance and the heat resistance from deteriorating. Examples of the alkali-soluble low-molecular compound include dialkylsulfonamide compounds, dialkylsulfonylimide (—SO ₂ —NH—CO—) compounds, and dialkyl disulfonylimide (—SO ₂ —NH—SO ₂ —) compounds. Mention may be made of compounds containing acidic groups. The content of the alkali-soluble low molecular compound is preferably 40% by weight or less, more preferably 30% by weight or less, based on the resin having a substituent that increases the solubility in an alkali developer by the acid. More preferably, it is 25 weight% or less.
Moreover, you may add other components, such as surfactant, a pigment | dye, a stabilizer, a coating property improving agent, and a dye as needed.

(B) Formation of photosensitive composition layer (B) In order to form a layer, it is also possible to apply each of the above components by dissolving them in an appropriate solvent. It is also possible to form a film in the form of a film and laminate it.
When the layer (B) is formed by a coating method, any solvent may be used as long as the solution of the photosensitive composition can form a uniform coating film by a known method such as a spin coating method. From this point of view, it is preferably applied as a solution having a solid content of about 30 to 60% by weight.
(B) What is preferable as a solvent to be used when the layer is a positive composition is a solvent that can sufficiently dissolve a component composed of the polymer compound and the photoacid generator and can form a uniform coating film with the solution. Any of these may be used, and these may be used alone or in combination of two or more.

  Specifically, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, tertiary butyl alcohol, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monoethyl ether acetate, methyl lactate, ethyl lactate, 2-methoxybutyl acetate, 2-Ethoxyethyl acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, N-methyl-2-pyrrolidinone, cyclohexanone, cyclopentanone, cyclohexanol, methyl ethyl ketone, 1,4 -Dioxane, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol monoiso Ropirueteru, diethylene glycol monomethyl ether, but diethylene glycol dimethyl ether, but is not limited thereto.

As the solvent used when the layer (B) is a positive composition, solvents such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether and the like are preferable. Alternatively, a mixed solvent thereof may be used, but the invention is not limited to these.
Whether the layer (B) is formed by a coating method or a laminate method, the thickness is preferably 5 to 50 μm, more preferably 10 to 40 μm.

(B) A plating resist is formed by exposing and developing the layer.
Pattern exposure is usually performed using a mask exposure method performed through a mask pattern, a laser direct drawing exposure method, or by arranging a plurality of mirrors, and changing the angle of each mirror as necessary so that the exposure light can be emitted. It is carried out by a method such as irradiating an actinic ray in an image form by a direct drawing method such as a direct drawing method that forms an image.

  As a direct drawing method in which exposure light becomes an image by arranging a plurality of mirrors and changing the angle of each mirror as necessary, for example, a mirror of about 13 to 17 μm square is 480,000 to 800,000. There is a direct drawing method in which the exposure light is imaged by arranging approximately one and changing the angle of each mirror as necessary. More specifically, for example, "Digital Light Processing" exposure method (DLP (Digital Light Processing)) of Texas Instruments, "Data Direct Imaging System" of Pentax, "Maskless Lithography System" of BALL Conductor (Maskless Lithography System) "and the like. The arrayed mirrors that perform the core function of the direct drawing method are referred to as “micromirror array”, “two-dimensional display element”, “DMD (Digital Mirror Device)”, and the like.

As a light source for exposure, a known light source such as a carbon arc lamp, a mercury vapor arc lamp, a high-pressure mercury lamp, a xenon lamp, an Ar ion laser, a semiconductor laser, an LED, or the like that effectively emits ultraviolet light, visible light, or the like is used. It is done.
In the present invention, after the plating resist is formed by the (B) layer, further exposure is performed to generate a graft polymer in the (A) layer. Therefore, the exposure wavelength for patterning the (B) layer; It is preferable to select a wavelength different from the exposure wavelength used for the subsequent formation of the graft polymer. Therefore, in the step of patterning the layer (B), it is preferable to irradiate light having a wavelength of 400 to 450 nm, and more preferably light having a wavelength of 400 to 415 nm, from the viewpoint of suppressing the side reaction of the layer (A). When a light source that emits a lot of light having a wavelength of 365 nm or less, such as a mercury lamp, is used as the exposure light, it is preferable to irradiate the light with a wavelength of 365 nm or less using a filter by cutting 90% or more, and 99.0% or more It is more preferable to cut, and it is particularly preferable to cut 99.5% or more.
The light source is preferably a laser, more preferably a semiconductor laser diode, and particularly preferably a gallium nitride semiconductor laser and a blue laser. As the blue laser, a gallium nitride blue laser is preferable. Furthermore, when using a laser light source as exposure light, it is preferable to irradiate light having a wavelength of 400 to 450 nm, more preferably light having a wavelength of 400 to 415 nm, and particularly preferably light having a wavelength of 405 nm. In addition, the method of exposing by the direct drawing method in which the exposure light becomes an image by arranging about 480,000 to 800,000 mirrors of about 13 to 17 μm square and changing the angle of each mirror as necessary. It is preferably performed with light having a wavelength of 400 to 450 nm, more preferably light having a wavelength of 400 to 415 nm, and particularly preferably light having a wavelength of 400 to 410 nm.

Development is carried out by removing the unexposed areas by wet development with a developing solution such as an alkaline aqueous solution, aqueous developer, organic solvent, dry development, etc. In the positive type, the exposed part with improved developability is used in the negative type. Then, the uncured photosensitive composition layer in the unexposed area is removed to form a resist pattern.
Examples of the alkaline aqueous solution used for development include a dilute solution of 0.1 to 5 wt% sodium carbonate, a dilute solution of 0.1 to 5 wt% potassium carbonate, and a dilute solution of 0.1 to 5 wt% sodium hydroxide. Is mentioned. The pH of the alkaline aqueous solution is preferably in the range of 9 to 11, and the temperature is adjusted according to the developability of the photosensitive resin composition layer. Further, a surfactant, an antifoaming agent, an organic solvent, or the like may be mixed in the alkaline aqueous solution. Examples of the development method include a dip method, a spray method, brushing, and slapping.

Moreover, as a developing solution, it is also possible to use the suitable organic solvent according to the solubility of the high molecular compound to be used, or its mixed solvent.
Examples of the organic solvent and organic compound used include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, 2,6-dimethylcyclohexanone, and 3-methyl-2-cyclopentanone, methyl alcohol , Ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, cyclopentanol, cyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 3,5-dimethylcyclo Alcohols such as hexanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediol, etc., tetrahydrofuran, dioxane, ethyl acetate, butyl acetate, vinegar Isoamyl, benzene, toluene, xylene, phenol, acetonitrile, and an organic solvent such as dimethylformamide.

[Support]
The laminate for a printed wiring board of the present invention comprises at least the (A) layer and the (B) layer between a support serving as a base film and a protective layer, which will be described later, provided as desired. The support is used as a base of the laminate until the laminate of the present invention is brought into contact with a predetermined substrate or the like and used for forming a printed wiring board.
The base film that can be used for the support includes polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate, resin sheets such as polyamide, polyimide, and polycarbonate, and processed paper with controlled surface adhesion, such as release paper. Metal foils such as copper foil and aluminum foil.

The thickness of the support is generally 2 to 200 μm, more preferably 5 to 50 μm, still more preferably 10 to 30 μm. If the sheet used as the support is too thick, there is a problem in handling properties when the laminate is actually formed using the laminate, particularly when the laminate is laminated on a predetermined substrate or wiring. May come out.
In addition, the sheet surface constituting the support may be subjected to a release treatment in addition to the mat treatment and the corona treatment.
By making the width of the support about 5 mm longer than the width of the insulating film or polymer precursor layer, it is possible to prevent adhesion of the resin in the laminate when laminating with other layers, Advantages such as easy peeling of the support base film during use can be obtained.

[Adhesive layer, cushion layer]
When forming the laminate for a printed wiring board of the present invention, in order to improve the adhesion with other layers formed adjacent to the support, or to improve the cushioning during lamination, the adhesion In order to improve, after applying a resin varnish dissolved in a predetermined organic solvent on the surface of the base film serving as a support, the solvent is dried by heating and / or hot air blowing to form a room temperature solid resin composition, and an adhesive layer Alternatively, a cushion layer can be produced. Note that the adhesive layer or the cushion layer may be provided on the substrate side when the laminate is bonded.
Here, the organic solvent used for application of the resin varnish is usually a solvent, for example, ketones such as acetone, methyl ethyl ketone, cyclohexanone, acetic acid such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate. Esters, cellosolves such as cellosolve and butylcellosolve, carbitols such as carbitol and butylcarbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. It can be used in combination of more than one species.

[Protective layer]
As the resin film for forming the protective layer, the same material as that used for the support may be used, or a different material may be used. As well as the support, the surface adhesiveness is controlled, such as polyolefins such as polyethylene, polyvinyl chloride, and polypropylene, polyesters such as polyethylene terephthalate, polyamide, polycarbonate, and other resin sheets, and release paper. Processed paper, copper foil, metal foil such as aluminum foil, and the like.
The thickness of the protective layer (protective film) is generally 2 to 150 μm, more preferably 5 to 70 μm, and still more preferably 10 to 50 μm. Further, either the thickness of the protective film or the thickness of the support base film may be thicker than the other.
The protective film may be subjected to a release treatment in addition to the mat treatment and embossing.

  The laminate for a printed wiring board of the present invention obtained by laminating these layers is further laminated with this protective film, for example, wound into a roll and stored.

[Method for producing laminate for printed wiring board]
As a method for producing a laminate for a printed wiring board of the present invention, first, (A) an insulating resin composition layer containing a polymerization initiator in an insulating resin is provided on the support, and then ( B) A photosensitive composition layer that is cured or decomposed by exposure is formed, and (B) the photosensitive composition layer that is cured or decomposed by exposure is coated with a protective layer, or on the support, (B) A photosensitive composition layer that is cured or decomposed by exposure is formed, then (A) an insulating film is formed, and the surface of (A) layer is covered with a protective layer.
Thus, the laminated body for printed wiring boards of this invention is obtained.

[Manufacture of printed wiring board using laminate for printed wiring board]
In the case of a support in which the laminate of the present invention is peeled off a protective film and adhered to an arbitrary solid surface, and then the support is peeled off or an exposure light source for energy application can be dropped. Then, by exposing a desired region as it is, a patterned plating resist layer made of (B) a photosensitive layer is formed on the surface of the exposed region. In this state, the surface is brought into contact with a polymer precursor having an unsaturated double bond capable of radical polymerization, which will be described in detail below, and an electroless plating catalyst or a functional group capable of interacting with the precursor, exposure, heating, etc. (A) With the active point generated from the initiator in the insulating film as a base point, a strong chemical bond is generated between the insulating film / polymer precursor and a graft polymer is formed. At this time, in the region where the plating resist by the (B) layer exists, the contact between the (A) insulating film and the polymer precursor is hindered, so that the graft polymer is generated only in the region where the plating resist does not exist. Thereafter, the unreacted polymer precursor is removed, an electroless plating catalyst is attached to the generated graft polymer, and then electroless plating is performed, so that the plating film is a plating resist [residual in the graft polymer generation region. (B) layer] is selectively grown in a region where the layer does not exist, so that a printed wiring board having a high definition and sufficient thickness or a laminate having a conductive layer for forming a printed wiring board can be obtained. .

Next, the reactive polymer precursor used for producing the graft polymer will be described.
A reactive polymer precursor forms a cross-linked structure between a compound (polymerizable compound) that can generate a graft polymer by applying energy such as exposure, or an adjacent layer by applying energy, and adheres to both. It means a compound that can improve the property, and further has a partial structure capable of adhering a conductive material as described below, and the conductivity of the radically polymerizable unsaturated double bond and electroless plating catalyst or its precursor . It is a polymer compound having a functional group capable of interacting with a material. Since the polymer compound produced by the reaction of these polymer precursors (hereinafter referred to as graft polymer as appropriate) adheres an electroless plating catalyst or the like, the polymer precursor is polymerized. A partial structure that can form a reaction or a crosslinked structure and is necessary for bonding to the insulating resin composition layer, such as “unsaturated double bond capable of radical polymerization” and an electroless plating catalyst described later the Ru with a compound having both "electroless plating catalyst or the like and a functional group capable of interacting 'required to adhere to the graft polymer.

  As a method of bringing the reactive polymer precursor into contact, a solution obtained by dissolving and dispersing the polymer precursor in an appropriate solvent or dispersion medium is applied to the surface of the laminate after patterning the layer (B). And a method of immersing the laminate in such a dissolved / dispersed liquid. When the layer containing the polymer precursor (reactive polymer precursor layer) is formed by dipping on the (B) layer, the substrate on which the (B) layer is patterned is 0.5 to 70. What is necessary is just to take the method of immersing in the polymer precursor solution of 5% by weight for several seconds to several tens of minutes. However, applying a method of forming by coating described later can form a layer containing a polymer precursor in an amount necessary for graft formation as designed, and is also preferable from the viewpoint of workability.

(Polymerizable compound)
A representative compound among the polymer precursors used in the present invention is a polymerizable compound capable of undergoing a polymerization reaction. The polymerizable compound is a compound having an unsaturated double bond capable of radical polymerization in the molecule.
Examples of the functional group containing “radical polymerizable unsaturated double bond” include a vinyl group, a vinyloxy group, an allyl group, an acryloyl group, and a methacryloyl group. Among these, the acryloyl group and the methacryloyl group are highly reactive, and good results are obtained.
The radical polymerizable unsaturated compound may be used Ri compound der having a radical polymerizable group, a reportage Lima over that having a polymerizable unsaturated group.
As another embodiment of the polymer precursor, the reaction of the active group in the molecule, for example, an epoxy group, an isocyanate group, having a like reactive activating groups as typified by an azo group Lupo Rimmer Examples thereof include a compound or a combination of a crosslinking agent and a crosslinking compound.

The polymer precursor further needs to have a functional group capable of interacting with an electroless plating catalyst described later or an electroless plating catalyst that is a partial structure to which the precursor can be attached.
The functional group capable of interacting with the electroless plating catalyst is a functional group having a positive charge such as ammonium or phosphonium, or a negative charge such as a sulfonic acid group, a carboxyl group, a phosphoric acid group or a phosphonic acid group. Examples thereof include acidic groups that can be dissociated into negative charges. In addition, nonionic polar groups such as a hydroxyl group, an amide group, a sulfonamide group, an alkoxy group, and a cyano group can also be used.
Examples of other functional groups having affinity with the electroless plating catalyst include hydrophilic groups.

The polymer precursor according to the present invention will be described in detail by taking a polymerizable compound as a representative example as an example. the polymerizable compound having an equal functional group capable of interacting with a high molecular, average molecular weight flat is selected in the range of 1,000 to 500,000. Such a polymer can be obtained by methods such as addition polymerization such as normal radical polymerization and anionic polymerization, and polycondensation.

Specifically, in the present invention, it has an unsaturated double bond capable of radical polymerization (hereinafter appropriately referred to as a polymerizable unsaturated group) and has a functional group capable of interacting with an electroless plating catalyst. as the polymer compound the ease of attachment and adsorption of these compounds, and in view of the removal easiness of unreacted material after graft reaction, has a hydrophilic group which is a polar group, preferably a hydrophilic polymer over .

-Hydrophilic polymer having a polymerizable unsaturated group-
The hydrophilic polymer having a polymerizable unsaturated group is a radically polymerizable group-containing hydrophilic polymer in which an ethylene addition polymerizable unsaturated group such as a vinyl group, an allyl group or a (meth) acryl group is introduced in the molecule. Point to. This radical polymerizable group-containing hydrophilic polymer needs to have a polymerizable group at the main chain end and / or side chain, and preferably has a polymerizable group at both of them. Hereinafter, a hydrophilic polymer having a polymerizable group (at the main chain end and / or side chain) is referred to as a radical polymerizable group-containing hydrophilic polymer.

Such a radically polymerizable group-containing hydrophilic polymer can be synthesized as follows. As a synthesis method, (a) a method of copolymerizing a hydrophilic monomer and a monomer having an ethylene addition polymerizable unsaturated group, (b) copolymerizing a hydrophilic monomer and a monomer having a double bond precursor, Next, a method of introducing a double bond by treatment with a base or the like, and (c) a method of reacting a functional group of a hydrophilic polymer with a monomer having an ethylene addition polymerizable unsaturated group. Among these, from the viewpoint of synthesis suitability, (c) a method of reacting a functional group of a hydrophilic polymer with a monomer having an ethylene addition polymerizable unsaturated group is particularly preferable.
In the methods (a) and (b), the hydrophilic monomer used for the synthesis of the radical polymerizable group-containing hydrophilic polymer includes (meth) acrylic acid or its alkali metal salt and amine salt, itaconic acid or its alkali. Metal salt and amine salt, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, N-monomethylol (meth) acrylamide, N-dimethylol (meth) acrylamide, allylamine or its hydrohalide, 3-vinylpropion Acid or alkali metal salt and amine salt thereof, vinyl sulfonic acid or alkali metal salt and amine salt thereof, 2-sulfoethyl (meth) acrylate, polyoxyethylene glycol mono (meth) acrylate, 2-acrylamido-2-methylpropanesulfone Monomers having hydrophilic groups such as carboxyl groups, sulfonic acid groups, phosphoric acid groups, amino groups or salts thereof, hydroxyl groups, amide groups and ether groups, such as acid phosphooxypolyoxyethylene glycol mono (meth) acrylate Can be mentioned.
As the hydrophilic polymer used in the method (c), a hydrophilic homopolymer or copolymer obtained using at least one selected from these hydrophilic monomers is used.

  When the radically polymerizable group-containing hydrophilic polymer is synthesized by the method (a), examples of the monomer having an ethylene addition polymerizable unsaturated group that is copolymerized with the hydrophilic monomer include an allyl group-containing monomer. Examples include allyl (meth) acrylate and 2-allyloxyethyl methacrylate. Further, when the radical polymerizable group-containing hydrophilic polymer is synthesized by the method (b), a monomer having a double bond precursor that is copolymerized with a hydrophilic monomer is 2- (3-chloro-1-oxopropoxy). ) Ethyl methacrylate. Further, when the radical polymerizable group-containing hydrophilic polymer is synthesized by the method (c), a reaction between a carboxyl group, an amino group or a salt thereof in the hydrophilic polymer and a functional group such as a hydroxyl group and an epoxy group is performed. It is preferable to introduce an unsaturated group using it. Examples of the monomer having an addition polymerizable unsaturated group used for this purpose include (meth) acrylic acid, glycidyl (meth) acrylate, allyl glycidyl ether, and 2-isocyanatoethyl (meth) acrylate.

Further, because used as the polymer of the polymerizable compound in the present invention, it is easy to prepare a polymerizable compound-containing liquid composition having a viscosity suitable for the layer formed by a coating method, also, the liquid compositions In the laminate of the present invention, (A) a reactive polymer precursor layer can be easily formed on the support or on the (B) insulating resin composition layer described later by applying and drying the coating. It is Ru can.

For these reasons, the use of port Rimmer as a polymer precursor, a "polymer precursor containing layer" having a uniform thickness can be easily formed, as a result, the generation region of the homogeneous graft polymer It can be seen that it is formed. Therefore, if as a polymerizable compound to form a laminate of the present invention have use the port Rimmer, by using the laminate, excellent conductivity, and a conductive layer excellent in the uniformity simple way A printed wiring board formed in (1) can be obtained.
As described above, in view of manufacturability, using ports Rimmer as a polymerizable compound, these solutions, for example, by applying and drying a surface of the insulating film made of an epoxy resin to form a polymer precursor layer Is most preferred.
High molecular precursors are those polymerizable compound in the total solid content of the layer, more preferably it contained about 5 to 100 wt% and preferably in the range of 30 to 100 wt%.

The polymer precursor may be included in a solution or dispersion and directly contacted with the laminate, but the layer containing the polymer precursor can be formed on the patterned laminate surface as described above. Street. Hereinafter, other components of the layer containing the polymer precursor will be described.
The polymer precursor-containing layer is formed by containing various components necessary for layer formation in addition to the polymerizable compound as long as the effects of the present invention are not impaired.
For example, various compounds such as a binder, a plasticizer, a surfactant, and a viscosity modifier for improving film properties can be contained.
(binder)
The binder is used to form a polymer precursor layer together with the polymer precursor (polymerizable compound), and is useful for improving film properties. When the polymerizable group compound may form a layer alone, not name a particular need. The binder for this purpose is not particularly limited as long as it is mixed with a polymerizable group-containing hydrophilic compound and forms a film, but is preferably a water-soluble oligomer or polymer having a molecular weight of 500 or more.
These polymers include (meth) acrylate polymers such as polyacrylic acid, polymethacrylic acid, polyvinyl alcohol, polybutyral, polyvinylpyrrolidone, polyethylene oxide, polyethyleneimine, polyacrylamide, carboxymethylcellulose, hydroxyethylcellulose, sesulose polymers, In addition to synthetic polymers such as, natural hydrophilic polymers such as gelatin, starch, gum arabic, and sugar can be used.
When using a binder together, the content is preferably 0 to 95% by mass, more preferably 0 to 70% by mass in terms of solid content.

(Plasticizer, surfactant, viscosity modifier)
These compounds are used to improve the coating surface properties when forming a film of the polymer precursor layer, or to give the film flexibility and to suppress the occurrence of cracks when folded in a film state. Is done. As the plasticizer, surfactant, and viscosity modifier, known materials that are generally used are used.

(Formation of reactive polymer precursor-containing layer)
The polymer precursor layer is formed by applying and drying a coating solution prepared by dissolving the above-described components in an appropriate solvent on the surface of the laminate of the present invention after the layer (B) is patterned. The
As the solvent, water and an organic solvent are used. As the organic solvent, either a hydrophilic solvent or a hydrophobic solvent can be used, but a solvent having a high affinity for water is particularly useful. Specifically, alcohol solvents such as methanol, ethanol and 1-methoxy-2-propanol, ketone solvents such as acetone and methyl ethyl ketone, ether solvents such as tetrahydrofuran, and nitrile solvents such as acetonitrile are preferable.
The solid concentration of the coating solution is preferably 0.1 to 80% by mass.
Application is performed by a conventional method, for example, blade coating method, rod coating method, squeeze coating method, reverse roll coating method, transfer coat coating method, spin coating method, bar coating method, air knife method, gravure printing method, spray coating. And a known coating method.

The thickness of the layer containing the polymer precursor is preferably in the range of 0.1 μm to 10 μm, and more preferably in the range of 0.2 to 5 μm. Within this range, the thickness of the graft polymer layer formed thereafter is in a suitable range, and excellent adhesion can be ensured even when an electroless plating catalyst or the like is attached in the subsequent steps.
After forming the polymer precursor layer, the thickness of the graft polymer layer formed by applying energy such as exposure is preferably in the range of 0.1 μm to 0.7 μm. Therefore, the thickness of the polymer precursor layer is set to 10 μm. Even if it is too thick, not only will the material be involved in graft polymer formation, which will lead to increased costs, but it will also be difficult for the exposure light source to reach the depths, making it difficult to remove unnecessary graft polymer precursor materials. It brings many problems such as becoming.

  In the laminate of the present invention, on the surface of the support, an insulating resin such as an epoxy resin, a polyimide resin, a liquid crystalline resin, or a polyarylene resin is contained in a polymerization initiator to provide an initiator-containing insulator layer. The main feature is that a photosensitive layer that can form a plating resist is provided adjacent to it, and this layer is applied to the surface of any substrate or wiring to give energy. Thus, an insulator layer having desired characteristics and a patterned plating resist layer formed on the surface thereof can be easily formed. Thereafter, the polymer precursor layer is brought into contact with the surface of the laminate, and energy is applied to produce a graft polymer directly bonded to the exposed insulating film surface (that is, not covered with the (B) layer). To do. Since this graft polymer has excellent affinity with the electroless plating catalyst or its precursor, it has excellent adhesion of the formed electroless plating film. By using the laminate for a printed wiring board of the present invention, it is smooth and uniform. Such a conductive film can be formed in a desired region in accordance with energy application.

In the present invention, by including a polymerization initiator in the insulating resin, the adhesion between the insulating film and the graft polymer formed thereon becomes strong, and a strong adhesion is exhibited.
The reason for this is not clear, but the addition of a polymerization initiator to the insulating resin layer increases the density of the surface graft, which increases the interaction with the electroless plating catalyst layer, resulting in improved adhesion. Can be considered.
In addition, this technique is a wide technique that can be applied to general insulating resins useful in the field of electronic materials such as polyimide and epoxy resin.

(Granting energy)
Formation of the graft polymer in the present invention is performed by irradiation with radiation such as heat or light. Heating is performed using a heater or infrared rays. Examples of the light source include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, a carbon arc lamp, and an LED. Examples of radiation include electron beams, X-rays, ion beams, and far infrared rays. Also, g-line, i-line, deep-UV light, and high-density energy beam (laser beam) are used.
In addition, after the plating resist is formed by the (B) layer, further exposure is performed to form a graft polymer in the (A) layer. Therefore, as described above, the exposure wavelength for patterning the (B) layer and It is preferable to select a wavelength different from the exposure wavelength used for the subsequent graft polymer formation.
Specifically, for example, when light having a wavelength of 400 to 450 nm, which is a suitable wavelength for forming the (B) layer, is used, it is preferable to irradiate light having a wavelength of 150 to 400 nm for forming the graft polymer. A light of ˜370 nm is more preferable.
(B) When there is an overlap between the wavelength suitable for layer formation and the wavelength suitable for graft polymer formation, a part of the initiator contained in the (A) layer is deactivated during (B) layer formation, and the graft Since the production efficiency of the polymer is deteriorated, it is not preferable.
Thereafter, the unreacted polymer precursor is removed by washing with water or an organic solvent.

  High adhesion between the insulating film and the electroless plating catalyst is as follows. 1. Strong and high-density bond between the insulating film and the graft polymer; This is achieved by bonding the produced graft polymer and the electroless plating catalyst or the like with a strong interaction. It is demonstrated by. This is achieved. In order to exhibit these effects, it is important to select a compound that strongly interacts with the graft polymer and the electroless plating catalyst in addition to adding a polymerization initiator to the insulating film.

Hereinafter, a typical method for attaching an electroless plating catalyst or the like to the graft polymer and then forming a conductive layer will be described.
In the present invention, an electroless plating catalyst or a precursor thereof is applied to the graft polymer formed on the surface of the insulating film, and the electroless plating is performed to form a conductive layer in a pattern, but the conductivity is further increased. Therefore, a method such as electroplating may be added.

In the step of applying electroless plating catalyst or precursor thereof to the generated graft polymer and performing electroless plating, a graft polymer having a functional group interacting with the electroless plating catalyst or precursor thereof is generated, and the graft After applying an electroless plating catalyst or a precursor thereof to the polymer, a method of forming a metal thin film by performing electroless plating is employed. In this embodiment, since the graft polymer having a functional group that interacts with the electroless plating catalyst or its precursor is directly bonded to the insulating resin composition layer, the formed metal thin film has high strength as well as conductivity. And show wear resistance. Moreover, a conductive film having a desired thickness can be easily formed by further performing electrolytic plating using the electroless plating film obtained here as an electrode.
In the present invention, since the non-generated region of the graft polymer is covered with the layer (B) having a plating resist function, the conductive film formed by electroless plating or subsequent electroplating is plated. Since it grows selectively only in a region where no resist exists, a high-resolution conductive film is formed even if the thickness is sufficient.

In the present invention, the graft polymer has an interactive group that interacts with the electroless plating catalyst or a precursor thereof, and a step of applying the electroless plating catalyst or the precursor thereto (application of an electroless plating catalyst or the like) The conductive film is formed by sequentially performing a process) and a process of performing electroless plating and forming a metal thin film (electroless plating process). That is, a graft polymer having a functional group (that is, a polar group) that interacts with an electroless plating catalyst or a precursor thereof interacts with the electroless plating catalyst or a precursor thereof, and then undergoes an electroless plating treatment to form a metal. A thin film will be formed.

As a result, a metal (fine particle) film is formed. When a metal thin film (continuous layer) is formed, a region with particularly high conductivity is formed. Here, after adsorbing the fine particles, a heating step can be performed for the purpose of improving conductivity.
Hereinafter, this process will be described in detail.

<Application process for electroless plating catalyst>
In this step, an electroless plating catalyst or a precursor thereof is applied to the graft polymer generated in the surface grafting step.
[Electroless plating catalyst]
The electroless plating catalyst used in this step is mainly a zero-valent metal, and examples thereof include Pd, Ag, Cu, Ni, Al, Fe, and Co. In the present invention, Pd and Ag are particularly preferable because of their good handleability and high catalytic ability. As a method for fixing the zero-valent metal to the interactive region, for example, a metal colloid whose charge is adjusted so as to interact with an interactive group on the interactive region is applied to the interactive region. A technique is used. In general, a metal colloid can be prepared by reducing metal ions in a solution containing a charged surfactant or a charged protective agent. The charge of the metal colloid can be adjusted by the surfactant or the protective agent used here, and the metal colloid having the charge adjusted in this way can interact with the interactive group (polar group) of the graft polymer. By making it act, a metal colloid (electroless plating catalyst) can be made to adhere to a graft polymer.

[Electroless plating catalyst precursor]
The electroless plating catalyst precursor used in this step can be used without particular limitation as long as it can become an electroless plating catalyst by a chemical reaction. Mainly, metal ions of zero-valent metal used in the electroless plating catalyst are used. The metal ion that is an electroless plating catalyst precursor becomes a zero-valent metal that is an electroless plating catalyst by a reduction reaction. The metal ion that is the electroless plating catalyst precursor is applied to the substrate in the step (b), and before being immersed in the electroless plating bath, the metal ion is separately changed to a zero-valent metal by a reduction reaction as an electroless plating catalyst. Alternatively, the electroless plating catalyst precursor may be immersed in an electroless plating bath and changed to a metal (electroless plating catalyst) by a reducing agent in the electroless plating bath.

In practice, the metal ion that is the electroless plating precursor is imparted to the graft polymer in the form of a metal salt. The metal salt used is not particularly limited as long as it is dissolved in a suitable solvent and dissociated into a metal ion and a base (anion), and M (NO ₃ ) _n , MCl _n , M _{2 / n} (SO ₄ ), M _{3 / n} (PO ₄ ) (M represents an n-valent metal atom), and the like. As a metal ion, the thing which said metal salt dissociated can be used suitably. Specific examples include, for example, Ag ions, Cu ions, Al ions, Ni ions, Co ions, Fe ions, and Pd ions, and Ag ions and Pd ions are preferable in terms of catalytic ability.

  As a method of applying a metal colloid as an electroless plating catalyst or a metal salt as an electroless plating precursor to a graft polymer, the metal colloid is dispersed in an appropriate dispersion medium, or the metal salt is dissolved in an appropriate solvent. Then, a solution containing the dissociated metal ions is prepared, and the solution is applied to the surface of the insulating resin composition layer where the graft polymer exists, or an insulating resin composition layer having the graft polymer in the solution is formed. What is necessary is just to immerse. By contacting a solution containing a metal ion, a metal ion is attached to an interactive group of the graft polymer by using an ion-ion interaction or a dipole-ion interaction. The active region can be impregnated with metal ions. From the viewpoint of sufficiently performing such adhesion or impregnation, the metal ion concentration or the metal salt concentration in the solution to be contacted is preferably in the range of 0.01 to 50% by mass, preferably 0.1 to 30%. More preferably, it is in the range of mass%. Further, the contact time is preferably about 1 minute to 24 hours, more preferably about 5 minutes to 1 hour.

<Electroless plating process>
In this step, the conductive film (metal film) is formed by performing electroless plating on the insulating resin composition layer to which the electroless plating catalyst or the like is applied from the electroless plating catalyst or the like applying step. The That is, by performing electroless plating in this step, a high-density conductive film (metal film) is formed on the graft polymer obtained by the above step. The formed conductive film (metal film) has excellent conductivity and adhesion.

[Electroless plating]
Electroless plating refers to an operation of depositing a metal by a chemical reaction using a solution in which metal ions to be deposited as a plating are dissolved.
The electroless plating in this step is, for example, after removing the excess electroless plating catalyst (metal) by washing the substrate provided with the electroless plating catalyst obtained in the electroless plating catalyst application step, etc. It is performed by immersing in an electroless plating bath. As the electroless plating bath to be used, a generally known electroless plating bath can be used.
Further, when the substrate to which the electroless plating catalyst precursor is applied is immersed in an electroless plating bath in a state where the electroless plating catalyst precursor is attached to or impregnated with the graft polymer, the substrate is washed with water to remove an excess precursor. After removing the body (metal salt, etc.), it is immersed in an electroless plating bath. In this case, reduction of the precursor and subsequent electroless plating are performed in the electroless plating bath. As the electroless plating bath used here, a generally known electroless plating bath can be used as described above.

The composition of a general electroless plating bath is as follows: 1. metal ions for plating, 2. reducing agent; Additives (stabilizers) that improve the stability of metal ions are mainly included. In addition to these, the plating bath may contain known additives such as a plating bath stabilizer.
As the types of metals used in the electroless plating bath, copper, tin, lead, nickel, gold, palladium, and rhodium are known, and among these, copper and gold are particularly preferable from the viewpoint of conductivity.
In addition, there are optimum reducing agents and additives according to the above metals. For example, a copper electroless plating bath contains Cu (SO ₄ ) ₂ as a copper salt, HCOH as a reducing agent, and a chelating agent such as EDTA or Rochelle salt as a copper ion stabilizer as an additive. The plating bath used for electroless plating of CoNiP includes cobalt sulfate and nickel sulfate as metal salts, sodium hypophosphite as a reducing agent, sodium malonate, sodium malate and sodium succinate as complexing agents. It is included. Moreover, the electroless plating bath of palladium contains (Pd (NH ₃ ) ₄ ) Cl ₂ as metal ions, NH ₃ and H ₂ NNH ₂ as reducing agents, and EDTA as a stabilizer. These plating baths may contain components other than the above components.

  The film thickness of the conductive film (metal film) thus formed can be controlled by the concentration of the metal salt or metal ion in the plating bath, the immersion time in the plating bath, the temperature of the plating bath, or the like. From the viewpoint of conductivity, it is preferably 0.5 μm or more, and more preferably 3 μm or more. Further, the immersion time in the plating bath is preferably about 1 minute to 3 hours, and more preferably about 1 minute to 1 hour.

  The conductive film (metal film) obtained as described above has finely dispersed fine particles of electroless plating catalyst and plating metal in the surface graft film by cross-sectional observation by SEM, and further, a relatively large amount of It was confirmed that large particles were precipitated. Since the interface is a hybrid state of the graft polymer and fine particles, the adhesion was good even if the unevenness difference of the interface between the substrate (organic component) and the inorganic substance (electroless plating catalyst or plating metal) was 100 nm or less. .

<Electroplating process>
After performing the electroless plating step, there may be a step of performing electroplating (electroplating step) for the purpose of improving the properties of the conductive film.
In this step, after electroless plating in the electroless plating step, electroplating can be performed using the metal film (conductive film) formed in this step as an electrode. As a result, a metal film having an arbitrary thickness can be easily formed on the basis of a metal film having excellent adhesion to the insulating resin composition layer. By adding this step, the metal film can be formed to a thickness according to the purpose, and the electroless plating catalyst obtained by this aspect is suitable for various applications.
As the electroplating method in this embodiment, a conventionally known method can be used. In addition, as a metal used for the electroplating of this process, copper, chromium, lead, nickel, gold, silver, tin, zinc, etc. are mentioned. More preferred.

  The film thickness of the metal film obtained by electroplating differs depending on the application, and can be controlled by adjusting the concentration of metal contained in the plating bath, the dipping time, or the current density. In addition, from the viewpoint of conductivity, the film thickness when used for general electric wiring or the like is preferably 0.3 μm or more, and more preferably 3 μm or more.

  In addition, as described above, the electroplating process in the present invention can be applied to mounting of an IC or the like, for example, by performing electroplating in addition to forming a patterned metal film with a thickness according to the purpose. It can also be done for purposes such as The plating performed for this purpose is selected from the group consisting of nickel, palladium, gold, silver, tin, solder, rhodium, platinum, and compounds thereof on the conductive film or metal pattern surface formed of copper or the like. It can be performed using the material to be used.

  After the formation of the conductive film, the plating resist composed of the layer (B) and the unreacted polymer precursor are no longer necessary, so that a step of removing this can be performed. Peeling can be performed by spraying a stripping solution or immersing the formed substrate in the stripping solution. The stripping solution differs depending on the type of resist. Generally, the resist or the solvent that swells the resist or the solution is wiped by spraying, or the formed substrate is immersed in the stripping solution to swell the resist. Peel off. At this time, the unexposed portion of the polymer precursor layer can also be peeled off at the same time as the layer (B). However, even when the unexposed portion of the polymer precursor layer is not completely removed, the washing with water is further repeated. Is removed.

As described above, by using the laminate of the present invention, a printed wiring board having excellent characteristics can be easily formed on an arbitrary solid surface. That is, without roughening the surface of the insulating resin material layer having heat resistance and low dielectric constant such as epoxy resin, polyimide resin, liquid crystalline resin, polyarylene resin, etc. used as a substrate in the printed wiring board field, It can be used for forming a circuit made of a metal film material that exhibits high adhesion strength and has a sufficient thickness.
Using a conductive material such as a copper-clad laminate obtained by the production method of the present invention, for example, by a known etching process, the fineness of 20 microns or less, which has been difficult with conventional techniques, and adhesion strength High copper wiring can be formed.

(Manufacturing method of multilayer printed wiring board)
Next, an example is given and demonstrated about the manufacturing method of the multilayer printed wiring board using the laminated body for printed wiring boards of this invention.
When the laminated body of the invention is bonded to the patterned inner layer circuit board, after removing the protective film, the insulating resin composition layer is bent or deformed from the support (base film) side so as to contact the inner layer circuit. An insulating resin composition layer with a photosensitive layer (insulating film) that can be laminated while being pressurized and heated. By laminating under conditions where the resin flow during lamination is greater than the conductor thickness of the inner layer circuit and half the depth of the through hole of the inner layer circuit and / or the depth of the surface via hole, Resin filling in the hole and / or the surface via hole can be performed simultaneously and collectively.
The inner layer circuit board may have a substrate such as glass epoxy, metal, polyester, polyimide, thermosetting polyphenylene ether, polyamide, polyaramid, paper, glass cloth, glass nonwoven fabric, liquid crystal polymer, etc. A substrate using an epoxy resin, an imide resin, a BT resin, a PPE resin, a tetrafluoroethylene resin, or the like as a resin can be used, and the circuit surface may be roughened or not processed in advance. good.

Lamination may be batch type or continuous roll type under reduced pressure, and may be laminated on one side or on both sides simultaneously, but it is preferable to laminate on both sides simultaneously. The laminating conditions as described above vary depending on the melt viscosity during heating, the thickness and the through hole diameter, depth and / or surface via hole diameter, and depth of the inner layer circuit board of the composition constituting the room temperature solid insulating resin layer in the present invention. However, in general, the pressure bonding temperature is 70 to 200 ° C., the pressure bonding pressure is 1 to 10 kgf / cm ² , and the lamination is preferably performed under a reduced pressure of 20 mmHg or less. When the through-hole diameter is large and deep, that is, when the plate thickness is large, the resin composition is thick, and lamination conditions at high temperature and / or high pressure are required.

Generally, the resin can be satisfactorily filled with a plate thickness of about 1.4 mm or less and a through-hole diameter of about 1 mm or less. In addition, the surface smoothness of the resin composition after lamination becomes better as the support base film is thicker, but it is disadvantageous for embedding the resin without voids between the circuit patterns. Therefore, the support base film has a conductor thickness of ± 20 μm. This is true. However, if the conductor thickness of the inner layer circuit is thick, the surface smoothness and thickness of the resin on the pattern is not sufficient, or if the through hole and the surface via hole are large and deep, a dent is formed on the hole. If the laminate for multilayer printed wiring boards of the present invention is further laminated thereon, various conductor thicknesses and board thicknesses can be accommodated. After lamination, the support base film is peeled off after cooling to around room temperature.
After laminating the laminate for the printed wiring board on the inner layer circuit board, if necessary, a wiring pattern is formed on the heat-cured resin composition. Depending on the type of resin composition constituting the laminate for a wiring board, etc., and depending on the curing temperature of these forming materials, it is selected in the range of 20 to 120 minutes at 120 to 220 ° C.

The wiring pattern is formed as follows. After lamination, the support film is peeled off, the active light (for example, electron beam, UV light, etc.) corresponding to the portion where the conductive layer is formed is irradiated, developed, and a patterned plating resist is formed on the insulating film surface. Form a layer. Thereafter, a polymer precursor is brought into contact therewith, energy is applied, and a graft polymer directly bonded to the insulating film is generated. The light irradiation method may be direct irradiation with a laser or the like, or the pattern mask may be placed in close contact and irradiated through it. Further, in this embodiment, in the region where the plating resist is present, the contact between the insulating film and the polymer precursor is hindered. Therefore, this energy application may be performed over the entire surface such as heating.
Thereafter, the unreacted polymer precursor that does not participate in the formation of the graft polymer is removed by washing treatment. The formation of the graft polymer and the removal of the unreacted material by the light irradiation may be performed after the next drilling step. Next, a predetermined through hole and / or via hole portion is drilled with a laser and / or a drill.

  If necessary, the surface of the polymer precursor layer is roughened by a dry method and / or a wet method. Examples of the dry roughening method include mechanical polishing such as buffing and sandblasting, plasma etching, and the like. On the other hand, the wet roughening method includes chemical treatment such as a method using an oxidizing agent such as permanganate, dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid, a strong base or a resin swelling solvent. . In the present invention, sufficient roughening is not necessarily required, and it is sufficient to remove smear generated when drilling a through hole and / or via hole with a laser and / or a drill.

Next, an electroless plating catalyst or a precursor thereof is attached to the graft polymer generation region by the above-described method, and a wiring pattern (conductive layer) is formed by electroless plating. A more detailed method for forming a wiring pattern (conductive layer) by electroless plating is as follows.
In order to attach a plating catalyst to the graft polymer fixed on the insulating film, it is immersed in a plating catalyst solution (for example, a silver nitrate aqueous solution or a tin-palladium colloid solution). Palladium as an electroless plating catalyst. Metal fine powders such as gold, platinum, silver, copper, nickel, cobalt, tin and / or their halides, oxides, hydroxides, sulfides, peroxides, amine salts, sulfates, nitrates, organic Examples thereof include acid salts and organic chelate compounds. Moreover, what adsorb | sucked these to various inorganic components may be used. In this case, the inorganic components include colloidal silica, calcium carbonate, magnesium carbonate, magnesium oxide, barium sulfate, barium titanate, silicon oxide, amorphous silica, talc, clay, mica, etc., as well as alumina and carbon. Any fine powder may be used. Further, the size of the fine powder at this time is preferably an average particle diameter of 0.1 to 50 μm.

Next, the plating catalyst solution remaining in the portion where the wiring pattern is not formed is removed by washing. The immature region of the graft polymer is covered with the patterned (B) layer that is a plating resist, and the plating catalyst cannot be fixed, and the plating catalyst solution is removed. Next, the electroless plating is performed on the portion where the wiring pattern conductor layer is to be formed, so that the conductor layer is formed and a multilayer printed wiring board can be manufactured.
After the conductor layer is formed in this manner, the thermosetting resin is cured by annealing at 120 to 220 ° C. for 20 to 120 minutes as necessary, and the peel strength of the conductive layer is further increased. It can also be improved.
Finally, the (B) plating resist layer that has become unnecessary can be removed.
When the printed wiring board laminate of the present invention is used, the resulting printed wiring board is excellent in surface smoothness. Therefore, the above-described production method is repeated a plurality of times, and the build-up layer is laminated in multiple stages to obtain a multilayer printed wiring board. It can also be manufactured.

  The laminate for a printed wiring board according to the present invention roughens the surface of the insulating film by using a heat-resistant, low dielectric constant resin such as an epoxy resin, a polyimide resin, a liquid crystalline resin, or a polyarylene resin as a material for the insulating film. This is useful for forming a printed wiring board and a flexible wiring board that exhibit high adhesion strength.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
[Example 1]
A polyethylene terephthalate film having a thickness of 16 μm was prepared as a support, and a photosensitive resin layer was formed on the surface as follows without performing surface treatment or pretreatment.
The following photosensitive layer coating solution 1 was applied by a die coater so that the thickness after drying was 15 μm, and dried at 80 ° C. to 120 ° C. to form a photosensitive composition layer (B).

[Photosensitive layer coating solution 1]
Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymer composition (mass ratio): 50/20/7/23,
(Mass average molecular weight: 90,000, acid value 150) 15 parts by mass / polysynthetic monomer represented by the following structural formula (M) 7.0 parts by mass / 1/2 molar ratio addition of hexamethylene diisocyanate and tetraethylene oxide monomethacrylate 7.0 parts by mass of N-methylacridone 0.11 parts by mass 2,2-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole 2.17 parts by mass 2 -Mercaptobenzimidazole 0.23 parts by mass-Malachite green oxalate 0.02 parts by mass-Leuco Crystal Violet 0.26 parts by mass-Methyl ethyl ketone 40 parts by mass-1-methoxy-2-propanol 20 parts by mass

  In the structural formula (M), m and n each represent the number of moles of ethylene oxide added, and m + n is 10.

Next, the (A) insulating resin composition layer was formed on the formed (B) photosensitive composition layer as follows.
(Formation of an epoxy insulator layer containing an initiator)
20 parts by mass of bisphenol A type epoxy resin (epoxy equivalent 185, Epicoat 828 manufactured by Yuka Shell Epoxy Co., Ltd.) (hereinafter, all compounding amounts are expressed in parts by mass), cresol novolac type epoxy resin (epoxy equivalent 215, Dainippon Ink, Ltd.) 45 parts of Chemical Industry Co., Ltd. Epicron N-673), 32 parts of phenol novolac resin (phenolic hydroxyl group equivalent 105, Phenolite manufactured by Dainippon Ink & Chemicals, Inc.) 20 parts of ethyl diglycol acetate, 20 parts of solvent naphtha The mixture is heated and dissolved with stirring and cooled to room temperature, and then the phenoxy resin cyclohexanone varnish (YL6747H30 manufactured by Yuka Shell Epoxy Co., Ltd., nonvolatile content 30% by mass, weight average molecular weight 47000) composed of Epicoat 828 and bisphenol S is added thereto. 30 parts and 2-fe Le-4,5-bis (hydroxymethyl) 0.8 parts imidazole, 2 parts of finely divided silica, were added 0.5 parts of silicone antifoaming agent to prepare a epoxy resin varnish.

Furthermore, 10 parts of the polymerization initiating polymer P synthesized by the following method was added to this mixture, stirred and dissolved to prepare an epoxy resin varnish with an initiator. This epoxy resin varnish was coated on the support on which the photosensitive composition layer (B) was coated with a die coater so that the thickness after drying was 75 μm, and dried at 80 ° C. to 120 ° C. for insulation. A resin composition layer was formed.
When the dielectric constant and dielectric loss tangent at 1 GHz of the formed insulating resin composition layer were measured by a cavity resonator perturbation method, the dielectric constant was 3.5 and the dielectric loss tangent was 0.05.

(Synthesis of polymerization initiating polymer P)
30 g of propylene glycol monomethyl ether (MFG) was added to a 300 ml three-necked flask and heated to 75 degrees. [2- (Acryloyloxy) ethyl] (4-benzoylbenzoyl) dimethyl ammonium bromide 8.1g, 2-Hydroxyethylmethacrylate 9.9-g, isopropymethylmetha-2-methyl-1,2-propylmethylmethacrylate-2-methyl-1,2-azomethyl-2-methyl-2-azomethyl-2 ) A solution of 0.43 g and MFG 30 g was added dropwise over 2.5 hours. Thereafter, the reaction temperature was raised to 80 ° C., and the reaction was further continued for 2 hours to obtain a polymer P having a polymerization initiating group.

  Furthermore, a laminate for a printed wiring board according to the present invention, in which a 20 μm polypropylene film is disposed as a protective layer, a photosensitive layer and an insulating layer are formed on the support by coating, and the surface is covered with the protective layer. Body 1 was obtained.

(Production of printed wiring board using laminate for printed wiring board)
(1) Application of laminate for printed wiring board on substrate Using laminate film 1 for printed wiring board obtained above, a substrate on which wiring is to be formed (patterned glass epoxy inner layer circuit board (conductor) On the thickness 18 μm)), the laminate film for printed wiring board is disposed so that the protective layer is peeled off and the substrate and the insulating film are laminated, and the vacuum laminator is used at 100 MPa to 110 ° C. at a pressure of 0.2 MPa. It was made to adhere according to conditions.
(2) Exposure (formation of plating resist)
Next, the support of the laminate film 1 was peeled off, and pattern exposure and development processing were performed by the following method, and a patterned photosensitive layer (plating resist) was formed on the insulating resin composition layer. A patterned laminate was obtained.
For the exposure, a mask having a wiring pattern with a line width / space width of 10/10 (μm) is brought into close contact, and further, 99.5% or more of light having a wavelength of 365 nm or less is cut thereon by Sigma Kogyo Co., Ltd. Using a parallel light exposure machine (Oak Seisakusho, product name EXM-1201) with a sharp cut filter SCF-100S-39L and a 5 kW short arc lamp as the light source, exposure is performed at a wavelength of 405 nm and an exposure amount of 12 mJ / cm ^2. Went.
Next, an unexposed portion was removed by spraying a 1.0 wt% sodium carbonate aqueous solution at 30 ° C. for 24 seconds.

(3) Formation of graft polymer)
Next, a polymer having an acrylic group as a polymerizable compound and a carboxyl group as an interactive group on the surface of the patterned laminate (hydrophilic polymer having a polymerizable group in a side chain: P-1, the following) A liquid composition 1 having the following composition is obtained by a spin coater and dried at 100 ° C. for 1 minute to provide a polymer precursor-containing layer having a thickness of 2 μm. Then, a washing treatment was performed to obtain a surface graft material in which a graft polymer was formed in a pattern on the insulating resin composition layer, and an unformed region of the graft polymer was covered with the layer (B).
The exposure was performed at room temperature for 1 minute using an exposure machine: an ultraviolet irradiation device (UVX-02516S1LP01, manufactured by USHIO INC.). After the exposure, it was thoroughly washed with pure water. By this exposure, (A) the graft polymer bonded to the insulating film was generated, and the surface graft pattern material 1 was obtained.

(Synthesis example: Synthesis of polymer P-1 having a double bond)
Polyacrylic acid (average molecular weight 25000, Wako Pure Chemical Industries) 60 g and hydroquinone (Wako Pure Chemical Industries) 1.38 g (0.0125 mol) were placed in a 1 liter three-necked flask equipped with a condenser and N, N-dimethylacetamide. (DMAc, Wako Pure Chemical Industries) 700 g was added and stirred at room temperature to obtain a uniform solution. While stirring the solution, 64.6 g (0.416 mol) of 2-methacryloyloxyethyl isocyanate (Karenz MOI, Showa Denko) was added dropwise. Subsequently, 0.79 g (1.25 × 10 ⁻³ mol) of di-n-butyltin dilaurate (Tokyo Chemical Industry) suspended in 30 g of DMAc was added dropwise. Heated in a 65 degree water bath with stirring. After 5 hours, the heating was stopped and the mixture was naturally cooled to room temperature. The reaction solution had an acid value of 7.105 mmol / g and a solid content of 11.83%.

  300 g of the reaction solution was placed in a beaker and cooled to 5 degrees with an ice bath. While stirring the reaction solution, 41.2 ml of 4N aqueous sodium hydroxide solution was added dropwise over about 1 hour. The temperature of the reaction solution during the dropwise addition was 5 to 11 degrees. After the dropping, the reaction solution was stirred at room temperature for 10 minutes, and the solid content was removed by suction filtration to obtain a brown solution. The solution was reprecipitated with 3 liters of ethyl acetate, and the precipitated solid was collected by filtration. The solid was reslurried overnight with 3 liters of acetone. The solid was filtered off and vacuum dried for 10 hours to obtain a light brown powder P-1.

(Liquid composition 1 containing a polymerizable compound)
-Hydrophilic polymer (P-1) having a polymerizable group in the side chain 3.1 g
・ Water 24.6g
1-methoxy-2-propanol 12.3 g

(Production of printed wiring board using laminate for printed wiring board)
(4) Adhesion and confirmation of electroless plating catalyst etc. Electroless plating catalyst is applied to the surface graft pattern material 1 obtained by the laminate of the present invention obtained as described above, and electroless plating is performed. Thus, the wiring board of Example 1 was obtained.
(Implementation of electroless plating and electrolytic plating process)
The surface graft pattern material 1 was immersed in a 0.1% by mass aqueous solution of silver nitrate (manufactured by Wako Pure Chemical Industries) for 1 hour, and then washed with distilled water. Then, the electroconductive plating material of Example 1 was produced by immersing in an electroless plating bath having the following composition for 240 minutes for electroless plating.
<Electroless plating bath components>
・ 0.3 g of copper sulfate
・ Tartaric acid NaK 1.7g
・ Sodium hydroxide 0.7g
・ Formaldehyde 0.2g
・ Water 48g

[Evaluation of conductive pattern material]
(Surface unevenness)
The surface unevenness of the obtained conductive material was measured with Nanopics (Nanopics 1000, manufactured by Seiko Instruments Inc., using DFM cantilever). The result was a surface irregularity Rz = 450 nm.
(Measurement of metal film thickness)
When measured using a DFM cantilever, a film thickness of 6 μm was observed. Therefore, it can be seen that this metal pattern has a metal film thickness that can sufficiently achieve conductivity.
(Adhesion strength evaluation)
A copper plate (thickness: 50 μm) was bonded to the surface of the conductive material on which the metal film was formed with an epoxy adhesive (Araldite, manufactured by Ciba Geigy), dried at 140 ° C. for 4 hours, and then subjected to a 90-degree peeling test based on JIS C6481. went. The peeling apparatus used was a tensile tester AGS-J manufactured by Shimadzu Corporation. The result was 0.8 kN / m.

  As is clear from the above results, the conductive material obtained by the production method of the present invention has small surface irregularities, a sufficient thickness on the smooth insulator layer surface, and adhesion to the substrate. It was found that an excellent metal film was formed. Further, a conductive pattern material having a multilayer wiring can be easily obtained by repeating these steps using the laminate of the present invention on the surface of the substrate on which the conductive pattern is formed as described above. I understand that

(Example 2)
In the production of the conductive pattern material 1 in Example 1, the wiring was connected so that electricity would flow to the conductive pattern on the substrate on which the conductive pattern was produced by electroless plating. The conductive pattern material 2 of Example 2 was produced by plating.

<Composition of electroplating bath>
・ Copper sulfate 38g
・ 95 g of sulfuric acid
・ Hydrochloric acid 1mL
・ Copper Greeme PCM (Meltex Co., Ltd.) 3mL
・ Water 500g

[Evaluation of conductive pattern material]
When evaluated in the same manner as in Example 1, the surface unevenness: Rz = 300 nm, the metal film thickness: 14 μm, the adhesion strength was 0.9 kN / m, and the resistance of the conductivity further decreased. From this, it can be seen that the electroconductivity followed by electroplating further improves the pattern conductivity.

Claims (7)

A laminate for producing a printed wiring board, comprising: an insulating resin composition layer containing a polymerizable compound and a polymerization initiator on a support; and a photosensitive composition layer that is cured or decomposed by exposure. make use of,
A step of laminating an insulating resin composition layer and a photosensitive composition layer on a substrate so as to be positioned in this order, and applying energy from the photosensitive composition layer side in a pattern, developing, and developing the photosensitive composition A reactive polymer having a functional group capable of interacting with an unsaturated double bond capable of radical polymerization and an electroless plating catalyst or its precursor on the surface of the laminate; contacting a composition containing the precursor, by performing the application of energy, the insulating resin composition layer, to produce a polymer compound that have the electroless plating catalyst or its precursor and a functional group capable of interacting conductive to form a polymer compound producing step, the catalyst adhering step of adhering an electroless plating catalyst or a precursor thereof in the generation region of the polymer compound, a circuit pattern by performing electroless plating A layer forming step, a method for manufacturing a printed wiring board and having a photosensitive composition layer removing step, in this order to remove the photosensitive composition layer remaining. The method further includes a step of performing electroplating after the conductive layer forming step of forming a circuit pattern by performing the electroless plating and before the photosensitive composition layer removing step. The manufacturing method of the printed wiring board of Claim 1 . The pattern forming process energy application in the energy imparted and the polymer compound producing step in a exposure both, and the exposure wavelength at the exposure wavelength and a polymer compound producing step in the pattern forming step, according to claim 1 or different wavelengths A method for producing a printed wiring board according to claim 2 . A printed wiring board in which the step of laminating the insulating resin composition layer and the photosensitive composition layer on the substrate in this order has the photosensitive resin layer and the insulating resin composition layer on the support in this order. The printed wiring board according to any one of claims 1 to 3, which is a step of peeling the support after laminating the laminate for production so that the substrate and the insulating resin composition layer are in close contact with each other. Manufacturing method. In the non-existing region of the pattern composed of the photosensitive resin composition layer, the polymer compound generation step includes an unsaturated double bond capable of radical polymerization on the surface of the exposed insulating resin composition layer and an electroless plating catalyst or its The reactive polymer precursor having a functional group capable of interacting with the precursor binds to the electroless plating catalyst directly bonded to the insulating resin composition layer or the functional group capable of interacting with the precursor. the method for manufacturing a a step of producing a graft polymer of chromatic claims 1 to printed wiring board according to any one of claims 4. The insulating resin composition layer in the laminate for a printed wiring board is made of a resin having a dielectric constant of 5 or less and a dielectric loss tangent of 0.5 or less at 1 GHz, the energy application is exposure or heating, and the print The laminated body for a wiring board has a protective film on the surface of the uppermost layer, peels off the support or the protective film, and laminates the exposed layer on a substrate for use. The manufacturing method of the printed wiring board of any one of Claims 1. Wherein said substrate is a printed wiring board having a conductive layer formed of the conductive layer is formed on a printed wiring board, and forming a circuit pattern by using the printed wiring board fabrication laminate The manufacturing method of the multilayer printed wiring board of any one of Claims 1 thru | or 6 .