JP2006281481A - Process film for manufacturing laminated circuit board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a process film for manufacturing a laminated circuit board capable of forming a good hole at the time of processing of a via-hole, not causing the trouble caused by flotation or peeling when filling the hole with conductive paste and excellent in the peelability from the laminated circuit board. <P>SOLUTION: The process film for manufacturing the laminated circuit board has a base material film and the resin layers formed on both sides of the base material film and is characterized in that each of the resin layers on both sides of the base material film is a layer comprising the cured material of an active energy beam curable resin composition or a layer comprising an alkyd resin and/or an acrylic resin. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a process film for manufacturing a laminated circuit board. More specifically, the present invention is a process film used in the production of a multilayer circuit board that requires the formation of an inner via hole, which can form a good hole during via hole processing, and floats when the conductive paste is filled in the hole. The present invention relates to a process film for manufacturing a laminated circuit board that does not cause problems due to peeling and has excellent releasability from the board.

In recent years, with the miniaturization, high performance, and high speed of electrical and electronic equipment, printed wiring boards have been required to have high-density mounting and high-density wiring. Printed wiring boards are attracting attention. Build-up type multilayer printed wiring boards are formed by stacking insulating layers, conductor layers and interlayer connection via holes one by one, and various manufacturing methods are known depending on the insulating layer forming method and via hole forming method. Yes.
In such a method of manufacturing a multilayer printed wiring board, in order to make the circuits on the substrates in the laminated circuit board conductive, inner via holes are formed and filled with a conductive paste. As a method for processing the inner via hole, a method using a carbon dioxide gas laser has recently become common as the diameter of the via hole is reduced.
In this via hole processing step, a process film is used for masking in order to avoid adhesion of the conductive paste to unnecessary portions when the conductive paste is filled. Specifically, the process film is heated and laminated on a resin substrate manufacturing sheet called a prepreg, and then via hole processing is performed using a carbon dioxide laser or the like. The process film also plays a role of preventing contamination during prepreg conveyance. And after filling with the conductive paste, the process film is peeled from the prepreg, and a prepreg having a via hole filled with the conductive paste can be obtained.
For such a laminated circuit board manufacturing process film, good holes can be formed at the time of via hole processing, and there is no problem caused by floating or peeling when filling the hole with conductive paste, and peeling from the substrate The property is required to be good.
Conventionally, as a process film for manufacturing a laminated circuit board, a fluorine-based film or a polyester film coated with a silicone-based release agent has been used. However, a fluorine-based film is very expensive and discarded after use. There was a problem that processing was difficult. Further, the polyester film coated with the silicone release agent has a problem that the adhesion to the substrate is low, and the float or peeling is likely to occur during the via hole processing.
Furthermore, a release film using a cast film made of a resin containing a syndiotactic styrene-based polymer as a main component (see, for example, Patent Document 1), a substrate having a light transmittance of 10% or less at a wavelength of 300 to 380 nm A masking tape in which an adhesive layer is formed on one side of the layer (for example, see Patent Document 2) is disclosed.
However, the release film requires high temperature and high pressure to be attached to the prepreg, and the release film and the masking tape sufficiently satisfy all the required performance for the process film for manufacturing the laminated circuit board. It does not meet.
JP 11-349703 A JP 2002-322438 A

  Under such circumstances, the present invention is a process film used when producing a multilayer circuit board that requires the formation of an inner via hole, and can form a good hole at the time of via hole processing, and has conductivity to the hole. The object of the present invention is to provide a process film for manufacturing a laminated circuit board which does not cause a problem due to floating or peeling at the time of paste filling and is excellent in peelability from the board.

As a result of intensive research to develop a process film for manufacturing a laminated circuit board having the above-mentioned preferable properties, the present inventors have obtained a resin layer, preferably a specific resin layer on both sides of the base film with a predetermined thickness. The process film formed in this way was found to be suitable for the purpose, and the present invention was completed based on this finding.
That is, the present invention
(1) A process film for manufacturing a laminated circuit board, comprising a base film and resin layers formed on both sides thereof,
(2) The process film for manufacturing a laminated circuit board according to the above (1), wherein the resin layers formed on both surfaces have a thickness of 0.1 to 10 μm, respectively.
(3) The above (1), wherein the resin layers on both sides formed on the base film are both a layer made of a cured product of the active energy ray-curable resin composition, or a layer made of an alkyd resin and / or an acrylic resin. Or a process film for manufacturing a laminated circuit board according to (2),
(4) The resin layer on one surface formed on the base film is a layer made of a cured product of the active energy ray-curable resin composition, and the resin layer on the other surface is an alkyd resin and / or an acrylic resin. The process film for manufacturing a laminated circuit board according to the above item (1) or (2), which is a layer made of resin
(5) The active energy ray-curable resin composition comprises (A) an active energy ray-polymerizable monomer and / or oligomer having two or more polymerizable unsaturated groups in the molecule, and (B) a photopolymerization initiator. A process film for producing a laminated circuit board according to (3) or (4) above, which is a photocurable resin composition comprising:
(6) The laminated circuit board manufacturing process film according to any one of (3) and (4) above, wherein the alkyd resin and the acrylic resin have a crosslinked structure, and (7) the thickness of the base film The process film for producing a laminated circuit board according to any one of (1) to (6), wherein the thickness is 10 to 60 μm,
Is to provide.

  According to the present invention, it is a process film used in the production of a multilayer circuit board that requires the formation of an inner via hole, and a good hole can be formed at the time of via hole processing, and floating or peeling at the time of filling the hole with a conductive paste. It is possible to provide a process film for manufacturing a laminated circuit board that does not cause a problem due to the above and has excellent peelability from the substrate.

The process film for producing a laminated circuit board according to the present invention (hereinafter sometimes simply referred to as “process film”) has a base film and resin layers formed on both sides thereof.
The base film in the process film of the present invention is not particularly limited as long as it has the necessary mechanical properties, heat resistance, durability, and the like as the base of the process film for manufacturing a laminated circuit board. Polyester film such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene film, polypropylene film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, Polymethylpentene film, Polysulfone film, Polyetheretherketone film, Polyethersulfone film, Polyphenylene sulfide film, Polyether De films, polyimide films, fluororesin films, polyamide films, acrylic resin films, norbornene resin films, cycloolefin resin films or the like.
The thickness of the base film is not particularly limited, but since a resin layer is provided on both sides thereof, it is usually about 10 to 60 μm, preferably 15 to 50 μm, considering workability at the time of use and suitability for laser processing. It is.
In addition, this base film may be subjected to surface treatment or primer treatment on one side or both sides by an oxidation method or a concavo-convex method, if desired, for the purpose of improving the adhesion with the resin layer provided on the surface. it can. Examples of the oxidation method include corona discharge treatment, plasma discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, and the like. Examples include solvent processing methods. These surface treatment methods are appropriately selected according to the type of the base film, but generally, the corona discharge treatment method is preferably used from the viewpoints of effects and operability.

The resin layers formed on both surfaces of the base film are (1) a layer made of a cured product of an active energy ray-curable resin composition, and (2) a layer made of an alkyd resin and / or an acrylic resin. It is preferable.
In the process film of the present invention, both of the resin layers formed on the base film are a layer made of a cured product of an active energy ray-curable resin composition, or a layer made of an alkyd resin and / or an acrylic resin. The resin layer on one side formed on the base film may be a layer made of a cured product of the active energy ray-curable resin composition, and the resin layer on the other side may be an alkyd resin and / or Alternatively, it may be a layer made of an acrylic resin.
Thus, by forming the resin layer on both surfaces of the base film, the required performance for the process film for manufacturing a laminated circuit board, that is, a good hole can be formed at the time of via hole processing, and the conductivity to the hole can be formed. It is possible to satisfy performances such as no problem due to floating or peeling when filling the conductive paste, and excellent peelability from the substrate.
In order to satisfy the required performance sufficiently, the thickness of each resin layer is preferably 0.1 to 10 μm, and more preferably 0.5 to 8 μm.
When the resin layer is a layer made of a cured product of an active energy ray curable resin composition, the active energy ray curable resin composition includes two active energy ray curable polymerizable compounds in the molecule. The active energy ray polymerizable monomer and / or oligomer having the above polymerizable unsaturated group can be used.
The active energy ray-curable polymerizable compound refers to a polymerizable compound having energy quanta in an electromagnetic wave or a charged particle beam, that is, a polymerizable compound that is crosslinked and cured by irradiation with ultraviolet rays or an electron beam.
When the active energy ray is an actinic ray such as ultraviolet ray, a photopolymerization initiator is usually used together with the active energy ray polymerizable monomer and / or oligomer. On the other hand, when the active energy ray is an electron beam, the photopolymerization initiator may not be used. In the present invention, it is preferable to use actinic rays such as ultraviolet rays as active energy rays. Therefore, the active energy ray-curable resin composition comprises (A) an active energy ray-polymerizable monomer and / or oligomer having two or more polymerizable unsaturated groups in the molecule, and (B) a light containing a photopolymerization initiator. A curable resin composition is preferred.

  In this photocurable resin composition, examples of the active energy ray polymerizable monomer having two or more polymerizable unsaturated groups in the molecule used as the component (A) include 1,4-butanediol di (meta ) Acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol adipate di (meth) acrylate, hydroxypivalate neopentyl glycol di ( (Meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone-modified dicyclopentenyl di (meth) acrylate, ethylene oxide-modified phosphoric acid di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) Acrylate, trimer Roll propane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris Examples thereof include polyfunctional acrylates such as (acryloxyethyl) isocyanurate, propionic acid-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate. These active energy ray polymerizable monomers may be used alone or in combination of two or more.

On the other hand, the active energy ray polymerizable oligomer includes a radical polymerization type and a cationic polymerization type. Examples of the radical polymerization type active energy ray polymerizable oligomer include a polyester acrylate type, an epoxy acrylate type, a urethane acrylate type, and a polyol acrylate type. Etc.
Here, as the polyester acrylate oligomer, for example, by esterifying hydroxyl groups of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with (meth) acrylic acid, It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding alkylene oxide to a polyvalent carboxylic acid with (meth) acrylic acid. The epoxy acrylate oligomer can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it. The urethane acrylate oligomer can be obtained, for example, by esterifying a polyurethane oligomer obtained by reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid. Furthermore, the polyol acrylate oligomer can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid. These active energy ray polymerizable oligomers may be used alone or in combination of two or more.
On the other hand, examples of the cationic polymerization type active energy ray polymerizable oligomer include epoxy, oxetane resin, vinyl ether resin and the like. Here, the epoxy resin is obtained by oxidizing a compound obtained by epoxidizing polyhydric phenols such as bisphenol resin or novolak resin with epichlorohydrin, etc., a linear olefin compound or a cyclic olefin compound with a peroxide or the like. And the like.

  In addition, as the photopolymerization initiator of the component (B), among radically polymerizable photopolymerizable oligomers and photopolymerizable monomers among active energy ray polymerizable oligomers and monomers, for example, benzoin, benzoin methyl ether Benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy 2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 4- (2 -Hydroxyethoxy Ii) phenyl-2 (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2 -Aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethyl ketal, acetophenone dimethyl ketal, p-dimethylamine benzoate, etc. Can be mentioned. Examples of the photopolymerization initiator for the cationic polymerization type photopolymerizable oligomer include oniums such as aromatic sulfonium ions, aromatic oxosulfonium ions, and aromatic iodonium ions, tetrafluoroborate, hexafluorophosphate, hexafluoroantimony. And compounds composed of anions such as nitrates and hexafluoroarsenates. These may be used singly or in combination of two or more, and the blending amount thereof is usually 0.1 with respect to 100 parts by mass of the photopolymerizable monomer and / or photopolymerizable oligomer. It is selected in the range of 2 to 10 parts by mass.

The active energy ray-curable resin composition used in the present invention, preferably the photocurable resin composition, is added to the above-mentioned active energy ray-curable polymerizable compound, photopolymerization initiator, and various kinds of additives in an appropriate solvent. By adding components, such as monofunctional active energy ray polymerizable monomers, antioxidants, ultraviolet absorbers, light stabilizers, leveling agents, antifoaming agents, colorants, etc., at predetermined ratios, respectively, or dissolving or dispersing them, Can be prepared.
Examples of the monofunctional active energy ray polymerizable monomer include cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and isobonyl (meth) acrylate.
Examples of the solvent used here include aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride and ethylene chloride, alcohols such as methanol, ethanol, propanol, and butanol. And ketones such as acetone, methyl ethyl ketone, 2-pentanone, isophorone, and cyclohexanone, esters such as ethyl acetate and butyl acetate, and cellosolv solvents such as ethyl cellosolve.
The concentration and viscosity of the composition thus prepared are not particularly limited as long as they can be coated, and can be appropriately selected according to the situation.
Next, the above composition is applied to one side or both sides of the base film using a conventionally known method such as a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, or a gravure coating method. After coating, a coating film is formed and, if desired, heat drying is performed, and then the coating film is cured by irradiating this with an active energy ray, whereby a resin layer is formed.
As the active energy ray, for example, actinic rays such as ultraviolet rays are preferable. The ultraviolet rays are obtained with a high-pressure mercury lamp, a fusion H lamp, a xenon lamp or the like, and the irradiation amount is usually 100 to 500 mJ / cm ² .
The thickness of the resin layer thus formed is usually 0.1 to 10 μm, preferably 0.5 to 8 μm as described above.
On the other hand, when the resin layer is a layer made of an alkyd resin and / or an acrylic resin, the alkyd resin or the acrylic resin preferably has a crosslinked structure.

Formation of the alkyd resin layer having a crosslinked structure uses, for example, a method in which a layer comprising a thermosetting resin composition containing (X) an alkyd resin, (Y) a crosslinking agent, and (Z) a curing catalyst as required is heated and cured. Can do.
The alkyd resin as the component (X) is not particularly limited, and can be appropriately selected from conventionally known alkyd resins. This alkyd resin is a resin obtained by a condensation reaction between a polyhydric alcohol and a polybasic acid, and is a non-convertible alkyd which is modified with a condensate of a dibasic acid and a dihydric alcohol or a non-drying oil fatty acid. There are resins and convertible alkyd resins which are condensates of dibasic acids and trivalent or higher alcohols, and any of them can be used in the present invention.
Examples of the polyhydric alcohol used as a raw material of the alkyd resin include dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, and neopentyl glycol, glycerin, trimethylolethane, Examples thereof include trihydric alcohols such as trimethylolpropane, and polyhydric alcohols such as diglycerin, triglycerin, pentaerythritol, dipentaerythritol, mannitol, and sorbit. These may be used individually by 1 type and may be used in combination of 2 or more type.

Examples of the polybasic acid include aromatic polybasic acids such as phthalic anhydride, terephthalic acid, isophthalic acid, and trimetic anhydride, aliphatic saturated polybasic acids such as succinic acid, adipic acid, and sebacic acid, maleic acid, Diels such as aliphatic unsaturated polybasic acids such as maleic anhydride, fumaric acid, itaconic acid, citraconic anhydride, cyclopentadiene-maleic anhydride adduct, terpene-maleic anhydride adduct, rosin-maleic anhydride adduct -The polybasic acid by Alder reaction etc. can be mentioned. These may be used individually by 1 type and may be used in combination of 2 or more type.
On the other hand, examples of the modifying agent include octylic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, eleostearic acid, ricinoleic acid, dehydrated ricinoleic acid, coconut oil, linseed oil, and kili oil. , Castor oil, dehydrated castor oil, soybean oil, safflower oil, and their fatty acids. These may be used individually by 1 type and may be used in combination of 2 or more type.
In the present invention, the alkyd resin of component (X) may be used alone or in combination of two or more.

Examples of the crosslinking agent for the component (Y) include not only amino resins such as melamine resins and urea resins, but also urethane resins, epoxy resins, and phenol resins.
Here, the melamine resin can be produced by reacting melamine and formaldehyde in the presence of a basic catalyst. At this time, by adjusting the amount ratio of melamine and formaldehyde, the primary and triazine nuclei are obtained. The number of secondary amino groups can be controlled.
In the present invention, the melamine resin thus obtained can be reacted with an appropriate alcohol in the presence of an acidic catalyst, if desired, and a methylol group partially alkyl etherified. The alcohol used at this time is preferably a lower alcohol, and examples thereof include methyl alcohol and butyl alcohol. The type of alcohol and the etherification rate are not particularly limited, and are appropriately selected in consideration of compatibility with the alkyd resin, solubility in solvents, curability of the resulting resin composition, adhesion to the substrate, and the like. be able to.
In the present invention, the crosslinking agent of the component (Y) may be used alone or in combination of two or more.
In the said thermosetting resin composition, the ratio of the said (X) component and (Y) component has the preferable range of 70:30 thru | or 10:90 by solid content mass ratio. When the ratio of the component (X) is more than the above range, the cured product cannot obtain a sufficient cross-linked structure, which causes a decrease in peelability. On the other hand, if the proportion of the component (X) is less than the above range, the cured product becomes hard and brittle, and the peelability is lowered. A more preferable ratio of the component (X) to the component (Y) is 65:35 to 10:90 in terms of solid content mass ratio, and a range of 60:40 to 20:80 is particularly preferable.

In the said thermosetting resin composition, an acidic catalyst can be used as a curing catalyst of (Z) component. There is no restriction | limiting in particular as this acidic catalyst, It can select suitably from well-known acidic catalysts conventionally known as a crosslinking reaction catalyst of an alkyd resin. As such an acidic catalyst, for example, an organic acidic catalyst such as p-toluenesulfonic acid and methanesulfonic acid is suitable. This acidic catalyst may be used individually by 1 type, and may be used in combination of 2 or more type. Moreover, the usage-amount is 0.1-40 mass parts normally with respect to a total of 100 mass parts of the said (X) component and (Y) component, Preferably it is 0.5-30 mass parts, More preferably, it is 1-1. It is selected in the range of 20 parts by mass.
The thermosetting resin composition is usually used in the form of an organic solvent solution for convenience in use. The organic solvent used at this time can be appropriately selected from known solvents that have good solubility in the components (X) and (Y) and are inert to them. Examples of such a solvent include toluene, xylene, methanol, ethanol, isobutanol, n-butanol, acetone, methyl ethyl ketone, and tetrahydrofuran. These may be used individually by 1 type and may be used in combination of 2 or more type.
In these organic solvents, the (X) component, the (Y) component, and the (Z) component and various additive components used as required are respectively added at a predetermined ratio to adjust the viscosity to be coatable. Thus, the thermosetting resin composition is obtained. There is no restriction | limiting in particular as an additive component used in this case, From the well-known additive component conventionally known as an additive component of an alkyd resin, it can select suitably and can be used. For example, an antistatic agent such as a cationic surfactant, other resins such as an acrylic resin for adjusting flexibility and viscosity, a leveling agent, an antifoaming agent, a coloring agent, and the like can be used.
The thermosetting resin composition thus obtained is applied to one side or both sides of the base film, for example, bar coating method, reverse roll coating method, knife coating method, roll knife coating method, gravure coating method, air doctor coating method. The resin layer can be formed by coating by a conventionally known coating method such as a doctor blade coating method and heating and curing at a temperature of about 80 to 150 ° C. for several tens of seconds to several minutes.
The thickness of the resin layer thus formed is usually 0.1 to 10 μm, preferably 0.5 to 8 μm as described above.

The formation of the acrylic resin layer having a cross-linked structure is, for example, a method in which a layer made of an acrylic resin composition containing a (meth) acrylic acid ester copolymer having a cross-linkable functional group and a cross-linking agent is heated and cured. Can be used.
The (meth) acrylic acid ester-based copolymer having a crosslinkable functional group includes a (meth) acrylic acid ester having an alkyl group of 1 to 20 carbon atoms and a functional group having an active hydrogen. The copolymer of a body and the other monomer used depending on necessity can be mentioned preferably.
Here, examples of the (meth) acrylic acid ester having 1 to 20 carbon atoms of the alkyl group in the ester portion include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth ) Butyl acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, Examples include dodecyl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, and the like. These may be used alone or in combination of two or more.

On the other hand, examples of the monomer having a functional group having active hydrogen include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth) (Meth) acrylic acid hydroxyalkyl esters such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; monomethylaminoethyl (meth) acrylate, (meth) acrylic Monoethylaminoethyl acid, monomethylaminopropyl (meth) acrylate, monoalkylaminoalkyl (meth) acrylate such as monoethylaminopropyl (meth) acrylate; acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid And ethylenically unsaturated carboxylic acids such as citraconic acid. These monomers may be used independently and may be used in combination of 2 or more type.
Examples of other monomers used as desired include vinyl esters such as vinyl acetate and vinyl propionate; olefins such as ethylene, propylene and isobutylene; halogenated olefins such as vinyl chloride and vinylidene chloride; styrene Styrene monomers such as α-methylstyrene; diene monomers such as butadiene, isoprene and chloroprene; nitrile monomers such as acrylonitrile and methacrylonitrile; acrylamide, N-methylacrylamide, N, N- Examples include acrylamides such as dimethylacrylamide. These may be used alone or in combination of two or more.

In the acrylic resin composition, the (meth) acrylic acid ester copolymer used as a resin component is not particularly limited as to its copolymerization form, and may be any of random, block, and graft copolymers. Good. The molecular weight is preferably 300,000 or more in terms of weight average molecular weight.
In addition, the said weight average molecular weight is the value of polystyrene conversion measured by the gel permeation chromatography (GPC) method.
In the present invention, this (meth) acrylic acid ester copolymer may be used alone or in combination of two or more.
There is no restriction | limiting in particular as a crosslinking agent in this acrylic resin composition, Arbitrary things can be suitably selected and used from what was conventionally used as a crosslinking agent in acrylic resin. Examples of such crosslinking agents include polyisocyanate compounds, epoxy resins, melamine resins, urea resins, dialdehydes, methylol polymers, aziridine compounds, metal chelate compounds, metal alkoxides, and metal salts. A compound is preferably used.
Examples of the polyisocyanate compound include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, and hydrogenated diphenylmethane diisocyanate. Polyisocyanates, etc., and biurets, isocyanurates, and adducts that are a reaction product with low molecular active hydrogen-containing compounds such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil, etc. Can be mentioned.

In this invention, this crosslinking agent may be used individually by 1 type, and may be used in combination of 2 or more type. Further, the amount used depends on the kind of the crosslinking agent, but is usually 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the (meth) acrylic ester copolymer. It is selected in the range of mass parts.
Various additives such as antioxidants, ultraviolet absorbers, light stabilizers, softeners, fillers, colorants and the like are optionally added to the acrylic resin composition as long as the object of the present invention is not impaired. can do.
The acrylic resin composition thus obtained is applied to one side or both sides of the base film, for example, bar coating method, reverse roll coating method, knife coating method, roll knife coating method, gravure coating method, air doctor coating method. The resin layer can be formed by coating by a conventionally known coating method such as a doctor blade coating method and heating and curing at a temperature of about 80 to 120 ° C. for several tens of seconds to several minutes.
The thickness of the resin layer thus formed is usually 0.1 to 10 μm, preferably 0.5 to 8 μm as described above.
The process film for producing a laminated circuit board of the present invention produced in this manner is preferably used as a process film particularly in the production of a multilayer circuit board in a build-up type multilayer printed wiring board. In the manufacturing method of a multilayer printed wiring board, in order to make the circuit on the board | substrate in a laminated circuit board conduct | electrically_connect, forming an inner via hole and filling it with a conductive paste is performed.
In this via hole processing step, when filling the conductive paste, the process film of the present invention is used for masking to avoid adhesion of the conductive paste to unnecessary portions. Specifically, the process film of the present invention is usually heat-laminated on a prepreg at a temperature of 50 to 150 ° C., and then via hole processing is performed using a carbon dioxide gas laser or the like.
The process film of the present invention can form a good hole at the time of via hole processing, does not cause a problem due to floating or peeling at the time of filling the conductive paste into the hole, and has a property excellent in peelability from the substrate, It is used suitably for the said use.
Here, the peeling force required to peel off the process film of the present invention from the prepreg is preferably 1 to 50 mN / 50 mm, more preferably 5 to 45 mN / 50 mm. In addition, peeling force is the value measured by the method shown below.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
In addition, evaluation of the process film obtained in each example was performed in accordance with the method shown below.
(1) Laser processing suitability First, a test sample shown in FIG. 1 is prepared using each process film. FIG. 1 is a schematic cross-sectional view of a test sample, in which a process film 4 in which a resin layer A2 is provided on one side of a base film 1 and a resin layer B3 is provided on the other side, and a resin layer B3 is provided on a prepreg 5. The sample 10 for a test is produced by heat laminating on condition of 120 degreeC and 0.5 m / min so that it may face, and laser workability is evaluated.
From the resin layer A2 side of the process film in the test sample, laser light is irradiated using a carbon dioxide laser to provide through holes, and the surface of the through holes on the resin layer A2 side and the resin layer B3 side are scanned with an electron microscope. Observe by (SEM).
The material that does not have a resin bulge and through-hole retraction phenomenon (a phenomenon in which the diameter of the through-hole of the resin layer B3 is significantly smaller than the through-hole of the resin layer A2) is accepted as a pass ○. Although there is no swell of the resin or a phenomenon that the through hole recedes slightly, Δ is given, and those that are clearly seen are rejected X.
In addition, as a prepreg, a resin varnish having the following composition was impregnated into a base material made of an aramid non-woven fabric [manufactured by DuPont Teijin Advanced Paper Co., Ltd., trade name “Surmount N-718 # 100”], and dried by heating at 150 ° C. for 5 minutes. A prepreg having a resin content of 58% by mass was obtained.
Composition of the resin varnish used:
Bisphenol A type epoxy resin [epoxy equivalent 800-900, manufactured by Japan Epoxy Resin, trade name “Epicoat 1055”] 80 parts by mass Bisphenol A type epoxy resin [epoxy equivalent 184-194, manufactured by Japan Epoxy Resin, trade name “Epicoat” 828 "] 20 parts by mass Dicyandiamide" curing agent "1.5 parts by mass Methyl ethyl ketone" Solvent "300 parts by mass (2) Peelability A test sample prepared in the same manner as in (1) above was subjected to conditions of 23 ° C and 50% RH. After leaving for 1 hour, the process film is peeled by hand, and the peelability is evaluated according to the following criteria.
○: The prepreg does not cause cohesive failure during peeling.
X: The prepreg causes cohesive failure during peeling.
(3) Peeling force A test sample prepared in the same manner as in (1) above was cut into a width of 50 mm and a length of 150 mm and left to stand at 23 ° C. and 50% RH for 1 hour, and then the prepreg surface was a stainless steel plate. The peel strength when the process film was peeled off at a peeling speed of 300 mm / min and a peeling angle of 180 degrees was measured with a tensile tester. The unit is mN / 50 mm.

Example 1
To 100 parts by mass of a mixture of stearyl-modified alkyd resin and methylated melamine resin [manufactured by Hitachi Chemical Co., Ltd., trade name “Tesfine 303”, solid content 20% by mass], 3 parts by mass of p-toluenesulfonic acid was added and mixed. A thermosetting resin solution was prepared.
Next, this thermosetting resin solution was applied to a polyethylene terephthalate (PET) film having a thickness of 19 μm [trade name “Diafoil R310” manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.] using Myerbar # 4, and the temperature was 1 at 130 ° C. It was dried for a minute to form a thermosetting resin layer (resin layer A) having a thickness of 1.0 μm.
Subsequently, 100 parts by mass of a polyfunctional acrylic resin [manufactured by Nippon Kayaku Co., Ltd., trade name “Kayarad DPHA”] and 5 parts by mass of a photopolymerization initiator [manufactured by Ciba Specialty Chemicals, trade name “Irgacure 651”] are mixed. The solution was diluted with methyl ethyl ketone and toluene so that the solid content was 12.5% by mass to prepare an ultraviolet curable resin solution.
Next, the UV curable resin solution is applied to the opposite surface of the PET film on which the thermosetting resin layer is formed using a Myer bar # 4, dried at 80 ° C. for 1 minute, and then irradiated with UV rays at 300 mJ / cm. Irradiation was carried out at a dose of ² to form a 1.0 μm thick UV curable resin layer (resin layer B). Thus, the process film for laminated circuit board manufacture by which the resin layer was formed on both surfaces of the base film was produced, and the performance was evaluated. The results are shown in Table 1.
Example 2
In Example 1, a laminated circuit board was manufactured in the same manner as in Example 1 except that a PET film with a thickness of 38 μm [trade name “Diafoil T100-38” manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.] was used as the base film. Process films were prepared and their performance was evaluated. The results are shown in Table 1.
Example 3
In Example 1, except that an ultraviolet curable resin layer was provided as the resin layer A and a thermosetting resin layer was provided as the resin layer B, a process film for producing a laminated circuit board was produced in the same manner as in Example 1, and the performance was improved. evaluated. The results are shown in Table 1.
Example 4
A UV curable resin solution was applied to one side of a 19 μm-thick PET film [trade name “Diafoil R310” manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.], dried, and irradiated with ultraviolet rays in the same manner as in Example 1. An ultraviolet curable resin layer having a thickness of 1.0 μm was formed. Next, a process film for producing a laminated circuit board having a 1.0 μm-thick UV curable resin layer formed on the opposite surface of the base film and having UV curable resin layers on both sides was prepared in the same manner as described above.
The evaluation results of this process film are shown in Table 1.
Example 5
A thermosetting resin solution was applied to one side of a PET film with a thickness of 19 μm [trade name “Diafoil R310” manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.], and dried at 130 ° C. for 1 minute. Thus, a thermosetting resin layer having a thickness of 1.0 μm was formed. Next, a thermosetting resin layer having a thickness of 1.0 μm was formed on the opposite surface of the base film in the same manner as described above, and a process film for producing a laminated circuit board having thermosetting resin layers on both surfaces was produced.
The evaluation results of this process film are shown in Table 1.
Example 6
In Example 1, a laminated circuit board was produced in the same manner as in Example 1 except that a PET film having a thickness of 50 μm [manufactured by Mitsubishi Chemical Polyester Film Co., Ltd., trade name “Diafoil T100-50S”] was used as the base film. Process films were prepared and their performance was evaluated. The results are shown in Table 1.
Comparative Example 1
In Example 1, the same operation as in Example 1 was performed except that the resin layer A was not provided, and a process for producing a laminated circuit board in which an ultraviolet curable resin layer (resin layer B) was provided on one side of the base film. Films were produced and their performance was evaluated. The results are shown in Table 1.
Comparative Example 2
In Example 1, the same operation as in Example 1 was performed except that the resin layer B was not provided, and a process for producing a laminated circuit board in which a thermosetting resin layer (resin layer A) was provided on one side of the base film. Films were produced and their performance was evaluated. The results are shown in Table 1.

  The process film for manufacturing an integrated circuit board of the present invention can form a good hole at the time of via hole processing, does not cause a problem due to floating or peeling at the time of filling a conductive paste into the hole, and has a peelability from the substrate. It has excellent characteristics and is suitably used as a process film for producing a multilayer circuit board in a build-up type multilayer printed wiring board.

It is a schematic sectional drawing of the sample for a test for evaluating a process film.

Explanation of symbols

1 base film 2 resin layer A
3 Resin layer B
4 process film 5 prepreg 10 test sample

Claims (7)

  A process film for producing a laminated circuit board, comprising a base film and resin layers formed on both sides thereof.   The process film for manufacturing a laminated circuit board according to claim 1, wherein the resin layers formed on both surfaces have a thickness of 0.1 to 10 μm, respectively.   3. The resin layers on both sides formed on the base film are layers made of a cured product of an active energy ray-curable resin composition, or layers made of an alkyd resin and / or an acrylic resin. Process film for manufacturing laminated circuit boards.   The resin layer on one surface formed on the base film is a layer made of a cured product of the active energy ray-curable resin composition, and the resin layer on the other surface is made of an alkyd resin and / or an acrylic resin. The process film for producing a laminated circuit board according to claim 1, wherein the process film is a layer.   The active energy ray-curable resin composition comprises (A) an active energy ray-polymerizable monomer and / or oligomer having two or more polymerizable unsaturated groups in the molecule, and (B) a photopolymerization initiator. The process film for producing a laminated circuit board according to claim 3, which is a mold resin composition.   The process film for producing a laminated circuit board according to claim 3, wherein the alkyd resin and the acrylic resin have a crosslinked structure.   The process film for manufacturing a laminated circuit board according to any one of claims 1 to 6, wherein the base film has a thickness of 10 to 60 µm.

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