WO2006025092A1

WO2006025092A1 - Photosensitive film

Info

Publication number: WO2006025092A1
Application number: PCT/JP2004/012494
Authority: WO
Inventors: Kimihiro Yoshizako; Masao Kubota; Takeshi Ohashi; Tatsuya Ichikawa
Original assignee: Hitachi Chemical Co., Ltd.
Priority date: 2004-08-30
Filing date: 2004-08-30
Publication date: 2006-03-09
Also published as: JPWO2006025092A1

Abstract

A photosensitive film comprising a laminate of a resin film (10) and a photosensitive resin composition layer (14) which can be rolled into a photosensitive element is characterized in that the laminate is provided with a cushion layer (12) exhibiting higher adhesion to the resin film (10) than to the photosensitive resin composition layer (14) between the resin film (10) and the photosensitive resin composition layer (14) for bonding them, the resin film (10) is arranged at one end of the laminate in the laminating direction, the photosensitive resin composition layer (14) is arranged at the other end of the laminate in the laminating direction, and the photosensitive resin composition layer (14) does not substantially exhibit adhesiveness to the resin film (10) at room temperature.

Description

Specification

Photosensitive film

Technical field

[0001] The present invention relates to a photosensitive film.

Background art

[0002] In the field of manufacturing printed wiring boards, as a resist material used for plating, etching, and the like, a photosensitive resin composition and a photosensitive film in which this is laminated on a resin film and covered with a protective film are widely used. You're being. When manufacturing a printed wiring board using such a photosensitive film, first, the photosensitive film is laminated on the substrate, subjected to pattern exposure, and then the unexposed portion is removed with a developer. Plating or etching treatment is performed and finally the hardened portion is peeled off from the substrate.

[0003] In recent years, the density of printed wiring boards has been increased, and a high resolution of the photosensitive film is required. A thin film of the photosensitive resin composition layer is effective for increasing the resolution of the photosensitive film. However, since the amount of the photosensitive resin composition layer that follows the surface irregularities of the substrate decreases, However, this photosensitive film has a problem that the unadhered portion between the substrate and the photosensitive resin composition layer increases, and a sufficient production yield cannot be obtained.

[0004] Also, in the conventional photosensitive film, when the photosensitive resin composition layer is thinned, the resin film is required to have a predetermined thickness and hardness in order to maintain the strength required for the photosensitive film. Is done. Therefore, the flexibility of the entire photosensitive film is reduced, and the photosensitive resin composition layer hardly follows the irregularities on the surface of the substrate to be laminated. As a result, the substrate and the photosensitive resin composition layer There were many unbonded parts, and there was a problem that sufficient production yield could not be obtained.

[0005] Various methods have been proposed to improve such problems. For example, a method of laminating a photosensitive film after applying water to a substrate (see, for example, Patent Document 1 and Patent Document 2). ), Laminating a liquid resin on the substrate to form an adhesive intermediate layer, and then laminating the photosensitive film (see, for example, Patent Document 3), laminating the photosensitive film under reduced pressure using a vacuum laminator. (For example, see Patent Document 4 and Patent Document 5) Has been.

[0006] Further, for high resolution requirements, the resolution can be greatly improved if exposure can be performed with a pattern mask directly attached to the photosensitive resin composition layer. However, the conventional photosensitive resin composition layer has high adhesiveness, and if the pattern mask is directly adhered, the pattern mask is difficult to peel due to the adhesiveness, and further, the pattern mask is contaminated. There was a problem. Therefore, a photosensitive film in which a non-adhesive photosensitive resin composition layer, an adhesive photosensitive resin composition layer, and a protective film are sequentially laminated on a resin film (for example, Patent Document 6 and Patent Reference 7) has been proposed.

[0007] In recent years, a method for reducing waste has been demanded from the viewpoint of measures against environmental problems. The protective film used in the conventional photosensitive film is used only to protect the photosensitive resin composition layer when the photosensitive film is wound and stored in a tool shape, and the protective film is used. Waste can be reduced if the photosensitive film can be rolled up and stored in a roll. However, when a photosensitive film having a structure in which a resin film and a photosensitive resin composition layer having a high adhesive strength are sequentially laminated is scraped in a tool shape, the photosensitive resin composition layer is formed on both sides of the resin film. However, it becomes difficult to laminate the resin film and the photosensitive resin composition layer on the substrate. Therefore, a method in which the back surface of the resin film is treated with a release layer so that the photosensitive resin composition layer adheres only on the surface of the resin film (see, for example, Patent Document 8), the photosensitive resin composition on the resin film. A method of sequentially laminating a layer and a non-adhesive outer layer (for example, see Patent Document 9) has been proposed.

[0008] Patent Document 1: Japanese Patent Laid-Open No. 57-21890

Patent Document 2: Japanese Patent Application Laid-Open No. 57-21891

Patent Document 3: JP-A 52-154363

Patent Document 4: Japanese Patent Publication No.53-31670

Patent Document 5: Japanese Patent Application Laid-Open No. 51-63702

Patent Document 6: JP-A-2-230149

Patent Document 7: Japanese Patent Laid-Open No. 3-17650 Patent Document 8: US Pat. No. 4,293,635

Patent Document 9: Japanese Unexamined Patent Publication No. 2001-175000

Disclosure of the invention

Problems to be solved by the invention

[0009] However, in the manufacturing methods described in Patent Documents 1 and 2, in order to uniformly deposit a thin layer of water, the substrate surface must be cleaned, and when there are small-diameter through-holes, The moisture and the photosensitive resin composition layer that have accumulated in the through holes react with each other to immediately reduce the developability, resulting in problems such as insufficient production yield.

[0010] In addition, in the manufacturing method described in Patent Document 3, a sufficient production yield cannot be obtained because the developability and peelability of small-diameter through-holes are reduced, and there are problems such as an increase in cost due to liquid resin coating. was there.

[0011] Further, in the manufacturing methods described in Patent Documents 4 and 5, since the apparatus is expensive and time is required for evacuation, it is rarely used for normal circuit formation after the conductor is formed. It is only used as a permanent mask laminate. Even when the permanent mask is laminated, it is desired to further improve the followability to the conductor.

[0012] And, the photosensitive film described in Patent Document 69 has a photosensitive resin composition that follows the surface irregularities of the substrate when the photosensitive resin composition layer is thinned for higher resolution. In order to reduce, the unadhered part of a board | substrate and the photosensitive resin composition layer increased, and there existed a problem that sufficient manufacture yield was not obtained.

The present invention has been made in view of the above problems, and even when the photosensitive resin composition layer is thinned, the photosensitive resin composition layer follows the unevenness of the surface of the adherend. Laminating with good properties, generation of unadhered parts between the adherend and the photosensitive resin composition layer is sufficiently suppressed, and a high production yield can be realized, and a roll can be formed without using a protective film. An object of the present invention is to provide a photosensitive film that can be scraped off and stored, and can be laminated with the photosensitive resin composition layer on the adherend by releasing the roll force when used. Means for solving the problem

In order to achieve the above object, the present invention comprises a resin film and a photosensitive resin composition layer. A photosensitive element that can be rolled up in a roll shape, and the laminated body binds them between the resin film and the photosensitive resin composition layer. A cushion layer having an adhesive force with respect to the resin film greater than an adhesive force with respect to the photosensitive resin composition layer; the resin film is disposed at one end in the stacking direction of the laminate; and the photosensitive resin composition layer Is disposed at the other end of the laminate in the laminating direction, and the photosensitive resin composition layer does not substantially exhibit adhesiveness to the resin film at room temperature. I will provide a.

[0015] Here, the photosensitive resin composition layer is “not substantially sticky at room temperature to the resin film” means that the resin film and the photosensitive resin composition layer are at room temperature (20 This means that the adhesive (adhesive) force of the photosensitive resin composition layer to the resin film when it is manually press-bonded at ° C) is so small that the resin film peels from the photosensitive resin composition layer by its own weight. Here, when the photosensitive resin composition layer does not substantially stick to the resin film at room temperature, the adhesive strength of the photosensitive resin composition layer to the resin film (180 ° peel strength, J IS Z 0237 ) Is preferably 5 N / m or less at 20 ° C. and 60% RH.

[0016] In the laminate including the resin film, the photosensitive resin composition layer, and the cushion layer constituting the photosensitive element, the resin film is disposed at one end in the stacking direction of the laminate, and the photosensitive resin. The composition layer is disposed at the other end in the stacking direction of the stacked body. That is, the photosensitive element does not have a protective film on the photosensitive resin composition layer. Here, the “protective film” refers to a film made of an inert polyolefin film such as polyethylene or polypropylene for protecting the photosensitive resin composition layer during storage of the photosensitive film.

[0017] Since the photosensitive film of the present invention includes the cushion layer, the conventional photosensitive film cannot be laminated on the resin film, and has substantially adhesiveness to the resin film at room temperature. It becomes possible to laminate a photosensitive resin composition layer not shown. The photosensitive film of the present invention having a photosensitive resin composition layer that does not substantially exhibit adhesiveness to the resin film can be rolled up and stored without using a protective film. When the roll force is unwound, it can be easily unwound between the resin film and the photosensitive resin composition layer. Therefore, it does not require a protective film, Waste and cost can be reduced.

[0018] In addition, the photosensitive film of the present invention having a cushion layer is photosensitive at the time of lamination due to the presence of the cushion layer even when the photosensitive resin composition layer is thinned for higher resolution. The resin composition layer can be closely adhered along the unevenness of the adherend surface, and the occurrence of unbonded portions between the adherend and the photosensitive resin composition layer can be sufficiently suppressed. Thus, a sufficient production yield can be obtained.

[0019] Furthermore, since the cushion layer has a greater adhesive force to the resin film than an adhesive force to the photosensitive resin composition layer, when the resin film is peeled from the photosensitive resin composition layer, The cushion layer can be integrally peeled off at the same time, and work efficiency can be improved.

[0020] Further, in order to obtain the above-described effect of the present invention more reliably, in the photosensitive film, the adhesive force of the photosensitive resin composition layer to the resin film is 5 N / m or less, The adhesive force of the cushion layer to the resin film is preferably 1 ON / m or more, and the adhesive force of the cushion layer to the photosensitive resin composition layer is preferably 0.5-10 N / m.

[0021] The photosensitive film of the present invention satisfying the relationship of strong adhesive force is from a state of being rolled up so that the resin film and the photosensitive resin composition layer are in contact with each other without using a protective film. In addition, the resin film and the photosensitive resin composition layer can be more easily and reliably unwound, and the resin film and the cushion layer can be more reliably removed when the resin film is peeled from the photosensitive resin composition layer. Can be simultaneously peeled off.

[0022] Furthermore, in the photosensitive film, it is preferable that the adhesive force of the tack layer to the photosensitive resin composition layer is larger than the adhesive force of the photosensitive resin composition layer to the resin film.

[0023] The photosensitive film of the present invention satisfying the relationship between force and adhesive strength can be more easily and reliably unraveled between the resin film and the photosensitive resin composition layer from the state of being rolled up. Is possible.

The invention's effect

[0024] According to the photosensitive film of the present invention, when the photosensitive resin composition layer is thinned, However, the photosensitive resin composition layer is laminated with good conformity to the irregularities on the surface of the adherend, and the occurrence of unbonded portions between the adherend and the photosensitive resin composition layer is suppressed, so that a high production yield can be achieved. Can be realized. Further, since the photosensitive film of the present invention has excellent followability, it has the advantage that it can be laminated as it is using a conventional laminating apparatus. Furthermore, the photosensitive film of the present invention can be rolled up without using a protective film, and can be easily unwound between the resin film and the photosensitive resin composition layer when unrolling. , Waste and cost can be reduced Brief description of the drawings

FIG. 1 is a cross-sectional view of a photosensitive film that is useful in an embodiment of the present invention.

FIG. 2 (a) is a perspective view when the photosensitive film of FIG. 1 is rolled up, and FIG. 2 (b) is an enlarged cross-sectional view inside the broken line of (a).

FIG. 3 (a) and (e) are process diagrams schematically showing a first method of forming a resist pattern using the photosensitive film of the present invention.

[FIG. 4] (a) and (d) are process diagrams schematically showing a second method of forming a resist pattern using the photosensitive film of the present invention.

Explanation of symbols

[0026] 1 ... photosensitive film, 10 ... resin film, 12 ... cushion layer, 14 ... photosensitive resin composition layer, 18 ... circuit forming substrate, 22 ... pattern mask.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, preferred embodiments of the photosensitive film according to the present invention will be described with reference to the drawings. In the description of the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. In addition, (meth) acrylic acid in the present invention means acrylic acid and methacrylic acid corresponding to it, (meth) acrylate means acrylate and corresponding metatalylate, and (meth) acryloyl group means It means an allyloyl group and the corresponding methacryloyl group.

FIG. 1 is a cross-sectional view showing the photosensitive film 1 of the present invention, and FIG. 2 (a) is a perspective view of the photosensitive film 1 of FIG. 2 (b) shows the expansion inside the broken line in Fig. 2 (a). It is a big picture.

As shown in FIG. 1, the photosensitive film 1 is composed of a laminate including a resin film 10 and a photosensitive resin composition layer 14 and a cushion layer 12 for binding them. . The cushion layer 12 has an adhesive force to the resin film 10 larger than an adhesive force to the photosensitive resin composition layer 14. The photosensitive film 1 is not provided with a protective film on the surface F1 of the photosensitive resin composition layer 14 opposite to the cushion layer 12, and the photosensitive resin composition layer 14 is a resin film as the outermost layer. It is arranged at the position farthest from 10 in the stacking direction of the stack.

In addition, the photosensitive film 1 can be stored in the form of a roll by winding one end of the photosensitive film 1 on a core 16 as shown in FIG. 2 (a) during storage. . At this time, as shown in FIG. 2 (b), the resin film 10 and the photosensitive resin composition layer 14 are in contact with each other, but the photosensitive resin composition layer 14 is substantially in contact with the resin film 10. Therefore, when the photosensitive film 1 is unrolled, it can be easily unwound between the resin film 10 and the photosensitive resin composition layer 14.

[0031] Here, the adhesive strength of the cushion layer 12 to the photosensitive resin composition layer 14 is tl, the adhesive strength of the cushion layer 12 to the resin film 10 is t2, and the photosensitive resin composition layer 14 to the resin film 10 is When the adhesive strength is t3, tl is preferably 0.5-10 N / m, more preferably 1-5 N / m. If tl is less than 0.5 N / m, air tends to easily enter between the cushion layer 12 and the photosensitive resin composition layer 14 during lamination, and if it exceeds 10 N / m, the resin film 10 and the cushion When the layer 12 is peeled from the photosensitive resin composition layer 14, the photosensitive resin composition layer 14 tends to peel off at the same time.

[0032] Further, t2 is preferably 10 N / m or more, more preferably lOONZm or more. When t2 is less than 10 N / m, the cushion layer 12 tends to be easily peeled from the resin film 10 when the resin film 10 and the cushion layer 12 are peeled from the photosensitive resin composition layer 14.

[0033] Furthermore, t3 needs to be 5 N / m or less, preferably 2 NZm or less, more preferably 0.5 NZm or less, and even more preferably 0.3 NZm or less. If t3 exceeds 5 N / m, roll photosensitive film 1 in a roll and store it. When the photosensitive film 1 is laminated to the substrate so that the photosensitive resin composition layer 14 is peeled from the resin film 10 and the photosensitive resin composition layer 14 is in contact with the substrate, It is easy to get wrinkles or streaks into film 1. Further, when exposure is performed with the pattern mask in close contact with the photosensitive resin composition layer 14, there is a possibility that the pattern mask is contaminated by the photosensitive resin composition layer 14.

[0034] Further, the value of tl / t3 and the value of t2Ztl are each preferably 1.05 or more, more preferably 1.5 or more, and further preferably 2.0 or more. When the value of tlZt3 is 1.05 or more, when the photosensitive film 1 that has been scraped off and stored in a roll is unwound from the roll, it is more between the resin film 10 and the photosensitive resin composition layer 14. It tends to be easy and reliable. Further, when the value of t2 / tl is 1.05 or more, when the resin film 10 is peeled from the photosensitive resin composition layer 14, the resin film 10 and the cushion layer 12 are in a bound state. It tends to be possible to peel them off at the same time. Note that tl, t2 and t3 indicate 180 ° peel strength between each layer at 20 ° C and 60% RH (also called peel strength or peel adhesion), and the peel strength conforms to JIS Z 0237. It can be measured under the test conditions of a specimen width of 20mm and a pulling speed of 300mm / min.

[0035] As the resin film 10 useful for the present invention, for example, a polymer film having heat resistance and solvent resistance, such as polyethylene terephthalate, polypropylene, polyethylene, and polyester, is preferably used. Such a resin film 10 may have a single layer structure or a laminated structure in which films having a plurality of compositions are laminated.

[0036] The thickness of the resin film 10 is preferably 2-100 / im, more preferably 5-20 / im, and particularly preferably 8-16zm. If this thickness is less than 10%, the resin film 10 tends to be easily broken when the resin film 10 is peeled off.

When the thickness exceeds 0 μm, the flexibility of the photosensitive film 1 as a whole is lowered, and the followability to the unevenness of the surface to be laminated tends to be lowered.

[0037] The photosensitive resin composition layer 14 useful for the present invention comprises (A) a binder polymer, (B) a photopolymerizable compound having an ethylenically unsaturated bond, and (C) a photopolymerizable initiator. It is preferable that it is a layer which consists of a photosensitive resin composition containing this. [0038] Here, the binder polymer as component (A) preferably contains a carboxyleno group from the viewpoint of alkali developability. For example, a polymerizable monomer having a carboxynole group and other monomers It can be produced by radical polymerization of a polymerizable monomer. As the polymerizable monomer having a strong lpoxyl group, methacryloleic acid, acrylic acid, maleic acid and the like are preferable.

[0039] (A) The acid value of the binder polymer is preferably 50 500 mgK0H / g, more preferably 100-300 mgKOHZg. When the acid value is less than 50 mg KOHZg, the development time tends to be remarkably delayed, and when it exceeds 500 mg KOHZg, the developer resistance of the photocured resist tends to be lowered.

[0040] (A) The weight average molecular weight of the binder polymer is preferably 5,000 to 300,000, more preferably 10,000 to 150,000. When the weight average molecular weight force S is less than 5,000, the developer resistance tends to be remarkably lowered, and when it exceeds 300,000, the development time tends to be longer. The weight average molecular weight and number average molecular weight in the present invention are values measured by gel permeation chromatography and converted to standard polystyrene.

[0041] In addition, the binder polymer as component (A) preferably contains styrene or a styrene derivative as a polymerizable monomer because of its flexible standpoint. Examples of the styrene derivative include α-methylstyrene.

[0042] When the above styrene or styrene derivative is contained as a polymerizable monomer, from the viewpoint of improving both adhesion and release properties, 0.1 to 70% by weight based on the total weight of the monomer It is preferable to contain 1 to 60% by weight. It is particularly preferable to contain 1.5 to 50% by weight. If the content is less than 0.1% by weight, the adhesion tends to be inferior, and if it exceeds 70% by weight, the peeled piece becomes remarkably large and the peel time becomes longer.

[0043] (ii) Examples of the binder polymer include acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, phenol resins, and the like. From the viewpoint of alkali developability, an acrylic resin is preferable. These can be used alone or in combination of two or more. [0044] (A) The binder polymer can be produced, for example, by radical polymerization of a polymerizable monomer. Examples of the polymerizable monomer include polymerizable styrene derivatives substituted at the α-position or aromatic ring such as styrene, birtoluene, α-methylstyrene, acrylamide such as diacetone acrylamide, acrylonitrile, Vinylol esters of butyl alcohol such as η_butyl ether, (meth) acrylic acid alkyl esters, (meth) acrylic acid tetrahydrofurfuryl esters, (meth) acrylic acid dimethylaminoethyl esters, (meth) acrylic acid jetyls Aminoethyl ester, (Meth) acrylic acid glycidyl ester, 2, 2, 2_trifluoroethyl (meth) acrylate, 2, 2, 3, 3-tetrafluoropropyl (meth) acrylate, (meta ) Acrylic acid, bromo (meth) acrylic acid, chloro ( M) Acrylic acid, / 3-Frinole (meth) acrylic acid, / 3-Styrinole (meth) acrylic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, etc. Examples include acid monoesters, fumaric acid, cinnamic acid, α_cyanocycin acid, itaconic acid, crotonic acid, and propiolic acid.

As the above (meth) acrylic acid alkyl ester, for example, the following general formula (II)

CH = C (R ³ ) _CO ○ R ⁴ (II)

2

[Wherein R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents an alkyl group having 1 to 12 carbon atoms.

₀ ]

And compounds in which the alkyl group of these compounds is substituted with a hydroxyl group, an epoxy group, a halogen group or the like.

[0046] Examples of the alkyl group having 1 to 12 carbon atoms represented by R ⁴ in the general formula (II) include, for example, a methylol group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and heptyl. Group, octyl group, nonyl group, decyl group, undecinole group, dodecyl group and structural isomers thereof. Examples of the monomer represented by the general formula (II) include, for example, (meth) atalinoleic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester maleate, (meth) acrylic acid butyl ester, (Meth) acrylic acid pentyl ester, (meth) acrylic acid hexyl ester, (meth) acrylic acid heptyl ester, (meth) acrylic acid octanoester, (meth) acrylic acid 2_ethylhexyl ester, (meta ) Nonyl ester of acrylic acid, (meth) decyl acrylate, (meth) undecyl acrylate, ( ) Acrylic acid dodecyl ester and the like. These can be used alone or in combination of two or more.

[0047] The binder polymer as component (A) in the present invention includes (anhydrous) phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, (anhydrous) maleic acid, fumaric acid, adipic acid trianhydride. Divalent or higher carboxylic acids such as merit acid and pyromellitic anhydride and ethylene glycol, propylene glycol, 1,3-butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, neopentyl glycol, hydrogenated biphenolate A, Polyester resins obtained by esterification with dihydric or higher alcohols such as glycerin and trimethylolpropane can also be used. Examples of the epoxy resin include bisphenol epoxy resin, novolac epoxy resin, and the like, and those added with monovalent carboxylic acids such as acetic acid, oxalic acid, and (meth) acrylic acid.

[0048] These (A) binder polymers are used alone or in combination of two or more. Examples of the binder polymer used in combination of two or more types include, for example, two or more types of binder polymers composed of different copolymerization components, two or more types of binder polymers having different weight average molecular weights, and two having different dispersities. More than one type of binder polymer. The degree of dispersion here means the value of weight average molecular weight / number average molecular weight.

[0049] From the viewpoint of improving the resolution, the photopolymerizable compound having an ethylenically unsaturated bond as the component (B) is prepared from 2, 2_bis (4-(((meth) ataryloxypolyalkoxy) phenyl) propane. It is particularly preferable when the thickness of the photosensitive resin composition layer 14 that is preferably contained is 0.1-15 / m. 2, 2-Bis (4 (((meth)) aryloxypolyalkoxy) phenyl) The thickness of the propane-containing photosensitive resin composition layer 14 is more from the viewpoint of higher density printed wiring and higher resolution. It is preferably 1 to 15 zm, more preferably 2 to 7 μm.

[0050] The above 2,2_bis (4-((meth) atalyloxypolyalkoxy) phenyl) propane is used alone or in combination with other polymerizable compounds. Further, 2,2_bis (4 ((meth) atalyloxypolyalkoxy) phenyl) propane is preferably one having a structure represented by the following general formula (I). [Chemical 1]

[0051] In the above general formula (I), R ¹ and R ² each independently represent a hydrogen atom or a methyl group, preferably a methyl group. In the above general formula (I), X ¹ and X ² each independently represents an alkylene group having 2 to 6 carbon atoms, more preferably an ethylene group or a propylene group. In the above general formula (I), p and q are positive integers selected so that p + q = 4-40, and the value of p + q is preferably 6 34 8 30 That power S is more preferred 8 28 is more preferred 8 20 is particularly preferred 8 16 is highly preferred 8 16 is most preferred 8-12. When the value of p + q is less than 4, the compatibility with (A) the binder polymer that is one of the components constituting the photosensitive resin composition layer 14 is lowered, and the photosensitive film is laminated on the circuit forming substrate. When the value of p + q exceeds 40, the hydrophilicity increases, and the resist image tends to be peeled off during development or the resistance to plating against immediate soldering tends to decrease. .

[0052] Examples of the alkylene group having 2 to 6 carbon atoms include an ethylene group, a propylene group, an isopropylene group, a butylene group, a pentylene group, and a hexylene group. From the viewpoint of force S, resolution, and plating resistance, Group, isopropylene group is preferred.

[0053] The aromatic ring in the general formula (I) may have a substituent. Examples of the substituent include a halogen atom, an alkyl group having 1 to 20 carbon atoms, and a carbon number of 3— 10 cycloal Kill group, aryl group having 6 to 18 carbon atoms, phenacyl group, amino group, alkynoleamino group having 1 to 10 carbon atoms, dialkylamino group having 2 to 20 carbon atoms, nitro group, cyano group, carbonyl group, mercapto group, C 11 -C 10 alkyl mercapto group, allyl group, hydroxyl group, C 1 -C 20 hydroxyalkyl group, carboxyl group, alkyl group having 1 to 10 carbon atoms Rboxyalkyl group, alkyl group carbon number 1 1 to 10 acyl group, 1 to 20 alkoxy group, 1 to 20 alkoxy group, 1 to 20 alkoxy group, 2 to 10 alkyl group, norebonyl group, 2 to 10 alkenyl group, 2 to 10 carbon atoms And an N-alkylcarbamoyl group or a group containing a heterocyclic ring, an aryl group substituted with these substituents, and the like. The above substituents may form a condensed ring. In addition, hydrogen atoms in these substituents may be substituted with the above substituents such as halogen atoms. When the number of substituents is 2 or more, each of the two or more substituents may be the same or different.

[0054] Examples of the compound represented by the general formula (I) include 2, 2_bis (4-((meth) atarioxyxypolyethoxy) phenyl) propane, 2, 2_bis (4- (Meth) Atalyloxypolypropoxy) Phenyl) propane, 2, 2_bis (4 -— ((Meth) Atalyloxypolybutoxy) phenyl) Propane, 2, 2_Bis (4 -— ((Meth) Atalyloxypoly Examples thereof include bisphenol A-based (meth) ataretoy compounds such as ethoxypolypropoxy) phenyl) propan and the like.

[0055] Examples of the 2,2_bis (4 ((meth) atalyloxypolyethoxy) phenyl) propane include 2,2_bis (4-(((meth) atalyoxydiethoxy) phenyl) propane, 2, 2_bis (4- (((meth)) talyloxytriethoxy) phenyl) propane, 2,2-bis (4-(((meth) atalyloxytetraethoxy) phenyl) propane, 2, 2-bis (4- (((Meth) Atalyloxypentaethoxy) phenyl) propane, 2, 2_bis (4 — (((Meth) Atalyloxyhexaethoxy) phenyl) propane, 2, 2_bis (4 — (((Meth) Atalyloxyheptaethoxy) ) Phenyl) propane, 2, 2 —bis (4 — ((meth) atarioxyxethoxyethoxy) phenyl) propane, 2,2-bis (4 — (((meth) atalyloxynonaethoxy) phenyl) propane, 2 , 2—Bis (4— ((Meta ) Atari mouth oxyde force (Ethoxy) phenyl), 2, 2_bis (4— ((meth) Atari mouth xydeca ethoxy) phenyl), 2, 2—bis (4— ((meth) Atari Roxydodecaethoxy) phenyl), 2,2-bis (4-((meth) acryloxytridecaethoxy) phenyl), 2,2-bis (4-((meth) atarioxyxydecadecoxy) phenyl ), 2, 2_bis (4-(((meth)) talyloxypentadecaethoxy) phenyl), 2, 2_bis (4 _ ((meth) atoxyhexadex ethoxy) phenyl), etc., and 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is a BPE-500 (new Nakamura Kagaku Kogyo Co., Ltd. (product name) is commercially available, and 2, 2-bis (4- (methacryloxypentadecaethoxy) phenyl) is BPE_1300 (Shin Nakamura ), Product name) and commercially available. These may be used alone or in combination of two or more.

[0056] Examples of the 2,2_bis (4-(((meth)) talyloxypolypropoxy) phenyl) propane include, for example, 2,2_bis (4-(((meth) atalyoxydipropoxy) phenyl) propane. 2, 2-bis (4-(((meth) acryloyltripropoxy) phenyl) propane, 2, 2_bis (4-(((meth) acryloxytetrapropoxy) phenyl) propane, 2, 2_bis (4-(((Meth) Atarioxypentapropoxy) phenyl) propane), 2, 2_bis (4 — (((Meth) Atalyloxyhexapropoxy) phenyl) propane, 2, 2_bis (4 — ((Meta ) Ataryloxyheptapropoxy) Feninore) Propane, 2, 2_bis (4 — (((Meth) Atarioxyxapropoxy) Phenyl) Propane, 2, 2 Bis (4 (((Meth) Atalyloxynonapropoxy) ) Hueninore) Propa , 2, 2 bis (4- ((meth) atari mouth oxyde propoxy) phenyl), 2, 2-bis (4- ((meth) atta oxydeca propoxy) phenyl), 2, 2 _Bis (4-(((Meth) Atalyloxidedecapropoxy) phenyl), 2,2-Bis (4-(((Meth) Atalyloxytridecapropoxy) phenyl), 2,2-Bis (4- ( (Meth) atari-oxytetradecapropoxy) phenyl), 2, 2-bis (4- ((meth) ataloxypentadecapropoxy) phenyl), 2, 2_bis (4— ((meta) Atari mouth hexade force propoxy) phenyl) and the like. These may be used alone or in combination of two or more.

[0057] Examples of the 2,2_bis (4-(((meth)) talyloxypolyethoxypolypropoxy) phenyl) propan include, for example, 2,2_bis (4-(((meth)) talioxydiethoxy) Kutapropoxy) phenyl) propane, 2,2_bis (4 — (((meth) atalyoxytetraethoxytetrapropoxy) phenyl) propane, 2,2_bis (4 — (((meth)) talyloxyhexaethoxyhexa And propoxy) phenyl) propane. These may be used alone or in combination of two or more.

[0058] (B) The photopolymerizable compound having an ethylenically unsaturated bond includes 2, 2_bis as described above. In addition to the force for which (4 _ ((meth) ataryloxypolyalkoxy) phenyl) propane is preferably used, various photopolymerizable compounds can be used. For example, a compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid, a compound obtained by reacting a glycidyl group-containing compound with j3 _unsaturated carboxylic acid, a urethane monomer, non-phenol Enildioxylene (meth) atalylate, γ—Black mouthpiece / 3—Hydroxypropyl _ / 3, One (meth) Ataloyloxychettinore _ο—Phthalate, / 3—Hydroxyethyl —j3 '— ( And (meth) acryloyloxychetyl _o_phthalate, / 3-hydroxypropyl _'- (meth) attaylyloxychetyl o_phthalate, (meth) acrylic acid alkyl ester and the like.

[0059] Examples of the compound obtained by reacting the polyhydric alcohol with 3,3-unsaturated carboxylic acid include, for example, polyethylene glycol di (meth) acrylate, propylene having a number of ethylene groups of 214. Polypropylene glycol di (meth) acrylate with 2-14 groups, trimethylolpropane ethoxytri (meth) acrylate, trimethylol propanediethoxy tri (meth) acrylate, trimethylol propane triethoxy tri ( (Meth) acrylate, trimethylol propane tetraethoxy tri (meth) acrylate, trimethylol propane penta ethoxy tri (meth) acrylate, tetramethylol methane tri (meth) acrylate, tetramethylol methane tetra (meth) acrylate, number of propylene groups 2 14 is a polypropylene grayed Rikoruji (meth) Atari rate, dipentaerythritol penta (meth) Atari rate, to Jipen data erythritol hexa (meth) Atari rate, and the like.

[0060] Examples of the α 1, β 2 -unsaturated carboxylic acid include (meth) acrylic acid and the like.

[0061] Examples of the glycidinole group-containing compound include trimethylolpropane triglycidyl ether tri (meth) acrylate, 2,2-bis (4- (meth) talyloxy-2-hydroxy-propyl pyroxy) phenyl, and the like. Can be mentioned.

[0062] Examples of the urethane monomer include (meth) acrylic monomers having a Η group at the β-position, isophorone diisocyanate, 2, 6_toluene diisocyanate, 2, 4_toluene diisocyanate, 1 , 6_ Hexamethylene diisocyanate, etc., reaction product with tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, O-modified urethane di (meth) acrylate, EO, PO-modified urethane di (meth) acrylate. Note that EO represents ethylene oxide, and the EO-modified compound has a block structure of an ethylene oxide group. PO represents propylene oxide, and the PO-modified compound has a block structure of propylene oxide groups.

[0063] Examples of the (meth) acrylic acid alkyl ester include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid 2_ethylhexyl. Examples include esters.

[0064] These (B) photopolymerizable compounds having an ethylenically unsaturated bond include 2,2-bis (41-((meth) atalyloxypolyalkoxy) phenyl) propane, alone or in combination of two or more. Used in combination.

[0065] Examples of the photopolymerization initiator as component (C) include benzophenone, N ,, '-tetramethylolene 4,4'-diaminobenzophenone (Michler ketone), 4,4'one bisjetylamino. Benzophenone, Ν, N'-Tetraethinole 4, 4'-Diaminobenzozoenone, 4-Methoxy-1-4'-dimethylaminobenzophenone, 2_benzyl-2-dimethylamino_1_ (4-morpholinophenyl) -butanone 1, 2-Methylenole 1_ [4_ (Methylthio) phenyl] —2_morpholinopropanone 1 and other aromatic ketones, 2-ethyl anthraquinone, phenanthrenequinone, 2-tert-butyl anthraquinone, Ottamethyl anthraquinone, 1,2-benzanthraquinone, 2,3-benthanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1 croro Quinones such as anthraquinone, 2-methylanthraquinone, 1,4 mononaphthoquinone, 9,10-phenanthara quinone, 2-methinole 1,4-naphthoquinone, 2,3-dimethylanthraquinone, benzoin methyl ether, benzoinethyl ether Benzoin ether compounds such as benzoin phenyl ether, benzoin compounds such as benzoin, methyl benzoin and ethyl benzoin, benzyl derivatives such as benzyl dimethyl 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) — 4, 5—Diphenylimidazolunimer, 2 _ (p-methoxyphenyl) — 4, 5— Phenylene Ruimidazo one Runi mer 2 such, 4, 5_ Toriari Ruimidazo one Runi monomer, 9-phenylene Ruakurijin, 1, 7_ bis (9, 9, - Atarijiniru) Cheb Atanidine derivatives such as tan, N_phenyldaricin, N_phenyldaricin derivatives, tamarin compounds and the like. In addition, the aryl group substituents of the two 2, 4, 5-triarylimidazoles may be the same and give the target compound, or differently asymmetric compounds. In addition, thixanthone compounds and tertiary amine compounds may be combined, such as a combination of jetylthioxanthone and dimethylaminobenzoic acid. From the standpoint of adhesion and sensitivity, 2,4,5-triarylimidazole dimer is more preferred. These may be used alone or in combination of two or more.

[0066] The blending amount of component (A) is preferably 30 to 80 parts by weight, with the total amount of component (A) and component (B) being 100 parts by weight. preferable. If the blending amount is less than 30 parts by weight, the photocured product tends to be brittle and the coating property tends to be poor when used as a photosensitive film, and if it exceeds 80 parts by weight, the photosensitivity tends to be insufficient. .

[0067] The blending amount of component (B) is preferably 30-55 parts by weight, preferably 20 60 parts by weight, with the total amount of component (A) and component (B) being 100 parts by weight. preferable. If this amount is less than 20 parts by weight, the photosensitivity tends to be insufficient, and if it exceeds 60 parts by weight, the photocured product tends to become brittle.

[0068] The blending amount of component (C) is preferably 0.1 to 20 parts by weight, with the total amount of component (ii) and component (ii) being 100 parts by weight. 0.2-10 parts by weight More preferably, it is a part. If the blending amount is less than 0.1 part by weight, the photosensitivity tends to be insufficient, and if it exceeds 20 parts by weight, the absorption at the surface of the composition increases during exposure and the internal photocuring is not satisfactory. There is a tendency to be sufficient.

[0069] In addition, the photosensitive resin composition layer 14 may be coated with a dye such as malachite green, a photochromic ljj such as tribromophenylsulfone or leucocrystal violet, a thermochromic inhibitor, P if necessary. -Plasticizers such as toluenesulfonamide, pigments, fillers, antifoaming agents, flame retardants, stabilizers, adhesion promoters, leveling agents, peeling accelerators, antioxidants, fragrances, imaging agents, thermal crosslinking The agent can be contained in an amount of about 0.01-20 parts by weight per 100 parts by weight of the total amount of component (A) and component (B). These may be used alone or in combination of two or more.

[0070] The photosensitive resin composition layer 14 is used for increasing the density and resolution of printed wiring. Therefore, it is preferable that the thickness is 0 · 1—50 μ Sη S, more preferably 0.1—25 / im 1 1 15 μ ΐη is still more preferable 1 1 8 / It is particularly preferable to be im, and 2-7 / m is most preferable. According to the photosensitive element 1 of the present invention, even when the photosensitive resin composition layer 14 is thin-filmed in this way, the photosensitive resin composition layer has good follow-up along the unevenness of the adherend surface. 14 can be laminated.

[0071] Further, the transmittance of the photosensitive resin composition layer 14 with respect to ultraviolet rays having a wavelength of 365 nm is preferably 575%, more preferably 760%, and more preferably 1040%. Particularly preferred. If the transmittance is less than 5%, the adhesion tends to be inferior, and if it exceeds 75%, the resolution tends to be inferior. The transmittance can be measured with a UV spectrometer. Examples of the UV spectrometer include a 228A type W beam spectrophotometer manufactured by Hitachi, Ltd.

[0072] Further, the photosensitive resin composition layer 14 may have a laminated structure in which two or more photosensitive resin composition layers having different compositions and the like are laminated. In this case, the relationship of the adhesive force between the photosensitive resin composition layer 14 and the cushion layer 12 described above is satisfied and reduced between the photosensitive resin composition layer on the cushion layer 12 side and the cushion layer 12. The above-mentioned relationship of adhesive strength between the photosensitive resin composition layer 14 and the resin film 10 is satisfied between the photosensitive resin composition layer on the opposite side of the cushion layer 12 and the resin film 10. I'll be done.

[0073] Preferably, the cushion layer 12 useful for the present invention contains a copolymer of ethylene and a monomer copolymerizable with the ethylene. More preferably, it is an ethylene-ethyl (meth) acrylate copolymer. Here, the ratio of ethylene based on the total amount of monomers constituting the copolymer in the ethylene vinyl acetate copolymer, and the copolymer in the ethylene ethyl (meth) acrylate copolymer The proportion of ethylene based on the total amount of the constituent monomers is preferably 50 to 90% by weight, more preferably 50 to 80% by weight, and even more preferably 50 to 70% by weight. When the proportion of ethylene is less than 50% by weight, even when a copolymer is used, the adhesion between the cushion layer 12 and the photosensitive resin composition layer 14 tends to be too high and peeling tends to be difficult. is there. On the other hand, when the proportion of ethylene exceeds 90% by weight, the cushion layer 12 and the photosensitive resin are used in any copolymer. Adhesiveness with the fat composition layer 14 tends to be too small, and it becomes difficult to produce the photosensitive film 1 including the cushion layer 12.

[0074] The thickness of the cushion layer 12 is preferably 1 to 100 µm, preferably 5 to 50 µm, more preferably force S, and particularly preferably 10 to 40 zm. When the thickness of the cushion layer 12 is less than 1 zm, the followability to the unevenness of the surface to be laminated tends to decrease. On the other hand, when the thickness exceeds 100 zm, the cost tends to increase.

[0075] The cushion layer 12 contains at least one of the components (A), (B), and (C) described above as long as the effects of the present invention are not impaired. I prefer it. This tends to prevent the components (B) and (C) from transferring to the cushion layer 12 from the photosensitive resin composition layer 14.

[0076] Further, the cushion layer 12 may have a laminated structure in which two or more cushion layers having different compositions or the like are laminated. In this case, the relationship of the adhesive force between the cushion layer 12 and the photosensitive resin composition layer 14 described above is between the cushion layer on the photosensitive resin composition layer 14 side and the photosensitive resin composition layer 14. As long as it is satisfied, the relationship of the adhesive force between the cushion layer 12 and the resin film 10 described above should be satisfied between the cushion layer on the resin film 10 side and the resin film 10. Les.

In the present invention, in order to laminate the cushion layer 12 on the resin film 10, for example, a resin constituting the cushion layer having the above-described composition may be applied on the resin film 10. If necessary, dissolve the above resin in a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cetyl sorb, cetyl sorb, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, or a mixed solvent thereof. It can be applied as a solution with a solid content of 10-50% by weight.

[0078] Further, in order to laminate the photosensitive resin composition layer 14 on the cushion layer 12, for example, a photosensitive resin composition having the above-described composition may be applied on the cushion layer 12. When coating, if necessary, solvents such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cetyl sorb, ethyl cetyl sorb, toluene, N, N-dimethylformamide, polypropylene alcohol monomethyl ether, or mixed solvents thereof The above-mentioned photosensitive resin composition can be dissolved in and applied as a solution having a solid content of about 30 to 70% by weight. wear.

Next, a method for forming a resist pattern using the above-described photosensitive film of the present invention will be described with reference to FIGS. 3 (a)-(e) and 4 (a)-(d). .

FIGS. 3A and 3E are cross-sectional views schematically showing a first method for forming a resist pattern. According to the first forming method, first, as shown in FIG. 3 (a), the resin film 10, the cushion layer 12, and the photosensitive resin composition layer 14 are laminated in this order on the surface of the circuit forming substrate 18. The photosensitive film 1 is pressure-bonded using a roller 20 so that the photosensitive resin composition layer 14 is in contact with the circuit forming substrate 18, and the circuit forming substrate as shown in FIG. A lamination process is performed in which the photosensitive resin composition layer 14, the cushion layer 12, and the resin film 10 are laminated on the layer 18 in this order. Next, as shown in FIG. 3 (c), the cushion layer 12 and the resin film 10 are removed to obtain a laminated substrate including the photosensitive resin composition layer 14 on the circuit forming substrate 18.

Next, as shown in FIG. 3 (d), by using a pattern mask 22 having a transparent portion with respect to an actinic ray such as ultraviolet rays, a predetermined portion of the photosensitive resin composition layer 14 in the laminated substrate is used. An exposure process is performed in which a photosensitive portion is formed by irradiating actinic rays. Then, as shown in FIG. 3 (), a developing process for removing the photosensitive resin composition layer 14 other than the photosensitive portion is performed to form a resist pattern 24.

FIGS. 4A to 4D are cross-sectional views schematically showing a second method for forming a resist pattern. According to the second forming method, first, as shown in FIGS. 4 (a) and (b), the laminating process described with reference to FIGS. 3 (a) and (b) in the first forming method is performed. In the same procedure, a laminated substrate in which the photosensitive resin composition layer 14, the cushion layer 12, and the resin film 10 are laminated in this order on the circuit forming substrate 18 is obtained.

Next, as shown in FIG. 4 (c), a pattern mask 22 having a transparent portion with respect to actinic rays such as ultraviolet rays is disposed on the resin film 10, and the resin film 10 and the cushion layer 12 are attached. Then, an exposure step is performed in which a predetermined portion of the photosensitive resin composition layer 14 in the laminated substrate is irradiated with actinic rays to form a photosensitive portion. Then, as shown in FIG. 4 (d), after removing the resin film 10 and the cushion layer 12, an image forming process for removing the photosensitive resin composition layer 14 other than the photosensitive portion is performed, whereby the resist pattern 24 is formed. Let it form. [0084] In the laminating step that is effective in the first and second forming methods, as a method of laminating the photosensitive resin composition layer 14 on the circuit forming substrate 18, for example, the photosensitive resin composition layer 1 is used. There is a method of laminating by heating 4 to about 70-130 ° C and pressure-bonding to the circuit forming substrate 18 with a pressure of about 0.1-IMPa (about 1 lOkgfZcm ² ). At this time, lamination may be performed under reduced pressure from the viewpoint of adhesion and followability. In addition, in order to further improve the stackability, the circuit forming substrate 18 may be preheated. The surface on which the circuit forming substrate 18 is laminated is usually a metal surface, but is not particularly limited. Furthermore, by using the photosensitive film 1 of the present invention in which unevenness may exist on the surface of the circuit-forming substrate 18, it is possible to laminate with good conformity to the unevenness.

The photosensitive resin composition layer 14 that has been laminated in the first and second forming methods in the exposure step has an actinic ray imaged through a negative or positive pattern mask 22 called artwork. Irradiated. At this time, if the resin film 10 and the cushion layer 12 existing on the photosensitive resin composition layer 14 are transparent, they may be irradiated with actinic rays as they are, and if they are opaque, they are removed. It is necessary to irradiate from. As the light source of the actinic ray, a known light source such as a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, or a xenon lamp is used. Also, those that effectively emit visible light, such as photographic flood bulbs and solar lamps, are used.

The development steps according to the first and second forming methods are performed by removing a non-exposed portion by wet development, dry development or the like, and developing to form a resist pattern. In the case of wet development, a developer corresponding to the photosensitive resin composition such as alkaline aqueous solution, aqueous developer, organic solvent developer, etc. is used, for example, spraying, rocking immersion, brushing, scraping, etc. Development is performed by a known method.

[0087] As the developer, a safe and stable developer having good operability such as an alkaline aqueous solution is used. Examples of the base of the alkaline aqueous solution include alkali hydroxides such as lithium, sodium or potassium hydroxide, alkali carbonates such as lithium, sodium, potassium or ammonium carbonate or bicarbonate, potassium phosphate, Alkali metal phosphates such as sodium phosphate, alkali metals such as sodium pyrophosphate and potassium pyrophosphate Pyrophosphate is used. Examples of the alkaline aqueous solution used for development include 0.1 to 5% by weight sodium carbonate dilute solution, 0.1 to 5% by weight potassium carbonate dilute solution, 0.1 to 5% by weight sodium hydroxide dilute solution, A dilute solution of 0.1-5% by weight sodium tetraborate is preferred. The pH of the alkaline aqueous solution used for development is preferably in the range of 9-11. The temperature is adjusted according to the developability of the photosensitive resin composition layer 14. In addition, a surface active agent, an antifoaming agent, and a small amount of an organic solvent for accelerating development may be mixed in the alkaline aqueous solution.

[0088] The aqueous developer is composed of water or an aqueous alkali solution and one or more organic solvents. Here, as the base of the alkaline aqueous solution in the aqueous developer, in addition to the above-mentioned bases, for example, borax sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-aminoamino. Examples include 2-hydroxymethylolene 1,3-propanediol, 1,3-diaminopropanolol_2_morpholine, and the like. The pH of the developer is preferably pH 8-12, more preferably pH 9-10, within a range where the resist can be sufficiently developed. Examples of the organic solvent include triacetone alcohol, acetone, ethyl acetate, alkoxy ethanol having an alkoxy group having 1 to 14 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether. And ethylene glycol monobutyl ether. These may be used alone or in combination of two or more. The concentration of the organic solvent is usually preferably 2 to 90% by weight. The temperature can be adjusted according to the developability. Further, a small amount of a surfactant, an antifoaming agent and the like can be mixed in the aqueous developer.

Examples of the organic solvent-based developer include 1,1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, γ_petit-mouth rataton, etc. Is mentioned. These organic solvents are preferably supplemented with water in the range of 1 to 20% by weight in order to prevent ignition.

[0090] In the development step, two or more development methods may be used in combination as required.

Development methods include dip method, battle method, spray method, brushing, and slapping, and the high pressure spray method is the most suitable for improving resolution. [0091] As processing after development, the resist pattern may be further cured by heating at about 60 to 250 ° C or exposure at about 0.2 to 10 mj / cm ² as necessary.

Next, a method for manufacturing a printed wiring board using the resist pattern forming method described above will be described. The method for producing a printed wiring board is such that the circuit forming substrate on which the resist pattern is formed is etched or stuck by the above-described resist pattern forming method.

The circuit forming substrate is etched or attached by etching or attaching the surface of the circuit forming substrate by a conventionally known method using the developed resist pattern as a mask.

[0094] As an etching solution used for the above etching, for example, a cupric chloride solution, a ferric chloride solution, an alkaline etching solution, a hydrogen peroxide-based etching solution, etc. can be used. From this point, it is preferable to use a salty ferric solution

[0095] Examples of plating methods used for the above plating include copper plating such as copper sulfate plating, copper pyrophosphate plating, and soldering such as high-throw soldering. Nickel plating), nickel plating such as nickel sulfamate plating, hard gold plating, and gold plating such as soft gold plating.

[0096] After etching or plating, the resist pattern can be peeled off with a stronger alkaline aqueous solution than, for example, an alkaline aqueous solution used for development. Examples of this strong aqueous solution include: 1-10% by weight sodium hydroxide aqueous solution, 1-10% by weight

A potassium hydroxide aqueous solution or the like is used. Examples of the peeling method include a dipping method and a spray method, and the dipping method and the spray method may be used alone or in combination. The printed wiring board on which the resist pattern is formed may be a multilayer printed wiring board.

[0097] Further, when the above-mentioned plating is performed on a circuit forming substrate including an insulating layer and a conductor layer formed on the insulating layer, it is necessary to remove the conductor layers other than the pattern. . As this removal method, for example, a method of lightly etching after removing the resist pattern, or soldering after the above-mentioned plating, and then peeling off the resist pattern. Thus, a method of masking the wiring portion with solder and then processing with an etching solution capable of etching only the conductor layer can be used.

Example

Hereinafter, the present invention will be described more specifically based on Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[0099] (Example 1 1 4 and Comparative Example 1 1 2)

[Preparation of photosensitive resin composition layer material]

A solution of photosensitive resin composition layer material (I) was prepared by blending the materials shown in Table 1, and a solution of photosensitive resin composition layer material (II) was prepared by blending the materials shown in Table 2.

[0100] [Table 1]

[0101] [Table 2] Blending amount

Item Material

(Parts by weight) Methacrylic acid-methyl methacrylate-styrene (weight ratio: 30

(A) Component 20/50, weight average molecular weight: 40,000) copolymer (acid value 1 60)

93mgKOH / g)

2, 2_bis ((4-methacryloxypentaethoxy) phenyl) propyl

30

Mouth bread

(B) component

r—Black mouth——Hydroxypropyl— 'One methacryloyl

Ten

Oxichetil o-phthalate

2— (o—Black mouth phenyl) _4, 5—Diphenyl imidazole

Three

Component (C) Dimer

4, 4 'One bisjet ^ / Reaminobenzofuenone 0.2

Coloring agent Leuco Crystal Violet 0.5

Dye Malachite Green 0. 05

Case 1 0

Toluene 1 0

Solvent

Methanol 3

N, N-dimethylformamide 3

[0102] [Production of cushion layer material]

The materials shown in Table 3 were blended to prepare a solution of cushion layer materials (I) and (II).

[0103] [Table 3]

[Preparation of photosensitive film]

As Example 1, a 16 μΐη-thick polyethylene terephthalate film (trade name: G2-16, manufactured by Teijin Ltd.) was used as the resin film, and the cushion layer material (I) solution was dried on the resin film. The film was uniformly applied to a thickness of 20 μm and dried for 10 minutes with a 115 ° C hot air convection dryer to form a cushion layer. Next, the solution of the photosensitive resin composition layer material (I) is uniformly applied onto the cushion layer so that the thickness after drying becomes 5 / m, and is heated with a 100 ° C hot air convection dryer. A photosensitive resin composition layer was formed by drying for 10 minutes to obtain a photosensitive film of Example 1.

[0105] The photosensitive film of Example 2-4 was prepared in the same manner as in Example 1 except that the solution of the photosensitive resin composition layer material and the solution of the cushion layer material shown in Table 4 were used. Produced.

[0106] Further, after the photosensitive resin composition layer material shown in Table 4 was used, and the photosensitive resin composition layer was formed on the resin film in the same manner as in Example 1, the photosensitive resin composition A 22 μm thick polyethylene film (manufactured by Tamapoly Co., Ltd., trade name: NF-13) was laminated as a protective film on the physical layer to prepare photosensitive films of Comparative Examples 1 and 2.

[0107] [Table 4]

[0108] <Evaluation test for ease of unrolling>

First, the photosensitive films obtained in Examples 1 and 4 and Comparative Examples 1 and 2 were each rolled up in a roll shape with the resin film facing outward.

[0109] Next, the copper surface of a glass epoxy board (made by Hitachi Chemical Co., Ltd., product name: MCL-E67-35S) with a 35 μm thick copper foil laminated on one side has a brush equivalent to # 600 Polishing was performed using a polishing machine (manufactured by Sankeisha), washed with water, and then dried with an air flow to obtain a copper clad laminate.

[0110] After heating the obtained copper-clad laminate to 80 ° C, using a high-temperature laminator (manufactured by Hitachi Chemical Co., Ltd., trade name: HLM-3000), Examples 1 to 4 and Comparative Example 1, The photosensitive film obtained in 2 was laminated on the substrate with the photosensitive resin composition layer facing the substrate and the resin film side touching the laminate roll to obtain a laminated substrate. In Comparative Examples 1 and 2, lamination was performed while removing the protective film. At this time, Example 1 Regarding the photosensitive film obtained in (1), it was visually evaluated whether or not the photosensitive film in the state of being rolled up could be easily unwound. When X can be easily unraveled between the photosensitive resin composition layer and the cushion layer, X is when it is difficult to unravel between the photosensitive resin composition layer and the cushion layer. The results are shown in Table 5. The laminating roll speed during lamination is 1.5mZ, and the laminating roll temperature is 110. C, the cylinder pressure of the roll was 0.4 MPa (4 kgf / cm ² ).

[0111] <Resolution evaluation test>

In the above <Evaluation test for ease of unrolling from roll>, the laminated substrate obtained by laminating the photosensitive films of Examples 1 and 4 and Comparative Examples 1 and 2 was cooled to 23 ° C, and then Example 1 In the case of the laminated substrate using the photosensitive film obtained in 4, the resin film and the cushion layer are peeled off, and in the case of the laminated substrate using the photosensitive film obtained in Comparative Examples 1 and 2, the resin film Only peeled off.

[0112] Then, on the photosensitive resin composition layer, the line width / space width as a photo tool having a 21-step step tablet as a negative and a negative for resolution evaluation is 400/6/400/47. Using an exposure machine (Oak Seisakusho, Model: EXM—1201) with a high-pressure mercury lamp lamp, and a pattern mask having a wiring pattern of (unit: / im), it is possible to develop a striker 21-step tablet. The exposure was performed with an energy amount that would result in a remaining number of steps of 70.

[0113] After the exposure, the photosensitive resin composition layer was spray-developed with a 1% by weight aqueous sodium carbonate solution (30 ° C) for 10-15 seconds (spray pressure: 0.18 MPa (l. 8 kgf / cm ² )). Then, the resist pattern was formed by removing the unexposed part and developing. The value of the minimum space width with no development residue of the obtained resist pattern was measured as the resolution, and the results are shown in Table 5. The smaller the value, the better the resolution.

[0114] <Roughness follow-up evaluation test>

The photosensitive film of the example was laminated on a copper-clad laminate in the same manner as in the above <evaluation test for ease of unrolling from roll> to obtain a laminated substrate. A copper-clad laminate having a resist pattern was obtained in the same manner as in the resolution evaluation test except that a pattern mask having a line width Z space width of 1 000/100 (unit: μm) was used. Copper-clad product obtained in the next stage Lamellae were immersed LOOG / L 1 one 10 minute persulfate Anmoniumu solution (30 ° C), and further, a resist pattern stripping solution (3 wt ^_0/0 Na_〇_H solution, 45 ° C, spray pressure: 0 2MPa (2kgf / cm ² )) were peeled to obtain different copper-clad laminates with a dent width of 100 / im and a dent depth of 110 / im in steps of 1 μm.

[0115] After heating the obtained copper-clad laminate to 80 ° C, using a high-temperature laminator, Example 1

4 and the photosensitive films obtained in Comparative Examples 1 and 2 were laminated so that the photosensitive resin composition layer was directed to the copper-clad laminate and the resin film was in contact with the laminate roll to obtain a laminated substrate. In Comparative Examples 1 and 2, lamination was performed while removing the protective film. Lamination is performed so that the axis of the laminating roll is parallel to the length direction of the recess of the copper clad laminate. The laminating roll speed is 1.5 m / min and the laminating roll temperature is 110. C, the cylinder pressure of the roll was 0.4 MPa (4 kgf / cm ² ).

[0116] Next, after the obtained multilayer substrate was cooled to 23 ° C, in the case of the photosensitive film obtained in Example 1-14, the resin film and the cushion layer were peeled off, and in Comparative Examples 1 and 2, In the case of the obtained photosensitive film, only the resin film was peeled off.

[0117] On the photosensitive resin composition layer, a line tool / space width as a photo tool having a 21-step step tablet as a negative and a resolution evaluation negative is 100/100 (unit: / m) A pattern mask having a wiring pattern is placed in close contact with the direction perpendicular to the length of the dent of the substrate and adhered, and an exposure machine with a high-pressure mercury lamp lamp is used to develop a stove 21-step tablet. The exposure was performed with an energy amount so that the remaining number of remaining steps was 6.0.

[0118] After exposure, the photosensitive resin composition layer is spray-developed with 1 wt% sodium carbonate aqueous solution (30 ° C) for 10-15 seconds (spray pressure: 0.18 MPa (l. 8 kgf / cm ² )) light A resist pattern was formed on the substrate by removing portions other than the cured portion and developing. For the substrate on which the resist pattern is formed, a salty cupric etchant (2 mol ZL CuCl, 2N-

2

HC1 aqueous solution, 50. C) is sprayed for 100 seconds (spray pressure: 0.2MPa (2kgf / cm ² ) to dissolve the copper that is not protected by the resist, and the resist pattern is stripped (3 wt./^&〇1) ^ Aqueous solution, 45 ° C, spray pressure: 0.2 MPa (2 kgf / cm ² )) was peeled off to produce a printed wiring board on which copper lines were formed. [0119] If the photosensitive film does not sufficiently follow the recess on the substrate, a gap is formed between the resist and the substrate, so that the copper line penetrates at the intersection of the resist and the recess, and the copper Melts and a continuous copper line cannot be obtained, resulting in a disconnection failure. When printed wiring boards are made using copper-clad laminates with different dent depths, the dent depth (μm) at which disconnection starts is determined as the ruggedness tracking capability (the larger this value, the higher the tracking capability). The results are shown in Table 5. In general, the range of unevenness followability that can be used practically is considered to be as follows.

[0120] <Pattern mask contamination evaluation test>

The surface of the pattern mask used in the resolution evaluation test, which was adhered onto the photosensitive resin composition layer, was visually observed to evaluate the pattern mask contamination. Here, the area strength of the pattern mask portion where the photosensitive resin composition adheres to it. If the area of the pattern mask is less than 1% of the total area of the contact surface with the photosensitive resin composition layer, there is no pattern mask contamination. If it exceeds 1%, the pattern mask is considered to be contaminated. The results are shown in Table 5.

[0121] <Peel strength evaluation test>

Example 11 A laminated substrate was prepared by laminating the photosensitive film of 4 on a copper-clad laminate in the same manner as in the above <Evaluation test for ease of unrolling from roll>. Further, after laminating the light-sensitive film of Example 1-14 on the copper clad laminate in the same manner as in the above <Evaluation test for ease of unrolling>, the cushion layer and the resin film were peeled off and remained. A laminated substrate was prepared by laminating a resin film on the photosensitive resin composition under the same conditions as when the photosensitive film was laminated. After leaving these test pieces (laminated substrates) at 20 ° C and 60% RH for 2 hours, the adhesion of the cushion layer to the photosensitive resin composition layer (180 ° peel strength) tl, and the photosensitivity to the resin film The adhesive strength (180 ° peel strength) t3 of the resin composition layer was measured using a rheometer at a pulling speed of 300 mmZmin. The results are shown in Table 5. The adhesive strength of the cushion layer to the resin film (180 ° peel strength) t2 was 100 N / m or more and could not be peeled off.

[0122] [Table 5] Item Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Resolution (W m) 1 5 1 5 1 8 1 8 1 5 1 8 Concavity and convexity tracking (Aim) 6 6 6 6 1 1 Pattern 1 mask contamination Yes Yes No No Yes No Adhesive strength t1 F. 0 1 0. 0 4. 0 5. 0--

(N / m) t3 2. 5 2. 5 0. 5 0. 5 ― ― Ease of unrolling from the roll ○ ○ ○ ○ ―-

[0123] From the above results, it was confirmed that the photosensitive film of the present invention (Examples 1 to 4) had excellent unevenness followability as compared with the photosensitive film of Comparative Examples 1 and 12. . Further, it was confirmed that the photosensitive films of Examples 3 and 4 had no pattern mask contamination. In addition, it is clear that the photosensitive film of Example 1-4 can be easily unwound in a state in which the resin film, the cushion layer, and the photosensitive resin composition layer are sequentially laminated from the state of being rolled up. there were.

Industrial applicability

[0124] As described above, according to the photosensitive film of the present invention, even when the photosensitive resin composition layer is thinned, the photosensitive resin composition layer becomes uneven on the surface of the adherend. Since it is laminated with good followability and the occurrence of unbonded portions between the adherend and the photosensitive resin composition layer is suppressed, a high production yield can be realized. In addition, since the photosensitive film of the present invention has excellent followability, it has an advantage that it can be laminated as it is using a conventional laminating apparatus. Furthermore, the photosensitive film of the present invention can be easily unwound between the resin film and the photosensitive resin composition layer when it is rolled up without using a protective film and the roll force is released. , Power to reduce waste and cost.

Claims

The scope of the claims

[1] A photosensitive element that has a laminate strength including a resin film and a photosensitive resin composition layer and can be wound into a roll.

The laminate includes a cushion layer that binds the resin film and the photosensitive resin composition layer, and has a larger adhesive force to the resin film than the adhesive force to the photosensitive resin composition layer. Prepared,

The resin film is disposed at one end in the stacking direction of the laminate, and the photosensitive resin composition layer is disposed at the other end in the stacking direction of the laminate,

The photosensitive resin composition layer is substantially free of adhesiveness at room temperature with respect to the resin film.

[2] The adhesive strength of the photosensitive resin composition layer to the resin film is 5 N / m or less, the adhesive strength of the cushion layer to the resin film is 10 N / m or more, and the photosensitive property 2. The photosensitive film according to claim 1, wherein the adhesive force of the cushion layer to the resin composition layer is 0.5-10 N / m.

[3] The photosensitive member according to claim 1 or 2, wherein the adhesive force of the cushion layer to the photosensitive resin composition layer is larger than the adhesive force of the photosensitive resin composition layer to the resin film. Sex film.

[4] The photosensitive resin composition layer includes (A) a binder polymer, (B) a photopolymerizable compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator. The photosensitive film according to claim 1, wherein the photosensitive film is a layer having a strong resin composition.

[5] The component (B) contains 2,2-bis (4-((meth) ataryloxypolyalkoxy) phenyl) propane represented by the following general formula (I): 4. The photosensitive fine rem described in 4.

[Chemical 1]

[Wherein, R ¹ and R ² each independently represent a hydrogen atom or a methyl group, X ¹ and X ² each independently represent an alkylene group having 26 carbon atoms, and p and q are p + q = 4 Indicates a positive integer chosen to be 40. ]

6. The photosensitive film according to claim 15, wherein the cushion layer contains a copolymer of ethylene and a monomer copolymerizable therewith.

[7] The copolymer includes an ethylene-butyl acetate copolymer having an ethylene ratio of 50 to 90% by weight based on the total amount of monomers constituting the copolymer, and / or the copolymer. 7. The photosensitive film according to claim 6, wherein the photosensitive film is an ethylene ethyl (meth) acrylate copolymer having a proportion of ethylene of 50 to 90% by weight based on the total amount of the constituent monomers.