JP3410527B2 - Photoresist film for image formation of printed circuit boards - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to a printed circuit board.BoardMinute
Photoresist film used for image formation in the field
More specifically, the adhesion between the photosensitive resin layer and the support film
Good performance, especially for the production efficiency of high-density printed circuit boards.
Regarding photoresist film that can be improved
You. [0002] 2. Description of the Related Art Conventionally, printed circuit boards, especially
For forming fine wiring circuits usually called industrial substrates
In general, a copper-clad laminate with copper foil on the surface
Laminate the resist film and pass through the pattern mask.
Exposure and development and plating or etching
The photoresist film has a light-transmitting support
Body film, photosensitive resin layer and protective film
To form an image using this, first,
After peeling the lum, press the photosensitive resin layer onto the copper-clad laminate
And apply a positive pattern mask on the light-transmitting support film.
Adhere to active light (usually ultraviolet light) (expose)
After peeling off the carrier film, remove the alkaline aqueous solution or organic solvent
Spraying or dipping to form a resist pattern (development),
After applying metal plating to the exposed copper foil,
Remove the cured resist with an aqueous solution or an organic solvent.
Stripping) and finally iron chloride, copper chloride, hydrogen peroxide / sulfuric acid
Copper foil exposed with a solution of acid, alkaline ammonia, etc.
Method of removing (etching) part or negative pattern
The method of etching and removing the resist after development in
I have been. [0003] The actual printed circuit board manufacturing process
Is called a laminator on the cut copper-clad laminate.
The photoresist film is laminated by the heated roll.
After cutting the resulting laminate into the desired size
The pattern is formed by the exposure and development steps as described above.
However, the chips of the laminate generated at this time
If brought into the exposure machine, it will cause adverse effects during pattern exposure.
You. Therefore, in order to remove the chips,
A method of treating the surface of the laminate with an adhesive roller is implemented
ing. However, with conventional photoresist films,
Has low adhesion between the photosensitive resin layer and the support film,
Between the photosensitive resin layer and the support film during the application roller treatment
A peeling phenomenon was observed, and air entered between the layers, causing oxygen damage.
There is a problem that pattern formation cannot be done due to harm
Was. That is, the adhesion between the adhesive roller and the support film
Exposure to force (usually less than 1 to 30 g / inch)
Adhesion between the conductive resin layer and the support film is required
is there. Recently, as a countermeasure against this, an adhesive table
There is no attempt to improve the adhesive strength by performing corona discharge treatment on the surface.
Have been. (JP-A-5-142777) [Problems to be solved by the present invention] However, in the above method, the corona discharge
It is effective immediately after electric treatment, but the effect decreases with time.
Not only can be seen, but also
If a fat layer is laminated, the adhesion will be too high and the printed circuit board
When peeling the support film after pattern exposure during board production
There is a risk of delamination between the photosensitive resin layer and the substrate.
It is difficult to control the effective adhesive force, and
Dispersion of discharge distribution during processing and uniform adhesive strength
It also has the disadvantage of not having. [0006] Means for Solving the Problems Accordingly, the present inventor has
As a result of intensive research to solve these problems,
The surface of the photosensitive resin layer side
The sheet resistivity is 10⁹-10¹¹Ω (JIS K 6911
Value measured by the resistivity method).
And byDirectly laminatedPhotosensitive resin layer and support film
Has excellent adhesiveness of the
When the support film is peeled off after the
It was found that delamination of the substrate did not occur, and the present invention was completed.
Has come to fruition. Hereinafter, the present invention will be described in detail. The present invention
The support film used for the surface in contact with the photosensitive resin layer,
In other words, the surface resistivity of the bonding surface10 ⁹ -10 ¹¹ Ω
It is essential that the resistivity is10 ⁹ Fill less than Ω
Is difficult to manufacture, and the film has high adhesion.
As described above, photosensitivity during the production of printed circuit boards
Delamination between the resin layer and the substrate occurs, and conversely, the resistivity becomes10
¹¹ If it exceeds Ω, the required adhesive strength cannot be obtained. Ma
In addition, there is a preferable range of the adhesive force for the above-mentioned reason,
It is preferably 30 to 150 g / inch, more preferably 40 g / inch.
１００100 g / inch (180 ° in standard condition, 200 °
mm / min tensile peel strength). The material of the film is usually
Used as a support film for dying films
Material, for example, polyolefin such as polypropylene
Resin, polyethylene terephthalate, polybutylene
Polyester resin such as phthalate, nylon resin
And the like. The surface of the present invention using the film material
As a method for obtaining a support film having resistivity, a known method is known.
For example, the film material may be polyethylene
Polyethylene glycol-based compounds such as recall diamine
And polyether-based compounds such as polyether polyamides
The method of compounding and forming a film, and on the resin film surface after film formation
Examples of the method include a method of coating the above compound. In the former method, the film material used
Can not be said unconditionally due to the combination of
The compounding amount of the compound is from 0.001 to 10% by weight.
It is preferably selected. In the latter method, the compound
To apply the solution using a known coating device
Thus, the coating thickness is usually 1 μm or less. Ma
In the latter method, the adhesive surface on the photosensitive resin layer side
Needless to say, Mino coating is sufficient. [0010] The melting point of the above-mentioned support film is sensitive.
150 ° C. or higher is preferred in consideration of coatability of the light-sensitive resin composition.
And particularly preferably 200 ° C. or higher. Obtained as above
Film is stretched (uniaxial or biaxial)
Or an unstretched film, but preferably
Axial stretching is practical. A city that meets the above conditions
As sales films, "Lumirror 22AQ45",
"Lumirror T94", "Trefane BO2500" (I
The gap is also manufactured by Toray Industries, Inc.), "Espet E7313"
(Manufactured by Toyobo Co., Ltd.). The photosensitive resin constituting the photosensitive resin layer of the present invention
There is no particular limitation on the fat, and various types can be used.
A photosensitive resin composition that can be developed with an aqueous alkaline solution
It is preferable that As a general example of the composition
Are (a) a polymer component, (b) a monomer component, and (c) light
Contains a polymerization initiator or photopolymerization initiator system as an essential component
There is something. The polymer component (a) has a molecular weight of 1
It is a polymer containing a carboxyl group in 000 or more,
Vinyl copolymer, polyester resin, etc.
Alternatively, two or more kinds are used in combination. For vinyl copolymer
The components used include (meth) acrylic acid,
(T) methyl acrylate, ethyl (meth) acrylate,
Propyl (meth) acrylate, Buty (meth) acrylate
2-hydroxyethyl (meth) acrylate, 2-
Ethylhexyl (meth) acrylate, (meth) acryl
Methoxyethyl luate, styrene, (meth) acrylamide
, (Meth) acrylonitrile, vinyl acetate, vinyl acetate
Rucol and the like. The polyester resin is (phthalic anhydride),
Isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride
Acid, (anhydride) maleic acid, fumaric acid, adipic acid, none
Divalent or higher valences such as water trimellitic acid, pyromellitic anhydride, etc.
Rubonic acid and ethylene glycol, propylene glycol
1,3-butanediol, diethylene glycol,
Dipropylene glycol, triethylene glycol, ne
Opentyl glycol, hydrogenated bisphenol A, grease
Divalent or higher alcohols such as serine and trimethylolpropane
Obtained by an esterification reaction with phenol. The polymer is
All have a molecular weight of 1000 or more, preferably 1000 to
Must be 200,000. The monomer component (b) is photopolymerizable.
Vinyl monomer, ethylene glycol di (meth)
Acrylate, polyethylene glycol di (meth) ac
Related, propylene glycol di (meth) aclay
G, polypropylene glycol di (meth) aclay
G, neopentyl glycol di (meth) acrylate,
1,6-hexanediol di (meth) acrylate,
2,2-bis [4- (meth) acryloxypropoxy
Phenyl] propane, trimethylolpropane
TA) Acrylate, pentaerythritol tri (meth)
Acrylate, tri (meth) acryloxyethylphosph
Tris (2-hydroxyethyl) isocyanurate
Tototri (meth) acrylate, pentaerythritol
(Meth) acrylate, ethylene glycol diglycidide
Ruether di (meth) acrylate, glycerin rig
Risidyl ether tri (meth) acrylate
These are used alone or in combination of two or more.
The mixing weight ratio of the above (a) and (b) is (a) / (b)
= 80 / 20-40 / 60, preferably 70 / 30-5
0/50 is advantageous. (C) Photopolymerization initiator or photopolymerization initiator system
As 2-ethylanthraquinone, 2-t-butyl
Anthraquinone, octamethylanthraquinone, 1,2
-Benzanthraquinone, 2,2-diphenylanthra
Substituted or unsubstituted polynuclear quinones such as quinone, diacetyl
Diketones such as benzyl and benzyl, benzoin, pivalone, etc.
Α-ketaldonyl alcohols and ethers, α-
Phenylbenzoin, α, α-diethoxyacetopheno
Benzophenone, 4,4-bisdialkylaminoben
Photopolymerization initiators such as aromatic ketones such as nzophenone
And these may be used alone or in combination. The photopolymerization initiator system includes 2,4,5-
Liarylimidazole dimer and 2-mercaptobenzo
Quinazole, leuco crystal violet, tris
(4-diethylamino-2-methylphenyl) methane, etc.
And the like. In addition, the light is opened by itself.
Although it does not have initial properties, it can be used in combination with the above substances
Photoinitiator system with better overall photoinitiation performance
Such an additive as follows can be used. like this
As an additive, triethanolamine for benzophenone
Tertiary amines such as ruamine; Photopolymerization initiator or
The photopolymerization initiator system is used in the photosensitive resin composition in an amount of 0.05 to 2%.
It is used in the range of 0% by weight. In the photosensitive resin composition
Are dyes, color pigments, adhesion improvers, polymerization inhibitors,
Can contain surface improvers, plasticizers, flame retardants, etc.
You. Further, a photosensitive resin using the photosensitive resin described above.
The thickness of the fat layer is 5 to 100 μm, preferably 10 to 10 μm.
50 μm. The photoresist film of the present invention,
On the support film, the photosensitive resin composition solution
Obtained by coating. The support film is
When using a photoresist film in the form of a roll,
The photosensitive resin layer is a protective film (usually polyethylene film).
Transfer) to the film and dust adheres to the photosensitive resin layer
Layered on the photosensitive resin layer to prevent
The thickness of the protective film is preferably 5 to 50.
μm is appropriate. The photoresist film is formed on a support film.
A photosensitive resin layer on the film, and a protective film on it
And a method of manufacturing the support
A photosensitive resin layer is formed on the film, and then a protective film is formed.
A method of laminating a polyethylene film etc. as a film
Representative. An image is formed using the photoresist film.
To form Peel off the protective film of the photoresist film,
Lay the optical resin layer so that it contacts the substrate, and
And crimp. As base material, copper plate, iron plate, aluminum plate,
Stainless steel plate, etc. and inorganic or electrically insulating
Is a laminate of copper or aluminum foil on the surface of an organic substrate
Well-known things can be used. Perform any secondary processing as necessary. The pattern mask is brought into vacuum contact with the
Through exposure to active light such as ultraviolet light. The resist on the substrate exposed by peeling the support film
Is sprayed or immersed in the developing solution and developed to form an image.
The developing solution used is sodium carbonate, caustic soda, etc.
Aqueous alkali solution and modified 1,1,1-trichloroethane
Etc. Furthermore, triethanolamine, butyl cellosol
An organic solvent such as an organic solvent can also be added. The developed photoresist film is removed
When using for a jack, first perform necessary pre-processing.
After that, copper sulfate plating, copper pyrophosphate plating,
For plating, tin plating, nickel plating, gold plating, etc.
Performing a plating process. Alkaline aqueous solutions such as caustic soda and caustic
Remove the photoresist with styrene etc. and expose the exposed metal
Plates and metal foils are made of ferrous chloride, cupric chloride, hydrogen peroxide
/ Etching with a solution such as sulfuric acid or alkaline ammonia
To remove. Use the developed photoresist for tenting or etching
When using for etching, the same etching as above
Remove the exposed metal plate or metal foil part with the liquid, then
Alkaline aqueous solution such as soda and caustic potash and methylene chloride
Then, the resist is removed. [0020] The photoresist film of the present invention has a specific support.
Since the carrier film is used, contact with the photosensitive resin layer
Excellent adhesion, printed circuit baseBoardEffectively implemented in the field
Useful as a photoresist film for image formation
You. [0021] The present invention will be described in more detail with reference to the following examples.
I will tell. “Parts” indicates parts by weight. Example 1 (Preparation of photosensitive resin composition) Acrylic resin (methacrylic resin)
Methyl acrylate / n-butyl acrylate / methacrylic acid = 5
7/20/23 weight ratio copolymer having a molecular weight of about 104,000
Is methyl ethyl ketone / methyl cellosolve = 6/4 weight
Dissolved in a mixed solvent at a specific ratio.
%) 150 parts, trimethylolpropane triacryle
10 parts, polypropylene glycol # 400 dial
30 parts of acrylate, 5 parts of benzophenone, N, N'-teto
Laethyl-4,4'-diaminobenzophenone 0.2
Parts, malachite green 0.03 parts and methyl ethyl ketone
30 parts ton was uniformly mixed. (Preparation of Photoresist Film) JIS
  Surface resistivity 5 × 10 measured according to K 6911^Ten
Ω polyester film (trade name “Lumirror 22AQ”
45 ", melting point 260 ° C, manufactured by Toray Industries, Inc.
And the above photosensitive resin composition on the film.
Coating, drying at 80 ° C for 10 minutes, pinhole with a film thickness of 40 μm
There was no coating film having no tackiness. Then,
A protective film of 40 μm thick polyethylene film
To form a photoresist film
Was. (Manufacture of Printed Circuit Board)
Remove the protective film from the photoresist film,
A copper-clad laminate with a copper thickness of 35 μm heated to 70 ° C. (25.
4 mm x 100 mm x 1.6 mm)
Is roll-bonded at 110 ° C to make contact with the copper part.
Photoresist film pressed to the same size as the layer plate
Was cut into an evaluation specimen. The test specimen was heated at 22 ° C and 60%
After standing at RH for 1 day, between the support film and the photosensitive resin layer
The adhesive force was measured (1 at a pulling speed of 200 mm / min).
80 ° peel test) As a result, at 42 g / inch, the viscosity
The adhesive strength of the wearing roller was exceeded. In addition, the support after exposure
Assuming the step of peeling the carrier film, the heated state (30
(° C, 60% RH), the adhesive strength of the specimen was
As a result of the measurement, the photosensitive resin layer and the copper-clad at 60 g / inch.
No delamination of the laminate was observed. Examples 2-3 and Comparative Examples 1 and 2 Using the support films shown in Table 1, the same as in Example 1
An evaluation was performed. In Comparative Example 2, the corona discharge treatment was performed.
The used film was used. Evaluation results of Examples and Comparative Examples
It is shown in Table 2. [0025] [Table 1]             Surface resistivity Melting point Material(Ω) (° C) Example 1 5 × 10^Ten      260 polyester resin   〃2 1 × 10⁹       260 polyester resin〃 3 1 × 10 ⁹ 260 Polyester resin Comparative Example 1 1 × 10¹⁶      260 polyester resin〃 ²¹ × 10 ¹⁶ 260 Polyester resin Note) The support films used in the above evaluation are as follows.   Example 1; “Lumirror 22AQ45”, thickness 22 μm, manufactured by Toray Industries, Inc.     〃 2; “Lumirror T94”, thickness 25 μm, manufactured by Toray Industries, Inc.     ３ 3; “Espet E7313”, thickness 25 μm, manufactured by Toyobo Co., Ltd.   Comparative Example 1 “Lumirror T70”, thickness 20 μm, manufactured by Toray Industries, Inc.     〃2: “VC-20”, thickness 20 μm, with corona discharge treatment, Teijin Limited               Company [0026] [Table 2]              Adhesive strengthBonding force (G / inch) (g / inch) Delamination Example 1 42 60 None   〃 250 80 None３ 3 40 55 None Comparative Example 1 10 15 None〃 2 150 Cannot be measured Yes [0027] The photoresist film of the present invention is characterized by
Because a constant support film is used, the photosensitive resin layer
Excellent adhesion to printed circuit boardBoardEffective in the field
Used as a photoresist film for image formation
It is for.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-6-35200 (JP, A) JP-A-7-28232 (JP, A) JP-A-62-139547 (JP, A) JP-A-3-35 245151 (JP, A) JP-A-61-41143 (JP, A) JP-A-61-193148 (JP, A) JP-A-62-293689 (JP, A) JP-A-63-74052 (JP, A) JP-A-62-8144 (JP, A) JP-A-49-43630 (JP, A) JP-A-58-63726 (JP, A) JP-A-58-62040 (JP, A) JP-A-2-90165 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) G03F ^7/ 00-7/42

Claims (1)

(57) [Claims 1] At least a photosensitive resin layer and a support film are directly laminated, and the surface resistivity of the support film on the photosensitive resin layer side is 10 ⁹ to 10 ¹¹ Ω. A photoresist film for forming an image on a printed circuit board, characterized in that: