JP2847720B2 - Photoresist film - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a photoresist film. More specifically, the present invention relates to a photoresist film made of a substrate having excellent release properties and lubricity.

[Related Art] In recent years, photoresist films have been widely used in the production of printed wiring circuit boards and the like. Usually, a photoresist film is a laminated structure composed of a support layer / photoresist layer / protective layer. As the support layer of the photoresist film or the base material of the protective layer, its mechanical properties, optical properties, Polyester films excellent in properties, heat resistance, chemical resistance and the like are mainly used. In general, it is desired that the photoresist layer be non-adhesive and easy to handle, and that the photoresist layer maintain an adhesive property that can withstand the development and etching steps with respect to the conductive substrate. However, if the composition of the photoresist layer is changed in order to improve the productivity by speeding up the production of a printed circuit or the like, or to improve the adhesion of the photoresist layer to the conductive substrate, depending on the composition of the photoresist, the support may be changed depending on the composition of the photoresist. Adhesion to the layer and the protective layer is increased, and defects such as poor flatness and smoothness of the photoresist layer due to poor peeling from the substrate, poor workability during processing, etc. It is known that the layers cannot be separated and are sometimes difficult to use. For this reason, various studies have hitherto been made to reduce the peeling force between the support layer or the protective layer and the photoresist layer. As such a photoresist film, a photoresist film formed of a base material having a polyester film surface coated with crosslinkable silicon or wax is known.

[Problems to be Solved by the Invention] However, the above-mentioned photoresist film has the following problems.

That is, in a photoresist film composed of a base material coated with crosslinkable silicon or wax on the polyester film surface, even if the desired releasability is obtained, the transfer of silicon or wax to the photoresist layer results in The adhesion between the photoresist layer and the conductive substrate is reduced, and various adverse effects are likely to increase in post-processing. Furthermore, silicon or wax attached to the photoresist layer may contaminate the equipment in each process or cause a decrease in the performance of a developer or the like.

An object of the present invention is to solve these disadvantages of the prior art, and to provide a photoresist film comprising a substrate having excellent release properties, and also excellent in slipperiness and heat resistance.

[Means for Solving the Problems] The present invention provides a coating layer comprising a water-dispersible fluorine-containing polymer resin obtained by using a vinyl polymer monomer having a perfluoroalkyl group as a main component on at least one surface of a polyester film. Is provided, a photoresist film further provided with a photoresist layer on the coating layer,
The coating layer has a fluorine content of 5 to 50% by weight and an ASTM
The gist of the present invention is a photoresist film having a slipperiness of 0.40 to 0.52 as measured according to -D-1894-63.

In the present invention, the polyester is a well-known polyester, specifically, for example, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, bis-α, β (2-chlorophenoxy) ethane-4,4′-dicarboxylic acid, adipine acid,
At least one bifunctional carboxylic acid such as sebacic acid;
Examples include polyesters obtained by polycondensing at least one kind of glycol such as ethylene glycol, triethylene glycol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol and the like. Further, the polyester may be blended with another polymer or copolymerized within a range not to impair the object of the present invention, and may include an antioxidant, a heat stabilizer, a lubricant, a pigment, an ultraviolet absorber and the like. It may be. The intrinsic viscosity of the polyester (measured in orthochlorophenol at 25 ° C) is 0.4-2.0
And preferably those having a range of 0.5 to 1.0 are usually used.

In the present invention, it is preferable to use polyethylene terephthalate or polyethylene-2,6-naphthalate as the polyester because particularly excellent effects can be obtained.

The coating layer referred to in the present invention is a layer composed of a water-dispersible fluorine-containing polymer resin obtained mainly from a vinyl polymer monomer having a perfluoroalkyl group. The main component refers to a resin in which the vinyl polymerizable monomer having a perfluoroalkyl group is at least 50%, preferably at least 65%, more preferably at least 75% in the resin, and optionally containing other substances. Is also good. In the present invention, such a coating layer is provided on at least one surface of the polyester film. When provided on both surfaces, the description of the layer described below is applied to at least one of the polyester films. .

The water-dispersible fluorine-containing polymer resin referred to in the present invention is a vinyl polymer monomer having a perfluoroalkyl group and an alkyl group substituted with a fluorine atom, a vinyl polymer monomer containing no functional group or the like. It is a copolymer resin with at least one kind, has a perfluoroalkyl group having 4 or more carbon atoms, preferably 6 to 12 and has a molecular weight of preferably about 500 to about 200,000, and has good affinity with the base substrate. Things are desirable.

The vinyl polymerizable monomer having a perfluoroalkyl group is a compound having a perfluoroalkyl group having 4 or more carbon atoms, preferably 6 to 12, in which hydrogen of a hydrocarbon is substituted with a fluorine atom. ₇ F ₁₅ COOCH = CH ₂ , C ₈ F ₁₇
C ₄ H ₈ OCOCH = CH ₂ , C ₇ F ₁₅ C ₂ H ₄ OCOC (CH ₃ ) = CH ₃ , C ₁₂ F ₂₅ C
₃ H ₆ OCOCH = CH ₂ , C ₉ F ₁₉ C ₃ H ₆ OCOCH = CH ₂ , C ₅ F ₁₁ CH ₂ OCOC
(CH ₃ ) = CH ₂ , C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) C ₂ H ₄ OCOCH = CH ₂ , C ₈ F
₁₇ SO ₂ N (CH ₃ ) C ₂ H ₄ OCOCH = CH ₂ , C ₈ F ₁₇ SO ₂ N (C ₂ H ₅ ) C ₂ H _{4
OCOC (CH 3) = CH 2} , C 7 F 15 CON (C 2 H 5) C 2 H 4 OCOC (CH 3)
_{= CH 2, C 8 F 17} C 2 H 4 OCOCH = CH 2, C 8 F 17 SO 2 NHC 2 H 4 SO 2 CH = C
_{H 2, C 8 F 17 SO} 2 N (C 2 H 5) C 2 H 4 OCOCH = CHCOOC 4 H 9, C 8 F 17 SO
_{2 N (CH 3) C 10} H 20 COOCH 2 CH = CH 2, C 8 F 16 SO 2 N (C 2 H 4 OCOCH
_{= CH 2) 2, C 2} F 5 (OC 2 F 4) 4 CON (CH 3) C 2 H 4 OCOCH = C
H ₂ , (CF ₃ ) ₂ CFOC ₅ H ₁₀ OCOCH = CH ₂ , C ₈ F ₁₇ CH ₂ C (OH) HCH
₂ OCOC (CH ₃ ) = CH _2, and at least one selected from these is applied, but is not particularly limited.

Examples of the vinyl polymerizable monomer containing no fluorine atom to be copolymerized with the compound include a hydrocarbon-based vinyl polymerizable monomer, a hydrocarbon-based non-conjugated divinyl polymer monomer, and a functional group-containing vinyl polymerizable monomer. And the like.Examples of the hydrocarbon-based vinyl polymerizable monomer include, for example, methyl acrylate, methyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, isoamyl acrylate, Isoamyl methacrylate, 2-ethylhexyl acrylate, 2-methacrylic acid 2-
Ethylhexyl, octyl acrylate, octyl methacrylate, octadecyl acrylate, octadecyl methacrylate, lauryl acrylate, lauryl methacrylate,
Cetyl acrylate, cetyl methacrylate, N, N-diethylaminoethyl acrylate, N, N-diethylaminoethyl methacrylate, vinyl acetate, vinyl propionate, vinyl capryate, vinyl laurate, vinyl stearate, styrene, α-methylstyrene , P-methylstyrene, vinyl fluoride, vinyl chloride, vinyl bromide, denenylidene fluoride, vinylidene chloride, allyl heptanoate,
Aryl acetate, allyl caprate, allyl caproate, vinyl methyl ketone, vinyl ethyl ketone, 1,3-
Examples of butadiene, 2-chloro-1,3-butadiene, 2,3-dichloro-1,3-butadiene, isoprene, and hydrocarbon-based non-conjugated divinyl polymerizable monomers include ethylene glycol diacrylate and ethylene glycol diacrylate. Methacrylate, propylene glycol diacrylate, diethylene glycol dimethacrylate,
Polyethylene glycol dimethacrylate, divinylbenzene, vinyl acrylate, dibromoneopentyl glycol dimethacrylate, and functional group-containing vinyl polymerizable monomers include, for example, acrylic acid, methacrylic acid, acrylamide, methacrylamide, N-methylolacrylamide, N -Butoxymethyl acrylamide, diacetone acrylamide,
Methylol diacetone acrylamide, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, and the like are selected from, but not particularly limited to, these. .

The water-dispersible fluorine-containing polymer resin is produced by a known emulsion polymerization method, and usually, an anionic, cationic, amphoteric or nonionic surfactant is used as an emulsifier, and the preferred content is Based on the weight of all monomers
0.5 to 15%.

For the coating layer, a urea-based, melamine-based, acrylamide-based, polyamide-based, etc. methylolated or alkylolized crosslinking agent is used to improve the adhesion, water resistance, solvent resistance, and mechanical strength of the coating layer. , A reactive compound such as an epoxy compound, an aziridine compound, a blocked polyisocyanate, or a vinyl compound. Further, if necessary, known additives in an amount that does not impair the effects of the present invention, such as an antifoaming agent, a coating improver, a thickener, an antistatic agent, an antioxidant, an ultraviolet absorber, a dye, a pigment, A lubricant or the like may be contained.

The polyester film constituting the film of the present invention,
Mechanical strength and dimensional stability, biaxially oriented by a conventional method in terms of rigidity, etc., the surface roughness Ra of the polyester film is 0.5 μm or less, preferably 0.3 μm or less, more preferably 0.2 μm or less This is desirable because it prevents the surface roughness and surface defects of the photoresist layer formed on the film and enables precise printing. The optical haze (turbidity) and thickness of the polyester film are not particularly limited, but those having an optical haze of 5.0% or less, preferably 2.0% or less are desirable because the transmittance of active light is increased. 500
μm is preferable, and the range of 5 to 300 μm is more preferable, and the handleability in practical use as a substrate base is excellent.

The laminated thickness of the coating layer constituting the film of the present invention is 0.005.
~ 2.0 μm is preferred. The range of 0.01 to 0.5 μm is more preferable. If the lamination thickness is less than 0.005 μm, it is difficult not only to achieve uniform lamination but also to obtain a coating layer that is durable against deformation due to external force. When the thickness exceeds 2.0 μm, the transparency is reduced, and in some cases, the adhesion of the coating layer is reduced and the coating layer is liable to delaminate.

In the film of the present invention, the fluorine content of the coating layer is 5 to 50% by weight, preferably 10 to 40% by weight, more preferably 15 to 30% by weight.
It must be in the range of% by weight and have a slipperiness of 0.40 to 0.52 as measured according to ASTM-D-1984-63. That is, when the fluorine content is 5% by weight or less, the releasability and the lubricity of the photoresist film are deteriorated, and adverse effects such as surface defects are increased in the photoresist layer. If the content exceeds 50% by weight, the coating property deteriorates,
There is a tendency that it is difficult to form a uniform coating layer, and if the slipperiness is out of the above range, the wettability with the base material is likely to be deteriorated, leading to poor molding of the photoresist layer. Is not preferred because of

In addition, the coating layer of the film of the present invention is desirably heat-treated after being oriented in one direction, and since the fluorine atoms are easily arranged on the surface of the coating layer by the stretching / heat-treating action, the releasability as a photoresist film is improved. Both the lubricity and the lubricity are excellent.

Next, the manufacturing method of the present invention will be described. First, after thoroughly drying the polyester pellets polymerized by a conventional method, a known extruder, preferably co-feed to a melt extruder having a compression ratio of 3.8 or more, the temperature at which the pellets are melted, the temperature at which the polymer decomposes or less. At a temperature of, a sheet is melt-extruded from a slit die and solidified by cooling to produce an unstretched sheet. At this time, the intrinsic viscosity of the unstretched sheet is desirably 0.5 or more from the viewpoint of film properties. Next, on the unstretched sheet or a film obtained by stretching the unstretched sheet 2.0 to 5.0 times at 70 to 120 ° C., a coating material prepared in a predetermined amount of the composition is applied, and the coating film is dried to a predetermined amount. After the application layer of
At 70 to 150 ° C, the film is stretched 2.0 to 5.0 times in the transverse direction. Further, the biaxially oriented film is heat-treated at 150 to 240 ° C. for 1 to 60 seconds while giving 0 to 10% relaxation.

The application method is not particularly limited, and an extrusion lamination method or a melt coating method may be used.However, a gravure coating method, a reverse coating method, or the like of a water-oxidized coating material can be used because a thin film can be coated at a high speed. It is preferable to apply a known method such as a kiss coat method, a die coat method, and a metaling bar code method. At this time, if necessary, a known surface treatment such as a corona discharge treatment in air or other various atmospheres is performed on the film before coating, so that not only the coatability is improved but also the coating layer is formed. It can be formed more firmly on the film surface. The concentration of the coating material and the conditions for drying the coating film are not particularly limited, but the drying conditions for the coating film are desirably performed within a range that does not adversely affect the properties of the polyester film.

Next, a polyester film provided with the coating layer is used as a support, and a coating material prepared by adjusting a photoresist to a predetermined amount is applied on the surface thereof, and the coating film is dried to provide a predetermined resist layer. By laminating a polyolefin film or the polyester film, a photoresist film can be obtained. At this time, the photoresist layer can be more uniformly formed on the surface of the coating layer by performing a known corona discharge treatment or a plasma treatment (in air, in nitrogen, in carbon dioxide, or the like) in advance.
As a method of applying the coating material, a known air doctor coating method, air knife coating method, reverse coating method, gravure coating method, kiss coating method, cast coating method, or the like can be applied. The concentration of the coating material and the conditions for drying the coating film are preferably set within a range that does not adversely affect the coating properties and the photoresist.

[Evaluation Method] The characteristic values of the present invention are based on the following measurement methods and evaluation criteria.

(1) Slipperiness (μs) The static friction coefficient μs between the coated layer surface and the uncoated layer surface was measured by ASTM-D-1894-63.

(2) Thickness of coating layer (μ) A cellophane tape is attached to the coating layer, and the coating layer at the end of the cellophane tape is dissolved and removed with a solvent such as dimethylformamide. Next, the cellophane tape was peeled off, and the boundary between the surface protected by the cellophane tape and the surface that had been dissolved and removed was measured with a Kosaka Lab.

When the above method was difficult, the ultrathin section of the laminated film was observed using a transmission electron microscope model HU-12 manufactured by Hitachi, Ltd. to determine the thickness.

(3) Coating property of coating layer The coating state of the coating layer surface or the aluminum-deposited coating layer surface was visually judged and evaluated as follows.

：: There is no coating defect. (Good coatability) Δ: There are some coating defects.

×: Many coating defects. (Poor coating properties) (4) Fluorine content A fluorine compound is burned in a combustion flask filled with oxygen using a platinum catalyst and then absorbed by an absorbent. To this, Alfson solution was added and allowed to stand for 1 hour.
Was measured by a method (Alizarin complexone method) for determining fluorine content from a calibration curve prepared in advance.

(5) Releasability A photoresist having the following composition is applied on the coating layer and dried to form a photoresist layer having a thickness of 0.7 mm. As a protective layer, the same film as the support layer is laminated under pressure. A resist film was obtained. Next, the protective layer was peeled off, and a 50 μm copper foil was laminated on the photoresist layer by pressure bonding with a hot roll at 120 ° C., and the peeling force between the support layer and the photoresist layer was determined according to JIS-K-6854 ( 180 ° peeling). The criterion was that the releasability was good when the peeling force was less than 500 g, and the releasability was poor when the peeling force was 500 g or more.

(Composition of photoresist) ・ Methyl methacrylate-acrylonitrile-acrylated glycidyl acrylate copolymer (molar ratio 90: 5: 5) 95 parts by weight ・ Methyl methacrylate-2-hydroxyethyl acrylate copolymer (molar ratio) 90:10) 75 parts by weight ・ Triethylene glycol acetate 26 parts by weight ・ tert-butylanthraquinone 14 parts by weight ・ 2,2′-methylenebis (4-ethyl-6-tert-butylphenol) 35 parts by weight ・ Ethyl violet 2.5 parts by weight Part: methyl ethyl ketone 800 parts by weight (6) Coating property of photoresist layer Using the photoresist of (5) above, the coating state of the surface of the resist layer applied on the coating layer is visually determined, and The evaluation was performed using the same criteria as in 3).

[Function of the Invention] The present invention provides a coating layer having a specific fluorine content on a polyester film by using a water-dispersible fluorine-containing polymer resin, thereby obtaining the following excellent effects. Was completed.

[Effects of the Invention] (1) There is no transfer material to the photoresist layer as a protective layer or a support layer of the photoresist film, and both the releasability and the slipperiness are excellent.

(2) Since excellent releasability is maintained for a wide range of photoresists, productivity of printed circuits and the like can be improved.

(3) Since it is excellent in slipperiness, it is excellent in winding property, winding form, and handleability in post-processing in a photoresist film manufacturing process.

EXAMPLES The present invention will be described with reference to the following Examples and Comparative Examples.
The present invention is not limited to these.

Example 1 A homopolymer chip of polyethylene terephthalate produced by a conventional method (intrinsic viscosity = 0.62, melting point: 259 ° C.)
Was dried under reduced pressure (3 mmHg) at 180 ° C. for 2 hours. This chip
Coextruded at 280 ° C with a screw having a compression ratio of 3.8, melt-extruded from a T-type die, and applied a surface temperature using an electrostatic application method.
After being wound around a cooling drum at 20 ° C. to be cooled and solidified to form an unstretched film, the obtained film is stretched 3.3 times in the longitudinal direction by roll stretching at 90 ° C., and the surface is subjected to a corona discharge treatment. Acrylic fluororesin "MF with a fluorine content of 32% by weight as a water-dispersible fluorine-containing polymer resin" MF
An aqueous coating material in which A "-7 (manufactured by Matsumoto Yushi Seiyaku Co., Ltd.) was uniformly dispersed at a concentration of 3.0% by weight was applied to one surface of the uniaxially stretched film by a metaling bar method, and the applied layer was dried. The film was stretched 3.6 times in the transverse direction at 100 ° C, and heat-treated at 210 ° C for 15 seconds while relaxing 2% in the transverse direction to obtain a 38 µm thick photoresist film base material with a coating layer 0.08 µm laminated. The properties of the base material thus obtained were as good as those shown in Table 1. The characteristics of the photoresist film when this film was used as a support layer were as follows.
As shown in the table, the releasability was excellent.

Examples 2 and 3 Comparative Examples 1 and 2 The same procedure as in Example 1 was repeated except that the fluorine content of the water-dispersible fluorine-containing polymer resin and the thickness of the coating layer were changed. A substrate was obtained.
These properties are shown in Table 1. As shown in Table 1, when the photoresist film is within the scope of the present invention (Examples 2 and 3), a photoresist film excellent in mold release properties and slipperiness can be obtained. When it is out of the range (Comparative Examples 1 and 2), it can be seen that a photoresist film excellent in both releasing property and lubricity cannot be obtained.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-62-227140 (JP, A) JP-A-62-253138 (JP, A) JP-A-62-42160 (JP, A) JP-A-59-227 202457 (JP, A) JP-A-49-105523 (JP, A) JP-T-55-501072 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) G03F 7/00-7 / 18

Claims (2)

(57) [Claims] 1. A coating layer comprising a water-dispersible fluorine-containing polymer resin obtained by using a vinyl polymer monomer having a perfluoroalkyl group as a main component on at least one surface of a polyester film. A photoresist film provided with a photoresist layer,
The coating layer has a fluorine content of 5 to 50% by weight and an ASTM
-A photoresist film having a slipperiness of 0.40 to 0.52 as measured by D-1894-63. 2. The method according to claim 1, wherein the photoresist film is provided with a coating layer on at least one surface of a polyester film stretched in one direction, and then a photoresist layer is formed on the coating layer of the film stretched in a direction perpendicular to the direction. The photoresist film according to claim 1, wherein the photoresist film is provided.