CN116601567A - Polyester film, dry film resist, and method for producing polyester film - Google Patents

Polyester film, dry film resist, and method for producing polyester film Download PDF

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Publication number
CN116601567A
CN116601567A CN202180084865.9A CN202180084865A CN116601567A CN 116601567 A CN116601567 A CN 116601567A CN 202180084865 A CN202180084865 A CN 202180084865A CN 116601567 A CN116601567 A CN 116601567A
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China
Prior art keywords
polyester film
film
polyester
particles
main surface
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CN202180084865.9A
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Chinese (zh)
Inventor
宫宅一仁
丰岛悠树
江夏泰雄
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Fujifilm Corp
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Fujifilm Corp
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Publication of CN116601567A publication Critical patent/CN116601567A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention addresses the problem of providing an optical polyester film which has excellent scratch resistance and can form a resist pattern having excellent pattern linearity even when a high-definition resist pattern is formed using a dry film by using the film in the manufacture of a dry film resist. The present invention also provides a method for producing a dry film resist and a polyester film. The polyester film of the present invention is an optical polyester film comprising: a polyester substrate substantially free of particles; and a particle-containing layer containing particles and a resin, which is disposed on at least one surface of the polyester substrate, wherein the polyester film has a 1 st main surface and a 2 nd main surface, the 2 nd main surface being a surface of the particle-containing layer on the opposite side from the polyester substrate side, the 2 nd main surface having a maximum cross-sectional height SRt of 20 to 150nm, and the particle-containing layer having a thickness of 1 to 200nm.

Description

Polyester film, dry film resist, and method for producing polyester film
Technical Field
The present invention relates to a polyester film, a dry film resist, and a method for producing a polyester film.
Background
From the viewpoints of processability, mechanical properties, electrical properties, dimensional stability, transparency, chemical resistance, and the like, polyester films are widely used, for example, as a support and protective film for dry film resists. The dry film resist has a structure in which a photosensitive resin layer (photoresist layer) is laminated on a support, and then a protective film is laminated thereon. In recent years, dry film resists have been used for etching in wiring formation processes, protective film formation for protecting wiring portions such as copper, ITO (indium tin oxide), silver nanoparticles, and interlayer insulating films in the field of touch panels.
Patent document J discloses a polyester film for a superfine line photoresist, which is a laminated polyester film comprising a polyester film as a support and a resist layer provided on one side of the support, wherein the laminated film has a haze of 1.0% or less, the surface of the laminated film on the side opposite to the resist layer side has a predetermined surface specific resistance and abrasion resistance index, and the number of surface scratches is smaller than a predetermined value.
Technical literature of the prior art
Patent literature
Patent document 1: japanese patent laid-open No. 2006-327158
Disclosure of Invention
Technical problem to be solved by the invention
Conventionally, the following techniques are known: when a laminate such as the Dry Film Resist (DFR) is produced using a polyester film as a support, a surface layer containing particles is provided on the surface of the polyester film in order to prevent scratches from being generated by adhesion of the films to each other.
On the other hand, with recent higher resolution (finer) resist patterns, higher performance than ever is required for the support constituting the DFR with respect to performance (thinning, low haze, etc.) that can contribute to higher resolution resist patterns.
The inventors of the present invention have found that, as a result of forming a fine resist pattern (particularly, an L/S pattern of 10 μm or less) having a narrower pattern width using DFR having a polyester film containing particles as a support, the pattern linearity of the resist pattern may be lowered depending on the characteristics of the polyester film.
In view of the above-described circumstances, an object of the present invention is to provide a polyester film which is excellent in scratch resistance and which can form a resist pattern excellent in pattern linearity even when a high-definition resist pattern is formed using a dry film by using the polyester film for the production of a dry film resist.
The present invention also provides a method for producing a dry film resist and a polyester film.
Means for solving the technical problems
As a result of intensive studies on the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by the following configuration.
〔1〕
A polyester film for optical use, comprising: a polyester substrate substantially free of particles; and a particle-containing layer containing particles and a resin, which is disposed on at least one surface of the polyester substrate, wherein the polyester film has a 1 st main surface and a 2 nd main surface, and wherein the 2 nd main surface is a surface of the particle-containing layer on the opposite side of the polyester substrate, the 2 nd main surface has a maximum cross-sectional height SRt of 20 to 150nm, and the particle-containing layer has a thickness of 1 to 200nm.
〔2〕
The polyester film according to [ 1 ], which is a polyester film for dry film resist production.
〔3〕
The polyester film according to [ 2 ], wherein,
the surface free energy of the 2 nd main surface is 50mJ/m 2 The following is given.
〔4〕
The polyester film according to [ 2 ] or [ 3 ], wherein,
the resin contains an acrylic resin.
〔5〕
The polyester film according to [ 4 ], wherein,
the acrylic resin is a copolymer having a structural unit derived from styrene and a structural unit derived from (meth) acrylate.
〔6〕
The polyester film according to [ 4 ] or [ 5 ], wherein,
the acrylic resin has a structural unit derived from a (meth) acrylate having an unsubstituted alkyl group having 1 to 4 carbon atoms in the ester moiety and a structural unit derived from a (meth) acrylate having an unsubstituted alkyl group having 5 to 10 carbon atoms in the ester moiety.
〔7〕
The polyester film according to any one of [ 1 ] to [ 6 ], wherein,
the thickness of the polyester film is 1-35 mu m.
〔8〕
The polyester film according to any one of [ 1 ] to [ 7 ], wherein,
the maximum cross-sectional height SRt of the 2 nd main surface is 20 to 40nm.
〔9〕
The polyester film according to any one of [ 1 ] to [ 8 ], wherein,
the density D (unit: unit/. Mu.m) of the particles constituting the protrusions of the 2 nd main surface 2 ) Maximum section height SRt (unit: nm) is 600 or less.
〔10〕
The polyester film according to any one of [ 1 ] to [ 9 ], wherein,
the particle-containing layer further contains a hydrocarbon surfactant.
〔11〕
The polyester film according to any one of [ 1 ] to [ 10 ], wherein,
the above resin has a crosslinked structure.
〔12〕
The polyester film according to any one of [ 1 ] to [ 11 ], wherein,
the particle-containing layer further contains wax.
〔13〕
The polyester film according to any one of [ 1 ] to [ 12 ], wherein a maximum cross-sectional height SRt of the 1 st main surface is 5 to 40nm.
〔14〕
The polyester film according to any one of [ 1 ] to [ 13 ], wherein,
the surface average roughness SRa of the 1 st main surface is 0 to 5.0nm, and the surface average roughness SRa of the 2 nd main surface is 1.0 to 5.0nm.
〔15〕
The polyester film according to any one of [ 1 ] to [ 14 ], wherein,
the surface free energy of the 1 st main surface is 50-70 mJ/m 2 。
〔16〕
A dry film resist, comprising: the polyester film according to any one of [ 1 ] to [ 15 ]; and a photosensitive resin layer provided on the 1 st main surface of the polyester film.
〔17〕
The dry film resist according to [ 16 ], wherein,
The photosensitive resin layer contains a polymer, a polymerizable compound, and a photopolymerization initiator.
〔18〕
The method for producing a polyester film according to any one of [ 1 ] to [ 15 ], which comprises: and a step of forming a particle-containing layer by in-line coating a polyester substrate substantially free of particles with a particle-containing layer-forming composition containing particles and a resin, wherein the particles dispersed in the particle-containing layer-forming composition have an average particle diameter of 10 to 250nm.
Effects of the invention
According to the present invention, it is possible to provide an optical polyester film which is excellent in scratch resistance and which can form a resist pattern excellent in pattern linearity even when a high-definition resist pattern is formed using a dry film by using the film for the production of a dry film resist.
Further, according to the present invention, a method for producing a dry film resist and a polyester film can be provided.
Drawings
Fig. 1 is a cross-sectional view showing an example of the structure of a polyester film according to the present invention.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within the scope of the object of the present invention.
In the present invention, the numerical range indicated by the term "to" refers to a range including the numerical values described before and after the term "to" as a lower limit value and an upper limit value. In the numerical ranges described in stages in the present invention, the upper limit or the lower limit described in a certain numerical range may be replaced with the upper limit or the lower limit of the numerical range described in other stages. In the numerical ranges described in the present invention, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value described in the examples.
In the present invention, when a plurality of substances corresponding to the respective components are present in the composition, the amount of the respective components in the composition refers to the total amount of the plurality of substances present in the composition unless otherwise specified.
In the present invention, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended purpose of the process can be achieved.
In the present invention, a combination of 2 or more preferred modes is a more preferred mode.
In the present invention, the term "polyester film" includes both a polyester base material monomer and a laminate of a polyester base material and a particle-containing layer.
In the present invention, the term "longitudinal direction" means the longitudinal direction of the polyester film when the polyester film is produced, and the term "conveyance direction" and the term "machine direction" are the same.
In the present invention, the "width direction" means a direction orthogonal to the longitudinal direction. In the present invention, "orthogonal" is not limited to strict orthogonality, but includes substantially orthogonal. "substantially orthogonal" means intersecting at 90++5°, preferably at 90++3°, more preferably at 90++1°.
In the present invention, the "film width" refers to the distance between both ends of the polyester film in the width direction.
In the present invention, "(meth) acrylate" means at least one of acrylate and methacrylate, "(meth) acrylic acid" means at least one of acrylic acid and methacrylic acid, and "(meth) acrylic acid" means at least one of acrylic acid and methacrylic acid.
In the present specification, unless otherwise specified, "exposure" includes not only exposure using light but also drawing using a particle beam such as an electron beam or an ion beam. Examples of the light used for exposure include an open spectrum of a mercury lamp, extreme ultraviolet rays typified by excimer laser, extreme ultraviolet rays (EUV light), active rays (active energy rays) such as X-rays and electron beams, and the like.
[ polyester film ]
The polyester film according to the present invention (hereinafter, also referred to as "present film") is an optical polyester film comprising: a polyester substrate substantially free of particles; and a particle-containing layer (hereinafter also referred to as a "specific layer") containing particles and a resin, which is disposed on at least one surface of the polyester substrate, wherein the polyester film has a 1 st main surface and a 2 nd main surface.
In the present film, the 2 nd main surface is the surface of the specific layer on the opposite side to the polyester substrate side, the maximum cross-sectional height SRt of the 2 nd main surface is 20 to 150nm, and the thickness of the specific layer is 1 to 200nm.
[ Structure ]
The structure of the present film will be described with reference to the accompanying drawings.
Fig. 1 is a cross-sectional view showing an example of the structure of the present film. The polyester film 1 includes a polyester substrate 2 and a specific layer 3 having a specific thickness disposed on at least one surface of the polyester substrate 2, and the polyester film 1 has a 1 st main surface 1a and a 2 nd main surface 1b.
The specific layer 3 contains particles not shown, and the polyester substrate 2 contains substantially no particles.
As shown in fig. 1, the two surfaces of the polyester film 1 are referred to as a 1 st main surface 1a and a 2 nd main surface 1b.
Of these, the 2 nd main surface 1b is the surface opposite to the surface facing the polyester substrate 2 of the specific layer 3. That is, the specific layer 3 is the outermost layer of the polyester film 1. The 2 nd main surface 1b has the above-specified maximum cross-sectional height SRt.
By having the above-described structure, the present film exhibits an effect of providing a polyester film (hereinafter, at least one of these effects is also referred to as "effect of the present invention"), which is excellent in scratch resistance, and can produce a dry film resist excellent in pattern linearity of a resist pattern even when used for forming a finer resist pattern.
The reason why the present film exerts the above-described effects of the present invention is not clear, but is presumed as follows.
As described above, in order to improve scratch resistance in producing DFR, a polyester film for DFR production often contains particles.
However, according to the studies by the present inventors, it is presumed that when a photosensitive resin layer is formed on the surface of a polyester film containing particles to produce DFR and a fine resist pattern is formed using the obtained DFR, the particles contained in the polyester film and/or transfer marks formed by transferring the uneven structure formed by the particles on the surface of the polyester film onto the photosensitive resin layer scatter irradiation light at the time of pattern exposure, and there is a possibility that the pattern linearity is lowered.
In contrast, in the present film, it is presumed that by using a polyester substrate containing substantially no particles as a substrate constituting the polyester film, scattering of pattern exposure caused by the particles can be suppressed, and by reducing transfer marks formed on a photosensitive resin layer laminated on the polyester film, scattering of pattern exposure can also be suppressed. Further, since the particle-containing layer having a small thickness and having a maximum cross-sectional height SRt of a specific value or less is formed on the surface (the 2 nd main surface) of the film on the side where the photosensitive resin layer is not laminated, scattering of pattern exposure on the surface of the particle-containing layer can be suppressed. It is considered that by using the above-described feature structure of the present film, scattering at the time of pattern exposure is suppressed, and a resist pattern having high definition and excellent pattern linearity can be formed.
In the present film, it is considered that the occurrence of scratches due to the adhesion between films caused by the decrease in the sliding property is suppressed because the maximum cross-sectional height SRt of the particle-containing layer is a specific value or more, and that the scratch resistance of the polyester film which is advantageous for the production of DFR is ensured by suppressing the falling-off of particles which are the cause of the occurrence of scratches because the maximum cross-sectional height SRt of the particle-containing layer is a specific value or less.
Hereinafter, even when a DFR is produced using the polyester film and a high-definition resist pattern is formed using the DFR, the characteristics of a resist pattern having excellent pattern linearity can be simply described as "excellent pattern linearity".
The specific mode of the present film is not particularly limited as long as the film has the polyester base material and the specific layer and the maximum cross-sectional height SRt of the 2 nd main surface is defined within the above range, and may have a mode other than the structure shown in fig. 1.
For example, in the structure shown in fig. 1, the 1 st main surface 1a of the polyester film 1 is the surface of the polyester substrate 2 on the side opposite to the specific layer 3 side, but on the surface of the polyester substrate on the side opposite to the specific layer side, another layer whose surface on one side is the 1 st main surface may be arranged. Examples of such other layers include an adhesion layer, a release layer, an antistatic layer, and an oligomer deposition preventing layer.
In the structure shown in fig. 1, the specific layer 3 is disposed on only one side of the polyester substrate 2, but may be disposed on both sides.
In the structure shown in fig. 1, the specific layer 3 is disposed in contact with the surface of the polyester substrate 2, but an intermediate layer such as a primer layer may be provided between the specific layer and the polyester substrate.
The thickness of the other layer is preferably 1nm to 1. Mu.m, more preferably 30 to 500nm.
The layers of the present film will be described in detail below.
< polyester substrate >
The polyester base material is a film-like object containing polyester as a main polymer component. The "main polymer component" herein means a polymer having the largest content (mass) of all polymers contained in the film.
The polyester base material may contain 1 kind of polyester alone or 2 or more kinds of polyesters.
(polyester)
Polyesters are polymers having ester linkages in the backbone. The polyester is usually formed by polycondensing a dicarboxylic acid compound to be described later with a diol compound.
The polyester is not particularly limited, and known polyesters can be used. Examples of the polyester include polyethylene terephthalate (PET), polyethylene-2, 6-naphthalate (PEN), and copolymers thereof, and PET is preferable.
The intrinsic viscosity of the polyester is preferably 0.50dl/g or more and less than 0.80dl/g, more preferably 0.55dl/g or more and less than 0.70dl/g.
The melting point (Tm) of the polyester is preferably 220 to 270℃and more preferably 245 to 265 ℃.
The glass transition temperature (Tg) of the polyester is preferably 65 to 90℃and more preferably 70 to 85 ℃.
The method for producing the polyester is not particularly limited, and a known method can be used. For example, polyesters can be produced by polycondensing at least 1 dicarboxylic acid compound with at least 1 diol compound in the presence of a catalyst.
Catalyst-
The catalyst used in the production of the polyester is not particularly limited, and a known catalyst that can be used for the synthesis of the polyester can be used.
Examples of the catalyst include alkali metal compounds (for example, potassium compounds and sodium compounds), alkaline earth metal compounds (for example, calcium compounds and magnesium compounds), zinc compounds, lead compounds, manganese compounds, cobalt compounds, aluminum compounds, antimony compounds, titanium compounds, germanium compounds and phosphorus compounds. Among them, titanium compounds are preferred from the viewpoints of catalyst activity and cost.
The catalyst may be used in an amount of 1 or 2 or more. Preferably, at least 1 metal catalyst selected from the group consisting of potassium compounds, sodium compounds, calcium compounds, magnesium compounds, zinc compounds, lead compounds, manganese compounds, cobalt compounds, aluminum compounds, antimony compounds, titanium compounds and germanium compounds and phosphorus compounds are used in combination, more preferably, titanium compounds and phosphorus compounds are used in combination.
As the titanium compound, an organic chelate titanium complex is preferable. The organic chelate titanium complex is a titanium compound having an organic acid as a ligand.
Examples of the organic acid include citric acid, lactic acid, trimellitic acid, and malic acid.
As the titanium compound, those described in paragraphs 0049 to 0053 of japanese patent No. 5575671, the contents of which are incorporated herein by reference, can also be used.
Dicarboxylic acid compounds
Examples of the dicarboxylic acid compound include dicarboxylic acids such as aliphatic dicarboxylic acid compounds, alicyclic dicarboxylic acid compounds and aromatic dicarboxylic acid compounds, and dicarboxylic acid esters such as methyl ester compounds and ethyl ester compounds of these dicarboxylic acids. Among them, aromatic dicarboxylic acid or aromatic dicarboxylic acid methyl ester is preferable.
Examples of the aliphatic dicarboxylic acid compound include malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, dimer acid, eicosanedioic acid, pimelic acid, azelaic acid, methylmalonic acid and ethylmalonic acid.
Examples of the alicyclic dicarboxylic acid compound include adamantanedicarboxylic acid, norbornene dicarboxylic acid, cyclohexane dicarboxylic acid and decalin dicarboxylic acid.
Examples of the aromatic dicarboxylic acid compound include terephthalic acid, isophthalic acid, phthalic acid, 1, 4-naphthalenedicarboxylic acid, 1, 5-naphthalenedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, 1, 8-naphthalenedicarboxylic acid, 4' -diphenyldicarboxylic acid, 4' -diphenylenedicarboxylic acid, sodium sulfoisophthalic acid, phenylindane dicarboxylic acid, anthracene dicarboxylic acid, phenanthrene dicarboxylic acid, and 9,9' -bis (4-dicarboxyphenyl) fluorenoic acid, and methyl esters thereof.
Among them, terephthalic acid, methyl terephthalate, 2, 6-naphthalenedicarboxylic acid or methyl 2, 6-naphthalenedicarboxylic acid is preferable, and terephthalic acid or methyl terephthalate is more preferable.
The dicarboxylic acid compound may be used in an amount of 1 or 2 or more. In the case of using terephthalic acid as the dicarboxylic acid compound, terephthalic acid may be used alone or may be copolymerized with other aromatic dicarboxylic acids such as isophthalic acid or aliphatic dicarboxylic acids.
Diol compound-
Examples of the diol compound include aliphatic diol compounds, alicyclic diol compounds, and aromatic diol compounds, and aliphatic diol compounds are preferable.
Examples of the aliphatic diol compound include ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 2-butanediol, 1, 3-butanediol, and neopentyl glycol, and ethylene glycol is preferable.
Examples of the alicyclic diol compound include cyclohexanedimethanol, spiro diol and isosorbide.
Examples of the aromatic diol compound include bisphenol A, 1, 3-benzenedimethanol, 1, 4-benzenedimethanol, and 9,9' -bis (4-hydroxyphenyl) fluorene.
The diol compound may be used in an amount of 1 or 2 or more.
Blocking agent-
In the production of the polyester, a capping agent may be used as needed. By using a capping agent, a structure derived from the capping agent is introduced at the end of the polyester.
The blocking agent is not limited, and a known blocking agent can be used. Examples of the blocking agent include oxazoline compounds, carbodiimide compounds, and epoxy compounds.
As the blocking agent, reference may be made to those described in paragraphs 0055 to 0064 of japanese patent application laid-open No. 2014-189002, the contents of which are incorporated herein by reference.
Production conditions-
The reaction temperature is not limited and may be appropriately set according to the starting material. The reaction temperature is preferably 260 to 300℃and more preferably 275 to 285 ℃.
The pressure is not limited and may be appropriately set according to the material. The pressure is preferably 1.33X10 -3 ～1.33×10 - 5 MPa, more preferably 6.67×10 -4 ～6.67×10 -5 MPa。
As a method for synthesizing polyesters, the method described in paragraphs 0033 to 0070 of japanese patent No. 5575671, the contents of which are incorporated herein by reference, can also be used.
The content of the polyester in the polyester base material is preferably 85 mass% or more, more preferably 90 mass% or more, further preferably 95 mass% or more, and particularly preferably 98 mass% or more, relative to the total mass of the polymers in the polyester base material.
The upper limit of the content of the polyester is not limited, and can be appropriately set in a range of 100 mass% or less relative to the total mass of the polymer in the polyester base material.
In the case where the polyester substrate contains polyethylene terephthalate, the content of polyethylene terephthalate is preferably 90 to 100 mass%, more preferably 95 to 100 mass%, further preferably 98 to 100 mass%, and particularly preferably J00 mass% with respect to the total mass of the polyester in the polyester substrate.
The polyester base material may contain components other than polyester (for example, catalyst, unreacted raw material component, particles, water, and the like).
From the viewpoint of excellent pattern linearity, the polyester base material contains substantially no particles. Examples of the particles include particles contained in a specific layer described below. The term "substantially free of particles" is defined as that when the element derived from the particles is quantitatively analyzed on the polyester substrate by fluorescent X-ray analysis, the content of the particles is 50 mass ppm or less, preferably 10 mass ppm or less, and more preferably the detection limit or less, relative to the total mass of the polyester substrate. This is because, even if particles are not positively added to the polyester substrate, there is a possibility that a contaminating component derived from foreign matters, a raw resin, or dirt adhering to a production line or a device in a production process of the polyester substrate may be peeled off and mixed into the polyester substrate.
From the viewpoint of improving the transferability, the thickness of the polyester base material is preferably 100 μm or less, more preferably 50 μm or less, and still more preferably 35 μm or less. The lower limit of the thickness is not particularly limited, but is preferably 1 μm or more, more preferably 4 μm or more, and still more preferably 10 μm or more from the viewpoint of improving strength and workability.
The thickness of the polyester substrate was measured according to the method for measuring the thickness of a polyester film described later.
< specific layer >
The specific layer is a layer containing particles and a resin, and is formed on at least one surface of the polyester substrate. The surface of the specific layer opposite to the surface facing the polyester substrate constitutes the 2 nd main surface.
The film has the above specific layer, and thus can exhibit the effect of the present invention, which is excellent in balance between scratch resistance and pattern linearity.
The specific layer may be provided directly on the surface of the polyester substrate or may be provided on the surface of the polyester substrate with another layer interposed therebetween, but is preferably provided directly on the surface of the polyester substrate from the viewpoint of further excellent adhesion. That is, the surface on the 1 st main surface side of the specific layer is preferably in contact with the polyester substrate.
The specific layer is not particularly limited as long as it contains particles and a resin, has a thickness of 1 to 200nm, and has a specific maximum cross-sectional height SRt on the 2 nd main surface. The specific layer may contain additives other than the particles and the resin.
(particles)
The particles contained in the specific layer are not particularly limited as long as the maximum section height SRt of the 2 nd main surface is contained in the above-described range and the thickness of the specific layer is contained in the above-described range.
The average particle diameter of the particles is, for example, 1 to 250nm. From the viewpoint of further excellent effects of the present invention, the average particle diameter of the particles is preferably 150nm or less, more preferably 130nm or less, and still more preferably 100nm or less. Further, the lower limit is preferably 10nm or more, more preferably 30nm or more, from the viewpoint of further excellent effects of the present invention.
The average particle diameter of the particles contained in the specific layer is preferably larger than the thickness of the specific layer.
As the particles contained in the specific layer, 1 type of particles may be used alone, or 2 or more types of particles may be used.
When the specific layer contains 2 or more kinds of particles having different particle diameters, the specific layer preferably contains at least 1 kind of particles having an average particle diameter within the above range, and more preferably 2 or more kinds of particles having different particle diameters are particles having average particle diameters within the above range.
The average particle diameter of the particles contained in the specific layer was determined by using a scanning electron microscope (SEM: scanning Flectron Microscope) and the following method. That is, the 2 nd main surface of the polyester film was observed at 20000 times magnification using SEM. The arbitrarily selected 10 fields of view were observed, and for particles identifiable as protrusions in each field of view (particles identifiable as protrusions protruding from the base surface), the area of each particle was measured using image software, and the diameter of a circle having the same area (area circle equivalent diameter) was calculated. The arithmetic average of the area circle equivalent diameters obtained was taken as the average particle diameter of the particles. In this case, even if dust and/or coarse particles having agglomerated at least 1 μm are present, these dust and coarse particles having agglomerated are not counted when the average particle diameter is calculated.
In the measurement of the average particle diameter, the particle diameter (2-order particle diameter) of the 2-order particles in the agglomerated state was measured for the agglomerated particles.
Examples of the particles contained in the specific layer include organic particles and inorganic particles. Among them, inorganic particles are preferable from the viewpoint of further improving film winding quality, haze, and durability (for example, thermal stability).
As the organic particles, resin particles are preferable. Examples of the resin constituting the resin particles include acrylic resins such as polymethyl methacrylate (PMMA), polyester resins, silicone resins, and styrene-acrylic resins. The resin particles preferably have a crosslinked structure. Examples of the resin particles having a crosslinked structure include divinylbenzene crosslinked particles.
Examples of the inorganic particles include silica particles ((Silicon dioxide particles), colloidal silica), titania particles (titanium oxide particles), calcium carbonate, barium sulfate, and alumina particles (aluminum oxide particles). Among the above, silica particles are preferable as the inorganic particles from the viewpoint of further improving haze and durability.
The shape of the particles is not particularly limited, and examples thereof include rice grains, spheres, cubes, spindles, flakes, agglomerates, and irregular shapes. The aggregation state refers to a state in which 1 st order particles are aggregated. The shape of the particles in a coagulated form is not limited, and a spherical shape or an irregular shape is preferable.
The particles may be particles having a hollow structure (hollow particles) or particles not having a hollow structure (solid particles), but solid particles are preferable from the viewpoint of more excellent pattern linearity (transparency). In the present specification, the hollow structure means a structure composed of an internal cavity and a shell surrounding the cavity. When the particles are solid particles, the change in refractive index is small, and light scattering can be suppressed.
As the aggregated particles having no hollow structure, fumed silica particles are preferable. Examples of commercially available products include the AEROSIL series manufactured by NIPPON AEROSIL co.
As the non-aggregated particles having no hollow structure, colloidal silica particles are preferable. Examples of commercially available products include SNOWTEX series manufactured by Nissan Chemical Industries, ltd.
From the viewpoints of the transport property and the coatability of the release layer, the content of particles in the specific layer is preferably 0.1 to 30 mass%, more preferably 1 to 25 mass%, even more preferably 1 to 15 mass%, and particularly preferably 1 to 5 mass% relative to the total mass of the specific layer.
The content of the particles is preferably 0.0001 to 0.01 mass%, more preferably 0.0005 to 0.005 mass% based on the total mass of the polyester film.
In addition, from the viewpoint of further excellent effects of the present invention, it is preferable that the content of particles having an average particle diameter of more than 250nm in the specific layer is small. Examples of such particles include particles having an average particle diameter of more than 250nm, particles having an average particle diameter of 2 times of particles obtained by aggregation of the particles, and foreign substances such as dust which are inevitably mixed.
[ resin ]
The resin contained in the specific layer is not particularly limited, and examples thereof include acrylic resins, urethane resins, polyesters, and polyolefins.
The specific layer is preferably formed by coating an aqueous dispersion of resin particles. In this regard, as the resin, an acid-modified resin is preferable. Examples of the acid-modified resin include an acrylic resin having a structural unit derived from (meth) acrylic acid and a polyolefin having a carboxyl group, which will be described later.
Further, from the viewpoint of further improving scratch resistance while keeping the surface free energy of the specific layer within a desired range, acrylic resins are preferable.
Acrylic resin
In the present specification, the acrylic resin means a polymer having a structural unit derived from (meth) acrylate as a main component.
In the present specification, the term "a polymer having" a structural unit derived from a certain monomer as a main component means that the structural unit is 50 mol% or more with respect to all structural units of the polymer.
The acrylic resin is not particularly limited as long as it has a structural unit derived from a (meth) acrylate, and may be a homopolymer of 1 (meth) acrylate or a copolymer of 2 or more (meth) acrylates.
The acrylic resin preferably contains a structural unit derived from a (meth) acrylic acid ester having an alkyl group at an ester position (alkyl (meth) acrylate).
The alkyl group in the alkyl (meth) acrylate may further have a substituent. Examples of the substituent include aryl, hydroxy and alkoxy groups, and phenyl, hydroxy and alkoxy groups having 1 to 3 carbon atoms are preferable. The number of carbon atoms of the alkyl group (more preferably, unsubstituted alkyl group) which may have a substituent in the alkyl (meth) acrylate is preferably 1 to 15, more preferably 1 to 10.
In particular, from the viewpoint of easy adjustment of the surface energy within a desired range, an acrylic resin having a structural unit derived from a (meth) acrylate having an unsubstituted alkyl group having 1 to 4 carbon atoms in the ester moiety and a structural unit derived from a (meth) acrylate having an unsubstituted alkyl group having 5 to 10 carbon atoms in the ester moiety is preferable.
Specific examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.
The acrylic resin may be a copolymer of at least 1 (meth) acrylate and at least 1 vinyl monomer other than (meth) acrylate, for example, (meth) acrylamide, (meth) acrylic acid, styrene, and the like.
Among them, from the viewpoint of more excellent suppression of scratches of the film, an acrylic resin having a copolymer of a structural unit derived from styrene and a structural unit derived from (meth) acrylate is preferable.
The acrylic resin preferably has an acid-modified component. The acrylic resin preferably contains a structural unit derived from (meth) acrylic acid as an acid modifying component. The (meth) acrylic acid may form an acid anhydride or may be neutralized with at least one selected from alkali metals, organic amines and ammonia.
In the acrylic resin, the content of the structural unit derived from the (meth) acrylic acid ester is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more, relative to all the structural units of the acrylic resin. The upper limit of the content of the structural unit derived from (meth) acrylic acid ester is not particularly limited, and may be 100% by mass with respect to all the structural units of the acrylic resin.
When the acrylic resin has structural units derived from monomers other than (meth) acrylic acid esters, the content thereof is preferably 0 to 30% by mass, more preferably 0.1 to 10% by mass, relative to all the structural units of the acrylic resin.
When the acrylic resin has a structural unit containing an acid modifying group, the content thereof is preferably 0.1 to 10% by mass, more preferably 1 to 10% by mass, relative to all the structural units of the acrylic resin, of the structural unit derived from (meth) acrylic acid. By setting the content of the structural unit having an acid modifying group in the above range, electrification can be suppressed, and the acid value of the acrylic resin can be reduced, so that the surface free energy of the 2 nd main surface can be adjusted to be within a desired range.
The acid value of the acrylic resin is preferably 30mgKOH/g or less, more preferably 20mgKOH/g or less. The lower limit of the acid value is not particularly limited, but is, for example, 0mgKOH/g, and is preferably 2mgKOH/g or more from the viewpoint of coating as an aqueous dispersion.
The acid value here is the mass [ mg ] of potassium hydroxide required for neutralizing 1g of the sample, and in this specification, the unit is referred to as mgKOH/g. The acid value can be calculated, for example, from the average content of acid groups in the compound.
The method for producing the acrylic resin is not particularly limited, and it can be produced by polymerizing 1 or more (meth) acrylates with any monomer other than (meth) acrylates by a known method.
The specific layer may contain 1 resin alone or 2 or more resins. Examples of the resins used in combination include various types of acrylic resins, urethane resins, polyolefin and polyesters. In addition, from the viewpoint of further excellent durability, the resin contained in the specific layer preferably has a crosslinked structure. The resin having a crosslinked structure can be formed by crosslinking the resin using a crosslinking agent described later.
From the viewpoint of adjusting the maximum cross-sectional height SRt within a desired range, the content of the resin is preferably 30 to 99.8 mass%, more preferably 50 to 99.5 mass% with respect to the total mass of the specific layer.
(additive)
The specific layer may contain additives other than the above-mentioned particles and resin.
Examples of the additive contained in the specific layer include surfactants, waxes, crosslinking agents, antioxidants, ultraviolet absorbers, colorants, reinforcing agents, plasticizers, antistatic agents, flame retardants, rust inhibitors, antifoaming agents, foaming agents, lubricants, thickeners, and mold inhibitors.
Surfactant-containing compositions
The specific layer preferably has a surfactant from the viewpoint of improving the smoothness of the region other than the region where the protrusions formed by the particles are present on the 2 nd main surface. The smoothness of the above region of the 2 nd main surface improves, and the surface roughness of the 2 nd main surface becomes small due to reasons other than particles, whereby SRt can be controlled within a desired range, and the effects of the present invention can be improved.
The surfactant is not particularly limited, and examples thereof include silicone surfactants, fluorine surfactants, and hydrocarbon surfactants are preferable from the viewpoint of easy adjustment of surface free energy.
The silicone surfactant is not particularly limited as long as it is a surfactant having a silicon-containing group as a hydrophobic group, and examples thereof include polydimethylsiloxane, polyether-modified polydimethylsiloxane, and polymethylalkylsiloxane.
Examples of the commercially available silicone surfactants include BYK (registered trademark) -306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, BYK-347, BYK-348 and BYK-349 (manufactured by BYK corporation above), KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-643, KF-6020, X-22-4515, KF-6011, KF-6012, KF-6015 and KF-6017 (manufactured by Shin-Etsu Chemical Co., ltd.).
The fluorine-based surfactant is not particularly limited as long as it is a surfactant having a fluorine-containing group as a hydrophobic group, and examples thereof include perfluorooctane sulfonic acid and perfluorocarboxylic acid.
Examples of the commercial products of the fluorine-based surfactant include MEGAFACE (registered trademark) F-114, F-410, F-440, F-447, F-553, and F-556 (manufactured by DIC Corporation, above) and Surflon (registered trademark) S-211, S-221, S-231, S-233, S-241, S-242, S-243, S-420, S-661, S-651, and S-386 (AGC SEIMI CHEMICAL CO., LTD).
From the viewpoint of improving the environmental suitability, the fluorine-based surfactant is preferably a surfactant derived from a substitute material of a compound having a linear perfluoroalkyl group having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS).
Examples of the hydrocarbon surfactant include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants.
Examples of the anionic surfactant include alkyl sulfate, alkylbenzenesulfonate, alkyl phosphate and fatty acid salt.
Examples of the nonionic surfactant include polyalkylene glycol mono-or dialkyl ethers, polyalkylene glycol mono-or dialkyl esters, and polyalkylene glycol monoalkyl esters/monoalkyl ethers.
Examples of the cationic surfactant include primary to tertiary alkylamine salts and quaternary ammonium compounds.
The amphoteric surfactant includes surfactants having both anionic and cationic sites in the molecule.
Examples of commercial products of anionic surfactants include RAPISOL (registered trademark) A-90, A-80, BW-30, B-90 and C-70 (manufactured by NOF CORPORATION, supra), NIKKOL (registered trademark) OTP-100 (manufactured by Nikko Chemicals Co., ltd., supra), KOHACOOL (registered trademark) ON, L-40 and Photonol (registered trademark) 702 (manufactured by TOHO Chemical Industry Co., ltd., supra), and BEAULIGHT (registered trademark) A-5000 and SSS (manufactured by Sanyo Chemical Industries, ltd., supra).
Examples of the commercial products of the nonionic surfactant include NAROACTY (registered trademark) CL-95 and HN-100 (trade name: sanyo Chemical Industries, manufactured by Ltd.), RISOREX BW400 (trade name: KOKYU ALCOHOL KOGYO CO., manufactured by LTD.), EMASEX (registered trademark) ET-2020 (manufactured by NIHON EMULSION Co., ltd.), and Surfynol (registered trademark) 104E, 420, 440, 465 and DYNOL (registered trademark) 604, 607 (manufactured by Nissin Chemical Co., ltd.).
From the viewpoint of forming a particle-containing layer having a smooth surface without interfering with the dispersion of the resin, when used in combination with the acid-modified resin, an anionic surfactant and/or a nonionic surfactant is preferable, and an anionic surfactant is more preferable. That is, from the viewpoint of improving the surface smoothness, the surfactant is more preferably an anionic hydrocarbon surfactant.
From the viewpoint of further improving the smoothness, the anionic hydrocarbon surfactant preferably has a plurality of hydrophobic end groups. The hydrophobic end group may be a part of a hydrocarbon group of the hydrocarbon surfactant. For example, a hydrocarbon surfactant having a hydrocarbon group containing a branched structure at the end will have a plurality of hydrophobic end groups.
Examples of anionic hydrocarbon surfactants having a plurality of hydrophobic end groups include sodium di-2-ethylhexyl sulfosuccinate (having 4 hydrophobic end groups), sodium di-2-ethyloctyl sulfosuccinate (having 4 hydrophobic end groups), and branched alkylbenzene sulfonate (having 2 hydrophobic end groups).
The surfactant may be used in an amount of 1 or 2 or more.
The content of the surfactant is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, and still more preferably 0.5 to 2% by mass, based on the total mass of the specific layer, from the viewpoint of further excellent antistatic property and surface smoothness at the time of forming the release layer.
Wax-
From the viewpoint of easy adjustment of the surface free energy, it is preferable that the specific layer further contains wax.
The wax is not particularly limited, and may be either natural wax or synthetic wax. Examples of natural waxes include carnauba wax, candelilla wax, beeswax, montan wax, paraffin wax, and petroleum wax. Further, a lubricant described in paragraph 0087 of the specification of international publication No. 2017/169844 can also be used.
Examples of the commercially available wax include the Cellosol (registered trademark) series (CHUKYO YUSHI co., ltd.).
The content of the wax is preferably 0 to 10 mass% relative to the total mass of the specific layer.
Crosslinking agent-
The resin contained in the specific layer preferably has a crosslinked structure formed using a crosslinking agent. The crosslinking agent is not particularly limited, and a known crosslinking agent can be used.
Examples of the crosslinking agent include melamine compounds, oxazoline compounds, epoxy compounds, isocyanate compounds and carbodiimide compounds, and particularly preferable are oxazoline compounds and carbodiimide compounds.
Examples of the commercial products include CARBODILITE (registered trademark) V-02-L2 (manufactured by Nisshinbo Holdings inc. And registered trademark) K-2020E (manufactured by NIPPON shokubaci co., ltd.). For details of the epoxy compound, isocyanate compound and melamine compound, refer to paragraphs 0081 to 0083 of Japanese patent application laid-open No. 2015-163457. The crosslinking agents described in paragraphs 0082 to 0084 of the specification of International publication No. 2017/169844 can also be preferably used. As the carbodiimide compound, reference is made to paragraphs 0038 to 0040 of Japanese patent application laid-open No. 2017-087421.
Regarding the oxazoline compound, the carbodiimide compound and the isocyanate compound, a crosslinking agent described in paragraphs 0074 to 0075 of the specification of International publication No. 2018/034294 can also be preferably used.
The content of the crosslinking agent is preferably 0 to 50 mass% relative to the total mass of the specific layer.
From the viewpoint that the coatability of the specific layer is not deteriorated when the specific layer is formed by aggregation with a resin and/or particles, the content of the cationic organic compound in the specific layer is preferably small.
(thickness)
The thickness of the specific layer is preferably from 1 to 200nm, more preferably from 10 to 100nm, and even more preferably from 20 to 100nm, from the viewpoint of more excellent effect of the present invention, and from the viewpoint of manufacturing suitability of the specific layer and reduction in haze.
The thickness of the specific layer was an arithmetic average of the thicknesses of 5 portions of a slice having a vertical cross section to the main surface of the polyester film measured using a Scanning Electron Microscope (SEM) or a transmission electron microscope (TEM: transmission Electron Microscope) after the slice was prepared.
When a particular layer is soft and it is difficult to stably produce a cross-sectional slice, a spectrophotometer can be used for measurement. Specifically, a unit capable of measuring absolute reflectance is provided on a spectrophotometer, and an absolute reflectance spectrum (specific layer surface) at an incident angle of 5 degrees is measured. The film thickness of the specific layer can be obtained by fitting the reflectance spectrum to a spectrum calculated by taking the refractive indices of the specific layer and the polyester base material and the film thickness of the specific layer as parameters.
The method of forming the specific layer will be described in detail in the "specific layer forming step" described later.
[ physical Properties, etc. ]
Next, the physical properties of the present film and the like will be described.
(surface free energy of the 2 nd major surface)
The surface free energy of the 2 nd main surface of the film is preferably 60mJ/m 2 Hereinafter, more preferably 50mJ/m 2 Hereinafter, it is more preferably 25 to 50mJ/m 2 Particularly preferably 30 to 50mJ/m 2 . By setting the surface free energy of the 2 nd main surface within the above range, even if the maximum cross-sectional height SRt of the 2 nd main surface is within the above range, a polyester film which is excellent in scratch resistance, which is free from adhesion of foreign matters such as dust, and which is less likely to cause scratches on the film surface can be obtained.
The surface free energy of the 2 nd main surface (surface of the specific layer) can be adjusted by selecting the types of particles, resins, and additives contained in the specific layer and the content thereof, for example.
The surface free energy of the 2 nd main surface of the polyester film can be measured by a method described later.
(surface free energy of the 1 st major surface)
From the viewpoint of antistatic property at the time of winding the present film, the surface free energy of the 1 st main surface is preferably 40 to 80mJ/m 2 More preferably 50 to 70mJ/m 2 。
Further, a film having a large difference between the surface free energy of the 1 st main surface and the surface free energy of the 2 nd main surface is preferable because it is difficult to charge the film. The difference between the surface free energy of the 1 st main surface and the surface free energy of the 2 nd main surface is preferably 1 to 35mJ/m 2 More preferably 10 to 30mJ/m 2 。
The surface free energy of the 1 st main surface can be adjusted according to the kind of the resin and the additive forming the layer having the 1 st main surface. For example, when the specific layer is provided only on one side of the polyester substrate and the 1 st main surface is the surface of the polyester substrate on the side opposite to the specific layer side, the surface free energy of the 1 st main surface can be adjusted according to the kind of polyester forming the polyester substrate and the additive and their contents. When the non-polyester resin layer is provided, the surface free energy of the 1 st main surface can be adjusted according to the type of the non-polyester resin and the additive contained in the non-polyester resin layer and the content thereof. When the specific layers are provided on both surfaces of the polyester substrate, the surface free energy of the 1 st main surface can be adjusted according to the types of the resin and the additive contained in the specific layer on the side where the 1 st main surface is formed and the content thereof.
(maximum section height SRt of the 2 nd main surface, surface average roughness SRa)
In the present film, the maximum cross-sectional height SRt of the 2 nd main surface is 20 to 150nm. By setting the maximum cross-sectional height SRt of the 2 nd main surface within the above range, a polyester film excellent in balance between scratch resistance and pattern linearity can be obtained.
From the above point of view, the maximum cross-sectional height SRt of the 2 nd main surface is preferably 20 to 100nm, more preferably 20 to 40nm.
In the present film, the surface average roughness SRa of the 2 nd main surface is preferably 0.5 to 10.0nm, more preferably 1.0 to 8.0nm, and even more preferably 1.0 to 5.0nm, from the viewpoint of further excellent stability in suppressing transfer marks.
The maximum cross-sectional height SRt of the 2 nd main surface (surface of the specific layer) and the surface average roughness SRa can be adjusted, for example, according to the average particle diameter and content of the particles contained in the specific layer and the thickness of the specific layer. When the specific layer is formed by in-line coating, the above adjustment can be made more easily.
The maximum cross-sectional height SRt and the surface average roughness SRa of the 2 nd main surface of the polyester film can be measured by a method described later.
(maximum section height SRt of the 1 st main surface, surface average roughness SRa)
From the viewpoint of smoothing layers such as photosensitive resin layers laminated in the production of DFR, the 1 st main surface is preferably as smooth as possible. Specifically, the maximum cross-sectional height SRt of the 1 st main surface is preferably 1 to 60nm, more preferably 5 to 40nm. The surface average roughness SRa of the 1 st main surface is preferably 0 to 10.0nm, more preferably 0 to 5.0nm.
The maximum section height SRt of the 1 st main surface and the surface average roughness SRa can be adjusted by: the specific layer is provided only on one side, and the polyester substrate is substantially free from particles, and the type of polyester constituting the polyester substrate, the type of additive, and the like are selected so as to form a film smoothly. And, when the non-polyester resin layer is provided, it can be adjusted by: no particles are added in the non-polyester resin layer; selecting the type of the non-polyester resin and the additive (surfactant, etc.) forming the non-polyester resin layer; and forming a smooth particle-containing layer.
The maximum cross-sectional height SRt of the 1 st main surface and the surface average roughness SRa can be measured by the method of measuring the maximum cross-sectional height SRt of the 2 nd main surface and the surface average roughness SRa.
(particle Density D of the 2 nd major surface)
From the viewpoint of further excellent effects of the present invention, the present film has a density D (unit: unit/. Mu.m) of particles constituting the protrusions of the 2 nd main surface 2 Also referred to as "particle density D") is preferably 1 to 10 particles/μm 2 More preferably 1 to 5 pieces/μm 2 。
The particle density D can be adjusted according to, for example, the average particle diameter and content of particles contained in the specific layer and the thickness of the specific layer, similarly to the maximum cross-sectional height SRt and the surface average roughness SRa. When the specific layer is formed by in-line coating, the above adjustment can be made more easily.
The particle density D of the particles constituting the protrusions on the 2 nd main surface of the polyester film can be measured by a method described later.
(product of maximum section height SRt of principal surface 2 and particle density D)
In the present film, the particle density D (unit: unit/. Mu.m) of the 2 nd main surface is as follows 2 ) Maximum section height SRt (unit: nm), is preferably 1000 or less, more preferably 600 or less, and still more preferably 130 or less. The lower limit is not particularly limited, but is preferably 1 or more, more preferably 20 or more, and still more preferably 50 or more from the viewpoint of further excellent scratch resistance.
(orientation)
The film is a biaxially oriented polyester film. In the present invention, "biaxial orientation" refers to a property having molecular orientation in biaxial directions.
Molecular orientation was measured using a microwave transmission type molecular orientation instrument (for example, manufactured by MOA-6004,Oji Scientific Instruments). The angle formed by the biaxial directions is preferably 90 ° ± 5 °, more preferably 90 ° ± 3 °, further preferably 90 ° ± 1 °. The film preferably has molecular orientation in the longitudinal direction and the width direction.
(expansion ratio)
The expansion ratio of the polyester film in the width direction at 90℃is preferably-0.15 to 0.15%, more preferably-0.10 to 0.10%, even more preferably 0 to 0.10%, and particularly preferably 0 to 0.05% relative to the film width at 30 ℃.
By adjusting the expansion ratio of the polyester film in the width direction at 90 ℃ within the above range, not only the expansion of the film in the width direction during heating can be suppressed, but also the expansion ratio unevenness at each portion of the film surface can be reduced. As a result, it was observed that the occurrence of the streak-like defect region due to heating can be suppressed.
The expansion ratio in the width direction at 90℃was measured by the following method using a thermo-mechanical analysis device.
(1) A sample adjusted to a length of at least 20mm in a direction parallel to the width direction of the biaxially oriented film and adjusted to a length of 4mm in a direction orthogonal to the width direction of the biaxially oriented film was prepared.
(2) A sample having a width of 4mm and a length (distance between chucks) of 20mm was subjected to a tensile load of 0.1g using a thermo-mechanical analysis device (for example, TMA-60, manufactured by SHIMADZU CORPORATION.).
(3) The length value of the sample at each temperature (. Degree.C.) is obtained by heating the sample at a heating rate of 5℃per minute from a temperature of 20℃or higher and less than 30℃and preferably 25℃to 150 ℃.
(4) From the length (L30) of the sample at 30℃and the length (L90) at 90℃the expansion ratio in the width direction at 90℃was determined using the following formula. In the present invention, the expansion ratio in the width direction is an arithmetic average of expansion ratios obtained using 5 samples. In addition, a positive expansion ratio means expansion, and a negative expansion ratio means contraction.
The formula: expansion ratio (%) = (L90-L30)/l30×100
The expansion ratio in the width direction of the polyester film can be adjusted by appropriately setting the stretching ratio, the heat treatment temperature, and the film width during cooling in the process of producing a biaxially oriented film, for example.
(film Density)
The density of the polyester film is preferably 1.39 to 1.41g/cm 3 More preferably 1.395-1.405 g/cm 3 Further preferably 1.398 to 1.400g/cm 3 。
The density of the polyester film can be measured using an electronic densitometer (product name "SD-200L", manufactured by alfa mirageco., ltd.).
(thickness)
From the viewpoint of improving the transferability, the thickness of the polyester film is preferably 100 μm or less, more preferably 50 μm or less, and still more preferably 35 μm or less. The lower limit of the thickness is not particularly limited, but is preferably 1 μm or more, more preferably 5 μm or more, and still more preferably 10 μm or more, from the viewpoint of excellent handleability.
The thickness of the polyester film was an arithmetic average of the thicknesses of 5 portions measured by a continuous stylus film thickness meter.
Further, from the viewpoint of further excellent surface smoothness of the 1 st main surface of the release layer, the variation in thickness of the polyester film is preferably 7% or less of the average thickness of the polyester film, and more preferably 5% or less of the average thickness of the polyester film. The lower limit of the thickness deviation is not particularly limited, and may be 0% or more of the average thickness of the polyester film.
The thickness deviation can be measured by a method described later.
[ method of manufacture ]
As a method for producing the present film (hereinafter, also referred to as "the present production method"), for example, a method having a specific layer forming step of forming a specific layer containing particles and a resin on a polyester substrate substantially containing no particles is given. As the specific layer forming step, the following steps are preferable: the polyester substrate is coated on-line with a particle-containing layer-forming composition containing particles and a resin to form a specific layer.
The present production method includes a biaxial stretching step of biaxially stretching an unstretched polyester film having a polyester base material substantially free of particles.
The biaxial stretching may be simultaneous biaxial stretching in which longitudinal stretching and transverse stretching are simultaneously performed, or sequential biaxial stretching in which longitudinal stretching and transverse stretching are performed in multiple stages of 2 stages or more. Examples of the mode of the sequential biaxial stretching include longitudinal stretching, transverse stretching, longitudinal stretching, transverse stretching, longitudinal stretching, and transverse stretching, and preferably longitudinal stretching and transverse stretching.
The present manufacturing method will be specifically described.
As the present manufacturing method, for example, there is a method comprising: an extrusion molding step of extruding a molten resin containing a raw material polyester in a film form to form an unstretched polyester film having a polyester base material substantially free of particles; a biaxial stretching step of stretching an unstretched polyester film in a conveying direction to form a uniaxially oriented polyester film, and a transverse stretching step of stretching a uniaxially oriented polyester film in a width direction to form a biaxially oriented polyester film; a heat setting step of heating the biaxially oriented polyester film to heat set the biaxially oriented polyester film; a heat relaxation step of heating the polyester film heat-set by the heat setting step at a temperature lower than that of the heat setting step to thermally relax the polyester film; a cooling step of cooling the polyester film thermally relaxed by the thermal relaxation step, and an expanding step of expanding the thermally relaxed polyester film in the width direction in the cooling step; and a specific layer forming step of applying, on-line, at least one surface of the polyester substrate substantially free of particles, using a composition for forming a particle-containing layer containing particles and a resin, to provide a specific layer.
< extrusion molding Process >
The extrusion molding step is a step of extruding a molten resin containing a raw polyester in a film form by an extrusion molding method to form an unstretched polyester film substantially free of particles. The meaning of the raw material polyester is the same as that of the polyester described in the item (polyester) above.
The extrusion molding method is a method of molding a raw material resin into a desired shape by extruding a melt of the raw material resin from an extrusion die using a known extruder.
The melt can be extruded in a single layer or in multiple layers.
The melt extruded from the extrusion die is cooled to be formed into a film shape. For example, the melt can be formed into a film by bringing the melt into contact with a casting roll and cooling and solidifying the melt on the casting roll.
The temperature of the casting roll is preferably higher than (Tg-10) DEG C and lower than (Tg+30). The "Tg" mentioned above refers to the glass transition temperature of the polyester constituting the film.
Here, the temperature of the polyester film and each member in the present manufacturing method can be measured using a non-contact thermometer (for example, a radiation thermometer).
The cooled molded article (unstretched polyester film) is peeled from the cooling member such as a casting roll by using a peeling member such as a peeling roll.
< biaxial stretching Process >
The biaxial stretching step comprises: a longitudinal stretching step of stretching an unstretched polyester film in a transport direction (hereinafter also referred to as "longitudinal stretching") to form a uniaxially oriented polyester film; and a transverse stretching step of stretching the uniaxially oriented polyester film in the width direction (hereinafter also referred to as "transverse stretching") to form a biaxially oriented polyester film.
(longitudinal stretching step)
In the longitudinal stretching process, the unstretched polyester film is preferably preheated before longitudinal stretching. By preheating the unstretched polyester film, the polyester film can be easily stretched in the machine direction.
The preheating temperature of the unstretched polyester film is preferably (Tg-30) to (Tg+40) DEG C, more specifically, 60 to 100 ℃.
The stretching roller described later may have a function of preheating the film.
The longitudinal stretching can be performed by, for example, stretching an unstretched polyester film in the longitudinal direction while applying tension between 2 or more pairs of stretching rolls provided in the conveying direction.
The conveying speed (circumferential speed) of the film of 1 pair of stretching rollers a disposed upstream in the conveying direction and 1 pair of stretching rollers B disposed downstream in the conveying direction in the longitudinal stretching step is not particularly limited as long as the conveying speed of the film of the stretching rollers a is slower than the conveying speed of the film of the stretching rollers B. The film transfer speed of the stretching roll A is preferably 5 to 60 m/min. The film transfer speed of the stretching roll B is preferably 40 to J60 m/min.
The stretching ratio in the longitudinal stretching step is appropriately set according to the application, and is preferably 2.0 to 5.0 times.
The stretching speed in the longitudinal stretching step is preferably 800 to 1500%/sec. The "stretching speed" is a value obtained by dividing the length Δd of the polyester film stretched in the longitudinal stretching step in the conveying direction of the polyester film before stretching by the length d0 of the polyester film in the conveying direction, and is expressed as a percentage.
In the longitudinal stretching step, the unstretched polyester film is preferably heated. This is because it is easily stretched in the longitudinal direction by heating.
The heating temperature in the longitudinal stretching step is preferably (Tg-20) to (Tg+50) DEG C, more specifically, preferably 70 to 120 ℃.
(transverse stretching step)
The transverse stretching step is a step of transversely stretching the uniaxially oriented polyester film.
In the transverse stretching process, the polyester film is preferably preheated before transverse stretching. By preheating the polyester film, the polyester film can be easily stretched in the transverse direction.
The preheating temperature is preferably (Tg-10) to (Tg+60) ℃and, specifically, preferably 80 to 120 ℃.
The stretching ratio (transverse stretching ratio) of the uniaxially oriented polyester film in the transverse stretching step is not particularly limited, but is preferably greater than the stretching ratio in the longitudinal stretching step, more preferably 3.0 to 6.0 times.
The area magnification expressed as the product of the stretch magnification in the longitudinal stretching step and the stretch magnification in the transverse stretching step is preferably 12.8 to 15.5 times from the viewpoint that the molecular orientation in the film width direction is good and the state in which the molecular orientation is not easily maintained at the time of heat treatment is not easily relaxed.
The heating temperature in the transverse stretching step is preferably (Tg-10) to (Tg+80) ℃and more specifically, 100 to 140 ℃.
The stretching speed in the transverse stretching step is preferably 8 to 45%/sec.
< Heat setting Process >
In the present production method, the heat-setting step and the thermal relaxation step are preferably performed as the heat treatment of the polyester film stretched in the transverse direction by the transverse stretching step.
The biaxially oriented polyester film obtained by the transverse stretching step is heated and heat-set, whereby the polyester can be crystallized and shrinkage of the polyester film can be suppressed.
The surface temperature (heat-setting temperature) of the polyester film in the heat-setting step is not particularly limited, but is preferably 190 to 240 ℃.
The heating time in the heat setting step is preferably 5 to 50 seconds.
< thermal relaxation Process >
The following thermal relaxation step is preferably performed: the polyester film heat-set by the heat-setting process is heat-relaxed by heating it at a temperature lower than that of the heat-setting process. The residual strain of the polyester film can be relaxed by thermal relaxation.
The surface temperature (thermal relaxation temperature) of the polyester film in the thermal relaxation step is preferably a temperature lower than the heat setting temperature by 5 ℃ or more, specifically, the thermal relaxation temperature is preferably 100 to 235 ℃.
< Cooling Process >
The present production method preferably includes a cooling step of cooling the thermally relaxed polyester film.
Examples of the method for cooling the polyester film in the cooling step include a method of blowing air (preferably cold air) to the film and a method of bringing the film into contact with a temperature-adjustable member (for example, a temperature-controlled roller).
The cooling rate of the polyester film in the cooling step is not particularly limited, but is preferably higher than 2000 ℃/min and lower than 4000 ℃/min from the viewpoint of reducing the thickness unevenness of the release layer laminated on the biaxially oriented film.
The heat setting step, the thermal relaxation step, and the cooling step in the present manufacturing method are preferably performed sequentially and continuously. This is because the load (heat history) on the polyester film due to repeated heating and cooling can be reduced, and the internal strain in the film can be reduced, thereby suppressing the occurrence of streak defects.
< expansion Process >
In the cooling step, it is also preferable to perform a step of expanding the thermally relaxed polyester film in the width direction.
The expansion ratio in the width direction of the polyester film passing through the expansion step, that is, the ratio of the film width at the end of the cooling step to the film width before the start of the cooling step is preferably 0 to 1.3%.
< specific layer Forming Process >
As the specific layer forming step, a step of forming a specific layer by in-line coating with a composition for forming a particle-containing layer (hereinafter, also referred to as "composition a") containing particles and a resin will be described. The specific layer formed on at least one surface of the polyester substrate by the specific layer forming step has the same meaning as the layer described in detail in the item < specific layer >.
The formation of the specific layer may be performed at any stage of the present manufacturing method, and examples thereof include: a method of forming a coating film on one or both surfaces of an unstretched or stretched polyester substrate and drying as required.
First, a method of forming a specific layer using the composition a will be described.
The composition a can be prepared by mixing particles and resin contained in a specific layer, and if necessary, additives and solvents.
Examples of the solvent include water, ethanol, toluene, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether. Among them, water is preferable from the viewpoints of environment, safety and economy.
The composition A may contain 1 solvent alone or 2 or more solvents.
The content of the solvent is preferably 80 to 99% by mass, more preferably 90 to 98% by mass, relative to the total mass of the composition a.
That is, the total content of the components (solid components) other than the solvent in the composition a is preferably 0.5 to 20% by mass, more preferably 1 to 10% by mass, based on the total mass of the composition a.
The particles, resin and additives contained in the composition a, including preferred modes thereof, are as described in detail in the item < specific layer >. When commercial products are used as the particles contained in the composition a, the catalogue value of these commercial products may be used as the average particle diameter of the particles.
The content of each component in the coating liquid is preferably adjusted so that the content of each component is the same as the preferable content of each component with respect to the total mass of the specific layer with respect to the total mass of the solid component of the composition a, with respect to each component in the composition a except for the solvent.
The method of applying the composition a is not particularly limited, and a known method can be used. Examples of the coating method include a spray coating method, a slit coating method, a roll coating method, a doctor blade coating method, a spin coating method, a bar coating method, and a dip coating method.
In the specific layer forming step, an in-line coating method is applied in which a coating liquid is coated on one or both surfaces of a polyester substrate while the polyester substrate is conveyed. By applying the in-line coating method, the heating time of the polyester substrate in the production process is shortened, and the heat history is not present, so that the streak-like defect region of the polyester film can be reduced.
In the in-line coating method, the polyester substrate of the coating composition a may be an unstretched polyester substrate or a uniaxially oriented polyester substrate, but preferably a uniaxially oriented polyester substrate. That is, it is preferable to perform the specific layer forming step by the in-line coating method between the longitudinal stretching step and the transverse stretching step. By simultaneously stretching the uniaxially oriented polyester substrate and the specific layer in the transverse direction, the adhesion between the polyester substrate and the specific layer can be improved.
The production method may include a winding step of winding the biaxially oriented polyester film obtained through the above steps to obtain a roll-shaped biaxially oriented polyester film.
The present production method may further include a trimming step of cutting at least one end portion of the polyester film in the width direction by continuously cutting the polyester film in the conveying direction before the winding step is performed.
The conveyance speed of the polyester film in each step of the production method other than the longitudinal stretching step is not particularly limited, but is preferably 50 to 200 m/min from the viewpoint of productivity and quality.
After the cooling step, the tension applied to the polyester film in the conveying direction until the polyester film is wound in the winding step is preferably 3 to 30N/m.
[ use ]
The film is excellent in transparency and smoothness, and is therefore suitable for use as an optical polyester film.
Among them, the film is excellent in scratch resistance and pattern linearity, and therefore is suitable for use as a polyester film for dry film resist production. The dry film resist produced by using the film can form a resist pattern excellent in pattern linearity even when a high-definition resist pattern is formed, and thus can be suitably used for forming a resist pattern.
The dry film resist produced by using the present film and the method for producing the dry film resist using the present film will be described later.
The film is excellent in transparency and smoothness, and therefore is also suitable for optical applications other than dry film resist production. More specifically, the film can be suitably used as a separator for various protective films for various applications such as dry film resists, support films for various applications such as decorative plates and decorative sheets, films for molding such as decorative layers and resin sheets, release films for various applications such as optical display films, conductive films, and ceramic sheet production, films for semiconductor production processes, films for polarizing plate production processes, films for magnetic tapes, and pressure-sensitive adhesive films for labels, medical applications, and office supplies.
[DFR]
The DFR of the present invention has the present film as a temporary support and a photosensitive resin layer provided on the 1 st main surface of the present film, and is used as a photosensitive transfer member.
The DFR may have an intermediate layer between the present film and the photosensitive resin layer.
Here, the intermediate layer refers to all layers existing between the temporary support and the photosensitive resin layer.
The DFR of the present invention has the present film as a temporary support. The temporary support means a support that can be peeled off.
The present film is as described above.
As the photosensitive resin layer, a known photosensitive resin layer can be used, but since the lamination property at high speed is more excellent, a negative type photosensitive resin layer is preferable. Specifically, a polymerizable compound having a monomer having a double bond, a polymer (preferably a polymer having an acid group), and a photopolymerization initiator are preferable.
As the photosensitive resin layer, for example, a photosensitive resin layer described in japanese patent application laid-open No. 2016-224162 can be used. Further, a preferable embodiment is a photosensitive resin layer containing a binder polymer, an ethylenically unsaturated compound, and a photopolymerization initiator as described in the specification of international publication No. 2018/105313. More preferable examples thereof include a photosensitive resin layer having an alkali-soluble acrylic resin having a cyclic structure, a polyfunctional acrylate, an oxime photopolymerization initiator, or a bisimidazole photopolymerization initiator.
The DFR preferably has a protective film on a surface of the photosensitive resin layer on a side opposite to the temporary support side.
The present film is also preferably used as a protective film.
[ method for producing DFR ]
The method for producing the DFR of the present invention is not particularly limited, and the DFR of the present invention can be produced by a known production method.
As a method for producing DFR, for example, the following methods are given: sequentially mixing the constituent components of the layers and the solvent according to a desired layer structure to prepare a composition for forming each layer such as a thermoplastic resin composition; and a step of forming each layer by applying the composition to the 1 st main surface of the film and then drying the coating layer, thereby producing the DFR having the film, the intermediate layer and the photosensitive resin layer in this order.
The DFR of the present invention has an excellent effect of being able to form a resist pattern excellent in pattern linearity even when used to form a high-definition resist pattern.
Therefore, the DFR of the present invention is preferably used for manufacturing resist patterns and circuit wiring.
Examples
The present invention will be described in further detail with reference to the following examples. The materials, amounts used, proportions, treatment contents and treatment sequences shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below. In addition, "parts", "ppm" and "%" are mass basis unless otherwise indicated.
Hereinafter, in this example, the "film" simply labeled includes not only the polyester base material monomer and the polyester base material and particle-containing layer, but also all of an unstretched film, a uniaxially oriented film, and a biaxially oriented film.
In each step of this example, a non-contact thermometer (AD-5616 (product name), manufactured by a & D company, emissivity 0.95) was used to measure the temperature of the width-direction central portion of the film 5 times, and the arithmetic average of the obtained measured values was used as the measured value of the surface temperature of the film.
[ example 1 ]
< extrusion molding Process >
Polyethylene terephthalate pellets were produced using a titanium compound (citric acid chelate titanium complex, manufactured by VERTEC AC-420,Johnson Matthey), a magnesium compound (magnesium acetate tetrahydrate), and a phosphorus compound (trimethyl phosphate) as a polymerization catalyst described in japanese patent No. 5575671. The contents of magnesium, phosphorus and titanium contained in the pellets were 82 mass ppm, 73 mass ppm and 9 mass ppm, respectively, relative to the total mass of the pellets. The obtained pellets were dried to a water content of 50ppm or less, and then charged into a hopper of a single-shaft kneading extruder having a diameter of 30mm, and then melted and extruded at 280 ℃. After passing the melt through a filter (pore size 2 μm), it was extruded from a die to a cooling drum at 25℃to thereby obtain an unstretched film composed of polyethylene terephthalate and free of particles. The extruded melt (melt) was brought into close contact with the cooling drum by an electrostatic application method.
The melting point (Tm) of polyethylene terephthalate constituting the unstretched film was 258 ℃ and the glass transition temperature (Tg) was 80 ℃.
< longitudinal stretching Process >
The longitudinal stretching process was performed on the unstretched film by the following method.
The pre-heated unstretched film was passed between 2 pairs of rolls having different peripheral speeds and stretched in the machine direction (conveying direction) under the following conditions, thereby producing a uniaxially oriented film.
(longitudinal stretching conditions)
Preheating temperature: 75 DEG C
Stretching temperature: 90 DEG C
Stretching multiplying power: 3.4 times
Stretching speed: 1300%/second
< particle-containing layer Forming Process >
The following composition 1 (composition for forming a particle-containing layer) was applied to one side of a uniaxially oriented film (polyester base material) stretched in the machine direction by a bar coater, and the resulting coated film was dried by hot air at 100 ℃. At this time, the coating amount of the composition 1 was adjusted so that the thickness of the particle-containing layer formed became 40nm.
(composition 1)
Composition 1 was prepared by mixing the ingredients shown below. The prepared composition 1 was subjected to filtration treatment using a filter (F20, manufactured by MAHLE Japan ltd.) having a pore size of 6 μm and membrane degassing (2×6Radial Flow Super Phobic (manufactured by Polypore co., ltd.)), and then the obtained composition 1 was coated on the surface of a uniaxially oriented film.
Acrylic resin (resin A1) (aqueous dispersion of a copolymer obtained by mixing, as a solid component, 27.5 mass% of polymerized methyl methacrylate, styrene, 2-ethylhexyl acrylate, 2-hydroxyethyl methacrylate and acrylic acid (contained in a mass ratio of 59:8:26:5:2): 167 parts of
Anionic hydrocarbon surfactant (surfactant W-1) ("RAPISOL (registered trademark) A-90", sodium di-2-ethylhexyl sulfosuccinate, manufactured by NOF CORPORATION, solid content 1% by mass aqueous dilution): 55.7 parts
Nonionic surfactant (surfactant W-2) ("NAROACTY (registered trademark) CL95", sanyo Chemical Industries, ltd. Manufactured, polyoxyalkylene alkyl ether, solid content 100 mass%): 0.7 part
Wax 1 ("Cellosol (registered trademark) 524", CHUKYO YUSHI co., ltd. Manufactured, carnauba wax dispersion, solid content 30 mass%): 7 parts of
Crosslinker 1 ("carbodiimida (registered trademark) V-02-L2", manufactured by Nisshinbo Chemical inc., CARBODIIMIDE compound, solid content 10 mass% aqueous dilution): 20.9 parts of
Non-agglomerated particles (particle 1) ("SNOWTEX (registered trademark) XL", average particle diameter 50nm, colloidal silica, nissan Chemical Industries, ltd. Manufactured, solid content 40 mass% aqueous dispersion): 2.8 parts of
Water: 743 parts
< transverse stretching Process >
The biaxially oriented film was produced by stretching the film subjected to the longitudinal stretching step and the particle-containing layer forming step in the width direction using a tenter under the following conditions.
(transverse stretching conditions)
Preheating temperature: 100 DEG C
Stretching temperature: 120 DEG C
Stretching multiplying power: 4.2 times
Stretching speed: 50%/second
< Heat setting Process >
The biaxially oriented film subjected to the transverse stretching step was heated by using a tenter under the following conditions, whereby a heat-setting step of heat-setting the film was performed.
(Heat setting conditions)
Heat setting temperature: 227 DEG C
Heat setting time: for 6 seconds
< thermal relaxation Process >
Then, the heat-set film is heated under the following conditions, whereby a thermal relaxation step of relaxing the tension of the film is performed. In the thermal relaxation step, the distance between the holding members of the tenter holding both ends of the film (the tenter width) is narrowed, whereby the film width is reduced as compared with the film width at the end of the heat setting step. The following thermal relaxation rate Lr was obtained from the equation lr= (L1-L2)/l1×100 based on the film width L2 at the end of the thermal relaxation process with respect to the film width L1 at the beginning of the thermal relaxation process.
(thermal relaxation conditions)
Thermal relaxation temperature: 190 DEG C
Thermal relaxation rate Lr:4%
< Cooling Process and expansion Process >
The film thus thermally relaxed was subjected to a cooling step of cooling under the following conditions. In the cooling step, a step of expanding the width of the film by expanding the width of the tenter is performed as compared with the case where the thermal relaxation step is completed.
The residence time after the film is fed into the cooling unit 50 of the stretching machine 100 and before the film is fed out is set as a cooling time ta, and the temperature difference Δt (°c) between the film surface temperature measured when the film is fed into the cooling unit 50 and the film surface temperature measured when the film is fed out of the cooling unit 50 is divided by the cooling time ta to obtain the cooling rate described below.
The following expansion ratio Δl is obtained from the expression Δl= (L3-L2)/l2×100, based on the film width L3 at the end of the cooling process and the film width L2 of the polyester film at the beginning of the cooling process.
(Cooling conditions)
Cooling rate: 2500 ℃/min
(expansion condition)
Expansion ratio deltal: 0.6%
< winding Process >
The film cooled in the cooling step was continuously cut at 20cm positions from both ends in the width direction of the film along the conveying direction by using a trimming device, and both ends of the film were trimmed. Then, after extrusion processing (knurling treatment) was performed on the region from both ends of the film to 10mm in the width direction, the film was wound up at a tension of 40 kg/m.
By the above method, a biaxially oriented film was produced. The biaxially oriented film obtained had a width of 1.5m and a roll length of 7000m. As a result of measuring the thicknesses of the polyester base material and the particle-containing layer of the obtained biaxially oriented film by SEM, the thickness of the polyester base material was 16 μm and the thickness of the particle-containing layer was 40nm.
[ examples 2 to 16 ]
In the particle-containing layer forming step, biaxially oriented films were produced in the same manner as described in example 1, except that compositions 2 to 16 having the compositions described in table 1 below were used instead of the composition 1 used as the particle-containing layer forming composition in example 1, and the coating amounts of the compositions were adjusted so that the thicknesses of the particle-containing layers became the values described in table 2 below.
Comparative examples 1 to 2
In the particle-containing layer forming step, biaxially oriented films were produced in the manner described in example 1, except that compositions C1 and C2 having the compositions described in table 1 below were used in place of the composition 1 used as the particle-containing layer forming composition in example 1, and the thicknesses of the particle-containing layers were adjusted so as to have the values described in table 2 below.
[ comparative example 3 ]
A biaxially oriented film was produced by the method described in example 1, except that alumina particles having an average particle diameter of 50nm were added in an amount of 0.5 mass% relative to the entire resin particles when the polyethylene terephthalate particles in the extrusion molding step described in example 1 were produced.
In Table 1, the particles 1 to 6 in the "particle" column, the resins A1 to A3, C and D in the "resin" column, the W-1 to W-3 in the "surfactant" column, the wax 1 in the "wax" column and the crosslinking agents 1 to 3 in the "crosslinking agent" column represent the following components, respectively.
In table 1, the expression "amount (%)" indicates the content (unit: mass%) of each component relative to the total mass of the solid components of the composition for forming a particle-containing layer.
(particles)
Particle 1: colloidal silica (Nissan Chemical Indus Lries, ltd. Manufactured "SNOWTEX XL", average particle size 50 nm)
Particle 2: colloidal silica (Nissan Chemical Industries, ltd. Manufactured "SNOWTEX YL", average particle size 50-80 nm)
Particle 3: colloidal silica (Nissan Chemical Industries, ltd. Manufactured "SNOWTEX ZL", average particle size 70-100 nm)
Particle 4: condensed silica (AEROSIL OX50, NIPPON AEROSIL CO., LTD. Manufactured by Etsche. Average particle size 200nm, average primary particle size 40 nm)
Particle 5: porous silica (average particle size 1.8 μm)
The particles 1 to 5 are particles having no hollow structure.
[ resin ]
Resin A1: acrylic resin (copolymer, aqueous dispersion obtained by emulsion polymerization of methyl methacrylate, styrene, 2-ethylhexyl acrylate, 2-hydroxyethyl methacrylate and acrylic acid in a mass ratio of 59:8:26:5:2)
Resin A3: acrylic resin (aqueous dispersion obtained by neutralizing a copolymer obtained by polymerizing methyl methacrylate, 2-hydroxyethyl methacrylate and methacrylic acid at a mass ratio of 28:48:24)
Resin C: acid-modified polyolefin (Sumitomo Seika Chemicals Company, limited. Manufactured "Seixen (registered trademark) N", aqueous Dispersion)
Resin D: polyurethane resin (aqueous dispersion of polyurethane resin synthesized by the following method)
43.75 parts of 4, 4-dicyclohexylmethane diisocyanate, 12.85 parts of dimethylolbutanoic acid, 153.41 parts of polyhexamethylene carbonate diol having a number average molecular weight of 2000, 0.03 part of dibutyltin dilaurate and 84.00 parts of acetone as a solvent were charged into a 4-neck flask equipped with a stirrer, a Diels condenser (Dimroth condenser), a nitrogen inlet tube, a silica gel drying tube and a thermometer, and the reaction solution was stirred under a nitrogen atmosphere at 75℃for 3 hours, whereby it was confirmed that the reaction solution reached a predetermined amine equivalent. Subsequently, the reaction solution was cooled to 40 ℃, and then 8.77 parts of triethylamine was added thereto to obtain a polyurethane prepolymer. Then, 450 parts of water was added to a reaction vessel equipped with a high-speed stirring homogenizer at 25℃and the polyurethane prepolymer solution was added and mixed with stirring at 2000rpm to disperse the water. Then, an aqueous dispersion of a polyurethane resin having a solid content of 37% was prepared by removing acetone and a part of water under reduced pressure.
(surfactant)
W-1: anionic hydrocarbon surfactant (NOF CORPORATION "RAPISOL (registered trademark) A-90")
W-2: nonionic surfactant (Sanyo Chemical Industries, ltd. Manufactured "NAROACTY (registered trademark) CL 95), polyoxyalkylene alkyl ether, solid content 100% by mass)
W-3: fluorine-based surfactant (AGC SEIMI CHEMICAL CO., LTD manufacturing "Surflon (registered trademark) S-211")
(wax)
Wax 1: carnauba wax (CHUKYO YUSHI co., ltd. Manufactured "Cellosol (registered trademark) 524")
(crosslinking agent)
Crosslinking agent 1: carbodiimide crosslinking agent (Nisshinbo Chemical Inc. manufactured "CARBODILITE (registered trademark) V-02-L2")
Crosslinking agent 2: melamine crosslinking agent (hexamethoxy methylolmelamine)
Crosslinking agent 3: oxazoline crosslinking agent (NIPPON SHOKUBIAI CO., LTD. Manufactured by EPOCROS WS-700)
TABLE 1
[ measurement of physical Properties of biaxially oriented film ]
The following properties were measured for each of the biaxially oriented films of examples 1 to 16 and comparative examples 1 to 3.
< maximum section height SRt, surface average roughness SRa >
The maximum section height SRt of the 2 nd main surface of the biaxially oriented film and the surface average roughness SRa were measured by the following methods.
The surface of the particle-containing layer side of the produced biaxially oriented film was measured using an optical interferometer (manufactured by Vertscan 3300G Lite,Hitachi High-Tech Corporation) under the following conditions, and then analyzed by using built-in data analysis software (VS-measurement 5), whereby the maximum section height SRt (labeled "St" in the optical interferometer) and the surface average roughness SRa (labeled "Sa" in the optical interferometer) of the 2 nd main surface of the biaxially oriented film were obtained.
In the measurement of the maximum cross-sectional height SRt, the maximum value of the measured values obtained in 5 measurements in which the measurement position is changed is employed, and in the measurement of the surface average roughness SRa, the average value of the measured values obtained in 5 measurements in which the measurement position is changed is employed. The measured maximum section height SRt of the 2 nd main surface and the surface average roughness SRa are shown in table 2.
(measurement conditions)
Measurement mode: WAVE mode
Objective lens: 50 times of
Measurement area: 186 μm by 155 μm
The maximum section height SRt of the 1 st main surface and the surface average roughness SRa of the biaxially oriented film were measured by the same method as described above. In either embodiment, the maximum cross-sectional height SRt of the 1 st major surface is 18nm and the maximum cross-sectional height SRa of the 1 st major surface is 1nm.
< surface free energy >
The surface free energy of the 2 nd major surface of the biaxially oriented film was measured by the following method.
A droplet was dropped onto the surface of the particle-containing layer side of the produced biaxially oriented film at 25 ℃ using a contact angle meter (Kyowa Interface Science co., ltd., manufactured, DROPMASTER-501), and the contact angle after the droplet was attached to the surface for 1 second was measured. 2. Mu.L of purified water, 1. Mu.L of diiodomethane and 1. Mu.L of ethylene glycol were used as droplets, and based on the respective contact angles measured, the droplets were prepared by North Amaki +.The method of (Kitazaki and Hata) calculates the surface free energy. The surface free energy of the 2 nd main surface measured is shown in table 2.
As a result of measuring the surface free energy of the 1 st main surface of the biaxially oriented film by the same method as described above, in any of the examples, the surface free energy of the 1 st main surface was 59.7mJ/m 2 。
< average particle diameter, particle Density D >
The average particle diameter and the particle density D of the particles contained in the particle-containing layer were measured by the following methods.
The surface of the particle-containing layer side of the biaxially oriented film was observed with a scanning electron microscope (manufactured by SEM, hitachi High-Tech corporation, S4700) at 20000 magnification, to obtain an observation image with 10 fields of view. For particles identifiable as protrusions from the obtained image data, the area of each particle was measured using image software and converted into a diameter of a circle having the same area (area circle equivalent diameter) to obtain the particle diameter of each particle, and then the arithmetic average value of the particles was calculated.
Then, a value obtained by dividing the number of particles identifiable from the image data of each field of view by the field area is calculated as the particle density D (unit: unit/. Mu.m 2 )。
In the measurement of the average particle diameter and the particle density D, dust and agglomerated coarse particles are not counted as particles.
< thickness deviation >
From the produced biaxially oriented film, a sample having a length of 10m was collected in the longitudinal direction. The thickness of the sample was measured in the range of 10m along the length direction using a continuous stylus film thickness meter (TOF-6R001,Yamabun Electronics Co, manufactured by ltd.). The measurement was performed at 5 different positions in the width direction. From the obtained measured values, a value ((maximum thickness-minimum thickness)/average thickness) obtained by dividing the difference between the maximum value and the minimum value by the arithmetic average value of all the measured values was calculated as the thickness deviation.
As a result, the thickness variation of the biaxially oriented films produced in each example and each comparative example was 4.5%.
[ evaluation ]
The biaxially oriented films of examples 1 to 16 and comparative examples 1 to 3 were evaluated as follows. The evaluation results are shown in table 2.
< Pattern Linearity (LWR) >)
The biaxially oriented film having been subjected to the cooling step in each example and each comparative example was coated with a coating liquid for forming a thermoplastic resin layer comprising the following formulation F on the 1 st main surface which was the surface on the opposite side to the particle-containing layer, and the obtained coating film was dried at 80 ℃. Next, a coating liquid for forming a water-soluble resin layer composed of the following formulation G was applied onto the thermoplastic resin layer, and the obtained coating film was dried at 80 ℃ to form a water-soluble resin layer. Further, a photosensitive resin layer was formed by applying a coating liquid for forming a photosensitive resin layer composed of the following formulation H onto a water-soluble resin layer, and then drying the obtained coating film at 80 ℃. Finally, a PET film (manufactured by tolay INDUSTRIES, INC., lumirror 16ks 40) was pressure-bonded to the surface of the photosensitive resin layer as a protective film, and the obtained laminate was wound up to produce a roll-shaped photosensitive transfer member.
The photosensitive transfer member is an example of DFR, and has a layer structure composed of a biaxially oriented film, a thermoplastic resin layer, a water-soluble resin layer, a photosensitive resin layer, and a protective film. The thickness of the thermoplastic resin layer was 2. Mu.m, the thickness of the water-soluble resin layer was 1. Mu.m, and the thickness of the photosensitive resin layer was 2. Mu.m.
< formulation F: coating liquid for Forming thermoplastic resin layer ]
22.7 parts of a copolymer (aqueous dispersion having a molecular weight of 3 ten thousand and a solid content of 30%) obtained by polymerizing benzyl methacrylate, methacrylic acid and acrylic acid, the mass ratio of the monomers being =75:10:15
3, 6-bis (diphenylamino) fluoran: 0.12 part
Oxime sulfonate photoacid generator (synthesized according to paragraph 0227 of Japanese patent application laid-open No. 2013-047765): 0.2 part
Tricyclodecane dimethanol diacrylate: 3.32 parts
UV curable urethane acrylate oligomer (TAISEI FINE CHEMICAL CO, & ltd. Manufactured "8UX-015A",15 functional): 1.66 parts
Multifunctional acrylate monomer (TOAGOSEI co., ltd. Manufactured "arofix (registered trademark) TO-2349"): 0.55 part
Surfactant (DIC Corporation "MEGAFACE (registered trademark) F-552"): 0.02 part
< formulation G: coating liquid for Forming Water-soluble resin layer-
Polyvinyl alcohol (Kuraray co., ltd. Manufactured "Kuraray POVAL (registered trademark) 4-88 LA"): 3.22 parts
Polyvinylpyrrolidone (NIPPON shokubaci co., ltd. Manufactured "K-30"): 1.49 parts
Surfactant (DIC Corporation "MEGAFACE F-444"): 0.0035 parts
Methanol (MITSUBISHI GAS CHEMICAL compass, inc.): 57.1 parts
Ion-exchanged water: 38.12 parts
< formulation H: coating liquid for Forming photosensitive resin layer ]
Copolymers polymerized from styrene, methacrylic acid and methyl methacrylate (mass ratio of monomers=52:29:19, molecular weight 6 ten thousand, aqueous dispersion with a solid content of 30%): 25.2 parts of
Colorless crystal violet: 0.06 part
Photopolymerization initiator (2- (2-chlorophenyl) -4, 5-diphenylimidazole dimer): 1.03 parts
4,4' -bis (diethylamino) benzophenone: 0.04 part
N-phenylcarbamoylmethyl-N-carboxymethylaniline: 0.02 part
Ethoxylated bisphenol-a dimethacrylate (Shin-Nakamura Chemical co., ltd. Manufactured "NK ESTER BPE-500"): 5.61 parts
Multifunctional acrylate monomer (TOAGOSEI co., ltd. Manufactured "ARONIX M-270"): 0.58 part
Phenothiazine: 0.04 part
4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolone: 0.002 parts
Surfactant (DIC Corporation "MEGAFACE F-552"): 0.048 part
Propylene glycol monomethyl ether acetate: 19.7 parts of
Methyl ethyl ketone: 43.8 parts
A PET substrate with a copper layer was fabricated by forming a copper layer having a thickness of 200nm on a polyethylene terephthalate (PET) film having a thickness of 100 μm by a sputtering method.
The roll-shaped photosensitive transfer member produced in the above was unwound, and the protective film was peeled off from the photosensitive transfer member. Next, the photosensitive transfer member and the PET substrate with a copper layer were bonded to each other so that the photosensitive resin layer exposed by peeling the protective film and the copper layer were in contact with each other, thereby obtaining a laminate. The bonding step was performed at a roll temperature of 100℃and a linear pressure of 1.0MPa and a linear velocity of 4.0 m/min.
From the biaxially oriented film side of the obtained laminate, a photosensitive resin layer was exposed by irradiation with an ultra-high pressure mercury lamp (exposure dominant wavelength: 365 nm) through a photomask. The photomask used in the exposure had a line-and-space pattern with a width ratio (duty ratio) of the transmission region to the light-shielding region of 1:1 and a line width (and space width) of 6 μm. The exposure amount of the photosensitive resin layer was adjusted so that the line width of the resist pattern formed by exposure to the irradiation light became 6 μm.
After the biaxially oriented film was peeled from the exposed laminate, the laminate was subjected to spray development using a 1.0% aqueous sodium carbonate solution at a liquid temperature of 25 ℃ for 30 seconds. By this development step, the unexposed photosensitive resin layer, and the water-soluble resin layer and the thermoplastic resin layer laminated on the unexposed photosensitive resin layer were removed from the laminate, and a resist pattern having a line width of 6 μm and a space pattern was formed on the surface of the copper layer.
The pattern width (line width of the photosensitive resin layer) of 20 sites arbitrarily selected was measured with respect to the resist pattern formed by the above method using a Scanning Electron Microscope (SEM). From the obtained line width data, a standard deviation σ was calculated, and a value 3 times the standard deviation σ was defined as LWR (Line Width Roughness: line width roughness), which was used as an index of pattern linearity.
By definition, it is preferable that the smaller the LWR, the smaller the line width variation. The pattern of 6 μm line width was evaluated by LWR values as follows. It can be said that the smaller the value of LWR, the more excellent the pattern linearity. Further, it can be said that the more excellent the pattern linearity is, the more excellent the roughness (edge roughness) of the line width is.
The pattern linearity of the produced resist pattern is preferably any one of "a" to "C", more preferably "a" or "B", and still more preferably "a".
(evaluation criterion of Pattern linearity)
A: LWR < 300nm: the circuit wiring substrate is very preferable.
B: LWR is more than or equal to 300nm and less than 500nm: the circuit wiring board is preferable.
C: LWR is more than or equal to 500nm and less than 700nm: can be used as a circuit wiring substrate.
D: LWR is less than or equal to 700nm: the wide variation in line width is not preferable because it causes a circuit failure.
< scratch resistance >
From the roll-shaped biaxially oriented films produced in each example and each comparative example, 1.5m×2m samples were collected from 3 points, i.e., the roll end, a position half the roll length, and the unreeled portion. The occurrence of scratch-like defects in the inspection range of 1.5m×2m was inspected by visually observing the 1 st main surface of the obtained biaxially oriented film using a prasugrel lamp (polar light). The abrasion resistance of the biaxially oriented film was evaluated according to the following criteria based on the inspection results.
(evaluation criterion of scratch resistance)
A: no scratch-like defects were observed within the inspection range.
B: some scratch-like defects were observed within the inspection range, but within the allowable range.
C: a number of significant scratch-like defects were observed within the inspection range.
The physical properties and evaluation results of the biaxially oriented films produced in each example and each comparative example are shown in table 2.
In the table, the column "average particle diameter" of the "particle-containing layer" indicates the average particle diameter (unit: μm) of the particles contained in the particle-containing layer. The "-" in the column of "average particle diameter" indicates that no particles were observed by the above measurement method.
In the table, the column "D X SRt" of the "2 nd main surface" indicates the particle density D (unit: individual/. Mu.m) of particles constituting the projections of the 2 nd main surface 2 ) Maximum section height SRt from main surface 2 (unit: nm).
TABLE 2
From table 2, it is confirmed that the biaxially oriented polyester films of examples 1 to 16 according to the present invention are more excellent in the effect of the present invention than those of comparative examples 1 to 3.
Further, it was confirmed that when the maximum cross-sectional height SRt of the 2 nd main surface of the biaxially oriented film was 40nm or less, the pattern linearity was more excellent (comparison of examples 1 to 13).
It was confirmed that when the particle-containing layer of the biaxially oriented film contains an acrylic resin, the biaxially oriented film is more excellent in scratch resistance (comparison of examples 1, 5 and 15).
It was confirmed that when the surface free energy of the 2 nd main surface of the biaxially oriented film was 50mJ/m 2 In the following, the biaxially oriented film was more excellent in scratch resistance (comparison of examples 7 and 10 and examples 13 and 15).
It was confirmed that when the particle density D (unit: individual/. Mu.m 2 ) Maximum section height SRt from main surface 2 (unit: nm) is 600 or less, the pattern linearity is more excellent, and when the product (d× SRt) is 130 or less, the pattern linearity is more excellent (comparison of examples 1 to 13).
It was confirmed that the pattern linearity was more excellent when the thickness of the particle-containing layer was 100nm or less (comparison of examples 1 to 3 and 16).
Symbol description
1-polyester film, 1 a-1 st main surface, 1 b-2 nd main surface, 2-polyester substrate, 3-specific layer (particle-containing layer).

Claims (18)

1. A polyester film for optical use, comprising:
a polyester substrate substantially free of particles; a kind of electronic device with high-pressure air-conditioning system
A particle-containing layer containing particles and a resin, the particle-containing layer being disposed on at least one surface of the polyester substrate,
the polyester film has a 1 st major surface and a 2 nd major surface,
the 2 nd main surface is a surface of the particle-containing layer on the opposite side of the polyester substrate side,
The maximum section height SRt of the 2 nd main surface is 20nm to 150nm,
the particle-containing layer has a thickness of 1nm to 200nm.
2. The polyester film according to claim 1, which is a polyester film for dry film resist production.
3. The polyester film according to claim 1 or 2, wherein,
the surface free energy of the 2 nd main surface is 50mJ/m 2 The following is given.
4. The polyester film according to claim 3, wherein,
the resin contains an acrylic resin.
5. The polyester film according to claim 4, wherein,
the acrylic resin is a copolymer having a structural unit derived from styrene and a structural unit derived from (meth) acrylate.
6. The polyester film according to claim 4 or 5, wherein,
the acrylic resin has a structural unit derived from a (meth) acrylate having an unsubstituted alkyl group having 1 to 4 carbon atoms in the ester moiety and a structural unit derived from a (meth) acrylate having an unsubstituted alkyl group having 5 to 10 carbon atoms in the ester moiety.
7. The polyester film according to any one of claims 1 to 6, wherein,
the thickness of the polyester film is 1-35 mu m.
8. The polyester film according to any one of claims 1 to 7, wherein,
The maximum section height SRt of the 2 nd main surface is 20 nm-40 nm.
9. The polyester film according to any one of claims 1 to 8, wherein,
the protrusion constituting the 2 nd main surfaceThe product of the density D of the particles and the maximum section height SRt of the 2 nd main surface, namely D× SRt, is 600 or less, and the unit of the density D is one/μm 2 The maximum cross-sectional height SRt is in nm.
10. The polyester film according to any one of claims 1 to 9, wherein,
the particle-containing layer further contains a hydrocarbon surfactant.
11. The polyester film according to any one of claims 1 to 10, wherein,
the resin has a crosslinked structure.
12. The polyester film according to any one of claims 1 to 11, wherein,
the particle-containing layer also contains a wax.
13. The polyester film according to any one of claims 1 to 12, wherein,
the maximum section height SRt of the 1 st main surface is 5nm to 40nm.
14. The polyester film according to any one of claims 1 to 13, wherein,
the 1 st main surface has a surface average roughness SRa of 0nm to 5.0nm, and
the surface average roughness SRa of the 2 nd main surface is 1.0 nm-5.0 nm.
15. The polyester film according to any one of claims 1 to 14, wherein,
The surface free energy of the 1 st main surface is 50mJ/m 2 ～70mJ/m 2 。
16. A dry film resist, comprising:
the polyester film of any one of claims 1 to 15; a kind of electronic device with high-pressure air-conditioning system
A photosensitive resin layer provided on the 1 st main surface of the polyester film.
17. The dry film resist of claim 16, wherein,
the photosensitive resin layer contains a polymer, a polymerizable compound, and a photopolymerization initiator.
18. A method of producing the polyester film according to any one of claims 1 to 15, which has:
a step of forming a particle-containing layer by in-line coating a polyester substrate substantially free of particles with a particle-containing layer-forming composition containing particles and a resin,
the particles dispersed in the composition for forming a particle-containing layer have an average particle diameter of 10nm to 250nm.
CN202180084865.9A 2020-12-17 2021-12-02 Polyester film, dry film resist, and method for producing polyester film Pending CN116601567A (en)

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