JP2021163192A - Forming method of resin pattern, forming method of conductive pattern, lamination polyester film, photosensitive transfer material, resin pattern and touch panel - Google Patents

Abstract

To provide a forming method of a resin pattern, a forming method of a conductive pattern, a lamination polyester film, a photosensitive transfer material, the resin pattern and a touch panel.SOLUTION: A forming method of a resin pattern includes in this order: a process for laminating a photosensitive transfer material having a temporary support body and a photosensitive resin layer supported to the temporary support body by making an outermost layer at a side having the photosensitive resin layer contact with a baseboard with respect to the temporary support body; a process for pattern-exposing the photosensitive resin layer; and a process for forming the resin pattern by developing the exposed photosensitive resin layer. The temporary support body has a base material layer and a particle-containing layer containing particles at least at a face at a side opposite to the photosensitive resin layer side. A haze value is smaller than 0.5%, and a dynamic friction coefficient between the particle-containing layer and acrylonitrile butadiene rubber is equal to or less than 0.7.SELECTED DRAWING: None

Description

The present disclosure relates to a resin pattern manufacturing method, a conductive pattern manufacturing method, a laminated polyester film, a photosensitive transfer material, a resin pattern, and a touch panel.
Regarding.

In display devices equipped with a touch panel such as a capacitance type input device (organic electroluminescence (EL) display device, liquid crystal display device, etc.), the electrode pattern corresponding to the sensor of the visual recognition part, the peripheral wiring part, and the take-out wiring part Circuit wiring such as the wiring of is provided inside.

For the formation of patterned circuit wiring, it has been considered to use a photosensitive transfer material (so-called dry film resist) because the number of steps for obtaining the required pattern shape is small. In recent years, dry film photoresist has been studied. Is used in the touch panel field for etching applications in a wiring forming process, protective film forming applications for protecting wiring portions such as copper, ITO (indium tin oxide), and silver nanoparticles, and interlayer insulating film applications. Specifically, a photosensitive composition layer (that is, a layer of a photosensitive resin composition) is formed on a substrate using a dry film resist, and the photosensitive composition layer is passed through a mask having a pattern, or the like. A method of forming a circuit wiring by subjecting a pattern to a resist pattern by developing a photosensitive composition layer after exposure to obtain a resist pattern and then etching a substrate is widely used.

The dry film resist has, for example, a laminated structure in which a photosensitive resin layer (also referred to as a photoresist layer or a resist layer) is laminated on a support (that is, a base material) and then sandwiched between protective films. ..

Polyester films are used in a wide range of applications from the viewpoint of processability and the like, and are also used as supports or protective films for such dry film resists.

As an example of disclosing a technique relating to a polyester film, Patent Document 1 states that one surface (A) of a polyester film has a three-dimensional average surface roughness of 10 nm or less, and the surface specific resistance value Ω of the other surface (B). In a polyester film roll having a logΩ value of 12 or more, the amount of charge when the film is pulled out from the polyester film roll is in the range of ± 1.5 kV and raised in the region of the pulling speed of 0 m / min or more and 120 m / min or less. A polyester film roll is disclosed, which is characterized in that the number of defects in the shape is 5 pieces / 5,000 m ^{2 or less.}

Patent Document 2 states that the three-dimensional average surface roughness of one surface (A) of a polyester film is 10 nm or less, and the surface specific resistance value (Ω) of the other surface (B) is in a specific range. A polyester film roll formed by winding a film, and the amount of unwinding charge (E) in the polyester film when the polyester film is unwound from the polyester film roll at an unwinding speed of more than 0 m / min and 150 m / min or less. Is disclosed, and the polyester film roll is characterized in that the height difference on the polyester film is 3 mm or more and the number of raised defects is 5 pieces / 5000 m ^{2 or less.}

Patent Document 3 describes a laminated film in which a release layer containing a silicone resin component is provided on at least one surface of a polyester film, and the dynamic friction coefficient (μdR) of the release layer with respect to rubber and the release layer of the laminated film are described. The relationship of the dynamic friction coefficient (μdM) with respect to the metal on the surface opposite to the provided surface satisfies the following formula (1), and the centerline average roughness (Ra) of the surface of the release layer is 30 nm or less. The release film is disclosed.
| ΜdR-μdM | ≤0.5 ... (1)

Japanese Unexamined Patent Publication No. 2005-187779 Japanese Unexamined Patent Publication No. 2004-196873 Japanese Unexamined Patent Publication No. 2000-11789

In recent years, with the increase in definition in the formation of wiring and the like, the demand for high definition of patterns formed by using a photosensitive transfer material such as a dry film resist has been increasing more and more.
As a component of the photosensitive transfer material for forming a high-definition pattern, it has been studied to use a temporary support having an optically advantageous low haze value. As a method for obtaining a temporary support having a low haze value, it is conceivable to reduce the number of particles contained in the resin-containing layer conventionally provided on the base material (support) in the temporary support. However, if the number of particles is simply reduced, there arises a problem that wrinkles are generated when laminating with the opposing base material using the photosensitive transfer material.

This disclosure has been made in view of the above circumstances.
One embodiment of the present disclosure is an object of the present invention to provide a method for producing a resin pattern in which wrinkles are suppressed when laminating using a photosensitive transfer material.
Another embodiment of the present disclosure is an object of the present invention to provide a method for producing a conductive pattern including the above method for producing a resin pattern.
Yet another embodiment of the present disclosure is an object of providing a photosensitive transfer material suitably applied to the method for producing a resin pattern, and a laminated polyester film useful as a component of the photosensitive transfer material. ..
Yet another embodiment of the present disclosure is intended to provide a resin pattern or touch panel obtained using the photosensitive transfer material.

The disclosure includes the following embodiments:
<1> A photosensitive transfer material having a temporary support and a photosensitive resin layer supported by the temporary support is brought into contact with the substrate with the outermost layer on the side having the photosensitive resin layer with respect to the temporary support. The step of laminating the photosensitive resin layer, the step of pattern-exposing the photosensitive resin layer, and the step of developing the exposed photosensitive resin layer to form a resin pattern are included in this order.
The temporary support has a base material layer and a particle-containing layer containing particles on at least the surface of the base material layer opposite to the photosensitive resin layer side, and the haze value is less than 0.5%. Yes, and the dynamic friction coefficient between the particle-containing layer and the acrylonitrile butadiene rubber is 0.7 or less.
Resin pattern manufacturing method.
<2> The method for producing a resin pattern according to <1>, wherein the base material layer of the temporary support is a polyester film layer.
<3> The method for producing a resin pattern according to <2>, wherein the base material of the temporary support is a biaxially oriented polyester film layer.
<4> The method for producing a resin pattern according to any one of <1> to <3>, wherein the temporary support has a thickness of 30 μm or less.
<5> The method for producing a resin pattern according to any one of <1> to <4>, wherein the temporary support has a thickness of 10 μm or more.
<6> The method for producing a resin pattern according to any one of <1> to <5>, wherein the surface roughness Rp of the particle-containing layer is 0.1 μm to 0.5 μm.
<7> The method for producing a resin pattern according to any one of <1> to <6>, wherein the dynamic friction coefficient is 0.2 or more.
<8> The method for producing a resin pattern according to any one of <1> to <7>, wherein the particle-containing layer contains wax.
<9> The method for producing a resin pattern according to any one of <1> to <8>, wherein the particle-containing layer contains the particles having different average particle diameters.
<10> A step of forming a resin pattern on the conductive layer by using the method for producing a resin pattern according to any one of <1> to <9>.
A method for producing a conductive pattern, comprising a step of etching the conductive layer using the obtained resin pattern as a mask to form a conductive pattern.
<11> A polyester layer and a particle-containing layer containing particles on at least one surface of the polyester film layer, having a haze of less than 0.5%, and the particle-containing layer and acrylonitrile butadiene rubber. A laminated polyester film having a dynamic friction coefficient of 0.7 or less.
<12> The laminated polyester film according to <11>, which is used as a temporary support of a photosensitive transfer material.
<13> A photosensitive transfer material having a temporary support and a photosensitive resin layer supported by the temporary support, wherein the temporary support is the laminated polyester film according to <11> or <12>. ..
<14> A touch panel having a conductive pattern obtained by the method for manufacturing a conductive pattern according to <10>.
<15> A resin pattern obtained by the method for producing a resin pattern according to any one of <1> to <9>.
<16> A touch panel having the resin pattern according to <15>.

According to one embodiment of the present disclosure, it is possible to provide a pattern manufacturing method in which wrinkles are suppressed when laminating using a photosensitive transfer material.
According to another embodiment of the present disclosure, it is possible to provide a method for producing a conductive pattern including the above-mentioned method for producing a pattern.
According to still another embodiment of the present disclosure, it is possible to provide a photosensitive transfer material suitably applied to the method for producing a resin pattern, and a laminated polyester film useful as a component of the photosensitive transfer material. ..
According to still another embodiment of the present disclosure, it is possible to provide a resin pattern or a touch panel obtained by using the above-mentioned photosensitive transfer material.

It is a top view which shows an example of the biaxial stretching machine.

Hereinafter, embodiments of the present disclosure will be described in detail. The present disclosure is not limited to the following embodiments, and can be carried out with appropriate modifications within the scope of the purpose of the present disclosure.

In the present disclosure, the numerical range represented by using "~" means a range including the numerical values before and after "~" as the lower limit value and the upper limit value. In the numerical range described stepwise in the present disclosure, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described stepwise. Further, in the numerical range described in the present disclosure, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value shown in the examples.
In the present disclosure, the amount of each component in the composition means the total amount of the plurality of substances present in the composition when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified. ..
In the present disclosure, the term "process" is included in the term "process" as long as the intended purpose of the process is achieved, not only in an independent process but also in cases where it cannot be clearly distinguished from other processes. ..
In the present disclosure, "% by mass" and "% by weight" are synonymous, and "parts by mass" and "parts by weight" are synonymous.

In the present disclosure, "biaxial orientation" means a property having molecular orientation in the biaxial direction.

In the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.

(Manufacturing method of resin pattern and its application, and laminated polyester film)
In the method for producing a resin pattern according to one embodiment of the present disclosure, a photosensitive transfer material having a temporary support and a photosensitive resin layer supported by the temporary support is used, and a photosensitive resin layer is applied to the temporary support. A step of contacting the outermost layer on the holding side with a substrate (preferably a substrate having a conductive layer) for laminating (hereinafter, also referred to as a “lamination step”) and a step of pattern-exposing the photosensitive resin layer (hereinafter, “exposure”). A step of developing the exposed photosensitive resin layer to form a resin pattern (hereinafter, also referred to as a “development step”) is included in this order, and the temporary support is a base material. It has a particle-containing layer containing particles on at least the surface of the base material layer opposite to the photosensitive resin layer side, has a haze value of less than 0.5%, and has the particle-containing layer and acrylonitrile butadiene. The dynamic friction coefficient with the rubber is 0.7 or less.

The resin pattern manufacturing method of the present disclosure can be suitably used for forming a resist used for forming a conductive pattern, forming a resin pattern (cured film pattern) of a touch panel, and the like.

In the resin pattern manufacturing method of the present disclosure, the occurrence of wrinkles can be suppressed when laminating by using a photosensitive transfer material having the above structure.

The reason why the method for producing the resin pattern of the present disclosure exerts the above effect is not clear, but it is presumed as follows.
In order to meet the demand for high-definition patterning and obtain a temporary support having a low haze value, for example, it is possible to reduce the number of particles contained in the resin-containing layer conventionally provided on the base material (support). Conceivable. However, if the number of particles is simply reduced, wrinkles will occur when laminating with the opposing substrate using the photosensitive transfer material. It is considered that this is because the slipperiness of the photosensitive transfer material and the laminate roll is impaired by heating during laminating. On the other hand, in the photosensitive transfer material used in the resin pattern manufacturing method of the present disclosure, the temporary support has a base material layer and a particle-containing layer, and is between the particle-containing layer and the acrylonitrile butadiene rubber. By setting the dynamic friction coefficient of 0.7 or less, the occurrence of wrinkles during lamination is suppressed while ensuring a low haze value of less than 0.5%, which is suitable for forming a high-definition resin pattern. it is conceivable that.

On the other hand, the documents disclosing the conventional photosensitive transfer material and the polyester applicable to the photosensitive transfer material include the above-mentioned Patent Documents 1 to 3, and the dynamic friction between the particle-containing layer and the acrylonitrile butadiene rubber. There is no focus on coefficients.

The resin pattern manufacturing method of the present disclosure is suitably applied to the conductive pattern manufacturing method.
The method for producing the conductive pattern of the present disclosure is not limited as long as it is a method using the method for producing the resin pattern according to the present disclosure, and the resin pattern is formed on the conductive layer by using the method for producing the resin pattern of the present disclosure. It is preferable to have a step and a step of etching the conductive layer using the obtained resin pattern as a mask to form a conductive pattern (hereinafter, also referred to as “etching step”).
The method for manufacturing a conductive pattern of the present disclosure can be suitably used as a method for manufacturing a circuit wiring.

It is preferable that the method for producing the resin pattern according to the present disclosure and the method for producing the conductive pattern according to the present disclosure are each performed by a roll-to-roll method. The roll-to-roll method is a structure in which a substrate that can be wound and unwound is used as the substrate, and the substrate or the substrate is included before any of the steps included in the resin pattern manufacturing method or the conductive pattern manufacturing method. It includes a step of unwinding a body (also referred to as a “unwinding step”) and a step of winding a substrate or a structure including the substrate (also referred to as a “winding step”) after any of the steps. A method in which at least one of the steps (preferably all steps or all steps other than the heating step) is performed while transporting the substrate or the structure including the substrate. The unwinding method in the unwinding step and the winding method in the winding step are not limited, and a known method may be used in the manufacturing method to which the roll-to-roll method is applied.

In the present disclosure, a laminated polyester film can be preferably used as a temporary support for the photosensitive transfer material.

The present disclosure comprises, as another embodiment, a polyester film layer and a particle-containing layer containing particles on at least one surface of the polyester film layer, having a haze of less than 0.5% and having a haze of less than 0.5%. A laminated polyester film having a dynamic friction coefficient between the particle-containing layer and acrylonitrile butadiene rubber of 0.7 or less is included.

Hereinafter, each step included in the method for producing a resin pattern and the method for producing a conductive pattern according to the present disclosure will be described with the description of the laminated polyester film of the present disclosure applied as a suitable component thereof. Unless otherwise specified, the contents described for each step included in the resin pattern manufacturing method according to the present disclosure shall also be applied to each step included in the conductive pattern manufacturing method according to the present disclosure. ..

<< Laminating process >>
In the method for producing a resin pattern according to the present disclosure, the photosensitive transfer material according to the present disclosure may be referred to as an outermost layer (hereinafter, "first surface") on the side having the photosensitive resin layer with respect to the temporary support. ) Is brought into contact with a substrate (preferably a substrate having a conductive layer) and laminated (lamination step).

In the laminating step, the first surface of the photosensitive resin layer and the substrate (or the conductive layer when the conductive layer is provided on the surface of the substrate) are brought into contact with each other, and the photosensitive transfer material and the substrate are pressure-bonded (that is, that is). It is preferable to laminate). According to the above aspect, since the adhesion between the first surface of the photosensitive resin layer and the substrate is improved, the formed resin pattern can be suitably used as an etching resist.

When the photosensitive transfer material has a cover film, the cover film may be removed from the photosensitive transfer material, and then the photosensitive transfer material and the substrate may be bonded together.

When a layer other than the cover film (for example, a high refractive index layer and / or a low refractive index layer) is arranged outside the photosensitive resin layer on the first surface of the photosensitive transfer material, the first surface And the substrate may be bonded to each other via a layer other than the cover film.

The method of crimping the photosensitive film and the substrate is not limited, and is performed by superimposing the first surface of the photosensitive transfer material and the substrate, and applying pressure and heating by means such as a roll. Is preferable. Further, for bonding, a laminator, a vacuum laminator, and an auto-cut laminator capable of further increasing productivity can be used.

[substrate]
The substrate is not limited, and a known substrate can be used. The substrate is preferably a substrate having a conductive layer, and more preferably a substrate having a base material and a conductive layer on a part or the entire surface of the base material. The substrate may have any layer other than the conductive layer, if necessary.

Examples of the base material constituting the substrate include a glass base material, a silicon base material, and a film base material.

The base material constituting the substrate is preferably transparent. In the present disclosure, "transparent" means that the transmittance of light having a wavelength of 400 nm to 700 nm is 80% or more.
The refractive index of the base material is preferably 1.50 to 1.52.

Examples of the transparent glass base material include tempered glass represented by Corning's gorilla glass. Further, as the transparent glass base material, for example, the materials used in JP-A-2010-86684, JP-A-2010-152809, and JP-A-2010-257492 can be used.

When a film base material is used, it is preferable to use a film base material having low optical distortion and / or high transparency. Examples of the film substrate as described above include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, and cycloolefin polymer.

The base material constituting the substrate used in the roll-to-roll method is preferably a film base material. Further, when the circuit wiring for the touch panel is manufactured by the roll-to-roll method, the base material is preferably a sheet-like resin composition.

Examples of the conductive layer include a general circuit wiring and a conductive layer used for touch panel wiring. The conductive layer may be at least one selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer from the viewpoint of conductivity and fine wire forming property. A metal layer is more preferable, and a copper layer or a silver layer is particularly preferable.

The substrate may have one layer alone or two or more conductive layers. A substrate having two or more conductive layers preferably has a plurality of conductive layers made of different materials.

Examples of the material of the conductive layer include metals and conductive metal oxides. Examples of the metal include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag, and Au. Examples of the conductive metal oxide include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and SiO ₂ . In the present disclosure, "conductive" means that the volume resistivity is less than ^{1 × 10 6 Ωcm.} The volume resistivity of the conductive metal oxide is preferably less than ^{1 × 10 4 Ωcm.}

When a resin pattern is produced using a substrate having a plurality of conductive layers, it is preferable that at least one of the plurality of conductive layers contains a conductive metal oxide.

As the conductive layer, an electrode pattern corresponding to a sensor of a visual recognition portion used in a capacitive touch panel or wiring of a peripheral extraction portion is preferable.

<Photosensitive transfer material>
The photosensitive transfer material used in the method for producing a resin pattern of the present disclosure includes a temporary support and a photosensitive resin layer supported by the temporary support.
In the photosensitive transfer material, the temporary support has a particle-containing layer containing particles on the surface opposite to the photosensitive resin layer side of the base material layer and at least the base material layer, and has a haze of 0.5%. Is less than.
In the photosensitive transfer material, the photosensitive resin layer may be laminated on the temporary support directly or via an arbitrary layer.
In the photosensitive transfer material, an arbitrary layer may be laminated in addition to the particle-containing layer on the surface of the photosensitive resin layer opposite to the side on which the temporary support is arranged. Optional layers include, for example, a cover film and other layers described below.

<< Temporary support and its components >>
The temporary support contained in the photosensitive transfer material of the present disclosure has a base material layer and a particle-containing layer containing particles on a surface opposite to the photosensitive resin layer side of the base material layer at least, and has a haze of 0. It is less than 5.5%, and the dynamic friction coefficient between the particle-containing layer and the acrylonitrile butadiene rubber is 0.7 or less.

In the method for producing a resin pattern of the present disclosure, the coefficient of kinetic friction between the particle-containing layer and the acrylonitrile butadiene rubber is used as an index for suppressing the occurrence of wrinkles during lamination. Since the coefficient of kinetic friction between the particle-containing layer and the acrylonitrile butadiene rubber is 0.7 or less, the occurrence of wrinkles is better suppressed during laminating. The coefficient of kinetic friction is preferably 0.2 or more, and more preferably 0.3 or more, from the viewpoint of suppressing slip during transportation.
In the present disclosure, the acrylonitrile butadiene rubber is an element selected assuming one aspect of the material constituting the laminate roll.

In the present disclosure, the coefficient of kinetic friction is measured under the following conditions in accordance with JIS K7125: 1999.
The measurement is performed 10 times on the object to be measured, and the value obtained by rounding off the arithmetic mean value of the obtained value to the third decimal place is defined as the dynamic friction coefficient in the present disclosure.
-Measurement conditions-
Acrylonitrile butadiene rubber: Trade name: White EC270 (Rubber sheet manufactured by Kanuki Roller Co., Ltd.) The rubber sheet is cut to the same size as the measurement weight and attached to the measurement weight with double-sided tape. In addition, "White EC270" is antistatic treated so that the friction coefficient is not affected by charging so that it becomes 12V in the withstand voltage measurement based on JIS-L-1094B, and the shore A hardness is 71.
Measuring device: Autograph AG-X (manufactured by Shimadzu Corporation)
Measurement atmosphere: Humidity control at 23 ° C and 65% RH

The above-mentioned dynamic friction coefficient can be adjusted by adjusting the type and content of the components forming the layer such as particles contained in the particle-containing layer, adding particles to the base material layer, and the like.

The thickness of the temporary support is not limited. The thickness of the temporary support may be determined, for example, according to the strength of the temporary support, the light transmittance, the material, and the flexibility required for bonding the photosensitive transfer material to the substrate.

The average thickness of the temporary support is preferably 100 μm or less, and more preferably 30 μm or less. Further, the average thickness of the temporary support is preferably 5 μm or more, and more preferably 10 μm or more, from the viewpoint of ease of handling and versatility.

In the present disclosure, the average thickness of the elements constituting the photosensitive transfer material (that is, the temporary support, the base material layer and the particle-containing layer constituting the temporary support, the photosensitive resin layer, and the cover film) is included. Is measured by the following method.
A scanning electron microscope (SEM) is used to observe a cross section of the photosensitive transfer material in a direction perpendicular to the main surface (ie, in the thickness direction). Based on the obtained observation image, the thickness of the target component is measured at 5 points. The average thickness of the target component is obtained by arithmetically averaging the measured values.
The average thickness of the elements constituting the laminated polyester film of the present disclosure (that is, the polyester film layer and the particle-containing layer are included) is also measured in the same manner as described above.

The temporary support preferably has light transmission. Since the temporary support has light transmission property, when the photosensitive resin layer is exposed, the photosensitive resin layer can be exposed through the temporary support.
In the present disclosure, "having light transmittance" means that the transmittance of light having a wavelength used for pattern exposure is 50% or more.

..
In the temporary support, the transmittance of light having a wavelength (preferably a wavelength of 365 nm) used for pattern exposure (that is, the transmittance of light irradiated in the exposure step) is determined from the viewpoint of improving the exposure sensitivity of the photosensitive resin layer. , 60% or more, more preferably 70% or more. In the present disclosure, the "transmittance" refers to a layer to be measured with respect to the intensity of the incident light when light is incident in a direction perpendicular to the main surface of the layer to be measured (that is, in the thickness direction). It is the ratio of the intensity of the emitted light that has passed through and emitted. The transmittance is measured using MCPD Series manufactured by Otsuka Electronics Co., Ltd.

The haze value of the temporary support is less than 0.5%, more preferably 0.4% or less. The smaller the haze, the better, so the lower limit of the haze is not limited. If the lower limit of the haze is set for convenience, it is 0% or more.
When the haze value of the temporary support is within the above range, the scattering of light when the photosensitive resin layer supported by the temporary support is exposed is effectively suppressed in the exposure step, and the resin pattern after the development step is achieved. Distortion, loss, etc. are suppressed, and a resin pattern with a good wall surface condition can be formed.

The haze value is measured using a haze meter by a method according to JIS K 7105: 1981. The haze value described in the present disclosure is a value measured using a haze meter (NDH-2000, manufactured by Nippon Denshoku Industries Co., Ltd.).

-Particle-containing layer-
In the temporary support, the particle-containing layer may be arranged on only one surface of the temporary support, or may be arranged on both sides.
In the photosensitive transfer material according to the present disclosure, the temporary support has a particle-containing layer at least on the surface opposite to the photosensitive resin layer side. The particle-containing layer on the surface opposite to the photosensitive resin layer side is the outermost layer.

In the present disclosure, the particle-containing layer is preferably provided as a coating layer on the base material layer of the temporary support.

= Particle =
Examples of the particles contained in the particle-containing layer include organic particles and inorganic particles.
The particles are preferably inorganic particles from the viewpoint of suppressing the generation of wrinkles, haze, and durability (for example, thermal stability).

As the organic particles, resin particles are preferable. Examples of the resin particles include acrylic resin particles, polyester resin particles, silicone resin particles, and styrene-acrylic resin particles. The resin particles preferably have a crosslinked structure.

Examples of the inorganic particles include silica particles (silicon dioxide particles), titania particles (titanium oxide particles), calcium carbonate, barium sulfate, and alumina particles (aluminum oxide particles). Among the above, the inorganic particles are preferably silica particles from the viewpoint of haze and durability.

The silica particles are not limited, and known silica particles can be used. Examples of the silica particles include fumed silica and colloidal silica.

Fumed silica particles can be obtained, for example, by reacting a compound containing a silicon atom with oxygen and hydrogen in the gas phase. Examples of the silicon compound as a raw material include silicon halide (for example, silicon chloride).

Colloidal silica particles can be synthesized, for example, by a sol-gel method in which a raw material compound is hydrolyzed and condensed. Examples of the raw material compound of colloidal silica include alkoxysilicon (for example, tetraethoxysilane) and halogenated silane compound (for example, diphenyldichlorosilane).

The form of the silica particles may be primary particles or aggregates of primary particles (that is, aggregated silica particles).

The particles may be synthetic products or commercially available products.

The lower limit of the average particle size of the particles in the particle-containing layer is preferably 0.01 μm or more, and more preferably 0.04 μm or more. When the average particle size of the particles is 0.01 μm or more, the winding quality of the photosensitive transfer material can be further improved.

The upper limit of the average particle size of the particles in the particle-containing layer is preferably 0.4 μm or less, and more preferably 0.3 μm or less. When the average particle size of the particles is 0.4 μm or less, the occurrence of transfer failure can be further suppressed.

The average particle size of the particles is determined by arithmetically averaging the particle size of 50 particles randomly selected from a scanning electron microscope (SEM) image.

The particle-containing layer may contain one type of particles alone or may contain two or more types of particles.

The particle content may be 0.01% by mass to 15% by mass with respect to the total mass of the particle-containing layer from the viewpoint of suppressing the generation of wrinkles when laminating the photosensitive transfer material and haze. It is preferably 0.1% by mass to 10% by mass, and particularly preferably 0.5% by mass to 6% by mass.

One of the preferred embodiments of the particle-containing layer is an embodiment containing particles having different average particle diameters from the viewpoint of adjusting the dynamic friction coefficient. The average particle size referred to here means a median size.
The particles having different average particle diameters are preferably a combination of particles A having an average particle diameter of less than 100 nm and particles B having an average particle diameter of 100 nm or more. The particles A and B may be one kind of particles or a mixture of two or more kinds of particles, respectively.

The average particle size of the particles A is less than 100 nm, preferably 10 nm to 80 nm, and more preferably 20 nm to 60 nm.
Examples of the particles A include particles having an average particle diameter of less than 100 nm among the particles exemplified above, and colloidal silica or alumina having an average particle diameter of less than 100 nm is more preferable.

The average particle size of the particles B is 100 nm or more, preferably 100 to 400 nm, and more preferably 100 to 300 nm. The average particle size of the particles B is preferably larger than the thickness of the particle-containing layer.
Further, the particle B is preferably smaller than the content of the particle A.
Examples of the particles B include particles having an average particle diameter of 100 or more among the particles exemplified above, and silica particles having an average particle diameter of 100 nm or more are more preferable.
The content ratio A: B) of the particles A and the particles B is preferably 10: 1 to 1: 1 and more preferably 6: 1 to 2: 1 on a mass basis.

= Wax =
The particle-containing layer preferably contains wax.
Wax is a general term for compounds that are solid at room temperature (25 ° C) and become liquid when heated. Whether or not it becomes a liquid in a heated state can be visually confirmed by a method conforming to JIS K6220-1 (2001).

In the particle-containing layer, one of the suitable elements that contributes to the adjustment of the dynamic friction coefficient is the inclusion of wax.
Specific examples of waxes include carnauba wax, candelilla wax, rice wax, wood wax, jojoba oil, palm wax, rosin-modified wax, auricury wax, sugar cane wax, espart wax, bark wax and other vegetable waxes; , Lanorin, whale wax, ibota wax, cellac wax and other animal waxes; montan wax, ozokelite, ceresin wax and other mineral waxes; paraffin wax, microcrystallin wax, petrolactam and other petroleum waxes; Examples thereof include synthetic hydrocarbon waxes (polyolefin waxes) such as waxes, polyethylene oxide waxes, polypropylene waxes, and polypropylene oxide waxes.

The wax may be used alone or in combination of two or more.
The content of the wax is not particularly limited, but is preferably 60% by mass or less, more preferably 1% by mass to 50% by mass, and 2% by mass to 40% by mass with respect to the total mass of the particle-containing layer. It is more preferably mass%.

= Resin =
The particle-containing layer preferably contains a resin.
In the present disclosure, the resin refers to a polymer having a weight average molecular weight of 3000 or more.
In the present disclosure, the weight average molecular weight and the weight average molecular weight can be measured by using gel permeation chromatography (GPC).

The resin can function as a binder. Examples of the resin include polyacrylic, polyurethane, polyester, and polyolefin. From the viewpoint of selecting an appropriate hardness as a binder, polyacrylic is preferable.

The polyacrylic is not limited as long as it is a polymer having a structural unit derived from at least one compound selected from the group consisting of an acrylic acid ester and a methacrylic acid ester, and known polyacrylics can be used. The polyacrylic may have a structural unit derived from a compound other than the acrylic acid ester and the methacrylic acid ester (for example, an olefin compound and a styrene compound).

The polyurethane is not limited as long as it is a polymer having a urethane bond, and known polyurethane can be used. Polyurethane is usually produced by reacting an isocyanate compound with a polyol compound.

As the polyester, a polyester described later can be applied, and the preferred type is also the same.

The polyolefin is not limited, and known polyolefins can be used. Examples of the polyolefin include polyethylene and polypropylene.

The particle-containing layer may contain one kind of resin alone or may contain two or more kinds of resins.

The resin content is preferably 30% by mass to 80% by mass, preferably 40% by mass to 70% by mass, based on the total mass of the particle-containing layer, from the viewpoint of the durability of the particle-containing layer and the dispersibility of the particles. It is more preferably mass%, and particularly preferably 45% by mass to 65% by mass.

= Other compounds =
Further, the particle-containing layer may contain other compounds other than those described above.
Examples of other compounds include surfactants, cross-linking agents, and film-forming aids.

As the surfactant, any of anionic type, cationic type, nonionic type (nonionic type), and amphoteric can be used. Preferred surfactants are anionic surfactants and nonionic surfactants.

Examples of anionic surfactants include Lapizol (registered trademark) A-90 (manufactured by NOF Corporation), Sanded BL (manufactured by Sanyo Chemical Industries, Ltd.) and Nikkor SCS (Nikko Chemicals Co., Ltd.). Examples of nonionic surfactants include Naroacty (registered trademark) CL95 (manufactured by Sanyo Chemical Industries, Ltd.).
Examples of the surfactant include the surfactant described in the Surfactant Physical Characteristics Performance Handbook (Technical Information Association).

The surfactant may be used alone or in combination of two or more.
The content of the surfactant is not particularly limited, but is preferably 10% by mass or less, more preferably 0.001% by mass to 10% by mass, and 0, based on the total mass of the particle-containing layer. It is more preferably 0.01% by mass to 3% by mass.

Examples of the cross-linking agent include known cross-linking agents such as carbodiimide compounds, oxazoline compounds, epoxy compounds, melamine compounds, and isocyanate compounds.
Examples of cross-linking agents include Carbodilite (registered trademark) V-02-L2 (manufactured by Nisshinbo Chemical Co., Ltd.), Epocross (registered trademark) WS-700 (manufactured by Nippon Shokubai Co., Ltd.), and Denacol (registered trademark) EX614B (registered trademark). Examples thereof include Nagase ChemteX Corporation (manufactured by Nagase ChemteX Corporation) and Duranate (registered trademark) WM44 (manufactured by Asahi Kasei Chemicals Co., Ltd.).

The cross-linking agent may be used alone or in combination of two or more.
The content of the cross-linking agent is not particularly limited, but is more preferably 1% by mass to 50% by mass and further preferably 2% by mass to 20% by mass with respect to the total mass of the particle-containing layer.

From the viewpoint of the coefficient of kinetic friction, the particle-containing layer preferably has a surface roughness Rp (maximum mountain height) of 0.1 μm to 0.5 μm, more preferably 0.1 μm to 0.4 μm. The surface roughness Rp of the particle-containing layer is preferably the surface roughness of the outermost layer of the temporary support.

In the present disclosure, the surface roughness Rp was measured at five randomly selected locations on the surface of the particle-containing layer using the following measuring device, and averaged by omitting the minimum and maximum values among the obtained measured values. Let it be a value.
(measuring device)
Keyence Laser Microscope "VK-X200"
(Measurement condition)
・ Horizontal measurement distance: 276 μm
-Z-axis distance: 6.975 μm
-Objective lens: 50x (XY: 135nm / pixel, Z: 0.1nm / digit)
・ Filter: OFF
・ Cut-Off: 0.08mm setting

The thickness of the particle-containing layer is preferably 0.01 μm to 0.3 μm, more preferably 0.02 μm to 0.1 μm, and 0.02 μm to 0, from the viewpoint of manufacturing suitability of the particle-containing layer. It is particularly preferably .08 μm. The thickness of the particle-containing layer is an arithmetic mean value of the thicknesses of the five points measured by the method described above.

Examples of the method for forming the particle-containing layer include a method using a coating liquid for forming a particle-containing layer. The particle-containing layer can be formed, for example, by applying a coating liquid for forming a particle-containing layer on a polyester film or the like and drying it if necessary.

As a method for forming the temporary support containing the particle-containing layer, a known method such as a coextrusion method can be appropriately used in addition to coating. As the coextrusion method, for example, the method disclosed in Japanese Patent Application Laid-Open No. 2019-65271 can be used.

The coating liquid for forming a particle-containing layer can be prepared by mixing each of the above components and a solvent.
Examples of the solvent include water, hexane, acetone, ethanol, tetrahydrofuran, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether. Among the above, the solvent is preferably water from the viewpoint of environment, safety and economy.

The coating liquid for forming a particle-containing layer may contain one type of solvent alone, or may contain two or more types of solvents.

The content of the solvent is preferably 80% by mass to 99% by mass, more preferably 90% by mass to 98% by mass, based on the total mass of the coating liquid for forming the particle-containing layer.

The coating method is not 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 blade coating method, a spin coating method, a bar coating method, and a dip coating method.

-Base layer-
In the temporary support, examples of the base material layer include a glass substrate or a layer made of a resin film (also referred to as a resin film layer). The base material layer in the temporary support is preferably a resin film layer from the viewpoint of strength, flexibility, and light transmission.

Examples of the resin film constituting the base material layer in the temporary support include a polyester film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. The resin film is preferably a polyester film, more preferably a bi-oriented polyester film.

That is, the temporary support has a polyester film layer (preferably a layer made of a biaxially oriented polyester film) and a particle-containing layer containing particles on at least one surface of the polyester film layer, and has a haze. A laminated polyester film having a dynamic friction coefficient of less than 0.5% and between the particle-containing layer and the nitrile butadiene rubber is preferably 0.7 or less.

The above-mentioned laminated polyester film is the laminated polyester film of the present disclosure.
In other words, the laminated polyester film of the present disclosure is preferably used as a temporary support of the photosensitive transfer material, and the photosensitive transfer material of the present disclosure has a photosensitive resin layer supported by the temporary support. However, it is preferable that the temporary support is the laminated polyester film of the present disclosure.

When the particle-containing layer is formed on the polyester film layer by using the particle-containing layer forming coating liquid, the polyester film to which the particle-containing layer forming coating liquid is applied may be an unstretched film and is uniaxially stretched. It may be a film or a biaxially stretched film. The method for forming the particle-containing layer is preferably a method of applying a coating liquid for forming a particle-containing layer on the uniaxially stretched polyester film from the viewpoint of adhesion between the polyester film base material and the particle-containing layer. For example, a particle-containing layer is formed by applying a coating liquid for forming a particle-containing layer on a uniaxially stretched polyester film, and then the uniaxially stretched polyester film layer and the particle-containing layer are simultaneously stretched to form a polyester film layer and particles. The adhesion of the containing layer can be improved. The specific method of stretching will be described later.

-Biaxially oriented polyester film-
Hereinafter, the biaxially oriented polyester film will be described in detail.
In the present disclosure, "biaxial orientation" means a property having molecular orientation in the biaxial direction.
The molecular orientation is measured using a microwave transmission type molecular orientation meter (for example, MOA-6004, manufactured by Oji Measuring Instruments Co., Ltd.). The angle formed in the biaxial direction is preferably 90 ° ± 5 °, more preferably 90 ° ± 3 °, and particularly preferably 90 ° ± 1 °. The biaxially oriented polyester film according to the present disclosure preferably has molecular orientation in the longitudinal direction and the width direction.

In the present disclosure, the "width direction" means a direction orthogonal to the longitudinal direction. If the width direction is unknown, the direction with the strongest orientation is among the orientations measured using a microwave transmission type molecular orientation meter (for example, MOA-6004, manufactured by Oji Measuring Instruments Co., Ltd.). Is the width direction.

In the present disclosure, the term "orthogonal" is not limited to strict orthogonality, but includes substantially orthogonality. "Approximately orthogonal" means intersecting at 90 ° ± 5 °, preferably intersecting at 90 ° ± 3 °.
It is more preferable to intersect at 90 ° ± 1 °.

= Polyester =
The biaxially oriented polyester film is a biaxially oriented polyester film containing polyester as a main polymer component. Here, the "main polymer component" means the polymer having the largest content ratio (mass%) among all the polymers contained in the film.

Polyester is a polymer having an ester bond in the main chain. Polyester is usually formed by polycondensing a dicarboxylic acid compound and a diol compound, which will be described later.

The polyester is not limited, and known polyesters can be used. Examples of the polyester include polyethylene terephthalate (PET) and polyethylene-2,6-naphthalate (PEN). Among the above, the polyester is preferably polyethylene terephthalate. That is, the biaxially oriented polyester film according to the present disclosure is preferably a biaxially oriented polyethylene terephthalate film.

The intrinsic viscosity of polyester is preferably 0.50 dl / g or more and less than 0.80 dl / g. More preferably, it is 0.55 dl / g or more and less than 0.70 dl / g.

The biaxially oriented polyester film may contain one kind of polyester alone or may contain two or more kinds of polyesters.

The polyester content is preferably 85% by mass or more, more preferably 90% by mass or more, and 95% by mass or more, based on the total mass of the polymer in the biaxially oriented polyester film. Is more preferable, and 98% by mass or more is particularly preferable.
The upper limit of the polyester content is not limited and can be appropriately set within a range of 100% by mass or less with respect to the total mass of the polymer in the biaxially oriented polyester film.

The polyester content is preferably 85% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, based on the total mass of the biaxially oriented polyester film. It is particularly preferably 98% by mass or more. The upper limit of the polyester content is not limited and can be appropriately set within a range of 100% by mass or less with respect to the total mass of the biaxially oriented polyester film.

When the biaxially oriented polyester film according to the present disclosure contains polyethylene terephthalate, the content of polyethylene terephthalate may be 90% by mass to 100% by mass with respect to the total mass of the polyester in the biaxially oriented polyester film. It is more preferably 95% by mass to 100% by mass, further preferably 98% by mass to 100% by mass, and particularly preferably 100% by mass.

(Polyester manufacturing method)
The method for producing polyester is not limited, and a known method can be used. For example, polyester can be produced by polycondensing at least one dicarboxylic acid compound and at least one diol compound in the presence of a catalyst.

Examples of the dicarboxylic acid compound include an aliphatic dicarboxylic acid compound, an alicyclic dicarboxylic acid compound, and an aromatic dicarboxylic acid compound.
Examples of the diol compound include an aliphatic diol compound, an alicyclic diol compound, and an aromatic diol compound.
Examples of the catalyst include alkali metal compounds, alkaline earth metal compounds, zinc compounds, lead compounds, manganese compounds, cobalt compounds, aluminum compounds, antimony compounds, titanium compounds, germanium compounds, and phosphorus compounds.
A known end-capping agent can be used in the production of polyester, if necessary. Examples of the terminal encapsulant include an oxazoline compound, a carbodiimide compound, and an epoxy compound.

As a method for synthesizing polyester, a known synthetic method can be applied, and for example, the methods described in paragraphs 0033 to 0070 of Japanese Patent No. 5575671 can be used. The description of the above publication is incorporated herein by reference.

The haze value of the biaxially oriented polyester film is less than 0.5%, more preferably 0.4% or less. Since the smaller the haze value is, the more preferable it is, the lower limit of the haze value is not limited. If the lower limit of the haze value is set for convenience, it is 0% or more.
When the haze value of the biaxially oriented polyester film is within the above range, scattering of light is suppressed when the photosensitive resin layer (that is, the resist layer) is laminated on the film and then irradiated with light such as ultraviolet rays for exposure. The patterning of the obtained resin pattern (resist pattern) after development is suppressed from being distorted and missing, and the state of the wall surface of the resist pattern is also improved. In addition, the light transmittance is also good.

Haze is measured by the method described above.

In the biaxially oriented polyester film, the ^{b * value in the L *} a ^* b ^* color system is preferably 0 to 1, more preferably 0 to 0.8, and 0 to 0.6. It is more preferable, and it is particularly preferable that it is 0 to 0.4. Since ^{the yellowness of the film can be reduced by setting the b *} value in the ^{L *} a ^* b ^* color system to 0 to 1, the hue of the film can be made close to colorless. As a result, for example, in applications where high visibility is required (for example, a display device), the biaxially oriented polyester film according to the present disclosure can be preferably applied.

^{The b *} value in the L ^* a ^* b ^* color system is measured by a transmission method using a spectrocolorimeter (for example, SE-2000, manufactured by Nippon Denshoku Industries Co., Ltd.).

= Surface roughness SRa =
When the biaxially oriented polyester film is used as the base material layer (support) of the dry film resist, the center line average surface roughness SRa (A) of one surface (this surface is referred to as the surface (A)) is less than 7 nm and The ten-point average surface roughness SRz (A) is less than 400 nm, and the other surface (this surface is referred to as the surface (B)) has SRa (B) of less than 10 nm and SRz (B) of less than 700 nm. Is preferable. More preferably, SRz (A) is less than 100 nm, SRz (B) is 100 nm or more and less than 700 nm, and there is a difference between the surface (A) and the surface (B) in terms of achieving both performance and handling.
It is preferable to use a photosensitive resin layer (resist layer) laminated on the surface (A) side.

By achieving the surface roughness in the above range in the biaxially oriented polyester film, appropriate smoothness that suppresses the influence of reflection on the film surface during exposure can be obtained, and a high-definition resist pattern (resin pattern) is formed. It is possible, and at the same time, handleability during processing can be obtained. When SRa (B) is 10 nm or more, or SRz (B) is 700 nm or more, light reflection due to unevenness of light incident angle in the exposure process due to unevenness and unevenness transferred from the film to the resist surface or Due to the influence of scattering, the resist pattern tends to be missing. SRa (B) is more preferably 1 nm or more and less than 10 nm, and SRz (B) is more preferably 10 nm or more and less than 700 nm. On the other hand, it is preferable that SRa (A) is 1 nm or more and less than 7 nm and SRz (A) is 10 nm or more and less than 400 nm.

SRa (B) is more preferably 3 nm or more and less than 10 nm, and SRz (B) is more preferably 100 nm or more and less than 500 nm. In order to make the surface roughness of the A layer and the B layer within the above range, specific organic particles or inorganic particles are added to the polyester resin constituting the layer having the A surface (A layer) and the layer having the B surface (B layer). This can be achieved by including a specific amount of particles.

= Particle =
The biaxially oriented polyester film may contain particles in a region of at least one surface in the thickness direction up to 5% of the film thickness. When the polyester film contains particles in the above region, the winding quality of the film can be improved.

In the present disclosure, the term "containing particles in a region" is not limited to the presence of particles in the entire designated region, but includes the presence of particles in at least a part of the designated region. .. For example, when the film contains particles in a region of up to 5% of the film thickness in the thickness direction from the surface, the particles are present in the entire region of up to 5% of the film thickness in the thickness direction from the surface. The particles may be present in a region closer to the surface (for example, a region up to 1% of the film thickness in the thickness direction from the surface).

The biaxially oriented polyester film preferably contains particles in a region of at least one surface up to 1% of the film thickness in the thickness direction, and has a film thickness of 0. It is more preferable to contain the particles in a region of up to 5%, and it is particularly preferable to contain the particles in a region of up to 0.2% of the film thickness in the thickness direction from at least one surface.

As the particles, the particles described in the above particle-containing layer can be applied, and the preferred types are also the same.

The average particle size of the particles is determined by the method described above.

The biaxially oriented polyester film according to the present disclosure may contain particles of one type alone, or may contain particles of two or more types.

The particle content is preferably 0.0001% by mass to 0.01% by mass with respect to the total mass of the biaxially oriented polyester film from the viewpoint of improving the winding quality of the film and suppressing transfer failure. , 0.0005% by mass to 0.005% by mass, more preferably 0.0008% by mass to 0.004% by mass.

= Thickness =
The thickness of the biaxially oriented polyester film is preferably 10 μm to 100 μm, more preferably 10 μm to 50 μm, and 12 μm to 40 μm from the viewpoint of handling suitability (particularly, handling suitability when laminating the film). Is particularly preferred. When the thickness is 10 μm or more, good strength can be obtained and handling in the processing step becomes easy, and when it is 50 μm or less, a better haze value can be obtained.

= Dimensional change rate =
In the biaxially oriented polyester film, when the dimensional change rate is within the following range, distortion and wrinkles due to heat shrinkage in the DFR processing step can be suppressed, which is preferable. The dimensional change rate can be achieved by appropriately adjusting the conditions such as relaxation and heat treatment under the film forming conditions by a known method. The dimensional change rate at 150 ° C. is preferably less than 3% in the longitudinal direction and less than 2.5% in the width direction, and more preferably 0.5% or more and less than 2% in the longitudinal direction and 1% or more and less than 2% in the width direction. The dimensional change rate at 100 ° C. is preferably less than 1% in both the longitudinal direction and the width direction, and more preferably less than 0.8%. When the dimensional change rate is within the above range, the flatness when the photosensitive resin layer (resist layer) is applied tends to be improved.

= F-5 value =
In the biaxially oriented polyester film, the strength when the film in the longitudinal direction is stretched by 5% (hereinafter, this value is referred to as F-5 value) is preferably 70 MPa or more and less than 150 MPa. If the F-5 value in the longitudinal direction is less than 70 MPa, the processing characteristics may deteriorate due to scratches due to insufficient strength. On the other hand, if the F-5 value in the longitudinal direction is 150 MPa or more, it may be difficult to achieve compatibility with the F-5 value in the width direction. The F-5 value in the longitudinal direction is preferably 80 MPa or more and less than 140 MPa, and more preferably 90 MPa or more and less than 130 MPa.

Further, it is preferable that the F-5 value in the width direction is 80 MPa or more and less than 160 MPa. When the F-5 value in the width direction is in the above range, the deterioration of the processing characteristics due to the occurrence of scratches due to insufficient strength is suppressed, and the compatibility with the F-5 value in the longitudinal direction is also good. It is preferably 90 MPa or more and less than 150 MPa, and more preferably 100 MPa or more and less than 140 MPa.

= Breaking strength =
In the biaxially oriented polyester film, the breaking strength in the longitudinal direction is preferably 200 MPa or more and less than 360 MPa, and more preferably 220 MPa or more and less than 340 MPa. The breaking strength in the width direction is preferably 260 MPa or more and less than 420 MPa, and particularly preferably 280 MPa or more and less than 400 MPa.

The above F-5 value and breaking strength can be achieved by appropriately adjusting the stretching temperature and stretching ratio in the longitudinal and horizontal directions.

= Fine particles in polyester film =
In the biaxially oriented polyester film, the number of fine particles of 1.5 μm or more and less than 4.5 μm contained in each of the square small pieces having a side of 5 mm is preferably 0 to 200. The fine particles of 1.5 μm or more and less than 4.5 μm include primary particles having a diameter of 1.5 μm or more and less than 4.5 μm and primary particle aggregates having a diameter of 1.5 μm or more and less than 4.5 μm. included. If the primary particle is not a perfect sphere, the longest width of the primary particle is taken as the diameter of the primary particle. When the primary particle aggregate is not a perfect sphere, the longest width of the primary particle aggregate is taken as the diameter of the primary particle aggregate.

When the number of fine particles of 1.5 μm or more and less than 4.5 μm contained in a square piece having a side of 5 mm of the polyester film is 0 to 200, the focal position at the time of exposure shifts. It is possible to suppress line width thickening and deterioration of resolution. When fine particles having a size of 1.5 μm or more and less than 4.5 μm are present, the influence on these performances is small in normal exposure, but the substrate is distorted or the substrate is subjected to the exposure method by direct drawing. If the exposed portion is out of focus due to insufficient adsorption or unevenness on the surface of the substrate, the effect of light scattering by the fine particles becomes large. As a result, the line width becomes thicker and the resolution (particularly the omission) deteriorates. In the case of fine particles larger than 4.5 μm, the resolution deteriorates even during normal exposure, so it is preferable that the polyester film does not contain fine particles larger than 4.5 μm as much as possible. In the polyester film, the number of fine particles larger than 4.5 μm contained in each small piece when a square piece having a side of 5 mm is cut out is preferably 0 to 20, preferably 0 to 10. It is more preferable to have 0 to 5, more preferably 0 to 5, and particularly preferably 0 to 1.

From the viewpoint of suppressing line width thickening and deterioration of resolution when the focal position shifts during exposure, the number of fine particles of 1.5 μm or more and less than 4.5 μm contained in a small piece of polyester film is 180 or less. It is preferable that there are 150 or less, 120 or less is preferable, 100 or less is preferable, 80 or less is more preferable, 50 or less is more preferable, 30 or less is further preferable, and 20 or less is more preferable. It is preferable, 15 or less is particularly preferable, 10 or less is further preferable, and 5 or less is most preferable.

The fine particles of 1.5 μm or more and less than 4.5 μm contained in the polyester film are, for example, inorganic fine particles or organic fine particles, such as lubricants, aggregates of additives, foreign substances mixed in raw materials, foreign substances mixed in the manufacturing process, and the like. There is. Specific examples of the fine particles include inorganic particles such as calcium carbonate, calcium phosphate, silica (silicon dioxide), kaolin, talc, titanium dioxide, alumina (aluminum oxide), barium sulfate, calcium fluoride, lithium fluoride, zeolite, and molybdenum sulfide. , Crosslinked polymer particles, organic particles such as calcium oxalate and the like. These may be used alone or in combination of two or more.
The fine particles are blended into the film according to a conventional method. In order to produce the polyester film of the present disclosure, for example, a method of filtering the resin with a filter having a mesh size of 4.5 μm or less can be mentioned.

[Manufacturing method of biaxially oriented polyester film]
Examples of the method for producing a biaxially oriented polyester film include a method of biaxially stretching an unstretched polyester film obtained by an extrusion molding method.

The extrusion molding method is a method of molding a raw material resin into a desired shape by, for example, extruding the raw material resin using an extruder.

The biaxial stretching may be a simultaneous biaxial stretching in which the longitudinal stretching and the transverse stretching are performed at the same time, or may be a sequential biaxial stretching in which the longitudinal stretching and the transverse stretching are divided into two stages or two or more stages. good. Examples of the form of sequential biaxial stretching include, but are limited to, longitudinal stretching → transverse stretching, longitudinal stretching → transverse stretching → longitudinal stretching, longitudinal stretching → longitudinal stretching → transverse stretching, and transverse stretching → longitudinal stretching. It's not something. Among the above, longitudinal stretching → transverse stretching is preferable.

The apparatus used for biaxial stretching is not limited, and a known biaxial stretching machine can be used. Hereinafter, an example of the biaxial stretching machine will be described with reference to the drawings.

As shown in FIG. 1, the biaxial stretching machine 100 includes a pair of annular rails 60a and 60b, and gripping members 2a to 2l attached to each annular rail and movable along the rails. The annular rails 60a and 60b are arranged symmetrically with respect to each other with the film 200 interposed therebetween. In the biaxial stretching machine 100, the film 200 can be stretched in the width direction by gripping the film 200 with the gripping members 2a to 2l and moving the film 200 along the rail.

The biaxial stretching machine 100 has a region including a preheating section 10, a stretching section 20, a heat fixing section 30, a heat relaxation section 40, and a cooling section 50.

The preheating section 10 is a region for preheating the film 200.

The stretched portion 20 is a region in which the preheated film 200 is stretched by applying tension in the direction of the arrow TD (film width direction), which is a direction orthogonal to the direction of the arrow MD (longitudinal direction). For example, as shown in FIG. 1, in the stretched portion 20, the film 200 is stretched from the width L0 to the width L1.

The heat fixing portion 30 is a region where the tensioned film 200 is heated and heat-fixed while being tensioned.

The heat relaxation unit 40 is a region for heat-relaxing the tension of the heat-fixed film 200 by heating the heat-fixed film 200.

The cooling unit 50 is a region for cooling the heat-relaxed film 200. By cooling the film 200, the shape of the film 200 can be fixed. In FIG. 1, a film 200 having a width L2 that has passed through the cooling unit 50 is shown.

Gripping members 2a, 2b, 2e, 2f, 2i, and 2j that can move along the annular rail 60a are attached to the annular rail 60a. Gripping members 2c, 2d, 2g, 2h, 2k, and 2l that can move along the annular rail 60b are attached to the annular rail 60b.

The gripping members 2a, 2b, 2e, 2f, 2i, and 2j grip one end of the film 200 in the direction of the arrow TD. The gripping members 2c, 2d, 2g, 2h, 2k, and 2l grip the other end of the film 200 in the direction of the arrow TD. The gripping members 2a to 2l are generally referred to as chucks, clips, and the like.

The gripping members 2a, 2b, 2e, 2f, 2i, and 2j move counterclockwise along the annular rail 60a. The gripping members 2c, 2d, 2g, 2h, 2k, and 2l move clockwise along the annular rail 60b.

The gripping members 2a to 2d move along the annular rail 60a or 60b while gripping the end portion of the film 200 in the preheating portion 10, pass through the stretching portion 20, the heat fixing portion 30, and the heat relaxing portion 40, and then the cooling portion. Proceed to 50. Next, the gripping members 2a and 2b and the gripping members 2c and 2d are end portions on the downstream side in the direction of the arrow MD of the cooling unit 50 (for example, the gripping release point P and the grip release point Q in FIG. 1) in the order of transport direction. After separating the end portion of the film 200 at), the film further moves along the annular rail 60a or 60b and returns to the preheating portion 10. In the above process, the film 200 moves in the direction of the arrow MD to preheat the preheating section 10, stretch the stretched section 20, heat-fix the heat-fixing section 30, and heat-relaxing the heat-relaxing section 40. And the cooling unit 50 is cooled and stretched laterally.

By adjusting the moving speed of the gripping members 2a to 2l, the transport speed of the film 200 can be adjusted. Further, each of the gripping members 2a to 2l can independently change the moving speed.

As described above, the biaxial stretching machine 100 enables lateral stretching in the stretching portion 20 to stretch the film 200 in the direction of the arrow TD. On the other hand, the biaxial stretching machine 100 can also stretch the film 200 in the direction of the arrow MD by changing the moving speed of the gripping members 2a to 2l. That is, it is also possible to perform simultaneous biaxial stretching using the biaxial stretching machine 100.

The biaxial stretching machine 100 may further have other gripping members in addition to the gripping members 2a to 2l in order to support the film 200 (not shown).

Next, an example of a method for producing a biaxially oriented polyester film according to the present disclosure will be specifically described.

The method for producing a biaxially oriented polyester film according to the present disclosure includes a step of forming an unstretched polyester film by melt-extruding polyester (hereinafter, also referred to as an “extrusion molding step”) and the unstretched polyester film. A step of stretching in the longitudinal direction (hereinafter, also referred to as "longitudinal stretching step"), a step of stretching the polyester film stretched in the longitudinal direction in the width direction (hereinafter, also referred to as "transverse stretching step"), It is preferable to have.

(Extrusion molding process)
In the extrusion molding step, an unstretched polyester film is formed by melt-extruding polyester.

Examples of the melt extrusion method include a method using an extruder. For example, melt extrusion is performed by heating polyester to a temperature equal to or higher than the melting point using an extruder equipped with one or more screws, and rotating the screw to melt and knead the polyester. Polyester is melted in an extruder by heating and kneading with a screw to form a melt.

The melt is extruded from the extrusion die through a gear pump, a filter and the like. The extrusion die is also simply referred to as a "die" (JIS B8650: 2006, a) Extruder, see No. 134). The melt may be extruded in a single layer or in multiple layers.

In melt extrusion, it is preferable to replace the inside of the extruder with nitrogen from the viewpoint of suppressing thermal decomposition (for example, hydrolysis of polyester) in the extruder. Further, the extruder is preferably a twin-screw extruder because the kneading temperature can be kept low.

The melt extruded from the extrusion die is cooled to form a film. 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. In cooling the melt, it is preferable to blow air (preferably cold air) on the melt.

The temperature of the casting roll is preferably more than (Tg-10 ° C.) and (Tg + 30 ° C.) or less, more preferably (Tg-7 ° C.) to (Tg + 20 ° C.), and particularly preferably (Tg-5 ° C.) to (Tg + 10 ° C.). preferable. "Tg" is the glass transition temperature of polyester.

When a casting roll is used in the extrusion molding step, it is preferable to improve the adhesion between the casting roll and the melt. Examples of the method for improving the adhesion include an electrostatic application method, an air knife method, an air chamber method, a vacuum nozzle method, and a touch roll method.

The molded product (unstretched polyester film) cooled using a casting roll or the like is stripped from a cooling member such as a casting roll by using a stripping member such as a stripping roll.

(Biaxial stretching)
-Vertical stretching process-
In the longitudinal stretching step, the unstretched polyester film is stretched in the longitudinal direction (hereinafter, also referred to as "longitudinal stretching").

In the longitudinal stretching step, it is preferable to preheat the unstretched polyester film before the longitudinal stretching. By preheating the unstretched polyester film, the polyester film can be easily stretched vertically.

The preheating temperature is preferably (Tg-10 ° C.) to (Tg + 60 ° C.), preferably (Tg ° C.).
~ (Tg + 50 ° C.) is more preferable. Specifically, the preheating temperature is preferably 60 ° C to 100 ° C, more preferably 65 ° C to 80 ° C.

The longitudinal stretching can be performed, for example, by applying tension between two or more pairs of nip rolls installed in the transport direction while transporting the unstretched polyester film in the longitudinal direction. For example, when a pair of nip rolls A are installed on the upstream side in the transport direction and a pair of nip rolls B are installed on the downstream side in the transport direction, the rotation speed of the nip roll B is set to the rotation speed of the nip roll A when the unstretched polyester film is conveyed. At higher speeds, the unstretched polyester film is stretched in the longitudinal direction.

The draw ratio in the longitudinal stretching step is preferably smaller than the stretching ratio in the transverse stretching step described later. The stretching ratio in the longitudinal stretching step is preferably 2.0 to 5.0 times, more preferably 2.5 to 4.0 times, and 2.8 to 4.0 times. Is particularly preferred.

The heating temperature in the longitudinal stretching step is preferably (Tg-20 ° C.) to (Tg + 50 ° C.), more preferably (Tg-10 ° C.) to (Tg + 40 ° C.), and (Tg ° C.) to (Tg + 30 ° C.). ℃) is particularly preferable. Specifically, the heating temperature in the longitudinal stretching step is preferably 70 ° C. to 120 ° C., more preferably 80 ° C. to 110 ° C., and particularly preferably 85 ° C. to 100 ° C.

Examples of the method of heating the unstretched polyester film include a method of heating a roll such as a nip roll that comes into contact with the unstretched polyester film. Examples of the method of heating the roll include a method of providing a heater or a pipe through which a hot solvent can flow inside the roll. In addition to the above, for example, a method of blowing warm air on the unstretched polyester film, a method of contacting the unstretched polyester film with a heat source such as a heater, and a method of heating the unstretched polyester film by passing it in the vicinity of the heat source can be mentioned.

The stretching speed in the longitudinal stretching step is preferably 800% / sec to 1500% / sec, more preferably 1000% / sec to 1400% / sec, and 1200% / sec to 1400% / sec. Is particularly preferred. Here, the "stretching speed" is a value expressed as a percentage by dividing the length Δd stretched for 1 second from the length d0 before stretching by the length d0 before stretching.

-Transverse stretching process-
In the transverse stretching step, the polyester film stretched in the longitudinal direction is stretched in the width direction (hereinafter, also referred to as "transverse stretching").

In the transverse stretching step, it is preferable to preheat the polyester film stretched in the longitudinal direction before the transverse stretching. By preheating the polyester film, the polyester film can be easily stretched laterally.

The preheating temperature is preferably (Tg-10 ° C.) to (Tg + 60 ° C.), more preferably (Tg ° C.) to (Tg + 50 ° C.). Specifically, the preheating temperature is preferably 80 ° C. to 120 ° C., more preferably 90 ° C. to 110 ° C.

The stretching ratio in the transverse stretching step is preferably larger than the stretching ratio in the longitudinal stretching step. The stretching ratio in the transverse stretching step is preferably 3.0 to 6.0 times, more preferably 3.5 to 5.0 times, and 3.5 to 4.5 times. Is particularly preferred.

The area magnification represented by the product of the stretching ratio in the longitudinal stretching step and the stretching ratio in the transverse stretching step is preferably 12.8 times to 15.5 times, preferably 13.5 times to 15.2 times. It is more preferable that there is, and it is particularly preferable that it is 14.0 times to 15.0 times. When the area magnification is 12.8 times or more, the molecular orientation in the film width direction becomes good. Further, when the area magnification is 15.5 times or less, it is easy to maintain a state in which the molecular orientation is difficult to be relaxed when subjected to the heat treatment.

The heating temperature in the transverse stretching step is preferably (Tg-10 ° C.) to (Tg + 80 ° C.), more preferably (Tg ° C.) to (Tg + 70 ° C.), and (Tg ° C.) to (Tg + 60 ° C.). Is particularly preferable. Specifically, the heating temperature in the transverse stretching step is preferably 100 ° C. to 140 ° C., more preferably 110 ° C. to 135 ° C., and particularly preferably 115 ° C. to 130 ° C.

The stretching speed in the transverse stretching step is preferably 8% / sec to 45% / sec, more preferably 10% / sec to 30% / sec, and 15% / sec to 20% / sec. Is particularly preferred.

When producing a biaxially oriented polyester film having a particle-containing layer, it is preferable to apply a coating liquid for forming a particle-containing layer on the polyester film stretched in the longitudinal direction, and then laterally stretch the film. By the above method, the adhesion of the particle-containing layer can be improved.

(Heat treatment process)
The method for producing a biaxially oriented polyester film according to the present disclosure preferably includes a step of heat-treating the polyester film stretched in the width direction (hereinafter, also referred to as a "heat treatment step"). Examples of the heat treatment step include a heat fixing step and a heat relaxation step. The heat treatment step preferably has at least one of a heat fixing step and a heat relaxation step, and more preferably has a heat fixing step and a heat relaxation step.

-Heat fixing process-
In the heat fixing step, the polyester film stretched in the width direction is heat-fixed by heating. Since the polyester can be crystallized by heat fixing, shrinkage of the polyester film can be suppressed.

The heating temperature in the heat fixing step is preferably 190 ° C. to 240 ° C., more preferably 200 ° C. to 240 ° C., and particularly preferably 210 ° C. to 230 ° C.

In the heat fixing step, the variation in the maximum film surface temperature in the film width direction is preferably 0.5 ° C. to 10.0 ° C., more preferably 0.5 ° C. to 7.0 ° C.
It is more preferably 0.5 ° C to 5.0 ° C, and particularly preferably 0.5 ° C to 4.0 ° C. By adjusting the variation in the maximum film surface temperature in the film width direction within the above range, the variation in the crystallinity in the width direction can be suppressed.

Examples of the heating method include a method of applying hot air to the film and a method of radiant heating of the film. Examples of the device used in the method of radiant heating include an infrared heater.

The heating time in the heat fixing step is preferably 5 seconds to 50 seconds, more preferably 5 seconds to 30 seconds, and particularly preferably 5 seconds to 10 seconds.

-Heat relaxation process-
In the heat relaxation step, heat is relaxed by heating the polyester film stretched in the width direction. Residual strain of the polyester film can be alleviated by heat relaxation.

The heating temperature in the heat relaxation step is preferably 5 ° C. or higher lower than the heating temperature in the heat fixing step, more preferably 15 ° C. or higher, and even more preferably 25 ° C. or higher. , 30 ° C. or higher is particularly preferable.

The lower limit of the heating temperature in the heat relaxation step is preferably 100 ° C. or higher, more preferably 110 ° C. or higher, and particularly preferably 120 ° C. or higher.

Examples of the heating method include a method of applying hot air to the film and a method of radiant heating of the film. Examples of the device used in the method of radiant heating include an infrared heater.

(Cooling process)
The method for producing a biaxially oriented polyester film according to the present disclosure preferably includes a step of cooling the heat-treated polyester film (hereinafter, also referred to as a "cooling step").

Examples of the cooling method include a method of blowing air (preferably cold air) on the film and a method of bringing the film into contact with a temperature-adjustable member (for example, a temperature control roll).

The average cooling rate in the cooling step is preferably 500 ° C./min to 4000 ° C./min, more preferably 1000 ° C./min to 3500 ° C./min, and 1500 ° C./min to 3000 ° C./min. Is particularly preferred. By adjusting the average cooling rate within the above range, the film surface temperature in the cooling step can be made uniform, so that the uneven expansion rate in the width direction can be reduced. The average cooling rate is determined using a non-contact thermometer (for example, a radiation thermometer). For example, the cooling time (Z / S) from 150 ° C. to 70 ° C. is determined from the distance Z between the point where the film surface temperature reaches 150 ° C. and the point where the film surface temperature reaches 70 ° C. and the film transport speed S. Ask. Next, the average cooling rate is obtained by calculating (150-70) / (Z / S).

<< Photosensitive resin layer >>
The photosensitive resin layer contained in the photosensitive transfer material of the present disclosure is preferably a negative photosensitive resin layer in which the solubility of the exposed portion in the developing solution is reduced by exposure and the non-exposed portion is removed by development. However, the photosensitive resin layer is not limited to the negative photosensitive resin layer, and even if the photosensitive resin layer is a positive photosensitive resin layer in which the solubility of the exposed portion in the developing solution is improved by exposure and the exposed portion is removed by development. good.

In certain embodiments, the photosensitive resin layer preferably contains a polymer A, a polymerizable compound B, and a photopolymerization initiator. In certain embodiments, the photosensitive resin layer comprises 10% by mass to 90% by mass of the polymer A, 5% by mass to 70% by mass of the polymerizable compound B, and 0, based on the total mass of the photosensitive resin layer. It is preferable to contain 0.01% by mass to 20% by mass of a photopolymerization initiator. The polymer A, the polymerizable compound B, and the photopolymerization initiator will be described later.

(Polymer A)
The photosensitive resin layer preferably contains the polymer A. The polymer A is preferably an alkali-soluble polymer. Alkali-soluble polymers include polymers that are easily soluble in alkaline substances.

The acid value of the polymer A is preferably 220 mgKOH / g or less, and more preferably less than 200 mgKOH / g, from the viewpoint of improving the resolution by suppressing the swelling of the photosensitive resin layer due to the developing solution. It is preferably less than 190 mgKOH / g, especially preferably less than 190 mgKOH / g. The lower limit of acid value is not limited. The acid value of the polymer A is preferably 60 mgKOH / g or more, more preferably 120 mgKOH / g or more, further preferably 150 mgKOH / g or more, and 170 mgKOH / g or more, from the viewpoint of more excellent developability. It is particularly preferable that it is g or more. The acid value of the polymer A can be adjusted, for example, by the type of the structural unit constituting the polymer A and the content of the structural unit containing an acid group.

In the present disclosure, the acid value is the mass (mg) of potassium hydroxide required to neutralize 1 g of the sample. In the present disclosure, the unit of acid value is described as mgKOH / g. The acid value can be calculated, for example, from the average content of acid groups in the compound.

The weight average molecular weight (Mw) of the polymer A is preferably 5,000 to 500,000. It is preferable that the weight average molecular weight is 500,000 or less from the viewpoint of improving the resolvability and the developability. The weight average molecular weight of the polymer A is more preferably 100,000 or less, further preferably 60,000 or less, and particularly preferably 50,000 or less. On the other hand, it is preferable to set the weight average molecular weight to 5,000 or more from the viewpoint of controlling the properties of the developed aggregate, the edge fuse property, and the cut chip property. The weight average molecular weight of the polymer A is more preferably 10,000 or more, further preferably 20,000 or more, and particularly preferably 30,000 or more. The edge fuse property refers to the degree to which the photosensitive resin layer easily protrudes from the end face of the roll when the photosensitive film is wound into a roll. The cut chip property refers to the degree of ease with which the chip flies when the unexposed film is cut with a cutter. For example, when the chip adheres to the surface of the photosensitive film, the chip is transferred to the mask in the exposure process, which causes a defective product.

The dispersity of the polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, and even more preferably 1.0 to 4.0. It is particularly preferably 0 to 3.0. In the present disclosure, the degree of dispersion is the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight).

The polymer A preferably has a structural unit derived from a monomer having an aromatic hydrocarbon group, from the viewpoint of suppressing the line width thickening when the focal position is deviated during exposure and the deterioration of resolution.

Examples of the aromatic hydrocarbon group include a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group.

The content ratio of the structural unit derived from the monomer having an aromatic hydrocarbon group in the polymer A is preferably 20% by mass or more, preferably 30% by mass or more, based on the total mass of the polymer A. More preferably, it is more preferably 40% by mass or more, particularly preferably 45% by mass or more, and most preferably 50% by mass or more. The upper limit of the content ratio of the structural unit derived from the monomer having an aromatic hydrocarbon group is not limited. The content ratio of the structural unit derived from the monomer having an aromatic hydrocarbon group in the polymer A is preferably 95% by mass or less, preferably 85% by mass or less, based on the total mass of the polymer A. Is more preferable. When the photosensitive resin layer contains a plurality of types of polymers A, the content ratio of the structural unit derived from the monomer having an aromatic hydrocarbon group is determined as a weight average value.

Examples of the monomer having an aromatic hydrocarbon group include a monomer having an aralkyl group, styrene, and a polymerizable styrene derivative (for example, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-). Vinyl benzoic acid, styrene dimer, and styrene trimmer). The monomer having an aromatic hydrocarbon group is preferably a monomer having an aralkyl group or styrene.

Examples of the aralkyl group include a substituted or unsubstituted phenylalkyl group (excluding a benzyl group) and a substituted or unsubstituted benzyl group, and a substituted or unsubstituted benzyl group is preferable.

Examples of the monomer having a phenylalkyl group include phenylethyl (meth) acrylate.

Examples of the monomer having a benzyl group include a (meth) acrylate having a benzyl group (for example, benzyl (meth) acrylate and a chlorobenzyl (meth) acrylate), a vinyl monomer having a benzyl group (for example, vinylbenzyl chloride, and the like). Vinyl benzyl alcohol). The monomer having a benzyl group is preferably a benzyl (meth) acrylate.

In certain embodiments, when the structural unit derived from the monomer having an aromatic hydrocarbon group in the polymer A is the structural unit derived from the benzyl (meth) acrylate, the benzyl (meth) acrylate single amount in the polymer A is used. The content ratio of the structural unit derived from the body is preferably 50% by mass to 95% by mass, more preferably 60% by mass to 90% by mass, and 70% by mass, based on the total mass of the polymer A. It is more preferably% to 90% by mass, and particularly preferably 75% by mass to 90% by mass.

In a certain embodiment, when the structural unit derived from the monomer having an aromatic hydrocarbon group in the polymer A is the structural unit derived from styrene, the content ratio of the structural unit derived from styrene in the polymer A is determined. It is preferably 20% by mass to 50% by mass, more preferably 25 to 45% by mass, still more preferably 30% by mass to 40% by mass, and 30% by mass, based on the total mass of the polymer A. It is particularly preferably from mass% to 35% by mass.

The polymer A having a structural unit derived from a monomer having an aromatic hydrocarbon group includes a monomer having an aromatic hydrocarbon group, a first monomer described later, and a second simpler described later. It is preferably a copolymer obtained by polymerizing at least one selected from the group consisting of monomers.

The polymer A may be a polymer having no structural unit derived from a monomer having an aromatic hydrocarbon group. The polymer A containing no structural unit derived from a monomer having an aromatic hydrocarbon group is at least one kind of the first monomer (excluding the monomer having an aromatic hydrocarbon group) described later. It is preferable that the polymer is obtained by polymerizing the above, and at least one of the first monomer (excluding the monomer having an aromatic hydrocarbon group) described later and the second simpler described later. It is more preferable that it is a copolymer obtained by polymerizing at least one of a dimer (excluding a monomer having an aromatic hydrocarbon group).

In a certain embodiment, the polymer A is preferably a polymer obtained by polymerizing at least one of the first monomers described later, and is preferably the same as at least one of the first monomers described below. It is more preferable that the copolymer is obtained by polymerizing with at least one of the second monomers described later.

The first monomer is a monomer having a carboxy group and at least one polymerizable unsaturated group in the molecule. Examples of the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid semiester. The first monomer is preferably (meth) acrylic acid.

The content ratio of the structural unit derived from the first monomer in the polymer A is preferably 5% by mass to 50% by mass, and 10% by mass to 40% by mass, based on the total mass of the polymer A. Is more preferable, and 15% by mass to 30% by mass is particularly preferable.

The second monomer is a monomer having no acidic group, having an ester group, and having at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include a (meth) acrylate compound, an ester compound of vinyl alcohol, and (meth) acrylonitrile. In the present disclosure, "(meth) acrylonitrile" includes both acrylonitrile, methacrylonitrile, or acrylonitrile, and methacrylonitrile.

Examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. (Meta) acrylic acid alkyl esters such as tert-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate Can be mentioned.

Examples of the ester compound of vinyl alcohol include vinyl acetate.

The second monomer is preferably at least one selected from the group consisting of methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and n-butyl (meth) acrylate, and is preferably methyl (meth). More preferably, it is an acrylate.

The content ratio of the structural unit derived from the second monomer in the polymer A is preferably 5% by mass to 60% by mass, and 15% by mass to 50% by mass, based on the total mass of the polymer A. Is more preferable, and 20% by mass to 45% by mass is particularly preferable.

The polymer A is composed of a structural unit derived from a monomer having an aralkyl group and a structural unit derived from styrene from the viewpoint of suppressing the line width thickening when the focal position is deviated during exposure and the deterioration of resolution. It is preferable to include at least one selected from the group. For example, the polymer A is a copolymer containing a structural unit derived from methacrylic acid, a structural unit derived from benzyl methacrylate, a structural unit derived from styrene, a structural unit derived from methacrylic acid, and methyl. It is preferably at least one selected from the group consisting of copolymers containing a structural unit derived from methacrylate, a structural unit derived from benzyl methacrylate, and a structural unit derived from styrene.

In certain embodiments, the polymer A has 25% by mass to 40% by mass of structural units derived from a monomer having an aromatic hydrocarbon group and 20% by mass to 20% by mass of structural units derived from the first monomer. A polymer containing 35% by mass and 30% by mass to 45% by mass of a structural unit derived from the second monomer is preferable.

In certain embodiments, the polymer A contains 70% by mass to 90% by mass of structural units derived from a monomer having an aromatic hydrocarbon group, and 10% by mass of a structural unit derived from a first monomer. It is preferably a polymer containing ~ 25% by mass.

The glass transition temperature (Tg) of the polymer A is preferably 30 ° C. to 135 ° C. When the Tg of the polymer A is 135 ° C. or lower in the photosensitive resin layer, it is possible to suppress the line width thickening and the deterioration of the resolution when the focal position at the time of exposure is deviated. From the above viewpoint, the Tg of the polymer A is more preferably 130 ° C. or lower, further preferably 120 ° C. or lower, and particularly preferably 110 ° C. or lower. Further, it is preferable that the Tg of the polymer A is 30 ° C. or higher from the viewpoint of improving the edge fuse resistance. From the above viewpoint, the Tg of the polymer A is more preferably 40 ° C. or higher, further preferably 50 ° C. or higher, particularly preferably 60 ° C. or higher, and most preferably 70 ° C. or higher. preferable.

The polymer A may be a commercially available product or a synthetic product. Polymer A is synthesized, for example, by diluting at least one of the above-mentioned monomers with a solvent (for example, acetone, methyl ethyl ketone, or isopropanol) and a radical polymerization initiator (for example, benzoyl peroxide or azoisobuty) in a solution. Butyronitrile) is preferably added in an appropriate amount, and then heated and stirred. In some cases, the synthesis is carried out while dropping a part of the mixture into the reaction solution. After completion of the reaction, a solvent may be further added to adjust the concentration to a desired level. As the synthesis means, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.

The photosensitive resin layer may contain one kind alone or two or more kinds of polymers A. When the photosensitive resin layer contains two or more kinds of polymers A, the photosensitive resin layer contains two or more kinds of polymers A having a structural unit derived from a monomer having an aromatic hydrocarbon group. Alternatively, the polymer A having a structural unit derived from a monomer having an aromatic hydrocarbon group and the polymer A not containing a structural unit derived from a monomer having an aromatic hydrocarbon group may be contained. preferable. In the latter case, the content ratio of the polymer A having a structural unit derived from the monomer having an aromatic hydrocarbon group is preferably 50% by mass or more, preferably 70% by mass or more, based on the total mass of the polymer A. It is more preferably mass% or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more.

The content ratio of the polymer A is preferably 10% by mass to 90% by mass, more preferably 30% by mass to 70% by mass, and 40% by mass to the total mass of the photosensitive resin layer. It is particularly preferably 60% by mass. It is preferable that the content ratio of the polymer A to the photosensitive resin layer is 90% by mass or less from the viewpoint of controlling the developing time. On the other hand, it is preferable that the content ratio of the polymer A to the photosensitive resin layer is 10% by mass or more from the viewpoint of improving the edge fuse resistance.

(Polymerizable compound B)
The photosensitive resin layer preferably contains a polymerizable compound B having a polymerizable group. In the present disclosure, the "polymerizable compound" means a compound that polymerizes under the action of a polymerization initiator described later. The polymerizable compound B is a compound different from the polymer A.

The polymerizable group in the polymerizable compound B is not limited as long as it is a group involved in the polymerization reaction. Examples of the polymerizable group in the polymerizable compound B include a group having an ethylenically unsaturated group (for example, a vinyl group, an acryloyl group, a methacryloyl group, a styryl group, and a maleimide group), and a group having a cationically polymerizable group. (For example, an epoxy group and an oxetane group) can be mentioned. The polymerizable group is preferably a group having an ethylenically unsaturated group, and more preferably an acryloyl group or a metaacryloyl group.

The polymerizable compound B is preferably a compound having one or more ethylenically unsaturated groups in one molecule (that is, an ethylenically unsaturated compound) in that the photosensitive resin layer is more photosensitive. More preferably, it is a compound having two or more ethylenically unsaturated groups in one molecule (ie, a polyfunctional ethylenically unsaturated compound). In addition, the number of ethylenically unsaturated groups contained in one molecule of the ethylenically unsaturated compound is preferably 6 or less, and preferably 3 or less, in terms of being excellent in resolution and peelability. It is more preferable, and it is particularly preferable that the number is two or less.

The ethylenically unsaturated compound is preferably a (meth) acrylate compound having one or more (meth) acryloyl groups in one molecule.

The polymerizable compound B is a compound having two ethylenically unsaturated groups in one molecule (that is, bifunctional ethylenically) from the viewpoint of having a better balance of photosensitivity, resolution, and peelability in the photosensitive resin layer. It is preferably at least one selected from the group consisting of (unsaturated compounds) and compounds having three ethylenically unsaturated groups in one molecule (that is, trifunctional ethylenically unsaturated compounds), preferably in one molecule. It is more preferable that the compound has two ethylenically unsaturated groups.

In the photosensitive resin layer, the ratio of the content of the bifunctional ethylenically unsaturated compound to the content of the polymerizable compound B is preferably 60% by mass or more from the viewpoint of excellent peelability of the photosensitive resin layer. It is more preferably more than 70% by mass, and particularly preferably 90% by mass or more. The upper limit of the content ratio of the bifunctional ethylenically unsaturated compound to the content of the polymerizable compound B is not limited and may be 100% by mass. That is, all the polymerizable compounds B contained in the photosensitive resin layer may be bifunctional ethylenically unsaturated compounds.

-Polymerizable compound B1-
The photosensitive resin layer according to the present invention preferably contains a polymerizable compound B1 having one or more aromatic rings and two ethylenically unsaturated groups in one molecule. The polymerizable compound B1 is a bifunctional ethylenically unsaturated compound having one or more aromatic rings in one molecule among the above-mentioned polymerizable compounds B.

In the photosensitive resin layer, the ratio of the content of the polymerizable compound B1 to the content of the polymerizable compound B is preferably 40% by mass or more, preferably 50% by mass or more, from the viewpoint of better resolution. More preferably, it is more preferably 55% by mass or more, and particularly preferably 60% by mass or more. The upper limit of the ratio of the content of the polymerizable compound B1 to the content of the polymerizable compound B is not limited. The ratio of the content of the polymerizable compound B1 to the content of the polymerizable compound B is preferably 99% by mass or less, more preferably 95% by mass or less, and 90% by mass or less from the viewpoint of peelability. Is more preferable, and 85% by mass or less is particularly preferable.

Examples of the aromatic ring in the polymerizable compound B1 include an aromatic hydrocarbon ring (for example, a benzene ring, a naphthalene ring, and an anthracene ring) and an aromatic heterocycle (for example, a thiophene ring, a furan ring, a pyrrole ring, and an imidazole ring. Triazole ring and pyridine ring), and fused rings thereof. The aromatic ring is preferably an aromatic hydrocarbon ring, more preferably a benzene ring. The aromatic ring may have a substituent.

The polymerizable compound B1 preferably has a bisphenol structure from the viewpoint of improving the resolution by suppressing the swelling of the photosensitive resin layer due to the developing solution. Examples of the bisphenol structure include a bisphenol A structure derived from bisphenol A (that is, 2,2-bis (4-hydroxyphenyl) propane) and bisphenol F (that is, 2,2-bis (4-hydroxyphenyl) methane). Examples include a bisphenol F structure derived from bisphenol B and a bisphenol B structure derived from bisphenol B (that is, 2,2-bis (4-hydroxyphenyl) butane). The bisphenol structure is preferably a bisphenol A structure.

Examples of the polymerizable compound B1 having a bisphenol structure include a compound having a bisphenol structure and two polymerizable groups (preferably (meth) acryloyl groups) bonded to both ends of the bisphenol structure. Each polymerizable group may be directly attached to the bisphenol structure. Each polymerizable group may be attached to the bisphenol structure via one or more alkyleneoxy groups. The alkyleneoxy group added to both ends of the bisphenol structure is preferably an ethyleneoxy group or a propyleneoxy group, and more preferably an ethyleneoxy group. The number of alkyleneoxy groups added to the bisphenol structure is not limited, but is preferably 4 to 16 per molecule, and more preferably 6 to 14.

Regarding the polymerizable compound B1 having a bisphenol structure, Japanese Patent Application Laid-Open No. 2016-22416
It is described in paragraphs 0072 to 0080 of the second publication. The contents of the above publication are incorporated herein by reference.

The polymerizable compound B1 is preferably a bifunctional ethylenically unsaturated compound having a bisphenol A structure, and more preferably 2,2-bis (4-((meth) acryloxypolyalkoxy) phenyl) propane. ..

Examples of 2,2-bis (4-((meth) acryloxipolyalkoxy) phenyl) propane include 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane (FA-324M, Hitachi Chemical Co., Ltd.). Company), 2,2-bis (4- (methacryloxyethoxypropoxy) phenyl) propane, 2,2-bis (4- (methacryloxypentethoxy) phenyl) propane (BPE-500, Shin-Nakamura Chemical Industry Co., Ltd.) , 2,2-Bis (4- (methacryloxydodecaethoxytetrapropoxy) phenyl) propane (FA-3200MY, Hitachi Chemical Co., Ltd.), 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane ( BPE-1300, Shin-Nakamura Chemical Industry Co., Ltd.), 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane (BPE-200, Shin-Nakamura Chemical Industry Co., Ltd.), and ethoxylated (10) bisphenol A Diacrylate (NK ester A-BPE-10, Shin-Nakamura Chemical Industry Co., Ltd.) can be mentioned.

Examples of the polymerizable compound B1 include a compound represented by the following general formula (I).

In the general formula (I), R ₁ and R ₂ independently represent a hydrogen atom or a methyl group, A represents C ₂ H ₄ , B represents C ₃ H ₆ , and n. ₁ and n ₃ are independently integers from _{1 to} 39, n 1 + n ₃ are integers from 2 to 40, and n _{2 and n 4} are independently from 0 to 29, respectively. N ₂ + n ₄ is an integer from 0 to 30, and the sequence of repeating units of-(A-O)-and-(BO)-is random or block. good. In the case of a block, either − (A—O) − or − (BO) − may be on the bisphenyl group side. n ₂ + n ₄ is preferably an integer of 0 to 10, more preferably an integer of 0 to 4, further preferably an integer of 0 to 2, and particularly preferably 0. In certain embodiments, n ₁ + n ₂ + n ₃ + n ₄ is preferably an integer of 2 to 20, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 12.

The photosensitive resin layer may contain one kind alone or two or more kinds of polymerizable compounds B1.

The content ratio of the polymerizable compound B1 in the photosensitive resin layer is preferably 10% by mass or more, preferably 20% by mass or more, based on the total mass of the photosensitive resin layer from the viewpoint of better resolution. Is more preferable. The upper limit of the content ratio of the polymerizable compound B1 is not limited. The content ratio of the polymerizable compound B1 in the photosensitive resin layer is preferably 70% by mass or less, preferably 60% by mass or less, based on the total mass of the photosensitive resin layer from the viewpoint of transferability and edge fuse resistance. Is more preferable.

The photosensitive resin layer may contain a polymerizable compound B other than the polymerizable compound B1. Examples of the polymerizable compound B other than the polymerizable compound B1 include a monofunctional ethylenically unsaturated compound (that is, a compound having one ethylenically unsaturated group in one molecule) and a bifunctional ethylenically having no aromatic ring. Unsaturated compounds (ie, compounds that do not have an aromatic ring in one molecule and have two ethylenically unsaturated groups), and trifunctional or higher functional ethylenically unsaturated compounds (ie, in one molecule). Compounds having 3 or more ethylenically unsaturated groups).

Examples of the monofunctional ethylenically unsaturated compound include ethyl (meth) acrylate, ethylhexyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinate, polyethylene glycol mono (meth) acrylate, and polypropylene glycol mono (meth) acrylate. , And phenoxyethyl (meth) acrylate.

Examples of the bifunctional ethylenically unsaturated compound having no aromatic ring include alkylene glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylate, urethane di (meth) acrylate, and trimethylolpropane diacrylate.

Examples of the alkylene glycol di (meth) acrylate include tricyclodecanedimethanol diacrylate (A-DCP, Shin-Nakamura Chemical Industry Co., Ltd.), tricyclodecanedimethanol dimethacrylate (DCP, Shin-Nakamura Chemical Industry Co., Ltd.), and the like. 1,9-Nonandiol diacrylate (A-NOD-N, Shin-Nakamura Chemical Industry Co., Ltd.), 1,6-Hexanediol diacrylate (A-HD-N, Shin-Nakamura Chemical Industry Co., Ltd.), Ethylene glycol dimethacrylate , 1,10-decanediol diacrylate, and neopentyl glycol di (meth) acrylate.

Examples of the polyalkylene glycol di (meth) acrylate include polyethylene glycol di (meth) acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di (meth) acrylate.

Examples of the urethane di (meth) acrylate include propylene oxide-modified urethane di (meth) acrylate, and ethylene oxide and propylene oxide-modified urethane di (meth) acrylate. Examples of commercially available products include 8UX-015A (Taisei Fine Chemical Co., Ltd.), UA-32P (Shin Nakamura Chemical Industry Co., Ltd.), and UA-1100H (Shin Nakamura Chemical Industry Co., Ltd.).

Examples of the trifunctional or higher functional ethylenically unsaturated compound include dipentaerythritol (tri / tetra / penta / hexa) (meth) acrylate, pentaerythritol (tri / tetra) (meth) acrylate, and trimethylolpropane tri (meth). Examples thereof include acrylates, trimethylolpropane tetra (meth) acrylates, trimethylolethanetri (meth) acrylates, tri (meth) acrylates of isocyanurates, glycerintri (meth) acrylates, and alkylene oxide modified products thereof. In the present disclosure, "(tri / tetra / penta / hexa) (meth) acrylate" is a concept that includes tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (meth) acrylate. be. In the present disclosure, "(tri / tetra) (meth) acrylate" is a concept including tri (meth) acrylate and tetra (meth) acrylate.

Examples of the alkylene oxide-modified product of the trifunctional or higher functional ethylenically unsaturated compound include caprolactone-modified (meth) acrylate compound (for example, KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd.) and Shin-Nakamura Chemical Industry Co., Ltd. A-9300-1CL), alkylene oxide-modified (meth) acrylate compound (for example, KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E manufactured by Shin-Nakamura Chemical Industry Co., Ltd., Shin-Nakamura Chemical Industry Co., Ltd. A-9300, EBECRYL (registered trademark) 135), ethoxylated glycerin triacrylate (for example, A-GLY-9E, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), Aronix (registered trademark) TO Examples thereof include -2349 (Toa Synthetic Co., Ltd.), Aronix M-520 (Toa Synthetic Co., Ltd.), and Aronix M-510 (Toa Synthetic Co., Ltd.).

Examples of the polymerizable compound B other than the polymerizable compound B1 include the polymerizable compounds having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942.

In certain embodiments, the photosensitive resin layer preferably contains a polymerizable compound B1 and a trifunctional or higher functional ethylenically unsaturated compound, with the polymerizable compound B1 and two or more trifunctional or higher ethylenically unsaturated compounds. More preferably, it contains a compound. In the above embodiment, the mass ratio of the polymerizable compound B1 to the trifunctional or higher ethylenically unsaturated compound ([total mass of the polymerizable compound B1]: [total mass of the trifunctional or higher ethylenically unsaturated compound] is It is preferably 1: 1 to 5: 1, more preferably 1.2: 1 to 4: 1, and particularly preferably 1.5: 1-3: 1.

The weight average molecular weight (Mw) of the polymerizable compound B is preferably 200 to 3,000, more preferably 280 to 2,200, and particularly preferably 300 to 2,200.

The photosensitive resin layer may contain one kind alone or two or more kinds of polymerizable compounds B.

The content ratio of the polymerizable compound B in the photosensitive resin layer is preferably 10% by mass to 70% by mass, more preferably 20% by mass to 60% by mass, based on the total mass of the photosensitive resin layer. It is preferably 20% by mass to 50% by mass, and particularly preferably 20% by mass.

(Arbitrary ingredient)
The photosensitive resin layer may contain components other than the above-mentioned components (hereinafter, may be referred to as “arbitrary components”). Optional components include photopolymerization initiators, dyes, surfactants, and additives other than the above components.

-Photopolymerization initiator-
The photosensitive resin layer preferably contains a photopolymerization initiator. The photopolymerization initiator is a compound that receives active light (for example, ultraviolet rays, visible light, and X-rays) to initiate polymerization of a polymerizable compound (for example, polymerizable compound B).

The photopolymerization initiator is not limited, and a known photopolymerization initiator can be used. Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator, and a photoradical polymerization initiator is preferable.

Examples of the photoradical polymerization initiator include a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an α-aminoalkylphenone structure, a photopolymerization initiator having an α-hydroxyalkylphenone structure, and an acylphosphine oxide. Examples thereof include a photopolymerization initiator having a structure and a photopolymerization initiator having an N-phenylglycine structure.

The photosensitive resin layer is a dimer of 2,4,5-triarylimidazole as a photoradical polymerization initiator from the viewpoints of photosensitivity, visibility of exposed parts, visibility of unexposed parts, and resolution. And at least one selected from the group consisting of derivatives of 2,4,5-triarylimidazole dimer. The two 2,4,5-triarylimidazole dimers and their derivatives may have the same or different structures.

Derivatives of the 2,4,5-triarylimidazole dimer include, for example, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) 4,5-di. (Methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, and 2- (P-Methenylphenyl) -4,5-diphenylimidazole dimer.

Examples of the photoradical polymerization initiator include the polymerization initiators described in paragraphs 0031 to 0042 of JP2011-95716A and paragraphs 0064 to 0081 of JP2015-14783A.

Examples of the photoradical polymerization initiator include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p, p'-dimethoxybenzyl), and benzophenone.

Commercially available photoradical polymerization initiators include, for example, TAZ-110 (Midori Chemical Co., Ltd.), TAZ-111 (Midori Chemical Co., Ltd.), 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-Tetraphenyl-1,2'-biimidazole (Tokyo Kasei Kogyo Co., Ltd.), 1- [4- (Phenylthio)] phenyl-1,2-octanedione-2- (O-benzoyloxime) ( Product name: IRGACURE (registered trademark) OXE-01, BASF), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] etanone-1- (O-acetyloxime) (Product name: IRGACURE OXE-02, BASF), IRGACURE OXE-03 (BASF), IRGACURE OXE-04 (BASF), 2- (dimethylamino) -2-[(4-methylphenyl) methyl]- 1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name: Omnirad 379EG, IGM Resins VV), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane -1-one (trade name: Omnirad 907, IGM Resins VV), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methyl Propane-1-one (trade name: Omnirad 127, IGM Resins VV), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 (trade name: Omnirad 369, IGM) Resins VV), 2-Hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Omnirad 1173, IGM Resins VV), 1-hydroxycyclohexylphenylketone (trade name:) Omnirad 184, IGM Resins B.V.), 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name: Omnirad 651, IGM Resins B.V.), 2,4,6- Methylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H, IGM Resins VV), bis (2,4,6-trimethylbenzoyl) phenylphosphinoxide (trade name: Om) nirad 819, IGM Resins B.I. V. , Oxym ester-based photopolymerization initiator (trade name: Lunar 6, DKSH Japan Co., Ltd.), 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenylbisimidazole (2- (2-Chlorophenyl) -4,5-diphenylimidazole dimer) (trade name: B-CIM, Hampton), and 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer (2). Product name: BCTB, Tokyo Kasei Kogyo Co., Ltd.).

A photocationic polymerization initiator (ie, a photoacid generator) is a compound that receives active light to generate an acid. As the photocationic polymerization initiator, a compound that is sensitive to active light having a wavelength of 300 nm or more, preferably a wavelength of 300 to 450 nm and generates an acid is preferable. However, the chemical structure of the photocationic polymerization initiator is not limited. In addition, a photocationic polymerization initiator that is not directly sensitive to active light with a wavelength of 300 nm or more is also a sensitizer if it is a compound that is sensitive to active light with a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. Can be preferably used in combination with.

The photocationic polymerization initiator is preferably a photocationic polymerization initiator that generates an acid having a pKa of 4 or less, and more preferably a photocationic polymerization initiator that generates an acid having a pKa of 3 or less. A photocationic polymerization initiator that generates 2 or less acids is particularly preferable. The lower limit of pKa is not limited. The pKa of the acid generated from the photocationic polymerization initiator is preferably -10.0 or more, for example.

Examples of the photocationic polymerization initiator include an ionic photocationic polymerization initiator and a nonionic photocationic polymerization initiator.

Examples of the ionic photocationic polymerization initiator include onium salt compounds (for example, diaryliodonium salt compounds and triarylsulfonium salt compounds), and quaternary ammonium salt compounds.

Examples of the ionic photocationic polymerization initiator include the ionic photocationic polymerization initiator described in paragraphs 0114 to 0133 of JP-A-2014-85643.

Examples of the nonionic photocationic polymerization initiator include trichloromethyl-s-triazine compounds, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Examples of the trichloromethyl-s-triazine compound, the diazomethane compound, and the imide sulfonate compound include the compounds described in paragraphs 0083 to 0088 of JP2011-221494A. Examples of the oxime sulfonate compound include the compounds described in paragraphs 0084 to 0088 of International Publication No. 2018/179640.

The photosensitive resin layer preferably contains a photoradical polymerization initiator, and is selected from the group consisting of 2,4,5-triarylimidazole dimers and derivatives of 2,4,5-triarylimidazole dimers. It is more preferable to contain at least one of the above-mentioned substances.

The photosensitive resin layer may contain one kind alone or two or more kinds of photopolymerization initiators.

The content ratio of the photopolymerization initiator in the photosensitive resin layer is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on the total mass of the photosensitive resin layer. It is particularly preferably 1.0% by mass or more. The upper limit of the content ratio of the photopolymerization initiator is not limited. The content ratio of the photopolymerization initiator is preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total mass of the photosensitive resin layer.

-Dye-
The photosensitive resin layer has a maximum absorption wavelength of 450 nm in the wavelength range of 400 nm to 780 nm at the time of color development from the viewpoints of visibility of the exposed portion, visibility of the non-exposed portion, pattern visibility after development, and resolution. It is preferable to include a dye (hereinafter, may be referred to as "dye N") whose maximum absorption wavelength is changed by an acid, a base, or a radical. Although the detailed mechanism is unknown, the inclusion of the dye N in the photosensitive resin layer improves the adhesion to the layers adjacent to the photosensitive resin layer (for example, the temporary support and the intermediate layer), and the resolution is improved. Better in sex.

In the present disclosure, the term "maximum absorption wavelength changes by acid, base, or radical" used with respect to a dye is a mode in which a dye in a color-developing state is decolorized by an acid, base, or radical. It may mean any aspect of a mode in which the dye in the above color is developed by an acid, a base or a radical, and a mode in which the dye in a color-developing state changes to a color-developing state of another hue.

Specifically, the dye N may be a compound that changes from the decolorized state by exposure to develop a color, or may be a compound that changes from the decolorized state by exposure to decolorize. In the above aspect, the dye N may be a dye whose color development or decolorization state is changed by the action of an acid, a base, or a radical generated by exposure. Further, the dye N may be a dye whose color development or decolorization state changes due to a change in the state (for example, pH) in the photosensitive resin layer due to an acid, a base, or a radical generated by exposure. good. On the other hand, the dye N may be a dye whose color development or decolorization state changes by directly receiving an acid, a base, or a radical as a stimulus without exposure.

The dye N is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical from the viewpoint of visibility of an exposed portion, visibility of a non-exposed portion, and resolution, and the maximum absorption wavelength is changed by a radical. It is more preferable that the dye is a radical.

The photosensitive resin layer contains both a dye whose maximum absorption wavelength is changed by radicals and a photoradical polymerization initiator as the dye N from the viewpoints of visibility of the exposed part, visibility of the non-exposed part, and resolution. It is preferable to include it.

The dye N is preferably a dye that develops color with an acid, a base, or a radical from the viewpoint of visibility of the exposed portion and visibility of the non-exposed portion.

As an example of the color development mechanism of dye N, photoradical polymerization is carried out by exposing a photosensitive resin layer containing a photoradical polymerization initiator, a photocationic polymerization initiator (that is, a photoacid generator), or a photobase generator. A mode in which a radical-reactive dye, an acid-reactive dye, or a base-reactive dye (for example, a leuco dye) is colored by a radical, an acid, or a base generated from an initiator, a photocationic polymerization initiator, or a photobase generator. Can be mentioned.

In the dye N, the maximum absorption wavelength in the wavelength range of 400 nm to 780 nm at the time of color development is preferably 550 nm or more, preferably 550 nm to 700 nm, from the viewpoint of the visibility of the exposed portion and the visibility of the non-exposed portion. More preferably, it is particularly preferably 550 to 650 nm.

Further, the dye N may have one or two or more maximum absorption wavelengths in the wavelength range of 400 nm to 780 nm at the time of color development. When the dye N has two or more maximum absorption wavelengths in the wavelength range of 400 nm to 780 nm at the time of color development, the maximum absorption wavelength having the highest absorbance among the two or more maximum absorption wavelengths may be 450 nm or more.

For the maximum absorption wavelength of dye N, the transmission spectrum of a solution containing dye N (liquid temperature 25 ° C.) is measured in the range of 400 nm to 780 nm using a spectrophotometer (UV3100, Shimadzu Corporation) in an atmospheric atmosphere. Then, the measurement is performed by detecting the wavelength at which the light intensity becomes the minimum (maximum absorption wavelength).

Examples of the dye that develops or decolorizes by exposure include leuco compounds. Examples of dyes that are decolorized by exposure include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes. The dye N is preferably a leuco compound from the viewpoint of the visibility of the exposed portion and the visibility of the non-exposed portion.

Examples of the leuco compound include a leuco compound having a triarylmethane skeleton (triarylmethane dye), a leuco compound having a spiropyran skeleton (spiropylan dye), a leuco compound having a fluorane skeleton (fluorane dye), and a diarylmethane skeleton. It has a leuco compound (diarylmethane dye) having a leuco compound (diarylmethane dye), a leuco compound having a rhodamine lactam skeleton (rodamine lactam dye), a leuco compound having an indrill phthalide skeleton (indrill phthalide dye), and a leuco auramine skeleton. Leuco compounds (leuco auramine dyes) can be mentioned. The leuco compound is preferably a triarylmethane dye or a fluorane dye, and more preferably a leuco compound having a triphenylmethane skeleton (triphenylmethane dye) or a fluorane dye.

The leuco compound preferably has a lactone ring, a surujin ring, or a sultone ring from the viewpoint of visibility of the exposed portion and visibility of the non-exposed portion. By reacting the lactone ring, sultin ring, or sulton ring contained in the leuco compound with a radical generated from the photoradical polymerization initiator or an acid generated from the photocationic polymerization initiator, the leuco compound is changed to a closed ring state. The color can be decolorized, or the radical compound can be changed to a ring-opened state to develop a color. The leuco compound is preferably a compound having a lactone ring, a sultone ring, or a sultone ring, and the lactone ring, the sultone ring, or the sultone ring is opened by a radical or an acid to develop a color. It is more preferable that the compound has, and the lactone ring is opened by a radical or an acid to develop a color.

Specific examples of leuco compounds include p, p', p "-hexamethyltriaminotriphenylmethane (leucocrystal violet), Pergascript Blue SRB (Ciba Geigy), crystal violet lactone, malakite green lactone, benzoyl leucomethylene blue, 2 -(N-phenyl-N-methylamino) -6- (N-p-tolyl-N-ethyl) aminofluorane, 2-anilino-3-methyl-6- (N-ethyl-p-toluizino) fluorane, 3,6-dimethoxyfluorane, 3- (N, N-diethylamino) -5-methyl-7- (N, N-dibenzylamino) fluorane, 3- (N-cyclohexyl-N-methylamino) -6- Methyl-7-anilinofluorane, 3- (N, N-diethylamino) -6-methyl-7-anilinofluorane, 3- (N, N-diethylamino) -6-methyl-7-xylidinofluorane , 3- (N, N-diethylamino) -6-methyl-7-chlorofluorine, 3- (N, N-diethylamino) -6-methoxy-7-aminofluorane, 3- (N, N-diethylamino) -7- (4-Chloroanilino) fluorane, 3- (N, N-diethylamino) -7-chlorofluorane, 3- (N, N-diethylamino) -7-benzylaminofluorane, 3- (N, N-) Diethylamino) -7,8-benzofluorolane, 3- (N, N-dibutylamino) -6-methyl-7-anilinofluorane, 3- (N, N-dibutylamino) -6-methyl-7- Xylidinofluorane, 3-piperidino-6-methyl-7-anilinofluoran, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3,3-bis (1-ethyl-2-methylindol-) 3-yl) phthalide, 3,3-bis (1-n-butyl-2-methylindole-3-yl) phthalide, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3 -(4-Diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindole-3-yl) -4-zaphthalide, 3- (4-diethylaminophenyl) -3- (1-ethyl-2) -Methylindole-3-yl) phthalide and 3', 6'-bis (diphenylamino) spiroisobenzofuran-1 (3H), 9'-[9H] xanthen-3-one can be mentioned.

Examples of the dye N include dyes. Specific examples of dyes include Brilliant Green, Ethyl Violet, Methyl Green, Crystal Violet, Basic Fuxin, Methyl Violet 2B, Kinaldine Red, Rose Bengal, Metanyl Yellow, Timor Sulfophthalene, Xylenol Blue, Methyl Orange, Paramethyl. Red, Congofred, Benzopurpurin 4B, α-Naftil Red, Nile Blue 2B, Nile Blue A, Methyl Violet, Malakite Green, Parafuxin, Victoria Pure Blue-Naphthalene Sulfonate, Victoria Pure Blue BOH (Hodoya Chemical Industry Co., Ltd.) Company), Oil Blue # 603 (Orient Chemical Industry Co., Ltd.), Oil Pink # 312 (Orient Chemical Industry Co., Ltd.), Oil Red 5B (Orient Chemical Industry Co., Ltd.), Oil Scarlet # 308 (Orient Chemical Industry Co., Ltd.), Oil Red OG (Orient Chemical Industry Co., Ltd.), Oil Red RR (Orient Chemical Industry Co., Ltd.), Oil Green # 502 (Orient Chemical Industry Co., Ltd.), Spiron Red BEH Special (Hodogaya Chemical Industry Co., Ltd.), m-cresol purple , Cresol Red, Rhodamine B, Rhodamine 6G, Sulfolodamine B, Auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-p- N, N-bis (hydroxyethyl) amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and 1-β-naphthyl-4-p-diethylaminophenylimino- 5-Pyrazolone can be mentioned.

The dye N is preferably a dye whose maximum absorption wavelength is changed by radicals from the viewpoints of visibility of exposed parts, visibility of non-exposed parts, pattern visibility after development, and resolution, and color is developed by radicals. It is more preferable that the dye is a radical.

The dye N is preferably leuco crystal violet, crystal violet lactone, brilliant green, or Victoria pure blue-naphthalene sulfonate.

The photosensitive resin layer may contain one kind alone or two or more kinds of dyes N.

The content ratio of the dye N is 0.1 mass with respect to the total mass of the photosensitive resin layer from the viewpoints of the visibility of the exposed portion, the visibility of the non-exposed portion, the pattern visibility after development, and the resolution. % Or more, more preferably 0.1% by mass to 10% by mass, further preferably 0.1% by mass to 5% by mass, and 0.1% by mass to 1% by mass. It is particularly preferable to have.

The content ratio of the dye N means the content ratio of the dye when all of the dye N contained in the photosensitive resin layer is in a colored state. Hereinafter, a method for quantifying the content ratio of dye N will be described by taking a dye that develops color by radicals as an example. Two solutions are prepared by dissolving the dye (0.001 g) and the dye (0.01 g) in methyl ethyl ketone (100 mL). IRGACURE OXE-01 (BASF) is added to each of the obtained solutions as a photoradical polymerization initiator, and then radicals are generated by irradiating with light of 365 nm to bring all the dyes into a colored state. Next, in an air atmosphere, the absorbance of each solution having a liquid temperature of 25 ° C. is measured using a spectrophotometer (UV3100, Shimadzu Corporation) to prepare a calibration curve. Next, the absorbance of the solution in which all the dyes are colored is measured by the same method as above except that the photosensitive resin layer (3 g) is dissolved in methyl ethyl ketone instead of the dye. From the absorbance of the obtained solution containing the photosensitive resin layer, the content of the dye contained in the photosensitive resin layer is calculated based on the calibration curve.

-Surfactant-
The photosensitive resin layer preferably contains a surfactant from the viewpoint of thickness uniformity. Examples of the surfactant include anionic surfactants, cationic surfactants, nonionic (nonionic) surfactants, and amphoteric surfactants, and nonionic surfactants are preferable.

Examples of the nonionic surfactant include a polyoxyethylene higher alkyl ether compound, a polyoxyethylene higher alkylphenyl ether compound, a higher fatty acid diester compound of polyoxyethylene glycol, a silicone-based nonionic surfactant, and a fluorine-based nonionic property. Surfactants can be mentioned.

The photosensitive resin layer preferably contains a fluorine-based nonionic surfactant from the viewpoint of being more excellent in resolution. It is considered that the photosensitive resin layer contains a fluorine-based nonionic surfactant to suppress the penetration of the etching solution into the photosensitive resin layer and reduce the side etching. Commercially available products of the fluorine-based nonionic surfactant include, for example, Megafvck (registered trademark) F-551, F-552 (DIC Corporation), and Megafvck F-554 (DIC Corporation).

Examples of the surfactant include the surfactant described in paragraphs 0120 to 0125 of International Publication No. 2018/179640, the surfactant described in paragraph 0017 of Japanese Patent No. 45027884, and JP-A-2009-237362. The surfactants described in paragraphs 0060 to 0071 of the publication are also mentioned.

The photosensitive resin layer may contain one type alone or two or more types of surfactants.

The content ratio of the surfactant is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 3% by mass, based on the total mass of the photosensitive resin layer.

-Additives-
The photosensitive resin layer may contain a known additive in addition to the above components, if necessary. Examples of the additive include a radical polymerization inhibitor, a sensitizer, a plasticizer, a heterocyclic compound, a benzotriazole compound, a carboxybenzotriazole compound, a resin other than the polymer A, and a solvent. The photosensitive resin layer may contain one kind alone or two or more kinds of additives.

The photosensitive resin layer may contain a radical polymerization inhibitor. Examples of the radical polymerization inhibitor include the thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784. The radical polymerization inhibitor is preferably phenothiazine, phenoxazine, or 4-methoxyphenol. Examples of the radical polymerization inhibitor other than the above include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, and diphenylnitrosamine. It is preferable to use a nitrosophenylhydroxyamine aluminum salt as a radical polymerization inhibitor so as not to impair the sensitivity of the photosensitive resin layer.

The photosensitive resin layer may contain a benzotriazole compound. Examples of the benzotriazole compound include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole, and the like. Examples thereof include bis (N-2-ethylhexyl) aminomethylene-1,2,3-triltriazole and bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole.

The photosensitive resin layer may contain a carboxybenzotriazole compound. Examples of the carboxybenzotriazole compound include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, and N- (N, N-di-2-ethylhexyl) aminomethylene. Examples thereof include carboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylene carboxybenzotriazole, and N- (N, N-di-2-ethylhexyl) aminoethylene carboxybenzotriazole. Examples of commercially available products of the carboxybenzotriazole compound include CBT-1 (Johoku Chemical Industry Co., Ltd.).

The ratio of the total content of the radical polymerization inhibitor, the benzotriazol compound, and the carboxybenzotriazol compound may be 0.01% by mass to 3% by mass with respect to the total mass of the photosensitive resin layer. It is preferably 0.05% by mass to 1% by mass, more preferably. It is preferable that the ratio of the total content of each of the above components is 0.01% by mass or more from the viewpoint of imparting storage stability to the photosensitive resin layer. On the other hand, it is preferable that the ratio of the total content of each of the above-mentioned components is 3% by mass or less from the viewpoint of maintaining the sensitivity and suppressing the decolorization of the dye.

The photosensitive resin layer may contain a sensitizer. The sensitizer is not limited, and a known sensitizer can be used. In addition, dyes and pigments can also be used as the sensitizer. Examples of the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, and triazole compounds (for example, 1,2,4-triazole), stillben compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoaclydin compounds.

The photosensitive resin layer may contain one type alone or two or more types of sensitizers.

When the photosensitive resin layer contains a sensitizer, the content ratio of the sensitizer can be appropriately selected depending on the purpose, but from the viewpoint of improving the sensitivity to the light source and improving the curing rate by balancing the polymerization rate and the chain transfer. It is preferably 0.01% by mass to 5% by mass, more preferably 0.05% by mass to 1% by mass, based on the total mass of the photosensitive resin layer.

The photosensitive resin layer may contain at least one selected from the group consisting of a plasticizer and a heterocyclic compound. Examples of the plasticizer and the heterocyclic compound include the compounds described in paragraphs 097 to 0103 and 0111 to 0118 of International Publication No. 2018/179640.

The photosensitive resin layer may contain a resin other than the polymer A. Resins other than the polymer A include acrylic resins, styrene-acrylic copolymers (however, limited to copolymers having a styrene content of 40% by mass or less), polyurethane resins, polyvinyl alcohols, polyvinyl formals, and polyamide resins. Examples thereof include polyester resin, polyamide resin, epoxy resin, polyacetal resin, polyhydroxystyrene resin, polyimide resin, polybenzoxazole resin, polysiloxane resin, polyethyleneimine, polyallylamine, and polyalkylene glycol.

The photosensitive resin layer may contain a solvent. When the photosensitive resin layer is formed by the photosensitive resin composition containing a solvent, the solvent may remain in the photosensitive resin layer. The solvent will be described later.

The photosensitive resin layer can be used as an additive, for example, as a metal oxide particle, an antioxidant, a dispersant, an acid growth agent, a development accelerator, a conductive fiber, a thermal radical polymerization initiator, a thermal acid generator, or an ultraviolet absorber. , At least one selected from the group consisting of thickeners, cross-linking agents, organic precipitation inhibitors, and inorganic precipitation inhibitors. Additives are described, for example, in paragraphs 0165 to 0184 of JP2014-85643A. The contents of the above publication are incorporated herein by reference.

(thickness)
The average thickness of the photosensitive resin layer is generally 0.1 μm to 300 μm. The average thickness of the photosensitive resin layer is preferably 0.1 μm or more, more preferably 0.2 μm or more, further preferably 0.5 μm, and particularly preferably 1 μm or more. The average thickness of the photosensitive resin layer is preferably 100 μm or less, more preferably 50 μm or less, further preferably 15 μm or less, and particularly preferably 8 μm or less. When the average thickness of the photosensitive resin layer is within the above range, the developability of the photosensitive resin layer can be improved and the resolution can be improved.

In certain embodiments, the average thickness of the photosensitive resin layer is preferably 0.1 μm to 15 μm, more preferably 0.5 μm to 5 μm, and even more preferably 0.5 μm to 4 μm. It is particularly preferably 0.5 μm to 3 μm.

(Transmittance)
In the photosensitive resin layer, the transmittance of light having a wavelength of 365 nm is preferably 10% or more, more preferably 30% or more, and particularly preferably 50% or more, from the viewpoint of being more excellent in adhesion. .. The upper limit of transmittance is not limited. In the photosensitive resin layer, the transmittance of light having a wavelength of 365 nm is preferably 99.9% or less.

(Formation method)
The method for forming the photosensitive resin layer is not limited as long as it is a method capable of forming a layer containing the above components. Examples of the method for forming the photosensitive resin layer include a method of applying the photosensitive resin composition to the surface of the temporary support and then drying the coating film of the photosensitive resin composition.

Examples of the photosensitive resin composition include a composition containing a polymer A, a polymerizable compound B, an optional component, and a solvent. The photosensitive resin composition preferably contains a solvent in order to adjust the viscosity of the photosensitive resin composition and facilitate the formation of the photosensitive resin layer.

The solvent is not limited as long as it can dissolve or disperse the polymer A, the polymerizable compound B, and any component, and a known solvent can be used. Examples of the solvent include an alkylene glycol ether solvent, an alkylene glycol ether acetate solvent, an alcohol solvent (for example, methanol and ethanol), a ketone solvent (for example, acetone and methyl ethyl ketone), and an aromatic hydrocarbon solvent (for example, toluene). Examples include aprotonic polar solvents (eg, N, N-dimethylformamide), cyclic ether solvents (eg, tetrahydrofuran), ester solvents, amide solvents, and lactone solvents.

The photosensitive resin composition preferably contains at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. The photosensitive resin composition comprises at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, and at least one selected from the group consisting of a ketone solvent and a cyclic ether solvent. It is more preferable to include it. It is particularly preferable that the photosensitive resin composition contains at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, a ketone solvent, and a cyclic ether solvent.

Examples of the alkylene glycol ether solvent include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether, and dipropylene glycol dialkyl ether. Be done.

Examples of the alkylene glycol ether acetate solvent include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate.

As the solvent, the solvent described in paragraphs 0092 to 0094 of International Publication No. 2018/179640 and the solvent described in paragraph 0014 of JP-A-2018-177789 may be used. These contents are incorporated herein by reference.

The photosensitive resin composition may contain one kind alone or two or more kinds of solvents.

The content ratio of the solvent in the photosensitive resin composition is preferably 50 parts by mass to 1,900 parts by mass, and 100 parts by mass to 900 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition. It is more preferable that it is a part.

The method for preparing the photosensitive resin composition is not limited. As a method for preparing the photosensitive resin composition, for example, a photosensitive resin composition is prepared by preparing a solution in which each component is dissolved in a solvent in advance and mixing the obtained solutions in a predetermined ratio. The method can be mentioned. The photosensitive resin composition is preferably filtered using a filter having a pore size of 0.2 μm to 30 μm before forming the photosensitive resin layer.

The method for applying the photosensitive resin composition is not limited, and a known method can be used. Examples of the coating method include slit coating, spin coating, curtain coating, and inkjet coating.

Further, the photosensitive resin layer may be formed by applying the photosensitive resin composition on a cover film described later and drying it.

<< Cover film >>
The photosensitive transfer material preferably has a cover film (also referred to as a protective film). According to the cover film, the surface of the layer (for example, the photosensitive resin layer) in contact with the cover film can be protected. In certain embodiments, the photosensitive transfer material more preferably has a cover film that is in contact with the surface of the photosensitive resin layer opposite to the side on which the temporary support is arranged.

Examples of the cover film include a resin film and paper. The cover film is preferably a resin film from the viewpoint of strength and flexibility.

Examples of the resin film include a polyethylene film, a polypropylene film, a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. The resin film is preferably a polyethylene film, a polypropylene film, or a polyethylene terephthalate film.

The thickness of the cover film is not limited. The average thickness of the cover film is preferably 5 μm to 100 μm, more preferably 10 μm to 50 μm, and particularly preferably 10 μm to 20 μm.

The arithmetic mean roughness Ra of the surface of the cover film on the side on which the photosensitive resin layer is arranged is preferably 0.3 μm or less, and more preferably 0.1 μm or less, from the viewpoint of excellent resolution. , 0.05 μm or less is particularly preferable. When the arithmetic mean roughness of the surface on the side where the photosensitive resin layer of the cover film is arranged is within the above range, the uniformity of the thickness of the photosensitive resin layer and the formed resin pattern is improved. The lower limit of the arithmetic mean roughness Ra is not limited. The arithmetic mean roughness Ra of the surface of the cover film on the side on which the photosensitive resin layer is arranged is preferably 0.001 μm or more. The arithmetic mean roughness Ra of the surface of the cover film on the side on which the photosensitive resin layer is arranged is measured by a method according to the method for measuring the arithmetic mean roughness Ra described in the above section “Temporary Support”.

[Other layers]
The photosensitive transfer material may have a layer other than the above-mentioned layer (hereinafter, referred to as “another layer”). Other layers include thermoplastics, intermediate layers, and contrast enhancement layers.

(Thermoplastic resin layer)
The photosensitive transfer material may have a thermoplastic resin layer. In certain embodiments, the photosensitive transfer material preferably has a thermoplastic resin layer between the temporary support and the photosensitive resin layer. Since the photosensitive film has a thermoplastic resin layer between the temporary support and the photosensitive resin layer, the followability to the substrate in the process of being bonded to the substrate is improved, and the substrate and the photosensitive transfer material can be separated from each other. This is because the adhesion between layers is improved as a result of suppressing the mixing of air bubbles between them.

The thermoplastic resin layer preferably contains an alkali-soluble resin.
The thermoplastic resin layer may further contain components such as a dye, a compound that generates an acid, a base, or a radical by light, a plasticizer, a surfactant, a sensitizer, an additive, and the like.

Further, the thermoplastic resin layer is described in paragraphs 0189 to 0193 of Japanese Patent Application Laid-Open No. 2014-85643. The contents of the above publication are incorporated herein by reference.

(thickness)
The thickness of the thermoplastic resin layer is not limited. The average thickness of the thermoplastic resin layer is preferably 1 μm or more, and more preferably 2 μm or more, from the viewpoint of adhesion to the layer adjacent to the thermoplastic resin layer. The upper limit of the average thickness of the thermoplastic resin layer is not limited. From the viewpoint of developability and resolvability, the average thickness of the thermoplastic resin layer is preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less.

(Formation method)
The method for forming the thermoplastic resin layer is not limited as long as it is a method capable of forming a layer containing the above components. Examples of the method for forming the thermoplastic resin layer include a method in which the thermoplastic resin composition is applied to the surface of the temporary support and the coating film of the thermoplastic resin composition is dried.

Examples of the thermoplastic resin composition include a composition containing the above-mentioned components. The thermoplastic resin composition preferably contains a solvent in order to adjust the viscosity of the thermoplastic resin composition and facilitate the formation of the thermoplastic resin layer.

The preparation of the thermoplastic resin composition and the formation of the thermoplastic resin layer may be carried out according to the method for preparing the photosensitive resin composition and the method for forming the photosensitive resin layer described above. For example, it is obtained after preparing a thermoplastic resin composition by preparing a solution in which each component contained in the thermoplastic resin layer is dissolved in a solvent in advance and mixing the obtained solutions in a predetermined ratio. The thermoplastic resin layer can be formed by applying the thermoplastic resin composition to the surface of the temporary support and drying the coating film of the thermoplastic resin composition. Further, after forming the photosensitive resin layer on the cover film described later, the thermoplastic resin layer may be formed on the surface of the photosensitive resin layer.

(Middle layer)
The photosensitive film according to the present disclosure preferably has an intermediate layer between the thermoplastic resin layer and the photosensitive resin layer. According to the intermediate layer, it is possible to suppress the mixing of components when forming a plurality of layers and during storage.

The intermediate layer is preferably a water-soluble layer from the viewpoint of developability and suppressing mixing of components during application of the plurality of layers and storage after application. In the present disclosure, "water-soluble" means that the solubility in 100 g of water having a liquid temperature of 22 ° C. and a pH of 7.0 is 0.1 g or more.

Examples of the intermediate layer include an oxygen blocking layer having an oxygen blocking function, which is described as a “separation layer” in JP-A-5-72724. Since the intermediate layer is an oxygen blocking layer, the sensitivity at the time of exposure is improved, the time load of the exposure machine is reduced, and as a result, the productivity is improved. The oxygen blocking layer used as the intermediate layer may be appropriately selected from known layers. The oxygen blocking layer used as the intermediate layer is preferably an oxygen blocking layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an alkaline aqueous solution (1% by mass aqueous solution of sodium carbonate at 22 ° C.).

The intermediate layer preferably contains a resin, and may contain an additive (for example, a surfactant) if necessary.

The thickness of the intermediate layer is not limited. The average thickness of the intermediate layer is preferably 0.1 μm to 5 μm, and more preferably 0.5 μm to 3 μm. When the thickness of the intermediate layer is within the above range, the oxygen blocking property is not deteriorated, the mixing of the components at the time of forming a plurality of layers and at the time of storage can be suppressed, and the intermediate layer at the time of development can be suppressed. The increase in removal time can be suppressed.

The method for forming the intermediate layer is not limited as long as it is a method capable of forming a layer containing the above components. Examples of the method for forming the intermediate layer include a method in which the composition for the intermediate layer is applied to the surface of the thermoplastic resin layer or the photosensitive resin layer, and then the coating film of the composition for the intermediate layer is dried.

Examples of the composition for the intermediate layer include a composition containing a resin and an optional additive. The composition for the intermediate layer preferably contains a solvent in order to adjust the viscosity of the composition for the intermediate layer and facilitate the formation of the intermediate layer. The solvent is not limited as long as it is a solvent that can dissolve or disperse the resin. The solvent is preferably at least one selected from the group consisting of water and a water-miscible organic solvent, and more preferably water or a mixed solvent of water and a water-miscible organic solvent.

(Contrast enhancement layer)
The photosensitive film according to the present disclosure may have a contrast enhancement layer. The contrast enhancement layer is described in, for example, paragraph 0134 of International Publication No. 2018/179640 and paragraphs 0194 to 0196 of JP2014-85643A. The contents of these publications are incorporated herein by reference.

<< Exposure process >>
The method for producing a resin pattern of the present disclosure includes a step (exposure step) of pattern-exposing the photosensitive resin layer after the laminating step.

The detailed arrangement and specific size of the pattern in the pattern exposure are not limited.
When the conductive pattern is applied to the circuit wiring, at least the pattern is arranged so that the display quality of the display device (for example, a touch panel) provided with the input device having the circuit wiring is improved and the area occupied by the take-out wiring is reduced. A part (preferably the electrode pattern of the touch panel and / or the portion of the take-out wiring) preferably includes a thin wire having a width of 20 μm or less, and more preferably contains a thin wire having a width of 10 μm or less.

The light source used for exposure may be a light source that irradiates the photosensitive resin layer with light having a wavelength that allows exposure (for example, 365 nm or 405 nm). Specific light sources include, for example, ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and LEDs (Light Emitting Diodes).

Exposure ^is preferably ^{5mJ / cm 2 ~200mJ / cm 2} , more preferably ^{10mJ / cm 2 ~100mJ / cm 2} .

In the exposure step, the temporary support may be peeled off from the photosensitive resin layer and then the pattern exposure may be performed. Before the temporary support is peeled off, the temporary support is exposed to the pattern through the temporary support, and then the temporary support is peeled off. You may.
When the temporary support is peeled off before the exposure, the mask may be exposed in contact with the photosensitive layer, or may be exposed in close proximity without contact.
When the temporary support is exposed without being peeled off, the mask may be exposed in contact with the temporary support, or may be exposed in close proximity without contact. In order to prevent mask contamination due to contact between the photosensitive resin layer and the mask and to avoid the influence of foreign matter adhering to the mask on the exposure, it is preferable to perform pattern exposure without peeling off the temporary support.

The exposure method is a contact exposure method in the case of contact exposure, a proximity exposure method in the case of a non-contact exposure method, a lens-based or mirror-based projection exposure method, a direct exposure method using an exposure laser, or the like. It can be appropriately selected and used.
In the case of a lens-based or mirror-based projection exposure method, an exposure machine having an appropriate numerical aperture (NA) of the lens can be used according to the required resolving power and depth of focus.
In the case of the direct exposure method, drawing may be performed directly on the photosensitive resin layer, or reduced projection exposure may be performed on the photosensitive resin layer via a lens. Further, the exposure may be performed not only in the atmosphere but also under reduced pressure or vacuum. Further, a liquid such as water may be interposed between the light source and the photosensitive resin layer for exposure.

<< Development process >>
The method for producing a resin pattern of the present disclosure includes a step of developing a photosensitive resin layer to form a resin pattern after the above-mentioned exposure step.

The photosensitive resin layer can be developed using a developing solution. The type of developer is not limited as long as the image portion (exposed portion) or non-image portion (non-exposed portion) of the photosensitive resin layer can be removed. As the developing solution, a known developing solution (for example, the developing solution described in JP-A-5-72724) can be used.

The developer is preferably an alkaline aqueous solution-based developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05 mol / L to 5 mol / L. The developer may contain a water-soluble organic solvent and / or a surfactant. As the developing solution, the developing solution described in paragraph 0194 of International Publication No. 2015/093271 is also preferable.

The development method is not particularly limited, and may be any of paddle development, shower development, shower and spin development, and dip development. Shower development is a development process in which an exposed portion or a non-exposed portion is removed by spraying a developing solution onto the photosensitive resin layer after exposure by a shower.

After the developing step, it is preferable to spray the cleaning agent with a shower and rub with a brush to remove the developing residue.

The temperature of the developer is not limited. The liquid temperature of the developing solution is preferably 20 ° C to 40 ° C.

For example, when the photosensitive transfer material contains a thermoplastic resin and an intermediate layer, in the developing process, the thermoplastic resin, together with the image portion (exposed portion) or the non-image portion (non-exposed portion) of the photosensitive resin layer, And the intermediate layer is also removed. Further, in the developing step, the thermoplastic resin layer and the intermediate layer may be removed by dissolution or dispersion in a developing solution.

<< Etching process >>
In the method for manufacturing a conductive pattern of the present disclosure, a resin pattern is formed on a conductive layer using the method for manufacturing a resin pattern of the present disclosure, and then the conductive layer is etched using the obtained resin pattern as a mask to obtain a conductive pattern. Includes a step of forming (etching step).

In the etching step, the conductive layer is etched by using the resin pattern as a mask (that is, an etching resist). As a method of etching treatment, a known method can be applied. Examples of the etching treatment method include the methods described in paragraphs 0209 to 0210 of JP2017-120435A, the methods described in paragraphs 0048 to 0054 of JP2010-152155A, and immersion in an etching solution. Examples include a wet etching method and a dry etching (for example, plasma etching) method.

As the etching solution used in the wet etching method, an acidic or alkaline etching solution may be appropriately selected according to the object to be etched.

Examples of the acidic etching solution include an aqueous solution of an acidic component alone selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid, an acidic component, and ferric chloride. Examples thereof include a mixed aqueous solution with a salt selected from the group consisting of ammonium fluoride and potassium permanganate. The acidic component may be a component in which a plurality of acidic components are combined.

Examples of the alkaline etching solution include an aqueous solution of an alkaline component alone selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonia, an organic amine, and a salt of an organic amine (for example, tetramethylammonium hydroxide). , A mixed aqueous solution of an alkaline component and a salt (for example, potassium permanganate). The alkaline component may be a component in which a plurality of alkaline components are combined.

<< Removal process >>
The method for producing a conductive pattern of the present disclosure preferably includes a step of removing the remaining resin pattern (hereinafter, may be referred to as a "removal step"). The removal step is preferably performed after the etching step.

Examples of the method for removing the remaining resin pattern include a method for removing the remaining resin pattern by chemical treatment. The method for removing the remaining resin pattern is preferably a method for removing the remaining resin pattern using a removing liquid. As a method using the removing liquid, for example, the substrate having the remaining resin pattern is immersed in the removing liquid during stirring at a liquid temperature of preferably 30 to 80 ° C., more preferably 50 to 80 ° C. for 1 to 30 minutes. There is a way to do it.

Examples of the removing liquid include a removing liquid in which an inorganic alkaline component or an organic alkaline component is dissolved in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution thereof. Examples of the inorganic alkaline component include sodium hydroxide and potassium hydroxide. Examples of the organic alkali component include a primary amine compound, a secondary amine compound, a tertiary amine compound, and a quaternary ammonium salt compound.

The method of removing the residual resin pattern using the removing liquid is not limited to the dipping method, and may be a known method other than the dipping method (for example, a spray method, a shower method, and a paddle method).

<< Other processes >>
The method for producing a conductive pattern of the present disclosure may include an arbitrary step other than the above-mentioned steps (hereinafter, may be referred to as "another step"). Examples of other steps include the steps shown below. However, the other steps are not limited to the steps shown below.

[Cover film peeling process]
When the photosensitive transfer material has a cover film, the method for producing the resin pattern of the present disclosure preferably includes a step of peeling the cover film from the photosensitive transfer material. The method for peeling the cover film is not limited, and a known method can be applied.

[Step to reduce visible light reflectance]
The method for producing a conductive pattern of the present disclosure may include a step of reducing the reflectance of a part or all of the conductive layer on the substrate.

Examples of the treatment for reducing the visible light reflectance of the conductive layer include an oxidation treatment. When the conductive layer contains copper, the visible light reflectance of the conductive layer can be lowered by converting copper into copper oxide by an oxidation treatment and blackening the conductive layer.

For the treatment of reducing the visible light reflectance of the conductive layer, refer to paragraphs 0017 to 0025 of JP-A-2014-150118 and paragraphs 0041, 0042, 0048, and 0058 of JP-A-2013-206315. Have been described. The contents of these publications are incorporated herein by reference.

[Step of forming an insulating film and step of forming a new conductive layer on the surface of the insulating film]
When the method for manufacturing a conductive pattern of the present disclosure is applied to a method for manufacturing a circuit wiring, a step of forming an insulating film on the surface of the circuit wiring and a step of forming a new conductive layer on the surface of the insulating film. , Is also preferably included. By the above steps, two electrode patterns insulated via an insulating film can be formed.

The method of forming the insulating film is not limited. In the step of forming the insulating film, for example, the insulating film may be formed by a known method for forming a permanent film. Further, an insulating film having a desired pattern may be formed by photolithography using a photosensitive material having an insulating property.

In the step of forming a new conductive layer on the insulating film, for example, a new conductive layer having a desired pattern may be formed by photolithography using a photosensitive material having conductivity.

In the method for manufacturing a circuit wiring, it is also preferable to use a substrate having conductive layers on both surfaces of the base material, and to form a circuit on each of the conductive layers sequentially or simultaneously. According to the above method, for example, a touch panel circuit wiring having a first conductive pattern formed on one surface of the base material and a second conductive pattern formed on the other surface of the base material can be formed. Further, it is also preferable to form the circuit wiring for the touch panel on both sides of the base material by roll-to-roll according to the circuit wiring manufacturing method according to the present disclosure.

<< Applications of resin patterns and conductive patterns >>
The resin pattern produced by the method for producing a resin pattern of the present disclosure and the conductive pattern produced by the method for producing a conductive pattern of the present disclosure can be applied to various uses.

Particularly suitable application targets of the resin pattern or the conductive pattern include, for example, an input device, a touch panel is preferable, and a capacitance type touch panel is more preferable.

Further, the input device can be applied to various display devices (for example, an organic EL display device and a liquid crystal display device). Specifically, the resin pattern produced by the resin pattern manufacturing method of the present disclosure can be suitably applied as a protective film for circuit wiring included in a touch panel.

Further, the conductive pattern manufactured by the method for manufacturing the conductive pattern of the present disclosure can be suitably applied as a circuit wiring provided in the touch panel.

Examples of the detection method on the touch panel include a resistance film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method. The detection method is preferably a capacitance method.

The touch panel type includes a so-called in-cell type (for example, the configuration shown in FIGS. 5, 6, 7, and 8 of Japanese Patent Application Laid-Open No. 2012-517501), a so-called on-cell type (for example, Japanese Patent Application Laid-Open No. 2013-168125). The configuration shown in FIG. 19 and the configurations shown in FIGS. 1 and 5 of JP2012-89102A), OGS (One Glass Solution) type, and TOR (Touch-on-Lens) type (for example, JP-A-2012). The configuration described in FIG. 2 of 2013-54727), various out-cell types (for example, GG, G1 and G2, GFF, GF2, GF1, and G1F), and other configurations (for example, Japanese Patent Application Laid-Open No. 2013-164871). The configuration shown in FIG. 6) can be mentioned.

Hereinafter, the present disclosure will be described in detail by way of examples, but the present disclosure is not limited thereto. Unless otherwise specified, "parts" are based on mass.

<Example 1>
1. 1. Fabrication of laminated polyester film [extrusion molding]
Pellets A of polyethylene terephthalate produced using the titanium compound (citrate chelate titanium complex, VERTEC AC-420, manufactured by Johnson Matthey) described in Japanese Patent No. 5575671 as a polymerization catalyst are dried to a water content of 50 ppm or less. After that, it was put into the hopper of a uniaxial kneading extruder having a diameter of 30 mm, and then melted and extruded at 280 ° C. The melt was passed through a filter (pore diameter 3 μm) and then extruded from the die onto a cooling roll at 25 ° C. to obtain an unstretched film. The extruded melt was brought into close contact with the cooling roll by using an electrostatic application method.

[Stretching and coating]
The unstretched film was sequentially biaxially stretched by the following method.
(A) Longitudinal stretching The unstretched film was stretched in the longitudinal direction (conveyance direction) by passing it between two pairs of nip rolls having different peripheral speeds. The longitudinal stretching was carried out with a preheating temperature of 75 ° C., a stretching temperature of 90 ° C., a stretching ratio of 3.4 times, and a stretching speed of 1300% / sec.
(B) Coating The following coating liquid 1 for forming a particle-containing layer was coated on one side of the vertically stretched film with a bar coater so as to ^{have a concentration of 5.6 g / m 2.}
(C) Transverse stretching The film subjected to the above longitudinal stretching and the above coating was laterally stretched under the following conditions using a tenter.
-Conditions-
Preheating temperature: 100 ° C
Stretching temperature: 120 ° C
Stretching ratio: 4.2 times Stretching speed: 50% / sec

(Preparation of coating liquid 1 for forming a particle-containing layer)
A coating liquid 1 for forming a particle-containing layer was prepared by mixing each of the components shown below.
-Polyacrylic (AS-563A, manufactured by Daicel FineChem Co., Ltd., solid content 27.5% by mass): 145 parts-Nonion-based surfactant (Naro Acty (registered trademark) CL95, manufactured by Sanyo Kasei Kogyo Co., Ltd., solid content 100) Mass%): 0.7 parts-Anionic surfactant (Lapisol® A-90, manufactured by Nichiyu Co., Ltd., solid content 1% by mass water-diluted): 111 parts-Carnauba wax dispersion (Cerozole (registered) Trademark) 524, manufactured by Chukyo Yushi Co., Ltd., solid content 30% by mass): 26 parts · Carbodiimide compound (Carbodilite (registered trademark) V-02-L2, manufactured by Nisshinbo Chemical Co., Ltd., solid content 10% by mass, diluted with water): 18 Parts ・ Colloidal silica (Snowtex (registered trademark) XL, manufactured by Nissan Chemical Co., Ltd., average particle size 50 nm, solid content 10% by mass, diluted with water): 2.8 parts ・ Water: 695 parts

The obtained coating liquid was filtered with a 6 μm filter (F20, manufactured by Mahle Filter Systems Corp.) and membrane degassed (2x6 Radial Flow Superphobic, manufactured by Polypore Co., Ltd.) after preparation and before coating.

[Heat fixation and heat relaxation]
The stretched film after the longitudinal stretching and the transverse stretching was heat-fixed under the following conditions. Further, after heat fixing, the tenter width was reduced, heat was relaxed under the following conditions, and then cooling was performed.
(Heat fixing condition)
Heat fixation temperature: 227 ° C
Heat fixing time: 6 seconds (heat relaxation conditions)
Heat relaxation temperature: 190 ° C
Heat relaxation rate: 4%
(Cooling conditions)
Cooling rate: 2500 ° C / min

[Take-up]
After the above heat fixing and heat relaxation, both ends of the film were trimmed, and then the end of the film was extruded (knurled) with a width of 10 mm, and then the stretched film was wound up at a tension of 40 kg / m. By the above method, a laminated polyester film 1 having a base material layer (polyester film layer) made of a biaxially oriented polyester film (PET: polyethylene terephthalate) having a thickness of 25 μm and a particle-containing layer having a thickness of 0.04 μm was obtained. .. The width of the obtained laminated polyester film 1 was 1.5 m, and the winding length was 7,000 m.

2. Preparation of Photosensitive Transfer Material Using the obtained laminated polyester film 1, the photosensitive transfer material 1 was prepared as follows.

<Abbreviation>
The abbreviations shown below mean the following compounds, respectively.
"MAA": Methacrylic acid (Fujifilm Wako Pure Chemical Industries, Ltd.)
"MMA": Methyl methacrylate (Fujifilm Wako Pure Chemical Industries, Ltd.)
"PGMEA": Propylene glycol monomethyl ether acetate (Showa Denko KK)
"St": Styrene (Fuji Film Wako Pure Chemical Industries, Ltd.)
"V-601": 2,2'-azobis (isobutyric acid) dimethyl (Fujifilm Wako Pure Chemical Industries, Ltd., polymerization initiator)

<Polymer A-1>
PGMEA (116.5 parts by mass) was placed in a three-necked flask, and the temperature was raised to 90 ° C. under a nitrogen atmosphere. While maintaining the liquid temperature in the three-necked flask at 90 ° C ± 2 ° C, St (52.0 parts by mass), MMA (19.0 parts by mass), MAA (29.0 parts by mass) were added to the three-necked flask. Parts), V-601 (4.0 parts by mass), and PGMEA (116.5 parts by mass) were added dropwise over 2 hours. After completion of the dropping, the mixed solution was stirred for 2 hours while maintaining the liquid temperature at 90 ° C. ± 2 ° C. to obtain a composition containing 30.0% by mass of the polymer A-1. The acid value of polymer A-1 is 189 mgKOH / g.

<Polymerizable compound B>
The following compounds were prepared as the polymerizable compound B.
B-1: NK ester BPE-500 (2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane, Shin Nakamura Chemical Industry Co., Ltd.)
B-2: Aronix M-270 (Polypropylene glycol diacrylate, Toagosei Co., Ltd.)

<Photopolymerization initiator>
The following compounds were prepared as photopolymerization initiators.
C-1: B-CIM (photoradical polymerization initiator, 2- (2-chlorophenyl) -4,5-diphenylimidazole dimer, manufactured by Hampford)
C-2: EAB-F (photoradical polymerization initiator (sensitizer), 4,4'-bis (diethylamino) benzophenone, Tokyo Chemical Industry Co., Ltd.)

<Dye>
The following compounds were prepared as dyes.
-D-1: LCV (Leuko Crystal Violet, Yamada Chemical Co., Ltd., dye that develops color by radicals)

<Surfactant>
The following compounds were prepared as surfactants.
・ E-1: Mega Fvck F552 (DIC Corporation)

<Preparation of thermoplastic resin composition>
A thermoplastic resin composition was prepared by mixing the following components.
・ Copolymer of benzyl methacrylate, methacrylic acid, and acrylic acid (solid content concentration: 30.0% by mass, Mw: 30,000, acid value: 153 mgKOH / g): 42.85 parts ・ NK ester A-DCP (tricyclo) Decandimethanol diacrylate, Shin-Nakamura Chemical Industry Co., Ltd.): 4.63 parts ・ 8UX-015A (polyfunctional urethane acrylate compound, Taisei Fine Chemical Co., Ltd.): 2.31 parts by mass ・ Aronix TO-2349 (having carboxy group) Polyfunctional acrylate compound, Toa Synthetic Co., Ltd.): 0.77 parts-Compounds having the structure shown below (photoacid generators, compounds synthesized according to the method described in paragraph 0227 of JP2013-47765A): 0. 32 copies

-Compounds with the structure shown below (dyes that develop color with acid): 0.08 parts

・ E-1: 0.03 parts ・ Methyl ethyl ketone (Sankyo Chemical Co., Ltd.): 39.50 parts ・ PGMEA: 9.51 parts

<Preparation of composition for intermediate layer>
A composition for an intermediate layer was prepared by mixing the following components.
・ Ion exchanged water: 38.12 parts ・ Methanol (Mitsubishi Gas Chemical Company, Inc.): 57.17 parts ・ Clarepovar PVA-205 (polyvinyl alcohol, Kuraray Co., Ltd.): 3.22 parts ・ Polyvinylpyrrolidone K-30 (stock) Company Japan Catalyst): 1.49 copies ・ Megafuck F-444 (Fluorine-based nonionic surfactant, DIC Co., Ltd.): 0.0015 copies

<Preparation of photosensitive resin composition>
A photosensitive resin composition was prepared by mixing the following components.
・ Polymer A-1 (solid content concentration 30.0% by mass): 21.87 parts ・ B-1: 4.85 parts ・ B-2: 0.51 parts ・ C-1: 0.89 parts ・ C -2: 0.05 parts-D-1: 0.053 parts-E-1: 0.02 parts-Phenothiazine (Fujifilm Wako Pure Chemical Industries, Ltd.): 0.025 parts-1-phenyl-3-pyrazolidone (1-phenyl-3-pyrazolidone) Fujifilm Wako Pure Chemical Industries, Ltd.): 0.001 parts ・ Methyl ethyl ketone (Sankyo Chemical Co., Ltd.): 30.87 parts ・ PGMEA: 33.92 parts ・ tetrahydrofuran (THF, Mitsubishi Chemical Co., Ltd.): 6.93 parts

The coating width of the thermoplastic resin composition is 1.53 m using a slit-shaped nozzle on the surface of the laminated polyester film 1 opposite to the side having the particle-containing layer, and the thickness after drying is 2. The thermoplastic resin composition was applied so as to have a thickness of 0 μm. The formed thermoplastic resin composition was dried at 80 ° C. for 40 seconds to form a thermoplastic resin layer.

The composition for the intermediate layer was applied to the surface of the formed thermoplastic resin layer using a slit-shaped nozzle so that the coating width was 1.53 m and the thickness after drying was 1.0 μm. The coating film of the composition for the intermediate layer was dried at 80 ° C. for 40 seconds to form an intermediate layer.

A photosensitive resin composition was applied to the surface of the formed intermediate layer using a slit-shaped nozzle so that the coating width was 1.53 m and the thickness after drying was 2.0 μm. The photosensitive resin layer was formed by drying the coating film of the photosensitive resin composition at 80 ° C. for 40 seconds.

A PET film (Lumirror 16QS62, Toray Industries, Inc., arithmetic average roughness (Ra value): 0.02 μm, thickness: 16 μm, width: 1.54 m) is pressure-bonded to the surface of the formed photosensitive resin layer as a cover film. By doing so, the photosensitive transfer material 1 was produced. The produced photosensitive transfer material 1 was wound up in a roll shape for 4,000 m.

<Example 2>
A laminated polyester film 2 was obtained in the same manner as in Example 1 except that the coating liquid 2 for forming a particle-containing layer prepared by mixing each component shown below was used.
Next, a photosensitive transfer material 2 was obtained in the same manner as in Example 1 except that the laminated polyester film 2 was used instead of the laminated polyester film 1.

(Coating liquid for forming a particle-containing layer 2)
-Polyacrylic (AS-563A, manufactured by Daicel FineChem Co., Ltd., solid content 27.5% by mass): 167 parts-Nonion-based surfactant (Naroacty (registered trademark) CL95, manufactured by Sanyo Kasei Kogyo Co., Ltd., solid content 100 Mass%): 0.7 parts, anionic surfactant (Lapisol (registered trademark) A-90, manufactured by Nichiyu Co., Ltd., solid content 1% by mass, diluted with water): 55.7 parts, carnauba wax dispersion (cellozole) (Registered trademark) 524, manufactured by Chukyo Yushi Co., Ltd., solid content 30% by mass): 7 parts, carbodiimide compound (Carbodilite (registered trademark) V-02-L2, manufactured by Nisshinbo Chemical Co., Ltd., solid content 10% by mass, diluted with water) : 20.9 parts, colloidal silica (Snowtex (registered trademark) XL, manufactured by Nissan Chemical Co., Ltd., solid content 40% by mass, particles A): 2.8 parts, silica ultrasonic aqueous dispersion (Aerosil OX50, Nippon Aerosil) Made by Co., Ltd., solid content 10% by mass, average particle diameter (median diameter) 0.2 μm, particle B): 1.5 parts, water: 743 parts

<Example 3>
A laminated polyester film 3 was obtained in the same manner as in Example 1 except that the coating liquid 3 for forming a particle-containing layer prepared by mixing each component shown below was used.
Next, a photosensitive transfer material 3 was obtained in the same manner as in Example 1 except that the laminated polyester film 3 was used instead of the laminated polyester film 1.

(Coating liquid for forming a particle-containing layer 3)
-Polyacrylic (AS-563A, manufactured by Daicel FineChem Co., Ltd., solid content 27.5% by mass): 119 parts-Nonion-based surfactant (Naro Acty (registered trademark) CL95, manufactured by Sanyo Kasei Kogyo Co., Ltd., solid content 100) Mass%): 0.7 parts-Anionic surfactant (Lapisol® A-90, manufactured by Nichiyu Co., Ltd., solid content 1% by mass water-diluted): 111 parts-Carnauba wax dispersion (Cerozole (registered) Trademark) 524, manufactured by Chukyo Yushi Co., Ltd., solid content 30% by mass): 53 parts · Carbodiimide compound (Carbodilite (registered trademark) V-02-L2, manufactured by Nisshinbo Chemical Co., Ltd., solid content 10% by mass, diluted with water): 15 Part ・ Colloidal silica (Snowtex (registered trademark) XL, manufactured by Nissan Chemical Co., Ltd., solid content 40% by mass): 2.8 parts ・ Water: 695 parts

<Example 4>
The particle-containing layer-forming coating solution 4 in which the carnauba wax dispersion in the particle-containing layer-forming coating solution 1 was changed to the polyolefin wax dispersion MGP-055 (manufactured by Maruyoshi Chemical Co., Ltd., solid content: 30% by mass) was used. A laminated polyester film 4 was obtained in the same manner as in Example 1 except for the above.
Next, a photosensitive transfer material 4 was obtained in the same manner as in Example 1 except that the laminated polyester film 4 was used instead of the laminated polyester film 1.

<Example 5>
80 parts of pellet A and 10 parts of 10 mass% water slurry of particles obtained by cross-linking polystyrene having a particle diameter of 0.45 μm with divinylbenzene (cross-linked polystyrene particles produced as described below) were supplied to a twin-screw kneading extruder. By keeping the vent holes at a reduced pressure of 1 kPa or less and removing water, a master batch A containing 1% by mass of silica particles was obtained.
The pellet A is the same pellet as the pellet A used in Example 1 (the same applies hereinafter).

[Manufacturing of crosslinked polystyrene particles]
After adding 3.2 parts by mass of potassium persulfate and 0.15 parts by mass of sodium lauryl sulfate to 1500 parts by mass of demineralized water and dissolving them uniformly, a mixed solution of 92 parts by mass of styrene and 8 parts by mass of divinylbenzene was added. The polymerization reaction was carried out at 70 ° C. for 24 hours while stirring in a nitrogen gas atmosphere.

80 parts of pellet A and 10 parts of 10% by mass water slurry (alumina sol 520, manufactured by Nissan Chemical Industries, Ltd.) of alumina particles having a particle diameter of 0.10 μm were supplied to a twin-screw kneading extruder to vent holes. Was maintained at a reduced pressure of 1 kPa or less to remove water, thereby obtaining a master batch B containing 1% by mass of alumina particles.

80 parts of pellet A and 10 parts of 10% by mass water slurry of colloidal silica particles (Snowtex YL, manufactured by Nissan Chemical Industries, Ltd.) having a particle diameter of 0.06 μm were supplied to a twin-screw kneading extruder to vent holes. Was maintained at a reduced pressure of 1 kPa or less to remove water, thereby obtaining a master batch C containing 1 wt% of silica particles.

93 parts of pellet A, 2 parts of masterbatch A, and 5 parts of masterbatch C were blended to obtain a mixture X.

42 parts of pellet A, 10 parts of masterbatch B, and 48 parts of masterbatch C were blended to obtain a mixture Y.

After the pellet A, the mixture X and the mixture Y are dried to a moisture content of 50 ppm or less, they are put into an extruder so that the intermediate layer becomes pellet A, melted at 280 ° C., merged and laminated with a layer merging block, and X. A sheet having a three-layer structure having a layer / A layer / Y layer was produced. The extruded melt was brought into close contact with the cooling roll on the X layer side by using an electrostatic application method.
After the longitudinal stretching, a laminated polyester film 5 was obtained in the same manner as in Example 1 except that no coating was performed.

Next, a photosensitive transfer material 5 was obtained in the same manner as in Example 1 except that the laminated polyester film 5 was used instead of the laminated polyester film 1.

<Comparative example 1>
A laminated polyester film 6 was obtained in the same manner as in Example 1 except that the coating liquid 5 for forming a particle-containing layer prepared by mixing each component shown below was used.
Next, a photosensitive transfer material 6 was obtained in the same manner as in Example 1 except that the laminated polyester film 6 was used instead of the laminated polyester film 1.

(Coating liquid 5 for forming a particle-containing layer)
-Polyacrylic (AS-563A, manufactured by Daicel FineChem Co., Ltd., solid content 27.5% by mass): 167 parts-Nonion-based surfactant (Naro Acty (registered trademark) CL95, manufactured by Sanyo Kasei Kogyo Co., Ltd., solid content 100) Mass%): 0.7 parts-Anionic surfactant (Lapisol® A-90, manufactured by Nichiyu Co., Ltd., solid content 1% by mass water-diluted): 111 parts-Carnauba wax dispersion (Cerozole (registered) Trademark) 524, manufactured by Chukyo Yushi Co., Ltd., solid content 30% by mass): 5.2 parts, carbodiimide compound (carbodilite (registered trademark) V-02-L2, manufactured by Nisshinbo Chemical Co., Ltd., solid content 10% by mass, diluted with water) : 21 parts, colloidal silica (Snowtex (registered trademark) XL, manufactured by Nissan Chemical Co., Ltd., solid content 40% by mass): 2.8 parts, water: 691 parts

<Comparative example 2>
The laminated polyester film 7 was prepared in the same manner as in Example 1 except that the particle-containing layer forming coating liquid 6 in which the amount of colloidal silica in the particle-containing layer forming coating liquid 1 was changed to 5.6 parts was used. Obtained.
Next, a photosensitive transfer material 7 was obtained in the same manner as in Example 1 except that the laminated polyester film 7 was used instead of the laminated polyester film 1.

<Measurement>
With respect to the obtained laminated polyester films 1 to 7, the coefficient of kinetic friction, the haze value, and the surface roughness Rp were measured by the above-mentioned measuring methods. The results are shown in Table 1.

[Evaluation of wrinkles caused by lamination]
A PET substrate with a copper layer having a copper layer formed by a sputtering method at a thickness of 200 nm was used on a polyethylene terephthalate (PET) film having a thickness of 100 μm.
Each of the produced photosensitive transfer materials 1 to 7 was cut into a size of 50 cm × 50 cm to obtain a sample piece, and the cover film of the obtained sample piece was peeled off, and the roll temperature was 90 ° C., the linear pressure was 1.0 MPa, and the linear velocity. 4.0 m / min. It was laminated on a PET film with a copper layer under the same laminating conditions. The occurrence of wrinkles at that time was visually observed and evaluated according to the following criteria. The results are shown in Table 1.
(standard)
A: No wrinkles occur.
B: Wrinkles occurred.

The fact that no wrinkles are observed in this evaluation means that the occurrence of wrinkles is suppressed in the laminating step of the resin pattern manufacturing method.

From Table 1, it was found that the occurrence of wrinkles during laminating was suppressed in Examples 1 to 5 as compared with Comparative Examples 1 and 2.

<Examples 100 to 104>
Four PET substrates with a copper layer were produced by forming a copper layer having a thickness of 500 nm on a PET film having a thickness of 188 μm by a sputtering method.
Under the following laminating conditions, each of the photosensitive transfer materials 1 to 5 was bonded to the PET substrate with a copper layer obtained above, and then allowed to stand for 3 hours.
(1) Crimping roll temperature: 120 ° C
(2) Linear pressure: 1.0 MPa
(3) Line speed: 0.5 m / min

After 3 hours, the photosensitive resin layer was exposed through a mask (Duty ratio = 1: 1) for forming a line-and-space pattern having a line width of 10 μm without peeling off the temporary support. An ultra-high pressure mercury lamp was used as the light source for exposure. The exposure amount was adjusted within a range in which the line width of the resin pattern formed by development was 10 μm.

The temporary support was peeled off from the surface of the photosensitive resin layer, and the photosensitive resin layer was developed. Specifically, shower development was carried out for 30 seconds using a 1.0 mass% sodium carbonate aqueous solution at 25 ° C.

The copper layer was etched with a copper etching solution (Kanto Chemical Co., Inc., Cu-02). Specifically, shower etching was performed at 27 ° C. for 40 seconds.

The remaining resin pattern was peeled off using a stripping solution (Kanto Chemical Co., Inc., KP-301). The line width of the obtained copper pattern (conductive pattern) was measured using an optical microscope.
It was confirmed that a conductive pattern of 10 μm, which is a target value of the line width, was formed in any of the photosensitive transfer materials 1 to 5.

2a to 2l: Gripping member 10: Preheating part 20: Stretching part 30: Heat fixing part 40: Heat relaxation part 50: Cooling part 60a, 60b: Circular rail 100: Biaxial stretching machine 200: Film P, Q: Gripping release point MD: Film transport direction (longitudinal direction)
TD: Film width direction L0, L1, L2: Film width

Claims (16)

A step of laminating a photosensitive transfer material having a temporary support and a photosensitive resin layer supported by the temporary support by bringing the outermost layer of the temporary support on the side having the photosensitive resin layer into contact with a substrate. A step of pattern-exposing the photosensitive resin layer and a step of developing the exposed photosensitive resin layer to form a resin pattern are included in this order.
The temporary support has a base material layer and a particle-containing layer containing particles on at least a surface of the base material layer opposite to the photosensitive resin layer side, and has a haze value of less than 0.5%. Yes, and the dynamic friction coefficient between the particle-containing layer and the acrylonitrile butadiene rubber is 0.7 or less.
Resin pattern manufacturing method. The method for producing a resin pattern according to claim 1, wherein the base material layer of the temporary support is a polyester film layer. The method for producing a resin pattern according to claim 2, wherein the base material layer of the temporary support is a biaxially oriented polyester film layer. The method for producing a resin pattern according to any one of claims 1 to 3, wherein the temporary support has a thickness of 30 μm or less. The method for producing a resin pattern according to any one of claims 1 to 4, wherein the temporary support has a thickness of 10 μm or more. The method for producing a resin pattern according to any one of claims 1 to 5, wherein the surface roughness Rp of the particle-containing layer is 0.1 μm to 0.5 μm. The method for producing a resin pattern according to any one of claims 1 to 6, wherein the dynamic friction coefficient is 0.2 or more. The method for producing a resin pattern according to any one of claims 1 to 7, wherein the particle-containing layer contains wax. The method for producing a resin pattern according to any one of claims 1 to 8, wherein the particle-containing layer contains the particles having different average particle diameters. A step of forming a resin pattern on a conductive layer by using the method for producing a resin pattern according to any one of claims 1 to 9.
A method for producing a conductive pattern, comprising a step of etching the conductive layer using the obtained resin pattern as a mask to form a conductive pattern. A polyester film layer and a particle-containing layer containing particles on at least one surface of the polyester film layer, having a haze of less than 0.5%, and the particle-containing layer and acrylonitrile butadiene rubber. A laminated polyester film having a dynamic friction coefficient of 0.7 or less. The laminated polyester film according to claim 11, which is used as a temporary support of a photosensitive transfer material. A photosensitive transfer material having a temporary support and a photosensitive resin layer supported by the temporary support, wherein the temporary support is the laminated polyester film according to claim 11 or 12. A touch panel having a conductive pattern obtained by the method for manufacturing a conductive pattern according to claim 10. A resin pattern obtained by the method for producing a resin pattern according to any one of claims 1 to 9. A touch panel having the resin pattern according to claim 15.

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