JP7275064B2 - Method for manufacturing resin pattern, method for manufacturing conductive pattern, laminated polyester film, photosensitive transfer material, resin pattern, and touch panel - Google Patents

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 a display device with a touch panel such as a capacitive input device (organic electroluminescence (EL) display device, liquid crystal display device, etc.), the electrode pattern corresponding to the sensor in the visible part, the peripheral wiring part, and the lead-out wiring part Circuit wiring such as wiring of

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

A dry film resist, for example, has 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 standpoint of workability and the like, and are also used as supports or protective films for such dry film resists.

As an example of disclosing a technology related to a polyester film, Patent Document 1 discloses that one surface (A) of the polyester film has a three-dimensional average surface roughness of 10 nm or less, and the other surface (B) has a surface specific resistance value of Ω. In the polyester film roll having a logΩ value of 12 or more, the charge amount when pulling out the film from the polyester film roll is in the range of ± 1.5 kV in the pulling speed range of 0 m / min to 120 m / min and is raised A polyester film roll characterized by having 5 or less defects per 50,000 m ² is disclosed.

In Patent Document 2, one surface (A) of the polyester film has a three-dimensional average surface roughness of 10 nm or less, and the other surface (B) has a specific surface resistance value (Ω) in a specific range Polyester A polyester film roll obtained by winding a film, wherein the unwinding charge amount (E) of the polyester film when unwinding the polyester film from the polyester film roll at an unwinding speed of more than 0 m/min and 150 m/min or less is within a specific range, and the number of protruding defects having a height difference of 3 mm or more on the polyester film is 5/5000 m ² or less.

Patent Document 3 discloses a laminated film in which a release layer containing a silicone resin component is provided on at least one side of a polyester film. The relationship between the surface provided and the surface opposite to the metal dynamic friction coefficient (μdM) satisfies the following formula (1), and the center line average roughness (Ra) of the release layer surface is 30 nm or less. A release film is disclosed.
|μdR−μdM|≦0.5 (1)

JP 2005-187779 A JP 2004-196873 A JP-A-2000-11789

2. Description of the Related Art In recent years, along with higher definition in the formation of wiring and the like, there is an increasing demand for higher definition of patterns formed using photosensitive transfer materials such as dry film resists.
The use of an optically advantageous temporary support with a low haze value as a component of a photosensitive transfer material for forming a high-definition pattern has been studied. As a method for obtaining a temporary support with a low haze value, it is conceivable to reduce the number of particles contained in a resin-containing layer conventionally provided on a substrate (support) in a temporary support. However, if the number of particles is simply reduced, there arises a problem that wrinkles are generated when the photosensitive transfer material is laminated with the counter substrate.

The present disclosure has been made in view of the circumstances described above.
An object of one embodiment of the present disclosure is to provide a method for producing a resin pattern in which the generation of wrinkles is suppressed when performing lamination using a photosensitive transfer material.
Another embodiment of the present disclosure aims to provide a method for manufacturing a conductive pattern including the method for manufacturing a resin pattern.
Still another embodiment of the present disclosure aims 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. .
Yet another embodiment of the present disclosure aims to provide a resin pattern or touch panel obtained using the photosensitive transfer material.

The present 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. pattern exposure of the photosensitive resin layer, and development of the exposed photosensitive resin layer to form a resin pattern in this order,
The temporary support has a base layer and a particle-containing layer containing particles on at least the surface of the base layer opposite to the photosensitive resin layer side, and has a haze value of less than 0.5%. and the dynamic friction coefficient between the particle-containing layer and the acrylonitrile-butadiene rubber is 0.7 or less,
A method for manufacturing a resin pattern.
<2> The method for producing a resin pattern according to <1>, wherein the substrate layer of the temporary support is a polyester film layer.
<3> The method for producing a resin pattern according to <2>, wherein the substrate 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 particle-containing layer has a surface roughness Rp of 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 a conductive layer using the resin pattern manufacturing method according to any one of <1> to <9>;
and forming a conductive pattern by etching the conductive layer using the obtained resin pattern as a mask.
<11> A polyester layer and a particle-containing layer containing particles on at least one surface of the polyester film layer, the haze being 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 comprising 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 producing 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 that suppresses the occurrence of wrinkles when performing lamination using a photosensitive transfer material.
According to another embodiment of the present disclosure, it is possible to provide a method for manufacturing a conductive pattern, including the pattern manufacturing method described above.
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 touch panel obtained using the photosensitive transfer material.

It is a top view which shows an example of a 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 implemented with appropriate modifications within the scope of the purpose of the present disclosure.

In the present disclosure, a numerical range represented using "to" means a range including the numerical values described before and after "to" as lower and upper limits. In the numerical ranges described step by step in the present disclosure, upper or lower limits described in a certain numerical range may be replaced with upper or lower limits of other numerical ranges described step by step. In addition, in the numerical ranges described in the present disclosure, upper or lower limits described in a certain numerical range may be replaced with values shown in Examples.
In the present disclosure, the amount of each component in the composition means the total amount of the multiple substances present in the composition unless otherwise specified when there are multiple substances corresponding to each component in the composition. .
In the present disclosure, the term "step" includes not only independent steps, but also if the intended purpose of the step is achieved even if it cannot be clearly distinguished from other steps. .
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, "biaxially oriented" means the property of having molecular orientation in biaxial directions.

In the present disclosure, a combination of two or more preferred aspects is a more preferred aspect.

(Resin pattern manufacturing method and its application, and laminated polyester film)
A method for producing a resin pattern, which is one embodiment of the present disclosure, comprises a photosensitive transfer material having a temporary support and a photosensitive resin layer supported by the temporary support, and placing the photosensitive resin layer on the temporary support. A step of laminating the outermost layer on the side having the side in contact with the substrate (preferably a substrate having a conductive layer) (hereinafter also referred to as a “laminating step”); and a step of developing the exposed photosensitive resin layer to form a resin pattern (hereinafter also referred to as a “development step”). A layer and a particle-containing layer containing particles on at least the surface of the substrate layer opposite to the photosensitive resin layer side, the haze value being less than 0.5%, and the particle-containing layer and acrylonitrile-butadiene The coefficient of dynamic friction with 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) possessed by a touch panel, and the like.

The resin pattern manufacturing method of the present disclosure can suppress the occurrence of wrinkles during lamination by using the photosensitive transfer material having the above configuration.

Although the reason why the resin pattern manufacturing method of the present disclosure produces the above effects is not clear, it is speculated as follows.
In order to meet the demand for high-definition patterning and obtain a temporary support with a low haze value, for example, it is possible to reduce the number of particles contained in a resin-containing layer conventionally provided on a substrate (support). Conceivable. However, if the number of particles is simply reduced, wrinkles will occur when the photosensitive transfer material is laminated with the counter substrate. This is presumably because the slipperiness between the photosensitive transfer material and the lamination roll is impaired during heating during lamination. 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 the particle-containing layer and the acrylonitrile-butadiene rubber By setting the coefficient of dynamic friction to 0.7 or less, the occurrence of wrinkles during lamination is suppressed while ensuring a low haze value of less than 0.5% suitable for forming high-definition resin patterns. it is conceivable that.

On the other hand, documents disclosing conventional photosensitive transfer materials and polyesters that can be applied to photosensitive transfer materials include the above-mentioned Patent Documents 1 to 3. There is no focus on coefficients.

The method for manufacturing a resin pattern of the present disclosure is suitably applied to a method for manufacturing a conductive pattern.
The method for producing a conductive pattern of the present disclosure is not limited as long as it is a method using the method for producing a resin pattern according to the present disclosure, and a resin pattern is formed on a conductive layer using the method for producing a resin pattern according to the present disclosure. 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 an “etching step”).
The method for manufacturing a conductive pattern according to the present disclosure can be suitably used as a method for manufacturing circuit wiring.

The resin pattern manufacturing method according to the present disclosure and the conductive pattern manufacturing method according to the present disclosure are each preferably performed by a roll-to-roll method. The roll-to-roll method uses a substrate that can be wound and unwound as a substrate, and before any step included in the resin pattern manufacturing method or the conductive pattern manufacturing method, the substrate or a structure including the substrate A step of unwinding the body (also referred to as an “unwinding step”), and a step of winding up the substrate or a structure containing the substrate after any of the steps (also referred to as a “winding step”), A method in which at least one of the steps (preferably all steps or all steps other than the heating step) is performed while the substrate or a structure including the substrate is being transported. 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 a manufacturing method applying a roll-to-roll system.

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

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

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 below, including a description of the laminated polyester film of the present disclosure applied as a suitable component thereof. It should be noted that unless otherwise specified, the contents described for each step included in the method for manufacturing a resin pattern according to the present disclosure also apply to each step included in the method for manufacturing a conductive pattern according to the present disclosure. .

<<Lamination process>>
In the method for producing a resin pattern according to the present disclosure, the photosensitive transfer material according to the present disclosure is placed on the outermost layer on the side having the photosensitive resin layer with respect to the temporary support (hereinafter sometimes referred to as the “first surface”). .) is brought into contact with a substrate (preferably a substrate having a conductive layer) to laminate (lamination step).

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

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

When a layer other than a 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 together via a layer other than the cover film.

The method of pressure-bonding the photosensitive film and the substrate is not limited, and may be carried out by superimposing the first surface of the photosensitive transfer material and the substrate and applying pressure and heat using means such as rolls. is preferred. Also, laminator, vacuum laminator, and auto-cut laminator that can further improve productivity can be used for bonding.

[substrate]
The substrate is not limited, and known substrates can be used. The substrate is preferably a substrate having a conductive layer, and more preferably a substrate having a substrate and a conductive layer partially or entirely on the surface of the substrate. The substrate may optionally have any layers other than the conductive layer.

Examples of base materials that constitute the substrate include glass base materials, silicon base materials, and film base materials.

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

Transparent glass substrates include, for example, tempered glass typified by Corning Gorilla Glass. As the transparent glass substrate, for example, materials used in JP-A-2010-86684, JP-A-2010-152809, and JP-A-2010-257492 can be used.

When a film substrate is used, it is preferable to use a film substrate with low optical distortion and/or high transparency. Examples of such film substrates include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetylcellulose, and cycloolefin polymers.

The substrate constituting the substrate used in the roll-to-roll method is preferably a film substrate. Moreover, when manufacturing the circuit wiring for touchscreens by a roll-to-roll method, it is preferable that a base material is a sheet-shaped resin composition.

Examples of the conductive layer include conductive layers used for general circuit wiring or touch panel wiring. The conductive layer is 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 line formation. A metal layer is more preferred, and a copper layer or silver layer is particularly preferred.

The substrate may have a single conductive layer 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.

Materials for the conductive layer include, for example, metals and conductive metal oxides. Metals include, for example, Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag, and Au. Conductive metal oxides include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and _SiO2 . In the present disclosure, "conductivity" means having a volume resistivity of less than 1×10 ⁶ Ωcm. The conductive metal oxide preferably has a volume resistivity of less than 1×10 ⁴ Ωcm.

When manufacturing a resin pattern using a substrate having a plurality of conductive layers, at least one of the plurality of conductive layers preferably contains a conductive metal oxide.

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

<Photosensitive transfer material>
A photosensitive transfer material used in the resin pattern manufacturing method 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 base layer and a particle-containing layer containing particles on at least the surface of the base layer opposite to the photosensitive resin layer side, and has a haze of 0.5%. is less than
In the photosensitive transfer material, the photosensitive resin layer may be laminated directly or via any layer on the temporary support.
In the photosensitive transfer material, an arbitrary layer may be laminated in addition to the particle-containing layer on the side 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 constituent elements>>
The temporary support included in the photosensitive transfer material of the present disclosure has a base layer and a particle-containing layer containing particles on at least the surface of the base layer opposite to the photosensitive resin layer side, and has a haze of 0. 5%, and the dynamic friction coefficient between the particle-containing layer and the acrylonitrile-butadiene rubber is 0.7 or less.

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

In the present disclosure, the dynamic friction coefficient 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 average value of the obtained values to the third decimal place is used as the dynamic friction coefficient in the present disclosure.
-Measurement condition-
Acrylonitrile-butadiene rubber: Product name: White EC270 (rubber sheet manufactured by Kanuki Roller Co., Ltd.) The rubber sheet is cut to the same size as the weight for measurement, and attached to the weight for measurement with a double-faced tape. In addition, "White EC270" has been subjected to antistatic treatment so that the friction coefficient is not affected by electrification, so that the withstand voltage measurement conforming to JIS-L-1094B is 12 V, and the Shore A hardness is 71.
Measuring device: Autograph AG-X (manufactured by Shimadzu Seisakusho)
Measurement atmosphere: Humidity controlled at 23°C and 65% RH

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

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

The average thickness of the temporary support is preferably 100 μm or less, more preferably 30 μm or less. Furthermore, the average thickness of the temporary support is preferably 5 μm or more, 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 layer and particle-containing layer constituting the temporary support, the photosensitive resin layer, and the cover film are included.) is measured by the following method.
Using a scanning electron microscope (SEM), a cross section in the direction perpendicular to the main surface of the photosensitive transfer material (that is, thickness direction) is observed. Based on the observed image obtained, the thickness of the target component is measured at five points. The average thickness of the component of interest is determined by arithmetically averaging the measurements.
The average thickness of the elements constituting the laminated polyester film of the present disclosure (including the polyester film layer and the particle-containing layer) is also measured in the same manner as described above.

The temporary support preferably has optical transparency. Since the temporary support has optical transparency, the photosensitive resin layer can be exposed through the temporary support when exposing the photosensitive resin layer.
In the present disclosure, "having light transparency" means that the transmittance of light at the 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. , is preferably 60% or more, more preferably 70% or more. In the present disclosure, the term “transmittance” refers to the intensity of incident light when light is incident in a direction perpendicular to the main surface of the layer to be measured (that is, the thickness direction). It is the ratio of the intensity of the emitted light that has passed through. 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. Since haze is preferably as small as possible, the lower limit of haze is not limited. If the lower limit of haze is set for convenience, it is 0% or more.
When the haze value of the temporary support is in the above range, in the exposure process, the scattering of light when exposing the photosensitive resin layer supported by the temporary support is effectively suppressed, and the resin pattern after the development process. Distortion, omission, etc. are suppressed, and a resin pattern having a good wall condition can be formed.

A haze value is measured by a method according to JIS K 7105:1981 using a haze meter. The haze value described in this 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 only on one side 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. The particle-containing layer on the side opposite to the photosensitive resin layer is the outermost layer.

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

＝Particles＝
Particles contained in the particle-containing layer include organic particles and inorganic particles.
The particles are preferably inorganic particles from the viewpoint of wrinkle suppression, haze, and durability (for example, thermal stability).

Resin particles are preferable as the organic particles. Examples of 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 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.

Silica particles are not limited, and known silica particles can be used. Silica particles include, for example, fumed silica and colloidal silica.

Fumed silica particles can be obtained, for example, by reacting a compound containing silicon atoms with oxygen and hydrogen in the gas phase. Examples of silicon compounds used as raw materials include silicon halides (eg, silicon chloride).

Colloidal silica particles can be synthesized, for example, by a sol-gel method in which raw material compounds are hydrolyzed and condensed. Raw material compounds for colloidal silica include, for example, alkoxy silicon (eg, tetraethoxysilane) and halogenated silane compounds (eg, diphenyldichlorosilane).

The silica particles may be in the form of 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 diameter of the particles in the particle-containing layer is preferably 0.01 μm or more, more preferably 0.04 μm or more. When the average particle diameter 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 diameter of the particles in the particle-containing layer is preferably 0.4 μm or less, more preferably 0.3 μm or less. When the average particle diameter 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 obtained by arithmetically averaging the particle sizes of 50 particles randomly selected from the scanning electron microscope (SEM) image.

The particle-containing layer may contain a single type of particles, or may contain two or more types of particles.

The content of the particles is preferably 0.01% by mass to 15% by mass with respect to the total mass of the particle-containing layer from the viewpoints of wrinkle generation suppression and haze when the photosensitive transfer material is laminated. 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 one in which particles having different average particle sizes are contained from the viewpoint of adjusting the dynamic friction coefficient. The average particle size referred to here means the median size.
Particles having different average particle sizes are preferably a combination of particles A having an average particle size of less than 100 nm and particles B having an average particle size of 100 nm or more. Particles A and particles B may each be one type of particles or a mixture of two or more types of particles.

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

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

＝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. It can be visually confirmed by a method based on JIS K6220-1 (2001) whether it becomes a liquid when heated.

In the particle-containing layer, one of the preferred factors contributing to the adjustment of the coefficient of dynamic friction is the inclusion of wax.
Specific examples of waxes include plant waxes such as carnauba wax, candelilla wax, rice wax, wood wax, jojoba oil, palm wax, rosin-modified wax, ouricury wax, sugarcane wax, esparto wax, and bark wax; , lanolin, whale wax, wart wax, shellac wax; mineral waxes such as montan wax, ozokerite, ceresin wax; petroleum waxes such as paraffin wax, microcrystalline wax, petrolactam; Fischer-Tropsch wax, polyethylene Synthetic hydrocarbon wax (polyolefin wax) such as wax, oxidized polyethylene wax, polypropylene wax, and oxidized polypropylene wax;

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

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

A resin can function as a binder. Resins include, for example, polyacrylics, polyurethanes, polyesters, and polyolefins. Polyacryl is preferred from the viewpoint of selecting an appropriate hardness as a binder.

The polyacryl 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 acrylic acid esters and methacrylic acid esters, and known polyacryls can be used. Polyacryl may have structural units derived from compounds other than acrylic acid esters and methacrylic acid esters (for example, olefinic compounds and styrene compounds).

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

As the polyester, the polyester described later can be applied, and the preferred types are also the same.

The polyolefin is not limited, and known polyolefins can be used. Polyolefins include, for example, polyethylene and polypropylene.

The particle-containing layer may contain a single resin, or may contain two or more resins.

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

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

Any of anionic, cationic, nonionic (nonionic), or amphoteric surfactants can be used as surfactants. Preferred surfactants are anionic surfactants and nonionic surfactants.

Examples of anionic surfactants include RAPISOL (registered trademark) A-90 (manufactured by NOF Corporation), Sanded BL (manufactured by Sanyo Chemical Industries, Ltd.), and Nikkor SCS (manufactured by Nikko Chemicals Co., Ltd.). Examples of nonionic surfactants include Naloacty (registered trademark) CL95 (manufactured by Sanyo Chemical Industries, Ltd.).
Surfactants include, for example, surfactants described in the Handbook of Surfactant Properties and Performance (Technical Information Association).

Surfactants may be used singly 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, based on the total mass of the particle-containing layer. 0.01% by mass to 3% by mass is more preferred.

Examples of cross-linking agents 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.), Denacol (registered trademark) EX614B ( Nagase ChemteX Corp.), Duranate (registered trademark) WM44 (Asahi Kasei Chemicals Corp.), and the like.

The cross-linking agents may be used singly or in combination of two or more.
Although the content of the cross-linking agent is not particularly limited, it is more preferably 1% by mass to 50% by mass, still more preferably 2% by mass to 20% by mass, relative to the total mass of the particle-containing layer.

From the viewpoint of dynamic friction coefficient, the particle-containing layer preferably has a surface roughness Rp (maximum peak 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 is 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. value.
(measuring device)
Keyence laser microscope "VK-X200"
(Measurement condition)
・Horizontal measurement distance: 276 μm
・Z-axis direction distance: 6.975 μm
・Objective lens: 50x (XY: 135 nm/pixel, Z: 0.1 nm/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, more preferably 0.02 μm to 0.02 μm, from the viewpoint of suitability for manufacturing the particle-containing layer. 0.08 μm is particularly preferred. The thickness of the particle-containing layer is the arithmetic mean value of the thicknesses measured at five locations by the method described above.

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

As a method for forming the temporary support including the particle-containing layer, in addition to coating, known methods such as co-extrusion can be appropriately used. As the coextrusion method, for example, the method disclosed in JP-A-2019-65271 can be used.

The coating liquid for forming the particle-containing layer can be prepared by mixing the above components and a solvent.
Solvents include, for example, 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 viewpoints of environment, safety and economy.

The coating liquid for forming the particle-containing layer may contain a single solvent, or may contain two or more solvents.

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

A coating method is not limited, and a known method can be used. Examples of coating methods include spray coating, slit coating, roll coating, blade coating, spin coating, bar coating, and dip coating.

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

In the temporary support, the resin film constituting the substrate layer includes, for example, 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 of The laminated polyester film preferably has a content of less than 0.5% and a coefficient of dynamic friction between the particle-containing layer and the nitrile-butadiene rubber of 0.7 or less.

The above 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, the temporary support is preferably the laminated polyester film of the present disclosure.

When the particle-containing layer-forming coating liquid is used to form the particle-containing layer on the polyester film layer, the polyester film coated with the particle-containing layer-forming coating liquid may be an unstretched film or a uniaxially stretched film. It may be a film or a biaxially stretched film. From the viewpoint of adhesion between the polyester film substrate and the particle-containing layer, the method for forming the particle-containing layer is preferably a method of applying a particle-containing layer-forming coating liquid onto a uniaxially stretched polyester film. For example, after forming a particle-containing layer by applying a coating liquid for forming a particle-containing layer on a uniaxially stretched polyester film, the uniaxially stretched polyester film layer and the particle-containing layer are simultaneously stretched to obtain a polyester film layer and particles. Adhesion of the containing layer can be improved. A specific drawing method will be described later.

-Biaxially oriented polyester film-
The biaxially oriented polyester film will be described in detail below.
In the present disclosure, "biaxially oriented" means the property of having molecular orientation in biaxial directions.
Molecular orientation is measured using a microwave transmission type molecular orientation meter (for example, MOA-6004, manufactured by Oji Scientific Instruments Co., Ltd.). The angle formed by the two axial directions 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, "width direction" means a direction perpendicular to the longitudinal direction. In addition, when the width direction is unknown, the direction with the highest degree of orientation among the degrees of orientation measured using a microwave transmission type molecular orientation meter (eg, MOA-6004, manufactured by Oji Scientific Instruments Co., Ltd.) is the width direction.

In the present disclosure, the term "orthogonal" is not limited to strictly orthogonal, but includes substantially orthogonal. "Substantially orthogonal" means intersecting at 90° ± 5°, preferably intersecting at 90° ± 3°,
More preferably, they intersect at 90°±1°.

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

Polyester is a polymer having an ester bond in its 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. Polyesters include, for example, polyethylene terephthalate (PET) and polyethylene-2,6-naphthalate (PEN). Among these, 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 the 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 a single polyester, or may contain two or more polyesters.

The polyester content is preferably 85% by mass or more, more preferably 90% by mass or more, and 95% by mass or more relative to 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, and even more preferably 95% by mass or more, relative to the total mass of the biaxially oriented polyester film. 98% by mass or more is particularly preferred. 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 is 90% to 100% by weight with respect to the total weight of polyester in the biaxially oriented polyester film. It is preferably 95% by mass to 100% by mass, more preferably 98% by mass to 100% by mass, and particularly preferably 100% by mass.

(Method for producing polyester)
A 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.

Dicarboxylic acid compounds include, for example, aliphatic dicarboxylic acid compounds, alicyclic dicarboxylic acid compounds, and aromatic dicarboxylic acid compounds.
Diol compounds include, for example, aliphatic diol compounds, alicyclic diol compounds, and aromatic diol compounds.
Examples of catalysts 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 terminal blocking agent can be used for the production of the polyester, if necessary. Terminal blocking agents include, for example, oxazoline compounds, carbodiimide compounds, and epoxy compounds.

As a method for synthesizing the polyester, a known synthesis method can be applied, and for example, the method described in paragraphs 0033 to 0070 of Japanese Patent No. 5575671 can be used. The descriptions of the above publications are 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 haze value is preferably as small as possible, 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, after laminating a photosensitive resin layer (that is, a resist layer) on the film, light scattering is suppressed when exposing by irradiating light such as ultraviolet rays. As a result, the patterning of the resin pattern (resist pattern) obtained after development is suppressed from being distorted, missing, etc., and the condition of the wall surface of the resist pattern is improved. Also, the light transmittance is improved.

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. is more preferred, and 0 to 0.4 is particularly preferred. When the b ^* value in the L ^* a ^* b ^* color system is from 0 to 1, the degree of yellowness of the film can be reduced, and the hue of the film can be made close to colorless. As a result, for example, the biaxially oriented polyester film according to the present disclosure can be preferably applied in applications where high visibility is required (for example, display devices).

The b ^* value in the L ^* a ^* b ^* color system is measured by a transmission method using a spectral color difference meter (eg, SE-2000, manufactured by Nippon Denshoku Industries Co., Ltd.).

= surface roughness SRa =
When a biaxially oriented polyester film is used as a base layer (support) of a dry film resist, one surface (this surface is defined as the surface (A)) has a center line average surface roughness SRa (A) of less than 7 nm and Ten point average surface roughness SRz (A) is less than 400 nm, and the other surface (this surface is defined as surface (B)) has SRa (B) of less than 10 nm and SRz (B) of less than 700 nm is preferred. More preferably, SRz(A) is less than 100 nm and 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 laminate a photosensitive resin layer (resist layer) on the surface (A) side.

By achieving a surface roughness within the above range in the biaxially oriented polyester film, an appropriate smoothness is obtained to suppress the influence of reflection on the film surface during exposure, and a high-definition resist pattern (resin pattern) is formed. At the same time, handling during processing can be obtained. When SRa(B) is 10 nm or more, or SRz(B) is 700 nm or more, reflection of light due to unevenness of the incident angle of light in the exposure process due to unevenness transferred from the film to the resist surface and unevenness. Due to the influence of scattering, the resist pattern tends to come off. 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, SRa(A) is preferably 1 nm or more and less than 7 nm, and SRz(A) is preferably 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 set the surface roughness of the A layer and the B layer within the above range, specific organic particles or inorganic It can be achieved by, for example, containing a specific amount of particles.

＝Particles＝
The biaxially oriented polyester film may contain particles in an area of up to 5% of the film thickness through the thickness from at least one surface. 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 the 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, if a film contains particles within a region of up to 5% of the film thickness from the surface through the thickness, the particles are present throughout the region through the thickness of the surface up to 5% of the film thickness. Alternatively, 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 an area of up to 1% of the film thickness in the thickness direction from at least one surface, and 0.00% of the film thickness in the thickness direction from at least one surface. It is more preferred to have particles within an area of up to 5%, and it is particularly preferred to have particles within an area 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 particles is determined by the method described above.

A biaxially oriented polyester film according to the present disclosure may contain a single type of particles or may contain two or more types of particles.

The content of the particles 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 film winding quality and suppressing transfer failure. , more preferably 0.0005 mass % to 0.005 mass %, and particularly preferably 0.0008 mass % to 0.004 mass %.

＝Thickness＝
The thickness of the biaxially oriented polyester film is preferably 10 μm to 100 μm, more preferably 10 μm to 50 μm, more preferably 12 μm to 40 μm, from the viewpoint of handling suitability (especially 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 is 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, it is preferable that the dimensional change rate is within the following range, since the generation of distortion and wrinkles due to heat shrinkage in the DFR process can be suppressed. The dimensional change rate can be achieved by appropriately adjusting conditions such as relaxation and heat treatment in 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, more preferably 0.5% or more and less than 2% in the longitudinal direction, and more preferably 1% or more and less than 2% in the width direction. Moreover, 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, flatness tends to be better when the photosensitive resin layer (resist layer) is applied.

= F-5 value =
The biaxially oriented polyester film preferably has a strength of 70 MPa or more and less than 150 MPa when the film is stretched by 5% in the longitudinal direction (this value is hereinafter referred to as F-5 value). If the F-5 value in the longitudinal direction is less than 70 MPa, the lack of strength may result in the occurrence of flaws and the like, resulting in poor workability. 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, more preferably 90 MPa or more and less than 130 MPa.

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

＝Breaking strength＝
The longitudinal breaking strength of the biaxially oriented polyester film is preferably 200 MPa or more and less than 360 MPa, 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, 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 transverse directions.

= 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 square piece cut out from the biaxially oriented polyester film is preferably 0 to 200 pieces. The fine particles having a diameter 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 agglomerates having a diameter of 1.5 μm or more and less than 4.5 μm. included. When the primary particles are not perfectly spherical, the diameter of the primary particles is defined as the longest width of the primary particles. When the primary particle aggregates are not perfectly spherical, the diameter of the primary particle aggregates is defined as the longest width of the primary particle aggregates.

When the number of fine particles of 1.5 μm or more and less than 4.5 μm contained in a square piece of 5 mm on a side of the polyester film is 0 to 200, when the focal position during exposure is shifted Thickening of line width and deterioration of resolution can be suppressed. If fine particles with a size of 1.5 μm or more and less than 4.5 μm are present, the effect on the performance is small in normal exposure, but in the case of an exposure method such as direct writing, distortion of the substrate or displacement of the substrate to the stage may occur. If the focus of the exposed portion is shifted due to insufficient adsorption or unevenness of the substrate surface, the influence of light scattering by the fine particles increases. As a result, the line width is thickened and the resolution (especially the removal property) is deteriorated. In the case of fine particles larger than 4.5 μm, the resolution deteriorates even during normal exposure. Therefore, 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, more preferably 0 to 10. It is more preferable to have one, more preferably 0 to 5, and particularly preferably 0 to 1.

From the viewpoint of suppressing thickening of the line width and deterioration of resolution when the focus position during exposure is shifted, the number of fine particles of 1.5 μm or more and less than 4.5 μm contained in the small piece of the polyester film is 180 or less. preferably 150 or less, preferably 120 or less, preferably 100 or less, more preferably 80 or less, more preferably 50 or less, still more preferably 30 or less, and more preferably 20 or less. The number is preferably 15 or less, particularly preferably 10 or less, more preferably 10 or less, and most preferably 5 or less.

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, etc. There is Specific examples of 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, and organic particles such as calcium oxalate. These may be used alone or in combination of two or more.
The fine particles are incorporated into the film according to conventional methods. Methods for producing the polyester film of the present disclosure include, for example, filtering the resin through a filter having a mesh size of 4.5 μm or less.

[Method for producing biaxially oriented polyester film]
A method for producing a biaxially oriented polyester film includes, for example, a method of biaxially stretching an unstretched polyester film obtained by an extrusion molding method.

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

Biaxial stretching may be simultaneous biaxial stretching in which longitudinal stretching and lateral stretching are performed simultaneously, or sequential biaxial stretching in which longitudinal stretching and lateral stretching are divided into two stages or multiple stages of two or more stages. good. Examples of the form of sequential biaxial stretching include, but are not limited to, longitudinal stretching→lateral stretching, longitudinal stretching→lateral stretching→longitudinal stretching, longitudinal stretching→longitudinal stretching→lateral stretching, and lateral stretching→longitudinal stretching. not something. Among the above, longitudinal stretching→lateral stretching is preferable.

The device used for biaxial stretching is not limited, and a known biaxial stretching machine can be used. An example of the biaxial stretching machine will be described below 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-2l attached to each annular rail and movable along the rails. The annular rails 60a and 60b are arranged symmetrically 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 it along the rails.

The biaxial stretching machine 100 has a region consisting of a preheating section 10 , a stretching section 20 , a heat setting 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 stretching section 20 is a region where the preheated film 200 is stretched by applying tension in the direction of the arrow TD (film width direction) that is perpendicular to the direction of the arrow MD (longitudinal direction). For example, as shown in FIG. 1, in the stretching section 20, the film 200 is stretched from width L0 to width L1.

The heat setting part 30 is a region where the tensioned film 200 is heat-fixed while being tensioned.

The heat relaxation part 40 is a region for thermally relaxing the tension of the heat-set film 200 by heating the heat-set film 200 .

The cooling section 50 is the area that cools the thermally 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 section 50 is shown.

Attached to the annular rail 60a are gripping members 2a, 2b, 2e, 2f, 2i and 2j that are movable along the annular rail 60a. Attached to the annular rail 60b are gripping members 2c, 2d, 2g, 2h, 2k and 2l which are movable along the annular rail 60b.

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

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

The gripping members 2a to 2d move along the annular rail 60a or 60b while gripping the ends of the film 200 in the preheating section 10, pass through the stretching section 20, the heat fixing section 30, and the heat relaxation section 40, and reach the cooling section. Proceed to 50. Next, the gripping members 2a and 2b and the gripping members 2c and 2d are arranged at the downstream end of the cooling unit 50 in the direction of the arrow MD (for example, the grip release point P and the grip release point Q in FIG. 1) in order of the transport direction. ), it moves further along the annular rail 60a or 60b and returns to the preheating section 10. As shown in FIG. In the above process, the film 200 moves in the direction of the arrow MD, preheating in the preheating section 10, stretching in the stretching section 20, heat setting in the heat setting section 30, heat relaxation in the heat relaxation section 40, Then, it is cooled in the cooling section 50 and laterally stretched.

The conveying speed of the film 200 can be adjusted by adjusting the moving speed of the gripping members 2a to 2l. Also, the gripping members 2a to 2l can independently change their moving speeds.

As described above, the biaxial stretching machine 100 enables transverse stretching in which the film 200 is stretched in the direction of the arrow TD in the stretching section 20 . 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 movement 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-2l 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 a “longitudinal stretching step”), and a step of stretching the polyester film stretched in the longitudinal direction in the width direction (hereinafter also referred to as a “transverse stretching step”); It is preferred to have

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

The method of melt extrusion includes, for example, a method using an extruder. For example, melt extrusion is carried out using an extruder equipped with one or more screws, heating the polyester to a temperature above its melting point, and rotating the screws for melt-kneading. The polyester is melted in the extruder by heating and screw kneading to form a melt.

The melt is forced out of the extrusion die through gear pumps, filters, and the like. The extrusion die is also simply referred to as "die" (see JIS B8650:2006, a) Extruder, 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) inside the extruder. Further, the extruder is preferably a twin-screw extruder in that 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 contacting the melt with a casting roll and cooling and solidifying the melt on the casting roll. In cooling the melt, it is preferable to blow wind (preferably cold wind) to the melt.

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

When a casting roll is used in the extrusion molding process, it is preferable to increase the adhesion between the casting roll and the melt. Methods for increasing adhesion include, for example, an electrostatic application method, an air knife method, an air chamber method, a vacuum nozzle method, and a touch roll method.

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

(Biaxial stretching)
-Longitudinal 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 longitudinal stretching. By preheating the unstretched polyester film, the polyester film can be easily longitudinally stretched.

The preheating temperature is preferably (Tg - 10 ° C.) to (Tg + 60 ° C.), (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 when transporting the unstretched polyester film is set to the rotation speed of the nip roll A. Faster stretching stretches the unstretched polyester film in the longitudinal direction.

The draw ratio in the longitudinal stretching step is preferably smaller than the draw ratio in the later-described transverse stretching step. The draw ratio in the longitudinal drawing step is preferably 2.0 times to 5.0 times, more preferably 2.5 times to 4.0 times, and 2.8 times 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 preferred. 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 for heating the unstretched polyester film include a method for heating a roll such as a nip roll that contacts the unstretched polyester film. As a method of heating the roll, for example, a method of providing a heater or a pipe through which a hot solvent can flow is provided inside the roll. In addition to the above, there are, for example, a method of applying hot air to 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 near a heat source.

The stretching speed in the longitudinal stretching step is preferably 800%/second to 1500%/second, more preferably 1000%/second to 1400%/second, and 1200%/second to 1400%/second. is particularly preferred. Here, the “stretching speed” is a value obtained by dividing the length Δd of stretching in one second from the length d0 before stretching by the length d0 before stretching, which is expressed as a percentage.

- Lateral stretching process -
In the lateral 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 longitudinally stretched polyester film before transverse stretching. By preheating the polyester film, the polyester film can be easily laterally stretched.

The preheating temperature is preferably from (Tg-10°C) to (Tg+60°C), more preferably from (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 draw ratio in the lateral stretching step is preferably higher than the draw ratio in the longitudinal stretching step. The draw ratio in the transverse drawing step is preferably 3.0 times to 6.0 times, more preferably 3.5 times to 5.0 times, and 3.5 times to 4.5 times. is particularly preferred.

The area ratio represented by the product of the draw ratio in the longitudinal drawing step and the draw ratio in the transverse drawing step is preferably 12.8 times to 15.5 times, more preferably 13.5 times to 15.2 times. 14.0 times to 15.0 times is particularly preferable. When the area magnification is 12.8 times or more, the molecular orientation in the film width direction becomes favorable. Further, when the area magnification is 15.5 times or less, it is easy to maintain a state in which the molecular orientation is not easily relaxed when subjected to heat treatment.

The heating temperature in the lateral 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 preferred. Specifically, the heating temperature in the lateral 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 lateral stretching step is preferably 8%/second to 45%/second, more preferably 10%/second to 30%/second, and 15%/second to 20%/second. is particularly preferred.

When producing a biaxially oriented polyester film having a particle-containing layer, it is preferable to apply the particle-containing layer-forming coating liquid onto the polyester film stretched in the longitudinal direction, and then stretch the film in the transverse direction. 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 process include a heat setting process and a heat relaxation process. The heat treatment step preferably includes at least one of a heat setting step and a heat relaxation step, and more preferably includes a heat setting step and a heat relaxation step.

-Heat setting process-
In the heat setting step, the polyester film stretched in the width direction is heated to be heat set. Since polyester can be crystallized by heat setting, shrinkage of the polyester film can be suppressed.

The heating temperature in the heat setting 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 setting step, the maximum film surface temperature variation 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, particularly preferably 0.5°C to 4.0°C. By adjusting the variation in maximum film surface temperature in the width direction of the film within the above range, the variation in 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 heating the film by radiation. Devices used in the radiation heating method include, for example, infrared heaters.

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

-Thermal relaxation process-
In the thermal relaxation step, the polyester film stretched in the width direction is heated for thermal relaxation. Thermal relaxation can relax the residual strain of the polyester film.

The heating temperature in the thermal relaxation step is preferably lower than the heating temperature in the heat setting step by 5°C or more, more preferably by 15°C or more, and further preferably by 25°C or more. , a temperature lower than 30° C. is particularly preferred.

The lower limit of the heating temperature in the thermal 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 heating the film by radiation. Devices used in the radiation heating method include, for example, infrared heaters.

(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”).

Cooling methods include, for example, a method of blowing air (preferably cold air) to the film, and a method of contacting the film 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 process can be made uniform, so that the expansion coefficient unevenness in the width direction can be reduced. The average cooling rate is determined using a non-contact thermometer (eg radiation thermometer). For example, the cooling time (Z/S) from 150°C to 70°C is determined from the distance Z between the point at which the surface temperature of the film reaches 150°C and the point at which the film surface temperature reaches 70°C, and the transport speed S of the film. demand. The average cooling rate is then determined by calculating (150-70)/(Z/S).

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

In one embodiment, the photosensitive resin layer preferably contains a polymer A, a polymerizable compound B, and a photopolymerization initiator. In one embodiment, the photosensitive resin layer contains 10% to 90% by weight of polymer A, 5% to 70% by weight of polymerizable compound B, and 0% by weight, based on the total weight of the photosensitive resin layer. It preferably contains 0.01% to 20% by weight of photoinitiator. Polymer A, polymerizable compound B, and photopolymerization initiator will be described later.

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

The acid value of the polymer A is preferably 220 mgKOH/g or less, more preferably less than 200 mgKOH/g, from the viewpoint of better resolution by suppressing swelling of the photosensitive resin layer due to the developer. Preferably, less than 190 mg KOH/g is particularly preferred. The lower limit of acid value is not limited. From the viewpoint of better developability, the acid value of polymer A is preferably 60 mgKOH/g or more, more preferably 120 mgKOH/g or more, even more preferably 150 mgKOH/g or more, and 170 mgKOH/g. g or more is particularly preferred. The acid value of the polymer A can be adjusted, for example, by the type of structural units constituting the polymer A and the content of structural units containing acid groups.

In this disclosure, acid number is the mass (mg) of potassium hydroxide required to neutralize 1 g of sample. In this 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 polymer A is preferably from 5,000 to 500,000. A weight average molecular weight of 500,000 or less is preferable from the viewpoint of improving resolution and developability. The weight average molecular weight of polymer A is more preferably 100,000 or less, still more preferably 60,000 or less, and particularly preferably 50,000 or less. On the other hand, a weight average molecular weight of 5,000 or more is preferable from the viewpoint of controlling the properties of development aggregates, edge-fuse properties, and cut-chip properties. The weight average molecular weight of polymer A is more preferably 10,000 or more, still more preferably 20,000 or more, and particularly preferably 30,000 or more. Edge fuseability refers to the extent 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 easiness of chip flying when the unexposed film is cut with a cutter. For example, if a chip adheres to the surface of a photosensitive film, the chip will be transferred to the mask in the exposure process, resulting in defective products.

The dispersity of polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and 1 0 to 3.0 is particularly preferred. In this disclosure, dispersity is the ratio of weight average molecular weight to number average molecular weight (weight average molecular weight/number average molecular weight).

Polymer A preferably has a structural unit derived from a monomer having an aromatic hydrocarbon group from the viewpoint of suppressing widening of line width and deterioration of resolution when the focus position is shifted during exposure.

Aromatic hydrocarbon groups include, for example, substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups.

The content of structural units derived from a monomer having an aromatic hydrocarbon group in the polymer A is preferably 20% by mass or more, and is 30% by mass or more, relative to the total mass of the polymer A. more preferably 40% by mass or more, particularly preferably 45% by mass or more, and most preferably 50% by mass or more. There is no upper limit to the content of structural units derived from monomers having aromatic hydrocarbon groups. The content of structural units derived from a monomer having an aromatic hydrocarbon group in the polymer A is preferably 95% by mass or less, and 85% by mass or less, relative to the total mass of the polymer A. is more preferable. In addition, when the photosensitive resin layer contains a plurality of types of polymers A, the content of structural units derived from monomers having an aromatic hydrocarbon group is obtained as a weight average value.

Examples of monomers having an aromatic hydrocarbon group include monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4- vinyl benzoic acid, styrene dimers, and styrene trimers). The monomer having an aromatic hydrocarbon group is preferably a monomer having an aralkyl group or styrene.

Aralkyl groups include substituted or unsubstituted phenylalkyl groups (excluding benzyl groups) and substituted or unsubstituted benzyl groups, with substituted or unsubstituted benzyl groups being preferred.

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

Examples of monomers having a benzyl group include (meth)acrylates having a benzyl group (e.g., benzyl (meth)acrylate and chlorobenzyl (meth)acrylate), vinyl monomers having a benzyl group (e.g., vinylbenzyl chloride, and vinyl benzyl alcohol). The monomer having a benzyl group is preferably benzyl (meth)acrylate.

In one embodiment, when the structural unit derived from the monomer having an aromatic hydrocarbon group in the polymer A is a structural unit derived from benzyl (meth) acrylate, the benzyl (meth) acrylate monomer in the polymer A The content of structural units derived from the polymer is preferably 50% by mass to 95% by mass, more preferably 60% by mass to 90% by mass, relative to the total mass of polymer A, and 70% by mass. % to 90% by mass, particularly preferably 75% to 90% by mass.

In one embodiment, when the structural unit derived from the monomer having an aromatic hydrocarbon group in the polymer A is a structural unit derived from styrene, the content of the structural unit derived from styrene in the polymer A is With respect to the total mass of polymer A, it is preferably 20% by mass to 50% by mass, more preferably 25% to 45% by mass, even more preferably 30% by mass to 40% by mass, 30 % to 35% by weight is particularly preferred.

A polymer A having structural units 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 monomer 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 constituent units derived from a monomer having an aromatic hydrocarbon group. Polymer A not containing a structural unit derived from a monomer having an aromatic hydrocarbon group contains at least one first monomer (excluding a monomer having an aromatic hydrocarbon group) to be described later. is preferably a polymer obtained by polymerizing, and at least one of the first monomers described later (excluding monomers having an aromatic hydrocarbon group) and the second monomer described later More preferably, it is a copolymer obtained by polymerizing at least one monomer (excluding a monomer having an aromatic hydrocarbon group).

In one embodiment, the polymer A is preferably a polymer obtained by polymerizing at least one of the first monomers described below, and at least one of the first monomers described below and , and at least one of the second monomers described later are more preferably copolymers obtained by polymerizing.

The first monomer is a monomer having a carboxy group and at least one polymerizable unsaturated group in its 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 half ester. The first monomer is preferably (meth)acrylic acid.

The content of structural units derived from the first monomer in polymer A is preferably 5% by mass to 50% by mass, preferably 10% by mass to 40% by mass, based on the total mass of 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, an ester group, and at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include (meth)acrylate compounds, ester compounds of vinyl alcohol, and (meth)acrylonitrile. In the present disclosure, "(meth)acrylonitrile" includes acrylonitrile, methacrylonitrile, or both acrylonitrile and methacrylonitrile.

(Meth)acrylate compounds include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, (Meth)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 mentioned.

Vinyl alcohol ester compounds include, for example, 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. Acrylate is more preferred.

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

From the viewpoint of suppressing line width thickening and deterioration of resolution when the focus position during exposure is shifted, the polymer A contains structural units derived from a monomer having an aralkyl group, and structural units derived from styrene. It preferably contains at least one selected from the group consisting of: For example, polymer A is a copolymer containing a structural unit derived from methacrylic acid, a structural unit derived from benzyl methacrylate, and a structural unit derived from styrene, and a structural unit derived from methacrylic acid, methyl It is preferably at least one selected from the group consisting of copolymers containing structural units derived from methacrylate, structural units derived from benzyl methacrylate, and structural units derived from styrene.

In one embodiment, polymer A contains 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. It is preferably a polymer containing 35% by mass and 30% to 45% by mass of structural units derived from the second monomer.

In one embodiment, 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 structural units derived from the first monomer. It is preferable that the polymer contains up to 25% by mass.

The glass transition temperature (Tg) of polymer A is preferably 30°C to 135°C. In the photosensitive resin layer, when the polymer A has a Tg of 135° C. or lower, it is possible to suppress the thickening of the line width and the deterioration of the resolution when the focal position during exposure is shifted. From the above viewpoint, the Tg of the polymer A is more preferably 130° C. or lower, still more preferably 120° C. or lower, and particularly preferably 110° C. or lower. Moreover, 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 polymer A is more preferably 40° C. or higher, still more preferably 50° C. or higher, particularly preferably 60° C. or higher, and most preferably 70° C. or higher. preferable.

Polymer A may be a commercial product or a synthetic product. Synthesis of polymer A includes, for example, adding a radical polymerization initiator (e.g., benzoyl peroxide or azoiso Butyronitrile) is preferably added in an appropriate amount, followed by heating and stirring. In some cases, the synthesis is performed 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 desired concentration. As a means of synthesis, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.

The photosensitive resin layer may contain one type of polymer A alone, or two or more types of polymer A. When the photosensitive resin layer contains two or more types of polymer A, the photosensitive resin layer contains two or more types of polymer A having a structural unit derived from a monomer having an aromatic hydrocarbon group; Alternatively, a polymer A having a structural unit derived from a monomer having an aromatic hydrocarbon group and a polymer A not containing a structural unit derived from a monomer having an aromatic hydrocarbon group may be included. preferable. In the latter case, the content of the polymer A having a structural unit derived from a monomer having an aromatic hydrocarbon group is preferably 50% by mass or more, relative to the total mass of the polymer A, and 70% by mass. It is more preferably at least 80% by mass, even more preferably at least 90% by mass.

The content 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. 60% by mass is particularly preferred. From the viewpoint of controlling the development time, it is preferable to set the content of the polymer A to 90% by mass or less relative to the photosensitive resin layer. On the other hand, it is preferable from the viewpoint of improving the edge fuse resistance that the content of the polymer A in the photosensitive resin layer is 10% by mass or more.

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

The polymerizable group in the polymerizable compound B is not limited as long as it participates in the polymerization reaction. As the polymerizable group in the polymerizable compound B, for example, a group having an ethylenically unsaturated group (e.g., vinyl group, acryloyl group, methacryloyl group, styryl group, and maleimide group), and a group having a cationic polymerizable group (eg, epoxy group and oxetane group). The polymerizable group is preferably a group having an ethylenically unsaturated group, more preferably an acryloyl group or a methacryloyl group.

The polymerizable compound B is preferably a compound having one or more ethylenically unsaturated groups in one molecule (i.e., an ethylenically unsaturated compound) in that the photosensitive resin layer has more excellent photosensitivity. Compounds having two or more ethylenically unsaturated groups in one molecule (that is, polyfunctional ethylenically unsaturated compounds) are more preferred. Further, 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, from the viewpoint of superior resolution and peelability. More preferably, two or less is particularly preferable.

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

Polymerizable compound B is a compound having two ethylenically unsaturated groups in one molecule (i.e., bifunctional ethylenic unsaturated compound), and a compound having three ethylenically unsaturated groups in one molecule (i.e., trifunctional ethylenically unsaturated compound), preferably at least one selected from the group consisting of A compound having two ethylenically unsaturated groups in is more preferred.

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 difunctional ethylenically unsaturated compounds.

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

In the photosensitive resin layer, the content ratio of the polymerizable compound B1 to the content of the polymerizable compound B is preferably 40% by mass or more, more preferably 50% by mass or more, from the viewpoint of better resolution. 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 it is particularly preferable that it is 85% by mass or less.

Examples of the aromatic ring in the polymerizable compound B1 include aromatic hydrocarbon rings (e.g., benzene ring, naphthalene ring, and anthracene ring), aromatic heterocyclic rings (e.g., thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring and pyridine ring), and condensed rings thereof. The aromatic ring is preferably an aromatic hydrocarbon ring, more preferably a benzene ring. In addition, 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 developer. The bisphenol structure includes, for example, a bisphenol A structure derived from bisphenol A (ie, 2,2-bis(4-hydroxyphenyl)propane), bisphenol F (ie, 2,2-bis(4-hydroxyphenyl)methane). and bisphenol B structures derived from bisphenol B (ie, 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 compounds 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 through one or more alkyleneoxy groups. The alkyleneoxy groups added to both ends of the bisphenol structure are preferably ethyleneoxy groups or propyleneoxy groups, more preferably ethyleneoxy groups. The number of alkyleneoxy groups added to the bisphenol structure is not limited, but is preferably 4 to 16, more preferably 6 to 14, per molecule.

For the polymerizable compound B1 having a bisphenol structure, JP 2016-22416
No. 2, paragraphs 0072 to 0080. The contents of the above publication are incorporated herein by reference.

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

Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)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-(methacryloxypentaethoxy)phenyl)propane (BPE-500, Shin-Nakamura Chemical 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 Co., Ltd.), 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (BPE-200, Shin-Nakamura Chemical Co., Ltd.), and ethoxylated (10) bisphenol A Diacrylate (NK Ester A-BPE-10, Shin-Nakamura Chemical Co., Ltd.) can be mentioned.

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

In general formula (I), R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, A represents C ₂ H ₄ , B represents C ₃ H ₆ , n ₁ and n ₃ are each independently an integer of 1 to 39, n ₁ +n ₃ is an integer of 2 to 40, n ₂ and n ₄ are each independently an integer of 0 to 29 is an integer, and n ₂ +n ₄ is an integer of 0 to 30, and the arrangement of the repeating units of -(AO)- and -(B-O)- is random or even if it is a block good. In the case of a block, either -(AO)- or -(B-O)- may be on the side of the biphenyl group. n ₂ +n ₄ is preferably an integer of 0 to 10, more preferably an integer of 0 to 4, even more preferably an integer of 0 to 2, and particularly preferably 0. In one embodiment, n ₁ +n ₂ +n ₃ +n ₄ is preferably an integer of 2-20, more preferably an integer of 2-16, and particularly preferably an integer of 4-12.

The photosensitive resin layer may contain one polymerizable compound B1 alone or two or more polymerizable compounds B1.

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

The photosensitive resin layer may contain a polymerizable compound B other than the polymerizable compound B1. As the polymerizable compound B other than the polymerizable compound B1, for example, a monofunctional ethylenically unsaturated compound (i.e., a compound having one ethylenically unsaturated group in one molecule), a bifunctional ethylenic compound having no aromatic ring Unsaturated compounds (that is, compounds that do not have an aromatic ring in one molecule and have two ethylenically unsaturated groups), and trifunctional or higher ethylenically unsaturated compounds (that is, in one molecule compounds having 3 or more ethylenically unsaturated groups).

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

Bifunctional ethylenically unsaturated compounds having no aromatic ring include, for example, alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and trimethylolpropane diacrylate.

Alkylene glycol di(meth)acrylates include, for example, tricyclodecanedimethanol diacrylate (A-DCP, Shin-Nakamura Chemical Co., Ltd.), tricyclodecanedimethanol dimethacrylate (DCP, Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, Shin-Nakamura Chemical Co., Ltd.), ethylene glycol dimethacrylate , 1,10-decanediol diacrylate, and neopentyl glycol di(meth)acrylate.

Polyalkylene glycol di(meth)acrylates include, for example, polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di(meth)acrylate.

Urethane di(meth)acrylates include, for example, propylene oxide-modified urethane di(meth)acrylates, and ethylene oxide and propylene oxide-modified urethane di(meth)acrylates. Commercially available products include, for example, 8UX-015A (Taisei Fine Chemical Co., Ltd.), UA-32P (Shin-Nakamura Chemical Co., Ltd.), and UA-1100H (Shin-Nakamura Chemical Co., Ltd.).

Examples of trifunctional or higher ethylenically unsaturated compounds include dipentaerythritol (tri/tetra/penta/hexa) (meth) acrylate, pentaerythritol (tri/tetra) (meth) acrylate, trimethylolpropane tri(meth) Acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanurate tri(meth)acrylate, glycerin tri(meth)acrylate, 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 that includes tri(meth)acrylate and tetra(meth)acrylate.

Examples of alkylene oxide-modified tri- or higher ethylenically unsaturated compounds include caprolactone-modified (meth)acrylate compounds (e.g., KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., and Shin-Nakamura Chemical Co., Ltd. A-9300-1CL manufactured by), alkylene oxide-modified (meth) acrylate compounds (for example, KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E manufactured by Shin-Nakamura Chemical Co., Ltd., Shin-Nakamura Chemical Co., Ltd. and EBECRYL® 135 from Daicel Allnex), ethoxylated glycerin triacrylate (e.g., A-GLY-9E from Shin-Nakamura Chemical Co., Ltd.), Aronix® TO -2349 (Toagosei Co., Ltd.), Aronix M-520 (Toagosei Co., Ltd.), and Aronix M-510 (Toagosei Co., Ltd.).

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

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

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 polymerizable compound B alone or two or more.

The content 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, relative to the total mass of the photosensitive resin layer. Preferably, it is particularly preferably 20% by mass to 50% by mass.

(Optional component)
The photosensitive resin layer may contain components other than the components described above (hereinafter sometimes referred to as “optional components”). Optional components include photopolymerization initiators, dyes, surfactants, and additives other than the above components.

- Photoinitiator -
The photosensitive resin layer preferably contains a photopolymerization initiator. A photopolymerization initiator is a compound that receives actinic rays (eg, ultraviolet rays, visible rays, and X-rays) and initiates polymerization of a polymerizable compound (eg, polymerizable compound B).

The photopolymerization initiator is not limited, and known photopolymerization initiators can be used. Examples of photopolymerization initiators include radical photopolymerization initiators and cationic photopolymerization initiators, and radical photopolymerization initiators are preferred.

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

The photosensitive resin layer contains 2,4,5-triarylimidazole dimer, and 2,4,5-triarylimidazole dimer derivatives. The two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimer and its derivative may be the same or different.

Derivatives of 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-Methoxyphenyl)-4,5-diphenylimidazole dimer.

Examples of photoradical polymerization initiators also include polymerization initiators described in paragraphs 0031 to 0042 of JP-A-2011-95716 and paragraphs 0064 to 0081 of JP-A-2015-14783.

Photoradical polymerization initiators include, for example, ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p,p'-dimethoxybenzyl), and benzophenone.

Examples of commercially available photoradical polymerization initiators include 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 Chemical Industry Co., Ltd.), 1-[4-(phenylthio)]phenyl-1,2-octanedione-2-(O-benzoyloxime) ( Trade name: IRGACURE (registered trademark) OXE-01, BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) (trade 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 B.V.), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane -1-one (trade name: Omnirad 907, IGM Resins B.V.), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methyl Propane-1-one (trade name: Omnirad 127, IGM Resins B.V.), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (trade name: Omnirad 369, IGM) Resins B.V.), 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Omnirad 1173, IGM Resins B.V.), 1-hydroxycyclohexylphenyl ketone (trade name: Omnirad 184, IGM Resins B.V.), 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: Omnirad 651, IGM Resins B.V.), 2,4,6- trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H, IGM Resins B.V.), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819, IGM Resins B.V.); V. Co.), oxime 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, Hampford) and 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer ( trade name: BCTB, Tokyo Chemical Industry Co., Ltd.).

A photocationic polymerization initiator (that is, a photoacid generator) is a compound that generates an acid upon receiving an actinic ray. The photocationic polymerization initiator is preferably a compound that responds to actinic rays having a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid. However, the chemical structure of the photocationic polymerization initiator is not limited. In addition, for photocationic polymerization initiators that do not directly react to actinic rays with a wavelength of 300 nm or more, if they are compounds that react to actinic rays with a wavelength of 300 nm or more and generate an acid by using them in combination with a sensitizer, the sensitizer can be used. It can be preferably used in combination with.

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

Examples of photocationic polymerization initiators include ionic photocationic polymerization initiators and nonionic photocationic polymerization initiators.

Ionic photocationic polymerization initiators include, for example, onium salt compounds (eg, diaryliodonium salt compounds and triarylsulfonium salt compounds) and quaternary ammonium salt compounds.

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

Nonionic photocationic polymerization initiators include, for example, trichloromethyl-s-triazine compounds, diazomethane compounds, imidosulfonate compounds, and oximesulfonate compounds. Examples of trichloromethyl-s-triazine compounds, diazomethane compounds, and imidosulfonate compounds include compounds described in paragraphs 0083 to 0088 of JP-A-2011-221494. Further, the oxime sulfonate compound includes, for example, compounds described in paragraphs 0084 to 0088 of WO 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 include at least one of

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

The content 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, relative to the total mass of the photosensitive resin layer. A content of 1.0% by mass or more is particularly preferable. The upper limit of the content of the photopolymerization initiator is not limited. The content of the photopolymerization initiator is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total mass of the photosensitive resin layer.

-pigment-
The photosensitive resin layer has a maximum absorption wavelength of 450 nm in the wavelength range of 400 nm to 780 nm during color development from the viewpoints of visibility of exposed areas, visibility of unexposed areas, pattern visibility after development, and resolution. In addition to the above, it is preferable to include a dye whose maximum absorption wavelength is changed by an acid, a base, or a radical (hereinafter sometimes referred to as "dye N"). Although the detailed mechanism is unknown, when the photosensitive resin layer contains the dye N, the adhesion between the layers adjacent to the photosensitive resin layer (for example, the temporary support and the intermediate layer) is improved, and the resolution is improved. superior in terms of performance.

In the present disclosure, the term "maximum absorption wavelength changes due to acid, base, or radical" used with respect to a dye means that a dye in a colored state is decolored by an acid, a base, or a radical. It may mean any one of a mode in which the dye in (1) develops color with an acid, a base, or a radical, and a mode in which the dye in a coloring state changes to a coloring state of another hue.

Specifically, the dye N may be a compound that changes from a decolored state to develop color upon exposure, or may be a compound that changes from a developed state to decolor upon exposure. In the above embodiment, the dye N may be a dye that changes its coloring or decoloring state by the action of an acid, a base, or a radical generated by exposure. In addition, the dye N may be a dye that develops or decolors when the state (e.g., pH) of the photosensitive resin layer changes due to acid, base, or radicals generated by exposure. good. On the other hand, the dye N may be a dye that changes its coloring or decoloring state by directly receiving an acid, a base, or a radical as a stimulus without being exposed to light.

Dye N is preferably a dye whose maximum absorption wavelength changes with acid or radicals from the viewpoint of visibility in exposed areas, visibility in unexposed areas, and resolution, and the maximum absorption wavelength changes with radicals. It is more preferable that it is a dye that

From the viewpoints of visibility in exposed areas, visibility in unexposed areas, and resolution, 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. preferably included.

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

Examples of the coloring mechanism of dye N include photoradical polymerization by exposing a photosensitive resin layer containing a photoradical polymerization initiator, a photocationic polymerization initiator (i.e., a photoacid generator), or a photobase generator. A mode in which a radical-reactive dye, an acid-reactive dye, or a base-reactive dye (e.g., a leuco dye) develops color with radicals, acids, or bases generated from an initiator, a photocationic polymerization initiator, or a photobase generator. is mentioned.

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

In addition, the dye N may have one or two or more maximum absorption wavelengths in the wavelength range of 400 nm to 780 nm during color development. When the dye N has two or more maximum absorption wavelengths in the wavelength range of 400 nm to 780 nm during color development, the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths may be 450 nm or more.

The maximum absorption wavelength of Dye N is determined by measuring the transmission spectrum of a solution containing Dye N in the range of 400 nm to 780 nm (liquid temperature 25° C.) using a spectrophotometer (UV3100, Shimadzu Corporation) in an air atmosphere. and by detecting the wavelength at which the light intensity becomes minimum (maximum absorption wavelength).

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

Examples of leuco compounds include leuco compounds having a triarylmethane skeleton (triarylmethane dyes), leuco compounds having a spiropyran skeleton (spiropyran dyes), leuco compounds having a fluorane skeleton (fluoran dyes), and diarylmethane skeletons. a leuco compound (diarylmethane dye), a leuco compound having a rhodamine lactam skeleton (rhodamine lactam dye), a leuco compound having an indolylphthalide skeleton (indolylphthalide dye), and a leuco auramine skeleton Leuco compounds (leuco auramine dyes) can be mentioned. The leuco compound is preferably a triarylmethane-based dye or a fluoran-based dye, and more preferably a leuco compound having a triphenylmethane skeleton (triphenylmethane-based dye) or a fluoran-based dye.

The leuco compound preferably has a lactone ring, a sultine ring, or a sultone ring from the viewpoint of visibility in exposed areas and visibility in non-exposed areas. A lactone ring, a sultine ring, or a sultone ring contained in the leuco compound is reacted with a radical generated from a photoradical polymerization initiator or an acid generated from a photocationic polymerization initiator to change the leuco compound into a ring-closed state. Alternatively, the leuco compound can be changed to a ring-opened state to develop color. The leuco compound is preferably a compound that has a lactone ring, a sultine ring, or a sultone ring and develops a color when the lactone ring, sultine ring, or sultone ring is opened by a radical or an acid. It is more preferable to be a compound that has a lactone ring and opens a lactone ring with a radical or an acid to develop a color.

Specific examples of leuco compounds include p,p′,p″-hexamethyltriaminotriphenylmethane (leuco crystal violet), Pergascript Blue SRB (Ciba-Geigy), crystal violet lactone, malachite green lactone, benzoyl leuco methylene blue, 2 -(N-phenyl-N-methylamino)-6-(Np-tolyl-N-ethyl)aminofluorane, 2-anilino-3-methyl-6-(N-ethyl-p-toluidino)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-chlorofluorane, 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-benzofluorane, 3-(N,N-dibutylamino)-6-methyl-7-anilinofluorane, 3-(N,N-dibutylamino)-6-methyl-7- xylidinofluorane, 3-piperidino-6-methyl-7-anilinofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3,3-bis(1-ethyl-2-methylindole- 3-yl)phthalide, 3,3-bis(1-n-butyl-2-methylindol-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3 -(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-zaphthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2 -methylindol-3-yl)phthalide, and 3′,6′-bis(diphenylamino)spiroisobenzofuran-1(3H),9′-[9H]xanthen-3-one.

Examples of the dye N include dyes. Specific examples of dyes include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsine, methyl violet 2B, quinaldine red, rose bengal, methanyl yellow, thymolsulfophthalein, xylenol blue, methyl orange, paramethyl Red, Congo Fred, Benzopurpurin 4B, α-Naphthyl Red, Nile Blue 2B, Nile Blue A, Methyl Violet, Malachite Green, Parafuchsin, Victoria Pure Blue-Naphthalene Sulfonate, Victoria Pure Blue BOH (Hodogaya Chemical 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, sulforhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxanilino-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-pyrazolones.

Dye N is preferably a dye whose maximum absorption wavelength is changed by radicals from the viewpoints of visibility in exposed areas, visibility in unexposed areas, pattern visibility after development, and resolution, and color is developed by radicals. It is more preferable that it is a dye that

Dye N is preferably leuco crystal violet, crystal violet lactone, brilliant green, or victoria pure blue-naphthalene sulfonate.

The photosensitive resin layer may contain dyes N singly or in combination of two or more.

The content of the dye N is 0.1 mass with respect to the total mass of the photosensitive resin layer, from the viewpoint of the visibility of the exposed area, the visibility of the unexposed area, the pattern visibility after development, and the resolution. % or more, more preferably 0.1% by mass to 10% by mass, even more preferably 0.1% by mass to 5% by mass, and 0.1% by mass to 1% by mass. It is particularly preferred to have

The content ratio of the dye N means the content ratio of the dye when all the dyes N contained in the photosensitive resin layer are in a colored state. A method for quantifying the content of the dye N will be described below using a dye that develops color by radicals as an example. Prepare two solutions of dye (0.001 g) and dye (0.01 g) in methyl ethyl ketone (100 mL). After adding IRGACURE OXE-01 (BASF Corp.) as a radical photopolymerization initiator to each solution obtained, radicals are generated by irradiation with light of 365 nm, and all dyes are brought into a colored state. Next, in an air atmosphere, using a spectrophotometer (UV3100, Shimadzu Corporation), the absorbance of each solution having a liquid temperature of 25° C. is measured to prepare a calibration curve. Then, the absorbance of the solution in which all the dyes are developed is measured in the same manner as described above except that the photosensitive resin layer (3 g) is dissolved in methyl ethyl ketone instead of the dyes. 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-
From the viewpoint of thickness uniformity, the photosensitive resin layer preferably contains a surfactant. Examples of surfactants include anionic surfactants, cationic surfactants, nonionic (nonionic) surfactants, and amphoteric surfactants, with nonionic surfactants being preferred.

Examples of nonionic surfactants include polyoxyethylene higher alkyl ether compounds, polyoxyethylene higher alkylphenyl ether compounds, higher fatty acid diester compounds of polyoxyethylene glycol, silicone nonionic surfactants, and fluorine-based nonionic surfactants. Surfactants are included.

The photosensitive resin layer preferably contains a fluorine-based nonionic surfactant from the viewpoint of better resolution. It is believed that the inclusion of the fluorine-based nonionic surfactant in the photosensitive resin layer suppresses permeation of the etchant into the photosensitive resin layer, thereby reducing side etching. Commercially available fluorine-based nonionic surfactants include, for example, Megafac (registered trademark) F-551, F-552 (DIC Corporation), and Megafac F-554 (DIC Corporation).

Examples of surfactants include surfactants described in paragraphs 0120 to 0125 of International Publication No. 2018/179640, surfactants described in paragraph 0017 of Japanese Patent No. 4502784, and JP-A-2009-237362. Also included are surfactants described in paragraphs 0060 to 0071 of the publication.

The photosensitive resin layer may contain one kind of surfactant alone or two or more kinds of surfactants.

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

-Additive-
The photosensitive resin layer may contain known additives, if necessary, in addition to the above components. Examples of additives include radical polymerization inhibitors, sensitizers, plasticizers, heterocyclic compounds, benzotriazole compounds, carboxybenzotriazole compounds, resins other than polymer A, and solvents. The photosensitive resin layer may contain a single additive or two or more additives.

The photosensitive resin layer may contain a radical polymerization inhibitor. Examples of radical polymerization inhibitors include thermal polymerization inhibitors described in paragraph 0018 of Japanese Patent No. 4502784. Preferably, the radical polymerization inhibitor is phenothiazine, phenoxazine, or 4-methoxyphenol. Radical polymerization inhibitors other than the above include, for example, naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, and diphenylnitrosamine. In order not to impair the sensitivity of the photosensitive resin layer, it is preferred to use a nitrosophenylhydroxyamine aluminum salt as a radical polymerization inhibitor.

The photosensitive resin layer may contain a benzotriazole compound. Benzotriazole compounds include, for example, 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole and bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole.

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

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

The photosensitive resin layer may contain a sensitizer. The sensitizer is not limited, and known sensitizers can be used. Dyes and pigments can also be used as sensitizers. Sensitizers include, for example, dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2,4-triazoles), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds.

The photosensitive resin layer may contain a single sensitizer or two or more sensitizers.

When the photosensitive resin layer contains a sensitizer, the content of the sensitizer can be appropriately selected depending on the purpose. It is preferably 0.01% by mass to 5% by mass, more preferably 0.05% by mass to 1% by mass, relative to the total mass of the photosensitive resin layer.

The photosensitive resin layer may contain at least one selected from the group consisting of plasticizers and heterocyclic compounds. Plasticizers and heterocyclic compounds include, for example, compounds described in paragraphs 0097 to 0103 and paragraphs 0111 to 0118 of WO 2018/179640.

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

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

The photosensitive resin layer contains additives such as metal oxide particles, antioxidants, dispersants, acid multipliers, development accelerators, conductive fibers, thermal radical polymerization initiators, thermal acid generators, and ultraviolet absorbers. , a thickener, a cross-linking agent, an organic suspending agent, and at least one selected from the group consisting of an inorganic suspending agent. Additives are described, for example, in paragraphs 0165 to 0184 of JP-A-2014-85643. 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, still more 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, even more 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 one embodiment, the average thickness of the photosensitive resin layer is preferably 0.1 μm to 15 μm, more preferably 0.5 μm to 5 μm, even more preferably 0.5 μm to 4 μm, Particularly preferred is 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 better adhesion. . The upper limit of transmittance is not restricted. The photosensitive resin layer preferably has a transmittance of 99.9% or less for light with a wavelength of 365 nm.

(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 a photosensitive resin composition to the surface of the temporary support and then drying the coated film of the photosensitive resin composition.

Examples of the photosensitive resin composition include compositions containing a polymer A, a polymerizable compound B, optional components, 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 optional components, and known solvents can be used. Examples of solvents include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (e.g., methanol and ethanol), ketone solvents (e.g., acetone and methyl ethyl ketone), aromatic hydrocarbon solvents (e.g., toluene), Aprotic polar solvents (eg, N,N-dimethylformamide), cyclic ether solvents (eg, tetrahydrofuran), ester solvents, amide solvents, and lactone solvents are included.

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

Alkylene glycol ether solvents include, for example, 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.

Alkylene glycol ether acetate solvents include, for example, 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 WO 2018/179640 and the solvent described in paragraph 0014 of JP-A-2018-177889 may be used. The contents of these are incorporated herein by reference.

The photosensitive resin composition may contain one solvent alone or two or more solvents.

The content ratio of the solvent in the photosensitive resin composition is preferably 50 parts by mass to 1,900 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition, and 100 parts by mass to 900 parts by mass. Part is more preferred.

A method for preparing the photosensitive resin composition is not limited. As a method for preparing the photosensitive resin composition, for example, a solution in which each component is dissolved in a solvent is prepared in advance, and the obtained solutions are mixed in a predetermined ratio to prepare a photosensitive resin composition. method. 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.

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

Also, the photosensitive resin layer may be formed by applying a photosensitive resin composition onto a cover film described later and drying the composition.

<< cover film >>
The photosensitive transfer material preferably has a cover film (also called protective film). The cover film can protect the surface of the layer (for example, photosensitive resin layer) in contact with the cover film. In one embodiment, the photosensitive transfer material more preferably has a cover film in contact with the side of the photosensitive resin layer opposite to the side on which the temporary support is arranged.

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

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

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

The arithmetic mean roughness Ra of the surface of the cover film on which the photosensitive resin layer is arranged is preferably 0.3 μm or less, more preferably 0.1 μm or less, from the viewpoint of better resolution. , 0.05 μm or less. When the surface of the cover film on which the photosensitive resin layer is arranged has an arithmetic mean roughness within the above range, the thickness uniformity of the photosensitive resin layer and the formed resin pattern is improved. The lower limit of the arithmetic mean roughness Ra is not restricted. The arithmetic mean roughness Ra of the surface of the cover film 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 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 section "temporary support".

[Other layers]
The photosensitive transfer material may have layers other than the layers described above (hereinafter referred to as "other layers"). Other layers include thermoplastics, interlayers, and contrast enhancement layers.

(Thermoplastic resin layer)
The photosensitive transfer material may have a thermoplastic resin layer. In one embodiment, 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 bonding to the substrate is improved, and the substrate and the photosensitive transfer material are bonded. This is because the adhesion between the layers is improved as a result of suppressing the inclusion of air bubbles between the layers.

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 upon exposure to 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 JP-A-2014-85643. The contents of the above publication are incorporated herein by reference.

(thickness)
The thickness of the thermoplastic resin layer is not restricted. The average thickness of the thermoplastic resin layer is preferably 1 μm or more, 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 restricted. 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, from the viewpoint of developability and resolution.

(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 of applying a thermoplastic resin composition to the surface of the temporary support and drying the coating film of the thermoplastic resin composition.

Examples of thermoplastic resin compositions include compositions containing the above 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.

Preparation of the thermoplastic resin composition and formation of the thermoplastic resin layer may be carried out according to the method of preparing the photosensitive resin composition and the method of forming the photosensitive resin layer described above. For example, after preparing a thermoplastic resin composition by previously preparing a solution in which each component contained in the thermoplastic resin layer is dissolved in a solvent and mixing the obtained solutions in a predetermined ratio, A 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. Moreover, after forming a photosensitive resin layer on a cover film to be described later, a 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 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 suppression of mixing of components during coating of multiple layers and storage after coating. In the present disclosure, "water-soluble" means that the solubility in 100 g of water at pH 7.0 at a liquid temperature of 22°C 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 during exposure is improved and the time load of the exposure machine is reduced, resulting in improved productivity. 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 if necessary, may contain an additive (eg, surfactant).

The thickness of the intermediate layer is not restricted. The average thickness of the intermediate layer is preferably 0.1 μm to 5 μm, more preferably 0.5 μm to 3 μm. When the thickness of the intermediate layer is within the above range, it is possible to suppress the mixing of components when forming a plurality of layers and during storage without lowering the oxygen barrier property, and the intermediate layer during development. can suppress an increase in the removal time of

A 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 of applying the intermediate layer composition to the surface of the thermoplastic resin layer or the photosensitive resin layer, and then drying the coating film of the intermediate layer composition.

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

(contrast enhancement layer)
A photosensitive film according to the present disclosure may have a contrast enhancement layer. Contrast enhancement layers are described in, for example, paragraph 0134 of WO 2018/179640 and paragraphs 0194 to 0196 of JP-A-2014-85643. The contents of these publications are incorporated herein by reference.

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

The detailed arrangement and specific size of the pattern in pattern exposure are not limited.
When the conductive pattern is applied to the circuit wiring, the display quality of the display device (for example, touch panel) provided with the input device having the circuit wiring is improved, and the area occupied by the lead wiring is reduced. A portion (preferably, the electrode pattern and/or lead wiring portion of the touch panel) preferably includes fine lines with a width of 20 μm or less, and more preferably includes fine lines with a width of 10 μm or less.

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

The exposure dose is preferably 5 mJ/cm ² to 200 mJ/cm ² , more preferably 10 mJ/cm ² to 100 mJ/cm ² .

In the exposure step, pattern exposure may be performed after peeling the temporary support from the photosensitive resin layer, and before peeling the temporary support, pattern exposure is performed through the temporary support, and then the temporary support is peeled off. You may
When the temporary support is peeled off before exposure, the mask may be exposed in contact with the photosensitive layer, or may be exposed in close proximity without contact.
When exposure is performed without peeling off the temporary support, the mask may be exposed in contact with the temporary support, or may be exposed in close proximity without contact. In order to prevent contamination of the mask 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 carry out pattern exposure without peeling off the temporary support.

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

<<development process>>
The resin pattern manufacturing method of the present disclosure includes a step of developing the photosensitive resin layer to form a resin pattern after the exposure step.

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

The developer is preferably an aqueous alkaline solution 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 developer, the developer described in paragraph 0194 of WO 2015/093271 is also preferred.

The development method is not particularly limited, and may be any of puddle 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 showering.

After the development step, it is preferable to remove the development residue by spraying a detergent with a shower and rubbing with a brush.

The liquid temperature of the developer is not limited. The liquid temperature of the developer is preferably 20.degree. C. to 40.degree.

For example, when the photosensitive transfer material contains a thermoplastic resin and an intermediate layer, in the development step, the thermoplastic resin, and intermediate layers are also removed. Moreover, in the development step, the thermoplastic resin layer and the intermediate layer may be removed by dissolving or dispersing in a developer.

<< Etching process >>
In the method for producing a conductive pattern of the present disclosure, a resin pattern is formed on a conductive layer using the method for producing a resin pattern of the present disclosure, and then the resulting resin pattern is used as a mask to etch the conductive layer to obtain a conductive pattern. (etching step).

In the etching step, the conductive layer is etched using the resin pattern as a mask (that is, an etching resist). A known method can be applied as the etching method. As the etching method, for example, the method described in paragraphs 0209 to 0210 of JP-A-2017-120435, the method described in paragraphs 0048 to 0054 of JP-A-2010-152155, and immersion in an etching solution. Wet etching and dry etching (for example, plasma etching) may be used.

The etchant used in the wet etching method may be appropriately selected from acidic or alkaline etchants depending on the object to be etched.

Examples of acidic etching solutions include aqueous solutions of acidic components alone selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid, and acidic components, ferric chloride, A mixed aqueous solution with a salt selected from the group consisting of ammonium fluoride and potassium permanganate. The acidic component may be a combination of multiple acidic components.

Examples of the alkaline etchant include an aqueous solution of an alkaline component alone selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (e.g., tetramethylammonium hydroxide), and , a mixed aqueous solution of an alkali component and a salt (eg, potassium permanganate). The alkaline component may be a component obtained by combining a plurality of alkaline components.

<<Removal process>>
The method for manufacturing a conductive pattern according to the present disclosure preferably includes a step of removing the remaining resin pattern (hereinafter sometimes referred to as a “removal step”). The removing step is preferably performed after the etching step.

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

Examples of the remover include a remover obtained by dissolving an inorganic alkaline component or an organic alkaline component in water, dimethylsulfoxide, N-methylpyrrolidone, or a mixed solution thereof. Examples of inorganic alkaline components include sodium hydroxide and potassium hydroxide. Examples of organic alkali components include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds.

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

<<other processes>>
The method for manufacturing a conductive pattern according to the present disclosure may include arbitrary steps (hereinafter sometimes referred to as “other steps”) other than the steps described above. Other steps include the steps shown below. However, 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 a resin pattern of the present disclosure preferably includes a step of peeling off the cover film from the photosensitive transfer material. A method for peeling off the cover film is not limited, and a known method can be applied.

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

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

For the treatment of reducing the visible light reflectance of the conductive layer, paragraphs 0017 to 0025 of JP-A-2014-150118, and paragraphs 0041, 0042, 0048, and 0058 of JP-A-2013-206315. Are listed. 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 conductive pattern manufacturing method of the present disclosure is applied to the circuit wiring manufacturing method, the steps of forming an insulating film on the surface of the circuit wiring and forming a new conductive layer on the surface of the insulating film. , is also preferred. Through the above steps, two electrode patterns insulated via an insulating film can be formed.

A method for 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 permanent film forming method. Alternatively, an insulating film having a desired pattern may be formed by photolithography using an insulating photosensitive material.

In the step of forming a new conductive layer on the insulating film, for example, a conductive photosensitive material may be used to form a new conductive layer in a desired pattern by photolithography.

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

<<Applications of Resin Patterns and Conductive Patterns>>
The resin pattern manufactured by the resin pattern manufacturing method of the present disclosure and the conductive pattern manufactured by the conductive pattern manufacturing method of the present disclosure can be applied to various uses.

A particularly suitable application target of the resin pattern or conductive pattern is, for example, an input device, preferably a touch panel, more preferably a capacitive touch panel.

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 manufactured by the resin pattern manufacturing method of the present disclosure can be suitably applied as a protective film for circuit wiring provided in a touch panel.

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

Detection methods in touch panels include, for example, a resistive film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method. The detection method is preferably a capacitive method.

As the touch panel type, the so-called in-cell type (for example, the configuration shown in FIGS. 5, 6, 7 and 8 of Japanese Patent Application Laid-Open No. 2012-517051), the so-called on-cell type (for example, Japanese Patent Application Laid-Open No. 2013-168125 The configuration described in FIG. 19, and the configuration described in FIGS. 1 and 5 of JP-A-2012-89102), OGS (One Glass Solution) type, TOL (Touch-on-Lens) type (for example, JP-A 2013-54727), various out-cell types (for example, GG, G1 G2, GFF, GF2, GF1, and G1F), and other configurations (for example, Japanese Patent Application Laid-Open No. 2013-164871 configuration shown in FIG. 6).

EXAMPLES The present disclosure will be described in detail below with reference to Examples, but the present disclosure is not limited to these. "Parts" are based on mass unless otherwise specified.

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

[Stretching and coating]
The unstretched film was successively biaxially stretched by the following method.
(a) Longitudinal Stretching An unstretched film was stretched in the longitudinal direction (conveying direction) by passing it between two pairs of nip rolls having different circumferential speeds. The longitudinal stretching was performed at 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 On one side of the longitudinally stretched film, the following coating liquid 1 for forming a particle-containing layer was coated with a bar coater so as to be 5.6 g/m ² .
(c) Lateral Stretching The longitudinally stretched and coated film was laterally stretched using a tenter under the following conditions.
-conditions-
Preheating temperature: 100°C
Stretching temperature: 120°C
Stretch ratio: 4.2 times Stretching speed: 50%/sec

(Preparation of coating liquid 1 for forming particle-containing layer)
A coating liquid 1 for forming a particle-containing layer was prepared by mixing each component shown below.
・ Polyacrylic (AS-563A, manufactured by Daicel Finechem Co., Ltd., solid content 27.5% by mass): 145 parts ・ Nonionic surfactant (Naroacty (registered trademark) CL95, manufactured by Sanyo Chemical Industries, Ltd., solid content 100 % by mass): 0.7 parts Anionic surfactant (Rapisol (registered trademark) A-90, manufactured by NOF Corporation, solid content 1% by mass diluted with water): 111 parts Carnauba wax dispersion (Cerosol (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 Industries, average particle diameter 50 nm, solid content 10% by mass, diluted with water): 2.8 parts Water: 695 parts

The obtained coating solution was subjected to filtration through a 6 μm filter (F20, manufactured by Mahle Filter Systems Co., Ltd.) and membrane degassing (2×6 radial flow superphobic, manufactured by Polypore Co., Ltd.) before coating after preparation.

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

[Take-up]
After the heat setting and heat relaxation, both ends of the film were trimmed, then the film ends were extruded (knurled) with a width of 10 mm, and then the stretched film was wound with a tension of 40 kg/m. By the above method, a laminated polyester film 1 having a substrate layer (polyester film layer) made of a biaxially oriented polyester film (PET: polyethylene terephthalate) with a thickness of 25 μm and a particle-containing layer with a thickness of 0.04 μm was obtained. . The obtained laminated polyester film 1 had a width of 1.5 m and a winding length of 7000 m.

2. Production of Photosensitive Transfer Material Using the obtained laminated polyester film 1, a photosensitive transfer material 1 was produced 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 K.K.)
"St": Styrene (Fujifilm Wako Pure Chemical Industries, Ltd.)
"V-601": 2,2'-azobis (isobutyrate) dimethyl (Fujifilm Wako Pure Chemical Industries, Ltd., polymerization initiator)

<Polymer A-1>
PGMEA (116.5 parts by mass) was put into a three-necked flask and heated to 90°C in 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) are 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 dropping, the mixture 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 polymer A-1. The acid value of polymer A-1 is 189 mgKOH/g.

<Polymerizable compound B>
As the polymerizable compound B, the compounds shown below were prepared.
・ B-1: NK Ester BPE-500 (2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane, Shin-Nakamura Chemical Co., Ltd.)
・ B-2: Aronix M-270 (polypropylene glycol diacrylate, Toagosei Co., Ltd.)

<Photoinitiator>
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.)

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

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

<Preparation of thermoplastic resin composition>
A thermoplastic resin composition was prepared by mixing the following components.
· Benzyl methacrylate, methacrylic acid, and acrylic acid copolymer (solid content concentration: 30.0% by mass, Mw: 30000, acid value: 153 mgKOH / g): 42.85 parts · NK Ester A-DCP (tricyclo Decane dimethanol diacrylate, Shin-Nakamura Chemical 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 a carboxy group Polyfunctional acrylate compound, Toagosei Co., Ltd.): 0.77 parts Compound having the structure shown below (photoacid generator, compound synthesized according to the method described in paragraph 0227 of JP-A-2013-47765): 0.77 parts 32 copies

- A compound having the structure shown below (a dye that develops color with an 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 intermediate layer composition>
An intermediate layer composition was prepared by mixing the following components.
・Ion-exchanged water: 38.12 parts ・Methanol (Mitsubishi Gas Chemical Co., Ltd.): 57.17 parts ・Kuraray Poval PVA-205 (polyvinyl alcohol, Kuraray Co., Ltd.): 3.22 parts ・Polyvinylpyrrolidone K-30 (stock Company Nippon Shokubai): 1.49 parts ・ Megafac F-444 (fluorine-based nonionic surfactant, DIC Corporation): 0.0015 parts

<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 ( 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 Corporation): 6.93 parts

A thermoplastic resin composition was applied to the surface of the laminated polyester film 1 on the side opposite to the side having the particle-containing layer using a slit-like nozzle to a width of 1.53 m and a thickness of 2.0 m after drying. The thermoplastic resin composition was applied so as to have a thickness of 0 μm. A thermoplastic resin layer was formed by drying the formed coating film of the thermoplastic resin composition at 80° C. for 40 seconds.

The intermediate layer composition was applied to the surface of the formed thermoplastic resin layer using a slit nozzle so that the coating width was 1.53 m and the thickness after drying was 1.0 μm. The coating film of the intermediate layer composition 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 nozzle so that the coating width was 1.53 m and the thickness after drying was 2.0 μm. A 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 mean roughness (Ra value): 0.02 μm, thickness: 16 μm, width: 1.54 m) was crimped onto the surface of the formed photosensitive resin layer as a cover film. By doing so, a photosensitive transfer material 1 was produced. The produced photosensitive transfer material 1 was wound into a roll having a length of 4,000 m.

<Example 2>
A laminated polyester film 2 was obtained in the same manner as in Example 1, except that a coating liquid 2 for forming a particle-containing layer prepared by mixing the components 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 2 for forming particle-containing layer)
・ Polyacrylic (AS-563A, manufactured by Daicel Finechem Co., Ltd., solid content 27.5% by mass): 167 parts ・ Nonionic surfactant (Naroacty (registered trademark) CL95, manufactured by Sanyo Chemical Industries, Ltd., solid content 100 % by mass): 0.7 parts Anionic surfactant (Rapisol (registered trademark) A-90, manufactured by NOF Corporation, solid content 1% by mass diluted with water): 55.7 parts Carnauba wax dispersion (Cerosol (registered trademark) 524, manufactured by Chukyo Yushi Co., Ltd., solid content 30% by mass): 7 parts Carbodiimide compound (Carbodiimide (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 Industries, Ltd., solid content 40% by mass, particles A): 2.8 parts Silica ultrasonic water dispersion (Aerosil OX50, Nippon Aerosil Co., Ltd., solid content 10% by mass, average particle diameter (median diameter) 0.2 μm, particles 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 a coating liquid 3 for forming a particle-containing layer prepared by mixing the components 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 3 for forming particle-containing layer)
・ Polyacrylic (AS-563A, manufactured by Daicel Finechem Co., Ltd., solid content 27.5% by mass): 119 parts ・ Nonionic surfactant (Naroacty (registered trademark) CL95, manufactured by Sanyo Chemical Industries, Ltd., solid content 100 % by mass): 0.7 parts Anionic surfactant (Rapisol (registered trademark) A-90, manufactured by NOF Corporation, solid content 1% by mass diluted with water): 111 parts Carnauba wax dispersion (Cerosol (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 Industries, Ltd., solid content 40% by mass): 2.8 parts Water: 695 parts

<Example 4>
A particle-containing layer-forming coating liquid 4 was used in which the carnauba wax dispersion in the particle-containing layer-forming coating liquid 1 was changed to a polyolefin wax dispersion MGP-055 (manufactured by Maruyoshi Chemical Co., Ltd., solid content: 30% by mass). 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 a 10% by mass aqueous slurry of particles obtained by cross-linking polystyrene with divinylbenzene having a particle size of 0.45 μm (cross-linked polystyrene particles produced by the following method) were supplied to a twin-screw kneading extruder. A masterbatch A containing 1% by mass of silica particles was obtained by removing moisture while keeping the vent hole at a reduced pressure of 1 kPa or less.
In addition, said pellet A is the same pellet as the pellet A used in Example 1 (the same applies hereinafter).

[Production of crosslinked polystyrene particles]
After 3.2 parts by mass of potassium persulfate and 0.15 parts by mass of sodium lauryl sulfate were added to 1500 parts by mass of desalted water and uniformly dissolved, a mixed solution of 92 parts by mass of styrene and 8 parts by mass of divinylbenzene was added. A 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 aqueous slurry of alumina particles with a particle size of 0.10 μm (Aluminasol 520, manufactured by Nissan Chemical Industries, Ltd.) are supplied to a twin-screw kneading extruder, and a vent hole is provided. was maintained at a reduced pressure of 1 kPa or less to remove water, thereby obtaining a masterbatch B containing 1% by mass of alumina particles.

80 parts of pellet A and 10 parts of 10% by mass aqueous slurry of colloidal silica particles (Snowtex YL, manufactured by Nissan Chemical Co., Ltd.) with a particle size of 0.06 μm are supplied to a twin-screw kneading extruder, and vent holes are formed. was maintained at a reduced pressure of 1 kPa or less to remove moisture, thereby obtaining a masterbatch C containing 1 wt % of silica particles.

Mixture X was obtained by blending 93 parts of pellet A, 2 parts of masterbatch A, and 5 parts of masterbatch C.

Mixture Y was obtained by blending 42 parts of Pellets A, 10 parts of Masterbatch B, and 48 parts of Masterbatch C.

After drying the pellet A, the mixture X and the mixture Y to a moisture content of 50 ppm or less, they are put into an extruder so that the intermediate layer becomes the pellet A, melted at 280 ° C., merged and laminated in a layer junction block, and X A sheet having a three-layer structure of layer/A layer/Y layer was produced. The X layer side of the extruded melt was brought into close contact with the cooling roll using an electrostatic application method.
A laminated polyester film 5 was obtained in the same manner as in Example 1, except that coating was not performed after longitudinal stretching.

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 a particle-containing layer-forming coating liquid 5 prepared by mixing the following components 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 particle-containing layer)
・ Polyacrylic (AS-563A, manufactured by Daicel Finechem Co., Ltd., solid content 27.5% by mass): 167 parts ・ Nonionic surfactant (Naroacty (registered trademark) CL95, manufactured by Sanyo Chemical Industries, Ltd., solid content 100 % by mass): 0.7 parts Anionic surfactant (Rapisol (registered trademark) A-90, manufactured by NOF Corporation, solid content 1% by mass diluted with water): 111 parts Carnauba wax dispersion (Cerosol (registered Trademark) 524, manufactured by Chukyo Yushi Co., Ltd., solid content 30% by mass): 5.2 parts Carbodiimide compound (Carbodiimide (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 Industries, Ltd., solid content 40% by mass): 2.8 parts Water: 691 parts

<Comparative Example 2>
A 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>
The dynamic friction coefficient, haze value, and surface roughness Rp of the obtained laminated polyester films 1 to 7 were measured by the measurement methods described above. Table 1 shows the results.

[Evaluation of wrinkles caused by lamination]
A PET substrate with a copper layer was used, which was obtained by forming a copper layer with a thickness of 200 nm on a polyethylene terephthalate (PET) film with a thickness of 100 μm by a sputtering method.
Each of the prepared photosensitive transfer materials 1 to 7 was cut into a size of 50 cm × 50 cm to obtain a sample piece, 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 was 4.0 m/min. was laminated to a PET film with a copper layer under the lamination conditions of . The occurrence of wrinkles at that time was visually observed and evaluated according to the following criteria. Table 1 shows the results.
(standard)
A: No wrinkles.
B: Wrinkles occurred.

The fact that wrinkles are not observed in this evaluation means that wrinkles are suppressed in the lamination step of the method for producing a resin pattern.

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

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

After 3 hours, without removing the temporary support, the photosensitive resin layer was exposed through a mask (Duty ratio=1:1) for forming a line-and-space pattern with a line width of 10 μm. An ultra-high pressure mercury lamp was used as the light source for exposure. The exposure amount was adjusted so that 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 performed for 30 seconds using a 1.0 mass % sodium carbonate aqueous solution at 25°C.

The copper layer was etched using a copper etchant (Kanto Kagaku Co., Ltd., Cu-02). Specifically, shower etching was performed at 27° C. for 40 seconds.

Using a stripping solution (Kanto Kagaku Co., Ltd., KP-301), the remaining resin pattern was stripped. The line width of the resulting copper pattern (conductive pattern) was measured using an optical microscope.
It was confirmed that a conductive pattern with a line width of 10 μm, which is the target line width, was formed in any of the photosensitive transfer materials 1 to 5.

2a to 2l: gripping member 10: preheating unit 20: stretching unit 30: heat setting unit 40: heat relaxation unit 50: cooling unit 60a, 60b: annular rail 100: biaxial stretching machine 200: film P, Q: grip release point MD: Film transport direction (longitudinal direction)
TD: film width direction L0, L1, L2: film width

Claims (13)

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 having the photosensitive resin layer into contact with a substrate; , a step of exposing the photosensitive resin layer in a pattern, and a step of developing the exposed photosensitive resin layer to form a resin pattern, in this order;
The temporary support includes a base layer and a particle-containing layer (excluding an antistatic coating layer) containing particles on at least the surface of the base layer opposite to the photosensitive resin layer side. and a haze value of less than 0.5%, and a dynamic friction coefficient between the particle-containing layer and the acrylonitrile-butadiene rubber of 0.7 or less.
A method for manufacturing a resin pattern. 2. 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. 3. 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. 4. The method for producing a resin pattern according to claim 1, wherein the temporary support has a thickness of 30 μm or less. 5. The method for producing a resin pattern according to claim 1, wherein the temporary support has a thickness of 10 μm or more. 6. The method for producing a resin pattern according to claim 1, wherein the particle-containing layer has a surface roughness Rp of 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. 8. The method for producing a resin pattern according to claim 1, 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 using the resin pattern manufacturing method according to any one of claims 1 to 9;
and forming a conductive pattern by etching the conductive layer using the obtained resin pattern as a mask. It has a polyester film layer and a particle-containing layer (excluding an antistatic coating layer) containing particles on at least one surface of the polyester film layer, and has a haze of less than 0.5%. and a laminated polyester film, wherein the dynamic friction coefficient between the particle-containing layer and the acrylonitrile-butadiene rubber is 0.7 or less. 12. The laminated polyester film according to claim 11, which is used as a temporary support of a photosensitive transfer material. A photosensitive transfer material comprising 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.

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