CN115136073A

CN115136073A - Transfer film, and method for producing laminate

Info

Publication number: CN115136073A
Application number: CN202180015418.8A
Authority: CN
Inventors: 平木大介; 佐藤守正
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2020-02-27
Filing date: 2021-02-25
Publication date: 2022-09-30
Also published as: JPWO2021172455A1; WO2021172455A1

Abstract

The invention provides a transfer film which is excellent in winding property of a temporary support and excellent in resolution when a photosensitive composition layer is subjected to pattern exposure from the temporary support side, and a method for manufacturing a laminate using the transfer film. The transfer film of the present invention comprises a temporary support and a photosensitive composition layer disposed on the temporary support, wherein the temporary support has a haze of less than 30%, and the skewness Rsk of the surface of the temporary support on the photosensitive composition layer side exceeds 0.40.

Description

Transfer film, and method for producing laminate

Technical Field

The present invention relates to a transfer film and a method for manufacturing a laminate.

Background

Since the number of steps for obtaining a predetermined pattern is small, a method of exposing a photosensitive composition layer provided on an arbitrary substrate using a transfer film through a mask and then developing the layer is widely used.

For example, patent document 1 discloses a transfer film (photosensitive film) having a cushion layer between a support layer and a photosensitive layer (photosensitive composition layer).

Prior art documents

Patent document

Patent document 1: japanese patent No. 4479450

Disclosure of Invention

Technical problem to be solved by the invention

On the other hand, when the present inventors studied the characteristics of the transfer film described in patent document 1, they found that there was a problem in winding when the temporary support composed of the support layer and the buffer layer was peeled off after the photosensitive composition layer in the transfer film was laminated on the substrate by a roll-to-roll method, and the temporary support was wound and collected. Specifically, when the temporary support is wound up, wrinkles or square winding deformation occurs, and the temporary support cannot be stably wound up. If such a temporary support cannot be stably wound up, the substrate and the transfer film cannot be continuously transported in a roll-to-roll manner. Hereinafter, the temporary support that can be peeled off from the transfer film is referred to as being excellent in winding-up property of the temporary support.

In addition, the above-mentioned "square winding deformation" means that the winding surface does not have a beautiful curvature of a circular cross section, and an angle deformation point can be seen in some places.

When a pattern is formed using a transfer film, the transfer film is usually attached to a transfer target, and the photosensitive composition layer is pattern-exposed from the temporary support side. Even in this method, the resolution of the formed pattern is required to be excellent.

In view of the above circumstances, an object of the present invention is to provide a transfer film which is excellent in winding-up property of a temporary support and is excellent in resolution when pattern exposure is performed on a photosensitive composition layer from the temporary support side.

Another object of the present invention is to provide a method for producing a laminate using the transfer film.

Means for solving the technical problem

As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved by the following structure.

(1) A transfer film comprising a temporary support and a photosensitive composition layer disposed on the temporary support,

the temporary support has a haze of less than 30%,

the skewness Rsk of the surface of the temporary support on the photosensitive composition layer side exceeds 0.40.

(2) The transfer film according to (1), wherein,

the surface roughness Ra of the surface of the temporary support on the photosensitive composition layer side is less than 0.50 [ mu ] m.

(3) The transfer film according to (1) or (2), wherein,

the root mean square height RMS of the surface of the temporary support on the photosensitive composition layer side is less than 0.70 [ mu ] m.

(4) The transfer film according to any one of (1) to (3),

the temporary support comprises a support and a resin layer disposed on the support,

the resin layer is disposed on the photosensitive composition layer side,

the resin layer has a storage elastic modulus of 20MPa or less at 90 ℃.

(5) The transfer film according to (4), wherein,

when the storage elastic modulus of the resin layer at 90 ℃ is G and the thickness of the resin layer is H, the H/G is more than 0.2 [ mu ] m/MPa.

(6) The transfer film according to (4) or (5), wherein,

the thickness of the resin layer is 60 [ mu ] m or less.

(7) The transfer film according to any one of (4) to (6),

the resin layer includes a resin having repeating units derived from ethylene.

(8) The transfer film according to any one of (1) to (7), wherein,

the temporary support has a haze of 2% or more.

(9) The transfer film according to any one of (1) to (8), wherein,

the surface of the temporary support on the photosensitive composition layer side is subjected to embossing.

(10) A method for manufacturing a laminate, comprising:

a bonding step of bringing the photosensitive composition layer of the transfer film described in any one of (1) to (9) into contact with and bonding to a substrate having a conductive layer to obtain a substrate with a photosensitive composition layer, which has a temporary support, a photosensitive composition layer, and a substrate having a conductive layer in this order;

an exposure step of pattern-exposing the photosensitive composition layer from the temporary support;

a peeling step of peeling the temporary support from the substrate with the photosensitive composition layer; and

and a developing step of developing the exposed photosensitive composition layer to form a pattern.

Effects of the invention

According to the present invention, it is possible to provide a transfer film which is excellent in winding-up property of a temporary support and which is excellent in resolution when a photosensitive composition layer is pattern-exposed from the temporary support side.

Further, according to the present invention, a method for manufacturing a laminate using the transfer film can be provided.

Detailed Description

The present invention will be described in detail below.

In the present specification, the numerical range expressed by the term "to" means a range including numerical values before and after the term "to" as a lower limit value and an upper limit value.

In the numerical ranges recited in the present specification, the upper limit or the lower limit recited in a certain numerical range may be replaced with the upper limit or the lower limit recited in another numerical range recited in a stepwise manner. In the numerical ranges described in the present specification, the upper limit or the lower limit described in a certain numerical range may be replaced with the values shown in the examples.

The term "step" in the present specification is not limited to an independent step, and is also included in the present term as long as the desired purpose of the step can be achieved even when the term cannot be clearly distinguished from other steps.

In the present specification, "transparent" means that the average transmittance of visible light having a wavelength of 400 to 700nm is 80% or more, preferably 90% or more.

The average visible light transmittance is a value measured by a spectrophotometer, and can be measured, for example, by a spectrophotometer U-3310 manufactured by Hitachi, ltd.

In the present specification, unless otherwise specified, the content ratio of each structural unit of the polymer is a molar ratio.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present invention are molecular weights converted using polystyrene as a standard substance, which are detected by THF (tetrahydrofuran) or a differential refractometer using a Gel Permeation Chromatography (GPC) analyzer using a column of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all product names manufactured by TOSOH CORPORATION), unless otherwise specified.

In the present invention, the molecular weight distribution has a molecular weight of a compound having a weight average molecular weight (Mw) unless otherwise specified.

Also, in the present specification, unless otherwise specified, the refractive index is a value measured by an ellipsometer at a wavelength of 550 nm.

In the present specification, "(meth) acrylic acid" is a concept including both acrylic acid and methacrylic acid, and "(meth) acryloyloxy" is a concept including both acryloyloxy and methacryloyloxy.

The transfer film of the present invention is characterized in that the haze of the temporary support and the skewness Rsk of the surface of the temporary support on the photosensitive composition layer side are adjusted to predetermined ranges, respectively.

First, the present inventors studied the problems of the prior art and found that the resolution is improved by adjusting the haze of the temporary support to a predetermined range, and the take-up property of the temporary support is improved by adjusting the skewness Rsk of the surface of the temporary support on the photosensitive composition layer side to a predetermined range. The haze and skewness Rsk can be controlled by adjusting the uneven structure on the surface of the temporary support, the thickness of the temporary support (for example, the thickness of the resin layer in the temporary support), and the like. In particular, the uneven structure on the surface of the temporary support can be controlled by, for example, embossing, which will be described later.

The transfer film of the present invention has a temporary support and a photosensitive composition layer disposed on the temporary support.

Hereinafter, each member constituting the transfer film will be described in detail.

< temporary support >

The transfer film has a temporary support. The temporary support is a member for supporting the photosensitive composition layer described later, and is finally removed by a peeling treatment.

The temporary support has a haze of less than 30%. Among these, from the viewpoint of obtaining at least one effect of a point having more excellent windup property of the temporary support and a point having more excellent resolution when the photosensitive composition layer is subjected to pattern exposure on the temporary support side (hereinafter, also referred to as "point having more excellent effect of the present invention"), it is preferably 20% or less, and more preferably 15% or less. The lower limit is not particularly limited, but may be 2%.

As a method for measuring the haze of the temporary support, the following methods can be mentioned: a sample of the temporary support cut into 5cm square pieces was prepared, and the haze was measured from the surface side showing a predetermined skewness Rsk described later of the sample of the temporary support using a haze meter (model: NDH5000, NIPPON DENSHOKU indestries co., ltd.

The surface of the temporary support on the photosensitive composition layer side has an uneven structure.

The skewness Rsk of the surface of the temporary support on the photosensitive composition layer side exceeds 0.40. Among them, from the viewpoint of further improving the effect of the present invention, it is preferably 0.45 or more, and more preferably 0.50 or more. The upper limit is not particularly limited, but is preferably 1.50 or less, and more preferably 1.20 or less.

The surface roughness Ra of the surface of the temporary support on the photosensitive composition layer side is not particularly limited, but is preferably less than 0.50 μm, more preferably 0.40 μm or less, and further preferably 0.25 μm or less, from the viewpoint of further improving the effect of the present invention. The lower limit is not particularly limited, but is preferably 0.05 μm or more, and more preferably 0.10 μm or more.

The root mean square height RMS of the surface on the photosensitive composition layer side of the temporary support is not particularly limited, but is preferably less than 0.70 μm, more preferably 0.50 μm or less, and further preferably 0.30 μm or less, from the viewpoint of further improving the effect of the present invention. The lower limit is not particularly limited, but is preferably 0.05 μm or more, and more preferably 0.10 μm or more.

The surface of the temporary support was observed (50 times the target) with a laser microscope (VK-X100, manufactured by KEYENCE CORPORATION), and then the above skewness Rsk, surface roughness Ra, and root-mean-square height RMS were calculated according to JIS B0601(2001) using an analysis application (VK-H1 XA, manufactured by KEYENCE CORPORATION).

The temporary support is preferably a film, and more preferably a resin film. As the temporary support, a film which has flexibility and does not undergo significant deformation, shrinkage, or expansion under pressure or under pressure and heat can be used.

Examples of such a film include a polyethylene terephthalate film (for example, a biaxially stretched polyethylene terephthalate film), a cellulose triacetate film, a polystyrene film, a polyimide film, and a polycarbonate film.

Among these, a biaxially stretched polyethylene terephthalate film is preferable as the temporary support.

The film used as the temporary support is preferably free from deformation such as wrinkles, scratches, and the like.

The temporary support may have a single-layer structure or a multilayer structure.

Among them, from the viewpoint of further improving the effect of the present invention, it is preferable that the temporary support has a support and a resin layer disposed on the support, and the resin layer is disposed on the photosensitive composition layer side. That is, the temporary support is preferably a 2-layer structure having a support and a resin layer. When the temporary support has a 2-layer structure including the support and the resin layer, the skewness Rsk of the surface of the resin layer on the side opposite to the support side may be more than 0.40. The surface roughness Ra and the root-mean-square height RMS of the surface of the resin layer on the side opposite to the support are preferably within the above ranges.

The support is preferably a film, and more preferably a resin film. Examples of the resin film include the above-described films.

The resin layer is a layer that functions as a so-called cushion layer.

As a material constituting the resin layer, a thermoplastic resin is preferable. Specific examples thereof include polyolefins such as polyethylene and polypropylene; ethylene copolymers such as copolymers of ethylene and vinyl acetate and saponified products thereof, and copolymers of ethylene and acrylic acid esters and saponified products thereof; vinyl chloride copolymers such as polyvinyl chloride, copolymers of vinyl chloride and vinyl acetate, and saponified products thereof; vinylidene chloride copolymers; styrene copolymers such as polystyrene, copolymers of styrene and (meth) acrylic acid esters, and saponified products thereof; vinyl toluene copolymers such as polyvinyl toluene, copolymers of vinyl toluene and (meth) acrylic acid esters, and saponified products thereof; (meth) acrylate copolymers such as poly (meth) acrylate, a copolymer of butyl (meth) acrylate and vinyl acetate; and polyamide resins such as vinyl acetate copolymer nylon, N-alkoxymethylated nylon, and N-dimethylated nylon.

Among them, from the viewpoint of further improving the effect of the present invention, a resin having a repeating unit derived from ethylene is preferable, and polyethylene or an ethylene copolymer is preferable.

The storage elastic modulus of the resin layer at 90 ℃ is not particularly limited, but is preferably 20MPa or less, more preferably 15MPa or less, and even more preferably 10MPa or less, from the viewpoint of further improving the effects of the present invention. The lower limit is not particularly limited, but is preferably 0.01MPa or more.

The storage elastic modulus of the resin layer at 90 ℃ was determined by the following method.

First, a material constituting the resin layer (for example, particles for forming the resin layer) was dissolved in toluene to prepare a solution having a solid content concentration of 30% by mass, the solution was coated on a lightly peeled polyethylene terephthalate (25WZ, manufactured by TORAY INDUSTRIES, INC.) to a dry thickness of 50 μm, and the dried coating film was peeled to obtain a film for measurement (length: 35mm, width: 12mm) having a prescribed size. Using the obtained film for measurement, dynamic viscoelasticity measurement was performed under the following conditions, and the storage elastic modulus at 90 ℃.

The equipment model is as follows: TA Instrument RSA3

Frequency: 1Hz

Temperature range: raising the temperature from room temperature to 120 ℃ (the temperature raising speed is 5 ℃/min)

When the storage elastic modulus of the resin layer at 90 ℃ is G and the thickness of the resin layer is H, the value of H/G is not particularly limited, but from the viewpoint of more excellent effects of the present invention, it is preferably more than 0.2 μm/MPa, more preferably 0.5 μm/MPa or more. The upper limit is not particularly limited, but is often 15 μm/MPa or less.

The thickness of the resin layer is not particularly limited, but is preferably 60 μm or less from the viewpoint of further improving the effect of the present invention. The lower limit is not particularly limited, but is preferably 1 μm or more.

The thickness of the resin layer is a value obtained by observing a cross section including a direction perpendicular to the main surface of the layer using a Scanning Electron Microscope (SEM), measuring a layer thickness of an arbitrary 10 points or more from the obtained observation image, and calculating an average value thereof.

The temporary support preferably has high transparency, and the transmittance at 365nm is preferably 60% or more, and more preferably 70% or more.

From the viewpoint of pattern formability in pattern exposure through the temporary support and transparency of the temporary support, the number of fine particles, foreign substances, and defects contained in the temporary support is preferably small. The number of particles, foreign matters and defects having a diameter of 1 μm or more is preferably 50/10 mm ² Hereinafter, more preferably 10 pieces/10 mm ² Hereinafter, more preferably 3/10 mm ² The average particle size is preferably 0/10 mm ² 。

The thickness of the temporary support is not particularly limited, but is preferably 5 to 200 μm, and more preferably 10 to 150 μm from the viewpoint of easy handling and versatility.

The above-described uneven structure of the temporary support can be formed by a known method. For example, the above-described uneven structure can be formed by embossing the surface of the support.

< photosensitive composition layer >

The transfer film has a photosensitive composition layer. The photosensitive composition layer can be transferred onto a transfer object, and then exposed and developed to form a pattern on the transfer object.

As the photosensitive composition layer, a known photosensitive composition layer can be used, and may be a positive type or a negative type.

The positive photosensitive composition layer is a photosensitive composition layer in which the solubility of the exposed portion in the developer increases by exposure, and the negative photosensitive composition layer is a photosensitive composition layer in which the solubility of the exposed portion in the developer decreases by exposure.

Among them, the negative photosensitive composition layer is preferably used. When the photosensitive composition layer is a negative photosensitive composition layer, the pattern formed corresponds to the cured layer.

Hereinafter, the components contained in the negative photosensitive composition layer will be described in detail.

[ polymerizable Compound ]

The photosensitive composition layer may contain a polymerizable compound.

The polymerizable compound is a compound having a polymerizable group. Examples of the polymerizable group include a radical polymerizable group and a cation polymerizable group, and a radical polymerizable group is preferable.

The polymerizable compound preferably contains a radical polymerizable compound having an ethylenically unsaturated group (hereinafter, also simply referred to as "ethylenically unsaturated compound").

As the ethylenically unsaturated group, (meth) acryloyloxy group is preferable.

The ethylenically unsaturated compound preferably comprises more than 2 functional ethylenically unsaturated compounds. Here, the "ethylenically unsaturated compound having 2 or more functions" means a compound having 2 or more ethylenically unsaturated groups in one molecule.

As the ethylenically unsaturated compound, a (meth) acrylate compound is preferable.

The ethylenically unsaturated compound preferably contains, for example, a 2-functional ethylenically unsaturated compound (preferably a 2-functional (meth) acrylate compound) and a 3-or more-functional ethylenically unsaturated compound (preferably a 3-or more-functional (meth) acrylate compound) from the viewpoint of film strength after curing.

Examples of the 2-functional ethylenically unsaturated compound include tricyclodecane dimethanol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, and 1, 6-hexanediol di (meth) acrylate.

Examples of commercially available products of the 2-functional ethylenically unsaturated compound include tricyclodecane dimethanol diacrylate [ trade name: NK ESTER a-DCP, Shin Nakamura Chemical co., ltd. manufactured), tricyclodecane dimethanol dimethacrylate [ trade name: NK ESTER DCP, Shin Nakamura Chemical co., ltd. manufactured), 1, 9-nonanediol diacrylate [ trade name: NK ESTER a-NOD-N, Shin Nakamura Chemical co., ltd., manufactured), 1, 10-decanediol diacrylate [ trade name: NK ESTER A-DOD-N, Shin Nakamura Chemical Co., Ltd.,. manufactured by Ltd.,) and 1, 6-hexanediol diacrylate [ trade name: NK ESTER A-HD-N, Shin Nakamura Chemical Co., Ltd.

Examples of the ethylenically unsaturated compound having 3 or more functions include dipentaerythritol (tri/tetra/penta/hexa) (meth) acrylate, pentaerythritol (tri/tetra) (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, isocyanuric acid (meth) acrylate, and glycerol tri (meth) acrylate.

Here, "(tri/tetra/penta/hexa) (meth) acrylate" is a concept including tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (meth) acrylate. Further, "(tri/tetra) (meth) acrylate" is a concept including tri (meth) acrylate and tetra (meth) acrylate.

The upper limit of the number of functional groups of the 3-or more-functional ethylenically unsaturated compound is not particularly limited, and may be, for example, 20-or less-functional, or 15-or less-functional.

Examples of commercially available products of 3-or more-functional ethylenically unsaturated compounds include dipentaerythritol hexaacrylate [ product name: KAYARAD DPHA, SHIN-NAKAMURA CHEMICAL CO, LTD.).

The ethylenically unsaturated compounds more preferably comprise 1, 9-nonanediol di (meth) acrylate or 1, 10-decanediol di (meth) acrylate and dipentaerythritol (tri/tetra/penta/hexa) (meth) acrylate.

Examples of the ethylenically unsaturated compound include caprolactone-modified compounds of (meth) acrylate compounds [ Nippon Kayaku Co., Ltd., KAYARAD (registered trademark) DPCA-20 manufactured by Ltd., Shin Nakamura Chemical Co., Ltd., A-9300-1CL manufactured by Ltd. ], alkylene oxide-modified compounds of (meth) acrylate compounds [ Nippon Kayaku Co., KaYARAD (registered trademark) RP-1040 manufactured by Ltd., Shin Nakamura Chemicalo Co., Ltd., ATM-35E, A-9300 manufactured by Ltd., EBECRYL (registered trademark) 135 manufactured by Ltd., DAICEL-ALLNEX LTD., etc. ], and ethoxylated glycerol ESTERs [ Shin Nakamura Chemical Co., Ltd., NK ESTER A-GLY-9E manufactured by Ltd. ].

As the ethylenically unsaturated compound, a urethane (meth) acrylate compound can also be exemplified. The urethane (meth) acrylate compound is preferably a 3-or more-functional urethane (meth) acrylate compound. Examples of the 3-or more-functional urethane (meth) acrylate compound include 8UX-015A [ Taisei Fine Chemical Co., manufactured by Ltd ], NK ESTER UA-32P [ Shin Nakamura Chemical Co., manufactured by Ltd ], and NK ESTER UA-1100H [ Shin Nakamura Chemical Co., manufactured by Ltd ].

The ethylenically unsaturated compound preferably contains an ethylenically unsaturated compound having an acid group from the viewpoint of improving developability.

Examples of the acid group include a phosphoric acid group, a sulfonic acid group, and a carboxyl group. Among the above, as the acid group, a carboxyl group is preferable.

Examples of the ethylenically unsaturated compound having an acid group include 3 to 4 functional ethylenically unsaturated compounds having an acid group [ a compound having a carboxyl group introduced into a pentaerythritol tri-and tetraacrylate (PETA) skeleton (acid value: 80 to 120mgKOH/g) ] and 5 to 6 functional ethylenically unsaturated compounds having an acid group [ a compound having a carboxyl group introduced into a dipentaerythritol penta-and hexaacrylate (DPHA) skeleton (acid value: 25 to 70 mgKOH/g) ]. The ethylenically unsaturated compound having 3 or more functions of the acid group may be used together with the ethylenically unsaturated compound having 2 functions of the acid group as required.

As the ethylenically unsaturated compound having an acid group, at least one compound selected from the group consisting of an ethylenically unsaturated compound having 2 or more functions of a carboxyl group and a carboxylic anhydride thereof is preferable. When the ethylenically unsaturated compound having an acid group is at least one compound selected from the group consisting of ethylenically unsaturated compounds having 2 or more functions of a carboxyl group and carboxylic acid anhydrides thereof, the developability and the film strength are further improved.

Examples of the ethylenically unsaturated compound having 2 or more functional groups having a carboxyl group include ARONIX (registered trademark) TO-2349 (TOAGOSEI CO., manufactured by LTD.), ARONIX (registered trademark) M-520 (TOAGOSEI CO., manufactured by LTD.), and ARONIX (registered trademark) M-510 (TOAGOSEI CO., manufactured by LTD.).

As the ethylenically unsaturated compound having an acid group, the polymerizable compound having an acid group described in paragraphs [0025] to [0030] of Japanese patent laid-open No. 2004-239942 can be preferably used, and the contents described in this publication are incorporated herein by reference.

The molecular weight of the ethylenically unsaturated compound is preferably 200 to 3,000, more preferably 250 to 2,600, still more preferably 280 to 2,200, and particularly preferably 300 to 2,200.

In the ethylenically unsaturated compound, the content of the ethylenically unsaturated compound having a molecular weight of 300 or less is preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass or less, relative to the content of all the ethylenically unsaturated compounds contained in the photosensitive composition layer.

The photosensitive composition layer may contain 1 kind of ethylenically unsaturated compound alone, or may contain 2 or more kinds of ethylenically unsaturated compounds.

The content of the ethylenically unsaturated compound is preferably 1 to 70% by mass, more preferably 10 to 70% by mass, even more preferably 20 to 60% by mass, and particularly preferably 20 to 50% by mass, based on the total mass of the photosensitive composition layer.

When the photosensitive composition layer contains an ethylenically unsaturated compound having 2 or more functions, a monofunctional ethylenically unsaturated compound may be contained.

When the photosensitive composition layer contains the ethylenically unsaturated compound having 2 or more functions, the ethylenically unsaturated compound having 2 or more functions is preferably the main component in the ethylenically unsaturated compound contained in the photosensitive composition layer.

When the photosensitive composition layer contains the ethylenically unsaturated compound having 2 or more functions, the content of the ethylenically unsaturated compound having 2 or more functions is preferably 60 to 100% by mass, more preferably 80 to 100% by mass, and further preferably 90 to 100% by mass, based on the content of all the ethylenically unsaturated compounds contained in the photosensitive composition layer.

When the photosensitive composition layer contains an ethylenically unsaturated compound having an acid group (preferably, an ethylenically unsaturated compound having 2 or more functional groups having a carboxyl group or a carboxylic anhydride thereof), the content of the ethylenically unsaturated compound having an acid group is preferably 1 to 50% by mass, more preferably 1 to 20% by mass, and still more preferably 1 to 10% by mass, based on the total mass of the photosensitive composition layer.

[ polymerization initiator ]

The photosensitive composition layer may contain a polymerization initiator.

As the polymerization initiator, a photopolymerization initiator is preferable.

Examples of the photopolymerization initiator include a photopolymerization initiator having an oxime ester structure (hereinafter, also referred to as an "oxime-based photopolymerization initiator"), a photopolymerization initiator having an α -aminoalkylphenone structure (hereinafter, also referred to as an "α -aminoalkylphenone-based photopolymerization initiator"), a photopolymerization initiator having an α -hydroxyalkylphenone structure (hereinafter, also referred to as an "α -hydroxyalkylphenone-based polymerization initiator"), a photopolymerization initiator having an acylphosphine oxide structure (hereinafter, also referred to as an "acylphosphine oxide-based photopolymerization initiator"), and a photopolymerization initiator having an N-phenylglycine structure (hereinafter, also referred to as an "N-phenylglycine-based photopolymerization initiator").

The photopolymerization initiator preferably includes at least one selected from the group consisting of an oxime-based photopolymerization initiator, an α -aminoalkylbenzophenone-based photopolymerization initiator, an α -hydroxyalkylphenone-based polymerization initiator, and an N-phenylglycine-based photopolymerization initiator, and more preferably includes at least one selected from the group consisting of an oxime-based photopolymerization initiator, an α -aminoalkylbenzophenone-based photopolymerization initiator, and an N-phenylglycine-based photopolymerization initiator.

Further, examples of the photopolymerization initiator that can be used include the polymerization initiators described in paragraphs [0031] to [0042] of Japanese patent application laid-open No. 2011-095716 and paragraphs [0064] to [0081] of Japanese patent application laid-open No. 2015-014783.

Examples of commercially available photopolymerization initiators include 1- [4- (phenylthio) ] phenyl-1, 2-octanedione-2- (O-benzoyloxime) [ trade name: IRGACURE (registered trademark) OXE-01, manufactured by BASF corporation), 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone-1- (O-acetyloxime) [ trade name: IRGACURE (registered trademark) OXE-02, manufactured by BASF corporation), 8- [5- (2, 4, 6-trimethylphenyl) -11- (2-ethylhexyl) -11H-benzo [ a ] carbazolyl ] [2- (2, 2, 3, 3-tetrafluoropropoxy) phenyl ] methanone- (O-acetyloxime) [ product name: IRGACURE (registered trademark) OXE-03, manufactured by BASF corporation, 1- [4- [4- (2-benzofuranylcarbonyl) phenyl ] thio ] phenyl-4-methyl-1-pentanone-1- (O-acetyloxime) [ trade name: IRGACURE (registered trademark) OXE-04, manufactured by BASF corporation), 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl ] -1-butanone [ trade name: IRGACURE (registered trademark) 379EG manufactured by BASF corporation, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (trade name: IRGACURE (registered trademark) 907, manufactured by BASF corporation), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) benzyl ] phenyl } -2-methylpropan-1-one [ trade name: IRGACURE (registered trademark) 127, manufactured by BASF corporation), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 [ trade name: IRGACURE (registered trademark) 369 manufactured by BASF corporation, 2-hydroxy-2-methyl-1-phenyl-propan-1-one [ trade name: IRGACURE (registered trademark) 1173, manufactured by BASF corporation, 1-hydroxycyclohexyl phenyl ketone [ trade name: IRGACURE (registered trademark) 184, manufactured by BASF corporation), 2-dimethoxy-1, 2-diphenylethan-1-one [ trade name: IRGACURE 651, BASF corporation) and oxime ester compounds [ trade name: lunar (registered trademark) 6, manufactured by DKSH Japan K.K. ].

The photosensitive composition layer may contain 1 kind of photopolymerization initiator alone, or may contain two or more kinds of photopolymerization initiators.

The content of the photopolymerization initiator is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more, based on the total mass of the photosensitive composition layer. The upper limit of the content of the photopolymerization initiator is preferably 10 mass% or less, and more preferably 5 mass% or less, based on the total mass of the photosensitive composition layer.

[ alkali-soluble resin ]

The photosensitive composition layer may include an alkali-soluble resin.

The photosensitive composition layer contains an alkali-soluble resin, and thus the solubility of the photosensitive composition layer (unexposed portion) in the developer is improved.

As the alkali-soluble resin, alkali-soluble acrylic resin is preferable.

The alkali-soluble acrylic resin will be described in detail below.

In the present invention, the term "alkali-soluble" means that the dissolution rate is 0.01 μm/sec or more as determined by the following method.

A coating film (thickness: 2.0 μm) of a target compound (for example, a resin) was formed by applying a propylene glycol monomethyl ether acetate solution having a concentration of 25% by mass to a glass substrate, and then heating the solution in an oven at 100 ℃ for 3 minutes. The dissolution rate (. mu.m/sec) of the coating film was determined by immersing the coating film in a 1 mass% aqueous solution of sodium carbonate (liquid temperature 30 ℃).

In addition, when the target compound is insoluble in propylene glycol monomethyl ether acetate, the target compound is dissolved in an organic solvent (e.g., tetrahydrofuran, toluene, or ethanol) having a boiling point of less than 200 ℃ other than propylene glycol monomethyl ether acetate.

The alkali-soluble acrylic resin is not limited as long as it is an acrylic resin having the alkali solubility described above. Here, the "(meth) acrylic resin" refers to a resin containing at least one of a structural unit derived from (meth) acrylic acid and a structural unit derived from a (meth) acrylate ester.

The total proportion of the structural unit derived from (meth) acrylic acid and the structural unit derived from (meth) acrylic acid ester in the alkali-soluble acrylic resin is preferably 30 mol% or more, more preferably 50 mol% or more, based on the total amount of the alkali-soluble acrylic resin.

In the present invention, when the content of the "structural unit" is specified in terms of a mole fraction (molar ratio), the above-mentioned meaning of the "structural unit" is the same as that of the "monomer unit" unless otherwise specified. Also, in the present invention, when the resin or polymer has 2 or more specific structural units, the content of the above specific structural unit means the total content of the above 2 or more specific structural units unless otherwise specified.

The alkali-soluble acrylic resin preferably has a carboxyl group from the viewpoint of developability. As a method for introducing a carboxyl group into an alkali-soluble acrylic resin, for example, a method for synthesizing an alkali-soluble acrylic resin using a monomer having a carboxyl group is cited. By the above method, a monomer having a carboxyl group is introduced into the alkali-soluble acrylic resin as a structural unit having a carboxyl group. Examples of the monomer having a carboxyl group include acrylic acid and methacrylic acid.

The alkali-soluble acrylic resin may have 1 carboxyl group, or may have 2 or more carboxyl groups. The number of the structural units having a carboxyl group in the alkali-soluble acrylic resin may be 1, or 2 or more.

The content of the structural unit having a carboxyl group is preferably 5 to 50 mol%, more preferably 5 to 40 mol%, and further preferably 10 to 30 mol% with respect to the total amount of the alkali-soluble acrylic resin.

The alkali-soluble acrylic resin preferably has a structural unit containing an aromatic ring from the viewpoint of moisture permeability and strength after curing. The structural unit having an aromatic ring is preferably a structural unit derived from a styrene compound.

Examples of the monomer forming a structural unit having an aromatic ring include a monomer forming a structural unit derived from a styrene compound and benzyl (meth) acrylate.

Examples of the monomer forming the structural unit derived from the styrene compound include styrene, p-methylstyrene, α, p-dimethylstyrene, p-ethylstyrene, p-tert-butylstyrene, tert-butylstyrene and 1, 1-diphenylethylene, with styrene or α -methylstyrene being preferred and styrene being more preferred.

The structural unit having an aromatic ring in the alkali-soluble acrylic resin may be 1 kind alone, or 2 or more kinds.

When the alkali-soluble acrylic resin has a structural unit having an aromatic ring, the content of the structural unit having an aromatic ring is preferably 5 to 90 mol%, more preferably 10 to 80 mol%, and further preferably 15 to 70 mol% with respect to the total amount of the alkali-soluble acrylic resin.

The alkali-soluble acrylic resin preferably contains a structural unit having an alicyclic skeleton from the viewpoints of viscosity and strength after curing.

The alicyclic ring in the alicyclic skeleton may be monocyclic or polycyclic, and examples thereof include a dicyclopentane ring, a cyclohexane ring, an isophorone ring, and a tricyclodecane ring. Among the above, the alicyclic ring in the alicyclic skeleton is preferably a tricyclodecane ring.

Examples of the monomer forming a structural unit having an alicyclic skeleton include dicyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate.

The number of structural units having an alicyclic skeleton in the alkali-soluble acrylic resin may be 1 or 2 or more.

When the alkali-soluble acrylic resin has a structural unit having an aliphatic ring skeleton, the content of the structural unit having an aliphatic ring skeleton is preferably 5 to 90 mol%, more preferably 10 to 80 mol%, and further preferably 10 to 60 mol% with respect to the total amount of the alkali-soluble acrylic resin.

The alkali-soluble acrylic resin preferably has a reactive group from the viewpoint of viscosity and strength after curing.

The reactive group is preferably a radical polymerizable group, and more preferably an ethylenically unsaturated group. Also, when the alkali-soluble acrylic resin has an ethylenically unsaturated group, the alkali-soluble acrylic resin preferably has a structural unit having an ethylenically unsaturated group on a side chain.

In the present invention, "main chain" represents a relatively longest connecting chain in a molecule of a polymer compound constituting a resin, and "side chain" represents an atomic group branched from the main chain.

As the ethylenically unsaturated group, a (meth) acryloyl group or a (meth) acryloyloxy group is preferable, and a (meth) acryloyloxy group is more preferable.

The number of the structural units having an ethylenically unsaturated group in the alkali-soluble acrylic resin may be 1 single type or 2 or more types.

When the alkali-soluble acrylic resin has a structural unit having an ethylenically unsaturated group, the content of the structural unit having an ethylenically unsaturated group is preferably 5 to 70 mol%, more preferably 10 to 50 mol%, and further preferably 15 to 40 mol% with respect to the total amount of the alkali-soluble acrylic resin.

Examples of a method for introducing a reactive group into an alkali-soluble acrylic resin include a method in which an epoxy compound, a blocked isocyanate compound, an isocyanate compound, a vinyl sulfone compound, an aldehyde compound, a methylol compound, a carboxylic anhydride, and the like are reacted with a hydroxyl group, a carboxyl group, a primary amino group, a secondary amino group, an acetoacetyl group, a sulfonic acid, and the like.

As a preferred example of the method for introducing a reactive group into an alkali-soluble acrylic resin, there is a method in which an alkali-soluble acrylic resin having a carboxyl group is synthesized by a polymerization reaction, and then a glycidyl (meth) acrylate is reacted with a part of the carboxyl group of the alkali-soluble acrylic resin by a polymer reaction to introduce a (meth) acryloyloxy group into the alkali-soluble acrylic resin. By the above method, an alkali-soluble acrylic resin having a (meth) acryloyloxy group on a side chain can be obtained.

The polymerization reaction is preferably carried out at a temperature of 70 to 100 ℃, more preferably 80 to 90 ℃. As the polymerization initiator used for the above polymerization reaction, an azo-based initiator is preferable, and for example, V-601 (product name) or V-65 (product name) manufactured by FUJIFILM Wako Pure Chemical Corporation is more preferable. The polymerization reaction is preferably carried out at a temperature of 80 to 110 ℃. In the above-mentioned polymerization reaction, a catalyst such as an ammonium salt is preferably used.

The weight average molecular weight (Mw) of the alkali-soluble acrylic resin is preferably 10,000 or more, more preferably 10,000 to 100,000, and further preferably 15,000 to 50,000.

From the viewpoint of developability, the acid value of the alkali-soluble acrylic resin is preferably 50mgKOH/g or more, more preferably 60mgKOH/g or more, still more preferably 70mgKOH/g or more, and particularly preferably 80mgKOH/g or more. In the present invention, the acid value of the alkali-soluble acrylic resin is represented by JIS K0070: 1992.

From the viewpoint of suppressing dissolution into the developer, the upper limit of the acid value of the alkali-soluble acrylic resin is preferably 200mgKOH/g or less, and more preferably 150mgKOH/g or less.

From the viewpoint of pattern formability and reliability, the content of the residual monomer in each structural unit of the alkali-soluble resin in the photosensitive composition layer is preferably 1000 mass ppm or less, more preferably 500 mass ppm or less, and further preferably 100 mass ppm or less, with respect to the total mass of the alkali-soluble resin. The lower limit is not particularly limited, but is preferably 0.1 mass ppm or more, and more preferably 1 mass ppm or more.

Specific examples of the alkali-soluble acrylic resin are shown below. The content ratio (molar ratio) of each structural unit in the alkali-soluble acrylic resin described below can be appropriately set according to the purpose.

[ chemical formula 1]

[ chemical formula 2]

[ chemical formula 3]

The photosensitive composition layer may contain 1 alkali-soluble resin alone, or may contain 2 or more alkali-soluble resins.

From the viewpoint of developability, the content of the alkali-soluble resin is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and still more preferably 25 to 70% by mass, based on the total mass of the photosensitive composition layer.

[ Polymer comprising structural units having Carboxylic anhydride Structure ]

The photosensitive composition layer may further contain, as a binder, a polymer containing a structural unit having a carboxylic anhydride structure (hereinafter, also referred to as "polymer B"). The photosensitive composition layer contains the polymer B, and thus the developability and the strength after curing can be improved.

The carboxylic anhydride structure may be either a chain carboxylic anhydride structure or a cyclic carboxylic anhydride structure, and a cyclic carboxylic anhydride structure is preferred.

The ring of the cyclic carboxylic anhydride structure is preferably a 5-to 7-membered ring, more preferably a 5-or 6-membered ring, and still more preferably a 5-membered ring.

The structural unit having a carboxylic anhydride structure is preferably a structural unit containing in the main chain a 2-valent group obtained by removing 2 hydrogen atoms from a compound represented by the following formula P-1 or a structural unit in which a 1-valent group obtained by removing 1 hydrogen atom from a compound represented by the following formula P-1 is bonded to the main chain directly or via a 2-valent linking group.

[ chemical formula 4]

In the formula P-1, R ^A1a Represents a substituent, n ^1a R is ^A1a May be the same or different, Z ^1a Denotes a 2-valent group forming a ring containing-C (═ O) -O-C (═ O) -, n ^1a Represents an integer of 0 or more.

As a group consisting of R ^A1a Examples of the substituent include an alkyl group.

As Z ^1a The alkylene group has preferably 2 to 4 carbon atoms, more preferably 2 or 3 carbon atoms, and still more preferably 2 carbon atoms.

n ^1a Represents an integer of 0 or more. Z ^1a When n represents an alkylene group having 2 to 4 carbon atoms ^1a Preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and further preferably 0.

When n is ^1a When an integer of 2 or more is represented, a plurality of R's are present ^A1a May be the same or different. And, there are a plurality of R ^A1a The ring may be formed by bonding to each other, but preferably the ring is formed by not bonding to each other.

The structural unit having a carboxylic anhydride structure is preferably a structural unit derived from an unsaturated carboxylic anhydride, more preferably a structural unit derived from an unsaturated cyclic carboxylic anhydride, still more preferably a structural unit derived from an unsaturated alicyclic carboxylic anhydride, particularly preferably a structural unit derived from maleic anhydride or itaconic anhydride, and most preferably a structural unit derived from maleic anhydride.

The number of the structural units having a carboxylic anhydride structure in the polymer B may be 1 or 2 or more.

The content of the structural unit having a carboxylic anhydride structure is preferably 0 to 60 mol%, more preferably 5 to 40 mol%, and still more preferably 10 to 35 mol% based on the total amount of the polymer B.

The photosensitive composition layer may contain 1 kind of the polymer B alone, or may contain 2 or more kinds of the polymer B.

The content of the residual monomer in each structural unit of the polymer B in the photosensitive composition layer is preferably 1000 mass ppm or less, more preferably 500 mass ppm or less, and further preferably 100 mass ppm or less, with respect to the total mass of the polymer B, from the viewpoint of pattern formability and reliability. The lower limit is not particularly limited, but is preferably 0.1 mass ppm or more, and more preferably 1 mass ppm or more.

When the photosensitive composition layer contains the polymer B, the content of the polymer B is preferably 0.1 to 30% by mass, more preferably 0.2 to 20% by mass, further preferably 0.5 to 20% by mass, and particularly preferably 1 to 20% by mass, based on the total mass of the photosensitive composition layer, from the viewpoints of developability and strength after curing.

[ heterocyclic Compound ]

The photosensitive composition layer preferably contains a heterocyclic compound.

The heterocyclic ring of the heterocyclic compound may be any of monocyclic and polycyclic heterocyclic rings.

Examples of the hetero atom contained in the heterocyclic compound include a nitrogen atom, an oxygen atom and a sulfur atom. The heterocyclic compound preferably has at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, and more preferably has a nitrogen atom.

Examples of the heterocyclic compound include a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a triazine compound, a rhodanine compound, a thiazole compound, a benzothiazole compound, a benzimidazole compound, a benzoxazole compound, and a pyrimidine compound.

In the above, the heterocyclic compound is preferably at least one compound selected from the group consisting of a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a triazine compound, a rhodanine compound, a thiazole compound, a benzimidazole compound and a benzoxazole compound, and more preferably at least one compound selected from the group consisting of a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a thiazole compound, a benzothiazole compound, a benzimidazole compound and a benzoxazole compound.

Preferred specific examples of the heterocyclic compound are shown below. Examples of the triazole compound and benzotriazole compound include the following compounds.

[ chemical formula 5]

[ chemical formula 6]

Examples of the tetrazole compound include the following compounds.

[ chemical formula 7]

[ chemical formula 8]

Examples of the thiadiazole compound include the following compounds.

[ chemical formula 9]

Examples of the triazine compound include the following compounds.

[ chemical formula 10]

Examples of the rhodanine compound include the following compounds.

[ chemical formula 11]

Examples of the thiazole compound include the following compounds.

[ chemical formula 12]

Examples of the benzothiazole compound include the following compounds.

[ chemical formula 13]

Examples of the benzimidazole compound include the following compounds.

[ chemical formula 14]

[ chemical formula 15]

As the benzoxazole compound, the following compounds can be exemplified.

[ chemical formula 16]

The photosensitive composition layer may contain 1 kind of heterocyclic compound alone, or may contain 2 or more kinds of heterocyclic compounds.

When the photosensitive composition layer contains a heterocyclic compound, the content of the heterocyclic compound is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, further preferably 0.3 to 8% by mass, and particularly preferably 0.5 to 5% by mass, based on the total mass of the photosensitive composition layer.

[ aliphatic thiol Compound ]

The photosensitive composition layer preferably contains an aliphatic thiol compound.

When the photosensitive composition layer contains an aliphatic thiol compound, the aliphatic thiol compound and the radical polymerizable compound having an ethylenically unsaturated group undergo an ene-thiol reaction, and thus curing shrinkage of the formed film is suppressed and stress is relieved.

As the aliphatic thiol compound, a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (i.e., an aliphatic thiol compound having 2 or more functions) is preferable.

Among the above, the aliphatic thiol compound is preferably a polyfunctional aliphatic thiol compound, for example, from the viewpoint of adhesiveness of a formed pattern (particularly, adhesiveness after exposure).

In the present invention, the "polyfunctional aliphatic thiol compound" refers to an aliphatic compound having 2 or more thiol groups (also referred to as "mercapto groups") in the molecule.

The polyfunctional aliphatic thiol compound is preferably a low-molecular-weight compound having a molecular weight of 100 or more. Specifically, the molecular weight of the polyfunctional aliphatic thiol compound is more preferably 100 to 1,500, and still more preferably 150 to 1,000.

The number of functional groups of the polyfunctional aliphatic thiol compound is, for example, preferably 2 to 10 functional groups, more preferably 2 to 8 functional groups, and still more preferably 2 to 6 functional groups, from the viewpoint of adhesion of a pattern to be formed.

Examples of the polyfunctional aliphatic thiol compound include trimethylolpropane tris (3-mercaptobutyrate), 1, 4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), 1, 3, 5-tris (3-mercaptobutyryloxyethyl) -1, 3, 5-triazine-2, 4, 6(1H, 3H, 5H) -trione, trimethylolethane tris (3-mercaptobutyrate), tris [ (3-mercaptopropionyloxy) ethyl ] isocyanurate, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethyleneglycol bis (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), ethylene glycol bisthiopropionate, and the like, 1, 4-bis (3-mercaptobutyryloxy) butane, 1, 2-ethanedithiol, 1, 3-propanedithiol, 1, 6-hexamethylenedithiol, 2' - (ethylenedithio) diethylthiol, meso-2, 3-dimercaptosuccinic acid, and bis (mercaptoethyl) ether.

Among the above, as the polyfunctional aliphatic thiol compound, at least one compound selected from the group consisting of trimethylolpropane tris (3-mercaptobutyrate), 1, 4-bis (3-mercaptobutyryloxy) butane and 1, 3, 5-tris (3-mercaptobutyryloxyethyl) -1, 3, 5-triazine-2, 4, 6(1H, 3H, 5H) -trione is preferable.

Examples of the monofunctional aliphatic thiol compound include 1-octanethiol, 1-dodecanethiol, β -mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, and stearyl-3-mercaptopropionate.

The photosensitive composition layer may contain 1 kind of aliphatic thiol compound alone, or may contain 2 or more kinds of aliphatic thiol compounds.

When the photosensitive composition layer contains an aliphatic thiol compound, the content of the aliphatic thiol compound is preferably 5% by mass or more, more preferably 5 to 50% by mass, further preferably 5 to 30% by mass, and particularly preferably 8 to 20% by mass, based on the total mass of the photosensitive composition layer.

[ blocked isocyanate Compound ]

The photosensitive composition layer preferably contains a blocked isocyanate compound. The blocked isocyanate compound helps to increase the strength of the formed pattern.

Since the blocked isocyanate compound reacts with a hydroxyl group and a carboxyl group, for example, when at least one of the binder polymer and the radical polymerizable compound having an ethylenically unsaturated group has at least one of a hydroxyl group and a carboxyl group, the hydrophilicity of the formed film tends to decrease, and the function as a protective film tends to be enhanced. The blocked isocyanate compound is a "compound having a structure in which an isocyanate group of an isocyanate is protected (so-called masked) with a blocking agent".

The dissociation temperature of the blocked isocyanate compound is preferably 100 to 160 ℃, and more preferably 110 to 150 ℃.

In the present invention, the "dissociation temperature of the blocked isocyanate compound" means a temperature of an endothermic peak accompanying the deprotection reaction of the blocked isocyanate compound when measured by DSC (Differential scanning calorimetry) analysis using a Differential scanning calorimeter. As the differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be preferably used. However, the differential scanning calorimeter is not limited to the above-described differential scanning calorimeter.

Examples of the blocking agent having a dissociation temperature of 100 to 160 ℃ include active methylene compounds (malonic diester (dimethyl malonate, diethyl malonate, di-N-butyl malonate, di-2-ethylhexyl malonate, etc.)) and oxime compounds (formaldoxime, acetaldoxime, acetoxime, methylethylketoxime, cyclohexanone oxime, and other compounds having a structure represented by — C (═ N-OH) -in the molecule). Among the above, the end-capping agent having a dissociation temperature of 100 to 160 ℃ is preferably an oxime compound, for example, from the viewpoint of storage stability.

The blocked isocyanate compound preferably has an isocyanurate structure from the viewpoints of improvement of the brittleness of the film, improvement of the adhesion force to the transfer target, and the like. The blocked isocyanate compound having an isocyanurate structure can be obtained by, for example, subjecting hexamethylene diisocyanate to isocyanuric acid esterification for protection.

Among blocked isocyanate compounds having an isocyanurate structure, compounds having an oxime structure using an oxime compound as a blocking agent are preferable from the viewpoint that the dissociation temperature is more easily set in a preferable range than a compound having no oxime structure and the development residue is easily reduced.

The blocked isocyanate compound preferably has a polymerizable group, and more preferably a radical polymerizable group, from the viewpoint of the strength of the pattern to be formed.

Examples of the polymerizable group include an ethylenically unsaturated group such as a (meth) acryloyloxy group, a (meth) acrylamide group, and a styryl group, and a group having an epoxy group such as a glycidyl group. Among the above, as the polymerizable group, an ethylenically unsaturated group is preferable, and a (meth) acryloyloxy group is more preferable, from the viewpoints of surface flatness, development speed, and reactivity of the surface in the obtained pattern.

As the blocked isocyanate compound, commercially available products can be used. Examples of commercially available products of blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) AOI-BP, and Karenz (registered trademark) MOI-BP [ see above under the Showa Denko K.K. ] series ] and blocked DURANATE series [ see, for example, DURANATE (registered trademark) TPA-B80E, Asahi Kasei Chemicals Corporation ].

The photosensitive composition layer may contain 1 kind of blocked isocyanate compound alone, or may contain 2 or more kinds of blocked isocyanate compounds.

When the photosensitive composition layer contains a blocked isocyanate compound, the content of the blocked isocyanate compound is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, relative to the total mass of the photosensitive composition layer.

[ surfactant ]

The photosensitive composition layer preferably contains a surfactant.

Examples of the surfactant include those described in paragraphs [0017] of Japanese patent No. 4502784 and paragraphs [0060] to [0071] of Japanese patent application laid-open No. 2009-237362.

The surfactant is preferably a fluorine-based surfactant or a silicon-based surfactant. Commercially available fluorine-based surfactants include Megaface (registered trademark) F551A (manufactured by DIC Corporation).

Further, examples of commercially available fluorine-based surfactants include Megaface F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, MFS-578, MFS-579, MFS-586, MFS-587, R-41-LM, R-01, R-40, R-LM, R-40-LM, F-172, F-57, F-552, F-80, MFS-578, MFS-586, MFS-R-587, R-41, R-LM, R-01, R-40, R-LM, and F-b, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (see above, DIC Corporation), Fluorad FC430, FC431, FC171 (see above, Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (see above, AGC Inc), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (see above, OMNOVA Solutions), Ftergent 710FL, 710FM, FM 610FM, AD 601, ADH2, 602A, 215M, 245F, 251, 212M, 250, F209, 222F, 208G, LA, FS 710, 730, LM, 650AC, 681 (see above, Neos Corporation), etc.

Further, as the fluorine-based surfactant, an acrylic compound having a molecular structure having a functional group containing a fluorine atom, and when heated, a functional group portion containing a fluorine atom is cleaved and the fluorine atom is volatilized can also be preferably used. Examples of the fluorine-based surfactant include MAGAFACE DS series (chemical industry daily news (2016, 2, 22 days), and sunrise industry news (2016, 2, 23 days)), manufactured by DIC Corporation, for example, MAGAFACE DS-21. Further, as the fluorine-based surfactant, a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound is also preferably used.

Further, as the fluorine-based surfactant, a terminal-capped polymer can also be used.

Further, as the fluorine-based surfactant, a fluorine-containing polymer compound containing: a structural unit derived from a (meth) acrylate compound having a fluorine atom; and a structural unit derived from a (meth) acrylate compound having 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups).

Further, as the fluorine-containing surfactant, a fluorine-containing polymer having a group having an ethylenically unsaturated bond in a side chain can also be used. Examples thereof include MEGAFACE RS-101, RS-102, and RS-718K, RS-72-K (manufactured by DIC Corporation).

The fluorine-based surfactant is preferably a surfactant derived from a material alternative to a compound having a linear perfluoroalkyl group having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS), from the viewpoint of improving environmental compatibility.

As a commercial product of the silicon-based surfactant, DOWSIL (registered trademark) 8032 Additive is exemplified.

Further, specific examples of commercially available products of silicon-based surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (both of which are Dow Corning Toray Co., Ltd.), X-22-4952, X-22-4272, X-22-6266, KF-351 35354L, KF-355A, KF-945, KF-640, man KF-351, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, Kp-6001, td-6002 (both of which are Shin-Etsu Chemical Co., TSF 40, TSF 4440-4445, TSF 4452 (both of which are manufactured by Mole Inc.) 44F 4452, Toray 4445, and Moay Silicone 444460 (both of which are manufactured by Dow Corning Co., Ltd.), Toray Mat-4470 Co., Tsu 4452, and TsF 4452 (both of which are manufactured by Moay Silicone Co., TsF 4460, Mo 4452, TsF 4452, and M-4452 are manufactured by MsF-4470F-4452, BYK307, BYK323, BYK330 (manufactured by BYK Chemie GmbH).

The photosensitive composition layer may contain 1 kind of surfactant alone, or may contain two or more kinds of surfactants.

When the photosensitive composition layer contains a surfactant, the content of the surfactant is preferably 0.01 to 3% by mass, more preferably 0.05 to 1% by mass, and still more preferably 0.1 to 0.8% by mass, based on the total mass of the photosensitive composition layer.

[ Hydrogen-donating Compound ]

The photosensitive composition layer preferably contains a hydrogen donating compound. The hydrogen-donating compound has an action of further improving the sensitivity of the photopolymerization initiator to actinic rays, suppressing inhibition of polymerization of the polymerizable compound by oxygen, and the like.

Examples of the hydrogen-donating compound include amines, for example, those described in "Journal of Polymer Society" volume 10, 3173 (1972), Japanese patent publication No. 44-020189, Japanese patent publication No. 51-082102, Japanese patent publication No. 52-134692, Japanese patent publication No. 59-138205, Japanese patent publication No. 60-084305, Japanese patent publication No. 62-018537, Japanese patent publication No. 64-033104, and Research Disclosure No. 33825, to M.R. Sander et al.

Examples of the hydrogen donating compound include triethanolamine, ethyl p-dimethylaminobenzoate, p-formyldimethylaniline and p-methylthiodimethylaniline.

Further, examples of the hydrogen-donating compound include an amino acid compound (e.g., N-phenylglycine), an organic metal compound (e.g., tributylstannoic acid ester) disclosed in Japanese patent publication No. 48-042965, a hydrogen donor disclosed in Japanese patent publication No. 55-034414, and a sulfur compound (e.g., trithiane) disclosed in Japanese patent publication No. 6-308727.

The photosensitive composition layer may contain 1 kind of hydrogen donating compound alone, or may contain 2 or more kinds of hydrogen donating compounds.

When the photosensitive composition layer contains a hydrogen-donating compound, the content of the hydrogen-donating compound is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass, and further preferably 0.05 to 3% by mass, relative to the total mass of the photosensitive composition layer, from the viewpoint of enhancing the curing rate by a balance between the polymerization growth rate and the chain transfer.

[ other ingredients ]

The photosensitive composition layer may contain a component other than the above-described components (hereinafter, also referred to as "other component"). Examples of the other components include particles (e.g., metal oxide particles) and a colorant. Among them, the photosensitive composition preferably contains no colorant from the viewpoint of peelability of the coating film.

Examples of the other components include the thermal polymerization inhibitor described in paragraph [0018] of Japanese patent No. 4502784 and other additives described in paragraphs [0058] to [0071] of Japanese patent laid-open No. 2000-310706.

The photosensitive composition layer may contain particles for the purpose of adjusting the refractive index, light transmittance, and the like. Examples of the particles include metal oxide particles.

The metal in the metal oxide particles further includes semimetals such As B, Si, Ge, As, Sb and Te.

The average primary particle diameter of the particles is preferably 1 to 200nm, more preferably 3 to 80nm, from the viewpoint of pattern transparency, for example. The average primary particle size of the particles was calculated by measuring the particle size of any 200 particles using a Scanning Electron Microscope (SEM), and arithmetically averaging the measurement results. When the shape of the particles is non-spherical, the longest side is defined as the particle diameter.

The photosensitive composition layer may contain 1 kind of particles alone, or may contain 2 or more kinds of particles. When the photosensitive composition layer contains particles, only particles of 1 metal species, particles of different sizes, etc. may be contained, or 2 or more species may be contained.

The photosensitive composition layer preferably contains no particles, or the content of particles is more than 0% by mass and 35% by mass or less with respect to the total mass of the photosensitive composition layer, more preferably contains no particles, or the content of particles is more than 0% by mass and 10% by mass or less with respect to the total mass of the photosensitive composition layer, further preferably contains no particles, or the content of particles is more than 0% by mass and 5% by mass or less with respect to the total mass of the photosensitive composition layer, particularly preferably contains no particles, or the content of particles is more than 0% by mass and 1% by mass or less with respect to the total mass of the photosensitive composition layer, most preferably contains no particles.

The photosensitive composition layer may contain a small amount of a colorant (e.g., a pigment and a dye), and preferably contains substantially no colorant, for example, from the viewpoint of transparency.

When the photosensitive composition layer contains a colorant, the content of the colorant is preferably less than 1% by mass, more preferably less than 0.1% by mass, with respect to the total mass of the photosensitive composition layer.

[ impurities, etc. ]

The photosensitive composition layer may contain a predetermined amount of impurities.

Specific examples of the impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halyard, and ions thereof. Among them, the halide ions, sodium ions and potassium ions are preferably contained in the following amounts because they are easily mixed as impurities.

The content of impurities in the photosensitive composition layer is preferably 80ppm or less, more preferably 10ppm or less, and further preferably 2ppm or less, on a mass basis. The content of the impurity in the photosensitive composition layer can be 1ppb or more and 0.1ppm or more on a mass basis.

As a method for setting the impurities within the above range, the following methods can be cited: the photosensitive composition layer is prepared by selecting a material having a small content of impurities as a raw material of the photosensitive composition layer, preventing impurities from being mixed when the photosensitive composition layer is formed, and removing the impurities by washing. By this method, the amount of impurities can be set within the above range.

The impurities can be quantified by a known method such as ICP (Inductively Coupled Plasma) emission spectrometry, atomic absorption spectrometry, or ion chromatography.

The photosensitive composition layer preferably contains a small amount of compounds such as benzene, formaldehyde, trichloroethylene, 1, 3-butadiene, carbon tetrachloride, chloroform, N-dimethylformamide, N-dimethylacetamide, and hexane. The content of these compounds in the photosensitive composition layer is preferably 100ppm or less, more preferably 20ppm or less, and still more preferably 4ppm or less, by mass. The lower limit may be 10ppb or more, and may be 100ppb or more on a mass basis. These compounds can be contained in the same manner as the impurities of the above-mentioned metals. Further, the amount can be determined by a known measurement method.

From the viewpoint of improving reliability and laminatability, the content of water in the photosensitive composition layer is preferably 0.01 to 1.0 mass%, more preferably 0.05 to 0.5 mass%.

[ thickness of photosensitive composition layer ]

The thickness of the photosensitive composition layer is not particularly limited, but is preferably 10.0 μm or less, and more preferably 8.0 μm or less.

The lower limit of the thickness of the photosensitive composition layer is not limited. The smaller the thickness of the photosensitive composition layer is, the more the bending resistance can be improved. From the viewpoint of production suitability, the lower limit of the thickness of the photosensitive composition layer is preferably 0.05 μm or more. From the viewpoint of improving the protective property of the transparent conductive portion, the lower limit of the thickness of the photosensitive composition layer is preferably 0.5 μm or more, and more preferably 1.1 μm or more.

The thickness of the photosensitive composition layer was calculated as an average value of arbitrary 5 points measured by cross-sectional observation with a Scanning Electron Microscope (SEM).

[ refractive index of photosensitive composition layer ]

The refractive index of the photosensitive composition layer is preferably 1.47 to 1.56, more preferably 1.49 to 1.54.

[ color of photosensitive composition layer ]

The photosensitive composition layer is preferably achromatic. A of the photosensitive composition layer ^* The value is preferably-1.0 to 1.0, b of the photosensitive composition layer ^* The value is preferably-1.0 to 1.0.

< other layer >

The transfer film may contain other layers than the temporary support and the photosensitive composition layer.

[ protective film ]

The transfer film may have a protective film for protecting the photosensitive composition layer on a surface on a side opposite to the temporary support.

The protective film is preferably a resin film, and a resin film having heat resistance and solvent resistance can be used, and examples thereof include polyolefin films such as a polypropylene film and a polyethylene film. The protective film may be a resin film made of the same material as the temporary support.

The thickness of the protective film is preferably 1 to 100 μm, more preferably 5 to 50 μm, further preferably 5 to 40 μm, and particularly preferably 15 to 30 μm. The thickness of the protective film is preferably 1 μm or more from the viewpoint of excellent mechanical strength, and preferably 100 μm or less from the viewpoint of relative inexpensiveness.

< method for producing transfer film >

The method for producing the transfer film of the present invention is not particularly limited, and a known method can be used.

Among them, from the viewpoint of excellent productivity, a method of forming a photosensitive composition layer by applying a photosensitive composition on a temporary support and, if necessary, performing a drying treatment is preferred.

The above method will be described in detail below.

The photosensitive composition preferably contains a component (for example, a polymerizable compound, an alkali-soluble resin, a photopolymerization initiator, and the like) constituting the photosensitive composition layer and a solvent.

As the solvent, an organic solvent is preferable. Examples of the organic solvent include methyl ethyl ketone, propylene glycol monomethyl ether acetate (also known as 1-methoxy-2-propyl acetate), diethylene glycol ethyl methyl ether, cyclohexanone, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam, n-propanol, and 2-propanol. As the solvent, a mixed solvent of methyl ethyl ketone and propylene glycol monomethyl ether acetate or a mixed solvent of diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether acetate is preferable.

Further, as the solvent, an organic solvent (high boiling point solvent) having a boiling point of 180 to 250 ℃ can be used as necessary.

The photosensitive composition may contain 1 kind of solvent alone, or may contain two or more kinds of solvents.

When the photosensitive composition contains a solvent, the total solid content of the photosensitive composition is preferably 5 to 80% by mass, more preferably 5 to 40% by mass, and still more preferably 5 to 30% by mass, based on the total mass of the photosensitive composition.

When the photosensitive composition contains a solvent, the viscosity of the photosensitive composition at 25 ℃ is preferably 1 to 50 mPas, more preferably 2 to 40 mPas, and further preferably 3 to 30 mPas, from the viewpoint of coatability, for example. The viscosity was measured using a viscometer. As the VISCOMETER, a VISCOMETER (product name: VISCOMETER TV-22) manufactured by TOKI SANGYO CO. However, the viscometer is not limited to the above viscometer.

When the photosensitive composition contains a solvent, the surface tension of the photosensitive composition at 25 ℃ is preferably 5 to 100mN/m, more preferably 10 to 80mN/m, and still more preferably 15 to 40mN/m, from the viewpoint of coatability, for example. The surface tension was measured using a surface tensiometer. As the Surface tension meter, for example, a Surface tension meter (product name: Automatic Surface tensometer CBVP-Z) manufactured by Kyowa Interface Science Co., Ltd. However, the surface tension meter is not limited to the above surface tension meter.

Examples of the method for applying the photosensitive composition include a printing method, a spray coating method, a roll coating method, a bar coating method, a curtain coating method, a spin coating method, and a die coating method (that is, a slit coating method).

Examples of the drying method include natural drying, heat drying, and drying under reduced pressure. The above-described methods can be used alone or in combination of a plurality of them.

In the present invention, "drying" means removing at least a part of the solvent contained in the composition.

When the transfer film has a protective film, the transfer film is produced by bonding the protective film to the photosensitive composition layer.

The method for bonding the protective film to the photosensitive composition layer is not particularly limited, and known methods can be exemplified.

Examples of the means for bonding the protective film to the photosensitive composition layer include known laminators such as a vacuum laminator and an automatic cutting laminator.

The laminator includes any heatable roller such as a rubber roller, and is preferably capable of pressurization and heating.

< method for producing laminate >

By using the transfer film, the photosensitive composition layer can be transferred to an object to be transferred.

Among them, the method for producing a laminate preferably includes: a bonding step of bonding the photosensitive composition layer of the transfer film to a substrate having a conductive layer in contact therewith to obtain a substrate with a photosensitive composition layer, which has a temporary support, a photosensitive composition layer, and a substrate having a conductive layer in this order; an exposure step of pattern-exposing the photosensitive composition layer from the temporary support; a stripping step of stripping the temporary support from the substrate with the photosensitive composition layer; and a developing step of developing the exposed photosensitive composition layer to form a pattern.

In the laminate obtained by the above procedure, a pattern is arranged on the substrate having the conductive layer.

The sequence of the steps of the laminate will be described in detail below.

[ bonding Process ]

The bonding step is a step of bonding the photosensitive composition layer of the transfer film to the substrate having the conductive layer in contact with each other to obtain a substrate with a photosensitive composition layer, which has the temporary support, the photosensitive composition layer, and the substrate having the conductive layer in this order. By this bonding, the photosensitive composition layer and the temporary support are disposed on the substrate having the conductive layer.

In the bonding, the conductive layer is preferably pressure-bonded so as to be in contact with the surface of the photosensitive composition layer. In this manner, the pattern obtained after exposure and development can be preferably used as an etching resist when etching the conductive layer.

The method of pressure bonding is not particularly limited, and a known transfer method and lamination method can be used. Among these, it is preferable to stack the surface of the photosensitive composition layer on a substrate having a conductive layer, and to apply pressure and heat by a roller or the like.

The lamination can be performed using a known laminator such as a vacuum laminator and an automatic cutting laminator.

The substrate having a conductive layer has a conductive layer on a substrate, and an arbitrary layer may be formed as needed. That is, the substrate having the conductive layer is a conductive substrate having at least a substrate and a conductive layer disposed on the substrate.

Examples of the substrate include a resin substrate, a glass substrate, and a semiconductor substrate.

A preferred embodiment of the substrate is described in, for example, paragraph 0140 of international publication No. 2018/155193, which is incorporated herein.

The conductive layer is preferably at least one layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer, from the viewpoint of conductivity and fine wire formability.

Further, only 1 conductive layer may be disposed on the substrate, or 2 or more conductive layers may be disposed on the substrate. When 2 or more conductive layers are arranged, conductive layers having different materials are preferable.

A preferred embodiment of the conductive layer is described in, for example, paragraph 0141 of international publication No. 2018/155193, which is incorporated herein.

[ Exposure procedure ]

The exposure step is a step of pattern-exposing the photosensitive composition layer from the temporary support side.

Here, the "pattern exposure" refers to exposure in a pattern-like exposure manner, that is, in a manner such that an exposed portion and a non-exposed portion are present.

The detailed arrangement and specific dimensions of the pattern in the pattern exposure are not particularly limited. The pattern formed by the developing step described later preferably includes a thin line having a width of 20 μm or less, and more preferably a thin line having a width of 10 μm or less.

The light source for the pattern exposure can be appropriately selected and used as long as it can irradiate light in a wavelength range (for example, 365nm or 405nm) at least capable of curing the photosensitive composition layer. Among them, the dominant wavelength of exposure light for pattern exposure is preferably 365 nm.

The dominant wavelength is the wavelength having the highest intensity.

Examples of the light source include various lasers, Light Emitting Diodes (LEDs), ultra-high pressure mercury lamps, and metal halide lamps.

The exposure is preferably 5 to 200mJ/cm ² More preferably 10 to 200mJ/cm ² 。

Preferable examples of the light source, the exposure amount, and the exposure method for exposure are described in, for example, paragraphs [0146] to [0147] of International publication No. 2018/155193, and these contents are incorporated herein.

[ peeling Process ]

The peeling step is a step of peeling the temporary support from the substrate with the photosensitive composition layer.

The peeling method is not particularly limited, and the same mechanism as the coating peeling mechanism described in paragraphs [0161] to [0162] of jp 2010-072589 a can be used.

[ developing Process ]

The developing step is a step of forming a pattern by developing the exposed photosensitive composition layer.

The photosensitive composition layer can be developed using a developer.

As the developer, an alkaline aqueous solution is preferable. Examples of the basic compound that can be contained in the basic aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).

Examples of the development method include spin immersion development, shower development, spin development, and immersion development.

The developer preferably used in the present invention includes, for example, the developer described in paragraph [0194] of International publication No. 2015/093271, and the developing method preferably used includes, for example, the developing method described in paragraph [0195] of International publication No. 2015/093271.

The pattern (cured film of the photosensitive composition layer) formed by the above-described steps is preferably achromatic. Specifically, at L ^* a ^* b ^* In the color system, a of the pattern ^* The value is preferably-1.0 to 1.0, b of the pattern ^* The value is preferably-1.0 to 1.0.

[ post-exposure step and post-baking step ]

The method for producing the laminate may include a step of exposing the pattern obtained in the developing step (post-exposure step) and/or a step of heating the pattern obtained in the developing step (post-baking step).

When both the post-exposure step and the post-baking step are included, it is preferable to perform post-baking after the post-exposure.

[ etching Process ]

The method for manufacturing the laminate may include an etching step of etching the conductive layer in a region where no pattern is arranged in the obtained laminate.

In the etching step, the pattern formed from the photosensitive composition layer in the developing step is used as an etching resist, and the conductive layer is etched.

As the method of the etching treatment, known methods such as the method described in paragraphs [0209] to [0210] of Japanese patent application laid-open No. 2017-120435, the method described in paragraphs [0048] to [0054] of Japanese patent application laid-open No. 2010-152155, and the like, and the method based on dry etching such as known plasma etching can be applied.

[ removal Process ]

The method for manufacturing the laminate may include a removal step of removing the pattern.

The removal step can be performed as needed, but is preferably performed after the etching step.

The method of removing the pattern is not particularly limited, but a method of removing by a chemical treatment may be mentioned, and a removing solution is preferably used.

The pattern removal method includes a method of immersing the laminate having the pattern in a removing solution stirred at preferably 30 to 80 ℃ and more preferably 50 to 80 ℃ for 1 to 30 minutes.

Examples of the removing solution include a solution obtained by dissolving an inorganic base component such as sodium hydroxide or potassium hydroxide or an organic base component such as a primary amine compound, a secondary amine compound, a tertiary amine compound, or a quaternary ammonium salt compound in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution thereof.

The removal liquid may be used for removal by a spray method, a shower method, or a spin-coating immersion method.

[ other Processes ]

The method for producing a laminate of the present invention may include any step (other step) other than the above.

For example, the step of reducing the reflectance of visible light described in paragraph [0172] of international publication No. 2019/022089, the step of forming a new conductive layer on an insulating film described in paragraph [0172] of international publication No. 2019/022089, and the like can be mentioned, but the steps are not limited to these steps.

The laminate produced by the laminate production method of the present invention can be applied to various apparatuses. Examples of the device including the laminate include an input device, preferably a touch panel, and more preferably an electrostatic capacitance type touch panel. The input device can be applied to display devices such as organic electroluminescence display devices and liquid crystal display devices.

When the laminate is applied to a touch panel, the pattern formed from the photosensitive composition layer is preferably used as a protective film for the touch panel electrode. That is, the photosensitive composition layer included in the transfer film is preferably used for forming the touch panel electrode protection film.

The various compounds, compositions, materials and the like used in the present invention are preferably free of impurities such as metal components, moisture, isomers, fine particles, aggregates, precipitates, residual monomers and the like. The content of these impurities contained in each material is preferably 1 mass% or less, more preferably 1 mass ppm or less, still more preferably 1 mass ppb or less, and particularly preferably substantially not contained (detection limit of the measurement device). The method for reducing impurities can be selected as appropriate to suit the object to be removed, and for example, the methods disclosed in paragraphs 0321 to 0323 of jp 2019-174549 a and paragraphs 0083 to 0097 of pamphlet of international publication No. 2019/088268 can be used.

Examples

The present invention will be described in more detail with reference to examples. The materials, the amounts used, the ratios, the contents of the treatment, the procedure of the treatment, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "part" and "%" are based on mass.

In addition, the composition ratio in the polymer is a molar ratio unless otherwise specified.

< Synthesis of Polymer A-1 >

PGMEA (116.5 parts) was placed in a three-necked flask and heated to 90 ℃ under a nitrogen atmosphere. To a three-necked flask solution maintained at 90 ℃. + -. 2 ℃ was added dropwise a solution obtained by adding St (52.0 parts), MMA (19.0 parts), MAA (29.0 parts), V-601(4.0 parts) and PGMEA (116.5 parts) over a period of 2 hours. After completion of the dropwise addition, the mixture was stirred at 90. + -. 2 ℃ for 2 hours to obtain polymer A-1 (solid content concentration: 30.0%).

In addition, the abbreviations in the above synthesis examples represent the following compounds, respectively.

St: styrene (manufactured by FUJIFILM Wako Pure Chemical Corporation)

MAA: methacrylic acid (manufactured by FUJIFILM Wako Pure Chemical Corporation)

MMA: methyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation)

PGMEA: propylene glycol monomethyl ether acetate (manufactured by SHOWA DENKO K.K)

MEK: methyl Ethyl ketone (Sankyo Chemical Co., manufactured by LTD.)

V-601: dimethyl-2, 2' -azobis (2-methylpropionate) (manufactured by FUJIFILM Wako Pure Chemical Corporation)

< production of photosensitive composition 1>

The following components were mixed to prepare a photosensitive composition 1. The unit of the amount of each component is part by mass.

Polymer A-1 (solid content concentration 30.0%): 21.87 parts of

D-2(ARONIX M270(TOAGOSEI CO., LTD.)))): 0.51 part of

D-1(NK ester BPE-500(Shin-Nakamura Chemical Co., Ltd.)): 4.85 parts of

C-2(B-CIM, manufactured by Hampford corporation): 0.89 part

C-3 (photo radical polymerization initiator (sensitizer), 4, 4' -bis (diethylamino) benzophenone, manufactured by Tokyo Chemical Industry Co., Ltd.): 0.05 part

Phenothiazine (manufactured by FUJIFILM Wako Pure Chemica I Corporation): 0.025 parts

1-phenyl-3-pyrazolidinone (manufactured by FUJIFILM Wako Pure Chemical Corporation): 0.001 portion

B-2(LCV, leuco crystal violet, YAMADA CHEMICAL C0., manufactured by LTD.): 0.053 portion

E-1(Megaface F552 (manufactured by DIC Corporation)): 0.02 portion

Methyl ethyl ketone (MEK, SANKYO CHEMICAL co., ltd.): 30.87 parts

Propylene glycol monomethyl ether acetate (PGMEA, SHOWA DENKO k.k.): 33.92 parts of

Tetrahydrofuran (THF, manufactured by Mitsubishi Chemical Corporation): 6.93 parts

< example 1>

A resin layer having a thickness of 5 μm made of AN ethylene methacrylic acid copolymer (Nucrel AN4214C, made by DOW-MITSUI polymers co., ltd.) was disposed on a PET film (16KS40, made by TORAY additives, inc.) having a thickness of 16 μm by a melt extrusion method.

The resin layer in the laminate comprising the obtained PET film and the resin layer was embossed to obtain a temporary support exhibiting surface characteristics (Rsk, Ra, RMS) shown in table 1 described later.

Subsequently, the photosensitive composition 1 was applied to the surface of the temporary support on the resin layer side by using a slit nozzle, and passed through a drying zone at 80 ℃ for 40 seconds to form a photosensitive composition layer having a thickness of 3 μm.

Next, a PET film (16KS40, manufactured by TORAY additives, inc.) having a thickness of 16 μm was laminated as a protective film on the photosensitive composition layer to prepare a transfer film, which was wound up in a roll.

< examples 2 to 5 and comparative examples 1 to 4>

A transfer film was obtained by following the same procedure as in example 1, except that the thickness of the resin layer, the conditions of embossing, and the like were adjusted so as to obtain the characteristics shown in table 1 described below.

In comparative example 4, a temporary support on which embossing was not performed was used.

< example 6>

A transfer film was obtained in the same manner as in example 1, except that AN ethylene vinyl acetate copolymer (Evaflex EV550, DOW-MITSUI polychrome co., ltd. system) was used instead of the ethylene methacrylic acid copolymer (Nucrel AN4214C, DOW-MITSUI polychrome LS co., ltd. system), and conditions of embossing processing were adjusted so as to obtain the characteristics shown in table 1 described later, and the like.

< example 7>

A transfer film was obtained in the same manner as in example 1, except that AN ethylene methacrylic acid copolymer (Nucrel AN4229C, DOW-MITSUI polychrome co., ltd. system) was used instead of the ethylene methacrylic acid copolymer (Nucrel AN4214C, DOW-MITSUI polychrome co., ltd. system), and conditions of embossing processing were adjusted so as to obtain the characteristics shown in table 1 described later, and the like.

< windup Property >

A PET base layer having a thickness of 100 μm and a width of 500mm was bonded to a support by continuous thermal compression in a roll-to-roll manner at a temperature of 2m/min and a pressure of 0.8MPa between dryers at 100 ℃ with a transfer film having the same width, and a laminate in which a photosensitive composition layer and a temporary support were laminated on the support was wound up in a roll form.

Then, the temporary support was peeled off and conveyed at a speed of 2 m/min. At this time, the peeled temporary support is wound in a roll shape at a winding tension 25N. The winding properties were observed from the state of the coil at 100m winding time and evaluated according to the following criteria. The results are shown in table 1 below.

A: the appearance is free from any problem

B: an allowable degree of wrinkling or square entanglement was observed, but had no effect on shipping

C: stable conveyance is not possible due to the generation of wrinkles or square entanglement.

< resolution >

A copper layer having a thickness of 500nm was formed on a glass plate having a thickness of 0.7mm by a vapor deposition method, thereby preparing a glass substrate having a copper layer.

The transfer film thus produced was taken out, and after peeling off the protective film, the film was laminated on the glass substrate with the copper layer under lamination conditions of a roll temperature of 100 ℃, a line pressure of 0.8MPa, and a line speed of 2.0m/min so that the copper layer was in contact with the photosensitive composition layer.

Then, a photomask having various line width patterns (2 to 20 μm) with a line/space of 1/1 was used, and the thickness of the photomask was adjusted to 80mJ/cm from the temporary support side ² The temporary support is removed by stripping after exposure.

Subsequently, the resultant was subjected to spray development with a 1% aqueous solution of sodium carbonate at a liquid temperature of 25 ℃ and then washed with water to form a predetermined pattern on copper.

Thereafter, the minimum line width of the space opening was evaluated by an optical microscope (using a mask size value). The results are shown in table 1 below.

In addition, the storage elastic modulus, haze, Rsk, Ra, and RMS shown in table 1 were measured by the above-described methods.

In table 1, the column "haze (%)" indicates the haze (%) of the temporary support.

In table 1, the column "Rsk" indicates the skewness Rsk of the surface on the photosensitive composition layer side of the temporary support.

In table 1, the column "Ra (μm)" indicates the surface roughness Ra of the surface of the temporary support on the photosensitive composition layer side.

In table 1, the column "RMS (μm)" indicates the root-mean-square roughness RMS of the surface of the temporary support on the photosensitive composition layer side.

In Table 1, "> 20" indicates that all patterns of 2 to 20 μm were not resolved.

[ Table 1]

As shown in table 1, the transfer film of the present invention can provide desired effects.

The comparison of examples 1 to 7 confirmed that the effect is more excellent when the haze of the temporary support is 20% or less.

The comparison of examples 1 to 5 confirmed that the effect is more excellent when the skewness Rsk of the surface of the temporary support on the photosensitive composition layer side is 0.45 or more.

Claims

1. A transfer film comprising a temporary support and a photosensitive composition layer disposed on the temporary support,

the temporary support has a haze of less than 30%,

2. The transfer film according to claim 1,

3. The transfer film according to claim 1 or 2,

the root-mean-square height RMS of the surface of the temporary support on the photosensitive composition layer side is less than 0.70 [ mu ] m.

4. The transfer film according to any one of claims 1 to 3,

the temporary support has a support and a resin layer disposed on the support,

the resin layer is disposed on the side of the photosensitive composition layer,

the resin layer has a storage elastic modulus of 20MPa or less at 90 ℃.

5. The transfer film according to claim 4,

when the storage elastic modulus of the resin layer at 90 ℃ is represented by G and the thickness of the resin layer is represented by H, the H/G exceeds 0.2 μm/MPa.

6. The transfer film according to claim 4 or 5,

the thickness of the resin layer is 60 [ mu ] m or less.

7. The transfer film according to any one of claims 4 to 6,

the resin layer includes a resin having repeating units derived from ethylene.

8. The transfer film according to any one of claims 1 to 7,

the temporary support has a haze of 2% or more.

9. The transfer film according to any one of claims 1 to 8,

10. A method for manufacturing a laminate, comprising:

a bonding step of bringing the photosensitive composition layer of the transfer film according to any one of claims 1 to 9 into contact with and bonding to a substrate having a conductive layer to obtain a substrate with a photosensitive composition layer, the substrate having the temporary support, the photosensitive composition layer, and the substrate having the conductive layer in this order;