JP6446788B2 - Hollow structure, method for manufacturing the same, and electronic component having hollow structure - Google Patents

Description

  The present invention relates to a hollow structure, a method for manufacturing the same, and an electronic component having the hollow structure.

  In recent years, due to the high integration and miniaturization of semiconductor elements, the increase in capacity and cost of devices has been rapidly progressing. From the viewpoint of protecting a specific part of the element, an element in which the part is accommodated in a hollow structure is known. For example, a package of an element that exhibits an electrical function, represented by a surface acoustic wave (SAW) filter, has a hollow structure that accommodates an electrode pattern and a fine structure formed on the surface of a single crystal wafer. This prevents the part from coming into contact with other objects.

  Image sensors represented by CMOS and CCD sensors have a hollow structure in which a light receiving portion is covered with a glass lid. This is to protect the element from moisture and dust that hinder imaging, and to prevent light from the outside from being shielded. In addition, a hollow structure is employed in order to protect movable parts in MEMS (Micro Electro Mechanical System) for high frequency applications such as a gyro sensor or a millimeter wave radar.

  Conventionally, a hollow structure in an element has been formed by processing or bonding of an inorganic material. However, from the viewpoint of cost reduction by reducing the number of parts and the number of processes, and the demand for miniaturization and low profile of elements, a technique for forming a hollow structure using a resin has been studied. For example, as a method for forming a hollow structure, a photolithography technique using a photosensitive resin material can be given (see Patent Documents 1 to 3).

Japanese Patent No. 4664397 Special table 2003-523082 gazette JP 2008-250200 A

When forming a hollow structure using a photolithographic technique, it is necessary to form the frame part and ceiling part which comprise a hollow structure in steps. Specifically, for example, a frame portion is first formed on a substrate by performing the following steps.
-The process of forming the photosensitive resin layer on a board | substrate.
-A step of irradiating a predetermined portion of the photosensitive resin layer with an actinic ray to photocur the exposed portion.
-The process of removing parts other than an exposure part using a developing solution.
-The process of thermosetting the exposed part of the photosensitive resin layer.

Next, a ceiling part is formed so as to cover the region surrounded by the frame part. A ceiling part is formed through the following processes, for example.
-The process of forming the photosensitive resin layer used as a ceiling part on the frame part produced on the board | substrate.
-A step of irradiating the photosensitive resin layer with an actinic ray to cause photocuring.
-The process of thermosetting the photosensitive resin layer.

  When the hollow structure is formed by the photolithography technique, as described above, it is necessary to form the frame part and the ceiling part in stages, and there is room for improvement in that there are many process steps. Then, an object of this invention is to provide the method which can manufacture a hollow structure on a board | substrate easily with high precision.

  The present invention is a process of pressing a mold having a convex portion against one surface of a workpiece made of a resin composition, and the other end of the workpiece is not allowed to reach the other surface of the workpiece. A first step of leaving the resin composition between the surface and the tip, a second step of removing the mold from the workpiece and obtaining a workpiece in which the concave portion formed by the convex portion is formed on one surface, and a substrate; A third step of obtaining a structure having a hollow portion formed by the surface of the substrate and the concave portion by superimposing the surface of the substrate and the surface on which the concave portion of the workpiece is formed, the step of superposing the workpiece; In this order.

  By pressing the mold against the workpiece, a pattern with high accuracy can be easily formed on the workpiece. More specifically, a concave portion that does not penetrate from one surface of the workpiece to the other surface by pressing the die against the workpiece so that the tip of the convex portion of the die does not reach the other surface of the workpiece in the first step. The pattern including it can be formed easily. Then, the structure which has the hollow part formed of the surface of a board | substrate and a recessed part can be easily formed by superimposing the surface by the side in which the recessed part in a workpiece | work is formed, and a board | substrate. In the first step, the distance between the other surface of the workpiece and the tip depends on the thickness of the workpiece to be used, the shape or size of the recess to be used, or the type of electronic component to be manufactured, and from the viewpoint of the strength of the recess. It can be 1-95 μm.

  The method according to the present invention may further include a curing treatment step for proceeding curing of the resin composition constituting the workpiece after the second step or the third step. By performing the curing process step after the second step and before the third step, the shape of the pattern formed on the workpiece in the third step of overlapping the workpiece and the substrate can be favorably maintained. By performing the curing treatment step after the third step, the adhesiveness of the resin composition can be reduced. For example, in a 1st process, when a temporary base material etc. are used in order to press a type | mold with respect to a workpiece | work, a temporary base material can be easily peeled from a workpiece | work by reducing the adhesiveness of a resin composition.

  The curing treatment step may include irradiating the work with light. The heat resistance of a workpiece | work can be improved by advancing hardening of a resin composition by light irradiation. For example, prior to the process of heating and thermosetting the workpiece, by allowing the resin composition to cure by light irradiation, the workpiece can be sufficiently prevented from melting by heat, and the pattern formed on the workpiece Good shape can be maintained.

  The resin composition may contain (A) a photopolymerizable compound and (B) a photopolymerization initiator. By constituting the workpiece with such a resin composition, effects such as improvement in releasability by light irradiation can be obtained more remarkably.

  This invention provides the hollow structure manufactured by the said method, and an electronic component provided with the same. For example, a workpiece made of a resin composition in an electronic component may function as a permanent film.

  According to the present invention, a hollow structure can be easily manufactured on a substrate with high accuracy.

It is process drawing which shows one Embodiment of the manufacturing method of the hollow structure which concerns on this invention. It is a schematic diagram which shows the variation of the type | mold for forming a recessed part in a workpiece | work. It is a schematic diagram for demonstrating the residual film thickness of the workpiece | work after stamping.

  Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

<Method for producing hollow structure>
The method for manufacturing a hollow structure according to the present embodiment uses an imprint molding technique and includes the following steps.
1st process: The type | mold which has a convex part is pressed with respect to one surface of the workpiece | work consisting of a resin composition, and the other surface and front-end | tip of a workpiece | work are not made to reach | attain the front-end | tip part of a convex part to the other surface of a workpiece | work. The resin composition is left between the parts.
Second step: removing the mold from the workpiece and obtaining a workpiece in which the concave portion formed by the convex portion is formed on one surface.
Third step: Overlaying the substrate and the work, and superimposing the surface of the substrate and the surface on which the concave portion of the workpiece is formed, to obtain a structure having a hollow portion formed by the surface of the substrate and the concave portion. .

FIG. 1 is a process diagram specifically showing the manufacturing method according to the present embodiment. The hollow structure 50 having the hollow portion 20 can be obtained through the following steps (see (k) in FIG. 1). The hollow portion 20 is formed by the surface 2a of the substrate 2 and the recess 10c.
-The process of preparing the sheet | seat which has the temporary base material 1 and the workpiece | work 10a formed on the temporary base material 1 ((a) of FIG. 1).
-The process of pressing the type | mold 5 which has the convex part 5a on the surface F1 on the opposite side to the temporary base material 1 of the workpiece | work 10a. The mold 5 is pressed against the workpiece 10a so that the tip 5b of the convex portion 5a does not reach the surface F2 on the temporary base 1 side of the workpiece 10a. Thereby, the recessed part 10c inverted with respect to the convex part 5a can be formed in the surface F1 side of the workpiece | work 10b ((b)-(c) of FIG. 1).
A step of removing the mold 5 from the workpiece 10b in which the recess 10c is formed ((d) in FIG. 1).
A step of irradiating the workpiece 10b with light to advance the curing of the workpiece 10b ((e) in FIG. 1).
A step of laminating the workpiece 10b and the substrate 2 by superimposing the surface F1 on which the concave portion 10c of the workpiece 10b is formed and the substrate 2 ((f) of FIG. 1).
A step of applying heat to the workpiece 10b ((g) in FIG. 1).
-The process of irradiating the workpiece | work 10b with light from the temporary base material 1 side ((h) of FIG. 1).
-The process of peeling the temporary base material 1 from the workpiece | work 10b ((i) of FIG. 1).
A step of thermosetting the workpiece 10b ((j) in FIG. 1).

  FIG. 2 is a schematic diagram showing a variation of a mold for forming the recess 10c in the workpiece 10b. As shown to (a)-(g) of FIG. 2, the various type | molds 5 which have the level | step difference and / or taper shape, and contain the convex part 5a from which a width | variety changes in the thickness direction can be used. Using the mold 5 shown in FIG. 2, the workpiece 10b having the concave portions 10c corresponding to the shapes of the convex portions 5a can be manufactured through the same steps as in FIG.

<Workpiece production process>
The workpiece 10a is made of a resin composition, and is preferably formed by a method in which the film thickness is uniform, and more preferably flat. The preferable thickness of the workpiece 10a depends on the shape of the recess 10c to be manufactured. When the workpiece 10a has an appropriate thickness, the resin composition is easily filled, and the resin composition can be more effectively suppressed from remaining on the die 5 when the die 5 is removed from the workpiece 10b.

  What is necessary is just to determine the thickness of the workpiece | work 10a according to the shape or size of the recessed part 10c, or the kind of electronic component to produce, For example, it can be set as the range of 1-100 micrometers. If it is in this range, 1-15 micrometers may be sufficient, for example, 1-50 micrometers may be sufficient, 10-100 micrometers may be sufficient, or 1-10 micrometers may be sufficient. For example, if the thickness of the workpiece 10a is 10 to 100 μm and the mold 5 having a height of the convex portion 5a of 10 μm is used, the imprinting is performed while maintaining a good shape of the concave portion 10c. In addition, an interval (remaining film thickness) between the surface F2 of the workpiece 10b and the tip portion 5b of the convex portion 5a can be left.

  In addition, it is preferable that the space | interval (residual film thickness) of the surface F2 of the workpiece | work 10b and the front-end | tip part 5b of the convex part 5a shall be 1-95 micrometers from a viewpoint of the intensity | strength of the recessed part 10c. As shown in FIG. 3, the “residual film thickness” referred to here is obtained when the mold 5 having the convex portion 5 a is pressure-bonded to the workpiece 10 a while being heated and the mold 5 is removed to form the workpiece 10 b having the concave portion 10 c. The thickness d of the workpiece | work 10b which remains between the convex part 5a of the type | mold 5 and the temporary base material 1 is meant.

  The workpiece 10a is formed flat, for example, by applying a resin composition (hereinafter also referred to as “imprinting resin composition”) to the temporary substrate 1, and removing the solvent from the coating film as necessary. Can do. If necessary, the resin composition may be dissolved or dispersed in a solvent to prepare a coating solution, and the coating solution may be applied to the temporary substrate 1. The method of application is not particularly limited, and for example, a method such as spin coating or dip coating can be used. Details of the resin composition for imprint will be described later.

  Or the workpiece | work 10a can be previously formed on another base material, and the resin film for imprint which has the workpiece | work provided on the base material and the base material can also be prepared. Apply a resin composition for imprinting or a solution or dispersion thereof to a substrate, and dry the coating film by heating for 1 minute to 1 hour at, for example, 60 to 120 ° C. using a hot plate, oven, etc. A workpiece can be formed on the substrate.

  As the temporary substrate 1, an organic film such as polyethylene terephthalate, polycarbonate, polyethylene, polypropylene, or polyethersulfone can be used. From the viewpoint of heat resistance, polyethylene terephthalate, polycarbonate, polypropylene, and polyethersulfone are preferable. As the temporary substrate 1, a film having a thickness of 5 to 150 μm can be used. From the viewpoint of ensuring coverage and suppressing a decrease in resolution when exposure is performed through the temporary base material 1, the thickness of the temporary base material 1 is preferably 5 to 100 μm, and preferably 10 to 70 μm. More preferred.

  The temporary substrate 1 preferably has the following characteristics. First, the temporary base material 1 preferably has no release layer on the surface. In the step of pressing the mold 5 against the workpiece 10a and then peeling the mold 5 from the workpiece 10b, the adhesive strength between the temporary base 1 and the workpiece 10b is higher than the adhesive strength between the mold 5 and the workpiece 10b. This is because it is preferable to maintain good releasability from 5. Secondly, the temporary substrate 1 preferably has a property of transmitting actinic rays. In the step of peeling the temporary base material 1 from the work 10b after the surface F1 of the work 10b and the substrate 2 are opposed to each other and the work 10b is bonded to the substrate 2, the releasability of the work 10b and the temporary base material 1 is released. Is required to be high. This is because the release property between the workpiece 10b and the temporary substrate 1 can be improved by irradiating the temporary substrate 1 and the workpiece 10b with light. Third, the temporary substrate 1 preferably has a heat resistance of 150 ° C. or higher. This is because heat is applied to the temporary substrate 1 during bonding. Fourthly, from the viewpoint of efficiently carrying out the step of peeling the temporary base material 1 from the workpiece 10b, the temporary base material 1 preferably has moderate flexibility.

  A protective film selected from a polyethylene terephthalate film, a polyethylene film, a polypropylene film, and the like may be laminated on the workpiece 10a.

<Exposure process>
After the workpiece 10 a is formed on the temporary substrate 1, light (active light) may be applied to the workpiece 10 a from the side opposite to the temporary substrate 1. This light irradiation can improve the releasability of the surface of the workpiece 10a while maintaining the fluidity of the workpiece 10a suitable for imprinting. As a result, after the mold 5 is pressed against the workpiece 10a to form a pattern on the workpiece 10a, the adhesion of the workpiece 10a to the mold 5 is suppressed.

The type of light to be irradiated is not particularly limited. For example, at least one actinic ray selected from the group consisting of ultraviolet rays, visible rays, electron beams and X-rays is irradiated using a light source usually used in the field. The Among these, ultraviolet rays and visible rays are particularly preferable. The exposure amount is, for example, 1 to 4000 mJ / cm ² , preferably 1 to 2000 mJ / cm ² , more preferably 1 to 1000 mJ / cm ² , and particularly preferably 5 to 500 mJ / cm ^2. Can be appropriately adjusted in consideration of a suitable balance between the property and fluidity. When the exposure amount is increased, the releasability of the workpiece 10a is improved, and the fluidity of the workpiece 10a tends to be lowered. In particular, when the workpiece 10a contains a photopolymerizable compound, the release property and fluidity of the workpiece 10a are good by irradiating light with an exposure amount that allows the photopolymerization of the photopolymerizable compound to partially proceed. Balance can be easily achieved.

<Imprint>
Next, a mold 5 having convex portions 5a is prepared, and the mold 5 is pressed against one surface F1 of the workpiece 10a (first step). At this time, the resin composition remains between the surface F2 and the tip 5b of the workpiece 10a by adjusting so that the tip 5b of the convex portion 5a of the mold 5 does not reach the other surface F2 of the workpiece 10a. Let Thereby, the pattern including the recessed part 10c which does not penetrate to the other surface F2 in the one surface F1 side of the workpiece | work 10a is formed. The method of pressing the mold 5 against the workpiece 10a is not particularly limited, and a method of pressing the mold 5 by hand, a method of pressing the mold 5 at a high pressure using a press device, or the like can be used. As the mold 5, a silicon or quartz mold or the like can be used. The mold 5 may be subjected to a mold release process.

  When the mold 5 is pressed against the workpiece 10a, the resin composition constituting the workpiece 10a flows, whereby the space between the surface of the mold 5 and the surface F1 of the workpiece 10a is filled with the resin composition. Thereby, the workpiece | work 10b which has the recessed part 10c is formed. That is, the workpiece 10 a is patterned by imprinting using the mold 5. In the step of pressing the mold 5 against the workpiece 10a, it is preferable to heat the mold 5 particularly when the viscosity of the workpiece 10a is high in order to ensure a good filling property of the resin. The temperature of the mold 5 is preferably 40 ° C. or higher, more preferably 60 ° C. or higher, and still more preferably 80 ° C. or higher. The remaining film thickness of the target workpiece 10b is more reliably adjusted by adjusting the temperature of the mold 5. Can be achieved. Further, the imprint temperature is preferably set to 300 ° C. or lower for reasons such as preventing decomposition of the resin.

  The atmosphere when pressing the mold 5 against the workpiece 10a is not particularly limited, but it is preferable to perform the step under reduced pressure in order to prevent bubbles from remaining in the workpiece 10a. In particular, when the workpiece 10a contains a polymerizable unsaturated compound (photopolymerizable compound) having a carbon-carbon double bond such as a (meth) acryloyl group, an allyl group, or a vinyl group, the pressure is reduced in order to prevent polymerization inhibition due to oxygen. It is preferred to carry out the process below.

  After the workpiece 10b having a pattern is formed, the mold 5 is removed from the workpiece 10b (second step).

<Curing process>
After removing the mold 5, the workpiece 10b may be cured. Thereby, the pattern shape formed in the workpiece | work 10b can be maintained favorable. As the curing process, for example, light (active light) is irradiated from the side opposite to the temporary substrate 1 to cure the workpiece 10b. This light irradiation improves the heat resistance, and can sufficiently suppress the workpiece 10b from being melted by heat. For example, even if the workpiece 10b is stored at a temperature of room temperature or higher after imprinting, it is possible to suppress melting due to heat by passing through a curing process and to maintain a fine pattern dimension. It is advantageous. Further, in the step of bonding the surface F1 of the workpiece 10b on which the concave portion 10c is formed and the surface 2a of the substrate 2 facing each other, the pattern of the concave portion 10c formed on the workpiece 10b is satisfactorily maintained when bonding by thermocompression bonding it can.

The light irradiation can be performed by irradiating the work 10b with actinic rays such as ultraviolet rays and visible rays, similarly to the light irradiation before imprinting. Although the light curing sufficiently advanced, while so as not to lose adhesion, exposure amount, for example 1~4000mJ / cm ^2, is preferably adjusted within the range of 500~2000mJ / cm ^2. This photo-curing makes it difficult for the workpiece 10b to be softened during thermocompression bonding, and the shape of the pattern of the recess 10c can be maintained well. Therefore, it is preferable that the workpiece 10b is photocured before the surface of the workpiece 10b on which the concave portion 10c is formed and the main surface of the substrate 2 are bonded together. The effect of pattern holding by photocuring is particularly prominent when the workpiece 10b contains a photopolymerization initiator. The fact that the shape of the recess 10c of the workpiece 10b is easily maintained is particularly advantageous when, for example, a fine pattern is formed.

<Lamination process>
Next, the work 10b adheres to the surface of the substrate 2 by superimposing the surface F1 on which the concave portion 10c of the light-irradiated work 10b is formed and the surface 2a of the substrate 2. Thereby, the hollow structure 50 which has the hollow part 20 formed of the surface 2a and the recessed part 10c of the board | substrate 2 can be formed (3rd process). In the step of pressing the workpiece 10b against the substrate 2 (bonding step), in order to ensure good filling and adhesion of the resin composition, especially when the viscosity of the workpiece 10b is high, It is preferable to apply a load between the substrates 2 and to be heated at 40 ° C. or higher. Moreover, it is preferable that the temperature to heat is 300 degrees C or less for reasons, such as preventing decomposition | disassembly of resin. The pressure is preferably 3 kg / cm ² or less for reasons such as maintaining the shape of the workpiece 10b. By appropriately setting the conditions such as pressure, temperature, and time for pressing in the bonding step, the workpiece 2 can be bonded to the substrate 2 while maintaining the concave shape.

<Adhesive application>
In order to ensure adhesiveness, an adhesive may be applied on the substrate 2 that is the bonding destination. The adhesive layer is preferably formed by a method in which the film thickness becomes uniform. The preferred thickness of the adhesive layer is usually 1 to 100 μm, preferably 1 to 50 μm. The adhesive layer can be formed, for example, by applying the resin composition to the temporary substrate 1 and removing the solvent from the coating film as necessary. If necessary, the resin composition may be dissolved or dispersed in a solvent to prepare a coating solution, and the coating solution may be applied to the temporary substrate 1. The method of application is not particularly limited, and for example, a method such as spin coating or dip coating can be used.

  The adhesive may be a composition having adhesiveness, preferably a composition excellent in pattern formation with an alkali developer, and more preferably a composition excellent in low-temperature sticking property. As an adhesive resin composition, polyimide resin, polyhydroxyamide resin, epoxy resin, cyanate resin, bismaleimide resin, phenol resin, urea resin, melamine resin, alkyd resin, acrylic resin, unsaturated polyester resin, diallyl phthalate resin, Silicone resin, resorcinol formaldehyde resin, xylene resin, furan resin, polyurethane resin, ketone resin, triallyl cyanurate resin, polyisocyanate resin, resin containing tris (2-hydroxyethyl) isocyanurate, triallyl trimellitate In addition to resin containing, thermosetting resin synthesized from cyclopentadiene, thermosetting resin by trimerization of aromatic dicyanamide, compound that reacts with carboxyl group and / or hydroxyl group of alkali-soluble resin. As an amino group, isocyanate group, oxazoline group, carbodiimide group, it may be composed of compounds having an epoxy group. Among them, an epoxy resin, a cyanate resin, and a bismaleimide resin are preferable because they can have an excellent adhesive force at a high temperature, and it is particularly preferable that the resin is composed of an epoxy resin in terms of handleability and compatibility with a polyimide resin. .

  The adhesive layer may be irradiated with light. When the adhesive force is too strong, the adhesiveness can be reduced by irradiating with light, and the handleability is improved. The improvement in handleability by light irradiation is particularly noticeable when the adhesive layer contains a photopolymerization initiator and a photopolymerizable compound. On the other hand, when the adhesive layer is irradiated with light and further thermally cured, the adhesive property of the adhesive layer may be lost. In this case, the temperature condition for bonding the workpiece 10b and the substrate 2 may need to be relatively high. As a result of bonding at a high temperature, the shape retainability is lost, and it becomes difficult to produce a concave pattern with high accuracy. Therefore, it is preferable that the work 10b and the adhesive layer are thermally cured at the same time after the work 10b and the substrate 2 are bonded to each other through the adhesive layer formed on the substrate 2 instead of thermosetting the adhesive layer alone. .

<Curing process>
After the workpiece 10b having the recess 10c and the substrate 2 are bonded together, the temporary base material 1 is removed from the workpiece 10b. Before removing, the temporary base material 1 side may be irradiated with light as a curing treatment. By performing light irradiation, photocuring of the resin composition in the workpiece 10b proceeds, and the adhesiveness of the resin composition can be reduced. Thereby, the release property of the temporary base material 1 and the workpiece | work 10b can be improved, and the temporary base material 1 can be easily peeled from the workpiece | work 10b. Furthermore, by performing photocuring prior to the heat curing treatment, the work 10b can be sufficiently prevented from melting during the heat curing, and the pattern shape of the recess 10c can be maintained well. Effects such as pattern retention and improvement of releasability by photocuring appear more remarkably when the workpiece 10b contains a photopolymerization initiator. The fact that the pattern shape of the workpiece 10b is easily maintained is particularly advantageous when, for example, a fine pattern is formed.

  After the temporary base material 1 is removed from the workpiece 10b, the workpiece 10b is further cured, whereby the heat resistance, physical strength, and the like of the workpiece 10b can be increased. The workpiece 10b can be cured by heating the workpiece 10b, irradiating the workpiece 10b with light, or a combination thereof. The heating method for thermosetting is not particularly limited, but in order to avoid melting of the resin composition, the glass transition temperature of the resin composition in the workpiece 10b is set to 50 to 200 ° C. and is equal to or lower than the glass transition temperature of the workpiece 10b. The temperature is gradually raised while maintaining the temperature of. Thereby, even after thermosetting, the pattern formed on the workpiece 10b can be particularly easily held. Moreover, the thermal decomposition of resin can be prevented by making the temperature of heating into 300 degrees C or less. Thereby, the hollow structure 50 which has the hollow part 20 which has a sufficiently high dimensional accuracy can be obtained. In addition, the glass transition temperature of a resin composition can be measured by DSC (differential scanning calorimetry), for example.

  The hollow structure 50 manufactured by the method described above is applied to an electronic component, for example. In this case, a cured product of the resin composition (work) in the electronic component may function as a permanent film, for example.

<Resin composition for imprint>
The resin composition that can be suitably used to form the workpiece 10a in the method according to the present embodiment will be described in detail.

  The resin composition according to this embodiment preferably contains (A) a photopolymerizable compound and (B) a photopolymerization initiator.

(A) Photopolymerizable compound The resin composition according to this embodiment may contain one or more compounds having a photopolymerizable functional group as the photopolymerizable compound of the component (A). The number of photopolymerizable functional groups is not particularly limited, but two or more photopolymerizable groups in the molecule can be used from the viewpoints of curing speed during pattern formation and physical and chemical durability of the coating after curing. A compound having a functional group of The proportion of the compound having two or more photopolymerizable functional groups in the component (A) is preferably 30% by mass to 100% by mass, more preferably 40% by mass to 100% by mass, and still more preferably 50%. It is not less than 100% by mass.

  The photopolymerizable functional group may be, for example, at least one selected from the group consisting of a (meth) acryloyl group, a vinyl group, an allyl group, an epoxy group, and an oxetanyl group. Among these functional groups, a (meth) acryloyl group is preferable in order to shorten the curing time and realize high throughput. (A) The ratio of the compound which has a (meth) acryloyl group in the whole component becomes like this. Preferably they are 30 mass% or more and 100 mass% or less. The (meth) acryloyl group has a shorter chain (for example, an oxyethylene group) than a long chain (for example, the number of oxyethylene groups is 10 to 30) from the viewpoint of the flexibility of the resin composition after curing and the crosslinking density of the resin composition. Is more preferably 2-4). In addition, from the viewpoint of maintaining the shape of the resin composition before and after curing, the component (A) is preferably 0 to 300 parts by mass, more preferably 100 parts by mass of the heat resistant resin of the component (C) described later. It is 20-200 mass parts, More preferably, it is 50-200 mass parts.

  Examples of the compound having one (meth) acryloyl group include methyl (meth) acrylate, ethyl (meth) acrylate, (n-propyl) (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylic acid. -N-butyl, isobutyl (meth) acrylate, (sec) -butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acryl Decyl acid, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid-2- Hydroxypropyl, (meth) acrylic acid-3-hydroxypropyl, (meth) acrylic acid-2- Mono (meth) acrylates such as droxybutyl, (meth) acrylic acid-2-hydroxyphenylethyl, and N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-acryloylmorpholine, etc. It may be at least one selected from the group consisting of (meth) acrylamide.

  Examples of the compound having two or more (meth) acryloyl groups include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and diethylene glycol di (meth) acrylate. , Polyfunctional (meth) acrylates such as triethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol penta (meth) acrylate, and epoxy resin ( It may be at least one selected from the group consisting of so-called epoxy (meth) acrylates obtained by adding (meth) acrylic acid. Epoxy (meth) acrylates include, for example, bisphenol A type epoxy resins, hydrogenated bisphenol A type epoxy resins, brominated bisphenol A type epoxy resins, bisphenol F type epoxy resins, novolac type epoxy resins, phenol novolac type epoxy resins, cresol novolacs. Type epoxy resin, cycloaliphatic epoxy resin, N-glycidyl type epoxy resin, bisphenol A novolac type epoxy resin, chelate type epoxy resin, glyoxal type epoxy resin, amino group-containing epoxy resin, rubber-modified epoxy resin, dicyclopentadiene phenolic Derived from type epoxy resin, silicone modified epoxy resin or ε-caprolactone modified epoxy resin.

  Examples of the compound having one vinyl group include n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, octadecyl vinyl ether, monovinyl ether such as cyclohexyl vinyl ether, vinyl acetate, vinyl propionate, butyric acid. Monovinyl esters such as vinyl and vinyl benzoate; divinyl esters such as divinyl adipate; N-vinylamides such as N-vinylpyrrolidone and N-methyl-N-vinylacetamide; and styrene and 2,4-dimethyl-α-methyl Styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 2,6-dimethylstyrene, 3, -Dimethylstyrene, 3,5-dimethylstyrene, 2,4,6-trimethylstyrene, 2,4,5-trimethylstyrene, pentamethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, o- Chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-bromostyrene, m-bromostyrene, p-bromostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-hydroxystyrene, m- Hydroxystyrene, p-hydroxystyrene, 2-vinylbiphenyl, 3-vinylbiphenyl, 4-vinylbiphenyl, 1-vinylnaphthalene, 2-vinylnaphthalene, 4-vinyl-p-terphenyl, 1-vinylanthracene, α-methyl Styrene, o-isopropenyltoluene, m- Sopropenyl toluene, p-isopropenyl toluene, 2,4-dimethyl-α-methylstyrene, 2,3-dimethyl-α-methylstyrene, 3,5-dimethyl-α-methylstyrene, p-isopropyl-α-methyl It may be at least one selected from the group consisting of styrene derivatives such as styrene, α-ethylstyrene and α-chlorostyrene.

  Examples of the compound having two or more vinyl groups include ethylene glycol divinyl ether, 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, 1,9-nonanediol divinyl ether, and cyclohexanedimethanol divinyl ether. , Diethylene glycol divinyl ether, triethylene glycol divinyl ether, trimethylolpropane trivinyl ether, polyfunctional vinyl ethers such as pentaerythritol tetravinyl ether, divinylbenzene, and at least one selected from the group consisting of divinylbiphenyl.

  The compound having one allyl group may be at least one selected from allyl esters such as allyl alcohol, ethylene glycol monoallyl ether, allylamine, allyl glycidyl ether, allyl acetate, and allyl benzoate. The compound having two or more allyl groups may be, for example, at least one selected from the group consisting of diallylamine, diallyl 1,4-cyclohexanedicarboxylate, diallyl phthalate, diallyl terephthalate, and diallyl isophthalate.

  The compound having one epoxy group is selected from, for example, glycidol and cyclohexene oxide. Examples of the compound having two or more epoxy groups include bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, and phenol novolac type epoxy. Resin, cresol novolac type epoxy resin, alicyclic epoxy resin, N-glycidyl type epoxy resin, bisphenol A novolac type epoxy resin, chelate type epoxy resin, glyoxal type epoxy resin, amino group-containing epoxy resin, rubber-modified epoxy resin, It may be at least one selected from the group consisting of a dicyclopentadiene phenolic epoxy resin, a silicone-modified epoxy resin, and an ε-caprolactone-modified epoxy resin.

  The compound having one oxetanyl group is selected from, for example, 3-ethyl-3-hydroxymethyloxetane and 3-ethyl-3-methacryloxymethyloxetane. The compound having two or more oxetanyl groups is selected from, for example, Aron Oxetane OXT-121 (trade name) manufactured by Toagosei Co., Ltd., OXTP (trade name) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., and OXBP (trade name). It is.

  It is preferable that the resin composition which concerns on this embodiment contains the (meth) acrylate compound which has a urethane bond as a photopolymerizable compound. By including the (meth) acrylate compound which has a urethane bond in a resin composition, the heat resistance of the resin layer after hardening can be improved. More specifically, the high-temperature rigidity of the cured product of the resin layer is increased, the resin layer is further prevented from becoming brittle, and the resin layer can maintain good adhesion to the substrate and the like.

  Examples of the (meth) acrylate compound having a urethane bond include urethane (meth) acrylate and ethylene oxide (EO) -modified urethane di (meth) which are addition reaction products of a (meth) acrylic monomer having a hydroxyl group at the β-position and the like and a diisocyanate compound. Acrylate, ethylene oxide (EO) or propylene oxide (PO) modified urethane di (meth) acrylate, urethane (meth) acrylate having carboxyl group, diol compound, and bifunctional epoxy having two hydroxyl groups and two ethylenically unsaturated groups It may be at least one selected from the group consisting of a reaction product of (meth) acrylate and polyisocyanate.

  The (meth) acrylic monomer having a hydroxyl group at the β-position is at least selected from the group consisting of 2-hydroxyethyl (meth) acrylate, dipentaerythritol penta (meth) acrylate, and pentaerythritol tri (meth) acrylate, for example. One kind may be sufficient. The isocyanate compound may be, for example, at least one selected from the group consisting of isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-hexamethylene diisocyanate.

  Optimize the number of functional groups (number of (meth) acryloyloxy groups) and weight average molecular weight of (meth) acrylate compounds with urethane bonds to achieve both higher levels of heat resistance, rigidity and high adhesion. Is preferred. Thereby, since the range of the material which can be selected without increasing a viscosity excessively becomes wide, the viscosity of the resin composition for imprint apply | coated on a board | substrate can be adjusted easily. The viscosity of the resin composition for imprinting can be lowered by using a solvent, but by using a (meth) acrylate compound having a urethane bond with an appropriate number of functional groups and weight average molecular weight, the amount of the solvent Can be reduced. By reducing the amount of the solvent, it is easy to maintain good characteristics and reliability of the cured resin layer.

  The number of functional groups (number of (meth) acryloyloxy groups) of the (meth) acrylate compound having a urethane bond is preferably 2 to 15 from the viewpoints of heat resistance, adhesion, coatability, and pattern formability. The number of functional groups is more preferably 2 to 12, and still more preferably 2 to 10 from the viewpoint of the physical properties of the resin layer after curing and the stability of characteristics.

  When the number of functional groups is 2 or more, the heat resistance of the cured resin layer and the rigidity of the resin layer at high temperatures can be further increased. When the number of the functional groups is 15 or less, the cured resin layer can be prevented from becoming brittle and good adhesion can be obtained. Moreover, since the weight average molecular weight of a (meth) acrylate compound will not become large too much when the said functional group number is small, it is easy to adjust the viscosity of a resin composition to an appropriate range. Therefore, good coatability is easily obtained. Furthermore, after photo-curing and / or heat-curing, a large amount of unreacted (meth) acryloyl groups remain, and as a result, variations in physical properties and characteristics of the resin film can be more effectively avoided. .

  The weight average molecular weight (Mw) of the (meth) acrylate compound having a urethane bond is preferably 950 to 25000. The weight average molecular weight is more preferably 950 to 15000 from the viewpoint of improving coatability, and further preferably 950 to 11,000 from the viewpoint of compatibility. In the present specification, the value of the weight average molecular weight (Mw) means a value converted to standard polystyrene, which is measured using an eluent such as tetrahydrofuran or toluene by a gel permeation chromatography craft (GPC) method. .

  When the weight average molecular weight is 950 or more, the viscosity of the resin composition does not become too low, and it is possible to prevent the resin composition applied on the substrate from dripping. Moreover, it is preferable that a weight average molecular weight is 950 or more also from the point that formation of a thick film is easy and the reliability fall resulting from hardening shrinkage does not occur easily. When the weight average molecular weight is 25000 or less, the viscosity of the resin composition does not become too high, and particularly good coatability is obtained. Moreover, thick film formation is also easy.

［式中、ｎは５〜２０の整数を表す。］ Examples of the (meth) acrylate compound having a typical urethane bond include compounds represented by the following formulas (1) to (5), but are not limited thereto.

[Wherein n represents an integer of 5 to 20. ]

［式中、ｎは５〜２０の整数を表す。］

[Wherein n represents an integer of 5 to 20. ]

［式中、ｎは５〜２０の整数を表す。］

[Wherein n represents an integer of 5 to 20. ]

［式中、ｎは５〜２０の整数を表す。］

[Wherein n represents an integer of 5 to 20. ]

［式中、ｎは５〜２０の整数を表す。］

[Wherein n represents an integer of 5 to 20. ]

  As a commercial item of the said compound, as a compound represented by General formula (1), for example, UN-952 (functional group number: 10, Mw: 6500-11000) is a compound represented by General formula (2), for example. UN-904 (functional group number: 10, Mw: 4900) is a compound represented by the general formula (4), for example, UN-905 (functional group number: 15, Mw: 40000-200000). Moreover, as a commercial item of the (meth) acrylate compound which has a urethane bond, as a commercial item of the acrylate compound (compound which has an acryloyloxy group) which has a urethane bond, UN-333 (functional group number: 2, Mw: 5000), for example. ), UN-1255 (functional group number: 2, Mw: 8000), UN-2600 (functional group number: 2, Mw: 2500), UN-6200 (functional group number: 2, Mw: 6500), UN-3320HA (functional group number) : 6, Mw: 1500), UN-3320HC (functional group number: 6, Mw: 1500), UN-9000 PEP (functional group number: 2, Mw: 5000), UN-9200A (functional group number: 2, Mw: 15000), UN-3320HS (functional group number: 15, Mw: 4900), UN-6301 (functional group number: 2, Mw: 330) 0) (all are trade names, Negami Kogyo Co., Ltd.), TMCH-5R (trade name, Hitachi Chemical Co., Ltd.), KRM8452 (functional group number = 10, Mw = 1200), EBECRYL 8405 (urethane acrylate / 1, 6- Hexanediol diacrylate = 80/20 addition reaction product, number of functional groups = 4, Mw = 2700) (all are trade names, Daicel-Cytec Co., Ltd.).

  Examples of the methacrylate compound having a urethane bond (compound having a methacryloyloxy group) include UN-6060PTM (functional group number: 2, Mw: 6000, trade name, Negami Industrial Co., Ltd.), JTX-0309 (trade name, Hitachi Chemical) Co., Ltd.), UA-21 (trade name, Shin-Nakamura Chemical Co., Ltd.).

  From the viewpoint of improving heat resistance, the content of the (meth) acrylate compound having a urethane bond is preferably 10% by mass or more, more preferably 30% by mass, based on the total amount of the photopolymerizable compound as the component (A). As mentioned above, More preferably, it is 50 mass% or more. When the content is 10% by mass or more, various physical properties and characteristics required for coating properties and a cured product of the resin composition can be maintained at a higher level.

  In view of the coating properties of the resin composition and the physical properties and properties required for the cured product of the resin composition, in order to selectively blend other (meth) acrylate compounds described later, a urethane bond ( The content of (meth) acrylate is preferably 95% by mass or less, more preferably 85% by mass or less, and still more preferably 75% by mass or less.

  The resin composition according to this embodiment includes a (meth) acrylate compound having an amide bond, a compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid, a bisphenol A-based (meth) acrylate compound, glycidyl. At least one light selected from the group consisting of a compound obtained by reacting a group-containing compound with an α, β-unsaturated carboxylic acid, and a (meth) acrylic acid alkyl ester copolymer having an ethylenically unsaturated group It may contain a polymerizable compound. Among them, a (meth) acrylate compound having an amide bond can be preferably used in terms of increasing the tolerance of the imprint process in addition to improving resolution and adhesion.

  Among these, a (meth) acrylate compound having an amide bond is preferable in terms of increasing the tolerance of the imprint process in addition to improving heat resistance, resolution, and adhesion. The (meth) acrylate compound having an amide bond is preferably a compound represented by the following general formula (6) from the viewpoint of resolution and adhesion.

In formula (6), R ³¹ , R ³² and R ³³ each independently represent a divalent organic group, R ³⁴ represents a hydrogen atom or a methyl group, and R ³⁵ and R ³⁶ each independently represent hydrogen. An atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group is shown.

The divalent organic group as R ³¹ , R ³² or R ³³ is, for example, a phenylene group which may have a substituent, a pyridylene group which may have a substituent, a linear chain having 1 to 10 carbon atoms, or A branched alkylene group, a group having 1 to 10 carbon atoms including an alicyclic group which may have a substituent, or a hydroxyl group from bisphenol (such as 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane) Is a group formed by removing

  The compound represented by the general formula (6) can be obtained, for example, by reacting a compound having two oxazoline groups with a compound having two carboxy groups and / or a compound having two phenolic hydroxyl groups. . Thereby, a highly elastic and highly heat-resistant resin cured product is particularly easily formed.

Examples of the compound containing an oxazoline group used for synthesizing the compound represented by the formula (6) include a bisoxazoline represented by the following general formula (7). In the formula ^(7), R ^{33, R 35} and ^{R 36} have the same meanings as ^{R 33, R 35} and ^{R 36} in the formula (6).

  Examples of the bisoxazoline represented by the formula (7) include 2,2 ′-(1,3-phenylene) bis-2-oxazoline and 2,6-bis (4-isopropyl-2-oxazolin-2-yl). At least one selected from the group consisting of pyridine, 2,2′-isopropylidenebis (4-phenyl-2-oxazoline), and 2,2′-isopropylidenebis (4-tertiarybutyl-2-oxazoline) is there.

Examples of the compound having two phenolic hydroxyl groups (bisphenol) include biphenol, tetramethylbiphenol, dihydroxynaphthalene, dihydroxymethylnaphthalene, dihydroxydimethylnaphthalene, bis (4-hydroxyphenyl) ketone, and bis (4-hydroxy-3,5). -Dimethylphenyl) ketone, bis (4-hydroxy-3,5-dichlorophenyl) ketone, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, bis (4-hydroxy- 3,5-dichlorophenyl) sulfone, bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dichlorophenyl) Nyl) hexafluoropropane, bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxy-3,5-dimethylphenyl) dimethylsilane, bis (4-hydroxy-3,5-dichlorophenyl) dimethylsilane, bis (4 -Hydroxyphenyl) methane, bis (4-hydroxy-3,5-dichlorophenyl) methane, bis (4-hydroxy-3,5-dibromophenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2, 2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) Propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, bis (4- Droxyphenyl) ether, bis (4-hydroxy-3,5-dimethylphenyl) ether, bis (4-hydroxy-3,5-dichlorophenyl) ether, 9,9-bis (4-hydroxyphenyl) fluorene, 9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9,9-bis (4-hydroxy-3-bromophenyl) fluorene, 9, 9-bis (4-hydroxy-3-fluorophenyl) fluorene, 9,9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene 9,9-bis (4-hydroxy-3,5-dichlorophenyl) fluorene, and 9,9-bis (4- It may be at least one selected from the group consisting of (hydroxy-3,5-dibromophenyl) fluorene. Among these, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane is preferable. R ³¹ in the formula (1) is usually a residue obtained by removing a hydroxyl group from a compound having these two phenolic hydroxyl groups.

  The reaction between the compound having an oxazoline group and the compound having a carboxy group and / or the compound having a phenolic hydroxyl group is preferably performed at 50 to 200 ° C. If reaction temperature is 50 degreeC or more, reaction can be advanced efficiently, and if it is 200 degrees C or less, a side reaction can fully be suppressed. If necessary, the reaction may be carried out in a polar organic solvent such as dimethylformamide, dimethylacetamide, dimethylsulfoxide.

  Examples of the compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid include, for example, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups. Polypropylene glycol di (meth) acrylate, polyethylene polypropylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups, trimethylolpropane di (meth) acrylate, trimethylol Propane tri (meth) acrylate, ethylene oxide (EO) modified trimethylolpropane tri (meth) acrylate, propylene oxide (PO) modified trimethylolpropane tri (meth) acrylate, EO and PO modified trimethylolpropane tri (meth) acrylate Or at least one selected from the group consisting of tetramethylolmethane tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate Good.

  Examples of bisphenol A-based (meth) acrylate compounds include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxypolypropoxy). Phenyl) propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, and 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane It may be at least one selected from the group.

  The compound obtained by reacting a glycidyl group-containing compound with an α, β-unsaturated carboxylic acid is, for example, at least one epoxy selected from the group consisting of a novolac type epoxy resin, a bisphenol type epoxy resin and a salicylaldehyde type epoxy resin. The epoxy (meth) acrylate compound obtained by making resin and (meth) acrylic acid react may be sufficient.

  An acid-modified epoxy acrylate compound obtained by reacting an acid anhydride such as tetrahydrophthalic anhydride with the hydroxyl group of the epoxy (meth) acrylate compound can also be used as a photopolymerizable compound. As such an acid-modified epoxy acrylate compound, for example, EA-6340 (Shin Nakamura Chemical Co., Ltd., trade name) represented by the following general formula (8) is commercially available. In formula (8), m and n represent 0 or an integer of 1 or more, and the ratio of m to n is 100/0 to 0/100.

  Examples of (meth) acrylic acid alkyl ester copolymers having an ethylenically unsaturated group include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, and (meth) acrylic. It contains at least one (meth) alkyl acid ester selected from the group consisting of acid 2-ethylhexyl ester as a monomer unit.

  The (meth) acrylate compound used as the photopolymerizable compound of the component (A) preferably has a carbon-nitrogen bond and has an amide bond and / or a urethane bond from the viewpoint of improving heat resistance and adhesion ( More preferred are meth) acrylate compounds.

  The resin composition has a (meth) acrylate compound having an amide bond and a urethane bond from the viewpoint of improving the adhesion density by increasing the crosslink density, increasing the tolerance of the imprint process, and balancing heat resistance. It is preferable to contain a (meth) acrylate compound. In this case, the ratio of the (meth) acrylate compound having a urethane bond and the (meth) acrylate compound having an amide bond ((meth) acrylate compound having a urethane bond / (meth) acrylate compound having an amide bond) is preferably It is 40 / 60-90 / 10, More preferably, it is 50 / 50-85 / 15, More preferably, it is 60 / 40-80 / 20.

(B) Photopolymerization initiator The resin composition for imprints according to this embodiment may contain a photopolymerization initiator. Thereby, a photopolymerizable compound can be bridge | crosslinked efficiently by light irradiation and the viscoelasticity of a resin layer can be easily adjusted to the range suitable for an imprint process. When the resin layer having a pattern and the substrate are bonded together by thermocompression bonding, or when the resin layer is thermoset after the imprint process, the resin may melt and the pattern may be deformed due to the heating condition. However, since the resin composition contains a photoinitiator, the photopolymerizable compound can be efficiently cured by light irradiation after patterning, so that the pattern shape deteriorates due to thermal curing (sag of the pattern). Can be more effectively suppressed.

  The photopolymerization initiator is not particularly limited as long as it is a compound that generates a free radical by actinic rays. For example, acylphosphine oxide, oxime ester, aromatic ketone, quinones, benzoin ether compound, benzyl derivative, 2, 4 , 5-triarylimidazole dimer, acridine derivative, coumarin compound, N-phenylglycine, and at least one selected from the group consisting of N-phenylglycine derivatives. Among these, acylphosphine oxide and oxime ester are preferable from the viewpoint of improvement of photocurability and high sensitivity, and transparency of the cured film.

  Examples of the acylphosphine oxide include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (commercial product: “IRGACURE-819”, BASF Japan Ltd.), 2,4,6-trimethylbenzoyl-diphenyl. -Phosphine oxide (commercial item, "LUCIRIN TPO", BASF Japan Ltd.).

  Examples of the oxime ester include 1,2-octanedione-1- [4- (phenylthio) phenyl-2- (O-benzoyloxime) represented by the following formula (9) (commercially available product: “IRGACURE-OXE01”, BASF Japan Ltd.), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone-1- (O-acetyloxime) (commercially available product: “IRGACURE-OXE02”, BASF Japan Ltd.), and 1-phenyl-1,2-propanedione-2- [o- (ethoxycarbonyl) oxime] (commercial product: “Quantacure-PDO”, Nippon Kayaku Co., Ltd.) It may be at least one kind.

  Aromatic ketones include, for example, benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (ie Michler ketone), N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4. '-Dimethylaminobenzophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one (commercial product: “IRGACURE-651”, BASF Japan Ltd.), 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) -butan-1-one (commercial product: “IRGACURE-369”, BASF Japan Ltd.) and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1- At least selected from the group consisting of ON (commercial product: “IRGACURE-907”, BASF Japan Ltd.) It may be a species.

  The quinones are, for example, 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, and at least selected from the group consisting of 2,3-dimethylanthraquinone One kind may be sufficient.

  The benzoin ether compound may be at least one selected from the group consisting of benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether, for example.

  The benzyl derivative may be, for example, at least one selected from the group consisting of benzoin compounds such as benzoin, methylbenzoin, and ethylbenzoin, and benzyldimethyl ketal.

  2,4,5-Triarylimidazole dimer is, for example, 2- (2-chlorophenyl) -1- [2- (2-chlorophenyl) -4,5-diphenyl-1,3-diazol-2-yl ] 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, such as 4,5-diphenylimidazole, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, and 2- (p-methoxyphenyl) -4, It may be at least one selected from the group consisting of 5-diphenylimidazole dimers.

  The acridine derivative may be at least one selected from the group consisting of 9-phenylacridine and 1,7-bis (9,9′-acridinyl) heptane, for example.

  Coumarin compounds include, for example, 7-amino-4-methylcoumarin, 7-dimethylamino-4-methylcoumarin, 7-diethylamino-4-methylcoumarin, 7-methylamino-4-methylcoumarin, 7-ethylamino- 4-methylcoumarin, 7-dimethylaminocyclopenta [c] coumarin, 7-aminocyclopenta [c] coumarin, 7-diethylaminocyclopenta [c] coumarin, 4,6-dimethyl-7-ethylaminocoumarin, 4, 6-diethyl-7-ethylaminocoumarin, 4,6-dimethyl-7-diethylaminocoumarin, 4,6-dimethyl-7-dimethylaminocoumarin, 4,6-diethyl-7-ethylaminocoumarin, 4,6-diethyl -7-dimethylaminocoumarin, 2,3,6,7,10,11-hexanehydro-1H, H-cyclopenta [3,4] [1] benzopyrano- [6,7,8-ij] quinolizine 12 (9H) -one, 7-diethylamino-5 ′, 7′-dimethoxy-3,3′-carbonylbiscoumarin 3,3′-carbonylbis [7- (diethylamino) coumarin] and 7-diethylamino-3-thienoxysilkine may be at least one selected from the group consisting of

  The content of the photopolymerization initiator is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, and still more preferably 0 with respect to 100 parts by mass of the photopolymerizable compound (A). .75 to 5 parts by mass. When the content is within these ranges, the sensitivity and photocurability of the imprint resin composition are particularly enhanced, and the adjustment of the viscoelasticity of the resin layer and the retention of the pattern shape during thermosetting are further facilitated. Become.

(C) Heat Resistant Resin The resin composition according to the present embodiment is a compound different from the photopolymerizable compound selected from a polymer compound and a thermosetting resin (hereinafter sometimes referred to as “heat resistant resin”). May further be contained. Thereby, regarding the resin layer after curing, the effects of high heat resistance, thermal conductivity, heat cycle resistance, and high mounting reliability with respect to lead-free high-temperature solder can be obtained.

  Examples of the heat resistant resin include phenol resin, novolac resin, epoxy resin, unsaturated polyester resin, alkyd resin, furan resin, urea resin, melamine resin, polyurethane resin, aniline resin, thermosetting modified polyphenylene ether resin, thermosetting It may be at least one selected from the group consisting of polyimide resins, allyl resins, bismaleimide triazine resins, silicon resins, and benzoxazine resins. Among these, epoxy resins, phenol resins, urea resins, unsaturated polyester resins, allyl resins, thermosetting polyimide resins, bismaleimide triazine resins, thermosetting modified polyphenylene ether resins, silicon resins, and benzoxazine resins are suitable. The epoxy resin is an organic compound (thermosetting resin) having at least one oxirane ring (epoxy group).

  The thermosetting resin as the heat resistant resin is preferably used in combination with a curing agent. Curing agents include, for example, polyphenolic curing agents, polyamine curing agents, carboxylic acid hydrazides, diaminomaleonitrile, dicyandiamide and derivatives thereof, imidazoles, polyamine nylon salts and phosphates, and Lewis acids and amine complexes thereof. It may be at least one selected from more.

  The polymer compound used as the heat resistant resin may be a polyamic acid or a polyamic acid ester. The polyamic acid or polyamic acid ester is represented, for example, by the following general formula (10).

In Formula (10), R ¹ represents a tetravalent organic group, R ² represents a divalent organic group, R ³ represents a hydrogen atom or a monovalent organic group, and a plurality of R ³ in the same molecule May be the same or different.

R ¹ is not particularly limited, but is a group formed by removing four hydrogen atoms from, for example, benzene, biphenyl, naphthalene, benzophenone, cyclobutane, cyclohexane, xanthene, or thioxanthene from the viewpoint of excellent low thermal expansion. Also good. R ² may be, for example, a group formed by removing two hydrogen atoms from benzene, biphenyl, benzophenone, or cyclohexane. These skeletons may be substituted with one or more substituents selected from a methyl group, a trifluoromethyl group, a fluorine atom and a hydroxyl group.

The monovalent organic group as R ³ is, for example, an aliphatic or aromatic hydrocarbon group having 1 to 10 carbon atoms such as methyl group, ethyl group, isopropyl group, t-butyl group, phenyl group, benzyl group, It may be at least one selected from the group consisting of an alkoxyalkyl group having 2 to 10 carbon atoms such as a methoxyethyl group and a group formed by substituting a fluorine atom for these. Of these, a hydrogen atom, an ethyl group, a 2,2,2-trifluoroethyl group, an isopropyl group, a t-butyl group, and a benzyl group are preferable.

As the heat-resistant resin, polyhydroxyamide, which is a polybenzoxazole precursor that forms polybenzoxazole by ring closure by heating, is preferable because of its excellent heat resistance, mechanical properties, and electrical properties. This polyhydroxyamide has a structural unit represented by the following general formula (11), for example. The amide unit containing a hydroxy group is finally converted into an oxazole having excellent heat resistance, mechanical properties, and electrical properties by dehydration and ring closure during curing. In formula (11), R ¹¹ represents a tetravalent organic group, and R ¹² represents a divalent organic group.

  The polyhydroxyamide having the structural unit represented by the formula (11) can be synthesized from, for example, a dicarboxylic acid compound and a diamine compound having a hydroxy group. Specifically, after converting a dicarboxylic acid compound to a dihalide compound, a polyhydroxyamide having a structural unit represented by the formula (11) can be synthesized by reacting the dihalide compound with the diamine compound. As the dihalide compound, a dichloride compound is preferable.

  The dichloride compound can be synthesized by reacting a dicarboxylic acid compound with a halogenating agent. As the halogenating agent, those used in usual acid chlorideation reaction of carboxylic acid, for example, thionyl chloride, phosphoryl chloride, phosphorus oxychloride, phosphorus pentachloride and the like can be used.

  The synthesis of the dichloride compound should be carried out by reacting the dicarboxylic acid compound and the halogenating agent in a reaction solvent, or by reacting in an excess halogenating agent and then distilling off the excess halogenating agent. Can do. As a reaction solvent, N-methyl-2-pyrrolidone, N-methyl-2-pyridone, N, N-dimethylacetamide, N, N-dimethylformamide, toluene, benzene and the like can be used. When the reaction is carried out in a solvent, the amount of the halogenating agent is preferably 1.5 to 3.0 mol, more preferably 1.7 to 2.5 mol, relative to 1.0 mol of the dicarboxylic acid compound. When the reaction is performed in a halogenating agent, the amount of the halogenating agent is preferably 4.0 to 50 mol, more preferably 5.0 to 20 mol, relative to 1.0 mol of the carboxylic acid compound. The reaction temperature is preferably -10 to 70 ° C, more preferably 0 to 20 ° C.

  The reaction between the dichloride compound and the diamine is preferably performed in an organic solvent in the presence of a dehydrohalogenating agent. As the dehydrohalogenating agent, organic bases such as pyridine and triethylamine are usually used. As the organic solvent, N-methyl-2-pyrrolidone, N-methyl-2-pyridone, N, N-dimethylacetamide, N, N-dimethylformamide and the like can be used. The reaction temperature is preferably −10 to 30 ° C., more preferably 0 to 20 ° C.

In formula (6), the tetravalent organic group represented by R ¹¹ is generally a residue of a diamine compound having two amino groups and two hydroxy groups. The hydroxy group may be located at the ortho position of the amino group. R ¹¹ is preferably a group containing an aromatic ring. The number of carbon atoms in R ¹¹ is preferably 6 to 40. R ¹¹ is preferably a tetravalent group having 6 to 40 carbon atoms and containing an aromatic ring. In the diamine compound, it is preferable that both the amino group and the hydroxyl group are directly bonded to the aromatic ring in R ¹¹ .

  Examples of the diamine compound include 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, bis (3-amino-4-hydroxyphenyl) propane, Bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 2,2-bis (3-amino-4) -Hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane and 2,2-bis (4-amino-3-hydroxyphenyl) -1,1,1,3,3,3-hexa It may be at least one selected from the group consisting of fluoropropane.

  In addition to the structural unit of the formula (11), the polyhydroxyamide may further include a structural unit having no hydroxyl group. That is, the polyhydroxyamide may be, for example, a polymer represented by the following general formula (12).

In the formula (12), R ¹³ represents a tetravalent organic group, and R ¹² represents a divalent organic group. j and k represent mole fractions, and the sum of j and k is 100 mol%, preferably j is 60 to 100 mol% and k is 40 to 0 mol%. More preferably, j is 80 to 100 mol% and k is 20 to 0 mol%.

In formula (12), the divalent organic group represented by R ¹³ is generally a residue of a diamine compound having no hydroxyl group, which reacts with a dicarboxylic acid compound to form a polyamide structure. R ¹³ is preferably a divalent aromatic group or an aliphatic group. The number of carbon atoms is preferably 4 to 40, and more preferably a divalent aromatic group having 4 to 40 carbon atoms.

  Examples of the diamine compound having no hydroxyl group include 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenyl sulfide, benzidine, m- Phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl And at least one aromatic diamine compound selected from the group consisting of bis [4- (4-aminophenoxy) phenyl] ether and 1,4-bis (4-aminophenoxy) benzene. The diamine compound may be a diamine having a silicone group. Examples of the diamine having a silicone group include LP-7100, X-22-161AS, X-22-161A, X-22-161B, X-22-161C, and X-22-161E (all Shin-Etsu Chemical Co., Ltd., Product name) and the like, but are not limited thereto. These compounds can be used alone or in combination of two or more.

In the formulas (11) and (12), the divalent organic group represented by R ¹² is generally a residue of a dicarboxylic acid compound used to synthesize polyhydroxyamide. R ¹² is preferably a divalent group containing an aromatic ring. R ¹² preferably has 6 to 40 carbon atoms. R ¹² is more preferably a divalent group having 6 to 40 carbon atoms including an aromatic ring. It is preferred that none of the two carboxyl groups are bonded directly to the aromatic ring in R ^12.

  Examples of the dicarboxylic acid compound include isophthalic acid, terephthalic acid, 2,2-bis (4-carboxyphenyl) -1,1,1,3,3,3-hexafluoropropane, and 4,4′-dicarboxybiphenyl. 4,4′-dicarboxydiphenyl ether, 4,4′-dicarboxytetraphenylsilane, bis (4-carboxyphenyl) sulfone, 2,2-bis (p-carboxyphenyl) propane, 5-tert-butylisophthalic acid Aromatic dicarboxylic acids such as 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,6-naphthalenedicarboxylic acid, and 1,2-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid , 1,3-cyclopentanedicarboxylic acid, oxalic acid, malonic acid, succinic acid, etc. It may be at least one selected from the group consisting of carboxylic acid.

  When the content of the heat resistant resin is 100 parts by mass, the content of the photopolymerizable compound as the component (A) is preferably 0 to 300 parts by mass, more preferably 20 to 200 parts by mass, and still more preferably 50 to 50 parts by mass. 200 parts by mass. By keeping the contents of the heat-resistant resin and the photopolymerizable compound within these ranges and adjusting the temperature during imprinting, the pattern can be easily retained even after thermosetting. From the viewpoint of maintaining the shape of the concave pattern, the glass transition temperature of the heat resistant resin is preferably 40 to 300 ° C, more preferably 50 to 200 ° C.

(D) Other components The resin composition for imprints may contain an adhesion aid in order to improve the adhesion between the resin composition for imprints and the substrate, if necessary. Examples of the adhesion assistant include silane coupling agents such as γ-glycidoxysilane, aminosilane, and γ-ureidosilane. The content of the adhesion assistant is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, and still more preferably 0.1 to 100 parts by mass of the photopolymerizable compound (A). 5 to 2 parts by mass.

  Moreover, a thermal radical generator can be further added to the above-mentioned resin composition for imprints. Examples of the thermal radical generator include t-butylcumyl peroxide (perbutyl C), n-butyl 4,4-di- (t-butylperoxy) valerate (perhexa V), dicumyl peroxide (park mill D). And peroxides such as 1,1-di-t-hexylperoxycyclohexane (perhexa HC). The content of the thermal radical generator is preferably 0.1 to 30 parts by mass, more preferably 0.2 to 20 parts by mass, and 0.5 to 10 parts by mass with respect to 100 parts by mass of the component (A). Further preferred.

  Moreover, an inorganic filler can be added to the above-mentioned resin composition for imprints. By adding an inorganic filler, the fluidity of the imprint resin composition can be adjusted, and the process margin when the imprint resin composition is formed into a film can be increased. When forming a resin layer having a pattern by photolithography technology, it is generally difficult to contain an inorganic filler in the resin layer, but according to the imprint method, the resin layer containing the inorganic filler can be easily patterned. Can do.

  The shape of the inorganic filler may be any of a spherical shape, a crushed shape, a needle shape, or a plate shape, and a desired shape can be selected according to the particle size and the like. For example, an inorganic filler having a small particle diameter having a volume average particle diameter in the range of 10 nm to 1 μm and having a spherical or nearly spherical shape not only increases the elastic modulus at a high temperature of the resin composition for imprint, Mechanical strength can be improved. Furthermore, the effect of imparting thixotropy to the imprinted resin composition before curing and improving the coating property can also be obtained. Therefore, an inorganic filler having a small particle size is suitable when it is desired to further improve the physical properties and characteristics of the resin composition without substantially affecting the light transmission and light absorption. A large particle size inorganic filler having a volume average particle size in the range of 1 μm to 50 μm can greatly increase the elastic modulus at high temperatures of the resin composition for imprinting, and thus has a great effect on the shape retention of the pattern. Can be demonstrated. A plate-like inorganic filler is preferable in that the moisture absorption rate and moisture permeability of the cured product of the imprint resin composition can be significantly reduced. From these viewpoints, silica, alumina, or the like having a volume average particle size in the range of 10 nm to 50 μm can be preferably used as the inorganic filler.

  From the viewpoint of workability when applying the imprint resin composition to a temporary substrate or the like, a solvent is added to the imprint resin composition to prepare a resin composition solution or dispersion as a coating liquid. Also good. The solvent to be used is not particularly limited, but includes, for example, polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, propylene glycol monomethyl ether acetate, and γ-butyrolactone. It may be at least one selected from the group. The concentration of the resin composition for imprint in the coating solution is preferably 20 to 85% by mass, more preferably 30 to 80% by mass, based on the mass of the coating solution.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

<Synthesis of heat-resistant resin>
Hereafter, the synthesis method of the heat resistant resin which is (C) component is shown. The weight average molecular weight was determined by GPC method using a mixed solution of tetrahydrofuran and N, N-dimethylacetamide as an eluent. Details of the GPC method are as follows.
Device name: HLC-8320GPC (product name, Tosoh Corporation)
Column: TSKgel SuperAWM-H, TSKgelguardcolumn
SuperAW-H, TSKgel SuperH2500, TSKgel SuperH3000, TSKgel SuperH4000, TSKgelguardcolumn SuperHL (all, Tosoh Corporation)
Detector: UV, RI detector Column temperature: 40 ° C
Eluent: Mixed solution of tetrahydrofuran and N, N-dimethylacetamide (mixing ratio 1: 1)
Additives: lithium bromide monohydrate (0.03 mol / L), phosphoric acid (0.06 mol / L)
Flow rate: 0.35 ml / min Standard material: Polystyrene

  In a flask equipped with a stirrer, a thermometer, a condenser tube, and a nitrogen displacement device, 1.89 g of 3,5-diaminobenzoic acid (molecular weight 152.2, hereinafter abbreviated as “DABA”), aliphatic ether diamine (BASF Corporation) "D-400" (trade name), molecular weight 452.4) 15.21 g, 1,1,3,3-tetramethyl-1,3-bis (4-aminophenyl) disiloxane (Shin-Etsu Chemical Co., Ltd.) "LP-7100" (trade name), molecular weight 248.5) 0.39g, and N-methyl-2-pyrrolidinone (hereinafter abbreviated as "NMP") 116g.

  Next, 16.88 g of 4,4′-oxydiphthalic dianhydride (molecular weight 326.3, hereinafter abbreviated as “ODPA”) was added to the flask in small portions while the flask was cooled in an ice bath. After completion of the addition, the mixture was further stirred at room temperature (25 ° C.) for 5 hours.

  Next, a reflux condenser with a moisture receiver was attached to the flask, 70 g of xylene was added, the temperature was raised to 180 ° C. while blowing nitrogen gas, the temperature was maintained for 5 hours, and xylene was removed azeotropically with water. . The solution thus obtained was cooled to room temperature and then poured into distilled water for reprecipitation. The obtained precipitate was dried with a vacuum dryer to obtain a polyimide resin (hereinafter referred to as “polyimide PI-1”). When the GPC of the obtained PI-1 was measured, it was Mw = 33000 in terms of polystyrene. Moreover, the glass transition temperature (Tg) of obtained PI-1 was 55 degreeC.

<Preparation of resin composition for imprint>
The photopolymerizable compound as component (A), the photopolymerization initiator as component (B), the heat resistant resin as component (C), and the other components as component (D) are mixed with N, N- Mixing was performed in dimethylacetamide at the ratio shown in Table 1 to obtain a resin composition solution for imprinting in each example. The numbers in the table indicate the mass parts of the solid content of each component. The detail of each component in a table | surface is shown below.
(A) Component: Photopolymerizable compound · UN-904, UN-952 (trade name, urethane acrylate, Negami Industrial Co., Ltd.)
M-313 (trade name, isocyanuric acid EO-modified di- and triacrylate, Toa Gosei Co., Ltd.)
FA-321M (trade name, EO-modified bisphenol A dimethacrylate, Hitachi Chemical Co., Ltd.)
FA-7220M (trade name, amide bond-containing methacrylate, Hitachi Chemical Co., Ltd.)
・ BPE-100 (trade name, ethoxylated bisphenol A dimethacrylate, Shin-Nakamura Chemical Co., Ltd.)
Component (B): Photopolymerization initiator / I-819 (trade name, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, Ciba Specialty Chemicals Co., Ltd.)
(C) component: heat resistant resin / HK-1 (trade name, Toho Chemical Co., Ltd.)
・ PI-1
・ VG-3101L (trade name, high heat resistant trifunctional epoxy resin, Printec Co., Ltd.)
・ YDF-8170C (trade name, liquid BPF type high purity epoxy resin, Nippon Steel & Sumikin Chemical Co., Ltd.)
EHPE-3150 (trade name, 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol, Daicel Corporation)
・ TrisP-PA (trade name, trisphenol compound, Honshu Chemical Industry Co., Ltd.)
(D) Other components A-1160 (trade name, 3-ureidopropyltriethoxysilane, Momentive Performance Materials)
・ A-187 (trade name, 3-glycidoxypropyltrimethoxysilane, Momentive Performance Materials)
・ SZ-6030 (trade name, 3-methacryloxypropyltrimethoxysilane, Toray Dow Corning Co., Ltd.)
・ Park mill D (trade name, dicumyl peroxide, NOF Corporation)
・ AEROSIL R972 (trade name, dimethylsilylated silica, Nippon Aerosil Co., Ltd.)

Table 1 shows the number of functional groups (acryloyloxy groups) and weight average molecular weight of urethane acrylate. The weight average molecular weight (Mw) is determined by GPC method using tetrahydrofuran and N, N-dimethylacetamide as an eluent. Details of the GPC method are as follows.
Device name: HLC-8320GPC (product name, Tosoh Corporation)
Columns: TSKgel Super AWM-H, TSK gel guard column Super A W-H, TSK gel Super H 2500, TSK gel Super H 3000, TSK gel Super H 4000, TSK gel guard column Super H
Detector: UV, RI detector Column temperature: 40 ° C
Eluent: Mixed solution of tetrahydrofuran and N, N-dimethylacetamide
(Mixing ratio 1: 1)
Additives: lithium bromide monohydrate (0.03 mol / L), phosphoric acid (0.06 mol / L)
Flow rate: 0.35 ml / min Standard material: Polystyrene

<Preparation of resin film for imprint>
The solution of the resin composition for imprints and the solution of the resin composition for adhesion were each uniformly applied onto polyethylene terephthalate as a temporary substrate using an applicator. The applied solution was heated with a dryer at 120 ° C. for 20 minutes to remove the solvent. Thus, an imprinting resin film having a two-layer structure in which the adhesive resin layer and the imprinting resin layer (work) were laminated in this order from the surface side of the temporary base material was obtained. On top of that, a cover film was bonded to the obtained workpiece in order to prevent adhesion of dust, dust and the like.

<Evaluation of remaining film thickness>
After peeling the work cover film formed on the temporary base material, the work is placed on the test substrate (transparent polyethylene terephthalate film, product name “Purex Film A31”, Teijin DuPont Films Ltd.). Lamination was performed in the direction located on the side. Lamination was performed using a laminator. In the case of Examples 4 to 7, the workpiece laminated on the test substrate was irradiated with light at an exposure amount of 500 mJ / cm ² using a high-precision parallel exposure machine (Oak Manufacturing Co., Ltd.) (imprint). Previous light irradiation).

Next, after peeling the temporary base material from the workpiece, the workpiece is placed on a silicon mold together with the test substrate, and these are set on a crimping machine and heated while heating at 40-100 ° C. for 2 minutes at 8 MPa. Pressed. After pressurizing and removing the mold from the workpiece, the coating film of the patterned workpiece was observed using a scanning electron microscope, the remaining film thickness was measured, and evaluation was performed based on the following criteria.
A: The remaining film thickness is 1 μm or more.
B: The remaining film thickness is less than 1 μm.

<Evaluation of pattern retention before and after bonding>
Similar to the evaluation of the remaining film thickness, after removing the work cover film formed on the temporary substrate, the test substrate (transparent polyethylene terephthalate film, product name “Purex Film A31”, Teijin DuPont Films Ltd. The workpiece was laminated on the test substrate side. Lamination was performed using a laminator. In the case of Examples 4 to 7, the workpiece laminated on the test substrate was irradiated with light at an exposure amount of 500 mJ / cm ² using a high-precision parallel exposure machine (Oak Manufacturing Co., Ltd.) (imprint) Previous light irradiation).

Next, after peeling the temporary base material from the workpiece, the workpiece is placed on a silicon mold together with the test substrate, and these are set on a crimping machine and heated while heating at 40-100 ° C. for 2 minutes at 8 MPa. Pressed. After pressurizing and removing the mold from the workpiece, the workpiece on which the pattern was formed was irradiated with light at an exposure amount of 1000 to 3000 mJ / cm ² using a high-precision parallel exposure machine (Oak Manufacturing Co., Ltd.).

A workpiece having a pattern is placed on the substrate of the transfer destination in such a direction that the workpiece pattern is located on the substrate side, and these are set in a crimping machine and heated to 60 to 80 ° C. at 1 kg / cm ² for 30 seconds. The pressure was applied. After pressurization, light was irradiated through the test substrate at an exposure amount of 2000 mJ / cm ² .

A workpiece (hereinafter also referred to as a workpiece-attached substrate) bonded by thermocompression bonding to the substrate was observed using a scanning electron microscope, and pattern retention was evaluated based on the following criteria.
A: There is no change in shape before and after bonding.
B: There is a change in shape before and after bonding, and the shape cannot be maintained.

<Evaluation of pattern retention before and after curing>
Similar to the above-described evaluation of the remaining film thickness, after removing the work cover film formed on the temporary substrate, the test substrate (polyethylene terephthalate film having transparency, product name “Purex film A31”, Teijin DuPont) Film Co., Ltd.) was laminated in such a direction that the workpiece was positioned on the test substrate side. Lamination was performed using a laminator. In the case of Examples 4 to 7, the workpiece laminated on the test substrate was irradiated with light at an exposure amount of 500 mJ / cm ² using a high-precision parallel exposure machine (Oak Manufacturing Co., Ltd.) (imprint) Previous light irradiation).

Next, after peeling the temporary base material from the workpiece, the workpiece is placed on a silicon mold together with the test substrate, and these are set on a crimping machine and heated while heating at 40-100 ° C. for 2 minutes at 8 MPa. Pressed. After pressurizing and removing the mold from the workpiece, the workpiece on which the pattern was formed was irradiated with light at an exposure amount of 1000 to 3000 mJ / cm ² using a high-precision parallel exposure machine (Oak Manufacturing Co., Ltd.).

A workpiece having a pattern is placed on a transfer destination substrate in such a direction that the workpiece pattern is located on the substrate side, and these are set in a crimping machine and heated at 60 to 80 ° C. for 30 seconds while being 1 kg / cm ^2. Was pressurized. After pressurization, light was irradiated through the test substrate at an exposure amount of 2000 mJ / cm ² . Then, after heating at 150 degreeC for 1 hour in oven, the workpiece | work was thermoset by heating at 200 degreeC for 1 hour.

The cured workpiece (cured film) was observed using a scanning electron microscope, and pattern retention was evaluated based on the following criteria.
A: The workpiece is not melted.
B: Shape change due to melting is observed.

  As shown in Table 1, each of the imprint resin compositions of Examples 1 to 7 has a remaining film thickness by imprinting at an appropriate temperature depending on the composition, with the imprint temperature being 40 ° C. or higher. It was confirmed to have a part. Moreover, the resin composition for imprints of Examples 1 to 4 contains a photopolymerizable compound and a photopolymerization initiator, and the content of the photopolymerizable compound in the resin composition for imprint is 40. It is at least mass%. As a result, photocuring can be sufficiently progressed by exposure, and when the work having a pattern is bonded to the transfer destination substrate by thermocompression bonding and when the curing reaction is advanced by heat, the resin is melted by heat. It was possible to prevent.

  As shown in Examples 6-7, the photopolymerizable compound was changed from FA-321M, which is a long chain acrylate, to BPE-100Y, which is a short chain acrylate, and the blending ratio was further adjusted, so that Example 7 was The shape change before and after curing could be suppressed. In the compound having the same skeleton, the flexibility of the cured product can be reduced by changing the long chain acrylate to the short chain acrylate. In addition, since the molecular weight of the short-chain acrylate is smaller than that of the long-chain acrylate, the number of moles of the short-chain acrylate with respect to the entire heat-resistant resin or imprint resin composition increases, and the crosslinking density of the imprint resin composition Will increase. As a result, as shown in Example 7, it is considered that the shape before and after curing can be suppressed in the composition in which the heat-resistant resin containing the short-chain acrylate is applied and the blending ratio is adjusted.

DESCRIPTION OF SYMBOLS 1 ... Temporary base material, 2 ... Board | substrate, 2a ... The surface of a board | substrate, 5 ... type | mold, 5a ... convex part, 5b ... tip part, 10a, 10b ... workpiece | work, 10c ... recessed part, 20 ... hollow part, 50 ... hollow structure F1 ... one surface of the workpiece, F2 ... the other surface of the workpiece.

Claims (9)

(A) a step of pressing a mold having a convex portion against one surface of a first workpiece made of a resin composition containing a photopolymerizable compound and (B) a photopolymerization initiator, wherein the first A first step of allowing the resin composition to remain between the other surface of the first workpiece and the tip without reaching the tip of the convex portion to the other surface of the workpiece;
Remove the mold from the first workpiece, a second step of the recess formed by the convex portion to obtain a second workpiece which is formed on the front surface of the hand,
A step of superimposing the substrate and the second work, wherein the surface of the substrate and the surface of the second work on which the recess is formed are overlapped to form the surface of the substrate and the recess. A third step of obtaining a structure having a hollow portion;
Are provided in this order.   The method according to claim 1, further comprising a curing treatment step in which curing of the resin composition proceeds after the second step or the third step. The method according to claim 2, wherein the curing treatment step includes irradiating the second workpiece with light.   The method according to claim 2, wherein the curing treatment step is performed after the third step. The method according to claim 1, wherein the resin composition contains an inorganic filler . 6. The method according to claim 1, wherein in the first step, a distance between the other surface of the first workpiece and the tip is 1 to 95 μm. The method according to claim 1, wherein, in the first step, the first work is irradiated with light before the mold is pressed against the first work. The hollow structure produced by the method according to any one of claims 1-7. An electronic component comprising the hollow structure according to claim 8 .

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