Picture frame and manufacturing method thereof

Abstract

To provide a picture frame capable of suppressing deterioration of artworks by a formic acid and an acetic acid over a long period, and to provide a manufacturing method thereof.SOLUTION: A picture frame equipped with a frame member having a storage space for storing artworks and a storage member for surrounding at least part of the storage space includes: a transparent plate in which the storage member is arranged on the front side of the storage space; a back plate arranged on the back side of the storage space; and a liner arranged inside the frame member between the transparent plate and the back plate. The storage member includes a resin member arranged at least on the artwork side, and including an alicyclic structure-containing polymer. Volatilization volume of a formic acid from the resin member is less than 1 μg / g, and volatilization volume of an acetic acid from the resin member is less than 1 μg / g. The resin member is molded at a molding temperature higher than a boiling point of the acetic acid.SELECTED DRAWING: Figure 2

Description

[Technical field]

[0001] The present invention relates to a picture frame and a method for manufacturing the same. [Background technology]

[0002] In the exhibition of artworks, the artworks may be stored in a picture frame to protect them (Patent Documents 1 to 4). Picture frames used for such exhibitions have a glass or acrylic panel as a window material on the front side of the storage space for the artwork. In addition, a functional film may be attached to the window material to prevent lighting from being reflected and interfering with the appreciation of the artwork.

[0003] Gases containing formic acid and acetic acid may be generated from wood, paper, and resin materials that constitute the components of a picture frame, as well as from functional films. Such gases may cause deterioration of artworks. In response to this problem, for example, Patent Documents 3 and 4 disclose the use of polyethylene terephthalate (PET) in functional films as a material that generates less gases containing components that deteriorate artworks, such as organic acids including acetic acid. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 4697502 [Patent Document 2] Patent No. 6424550 [Patent Document 3] JP 2017-146467 A [Patent Document 4] JP 2017-196782 A Summary of the Invention [Problem to be solved by the invention]

[0005] However, since artworks may be exhibited for several decades, there is a concern that traces of formic acid and acetic acid may deteriorate the artworks over time. However, Patent Documents 1 to 4 do not recognize this problem, and do not consider any measures to address it.

[0006] The present invention has been made in consideration of the above-mentioned circumstances, and has as its main object to provide a picture frame that generates extremely little gas including formic acid and acetic acid and can prevent deterioration of artworks over a long period of time. [Means for solving the problem]

[0007] The present inventors have conducted extensive research to solve the above problems and have found that the amount of volatilization (generation) of formic acid and acetic acid can be extremely reduced by molding a resin containing an alicyclic structure-containing polymer under specific conditions, thereby completing the present invention.

[0008] [1] A picture frame comprising a frame member having a storage space capable of storing an artwork, and a storage member surrounding at least a portion of the storage space, wherein the storage member includes a transparent plate disposed on the front side of the storage space, a back panel disposed on the back side of the storage space, and a liner disposed inside the frame member between the transparent plate and the back panel, wherein the storage member is disposed at least on the artwork side and includes a resin member containing an alicyclic structure-containing polymer, wherein the amount of formic acid volatilized from the resin member is less than 1 μg / g, and the amount of acetic acid volatilized from the resin member is less than 1 μg / g. [2] The frame according to [1], wherein the resin member is at least one member selected from the transparent plate, the back plate, and the liner. [3] The frame according to [1], wherein the resin members are the transparent plate, the rear plate, and the liner. [4] The frame according to [1], wherein the resin member is a covering member that covers at least a portion of the transparent plate, the back plate, and the liner on the artwork side. [5] The frame according to [4], wherein the covering member covers the artwork side of all of the components, namely the transparent plate, the back plate, and the liner. [6] The frame described in [1], including a protective member disposed on the surface of the liner that overlaps the artwork. [7] The frame according to [6], wherein the resin member is the protective member. [8] A method for producing the frame according to [1], comprising the step (A) of molding a resin containing an alicyclic structure-containing polymer at a molding temperature of (the boiling point of acetic acid + 100°C) or higher (the boiling point of acetic acid + 200°C) or lower to obtain the resin member. [9] The method for producing a picture frame according to [8], further comprising a step (B) of drying the resin containing the alicyclic structure-containing polymer prior to the step (A), in which the resin containing the alicyclic structure-containing polymer is dried at a temperature of (Tg-60)°C or higher (Tg-10)°C, where Tg is the glass transition temperature of the resin containing the alicyclic structure-containing polymer. Effect of the Invention

[0009] According to the present invention, it is possible to provide a picture frame which generates very little gas including formic acid and acetic acid and can prevent deterioration of artworks for a long period of time. [Brief description of the drawings]

[0010] [Figure 1] FIG. 1 is an exploded view showing a schematic diagram of an example of a picture frame according to an embodiment of the present invention. [Diagram 2] FIG. 2 is a cross-sectional view illustrating the frame shown in FIG. [Diagram 3] FIG. 3 is a cross-sectional view that illustrates a schematic diagram of another example of a frame according to an embodiment of the present invention. [Figure 4] FIG. 4 is a cross-sectional view that illustrates a schematic diagram of another example of a frame according to an embodiment of the present invention. [Diagram 5] FIG. 5 is a cross-sectional view that illustrates a schematic diagram of another example of a frame according to an embodiment of the present invention. [Figure 6]FIG. 6 is a cross-sectional view that illustrates a schematic diagram of another example of a frame according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The present invention will be described in detail below with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples shown below, and may be modified and implemented as desired without departing from the scope of the claims of the present invention and their equivalents. The components of the embodiments shown below may be combined as appropriate. In addition, in the drawings, the same components are denoted by the same reference numerals, and their description may be omitted.

[0012] In the following description, unless otherwise specified, the terms "plate," "layer," and "film" may refer to rigid members or flexible members such as a resin film.

[0013] In the following description, a layer is said to be "directly" on another layer means that the two layers are in contact with each other, and there are no other layers between the two layers, unless otherwise specified.

[0014] [1. Overview of the frame] Fig. 1 is an exploded view showing a frame according to one embodiment of the present invention, and Fig. 2 is a cross-sectional view showing the frame shown in Fig. 1. The frame 10 shown in Fig. 1 includes a frame member 1 having a storage space A capable of storing an artwork 100. The frame 10 shown in Fig. 1 illustrates an example in which the frame member 1 has a front portion 11 located on its front side and a side wall portion 12 located on its side side. In the frame member 1, the artwork 100 can be stored in the storage space A, which is a three-dimensional space defined by the plane surrounded by the side wall portion 12 and the height of the side wall portion 12.

[0015] The frame 10 includes a storage member 2 surrounding at least a portion of the storage space A. The storage member 2 includes at least a transparent plate 21 arranged on the front side of the storage space A, a back panel 22 arranged on the back side of the storage space A, and a liner 23 arranged inside the frame member 1 between the transparent plate 21 and the back panel 22. The frame 10 shows an example in which the frame member 1 has a concave first fixing portion 13 on the back side of the front part 11 into which the transparent plate 21 is fitted and fixed, and a concave second fixing portion 14 on the back side of the side wall part 12 into which the back panel 22 is fitted and fixed, the transparent plate 21 is fixed by the first fixing portion 13, the back panel 22 is fixed by the second fixing portion 14, and the liner 23 is sandwiched between the transparent plate 21 and the back panel 22 inside the side wall part 12 of the frame member 1, thereby surrounding the storage space A.

[0016] In the picture frame 10, the storage member 2 is disposed at least on the side of the artwork 100, and includes a resin member 3 that contains an alicyclic structure-containing polymer. 1 and 2 show an example in which the resin member 3 is all of the transparent plate 21, the back plate 22, and the liner 23.

[0017] The resin member 3 is a member in which the amount of volatilization of formic acid and acetic acid is extremely small, each of which is less than 1 μg / g.

[0018] According to this embodiment, the storage member placed in the storage space of the frame can be made of a resin material that emits extremely little formic acid and acetic acid, making it possible to create a frame that can suppress deterioration of the artwork over a long period of time.

[0019] When an artwork is exhibited for a long period of time, it is desirable that the amount of volatilization of formic acid and acetic acid from the components constituting the frame be as small as possible. As a result of investigations conducted in consideration of the above-mentioned problems, the present inventors have found that the amount of volatilization of formic acid and acetic acid can be extremely reduced by molding a resin component containing an alicyclic structure-containing polymer at a molding temperature higher than the boiling point of acetic acid. The reason for this is unclear, but the present inventors speculate that it is as follows. However, the technical scope of the present invention is not limited to the reasons shown below.

[0020] Acrylic resin and polyethylene terephthalate resin, which have been used conventionally for picture frame components, contain ester bonds (-COO-), and therefore it is presumed that formic acid and acetic acid are generated as decomposition products during the synthesis of the resin and during the molding of the resin component. It is also presumed that formic acid and acetic acid are generated when a part of the resin containing ester bonds is decomposed by heating during molding. In contrast, alicyclic structure-containing polymers can be polymers that do not contain the O element as a constituent element, and therefore can be produced without the use of formic acid (HCOOH) or acetic acid (CH 3 It is also presumed that by molding a resin containing such an alicyclic structure-containing polymer at a temperature higher than the boiling point of acetic acid, even if the resin contains formic acid and acetic acid, these acids can be removed from the resin member obtained as a molded product by heating during molding.

[0021] For example, as shown in JP-A-11-166039, it is known that a process for molding an alicyclic structure-containing polymer at high temperature is included in a manufacturing method for an optical film, but the amount of volatilization of formic acid and acetic acid from a resin containing an alicyclic structure-containing polymer has not been known or sufficiently studied. It has been discovered for the first time that the amount of volatilization of formic acid and acetic acid from a resin containing an alicyclic structure-containing polymer can be extremely reduced, and the present invention applies this to a resin member used for a picture frame.

[0022] According to this embodiment, the storage member contains a resin material on the artwork side that emits extremely little formic acid and acetic acid, making it possible to provide a frame that can suppress deterioration of the artwork not only over a long period of time, but also in a short period of time.

[0023] [2. Storage materials] The storage member is a member that surrounds at least a portion of the storage space, and includes at least a transparent plate, a back plate, and a liner. The storage member also includes a resin member disposed on the artwork side.

[0024] [2.1. Plastic parts] The resin member is a member containing an alicyclic structure-containing polymer, and the amount of volatilized formic acid and the amount of volatilized acetic acid are less than a predetermined value.

[0025] (Amount of volatilization of formic acid and acetic acid from resin parts) The amount of formic acid volatilized from the resin workpiece is usually less than 1 μg / g, preferably less than 0.5 μg / g, more preferably less than 0.1 μg / g, and ideally 0 μg / g. The amount of acetic acid volatilized from the resin workpiece is usually less than 1 μg / g, preferably less than 0.5 μg / g, more preferably less than 0.1 μg / g, and ideally 0 μg / g. By having the amount of formic acid and acetic acid volatilized from the resin workpiece be less than the upper limit, deterioration of the artwork due to formic acid and acetic acid can be suppressed even when the artwork is stored in a frame for a long period of time.

[0026] The amount of formic acid volatilized from the resin member and the amount of acetic acid volatilized from the resin member can be determined as the amount of formic acid extracted in 1 g of the resin member and the amount of acetic acid extracted in 1 g of the resin member, which are measured by the following method. 0.5 g of the resin member is weighed into a Teflon (registered trademark) container as a sample, and then 15 mL of ultrapure water is added, the container is sealed, and the target component is extracted by heating at 100°C for 24 hours. Next, the obtained extract is analyzed by ion chromatography to determine the amount of formic acid extracted in 1 g of the resin member and the amount of acetic acid extracted in 1 g of the resin member.

[0027] (Resin material) The resin member includes an alicyclic structure-containing polymer. More specifically, the resin member is made of a resin including an alicyclic structure-containing polymer. Such a resin is preferably a thermoplastic resin.

[0028] The alicyclic structure-containing polymer is a polymer containing an alicyclic structure in a repeating unit. The alicyclic structure-containing polymer is usually excellent in mechanical strength, transparency, low water absorption, moisture resistance, dimensional stability and light weight. The alicyclic structure-containing polymer may be amorphous or crystalline.

[0029] The alicyclic structure-containing polymer having crystallinity means that the alicyclic structure-containing polymer has a melting point Tm, and more specifically, means that the melting point can be observed by a differential scanning calorimeter (DSC).

[0030] Examples of the alicyclic structure-containing polymer include a polymer obtained by polymerization reaction using a cyclic olefin as a monomer, or a hydrogenated product thereof. In addition, the alicyclic structure-containing polymer may be either a polymer containing an alicyclic structure in the main chain or a polymer containing an alicyclic structure in the side chain. Among them, the alicyclic structure-containing polymer preferably contains an alicyclic structure in the main chain. Examples of the alicyclic structure include a cycloalkane structure and a cycloalkene structure, and the cycloalkane structure is preferred from the viewpoint of thermal stability and the like.

[0031] The number of carbon atoms contained in one alicyclic structure is preferably 4 or more, more preferably 5 or more, more preferably 6 or more, and is preferably 30 or less, more preferably 20 or less, and particularly preferably 15 or less. When the number of carbon atoms contained in one alicyclic structure is within the above range, mechanical strength, heat resistance, and moldability are highly balanced.

[0032] The proportion of repeating units having an alicyclic structure in the alicyclic structure-containing polymer is preferably 30% by weight or more, more preferably 50% by weight or more, even more preferably 70% by weight or more, and particularly preferably 90% by weight or more. By increasing the proportion of repeating units having an alicyclic structure as described above, heat resistance can be improved. In the alicyclic structure-containing polymer, the remainder other than the repeating unit having the alicyclic structure is not particularly limited and can be appropriately selected depending on the intended use.

[0033] Examples of the polymer containing an alicyclic structure include (1) norbornene-based polymers, (2) monocyclic olefin polymers, (3) cyclic conjugated diene polymers, (4) vinyl alicyclic hydrocarbon polymers, and hydrogenated versions thereof. Among these, norbornene-based polymers and hydrogenated versions thereof are preferred from the viewpoints of transparency and moldability.

[0034] Examples of norbornene-based polymers include ring-opening polymers of monomers having a norbornene structure and their hydrogenated products; addition polymers of monomers having a norbornene structure and their hydrogenated products. Examples of ring-opening polymers of monomers having a norbornene structure include ring-opening homopolymers of one type of monomer having a norbornene structure, ring-opening copolymers of two or more types of monomers having a norbornene structure, and ring-opening copolymers of a monomer having a norbornene structure and any monomer that can be copolymerized therewith. Examples of addition polymers of monomers having a norbornene structure include addition homopolymers of one type of monomer having a norbornene structure, addition copolymers of two or more types of monomers having a norbornene structure, and addition copolymers of a monomer having a norbornene structure and any monomer that can be copolymerized therewith. Among these, the hydrogenated ring-opening polymers of monomers having a norbornene structure are particularly suitable from the viewpoints of moldability, heat resistance, low moisture absorption, low moisture permeability, dimensional stability, and light weight.

[0035] Examples of monomers having a norbornene structure include bicyclo[2.2.1]hept-2-ene (common name: norbornene), tricyclo[4.3.0.1 2,5 ]Deca-3,7-diene (common name: dicyclopentadiene), 7,8-benzotricyclo[4.3.0.1 2,5 ]deca-3-ene (common name: methanotetrahydrofluorene), tetracyclo[4.4.0.1 2,5 .1 7,10]dodec-3-ene (trivial name: tetracyclododecene) and derivatives of these compounds (for example, those having a substituent on the ring). Examples of the substituent include an alkyl group, an alkylene group, and a polar group. These substituents may be the same or different, and a plurality of them may be bonded to the ring. The monomer having a norbornene structure may be used alone or in combination of two or more kinds in any ratio.

[0036] A ring-opening polymer of a monomer having a norbornene structure can be produced, for example, by polymerizing or copolymerizing the monomer in the presence of a ring-opening polymerization catalyst.

[0037] An addition polymer of a monomer having a norbornene structure can be produced, for example, by polymerizing or copolymerizing the monomer in the presence of an addition polymerization catalyst.

[0038] The hydrogenated products of the ring-opening polymer and the addition polymer described above can be produced, for example, by hydrogenating the carbon-carbon unsaturated bonds in a solution of the ring-opening polymer and the addition polymer in the presence of a hydrogenation catalyst containing a transition metal such as nickel or palladium, preferably to 90% or more.

[0039] The weight average molecular weight (Mw) of the alicyclic structure-containing polymer is preferably 10,000 or more, more preferably 15,000 or more, and even more preferably 20,000 or more, and is preferably 100,000 or less, more preferably 80,000 or less, and even more preferably 50,000 or less. The alicyclic structure-containing polymer having such a weight average molecular weight has an excellent balance of mechanical strength, moldability, and heat resistance.

[0040] The molecular weight distribution (Mw / Mn) of the alicyclic structure-containing polymer is preferably 1.2 or more, more preferably 1.5 or more, particularly preferably 1.8 or more, and is preferably 3.5 or less, more preferably 3.4 or less, particularly preferably 3.3 or less. When the molecular weight distribution is the lower limit of the above range or more, the productivity of the alicyclic structure-containing polymer can be increased and the production cost can be reduced. When the molecular weight distribution is the upper limit or less, the amount of low molecular weight components is reduced, so that the stability of the layer containing the alicyclic structure-containing polymer can be improved.

[0041] The weight average molecular weight Mw and number average molecular weight Mn of the alicyclic structure-containing polymer can be measured in terms of polyisoprene by gel permeation chromatography (hereinafter abbreviated as "GPC") using cyclohexane as a solvent. If the resin does not dissolve in cyclohexane, they can be measured in terms of polystyrene by GPC using toluene as a solvent.

[0042] The glass transition temperature of the alicyclic structure-containing polymer is preferably 50° C. or higher, more preferably 70° C. or higher, particularly preferably 80° C. or higher, and preferably 200° C. or lower, more preferably 180° C. or lower, particularly preferably 170° C. or lower. The glass transition temperature of the alicyclic structure-containing polymer can be measured by differential scanning calorimetry based on JIS K7121. This measurement can be performed under the conditions of heating a sample from room temperature to 200° C. at 20° C. / min, then cooling to 40° C. at 20° C. / min, and heating from 40° C. to 200° C. at 10° C. / min.

[0043] Various products are commercially available as alicyclic structure-containing polymers. Therefore, the resin that is the raw material of the resin member can be prepared by using them as they are or by mixing them with other components as necessary. An example of such a commercially available product is the product name "ZEONOR" (manufactured by Zeon Corporation).

[0044] The content of the alicyclic structure-containing polymer in the resin member is preferably within a specific range relative to 100% by weight of the resin member. The specific range of the content of the alicyclic polymer is preferably 70% by weight or more, more preferably 80% by weight or more, even more preferably 90% by weight or more, and usually 100% by weight or less, preferably 99.99% by weight or less, more preferably 99.9% by weight or less, even more preferably 99% by weight or less, and particularly preferably 96% by weight or less.

[0045] The resin member includes at least an alicyclic structure-containing polymer, and may include optional components as necessary. Examples of the optional components include stabilizers such as colorants, antioxidants, ultraviolet absorbers, and light stabilizers; resin modifiers such as lubricants and plasticizers; and antistatic agents. In this embodiment, it is preferable that the optional components included in the resin member are components that do not include carboxylic acids and ester bonds. This is because the generation of formic acid and acetic acid as decomposition products of the resin due to heating or the like during molding of the resin member can be suppressed.

[0046] (Form of resin component) The resin member may be a member that is placed at least on the artwork side of the storage member, and its form is not limited.

[0047] The resin member is a member that can be disposed at least on the artwork side of the storage member. For example, the resin member can be at least one of the transparent plate, the back plate, and the liner of the storage member. In this case, the resin member can be any one of the components of the storage member described above. In FIG. 3, an example is shown in which the resin member 3 is the transparent plate 21, but this is not limited thereto, and the resin member may be a liner or a back plate, although not shown. In addition, although not shown, the resin member can be two types of members of the transparent plate, the back plate, and the liner of the storage member. In addition, as shown in FIG. 1 and FIG. 2, the resin member 3 can be all of the transparent plate 21, the back plate 22, and the liner 23 of the storage member 2. In this embodiment, from the viewpoint of reducing the influence of formic acid and acetic acid on the artwork, it is preferable that the resin member 3 is all of the transparent plate 21, the back plate 22, and the liner 23 of the storage member 2, as shown in FIG. 1 and FIG. 2.

[0048] Also, for example, the resin member may be a part of at least one of the transparent plate, the back plate, and the liner in the storage member. Specifically, as shown in FIG. 4, when the liner 23 has a part 231 made of wood and a part 232 made of resin, the part 232 may be the resin member 3. Although not shown, when a multilayer base material in which a layer containing an alicyclic structure-containing polymer and a layer containing a polymer other than the alicyclic structure-containing polymer are directly in contact with each other is used as the transparent plate or the back plate, the layer containing the alicyclic structure-containing polymer may be regarded as a covering member described later, but when there is no difference in thickness between the layers in the multilayer base material or when the layer containing the alicyclic structure-containing polymer is the thickest, the layer containing the alicyclic structure-containing polymer may be regarded as a transparent substrate or a back substrate that is partially composed of a resin member.

[0049] When the resin member is any one of the transparent substrate, rear substrate and liner in the housing member, or is a part of any one of the transparent substrate, rear substrate and liner, the resin member can be manufactured as a resin molded body.

[0050] Also, for example, the resin member can be a covering member that covers at least a part of the transparent plate, the back plate, and the liner on the artwork side. When the covering member covers at least a part of the transparent substrate, the back plate, and the liner on the artwork side, the covering member can be provided on at least one of the transparent substrate, the back plate, and the liner. In this case, the covering member may cover a part of the artwork side of the member to be covered, or may cover the entire artwork side. From the viewpoint of reducing the influence of formic acid and acetic acid on the artwork, it is preferable that the covering member covers the artwork side of all the members, the transparent plate, the back plate, and the liner, and it is particularly preferable that the resin member 3 as the covering member 4 covers the entire artwork 100 side of all the members, the transparent plate 21, the back plate 22, and the liner 23, as shown in FIG. 5.

[0051] The ratio of the area where the covering member is arranged to the total area of ​​the artwork side of the component to be covered (coverage rate of the covering member) is preferably 50% or more, more preferably 80% or more, and even more preferably 90% or more. When the coverage rate is equal to or more than the lower limit, the volatilization of formic acid and acetic acid from the component to be covered can be effectively suppressed by the covering member.

[0052] When the resin member is a coated member, the coated member may be manufactured, for example, as a film, and may be attached to a member to be coated with an adhesive or the like as necessary. When the resin member is a coated member, the coated member may be manufactured by applying a coating liquid containing the material of the coated member to the member to be coated. When the coated member is manufactured by a coating method, the amount of volatilization of formic acid and acetic acid from the coated member may be controlled to a predetermined value or less by adjusting the drying conditions of the coating film, for example, by heating and drying the coating film at a temperature higher than the boiling point of acetic acid.

[0053] The thickness of the covering member can be a thickness that can suppress the intrusion of formic acid and acetic acid volatilized from the storage member into the artwork. The thickness of the covering member can be, for example, 10 μm or more, preferably 30 μm or more, more preferably 50 μm or more, for example, 1000 μm or less, preferably 500 μm or less, more preferably 300 μm or less. When the thickness of the covering member is equal to or more than the lower limit, the intrusion of formic acid and acetic acid into the artwork can be sufficiently suppressed, and when the thickness of the covering portion is equal to or less than the upper limit, the covering portion can be easily arranged along the surface of the artwork side of the component to be covered.

[0054] As shown in FIG. 5, when covering member 4 is disposed on the artwork side of transparent plate 21, covering member 4 usually has a degree of transparency that does not interfere with the appreciation of the artwork.

[0055] As shown in FIG. 6, the storage member 2 may have a protective member 5 provided on the surface of the liner 23 that overlaps with the artwork 100, if necessary. The protective member 5 is arranged to prevent the liner 23 from being deteriorated by components of the artwork 100 (e.g., oil in an oil painting) due to direct contact between the liner 23 and the artwork 100. This protective member 5 is preferably a resin member 3 since it is usually arranged in direct contact with the artwork 100. In addition, it is preferable that the alicyclic structure-containing polymer contained in the resin member 3 constituting the protective member 5 is a polymer having crystallinity. This is because alicyclic structure-containing polymers having crystallinity have excellent chemical resistance and can effectively prevent the liner from being deteriorated by components of the artwork.

[0056] The "surface of the liner that overlaps with the artwork" refers to the surface that would be in contact with the artwork if no protective material were used.

[0057] The thickness of the protective member can be, for example, 100 μm or more, preferably 200 μm or more, more preferably 300 μm or more, and can be, for example, 1000 μm or less, preferably 700 μm or less, more preferably 500 μm or less. By having the protective member in the above range, deterioration of the storage member due to components from the artwork can be suppressed.

[0058] In the above, the embodiments have been explained separately: the resin member is the component constituting the storage member itself; the resin member is part of the component constituting the storage member; the resin member is a covering member; and the resin member is a protective member. However, the present invention is not limited to these embodiments, and several of the above-mentioned embodiments may be combined depending on the shape and size of the frame and the artwork to be stored.

[0059] (Other matters related to storage materials) The storage member is a member disposed so as to surround at least a portion of the storage space, and includes at least a transparent plate, a back plate, and a liner.

[0060] The transparent plate is a member provided on the front side of the storage space and protects the artwork. The transparent plate is also called the surface cover of the frame. The transparency of the transparent plate is not particularly limited as long as it does not interfere with the appreciation of the artwork stored in the frame, but it is preferable that the total light transmittance is high. The total light transmittance of the transparent plate is preferably 80% or more, more preferably 85% or more, and particularly preferably 90% or more. The total light transmittance can be measured using an ultraviolet-visible spectrometer in the wavelength range of 400 nm to 700 nm.

[0061] When the transparent plate itself is a resin member, the material of the transparent plate may be the above-mentioned alicyclic structure-containing polymer. In addition, the transparent plate may be made of a material used for a transparent plate in a known picture frame. Specifically, a glass plate or an acrylic plate may be used. When the transparent plate is a member other than a resin member such as a glass plate or an acrylic plate, it is preferable that the above-mentioned covering member is disposed on the surface on the artwork side.

[0062] The thickness and size of the transparent plate are similar to those of transparent plates that can be used in known picture frames, and can be appropriately adjusted depending on the size of the picture frame.

[0063] The back panel is a member provided on the back side of the storage space, and together with the transparent plate and the liner, holds the artwork within the storage space. The back panel is also called the back panel of a picture frame.

[0064] When the back panel itself is a resin member, the material of the back panel may be the above-mentioned alicyclic structure-containing polymer. In addition, the back panel may be made of a material used for back panels in known picture frames. Specifically, the material may be wood, paper, or a resin plate containing a polymer other than the alicyclic structure-containing polymer.

[0065] The thickness and size of the back member are similar to those of back panels that can be used in known picture frames, and can be appropriately adjusted depending on the application of the frame, etc.

[0066] The liner is a member that is placed inside the frame body and between the transparent plate and the back plate. The liner usually has an opening in the center that can hold the artwork. The liner is also a member that can provide a gap between the transparent plate and the artwork to prevent them from coming into direct contact with each other.

[0067] When the liner itself is a resin material, the liner material may be the above-mentioned alicyclic structure-containing polymer. The liner material may be a material used for the back panel of a known picture frame. Specifically, wood, paper, and resin materials containing polymers other than the alicyclic structure-containing polymer may be used.

[0068] The storage member may have a protective member provided on the surface of the liner that overlaps with the artwork, if necessary. The protective member may be in a form that does not allow the liner to come into direct contact with the artwork, and may be provided, for example, on a part of the surface of the liner that overlaps with the artwork, or on the entire surface of the liner that overlaps with the artwork.

[0069] [3. Frame components] The frame member has a storage space in which an artwork can be stored. A storage member for storing an artwork can be placed in the storage space of the picture frame. The frame member can be any known material. The frame member can be made of wood, paper, metal, resin, or a combination thereof.

[0070] 4. Optional configuration of the frame The frame has at least the above-mentioned frame member and the housing member, and may add any other components as necessary, such as a fastener for fixing the frame member to the back panel of the housing member, and an anti-reflection film disposed on the viewer side of the transparent panel of the housing member.

[0071] 5. Manufacturing method of picture frames The above-mentioned frame can be manufactured by a manufacturing method including a step of manufacturing a resin member containing an alicyclic structure-containing polymer and volatilizing less formic acid and acetic acid. Specifically, the frame can be manufactured by a manufacturing method including the following step A. Hereinafter, such a manufacturing method will be described as a manufacturing method of the frame of the present invention. Step (A): A step of obtaining a resin member by molding a resin containing an alicyclic structure-containing polymer at a molding temperature higher than the boiling point of acetic acid.

[0072] According to the manufacturing method of the present invention including step (A), the resin containing the alicyclic structure-containing polymer is molded at a molding temperature higher than the boiling point of acetic acid, so that the acetic acid contained in the material and formic acid having a boiling point lower than that of acetic acid can be removed, and thus a resin part with extremely small volatilization of formic acid and acetic acid can be manufactured. Therefore, a picture frame with suppressed deterioration of an artwork can be manufactured using such a resin part.

[0073] [5.1. Process (A): Molding process of resin parts] Step A is a step of molding a resin containing an alicyclic structure-containing polymer at a predetermined molding temperature to obtain a resin member.

[0074] The resin containing an alicyclic structure-containing polymer contains the above-mentioned alicyclic polymer and any optional component.

[0075] In the step (A), the resin containing the alicyclic structure-containing polymer supplied is preferably processed into a pellet-shaped resin.

[0076] A "pellet-like" resin is a solid resin in a granular shape. The specific shape of the pellet is generally an approximately cylindrical shape obtained by cutting a strand, but the present invention is not limited to this, and pellets of any shape can be used. The "approximately cylindrical shape" includes not only a strict cylindrical shape, but also a cylinder with an elliptical bottom diameter, a cylinder with a circular bottom diameter, and a so-called disk shape in which the height is smaller than the bottom diameter.

[0077] When the pelletized resin is roughly cylindrical, its dimensions may be, for example, a number average diameter of about 1 mm or more and 7 mm or less, and a number average length of about 4 mm or more and 8 mm or less.

[0078] The pellet-shaped resin can be produced, for example, by melting a resin containing an alicyclic structure-containing polymer, extruding it into a strand shape of a predetermined diameter, and then chopping it into pellets of the desired length using an appropriate strand cutter.

[0079] Examples of a method for molding the resin member include resin molding methods such as extrusion molding, injection molding, and press molding.

[0080] The molding temperature of the resin is higher than the boiling point of acetic acid (118°C). By adjusting the molding temperature based on the boiling point of acetic acid, formic acid (boiling point of formic acid: 101°C), which has a lower boiling point than acetic acid, can also be removed. The molding temperature of the resin is usually higher than the boiling point of acetic acid, preferably (boiling point of acetic acid + 83°C) or higher, more preferably (boiling point of acetic acid + 100°C) or higher, and even more preferably (boiling point of acetic acid + 150°C) or higher. The molding temperature of the resin is usually (boiling point of acetic acid + 200°C) or lower, preferably (boiling point of acetic acid + 183°C) or lower, more preferably (boiling point of acetic acid + 180°C) or lower, and even more preferably (boiling point of acetic acid + 160°C). The above range corresponds to the range of (boiling point of formic acid + 100°C) or higher and (boiling point of formic acid + 217°C) or lower. When the molding temperature of the resin is equal to or higher than the lower limit, formic acid and acetic acid in the resin can be removed, and when the molding temperature of the resin is equal to or lower than the upper limit, denaturation of the resin due to heating can be suppressed. The molding temperature of the resin refers to the temperature of the resin (molten resin) during molding.

[0081] [5.2. Step (B): Drying process of resin before molding] The method for producing a picture frame of the present invention may, if necessary, include a step (B) of drying the resin containing the alicyclic structure-containing polymer before the step (A). In the step (B), the alicyclic structure-containing polymer is dried at a temperature of (Tg-60)°C or higher (Tg-10)°C, where Tg (°C) is the glass transition temperature of the resin containing the alicyclic structure-containing polymer.

[0082] In the step (B), the resin containing the alicyclic structure-containing polymer is dried. In the step (B), it is preferable to dry the above-mentioned pellet-shaped resin.

[0083] The drying temperature of the resin is the glass transition temperature (Tg) of the resin containing the alicyclic structure-containing polymer or lower, specifically, (Tg-60) ° C or higher, preferably (Tg-50) ° C or higher, more preferably (Tg-40) ° C or higher, and (Tg-10) ° C or lower, preferably (Tg-15) ° C or lower, more preferably (Tg-20) ° C or lower. By having the drying temperature be lower than the upper limit, the pellets can be easily handled by suppressing thermal fusion between the pellets. In addition, by having the drying temperature be higher than the lower limit, the evaporation of formic acid and acetic acid in the pellets can be promoted. The glass transition temperature (Tg) of the resin containing the alicyclic structure-containing polymer can be measured by the same method as the glass transition temperature of the alicyclic structure-containing polymer described above.

[0084] The drying time of the resin is preferably 1 hour or more, preferably 1.5 hours or more, and more preferably 2 hours or more. The drying time may be, for example, 10 hours or less, preferably 8 hours or less, and more preferably 5 hours or less. This is because the evaporation of formic acid and acetic acid from the resin can be promoted by the drying time being within the above range.

[0085] The drying treatment in step (B) may be, for example, a vacuum drying treatment, a reduced pressure drying treatment in an air or nitrogen atmosphere, or normal pressure drying in an air or nitrogen atmosphere.

[0086] As for the period until the resin dried in step (B) is used in step (A), even if several days pass, the effect of step (B) is not lost, but the shorter the period, the more preferable. The storage period of the dried pellet-shaped resin at room temperature and normal pressure (23°C, about 1 atm) is preferably within 5 days, more preferably within 3 days, and even more preferably within 1 day.

[0087] Typically, a method for manufacturing a picture frame includes a step of manufacturing a resin member that emits little volatilization of formic acid and acetic acid as described above, followed by a step of combining the resin member with other constituent members of the frame (such as a frame member) to assemble the frame.

[0088] [6. Uses of picture frames] The picture frame according to the present invention is provided for storing and displaying artworks in its storage space. Since the picture frame according to the present invention contains a resin member that emits very little formic acid and acetic acid, deterioration of the artworks due to formic acid and acetic acid can be suppressed for a long period of time.

[0089] Concerning deterioration of artworks due to the volatilization of formic acid and acetic acid, for example, discoloration due to reaction between pigment components used in artworks and formic acid and acetic acid. For example, when lead pigments such as red lead are used in artworks, discoloration occurs due to high reactivity of formic acid and acetic acid with lead. In addition, when metals or shells are used in artworks, they may be deteriorated by formic acid and acetic acid.

[0090] Examples of artworks to which the frame of the present invention can be applied include, but are not limited to, oil paintings, watercolor paintings, Japanese paintings, woodblock prints, mother-of-pearl work, metalwork, and the like. EXAMPLES

[0091] The present invention will be described in detail below with reference to examples. However, the present invention is not limited to the examples shown below, and can be modified and carried out as desired without departing from the scope of the claims of the present invention and the scope of equivalents thereto.

[0092] In the following description, the units "%" and "parts" are by weight unless otherwise specified. Furthermore, the operations described below were carried out in air at room temperature and normal pressure (23°C and 1 atm) unless otherwise specified.

[0093] [Evaluation method] (Method for measuring the amount of volatilized formic acid and acetic acid) The amount of formic acid extracted from 1 g of sample, measured by the following procedure, was taken as the amount of formic acid volatilized from the sample, and the amount of acetic acid extracted from 1 g of sample was taken as the amount of acetic acid volatilized from the sample. 0.5 g of the sample was weighed into a Teflon (registered trademark) container, 15 mL of ultrapure water was added, the container was sealed, and the target components, formic acid and acetic acid, were extracted by heating at 100°C for 24 hours. The extracted liquid was analyzed by ion chromatography to measure the amount of formic acid extracted in 1 g of the sample and the amount of acetic acid extracted in 1 g of the sample. The measurement results were evaluated according to the following criteria.

[0094] A: The volatilization amount of formic acid is less than 1 μg / g, or the volatilization amount of acetic acid is less than 1 μg / g. B: The volatilization amount of formic acid is 1 μg / g or more and less than 2 μg / g, or the volatilization amount of acetic acid is 1 μg / g or more and less than 2 μg / g. C: The volatilization amount of formic acid is 2 μg / g or more, or the volatilization amount of acetic acid is 2 μg / g or more.

[0095] [Example 1] (Production of resin containing alicyclic structure-containing polymer) Tricyclo[4.3.0.1 2,5 ]Deca-3,7-diene (dicyclopentadiene; hereinafter, sometimes abbreviated as "DCP"), 7,8-benzotricyclo[4.4.0.1 2,5 .1 7,10 ]dec-3-ene (methanotetrahydrofluorene; hereinafter, sometimes abbreviated as "MTF"), and tetracyclo[4.4.0.1 2,5 .1 7,10 ]dodec-3-ene (tetracyclododecene; hereinafter, occasionally abbreviated as "TCD") was mixed in a weight ratio of 5 / 70 / 25. This mixture was subjected to ring-opening polymerization and then hydrogenated by a known method to obtain a DCP / MTF / TCD ring-opening polymer hydrogenated product as a resin containing an alicyclic structure-containing polymer.

[0096] The copolymerization ratio of each norbornene-based monomer in the obtained resin containing the alicyclic structure-containing polymer was calculated by gas chromatography analysis from the composition of the norbornene-based monomer remaining in the solution after polymerization, and was DCP / MTF / TCD=5 / 70 / 25, which was almost equal to the charged composition.

[0097] The weight average molecular weight (Mw) of the obtained resin containing an alicyclic structure-containing polymer was 34,000, the molecular weight distribution (Mw / Mn; Mn is the number average molecular weight) was 2.1, the hydrogenation rate was 99.9%, and the glass transition temperature Tg was 160°C.

[0098] The obtained resin containing the alicyclic structure-containing polymer was molded into a strand shape by hot melt extrusion molding, and then cut into pieces with a strand cutter to obtain a pellet-shaped resin.

[0099] (Drying of resin) The resulting resin pellets were dried at 110° C. for 4 hours.

[0100] (Forming of resin film) An extrusion film molding machine having a single-layer die was prepared. A dried pellet-like resin was supplied to the extrusion film molding machine, and melt extrusion molding was performed by extruding it from the die lip of the single-layer die. The set temperature of the die was 280°C. The film-like molten resin discharged from the die lip was received by a cast roll, cooled in a pinned state by an electrostatic pinning device, and transported downstream. The operating conditions of the cast roll were a peripheral surface temperature of 155°C and a peripheral speed of 5m / min. This operation resulted in a film having a thickness of 50 μm. The obtained resin film was used as a resin member containing an alicyclic structure-containing polymer, and the volatilization amounts of formic acid and acetic acid were measured.

[0101] [Comparative Example 1] As Comparative Example 1, an acrylic plate (a member containing an acrylic polymer) (manufactured by TruView, product name "OPTIUM MUSEUM ACRYLIC", 3 mm thick) was prepared, and the amount of volatilization of formic acid and acetic acid was measured.

[0102] [Comparative Example 2] As Comparative Example 2, a polyethylene terephthalate (PET) film (member containing a PET polymer) (manufactured by Toray Industries, Inc., U40, thickness 75 μm) was prepared, and the amount of volatilization of formic acid and acetic acid was measured.

[0103] The results are shown in Table 1. In Table 1, for the volatilized amount of formic acid and the volatilized amount of acetic acid, "<1" indicates that it is less than 1 μg / g.

[0104] [Table 1]

[0105] As shown in Example 1, it was confirmed that in a resin workpiece containing an alicyclic structure-containing polymer, the amount of volatilization of both formic acid and acetic acid from the resin workpiece could be made less than 1 μg / g. [Explanation of symbols]

[0106] 1 Frame members 2 Storage materials 3 Resin parts 4 Covering materials 5 Protective materials 21 Transparent plate 22 Back plate 23 Liner 100 works of art A Storage space

Claims

1. A picture frame comprising a frame member having a storage space for storing an artwork, and a storage member surrounding at least a portion of the storage space, The storage member includes a transparent plate disposed on the front side of the storage space, a rear plate disposed on the rear side of the storage space, and a liner disposed inside the frame member and between the transparent plate and the rear plate, the storage member is disposed at least on the artwork side and includes a resin member containing an alicyclic structure-containing polymer; A picture frame, in which the amount of formic acid volatilized from the resin member is less than 1 μg / g, and the amount of acetic acid volatilized from the resin member is less than 1 μg / g.

2. The frame according to claim 1 , wherein the resin member is at least one member selected from the group consisting of the transparent plate, the back plate, and the liner.

3. The picture frame according to claim 1 , wherein the transparent plate, the rear plate, and the liner are all made of resin members.

4. 2. The picture frame according to claim 1, wherein the resin member is a covering member that covers at least a portion of the transparent plate, the back plate and the liner on the side of the artwork.

5. 5. The picture frame of claim 4, wherein the covering member covers the art side of all of the following members: the transparent plate, the back plate, and the liner.

6. The picture frame of claim 1 , further comprising a protective member disposed on a surface of the liner that overlies the artwork.

7. The frame according to claim 6 , wherein the resin member is the protective member.

8. A method for manufacturing the picture frame according to claim 1, comprising the steps of: A method for manufacturing a picture frame, comprising: a step (A) of molding a resin containing an alicyclic structure-containing polymer at a molding temperature of (the boiling point of acetic acid + 100°C) or more and (the boiling point of acetic acid + 200°C) or less to obtain the resin member.

9. The method includes a step (B) of drying the resin containing the alicyclic structure-containing polymer before the step (A), The method for producing a picture frame according to claim 8, wherein in the step (B), the resin containing the alicyclic structure-containing polymer is dried at a temperature of (Tg-60)°C or higher (Tg-10)°C, where Tg (°C) is the glass transition temperature of the resin containing the alicyclic structure-containing polymer.

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