JP2020075499A - Tray for optical shaping and method for manufacturing the same - Google Patents

Abstract

To suppress peeling of a release layer from a tray for optical shaping in the optical shaping.SOLUTION: There is provided a tray for optical shaping, the tray for optical shaping stores a photocurable material having fluidity in the optical shaping. The tray for optical shaping comprises a tray body having a light irradiation surface, and a first layer that covers a surface in an opposite side to the light irradiation surface of the tray body and has a contact surface with the photocurable material. The first layer is composed of a cured product of a composition containing a fluorine-containing curable resin having a first reactive group directly or indirectly bonded to silicon. In the first layer, an interface between the first layer and an underlying layer and its vicinity, a residue in which a functional group derived from a material forming the underlying layer and the first reactive group react or interact with each other exists.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a stereolithography tray for containing a photocurable material in stereolithography.

  In a three-dimensional stereolithography technique such as a 3D printer, for example, a suspension-type stereolithography is drawing attention from the viewpoint that molding with a small amount of a photocurable material is possible.

  FIG. 3 is a schematic cross-sectional view for explaining the steps of a patterning method for three-dimensional stereolithography by a general hanging method. As shown in FIG. 3, in the hanging type stereolithography, first, the pattern forming surface 104 a of the platform 104 is dipped in the photocurable material (patterning material) 102 housed in the stereolithography tray 101. As a result, the liquid film 102a of the photocurable material 102 is formed between the pattern forming surface 104a and the release layer 101d arranged on the inner bottom surface of the tray body 101c of the stereolithography tray 101 (step (i)). .. A bottom portion 101b (specifically, an outer bottom surface) of the tray body 101c includes an exposure surface 101a that faces a light source 105 arranged below the stereolithography tray 101. The light L emitted from the light source 105 toward the pattern forming surface 104a passes through the bottom portion 101b of the tray body 101c and the release layer 101d and is absorbed by the liquid film 102a. As a result, the liquid film 102a is photo-cured to form the two-dimensional pattern 102b (step (ii)). After the step (ii), the pattern forming surface 104a is raised to further form the liquid film 102a of the patterning material between the pattern 102b and the release layer 101d (step (iii)). Then, the liquid film 102a is irradiated with light L from the light source 105 to cure the liquid film 102a and form another pattern 102b. As a result, another pattern 102b is stacked on the two-dimensional pattern 102b (step (iv)) to form a three-dimensional pattern. Furthermore, when the step (iii) and the step (iv) are repeated a plurality of times, three-dimensional patterns having various thicknesses are formed.

  As described above, in the hanging-type stereolithography, since the photo-curing pattern is peeled off from the inner bottom surface of the tray and lifted together with the platform, a release layer is formed on the inner bottom surface of the tray. From the viewpoint of taking out the photo-cured pattern without damage, the release layer is required to have a certain degree of elasticity and also to be transparent to the light from the light source. Therefore, silicone rubber is generally used for the release layer. Further, disposing a flexible elastic separation layer on the bottom of the tray has also been studied (for example, Patent Document 1).

  Patent Document 2 proposes that a release layer including at least a resin layer containing a resin having oxygen permeability is provided in a tray for stereolithography. In this case, an oxygen supply window for exposing the resin layer to the atmosphere is provided in order to supply oxygen into the resin layer. Oxygen supplied from the oxygen supply window hinders the curing reaction in the vicinity of the interface between the release layer and the photocurable material, thereby enhancing the releasability of the obtained photocurable pattern from the release layer.

JP, 2008-137392, A JP, 2017-159621, A

  Even when a tray provided with a release layer is used, the photo-curing pattern is formed in a state of being bound to the release layer, so it is necessary to peel it from the release layer with a certain amount of force. In hanging-type stereolithography, peeling stress may be applied to the release layer every time the photocuring pattern is peeled off, and the release layer may be whitened and deteriorated. When the release layer is deteriorated, the releasability is lowered and it becomes difficult to peel off the photocured pattern, and a larger peeling stress is applied to the release layer. Since the release layer is formed of a material having a high releasability such as silicone rubber, the releasability of the surface of the release layer on the inner bottom surface side of the tray is also high. Therefore, when a large peeling stress is applied to the release layer when peeling the photocured pattern, the release layer is peeled off from the tray.

One aspect of the present invention is a stereolithography tray that contains a photocurable material having fluidity in stereolithography,
A tray body having an exposure surface,
A first layer covering a surface of the tray body opposite to the exposure surface, and having a contact surface with the photocurable material;
The first layer is composed of a cured product of a composition containing a fluorine-containing curable resin having a first reactive group directly or indirectly bonded to silicon,
At the interface between the first layer and the underlayer of the first layer and in the vicinity thereof, a residue in which a functional group derived from the material forming the underlayer and the first reactive group react or interact with each other, It relates to existing stereolithography trays.

Another aspect of the present invention is a method for producing a stereolithography tray containing a photocurable material having fluidity in stereolithography.
A step of preparing a tray body having an exposed surface,
A curable resin composition containing a fluorine-containing curable resin having a first reactive group directly or indirectly bonded to silicon is applied so as to cover a surface of the tray body opposite to the exposed surface. A step of forming a coating film,
The coating film is cured to form a first layer having a contact surface with the photocurable material, and a functional group derived from the material forming the underlayer of the first layer and the first reactivity. And a step of reacting or interacting with a base to bring the first layer into close contact with the base layer.

  In stereolithography, peeling of the release layer from the tray for stereolithography can be suppressed.

It is a schematic longitudinal cross-sectional view of the tray for stereolithography according to an embodiment of the present invention. It is a schematic longitudinal cross-sectional view of the tray for stereolithography according to another embodiment of the present invention. It is a cross-sectional schematic diagram for demonstrating the process of the patterning method of the stereolithography by a general suspension system.

[Stereolithography]
The tray for stereolithography according to one aspect of the present invention accommodates a photocurable material having fluidity in stereolithography. Such a tray for stereolithography is generally called a resin tank. The stereolithography tray according to the above aspect includes a tray main body having an exposure surface, and a first layer that covers a surface of the tray main body opposite to the exposure surface and that has a contact surface with the photocurable material. The first layer is composed of a cured product of a composition containing a fluorine-containing curable resin having a first reactive group directly or indirectly bonded to silicon. At the interface between the first layer and the underlayer of the first layer and in the vicinity thereof, there are residues in which the functional group derived from the material forming the underlayer and the first reactive group react or interact with each other. The residue means a structure or a bond formed as a result of the reaction or interaction between the functional group derived from the material forming the underlayer and the first reactive group.

  In the conventional tray for stereolithography, the release layer that comes into contact with the photocurable material is formed of a material having a high release property such as silicone rubber. Since both surfaces of the release layer have high releasability, the adhesion of the release layer to the underlying layer tends to be low. Even when the mold release layer is provided on the tray, if the photocuring and the peeling of the photocurable pattern are repeated, the photocurable pattern becomes difficult to peel from the mold releasing layer, and a large peeling stress is applied to the mold releasing layer. Further, the photocurable material may penetrate into the inside of the release layer. In this case, the permeated photo-curable material is also photo-cured to be in an integrated state with the photo-curable pattern formed on the release layer. When the photocurable material that has penetrated inside the release layer is cured, the release layer is whitened and the light transmittance is impaired. Further, if the permeated photo-curable material is cured in a state where it is integrated with the photo-curable pattern, a particularly large peel stress is applied to the release layer when the photo-curable pattern is peeled from the release layer. When a large peel stress is repeatedly applied to the release layer, the release layer peels from the underlayer. The release surface from which the photo-curing pattern of the release layer is released and the release surface from which the release layer is released from the underlying layer are not smooth, and the light irradiating the photo-curable material is likely to be diffusely reflected. Cause. If peeling or whitening of the release layer occurs, it becomes difficult to continue stereolithography. In addition, conventionally, there is a case where a film-shaped release layer in a state of not being adhered to the inner bottom surface of the tray for stereolithography is used. In this case, when the photocurable pattern is peeled off, the film-shaped release layer is easily bent, and wrinkles are formed on the release layer, and it is difficult to ensure the accuracy of stereolithography. In particular, as the size of the stereolithography tray increases, wrinkles in the film-shaped release layer are likely to be formed.

  According to the above-described embodiment of the present invention, the first layer corresponding to the release layer is formed of the cured product of the composition containing the fluorine-containing curable resin having the first reactive group. At the interface between the first layer and the underlayer of the first layer and in the vicinity thereof, a residue in which the first reactive group bonded to silicon and the functional group derived from the material forming the underlayer react or interact with each other. Exists. Since the first layer and the underlayer are in a state of reacting or interacting with each other at the molecular level, it is possible to secure high adhesion between the first layer and the underlayer. Therefore, it is possible to secure high releasability to the underlying layer while securing releasability on the contact surface of the first layer with the photocurable material. Moreover, since the first layer is composed of a cured product of a composition containing a fluorine-containing curable resin, the penetration of the photocurable material into the first layer is suppressed, and high releasability can be secured. Therefore, even if the photocuring and the peeling of the photocuring pattern are repeated, the peeling of the first layer from the underlying layer can be suppressed. Since the transmission of the photocurable material to the first layer is suppressed, deterioration of the first layer such as whitening can be significantly suppressed. Further, since it is possible to secure high adhesion between the first layer and the base layer, it is possible to prevent the first layer from bending and becoming wrinkled, and it is possible to perform stereolithography with high accuracy.

  Note that commercially available adhesives include fluorine-containing adhesives and silicone-based adhesives. However, the adhesive is used to bond two or more adherends. Therefore, although it is possible to secure high adhesiveness or adhesiveness by using an adhesive, it is generally expected that it is difficult to secure releasability, which is a completely opposite characteristic.

  By using the stereolithography tray according to the above aspect, for example, in place of the tray 101 in FIG. 3, a three-dimensional stereolithography object can be formed through the steps shown in FIG.

The contact surface of the first layer with the photocurable material is a region that comes into contact with the photocurable material when the photocurable material is housed in the stereolithography tray.
The exposed surface of the tray body means a region of the surface of the tray body facing the light source, to which light (of the photocurable material) emitted from the light source can directly hit. In the hanging method, light is emitted from the bottom side of the tray body. Therefore, the exposed surface of the tray body is usually an area on the outer bottom surface of the tray body to which the light emitted from the light source can hit.

  The first base layer may be the tray body. In addition, the second layer may be disposed between the tray body and the first layer, and the second layer may be used as a base layer for the first layer.

  The functional group derived from the material forming the underlayer means a functional group contained in the material forming the underlayer at least at the stage of forming the first layer on the underlayer, and reacts with the first reactive group. Alternatively, it includes an interactable group or atom. The functional group may be present in the underlayer of the completed stereolithography tray, or may not be present. For example, when the foundation layer of the completed stereolithography tray is formed of a cured product of a curable material, the first layer can be formed on the foundation layer in a semi-cured state or a completely cured state. In the underlayer in such a state, the material forming the underlayer (semi-cured curable material or cured product of the curable material) may have the above functional group.

  In the present invention, the components of the stereolithography tray (the tray body, the first layer, the base layer, etc.) need to transmit the emitted light in the area exposed to the light emitted from the light source. .. In the stereolithography tray, at least in a region exposed to light, for example, the light transmittance to the light emitted from the light source is preferably 80% or more, and more preferably 90% or more. As the light emitted from the light source, for example, light in the visible light region from ultraviolet light is used.

FIG. 1 is a schematic vertical sectional view of a stereolithography tray according to an embodiment of the present invention. FIG. 2 is a schematic vertical sectional view of a tray for stereolithography according to another embodiment of the present invention.
In FIG. 1, the tray for stereolithography 1 includes a tray body 1c having an exposure surface 1a on a bottom portion 1b, and a first layer 1d that covers a surface of the tray body 1c opposite to the exposure surface 1a. In this case, the underlying layer of the first layer 1d becomes the tray body 1c.

  In FIG. 2, the tray 11 for stereolithography has a tray body 11c having an exposure surface 11a on a bottom portion 11b, a first layer 11d that covers the surface of the tray body 11c opposite to the exposure surface, a tray body 11c, and a first body 11c. A second layer 11e provided between the second layer 11d and the layer 11d. In this case, the underlying layer of the first layer 11d becomes the second layer 11e.

Hereinafter, the components of the tray for stereolithography will be described in more detail.
The tray for stereolithography includes a tray body that contains the photocurable material, and a first layer that is disposed on the inner surface of the tray body (that is, the side that contains the photocurable material). A second layer may be provided between the tray body and the first layer.

(First layer)
The first layer is arranged so as to cover the surface of the tray body opposite to the exposed surface, that is, the surface on the side containing the photocurable material. The first layer has a contact surface with the photocurable material. The first layer may be arranged at least in the exposed area in order to facilitate peeling of the photocurable pattern. From the viewpoint that the photocurable material is more uniformly irradiated with light and the photocurable pattern is easily peeled off, the first layer covers the entire inner bottom surface of the tray main body as shown in FIG. 1 or 2. It is preferable that they are arranged in

The first layer is composed of a cured product of a composition containing a fluorine-containing curable resin having a silicon-bonded first reactive group. The first reactive group may be directly bonded to silicon or indirectly bonded to silicon. Indirectly bonded means that the first reactive group is bonded to silicon via a linking group. The first reactive group is selected according to the type of functional group contained in the underlayer. Examples of the first reactive group include an alkoxy group, a hydroxy group, a vinyl group, a (meth) acryloyloxy group, an epoxy group, an amino group, a ureido group, an isocyanate group and a mercapto group. As the alkoxy group, a C _1-6 alkoxy group such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group (among others, a C _1-4 alkoxy group) is preferable. The epoxy group includes a glycidoxy group, an epoxycycloalkyl group and the like. The fluorine-containing curable resin may have one kind of first reactive group, or may have two or more kinds of first reactive groups. The fluorine-containing curable resin may be used alone or in combination of two or more. When using two or more kinds of fluorine-containing curable resins, the types of the first reactive groups may be the same or different. The acryloyloxy group and the methacryloyloxy group are collectively referred to as a (meth) acryloyloxy group.

The linking group may be any group as long as it can link silicon and a reactive group, and examples thereof include a divalent hydrocarbon group and a divalent group corresponding to a dialkylamine. Examples of the divalent hydrocarbon group include a linear or branched alkylene group, an arylene group, an arene dialkylene group, and the like. Examples of the alkylene group include C _1-6 alkylene groups such as methylene, ethylene, propylene, trimethylene, and butylene (C _1-4 alkylene groups, etc.). Examples of the arylene group include C _6-14 arylene groups such as phenylene, tolylene and naphthylene groups. Examples of the arenedialkylene group include C _6-10 arenedi C _1-4 alkylene groups such as a xylylene group. However, the linking group is not limited to these.

Among them, as the group first reactive group is bonded to a silicon, a silanol group (Si-OH), alkoxysilyl groups (Si-OR), vinylsilyl (Si-CH = CH _2), etc. are preferable. R is an alkyl group corresponding to an alkoxy group. Examples of the alkoxy group —OR include the alkoxy groups exemplified above.

  In the tray for stereolithography, the residue formed by the reaction or interaction between the first reactive group and the functional group of the underlayer is present at the interface between the first layer and the underlayer and its vicinity. Due to the presence of such a residue, adhesion between the first layer and the underlayer can be secured, and peeling of the first layer is suppressed. Examples of the reaction between the first reactive group and the functional group of the underlayer (or the second reactive group described later) include (a) a reaction between an epoxy group and an amino group, a hydroxy group or a carboxy group, (b) ) Reaction of amino group with chlorine atom, acid chloride group, epoxy group, isocyanate group, hydroxy group, amino group, sulfonic acid group, or carboxy group, (c) grafting reaction of vinyl group, (d) (meta ) Polymerization reaction of an acryloyloxy group and a functional group having a polymerizable unsaturated carbon-carbon bond, (e) reaction of an isocyanate group with an amino group, a hydroxy group, or a carboxy group, a mercapto group, an acid amide or carbon Examples thereof include reaction with a functional group having a carbon double bond. Further, as the reaction between the first reactive group and the functional group of the underlayer, a condensation reaction between the first reactive group and the second reactive group, or an addition between the first reactive group and the second reactive group The residue may be formed by utilizing a reaction. Examples of such a reaction include (f) a condensation reaction using an alkoxy group or a hydroxy group as the first reactive group, and (g) an addition reaction using a vinyl group as the first reactive group. Regarding the reaction (f), when the fluorine-containing curable resin has a silanol group or an alkoxysilyl group, it can be reacted with the functional group of the underlayer by utilizing the condensation reaction between silanol groups or alkoxysilyl groups. Regarding the reaction (g), when the fluorine-containing curable resin has a vinylsilyl group, it can be reacted with the functional group of the underlayer by utilizing the addition reaction between the vinylsilyl group and the hydrosilyl group. When the addition reaction between the first reactive group and the functional group of the underlayer is used, the adhesion between the first layer and the underlayer can be further enhanced. In addition, in the case of the addition reaction, since it is difficult for the first reactive group to remain on the surface of the first layer after the curing of the first layer, it becomes easier to secure high releasability by the first layer.

  The fluorine-containing curable resin contains silicon, a first reactive group directly or indirectly bonded to silicon, and fluorine, and its skeleton is not particularly limited as long as it is photocurable. From the viewpoint of easily taking out the photo-cured pattern without damage, the cured product forming the first layer preferably has rubber elasticity. Above all, the first layer is preferably composed of fluorine-containing silicone rubber. The fluorine-containing silicone rubber preferably contains an alkylene fluoride unit. From the viewpoint of securing appropriate rubber elasticity while suppressing the penetration of the photocurable material into the first layer, the fluorine-containing silicone rubber preferably contains at least a perfluorinated alkylene unit as the fluorinated alkylene unit. The fluorine-containing silicone rubber may contain a tetrafluoroethylene unit as the perfluorinated alkylene unit, but preferably contains at least a hexafluoropropylene unit from the viewpoint of easily securing an appropriate rubber elasticity. The fluorinated alkylene unit may be included in the fluorine-containing silicone rubber as a repeating structure of a fluorinated alkylene unit, may be included as a repeating structure of a fluorinated alkylene oxide unit, or is included as both of these. May be.

  As the fluorine-containing curable resin, a commercially available product may be used, or a resin synthesized by a known synthesis method or a combination thereof may be used. The fluorine-containing silicone rubber, for example, a compound having a repeating structure of a fluorinated alkylene unit or a fluorinated alkylene oxide unit and vinylsilyl groups at both ends, a fluorinated alkylene unit or a repeating structure of a fluorinated alkylene oxide unit and both ends of A composition obtained by mixing a compound having a hydrosilyl group, a hydrosilylation reaction catalyst, a diluent (solvent) and the like may be used. As the hydrosilylation reaction catalyst, for example, a platinum-based catalyst (for example, platinum group metal (including those supported on a carrier such as carbon or alumina), a platinum group metal-containing complex, etc.) is used, but is not limited thereto. It is not something that will be done. As a method for producing such a fluorine-containing silicone rubber, for example, the method for preparing a fluorine-containing elastomer composition described in JP 2008-115277 A can be referred to. As the compound having a repeating structure of a fluorinated alkylene unit or a fluorinated alkylene oxide unit and a vinylsilyl group or a hydrosilyl group at both ends, a commercially available product may be used, and a compound synthesized using a known synthesis method is used. You may. The vinylsilyl group or the hydrosilyl group can be introduced into the terminal of the main chain having a repeating structure of a fluorinated alkylene unit or a fluorinated alkylene oxide unit by using, for example, a coupling agent, but is not limited to this case.

  The Shore A hardness of the cured product forming the first layer at 23 ° C. is, for example, 80 or less, preferably 60 or less, and 55 or less or 50 or less from the viewpoint of ensuring the rubber elasticity of the first layer. It is more preferable that there is. The Shore A hardness at 23 ° C. of the cured product is preferably 1 or more from the viewpoint of easily peeling off the photocured pattern smoothly.

In the present specification, the Shore A hardness of the cured product can be measured according to JIS K6253: 2012 using a commercially available durometer (type A durometer) under the following conditions. Other conditions are in accordance with JIS K6253: 2012.
Test temperature: 23 ℃
Pressure plate and push needle: Type A pressure plate and push needle described in JIS K6253: 2012 Load: 1 kg
Size of test piece (cured product): length 30 mm x width 40 mm x thickness 4 mm or more (specifically, 4 mm)
Measurement position: Distance 5mm from the end of the test piece to the tip of the push needle
Measurement time: 5 seconds after contacting the test piece with the pressure plate Measurement points: 5 points

  The 1st layer can contain the well-known component as mix | blended with a mold release layer as needed.

The thickness of the first layer is, for example, 1 μm or more, and may be 10 μm or more or 20 μm or more. The thickness of the first layer is preferably 30 μm or more, more preferably 40 μm or more. The thickness of the first layer is, for example, 3 cm or less, may be 1 cm or less, and may be 1000 μm or less or 100 μm or less. When the thickness of the first layer is in such a range, appropriate elasticity of the first layer is easily obtained while suppressing the penetration of the photocurable material, and the photocured pattern is easily peeled off. Therefore, the releasability of the first layer can be easily ensured even if the photocuring of the photocurable material and the peeling of the photocurable pattern from the first layer are repeated. When the underlying layer is the tray body, the thickness of the first layer is preferably 10 μm or more. When the underlayer is the second layer, the thickness of the first layer is preferably 30 μm or more or 40 μm or more, and may be 1 mm or less or 100 μm or less.
The lower limit value and the upper limit value can be arbitrarily combined.

  The thickness of the first layer is 1 μm or more (or 10 μm or more) 3 cm or less, 1 μm or more (or 10 μm or more) 1 cm or less, 1 μm or more (or 10 μm or more) 1000 μm or less, 1 μm or more (or 10 μm or more) 100 μm or less, 20 μm or more ( Or 30 μm or more) 3 cm or less, 20 μm or more (or 30 μm or more) 1 cm or less, 20 μm or more (or 30 μm or more) 1000 μm or less, 20 μm or more (or 30 μm or more) 100 μm or less, 40 μm or more 3 cm or less (or 1 cm or less), or 40 μm or more It may be 1000 μm or less (or 100 μm or less).

  The thickness of the first layer is obtained from a photograph of a cross section parallel to the thickness direction of the first layer. In the cross-sectional photograph, the thickness of the first layer is obtained by measuring and averaging the thickness at arbitrary plural points (for example, 5 points) of the first layer.

  In Patent Document 2, oxygen permeability is imparted to the resin layer forming the release layer, and an oxygen supply window through which the resin layer is exposed to the atmosphere is provided. In Patent Document 2, the curing reaction in the vicinity of the interface between the release layer and the photocurable material is inhibited by oxygen supplied from the oxygen supply window, thereby facilitating the peeling of the photocuring pattern from the release layer. .. On the other hand, in the stereolithography tray according to the above aspect of the present invention, the specific material is used for the first layer, and the penetration of the photocurable material into the first layer is suppressed, whereby the light of the first layer is suppressed. Excellent releasability can be secured on the contact surface with the curable material. Therefore, in the tray for stereolithography according to the above aspect, it is not necessary to provide the oxygen supply window as described above in the first layer (and the second layer).

  The oxygen supply window is a portion exposed to the atmosphere in order to supply oxygen to the first layer and / or the second layer. That is, the oxygen supply window needs to be exposed to the atmosphere without coming into contact with the photocurable material after the photocurable material is stored in the stereolithography tray. Therefore, in the stereolithography tray according to the above aspect of the present invention, the first layer (and the second layer) is not exposed to the atmosphere after the photocurable material is housed during the stereolithography. Preferably. From this point of view, it is preferable that the first layer (and the second layer) be formed so as to cover the inner bottom surface of the tray body. The difference between the height of the portion where the inner side surface of the tray body contacts the first layer and the thickness of the first layer is preferably small, and this difference is preferably 1 mm or less or 100 μm or less. When the underlying layer is the second layer, the total height of the portions where the inner side surface of the tray body contacts the first layer and the second layer, and the thickness of the first layer and the second layer It is preferable that the difference from the sum of the above is within the above range.

  From the viewpoint of easily obtaining high releasability in the first layer, it is preferable that the contact angle of the contact surface with the photocurable material with respect to the photocurable material is high. Since such a first layer generally has a high contact angle with respect to water, in this specification, the releasability is expressed by using the contact angle with water instead of the contact angle with the photocurable material. .. The contact angle of water on the contact surface of the first layer with the photocurable material is, for example, preferably greater than 90 °, more preferably 95 ° or more, and may be 100 ° or more.

(Second layer)
When the second layer is provided, the second layer serves as a base layer with the first layer. The second layer is preferably formed between at least the first layer and the tray body in at least a region through which light is transmitted so that the light applied to the photocurable material becomes more uniform. From the same viewpoint, as shown in FIG. 2, the second layer is arranged so as to cover the entire inner bottom surface of the tray body, and the first layer is arranged so as to cover the entire surface of the second layer opposite to the tray body. Is more preferably arranged.

  The second layer contains a resin. The second layer is composed of a material having a functional group that reacts or interacts with the first reactive group of the first layer at least at the stage where the first layer is formed. The presence of such a functional group in the second layer at least when the first layer is formed improves the adhesion between the first layer and the second layer. Further, since the permeation of the photo-curable material into the first layer is suppressed, the releasability of the contact surface of the first layer with the photo-curable material is enhanced, so that the formation of the photo-curable pattern and the peeling are repeated. Also, peeling of the first layer and the second layer from the tray body is suppressed.

  The functional group has only to be capable of reacting or interacting with the first reactive group, and is appropriately selected according to the type of the first reactive group. The functional group preferably contains a reactive group that reacts with the first reactive group (second reactive group), and particularly preferably contains a silicon-bonded second reactive group. In such a case, the adhesion between the first layer and the second layer can be further enhanced by the reaction between the first reactive group and the second reactive group. At least at the stage where the first layer is formed, the functional group and the second reactive group contained in the material forming the second layer may be the same or different. In the second reactive group bonded to silicon, the second reactive group may be directly bonded to silicon or indirectly bonded via a linking group. Examples of the connecting group include, but are not limited to, those exemplified for the first layer.

  Examples of the second reactive group include the reactive groups exemplified for the above reactions (a) to (e) depending on the type of the first reactive group. Explaining the reaction (a) as an example, when the first reactive group is an epoxy group, the second reactive group is an amino group, a hydroxy group or a carboxy group. Also in the reactions (b) to (e), the second reactive group can be mentioned according to the case of the reaction (a). When the condensation reaction between silanol groups is used in the reaction (f), the hydroxy group contained in the silanol groups is mentioned as the second reactive group. When the condensation reaction between alkoxysilyl groups is used in the reaction (f), the alkoxy group contained in the alkoxysilyl group is mentioned as the second reactive group. The alkoxy group is selected from those exemplified for the first layer, for example. In the reaction (g), the hydrogen atom contained in the hydrosilyl group can be mentioned as the second reactive group.

  At the interface between the tray main body and the second layer and in the vicinity thereof, if necessary, a functional group derived from the material constituting the tray main body and the material forming the second layer (the above-mentioned functional group or the second reactive group). May also be present) to produce a residue. By forming such a residue, it becomes easy to secure high adhesion between the tray body and the second layer and the first layer even when the second layer is formed.

  The resin constituting the second layer may be any resin as long as the second layer has the above-mentioned functional group or second reactive group at the stage when the first layer is formed, and a thermoplastic resin and / or a curable resin may be used. Can be mentioned. The curable resin may be a photocurable resin or a thermosetting resin. The curable resin is converted into a cured product of the curable resin in the second layer of the completed stereolithography tray.

  Examples of the resin forming the second layer include rubber-like polymers, fluororesins, styrene resins, olefin resins and the like. The second resin may be a homopolymer or a copolymer. From the viewpoint of easily taking out the photocurable pattern without damage, it is preferable that the second layer also has rubber elasticity in addition to the first layer. From such a viewpoint, the second layer is preferably formed of a rubber-like polymer. Since the second layer also needs to have optical transparency, the rubber-like polymer is preferably, for example, silicone rubber or nitrile rubber. From the viewpoint of easy introduction of the second reactive group, the second layer is preferably formed of silicone rubber. Further, when the second layer is made of silicone rubber, it has a high affinity with the first layer made of fluorine-containing silicone rubber, which is advantageous in enhancing the adhesion between both layers.

  From the viewpoint of ensuring the rubber elasticity of the second layer, the Shore A hardness at 23 ° C. of the material forming the second layer (cured product or the like) is, for example, 90 or less, and may be 60 or less or 50 or less. .. The lower limit of Shore A hardness at 23 ° C. of the cured product is not particularly limited, but is, for example, 1 or more.

  When forming the second layer, the total thickness of the first layer and the second layer is, for example, 5 cm or less, and may be 3 cm or less or 1 cm or less, from the viewpoint of easily securing the light transmittance.

The ratio of the thickness of the first layer to the thickness of the base layer (second layer) is, for example, 0.001 to 1, may be 0.001 to 0.1, or may be 0.001 to 0.05 or It may be 0.01 to 0.05. When the thickness ratio is within such a range, the photo-curing pattern can be easily peeled from the first layer due to appropriate flexibility and / or elasticity of the second layer. Further, since a relatively inexpensive material such as silicone rubber can be used for the second layer, the cost can be suppressed while ensuring high adhesion between the first layer and the second layer.
The thickness of the second layer is measured according to the case of the thickness of the first layer.

As described above, according to the above aspect of the present invention, high releasability can be secured without providing an oxygen supply window in the second layer in addition to the first layer.
The second layer may contain an additive as required.

(Tray body)
The shape of the tray body is not particularly limited as long as it can accommodate the photocurable material. The tray main body includes, for example, a bottom having a shape such as a square or a circle, and a side wall extending in the height direction from the peripheral edge of the bottom. The tray body has, for example, a shape such as a plate or a bat.

  The exposed surface of the bottom of the tray body and an area in the vicinity thereof (preferably located below the patterned surface of the platform) so as not to block the light emitted from the light source toward the patterned surface of the platform. The area) can transmit light from the light source. It is not necessary that the peripheral portion of the bottom portion of the tray body, the side wall, and the like be able to transmit the light from the light source, but the entire tray body may be able to transmit the light from the light source (for example, transparent).

  The tray body is made of, for example, an organic material such as resin or an inorganic material such as glass. The light-irradiated area of the tray body is made of resin and / or glass. Examples of the resin that constitutes the tray body include resins that can transmit irradiated light, such as polycarbonate resin, acrylic resin, silicone resin, and rubber-like polymer (silicone rubber, acrylic rubber, etc.). The tray body may contain one kind of these materials, or may contain two or more kinds thereof. The tray body may contain known additives, if necessary.

  When the first base layer is the tray body, the tray body has a functional group that reacts or interacts with the first reactive group of the first layer at least at the stage when the first layer is formed. Composed of. The presence of such a functional group on the surface of at least the first layer side of the tray main body at least at the stage of forming the first layer improves the adhesion between the first layer and the tray main body as the underlayer. To do. Further, since the permeation of the photo-curable material into the first layer is suppressed, the releasability of the contact surface of the first layer with the photo-curable material is enhanced, so that the formation of the photo-curable pattern and the peeling are repeated. Also, peeling of the first layer from the tray body is suppressed.

  The functional group has only to be capable of reacting or interacting with the first reactive group, and is appropriately selected according to the type of the first reactive group. The functional group may include a reactive group that reacts with the first reactive group (third reactive group), for example, a silicon-bonded third reactive group. For the third reactive group, the description of the second reactive group can be referred to.

  The tray body is not formed with holes (or openings) for exposing the first layer and / or the second layer to the atmosphere so that the oxygen supply window is not formed in the first layer and the second layer. Preferably.

The stereolithography tray according to the above aspect of the present invention can be used, for example, in place of the stereolithography tray 101 in FIG. 3, and stereolithography can be performed by the procedure described above.
In FIG. 3, the case of the surface exposure method is taken as an example (steps (ii) and (iv)), but the exposure method is not particularly limited, and either point exposure or surface exposure may be used. As the light source, a known light source used for photocuring can be used. Examples of the point exposure method include a plotter method, a galvano laser (or galvano scanner) method, and an SLA (stereolithography) method. In the case of the surface exposure method, it is easy to use a projector as a light source. Examples of the projector include LCD (transmissive liquid crystal) system, LCoS (reflective liquid crystal) system, and DLP (registered trademark, Digital Light Processing) system. The exposure wavelength can be appropriately selected according to the type of components of the photocurable material.

[Photocurable material]
The photocurable material contained in the tray for stereolithography can be used without particular limitation as long as it is a photocurable material having fluidity used in stereolithography. The photocurable material includes, for example, a photocurable monomer and a photocurable precursor (photocurable oligomer, photocurable prepolymer, etc.), and may further include a photopolymerization initiator. The photocurable material is usually liquid at room temperature (for example, 20 to 35 ° C).

  As the photocurable monomer, a monomer that can be cured or polymerized by the action of radicals or cations generated by light irradiation is used. The radical polymerization photocurable monomer is preferably a polyfunctional monomer having a plurality of polymerizable functional groups. The number of polymerizable functional groups in the photocurable monomer is, for example, 2 to 8. Examples of the polymerizable functional group include a group having a polymerizable carbon-carbon unsaturated bond such as a vinyl group and an allyl group, and an epoxy group.

  More specifically, examples of the photocurable monomer include radical polymerizable monomers such as acrylic monomers, cationic polymerizable monomers such as epoxy monomers, vinyl monomers, and diene monomers. The photocurable monomers may be used alone or in combination of two or more.

  As the acrylic monomer, for example, a (meth) acrylic acid ester of polyol is used. The polyol may be, for example, an aliphatic polyol, and may have an aromatic ring or an aliphatic ring. In the present specification, acrylic acid ester and methacrylic acid ester are collectively referred to as (meth) acrylic acid ester or (meth) acrylate.

Examples of vinyl monomers include vinyl ethers such as polyol poly (vinyl ether), aromatic vinyl monomers such as styrene, and vinylalkoxysilanes. Examples of the polyol that constitutes the poly (vinyl ether) include the polyols exemplified for the acrylic monomer.
Examples of the diene-based monomer include isoprene and butadiene.

  Examples of the epoxy-based monomer include compounds having two or more epoxy groups in the molecule. The epoxy-based monomer may include, for example, an epoxycyclohexane ring or a 2,3-epoxypropoxy group.

  Examples of the photocurable precursor include oligomers of the above-exemplified photopolymerizable monomers, urethane acrylate oligomers, diallyl phthalate prepolymers, and the like. These can be made higher in molecular weight by photopolymerization. The diallyl phthalate prepolymer is an oligomer or polymer in which a plurality of diallyl phthalate units are connected. The diallyl phthalate prepolymer may contain one kind of diallyl phthalate unit, or may contain two or more kinds of diallyl phthalate units. The two or more types of diallyl phthalate units include, for example, a plurality of diallyl phthalate units having different substitution positions of allyloxycarbonyl groups. In addition, you may use the ortho type diallyl phthalate prepolymer containing the connecting chain of o-diallyl phthalate unit, the iso type diallyl phthalate prepolymer containing the connecting chain of m-diallyl phthalate unit, etc.

The weight average molecular weight of the photocurable precursor is, for example, 5,000 to 150,000, and may be 10,000 to 150,000 or 30,000 to 150,000.
In the present specification, the average molecular weight is an average molecular weight based on polystyrene measured by gel permeation chromatography.

  When a photocurable material containing a curable resin having a non-aromatic skeleton (for example, an aliphatic skeleton and / or an alicyclic skeleton) is used, it easily penetrates into a conventional release layer made of silicone rubber or the like. Therefore, during repeated formation of the photocurable pattern and peeling from the release layer, deterioration such as whitening of the release layer becomes remarkable, and the releasability is impaired. When the photo-curing pattern is peeled off in such a state, a large peeling stress is applied to the release layer, and the release layer is peeled off from the stereolithography tray. On the other hand, according to the above aspect of the present invention, even when a photocurable material containing a curable resin having a non-aromatic skeleton is used, penetration into the first layer is suppressed, The deterioration of the layer can be suppressed, and the peeling of the first layer from the underlayer can be suppressed.

  The photopolymerization initiator is activated by the action of light to start the polymerization of the photocurable monomer and / or precursor. Examples of the photopolymerization initiator include radical polymerization initiators that generate radicals by the action of light, and those that generate an acid (or cation) by the action of light (specifically, a cation generator). .. The photopolymerization initiators may be used alone or in combination of two or more. The photopolymerization initiator may be selected depending on the type of the photocurable monomer, for example, whether it is radically polymerizable or cationically polymerizable. Examples of the radical polymerization initiator (radical photopolymerization initiator) include alkylphenone photopolymerization initiators and acylphosphine oxide photopolymerization initiators.

The photo-curable material may further contain other known curable resins.
Further, the photocurable material may include known additives.

[Method for manufacturing tray for stereolithography]
In the tray for stereolithography according to the above aspect, a step of preparing a tray body, a step of forming a coating film of a curable resin composition that is a raw material of the first layer, and a step of curing the coating film to form the first layer Then, it can be manufactured by a manufacturing method including a step of closely adhering to the underlayer. When disposing the second layer, the manufacturing method further includes a step of forming the second layer before the coating film forming step. Each step will be described more specifically below.

(Preparation process of tray body)
The tray body may be a commercially available one, or may be manufactured by molding the material forming the tray body. In this way, the tray body is prepared. As the material of the tray body, the above-mentioned resin and / or glass is used. When the tray body serves as the first underlayer, it has a functional group capable of reacting or interacting with the first reactive group when the tray body is molded, and at least the surface of the molded tray body ( In particular, it is preferable to use a material in which a functional group remains on the inner surface) and its vicinity.

  The tray body is formed so that at least the exposed surface at the bottom and a region in the vicinity thereof can transmit light from the light source. Further, it is preferable to prepare without forming a hole (or an opening) for forming an oxygen supply window in the tray body.

(Second layer forming step)
The second layer is formed so as to cover the surface of the tray body opposite to the exposed surface (that is, the inner bottom surface of the tray body). The second layer may be formed on at least a portion of the inner bottom surface of the tray body located on the exposure surface, and may be formed so as to cover the entire inner bottom surface as illustrated in FIG. Further, the second layer may be formed so as to cover the entire inner bottom surface of the tray body and also cover a part of the inner side wall of the tray body.

  The second layer is formed by applying a coating agent containing at least a resin. The application of the coating agent may be performed after the application of the coating agent, if necessary. Drying may be performed under atmospheric pressure or under reduced pressure. Drying can also be performed under heating, if necessary.

  For example, when a thermoplastic resin is used as the resin, a coating agent containing the thermoplastic resin, a solvent for diluting the thermoplastic resin, and optionally additives is applied to at least a part of the inner bottom surface of the tray main body and dried. Thereby, the second layer can be formed.

When a curable resin is used as the resin, it is coated with a curable resin composition containing a curable resin, a curing agent, a curing accelerator, a curing catalyst and / or a polymerization initiator, and optionally additives. The second layer is formed by using as an agent and curing the coating film formed by coating. The curing may be performed under heating and / or under irradiation of light, if necessary.
The curable resin composition may be either a one-component curing type or a two-component curing type.

  When the curable resin composition is used, when forming the first layer, the cured state may be adjusted so that the second layer has a functional group that reacts with the first reactive group. .. For example, when subjected to the subsequent coating film forming step, the cured state may be adjusted so that the second layer is in a semi-cured state or a fully cured state, for example. The curable resin composition may include a solvent for dilution, if necessary. The solvent can be selected according to the type of constituent components of the curable resin composition. Even when the curable resin composition is used, it can be dried at an appropriate stage if necessary.

  The temperature and time for drying and curing may be determined according to the type of resin forming the second layer, the desired curing state, and / or the type of solvent.

  When forming the second layer, the functional group of the tray main body and the functional group derived from the material forming the second layer may react or interact with each other. For example, when the coating material is cured, dried and / or heated, a reaction or interaction between the functional groups proceeds to form a residue. By forming such a residue, the adhesion between the tray body and the second layer (and the first layer) can be enhanced.

(Coating film formation process)
In this step, a curable resin composition, which is a raw material for the first layer, is applied onto the underlayer to form a coating film. The coating film is formed so as to cover the surface of the tray body opposite to the exposed surface (that is, the inner bottom surface of the tray body). The coating film may be formed on at least a portion of the inner bottom surface of the tray body located on the exposure surface, and may be formed so as to cover the entire inner bottom surface as illustrated in FIG. 1 or 2. Further, the coating film may be formed so as to cover the entire inner bottom surface of the tray body and also a part of the inner side wall of the tray body. The coating film may be formed directly on a predetermined portion of the tray body, or may be formed via the second layer.

  The curable resin composition may include a fluorine-containing curable resin having a silicon-bonded first reactive group and be liquid at room temperature (for example, 20 to 35 ° C.). The curable resin composition contains a curing agent, a curing accelerator, a curing catalyst, and / or a polymerization initiator, etc., depending on the type of the curable resin. The curable resin composition may contain known components used in the release layer, such as additives, if necessary.

  The viscosity of the curable resin composition at 25 ° C. is, for example, 0.1 mPa · s or more and 10 Pa · s or less, preferably 0.1 mPa · s or more and 1 Pa · s or less, and 0.1 mPa · s or more 500 mPa -It is more preferable that it is s or less. When the viscosity is within such a range, it is easy to form a more uniform first layer, and it is easy to ensure high releasability.

The viscosity of the curable resin composition can be measured, for example, using an E-type viscometer (TVE-25 manufactured by Toki Sangyo Co., Ltd.) under the following conditions.
Temperature (circulating water temperature): 25 ° C
Rotor: cone plate (cone angle 1 ° 34 ')
Sample volume: 1.0 mL
Shear speed: 3.83 x rotor speed / s
Rotation speed: 100 rpm

Before forming the coating film, the viscosity of the curable resin composition may be adjusted by diluting with a solvent. At this time, it is preferable to dilute the curable resin composition used for forming the coating film so that the viscosity thereof falls within the above range. The solvent is selected according to the type of constituent components of the curable resin composition and the like. By diluting with a solvent, it becomes easier to form a more uniform first layer, and it is easy to ensure high releasability.
The curable resin composition may be either a one-component curing type or a two-component curing type.

  As the solvent, a volatile solvent is preferably used so that it can be removed in the subsequent adhesion step. As the solvent, an organic solvent is usually used, but water or a mixture of water and an organic solvent may be used depending on the type of the constituent components and / or the temperature of the adhesion step. Examples of the organic solvent include hydrocarbon, alcohol, ether, ester, ketone, amide, nitrile, sulfone and the like. A halogen-containing solvent such as a fluorine-containing solvent may be used as the solvent. The halogen-containing solvent is usually an organic solvent, and examples thereof include those obtained by introducing a halogen atom such as a fluorine atom into the above-exemplified organic solvents. The halogen atom includes a fluorine atom, chlorine, iodine, and / or bromine atom. From the viewpoint of high affinity with the fluorine-containing curable resin, a fluorine-containing solvent is preferable, and a halogen-containing solvent containing a fluorine atom and another halogen atom (for example, a chlorine atom) may be used. As the solvent, one kind may be used alone, or two or more kinds may be used in combination.

  After forming a coating film, you may dry as needed. Drying may be performed under atmospheric pressure or under reduced pressure. Drying can also be performed under heating, if necessary.

(Adhesion process)
In this step, the coating film formed in the coating film forming step (specifically, the curable resin composition contained in the coating film) is cured to form the first layer and the material forming the underlayer. The functional group derived from and the first reactive group are reacted or interacted with each other to bring the first layer into close contact with the underlayer. The reaction or interaction between the functional group and the first reactive group usually occurs in parallel as the curing reaction proceeds, but is not limited thereto. For example, if necessary, heating and / or light irradiation may be further performed after the curing reaction so that the reaction or interaction between the functional group and the first reactive group proceeds. When the functional group and the first reactive group react or interact with each other, a residue is formed at the interface between the underlayer and the first layer and in the vicinity thereof. Thereby, the adhesiveness between the first layer and the base layer can be enhanced.

  The first reactive group reacts with the functional group of the underlayer, the reaction component contained in the curable resin composition, and the like during the curing reaction and the like. Thereby, on the contact surface of the first layer with the photocurable material, the residual amount of the free first reactive group is reduced, and high releasability is secured. In particular, when a fluorine-containing curable resin having an alkoxysilyl group, a silanol group, and / or a vinylsilyl group (particularly a vinylsilyl group) as the first reactive group bonded to silicon is used, the photocurability of the first layer This is advantageous in ensuring high releasability at the contact surface with the material.

Curing of the curable resin composition may be carried out under heating and / or irradiation with light, if necessary. The curing temperature and time may be determined according to the composition of the curable resin composition and / or the type of solvent.
If necessary, drying may be performed at an appropriate stage of this process. Drying may be performed under atmospheric pressure or under reduced pressure. Drying may be performed under heating, if necessary.

[Example]
Hereinafter, the present invention will be specifically described based on Examples and Comparative Examples, but the present invention is not limited to the following Examples.

Examples 1-5
Acrylic resin vat (16 cm in width × 16 cm in width × 4 cm in depth) as a tray body was poured with a silicone addition type cured rubber having hydrosilyl groups at both ends (Toray Dow Corning Co., Sylgard 184), The second layer having a thickness of 4 mm was formed by curing by standing at room temperature (25 ° C.) for 24 hours. The Shore A hardness of the cured product of the silicone-added type cured rubber measured by the procedure described above is 50.

  A fluorine-containing silicone-added type cured rubber was applied onto the second layer, allowed to stand for a while, and then cured by heating at 80 ° C. overnight to form a first layer having a thickness shown in Table 1. In this way, a stereolithography tray having the first layer and the second layer as the underlying layer was formed. The Shore A hardness of the cured product (thickness: 4 mm) of the above-mentioned fluorine-containing silicone addition type cured rubber was 31, measured by the procedure described above.

The above-mentioned fluorine-containing silicone addition type cured rubber was prepared by the following procedure.
A solution (platinum concentration: 0.5% by mass) in which a platinum catalyst is dissolved in a solvent (hydrofluoroether C ₄ F ₉ OCH ₃ ) and a repeating structure of hexafluoropropylene oxide units, and vinyl silyl groups at both ends Solution A was prepared by mixing with the compound. A platinum-divinyltetramethyldisiloxane complex was used as the platinum catalyst.

A solution B was prepared by diluting a compound having a repeating structure of a fluorinated alkylene unit and having a hydrosilyl group at both ends with a solvent (hydrofluoroether C ₄ F ₉ OCH ₃ ).

  A fluorine-containing silicone addition type cured rubber (elastomer composition) was prepared by mixing the obtained solution B with the above solution A.

Comparative Example 1
A second layer was formed in the tray body in the same manner as in Example 1. The tray having the second layer was used as a tray for stereolithography without forming the first layer. Except for these, the same operation as in Example 1 was performed.

Comparative example 2
A second layer was formed in the tray body in the same manner as in Example 1. A fluorine-based coating agent containing polytetrafluoroethylene (PTFE) (Sumiron Lubricant Co., Ltd., Sumiron 2250 Spray PFOA-free) was applied onto the second layer and dried to form a 20 μm-thick first layer Formed. Except for these, the same operation as in Example 1 was performed.

<Evaluation>
Using the stereolithography trays obtained in the examples and the comparative examples, separation in the layer (the first layer in the examples and the comparative examples 2 and the second layer in the comparative examples 1) that was in contact with the sample was performed in the following procedure. The moldability and the adhesion of the layer in contact with the sample to the underlayer were evaluated.

(1) Releasability 3 parts by mass of an acylphosphine oxide photopolymerization initiator (manufactured by BASF, Irgacure819) is added to 100 parts by mass of dipentaerythritol hexaacrylate, and heated at 80 ° C. to obtain a uniform liquid state. A material (photocurable material) was obtained. A photo-curable material was housed in a tray for stereolithography, and a cylindrical sample having an outer diameter of 18 mm was produced by stereolithography. Stereolithography was performed using a SLA 3D printer (Novel 1.0A, manufactured by XYZ Printing Co.) under conditions of irradiation time per layer of 10 seconds and z-axis (height direction) pitch of 100 μm.

As an index of releasability, the state of the layer in contact with the sample after preparation of the sample or the degree of whitening was visually observed and evaluated according to the following criteria.
A: It remains transparent and no whitening is observed.
B: The part in contact with the sample is slightly white.
C: The part in contact with the sample is remarkably white.
D: When the cured product of the first layer was peeled from the first layer, the first layer was peeled from the second layer, and three-dimensional modeling could not be performed.

(2) Adhesiveness The first layer of the tray for stereolithography produced in the same manner as in Example or Comparative Example 2 was cut (cross-cut) into a size of 1 mm 2 mm × 2 mm. The transparent pressure-sensitive adhesive tape having a width of 25 mm, which was cut to a length of about 75 mm, was attached to the vicinity of the center of the notched portion so that the vicinity of the center in the length direction hits. At this time, the tape was rubbed by pressing it with a finger on the notched portion of the first layer so that at least a portion having a length of 20 mm near the center of the tape was flat. It was peeled off within 5 minutes after the tape was applied. At this time, in the cut portion where the tape was attached, the ratio (%) of the peeled portion was obtained, and the adhesion was evaluated according to the following criteria. The smaller the ratio of the peeled portion, the higher the adhesiveness.
A: The ratio of the peeled portion is 0%.
B: The ratio of the peeled portion is more than 0% and 50% or less.
C: The ratio of the peeled portion exceeds 50%.
Table 1 shows the evaluation results of the examples and comparative examples.

  In Comparative Example 1, when the height of the cylindrical sample was 10 cm, whitening was observed in the layer in contact with the sample, and when the height was 15 cm, remarkable whitening was observed. In Comparative Example 2, in the evaluation of releasability, when the cured product of the first layer was peeled off from the first layer, the first layer was peeled off from the second layer, and it was not possible to continue molding. . Further, in Comparative Example 2, in the adhesion test, all of the first layer was peeled (the ratio of the peeled portion was 100%).

  On the other hand, in the example, the releasability and the adhesion are greatly improved as compared with the comparative example. In Examples 1 to 4, even when a cylindrical sample having a height of 20 cm was formed, whitening of the first layer in contact with the sample was not observed. In Example 5, when a cylindrical sample having a height of 15 cm was formed, the portion of the surface of the first layer that was in contact with the sample was slightly white. Further, in the example, peeling of the first layer was not observed at all, and high adhesion could be secured. It is considered that such a result is due to the fact that the adhesion between the first layer and the underlayer is greatly improved by the addition reaction of the hydrosilyl group of the underlayer material and the vinylsilyl group of the first layer material.

  In the stereolithography tray according to the above aspect of the present invention, in the stereolithography, the cured product is easily peeled off from the first layer arranged on the inner bottom surface of the tray, and even after repeated use, the first layer is peeled off from the underlayer. Can be suppressed. Therefore, it is useful as a tray (or a resin tank) for accommodating a photocurable material used in a three-dimensional stereolithography apparatus using a 3D printer or the like.

  1, 11, 101: tray for stereolithography, 1a, 11a, 101a: exposed surface, 1b, 11b, 101b: bottom of tray body, 1c, 11c, 101c: tray body, 1d, 11d: first layer, 101d: Release layer, 11e: second layer, 102: photocurable material, 102a: liquid film, 102b: two-dimensional pattern, 104: platform, 104a: pattern forming surface, 105: light source, L: light

A first aspect of the present invention is a tray for stereolithography that contains a photocurable material having fluidity in stereolithography.
A tray body having an exposure surface,
A first layer covering a surface of the tray body opposite to the exposure surface, and having a contact surface with the photocurable material;
The first layer is composed of a cured product of a composition containing a fluorine-containing curable resin having a first reactive group directly or indirectly bonded to silicon,
At the interface between the first layer and the underlayer of the first layer and in the vicinity thereof, a residue in which a functional group derived from the material forming the underlayer and the first reactive group react or interact with each other, Exists ,
The functional group includes a second reactive group directly or indirectly bonded to silicon,
The residue, the Ru is formed with the first reactive group by the addition reaction of the second reactive group, to a tray for optical stereolithography.
A second aspect of the present invention is a tray for stereolithography that accommodates a photocurable material having fluidity in stereolithography.
A tray body having an exposure surface,
A first layer covering a surface of the tray body opposite to the exposure surface, and having a contact surface with the photocurable material;
The first layer is composed of a cured product of a composition containing a fluorine-containing curable resin having a first reactive group directly or indirectly bonded to silicon,
At the interface between the first layer and the underlayer of the first layer and in the vicinity thereof, a residue in which a functional group derived from the material forming the underlayer and the first reactive group react or interact with each other, Exists,
The first layer is made of fluorine-containing silicone rubber,
The underlayer relates to a stereolithography tray containing silicone rubber.

A third aspect of the present invention is a method for manufacturing the above-mentioned stereolithography tray,
A step of preparing a tray body having an exposed surface,
A curable resin composition containing a fluorine-containing curable resin having a first reactive group directly or indirectly bonded to silicon is applied so as to cover a surface of the tray body opposite to the exposed surface. A step of forming a coating film,
The coating film is cured to form a first layer having a contact surface with the photocurable material, and a functional group derived from the material forming the underlayer of the first layer and the first reactivity. And a step of reacting or interacting with a base to bring the first layer into close contact with the base layer.
A fourth aspect of the present invention is a method for manufacturing a stereolithography tray that contains a photocurable material having fluidity in stereolithography.
A step of preparing a tray body having an exposed surface,
A fluorine-containing curable resin having a first reactive group directly or indirectly bonded to silicon so as to cover a surface of the tray body opposite to the exposed surface, and 0.1 mPa at 25 ° C. A step of forming a coating film by applying a curable resin composition having a viscosity of s or more and 10 Pa · s or less,
The coating film is cured to form a first layer having a contact surface with the photocurable material, and a functional group derived from the material forming the underlayer of the first layer and the first reactivity. Reacting or interacting with a group to bring the first layer into close contact with the underlayer,
Prior to the coating film forming step, a step of forming a second layer containing a resin so as to cover the surface of the tray body opposite to the exposed surface,
The first layer forms the second layer as the base layer,
Before the coating film forming step, the present invention relates to a method for producing a stereolithography tray in which the viscosity of the curable resin composition is adjusted by diluting with a solvent containing a fluorine-containing solvent.

Claims (13)

A tray for stereolithography containing a photocurable material having fluidity in stereolithography,
A tray body having an exposure surface,
A first layer covering a surface of the tray body opposite to the exposure surface, and having a contact surface with the photocurable material;
The first layer is composed of a cured product of a composition containing a fluorine-containing curable resin having a first reactive group directly or indirectly bonded to silicon,
At the interface between the first layer and the underlayer of the first layer and in the vicinity thereof, a residue in which a functional group derived from the material forming the underlayer and the first reactive group react or interact with each other, An existing tray for stereolithography.   The tray for stereolithography according to claim 1, wherein the base layer is the tray main body or a second layer containing a resin disposed between the tray main body and the first layer. The base layer is the second layer,
The stereolithography tray according to claim 2, wherein a ratio of the thickness of the first layer to the thickness of the second layer is 0.001 to 1.   The optical modeling tray according to claim 1, wherein the first layer has a thickness of 1 μm or more and 1000 μm or less.   The stereolithography tray according to claim 1, wherein the functional group includes a second reactive group directly or indirectly bonded to silicon.   The stereolithography tray according to claim 5, wherein the residue is formed by an addition reaction between the first reactive group and the second reactive group.   The stereolithography tray according to any one of claims 1 to 6, wherein the cured product has a Shore A hardness at 23 ° C of 60 or less. The first layer is made of fluorine-containing silicone rubber,
The tray for stereolithography according to claim 1, wherein the base layer contains silicone rubber. A method of manufacturing a stereolithography tray containing a photocurable material having fluidity in stereolithography, comprising:
A step of preparing a tray body having an exposed surface,
A curable resin composition containing a fluorine-containing curable resin having a first reactive group directly or indirectly bonded to silicon is applied so as to cover a surface of the tray body opposite to the exposed surface. A step of forming a coating film,
The coating film is cured to form a first layer having a contact surface with the photocurable material, and a functional group derived from the material forming the underlayer of the first layer and the first reactivity. A step of reacting or interacting with a base to bring the first layer into close contact with the underlayer, and a method for producing a tray for stereolithography. Prior to the coating film forming step, a step of forming a second layer containing a resin so as to cover the surface of the tray body opposite to the exposed surface,
The method for manufacturing a stereolithography tray according to claim 9, wherein the first layer is formed by using the second layer as the base layer.   The method for producing a stereolithography tray according to claim 10, wherein the curable resin composition has a viscosity of 0.1 mPa · s or more and 10 Pa · s or less at 25 ° C.   The method for producing a stereolithography tray according to claim 11, wherein the viscosity of the curable resin composition is adjusted by diluting with a solvent before the coating film forming step.   The method for manufacturing a stereolithography tray according to claim 12, wherein the solvent contains a fluorine-containing solvent.

Images