WO2023195442A1 - Photocurable composition, cured product and method for producing cured product - Google Patents

Photocurable composition, cured product and method for producing cured product Download PDF

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WO2023195442A1
WO2023195442A1 PCT/JP2023/013795 JP2023013795W WO2023195442A1 WO 2023195442 A1 WO2023195442 A1 WO 2023195442A1 JP 2023013795 W JP2023013795 W JP 2023013795W WO 2023195442 A1 WO2023195442 A1 WO 2023195442A1
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cured product
photocurable
photocurable composition
present
resin
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PCT/JP2023/013795
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French (fr)
Japanese (ja)
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幸士 生田
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幸士 生田
春日製紙工業株式会社
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Priority to JP2023566995A priority Critical patent/JPWO2023195442A1/ja
Publication of WO2023195442A1 publication Critical patent/WO2023195442A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers

Definitions

  • the present invention relates to a photocurable composition containing ⁇ -1,3-glucan and a photocurable resin, a cured product of the photocurable composition, and a method for producing the cured product.
  • Photocurable resins are used for a variety of purposes, such as manufacturing three-dimensional structures and coating the surfaces of plastic products.
  • photocurable resins have lower strength and rigidity after curing than other resin materials. Therefore, in order to improve the mechanical strength of photocurable resins, it has been proposed to add fibrous fillers such as cellulose nanofibers to photocurable resins (see Patent Documents 1 and 2).
  • fibrous fillers such as cellulose nanofibers
  • the improvement effect was not sufficient, and in the case of fibrous fillers, there was also a problem that it was difficult to mix with the photocurable resin.
  • paramylon particles as a filler for resin.
  • this is not intended for photocurable resins, and the improvement effect was only an increase in the elastic modulus of about 10 to 30%.
  • An object of the present invention is to provide a photocurable composition from which a cured product with excellent strength and rigidity can be obtained, and a cured product with excellent strength and rigidity obtained from the photocurable composition.
  • the present inventor carried out studies to improve the mechanical strength of photocurable resins after curing, and unexpectedly discovered that by adding ⁇ -1,3-glucan to photocurable resins, photocuring It has been found that the mechanical strengths such as tensile strength, bending strength, and Young's modulus of the cured product can be significantly improved. Photocurable resins are often used in fields that do not require high strength or rigidity, and in the past, large improvements in strength and rigidity have not been achieved. No attempt was made to improve it. However, studies by the present inventors have made it possible to produce a cured product with a tensile strength of 50 MPa or more using a photocurable resin.
  • a photocurable composition containing ⁇ -1,3-glucan and a photocurable resin (2) The photocurable composition according to (1) above, wherein the ⁇ -1,3-glucan is paramylon. (3) The photocurable composition according to (1) or (2) above, wherein the content of ⁇ -1,3-glucan is 0.5 to 30% by mass relative to the content of the photocurable resin. thing. (4) A cured product of the photocurable composition according to any one of (1) to (3) above. (5) A method for producing a cured product, comprising irradiating the photocurable composition according to any one of (1) to (3) above with light.
  • the photocurable composition of the present invention can be photocured to produce a cured product with excellent strength and rigidity.
  • the cured product of the present invention is a cured product manufactured using a photocurable resin, it has excellent strength and rigidity.
  • a cured product having excellent strength and rigidity can be manufactured using a photocurable resin.
  • FIGS. 1(a) and 1(b) are images of paramylon used in Examples observed with a scanning electron microscope.
  • FIG. 2 is a diagram showing the results of Young's modulus measurements of Examples 1 to 4 and Comparative Example 1.
  • FIG. 3 is a diagram showing the results of tensile breaking strength measurements of Examples 1 to 4 and Comparative Example 1.
  • FIG. 4 is a diagram showing the results of tensile breaking strength measurements of Examples 5 to 7 and Comparative Example 1.
  • the photocurable composition of the present invention contains ⁇ -1,3-glucan and a photocurable resin.
  • a photocurable resin is a resin that undergoes a polymerization reaction, a crosslinking reaction, etc. of monomers and oligomers when exposed to light, and contains a photopolymerization initiator if necessary.
  • the state before being turned into a resin and hardened by irradiation with light is also referred to as a photocurable resin, and the photocurable resin in the present invention is also used in this sense.
  • the photocurable resin in the present invention is not particularly limited, and examples thereof include cationically polymerizable photocurable resins, radically polymerizable photocurable resins, etc.
  • the resin examples include epoxy resins, and examples of the radically polymerizable photocurable resin include urethane resins, acrylic resins, vinyl ether resins, and the like.
  • the photocurable composition of the present invention may contain one or more photocurable resins.
  • the wavelength of the irradiated light is not particularly limited, and may be, for example, a wavelength in the ultraviolet, visible, or infrared regions.
  • the photopolymerization initiator is not particularly limited, but includes, for example, a compound that absorbs light and generates polymerization initiating species such as radicals and cations.
  • the photocurable composition of the present invention may contain one or more photopolymerization initiators.
  • ⁇ -1,3-glucan is a polysaccharide produced by ⁇ -1,3-bonds of glucose.
  • the ⁇ -1,3-glucans in the present invention include those having a linear chain and those having a branched chain.
  • the origin of ⁇ -1,3-glucan in the present invention is not particularly limited, and it may be obtained by chemical synthesis or may be of biological origin. Examples of biological sources include ⁇ -1,3-glucans derived from bacteria, fungi, yeast, plants such as barley, and algae, such as paramylon, curdlan, laminaran, callose, lentinan, Schizophyllan and the like can be mentioned.
  • Paramylon derived from Euglena which is mentioned as a ⁇ -1,3-glucan derived from algae, is a particle in which triple helical structures formed by ⁇ -1,3-glucan chains are accumulated.
  • the photocurable composition of the present invention may contain one or more types of ⁇ -1,3-glucan.
  • the content ratio of the photocurable resin and ⁇ -1,3-glucan in the photocurable composition of the present invention is not particularly limited, for example, as the content of ⁇ -1,3-glucan, Based on the content of the curable resin, 0.001 to 99.9% by mass, 0.01 to 99.9% by mass, 0.01 to 99% by mass, 0.1 to 90% by mass, 0.1 to 70% by mass, 0.1-50% by mass, 0.1-40% by mass, 0.5-90% by mass, 0.5-70% by mass, 0.5-50% by mass, 0.5-40% by mass %, 0.5 to 30 mass %, 0.5 to 20 mass %, 0.5 to 10 mass %, 0.5 to 5 mass %, etc. can be mentioned as preferable ranges.
  • the photocurable composition of the present invention can be produced by mixing a photocurable resin and ⁇ -1,3-glucan.
  • the method for producing the photocurable composition of the present invention is not particularly limited, but for example, since photocurable resins are often in liquid form, ⁇ -1,3-glucan is added to the photocurable resin and stirred. It can be manufactured by When the photocurable resin is in a solid state, it may be used after being dissolved in a solvent or the like.
  • the form of ⁇ -1,3-glucan used may be solid such as granules, or liquid. There are no particular restrictions on the form, particle size, etc. of ⁇ -1,3-glucan as long as it can be mixed with the photocurable resin.
  • stirring and mixing method ordinary stirring and mixing methods can be used as appropriate, and stirring and mixing conditions such as temperature and time can also be appropriately selected according to the materials used.
  • the cured product of the present invention can be produced by irradiating the photocurable composition of the present invention with light.
  • the light source for irradiating light is not particularly limited, and examples thereof include various lasers, various lamps, etc., and a cured product can be produced by irradiating light with a wavelength corresponding to the photocurable composition used. Can be done. Conditions such as light intensity and irradiation time can be appropriately selected depending on the material used. Since the cured product of the present invention has excellent strength and rigidity, it can prevent or reduce gravitational deformation of the structure during stereolithography when producing a three-dimensional structure. Therefore, there is no need to provide a support (stay) for preventing gravitational deformation.
  • the cured product obtained by photocuring the photocurable composition of the present invention may be further subjected to temperature treatment.
  • the temperature of the temperature treatment is not particularly limited, and cooling treatment or heat treatment may be performed.
  • the properties of the cured product can be changed by temperature treatment. For example, by heat-treating the photocured cured body, the strength and rigidity of the cured body can be further increased.
  • heat treatment can suppress toxicity caused by uncured monomers, photopolymerization initiators, etc. contained in the cured product and impart biocompatibility to the cured product, which can be used for medical devices and food. etc. will be suitable.
  • the hardness of the cured body can be improved.
  • the temperature in the heat treatment is not particularly limited, and can be appropriately set together with the heating time. For example, a temperature lower than the melting point of the cured product can be mentioned.
  • the temperature in the heat treatment can be selected as appropriate depending on the resin, but the treatment temperature maintained after raising the temperature (hereinafter also referred to as heat treatment temperature) is, for example, less than the melting point, 70°C or higher, 80°C or higher, 90°C or higher.
  • the heat treatment temperature may be a temperature below the softening point or glass transition point of the resin, such as 70°C or higher, 80°C or higher, 90°C or higher, or 100°C or higher.
  • the heat treatment temperature may be a temperature higher than the softening point or glass transition point of the resin, and is not particularly limited as long as it is lower than the melting point.
  • the temperature may be higher than or equal to the softening point or glass transition point of the resin, but lower than or equal to 150° C. higher than the softening point or glass transition point of the resin, or lower than or equal to 100° C. higher than the softening point or glass transition point of the resin.
  • the heat treatment temperature may be, for example, a temperature 150°C higher than the softening point or glass transition point of the resin, but not lower than 70°C, 80°C or higher, 90°C or higher, 100°C or higher, or the like.
  • the temperature is 100°C higher than the softening point or glass transition point of , and examples include 70°C or higher, 80°C or higher, 90°C or higher, and 100°C or higher.
  • Examples 1 to 4 Euglena-derived resin was added to 6 g of an epoxy-based general-purpose photocurable resin (SCR751, D-MEC Co., Ltd.: critical exposure amount 20 mJ/cm 2 , glass transition temperature after curing 108°C) in the proportions (mass ratio) listed in Table 1.
  • Paramylon was added and mixed to prepare a photocurable composition.
  • the prepared photocurable composition was irradiated with ultraviolet rays using a UV lamp to produce a cured product.
  • a scanning electron microscope image of the paramylon used is shown in Figure 1.
  • Examples 5 to 7 The same general-purpose photocurable resin and paramylon as in Examples 1 to 4 were used. Using these, photocurable compositions were prepared in the same manner as in Examples 1 to 4 at the proportions (mass ratios) listed in Table 2, and after photocuring, the compositions were heated in air under the conditions listed in Table 2. A final cured product was obtained.
  • Example 1 Example 1 except that 5 g of an epoxy-based general-purpose photocurable resin (SCR751, D-MEC Co., Ltd., critical exposure amount 20 mJ/cm 2 , glass transition temperature after curing 108°C) was used, and paramylon was not added. A cured product was prepared by photocuring in the same manner as in 4. For comparison, Comparative Example 1 shows the mechanical properties of only a photocurable resin without paramylon after curing.
  • SCR751, D-MEC Co., Ltd. critical exposure amount 20 mJ/cm 2 , glass transition temperature after curing 108°C
  • the Young's modulus and tensile strength at break of the cured bodies obtained in Examples 1 to 7 and Comparative Example 1 were measured using the following methods. (Measurement of Young's modulus and tensile strength at break) Test pieces were prepared from the cured bodies obtained in Examples 1 to 7 and Comparative Example 1, and measured by a tensile test. The results of Young's modulus measurements of Examples 1 to 4 and Comparative Example 1 are shown in FIG. 2, and the results of tensile strength at break measurements are shown in FIG. Further, the results of tensile breaking strength measurements of Examples 5 to 7 and Comparative Example 1 are shown in FIG. The values shown in the bar graphs in FIGS. 2 to 4 are the average values of the results of five measurements.
  • Example 4 the cured products heated after photocuring (Examples 6 and 7) exhibited a tensile strength approximately 1.4 times higher than that before heating (Example 5), and paramylon was added.
  • the tensile strength at break was about 4 times that of the case without it (Comparative Example 1).
  • heating was performed at a temperature lower than the glass transition temperature after photocuring
  • Example 7 heating was performed at a temperature higher than the glass transition temperature after photocuring, but in both cases, the heat treatment had an effect of improving strength. Admitted.
  • Examples 8 to 10 The same general-purpose photocurable resin and paramylon as in Examples 1 to 4 were used. Using these, photocurable compositions were prepared in the same manner as in Examples 1 to 4 at the proportions (mass ratios) listed in Table 3, and then photocured, and then heated in air under the conditions listed in Table 3. A final cured product was obtained. The Vickers hardness of the obtained cured product was measured using a micro Vickers hardness tester (HM-221, manufactured by Mitutoyo Co., Ltd.). The test force for pressing the indenter was 0.02 kgf, and the lengths (d1, d2 ( ⁇ m)) of the diagonal line of the indentation were measured to determine the Vickers hardness. The results of the measurements were approximately 17 HV in Example 8, approximately 20 HV in Example 9, and approximately 28 HV in Example 10. The hardness of the heat-treated samples was higher than that of the non-heat-treated samples.
  • the photocurable composition of the present invention uses a photocurable resin, it is possible to obtain a cured product with high strength and rigidity. It can be suitably used in coatings, etc., and can also be suitably used in fields where high strength and rigidity are required, where photocurable resins could not be used in the past. Since the cured product of the present invention has high strength and rigidity, it can be suitably used in the same fields as mentioned above, and the heat-treated product can also be suitably used for medical equipment, food applications, etc. Specifically, for example, as an application in the medical field, the present invention performs a stereolithography method that has both strength and biocompatibility, such as micro medical devices, various biotest devices with internal flow channels, parts implanted in the body, etc.
  • applications in the industrial field include hardening the surface of furniture, improving the biocompatibility of the surface of furniture, manufacturing high-mix low-volume products using 3D printers (e.g. backup parts, etc.), and other applications such as food-grade products.
  • 3D printers e.g. backup parts, etc.
  • food-grade products examples include equipment and equipment parts, children's toys, and pet equipment.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

The present invention addresses the problem of providing: a photocurable composition which enables the achievement of a cured product that has excellent strength and stiffness; and a cured product which is obtained from a photocurable composition and has excellent strength and stiffness.　The present invention provides a photocurable composition which contains β-1,3-glucan and a photocurable resin. The present invention also provides a cured product of a photocurable composition which contains β-1,3-glucan and a photocurable resin.

Description

光硬化性組成物、硬化体及び硬化体の製造方法Photocurable composition, cured product, and method for producing the cured product
　本発明は、β－１，３－グルカンと光硬化性樹脂を含有する光硬化性組成物、前記光硬化性組成物の硬化体及び硬化体の製造方法に関する。 The present invention relates to a photocurable composition containing β-1,3-glucan and a photocurable resin, a cured product of the photocurable composition, and a method for producing the cured product.
　光硬化性樹脂は、三次元構造体の製造、プラスチック製品等の表面コートなどの様々な用途に使用されている。しかしながら、光硬化性樹脂は他の樹脂材料に比べて硬化後の強度や剛性が低い。そのため、光硬化性樹脂の機械的強度改善のために、セルロースナノファイバー等の繊維状の充填材を光硬化性樹脂に添加することが提案されている（特許文献１及び２参照）。しかし、その改善効果は十分ではなく、繊維状充填材の場合、光硬化性樹脂と混合し難いとの問題もあった。一方で、パラミロン粒子を樹脂の充填材として使用することが提案されている（特許文献３参照）。しかしながら、これは光硬化性樹脂を対象とするものでなく、その改善効果も弾性率が１０～３０％程度増加するにすぎなかった。 Photocurable resins are used for a variety of purposes, such as manufacturing three-dimensional structures and coating the surfaces of plastic products. However, photocurable resins have lower strength and rigidity after curing than other resin materials. Therefore, in order to improve the mechanical strength of photocurable resins, it has been proposed to add fibrous fillers such as cellulose nanofibers to photocurable resins (see Patent Documents 1 and 2). However, the improvement effect was not sufficient, and in the case of fibrous fillers, there was also a problem that it was difficult to mix with the photocurable resin. On the other hand, it has been proposed to use paramylon particles as a filler for resin (see Patent Document 3). However, this is not intended for photocurable resins, and the improvement effect was only an increase in the elastic modulus of about 10 to 30%.
特開２０１７－７１１６号公報JP 2017-7116 Publication 特許第６１５３６８０号公報Patent No. 6153680 特開２０１３－９１７１６号公報JP2013-91716A
　本発明の課題は、強度及び剛性に優れた硬化体を得ることができる光硬化性組成物、及び光硬化性組成物から得られる強度及び剛性に優れた硬化体を提供することである。 An object of the present invention is to provide a photocurable composition from which a cured product with excellent strength and rigidity can be obtained, and a cured product with excellent strength and rigidity obtained from the photocurable composition.
　本発明者は、光硬化性樹脂の硬化後の機械的強度を向上させるための検討を進めたところ、意外にも光硬化性樹脂にβ－１，３－グルカンを添加することにより、光硬化後の硬化体の引張強度、曲げ強度、ヤング率等の機械的強度を格段に向上させることができることを見いだした。光硬化性樹脂は高い強度や剛性を必要としない分野に使用されることが多く、従来、強度や剛性の大きな改善効果も得られていなかったことから、光硬化性樹脂の機械的強度を大きく向上させようという試みはなされていなかった。しかし、本発明者の検討により、光硬化性樹脂を用いて引張強度が５０ＭＰａ以上の硬化体を作製することも可能となった。この強度はエンジニアリングプラスチックの領域であり、もちろん従来の用途においても優れた効果を奏するものであるが、光硬化性樹脂を新たな用途に展開できるものである。加えて、本発明者は、β－１，３－グルカンを添加した光硬化性樹脂を光硬化させた後に、温度処理を行うことにより、硬化体の機械的強度を更に向上させる等の特性の調整ができることを見いだした。本発明は、こうして完成されたものである。 The present inventor carried out studies to improve the mechanical strength of photocurable resins after curing, and unexpectedly discovered that by adding β-1,3-glucan to photocurable resins, photocuring It has been found that the mechanical strengths such as tensile strength, bending strength, and Young's modulus of the cured product can be significantly improved. Photocurable resins are often used in fields that do not require high strength or rigidity, and in the past, large improvements in strength and rigidity have not been achieved. No attempt was made to improve it. However, studies by the present inventors have made it possible to produce a cured product with a tensile strength of 50 MPa or more using a photocurable resin. This strength is in the realm of engineering plastics, and of course it has excellent effects in conventional applications, but it also allows photocurable resins to be used in new applications. In addition, the present inventors have discovered that by photocuring a photocurable resin to which β-1,3-glucan has been added, and then subjecting it to temperature treatment, it is possible to further improve the mechanical strength of the cured product. I found that it can be adjusted. The present invention was thus completed.
　すなわち、本発明は以下に示す事項により特定されるものである。
（１）β－１，３－グルカンと光硬化性樹脂を含有する光硬化性組成物。
（２）β－１，３－グルカンがパラミロンであることを特徴とする上記（１）記載の光硬化性組成物。
（３）光硬化性樹脂の含有量に対するβ－１，３－グルカンの含有量が０．５～３０質量％であることを特徴とする上記（１）又は（２）記載の光硬化性組成物。
（４）上記（１）～（３）のいずれかに記載の光硬化性組成物の硬化体。
（５）上記（１）～（３）のいずれかに記載の光硬化性組成物に光を照射することを特徴とする硬化体の製造方法。
（６）光硬化性組成物に光を照射した後に、温度処理することを特徴とする上記（５）記載の硬化体の製造方法。
（７）温度処理が加熱処理であることを特徴とする上記（６）記載の硬化体の製造方法。 That is, the present invention is specified by the matters shown below.
(1) A photocurable composition containing β-1,3-glucan and a photocurable resin.
(2) The photocurable composition according to (1) above, wherein the β-1,3-glucan is paramylon.
(3) The photocurable composition according to (1) or (2) above, wherein the content of β-1,3-glucan is 0.5 to 30% by mass relative to the content of the photocurable resin. thing.
(4) A cured product of the photocurable composition according to any one of (1) to (3) above.
(5) A method for producing a cured product, comprising irradiating the photocurable composition according to any one of (1) to (3) above with light.
(6) The method for producing a cured product as described in (5) above, which comprises irradiating the photocurable composition with light and then subjecting it to temperature treatment.
(7) The method for producing a cured product as described in (6) above, wherein the temperature treatment is a heat treatment.
　本発明の光硬化性組成物は、光硬化させることにより強度及び剛性に優れた硬化体を製造することができる。本発明の硬化体は、光硬化性樹脂を用いて製造された硬化体でありながら強度及び剛性に優れる。本発明の製造方法は、光硬化性樹脂を用いて強度及び剛性に優れた硬化体を製造することができる。 The photocurable composition of the present invention can be photocured to produce a cured product with excellent strength and rigidity. Although the cured product of the present invention is a cured product manufactured using a photocurable resin, it has excellent strength and rigidity. According to the manufacturing method of the present invention, a cured product having excellent strength and rigidity can be manufactured using a photocurable resin.
図１（ａ）及び（ｂ）は、実施例で用いたパラミロンを走査型電子顕微鏡で観察した画像である。FIGS. 1(a) and 1(b) are images of paramylon used in Examples observed with a scanning electron microscope. 図２は、実施例１～４及び比較例１のヤング率測定の結果を示す図である。FIG. 2 is a diagram showing the results of Young's modulus measurements of Examples 1 to 4 and Comparative Example 1. 図３は、実施例１～４及び比較例１の引張破断強度測定の結果を示す図である。FIG. 3 is a diagram showing the results of tensile breaking strength measurements of Examples 1 to 4 and Comparative Example 1. 図４は、実施例５～７及び比較例１の引張破断強度測定の結果を示す図である。FIG. 4 is a diagram showing the results of tensile breaking strength measurements of Examples 5 to 7 and Comparative Example 1.
　本発明の光硬化性組成物は、β－１，３－グルカンと光硬化性樹脂を含有する。光硬化性樹脂とは、光によりモノマーやオリゴマーが重合反応、架橋反応等して樹脂化するものであり、必要に応じて光重合開示剤を含む。一般的に、光の照射により樹脂化して硬化する前の状態も光硬化性樹脂と言われており、本発明における光硬化性樹脂もこの意味で用いる。本発明における光硬化性樹脂としては、特に制限されるものではないが、例えば、カチオン重合性光硬化性樹脂、ラジカル重合性光硬化性樹脂等を挙げることができ、カチオン重合性光硬化性樹脂としては、エポキシ樹脂等を挙げることができ、ラジカル重合性光硬化性樹脂としては、ウレタン樹脂、アクリル樹脂、ビニルエーテル樹脂等を挙げることができる。本発明の光硬化性組成物は、光硬化性樹脂を１種又は２種以上含有してもよい。また、照射される光の波長も特に制限されず、例えば、紫外線、可視光、赤外線等の領域の波長であってもよい。光重合開示剤としては、特に制限されるものではないが、例えば、光を吸収してラジカル、カチオン等の重合開始種を生成する化合物を挙げることができ、具体的には、例えば、芳香族ケトン類等のカルボニル化合物、芳香族オニウム塩化合物、チオ化合物、オキシムエステル化合物、アシルホスフィンオキシド化合物、アルキルアミン化合物、オニウム塩、スルホニウム塩、ホスホニウム塩、及びピリジニウム塩等を挙げることができる。本発明の光硬化性組成物は、光重合開示剤を１種又は２種以上含有してもよい。 The photocurable composition of the present invention contains β-1,3-glucan and a photocurable resin. A photocurable resin is a resin that undergoes a polymerization reaction, a crosslinking reaction, etc. of monomers and oligomers when exposed to light, and contains a photopolymerization initiator if necessary. Generally, the state before being turned into a resin and hardened by irradiation with light is also referred to as a photocurable resin, and the photocurable resin in the present invention is also used in this sense. The photocurable resin in the present invention is not particularly limited, and examples thereof include cationically polymerizable photocurable resins, radically polymerizable photocurable resins, etc. Examples of the resin include epoxy resins, and examples of the radically polymerizable photocurable resin include urethane resins, acrylic resins, vinyl ether resins, and the like. The photocurable composition of the present invention may contain one or more photocurable resins. Furthermore, the wavelength of the irradiated light is not particularly limited, and may be, for example, a wavelength in the ultraviolet, visible, or infrared regions. The photopolymerization initiator is not particularly limited, but includes, for example, a compound that absorbs light and generates polymerization initiating species such as radicals and cations. Examples include carbonyl compounds such as ketones, aromatic onium salt compounds, thio compounds, oxime ester compounds, acylphosphine oxide compounds, alkylamine compounds, onium salts, sulfonium salts, phosphonium salts, and pyridinium salts. The photocurable composition of the present invention may contain one or more photopolymerization initiators.
　β－１，３－グルカンとは、グルコースのβ－１，３－結合により生じる多糖類である。本発明におけるβ－１，３－グルカンとしては、直鎖状のもの及び分岐鎖を有するものを含む。本発明におけるβ－１，３－グルカンとしては、その由来等特に制限されるものではなく、化学合成によって得られたものでもよく、生物由来のものでもよい。生物由来のものとしては、例えば、細菌、真菌、酵母、大麦等の植物、藻類など由来のβ－１，３－グルカンを挙げることができ、例えば、パラミロン、カードラン、ラミナラン、カロース、レンチナン、シゾフィラン等を挙げることができる。藻類由来のβ－１，３－グルカンとして挙げられるユーグレナ由来のパラミロンは、β－１，３－グルカン鎖により形成される３重らせん構造体が集積した粒子である。本発明の光硬化性組成物は、β－１，３－グルカンを１種又は２種以上含有してもよい。本発明の光硬化性組成物における光硬化性樹脂とβ－１，３－グルカンとの含有比率は特に制限されるものではないが、例えば、β－１，３－グルカンの含有量として、光硬化性樹脂の含有量に対して、０．００１～９９.９質量％、０．０１～９９．９質量％、０．０１～９９質量％、０．１～９０質量％、０．１～７０質量％、０．１～５０質量％、０．１～４０質量％、０．５～９０質量％、０．５～７０質量％、０．５～５０質量％、０．５～４０質量％、０．５～３０質量％、０．５～２０質量％、０．５～１０質量％、０．５～５質量％等を好ましい範囲として挙げることができる。 β-1,3-glucan is a polysaccharide produced by β-1,3-bonds of glucose. The β-1,3-glucans in the present invention include those having a linear chain and those having a branched chain. The origin of β-1,3-glucan in the present invention is not particularly limited, and it may be obtained by chemical synthesis or may be of biological origin. Examples of biological sources include β-1,3-glucans derived from bacteria, fungi, yeast, plants such as barley, and algae, such as paramylon, curdlan, laminaran, callose, lentinan, Schizophyllan and the like can be mentioned. Paramylon derived from Euglena, which is mentioned as a β-1,3-glucan derived from algae, is a particle in which triple helical structures formed by β-1,3-glucan chains are accumulated. The photocurable composition of the present invention may contain one or more types of β-1,3-glucan. Although the content ratio of the photocurable resin and β-1,3-glucan in the photocurable composition of the present invention is not particularly limited, for example, as the content of β-1,3-glucan, Based on the content of the curable resin, 0.001 to 99.9% by mass, 0.01 to 99.9% by mass, 0.01 to 99% by mass, 0.1 to 90% by mass, 0.1 to 70% by mass, 0.1-50% by mass, 0.1-40% by mass, 0.5-90% by mass, 0.5-70% by mass, 0.5-50% by mass, 0.5-40% by mass %, 0.5 to 30 mass %, 0.5 to 20 mass %, 0.5 to 10 mass %, 0.5 to 5 mass %, etc. can be mentioned as preferable ranges.
　本発明の光硬化性組成物は、光硬化性樹脂とβ－１，３－グルカンを混合することにより製造することができる。本発明の光硬化性組成物の製造方法は特に制限されないが、例えば、光硬化性樹脂は液体状であることが多いため、光硬化性樹脂にβ－１，３－グルカンを添加し、攪拌することにより製造することができる。光硬化性樹脂が固体状の場合は、溶媒等に溶解させて使用してもよい。使用するβ－１，３－グルカンの形態は、粒状等の固体状でもよく、液体状でもよい。光硬化性樹脂と混合できれば、β－１，３－グルカンの形態、粒径等は特に制限されない。攪拌、混合方法は、通常の攪拌、混合方法を適宜使用することができ、温度、時間等の攪拌、混合条件についても使用する材料に合わせて適宜選択することができる。 The photocurable composition of the present invention can be produced by mixing a photocurable resin and β-1,3-glucan. The method for producing the photocurable composition of the present invention is not particularly limited, but for example, since photocurable resins are often in liquid form, β-1,3-glucan is added to the photocurable resin and stirred. It can be manufactured by When the photocurable resin is in a solid state, it may be used after being dissolved in a solvent or the like. The form of β-1,3-glucan used may be solid such as granules, or liquid. There are no particular restrictions on the form, particle size, etc. of β-1,3-glucan as long as it can be mixed with the photocurable resin. As the stirring and mixing method, ordinary stirring and mixing methods can be used as appropriate, and stirring and mixing conditions such as temperature and time can also be appropriately selected according to the materials used.
　本発明の硬化体は、本発明の光硬化性組成物に光を照射することにより製造することができる。光を照射する光源は特に制限されず、例えば、各種レーザー、各種ランプ等を挙げることができ、使用する光硬化性組成物に対応する波長の光を照射することにより、硬化体を製造することができる。光の強さ、照射時間等の条件は使用する材料に合わせて適宜選択することができる。本発明の硬化体は、強度及び剛性に優れるため、三次元構造体の製造の際に、光造形中の構造の重力変形を防ぐ又は少なくすることができる。そのため、重力変形を防ぐ目的のサポート（ステー）を付ける必要がなくなる又は少なくなる。さらに、重力による微小なたわみを防ぐことができるので、加工精度が向上する。また、各種物品の表面にコートする場合、傷がつきにくくできる。例えば、机などの上面に本発明の光硬化性組成物を薄くコートし、紫外線等の光で硬化させて表面の強度を向上させる場合でも、傷のつきにくいコート層を形成することができる。 The cured product of the present invention can be produced by irradiating the photocurable composition of the present invention with light. The light source for irradiating light is not particularly limited, and examples thereof include various lasers, various lamps, etc., and a cured product can be produced by irradiating light with a wavelength corresponding to the photocurable composition used. Can be done. Conditions such as light intensity and irradiation time can be appropriately selected depending on the material used. Since the cured product of the present invention has excellent strength and rigidity, it can prevent or reduce gravitational deformation of the structure during stereolithography when producing a three-dimensional structure. Therefore, there is no need to provide a support (stay) for preventing gravitational deformation. Furthermore, since minute deflections due to gravity can be prevented, processing accuracy is improved. Furthermore, when coating the surface of various articles, it can be made less likely to be scratched. For example, even when the photocurable composition of the present invention is thinly coated on the top surface of a desk or the like and cured with light such as ultraviolet rays to improve the strength of the surface, a scratch-resistant coating layer can be formed.
　本発明の硬化体の製造方法においては、本発明の光硬化性組成物を光硬化させた硬化体を、更に温度処理してもよい。温度処理の温度は特に制限されるものでなく、冷却処理してもよく、加熱処理してもよい。温度処理することにより、硬化体の特性を変えることができる。例えば、光硬化させた硬化体を加熱処理することにより、硬化体の強度や剛性を更に高くすることができる。また、加熱処理することにより、硬化体に含まれる未硬化のモノマー、光重合開始剤等の影響による毒性を抑制して生体適合性を硬化体に付与することができるので、医療機器、食品用途等に適したものになる。加熱を、真空又は窒素雰囲気等の不活性ガス雰囲気で行うと、酸化による変色を防ぎ透明等の加熱前の状態を維持することが容易になる。また、本発明においては、光硬化させた硬化体を加熱処理すると、硬化体の硬度を向上させることができる。加熱処理の場合の温度は特に制限されず、加熱時間と合わせて適宜設定することができる。例えば、硬化体の融点未満の温度を挙げることができる。加熱処理における温度としては、樹脂により適宜選択できるが、昇温後に保持する処理温度（以下、加熱処理温度ともいう。）として、例えば、融点未満であって、７０℃以上、８０℃以上、９０℃以上、１００℃以上等を挙げることができる。また、加熱処理温度として、樹脂の軟化点又はガラス転移点以下の温度であって、７０℃以上、８０℃以上、９０℃以上、１００℃以上等を挙げることができる。加熱処理温度としては、樹脂の軟化点又はガラス転移点以上の温度でもよく、融点未満の温度であれば特に制限されるものではない。例えば、樹脂の軟化点又はガラス転移点の温度以上であって、樹脂の軟化点又はガラス転移点の温度よりも１５０℃高い温度以下、１００℃高い温度以下等を挙げることができる。また、加熱処理温度としては、例えば、樹脂の軟化点又はガラス転移点の温度よりも１５０℃高い温度以下であって、７０℃以上、８０℃以上、９０℃以上、１００℃以上等、あるいは樹脂の軟化点又はガラス転移点の温度よりも１００℃高い温度以下であって、７０℃以上、８０℃以上、９０℃以上、１００℃以上等を挙げることができる。 In the method for producing a cured product of the present invention, the cured product obtained by photocuring the photocurable composition of the present invention may be further subjected to temperature treatment. The temperature of the temperature treatment is not particularly limited, and cooling treatment or heat treatment may be performed. The properties of the cured product can be changed by temperature treatment. For example, by heat-treating the photocured cured body, the strength and rigidity of the cured body can be further increased. In addition, heat treatment can suppress toxicity caused by uncured monomers, photopolymerization initiators, etc. contained in the cured product and impart biocompatibility to the cured product, which can be used for medical devices and food. etc. will be suitable. When heating is performed in a vacuum or in an inert gas atmosphere such as a nitrogen atmosphere, discoloration due to oxidation can be prevented and the state before heating, such as transparency, can be easily maintained. Moreover, in the present invention, when the photocured cured body is heat-treated, the hardness of the cured body can be improved. The temperature in the heat treatment is not particularly limited, and can be appropriately set together with the heating time. For example, a temperature lower than the melting point of the cured product can be mentioned. The temperature in the heat treatment can be selected as appropriate depending on the resin, but the treatment temperature maintained after raising the temperature (hereinafter also referred to as heat treatment temperature) is, for example, less than the melting point, 70°C or higher, 80°C or higher, 90°C or higher. C or higher, 100 C or higher, and the like. Further, the heat treatment temperature may be a temperature below the softening point or glass transition point of the resin, such as 70°C or higher, 80°C or higher, 90°C or higher, or 100°C or higher. The heat treatment temperature may be a temperature higher than the softening point or glass transition point of the resin, and is not particularly limited as long as it is lower than the melting point. For example, the temperature may be higher than or equal to the softening point or glass transition point of the resin, but lower than or equal to 150° C. higher than the softening point or glass transition point of the resin, or lower than or equal to 100° C. higher than the softening point or glass transition point of the resin. In addition, the heat treatment temperature may be, for example, a temperature 150°C higher than the softening point or glass transition point of the resin, but not lower than 70°C, 80°C or higher, 90°C or higher, 100°C or higher, or the like. The temperature is 100°C higher than the softening point or glass transition point of , and examples include 70°C or higher, 80°C or higher, 90°C or higher, and 100°C or higher.
　以下、本発明の実施例を挙げて、本発明を具体的に説明するが、本発明の技術的範囲はこれらの例示に限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to Examples, but the technical scope of the present invention is not limited to these examples.
　［実施例１～４］
エポキシ系の汎用光硬化性樹脂（ＳＣＲ７５１、株式会社ディーメック：臨界露光量２０ｍＪ／ｃｍ２、硬化後のガラス転移温度１０８℃）６ｇに、表１に記載する割合（質量比）でユーグレナ由来のパラミロンを添加し混合して光硬化性組成物を調製した。調製した光硬化性組成物に、ＵＶランプにより紫外線を照射して、硬化体を作製した。使用したパラミロンの走査型電子顕微鏡の画像を図１に示す。 [Examples 1 to 4]
Euglena-derived resin was added to 6 g of an epoxy-based general-purpose photocurable resin (SCR751, D-MEC Co., Ltd.: critical exposure amount 20 mJ/cm 2 , glass transition temperature after curing 108°C) in the proportions (mass ratio) listed in Table 1. Paramylon was added and mixed to prepare a photocurable composition. The prepared photocurable composition was irradiated with ultraviolet rays using a UV lamp to produce a cured product. A scanning electron microscope image of the paramylon used is shown in Figure 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　［実施例５～７］
実施例１～４と同種の汎用光硬化性樹脂とパラミロンを使用した。これらを使用して表２に記載する割合（質量比）で実施例１～４と同様に光硬化性組成物を調製し光硬化させた後、表２に記載する条件で空気中で加熱して最終的な硬化体を得た。 [Examples 5 to 7]
The same general-purpose photocurable resin and paramylon as in Examples 1 to 4 were used. Using these, photocurable compositions were prepared in the same manner as in Examples 1 to 4 at the proportions (mass ratios) listed in Table 2, and after photocuring, the compositions were heated in air under the conditions listed in Table 2. A final cured product was obtained.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　［比較例１］
エポキシ系の汎用光硬化性樹脂（ＳＣＲ７５１、株式会社ディーメック：臨界露光量２０ｍＪ／ｃｍ２、硬化後のガラス転移温度１０８℃）５ｇを使用し、パラミロンを添加しなかったこと以外は実施例１～４と同様に光硬化させて硬化体を作製した。比較例１は比較のため、パラミロンを入れない光硬化性樹脂のみの硬化後の機械特性を示す。 [Comparative example 1]
Example 1 except that 5 g of an epoxy-based general-purpose photocurable resin (SCR751, D-MEC Co., Ltd., critical exposure amount 20 mJ/cm 2 , glass transition temperature after curing 108°C) was used, and paramylon was not added. A cured product was prepared by photocuring in the same manner as in 4. For comparison, Comparative Example 1 shows the mechanical properties of only a photocurable resin without paramylon after curing.
　実施例１～７及び比較例１で得られた硬化体についてヤング率と引張破断強度を以下の方法で測定した。
（ヤング率及び引張破断強度の測定）
実施例１～７及び比較例１で得られた硬化体から試験片を作製して、引張試験により測定した。実施例１～４及び比較例１のヤング率測定の結果を図２に、引張破断強度測定の結果を図３に示す。また、実施例５～７及び比較例１の引張破断強度測定の結果を図４に示す。図２～４の棒グラフに示す値は５回測定した結果の平均値である。図２～４から分かるように、パラミロンを添加した実施例１～４及び５で得られた硬化体は、パラミロンを添加しない比較例１で得られた硬化体に比べて２．８～４倍のヤング率と２．６～３．３倍の引張破断強度を示した。中でも、実施例２～４で得られた硬化体は、５０ＭＰａ近く又はそれ以上の引張強度を有していた。また、実施例１及び５に示されるように、パラミロンの含有量が光硬化性樹脂に対して１質量％や５質量％という少量でもヤング率や引張破断強度が大きく向上した。さらに、図４から分かるように、光硬化後に加熱した硬化体（実施例６及び７）では、加熱前（実施例５）に比べて約１．４倍の引張破断強度を示し、パラミロンを添加しない場合（比較例１）に比べて約４倍の引張破断強度を示した。実施例６では、光硬化後のガラス転移温度より低い温度で加熱し、実施例７では、光硬化後のガラス転移温度より高い温度で加熱したが、いずれも加熱処理により、強度の向上効果が認められた。 The Young's modulus and tensile strength at break of the cured bodies obtained in Examples 1 to 7 and Comparative Example 1 were measured using the following methods.
(Measurement of Young's modulus and tensile strength at break)
Test pieces were prepared from the cured bodies obtained in Examples 1 to 7 and Comparative Example 1, and measured by a tensile test. The results of Young's modulus measurements of Examples 1 to 4 and Comparative Example 1 are shown in FIG. 2, and the results of tensile strength at break measurements are shown in FIG. Further, the results of tensile breaking strength measurements of Examples 5 to 7 and Comparative Example 1 are shown in FIG. The values shown in the bar graphs in FIGS. 2 to 4 are the average values of the results of five measurements. As can be seen from Figures 2 to 4, the cured products obtained in Examples 1 to 4 and 5, in which paramylon was added, were 2.8 to 4 times larger than the cured products obtained in Comparative Example 1, in which paramylon was not added. Young's modulus and tensile strength at break of 2.6 to 3.3 times. Among them, the cured bodies obtained in Examples 2 to 4 had a tensile strength of nearly 50 MPa or more. Furthermore, as shown in Examples 1 and 5, even when the content of paramylon was as small as 1% by mass or 5% by mass based on the photocurable resin, Young's modulus and tensile strength at break were greatly improved. Furthermore, as can be seen from FIG. 4, the cured products heated after photocuring (Examples 6 and 7) exhibited a tensile strength approximately 1.4 times higher than that before heating (Example 5), and paramylon was added. The tensile strength at break was about 4 times that of the case without it (Comparative Example 1). In Example 6, heating was performed at a temperature lower than the glass transition temperature after photocuring, and in Example 7, heating was performed at a temperature higher than the glass transition temperature after photocuring, but in both cases, the heat treatment had an effect of improving strength. Admitted.
　［実施例８～１０］
実施例１～４と同種の汎用光硬化性樹脂とパラミロンを使用した。これらを使用して表３に記載する割合（質量比）で実施例１～４と同様に光硬化性組成物を調製し光硬化させた後、表３に記載する条件で空気中で加熱して最終的な硬化体を得た。得られた硬化体のビッカース硬さを、マイクロビッカース硬さ試験機（ＨＭ－２２１、（株）ミツトヨ製）で測定した。圧子を押し付ける試験力を０．０２ｋｇｆとし、圧痕の対角線の長さ（ｄ１、ｄ２（μｍ））を測定してビッカース硬さを求めた。測定の結果、実施例８では約１７ＨＶ、実施例９では約２０ＨＶ、実施例１０では約２８ＨＶであった。加熱処理を行ったものは、加熱処理しないものに比べて硬度が高くなっていた。 [Examples 8 to 10]
The same general-purpose photocurable resin and paramylon as in Examples 1 to 4 were used. Using these, photocurable compositions were prepared in the same manner as in Examples 1 to 4 at the proportions (mass ratios) listed in Table 3, and then photocured, and then heated in air under the conditions listed in Table 3. A final cured product was obtained. The Vickers hardness of the obtained cured product was measured using a micro Vickers hardness tester (HM-221, manufactured by Mitutoyo Co., Ltd.). The test force for pressing the indenter was 0.02 kgf, and the lengths (d1, d2 (μm)) of the diagonal line of the indentation were measured to determine the Vickers hardness. The results of the measurements were approximately 17 HV in Example 8, approximately 20 HV in Example 9, and approximately 28 HV in Example 10. The hardness of the heat-treated samples was higher than that of the non-heat-treated samples.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　本発明の光硬化性組成物は光硬化性樹脂を使用しているにもかかわらず、強度及び剛性の高い硬化体を得ることができるので、３Ｄプリンター等による３次元構造体の作製、各種表面コーティング等に好適に使用でき、加えて従来は光硬化性樹脂が使用できなかった高い強度や剛性が求められる分野においても好適に使用できる。本発明の硬化体は、高い強度や剛性を有するので、上記と同様の分野に好適に使用でき、加熱処理したものは、医療機器、食品用途等にも好適に利用できる。具体的には、例えば、医療分野への応用として、マイクロ医療機器、内部に流路を持つ各種バイオ検査デバイス、体内埋め込み部品等、本発明によると強度と生体適合性を併せ持つ光造形法を行うことができるので、適用分野が大幅に拡大する。また、例えば、産業分野への応用として、家具の表面硬化、家具の表面の生体適合性向上、３Ｄプリンターで作製する多品種少量品（例えば、バックアップパーツ等）、その他の応用として、食品用の機材や装置の部品、子供用の玩具、ペット用器材などを挙げることができる。 Although the photocurable composition of the present invention uses a photocurable resin, it is possible to obtain a cured product with high strength and rigidity. It can be suitably used in coatings, etc., and can also be suitably used in fields where high strength and rigidity are required, where photocurable resins could not be used in the past. Since the cured product of the present invention has high strength and rigidity, it can be suitably used in the same fields as mentioned above, and the heat-treated product can also be suitably used for medical equipment, food applications, etc. Specifically, for example, as an application in the medical field, the present invention performs a stereolithography method that has both strength and biocompatibility, such as micro medical devices, various biotest devices with internal flow channels, parts implanted in the body, etc. This greatly expands the field of application. In addition, for example, applications in the industrial field include hardening the surface of furniture, improving the biocompatibility of the surface of furniture, manufacturing high-mix low-volume products using 3D printers (e.g. backup parts, etc.), and other applications such as food-grade products. Examples include equipment and equipment parts, children's toys, and pet equipment.

Claims (7)

  1. β－１，３－グルカンと光硬化性樹脂を含有する光硬化性組成物。 A photocurable composition containing β-1,3-glucan and a photocurable resin.
  2. β－１，３－グルカンがパラミロンであることを特徴とする請求項１記載の光硬化性組成物。 The photocurable composition according to claim 1, wherein the β-1,3-glucan is paramylon.
  3. 光硬化性樹脂の含有量に対するβ－１，３－グルカンの含有量が０．５～３０質量％であることを特徴とする請求項１又は２記載の光硬化性組成物。 3. The photocurable composition according to claim 1, wherein the content of β-1,3-glucan is 0.5 to 30% by mass relative to the content of the photocurable resin.
  4. 請求項１～３のいずれかに記載の光硬化性組成物の硬化体。 A cured product of the photocurable composition according to any one of claims 1 to 3.
  5. 請求項１～３のいずれかに記載の光硬化性組成物に光を照射することを特徴とする硬化体の製造方法。 A method for producing a cured product, comprising irradiating the photocurable composition according to any one of claims 1 to 3 with light.
  6. 光硬化性組成物に光を照射した後に、温度処理することを特徴とする請求項５記載の硬化体の製造方法。 6. The method for producing a cured product according to claim 5, wherein the photocurable composition is subjected to a temperature treatment after being irradiated with light.
  7. 温度処理が加熱処理であることを特徴とする請求項６記載の硬化体の製造方法。
          7. The method for producing a cured product according to claim 6, wherein the temperature treatment is a heat treatment.
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