JPWO2019156163A1 - Photocurable compositions, shaped objects and hydrogels - Google Patents
Photocurable compositions, shaped objects and hydrogels Download PDFInfo
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- JPWO2019156163A1 JPWO2019156163A1 JP2019571143A JP2019571143A JPWO2019156163A1 JP WO2019156163 A1 JPWO2019156163 A1 JP WO2019156163A1 JP 2019571143 A JP2019571143 A JP 2019571143A JP 2019571143 A JP2019571143 A JP 2019571143A JP WO2019156163 A1 JPWO2019156163 A1 JP WO2019156163A1
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- Prior art keywords
- hydrogel
- polymer
- photopolymerization initiator
- polymerizable monomer
- polymer particles
- Prior art date
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- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- JUYQFRXNMVWASF-UHFFFAOYSA-M lithium;phenyl-(2,4,6-trimethylbenzoyl)phosphinate Chemical compound [Li+].CC1=CC(C)=CC(C)=C1C(=O)P([O-])(=O)C1=CC=CC=C1 JUYQFRXNMVWASF-UHFFFAOYSA-M 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- FTWUXYZHDFCGSV-UHFFFAOYSA-N n,n'-diphenyloxamide Chemical group C=1C=CC=CC=1NC(=O)C(=O)NC1=CC=CC=C1 FTWUXYZHDFCGSV-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000000045 pyrolysis gas chromatography Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical group OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
Classifications
-
- 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
-
- 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
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
- C08L101/14—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity the macromolecular compounds being water soluble or water swellable, e.g. aqueous gels
-
- 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
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/52—Amides or imides
- C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F20/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-acryloylmorpholine
-
- 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
- C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
Abstract
本発明の一態様に係る光硬化性組成物は、光重合開始剤と、重合性モノマーと、ポリマー粒子とを含み、前記光重合開始剤がホスフィン酸塩を含む。The photocurable composition according to one aspect of the present invention contains a photopolymerization initiator, a polymerizable monomer, and polymer particles, and the photopolymerization initiator contains a phosphinate.
Description
本発明は、光硬化性組成物、造形物及びハイドロゲルに関する。
本願は、２０１８年２月７日に、日本出願された特願２０１８−０２０３３７号に基づき優先権を主張し、その内容をここに援用する。The present invention relates to photocurable compositions, shaped objects and hydrogels.
The present application claims priority based on Japanese Patent Application No. 2018-020337 filed in Japan on February 7, 2018, the contents of which are incorporated herein by reference.
親水性のポリマーを含むハイドロゲルは、吸水性や保水性、柔軟性等の性質に優れるという特性を有することから注目を集めている有用な素材であり、医療、食品、土木等の様々な技術分野における利用が期待されている。
近年、機械物性に優れたハイドロゲルとして、架橋網目構造を有するポリマー同士、又は架橋網目構造を有するポリマーと直鎖ポリマーとが互いに絡み合った構造を有するハイドロゲルが提案されており、ハイドロゲルの応用分野のさらなる向上が期待される。Hydrogels containing hydrophilic polymers are useful materials that are attracting attention because they have excellent properties such as water absorption, water retention, and flexibility, and are used in various technologies such as medical care, food, and civil engineering. It is expected to be used in the field.
In recent years, as a hydrogel having excellent mechanical properties, a hydrogel having a structure in which polymers having a crosslinked network structure or a polymer having a crosslinked network structure and a linear polymer are entangled with each other has been proposed, and applications of the hydrogel have been proposed. Further improvement in the field is expected.
特許文献１には、所定の架橋ポリマー粒子、ビニル系単量体及び溶媒を含み、粘度が１０〜２０，０００ｍＰａ・ｓであるプレゲル溶液を重合して得られる高強度のハイドロゲルが記載されている。また、プレゲル溶液に光重合開始剤や熱重合開始剤を添加し、型枠等に流し込んだ後、ラジカル重合することにより前記ゲルを製造することが記載されている。 Patent Document 1 describes a high-strength hydrogel obtained by polymerizing a pregel solution containing predetermined crosslinked polymer particles, a vinyl monomer and a solvent and having a viscosity of 10 to 20,000 mPa · s. There is. Further, it is described that the gel is produced by adding a photopolymerization initiator or a thermal polymerization initiator to a pregel solution, pouring it into a mold or the like, and then radically polymerizing it.
本発明者らの検討によれば、特許文献１に記載の光重合開始剤（アシルホスフィンオキサイド系開始剤等）を添加した場合、プレゲル溶液が高粘度（例えば数千ｍＰａ・ｓ以上）になる。プレゲル溶液が高粘度であると、プレゲル溶液の注型時に気泡が入り、ハイドロゲルの透明性や表面平滑性が損なわれる。 According to the studies by the present inventors, when the photopolymerization initiator (acylphosphine oxide-based initiator, etc.) described in Patent Document 1 is added, the pregel solution becomes highly viscous (for example, several thousand mPa · s or more). .. If the pregel solution has a high viscosity, air bubbles will enter during casting of the pregel solution, and the transparency and surface smoothness of the hydrogel will be impaired.
本発明は、低粘度の光硬化性組成物、並びにこれを用いた造形物及びハイドロゲルを提供することを目的とする。 An object of the present invention is to provide a low-viscosity photocurable composition, and a modeled product and a hydrogel using the same.
本発明者らは、鋭意検討の結果、重合性モノマー、光重合開始剤、及びポリマー粒子を含む光硬化性組成物における光重合開始剤としてホスフィン酸塩を用いると、アシルホスフィンオキサイド系開始剤等を用いる場合に比べて、光硬化性組成物を低粘度にできることを見出し、本発明を完成させた。 As a result of diligent studies, the present inventors have found that when phosphinate is used as a photopolymerization initiator in a photocurable composition containing a polymerizable monomer, a photopolymerization initiator, and polymer particles, an acylphosphine oxide-based initiator and the like are used. We have found that the photocurable composition can have a lower viscosity than the case of using the above, and completed the present invention.
本発明は、以下の態様を有する。
〔１〕光重合開始剤と、重合性モノマーと、ポリマー粒子とを含み、
前記光重合開始剤がホスフィン酸塩を含む、光硬化性組成物。
〔２〕前記ホスフィン酸塩が、可視光域に吸収を有する〔１〕の光硬化性組成物。
〔３〕前記光重合開始剤の含有量が、前記重合性モノマーの総モル量に対して０．０１〜０．５モル％である〔１〕又は〔２〕の光硬化性組成物。
〔４〕前記ポリマー粒子の質量／前記光硬化性組成物から前記ポリマー粒子を除いた残部の質量で表される比が、１／１００〜１／２０の範囲内である〔１〕〜〔３〕のいずれかの光硬化性組成物。
〔５〕２５℃における粘度が５〜１０００ｍＰａ・ｓである〔１〕〜〔５〕のいずれかの光硬化性組成物。
〔６〕〔１〕〜〔５〕のいずれかの光硬化性組成物の硬化物を含む、造形物。
〔７〕〔１〕〜〔５〕のいずれかの光硬化性組成物の硬化物を含む、ハイドロゲル。
〔８〕光重合開始剤由来のホスフィン酸塩成分を含み、
極性溶媒の含有率が５０質量％以上である、ハイドロゲル。The present invention has the following aspects.
[1] Containing a photopolymerization initiator, a polymerizable monomer, and polymer particles,
A photocurable composition in which the photopolymerization initiator contains a phosphinate.
[2] The photocurable composition of [1], wherein the phosphinate has absorption in the visible light region.
[3] The photocurable composition according to [1] or [2], wherein the content of the photopolymerization initiator is 0.01 to 0.5 mol% with respect to the total molar amount of the polymerizable monomer.
[4] The ratio expressed by the mass of the polymer particles / the mass of the balance after removing the polymer particles from the photocurable composition is in the range of 1/100 to 1/20 [1] to [3]. ] Any of the photocurable compositions.
[5] The photocurable composition according to any one of [1] to [5], which has a viscosity at 25 ° C. of 5 to 1000 mPa · s.
[6] A modeled product containing a cured product of the photocurable composition according to any one of [1] to [5].
[7] A hydrogel containing a cured product of the photocurable composition according to any one of [1] to [5].
[8] Containing a phosphinate component derived from a photopolymerization initiator,
A hydrogel having a polar solvent content of 50% by mass or more.
本発明によれば、低粘度の光硬化性組成物、並びにこれを用いた造形物及びハイドロゲルを提供できる。 According to the present invention, it is possible to provide a low-viscosity photocurable composition, and a modeled product and a hydrogel using the same.
本明細書において、数値範囲を示す「〜」は、その前後に記載された数値を下限値及び上限値として含むことを意味する。
本明細書において、「ゲル」とは、ポリマー鎖同士が物理的もしくは化学的に結合することで網目構造を形成し、形成した網目構造に溶媒を取り込んで膨潤する構造体を意味する。
本明細書において、ハイドロゲルとは、ポリマーで構成された網目構造中に極性溶媒を取り込んでいる構造体を意味する。In the present specification, "~" indicating a numerical range means that the numerical values described before and after the numerical range are included as the lower limit value and the upper limit value.
As used herein, the term "gel" means a structure in which polymer chains are physically or chemically bonded to each other to form a network structure, and a solvent is taken into the formed network structure to swell.
As used herein, the term hydrogel means a structure in which a polar solvent is incorporated into a network structure composed of a polymer.
〔光硬化性組成物〕
本発明の光硬化性組成物（以下、「本組成物」とも記す。）は、光重合開始剤と、重合性モノマーと、ポリマー粒子とを含む。
本組成物は、必要に応じて、架橋剤、極性溶媒、その他の成分をさらに含んでいてもよい。[Photocurable composition]
The photocurable composition of the present invention (hereinafter, also referred to as “the present composition”) contains a photopolymerization initiator, a polymerizable monomer, and polymer particles.
The composition may further contain a cross-linking agent, a polar solvent and other components, if desired.
（光重合開始剤）
光重合開始剤としては、光ラジカル重合開始剤、光カチオン重合開始剤、光アニオン重合開始剤、レドックス系光重合開始剤等が挙げられる。取り扱いやすさの点で、光ラジカル重合開始剤が好ましい。光ラジカル重合開始剤は、光が照射されたときに、重合反応の起点となるラジカルを発生して重合を開始させる。光としては、可視光、紫外線、電子線等が挙げられる。(Photopolymerization initiator)
Examples of the photopolymerization initiator include a photoradical polymerization initiator, a photocationic polymerization initiator, a photoanionic polymerization initiator, and a redox-based photopolymerization initiator. A photoradical polymerization initiator is preferable in terms of ease of handling. When the photo-radical polymerization initiator is irradiated with light, it generates a radical that is the starting point of the polymerization reaction to initiate polymerization. Examples of light include visible light, ultraviolet rays, and electron beams.
光重合開始剤は、ホスフィン酸塩を含む。光重合開始剤としてホスフィン酸塩を用いることにより、アシルホスフィンオキサイド系開始剤等を用いる場合に比べて、本組成物を低粘度にできる。
ホスフィン酸塩は、典型的には、光ラジカル重合開始剤である。
ホスフィン酸塩は、可視光域に吸収を有することが好ましい。可視光域に吸収を有すると、本組成物を硬化させる光として可視光を使用でき、安全性の点で有利である。
なお、ホスフィン酸塩が可視光域に吸収を有するか否かは、吸光係数によって判定できる。ホスフィン酸塩の吸光係数は、所定濃度のホスフィン酸塩のメタノール溶液を１ｃｍの石英セルに流し込み、分光光度計（例えば島津製紫外可視分光光度計ＵＶ−１８００）を用いて紫外・可視吸収スペクトルを測定し、得られた吸光度を用いてＬａｍｂｅｒｔ−ｂｅｅｒの法則（以下の式）から計算することによって決定される。
Ａ＝ε×ｃ×ｄ
ただし、式中Ａは吸光度、εはモル吸光係数（Ｌ／（モル・ｃｍ））、ｃはモル濃度（モル／Ｌ）、ｄはセルの厚さ（ｃｍ）を表す。
ホスフィン酸塩を光ラジカル重合開始剤として用いるには、可視光領域におけるモル吸光係数が１００以上であれば、ラジカルを発生させるのに十分な光を吸収することができるため、好ましい。なお、可視光領域におけるモル吸光係数が１００以上であるとは、可視光領域のいずれかの波長におけるモル吸光係数の値が１００以上であればよく、可視光領域にモル吸光係数のピークが存在する必要はない。The photopolymerization initiator contains a phosphinate. By using the phosphinate as the photopolymerization initiator, the viscosity of the present composition can be reduced as compared with the case where an acylphosphine oxide-based initiator or the like is used.
The phosphinate is typically a photoradical polymerization initiator.
The phosphinate preferably has absorption in the visible light region. Having absorption in the visible light region allows visible light to be used as the light that cures the composition, which is advantageous in terms of safety.
Whether or not the phosphinate has absorption in the visible light region can be determined by the absorption coefficient. For the absorbance coefficient of phosphinate, a methanol solution of phosphinate having a predetermined concentration is poured into a 1 cm quartz cell, and an ultraviolet / visible absorption spectrum is obtained using a spectrophotometer (for example, Shimadzu ultraviolet-visible spectrophotometer UV-1800). It is determined by measuring and calculating from the Lambert-Beer's law (the following formula) using the obtained absorbance.
A = ε × c × d
However, in the formula, A represents the absorbance, ε represents the molar extinction coefficient (L / (molar cm)), c represents the molar concentration (molar / L), and d represents the cell thickness (cm).
In order to use phosphinate as a photoradical polymerization initiator, it is preferable that the molar absorption coefficient in the visible light region is 100 or more because sufficient light can be absorbed to generate radicals. The molar extinction coefficient in the visible light region is 100 or more as long as the molar extinction coefficient value at any wavelength in the visible light region is 100 or more, and a peak of the molar extinction coefficient exists in the visible light region. do not have to.
ホスフィン酸塩としては、例えば、フェニル（２，４，６−トリメチルベンゾイル）ホスフィン酸塩、ビス（２，４，６−トリメチルベンゾイル）ホスフィン酸塩が挙げられる。塩としては、例えばリチウム塩、ナトリウム塩が挙げられる。これらのホスフィン酸塩は、光ラジカル重合開始剤として機能する。また、可視光域に吸収を有する。 Examples of the phosphinate include phenyl (2,4,6-trimethylbenzoyl) phosphinate and bis (2,4,6-trimethylbenzoyl) phosphinate. Examples of the salt include a lithium salt and a sodium salt. These phosphinates function as photoradical polymerization initiators. It also has absorption in the visible light region.
光重合開始剤は、ホスフィン酸塩以外の他の光重合開始剤をさらに含んでいてもよい。
他の光重合開始剤としては、公知の光重合開始剤を使用できる。例えば可視光域に吸収を有する光ラジカル重合開始剤として、２−ベンジル−２−ジメチルアミノ−１−（４−モルホリノフェニル）ブタン−１−オン、２−（４−メチルベンジル）−２−ジメチルアミノ−１−（４−モルホリノフェニル）ブタン−１−オン、ビス（η５−２，４−シクロペンタジエン−１−イル）−ビス（２，６−ジフルオロ−３−（１Ｈ−ピロール−１−イル）フェニル）チタニウム、ビス（２，４，６−トリメチルベンゾイル）フェニルホスフィンオキシド、２，４，６−トリメチルベンゾイルジフェニルホスフィンオキシド、（２，４，６−トリメチルベンゾイル）エトキシフェニルホスフィンオキシド、ビス（２，６−ジメトキシベンゾイル）２，４，４−トリメチルペンチルホスフィンオキシド、チオキサントン、２−クロロチオキサントン、３−メチルチオキサントン、２，４−ジメチルチオキサントン、アントラキノン、２−メチルアントラキノン、２−エチルアントラキノン、２−ｔｅｒｔ−ブチルアントラキノン、２−アミノアントラキノン、１，２−オクタンジオン，１−（４−（フェニルチオ），２−（ｏ−ベンゾイルオキシム））、１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］−エタノン１−（Ｏ−アセチルオキシム）、カンファーキノン、トリアジン系光重合開始剤等が挙げられる。これらの光ラジカル重合開始剤はいずれか１種を単独で用いてもよく２種以上を組み合わせて用いてもよい。The photopolymerization initiator may further contain a photopolymerization initiator other than the phosphinate.
As another photopolymerization initiator, a known photopolymerization initiator can be used. For example, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one and 2- (4-methylbenzyl) -2-dimethyl are examples of photoradical polymerization initiators that have absorption in the visible light region. Amino-1- (4-morpholinophenyl) butane-1-one, bis (η5-2,4-cyclopentadiene-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl) ) Phenyl) Titanium, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, (2,4,6-trimethylbenzoyl) ethoxyphenylphosphine oxide, bis (2) , 6-Dimethoxybenzoyl) 2,4,4-trimethylpentylphosphine oxide, thioxanthone, 2-chlorothioxanthone, 3-methylthioxanthone, 2,4-dimethylthioxanthone, anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2- tert-butyl anthraquinone, 2-aminoanthraquinone, 1,2-octanedione, 1- (4- (phenylthio), 2- (o-benzoyloxime)), 1- [9-ethyl-6- (2-methylbenzoyl)) ) -9H-Carbazole-3-yl] -Etanone 1- (O-acetyloxime), phenylquinone, a triazine-based photopolymerization initiator and the like. Any one of these photoradical polymerization initiators may be used alone, or two or more thereof may be used in combination.
光重合開始剤中のホスフィン酸塩の割合は、光重合開始剤の総モル量に対し、０．０１〜１００モル％が好ましく、１〜１００モル％がより好ましく、５０〜１００モル％がさらに好ましい。ホスフィン酸塩の割合が前記範囲の下限値以上であると、本組成物をより低粘度にできる。 The ratio of the phosphinate in the photopolymerization initiator is preferably 0.01 to 100 mol%, more preferably 1 to 100 mol%, and further 50 to 100 mol% with respect to the total molar amount of the photopolymerization initiator. preferable. When the proportion of phosphinate is not more than the lower limit of the above range, the composition can have a lower viscosity.
（重合性モノマー）
重合性モノマーは、本組成物に光が照射されたときに、前記光重合開始剤の作用によって重合し、ポリマーを形成する。
重合性モノマーとしては、前記光重合開始剤を用いて重合可能な化合物であればよく、例えばラジカル重合性の不飽和基を有する化合物が挙げられる。重合性モノマーの具体例としては、以下の化合物が挙げられる。
２−アクリルアミド−２−メチルプロパンスルホン酸（ＡＭＰＳ）及びその塩、スチレンスルホン酸（ＳＳ）及びその塩、アクリル酸（ＡＡ）及びその塩、メタクリル酸及びその塩、ビニルピリジン、酢酸ビニル、スチレン（Ｓｔ）、アクリルアミド（ＡＡｍ）、モノ（又はジ）アルキルアクリルアミド（例えば、Ｎ−イソプロピルアクリルアミド、Ｎ，Ｎ−ジメチルアクリルアミド（ＤＭＡＡｍ））、ヒドロキシエチルアクリレート、２−（ジメチルアミノ）エチルメタクリレート、メチルメタクリレート（ＭＭＡ）、ラウリルアクリレート（ＬＡ）、ステアリルアクリレート（ＳＡ）、トリフルオロエチルアクリレート（ＴＦＥ）、２，２，２−トリフルオロエチルメチルアクリレート、２，２，３，３，３−ペンタフルオロプロピルメタクリレート、３−（ペルフルオロブチル）−２−ヒドロキシプロピルメタクリレート、１Ｈ，１Ｈ，９Ｈ−ヘキサデカフルオロノニメタクリレート、２，２，２−トリフルオロエチルアクリレート、２，３，４，５，６−ペンタフルオロスチレン、及びフッ化ビニリデン等。これらの重合性モノマーにおける塩としては、ナトリウム等のアルカリ金属塩、カルシウム等のアルカリ土類金属塩、亜鉛等の金属塩等が挙げられる。
重合性モノマーは１種を単独で用いてもよく２種以上を組み合わせて用いてもよい。すなわち、重合性モノマーから形成されるポリマーはホモポリマーであってもよくコポリマーであってもよい。(Polymerizable monomer)
When the composition is irradiated with light, the polymerizable monomer is polymerized by the action of the photopolymerization initiator to form a polymer.
The polymerizable monomer may be any compound that can be polymerized using the photopolymerization initiator, and examples thereof include compounds having a radically polymerizable unsaturated group. Specific examples of the polymerizable monomer include the following compounds.
2-acrylamide-2-methylpropanesulfonic acid (AMPS) and its salts, styrenesulfonic acid (SS) and its salts, acrylic acid (AA) and its salts, methacrylic acid and its salts, vinylpyridine, vinyl acetate, styrene ( St), acrylamide (AAm), mono (or di) alkylacrylamide (eg, N-isopropylacrylamide, N, N-dimethylacrylamide (DMAAm)), hydroxyethyl acrylate, 2- (dimethylamino) ethyl methacrylate, methyl methacrylate (eg, N-isopropylacrylamide, N, N-dimethylacrylamide (DMAAm)) MMA), lauryl acrylate (LA), stearyl acrylate (SA), trifluoroethyl acrylate (TFE), 2,2,2-trifluoroethylmethyl acrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 3- (Perfluorobutyl) -2-hydroxypropyl methacrylate, 1H, 1H, 9H-hexadecafluorononi methacrylate, 2,2,2-trifluoroethyl acrylate, 2,3,4,5,6-pentafluorostyrene, And vinylidene fluoride, etc. Examples of the salt in these polymerizable monomers include alkali metal salts such as sodium, alkaline earth metal salts such as calcium, and metal salts such as zinc.
One type of polymerizable monomer may be used alone, or two or more types may be used in combination. That is, the polymer formed from the polymerizable monomer may be a homopolymer or a copolymer.
本組成物の重合性モノマーから形成されるポリマーは、網目構造を有するポリマーであってもよく、網目構造を有しないポリマー（例えば直鎖状ポリマー）であってもよい。形成されるゲルの機械的強度がより優れる点では、網目構造を有することが好ましい。
重合性モノマーから形成されるポリマーを、網目構造を有するポリマーとする方法としては、本組成物に架橋剤を含有させる方法が挙げられる。この場合、重合性モノマーが光重合開始剤及び架橋剤の存在下に重合し、網目構造を有するポリマーが生成する。
重合性モノマーから形成されるポリマーを直鎖状ポリマーとする場合は、本組成物に架橋剤を含有させず、重合性モノマーを光重合開始剤の存在下、かつ架橋剤の不在下に重合する。The polymer formed from the polymerizable monomer of the present composition may be a polymer having a network structure or a polymer having no network structure (for example, a linear polymer). It is preferable to have a network structure in that the mechanical strength of the gel to be formed is more excellent.
Examples of a method for forming a polymer formed from a polymerizable monomer into a polymer having a network structure include a method in which the present composition contains a cross-linking agent. In this case, the polymerizable monomer is polymerized in the presence of the photopolymerization initiator and the cross-linking agent to produce a polymer having a network structure.
When the polymer formed from the polymerizable monomer is a linear polymer, the present composition is not contained with a cross-linking agent, and the polymerizable monomer is polymerized in the presence of a photopolymerization initiator and in the absence of a cross-linking agent. ..
（ポリマー粒子）
本組成物がポリマー粒子を含むことによって、本組成物から形成されるハイドロゲルは、本組成物中の重合性モノマーから形成されたポリマー（以下、「第２のポリマー」ともいう。）からなる連続相中にポリマー粒子が分散して存在している構成を有する。かかるハイドロゲルは、ポリマー粒子を含まない場合に比べて、機械物性に優れる。
また、ポリマー粒子は、増粘成分として機能する。増粘成分は、重合性モノマーや極性溶媒との相互作用によって、本組成物全体の粘度を高め、流動性を低下させる。増粘成分は、例えば、ハイドロゲルの機械物性の向上や、機能性の付与、ハイドロゲルの溶媒成分の乾燥抑制等の目的で用いられる。(Polymer particles)
When the present composition contains polymer particles, the hydrogel formed from the present composition comprises a polymer formed from the polymerizable monomer in the present composition (hereinafter, also referred to as “second polymer”). It has a structure in which polymer particles are dispersed and present in a continuous phase. Such a hydrogel is superior in mechanical properties as compared with the case where it does not contain polymer particles.
In addition, the polymer particles function as a thickening component. The thickening component increases the viscosity of the entire composition and lowers the fluidity by interacting with the polymerizable monomer and the polar solvent. The thickening component is used, for example, for the purpose of improving the mechanical properties of the hydrogel, imparting functionality, suppressing the drying of the solvent component of the hydrogel, and the like.
ポリマー粒子は、典型的には、前記重合性モノマーを含む溶液（例えば後述する第２の溶液）に膨潤可能である。これにより、組成物中の重合性モノマーを重合して第２のポリマーを形成したときに、ポリマー粒子を構成するポリマー（以下、「第１のポリマー」ともいう。）と第２のポリマーとが互いに絡み合った構造が形成される。
ポリマー粒子が前記液体に膨潤可能であることは、粒子が均一に分散し、系の粘度が上昇することにより確認できる。The polymer particles are typically swellable in a solution containing the polymerizable monomer (eg, a second solution described below). As a result, when the polymerizable monomer in the composition is polymerized to form the second polymer, the polymer constituting the polymer particles (hereinafter, also referred to as “first polymer”) and the second polymer are formed. Structures intertwined with each other are formed.
The fact that the polymer particles can be swollen in the liquid can be confirmed by the fact that the particles are uniformly dispersed and the viscosity of the system increases.
第１のポリマーとしては、例えば、重合性モノマーを重合したポリマー、多糖類（ジェラン、ヒアルロン酸、カラギーナン、キチン、アルギン酸等）、タンパク質（ゼラチン、コラーゲン等）が挙げられる。
重合性モノマーとしては、上述した重合性モノマーと同様のものが挙げられる。重合性モノマーは１種を単独で用いてもよく２種以上を組み合わせて用いてもよい。
ポリマー粒子を構成する第１のポリマーは、１種でもよく２種以上でもよい。Examples of the first polymer include polymers obtained by polymerizing polymerizable monomers, polysaccharides (gellan, hyaluronic acid, carrageenan, chitin, alginic acid, etc.), and proteins (gelatin, collagen, etc.).
Examples of the polymerizable monomer include the same as the above-mentioned polymerizable monomer. One type of polymerizable monomer may be used alone, or two or more types may be used in combination.
The first polymer constituting the polymer particles may be one kind or two or more kinds.
第１のポリマーは、網目構造を有するポリマーであってもよく、網目構造を有しないポリマー（例えば直鎖状ポリマー）であってもよい。形成されるゲルの機械的強度がより優れる点では、網目構造を有するポリマーであることが好ましい。
第１のポリマーが網目構造を有すると、形成されるハイドロゲルは、第１のポリマーの網目構造に第２のポリマーが侵入した構造を有するため、第１のポリマーが網目構造を有しない場合に比べて、機械的強度が優れる。
特に、第１のポリマー及び第２のポリマーが共に網目構造を有すると、形成されるハイドロゲルは、第１のポリマーと第２のポリマーとが相互に侵入する網目構造を有するため、機械的強度がより優れる。The first polymer may be a polymer having a network structure or a polymer having no network structure (for example, a linear polymer). A polymer having a network structure is preferable in that the mechanical strength of the formed gel is more excellent.
When the first polymer has a network structure, the hydrogel formed has a structure in which the second polymer has penetrated into the network structure of the first polymer, so that the first polymer does not have a network structure. In comparison, it has excellent mechanical strength.
In particular, when both the first polymer and the second polymer have a network structure, the formed hydrogel has a network structure in which the first polymer and the second polymer penetrate each other, and thus has mechanical strength. Is better.
ポリマー粒子の平均粒子径は、乾燥状態で、０．１〜１００００μｍが好ましく、０．１〜１０００μｍがより好ましく、０．１〜１００μｍが特に好ましい。平均粒子径が前記範囲の下限値以上であると、取扱い性がより優れる。平均粒子径が前記範囲の上限値以下であると、機械的強度がより優れる。
平均粒子径は、走査型電子顕微鏡により絶乾状態でのポリマー粒子１００個を観察し、各ポリマー粒子の最大径を求め、それらの平均値を算出することにより求める。The average particle size of the polymer particles in a dry state is preferably 0.1 to 10000 μm, more preferably 0.1 to 1000 μm, and particularly preferably 0.1 to 100 μm. When the average particle size is at least the lower limit of the above range, the handleability is more excellent. When the average particle size is not more than the upper limit of the above range, the mechanical strength is more excellent.
The average particle size is determined by observing 100 polymer particles in an absolutely dry state with a scanning electron microscope, determining the maximum diameter of each polymer particle, and calculating the average value thereof.
（極性溶媒）
極性溶媒は、比誘電率が１０以上の、常温で液状の化合物である。極性溶媒は、ポリマーによって構成された網目構造中に取り込まれてハイドロゲルを構成する。
比誘電率は、液体用誘電率測定キット（ＩＴＡＣＡ製）を用いて、２ＧＨｚの周波数、２５℃の条件で測定される値である。
極性溶媒としては、水、極性有機溶剤、水と極性有機溶剤との混合物等が挙げられる。極性有機溶剤の例としては、エチレングリコール、エタノール等のアルコール、アセトン等のケトン、イオン液体等が挙げられる。極性溶媒としては、扱いやすさや安全性の観点から水、アルコールが好ましく、入手の容易さや環境調和性の点で、水が特に好ましい。(Polar solvent)
The polar solvent is a compound having a relative permittivity of 10 or more and being liquid at room temperature. The polar solvent is incorporated into the network structure composed of the polymer to form a hydrogel.
The relative permittivity is a value measured under the conditions of a frequency of 2 GHz and 25 ° C. using a permittivity measurement kit for liquids (manufactured by ITACA).
Examples of the polar solvent include water, a polar organic solvent, a mixture of water and a polar organic solvent, and the like. Examples of the polar organic solvent include ethylene glycol, alcohols such as ethanol, ketones such as acetone, and ionic liquids. As the polar solvent, water and alcohol are preferable from the viewpoint of ease of handling and safety, and water is particularly preferable from the viewpoint of easy availability and environmental friendliness.
（架橋剤）
架橋剤としては、特に限定されず、重合性モノマーの種類に応じて公知のものを適宜用いることができる。
架橋剤としては、例えば、ラジカル重合性の不飽和基を２個以上有する多官能ビニル化合物が挙げられる。多官能ビニル化合物としては、形成されるゲルの機械的強度の点で、Ｎ，Ｎ’−メチレンビスアクリルアミド（ＭＢＡＡ）、エチレングリコールジメタクリレート（ＥＤＭＡ）、Ｎ，Ｎ’−ジエチレングリコールジメタクリレート（ＤＥＧＤＭＡ）等のジビニル化合物が好ましい。(Crosslinking agent)
The cross-linking agent is not particularly limited, and known ones can be appropriately used depending on the type of the polymerizable monomer.
Examples of the cross-linking agent include a polyfunctional vinyl compound having two or more radically polymerizable unsaturated groups. The polyfunctional vinyl compounds include N, N'-methylenebisacrylamide (MBAA), ethylene glycol dimethacrylate (EDM), and N, N'-diethylene glycol dimethacrylate (DEDMA) in terms of the mechanical strength of the gel formed. Divinyl compounds such as, etc. are preferable.
（他の成分）
他の成分としては、例えば、ポリマー粒子以外の増粘成分、光吸収剤、界面活性剤、シランカップリング剤、酸化防止剤、光安定化剤、金属不活性化剤、防錆剤、老化防止剤、吸湿剤、加水分解防止剤、重合禁止剤、レベリング剤等が挙げられる。これらの添加剤はいずれか１種を単独で用いてもよく２種以上を組み合わせて用いてもよい。
ポリマー粒子以外の増粘成分としては、例えば、無機粘土鉱物（モンモリロナイト、ヘクトライト等）、増粘剤（多糖類、カルボキシメチルセルロース等）等が挙げられる。(Other ingredients)
Other components include, for example, thickening components other than polymer particles, light absorbers, surfactants, silane coupling agents, antioxidants, light stabilizers, metal inactivating agents, rust inhibitors, and antiaging agents. Examples thereof include agents, hygroscopic agents, hydrolysis inhibitors, polymerization inhibitors, leveling agents and the like. Any one of these additives may be used alone, or two or more thereof may be used in combination.
Examples of the thickening component other than the polymer particles include inorganic clay minerals (montmorillonite, hectorite, etc.), thickeners (polysaccharides, carboxymethyl cellulose, etc.) and the like.
光吸収剤とは、光を吸収して熱エネルギーあるいは他の波長の光に変換する物質を示す。本組成物が光吸収剤を含むと、本組成物の３次元（３Ｄ）造形性がより優れ、本組成物から形成される３Ｄ構造の造形物の造形精度がより優れる。
光吸収剤としては、本組成物の硬化に用いる光を吸収可能なものであればよい。
光吸収剤としては、ベンゾトリアゾール構造、ベンゾフェノン構造、トリアジン構造、ベンゾエート構造、オキサルアニリド構造、サリシレート構造及びシアノアクリレート構造からなる群より選択される少なくとも１つの構造を有するものが好ましい。中でも、３Ｄ造形性の観点から、ベンゾトリアゾール構造、トリアジン構造及びベンゾフェノン構造からなる群より選択される少なくとも１つの構造を有するものが好ましい。これらの光吸収剤はいずれか１種を単独で用いてもよく２種以上を組み合わせて用いてもよい。A light absorber refers to a substance that absorbs light and converts it into heat energy or light of another wavelength. When the present composition contains a light absorber, the three-dimensional (3D) formability of the present composition is more excellent, and the modeling accuracy of the modeled object having a 3D structure formed from the present composition is more excellent.
The light absorber may be any as long as it can absorb the light used for curing the present composition.
As the light absorber, one having at least one structure selected from the group consisting of a benzotriazole structure, a benzophenone structure, a triazine structure, a benzoate structure, an oxalanilide structure, a salicylate structure and a cyanoacrylate structure is preferable. Among them, those having at least one structure selected from the group consisting of a benzotriazole structure, a triazine structure and a benzophenone structure are preferable from the viewpoint of 3D formability. Any one of these light absorbers may be used alone, or two or more thereof may be used in combination.
本組成物は、以下の条件Ａ及び条件Ｂのいずれか一方を満たすことが好ましい。これにより、本組成物中の重合性モノマーから形成される第２のポリマーの分子鎖が、ポリマー粒子内に侵入し易くなる。本組成物は、条件Ａを満たすことがより好ましい。
条件Ａ：ポリマー粒子を構成する第１のポリマーが、正又は負に荷電し得る基を有する不飽和モノマーに基づく構成単位を含み、組成物中の重合性モノマーが、電気的に中性である不飽和モノマーを含む。
条件Ｂ：ポリマー粒子を構成する第１のポリマーが、電気的に中性である不飽和モノマーに基づく構成単位を含み、組成物中の重合性モノマーが、正又は負に荷電し得る基を有する不飽和モノマーを含む。The composition preferably satisfies either of the following conditions A and B. As a result, the molecular chain of the second polymer formed from the polymerizable monomer in the present composition easily penetrates into the polymer particles. It is more preferable that the present composition satisfies the condition A.
Condition A: The first polymer constituting the polymer particles contains a structural unit based on an unsaturated monomer having a group that can be charged positively or negatively, and the polymerizable monomer in the composition is electrically neutral. Contains unsaturated monomers.
Condition B: The first polymer constituting the polymer particles contains a structural unit based on an unsaturated monomer that is electrically neutral, and the polymerizable monomer in the composition has a group capable of being positively or negatively charged. Contains unsaturated monomers.
正又は負に荷電し得る基を有する不飽和モノマーとしては、酸性基（例えば、カルボキシ基、リン酸基又はスルホン酸基）又は塩基性基（例えば、アミノ基）を有する不飽和モノマーが好ましい。具体例としては、２−アクリルアミド−２−メチルプロパンスルホン酸（ＡＭＰＳ）、アクリル酸（ＡＡ）、メタクリル酸、及びそれらの塩が挙げられる。
電気的に中性である不飽和モノマーとしては、例えば、スチレン（Ｓｔ）、アクリルアミド（ＡＡｍ）、Ｎ−イソプロピルアクリルアミド、Ｎ，Ｎ−ジメチル−アクリルアミド、ビニルピリジン、スチレン、メチルメククリレート（ＭＭＡ）、フッ素含有不飽和モノマー（例えば、トリフルオロエチルアクリレート（ＴＦＥ））、ヒドロキシエチルアクリレート、及び酢酸ビニルが挙げられる。As the unsaturated monomer having a group capable of being positively or negatively charged, an unsaturated monomer having an acidic group (for example, a carboxy group, a phosphoric acid group or a sulfonic acid group) or a basic group (for example, an amino group) is preferable. Specific examples include 2-acrylamide-2-methylpropanesulfonic acid (AMPS), acrylic acid (AA), methacrylic acid, and salts thereof.
Examples of the unsaturated monomer that is electrically neutral include styrene (St), acrylamide (AAm), N-isopropylacrylamide, N, N-dimethyl-acrylamide, vinylpyridine, styrene, and methyl meccrylate (MMA). , Fluorine-containing unsaturated monomers (eg, trifluoroethyl acrylate (TFE)), hydroxyethyl acrylate, and vinyl acetate.
本組成物中の重合性モノマーの含有量は、仕込みモル濃度として、０．０１〜１００モル／Ｌが好ましく、０．１〜５０モル／Ｌがより好ましく、０．１〜２５モル／Ｌが特に好ましい。この仕込みモル濃度は、本組成物を調製したときの、本組成物１Ｌ当たりの重合性モノマーのモル量である。重合性モノマーの含有量が前記範囲の下限値以上であると、ハイドロゲルの機械的強度がより優れる。重合性モノマーの含有量が前記範囲の上限値以下であると、ハイドロゲルの柔軟性、透明性がより優れる。
極性溶媒の含有量は、本組成物中の重合性モノマーの含有量に応じて設定できる。The content of the polymerizable monomer in the present composition is preferably 0.01 to 100 mol / L, more preferably 0.1 to 50 mol / L, and 0.1 to 25 mol / L as the charged molar concentration. Especially preferable. This charged molar concentration is the molar amount of the polymerizable monomer per 1 L of the present composition when the present composition is prepared. When the content of the polymerizable monomer is at least the lower limit of the above range, the mechanical strength of the hydrogel is more excellent. When the content of the polymerizable monomer is not more than the upper limit of the above range, the flexibility and transparency of the hydrogel are more excellent.
The content of the polar solvent can be set according to the content of the polymerizable monomer in the present composition.
光重合開始剤の含有量は、重合性モノマーの総モル量（１００モル％）に対して０．００１〜５モル％が好ましく、０．００１〜１モル％がより好ましく、０．０１〜０．５モル％が特に好ましい。光重合開始剤の含有量の含有量が前記範囲の下限値以上であると、本組成物の硬化性、ハイドロゲルの機械的強度がより優れる。光重合開始剤の含有量が前記範囲の上限値以下であると、ハイドロゲルの柔軟性がより優れる。 The content of the photopolymerization initiator is preferably 0.001 to 5 mol%, more preferably 0.001 to 1 mol%, and 0.01 to 0, based on the total molar amount (100 mol%) of the polymerizable monomer. 5.5 mol% is particularly preferred. When the content of the photopolymerization initiator is at least the lower limit of the above range, the curability of the present composition and the mechanical strength of the hydrogel are more excellent. When the content of the photopolymerization initiator is not more than the upper limit of the above range, the flexibility of the hydrogel is more excellent.
ポリマー粒子の含有量は、ポリマー粒子による効果が充分に得られるように、ポリマー粒子の種類に応じて適宜選定できる。
ポリマー粒子の質量／本組成物からポリマー粒子を除いた残部の質量で表される比は、１／１００〜１／２０の範囲内が好ましく、１／７５〜１／２０の範囲内がより好ましく、１／５０〜１／２５の範囲内がさらに好ましい。前記比が前記範囲の下限値以上であると、ポリマー粒子による効果が得られやすい。前記比が前記範囲の上限値以下であると、本組成物の粘度を充分に低くでき、ハイドロゲルの透明性、表面平滑性がより優れる。
なお、「本組成物からポリマー粒子を除いた残部」は、後述する第２の溶液に等しい。The content of the polymer particles can be appropriately selected according to the type of the polymer particles so that the effect of the polymer particles can be sufficiently obtained.
The ratio expressed by the mass of the polymer particles / the mass of the balance after removing the polymer particles from the composition is preferably in the range of 1/100 to 1/20, more preferably in the range of 1/75 to 1/20. , 1/50 to 1/25 is more preferable. When the ratio is at least the lower limit of the above range, the effect of the polymer particles can be easily obtained. When the ratio is not more than the upper limit of the above range, the viscosity of the present composition can be sufficiently lowered, and the transparency and surface smoothness of the hydrogel are more excellent.
The "remaining portion of the composition excluding the polymer particles" is equivalent to the second solution described later.
ポリマー粒子の質量／重合性モノマーの質量で表される比は、０．１／９９．９〜７０／３０が好ましく、１／９９〜６０／４０がより好ましく、５／９５〜５０／５０がさらに好ましい。この比は、ハイドロゲルにおける第１のポリマーの質量／第２のポリマーの質量で表される比とみなすことができる。この比が前記範囲内であると、ハイドロゲルの機械的強度がより優れる。 The ratio expressed by the mass of the polymer particles / the mass of the polymerizable monomer is preferably 0.1 / 99.9 to 70/30, more preferably 1/99 to 60/40, and 5/95 to 50/50. More preferred. This ratio can be regarded as the ratio expressed by the mass of the first polymer / the mass of the second polymer in the hydrogel. When this ratio is within the above range, the mechanical strength of the hydrogel is more excellent.
本組成物中の光吸収剤の含有量は、光重合開始剤の総モル量に対して０〜１０００モル％が好ましく、０〜７５０モル％がより好ましく、０〜５００モル％が特に好ましい。
又は光吸収剤の含有量は、光重合開始剤の総質量に対して０〜３０００質量％が好ましく、０〜２０００質量％がより好ましく、０〜１５００質量％が特に好ましい。
光吸収剤の含有量が前記範囲の下限値以上であると、３Ｄ造形性がより優れる。光吸収剤の含有量が前記範囲の上限値以下であると、ハイドロゲルの機械的強度がより優れる。The content of the light absorber in the present composition is preferably 0 to 1000 mol%, more preferably 0 to 750 mol%, and particularly preferably 0 to 500 mol% with respect to the total molar amount of the photopolymerization initiator.
Alternatively, the content of the light absorber is preferably 0 to 3000% by mass, more preferably 0 to 2000% by mass, and particularly preferably 0 to 1500% by mass with respect to the total mass of the photopolymerization initiator.
When the content of the light absorber is at least the lower limit of the above range, the 3D formability is more excellent. When the content of the light absorber is not more than the upper limit of the above range, the mechanical strength of the hydrogel is more excellent.
本組成物の２５℃における粘度は、５〜１０００ｍＰａ・ｓが好ましく、５〜７５０ｍＰａ・ｓがより好ましく、５〜５００ｍＰａ・ｓがさらに好ましく、１０〜１００ｍＰａ・ｓが特に好ましい。本組成物の粘度が前記範囲の下限値以上であると、ハイドロゲルの機械的強度がより優れる。本組成物の粘度が前記範囲の上限値以下であると、本組成物を注型する際に気泡が入り込んでハイドロゲルの透明性や表面平滑性が低下することを抑制できる。
粘度は、Ｂ型粘度計を用いて測定される値である。
前述のとおり、光酸発生剤としてホスフィン酸塩を用いることによって、本組成物の粘度を低減できる。その他、ポリマー粒子の含有量、重合性モノマーの濃度等によって本組成物の粘度を調整できる。The viscosity of the composition at 25 ° C. is preferably 5 to 1000 mPa · s, more preferably 5 to 750 mPa · s, further preferably 5 to 500 mPa · s, and particularly preferably 10 to 100 mPa · s. When the viscosity of the present composition is at least the lower limit of the above range, the mechanical strength of the hydrogel is more excellent. When the viscosity of the present composition is not more than the upper limit of the above range, it is possible to prevent bubbles from entering when the present composition is cast to reduce the transparency and surface smoothness of the hydrogel.
The viscosity is a value measured using a B-type viscometer.
As described above, the viscosity of the present composition can be reduced by using phosphinate as the photoacid generator. In addition, the viscosity of the present composition can be adjusted by adjusting the content of the polymer particles, the concentration of the polymerizable monomer, and the like.
本組成物は、光重合開始剤、重合性モノマー、ポリマー粒子、必要に応じて極性溶媒、架橋剤、他の成分を混合することにより製造できる。
本組成物の製造方法としては、特に限定するものではないが、例えば次のような方法を採用することができる。すなわち、まず、ポリマー粒子を作製する。別途、光重合開始剤と、重合性モノマーと、極性溶媒と、必要に応じて架橋剤とを混合し、ポリマー粒子以外の成分を含む溶液（以下、「第２の溶液」とも記す。）を作製する。次いで、作製したポリマー粒子と第２の溶液とを混合し、本組成物を得る。The composition can be produced by mixing a photopolymerization initiator, a polymerizable monomer, polymer particles, a polar solvent, a cross-linking agent, and other components, if necessary.
The method for producing the present composition is not particularly limited, but for example, the following method can be adopted. That is, first, polymer particles are produced. Separately, a photopolymerization initiator, a polymerizable monomer, a polar solvent, and a cross-linking agent, if necessary, are mixed to prepare a solution containing components other than the polymer particles (hereinafter, also referred to as “second solution”). To make. Then, the prepared polymer particles and the second solution are mixed to obtain the present composition.
以下に、ポリマー粒子の製造方法の一例を示す。ただし、ポリマー粒子の製造方法はこの例に限定されるものではない。
この例の製造方法では、まず、網目構造を有する第１のポリマーと液状媒体とを含む第１のゲルを調製する（第１のゲル調製工程）。次いで、必要に応じて、得られた第１のゲルを物理的に破壊し、粒状にする（第１のゲル破壊工程）。次いで、第１のゲル調製工程後又は第１のゲル破壊工程後の第１のゲルを乾燥し、必要に応じて粉砕し、乾燥ゲル粒子（ポリマー粒子）を得る。An example of a method for producing polymer particles is shown below. However, the method for producing polymer particles is not limited to this example.
In the production method of this example, first, a first gel containing a first polymer having a network structure and a liquid medium is prepared (first gel preparation step). Then, if necessary, the obtained first gel is physically broken and granulated (first gel breaking step). Next, the first gel after the first gel preparation step or the first gel breaking step is dried and, if necessary, pulverized to obtain dried gel particles (polymer particles).
第１のゲルの調製方法としては、液状媒体中で、重合性モノマーを重合開始剤及び架橋剤の存在下に重合させてゲルを得る方法が挙げられる。具体的には、重合性モノマー、重合開始剤、架橋剤及び液状媒体を含有する溶液（以下、第１の溶液ということもある。）を調製し、この第１の溶液中で重合性モノマーを重合させる方法が挙げられる。
重合性モノマーの重合方法は、特に限定されず、熱重合や光重合といった公知の重合方法を用いることができる。Examples of the first method for preparing a gel include a method of obtaining a gel by polymerizing a polymerizable monomer in a liquid medium in the presence of a polymerization initiator and a cross-linking agent. Specifically, a solution containing a polymerizable monomer, a polymerization initiator, a cross-linking agent, and a liquid medium (hereinafter, may be referred to as a first solution) is prepared, and the polymerizable monomer is contained in the first solution. A method of polymerization can be mentioned.
The polymerization method of the polymerizable monomer is not particularly limited, and a known polymerization method such as thermal polymerization or photopolymerization can be used.
重合開始剤としては、重合方法に応じて公知の重合開始剤を適宜用いることができる。
例えば、重合性モノマーを光重合する場合は、光重合開始剤が用いられる。光重合開始剤を用いる場合、この光重合開始剤は、本組成物に用いる光重合開始剤と同じであってもよく異なってもよい。
第１のゲルの調製に用いられる光重合開始剤としては、アルキルフェノン系開始剤、アシルホスフィンオキサイド系開始剤が好ましい。かかる光重合開始剤を用いると、形成されるゲルの機械的強度が良好である。
アシルホスフィンオキサイド系開始剤としては、ビス（２，４，６−トリメチルベンゾイル）フェニルホスフィンオキシド、２，４，６−トリメチルベンゾイルジフェニルホスフィンオキシド、（２，４，６−トリメチルベンゾイル）エトキシフェニルホスフィンオキシド、ビス（２，６−ジメトキシベンゾイル）２，４，４−トリメチルペンチルホスフィンオキシド等が挙げられる。
架橋剤としては、前述した架橋剤と同様のものが挙げられる。
液状媒体としては、水、有機溶剤等が挙げられ、入手の容易さや環境調和性の点で、水が好ましい。As the polymerization initiator, a known polymerization initiator can be appropriately used depending on the polymerization method.
For example, when photopolymerizing a polymerizable monomer, a photopolymerization initiator is used. When a photopolymerization initiator is used, the photopolymerization initiator may be the same as or different from the photopolymerization initiator used in the present composition.
As the photopolymerization initiator used in the preparation of the first gel, an alkylphenone-based initiator and an acylphosphine oxide-based initiator are preferable. When such a photopolymerization initiator is used, the mechanical strength of the formed gel is good.
Examples of the acylphosphine oxide-based initiator include bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and (2,4,6-trimethylbenzoyl) ethoxyphenylphosphine oxide. , Bis (2,6-dimethoxybenzoyl) 2,4,4-trimethylpentylphosphine oxide and the like.
Examples of the cross-linking agent include the same cross-linking agents as those described above.
Examples of the liquid medium include water and organic solvents, and water is preferable in terms of availability and environmental friendliness.
第１の溶液中の重合性モノマーの含有量は、第１のゲルの好ましい硬さを得る上で、仕込みモル濃度として、０．５〜４モル／Ｌが好ましく、１〜２モル／Ｌがより好ましい。この仕込みモル濃度は、第１の溶液を調製したときの、第１の溶液１Ｌ当たりの重合性モノマーのモル量である。 The content of the polymerizable monomer in the first solution is preferably 0.5 to 4 mol / L, preferably 1 to 2 mol / L, as the charged molar concentration in order to obtain a preferable hardness of the first gel. More preferred. This charge molar concentration is the molar amount of the polymerizable monomer per 1 L of the first solution when the first solution is prepared.
第１の溶液中の架橋剤の含有量は、重合性モノマーの総モル量に対して１〜２０モル％が好ましく、２〜１０モル％がより好ましい。重合性モノマーの総モル量に対する架橋剤の含有量（モル％）は、第１のポリマーの架橋密度に相当する。第１のポリマーの架橋密度が前記範囲の下限値以上であると、形成されるゲルの機械的強度がより優れる。第１のポリマーの架橋密度が前記範囲の上限値以下であると、形成されるゲルの柔軟性がより優れる。 The content of the cross-linking agent in the first solution is preferably 1 to 20 mol%, more preferably 2 to 10 mol%, based on the total molar amount of the polymerizable monomer. The content (mol%) of the cross-linking agent with respect to the total molar amount of the polymerizable monomer corresponds to the cross-linking density of the first polymer. When the crosslink density of the first polymer is equal to or higher than the lower limit of the above range, the mechanical strength of the formed gel is more excellent. When the crosslink density of the first polymer is not more than the upper limit of the above range, the flexibility of the formed gel is more excellent.
第１の溶液中の重合開始剤の含有量は、重合性モノマーの総モル量に対して０．００１〜５モル％が好ましく、０．０１〜１モル％がより好ましい。第１の溶液中の重合開始剤の含有量が、重合性モノマーの総モル量に対して多すぎると、第１のポリマーの分子量が小さくなるため第１のゲルが弱くなりやすく、少なすぎると第１の溶液がゲル化しないおそれがある。第１の溶液中の重合開始剤の含有量が前記範囲内であると、第１の溶液が充分にゲル化し、かつ第１のゲルの強度が優れる。 The content of the polymerization initiator in the first solution is preferably 0.001 to 5 mol%, more preferably 0.01 to 1 mol%, based on the total molar amount of the polymerizable monomer. If the content of the polymerization initiator in the first solution is too large with respect to the total molar amount of the polymerizable monomer, the molecular weight of the first polymer becomes small, so that the first gel tends to be weakened, and if it is too small. The first solution may not gel. When the content of the polymerization initiator in the first solution is within the above range, the first solution is sufficiently gelled and the strength of the first gel is excellent.
第１のゲル調製工程の後、第１のゲル破壊工程を行って第１のゲルを粒状にすると、第１のゲルの乾燥を短時間で行うことができるほか、乾燥後の粉砕が容易になる。
なお、蒲池ら（蒲池幹治、遠藤剛監修、「ラジカル重合ハンドブック」、１９９９年、エヌ・ティー・エス発行）に記載されるような、粒子状のポリマーを製造する一般的な方法である乳化重合法、懸濁重合法又は分散重合法等によって重合性モノマーを重合させ、粒状の第１のポリマーと液体を含むゲルを調製してもよい。When the first gel is granulated by performing the first gel breaking step after the first gel preparation step, the first gel can be dried in a short time and can be easily pulverized after drying. Become.
It should be noted that emulsification weight, which is a general method for producing a particulate polymer, as described in Gamaike et al. (Supervised by Mikiharu Gamaike and Tsuyoshi Endo, "Radical Polymerization Handbook", 1999, published by NTS). A gel containing a granular first polymer and a liquid may be prepared by polymerizing a polymerizable monomer by a legal, suspension polymerization method, dispersion polymerization method or the like.
第１のゲル調製工程で得た第１のゲル、又は第１のゲル破壊工程で粉砕した第１のゲルを乾燥し、必要に応じて粉砕することで、乾燥ゲル粒子が得られる。この乾燥ゲル粒子をポリマー粒子として使用できる。
乾燥方法としては、特に限定されず、例えば熱風乾燥、凍結乾燥等の公知の方法で行うことができる。乾燥は、液状媒体の含有率が１０質量％以下になるまで行うことが好ましい。乾燥条件は、例えば２０〜１３０℃であってよい。
乾燥後の第１のゲルの粉砕方法は特に限定されず、公知の方法で物理的に粉砕すればよい。例えば乳鉢と乳棒を用いて砕く方法でもよい。粉砕後、篩等を用いて粉砕物を分級してもよい。Dried gel particles are obtained by drying the first gel obtained in the first gel preparation step or the first gel pulverized in the first gel breaking step and pulverizing if necessary. The dried gel particles can be used as polymer particles.
The drying method is not particularly limited, and can be performed by a known method such as hot air drying or freeze drying. Drying is preferably carried out until the content of the liquid medium is 10% by mass or less. The drying conditions may be, for example, 20 to 130 ° C.
The method for pulverizing the first gel after drying is not particularly limited, and the first gel may be physically pulverized by a known method. For example, a method of crushing using a mortar and a pestle may be used. After pulverization, the pulverized product may be classified using a sieve or the like.
本組成物は、例えば、ハイドロゲルの製造に用いられる。本組成物を用いたハイドロゲルの製造方法は後で説明する。 This composition is used, for example, in the production of hydrogels. A method for producing a hydrogel using this composition will be described later.
以上説明した本組成物にあっては、光重合開始剤と、重合性モノマーと、ポリマー粒子とを含み、光重合開始剤がホスフィン酸塩を含むため、増粘成分として機能するポリマー粒子を含んでいながらも、低粘度である。そのため、本組成物を用いてハイドロゲルを形成する際に、本組成物中に気泡が残存したり、本組成物と型との間に気泡が残存したりしにくい。そのため、透明性、表面平滑性に優れたハイドロゲルを得ることができる。 The composition described above contains a photopolymerization initiator, a polymerizable monomer, and polymer particles, and since the photopolymerization initiator contains a phosphinate, it contains polymer particles that function as a thickening component. However, it has a low viscosity. Therefore, when a hydrogel is formed using the present composition, it is difficult for air bubbles to remain in the present composition or air bubbles to remain between the present composition and the mold. Therefore, a hydrogel having excellent transparency and surface smoothness can be obtained.
得られるハイドロゲルは、任意の形状に成形することができるため、高吸水性樹脂や紙おむつ、生理用品、ソフトコンタクトレンズ、屋内緑化用含水シート、衝撃吸収材料、精神・防音材料や子供の玩具等に用いることができる。
また、本組成物は、基材に塗布して硬化させることができるため、本組成物を、船底塗料、着氷防止塗料、防曇塗料、防汚塗料等の各種コーティング材料や、摩擦抵抗を低減したい部位（プロペラ、カテーテル、配管内の圧力損失低減等）に塗布する材料としても用いることができる。さらに、本組成物は粘度が低くハンドリング性に優れるため、光造形法式の３Ｄプリンタ用のインクとしても好適に用いることができる。Since the obtained hydrogel can be molded into any shape, highly water-absorbent resin, disposable diapers, sanitary products, soft contact lenses, water-containing sheets for indoor greening, shock absorbing materials, mental / soundproofing materials, children's toys, etc. Can be used for.
In addition, since this composition can be applied to a base material and cured, various coating materials such as ship bottom paint, icing prevention paint, antifogging paint, and antifouling paint, and frictional resistance can be applied to this composition. It can also be used as a material to be applied to the part to be reduced (propeller, catheter, pressure loss reduction in piping, etc.). Further, since this composition has a low viscosity and is excellent in handleability, it can be suitably used as an ink for a stereolithography type 3D printer.
〔造形物〕
本発明の造形物は、本組成物の硬化物を含む。本発明の造形物は、具体的には、少なくともポリマー粒子を構成する第１のポリマーと、本組成物中の重合性モノマーから形成されたポリマー（第２のポリマー）とを含む。[Modeled object]
The modeled product of the present invention includes a cured product of the present composition. Specifically, the modeled product of the present invention includes at least the first polymer constituting the polymer particles and the polymer formed from the polymerizable monomer in the present composition (second polymer).
本発明の造形物は、例えば、本組成物を型に入れ、本組成物に対して光（紫外線、可視光線、電子線等）を照射することにより製造できる。本組成物に対して光を照射すると、重合性モノマーが重合してポリマーが生成し、本組成物がゲル化してハイドロゲルとなる。得られたハイドロゲルを型から取り出して本発明の造形物としてもよく、必要に応じて、ハイドロゲルに対して他の処理を施してもよい。他の処理としては、例えば、極性溶媒の除去（乾燥）、極性溶媒への浸漬（膨潤）が挙げられる。 The modeled product of the present invention can be produced, for example, by placing the present composition in a mold and irradiating the present composition with light (ultraviolet rays, visible rays, electron beams, etc.). When the composition is irradiated with light, the polymerizable monomer polymerizes to form a polymer, and the composition gels to form a hydrogel. The obtained hydrogel may be taken out from the mold and used as a model of the present invention, and if necessary, the hydrogel may be subjected to other treatments. Other treatments include, for example, removal of the polar solvent (drying) and immersion in the polar solvent (swelling).
本発明の造形物は、臓器モデル等、種々の用途に用いることができる。 The modeled object of the present invention can be used for various purposes such as an organ model.
〔ハイドロゲル〕
本発明のハイドロゲルは、本組成物の硬化物を含む。本発明のハイドロゲルは、具体的には、少なくとも網目構造と、その内部に保持された極性溶媒とを含む。前記網目構造は、ポリマー粒子を構成する第１のポリマーと、重合性モノマーから形成されたポリマー（第２のポリマー）とによって構成される。[Hydrogel]
The hydrogel of the present invention contains a cured product of the present composition. Specifically, the hydrogel of the present invention contains at least a network structure and a polar solvent retained therein. The network structure is composed of a first polymer constituting polymer particles and a polymer formed from a polymerizable monomer (second polymer).
本発明のハイドロゲルの極性溶媒の含有率は、特に限定されず、例えば１０質量％以上であってよく、５０質量％以上であってよく、７０質量％以上であってよい。極性溶媒の含有率が高いほど、ハイドロゲルの透明性、柔軟性がより優れる。
本明細書において、「極性溶媒の含有率」とは、ハイドロゲルの総質量に対する極性溶媒の質量の割合である。ハイドロゲルに含まれる極性溶媒が水の場合、極性溶媒の含有率を「含水率」ともいう。The content of the polar solvent of the hydrogel of the present invention is not particularly limited, and may be, for example, 10% by mass or more, 50% by mass or more, or 70% by mass or more. The higher the content of the polar solvent, the better the transparency and flexibility of the hydrogel.
As used herein, the "protic solvent content" is the ratio of the mass of the polar solvent to the total mass of the hydrogel. When the polar solvent contained in the hydrogel is water, the content of the polar solvent is also referred to as "moisture content".
本組成物は光重合開始剤としてホスフィン酸塩を含むので、本発明のハイドロゲルは、光重合開始剤由来のホスフィン酸塩成分を含む。
光重合開始剤由来のホスフィン酸塩成分の構造は通常、本組成物中のホスフィン酸塩の構造とは異なる。本組成物中のホスフィン酸塩は、光が照射されると、二分子に開裂（−Ｐ（＝Ｏ）−Ｃ（＝Ｏ）−結合が開裂）してラジカルを発生する。例えばフェニル（２，４，６−トリメチルベンゾイル）ホスフィン酸塩の場合、下記式に示すように二分子に開裂してラジカルを発生する。Since the composition contains a phosphinate as a photopolymerization initiator, the hydrogel of the present invention contains a phosphinate component derived from the photopolymerization initiator.
The structure of the phosphinate component derived from the photopolymerization initiator is usually different from the structure of the phosphinate in the present composition. When the phosphinate in the present composition is irradiated with light, the two molecules are cleaved (-P (= O) -C (= O) -bond is cleaved) to generate radicals. For example, in the case of phenyl (2,4,6-trimethylbenzoyl) phosphinate, it is cleaved into two molecules to generate radicals as shown in the following formula.
光重合開始剤由来のホスフィン酸塩成分の含有量は、例えば、本発明のハイドロゲルの総質量に対して０．０００１〜０．５質量％である。
ハイドロゲルが光重合開始剤由来のホスフィン酸塩成分を含むか否か、及びこのホスフィン酸塩成分の含有量は、例えば、熱分解ガスクロマトグラフ（熱分解ＧＣ）等により確認できる。The content of the phosphinate component derived from the photopolymerization initiator is, for example, 0.0001 to 0.5% by mass with respect to the total mass of the hydrogel of the present invention.
Whether or not the hydrogel contains a phosphinate component derived from a photopolymerization initiator, and the content of this phosphinate component can be confirmed by, for example, a pyrolysis gas chromatograph (pyrolysis GC) or the like.
本発明のハイドロゲルは、例えば、本組成物を型に入れ、本組成物に対して光（紫外線、可視光線、電子線等）を照射することにより製造できる。本組成物に対して光を照射すると、重合性モノマーが重合してポリマーが生成し、本組成物がゲル化する。 The hydrogel of the present invention can be produced, for example, by placing the present composition in a mold and irradiating the present composition with light (ultraviolet rays, visible rays, electron beams, etc.). When the composition is irradiated with light, the polymerizable monomer polymerizes to form a polymer, and the composition gels.
本発明のハイドロゲルは、本組成物を用いているため、透明性、表面平滑性に優れる。
本発明のハイドロゲルは、前述のように、高吸水性樹脂や紙おむつ、生理用品、ソフトコンタクトレンズ、屋内緑化用含水シート、衝撃吸収材料、精神・防音材料や子供の玩具等、種々の用途に用いることができる。Since the hydrogel of the present invention uses the present composition, it is excellent in transparency and surface smoothness.
As described above, the hydrogel of the present invention can be used in various applications such as highly water-absorbent resins, disposable diapers, sanitary napkins, soft contact lenses, water-containing sheets for indoor greening, shock absorbing materials, mental and soundproofing materials, and children's toys. Can be used.
以下、本発明を実施例により更に詳しく説明するが、以下の実施例は本発明の範囲を限定するものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples do not limit the scope of the present invention.
（実施例１）
＜ポリマー粒子の作製＞
２−アクリルアミド−２−メチルプロパンスルホン酸ナトリウム塩（ＮａＡＭＰＳ）の５０質量％水溶液の４１．３ｇ（０．０９００モル）に、Ｎ，Ｎ’−メチレンビスアクリルアミド（ＭＢＡＡｍ）の０．５５５ｇ（０．００３６０ミリモル）と、光重合開始剤であるＩｒｇａｃｕｒｅ１１７３（ＢＡＳＦ社製、２−ヒドロキシ−２−メチル−１−フェニル−プロパン−１−オン）の０．０２１ｇ（０．０００１０モル）と、純水４１．３ｇを加えて第１の溶液を調製した。
第１の溶液を、ポリエチレンテレフタレート（ＰＥＴ）フィルム上に枠状のシリコーンゴムシート（厚さ２ｍｍ）を置いた型に流し込み、その上を別のＰＥＴフィルムで覆い、さらに上下をガラス板で挟んでサンプルを作製した。このサンプルに、光ベルト方式の紫外線照射装置を用いて紫外線を照射することにより、サンプル内の第１の溶液をゲル化した。得られたゲルを乾燥機で一晩以上乾燥させ、乾燥後のゲルを粉砕し、１００μｍの篩を通過する乾燥ゲル粒子を回収し、ポリマー粒子（粒子径１００μｍ以下）とした。(Example 1)
<Preparation of polymer particles>
To 41.3 g (0.0900 mol) of a 50 mass% aqueous solution of 2-acrylamide-2-methylpropanesulfonic acid sodium salt (NaAMPS), 0.555 g (0.) of N, N'-methylenebisacrylamide (MBAAm). Acrylamide), 0.021 g (0.00010 mol) of Irgacure 1173 (manufactured by BASF, 2-hydroxy-2-methyl-1-phenyl-propane-1-one), which is a photopolymerization initiator, and pure water 41. .3 g was added to prepare the first solution.
The first solution is poured into a mold in which a frame-shaped silicone rubber sheet (thickness 2 mm) is placed on a polyethylene terephthalate (PET) film, covered with another PET film, and further sandwiched between glass plates on the top and bottom. A sample was prepared. The first solution in the sample was gelled by irradiating this sample with ultraviolet rays using an optical belt type ultraviolet irradiation device. The obtained gel was dried in a dryer overnight or more, the dried gel was pulverized, and dried gel particles that passed through a 100 μm sieve were collected and used as polymer particles (particle size 100 μm or less).
＜光硬化性組成物の作製＞
Ｎ，Ｎ−ジメチルアクリルアミド（ＤＭＡＡｍ）の１９．８ｇ（０．２００モル）と、ＭＢＡＡｍの０．０３１ｇ（０．０００２０モル）と、リチウムフェニル（２，４，６−トリメチルベンゾイル）ホスフィネート（Ｌｉ−ＴＰＯ）の０．０５９ｇ（０．０００２０モル）と、純水７９．３ｇとを混合し、第２の溶液を得た。
上記のように作製したポリマー粒子と第２の溶液とを、ポリマー粒子の質量／第２の溶液の質量で表される比（以下、「１ｓｔ／２ｎｄ」ともいう。）が１／３０となるように混合し、ポリマー粒子を均一に分散、膨潤させ、光硬化性組成物を得た。<Preparation of photocurable composition>
19.8 g (0.200 mol) of N, N-dimethylacrylamide (DMAAm), 0.031 g (0.00020 mol) of MBAAm, and lithium phenyl (2,4,6-trimethylbenzoyl) phosphinate (Li-). 0.059 g (0.00020 mol) of TPO) and 79.3 g of pure water were mixed to obtain a second solution.
The ratio of the polymer particles prepared as described above and the second solution expressed by the mass of the polymer particles / the mass of the second solution (hereinafter, also referred to as “1st / 2nd”) is 1/30. The polymer particles were uniformly dispersed and swollen to obtain a photocurable composition.
＜ハイドロゲル（造形物）の作製＞
上記のように作製した光硬化性組成物を、ポリマー粒子の作製に用いたのと同様の型に流し込み、波長４０５ｎｍのＬＥＤ光を３０分間照射してポリマー粒子含有組成物をゲル化させ、ハイドロゲルを得た。<Making hydrogel (modeled object)>
The photocurable composition prepared as described above is poured into a mold similar to that used for preparing the polymer particles, and the polymer particle-containing composition is gelled by irradiating with LED light having a wavelength of 405 nm for 30 minutes. I got a gel.
＜評価＞
上記ハイドロゲルの作製に用いた光硬化性組成物及び得られたハイドロゲルについて以下の評価を行った。結果を表１に示す。
表１に、ポリマー粒子中の架橋剤（ＭＢＡＡｍ）のＮａＡＭＰＳの総モル量に対する含有量（モル％）、光硬化性組成物中の光重合開始剤の種類及び重合性モノマーの総モル量に対する含有量（モル％）、１ｓｔ／２ｎｄを併記した。<Evaluation>
The photocurable composition used for producing the above hydrogel and the obtained hydrogel were evaluated as follows. The results are shown in Table 1.
Table 1 shows the content (mol%) of the cross-linking agent (MBAAm) in the polymer particles with respect to the total molar amount of NaAMPS, the type of the photopolymerization initiator in the photocurable composition, and the content with respect to the total molar amount of the polymerizable monomer. The amount (mol%) and 1st / 2nd are also shown.
「粘度」
光硬化性組成物の２５℃における粘度（ｍＰａ・ｓ）を、Ｂ型粘度計を用いて測定した。"viscosity"
The viscosity (mPa · s) of the photocurable composition at 25 ° C. was measured using a B-type viscometer.
「ハイドロゲルの透明性」
ハイドロゲルを文字の書かれた紙の上に置き、ゲルを通して文字を目視で観察し、以下の基準で評価した。
〇（良好）：ゲルを通さずに見た場合と大差なく、文字をはっきりと視認できる。
×（不良）：文字をはっきりと視認することができない。"Transparency of hydrogel"
The hydrogel was placed on a piece of paper on which the letters were written, and the letters were visually observed through the gel and evaluated according to the following criteria.
〇 (Good): The characters can be clearly seen, not much different from when viewed without passing through the gel.
× (defective): Characters cannot be clearly seen.
「ハイドロゲルの表面平滑性」
ハイドロゲルを目視で観察し、以下の基準で評価した。
〇（良好）：表面に凹凸がなく滑らかである。
×（不良）：表面に凹凸が見られる。"Surface smoothness of hydrogel"
The hydrogel was visually observed and evaluated according to the following criteria.
〇 (Good): The surface is smooth with no irregularities.
× (defective): Unevenness is seen on the surface.
「３Ｄ造形性」
光硬化組成物の液面に目開きが１ｍｍ程度の金網を固定し、そこに波長４０５ｎｍの光を照射して液面付近に板状の硬化物を作製し、その後、金網を液中に沈めた。金網を沈めた際の光硬化性組成物の挙動、ならびに金網上に得られた硬化物を観察し、以下の基準で評価した。
◎（特に良好）：金網を沈めた際にすぐに液面が均一になり、かつ金網から下方向への硬化が１ｍｍ未満である。
○（良好）：金網を沈めた際に液面がすぐに均一にならない、または金網から下方向への硬化が１ｍｍ以上である。"3D formability"
A wire mesh having a mesh size of about 1 mm is fixed to the liquid surface of the photocuring composition, and light having a wavelength of 405 nm is irradiated therein to prepare a plate-shaped cured product near the liquid surface, and then the wire mesh is submerged in the liquid. It was. The behavior of the photocurable composition when the wire mesh was submerged and the cured product obtained on the wire mesh were observed and evaluated according to the following criteria.
⊚ (especially good): The liquid level becomes uniform immediately when the wire mesh is submerged, and the curing downward from the wire mesh is less than 1 mm.
◯ (Good): When the wire mesh is submerged, the liquid level does not become uniform immediately, or the curing downward from the wire mesh is 1 mm or more.
「ハイドロゲルの含水率」
ハイドロゲルの含水率（％）を、加熱乾燥式水分計ＭＳ−７０（エー・アンド・デイ社製）を用いて測定した。具体的には、ハイドロゲル約１ｇを２００℃に加熱して３分間保持した後に１５０℃に温度を下げてその温度を維持し、含水率の時間変化が０．５０質量％／分以内となった時点を乾燥状態（乾燥ゲル）として測定を終了し、以下の式により含水率を計算した。
含水率＝（乾燥前のハイドロゲルの質量（ｇ）−乾燥ゲルの質量（ｇ））／乾燥前のハイドロゲルの質量（ｇ）×１００"Hydrogel moisture content"
The water content (%) of the hydrogel was measured using a heat-drying moisture meter MS-70 (manufactured by A & D Co., Ltd.). Specifically, about 1 g of hydrogel is heated to 200 ° C. and held for 3 minutes, and then the temperature is lowered to 150 ° C. to maintain the temperature, and the time change of the water content is within 0.50 mass% / minute. The measurement was completed with the time point as a dry state (dry gel), and the water content was calculated by the following formula.
Moisture content = (mass of hydrogel before drying (g) -mass of dried gel (g)) / mass of hydrogel before drying (g) x 100
（実施例２）
実施例１において、１ｓｔ／２ｎｄを１／２５にした以外は実施例１と同様の操作を行った。評価結果を表１に示す。(Example 2)
In Example 1, the same operation as in Example 1 was performed except that 1st / 2nd was set to 1/25. The evaluation results are shown in Table 1.
（実施例３〜５）
実施例１において、第２の溶液に配合するＭＢＡＡｍの量を０．１５４ｇ（０．０００９９９モル）、純水の量を５９．７ｇに変更し、第２の溶液に光吸収剤として日本化薬社製のＫＡＹＡＰＨＯＲ ＡＳ１５０を表１に示す量で配合し、１ｓｔ／２ｎｄを表１に示す値にした以外は実施例１と同様の操作を行った。評価結果を表１に示す。
表１中、光吸収剤の量（モル％）は、光重合開始剤の総モル量に対する割合である。(Examples 3 to 5)
In Example 1, the amount of MBAAm to be blended in the second solution was changed to 0.154 g (0.009999 mol), the amount of pure water was changed to 59.7 g, and Nippon Kayaku was added to the second solution as a light absorber. The same operation as in Example 1 was carried out except that KAYAPHOR AS150 manufactured by the same company was blended in the amount shown in Table 1 and 1st / 2nd was set to the value shown in Table 1. The evaluation results are shown in Table 1.
In Table 1, the amount of the light absorber (mol%) is a ratio to the total molar amount of the photopolymerization initiator.
（実施例６）
実施例４において、ポリマー粒子中のＭＢＡＡｍのＮａＡＭＰＳの総モル量に対する含有量が表１の「ＭＢＡＡｍ（粒子中）」の欄に示す値となるようにポリマー粒子の作製におけるＭＢＡＡｍの使用量を変更した以外は実施例４と同様の操作を行った。評価結果を表１に示す。(Example 6)
In Example 4, the amount of MBAAm used in the production of the polymer particles was changed so that the content of MBAAm in the polymer particles with respect to the total molar amount of NaAMPS was the value shown in the column of "MBAAm (in the particles)" in Table 1. The same operation as in Example 4 was performed except for the above. The evaluation results are shown in Table 1.
（実施例７〜８）
実施例４において、第２の溶液に配合するＬｉ−ＴＰＯの量を表１に示すように変更するとともに、第２の溶液に、表１に示す量の２，４，６−トリメチルベンゾイルジフェニルホスフィンオキシド（ＴＰＯ）を配合した以外は実施例４と同様の操作を行った。評価結果を表１に示す。
表１中のＬｉ−ＴＰＯ、ＴＰＯそれぞれの量（モル％）は、重合性モノマーの総モル量に対する割合である。(Examples 7 to 8)
In Example 4, the amount of Li-TPO to be blended in the second solution was changed as shown in Table 1, and the amount of 2,4,6-trimethylbenzoyldiphenylphosphine shown in Table 1 was added to the second solution. The same operation as in Example 4 was carried out except that the oxide (TPO) was blended. The evaluation results are shown in Table 1.
The respective amounts (mol%) of Li-TPO and TPO in Table 1 are ratios to the total molar amount of the polymerizable monomer.
（比較例１）
実施例２において、Ｌｉ−ＴＰＯの代わりに、ビス（２，４，６−トリメチルベンゾイル）フェニルホスフィンオキシド（ＢＡＰＯ）（波長４０５ｎｍの吸光係数：８．９９０×１０２ｍＬ／（ｇ・ｃｍ））の０．００６７ｇ（０．０００１６ｍｏｌ）を用いた以外は実施例２と同様の操作を行った。評価結果を表１に示す。ただし、比較例１については、ハイドロゲルの透明性、表面平滑性が劣っていたので、３Ｄ造形性の評価は行わなかった。(Comparative Example 1)
In Example 2, instead of Li-TPO, 0 of bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (BAPO) (extinction coefficient at wavelength 405 nm: 8.990 × 102 mL / (g · cm)) The same operation as in Example 2 was performed except that 0067 g (0.00016 mol) was used. The evaluation results are shown in Table 1. However, in Comparative Example 1, since the transparency and surface smoothness of the hydrogel were inferior, the 3D formability was not evaluated.
光重合開始剤としてホスフィン酸塩を用いた実施例１〜６の光硬化性組成物は、低粘度であった。また、得られたハイドロゲルは、透明性、表面平滑性、３Ｄ造形性に優れていた。ホスフィン酸塩と他の光重合開始剤とを併用した実施例７〜８においても同様の結果が得られた。
一方、光重合開始剤として他の光重合開始剤を用いた比較例１の光硬化性組成物は、実施例１〜８に比べて高粘度であった。また、得られたハイドロゲルは、透明性に劣り、表面平滑性にも劣っていた。The photocurable compositions of Examples 1 to 6 using phosphinate as a photopolymerization initiator had a low viscosity. In addition, the obtained hydrogel was excellent in transparency, surface smoothness, and 3D formability. Similar results were obtained in Examples 7 to 8 in which the phosphinate was used in combination with another photopolymerization initiator.
On the other hand, the photocurable composition of Comparative Example 1 using another photopolymerization initiator as the photopolymerization initiator had a higher viscosity than that of Examples 1 to 8. In addition, the obtained hydrogel was inferior in transparency and surface smoothness.
Claims (8)
前記光重合開始剤がホスフィン酸塩を含む、光硬化性組成物。It contains a photopolymerization initiator, a polymerizable monomer, and polymer particles.
A photocurable composition in which the photopolymerization initiator contains a phosphinate.
極性溶媒の含有率が５０質量％以上である、ハイドロゲル。Contains a phosphinate component derived from a photopolymerization initiator
A hydrogel having a polar solvent content of 50% by mass or more.
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