WO2000029453A1 - Composition photodurcissable - Google Patents

Composition photodurcissable Download PDF

Info

Publication number
WO2000029453A1
WO2000029453A1 PCT/JP1999/006423 JP9906423W WO0029453A1 WO 2000029453 A1 WO2000029453 A1 WO 2000029453A1 JP 9906423 W JP9906423 W JP 9906423W WO 0029453 A1 WO0029453 A1 WO 0029453A1
Authority
WO
WIPO (PCT)
Prior art keywords
meth
radical polymerization
polymerization initiator
acrylate
compound
Prior art date
Application number
PCT/JP1999/006423
Other languages
English (en)
Japanese (ja)
Inventor
Keiko Kakinuma
Masao Arima
Original Assignee
Taiyo Ink Manufacturing Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Taiyo Ink Manufacturing Co., Ltd. filed Critical Taiyo Ink Manufacturing Co., Ltd.
Publication of WO2000029453A1 publication Critical patent/WO2000029453A1/fr

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • 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

Definitions

  • the present invention relates to a photocurable composition, in particular, can be used in various fields as an adhesive, a coating agent, a sealant, a resist agent, a molding material, etc., and has a high sensitivity to active energy.
  • a responsive photocurable composition can be used in various fields as an adhesive, a coating agent, a sealant, a resist agent, a molding material, etc., and has a high sensitivity to active energy.
  • Japanese Patent Application Laid-Open No. 2-196686 describes a photopolymerizable composition containing a compound having an unsaturated double bond capable of undergoing radical polymerization in a molecule, and an acylphosphinoxide compound as a photopolymerization initiator.
  • a technology for imparting conductivity by blending a conductive filler into an object is disclosed.
  • such a conventional photopolymerizable composition exhibits excellent curability when irradiated with ultraviolet light, but generally has low sensitivity to visible light and cannot achieve a practical polymerization rate.
  • ultraviolet light irradiation device Since a large amount of ultraviolet light and ozone generated from the ultraviolet light irradiation device is harmful to the human body, it is necessary to take measures to completely block ultraviolet light and ozone. Workers must be protected by safety glasses and protective gloves. Therefore, the ultraviolet light irradiation device cannot be easily installed anywhere, and it is necessary to provide facilities such as light-shielding equipment and exhaust equipment with sufficient measures.
  • a visible light irradiating device whose light amount is equivalent to that of a normal room light can be used. Visible light irradiators do not generate ultraviolet light or ozone and have no danger. Therefore, there is an advantage that it can be installed anywhere, regardless of the installation location.
  • the irradiation device can be miniaturized and can be built into small equipment.
  • a visible light irradiator is advantageous for miniaturization because, for example, only a single small fluorescent lamp for indoor lighting needs to be used as a light source, and no additional equipment is required. Therefore, it can be built into various small devices. Therefore, it can be used for devices for various purposes where conventional UV light irradiation devices could not be incorporated, and this can increase the added value of small devices.
  • the photocurable composition can be polymerized by a visible laser beam. Polymerization using a high-output visible laser beam is possible, and is an effective means for forming precise images. In addition to the method of irradiating the entire surface of the coating film of the photocurable composition with one visible laser beam through a mask, it is also possible to irradiate while scanning with a visible laser beam. Alternatively, a three-dimensional image can be formed.
  • the photocurable composition can be polymerized in a transparent mold.
  • the photocurable composition can be polymerized in a transparent mold, and as described above, it is possible to obtain a molded article having a complicated shape in combination with relatively easy polymerization of a deep portion. Can also.
  • the pigments and dyes When pigments and dyes are added to the photocurable composition, the pigments and dyes absorb ultraviolet light, which makes it difficult to polymerize with ultraviolet light.However, visible light has a long wavelength and is easily transmitted to the inside. Even in this case, polymerization is easy.
  • the photocurable composition can be polymerized by directly irradiating the human body with light.
  • the composition is suitable for use in which the photocurable composition is polymerized on the human body by directly or indirectly irradiating light to the human body for treatment or other purposes.
  • the photocurable composition can be applied to bonding of dental resin in the oral cavity.
  • a photocurable composition that can use visible light as a light source is useful in many respects and can be expected to be applied to various uses.
  • many conventional photocurable compositions cannot be polymerized by irradiation with visible light, and even when polymerizable, they have problems such as extremely low sensitivity and slow polymerization speed.
  • camphorquinone has been well known as a visible light polymerization initiator (for example, see Japanese Patent Application Laid-Open No. H2-252575, International Application Publication W094 / 14913).
  • a photocurable composition containing an ethylenically unsaturated compound together with phorfurquinone as a photopolymerization initiator is used, a long polymerization time is required due to a slow polymerization rate, and a long time is required for curing.
  • the light curing depth is not enough and the light curing depth is shallow.
  • the present invention has been made in view of the problems of the conventional visible light curable composition as described above, and is excellent not only in ultraviolet light but also in particular in light curing characteristics by irradiation of visible light, and has relatively low exposure.
  • a photocurable composition comprising a polymerization initiator and (C) a tertiary thiophosphite (that is, phosphite thioester) is provided.
  • the component (B) as a component of the photocurable composition of the present invention includes a photo-radical polymerization initiator (B-1) having an absorption wavelength of 400 nm or more, And a mixture of these initiators (B-1) and (B-2) (B-3).
  • the photocurable composition of the present invention Since such a photocurable composition has excellent sensitivity to visible light and ultraviolet light, the polymerization rate is high even when irradiated with both visible light and ultraviolet light, and it cures in an extremely short time. It is cured and has a deep curing depth, and has excellent light curing properties.
  • the photocurable composition of the present invention is as sensitive to ultraviolet light as visible light or more, and shows a sufficient polymerization rate.
  • the photocurable composition of the present invention has excellent storage stability.
  • the photocurable composition of the present invention can be cured by irradiating any of visible light and ultraviolet light. It is extremely effective. Further, since the photocurable composition of the present invention can use visible light as a light source, it can be applied to various uses, and its industrial value can be said to be extremely large. Other objects, features and advantages of the present invention will become apparent from the following description with reference to the drawings. BRIEF DESCRIPTION OF THE FIGURES Figure 1 is a partial sectional view showing the method of measuring the depth of cure;
  • FIG. 9 is an absorption spectrum diagram of a UV cut filter used for visible light irradiation in a gel time and gel fraction measurement test.
  • the photocurable composition of the present invention comprises a radical polymerization initiator (B) capable of initiating radical polymerization of the compound (A) in response to an active energy ray with respect to the ethylenically unsaturated compound (A). It is characterized by the addition of tertiary thiophosphite (C).
  • B radical polymerization initiator
  • C tertiary thiophosphite
  • the tertiary thiophosphite (C) activates the radical generated from the radical polymerization initiator (B) by irradiation with ultraviolet light or visible light to react with the ethylenically unsaturated compound (A). It is presumed that efficiency is improved.
  • (C) alone does not act as a photopolymerization initiator for visible light.
  • the radicals easily trap oxygen in the air and cause oxygen inhibition (polymerization failure due to oxygen).
  • the surface curability of the product is not sufficient.
  • the radical polymerization initiator (B) and the tertiary thiophosphite (C) are used in combination, since the photochemical reaction occurs quickly, the surface curing can be performed without causing a polymerization disorder due to oxygen. A photocurable composition having excellent properties is obtained.
  • the ethylenically unsaturated compound (A) which is a photopolymerizable component is not particularly limited as long as it is a compound in which the ethylenically unsaturated double bond undergoes radical polymerization by irradiation with active energy rays.
  • examples include acrylate compounds, unsaturated polyester compounds, unsaturated urethane compounds, styrene compounds, and butyl compounds.
  • (meth) acrylate compounds are particularly preferable, and the (meth) acrylate compounds are monofunctional, polyfunctional, monomeric, and oligomer (prepolymer).
  • acryloyl group may have a functional group other than an acryloyl group (methacryloyl group).
  • monomers such as substituted or unsubstituted aliphatic acrylates, alicyclic acrylates, aromatic acrylates and ethylene oxide-modified acrylates thereof, epoxy acrylates, urethane acrylates and the like.
  • Oligomers such as acrylates, polyester acrylates, polyether acrylates, polyall acrylates, alkyd acrylates, melamine acrylates, silicone acrylates, polybutadiene acrylates, and the corresponding methacrylates And the like.
  • (meth) acrylate is a general term for acrylate and methacrylate.
  • ethylenically unsaturated compound (A) examples include butoxymethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and hydroxethyl (Meth) acrylate, hydroxypropyl (meth) acrylate, glycerol (meth) acrylate, 4-((meth) acryloxytricyclo [5.2.1.0.2.6] decane , Sobornil (meth) acrylate, Isodesyl (meth) acrylate, Hue Noxityl (meth) acrylate, cyclohexyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl
  • Monofunctional (meth) acrylates such as mono (meth) acryloxyalkyltrialkoxysilane; acryloylmorpholine, N—vinylpyrrolidone, N, N—dimethylacrylamide, N-vinylcarbazole, Monofunctional monomers such as styrene, vinyl acetate, acrylonitrile, and trialkoxyvinylsilane; bisphenol-A-di (meth) acrylate, alkylene oxide-modified bisphenol-A-di (Meth) acrylate, 1,4-butanediol (meta) acrylate, 1,6—hexa Golgi (meth) acrylate, 1,9-nonangyl (me
  • (Meth) acrylate bis [4- (meth) acryloxymethyl] tris mouth [5.2.1.0.2.6] decane, bis [4- (meth) acryloxy1-2-hid Roxypropyloxyphenyl] propane, isophorone diisocyanate modified urethane (meth) acrylate, hexamethylene diisocyanate modified urethane (meth) acrylate, trimethylhexamethylene diisocyanate Urethane (meth) acrylate, trimethylhexamethylene diisocyanate-modified urethane (meth) acrylate, aliphatic epoxy-modified (meth) acrylate, oligosiloxanyldi (meth) acrylate, etc.
  • polyfunctional monomers such as (meth) acrylate and aryl (meth) acrylate.
  • These ethylenically unsaturated compounds may be used alone or in combination of two or more. Can be used in combination.
  • the photocurable composition of the present invention As the number of ethylenically unsaturated double bonds in the ethylenically unsaturated compound (A) increases, the polymerization rate upon irradiation with active energy rays increases. In addition, this photopolymerization rate is also affected by the type and molecular skeleton of the functional group in the ethylenically unsaturated compound. Polymerizes at a high polymerization rate. Therefore, in the photocurable composition of the present invention, the polymerization rate during photopolymerization can be adjusted by appropriately selecting the ethylenically unsaturated compound to be blended.
  • thioxanthones such as 2,4-dimethylthioxanthone, 2,4-getylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone; 2,4,6-trimethylbenzone (Bis) acyl phosphinoxides such as yldiphenyl phosphinoxide; bis (2,4-cyclopentene-1-yl) bis (2,6-difluoro-3- (1H-pyrrolidine 1) —Yl) 1-phenyl) titanium compounds such as titanium; 2-methyl-1- [4- (methylthio) phenyl] —a part of aminoacetophenones such as 2-morpholinopropan-1-one; camphorquinone, etc.
  • acyl phosphinoxides such as yldiphenyl phosphinoxide
  • anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone; benzophenones such as 4,4'-bis (ethylamino) benzophenone; 1-Hydroxyketones such as 1-hydroxy-1-cyclohexyl-1-phenylketone, 2-hydroxy-1-2-methyl-1-phenylphenyl-1-one; benzyl, 4,4,1 Some of the diketones such as dimethoxybenzyl; and some of the aminoacetophenones such as 2-benzyl-1-2-dimethylamino-11- (4-morpholinophenyl) butane-1-1.
  • benzophenones such as 4,4'-bis (ethylamino) benzophenone
  • 1-Hydroxyketones such as 1-hydroxy-1-cyclohexyl-1-phenylketone, 2-
  • aminoacetophenones such as 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and thioxanthones or axanthone Combination with minobenzophenone (see Fig.
  • these photo-radical polymerization initiators (B) include tertiary amines such as triethanolamine, ethyl phenylaminobenzoate, isoamyl dimethylaminobenzoate and dimethylaminoethyl methacrylate. Auxiliaries can be added.
  • photo-radical polymerization initiators (B) as described above, 2-hydroxy-1-2-methyl-1-phenylpronon-1-one, 1-hydroxy-cyclohexylphenyl-one-ketone, 1-hydroxy (4 -isopropylphenyl) 1 2 -hydroxy 1 -methylpropane 1 -one, 2-methyl- 1-[4-(methyl Ruthio) phenyl] — 2 morpholinopropane-1-one, 2 benzyl —2-dimethylamino-1- (4-morpholinophenyl) phenyloketone compound such as 1-butane non-1-1, (Bis) acylphosphinoxides such as bis (2,4,6-trimethylbenzoyl) -phenylphosphoxide are preferred.
  • the amount of the photoradical polymerization initiator (B) to be added is suitably from 0.1 to 20 parts by weight, preferably from 0.5 to 5 parts by weight, per 100 parts by weight of the ethylenically unsaturated compound (A). Parts by weight.
  • the amount of the photo-radical polymerization initiator (B) is less than 0.1 part by weight, it is difficult to obtain the above-mentioned effects by the combined use with the tertiary thiophosphite (C). If the amount is too large, the effect becomes saturated, which is not economical, and conversely, the composition may remain after photocuring and deteriorate the properties of the cured product, which is not preferable.
  • tertiary thiophosphite (C) to be combined with the photoradical polymerization initiator (B), tris (2-ethylhexyl-13-mercaptopropionate) phosphite, Lilaurilt lithiophosphite and the like can be mentioned, and they can be used alone or in combination.
  • the tertiary thiophosphite (C) is suitably used in an amount of 0.1 to 10 parts by weight, preferably 0.5 to 100 parts by weight, per 100 parts by weight of the ethylenically unsaturated compound (A). 5 parts by weight.
  • amount of the tertiary thiophosphite is less than 0.1 part by weight, it is difficult to obtain the above-described effects by using the radical polymerization initiator (B) in combination, and on the other hand, when the amount exceeds 10 parts by weight. Even if a large amount is blended, it is not economical because the effect is in a saturated state, and conversely, it is not preferable because it may remain after photocuring of the composition and deteriorate the properties of the cured product.
  • the photocurable composition of the present invention as described above, it is possible to appropriately add additives in addition to the components described above.
  • the curing shrinkage of the photocured product obtained from the composition of the present invention is reduced, the thermal expansion coefficient is reduced, the dimensional stability is improved, the elastic modulus is improved, the thermal conductivity is improved, the strength is improved, the toughness is improved, or the viscosity of the composition is adjusted.
  • an organic or inorganic filler can be blended.
  • the polymer may be a polymer, a ceramic, a metal, a metal oxide, a metal salt, or the like. In blending the above polymer, it is possible to dissolve, semi-dissolve or micro-disperse in the photocurable composition not as a filler but as a polymer blend or a polymer alloy.
  • the photocurable composition of the present invention may be blended with a coloring agent such as an organic or inorganic pigment or a dye as an additive, and provided for applications such as paints and inks.
  • a coloring agent such as an organic or inorganic pigment or a dye
  • other additives such as a softener, a plasticizer, a flame retardant, a storage stabilizer, an antioxidant, an ultraviolet absorber, a thixotropic agent, a cup A ring agent, a dispersion stabilizer, a fluidity-imparting agent and the like can be appropriately compounded.
  • Trimethylolpropane triacrylate 100 parts by weight and 2-benzyl-1-dimethylamino-1-(4-morpholinophenyl) butyl-1 (Ciba Specialty Chemicals) And 2 parts by weight of Irgacure 369) and 0.7 part by weight of trilauryl trithiophosphite were mixed to prepare a photocurable composition solution.
  • FIG. 2 shows an ultraviolet-visible absorption spectrum of Irgakiurea 369, which is a radical polymerization initiator (B-1).
  • FIG. 3 shows the UV-visible absorption spectrum of Irgacure 784, which is the radical polymerization initiator (B-1).
  • FIG. 4 shows the UV-visible absorption spectrum of Irgacure 819, which is a radical polymerization initiator (B-1).
  • FIG. 5 shows the UV-visible absorption spectrum of camphorquinone, which is the radical polymerization initiator (B-1).
  • FIG. 6 shows the UV-visible absorption spectrum of 2-E AQ, which is a radical polymerization initiator (B-2).
  • FIG. 7 shows the UV-visible absorption spectrum of a mixture of irgacure 907, which is a radical polymerization initiator (B-3), and DETX.
  • FIG. 8 shows an ultraviolet-visible absorption spectrum of a mixture of irgacure 184 and irgacure 819 which are radical polymerization initiators (B-1).
  • a photocurable composition solution was prepared by simply mixing 100 parts by weight of trimethylolpropane triacrylate and 2 parts by weight of trilauryltrithiophosphite without using a radical polymerization initiator.
  • Photocurable composition solutions of Comparative Examples 2 to 8 were prepared in the same manner as in Examples 1 to 7 except that trilauryl litiophosphite was not blended.
  • 0.2 ml of each sample was dropped on a 3 mm thick glass plate and used as an irradiation light source.
  • the sample was placed about 30 cm above the sample using a logen lamp, and irradiated through a UV cut filter Yuichi (L-42, manufactured by HOY A). During this time, the time until the sample gelled was measured while stirring the sample with a toothpick.
  • Fig. 9 shows the absorption spectrum of the UV cut filter used.
  • a black ring-shaped resin sealant (Brown Screw Robin SV-20, manufactured by Niommen Kagaku Glass Co., Ltd.) 1 (External size: 15 mm, internal diameter: 5 mm) 2 Paste the appropriate amount of sample S into it.
  • the irradiation spot 4 at the tip of the optical fiber 3 of a high-pressure mercury lamp (USHIO spot cure UIS-210, 102 manufactured by Shio Electric Co., Ltd.) was brought into close contact with the sealing agent 2 at the bottom of the container, and irradiated for 16 seconds. After the obtained cured product was washed with acetone, the height of the cured product was measured.
  • Table 1 Table 1, Table 2, and Table 3 show the results of measuring the gel time, gel fraction, and cure depth with respect to the reactivity to visible light, respectively.
  • Initiator for tertiary mouth light irradiation Initiator for tertiary mouth light irradiation
  • the photocurable composition solution prepared in Example 5 contained only a photoradical polymerization initiator having a wavelength of 400 nm or more (visible light) and no absorption wavelength as a radical polymerization initiator. It has the unique property of being photocured in the visible light range. Although this point is not always clear, it is presumed to be the effect of using tertiary thiophosphite in combination.
  • the gel fraction of each of the photocurable composition solutions of Examples 1, 5, 6 and Comparative Examples 1, 2, 6, and 7 was measured.
  • the measurement of the gel fraction for ultraviolet light is based on the gel In the method the fraction has established a high-pressure mercury lamp at a position above about 1 0 cm of vessel are the same except that the irradiation with an exposure amount 1 5 O m J / cm 2 without using a UV cutlet bets filters .
  • Table 4 shows the results of measuring the gel fraction indicating the reactivity to ultraviolet light in this manner.
  • Each of the photocurable composition solutions prepared in Examples 1 to 7 was allowed to stand at 25 ° C for one month and at 50 ° C for 7 days in a light-shielded state, and visually observed after the standing. Storage stability was evaluated by examining changes in properties and gel time. As a result, there was no change in properties or the like of any of the photocurable composition solutions, and it was found that the photocurable composition of the present invention had excellent storage stability.
  • the photocurable composition of the present invention can be applied to a wide range of applications such as adhesives, coating agents, paints, molding materials, human body related materials (dental materials), and image forming materials.
  • various modes can be adopted as the application form.

Landscapes

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

Abstract

L'invention se rapporte à une composition photodurcissable qui durcit lorsqu'elle est soumise à un rayonnement qui peut être ultraviolet mais également de la lumière visible. Cette composition contient (A) un composé éthylénique, (B) un amorceur de polymérisation radicalaire et (C) un thiophosphite tertiaire. L'amorceur (B) est (B-1) un amorceur de polymérisation radicalaire ayant des longueurs d'onde d'absorption supérieures à 400 nm, (B-2) un amorceur de polymérisation radicalaire ayant des longueurs d'onde d'absorption inférieures à 400 nm, ou un mélange de ces amorceurs (B-1) et (B-2). Cette composition peut être utilisée dans une large gamme d'applications et notamment dans des adhésifs, des matériaux de revêtement, des peintures, des matériaux de moulage, des matériaux dentaires et des matériaux pour la formation d'images.
PCT/JP1999/006423 1998-11-18 1999-11-17 Composition photodurcissable WO2000029453A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP10328251A JP2000154208A (ja) 1998-11-18 1998-11-18 光硬化性組成物
JP10/328251 1998-11-18

Publications (1)

Publication Number Publication Date
WO2000029453A1 true WO2000029453A1 (fr) 2000-05-25

Family

ID=18208137

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1999/006423 WO2000029453A1 (fr) 1998-11-18 1999-11-17 Composition photodurcissable

Country Status (2)

Country Link
JP (1) JP2000154208A (fr)
WO (1) WO2000029453A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113105799A (zh) * 2021-03-22 2021-07-13 鞍钢冷轧钢板（莆田）有限公司 一种含双光敏树脂骨架的耐指纹液

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004250673A (ja) * 2003-01-28 2004-09-09 National Institute For Materials Science ゲル化コロイド結晶前駆体とゲル化コロイド結晶、及びゲル化コロイド結晶の作製方法とその作製装置
JP5667808B2 (ja) * 2010-08-04 2015-02-12 Ｄｉｃグラフィックス株式会社 光重合開始剤組成物およびそれを用いた活性エネルギー線硬化型印刷インキ組成物
JP6764249B2 (ja) * 2016-04-27 2020-09-30 株式会社菱晃 硬化性樹脂組成物及びその硬化物、並びにコーティング材
JP2020122028A (ja) * 2017-05-10 2020-08-13 富士フイルム株式会社 硬化物の製造方法、積層シートの製造方法、及び、３次元構造物の製造方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59202458A (ja) * 1983-05-02 1984-11-16 Toray Ind Inc 感光性組成物
JPS6015428A (ja) * 1983-07-08 1985-01-26 Toray Ind Inc 感光性組成物
JPH03293670A (ja) * 1990-04-12 1991-12-25 Pilot Corp:The 光重合性組成物
JPH05255419A (ja) * 1992-03-12 1993-10-05 Toray Ind Inc カラーフィルタ用着色ペースト
JPH0725919A (ja) * 1993-07-15 1995-01-27 Mitsubishi Chem Corp 重合用組成物および樹脂材料
EP0884650A1 (fr) * 1997-05-21 1998-12-16 Brother Kogyo Kabushiki Kaisha Matériau d'enregistrement photosensible utilisant des microcapsules

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59202458A (ja) * 1983-05-02 1984-11-16 Toray Ind Inc 感光性組成物
JPS6015428A (ja) * 1983-07-08 1985-01-26 Toray Ind Inc 感光性組成物
JPH03293670A (ja) * 1990-04-12 1991-12-25 Pilot Corp:The 光重合性組成物
JPH05255419A (ja) * 1992-03-12 1993-10-05 Toray Ind Inc カラーフィルタ用着色ペースト
JPH0725919A (ja) * 1993-07-15 1995-01-27 Mitsubishi Chem Corp 重合用組成物および樹脂材料
EP0884650A1 (fr) * 1997-05-21 1998-12-16 Brother Kogyo Kabushiki Kaisha Matériau d'enregistrement photosensible utilisant des microcapsules

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113105799A (zh) * 2021-03-22 2021-07-13 鞍钢冷轧钢板（莆田）有限公司 一种含双光敏树脂骨架的耐指纹液

Also Published As

Publication number Publication date
JP2000154208A (ja) 2000-06-06

Similar Documents

Publication Publication Date Title
US4097994A (en) Dental restorative composition containing oligomeric BIS-GMA resin and Michler's ketone
US5100929A (en) (polyene-polythiol) dental compositions curable with visible light
JPS62246514A (ja) 歯科修復用組成物
JP2009519827A (ja) 可視光硬化システム、放射線への暴露によって硬化性組成物を硬化するために設計されたシステムに暴露された個人の健康上の危険性を低下する方法、基材と可視光硬化組成物を接合する方法
US20050113480A1 (en) Photopolymerization type dental surface coating material
CA2575449A1 (fr) Composition dentaire polymerisable par laser
EP0047097B1 (fr) Compositions dentaires pouvant être durcies par la lumière visible
JP4241956B2 (ja) 光硬化性組成物
CA2954748A1 (fr) Prothese dentaire
JPS5928569B2 (ja) 光重合性歯科用材料
WO2000029453A1 (fr) Composition photodurcissable
JP2008037907A (ja) 硬化性樹脂組成物
BRPI0713926A2 (pt) acrilatos curáveis através de diodos emissores de luz com amarelamento reduzidos
CN115286508A (zh) 一种含光引发剂基团的树脂单体及其制备方法和可光聚合组合物
JP2629060B2 (ja) 光重合性歯科用表面被覆材
US5883147A (en) Photopolymerizable adhesive composition
JPH0211608A (ja) 光硬化組成物に対するホスホネート開始剤
EP0583471B1 (fr) Adhesif photopolymerisable
JPS6314002B2 (fr)
JP3435857B2 (ja) 光重合性組成物
KR100530528B1 (ko) 광중합형의 치아수복용 고분자 복합체 조성물
JPS5971370A (ja) 紫外線硬化性被覆組成物
JP3202333B2 (ja) 光重合性組成物
JPH0513125B2 (fr)
Shete Photopolymerization of Cu (I)-catalyzed azide-alkyne cycloaddition (CuAAC)'click'-based networks for new-age materials

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): KR US

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)