WO2008019527A1 - Dérivés de phényl benzophénone et utilisations comme photoinitiateurs - Google Patents

Dérivés de phényl benzophénone et utilisations comme photoinitiateurs Download PDF

Info

Publication number
WO2008019527A1
WO2008019527A1 PCT/CN2006/002001 CN2006002001W WO2008019527A1 WO 2008019527 A1 WO2008019527 A1 WO 2008019527A1 CN 2006002001 W CN2006002001 W CN 2006002001W WO 2008019527 A1 WO2008019527 A1 WO 2008019527A1
Authority
WO
WIPO (PCT)
Prior art keywords
compound
formula
group
compound according
photoinitiator
Prior art date
Application number
PCT/CN2006/002001
Other languages
English (en)
Chinese (zh)
Inventor
Wenchao Zhao
Lili Jiang
Yonglin Wang
Qingjin Yan
Peng Luo
Shidian Han
Lixiu Yao
Junfeng Shao
Original Assignee
Insight High Technology 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 Insight High Technology Co., Ltd. filed Critical Insight High Technology Co., Ltd.
Priority to PCT/CN2006/002001 priority Critical patent/WO2008019527A1/fr
Priority to CNB2007100908219A priority patent/CN100569731C/zh
Publication of WO2008019527A1 publication Critical patent/WO2008019527A1/fr

Links

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
    • C08F2/46—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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C59/40—Unsaturated compounds
    • C07C59/76—Unsaturated compounds containing keto groups
    • C07C59/90—Unsaturated compounds containing keto groups containing singly bound oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
    • C07C69/708—Ethers
    • C07C69/712—Ethers the hydroxy group of the ester being etherified with a hydroxy compound having the hydroxy group bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/07—Aldehydes; Ketones

Definitions

  • the present invention relates to a class of macromolecularized phenylbenzophenone derivatives.
  • the derivative can be used as a photoinitiator, particularly a varnish for printing light, a printing ink or the like.
  • the invention also provides radiation curable compositions comprising at least one of the compounds of the invention as a photoinitiator. Background technique
  • Photoinitiators for varnish formulations require good cure speeds, especially good surface cure activity, low odor, low yellowness, and good solubility.
  • the tendency to migrate compounds and dissolve in external media should be as small as possible in order to comply with future legislative requirements. At present, it is increasingly difficult to meet the above requirements in the commercial products.
  • benzophenone is still the most widely used photoinitiator for ultraviolet (UV) cured overprint varnishes because of its good surface cure, high solubility, and low cost, and easy availability.
  • UV ultraviolet
  • benzophenone has a strong odor and is extremely easy to migrate from the print and dissolve into the food.
  • the compound of the present invention not only overcomes the above-mentioned defects of benzophenone and other existing photoinitiators, but also has the advantages of extremely low odor, high solubility in ultraviolet curing formulations, migration and tendency to be dissolved by an external medium, and, in some cases, In case, its unit weight The amount of reactivity is almost equivalent to benzophenone itself, and in most cases, its reactivity is higher than that of the commonly used benzophenone substitute. Summary of the invention
  • the present invention provides a compound represented by the formula (I),
  • G is a residue of a polyhydroxy compound, the number of hydroxyl groups in the polyhydroxy compound is N, and 2 ⁇ N ⁇ 6;
  • X is an integer, JL2 ⁇ x ⁇ N;
  • One of the groups R 1 and R 2 represents a hydrogen atom; the other group represents a hydrogen atom, a methyl group or an ethyl group;
  • a 1 or 2j
  • b is 4 or 5;
  • y is an integer from 1 to 10.
  • the present invention also provides a composition characterized in that the composition is composed of two or more compounds of the formula (I) in any ratio.
  • the invention also provides a photoinitiator comprising at least one compound of formula (I).
  • the invention also provides the use of a compound of formula (I) as a photoinitiator.
  • an energy curable liquid composition having the following composition:
  • a polymerizable component comprising at least one ethylenically unsaturated monomer or oligomer; a photoinitiator of the invention.
  • the present invention also provides that the energy-curing liquid composition of the present invention is placed under irradiation, in particular It is a method of preparing a cured polymer under ultraviolet radiation. detailed description
  • the formula of the present invention (the IM compound is represented by G-(A-C0CH 2 0- PBZ) x (PBZ represents phenyldibenzophenone); and (-C0CH 2 0- PBZ) X is The portion of the compound is represented by G-(A-) X and is referred to as the core of the compound.
  • the oxygen atom attached to the phenyl group of the phenylbenzophenone may be attached to any position of the phenyl group.
  • the oxygen atom is attached to the ortho or para position relative to the benzophenone. The difference in the position of the attachment has no substantial effect on the nature of the compound, especially as a photoinitiator.
  • A represents a group of the formula -f 0(0 ⁇ 111 1 )& ⁇ 7 ; more preferably A represents -fOCH 2 C3 ⁇ 43 ⁇ 4r, "fOC3 ⁇ 4CH 2 CH 2 C3 ⁇ 4 or
  • A can also be ⁇ O(CH 2 ) b CO3 ⁇ 4r or
  • X may be greater than or equal to 2
  • a plurality of -A- groups are present in this case, and these groups are independent of each other, that is, they may be the same or different, wherein a
  • the values of b, y may also be the same or different.
  • the core G-(A-) x groups of the compounds of the invention have a significant effect on the properties of the compounds.
  • the G- group contains one or more polyether and/or polyester segments of low degree of polymerization, which makes the compound tend to be liquid and contributes to its Dissolved in the coating formulation.
  • Compounds that are structurally similar but do not contain the above polyether and/or polyester segments are often unusable because they are solid and/or insoluble in the coating composition.
  • the molecular weight of the core G-(A-) x should not be too high, generally not more than 1200, preferably not more than 800, and the excessively high molecular weight makes the photoinitiator content per unit weight too low.
  • G is a residue of ethylene glycol, propylene glycol, butylene glycol, glycerol, trimethylolpropane, bistrihydroxydecylpropane, pentaerythritol or mepentaerythritol.
  • a residue of a polyhydroxy compound or "a residue of an alcohol” means a group remaining after a polyhydroxy compound or one or more hydroxyl groups in an alcohol loses a hydrogen atom.
  • the residue of CH 2 OHCH 2 0H is CH 2 0HCH 2 0- or -0CH 2 CH 2 0-.
  • other functional groups may be contained in addition to the hydroxyl group as long as these functional groups do not substantially adversely affect the synthesis or use of the compound of the present invention.
  • x is less than the number of hydroxyl groups contained in the polyhydroxy compound G, the compound of the present invention contains a free hydroxyl group.
  • esters may be esterified as needed, or when the compounds of the invention are prepared in the presence of an acid.
  • the nature of the ester thus obtained is not particularly limited, but is preferably a lower molecular weight fatty acid ester such as a C 2 - C 6 chain sulphate. Examples of such esters include acetates, propionates, butyrates and valerates.
  • the numbers &, b and y in the above formula may not be integers, since in the preparation of the compounds, when the raw materials used are not In the case of a single compound, the product obtained is a mixture of several compounds of the formula (I).
  • a, b and y are integers for each individual molecule of the product, and a single compound can also be isolated separately, and it will be understood by those skilled in the art that a single material can be used to make a single Compounds, but in practice, a mixture of these compounds is often used.
  • the compounds of the present invention can be prepared by well-known methods for preparing such compounds, and the exact synthetic route and reaction conditions selected will depend on the compound to be prepared.
  • the compound of the present invention can be obtained by benzotylation of o-phenylphenoxyacetic acid represented by formula (II) or p-phenylphenoxyacetic acid represented by formula (( )) (1-1) or (1- 2), which is then prepared by esterification with a core compound of the formula (IV), wherein A, X and G in the core compound are as described above.
  • the X -G (IV) reaction is preferably carried out in the presence of a solvent, and the nature of the solvent is not critical to the invention. The key is located as long as it has no adverse effect on the reagent or reaction.
  • Suitable solvents include: alkanes such as cyclohexane and the like; aromatic hydrocarbons such as benzene, 'nonylbenzene or xylene.
  • an acidic catalyst such as a sulfonic acid (for example with formic acid or methanesulfonic acid), a mineral acid (for example sulfuric acid, hydrochloric acid or polyphosphoric acid) or a Lewis acid (for example boron trifluoride or an organic titanate).
  • a sulfonic acid for example with formic acid or methanesulfonic acid
  • a mineral acid for example sulfuric acid, hydrochloric acid or polyphosphoric acid
  • a Lewis acid for example boron trifluoride or an organic titanate.
  • the reaction temperature can be varied within a relatively wide range depending on the conditions of the reaction and the nature of the reagents and the solvent, as long as the temperature is high enough to remove water generated during the reaction to ensure completion of the reaction. We have found that it is usually most convenient to carry out the reaction at temperatures close to the reflux temperature of the reaction mixture. The time required for the reaction varies widely depending on the reaction temperature. Under the above optimum conditions, it usually takes only 2 to 20 hours to react.
  • reaction After the completion of the reaction, it may be subjected to a post-treatment by a usual method, for example, washing the mixture with water and/or alkali water, drying, and then evaporating the solvent under reduced pressure to give a product.
  • a post-treatment by a usual method, for example, washing the mixture with water and/or alkali water, drying, and then evaporating the solvent under reduced pressure to give a product.
  • the compounds of the invention are particularly suitable for use as photoinitiators, for example as photoinitiators in photocurable varnishes or inks. However, they can also act as photoinitiators in many other energy curable liquid compositions.
  • the energy curable compositions employing the compounds of the present invention typically comprise at least one radiation curable monomer and/or oligomer, a compound of the invention, and optionally a reactive diluent.
  • the composition also includes a colorant, i.e., a pigment.
  • the radiation curable monomer or oligomer is preferably an ethylenically unsaturated compound, typically an acrylate oligomer or an acrylate monomer.
  • Suitable acrylate oligomers include: aliphatic or aromatic acrylate phthalates, polyether acrylates, polyester acrylates and epoxidized propionates (e.g., bisphenol A epoxy acrylate).
  • Suitable acrylate monomers include: hexanediol diacrylate, trimethylolpropane triacrylate, bistrihydroxydecylpropane tetraacrylate, dipentaerythritol pentaacrylate, polyether acrylate (eg ethoxylated) Trimethylolpropane triacrylate, glycerol propoxy triacrylate, ethoxylated pentaerythritol tetraacrylate, and epoxy acrylate (such as USB's Ebcryl 150), and diol diacrylate (for example, tripropylene glycol diacrylate).
  • the energy curable composition of the invention preferably comprises at least one synergist, such as a acrylate or a dimercaptoamino benzoate.
  • the synergist is preferably diterpene aminobenzoate, and in the case of varnish, the synergist is preferably an amino acrylate.
  • Some inks, such as those used in flexographic printing applications, may contain two different types of synergists as described above.
  • the amount of radiation curable monomer or oligomer, photoinitiator, synergist, and optional colorant will vary depending on the type of varnish or ink, the particular equipment used for coating, and the application. In a typical case, however, the photoinitiator plus synergist is present in an amount from 2% to 20% by weight based on the total weight of the composition.
  • the compound of the formula (I) When used as a photoinitiator in a varnish or ink, the compound of the formula (I) usually contains, in addition to the above-mentioned components, a pigment, a wax, a stabilizer and a rheology aid.
  • n represents the degree of polymerization, which can be roughly derived from the molecular weight of the compound, and the values of a plurality of ⁇ in the same structural formula may be different. Comparative example
  • the prepared sodium chloroacetate solution was added dropwise to the above o-phenylphenol sodium solution through a dropping funnel, and the reaction solution was kept refluxed, and the mixture was added dropwise over 4-5 hours, and reflux was continued for 3 hours.
  • the benzoyl chloride I 5 . 5g (0. llmol ) was added dropwise, and the dropping temperature ⁇ ⁇ should be kept at 20 °. C - 30 ° C; after the completion of the dropwise addition, the temperature was raised to between 50 ° C and 55 ° C, and the temperature was kept at this temperature for 6 hours.
  • a gram of a p-toluenesulfonic acid catalyst was placed in a solution of 3-1, 8.7 g (0. 035 raol) of polytetrahydrofuran (average molecular weight of 250) and 0.3 g of p-toluenesulfonic acid catalyst.
  • Azeotropic reflux was carried out for 2 hours in 200 ml of toluene.
  • the reaction solution was washed twice with 50 ml of a 0.1 M aqueous sodium carbonate solution and twice with 50 ml of deionized water.
  • the prepared sodium chloroacetate solution was added dropwise to the above p-phenylphenol sodium solution through a dropping funnel, and the reaction solution was kept refluxed, and the dropwise addition was completed 4 to 5 hours, and the reflux was continued for 3 hours.
  • the dropping rate ⁇ ⁇ should be maintained at a temperature between 20 ° C and -30 ° C; after the addition is completed, the temperature is raised to between 50 ° C and 55 ° C. This temperature was kept at this temperature for 6 hours.
  • the products prepared in the above Examples 3 to 6, 9, and 10, and the comparative examples were used as photoinitiators to prepare corresponding ultraviolet curable varnish preparations, and benzophenone and phenylbenzophenone were also used.
  • the photoinitiator is formulated into a corresponding UV curable varnish formulation.
  • the formulation of the formulation is shown in Table 2.
  • the resulting varnish formulation was applied to a tinplate using a 10 micron bar coater and cured at a speed of 100 meters per minute using a 60 watt/cm medium pressure mercury arc lamp. Record the number of passes under the lamp required to obtain a good surface and complete cure. The results are shown in the table below.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne des composés représentés par la formule (I) et leurs utilisations comme photoinitiateurs. Dans ladite formule, A est O, G est H, x=1; ou G est un résidu d'un composé de polyhydroxy, le nombre de groupes hydroxy dudit composé polyhydroxy étant N, et 2 ≤ N ≤ 6; x est un entier, et 2 ≤ x ≤ N; A représente indépendamment un groupe représenté par la formule -[O(CHR2CHR1)a]y-, -[O(CH2)bCO]y-, ou -[O(CH2)bCO](y-1)-[O(CHR2CHR1)a]-, R1 ou R2 étant hydrogène et l'autre étant hydrogène, méthyle ou éthyle, a étant 1 ou 2, b étant 4 ou 5, et y étant un entier de 1 à 10.
PCT/CN2006/002001 2006-08-08 2006-08-08 Dérivés de phényl benzophénone et utilisations comme photoinitiateurs WO2008019527A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/CN2006/002001 WO2008019527A1 (fr) 2006-08-08 2006-08-08 Dérivés de phényl benzophénone et utilisations comme photoinitiateurs
CNB2007100908219A CN100569731C (zh) 2006-08-08 2007-04-06 苯基二苯甲酮衍生物及其作为光引发剂的用途

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2006/002001 WO2008019527A1 (fr) 2006-08-08 2006-08-08 Dérivés de phényl benzophénone et utilisations comme photoinitiateurs

Publications (1)

Publication Number Publication Date
WO2008019527A1 true WO2008019527A1 (fr) 2008-02-21

Family

ID=39081900

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2006/002001 WO2008019527A1 (fr) 2006-08-08 2006-08-08 Dérivés de phényl benzophénone et utilisations comme photoinitiateurs

Country Status (1)

Country Link
WO (1) WO2008019527A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3929219A1 (fr) * 2020-06-23 2021-12-29 Hubergroup Deutschland GmbH Photo-initiateur polymère à faibles substances extractible et à faible migration pour applications de conditionnement d'aliments

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06263812A (ja) * 1993-03-12 1994-09-20 Toyo Ink Mfg Co Ltd 共重合性光開始剤組成物および光硬化性被覆組成物
US5407971A (en) * 1992-02-10 1995-04-18 Minnesota Mining And Manufacturing Company Radiation crosslinked elastomers
WO1997049664A1 (fr) * 1996-06-21 1997-12-31 Lambson Fine Chemicals Limited Photoamorceurs
CN1599713A (zh) * 2001-10-18 2005-03-23 科茨兄弟公开有限公司 多官能光引发剂

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5407971A (en) * 1992-02-10 1995-04-18 Minnesota Mining And Manufacturing Company Radiation crosslinked elastomers
JPH06263812A (ja) * 1993-03-12 1994-09-20 Toyo Ink Mfg Co Ltd 共重合性光開始剤組成物および光硬化性被覆組成物
WO1997049664A1 (fr) * 1996-06-21 1997-12-31 Lambson Fine Chemicals Limited Photoamorceurs
CN1599713A (zh) * 2001-10-18 2005-03-23 科茨兄弟公开有限公司 多官能光引发剂

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3929219A1 (fr) * 2020-06-23 2021-12-29 Hubergroup Deutschland GmbH Photo-initiateur polymère à faibles substances extractible et à faible migration pour applications de conditionnement d'aliments
WO2021259924A1 (fr) * 2020-06-23 2021-12-30 Hubergroup Deutschland Gmbh Photo-initiateur polymère peu extractible à faible migration pour des applications d'emballage alimentaire

Similar Documents

Publication Publication Date Title
EP1438282B1 (fr) Photo-initiateurs multifonctionnels
JP4777612B2 (ja) 多官能チオキサントン光開始剤
RU2529853C2 (ru) Новые фотоинициаторы
EP1812414B1 (fr) Photoinitiateurs a base de piperazino
CN102212150B (zh) 含助引发剂胺的可聚合硫杂蒽酮光引发剂及其制备方法
EP3316036B1 (fr) Sensibilisateur pour photodurcissement par del uv, son procédé de préparation et son application
ZA200406770B (en) Novel fused ring compounds and their use as cationic photoinitiators
FR2501688A1 (fr) Dialkylthioxanthones, procede de leur preparation, procede de photopolymerisation et composition de resine photopolymerisable utilisant ces composes
JP2013530994A (ja) チオキサントン−４−カルボン酸エステル及び製造方法並びに光開始剤組成物及び応用
JP2019527199A (ja) 新規の３−ケトクマリン、その製法及び光重合反応における光開始剤としてのその使用
ZA200406771B (en) Thioxanthone derivatives and their use as cationic photoinitiators
CN100569731C (zh) 苯基二苯甲酮衍生物及其作为光引发剂的用途
EP2638027B1 (fr) Thioxanthones faiblement extractibles
CN112574110B (zh) 酰基取代吡唑啉硫鎓盐衍生物的制备及其应用
CN110330501A (zh) 长波长香豆素肟酯类化合物及其制备和应用
WO2019101142A1 (fr) Dérivés dibutylfluorène et application de ceux-ci en tant que photo-initiateur
CN102250059A (zh) 含芳叔胺基和二羟基的硫杂蒽酮光引发剂及其制备方法
WO2008019527A1 (fr) Dérivés de phényl benzophénone et utilisations comme photoinitiateurs
TWI745897B (zh) 一種含有醯基哢唑衍生物和哢唑基肟酯的光引發劑組合物及其在光固化組合物中的應用
CN114369179A (zh) 光引发剂组合物、光固化组合物及含有其的产品
CN113444032A (zh) 一种咔唑肟酯化合物、制备方法、组合物及用途
CN102120783B (zh) 含脂肪族叔胺基的硫杂蒽酮光引发剂及其制备方法
WO2016000477A1 (fr) (4-phényl benzoyl)benzoate et son utilisation en tant que photoamorceur
JPS62201859A (ja) 新規なオキシムエステル化合物及びその合成法
CN112441953A (zh) 含二苯硫醚基酮甲酸酯水溶性光聚合引发剂及其制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 06775319

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

NENP Non-entry into the national phase

Ref country code: RU

122 Ep: pct application non-entry in european phase

Ref document number: 06775319

Country of ref document: EP

Kind code of ref document: A1