WO2008098414A1 - Derives de benzophenone polyfonctionnels et utilisations de ces derives en tant que photo-initiateurs - Google Patents

Derives de benzophenone polyfonctionnels et utilisations de ces derives en tant que photo-initiateurs Download PDF

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Publication number
WO2008098414A1
WO2008098414A1 PCT/CN2007/000484 CN2007000484W WO2008098414A1 WO 2008098414 A1 WO2008098414 A1 WO 2008098414A1 CN 2007000484 W CN2007000484 W CN 2007000484W WO 2008098414 A1 WO2008098414 A1 WO 2008098414A1
Authority
WO
WIPO (PCT)
Prior art keywords
compound
formula
composition
benzophenone
photoinitiators
Prior art date
Application number
PCT/CN2007/000484
Other languages
English (en)
Chinese (zh)
Inventor
Peng Luo
Wenchao Zhao
Lili Jiang
Lixiu Yao
Ronghui Hao
Qingjin Yan
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/CN2007/000484 priority Critical patent/WO2008098414A1/fr
Priority to CN2007101299148A priority patent/CN101434543B/zh
Publication of WO2008098414A1 publication Critical patent/WO2008098414A1/fr

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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
    • 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

Definitions

  • This invention relates to a class of benzophenone derivatives. These derivatives are useful as photoinitiators, particularly as photoinitiators in photocurable varnishes, printing inks and the like.
  • the invention also provides a photocurable composition 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. It is increasingly difficult to meet the above requirements with commercially available commercial photoinitiators.
  • benzophenone is still one of the most widely used photoinitiators 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 out of the print and dissolve into the food.
  • the unit weight reactivity of the photoinitiator is extremely important in photocuring. It has been found that if a photoinitiator is less reactive than benzophenone, the amount of initiator can be increased to a limited extent to maintain the cure speed of the formulation. However, after the concentration of the photoinitiator exceeds 10 to 12%, the non-acrylate functional material either exhibits the property of a plasticizer or lowers the crosslinking density of the cured film, resulting in an effect on its mechanical properties.
  • the present invention provides a compound of the formula (I):
  • n 0 or 1 ⁇
  • ⁇ is an integer of G-4, preferably an integer of 0-2;
  • y each independently selected from 1 or 2;
  • 11 2 , 11 3 , 11 4 are each independently selected from 8, - CH 3 or - CH 2 CH 3 , but are not H at the same time.
  • a mixture of compounds conforming to the formula (I) is often used in practice. Accordingly, the present invention also provides a composition characterized in that the composition contains two or more compounds of the formula (I).
  • the invention also provides the use of a compound of formula (I) as a photoinitiator.
  • a photocurable liquid composition comprising the following components:
  • a polymerizable component comprising at least one ethylenically unsaturated monomer or oligomer; a compound of the formula (I) of the present invention or the above composition containing the compound of the formula (I).
  • the present invention also provides a process for preparing a cured polymer by subjecting the photocurable liquid composition of the present invention to light radiation, such as ultraviolet light.
  • the compound of the formula (I) of the present invention overcomes the drawbacks of benzophenone and other existing photoinitiators, has an extremely low odor, has high solubility in an ultraviolet light-curing formulation composition, and has a low tendency to migrate and be dissolved by an external medium. advantage. Moreover, its unit weight reactivity is almost equivalent to benzophenone itself. In most cases, its reactivity is higher than the commonly used benzophenone substitutes. detailed description
  • the oxygen atom attached to the phenyl group of the benzophenone may be bonded to any position of the phenyl group.
  • the oxygen atom is bonded to the ortho or para position relative to the carbonyl group. The difference in the position of the attachment has no substantial effect on the properties of the compounds of the invention, especially as the nature of the photoinitiator.
  • R 3 is a branched chain Preferred is 2-mercapto-1, 3-propanediol, 2,2-dimethyl
  • a residue of -1,3-propanediol (neopentyl glycol), 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, preferably m and n Both are 0, y is 1 , is -01 3 , R 2 is H or a CH 3 ; or m, n and y are 1, ! ⁇ and R 3 are - CH 2 CH 3 , R 2 and R 4 are H; or m and n are both 0, y is 2, and -( 11 3 , R 2 is H.
  • residue of alcohol refers to a group remaining after the alcohol loses its hydroxyl group.
  • residue of neopentyl glycol is H 3 C ⁇ 3 .
  • the compounds of the present invention can be prepared by a conventional method for preparing an ester compound, and the specific synthesis route and reaction conditions selected depend on the compound to be produced.
  • the compound of the present invention can be obtained by a compound of the formula ( ⁇ ⁇ ) or formula ( ⁇ ⁇ )
  • the reaction is preferably carried out in the presence of a solvent.
  • a solvent The nature of the solvent is not critical to the invention as long as it does not adversely affect the reagent or reaction.
  • Suitable solvents include: alkanes such as cyclohexane, etc.; aromatic hydrocarbons such as benzene, toluene or dinonylbenzene.
  • the reaction is preferably carried out in an acidic catalyst such as a sulfonic acid (for example p-toluenesulfonic acid or sulfonic acid), a mineral acid (for example, acid, hydrochloric acid or polyphosphoric acid) or a Lewis acid (for example boron trifluoride or organic titanate).
  • an acidic catalyst such as a sulfonic acid (for example p-toluenesulfonic acid or sulfonic acid), a mineral acid (for example, acid, hydrochloric acid or polyphosphoric acid) or a Lewis acid (for example boron trifluoride or organic titanate).
  • a sulfonic acid for example p-toluenesulfonic acid or sulfonic acid
  • a mineral acid for example, acid, hydrochloric acid or polyphosphoric acid
  • a Lewis acid for example boron trifluoride or 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, thereby ensuring completion of the reaction.
  • the time required for the reaction can also vary over a considerable range, depending mainly on the reaction temperature. Under the above preferred conditions, usually only need to react 2 to 20 hours.
  • 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 solid product can be crystallized from a suitable solvent.
  • the compounds of the invention are particularly suitable for use as photoinitiators.
  • a compound of the invention or a mixture of two or more of the compounds of the invention may be used alone in a photocurable varnish or ink. In addition, they can be used in many other photocurable liquid compositions.
  • the photocurable liquid composition employing the compound of the present invention typically comprises at least one ethylenically unsaturated monomer and/or oligomer and a compound of formula (I) according to the invention, and may optionally further comprise 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 olefin oligomer or an acrylate monomer.
  • Suitable acrylate oligomers include: aliphatic or aromatic acrylic acid amino phthalates, polyether acrylates, polyester acrylates and epoxy acrylates (e.g., outer bismuth 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 Cytec's Ebcryl 150), and diol diacrylate (for example, tripropylene glycol diacrylate).
  • the photocurable composition of the present invention preferably contains at least one synergist such as an amino acrylate or a dimethylamino benzoate.
  • the synergist is preferably dimethylaminobenzoate.
  • the synergist is preferably an amino acrylate.
  • photocurable monomer or oligomer The amount of photocurable 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 use, which is the skill in the art. Well known to the person, or can be determined by simple experimentation according to the specific application. Usually the photoinitiator is used in an amount of from 2 to 20% by weight based on the total weight of the composition.
  • a pigment, a wax, a stabilizer, a rheology aid and the like are usually contained.
  • the invention is further illustrated by the following non-limiting examples.
  • the sources of the raw material compounds used in the following examples are shown in Table 1.
  • UV-curable varnish formulations 1-7 were prepared according to the following Table 3.
  • Epoxy acrylate oligomer (6210G, Changxing) 25
  • the resulting varnish formulation 1-7 was applied to a tinplate using a 10 micron bar coater and cured at a speed of 100 m/min 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 maximum odor is 5 and the minimum is 1. The yellowness is measured by the SC-80C automatic color difference meter. The results are shown in Table 4.

Abstract

L'invention concerne des composés de formule (I) et des compositions contenant au moins deux de ces composés. Dans la formule (I) : m représente 0 ou 1; n représente un entier compris entre 0 et 4; y représente indépendamment 1 ou 2; R1, R2, R3, R4 représentent indépendamment H?-CH3 ou -CH2CH3, à condition que R1, R2, R3, R4 ne représentent pas tous H. Les composés ou compositions selon l'invention peuvent être utilisés en tant que photo-initiateurs dans une composition liquide photodurcissable.
PCT/CN2007/000484 2007-02-12 2007-02-12 Derives de benzophenone polyfonctionnels et utilisations de ces derives en tant que photo-initiateurs WO2008098414A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/CN2007/000484 WO2008098414A1 (fr) 2007-02-12 2007-02-12 Derives de benzophenone polyfonctionnels et utilisations de ces derives en tant que photo-initiateurs
CN2007101299148A CN101434543B (zh) 2007-02-12 2007-07-20 多官能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/CN2007/000484 WO2008098414A1 (fr) 2007-02-12 2007-02-12 Derives de benzophenone polyfonctionnels et utilisations de ces derives en tant que photo-initiateurs

Publications (1)

Publication Number Publication Date
WO2008098414A1 true WO2008098414A1 (fr) 2008-08-21

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102811999A (zh) * 2011-10-24 2012-12-05 北京英力科技发展有限公司 二苯甲酮类大分子光引发剂

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
CN102811999A (zh) * 2011-10-24 2012-12-05 北京英力科技发展有限公司 二苯甲酮类大分子光引发剂
WO2013059975A1 (fr) * 2011-10-24 2013-05-02 北京英力科技发展有限公司 Photoinitiateur macromoléculaire à base de benzophénone

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