CN1634865A - Photosensitive quaternary ammonium salt and its preparation method and use - Google Patents
Photosensitive quaternary ammonium salt and its preparation method and use Download PDFInfo
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- CN1634865A CN1634865A CN 200410052045 CN200410052045A CN1634865A CN 1634865 A CN1634865 A CN 1634865A CN 200410052045 CN200410052045 CN 200410052045 CN 200410052045 A CN200410052045 A CN 200410052045A CN 1634865 A CN1634865 A CN 1634865A
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- ammonium salt
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- 150000003242 quaternary ammonium salts Chemical class 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 28
- 239000011248 coating agent Substances 0.000 claims abstract description 26
- 239000000853 adhesive Substances 0.000 claims abstract description 7
- 230000001070 adhesive effect Effects 0.000 claims abstract description 7
- -1 ammonium salt compound Chemical class 0.000 claims description 44
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims description 10
- 230000032050 esterification Effects 0.000 claims description 10
- 238000005886 esterification reaction Methods 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 9
- 239000004593 Epoxy Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 5
- 229950004394 ditiocarb Drugs 0.000 claims description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 claims description 3
- MZGNSEAPZQGJRB-UHFFFAOYSA-N dimethyldithiocarbamic acid Chemical compound CN(C)C(S)=S MZGNSEAPZQGJRB-UHFFFAOYSA-N 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 claims description 3
- WIHIUTUAHOZVLE-UHFFFAOYSA-N 1,3-diethoxypropan-2-ol Chemical compound CCOCC(O)COCC WIHIUTUAHOZVLE-UHFFFAOYSA-N 0.000 claims description 2
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 claims description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical class CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- XAKBSHICSHRJCL-UHFFFAOYSA-N [CH2]C(=O)C1=CC=CC=C1 Chemical group [CH2]C(=O)C1=CC=CC=C1 XAKBSHICSHRJCL-UHFFFAOYSA-N 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 2
- 229940073608 benzyl chloride Drugs 0.000 claims description 2
- DBDNZCBRIPTLJF-UHFFFAOYSA-N boron(1-) monohydride Chemical compound [BH-] DBDNZCBRIPTLJF-UHFFFAOYSA-N 0.000 claims description 2
- 125000006278 bromobenzyl group Chemical group 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
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- 238000010534 nucleophilic substitution reaction Methods 0.000 abstract description 2
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 150000003863 ammonium salts Chemical class 0.000 description 6
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- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
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- 150000001768 cations Chemical class 0.000 description 4
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- 229910021641 deionized water Inorganic materials 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 239000003504 photosensitizing agent Substances 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
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- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 3
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- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 2
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- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
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- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
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- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 2
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- PUGOMSLRUSTQGV-UHFFFAOYSA-N 2,3-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical compound C=CC(=O)OCC(OC(=O)C=C)COC(=O)C=C PUGOMSLRUSTQGV-UHFFFAOYSA-N 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- QXIQCNFSNJEMOD-UHFFFAOYSA-N 3-hydroxybutan-2-yl prop-2-enoate Chemical compound CC(O)C(C)OC(=O)C=C QXIQCNFSNJEMOD-UHFFFAOYSA-N 0.000 description 1
- QDALVWNPOLSBSK-UHFFFAOYSA-N 4-ethyl-3-phenylmorpholine Chemical compound CCN1CCOCC1C1=CC=CC=C1 QDALVWNPOLSBSK-UHFFFAOYSA-N 0.000 description 1
- OIYANYVIFQBNMS-UHFFFAOYSA-N 4-methyl-3-phenylmorpholine Chemical compound CN1CCOCC1C1=CC=CC=C1 OIYANYVIFQBNMS-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
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- 239000002202 Polyethylene glycol Substances 0.000 description 1
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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- 125000000129 anionic group Chemical group 0.000 description 1
- 150000008365 aromatic ketones Chemical group 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Epoxy Resins (AREA)
- Materials For Photolithography (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to double-effect photoactive quaternary ammonium salt used as photo-amine generator and free radical photoinitiator and its preparation method and their use as photo-amine generator and free radical photoinitiator, especially the photoinitiator used in photo-cured coating, photo-cured oil, photo-cured adhesive, and photoresist. In the invention, dialkylamino-aryl-one used as raw material reacts with alkyl halide or sulfuric ester for preparing photoactive quaternary ammonium salt by nucleophilic substitution.
Description
Technical field
The present invention relates to a class and be light amine-producing agent is again photosensitive quaternary ammonium salt of economic benefits and social benefits of free radical photo-initiation and preparation method thereof, and they are as the purposes of light trigger and Photobase generator, the light trigger in photo-cured coating, light-curable ink, curable adhesive and the photo-resist etc.
Background technology
Along with the enhancing day by day of environmental protection consciousness, national governments are severe day by day to the solvent evaporates control of Chemicals such as coating, printing ink.Therefore, the low solvent evaporates of research and development, oligosaprobic coating, printing ink become the inexorable trend of industry development energetically.In the world, powder coating, photo-cured coating and water-borne coatings have eco-friendly characteristics because of its lower solvent evaporates, so be called the dominant direction of current coating development.This wherein, ultraviolet-curing paint is to outshine othersOne branch of the tree is particularly thriving, except having eco-friendly characteristics, also has the advantage that energy consumption is low, curing is rapid, coating efficiency is high, abroad from the sixties in last century with its commercialization since, go through repeatedly technological change, develop very rapid, in recent years, the output of global photocuring product and output value every year are all with double-digit rate increase.
Ultraviolet light polymerization is meant that under the effect of UV-light the photoactive substance generation photochemical reaction in the system produces biologically active fragment, and reactive monomer or functionalized oligopolymer generation polymerization crosslinking are transformed into solid-state insoluble coating by liquid coating rapidly in the initiator system.It has do not contain organic solvent, environmental pollution is little, curing speed is fast, save the energy, the cured product performance is good, be suitable for high-speed automated production line and to advantages such as heat sensitive base material applications, therefore obtained at aspects such as coating, tackiness agent, printing-ink, photo-resists using widely.
Although photo-cured coating with respect to traditional solvent based coating, has been huge advance made aspect environment protection, all coating all components can both participate in crosslinked film forming in principle, do not have the solvent evaporates problem.But photo-cured coating is when ultraviolet light irradiation, crosslinking curing is quite fast, often just finish surface drying and absolutely dry within several seconds, must there be part propylene acid esters monomer not have enough time to participate in polymerization crosslinking in the coating system, rete just has been transformed into harder vitreous state, hinder the monomeric crosslinking polymerization of residual acrylic acid ester, residual monomer slowly migrates to the surface in cured film, cause hygienic safety hidden danger, this also is that present photo-cured coating, printing ink should not be used in the key reason on food, medicine, the toilet article packaging.At this problem, photo-cured coating, the printing ink of Water-borne modification are developed, this technology as thinner, has been exempted a large amount of small molecule active thinners that use in the traditional oils photo-curing coating with water, only contains resin, water, light trigger and a little auxiliary in the prescription.The light trigger of waterborne radiation curable coating, printing ink becomes a bottleneck of this technology, though Britain Great Lake company has released a series of water miscible light triggers, but all be the derived products of benzophenone and thioxanthone, belong to hydrogen-capture-type light initiator, light-initiated efficient own is not very high, and the hydrophilic light trigger of highly active cracking type relatively is short of.
According to the difference of initiator system, photocuring can be divided into radical photoinitiator curing system and cation photocuring system.Radical photoinitiator curing is good at soon with reaction, can guarantee higher working (machining) efficiency.Shrink seriously problems such as precision is not high, poor adhesive force but also have.Cationic curing system development is later, and it has, and volumetric shrinkage is little, strong adhesion, wear-resisting, hardness advantages of higher.Being specially adapted to needs the making of high-precision high-density printing electronic circuit, protection and rapid laser-shaping technique (stereolithography) and needs aspects such as strong adhesion, attrition resistant CD and fibre coating.But it also have curing speed slow, be subject to moisture inhibition, oligopolymer and the reactive thinner kind is few, cost is high, the cured product performance is difficult for shortcomings such as adjusting, thereby has limited its practical application.In addition, cation photocuring is based on the cation light initiator photodissociation and produces superpower protonic acid, and it is crosslinked to cause the epoxide group ring-opening polymerization.Even after curing is finished, still contain a large amount of protonic acids in the curing system, the long-term behaviour that not only endangers cured layer is also with base materials such as corroding metals.In view of this, people have studied photodissociation and have produced amine reagent, in the hope of by light-operated generation reactive amines, pass through later stage thermal treatment again, and the reactive amines catalysis that impels photodissociation to produce causes cross linking of epoxy resin and solidifies.Early stage ketoxime ester light amine-producing agent generally has lower light and produces amine efficient; the quaternary Photobase generator of the just grand research and development of Neckers and ridge, angle is based on aromatic ketone structure and α-quaternary ammonium group acetylize structures such as benzophenone; light product alkali efficient is not high, synthetic raw materials used difficult acquisition, practicability difficulty.And all only in epoxy-resin systems, use, do not attempt its pair curing performance.
Summary of the invention
The purpose of this invention is to provide photosensitive quaternary ammonium salt of a class and preparation method thereof, and they are as the purposes of the light trigger of photo-cured coating, light-curable ink, curable adhesive and photo-resist etc.Such photosensitive quaternary ammonium salt is the alkylaryl ketone derivatives that aromatic ring has the quaternary ammonium-substituted group, they have the dual-use function of free radical photo-initiation (comprising water-soluble light trigger) and light product alkali concurrently, and the radical photoinitiator light-initiated amine crosslinked and epoxy-resin systems that can be used for the acrylic acid oligomer system simultaneously solidifies.
The structure of photosensitive quaternary ammonium salt of the present invention is as the formula (1):
Formula (1)
In the formula (1):
R
1And R
2Be methyl, ethyl, sec.-propyl, normal-butyl, isobutyl-, benzyl, alkyl benzyl, alkoxy benzyl or halogeno-benzyl; R
1And R
2Identical or different, perhaps R
1And R
2Merge into-CH
2CH
2CH
2CH
2CH
2-;
R
3Be C
1～C
12Alkyl, hydroxyl, dimethylamino, diethylin, two hydroxyethylaminos, two hydroxypropyl amino, N-hydroxyethyl methylamino, N-hydroxyethyl ethylamino, two n-butyl amine bases, N-morpholinyl, N-Pyrrolidine base or N-hexahydropyridine base;
R
4, R
5And R
6Be C
1～C
12Alkyl, 2-hydroxyethyl, 2-hydroxypropyl, benzyl or phenacyl, R
4, R
5And R
6The three is identical or different, perhaps R
4And R
5Merge into-CH
2CH
2CH
2CH
2-,-CH
2CH
2CH
2CH
2CH
2-or-CH
2CH
2OCH
2CH
2-;
X
-For with quaternary ammonium cation paired negatively charged ion, have stronger being inclined to electronics, the two forms quaternary ammonium salt jointly, and negatively charged ion comprises tetraphenyl boron anion, triphenyl normal-butyl boron anion, N, N-dimethyl dithiocarbamic acid radical ion or N, N-diethyldithiocar bamic acid radical ion.
The photosensitive quaternary ammonium salt of the invention described above can prepare by the following method: structure amino arone as the formula (2) is dissolved in the organic solvent, and hierarchy of control temperature is at 50 ℃ to 180 ℃, and the excessive N-alkylating reagent of agitation and dropping is (in order to introduce radicals R
6), reacted 1～10 hour, concentrate, crystallization separates the photosensitive quaternary ammonium salt intermediate that must have quaternary ammonium-substituted aryl alkyl ketone structure; With the photosensitive quaternary ammonium salt intermediate of gained and sodium tetraphenylborate, triphenyl normal-butyl boron quaternary ammonium salt, N, N-dimethyl dithiocarbamate or N, the N-N,N-Diethyldithiocarbamic Acid carries out anionresin, further purify, make quaternary ammonium salt have the pairing negatively charged ion that is inclined to electronics, promptly obtain the photosensitive quaternary ammonium salt of target as the formula (1); Described N-alkylating reagent is ethylene bromohyrin, ethylene chlorhydrin, methyl-sulfate, ethyl sulfate, benzyl chloride, bromobenzyl, alpha-brominated methyl phenyl ketone or alpha-brominated myrceane; R in the formula (2)
1～R
5Definition identical with formula (1);
The amino arone of formula (2)
Organic solvent described in the aforesaid method is ethyl acetate, ethanol or Virahol etc., and consumption is generally the amino arone substrate organic solvent 80～200ml of every 1mol.The consumption of described N-alkylating reagent is the amino arone substrate of every 1mol N-alkylating reagent 1.0～2.0mol.
Aforesaid method of the present invention is a starting raw material with aminoaryl ketone, and with alkylating reagent effects such as haloalkane or sulfuric esters, nucleo philic substitution reaction is introduced R on nitrogen-atoms under mild conditions
6Group obtains photosensitive quaternary ammonium salt intermediate.Although synthetic substrate may have two tertiary amine nitrogen atoms, promptly on the alkylaryl ketone structure, a tertiary amine groups is connected on the aromatic ring, and another is connected on the alpha-carbon atom of fatty group one side.But the latter is because two high steric hindrance substituting group (R of alpha-position
1And R
2The alkylating tendency of N-takes place much smaller than the aromatic ring substituted-amino in influence group), so quaterisation occurs on the aromatic ring amino, forms product structure as the formula (1).
Photosensitive quaternary ammonium salt of the present invention has the dual-use function of free radical photo-initiation (comprising water-soluble light trigger) and light product alkali concurrently, above-mentioned photosensitive quaternary ammonium salt is scattered in acrylate diluting monomer and the acroleic acid esterification oligomer mixture, form the radical photoinitiator curing system, film, ultraviolet light irradiation promptly forms the crosslinking curing film in the short period of time.Or above-mentioned photosensitive quaternary ammonium salt is scattered in the higher cycloaliphatic epoxy resin of polymerization activity, film, the quaternary ammonium salt photodissociation produced tertiary amine, catalysis Resins, epoxy generation crosslinking curing to several minutes the irradiation several seconds under medium pressure mercury lamp.Suitable aliphatic epoxy resin is mainly 3,4-epoxy group(ing) heptanaphthenic acid-3, and 4-epoxy group(ing) hexamethylene methyl esters, bisphenol A epoxide resin is not suitable for cooperating with the photosensitive quaternary ammonium salt of the present invention because the polymerization crosslinking activity is too low.But, quaternary ammonium salt of the present invention both photodissociation causes radical polymerization in view of producing living radical, but photodissociation produces active tertiary amine again, promote that epoxy resin cure is crosslinked, therefore, can be applied in the compound system of acrylate monomer (or acroleic acid esterification oligopolymer) and Resins, epoxy ultraviolet light irradiation, quaternary ammonium salt photodissociation, difference is initiating methacrylates group and epoxide group crosslinking polymerization simultaneously, forms the inierpeneirating network structure of the easier adjusting of film properties.
But the photodissociation of quaternary ammonium salt alkyl ketone structure division produces living radical, can be in order to the crosslinking polymerization of initiating methacrylates monomer and acroleic acid esterification resin.At acrylate monomer be photo-cured coating, the esters of acrylic acid reactive thinner that light-curable ink and curable adhesive field are common, comprise (methyl) senecioate-hydroxyl ethyl ester (HEMA, HEA), (methyl) Propylene glycol monoacrylate, (methyl) vinylformic acid methoxy ethyl ester, (methyl) vinylformic acid ethoxy ethyl ester, 1,6-hexanediyl ester (HDDA), triethylene glycol diacrylate (TPGDA), Viscoat 295 (TMPTA), neopentylglycol diacrylate (NPGDA), propoxylated glycerol triacrylate (GPTA), polyethyleneglycol diacrylate (PEGDA), and ethoxylation and propenoxylated HDDA, TPGDA, TMPTA, NPGDA etc.Consider that from the solvability of photosensitizers ammonium salt the polyfunctional acrylic ester thinner of the HEMA of hydroxyl, HEA, (methyl) vinylformic acid tetrahydrofurfuryl alcohol ester and many ethoxylations is better to the quaternary ammonium salt solvability, favourable to the efficient that improves the photosensitizers ammonium salt.
Can mainly be meant that (bisphenol A type epoxy resin comprises their amine modification with the product of vinylformic acid esterification by ring opening for the Epocryl of various viscosity with the acroleic acid esterification oligopolymer of photosensitizers ammonium salt effect, the organic acid anhydride modification, the ether modification, the derived products of longer chain fatty acid modification), polyurethane acrylate resin (comprises polyether polyurethane-acrylate, the PAUR acrylate, the urethane acrylate of side chain bifunctional, the urethane polyfunctional acrylic ester of branching, aqurous ployurethane acrylate with side chain carboxyl group negative ion, urethane acrylate with polyoxyethylene segment), polyester acrylate resin (comprising the water-soluble polyester acrylate that has the carboxyl negative ion), polyether acrylate, has the acrylate copolymer of pendant acrylate groups etc.The different acrylate group of functionality is all arranged on these molecular resins, and in order to accept the living radical attack, it is crosslinked that radical polymerization takes place.The oligopolymer that viscosity is bigger need reduce viscosity with aforementioned acrylate reactive thinner.And oligopolymer is scarcely desirable to the solvability of photosensitizers ammonium salt, needs high polar monomer to assist dissolving to disperse.Photosensitive quaternary ammonium salt has the performance of water-soluble light trigger, can directly be dispersed in the aqueous dispersion of photocuring oligopolymer, forms the aqueous photo-curing system, is used for the basic components of photocuring water-borne coatings and photocuring water color ink.
Directly alkylation gained quaternary ammonium salt pairing negatively charged ion is halogen ion, sulfuric acid mono alkyl ester ion etc., though these quaternary ammonium salts have certain light-initiated activity, but the negatively charged ion electron donation a little less than, when doing the time spent with the electron deficiency quaternary ammonium salt of photoexcited state, be difficult to take place transfer transport, the probability that produces active tertiary amine through cracking is too low, and it is undesirable that light produces basic active.With these quaternary ammonium salts in solution with sodium tetraphenylborate (or ammonium salt), triphenyl normal-butyl boron sodium (or ammonium salt), N, N-dimethyl dithiocarbamate, N, N-N,N-Diethyldithiocarbamic Acid etc. carries out anionresin, in suitable solvent, be precipitated out voluntarily, obtain to have to be inclined to anionic photosensitive quaternary ammonium salt to electronics.This class quaternary ammonium salt removes has the photodestruciton reaction that the alkyl ketone structure takes place, outside the generation living radical, the aryl quaternary ammonium salt structure issues third contact of a total solar or lunar eclipse cracking for the effect of electronics negatively charged ion, produce living radical and tertiary amine, the former can cause radical polymerization equally, but the active epoxide group generation of latter's catalysis crosslinking reaction guarantees that quaternary ammonium salt of the present invention has free radical photo-initiation and Photobase generator double properties concurrently.Suitable Resins, epoxy is meant the resin of alicyclic class formation, as commercially available 3,4-epoxy group(ing) heptanaphthenic acid-3,4-epoxy group(ing) hexamethylene methyl esters (CY179 of Uvacure 1500 of UCB. S.A. (BE) Bruxelles Belgium and vapour Bagong department etc.) and contain 3, this property resin of other of 4-epoxycyclohexyl structure.
Photosensitive quarternary ammonium salt compound of the present invention can be used as light trigger and Photobase generator, is specially adapted to photo-cured coating, light-curable ink, curable adhesive or photo-resist based on acrylate monomer, acroleic acid esterification oligopolymer and alicyclic epoxy.
Photosensitive quarternary ammonium salt compound of the present invention is generally 0.1～10%wt as light trigger proportion in acrylatcs systems, is preferably 1～5%wt.
Photosensitive quarternary ammonium salt compound of the present invention is generally 1～5%wt as the light trigger Photobase generator proportion in acroleic acid esterification oligopolymer and Resins, epoxy mixed system of holding concurrently.
Photosensitive quaternary ammonium salt of the present invention is mixed by a certain percentage with (methyl) acrylate monomer of before chatting and/or acroleic acid esterification oligopolymer, film, utilize wavelength region to be 254nm～365nm under air ambient, intensity is greater than 10mW/cm
2Ultraviolet light irradiation 0.5～120 second, photosensitive quaternary ammonium salt photodissociation produces living radical, and causes (methyl) acrylate group polymerization crosslinking, forms the insoluble cured film.Photosensitive quaternary ammonium salt proportion in prescription is 0.1～10%, and particularly when photosensitive quaternary ammonium salt when proportion is 1～5% in monomer and/or oligopolymer mixed system, acrylate-based photopolymerization transformation efficiency can reach more than 40%, and the photocuring effect is comparatively desirable.
Photosensitive quaternary ammonium salt of the present invention is mixed by a certain percentage with the aliphatic epoxy resin of high reaction activity, film, utilize wavelength region to be 254nm～365nm under air ambient, intensity is greater than 10mW/cm
2Ultraviolet light irradiation 2～300 seconds, photosensitive quaternary ammonium salt photodissociation produces tertiary amine, the ring-opening polymerization of catalysis epoxide group forms the insoluble cured film.Because industrial medium pressure mercury lamp power reaches thousands of watts, thermal discharge is bigger, as long-time stop, and can be at 180 ℃ of high temperature of the highest generation of irradiation table top.The reactive amines that this heat condition can promote photodissociation to produce acts on epoxide group, and it is crosslinked to quicken the epoxy ring-opening polymerization.Photosensitive quaternary ammonium salt proportion in prescription is 0.1～10%, and particularly when photosensitive quaternary ammonium salt when proportion is 1～5% in monomer and/or oligopolymer mixed system, the photocuring effect is comparatively desirable, forms the insoluble cured film.
Photosensitive quaternary ammonium salt of the present invention is scattered in the compound system of (methyl) acrylate monomer, acroleic acid esterification oligopolymer and cycloaliphatic epoxy resin, film, under above-mentioned uv irradiation condition, can form the state that acrylate radical polymerization cross-linked network and cross linking of epoxy resin network are interweaved, promptly form inierpeneirating network structure, help improving, regulating the over-all properties of photocuring film.
Embodiment
Embodiment one:
The preparation of photosensitive quaternary ammonium salt: benzyl-(Irgacure 369 for 2-dimethylamino-1-(morpholinyl phenyl)-butanone-1 to add 0.04mol 2-in the there-necked flask that magnetic stirring apparatus, reflux condensing tube (band drying tube), thermometer and dropping funnel are housed, vapour Bagong department) and the vinyl acetic monomer crossed of 50ml drying treatment, be heated to the substrate dissolving, stir and slowly drip the dry neutral methyl-sulfate 6.51g (0.05mol that heavily steams down, pH=6), the backflow stirring reaction is 6 hours.After reaction finishes, remove with Rotary Evaporators and to desolvate, thick thick product N-(2-(N ', N '-dimethylamino)-2-benzyl-positive butyryl) phenyl-N-methylmorpholine methyl sulfate quaternary ammonium salt, product is soluble in water.Reaction equation as the formula (3).
Formula (3)
Embodiment two:
Anionresin: in the single port flask of agitator and constant pressure funnel is housed, add 2.58g embodiment synthetic quaternary ammonium salt intermediate and 50ml deionized water, stir the sodium tetraphenylborate aqueous solution 60ml that drips 3.8% percentage concentration down, about altogether 0.007mol sodium tetraphenylborate.Form white precipitate in the dropping process gradually, after dropwising, add the 50ml deionized water, fully stir, suction filtration is with the mixed solvent drip washing of small amount of acetone and water (V/V 1: 1).Drying, buff powder, be N-(2-(N ', N '-dimethylamino)-2-benzyl-positive butyryl) phenyl-N-methylmorpholine tetraphenyl boron quaternary ammonium salt through structure determination, be soluble in acetone, acetonitrile, be insoluble in water, ethanol and ether.245～146 ℃ of fusing points, 117～119 ℃ of substrate Irgacure 369 fusing points.Reaction as the formula (4).
Formula (4)
Embodiment three:
Benzyl-(Irgacure 369 for 2-dimethylamino-1-(morpholinyl phenyl)-butanone-1 to add 0.04mol 2-in the there-necked flask that magnetic stirring apparatus, reflux condensing tube (band drying tube), thermometer and dropping funnel are housed, vapour Bagong department) and the vinyl acetic monomer crossed of 50ml drying treatment, be heated to the substrate dissolving, stir and slowly drip the dry neutral ethyl sulfate 7.7g (0.05mol that heavily steams down, pH=6), the backflow stirring reaction is 6 hours.After reaction finishes, remove with Rotary Evaporators and to desolvate, thick thick product N-(2-(N ', N '-dimethylamino)-2-benzyl-positive butyryl) phenyl-N-ethylmorpholine Ethyl Sulfate quaternary ammonium salt, product is soluble in water.Reaction equation as the formula (5).
Formula (5)
Embodiment four:
Anionresin: in the single port flask of agitator and constant pressure funnel is housed, add 2.58g embodiment three synthetic quaternary ammonium salts intermediate and 50ml deionized water, stir the sodium tetraphenylborate aqueous solution 60ml that drips 3.8% percentage concentration down, about altogether 0.007mol sodium tetraphenylborate.Form white precipitate in the dropping process gradually, after dropwising, add the 50ml deionized water, fully stir, suction filtration is with the mixed solvent drip washing of small amount of acetone and water (V/V 1: 1).Drying, buff powder, be N-(2-(N ', N '-dimethylamino)-2-benzyl-positive butyryl) phenyl-N-ethylmorpholine tetraphenyl boron quaternary ammonium salt through structure determination, be soluble in acetone, acetonitrile, be insoluble in water, ethanol and ether.156～158 ℃ of fusing points.Reaction as the formula (6).
Formula (6)
Embodiment five:
The photosensitive quaternary ammonium salt of embodiment two gained is scattered in acrylate monomer and the epoxy acrylate oligomer mixed system, quaternary ammonium salt, HEMA, propylene oxide acid oligomer CN124 (Sartomer company) ratio are respectively 2%, 50%, 50%, film, under 2 * 1000W medium pressure mercury lamp, irradiation in air ambient, irradiation table top central light strength 57mW/cm
2(320～400nm scope), crawler belt walking speed 20m/min.The solidified coating performance sees Table 1.
Acrylic ester photocuring film essential property under the effect of table 1 tetraphenylboron quaternary ammonium salt
Initiator thickness (μ m) sticking power (level) snappiness (mm) pencil hardness shock strength
Irgacure?369 10 2 1 3H 50
Tetraphenylboron quaternary ammonium salt 10 21 4H 50
Embodiment six:
(UVacure 1592 with the photosensitive quaternary ammonium salt of embodiment two and commercially available sulfonium salt photoinitiator initiator, UCB. S.A. (BE) Bruxelles Belgium) is dispersed among the alicyclic epoxy oligopolymer Uvacure 1500 (UCB. S.A. (BE) Bruxelles Belgium) by 2.0% consumption respectively, on silicon chip, film, with the efficient medium pressure mercury lamp of 125W Philips irradiation 3min under air ambient, characterize with infrared absorption spectrum, the epoxide polymerization transformation efficiency that the tetraphenylboron quaternary ammonium salt causes is 70%, and the epoxide polymerization transformation efficiency that the sulfosalt cation light initiator causes is 55%.
Claims (9)
1. a class photosensitive quarternary ammonium salt compound as the formula (1):
Formula (1)
In the formula (1):
R
1And R
2Be methyl, ethyl, propyl group or benzyl; R
1And R
2Identical or different, perhaps R
1And R
2Merge into-H
2CH
2CH
2CH
2CH
2-;
R
3Be hydroxyl, dimethylamino, diethylin, two hydroxyethylaminos or N-morpholinyl;
R
4, R
5And R
6Be C
1～C
12Alkyl, 2-hydroxyethyl, benzyl or phenacyl, R
4, R
5And R
6Identical or different, perhaps R
4And R
5Merge into-CH
2CH
2CH
2CH
2CH
2-or-CH
2CH
2OCH
2CH
2-;
X-is tetraphenyl boron anion, triphenyl normal-butyl boron anion, N, N-dimethyl dithiocarbamic acid radical ion or N, N-diethyldithiocar bamic acid radical ion.
2. the preparation method of the described photosensitive quarternary ammonium salt compound of claim 1, amino arone as the formula (2) is dissolved in the organic solvent, hierarchy of control temperature is at 50 ℃ to 180 ℃, the excessive N-alkylating reagent of agitation and dropping, reacted 1～10 hour, and concentrated crystallization, separate, get photosensitive quaternary ammonium salt intermediate; With the photosensitive quaternary ammonium salt intermediate of gained and sodium tetraphenylborate, triphenyl normal-butyl boron tetrabutyl quaternary ammonium salt, N, N-dimethyl dithiocarbamate or N, the N-N,N-Diethyldithiocarbamic Acid carries out anionresin, further purify, make quaternary ammonium salt have the pairing negatively charged ion that is inclined to electronics, promptly obtain required photosensitive quaternary ammonium salt; Described organic solvent is ethyl acetate, ethanol or Virahol; Described N-alkylating reagent is ethylene bromohyrin, ethylene chlorhydrin, methyl-sulfate, ethyl sulfate, benzyl chloride, bromobenzyl, alpha-brominated methyl phenyl ketone or alpha-brominated myrceane; R in the formula (2)
1～R
5Definition identical with the formula (1) of claim 1;
Formula (2)
3. in accordance with the method for claim 2, the consumption that it is characterized in that described organic solvent is the amino arone substrate of every 1mol with organic solvent 80～200ml.
4. according to claim 2 or 3 described methods, the consumption that it is characterized in that described N-alkylating reagent is the amino arone substrate of every 1mol N-alkylating reagent 1.0～2.0mol.
5. the described photosensitive quarternary ammonium salt compound of claim 1 is as the purposes of light trigger and Photobase generator.
6. according to the described purposes of claim 5, it is characterized in that described photosensitive quarternary ammonium salt compound is as the light trigger in photo-cured coating, light-curable ink, curable adhesive or the photo-resist.
7. according to claim 5 or 6 described purposes, it is characterized in that described photosensitive quarternary ammonium salt compound is 0.1～10%wt as light trigger proportion in acrylatcs systems.
8. according to the described purposes of claim 7, it is characterized in that described photosensitive quarternary ammonium salt compound is 1～5%wt as light trigger proportion in acrylatcs systems.
9. according to claim 5 or 6 described purposes, it is characterized in that described photosensitive quarternary ammonium salt compound is 1～5%wt as the light trigger Photobase generator proportion in acroleic acid esterification oligopolymer and Resins, epoxy mixed system of holding concurrently.
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