JPH02133405A - Polymerizable composition containing ion dye and silica and photosensitive material containing said composition - Google Patents

Abstract

PURPOSE: To improve the hardness of a hardened material by mixing a free radical addition polymerizable or cross-linkable compound, a specified ion dye- reactive pair ion complex and silica.

CONSTITUTION: (a) A free radical addition polymerizable or cross-linkable compound which is preferably an ethylenic unsaturated compound, (b) an ion dye- reactive pair ion complex consisting of a cation dye-porate complex of the formula [D is cation dye; R¹, R², R³ and R⁴ are each alkyl, aryl, alkaryl, allyl, aralkyl, alkenyl, alkynyl, alicyclic group, or (un)saturated heterocyclic group] or anion dye compound which is a complex capable of emitting a free radical for starting the free radical polymerization or cross-linking of the component (a) in heating or exposure to a chemical ray, and (c) 0.5 wt.% or more, preferably, 0.75-1.25 wt.% of silica (e.g.; precipitated silica) are mixed.

COPYRIGHT: (C)1990,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides an improved polymerizable composition comprising an ionic dye complex, such as a cyanine dye-borate complex, as a photoinitiator, wherein the composition additionally comprises silica. Regarding.

U.S. Patent Application No. 944,605 (December 1, 1986)
(filed and granted on the 8th) discloses a photocurable 0T composition comprising a free radical addition polymerizable compound and a complex of an ionic dye and a counterion that directly or indirectly generates free radicals upon exposure to actinic radiation. Disclosed. These complexes are redox initiators characterized by being non-transient ion pairs that undergo highly efficient electron transfer. These compounds exhibit greater film speed when compared to other non-silver visible light sensitive initiators. The compositions cure upon exposure to light, but also undergo thermal polymerization when heated to high temperatures.

Photocurable compositions containing the above complexes are useful in a variety of applications including photoresists, photosensitive materials of the type described in commonly assigned U.S. Pat. No. 4,399,209, dental cements, etc. It is. One of the disadvantages of these compositions is that although they exhibit high film speeds, they do not cure as firmly as desired for some applications.

According to the present invention, the addition of small amounts of silica to the compositions described above substantially improves the hardness of the compositions. These silica-free compositions cure to sticky semi-solid materials. When as much as 5-1% silica is present, the composition hardens into an essentially non-tacky hard material.

In addition to improving hardness, silica catalyzes the autooxidation cycle, thereby reducing induction time and improving the shoulder 5 peed of the composition. It is generally accepted that oxygen inhibits free radical polymerization. The initiation of polymerization of the free radical photopolymerizable composition is delayed until the oxygen present in the composition is depleted by reaction with the photoinitiator. Cycles in which oxygen is depleted are known as autoxidation cycles. When the composition is heated to induce polymerization, the presence of silica reduces this induction time to 100% when the composition does not contain silica but has an oxygen concentration of 6.
It has been found that the induction time of the composition is reduced by an order of magnitude.

Accordingly, the present invention comprises a free radical addition polymerizable or crosslinkable compound, a complex of an ionic dye and a reactive counterion, and silica, wherein said complex upon heating or absorption of actinic radiation, in particular upon absorption of visible light, generates pressure free radicals. gives rise to
A polymerizable composition is provided. More particularly, the present invention provides photopolymerizable and thermally polymerizable compositions.

In a preferred embodiment of the invention, U.S. Patent Bundle 4.399
, 209 and 4,440,846, the photocurable composition is encapsulated with an imaging agent.

Colloidal silica, humid 9 silica and amorphous synthesis (
Substantially any form of silica can be used in the present invention, including precipitated silica. For photocurable compositions intended for encapsulation, precipitated silica is preferred over fumed silica because fumed silica forms a network that is larger than the average particle size of the microcapsules. Silica is available in hydrophobic as well as hydrophilic forms.

Although both forms are effective in improving the hardness of photocurable compositions, hydrophobic silica does not suffer from the same beneficial effect on shoulder velocity as hydrophilic silica. The silica is preferably used in as fine a powder form as possible, for example with a particle size of less than 1 micron, especially less than 0.1 micron.

One of the surprising discoveries that formed the basis of this invention was that silica'a
It is believed that the silica has a catalytic effect since the hardness of the cured composition is actually improved when used in small amounts, on the order of -0.5 m lid %. Silica is usually about 0.0175-1.
It is used in an amount of 25% debt.

Higher amounts of silica can be used, but in this case the composition becomes so chicken-trope that it becomes difficult to handle.

Preferred ionic dye complexes for use in the present invention are cationic dye-borate complexes.

Cationic dye-borate complexes are known in the art.

These manufacturing methods and their use in image forming systems are covered by U.S. Patent Bundle 3,
No. 567.453, No. 4,307,182, No. 4,6
No. 43.891, No. 4,447,521, and No. 4,
No. 450,227. The compound used in the present invention has the general formula (1): [wherein D is a cationic dye, and R1, R2, R3 and R4 are independently alkyl, aryl, alkaryl, allyl, aralkyl, alkenyl,
selected from the group consisting of alkynyl, alicyclic groups and saturated or unsaturated heterocyclic groups].

Useful dyes are those that form photoreducible but dark-stable complexes with the borate anion, and are the cationic methine, polymethine, triarylmethane, indoline, thiazine, xanthine, oxazine, and acridine dyes. In particular, the dyes are cationic cyanine, carbocyanine, hedenocyanine, rhodamine and azomethine dyes. In addition to being cationic dyes, the dyes must not contain complex neutralizing or desensitizing groups or groups that render them insufficiently dark-stable.

Particular examples of useful cationic dyes are methylene chloride, safranine O+ malachite green, cyanine dyes of general formula (II), and cyanine dyes of general formula (I).
n) lomemine dye: n-0.1.2.3 R Hayabusa Argyl Y = CH-CH,N CHs, C(CHs)
2.0, S, SeR', R-alkyl, aryl and combinations thereof.

The borate anion is designed so that upon exposure, the borate radical generated after electron transfer to the dye easily dissociates to form a radical as follows: BR' → BR-1-R'' (Formula 2 ) Particularly preferred anions are triphenylbutylborate anion and dorianisylbutylborate anion.

This is because these anions easily dissociate into triphenylphorane or dorianisylborane and butyl radicals. However, the tetrabutylborate anion does not work well, and this is believed to be because tetrabutylborate is unstable and readily accepts electrons from the dye as a reverse Ichiko transfer and does not dissociate sufficiently.

Similarly, the tetraphenylbore)It ion mophenyl radical is not easily formed and is therefore very insufficient.

几1. B2. It is preferable that at least one, but not more than three of R3 and R4 are alkyl groups.

a% tc': Each of 几3 and R4 has 20 carbon atoms
These typically have 1 to 7 carbon atoms, although they can be up to 7 carbon atoms. Particularly preferably, Groups 1 to 4 are a combination of an alkyl group and an aryl group or an aralkyl group, and more preferably a combination of six aryl groups and one alkyl group.

Typical examples of alkyl groups represented by R1 to R' are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, stearyl, and the like. Secondary alkyl groups are preferred. Alkyl groups can also be substituted, for example by one or more halogen, cyan, alkoxy, acyl, alkoxy or hibiroxy groups.

Typical aryl group represented by 7', C
fll is a substituted aryl group such as phenyl, naphthyl and eg anisyl. Alkaryl groups include methylphenyl, dimethylphenyl, and the like. A typical example of an aralkyl group represented by R1 to R'V is benzyl. Representative cycloaliphatic groups are cyclobutyl, cyclopentyl, and cyclohexyl groups. Examples of alkynyl groups are propynyl and ethynyl, with a vinyl group on the side of the alkenyl group.

In general, useful ionic dye compounds are identified empirically, but potentially useful dye and counterion combinations are based on the Weller equation (D, Roh
m) and A, Wel 1er (A, Wel 1er) 8.2
59-271], this formula is simplified as follows.

△q=EOx−Ered Ehv (Formula 6) In the formula, Δ
G is Gibbs free energy tear, B
ox is the oxidation potential of the borate anion BR4, fired is the reduction potential of the cationic dye, and Ehu is the energy of the light used to excite the dye. Useful compounds have negative free energy changes. Similarly, for compounds to be dark-stable, the difference between the reduction potential of the dye and the oxidation potential of the borate must be negative, ie Box-Ered)O.

As mentioned above, Equation 2 is a simplification and does not absolutely predict whether a compound will be useful in the present invention. There are many factors that influence this decision. One such factor is the effect of the monomer on the compound. Other factors are the semi-radial distance between the ions.
distance). Deviations from Weller's equation are possible if it yields too large a negative value. Furthermore, the Weller equation only predicts electron transfer and cannot predict whether a 1% compound is a sufficient polymerization initiator. This equation is a useful first-order approximation.

Specific examples of cationic dye-borate anionic compounds useful in the present invention are U.S. Pat.
(filed October 17, 2006, currently granted) and Yorotsu, J Published Patent Application No. 0233587.

Cationic dye-borate anionic compounds can be prepared by reacting borate and dye by counterion exchange in a known manner.

Leptos saborate of Hishiki x is a sodium salt such as sodium tetraphenylborate, sodium triphenylbutylborate, sodium dorianisylbutylborate.

Anionic dye compounds are also useful in the present invention.

Anionic dye of formula (IV) - iodonium ion, where D is an ionic dye. R and R are independently selected from the group consisting of aromatic nuclei, e.g. phenyl or naphthyl; n is 1 or 2] and an anionic dye of formula (V) - pyrylium, as defined above] are typical examples of anionic dye complexes.

Typical examples of ionic dyes are xanthine dyes and oxonol dyes. For example, rose bengal (几ose
Bengal), eosin, erythrosin, and fluorescein dyes are useful. In addition to iodonium and pyrylium ions, anionic dyes of other compounds and sulfonium and phosphonium cations are also believed to be useful.

As in the case of cationic dye compounds, useful dye-cation combinations are Wellerian! / [Thus, it can be confirmed as having negative free energy.

Specific examples of anionic dye compounds are also shown in the above-mentioned U.S. patent applications and patent applications at http://www.

The most typical examples of free radical addition polymerizable or crosslinkable compounds useful in the present invention are ethylenically unsaturated compounds, with Ii being polyethylenically unsaturated compounds. These compounds contain one or more ethylenically unsaturated groups (
There are both monomers containing eg vinyl and allyl groups) and polymers with terminal or pendant ethylenically unsaturated bonds. Such compounds are well known in the art, e.g., t is an acrylic or tu-acrylic ester of a polyhydric alcohol, such as trimethylolpronoξ, pentaerythritol, etc.; an acrylate or methacrylate terminated epoxy resin, an acrylate or methacrylate; Contains terminal polyester, etc. Representative examples include ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate ('r M P 'r A ), pentaerythritol detraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hydroxypentaacrylate ( DPHPA), hexanediol-1,6-dimethacrylate and diethylene glycol dimethacrylate.

The ionic dye compound is typically used in an amount up to about 1% by weight, based on the weight of the photocurable, photopolymerizable or crosslinkable material in the composition. It is used in an amount of about 0.2-0.5% by weight.

Although this compound can be used alone as an initiator, in this case film speeds tend to be very low and oxygen suppression is also observed. It has been found that it is preferable to use this compound in combination with an autooxidizer. Autooxidants are compounds that can deplete oxygen in free radical chain processes.

Examples of useful autooxidants are N,N-dialkylanilines and thiols. Examples of preferred N,N-dialkylanilines include groups in which one or more of the ortho-, meta- and para-positions are: methyl, ethyl, isopropyl, t
-butyl, 6.4-tetramethylene, phenyl, trifluoromethyl, acetyl, ethoxycarbonyl, carboxy, carboxylate, trimethylsilylmethyl, trimethylsilyl, triethylsilyl, trimethylgermanyl, triethylgermanyl, trimethylstannyl, triethylstannyl, Dialkylanilines substituted by n-butoxy, n-bentyloxy, phenoxy, hibiroxy, acetyloxy, methylthio, ethylthio, inpropylthio, thio-(mercapto-), acetylthio, fluoro, chloro, bromo and iodo.

Preferred N,N-dialkylanilines are those substituted with an alkyl group in the ortho position, in this example 2,6-diituprobyl-N.

N-) Methylaniline, 2,6-dinityl-N.

N-dimethylaniline, N,N,2,4.6-pentamethylaniline (PMA) and pt-butyl-N,N
-There is dimethylaniline.

Examples of useful thiols are 6-nitoxy 2-mercaptobenzothiazole and 2-mercaptobenzoxazole.

Preferably, the autooxidizer is used in the present invention at a concentration of about 4-5% by weight.

The polymerizable composition according to the invention is prepared by dispersing silica in monomers and adding a photoinitiator. The silica can be dispersed in the monomer in a glass ball mill and milled for several hours.

The compositions of the present invention can be coated onto a support in the conventional manner and used as photoresists or in photolithography to form polymeric images; , No. 209 and No. 4
, 440,846, and used to control the release of the imaging agent. The latter method typically involves imagewise exposure of the photosensitive material to actinic radiation and e.g. pressure,
exposure to a uniform destructive force, such as friction or ultrasonic energy, and the imaging agent is released from the microcapsules and reacts with the developer. The compositions of the present invention are also useful photocurable adhesives.

Although the invention has been described in detail with reference to preferred embodiments thereof, it will be understood that modifications and changes may be made thereto without departing from the scope of the invention as defined by the claims.

Preferred embodiments of the present invention are as follows.

1. A composition comprising a free radical addition polymerizable or crosslinkable compound, an ionic dye-reactive counterion complex, and silica, wherein the ionic dye-reactive counterion complex is heated or exposed to actinic radiation. A composition which is a complex capable of releasing free radicals which sometimes initiates free radical polymerization or crosslinking of said polymerizable or crosslinkable compound.

2. The composition according to 1 above, wherein the complex is a stable non-transient compound before exposure.

6. The composition according to the above 2, wherein the silica is selected from the group consisting of humic silica and precipitated silica.

4. The composition as described in 1 above, wherein the dye is a salt ion dye selected from the group consisting of xanthine dyes and oxonol dyes.

5. The composition as described in 1 above, wherein the dye is a cationic cyanine dye.

6. The composition as described in 1 above, wherein the polymerizable or crosslinkable compound is an ethylenically unsaturated compound.

Z. The composition according to 4 above, wherein the complex is an anionic dye-iodonium ion complex or an anionic dye-pyryllium ion complex.

8. 7. The composition according to 7 above, wherein the complex is a cationic dye-porate complex.

9. The composition of claim 1, wherein said silica is present in an amount greater than 0.5% by weight.

10. The composition of claim 9, wherein said silica is present in an amount of about 0.75 to 1.25% by weight.

11. A photosensitive material comprising a support having a photocurable composition layer on its surface, the composition comprising a free radical addition polymerizable or crosslinkable compound, an ionic dye-reactive counterion complex and silica. A photosensitive material comprising: a complex capable of absorbing actinic radiation and releasing free radicals that initiate free radical polymerization or crosslinking of the polymerizable or crosslinkable compound.

12. The photosensitive material as described in 11 above, wherein the complex is a stable, non-transient compound before exposure.

16. 11 above, wherein the dye is a cationic cyanine dye
Photosensitive materials as described.

14. The photosensitive material as described in 11 above, wherein the dye is an anionic dye selected from the group consisting of xandene dyes and oxonol dyes.

15. The photosensitive material as described in 11 above, wherein the photopolymerizable or crosslinkable compound is an ethylenically unsaturated compound.

16. The complex is a cationic dye-coated 9-nium-5
12. The photosensitive material as described in 11 above, which is an anionic dye-pyryllium ion complex or an anionic dye-pyryllium ion complex.

1Z The photosensitive material according to 16 above, wherein the dye is xanthine.

18. The photosensitive material according to 17 above, wherein the silica is present in an amount greater than 0.5 M%.

19 The silica has a weight of about 0.75 th! ■ to 1.2
18. The photosensitive material according to claim 17, present in an amount up to 5% by weight.

20. The photosensitive material as described in 11 above, wherein the photocurable composition is encapsulated in microcapsules.

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Claims (1)

[Scope of Claims] 1. A composition comprising a free radical addition polymerizable or crosslinkable compound, an ionic dye-reactive counterion complex, and silica, wherein the ionic dye-reactive counterion complex when heated or a composition that is capable of releasing free radicals upon exposure to actinic radiation that initiates free radical polymerization or crosslinking of said polymerizable or crosslinkable compound. 2. A photosensitive material comprising a support having a photocurable composition layer on its surface, the composition comprising a free radical addition polymerizable or crosslinkable compound, an ionic dye-reactive counterion complex, and silica. A photosensitive material comprising: a complex capable of absorbing actinic radiation and releasing free radicals that initiate free radical polymerization or crosslinking of the polymerizable or crosslinkable compound.