Photosensitive diacrylate and dimethacrylate compositions

Details Photosensitive diacrylate and dimethacrylate compositions Photosensitive diacrylate and dimethacrylate compositions

2001-09-17

2004-08-31

Robertson, Jeffrey B. (Department: 1712)

Coating processes

Direct application of electrical, magnetic, wave, or...

Polymerization of coating utilizing direct application of...

C427S517000, C522S068000, C522S120000, C522S121000, C522S123000, C525S529000, C525S530000, C525S531000, C525S922000

Reexamination Certificate

active

06783809

ABSTRACT:

The present invention relates to novel acrylates and methacrylates, to photosensitive compositions containing these compounds and to a process for the preparation of three-dimensional objects from said photosensitive compositons.
Radiation-sensitive liquid resins or resin systems can be used for a variety of utilities, typically as coating compositions, adhesives or photoresists. Quite generally, liquid resins or resin systems should also be suitable for fabricating three-dimensional objects by the stereolithographic technique described in U.S. Pat. No. 4,575,330; but many resins prove to be too viscous, whereas others are insufficiently light sensitve or suffer too severe shrinkage during the cure. The strength properties of the moulded articles or objects made from photocured resins are also often unsatisfactory.
Liquid resin systems for stereolithography comprising different mono- and diacrylates and mono- and dimethacrylates as well as a urethane acrylate or methacrylate and a monomeric or oligomeric diacrylate or methacrylate derived from bisphenol A or bisphenol F are disclosed in EP-A 425 441. When precured with laser light, these systems give green stages of superior green strength and, after the full cure, rigid-elastic objects whose flexibility is, however, insufficient for certain utilities.
EP-A 506 616 discloses liquid resin compositions of several acrylates and/or methacrylates which contain further hydroxyl group containing aliphatic or cycloaliphatic acrylates and/or methacrylates. The cured moulded articles made from these compositions by stereolithography have superior flexibility and tear propagation strength. A drawback of these compositions for processing in mechanical apparatus, however, is their rather high viscosity.
It has now been found possible to prepare novel hydroxyl group containing acrylates and methacrylates which, in conjunction with other acrylates or methacrylates, form low viscosity photocurable compositions which, when fully cured, give moulded articles of excellent flexibility.
Accordingly, the invention relates to compounds of formulae (Ia) and (Ib)
wherein the substituents R
1
are each independently of the other hydrogen or methyl, R
2
is an unsubstituted C
1
-C
20
alkyl group or a C
1
-C
20
alkyl group which is substituted by one or more than one substituent selected from the group consisting of hydroxy, C
6
-C
14
aryl and halogen, an unsubstituted phenyl group or a phenyl group which is substituted by one or more than one substituent selected from the group consisting of C
1
-C
6
alkyl, hydroxy or halogen, or is a radical of formula —CH
2
-OR
3
, wherein R
3
is an unsubstituted C
1
-C
20
alkyl group or a C
1
-C
20
alkyl group which is substituted by one or more than one substituent selected from the group consisting of hydroxy, C
6
-C
14
aryl and halogen, an unsubstituted phenyl group or a phenyl group which is substituted by one or more than one substituent selected from the group consisting of C
1
-C
6
alkyl, hydroxy and halogen, or is a C
2
-C
6
alkenyl group, a C
2
-C
20
acyl group or an unsubstituted cyclohexylcarbonyl group or a cyclohexylcarbonyl group which is substituted by one or more than one substituent selected from the group consisting of C
1
-C
6
alkyl, hydroxy and halogen, Z is a group of formulae (Ia)-(IIe)
wherein Y is a direct bond, C
1
-C
6
alkylene, —S—, —O—, —SO—, —SO
2
— or —CO—, and R
1
is hydrogen or methyl, and wherein the aromatic and cycloaliphatic rings of formulae (IIa)-(IIe) are unsubstituted or substituted by one or more than one substituent selected from the group consisting of C
1
-C
6
alkyl, chloro and bromo.
R
2
or R
3
as C
1
-C
20
alkyl may be branched or, preferably, straight-chain alkyl. Typical examples of such alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neo-pentyl, n-hexyl, octyl, decyl, dodecyl and icosyl.
The alkyl groups may also be substituted by one or more than one substituent selected from the group consisting of hydroxy, C
6
-C
14
aryl and halogen. Typical examples of substituted alkyl groups are hydroxymethyl, 2-hydroxyethyl, 2-hydroxypropyl, 2-chloropropyl, 2,3-dichlorobutyl, 2-phenylethyl and 2,3-diphenylbutyl.
R
3
as C
2
-C
6
alkenyl may be branched or, preferably, straight-chain alkenyl. Typical examples of alkenyl groups are vinyl, prop-1-enyl, prop-2-enyl, 2-methylprop-2-enyl, n-but-3-enyl, n-pent-4-enyl and n-hex-5-enyl. Alkenyl groups containing two or three catbon atoms are preferred, and vinyl prop-1-enyl and prop-2-enyl are especially preferred.
Typical examples of C
2
-C
20
acyl groups are acetyl, propionyl, n-butyryl, isobutyryl, pivaloyl, hexyloyl, octyloyl, tetradecyloyl, hexadecyloyl and octadecyloyl.
R
3
as phenyl or cyclohexylcarbonyl may be unsubstituted or substituted by one or more than one substituent selected from the group consisting of C
1
-C
6
alkyl, hydroxy and halogen. Typical examples of such groups are tolyl, xylyl, mesityl, 2-hydroxyphenyl, 4-hydroxyphenyl, 2-chlorophenyl, 4-chlorophenyl, 3,5-dichlorophenyl, 2,4-dichlorophenyl, 2,6-dimethylcyclohexylcarbonyl, 4-hydroxycyclohexylcarbonyl, p-hydroxybenzyl, p-chlorobenzyl and o-ethylbenzyl.
The aromatic and cycloaliphatic rings in formulae (IIa)-(IIe) are preferably unsubstituted
In the compounds of formulae (Ia) and (Ib) R
2
is preferably C
1
-C
20
alkyl, phenyl, C
1
-C
20
alkoxymethyl, phenoxymethyl or cyclohexycarbonloxymethyl.
Especially preferred compounds of formulae (Ia) and (Ib) are those wherein R
2
is n-butyl, phenyl, n-butoxymethyl, phenoxymethyl or cyclohexylcarbonyloxymethyl.
The most preferred meaning of R
2
is n-butoxymethyl.
Z in formulae (Ia) and (Ib) is preferably a group of formula (IIc) or (IIe).
Compounds of formulae (Ia) and (Ib) are especally preferred wherein Z is
The compounds of formulae (Ia) and (Ib) can be prepared by per se known processes. A further object of the invention is a process for the preparation of compounds of formulae (Ia) and (Ib), which comprises reacting a diglycidyl ether of formula (III)
wherein R
2
and Z have the above meanings, in a manner known per se, with acrylic or methacrylic acid.
The diglycidyl compounds of formula (III) are known and disclosed, inter alia, in EP-A 22 073.
The reaction of the diglycidyl compounds of formula (III) with acrylic or methacrylic acid normally gives a mixture of compounds (Ia) and (Ib), compound (Ia) being the main product and compound (Ib) being obtained in comparatively minor amounts (c. 10-20%). Separation of the two structurally isomeric compounds for use in photosensitive compositions is not necessary.
Illustratative specific examples of the diglycidyl compounds of formula (III) are:
2,2-bis[p-(3-butoxy-2-glycidyloxypropoxy)phenyl]propane,
2,2-bis[p-(3-methoxy-2-glycidyloxypropoxy)phenyl]propane,
2,2-bis[p-(3-ethoxy-2-glycidyloxypropoxy)phenyl]propane,
2,2-bis[p-(3-dodecyloxy-2-glycidyloxypropoxy)phenyl]propane,
2,2-bis[p-(3-tetradecyloxy-2-glycidyloxypropoxy)phenyl]propane,
2,2-bis[p-(3-benzyloxy-2-glycidyloxypropoxy)phenyl]propane,
bis[p-(3-butoxy-2-glycidyloxypropoxy)phenyl]methane,
1,3-bis[p-(3-phenoxy-2-glycidyloxypropoxy]benzene,
bis[p-(3-butoxy-2-glycidyloxypropoxy)phenyl]sulfone,
2,2-bis[p-(3-cyclohexoxy-2-glycidyloxypropoxy)phenyl]propane,
2,2-bis[4-(3-butoxy-2-glycidyloxypropoxy)-3,5-dibromophenyl]propane,
2,2-bis[p-(3-allyloxy-2-glycidyloxypropoxy)phenyl]propane,
2,2-bis[p-(3-phenoxy-2-glycidyloxypropoxy)phenyl]propane,
2,2-bis[4-(3-butoxy-2-glycidyloxypropoxy)cyclohexyl]propane,
2,2-bis[p-(3-cyclohexylcarbonyloxy-2-glycidyloxypropoxy)phenyl]propane,
2,2-bis[p-(2-glycidyloxyhexoxy)phenyl]propane, and
2,2-bis[p-(2-phenyl-2-glycidyloxyethoxy)phenyl]propane.
A further object of the invention is a photosensitive composition comprising
(a) 5-65% by weight of a compound of formula (Ia) or (Ib) according to claim
1
,
(b) 15-70% by weight of one or more than one bifunctional acrylate

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