U.S. patent application number 11/593372 was filed with the patent office on 2007-03-08 for polymeric material, containing a latent acid.
Invention is credited to Michael Heneghan.
Application Number | 20070054220 11/593372 |
Document ID | / |
Family ID | 9916403 |
Filed Date | 2007-03-08 |
United States Patent
Application |
20070054220 |
Kind Code |
A1 |
Heneghan; Michael |
March 8, 2007 |
Polymeric material, containing a latent acid
Abstract
Polymeric material, containing a latent acid which can be
converted to an acid by irradiation by a laser and optionally
further ingredients.
Inventors: |
Heneghan; Michael;
(Rheinfelden-Eichsel, DE) |
Correspondence
Address: |
CIBA SPECIALTY CHEMICALS CORPORATION;PATENT DEPARTMENT
540 WHITE PLAINS RD
P O BOX 2005
TARRYTOWN
NY
10591-9005
US
|
Family ID: |
9916403 |
Appl. No.: |
11/593372 |
Filed: |
November 6, 2006 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10477362 |
Nov 12, 2003 |
7150958 |
|
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PCT/EP02/06109 |
Jun 4, 2002 |
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11593372 |
Nov 6, 2006 |
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Current U.S.
Class: |
430/280.1 |
Current CPC
Class: |
Y10S 430/106 20130101;
G03C 1/73 20130101; C07D 277/72 20130101; Y10S 430/114 20130101;
G03F 7/0045 20130101; C09B 67/0077 20130101; B41M 5/3335 20130101;
B41M 5/3375 20130101 |
Class at
Publication: |
430/280.1 |
International
Class: |
G03C 1/00 20060101
G03C001/00 |
Goverment Interests
[0001] This application is a Divisional of application Ser. No.
10/477,362, filed Nov. 12, 2003, now granted which is the National
Stage of International Application No. PCT/EP 02/06109, filed Apr.
6, 2002 herein incorporated entirely by reference.
Foreign Application Data
Date |
Code |
Application Number |
Jun 12, 2001 |
GB |
0114265.2 |
Claims
1. Polymeric material, containing a latent acid, which can be
converted to an acid by irradiation by a laser, and optionally
further ingredients.
2. Polymeric material according to claim 1, wherein the latent acid
is of formula ##STR7## wherein the ring A can contain one or more
hetero atoms and/or can contain an anelated ring, R.sub.1 is
hydrogen, alkyl, alkenyl, aryl, R.sub.2, R.sub.3, R4 and R.sub.5
independently of each other are hydrogen or a functional
substituent, and R stands for C.sub.1-C.sub.6alkyl,
--Z.sub.1--Q.sub.1, or --Z.sub.2--Q.sub.2, wherein Z.sub.1 is a
single bond, S, NH or O and Q.sub.1 is a heterocyclic ring system
having from 5 to 9 ring atoms selected from C, S, O and N, with at
least 2 carbon atoms in the ring system, which may be substituted
one to three times with C.sub.1-C.sub.4alkyl or hydroxy,
mercaptobenzoxazole, mercaptobenzthiazole, and wherein Z.sub.2
stands for C.sub.1-C.sub.4alkylene, which can be substituted by
C.sub.1-C.sub.4alkyl or Q3, wherein Q.sub.3 stands for phenyl which
can be substituted one to three times with C.sub.1-C.sub.4alkyl,
hydroxy, C.sub.5-C.sub.8cycloalkyl and/or a heterocyclic ring
system having from 5 to 9 ring atoms selected from C, S, O and N,
with at least 2 carbon atoms in the ring system, and Q.sub.2 stands
for phenyl which can be substituted one to three times with
C.sub.1-C.sub.4alkyl, hydroxy, C.sub.5-C.sub.8cycloalkyl and/or a
heterocyclic ring system having from 5 to 9 ring atoms selected
from C, S, O and N, with at least 2 carbon atoms in the ring
system, with the proviso that the hydrogen atom at the C-atom in
a-position to R can be split off by irradiation.
3. Polymeric material according to claim 1, wherein the polymeric
material contains 0.001 to 10% by weight by weight of the latent
acid.
4. Polymeric material according to claim 1, wherein the polymeric
material contains as further ingredient a stabilizer, an
antioxidant or a softener.
5. Process for converting the polymeric material containing a
latent acid according to claim 1 into polymeric material containing
an acid, characterized in that the polymeric material containing a
latent acid is irradiated with UV-light.
6. Process according to claim 5, wherein irradiation is performed
with a UV-laser using UV-light of 285 to 400 nm.
7. Polymeric material obtained by a process according to claim 5.
Description
[0002] The present application relates to polymeric material
containing a latent acid, i.e. a compound which is not an acid but
which can be converted to an acid by the influence of
irradiation.
[0003] For specific technical applications, compositions are
requested containing compounds which are capable of reacting with
acids, however, such a reaction should be suppressed until a
predetermined moment. It is common practice in such cases to
separate the compounds and the acids by suitable measures, e.g. by
encapsulating them into coverings and destroying these coverings
when reaction is desired. This method is, however, not practicable
in many cases.
[0004] The present application describes an elegant solution for
that problem by using not acids but latent acids. Thus the
compounds capable of reacting with acids can be intimately mixed
with the latent acids without reaction. No covering material is
required. At the desired moment reaction can easily be achieved by
irradiating the mixture in a suitable manner to convert the latent
acid into the acid, which then reacts with the compound.
[0005] The present application concerns polymeric material,
containing a latent acid, which can be converted to an acid by
irradiation and optionally further ingredients.
[0006] As latent acids compounds are suitable which are not acids
per se and contain a proton, which can be split off by
irradiation.
[0007] Preferred latent acids are compounds of formula ##STR1##
wherein the ring A can contain one or more hetero atoms and/or can
contain an anelated ring, R.sub.1 is hydrogen, alkyl, preferably
C.sub.1-C.sub.20-alkyl, alkenyl, preferably
C.sub.2-C.sub.20-alkenyl, aryl, preferably phenyl or phenyl which
is substituted one to three times with C.sub.1-C.sub.4alkyl, or
C.sub.1-C.sub.4alkoxy, [0008] R.sub.2, R.sub.3, R4 and R.sub.5
independently of each other are hydrogen or a functional
substituent, and R stands for C.sub.1-C.sub.6alkyl,
--Z.sub.1--Q.sub.1, or --Z.sub.2--Q.sub.2, [0009] wherein Z.sub.1
is a single bond, S, NH or O, and Q.sub.1 is a heterocyclic ring
system having from 5 to 9 ring atoms selected from C, S, O and N,
with at least 2, preferably at least 3, more preferably at least 4
carbon atoms in the ring system, preferably Q.sub.1 stands for
morpholine, pyridine, which may be substituted one to three times
with C.sub.1-C.sub.4alkyl or hydroxy, mercaptobenzoxazole,
mercaptobenzthiazole, [0010] and wherein Z.sub.2 stands for
C.sub.1-C.sub.4alkylene, which can be substituted by
C.sub.1-C.sub.4alkyl or Q.sub.3, wherein Q3 stands for phenyl which
can be substituted one to three times with C.sub.1-C.sub.4alkyl,
hydroxy, C.sub.5-C.sub.8cycloalkyl and/or a heterocyclic ring
system having from 5 to 9 ring atoms selected from C, S, O and N,
with at least 2, preferably at least 3, more preferably at least 4
carbon atoms in the ring system, and Q.sub.2 stands for phenyl
which can be substituted one to three times with
C.sub.1-C.sub.4alkyl, hydroxy, C.sub.5-C.sub.8cycloalkyl and/or a
heterocyclic ring system having from 5 to 9 ring atoms selected
from C, S, 0 and N, with at least 2, preferably at least 3, more
preferably at least 4 carbon atoms in the ring system, with the
proviso that the hydrogen atom at the C-atom in a-position to R can
be split off by irradiation.
[0011] Preferably, Z.sub.2 stands for --CH.sub.2--,
--CH.sub.2--CH.sub.2-, -CH.sub.2--CHMe--, --CH.sub.2--CHQ.sub.3--,
in which Q.sub.3 stands for 4-hydroxy-3-i-propyl-6-methylphenyl,
4-hydroxy-3-tert.-butyl-6-methylphenyl, or
4-hydroxy-3-cyclohexyl-6-methylphenyl and Q.sub.2 stands for phenyl
or 4-hydroxy-3-i-propyl-6-methylphenyl,
4-hydroxy-3-tert.-butyl-6-methylphenyl, or
4-hydroxy-3-cyclohexyl-6-methylphenyl.
[0012] Suitable rings A are e.g. phenyl, naphthyl, pyridyl and
quinolinyl, phenyl and pyridyl are especially preferred.
[0013] R.sub.1 is preferably hydrogen, or methyl.
[0014] Functional substituents R.sub.2, R.sub.3, R4 and R.sub.5 are
e. 9. C.sub.1-C.sub.20-alkyl, preferably C.sub.1-C.sub.8-alkyl,
particularly preferred C.sub.1-C.sub.6-alkyl, especially preferred
C.sub.1-C.sub.4-alkyl, C.sub.5-C.sub.8-cycloalkyl,
C.sub.2-C.sub.20-alkenyl, preferred C.sub.2-C.sub.6-alkenyl,
C.sub.1-C.sub.6-alkoxy, hydroxy, halogen, nitro, cyano,
--SO.sub.2R', wherein R' is hydrogen, alkyl or a metallic cation
such as a alkali metal, e.g. sodium or potassium, or earth alkali
metal cation, e.g. calcium, or phenyl, which may be substituted one
to three times with hydroxy and/or Z.sub.21-R.sub.7, wherein
Z.sub.21 stands for C.sub.1-C.sub.4alkylene, which can be
substituted by C.sub.1-C.sub.4alkyl, and R.sub.7 stands for
hydrogen, C.sub.1-C.sub.4alkyl or phenyl, which may be substituted
one to three times with hydroxy, C.sub.1-C.sub.4alkyl and/or
Z.sub.22-R.sub.8, wherein Z.sub.22 stands for for
C.sub.1-C.sub.4alkylene, which can be substituted by
C.sub.1-C.sub.4alkyl, and R.sub.8 stands for a heterocyclic ring
system having from 5 to 9 ring atoms selected from C, S, O and N,
with at least 2, preferably at least 3, more preferably at least 4
carbon atoms in the ring system, preferably R.sub.8 stands for
morpholine. In a preferred embodiment of this invention R.sub.2,
R.sub.3, R4 and R.sub.5 are preferably independently of each other
hydrogen, C.sub.1-C.sub.20-alkyl or C.sub.2-C.sub.20-alkenyl or
substituted phenyl wherein hydroxy and Z.sub.21-R.sub.7 being the
substituents. Especially preferred compounds of formula (1) are
those wherein R.sub.2 and R.sub.3 are independently of each other
C.sub.1-C.sub.8-alkyl and R4 and R.sub.5 are each hydrogen.
[0015] Halogen means fluoro, chloro, bromo, or iodo, preferably
chloro.
[0016] Heterocyclic residue or heterocyclic ring system having at
least 2, preferably at least 3, more preferably at least 4 carbon
atoms means e.g. an optionally substituted monocyclic or
bicycliclic heterocyclic residue such as pyrrolidino, piperidino,
morpholino, benzthiazole, 1,2,4-triazole, imidazole, pyrazole,
tetrazole, thiazolin-2-thione, imidazolin-2-thione,
N-methyl-imidazolon-2-thione and
5-(3-phenyl-1,3,4-thia-diazol-2(3H)-thione), 2-pyridine,
4-pyridine, 3-pyridazine, 2-pyrimidine, 2-thiazole, 2-thioazoline,
3-(1,2,4-triazole) and 5-(2-mercapto-1,3,4-thiadiazole),
naphthyridine, purine and pteridine residues, benzimiazole,
benzotriazole, benzoxazolin-2-thione, 2-benzoxazole,
mercaptobenzoxazol, mercaptobenzthiazol and quinolinyl.
[0017] It is furthermore preferred that at least one of R.sub.2 and
R.sub.3 is in o-position to the OH-group.
[0018] The organic residue R can be of any kind with the proviso
that the hydrogen atom at the C-atom in a-position to R can be
split off by irradiation. Preferably R is a heterocyclic residue
which is bond via a nitrogen, oxygen or sulfur atom or is a
C.sub.1-C.sub.6-alkyl which is unsubstituted or substituted, e.g.
by hydroxy, C.sub.1-C.sub.6-alkoxy or unsubstituted or substituted
aryl, especially phenyl. Suitable substituents for aryl are
preferably the above-mentioned substituents R.sub.2 through
R.sub.5.
[0019] Most preferably R is a radical of mercaptobenzoxazol or
mercaptobenzthiazol or C.sub.1-C.sub.4-alkyl which is unsubstituted
or substituted by unsubstituted phenyl or phenyl carrying 1 to 4
substituents selected from the group consisting of
C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.4-alkoxy and hydroxy.
[0020] In preferred compounds of formula (1) the residue -CHRR, is
situated in o- or p-, especially in p-position to the OH-group.
[0021] C.sub.1-C.sub.20-alkyl means e.g. methyl, ethyl, n-,
i-propyl, n-, sec.-, iso-, tert.-butyl, n-pentyl, n-hexyl,
n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl,
n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl,
n-octadecyl, n-nonadecyl, n-eicosyl, preferably
C.sub.1C.sub.8-alkyl such as methyl, ethyl, n-, i-propyl, n-,
sec.-, iso-, tert.-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl,
particularly preferred C.sub.1-C.sub.6-alkyl such as methyl, ethyl,
n-, i-propyl, n-, sec.-, iso-, tert.-butyl, n-pentyl, n-hexyl,
especially preferred C.sub.1-C.sub.4-alkyl such as methyl, ethyl,
n-, i-propyl, n-, sec.-, iso-, tert.-butyl.
[0022] C.sub.5-C.sub.8-cycloalkyl stands for cyclopentyl,
cyclohexyl, cycloheptyl, or cyclooctyl, preferably cyclohexyl.
[0023] C.sub.2-C.sub.20-alkenyl stands for e.g. ethenyl, n-,
i-propenyl, n-, sec.-, iso-, tert.-butenyl, n-pentenyl, n-hexenyl,
n-heptenyl, n-octenyl, n-nonenyl, n-decenyl, n-undecenyl,
n-dodecenyl, n-tridecenyl, n-tetradecenyl, n-pentadecenyl,
n-hexadecenyl, n-heptadecenyl, n-octadecenyl, n-nonadecenyl,
n-eicosenyl, preferably C.sub.2-C.sub.6-alkyl such as ethenyl, n-,
i-propenyl, n-, sec.-, iso-, tert.-butenyl, n-pentenyl,
n-hexenyl.
[0024] C.sub.1-C.sub.6-alkoxy stands for e.g. methoxy, ethoxy, n-,
i-propoxy, n-, sec.-, iso-, tert.-butoxy, n-pentoxy, n-hexoxy.
[0025] Preferred polymeric material according to the present
invention contains a latent acid of formula (1) wherein [0026] the
ring A is phenyl or pyridyl, [0027] R.sub.1 is hydrogen, [0028]
R.sub.2 and R.sub.3 are independently of each other
C.sub.1-C.sub.4-alkyl, [0029] R4 and R.sub.5 are each hydrogen and
[0030] R is a heterocyclic residue, which is bond to the
CHR.sub.1-group via a nitrogen, oxygen or sulfur atom or is a
C.sub.1-C.sub.6-alkyl, which is unsubstituted or substituted.
[0031] Especially preferred compounds of formula (1) are the
following compounds: ##STR2## ##STR3##
[0032] The compounds of formula (1) are known or can be made in a
manner known per se, e. g. compound (2) according to GB 2,120,243
and compounds (5) and (6) as described in EP-A-330 613.
[0033] The compounds of the above formulae (7) and (8) are new.
These compounds also form part of the subject matter of the present
invention. They can be obtained in a conventional manner by
reaction of mercaptobenzothiazole with a 2,5-dialkylphenol and
paraformalde-hyde.
[0034] Polymeric material useable for the present invention is
preferably synthetic organic polymeric material, especially
material commonly used for electronic applications.
[0035] In particular the following polymers are preferred: [0036]
1. Polymers of monoolefins and diolefins, for example
polypropylene, polyisobutylene, polybut-1-ene,
poly-4-methylpent-1-ene, polyvinylcyclohexane, polyisoprene or
polybutadiene, as well as polymers of cycloolefins, for instance of
cyclopentene or norbornene, polyethylene (which optionally can be
crosslinked), for example high density polyethylene (HDPE), high
density and high molecular weight polyethylene (HDPE-HMW), high
density and ultrahigh molecular weight polyethylene (HDPE-UHMW),
medium density polyethylene (MDPE), low density polyethylene
(LDPE), linear low density polyethylene (LLDPE), (VLDPE) and
(ULDPE).
[0037] Polyolefins, i.e. the polymers of monoolefins exemplified in
the preceding paragraph, preferably polyethylene and polypropylene,
can be prepared by different, and especially by the following,
methods: [0038] a) radical polymerisation (normally under high
pressure and at elevated temperature). [0039] b) catalytic
polymerisation using a catalyst that normally contains one or more
than one metal of groups lVb, Vb, Vlb or Vil of the Periodic Table.
These metals usually have one or more than one ligand, typically
oxides, halides, alcoholates, esters, ethers, amines, alkyls,
alkenyls and/or aryls that may be either .pi. or
.sigma.-coordinated. These metal complexes may be in the free form
or fixed on substrates, typically on activated magnesium chloride,
titanium(III) chloride, alumina or silicon oxide. These catalysts
may be soluble or insoluble in the polymerisation medium. The
catalysts can be used by themselves in the polymerisation or
further activators may be used, typically metal alkyls, metal
hydrides, metal alkyl halides, metal alkyl oxides or metal
alkyloxanes, said metals being elements of groups Ia, IIa and/or
IIIa of the Periodic Table. The activators may be modified
conveniently with further ester, ether, amine or silyl ether
groups. These catalyst systems are usually termed Phillips,
Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene
or single site catalysts (SSC).
[0040] 2. Mixtures of the polymers mentioned under 1), for example
mixtures of polypropylene with polyisobutylene, polypropylene with
polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of
different types of polyethylene (for example LDPE/HDPE).
[0041] 3. Copolymers of monoolefins and diolefins with each other
or with other vinyl monomers, for example ethylene/propylene
copolymers, linear low density polyethylene (LLDPE) and mixtures
thereof with low density polyethylene (LDPE), propylene/but-l-ene
copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene
copolymers, ethylene/hexene copolymers, ethylene/methylpentene
copolymers, ethylene/heptene copolymers, ethylene/octene
copolymers, ethylene/vinylcyclohexane copolymers,
ethylene/cycloolefin copolymers (e.g. ethylene/norbornene like
COC), ethylene/1-olefins copolymers, where the 1-olefin is
generated in-situ; propylene/butadiene copolymers,
isobutylene/isoprene copolymers, ethylene/vinylcyclohexene
copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl
methacrylate copolymers, ethylene/vinyl acetate copolymers or
ethylene/acrylic acid copolymers and their salts (ionomers) as well
as terpolymers of ethylene with propylene and a diene such as
hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures
of such copolymers with one another and with polymers mentioned in
1) above, for example polypropylene/ethylene-propylene copolymers,
LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic
acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or
random polyalkylene/carbon monoxide copolymers and mixtures thereof
with other polymers, for example polyamides.
[0042] 4. Hydrocarbon resins (for example C.sub.5-Cg) including
hydrogenated modifications thereof (e.g. tackifiers) and mixtures
of polyalkylenes and starch.
[0043] Homopolymers and copolymers from 1.) - 4.) may have any
stereostructure including syndiotactic, isotactic, hemi-isotactic
or atactic; where atactic polymers are preferred. Stereoblock
polymers are also included.
[0044] 5. Polystyrene, poly(p-methylstyrene),
poly(a-methylstyrene).
[0045] 6. Aromatic homopolymers and copolymers derived from vinyl
aromatic monomers including styrene, a-methylstyrene, all isomers
of vinyl toluene, especially p-vinyltoluene, all isomers of ethyl
styrene, propyl styrene, vinyl biphenyl, vinyl naphthalene, and
vinyl anthracene, and mixtures thereof. Homopolymers and copolymers
may have any stereostructure including syndiotactic, isotactic,
hemi-isotactic or atactic; where atactic polymers are preferred.
Stereoblock polymers are also included.
[0046] 6a. Copolymers including aforementioned vinyl aromatic
monomers and comonomers selected from ethylene, propylene, dienes,
nitriles, acids, maleic anhydrides, maleimides, vinyl acetate and
vinyl chloride or acrylic derivatives and mixtures thereof, for
example styrene/butadiene, styrene/acrylonitrile, styrene/ethylene
(interpolymers), styrene/alkyl methacrylate,
styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl
methacrylate, styrene/maleic anhydride,
styrene/acrylonitrile/methyl acrylate; mixtures of high impact
strength of styrene copolymers and another polymer, for example a
polyacrylate, a diene polymer or an ethylene/propylene/diene
terpolymer; and block copolymers of styrene such as
styrene/butadiene/styrene, styrene/isoprene/styrene,
styrene/ethylene/butylene/styrene or
styrene/ethylene/propylene/styrene.
[0047] 6b. Hydrogenated aromatic polymers derived from
hydrogenation of polymers mentioned under 6.), especially including
polycyclohexylethylene (PCHE) prepared by hydrogenating atactic
polystyrene, often referred to as polyvinylcyclohexane (PVCH).
[0048] 6c. Hydrogenated aromatic polymers derived from
hydrogenation of polymers mentioned under 6a.).
[0049] Homopolymers and copolymers may have any stereostructure
including syndiotactic, isotactic, hemi-isotactic or atactic; where
atactic polymers are preferred. Stereoblock polymers are also
included.
[0050] 7. Graft copolymers of vinyl aromatic monomers such as
styrene or a-methylstyrene, for example styrene on polybutadiene,
styrene on polybutadiene-styrene or polybutadiene-acrylonitrile
copolymers; styrene and acrylonitrile (or methacrylonitrile) on
polybutadiene; styrene, acrylonitrile and methyl methacrylate on
polybutadiene; styrene and maleic anhydride on polybutadiene;
styrene, acrylonitrile and maleic anhydride or maleimide on
polybutadiene; styrene and maleimide on polybutadiene; styrene and
alkyl acrylates or methacrylates on polybutadiene; styrene and
acrylonitrile on ethylene/propylene/diene terpolymers; styrene and
acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates,
styrene and acrylonitrile on acrylate/butadiene copolymers, as well
as mixtures thereof with the copolymers listed under 6), for
example the copolymer mixtures known as ABS, MBS, ASA or AES
polymers.
[0051] 8. Halogen-containing polymers such as polychloroprene,
chlorinated rubbers, chlorinated and brominated copolymer of
isobutylene-isoprene (halobutyl rubber), chlorinated or
sulfochlorinated polyethylene, copolymers of ethylene and
chlorinated ethylene, epichlorohydrin homo- and copolymers,
especially polymers of halogen-containing vinyl compounds, for
example polyvinyl chloride, polyvinylidene chloride, polyvinyl
fluoride, polyvinylidene fluoride, as well as copolymers thereof
such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl
acetate or vinylidene chloride/vinyl acetate copolymers.
[0052] 9. Polymers derived from .alpha.,.beta.-unsaturated acids
and derivatives thereof such as polyacrylates and
polymethacrylates; polymethyl methacrylates, polyacrylamides and
polyacrylonitriles, impact-modified with butyl acrylate.
[0053] 10. Copolymers of the monomers mentioned under 9) with each
other or with other unsaturated monomers, for example
acrylonitrile/ butadiene copolymers, acrylonitrile/alkyl acrylate
copolymers, acrylonitrile/alkoxyalkyl acrylate or
acrylonitrile/vinyl halide copolymers or acrylonitrile/ alkyl
methacrylate/butadiene terpolymers.
[0054] 11. Polymers derived from unsaturated alcohols and amines or
the acyl derivatives or acetals thereof, for example polyvinyl
alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate,
polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or
polyallyl melamine; as well as their copolymers with olefins
mentioned in 1) above.
[0055] 12. Homopolymers and copolymers of cyclic ethers such as
polyalkylene glycols, polyethylene oxide, polypropylene oxide or
copolymers thereof with bisglycidyl ethers.
[0056] 13. Polyacetals such as polyoxymethylene and those
polyoxymethylenes, which contain ethylene oxide as a comonomer;
polyacetals modified with thermoplastic polyurethanes, acrylates or
MBS.
[0057] 14. Polyphenylene oxides and sulfides, and mixtures of
polyphenylene oxides with styrene polymers or polyamides.
[0058] 15. Polyurethanes derived from hydroxyl-terminated
polyethers, polyesters or polybutadienes on the one hand and
aliphatic or aromatic polyisocyanates on the other, as well as
precursors thereof.
[0059] 16. Polyamides and copolyamides derived from diamines and
dicarboxylic acids and/or from aminocarboxylic acids or the
corresponding lactams, for example polyamide 4, polyamide 6,
polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide
12, aromatic polyamides starting from m-xylene diamine and adipic
acid; polyamides prepared from hexamethylenediamine and isophthalic
or/and terephthalic acid and with or without an elastomer as
modifier, for example poly-2,4,4,-trimethylhexamethylene
terephthalamide or poly-m-phenylene isophthalamide; and also block
copolymers of the aforementioned polyamides with polyolefins,
olefin copolymers, ionomers or chemically bonded or grafted
elastomers; or with polyethers, e.g. with polyethylene glycol,
polypropylene glycol or polytetramethylene glycol; as well as
polyamides or copolyamides modified with EPDM or ABS; and
polyamides condensed during processing (RIM polyamide systems).
[0060] 17. Polyureas, polyimides, polyamide-imides, polyetherimids,
polyesterimids, polyhydantoins and polybenzimidazoles.
[0061] 18. Polyesters derived from dicarboxylic acids and diols
and/or from hydroxycarboxylic acids or the corresponding lactones,
for example polyethylene terephthalate, polybutylene terephthalate,
poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene
naphthalate (PAN) and polyhydroxybenzoates, as well as block
copolyether esters derived from hydroxyl-terminated polyethers; and
also polyesters modified with polycarbonates or MBS.
[0062] 19. Polycarbonates and polyester carbonates.
[0063] 20. Polyketones.
[0064] 21. Polysulfones, polyether sulfones and polyether
ketones.
[0065] 22. Crosslinked polymers derived from aldehydes on the one
hand and phenols, ureas and melamines on the other hand, such as
phenol/formaldehyde resins, urea/formaldehyde resins and
melamine/formaldehyde resins.
[0066] 23. Drying and non-drying alkyd resins.
[0067] 24. Unsaturated polyester resins derived from copolyesters
of saturated and unsaturated dicarboxylic acids with polyhydric
alcohols and vinyl compounds as crosslinking agents, and also
halogen-containing modifications thereof of low flammability.
[0068] 25. Crosslinkable acrylic resins derived from substituted
acrylates, for example epoxy acrylates, urethane acrylates or
polyester acrylates.
[0069] 26. Alkyd resins, polyester resins and acrylate resins
crosslinked with melamine resins, urea resins, isocyanates,
isocyanurates, polyisocyanates or epoxy resins.
[0070] 27. Crosslinked epoxy resins derived from aliphatic,
cycloaliphatic, heterocyclic or aromatic glycidyl compounds, e.g.
products of diglycidyl ethers of bisphenol A and bisphenol F, which
are crosslinked with customary hardeners such as anhydrides or
amines, with or without accelerators.
[0071] 28. Natural polymers such as cellulose, rubber, gelatin and
chemically modified homologous derivatives thereof, for example
cellulose acetates, cellulose propionates and cellulose butyrates,
or the cellulose ethers such as methyl cellulose; as well as rosins
and their derivatives.
[0072] 29. Blends of the aforementioned polymers (polyblends), for
example PP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS,
PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates,
POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS,
PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO,
PBT/PC/ABS or PBT/PET/PC.
[0073] Especially preferred is organic polymeric material made of
SAN (copolymer made of styrene and acrylonitrile), PP
(polypropylene), PE (polyethylene), PVC (polyvinylchloride), PET
(polyethyleneterephthalate), PET-G (glycole-modified PET), PMMA
(polymethylmethacrylate) and related polyacrylics, PS
(polystyrene), ASA (copolymer made of acrylonitrile, styrene,
acrylate), PA (polyamide), ABS (copolymer made of acrylonitrile,
styrene, butadiene), LLDPE (linear LDPE), LDPE (low density
polyethylene), HDPE (high density polyethylene) and polycarbonate,
most preferably polycarbonate. The polymeric material can also be a
mixture of two or more different polymers.
[0074] The polymeric material usually contains preferably 0,001 to
10% by weight, most preferably 0,01 to 5% by weight of the latent
acid (1). The polymeric material may also contain mixtures of two
or more of the latent acids.
[0075] The polymeric material and the latent acid usually form a
homogenous mixture. For specific applications, however,
compositions can be made in which the latent acid is enriched in a
specific part of the polymeric material, e.g. in the surface
areas.
[0076] The methods for incorporating the latent acid into the
polymeric material are in principle known. It is e.g. possible, to
dissolve the components in a solvent and then to remove the solvent
by evaporation. Another possibility is to melt polymeric material
together with the latent acid to get a homogeneous mixture or to
thoroughly knead a mixture of polymeric material and latent acid,
or to polymerize the corresponding monomers in the presence of the
latent acid.
[0077] In another embodiment of this invention, the latent acid (1)
is grafted on the polymer material by means known in the art. E.g.
the latent acid (1) is converted into a monomer, i.e. by
incorporating a functional polymerizable group, or a monomer is
used which is functionalized with a latent acid group. This allows
a graft polymerization on the existing polymeric material or a
copolymerization during the manufacturing the polymeric
material.
[0078] The polymeric material usually may contain further
ingredients, e. g. stabilizers, antioxidants, softeners etc. as are
commonly used for polymeric material.
[0079] To convert the latent acid into the corresponding acid, the
polymeric material is irradiated. Irradiation in this application
especially means irradiation with UV-light and especially with
UV-lasers. As a rule, the lasers used are commercially available.
The wavelength of the UV-light preferably is chosen in the range of
285 to 400 nm, particularly preferred in the range of 285 to 370
nm. The duration of irradiation depends on the components and on
the type of UV-source and be easily be determined by simple
experiments.
[0080] The inventive polymeric material containing a latent acid
can be used in a system for laser decoration if the polymeric
material additionally contains a colourless colour former which
gives a visible colour after reaction with an acid.
[0081] The following non-limitative examples illustrate the
invention in more detail. Parts and percentages are by weight,
unless otherwise stated.
EXAMPLE
Example 1
[0082] To a reaction flask are charged 16.7 g of
mercaptobenzothiazole, 16.4 g 2-t-butyl-5-methylphenol, 3.0 g
paraformaldehyde and 1 ml dibutylamine. The mixture is heated to
120.degree. C. and held at this temperature for 6 hours. After
cooling to room temperature 75 ml ethanol are added. Then the
mixture is heated to reflux for 2 hours and then cooled to
20.degree. C. and filtered. By trituration of the product with hot
methanol a product with melting point 177.9-183.9.degree. C. is
obtained. The product is of the following formula: ##STR4## Yield
22.5 g (65.6% theory).
Example 2
[0083] Repeating example 1, but replacing 2-t-butyl-5-methylphenol
by 15.0 g thymol gives a compound of formula ##STR5## Melting point
119.3-123.0. Yield 9.6 g (29.2% theory).
Example 3:
[0084] 100 parts of polycarbonate, and 1 part of the latent acid
according to example 1 and 1 part of the colour former of the
formula ##STR6## are dissolved in tetrahydrofurane. The solvent is
allowed to evaporate overnight.
[0085] A colourless homogeneous polymeric material is obtained.
Irradiation with a UV-laser at 355 nm produces blue marks at the
irradiated areas.
Examples 4 to 8
[0086] In a similar manner to example 3 the following latent acids
are incorporated in polycarbonate: TABLE-US-00001 Parts latent
Parts Colour Example Latent Acid acid Former 4 Compound (2) 1 1 5
Compound (8) 1 1 6 Compound (11) 1 1 7 Compound (12) 1 1 8 Compound
(13) 1 1
[0087] In each case irradiation with a laser at 355 nm produced a
clear blue mark.
* * * * *