European Polymer Journal 38 (2002) 387±392

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Synthesis of acrylic rosin derivatives and application as

negative photoresist
Jong Soon Lee, Sung Il Hong *
Department of Fiber and Polymer Science, College of Engineering, Seoul National University, Seoul 151-742, South Korea
Received 23 February 2000; received in revised form 14 August 2000; accepted 11 September 2000

Abstract
Functional monomers containing a rosin moiety, maleopimaric acid anhydride (MPA) and fumaropimaric acid
(FPA) were synthesized from gum rosin. Monofunctional acrylic rosin derivatives were synthesized from esteri®cation
of MPA and various acrylates, (2-hydroxyethyl acrylate) (HEA), 3-hydroxypropyl acrylate, and 4-hydroxybutyl ac-
rylate. Monofunctional monomers were copolymerized with (methyl methacrylate) (MMA) by radical polymerization.
Trifunctional acrylate was synthesized from FPA and HEA. All the monomers and polymers showed good solubility
and low absorbance in the UV region (200±400 nm). Negative patterns from rosin derivatives were obtained by two
methods, one is a photocuring method using trifunctional acrylate and copolymers, and the other is photocrosslinking
of copolymers using a photocrosslinker under UV (I-line) radiation. Negative photoresists containing rosin moiety
showed high contrast and minimum linewidth of 2.2 lm. Ó 2001 Elsevier Science Ltd. All rights reserved.

Keywords: Acrylic rosin derivatives; Negative photoresist; Photocuring method; Photocrosslinking method

1. Introduction structure of rosin. Therefore, it is expected that adhesive,

Rosin, or colophony, is a thermoplastic acidic pro-
duct isolated from exudate of living pine trees and from
freshly cut and/or aged bole and stump wood of various
species of pine [1]. The acidic constituents that make up
the major portion of rosin are known as resin acids.
They are monocarboxylic acids of alkylated hydro-
phenanthrene nuclei [2]. The predominant resin acid
in unmodi®ed rosins is abietic acid, which has the em-
pirical formula C20 H30 O2 [3]. Industrially, rosin has been
widely used as additives and modi®ers for various ap-
plications. For instance, rosin is e€ective as an adhesion
promoter, viscosity controller, etc. All these useful
properties are certainly related to the bulky alicyclic
*
Corresponding author. Tel.: +82-2-880-7198; fax: +82-2-
878-9453.
E-mail address: hongsipf@gong.snu.ac.kr (S.I. Hong).
stable, transparent and thermally stable polymer ®lms
will be obtained when the rosin moiety is incorporated
into the polymer structure. The Diels±Alder adduct of
rosin and maleic anhydride (RMA) has been extensively
used as raw material for the synthesis of rosin-contain-
ing polymers such as polyesterimides, polyamideimides,
etc. [4,5]. It was shown that these rosin-containing
polymers are thermally stable and possess attractive
polymer properties.
To better exploit the rosin-based properties in poly-
mers, i.e. adhesion, solubility, and transparency, we
investigated the synthesis and application of rosin-
containing negative photoresist in this work. Negative
photoresists are materials that become insoluble in
developing solutions when exposed to radiation (UV,
Excimer laser, etc.) [6,7]. Incorporation of rosin structure
into the photoresist polymer backbone is expected to
enhance the processibility as well as the resist perfor-
mance compared to the conventional negative photo-
resist materials. Important industrial applications of
these negative photoresist involve the fabrication of

0014-3057/01/$ - see front matter Ó 2001 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 1 4 - 3 0 5 7 ( 0 0 ) 0 0 2 0 4 - 4
388 J.S. Lee, S.I. Hong / European Polymer Journal 38 (2002) 387±392
printed electric circuit, black matrix, color ®lters for
LCD, and more.
Acrylate polymers with rosin moiety as a pendant
group and trifunctional acrylate of rosin moiety were
newly synthesized as the negative photoresist materials.
Maleopimaric acid anhydride (MPA) was obtained by the
literature method starting from reaction of rosin with
maleic anhydride [8]. Monofunctional acrylates were ob-
tained by esteri®cation of MPA and various acrylates, 2-
hydroxyethyl acrylate (HEA), 3-hydroxypropyl acrylate
(HPA) and 4-hydroxybutyl acrylate (HBA). The mono-
functional acrylates were copolymerized with methyl
methacrylate (MMA) by radical polymerization using
AIBN. Trifunctional acrylate (FPAHEA) was obtained
by esteri®cation of HEA and fumaropiaric acid (FPA).
The properties of copolymers containing rosin moiety
were investigated, and photocuring and photocross-
linking characteristics of the copolymers as negative
photoresist were studied.
2. Experimental
2.1. Synthesis of maleopimaric acid anhydride
Rosin (30.2 g, 0.1 mol) was heated to 180°C and
maintained for 2 h in the N2 atmosphere. The molten
rosin was slowly cooled to 120°C and 120 ml of acetic
acid was added slowly to the ¯uid with stirring. After
the solution was cooled to 70°C, 8.82 g (0.09 mol) of
maleic anhydride and 1.92 g (0.01 mol) of p-toluene
sulfonic acid (PTS) were added to the solution. The
solution was re¯uxed for 12 h and cooled to obtain
RMA. After two recrystallizations of RMA with acetic
acid, white crystals of MPA were produced. Yield: 48%;
1
H-NMR (CDCl3 ): d ˆ 10:5 (OH of COOH), 5.5 (s, 1H,
unsaturated proton from Diels±Alder reaction), 3.2±0.5
(aliphatic and alicyclic protons); IR (NaCl): m …cm 1 † ˆ
3300 (OH of COOH), 2975±2840 (aliphatic CH), 1840±
1800, 1780±1740 (C@O of anhydride), 1750±1725 (C@O
of carboxylic acid). Anal. calcd. for C24 H32 O5 : C, 71.97;
H, 8.05; O, 19.97. Found: C, 67.59; H, 7.40; O, 24.89.
2.2. Synthesis of fumaropimaric acid
MPA (8 g, 0.02 mol) was dissolved to the 1 N NaOH
solution in the autoclave apparatus and the solution was
heated to 200°C for 12 h with pressure. After neutral-
ization of the solution by 0.1 N HCl solution, white solid
product of FPA was obtained. Yield: 94%; 1 H-NMR
(CDCl3 ): d ˆ 10:5 (OH of COOH), 5.5 (s, 1H, unsatu-
rated proton), 3.2±0.5 (aliphatic and alicyclic protons);
IR (NaCl): m …cm 1 † ˆ 3300 (OH of COOH), 2975±2840
(aliphatic CH), 1750±1725 (C@O of carboxylic acid).
Anal. calcd. for C24 H34 O6 : C, 68.86; H, 8.19; O, 22.95.
Found: C, 66.28; H, 7.37; O, 25.75.
2.3. Synthesis of acrylates containing rosin moiety
(MPAHEA, MPAHPA, MPAHBA, and FPAHEA)
To excess SOCl2 , 8 g (0.02 mol) of MPA and few
drops of DMF (dimethyl formamide) were added. After
the solution was re¯uxed for 6 h, excess SOCl2 was ex-
cluded by azeotropic distillation with benzene and solid
MPA±Cl was obtained. To the 40 ml of THF (tetra-
hydrofurane), 5 g of MPA±Cl and excess HEA was
added and the solution was heated to 55±60°C for 48 h
in the presence of pyridine under N2 atmosphere. The
solution was poured into cold distilled water and vis-
cous product was precipitated. MPAHEA was ob-
tained by puri®cation of the product by silica gel
column chromatography …ethyl acetate=chloroform ˆ
1=3†. Other monomers were produced by the same pro-
cess for MPAHEA using rosin derivatives (MPA, FPA)
and acrylates (HEA, HPA and HBA). Yield: MPAHEA
(82%), MPAHPA (85%), MPAHBA (88%), FPAHEA
(83%); To all monomers, 1 H-NMR (CDCl3 ): d ˆ 6:4±5:8
(vinylic protons of acrylates), 5.5 (s, 1H, unsaturated
proton), 4.3 (±COO±CH2 ±), 3.0±0.5 (aliphatic and ali-
cyclic protons); IR (NaCl): m …cm 1 † ˆ 2975±2840 (ali-
phatic CH), 1840±1800, 1780±1740 (C@O of anhydride),
1750±1725 (C@O of carboxylic acid), 1635±1630 (C@C).
2.4. Copolymerization of monofunctional acrylates and
methyl methacrylate
The same moles of monofunctional monomer and
MMA were dissolved in THF and 3 mol% of initiator,
AIBN, was added to the solution and the total solid
content was adjusted to 5 wt.%. Oxygen was thoroughly
excluded from the reaction solution by several freeze±
pump±thaw cycles. After the ampoule containing the
solution was sealed, it was heated to 60±65°C for 48 h
with stirring and poured into ethanol. The precipita-
ted polymer was puri®ed by several reprecipitations
from solvent to ethanol. Copolymer 1: MPAHEA±
MMA (yield 84%); Copolymer 2: MPAHPA±MMA
(yield 78%), Copolymer 3: MPAHBA±MMA (yield 81%);
To all polymers, 1 H-NMR (CDCl3 ): d ˆ 5:5 (s, 1H,
unsaturated proton), 4.3 (±COO±CH2 ±), 3.5 (±COO±
CH3 of MMA), 3.2±0.5 (aliphatic and alicyclic protons);
IR (NaCl): C@C stretching band (m ˆ 1635±1630 cm 1 )
disappeared.
2.5. Photolithographic process
2.5.1. Photocuring method
Photoinitiator (5 mol%), TAZ110 (IGAKURE
Chem.), was added to dioxane solution of copolymer
 J.S. Lee, S.I. Hong / European Polymer Journal 38 (2002) 387±392
and trifunctional monomer, FPAHEA (50 wt.% to co-
polymer). The solution was ®ltered through a Te¯on
membrane ®lter (0.2 lm) and spin-coated onto silicon
wafer. (Spinning rate was adjusted to obtain 1lm ®lm
thickness.) The ®lm was cured under UV radiation (I-
line, 365 nm), with intensity of 3.5 mW/cm2 , and using
2±100 lm mask. After radiation, the ®lms were deve-
loped in base solution (TMAH, 25 wt.%).
2.5.2. Photocrosslinking method
Photocrosslinker (10 wt.% to copolymer), bis-azido-
benzylidene methylcyclohexanone (ABC, Aldrich Chem.
Co.), was added to dioxane solution of copolymer and
solid content was adjusted to 10 wt.%. Coating, expo-
sure and developing processes were carried out by the
same procedures as photocuring method.
3. Results and discussion
As rosin consists of many isomers of resin acids, e.g.
abietic acid, levopimaric acid, palustric acid, etc. [1±3], it
is very hard to isolate single isomer from rosin. In this
study, levopimaric acid was isolated to form MPA via
Diels±Alder reaction of rosin and maleic anhydride [8]
and MPA was functionalized to further applications.
Scheme 1 shows synthesis of acrylic rosin derivatives
from levopimaric acid (1) in rosin. Among the isomers in
rosin, abietic acid, neo-abietic acid and palustric acid
can be isomerized to levopimaric acid by heat or acid
treatment. Levopimaric acid is well known to form
Scheme 1. Synthesis of acrylate monomers containing rosin moiety.
389
an adduct (RMA) with maleic anhydride in accordance
with the Diels±Alder mechanism and MPA (2) was ob-
tained from further puri®cation of RMA. FPA was
obtained from hydrolysis of MPA by NaOH solution
at high temperature and pressure. Monofunctional (4)
and multifunctional (6) acrylic monomers were synthe-
sized from MPA via acid chloride intermediates, MPA±
Cl (3) and FPA±Cl (5).
Monofunctional monomers (MPAHEA, MPAHPA,
MPAHBA) containing rosin moiety were readily co-
polymerized with MMA by radical initiator, AIBN. Dou-
ble bond and anhydride ring in the MPA moiety were
stable during the esteri®cation and polymerization re-
action. This double bond in rosin structure is expected
to contribute to the photocrosslinking of copolymers by
the reaction with nitrene produced from bis-arylazide
type photoinitiator (ABC) by UV radiation [9]. Table 1
shows properties of the copolymers. Using di€erent ac-
rylic monomers, length of spacer group to rosin moiety
could be varied. As the length of spacer group was in-
creased, Tg of copolymer was decreased, but molecular
weight of copolymers was increased. The chemical
structures of photoinitiator (TAZ110) and photocross-
linker (ABC) are shown in Scheme 2. Fig. 1 shows
absorption spectra of copolymers, photoinitiator and
photocrosslinker. Copolymers of acrylic rosin deriva-
tives and MMA show some absorption in deep UV
range but virtually no absorption in I-line (365 nm)
range. Therefore, the activity of photoinitiator and
photocrosslinker (TAZ110, kmax ˆ 376 nm; ABC, kmax ˆ
360 nm), which have maximum absorption in this range,
is not inhibited by the presence of copolymers during
390 J.S. Lee, S.I. Hong / European Polymer Journal 38 (2002) 387±392

Table 1
Properties of copolymers containing rosin moiety
Copolymer Monomer/MMAa Tg b (°C) Mn c Mw c Mw =Mn c
d
Feed Result
1 1=1 1=1:2 122 9300 21,600 2.32
2 1=1 1=1:4 114 9800 24,100 2.45
3 1=1 1=1:3 97 13,400 30,700 2.29
a
Monomer composition in polymer (mole ratio).
b
Determined by DSC.
c
Determined by GPC with polystyrene standard in THF as eluent.
d
Determined by 1 H-NMR.

UV exposure process. From this result, it was noted that

Scheme 2. Structure of photoinitiator (TAZ110) and photo-
crosslinker (ABC).
the polymers containing rosin moiety have good optical
property to be used as photoresist materials. Because the
copolymers were very soluble in various common sol-
vents and showed adhesion property, no additives, adhe-
sion promotor, etc., were needed in spin-coating process.
Because the rosin moiety attached as the side chain of
copolymers contains anhydride group, these resist
polymers could be stripped by NaOH solution.
Fig. 2 shows the characteristic curves of copolymers
by photocuring method. It is seen that photocuring re-
action of copolymers and multifunctional monomer,
FPAHEA, changed the solubility of photoresists rapidly
in the speci®c exposure range by forming the entangled
network of homopolymers (or oligomers) of FPAHEA
and copolymers. Therefore these negative resists showed
relatively high contrast. Fig. 3 shows characteristic curves
of copolymers by photocrosslinking method. In this

Fig. 1. Absorption spectra of copolymers, photoinitiator Fig. 2. Characteristic curves of negative photoresists by photo-
(TAZ110) and photocrosslinker (ABC). curing method.
 J.S. Lee, S.I. Hong / European Polymer Journal 38 (2002) 387±392 391

Fig. 4. SEM photograph of negative pattern of copolymer 3 by

photocrosslinking method (line width: 2.2 lm; exposure dose:
35 mJ/cm2 ).

Fig. 3. Characteristic curves of negative photoresists by lithographic processes for ®ner patterns, 6 2 lm, and
photocrosslinking method. dry etching resistance of these resists are in progress.

method, sensitivities of copolymers were enhanced. As 4. Conclusions

shown in Figs. 2 and 3, copolymer 3 exhibited better
lithographic performance than other copolymers. It is
thought that this result is attributed to rapid change of
solubility by photocuring or photocrosslinking due to
higher molecular weight of copolymer 3 than other co-
polymers. Table 2 summarizes the lithographic results of
copolymers by two methods. From these results, it can be
concluded that the negative photoresists containing rosin
moiety form favorable negative patterns using I-line ra-
diation, and 2.2±10 lm patterns were easily obtained.
Negative pattern of copolymer 3 by photocrosslinking
method is shown in Fig. 4.
These negative resists from rosin, natural resource,
are expected to be applied to various industrial appli-
cations, electric circuit, black matrix, color ®lters for
LCD, micro-machining applications and more. Because
these copolymers contain alicyclic structure originating
from rosin moiety, it is expected that these resists will
show the dry etching resistance [10]. Investigation on the
· From rosin, the abundant natural resource, various
acrylic monomers and copolymers containing rosin
moiety were readily synthesized.
· Copolymers containing rosin moiety showed trans-
parency in UV region (k ˆ 200±400 nm), good solu-
bility, and adhesion property.
· Negative photoresists from copolymers containing
rosin moiety showed favorable sensitivity (12.6±84.6
mJ/cm2 ), contrast (1.81±2.85), and resolution (2.2±
10 lm).
Acknowledgements
This work was supported by a grant no. KOSEF 96-
0300-1501-3 from Korea Science and Engineering
Foundation.

Table 2
Lithography results of negative photoresists containing rosin moiety
Copolymer Photocuring Photocrosslinking
Sensitivity Contrast Line width Sensitivity Contrast Line width
(mJ/cm2 ) (lm) (mJ/cm2 ) (lm)
1 84.2 2.22 P 10 26.3 2.22 P 8.0
2 63.1 2.35 P 10 19.9 2.00 P 4.5
3 39.8 2.85 P 10 12.6 1.81 P 2.2
392 J.S. Lee, S.I. Hong / European Polymer Journal 38 (2002) 387±392
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