U.S. patent application number 12/922518 was filed with the patent office on 2011-04-14 for acrylic resin composition and moldings in which said composition is used.
Invention is credited to Tatsuya Kanagawa, Masahiko Minemura, Noriyoshi Ogawa.
Application Number | 20110086227 12/922518 |
Document ID | / |
Family ID | 41090769 |
Filed Date | 2011-04-14 |
United States Patent
Application |
20110086227 |
Kind Code |
A1 |
Minemura; Masahiko ; et
al. |
April 14, 2011 |
ACRYLIC RESIN COMPOSITION AND MOLDINGS IN WHICH SAID COMPOSITION IS
USED
Abstract
Provided are an acrylic resin composition with which the peeling
properties are improved when multi-layer sheets are formed and roll
attachment is reduced, and an acrylic/polycarbonate multi-layer
sheet having good environmental resistance and good producibility
in which said composition is used. A terminally-modified
polycarbonate resin (0.1 to 10 wt %) having terminal groups which
can be represented by general formula (1): (where R.sub.1
represents an alkylene group, R.sub.2 to R.sub.8 represent
hydrogen, an alkyl group, aryl group or the like, and a is an
integer from 1 to 1000) is compounded with an acrylic resin to
produce the acrylic resin composition, and this is molded into a
multi-layer sheet by co-extrusion with polycarbonate resin.
##STR00001##
Inventors: |
Minemura; Masahiko; (Gunma,
JP) ; Ogawa; Noriyoshi; (Ibaraki, JP) ;
Kanagawa; Tatsuya; (Osaka, JP) |
Family ID: |
41090769 |
Appl. No.: |
12/922518 |
Filed: |
February 23, 2009 |
PCT Filed: |
February 23, 2009 |
PCT NO: |
PCT/JP2009/053233 |
371 Date: |
December 13, 2010 |
Current U.S.
Class: |
428/412 ;
427/387; 525/100 |
Current CPC
Class: |
C09D 133/12 20130101;
C09D 133/02 20130101; C08L 33/02 20130101; B32B 27/08 20130101;
C08L 2666/18 20130101; Y10T 428/31507 20150401; C08G 64/186
20130101; C08L 33/02 20130101; C08F 220/14 20130101; C08L 33/12
20130101; C09D 133/12 20130101; C08L 33/12 20130101; C08F 220/14
20130101; C08L 69/00 20130101; C08L 69/00 20130101; C08L 69/00
20130101; C08F 222/1006 20130101 |
Class at
Publication: |
428/412 ;
525/100; 427/387 |
International
Class: |
C08L 33/08 20060101
C08L033/08; C08L 69/00 20060101 C08L069/00; B32B 27/08 20060101
B32B027/08; B05D 3/02 20060101 B05D003/02 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 17, 2008 |
JP |
2008-068605 |
Claims
1. An acrylic resin composition which comprises an acrylic resin as
a main component and a terminally-modified polycarbonate resin
having terminal groups represented by the following general formula
(1): ##STR00029## (In the formula (1), R.sub.1 represents an
alkylene group having 1 to 20 carbon atoms and R.sub.2 to R.sub.6
represent hydrogen, an alkyl group having 1 to 10 carbon atoms, an
aryl group having 6 to 12 carbon atoms or an alkenyl group having 2
to 10 carbon atoms. R.sub.7 and R.sub.8 represent hydrogen,
fluorine, chlorine, bromine, iodine, an alkyl group having 1 to 10
carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl
group having 2 to 10 carbon atoms, an alkoxy group having 1 to 5
carbon atoms or an aralkyl group having 7 to 17 carbon atoms. "a"
is an integer from 1 to 1000.)
2. The acrylic resin composition according to claim 1, wherein the
content of said terminally-modified carbonate resin is 0.1 to 10%
by weight.
3. The acrylic resin composition according to claim 1, wherein said
terminally-modified carbonate resin has the intrinsic viscosity of
0.05 to 1.5 dl/g.
4. The acrylic resin composition according to claim 1, wherein
R.sub.2 to R.sub.6 in said general formula (1) is hydrogen, a
methyl group, a butyl group or a phenyl group.
5. The acrylic resin composition according to claim 1, wherein
R.sub.1 in said general formula (1) is an alkylene group having 1
to 6 carbon atoms.
6. The acrylic resin composition according to claim 1, wherein "a"
in said general formula (1) is from 4 to 100.
7. The acrylic resin composition according to claim 1, wherein said
terminally-modified polycarbonate resin has repeating units
represented by the following general formula (2): ##STR00030## (In
the formula (2), R.sub.9 to R.sub.12 represent hydrogen, fluorine,
chlorine, bromine, iodine, an alkyl group having 1 to 9 carbon
atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group
having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon
atoms or an aralkyl group having 7 to 17 carbon atoms. "X"
represents a group selected from the group consisting of divalent
organic groups represented by the following formulas: ##STR00031##
(In the above formulas, R.sub.13 and R.sub.14 represent hydrogen,
fluorine, chlorine, bromine, iodine, an alkyl group having 1 to 9
carbon atoms, an alkoxy group having 1 to 5 carbon atoms or an aryl
group having 6 to 12 carbon atoms, or a group forming a carbon ring
or a heterocycle wherein R.sub.13 and R.sub.14 are bonded with each
other. R.sub.15 to R.sub.18 represent hydrogen, an alkyl group
having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon
atoms or an alkenyl group having 2 to 10 carbon atoms. R.sub.19 and
R.sub.20 represent an alkylene group having 1 to 20 carbon atoms.
"b" is an integer from 0 to 20. "c" is an integer from 1 to
1000.)
8. The acrylic resin composition according to claim 7, wherein said
repeating units represented by the general formula (2) are derived
from 2,2-bis(4-hydroxyphenyl)propane,
1,1-bis(4-hydroxyphenyl)cyclohexane,
2,2-bis(4-hydroxy-3-methylphenyl)propane,
bis(4-hydroxyphenyl)methane, 4,4'-biphenyldiol or
.alpha.,.omega.-bis[3-(o-hydroxyphenyl)propyl]polydimethylsiloxane.
9. The acrylic resin composition according to claim 7, wherein the
average degree of polymerization of said repeating units
represented by the general formula (2) is 7 to 200.
10. The acrylic resin composition according to claim 1, wherein
said acrylic resin is derived from monomers comprising an acrylic
monomer selected from the group consisting of acrylic acids,
acrylates and methacrylates as a main component.
11. The acrylic resin composition according to claim 10, wherein
said acrylic resin is polymethylmethacrylate copolymer.
12. The acrylic resin composition according to claim 1, which
further comprises fatty acid amides and/or higher alcohols.
13. A molded product obtained by molding the acrylic resin
composition according to claim 1.
14. The molded product according to claim 13, which is a film or
sheet molded product.
15. A multilayer laminated product which at least comprises a layer
formed of the acrylic resin composition according to claim 1 and a
layer formed of other resins.
16. The multilayer laminated product according to claim 15, which
is a polycarbonate resin laminated product wherein a polycarbonate
resin is used as said other resins and said layer formed of the
acrylic resin composition is laminated on one side or both sides of
the layer formed of the polycarbonate resin.
17. The multilayer laminated product according to claim 15, which
further comprises a hardcoat layer.
18. A process for producing the acrylic resin composition according
to claim 1, which comprises a process of mixing acrylic monomers
with a terminally-modified polycarbonate resin having terminal
groups represented by the following general formula (1) and
subsequently polymerizing said acrylic monomers by heat or light.
##STR00032## (In the formula (1), R.sub.1 represents an alkylene
group having 1 to 20 carbon atoms and R.sub.2 to R.sub.6 represent
hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group
having 6 to 12 carbon atoms or an alkenyl group having 2 to 10
carbon atoms. R.sub.7 and R.sub.8 represent hydrogen, fluorine,
chlorine, bromine, iodine, an alkyl group having 1 to 10 carbon
atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group
having 2 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon
atoms or an aralkyl group having 7 to 17 carbon atoms. "a" is an
integer from 1 to 1000.)
19. A process for producing a multilayer laminated product
comprising a layer formed of the acrylic resin composition
according to claim 1 and a layer formed of other resins, which
comprises a step of molding by co-extrusion of a resin forming said
layer formed of other resins with said acrylic resin
composition.
20. A process for producing a multilayer laminated product
comprising a layer formed of the acrylic resin composition
according to claim 1 and a layer formed of other resins, which
comprises a step of coating a mixture of acrylic monomers and a
terminally-modified polycarbonate resin having terminal groups
represented by the following general formula (1) on said layer
formed of other resins and subsequently polymerizing acrylic
monomers in said mixture by heat or light. ##STR00033## (In the
formula (1), R.sub.1 represents an alkylene group having 1 to 20
carbon atoms and R.sub.2 to R.sub.6 represent hydrogen, an alkyl
group having 1 to 10 carbon atoms, an aryl group having 6 to 12
carbon atoms or an alkenyl group having 2 to 10 carbon atoms.
R.sub.7 and R.sub.8 represent hydrogen, fluorine, chlorine,
bromine, iodine, an alkyl group having 1 to 10 carbon atoms, an
aryl group having 6 to 12 carbon atoms, an alkenyl group having 2
to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or
an aralkyl group having 7 to 17 carbon atoms. "a" is an integer
from 1 to 1000.)
Description
TECHNICAL FIELD
[0001] The present invention relates to an acrylic resin
composition comprising a specific terminal silicone-modified
polycarbonate resin. Moreover, it relates to moldings such as a
film, a sheet and a multilayer sheet with other resins having an
excellent releasability and low frictional properties in which said
acrylic resin composition is used, and to a process for producing
the same.
BACKGROUND ART
[0002] Acrylic resins are applied in various fields such as an
optical lens, a protection material for a liquid crystal panel and
an aquarium because of their excellent transparency and scratch
resistance. Above all, they are often used for a hard coating on
the other resins since the surface is hard and has excellent
scratch resistance. Especially, a polymer laminated body such as a
multilayer sheet in combination with polycarbonate which also has
excellent transparency and high impact resistance is quite suitable
for a field such as various kinds of windowpanes, a transparent
roof and a transparent panel member wherein scratch resistance and
impact resistance are required, and the demand is high.
[0003] Examples of way for laminating an acrylic resin with a
polycarbonate resin include known methods such as (1) a method of
co-extruding a polycarbonate resin and an acrylic resin to mold a
multilayer sheet and (2) a method of coating a monomer of the
acrylic resin on a polycarbonate resin sheet substrate and then
curing by light or heat. Of the two methods, the method (1) has
been commonly used in these days for the reason that the method (2)
has problems such as work environment pollution by volatilization
of acrylic monomers and complicated management of coating and/or
curing equipments. However, the method (1) also has problems that
releasability of the acrylic resin from the sheet molding roll at
the time of co-extrusion is poor, which would occasionally cause
deterioration in moldability and appearance.
[0004] In order to solve the above problems, methods of using an
acrylic resin composition comprising various types of lubricants
are disclosed (Patent Document 1, Patent Document 2). According to
these methods wherein lubricants such as fatty acid ester and fatty
acid amide are used, though roll releasing properties may be
improved, accumulation of lubricants on the roll and whitening
under the circumstances of high temperature and high humidity may
occur in some cases, and there is room for improvement.
[0005] Meanwhile, it is known to use a modified polycarbonate resin
having a silicone structure in its main chain (Patent Document 3).
Since this modified polycarbonate is a polymer having a high
molecular weight, problems caused by volatilization can be solved.
However, releasability thereof is not necessarily satisfactory and
there is room for improvement.
[0006] In addition, thought a modified polycarbonate having a
silicone structure in its molecular terminal itself is known
(Patent Document 4), there is no case of applying it to an acrylic
resin having different refraction index and compatibility, and
there is no knowledge about transparency, slidability and
environmental stability. [0007] Patent Document 1: Jpn. Pat.
Laid-Open Publication No. 2005-225018 [0008] Patent Document 2:
Jpn. Pat. Laid-Open Publication No. 2006-205478 [0009] Patent
Document 3: Jpn. Pat. Laid-Open Publication No. H05-200827 [0010]
Patent Document 4: Jpn. Pat. Laid-Open Publication No.
H07-258398
DISCLOSURE OF THE INVENTION
Problems to be Solved by the Invention
[0011] The problem to be solved by the present invention is to
solve the above-mentioned defects of the prior art, and to provide
an acrylic resin composition which is highly improved in
releasability from a molding roll at the time of manufacturing an
acrylic resin sheet, especially to provide an acrylic
resin/polycarbonate resin multilayer sheet wherein releasability of
an acrylic resin from a molding roll at the time of manufacturing a
multilayer sheet of a polycarbonate resin and an acrylic resin is
improved as well as accumulation of lubricants onto the roll is
reduced (low roll accumulation), and excellent appearance can be
maintained even under the circumstances of high temperature and
high humidity (excellence in environmental stability), and to
provide an acrylic resin composition which can form this kind of
multilayer sheets.
Means for Solving the Problems
[0012] The inventors of the present invention searched a new
lubricant to be blended with an acrylic resin, especially a
lubricant suitable for an acrylic resin composition for laminating
with a polycarbonate resin and paid intensive research efforts to
dissolve the above-mentioned problems, and as a result, they found
that a specific terminal silicone-modified polycarbonate resin was
a lubricant having excellent releasability, stability under high
temperature and high humidity and low roll accumulation, and thus
completed the present invention.
[0013] Thus, the present invention relates to an acrylic resin
composition and a process for producing the same, and in addition,
a molded product and a multilayer laminated product thereof, and a
process for producing the same shown below.
1) An acrylic resin composition which comprises an acrylic resin as
a main component and a terminally-modified polycarbonate resin
having terminal groups represented by the following general formula
(1):
##STR00002##
(In the formula (1), R.sub.1 represents an alkylene group having 1
to 20 carbon atoms and R.sub.2 to R.sub.6 represent hydrogen, an
alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to
12 carbon atoms or an alkenyl group having 2 to 10 carbon atoms.
R.sub.7 and R.sub.8 represent hydrogen, fluorine, chlorine,
bromine, iodine, an alkyl group having 1 to 10 carbon atoms, an
aryl group having 6 to 12 carbon atoms, an alkenyl group having 2
to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or
an aralkyl group having 7 to 17 carbon atoms. "a" is an integer
from 1 to 1000.) 2) The acrylic resin composition according to 1),
wherein the content of said terminally-modified carbonate resin is
0.1 to 10% by weight. 3) The acrylic resin composition according to
1) or 2), wherein said terminally-modified carbonate resin has the
intrinsic viscosity of 0.05 to 1.5 dl/g. 4) The acrylic resin
composition according to any one of 1) to 3), wherein R.sub.2 to
R.sub.6 in said general formula (1) is hydrogen, a methyl group, a
butyl group or a phenyl group. 5) The acrylic resin composition
according to any one of 1) to 4), wherein R.sub.1 in said general
formula (1) is an alkylene group having 1 to 6 carbon atoms. 6) The
acrylic resin composition according to any one of 1) to 5), wherein
"a" in said general formula (1) is from 4 to 100. 7) The acrylic
resin composition according to any one of 1) to 6), wherein said
terminally-modified polycarbonate resin has repeating units
represented by the following general formula (2):
##STR00003##
(In the formula (2), R.sub.9 to R.sub.12 represent hydrogen,
fluorine, chlorine, bromine, iodine, an alkyl group having 1 to 9
carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl
group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5
carbon atoms or an aralkyl group having 7 to 17 carbon atoms. "X"
represents a group selected from the group consisting of divalent
organic groups represented by the following formulas:
##STR00004##
(In the above formulas, R.sub.13 and R.sub.14 represent hydrogen,
fluorine, chlorine, bromine, iodine, an alkyl group having 1 to 9
carbon atoms, an alkoxy group having 1 to 5 carbon atoms or an aryl
group having 6 to 12 carbon atoms, or a group forming a carbon ring
or a heterocycle wherein R.sub.13 and R.sub.14 are bonded with each
other. R.sub.15 to R.sub.18 represent hydrogen, an alkyl group
having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon
atoms or an alkenyl group having 2 to 10 carbon atoms. R.sub.19 and
R.sub.20 represent an alkylene group having 1 to 20 carbon atoms.
"b" is an integer from 0 to 20. "c" is an integer from 1 to 1000.)
8) The acrylic resin composition according to 7), wherein said
repeating units represented by the general formula (2) are derived
from 2,2-bis(4-hydroxyphenyl) propane, 1,1-bis(4-hydroxyphenyl)
cyclohexane, 2,2-bis(4-hydroxy-3-methylphenyl) propane,
bis(4-hydroxyphenyl)methane, 4,4'-biphenyldiol or .alpha.,
.omega.-bis[3-(o-hydroxyphenyl)propyl]polydimethylsiloxane. 9) The
acrylic resin composition according to 7) or 8), wherein the
average degree of polymerization of said repeating units
represented by the general formula (2) is 7 to 200. 10) The acrylic
resin composition according to any one of 1) to 9), wherein said
acrylic resin is derived from monomers comprising an acrylic
monomer selected from the group consisting of acrylic acids,
acrylates and methacrylates as a main component. 11) The acrylic
resin composition according to 10), wherein said acrylic resin is
polymethylmethacrylate copolymer. 12) The acrylic resin composition
according to any one of 1) to 11), which further comprises fatty
acid amides and/or higher alcohols. 13) A molded product obtained
by molding the acrylic resin composition according to any one of 1)
to 12). 14) The molded product according to 13), which is a film or
sheet molded product. 15) A multilayer laminated product which at
least comprises a layer formed of the acrylic resin composition
according to 1) to 12) and a layer formed of other resins. 16) The
multilayer laminated product according to 15), which is a
polycarbonate resin laminated product wherein a polycarbonate resin
is used as said other resins and said layer formed of the acrylic
resin composition is laminated on one side or both sides of the
layer formed of the polycarbonate resin. 17) The multilayer
laminated product according to 15) or 16), which further comprises
a hardcoat layer. 18) A process for producing the acrylic resin
composition according to any one of 1) to 12), which comprises a
process of mixing acrylic monomers with a terminally-modified
polycarbonate resin having terminal groups represented by the
following general formula (1) and subsequently polymerizing said
acrylic monomers by heat or light.
##STR00005##
(In the formula (1), R.sub.1 represents an alkylene group having 1
to 20 carbon atoms and R.sub.2 to R.sub.6 represent hydrogen, an
alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to
12 carbon atoms or an alkenyl group having 2 to 10 carbon atoms.
R.sub.7 and R.sub.8 represent hydrogen, fluorine, chlorine,
bromine, iodine, an alkyl group having 1 to 10 carbon atoms, an
aryl group having 6 to 12 carbon atoms, an alkenyl group having 2
to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or
an aralkyl group having 7 to 17 carbon atoms. "a" is an integer
from 1 to 1000.) 19) A process for producing a multilayer laminated
product comprising a layer formed of the acrylic resin composition
according to any one of 1) to 12) and a layer formed of other
resins, which comprises a step of molding by co-extrusion of a
resin forming said layer formed of other resins with said acrylic
resin composition. 20) A process for producing a multilayer
laminated product comprising a layer formed of the acrylic resin
composition according to any one of 1) to 12) and a layer formed of
other resins, which comprises a step of coating a mixture of
acrylic monomers and a terminally-modified polycarbonate resin
having terminal groups represented by the following general formula
(1) on said layer formed of other resins and subsequently
polymerizing acrylic monomers in said mixture by heat or light.
##STR00006##
(In the formula (1), R.sub.1 represents an alkylene group having 1
to 20 carbon atoms and R.sub.2 to R.sub.6 represent hydrogen, an
alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to
12 carbon atoms or an alkenyl group having 2 to 10 carbon atoms.
R.sub.7 and R.sub.6 represent hydrogen, fluorine, chlorine,
bromine, iodine, an alkyl group having 1 to 10 carbon atoms, an
aryl group having 6 to 12 carbon atoms, an alkenyl group having 2
to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or
an aralkyl group having 7 to 17 carbon atoms. "a" is an integer
from 1 to 1000.)
EFFECTS OF THE INVENTION
[0014] The terminally-modified polycarbonate resin comprised in the
acrylic resin composition of the present invention has lower
volatility since it has a higher molecular weight than conventional
lubricants for an acrylic resin. In addition, since it has
polysiloxane groups at the terminal, the degree of freedom of
polysiloxane groups is higher than a modified polycarbonate having
a silicone structure in its main chain and slidability on the
surface of the resin is unexpectedly excellent, and an excellent
lubricating effect can be obtained in small amounts.
[0015] Therefore, the acrylic resin composition comprising the
terminally-modified polycarbonate resin like this can exhibit
excellent roll releasability without accompanying pollution
(accumulation of lubricants on a roll) or deterioration of
slidability caused by volatilization and/or a large-volume use of
lubricants. Moreover, a molded product formed of said acrylic resin
composition would not easily whitened even under the circumstances
of high temperature and high humidity, and can maintain an
excellent slidability.
[0016] Especially, in case of molding a multilayer laminated
product by co-extrusion with a polycarbonate resin, improvement of
the roll releasability of the acrylic resin layer as well as an
extreme reduction of the roll-adhered substances can be obtained.
Therefore, the polycarbonate resin laminated product using the
acrylic resin composition of the present invention does not cause
whitening under the circumstances of high temperature and high
humidity, and can maintain an excellent appearance. Thus, it is
suitable for a field wherein scratch resistance and impact
resistance are required such as various kinds of windowpane
materials, optical members, protecting sheets for LCD and EL
displays and the like.
BEST MODE FOR CARRYING OUT THE INVENTION
[0017] The acrylic resin composition of the present invention
comprises an acrylic resin as a main component and a
terminally-modified polycarbonate resin in addition thereto.
(1) Acrylic Resin
[0018] The acrylic resin, which is a main component of the resin
composition of the present invention, is not particularly limited
as far as it is a resin derived from mainly acrylic monomers.
Examples of the acrylic monomers include (meth)acrylic acids,
(meth)acrylates and (meth)acrylamides.
[0019] Examples of the (meth)acrylic acids include methacrylic acid
and acrylic acid. Examples of (meth)acrylates include alkyl
methacrylates having 1 to 20 carbon atoms such as methyl
methacrylate, ethyl methacrylate, propyl methacrylate, butyl
methacrylate, cyclohexyl methacrylate, octyl methacrylate, lauryl
methacrylate and stearyl methacrylate; alkyl acrylates having 1 to
20 carbon atoms such as methyl acrylate, ethyl acrylate, propyl
acrylate, butyl acrylate, octyl acrylate, lauryl acrylate and
stearyl acrylate; and glycidyl(meth)acrylates such as glycidyl
methacrylate and glycidyl acrylate. Examples of (meth)acrylamides
include methacrylamide and acrylamide.
[0020] These acrylic monomers can be used each independently or two
or more can be used in combination with each other. Among them,
methyl methacrylate is most preferable.
[0021] The acrylic resin derived from the above-mentioned acrylic
monomers can be a homopolymer derived from only one kind of the
above-mentioned acrylic monomers, or can be a copolymer derived
from two or more of the acrylic monomers in combination with each
other, or can be a copolymer of the acrylic monomers as a main
monomer in combination with less than 50% by weight of other vinyl
monomers. Examples of the other vinyl monomers include styrene,
.alpha.-methyl styrene, acrylonitrile, butadiene and vinyl
acetate.
[0022] Preferable examples of the acrylic resin to be used for the
present invention include polymethylmethacrylate and a copolymer
derived from methylmethacrylate as a main monomer. Most preferable
examples thereof include methylmethacrylate copolymer derived from
methylmethacrylate as a main monomer in combination with
methacrylate as a comonomer.
[0023] A process for producing an acrylic resin, in general, can be
classified into emulsion polymerization, suspension polymerization
and continuous polymerization. Any resins produced by any processes
of polymerization can be used as the acrylic resin to be used for
the present invention. It is preferable to use an acrylic resin
produced by suspension polymerization or continuous polymerization,
and it is more preferable to use an acrylic resin produced by
continuous polymerization. Continuous polymerization can be
classified into continuous mass polymerization and continuous
solution polymerization. According to the present invention,
acrylic resins obtained by either polymerization process can be
used.
[0024] According to continuous mass polymerization and continuous
solution polymerization, additives such as an emulsifier as
polymerization auxiliaries or a suspension dispersing agent are
never used. A polymerization initiator for initiating
polymerization and a chain transfer agent for adjusting a molecular
weight are simply added thereto. According to continuous solution
polymerization, examples of solvents include toluene, ethylbenzene,
xylene, hexane, octane, cyclohexane, methanol, ethanol, propanol,
butanol, acetone and methylethylketone. However, it is not
particularly limited to them as far as polymerization is carried
out efficiently and no residual solvent remains in the acrylic
resin obtained.
[0025] As a polymerization initiator, common azo polymerization
initiators or peroxide polymerization initiators can be selected.
Examples of azo polymerization initiators include
2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methyl-butyronitrile)
and 1,1'-azobis(cyclohexane-1-carbonitrile). Examples of peroxide
polymerization initiators include benzoyl peroxide,
di-t-butylperoxide and di-t-acylperoxide. However, it is not
particularly limited to them. As a chain transfer agent, it is
common to use mercaptans. Examples of the mercaptans include butyl
mercaptan, hexyl mercaptan, octyl mercaptan and dodecyl mercaptan.
However, it is not particularly limited to them
(2) Terminally-Modified Polycarbonate Resin
[0026] The terminally modified polycarbonate resin to be used for
the present invention is polycarbonate having a terminal
polysiloxane structure represented by the following general formula
(1):
##STR00007##
[0027] In the above formula (1), R.sub.1 represents an alkylene
group having 1 to 20 carbon atoms, preferably having 1 to 6 carbon
atoms. Examples of the alkylene group include an ethylene group, a
propylene group and a methyl ethylene group.
[0028] R.sub.2 to R.sub.6 represent a hydrogen atom, an alkyl group
having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon
atoms or an alkenyl group having 2 to 10 carbon atoms. They can be
same or different with each other. Examples of the alkyl group
having 1 to 10 carbon atoms include a methyl group, an ethyl group,
a n-propyl group, a n-butyl group and a cycloalkyl group such as a
cyclohexyl group. Examples of the aryl group having 6 to 12 carbon
atoms include a phenyl group and a tolyl group. Examples of the
alkenyl group having 2 to 10 carbon atoms include a vinyl group, an
allyl group, a hexenyl group and an octenyl group. Among them, a
hydrogen atom, a methyl group, an ethyl group, a butyl group and a
phenyl group are preferable.
[0029] R.sub.7 and R.sub.8 represent a group selected from the
group consisting of hydrogen, fluorine, chlorine, bromine, iodine,
an alkyl group having 1 to 10 carbon atoms (preferably having 1 to
4 carbon atoms), an aryl group having 6 to 12 carbon atoms, an
alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1
to 5 carbon atoms or an aralkyl group having 7 to 17 carbon atoms
(preferably having 7 carbon atom). These R.sub.7 and R.sub.8 can be
same or different with each other. Particularly preferable examples
of R.sub.7 and R.sub.8 include an alkyl group having 1 to 9 carbon
atoms and an aryl group having 6 to 12 carbon atoms. More
precisely, examples thereof include a methyl group, an ethyl group,
a propyl group, a n-butyl group, a sec-butyl group, a tert-butyl
group, a phenyl group and a methoxy group. Among them, a methyl
group, a butyl group and a phenyl group are most preferable.
[0030] Examples of polysiloxane groups comprised in the
above-mentioned general formula (1) include a group derived from
polydimethylsiloxane, polydiphenylsiloxane,
polymethylphenylsiloxane, polyvinylmethylsiloxane and polymethyl
hydrogen siloxane. Two or more of them can be comprised in
combination with each other.
[0031] The length of the polysiloxane group is represented by a
polymerization degree "a" in the general formula (1). "a" is 1 to
1000, preferably 4 to 100, more preferably 6 to 50. In order to
obtain sufficient characteristics of slidability by siloxane, it is
better that "a" is large to a certain degree. However, the polymer
with "a" which is larger than 1000 is not so practical since a
productive efficiency of the terminally-modified polycarbonate
resin may be declined as mentioned below. In addition, the
polymerization degree "a" only means an average degree of
polymerization, and in general, the degree of polymerization itself
has a distribution.
[0032] The polycarbonate resin forming the terminally-modified
polycarbonate resin having the terminal groups represented by the
above-mentioned general formula (1) of the present invention is not
particularly limited as far as it is a common polycarbonate resin.
Preferably, it is polycarbonate having the repeating unit
represented by the following general formula (2) (a carbonate
unit).
##STR00008##
[0033] In the above formula (2), R.sub.9 to R.sub.12 represent
hydrogen, fluorine, chlorine, bromine, iodine, an alkyl group
having 1 to 9 carbon atoms, an aryl group having 6 to 12 carbon
atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group
having 1 to 5 carbon atoms or an aralkyl group having 7 to 17
carbon atoms. The most preferable examples of R.sub.9 to R.sub.12
include hydrogen and a methyl group.
[0034] "X" represents a group selected from the group consisting of
divalent organic groups represented by the following formulas:
##STR00009##
[0035] In the above formulas, R.sub.13 and R.sub.14 represent
hydrogen, fluorine, chlorine, bromine, iodine, an alkyl group
having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon
atoms or an aryl group having 6 to 12 carbon atoms, or a group
forming a carbon ring or a heterocycle wherein R.sub.13 and
R.sub.14 are bonded with each other.
[0036] R.sub.15 to R.sub.18 represent a hydrogen atom, an alkyl
group having 1 to 10 carbon atoms, an aryl group having 6 to 12
carbon atoms or an alkenyl group having 2 to 10 carbon atoms carbon
atoms. They can be same or different with each other. Examples of
the alkyl group having 1 to 10 carbon atoms include a methyl group,
an ethyl group, a propyl group, a butyl group and a cycloalkyl
group such as a cyclohexyl group. Examples of the aryl group having
6 to 12 carbon atoms include a phenyl group and a tolyl group.
Examples of the alkenyl group having 2 to 10 carbon atoms include a
vinyl group, an allyl group, a hexenyl group and an octenyl group.
Among them, a hydrogen atom, a methyl group, a vinyl group and a
phenyl group are preferable.
[0037] R.sub.19 and R.sub.20 represent an alkylene group having 1
to 20 carbon atoms, preferably having 2 to 8 carbon atoms. Examples
thereof include an ethylene group, a n-propylene group and a
n-butylene group. "b" is an integer from 0 to 20. "c" is an integer
from 1 to 1000, preferably from 4 to 100, more preferably from 6 to
50.
[0038] Examples of the most preferable repeating unit represented
by the above general formula (2) include a structural unit derived
from 2,2-bis(4-hydroxyphenyl)propane,
1,1-bis(4-hydroxyphenyl)cyclohexane,
2,2-bis(4-hydroxy-3-methylphenyl) propane,
bis(4-hydroxyphenyl)methane, 4,4'-biphenyldiol or
.alpha.,.omega.-bis[3-(o-hydroxyphenyl)propyl]polydimethylsiloxane.
[0039] Examples of the preferable terminally-modified polycarbonate
resin to be used for the present invention include a polycarbonate
resin consisting of the repeating unit represented by the above
general formula (2) having the terminal structure represented by
the above general formula (1), more precisely, a polycarbonate
resin having the structure represented by the following general
formula (2'). In the following formula (2'), R.sub.9 to R.sub.12,
"X" and "n" represent the same meanings as in the above general
formula (2). "(A)" represents a terminal group represented by the
above general formula (1).
##STR00010##
[0040] In the above formula (2'), "n", which is an average degree
of polymerization, represents an integer of not less than 1,
preferably a number of 7 to 200 on average, more preferably a
number in the range of 20 to 100 on average.
[0041] The average molecular weight of the terminally-modified
polycarbonate resin is not particularly limited. It is preferable
that the intrinsic viscosity [.eta.] thereof is in the range from
0.05 to 1.5 [dl/g]. When the intrinsic viscosity is in this range,
it is easy to add and mix with an acrylic resin and is easy in
handling. Conversion of the intrinsic viscosity into a viscosity
average molecular weight (Mv) can be carried out by using
[intrinsic viscosity [.eta.]=1.23.times.10.sup.-4 Mv.sup.0.83].
[0042] In addition, in consideration of roll staining after a
long-term continuous molding, a temperature of 1% weight loss on
heating of the terminally-modified polycarbonate resin is
preferably between 230 and 490.degree. C., more preferably between
280 and 490.degree. C. When the temperature of 1% weight loss on
heating of the terminally-modified polycarbonate resin is lower
than 230.degree. C., the amount of volatilization at the time of
molding may increase and the effect of roll releasability may be
unstable.
[0043] The process for producing the terminally-modified
polycarbonate resin to be used for the present invention is not
particularly limited. For example, it is possible to produce by the
process disclosed in Japanese Patent Laid-Open Publication No.
H07-258398. More precisely, it can be produced by reacting
bisphenols represented by the following general formula (3) and a
monovalent phenol containing a polysiloxane group represented by
the following general formula (4) with a carbonate-forming
compound. In the following formula (3), R.sub.9 to R.sub.12 and "X"
represent the same meanings as R.sub.9 to R.sub.12 and "X" in the
general formula (2) respectively. Moreover, R.sub.1 to R.sub.8 and
"a" in the following general formula (4) represent the same
meanings as R.sub.1 to R.sub.8 and "a" in the general formula (1)
respectively.
##STR00011##
##STR00012##
[0044] The monovalent phenol containing a polysiloxane group
represented by the above general formula (4) can be produced by,
for example, addition reaction of monovalent phenol having an
unsaturated group (hereinafter, "unsaturated group-containing
monovalent phenol") with polysiloxane having a Si--H group at one
end (hereinafter, "hydrogen polysiloxane") under platinum
catalyst.
[0045] Examples of the hydrogen polysiloxane to be used for
producing the monovalent phenol containing a polysiloxane group
include polydimethylsiloxane, polydiphenylsiloxane,
polymethylphenylsiloxane, polyvinylmethylsiloxane and polymethyl
hydrogen siloxane, which have a Si--H group at the one end. Two or
more of them can be used in combination with each other.
[0046] The molecular weight of hydrogen polysiloxane is represented
by the polymerization degree "a" in the general formula (4). "a" is
1 to 1000, preferably 4 to 100, more preferably 6 to 50. In order
to obtain sufficient characteristics of slidability by siloxane, it
is better that "a" is large to a certain degree. However, the
polymer with "a" which is larger than 1000 is not so practical
because reactivity with the unsaturated group-containing monovalent
phenol may be deteriorated. In addition, since the hydrogen
polysiloxane is a polymer which is a mixture of various short-chain
polymers and long-chain polymers, the polymerization degree "a"
only means an average degree of polymerization, and in general, the
degree of polymerization itself has a distribution.
[0047] Examples of the unsaturated group-containing monovalent
phenol to be reacted with hydrogen polysiloxane include
p-hydroxystyrene, p-isopropenylphenol, o-allylphenol,
p-allylphenol, eugenol, isoeugenol, 2,6-dimethyl-4-allylphenol,
4-(1-butenyl)phenol, 4-(1-pentanyl)phenol, 4-(1-hexanyl)phenol,
4-(1-octanyl)phenol, 4-(1-decanyl)phenol, 4-(1-dodecanyl)phenol,
4-(1-tetradecanyl)phenol, 4-(1-hexadecanyl)phenol and
4-(1-nonadecanyl)phenol. Two or more of the compounds can be used
in combination with each other. Among them, the most preferable
compound is o-allylphenol.
[0048] Catalysts to be used for hydrosilylation (reaction of
hydrogen polysiloxane with unsaturated group-containing monovalent
phenol) can be either homogeneous or heterogeneous.
[0049] Examples of the catalysts include a platinum complex such as
chloroplatinic acid, metal platinum, octacarbonyl 2-cobalt, a
palladium complex and a rhodium complex.
[0050] The reaction is carried out in the solution in which
unsaturated group-containing monovalent phenol to be used for the
present invention is dissolved. Examples of the solvents include
halogenated hydrocarbons such as carbon tetrachloride, chloroform
and 1,2-dichloroethane, aromatic hydrocarbons such as benzene,
toluene and xylene, aromatic halides such as monochlorobenzene and
dichlorobenzene, methylethylketone, ethyl acetate, 1,4-dioxane,
cyclohexane and pyridine. In view of solubility and affinity with
catalyst, it is preferable to use aromatic hydrocarbons such as
benzene, toluene and xylene. In addition, the reaction temperature
is preferably not lower than 60.degree. C.
[0051] Examples of the monovalent phenol containing a polysiloxane
group represented by the above general formula (4) include
compounds having the following structures. In the following
structural formulae, a is an integer from 1 to 1000 and
(a+d).ltoreq.1000.
##STR00013## ##STR00014##
[0052] Two or more of the above-shown monovalent phenol containing
a polysiloxane group can be used in combination with each other.
Furthermore, in addition to the monovalent phenol containing a
polysiloxane group represented by the above general formula (4), it
is possible to use terminal terminating agents such as phenol,
alkyl-substituted phenols such as p-t-butylphenol and alkylester
substituted phenols such as p-hydroxyphenyl butylbenzoate in
combination. However, it is preferable to restrict the amount used
so as to be less than 50% by weight ratio based upon the monovalent
phenol containing a polysiloxane group represented by the above
general formula (4).
[0053] Examples of the bisphenols represented by the above general
formula (3) include 4,4'-biphenyldiol, bis(4-hydroxyphenyl)methane,
bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfone,
bis(4-hydroxy-3-methylphenyl)sulfone,
bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)sulfide,
bis(4-hydroxyphenyl)ketone, 1,1-bis(4-hydroxyphenyl)ethane,
2,2-bis(4-hydroxyphenyl)propane (bisphenol A; BPA),
2,2-bis(4-hydroxy-3-t-butylphenyl)propane,
2,2-bis(4-hydroxyphenyl)butane,
1,1-bis(4-hydroxyphenyl)cyclohexane,
2,2-bis(4-hydroxy-3-methylphenyl)propane,
2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane,
1,1-bis(4-hydroxyphenyl)-1-phenylethane,
bis(4-hydroxyphenyl)diphenylmethane,
2,2-bis(4-hydroxy-3-allylphenyl)propane,
3,3,5-trimethyl-1,1-bis(4-hydroxyphenyl)cyclohexane,
1,1-bis(4-hydroxy-2-methyl-5-t-butylphenyl)-2-methylpropane,
9,9-bis(4-hydroxy-3-ethylphenyl)fluorene,
9,9-bis(4-hydroxy-3-methylphenyl)fluorene,
9,9-bis(4-hydroxyphenyl)fluorene,
1,1-bis(4-hydroxyphenyl)cyclododecane,
1,1-bis(4-hydroxy-3-methylphenyl)cyclododecane,
2,2-bis(4-hydroxyphenyl)hexafluoropropane,
2,2-bis(4-hydroxy-3,5-dibromophenyl)propane,
.alpha.,.omega.-bis[3-(o-hydroxyphenyl)propyl]polydimethyldiphenyl-random
copolymeric siloxane,
.alpha.,.omega.-bis[3-(o-hydroxyphenyl)propyl]polydimethylsiloxane,
4,4'-[1,4-phenylene-bis(1-methylethylidene)]bisphenol, and
4,4'-[1,3-phenylene-bis(1-methylethylidene)]bisphenol.
[0054] Two or more of them can be used in combination with each
other.
[0055] Particularly, it is preferable to select
2,2-bis(4-hydroxyphenyl)propane,
1,1-bis(4-hydroxyphenyl)cyclohexane,
2,2-bis(4-hydroxy-3-methylphenyl)propane,
bis(4-hydroxyphenyl)methane, 4,4'-biphenyldiol or
.alpha.,.omega.-bis[3-(o-hydroxyphenyl)propyl]polydimethylsiloxane
among them.
[0056] Examples of the carbonate-forming compounds include
phosgenes and bisarylcarbonates such as diphenylcarbonate,
di-p-tolylcarbonate, phenyl-p-tolylcarbonate,
di-p-chlorophenylcarbonate, dinaphthylcarbonate and the like.
[0057] Regarding the process for producing the terminally-modified
polycarbonate resin to be used for the present invention, it can be
produced by reacting bisphenols and monovalent phenol containing a
polysiloxane group with a carbonate-forming compound by employing
publicly known methods used for producing polycarbonate from
bisphenol A such as a direct reaction process of bisphenols and
phosgene (a phosgene method) and an ester exchange reaction (a
transesterification method) of bisphenols with
bisarylcarbonates.
[0058] Of the phosgene method and the transesterification method,
it is preferable to employ the phosgene method in view of heat
resistance of monovalent phenol containing a polysiloxane group
represented by the general formula (4) and transesterification
rate. In the phosgene method, it is preferable to use the
monovalent phenol containing a polysiloxane group at the rate of
not more than 80% by weight based upon the total of all bisphenols
used, in view of reactivity of said monovalent phenol containing a
polysiloxane group.
[0059] In the phosgene method, in general, the bisphenols
represented by the general formula (3) and the monovalent phenol
containing a polysiloxane group represented by the general formula
(4) are reacted with phosgene under the presence of acid-binding
agents and solvents. Examples of the acid-binding agents include
pyridine and alkali metal hydroxides such as sodium hydroxide and
potassium hydroxide. Examples of the solvents include methylene
chloride, chloroform, chlorobenzene and xylene.
[0060] In addition, in order to accelerate the condensation
polymerization reaction, catalysts such as tertiary amines such as
triethylamine and quaternary ammonium salts can be used. For
adjusting the polymerization degree, the above-mentioned monovalent
phenol containing a polysiloxane group functions as a molecular
weight adjuster. If necessary, antioxidants such as sodium sulfite
and hydrosulfite and branching agents such as phloroglucin and
isatin bisphenol can be added in small amounts.
[0061] Generally, it is proper to conduct the reaction in a
temperature range between 0 and 150.degree. C., preferably between
5 and 40.degree. C. While the reaction time may vary depending on
the reaction temperature, it is normally between 0.5 minutes and 20
hours, preferably between 1 minute and 2 hours. It is desirable to
keep pH of the reaction system not below 10 during the
reaction.
[0062] In the transesterification method, in general, the
bisphenols represented by the general formula (3) and the
monovalent phenol containing a polysiloxane group represented by
the general formula (4) are mixed with bisarylcarbonate and are
reacted at high temperature under reduced pressure.
[0063] The reaction is generally carried out at a temperature range
between 150 and 350.degree. C., preferably between 200 and
300.degree. C. The ultimate pressure is preferably reduced to lmmHg
or less to remove the phenols, which are derived from said
bisarylcarbonate and are produced as a result of the
transesterification reaction, from the reaction system by
distillation.
[0064] While the reaction time varies depending on the reaction
temperature and the reduced pressure level, it is generally 1 to 12
hours. The reaction is preferably carried out in an atmosphere of
inert gas such as nitrogen or argon. If desired, the reaction can
be carried out by adding antioxidants and/or branching agents.
[0065] The terminally-modified polycarbonate resin synthesized by
the above-mentioned reactions can readily be added and mixed with
an acrylic resin. It is preferable that the polycarbonate resin has
an intrinsic viscosity [.eta.] in the range from 0.05 to 1.5 [dl/g]
as an easily handling range. Conversion of the intrinsic viscosity
into a viscosity average molecular weight (Mv) can be carried out
by using [intrinsic viscosity [.eta.]=1.23.times.10.sup.-4
Mv.sup.0.83]. In consideration of roll staining after a prolonged
continuous molding, a temperature of 1% weight loss on heating of
the terminally-modified polycarbonate resin is preferably between
230 and 490.degree. C., more preferably between 280 and 490.degree.
C. When the temperature of 1% weight loss on heating of the
terminally-modified polycarbonate resin is lower than 230.degree.
C., volatilization volume at the time of molding may increase and
the effect of roll releasability may be unstable.
[0066] In addition, at the time of synthesizing the
terminally-modified polycarbonate resin of the present invention,
all (100%) of the polycarbonate terminals are not necessarily
converted into the terminal group represented by the general
formula (1). In view of the residual amount of impurities and the
rate of reaction, it can be thought that not less than 80% of the
polycarbonate terminals are at least present as the terminal group
represented by the general formula (1), and furthermore the
carbonate resin having at least one siloxane at the terminal can be
obtained at a rate of not less than 90%. Examples of the terminal
having a structure other than the terminal group represented by the
general formula (1) include an unreacted phenol terminal and a
chloroformate terminal. Additionally, there may be one forming a
circular body which has no terminal.
[0067] The content of the silicone component of the
terminally-modified polycarbonate resin of the present invention is
preferably 1 to 50% by weight, more preferably 5 to 40% by weight
on average as Si element based upon the total amount of said
terminally-modified polycarbonate resin.
[0068] When Si elements are contained not only at the terminal like
in the case of using a polycarbonate resin having silicone
structures in its main chain, it is preferable that the content of
the terminal Si elements which are derived from terminal silicones
is not less than 40% by weight.
(3) Acrylic Resin Composition
[0069] The acrylic resin composition of the present invention is a
blend of an acrylic resin with a terminally-modified polycarbonate
resin. The content of the terminally-modified polycarbonate resin
is preferably 0.1 to 10% by weight. In addition, it is preferable
that the content is 0.5 to 5% by weight for the purpose of
improving molding roll releasability at the time of co-extrusion
with other resins. In case that the content is less than 0.1% by
weight, improvement of releasability and surface modification
effect may be insufficient. In case that the content is more than
10% by weight, transparency and appearance may be deteriorated.
[0070] In addition, it is possible to add known additives such as
ultraviolet absorbing agents, antioxidants and coloring agents to
the acrylic resin composition of the present invention depending on
various requirements. Furthermore, other lubricants can be
additionally used in combination with the terminally-modified
polycarbonate resin. Especially, when using a small amount of fatty
acid amides and/or higher alcohols in combination, releasability
can further be improved.
[0071] Examples of the fatty acid amides usable include
ethylene-bis-stearic acid amide, methylene-bis-stearic acid amide,
stearic acid amide and behenic acid amide. Examples of the higher
alcohols include stearyl alcohol, lauryl alcohol, behenyl alcohol
and palmityl alcohol.
[0072] In the case of using other lubricants like this, it is
preferable that the content of the other lubricants is in the range
from 0.05 to 1.0% by weight based upon the acrylic resin
composition, and it is preferable that the content thereof is in
the range from 1 to 40 parts by weight based upon 100 parts by
weight of the terminally-modified polycarbonate resin.
(4) Process for Producing the Acrylic Resin Composition
[0073] Examples of the process for producing the acrylic resin
composition of the present invention include a method of mixing the
terminally-modified polycarbonate resin of the present invention
with acrylic monomers and subsequently polymerizing the acrylic
monomers to form an acrylic resin and a method of mixing the
terminally-modified polycarbonate resin with an acrylic resin.
[0074] Regarding the method of mixing the terminally-modified
polycarbonate resin with acrylic monomers and subsequently
polymerizing the acrylic monomers, more precisely, a method of
dissolving or dispersing the terminally-modified polycarbonate
resin into acrylic monomers and subsequently adding a radical
initiator such as benzoyl peroxide, azobisisobutyronitrile,
benzophenone and
2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, and
further adding heat or light to polymerize (or to cure) is
used.
[0075] Examples of polymerization processes include suspension
polymerization, emulsion polymerization, bulk polymerization and
solution polymerization. In the case of using heat, it is
preferable to employ the conditions wherein heating temperature is
20 to 160.degree. C. and heating time is 0.1 to 24 hours. In the
case of using light, it is preferable to employ the conditions
wherein wavelength is 200 to 500 nm and irradiation time is 0.1 to
30 minutes.
[0076] The method of mixing acrylic monomers and the
terminally-modified polycarbonate resin is not particularly
limited. For example, a method of blending by a cylindrical rotary
blender or an agitator can be employed. In addition, divinyl
compounds such as N,N'-methylene-bis-acrylamide and ethyleneglycol
dimethacrylate can be added to the acrylic monomers as a
cross-linking agent.
[0077] When mixing the acrylic resin with the terminally-modified
polycarbonate resin, the terminally-modified polycarbonate resin
and other additives if necessary are added into the acrylic resin,
and subsequently kneading is conducted in the publicly-known
manners. Kneading is preferably conducted by using a mixer such as
a fixed container type mixer, vessel-rotary mixer and a roll type
mixer under the conditions at a temperature of from room
temperature to 270.degree. C. for 1 to 120 minutes.
[0078] When the layer of the acrylic resin composition is laminated
on the layer of the other resins as a hardcoat, it is preferable to
employ a method of mixing the terminally-modified polycarbonate
resin with the acrylic monomers and subsequently polymerizing the
acrylic monomer. On the other hand, when a multilayer laminated
product (a multilayer sheet) is molded by forming layers of the
other resins and the acrylic resin composition at a time by
co-extrusion, it is preferable to employ a method of mixing the
terminally-modified polycarbonate resin with the acrylic resin.
[0079] The acrylic resin composition of the present invention can
be used for molding by publicly-known molding methods. It can be
used for wet molding, compression molding, vacuum compression
molding, extrusion molding, injection molding, inflation molding
and the like. When extrusion molding or injection molding is
carried out using the acrylic resin composition independently, the
thickness of the molded product is preferably from 0.1 mm to 2 cm.
When multilayer molding is carried out by means of co-extrusion
with other resins and the like, the thickness thereof is preferably
from 10 to 100 .mu.m.
(5) Molded Product
[0080] The molded product of the present invention is a product
obtained by molding the above-mentioned acrylic resin composition
of the present invention. The method for obtaining the molded
product is not particularly limited and wet molding, compression
molding, vacuum compression molding, extrusion molding, injection
molding, inflation molding and the like can be employed.
[0081] Also the forms of the molded product are not particularly
limited. Molded products having various forms can be obtained
depending on the intended use. Among them, film or sheet molded
products are preferable according to the present invention.
[0082] In the case of a molded product formed singly of the acrylic
resin composition obtained by extrusion molding or injection
molding or a single-layer film or sheet molded product, the
thickness of the molded product is preferably from 0.1 mm to 2 cm,
though it can be determined depending on its intended use.
[0083] Examples of the molded products of the present invention
additional to the above-mentioned film or sheet molded products
include an injection-molded product, a compression-molded product,
a vacuum compression-molded product, an inflation-molded product
and a cast-molded product.
(6) Multilayer Laminated Product
[0084] The acrylic resin composition of the present invention can
form a multilayer laminated product in combination with other
resins. That is, the multilayer laminate product of the present
invention is characterized in that it at least comprises a layer
formed of the above-mentioned acrylic resin composition of the
present invention.
[0085] The methods for forming a multilayer laminated product are
not particularly limited. Examples of the methods include a method
of multilayer molding by co-extrusion of the acrylic resin
composition of the present invention with other resins, a method of
molding the acrylic resin composition of the present invention into
a film or a sheet and then laminating it with a film or a sheet
formed of the other resins, a method of extrusion molding of the
acrylic resin composition on a film or a sheet formed of the other
resins and a method of coating acrylic monomers on a film or a
sheet formed of the other resins and then forming the layer of the
acrylic resin composition by curing by heat or light irradiation.
Among them, a method using co-extrusion molding is particularly
preferable.
[0086] In the case of a multilayer laminated product of the acrylic
resin composition and the other resin, the thickness of the layer
of the acrylic resin composition is preferably from 10 to 100
.mu.m, more preferably from 15 to 80 .mu.m, though it can be
determined depending on its intended use. Regarding the ratio of
the thickness with the layer of the other resins, it is preferable
that [the layer of the acrylic resin composition]: [the layer of
the other resins]=1:1 to 1:200.
[0087] In the case when multilayer laminating by co-extrusion of
the acrylic resin composition of the present invention with the
other resins is carried out, the number of laminated layers,
combination of layers and order of layers are not particularly
limited. However, it is preferable that the acrylic resin
composition of the present invention at least forms the outermost
layer (a skin layer) of the multilayer laminate product.
[0088] Examples of the other resins which can form a multilayer
laminating product with the acrylic resin composition of the
present invention include polycarbonate, polyethylene
terephthalate, polybutylene terephthalate, polyethylene
naphthalate, polyarylate, polystyrene, ABS, MS, AS, polyamide,
polyoxymethylene, polyphenylene ether, polyvinylchloride,
polyvinylidene chloride, polyethylene, polypropylene, PTFE,
polysulfone, polyethersulfone, TPX, polycycloolefin and polyvinyl
adamantane. Among them, the combination with polycarbonate
excellent in transparency and impact resistance is suitable.
[0089] The process for producing the multilayer laminating product
of the present invention will be described below, as an
illustrative embodiment of a process for producing a multilayer
sheet by co-extrusion, taking the case of using a polycarbonate
resin as a substrate for example.
[0090] The extrusion equipment used for producing a multilayer
sheet is consisting of a main-extruder whereby a polycarbonate
resin forming a substrate layer is to be extruded and one or two
sub-extruder(s) whereby the acrylic resin composition which will be
coated on one or both sides of the substrate layer is to be
extruded. In general, as a sub-extruder, the one which is smaller
than the main-extruder is employed.
[0091] The temperature condition of the main-extruder is normally
from 230 to 290.degree. C., preferably from 240 to 280.degree. C.
The temperature condition of the sub-extruder is normally from 220
to 270.degree. C., preferably from 230 to 260.degree. C.
[0092] As a method for coating more than one of molten resins,
publicly known methods such as a feed block method and a
multi-manifold method can be employed. In this case, the molten
resin laminated by a feed block method is introduced to a sheet
molding die such as T-die to form a sheet, and subsequently it is
flowed into a molding roll having a mirror-finished surface (a
polishing roll) to form a bank.
[0093] The sheet molded product thus obtained is subjected to a
process of mirror finishing and cooling in the course of passing
through the molding roll to form a laminated body.
[0094] In the case of multi-manifold die, the melt resins laminated
in said die are also molded into a sheet in the die and then
mirror-finishing and cooling are carried out on the molding roll to
form a laminating body. The temperature of the die is normally from
250 to 320.degree. C., preferably from 270 to 300.degree. C. The
temperature of the molding roll is normally from 100 to 190.degree.
C., preferably from 110 to 180.degree. C. As the roll, a vertical
roll or a horizontal roll can be used accordingly.
[0095] It is also one of the preferable embodiments to place a
polymer filter having an opening of 10 .mu.m in front of the T-die
of the sub-extruder in order to remove fine foreign substances in
the acrylic resin composition. In addition, when cleaning level of
the sub-extruder is ensured, it is also one of the preferable
embodiments to place a polymer filter having an opening of 10 .mu.m
in the pelletizing process.
[0096] A hardcoat layer can be provided on the above-mentioned
multilayer laminated product of the present invention. The hardcoat
is provided on the outermost layer of the multilayer laminated
product. Therefore, the hardcoat is preferably provided on the
surface of the layer of the acrylic resin composition of the
present invention.
[0097] Hardcoat-treatment provided on the layer of the acrylic
resin composition is a treatment of laminating a hardcoat layer
which is cured by heat or active energy ray in order to improve
scratch resistance. Examples of coating materials curable by active
energy ray include a resin composition comprising one or more than
one resin consisting of monofunctional or polyfunctional acrylate
monomers or oligomers and a photopolymerization initiator as a
curing catalyst. Examples of heat-curable polymer coating materials
include polyorganosiloxanes and crosslinking type acrylic resins.
Some of these resin compositions are commercially available as a
hardcoat agent to be used for an acrylic resin or a polycarbonate
resin, and suitable ones can be selected accordingly in
consideration of compatibility with a coating line.
[0098] In these coating materials, various stabilizers such as an
ultraviolet absorbent, a light stabilizer and an antioxidant, a
leveling agent, an antifoaming agent, a thickening agent, an
antistatic agent and surfactants such as an anticlouding agent can
be added in addition to organic solvents, if necessary.
[0099] Hardcoat treatment provided on the surface of the
polycarbonate resin which is not co-extruded in the multilayer body
is carried out in order to improve scratch resistance, and a
hardcoat layer cured by active energy ray is laminated. Examples of
coating materials curable by active energy ray include a resin
composition comprising one or more than one resin consisting of
monofunctional or polyfunctional acrylate monomers or oligomers and
a photopolymerization initiator as a curing catalyst. Examples of
heat-curable polymer coating materials include polyorganosiloxanes
and crosslinking type acrylic resins. Some of these resin
compositions are commercially available as a hardcoat agent to be
used for an acrylic resin or a polycarbonate resin, and suitable
ones can be selected accordingly in consideration of compatibility
with a coating line.
[0100] In these coating materials, various stabilizers such as an
ultraviolet absorbent, a light stabilizer and an antioxidant, a
leveling agent, an antifoaming agent, a thickening agent, an
antistatic agent and surfactants such as an antifogging agent can
be added in addition to organic solvents, if necessary.
[0101] Examples of the coating materials to be cured by active
energy line on the layer of the acrylic resin composition include a
composition comprising 100 parts by weight of a photopolymerizable
composition (A) which comprises 2 to 80% by weight of a
bifunctional (meth)acrylate compound having the weight average
molecular weight of not higher than 300 and 20 to 98% by weight of
hexafunctional urethane acrylate oligomer copolymerizable therewith
and 1 to 10 parts by weight of a photopolymerization initiator
(B).
[0102] Examples of the bifunctional (meth)acrylate compound having
the molecular weight of not higher than 300 include
diethyleneglycol di(meth)acrylate, dipropyleneglycol
di(meth)acrylate, tripropyleneglycol diacrylate, 1,6-hexanediol
di(meth)acrylate, 2-(2'-vinyloxyethoxy)ethyl-(meth)acrylate and
1,4-butanediol diacrylate.
[0103] Examples of the hexafunctional urethane acrylate oligomers
include trade name "EB-220" manufactured by DAICEL CYTEC COMPANY
LTD., trade name "UN-3320 HC" manufactured by Negami Chemical
Industries Co., Ltd., trade name "UN-3320HA" manufactured by Negami
Chemical Industries Co., Ltd., trade name "UV-7600B" manufactured
by Nippon Synthetic Chemical Industry Co., Ltd., and trade name
"UV-7640B" manufactured by Nippon Synthetic Chemical Industry Co.,
Ltd.
[0104] Regarding the photopolymerization initiators (B), commonly
known compounds can be used. Examples thereof include benzoin,
benzophenone, benzoin ethylether, benzoin isopropylether,
2,2-dimethoxy-2-phenylacetophenone,
1-hydroxycyclohexylphenylketone,
2-hydroxy-2-methyl-1-phenylpropane-1-one, azobisisobutyronitrile
and benzoyl peroxide.
[0105] Examples of the method of curing using heat-curable polymer
coatings on the layer of acrylic resin include a method of using a
composition comprising the following (i), (ii) and (iii):
(i) 1 to 98 parts by weight of organotrialkoxysilane (C)
represented by the formula [R.sup.1Si(OR.sup.2).sub.3] wherein
R.sup.1 represents a substituted or non-substituted monovalent
hydrocarbon group, R.sup.2 represents an alkyl group, (ii) 1 to 98
parts by weight of a composition comprising 50 to 100 parts by
weight of a solution of colloidal silica having a particle diameter
of 4 to 20 nm which contains 10 to 50% by weight of silicic
anhydride (D) and (iii) 1.0 to 5.0 parts by weight of amine
carboxylate and/or a quaternary ammonium carboxylate (E).
[0106] R.sup.1 in the above-mentioned organotrialkoxysilane is
preferably a substituted or non-substituted monovalent hydrocarbon
group having 1 to 8 carbon atoms, examples of which include an
alkyl group such as a methyl group, an ethyl group, a n-propyl
group, a n-butyl group, an i-butyl group, a sec-butyl group, a
n-hexyl group and a n-heptyl group, .gamma.-chloropropyl group, a
vinyl group, a 3,3,3-trifluoropropyl group, a
.gamma.-glycidoxypropyl group, a .gamma.-methacryloxypropyl group,
a .gamma.-mercaptopropyl group, a phenyl group, and a
3,4-epoxycyclohexylethyl group.
[0107] R.sup.2 in the above-mentioned organotrialkoxysilane (C) is
an alkyl group having 1 to 5 carbon atoms, examples of which
include a methyl group, an ethyl group, a n-propyl group, a n-butyl
group, an i-butyl group, a sec-butyl group and a tert-butyl
group.
[0108] Examples of the organotrialkoxysilane (C) include
tetramethoxysilane, tetraethoxysilane, methyl trimethoxy silane,
methyl triethoxysilane, ethyl trimethoxysilane, ethyl
triethoxysilane, n-propyl trimethoxysilane, n-propyl
triethoxysilane, i-propyl trimethoxysilane, i-propyl
triethoxysilane, .gamma.-chloropropyltrimethoxysilane,
.gamma.-chloropropyl triethoxysilane, vinyl trimethoxysilane, vinyl
triethoxysilane, 3,3,3-trifluoropropyl trimethoxysilane,
3,3,3-trifluoropropyl triethoxysilane, .gamma.-glycidoxypropyl
trimethoxysilane, .gamma.-glycidoxypropyl triethoxysilane,
.gamma.-methacryloxypropyl trimethoxysilane,
.gamma.-methacryloxypropyl triethoxysilane, .gamma.-mercaptopropyl
trimethoxysilane, .gamma.-mercaptopropyl triethoxysilane, phenyl
trimethoxysilane, phenyl triethoxysilane, 3,4-epoxycylohexylethyl
trimethoxysilane, 3,4-epoxycylohexylethyl triethoxysilane, dimethyl
dimethoxysilane, diethyl dimethoxysilane, diethyl diethoxysilane,
di-n-propyl dimethoxysilane, di-n-propyl diethoxysilane,
di-i-propyldimethoxysilane, di-i-propyldiethoxysilane, diphenyl
dimethoxysilane and diphenyl diethoxysilane.
[0109] Among them, tetramethoxysilane, tetraethoxysilane, methyl
trimethoxy silane, methyl triethoxysilane, dimethyl dimethoxysilane
and dimethyl diethoxysilane are preferable.
[0110] The colloidal silica (D) composed of the above-mentioned
composition contains 10 to 50% by weight of silicic anhydride and
the average particle diameter of the colloidal silica is 4 to 20
nm. As a disperser of the colloidal silica (D) like this, water, an
organic solvent and a mixed solvent of water with at least one of
hydrophilic organic solvents such as lower aliphatic alcohol such
as methanol, ethanol, isopropanol, n-butanol and isobutanol; an
ethyleneglycol derivatives such as ethyleneglycol, ethyleneglycol
monobutylether and ethyleneglycol monoethylether acetate;
diethyleneglycol derivatives such as diethyleneglycol and
diethyleneglycol monobutylether; and diacetone alcohols can be
used. Among these aqueous solvents, water or a water-methanol mixed
solvent is preferable in view of dispersion stability and drying
characteristics of the dispersion media after coating.
[0111] Examples of commercial products wherein the colloidal silica
is dispersed in a basic aqueous solution include tradename "SNOWTEX
30" and "SNOWTEX 40", each manufactured by Nissan Chemical
Industries, Ltd., tradename "CATALOID S30" and "CATALOID S40" each
manufactured by Catalysts and Chemicals Industries Co., Ltd.
[0112] Examples of commercial products wherein the colloidal silica
is dispersed in an acidic aqueous solution include tradename
"SNOWTEX O" manufactured by Nissan Chemical Industries, Ltd.
[0113] Examples of commercial products wherein the colloidal silica
is dispersed in an organic solvent include tradenames "MA-ST",
"IPA-ST", "NBA-ST", "IBA-ST", "EG-ST", "XBA-ST", "NPC-ST",
"DMAC-ST", each manufactured by Nissan Chemical Industries,
Ltd.
[0114] Examples of amine carboxylate and/or quaternary ammonium
carboxylate (E) include dimethylamine acetate, ethanolamine
acetate, dimethylaniline formate, tetraethylammonium benzoate,
trimethylbenzylammonium acetate, tetramethylammonium acetate,
tetra-n-butylammonium acetate, tetraethylammonium acetate and
2-hydroxyethyl trimethylammonium acetate.
[0115] Examples of coating materials to be cured by using active
energy ray on a polycarbonate layer wherein the acrylic resin is
not co-extruded include an ultraviolet curable polymer coating
composition comprising 100 parts by weight of a photopolymerizable
composition (F) which comprises 20 to 60% by weight of
1,9-nonanediol diacrylate (b1) and 40 to 80% by weight of the other
compounds (b2) copolymerizable with said (b1) and 1 to 10 parts by
weight of a photopolymerization initiator (G).
[0116] Examples of the other compounds (b2) which are
copolymerizable with (b1) include multifunctional (meth)acrylate
monomers which are bifunctional or higher functional,
multifunctional urethane (meth)acrylate oligomers which are
bifunctional or higher functional (hereinafter, "multifunctional
urethane (meth)acrylate oligomer"), multifunctional polyester
(meth)acrylate oligomer which are bifunctional or higher functional
(hereinafter, "multifunctional polyester (meth)acrylate oligomer")
and multifunctional epoxy (meth)acrylate oligomer which are
bifunctional or higher functional (hereinafter, "multifunctional
epoxy(meth)acrylate oligomer").
[0117] These (meth)acrylate monomers and oligomers can be used each
independently or two or more of them can be used in combination
with each other.
[0118] Examples of the multifunctional (meth)acrylate monomers
include a monomer having more than one (meth)acryloyloxy group in a
molecule.
[0119] Typical examples of bifunctional (meth)acrylate monomers
include alkyleneglycol di(meth)acrylate, polyoxyalkyleneglycol
di(meth)acrylate, halogenated alkyleneglycol di(meth)acrylate,
fatty acid polyol-di(meth)acrylate, di(meth)acrylate with
alkyleneoxide adduct of bisphenol A or bisphenol F and epoxy
di(meth)acrylate with bisphenol A or bisphenol F. However, they are
not limited to the above compounds and various monomers can be
used.
[0120] Specific examples of bifunctional (meth)acrylate monomers
include 2-n-butyl-2-ethyl-1,3-propanediol diacrylate,
tripropyleneglycol diacrylate, tetraethyleneglycol diacrylate,
polyethyleneglycol di(meth)acrylate, polypropyleneglycol
diacrylate, triethyleneglycol dimethacrylate, 1,6-hexanediol
dimethacrylate and neopentylglycol dimethacrylate.
[0121] Examples of trifunctional or higher functional
(meth)acrylate monomers include trimethylolpropane trimethacrylate,
trimethylolpropane ethyleneoxide adduct triacrylate, glycerin
propyleneoxide adduct triacrylate and pentaerythritol
tetraacrylate.
[0122] Examples of multifunctional urethane (meth)acrylate
oligomers include an urethanization reaction product of
(meth)acrylate monomers having at least one (meth)acryloyloxy group
and hydroxy group in a molecule with polyisocyanate. Examples of
multifunctional urethane (meth)acrylate oligomers include an
urethanization reaction product of (meth)acrylate monomers having
at least one (meth)acryloyloxy group and hydroxy group in a
molecule with an isocyanate compound obtained by reacting polyols
with polyisocyanate.
[0123] Examples of (meth)acrylate monomers having at least one
(meth) acryloyloxy group and hydroxy group in a molecule to be used
for urethanization reaction include 2-hydroxyethyl(meth)acrylate,
2-hydroxypropyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate,
2-hydroxy-3-phenoxypropyl(meth)acrylate, glycerin di(meth)acrylate,
trimethylolpropane di(meth)acrylate, pentaerythritol
tri(meth)acrylate and dipentaerythritol penta(meth)acrylate.
[0124] Examples of polyisocyanates to be used for urethanization
reaction include di- or tri-isocyanates such as hexamethylene
diisocyanate, lysine diisocyanate, isophorone diisocyanate,
dicyclohexylmethane diisocyanate, tolylenediisocyanate,
xylylenediisocyanate, diisocyanates obtained by hydrogenating of
aromatic isocyanates among them such as hydrogenated
tolylenediisocyanate and hydrogenated xylylenediisocyanate,
triphenylmethane triisocyanate and dimethylenetriphenyl
triisocyanate and polyisocyanate obtained by polymerization of
diisocyanates.
[0125] Examples of polyols to be used for urethanization reaction
include, in general, aromatic polyols, aliphatic polyols and
alicyclic polyols, as well as polyesterpolyol and
polyetherpolyol.
[0126] Examples of the aliphatic polyols and alicyclic polyols
include 1,4-butanediol, 1,6-hexanediol, neopentylglycol,
ethyleneglycol, propyleneglycol, trimethylolethane,
trimethylolpropane, dimethylolheptane, dimethylol propionic acid,
dimethylol butyric acid, glycerin and hydrogenated bisphenol A.
[0127] Examples of polyester polyols include one obtained by
dehydration condensation reaction of the above-mentioned polyols
with polybasic carboxylic acid (or anhydride). Examples of the
polybasic carboxylic acid include succinic acid (anhydride), adipic
acid, maleic acid (anhydride), trimellitic acid (anhydride),
hexahydrophthalic acid (anhydride), phthalic acid (anhydride),
isophthalic acid and terephthalic acid. Examples of polyether
polyols include polyalkyleneglycol as well as
polyoxyalkylene-modified polyol obtained by reaction of the
above-mentioned polyols or phenols with alkyleneoxide.
[0128] The multifunctional polyester (meth)acrylate oligomers can
be obtained by dehydration condensation reaction of (meth) acrylic
acid, polybasic carboxylic acid (anhydride) and polyols. Examples
of the polybasic carboxylic acid (anhydride) to be used for the
dehydration condensation reaction include succinic acid
(anhydride), adipic acid, maleic acid (anhydride), itaconic acid
(anhydride), trimellitic acid (anhydride), pyromellitic acid
(anhydride), hexahydrophthalic acid (anhydride), phthalic acid
(anhydride), isophthalic acid and terephthalic acid. Examples of
the polyols to be used for the dehydration condensation reaction
include 1,4-butanediol, 1,6-hexanediol, diethyleneglycol,
triethyleneglycol, propyleneglycol, neopentylglycol,
dimethylolheptane, dimethylol propionic acid, dimethylol butyric
acid, trimethylolpropane, ditrimethylolpropane, pentaerythritol and
dipentaerythritol.
[0129] The multifunctional epoxy(meth)acrylate oligomers can be
obtained by addition reaction of polyglycidylether with
(meth)acrylic acid. Examples of the polyglycidylether include
ethyleneglycol diglycidylether, propyleneglycol diglycidylether,
tripropyleneglycol diglycidylether, 1,6-hexanediol diglycidylether
and bisphenol A diglycidylether.
[0130] As photopolymerization initiators to be used for the present
invention, commonly known compounds can be used. Examples thereof
include benzoin, benzophenone, benzoin ethylether, benzoin
isopropylether, 2,2-dimethoxy-2-phenylacetophenone,
1-hydroxycyclohexylphenylketone,
2-hydroxy-2-methyl-1-phenylpropane-1-one, azobisisobutyronitrile
and benzoyl peroxide. However, they are not limited to these
compounds.
[0131] Examples of applicable methods of coating a coating material
on a layer of the acrylic resin composition of the present
invention and/or a layer of a polycarbonate resin being not
co-extruded include brushing, rolling, dipping, flow coating, spray
coating, a roll coater coating, a flow coater coating and a method
proposed by Japanese Patent Laid Open Publication No. 2004-130540.
The thickness of a hardcoat layer cured by heat or active energy
ray is 1 to 20 .mu.m, preferably 2 to 15 .mu.m, more preferably 3
to 12 .mu.m. When the thickness of the hardcoat layer is less than
1 .mu.m, the effect of improvement of surface hardness tends to be
insufficient. On the other hand, even when the thickness is more
than 20 .mu.m, the effect of improvement of surface hardness would
not easily be further enhanced and it is costly disadvantageous,
and in addition, it may cause a deterioration of impact
resistance.
[0132] It is desirable that the hardcoat on the surface wherein the
acrylic resin is not laminated with 20 to 120 .mu.m thick, which is
a hardcoat on the internal surface when used as a finished product,
prevent cracks under the stress of 20 MPa.
[0133] When cracks occur under the stress of not higher than 20
MPa, cracks would occur on the internal surface when it is used as
a finished product and may be hard to use.
[0134] An antireflective layer can be provided on the hardcoat. As
the antireflective layer, a laminate wherein two or more layers
including a higher refractive index layer and a lower refractive
index layer are laminated so that the lower refractive index layer
becomes the outermost surface layer is preferable. Materials
forming the higher refractive index layer are not particularly
limited, and examples thereof include metal oxide such as
TiO.sub.2, Y.sub.2O.sub.3, La.sub.2O.sub.3, ZrO.sub.2 and
Al.sub.2O.sub.3.
[0135] Materials forming the lower refractive index layer are not
particularly limited, and examples thereof include metal oxide and
metal fluoride such as SiO.sub.2, MgF.sub.2, LiF, 3NaF.AlF.sub.3,
AlF.sub.3 and Na.sub.3AlF.sub.6.
[0136] Regarding the thickness of the antireflective layer, though
depending on the design of the antireflective layer, it is common
to be used in the thickness range wherein the lower limit is 10 nm
and the upper limit is 300 nm.
[0137] Methods of forming an antireflective layer on a hardcoat
layer are not particularly limited, and examples thereof include
publicly known methods such as spattering, deposition, plasma CVD
and coating.
(7) Polycarbonate Resin Laminated Product
[0138] The acrylic resin composition of the present invention can
form a multilayer laminated product laminated with a polycarbonate
resin. In this type of laminated product (a polycarbonate resin
laminated product), the acrylic resin composition of the present
invention can be provided on one side or both sides of the
polycarbonate resin layer.
[0139] The polycarbonate resin laminated product can preferably be
produced by multilayer molding using co-extrusion of the acrylic
resin composition of the present invention with a polycarbonate
resin.
[0140] The film thickness of the layer of the acrylic resin
composition (a skin layer) in the polycarbonate resin laminated
product is preferably 10 to 100 .mu.m, more preferably 15 to 80
.mu.m, further preferably 20 to 70 .mu.m. In case of not thicker
than 10 .mu.m, transparency and appearance may be deteriorated
caused by turbulence of the laminated interfacial surface. In case
of thicker than 100 .mu.m, impact resistance of the polycarbonate
resin layer may bee remarkably deteriorated, and in addition, it is
economically disadvantageous.
[0141] The polycarbonate resin usable for a substrate of the
multilayer sheet (a polycarbonate resin laminated product) of the
present invention is not particularly limited as far as it is a
resin obtained by the above-mentioned known methods for producing a
polycarbonate resin. Examples thereof include a resin obtained by
reacting carbonate-forming compounds with divalent phenols
(bisphenols).
[0142] Examples of the bisphenols include 4,4'-biphenyldiol,
bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)ether,
bis(4-hydroxyphenyl)sulfone, bis(4-hydroxy-3-methylphenyl)sulfone,
bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)sulfide,
bis(4-hydroxyphenyl)ketone, 1,1-bis(4-hydroxyphenyl)ethane,
2,2-bis(4-hydroxyphenyl)propane (bisphenol A; BPA),
2,2-bis(4-hydroxy-3-t-butylphenyl)propane,
2,2-bis(4-hydroxyphenyl)butane,
1,1-bis(4-hydroxyphenyl)cyclohexane,
2,2-bis(4-hydroxy-3-methylphenyl)propane,
2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane,
1,1-bis(4-hydroxyphenyl)-1-phenylethane,
bis(4-hydroxyphenyl)diphenylmethane,
2,2-bis(4-hydroxy-3-allylphenyl)propane,
3,3,5-trimethyl-1,1-bis(4-hydroxyphenyl)cyclohexane,
1,1-bis(4-hydroxy-2-methyl-5-t-butylphenyl)-2-methylpropane,
9,9-bis(4-hydroxy-3-ethylphenyl)fluorene,
9,9-bis(4-hydroxy-3-methylphenyl)fluorene,
9,9-bis(4-hydroxyphenyl)fluorene,
1,1-bis(4-hydroxyphenyl)cyclododecane,
1,1-bis(4-hydroxy-3-methylphenyl)cyclododecane,
2,2-bis(4-hydroxyphenyl)hexafluoropropane,
2,2-bis(4-hydroxy-3,5-dibromophenyl)propane,
.alpha.,.omega.-bis[3-(o-hydroxyphenyl)propyl]polydimethyldiphenyl-random
copolymeric siloxane,
.alpha.,.omega.-bis[3-(o-hydroxyphenyl)propyl]polydimethylsiloxane,
4,4'-[1,4-phenylene-bis(1-methylethylidene)]bisphenol and
4,4'-[1,3-phenylene-bis(1-methylethylidene)]bisphenol.
[0143] Two or more of them can be used in combination with each
other. Among them, it is especially preferable to use a
polycarbonate resin derived from 2,2-bis(4-hydroxyphenyl)propane as
a substrate.
[0144] As a molecular weight of the polycarbonate resin as a
substrate of the multilayer laminated product (a polycarbonate
resin laminated product) of the present invention, the viscosity
average molecular weight thereof is normally 15,000 to 40,000,
preferably 18,000 to 30,000. Various additives commonly used can be
added to the polycarbonate resin. Examples of the additives include
an ultraviolet absorbent, an antioxidant, a color protecting agent,
a flame retardant and a coloring agent.
[0145] The thickness of the polycarbonate resin layer is preferably
0.04 to 2.0 mm for the usage of the present invention wherein being
thinner and lighter and punching processability are required. When
the thickness of the polycarbonate resin layer is less than 0.04
mm, it may be difficult to produce the polycarbonate resin laminate
product by co-extrusion since the minimum required strength for
molding is insufficient. When the thickness thereof is more than
2.0 mm, the necessity of the acrylic resin composition of the
present invention is reduced because it is possible to provide
sufficient roll releasability even by using acrylic resin
compositions comprising conventional lubricants by means of
optimization of molding conditions. As might be expected, it is
possible to use the acrylic resin composition of the present
invention at the thickness of more than 2.0 mm as well.
EXAMPLES
[0146] The present invention will be described in more detail below
referring to Examples. Note that the scope of the present invention
is not limited by the following examples. In the following
sentences, "%" means "% by weight" if not otherwise specified.
Examples of Synthesis 1
[0147] A terminally-modified polycarbonate resin was synthesized in
the same manner as described in Example 1 of Japanese Patent Laid
Open Publication No. H07-258398. More precisely,
[0148] 912 g of 2,2-bis(4-hydroxyphenyl)propane (hereinafter,
"BPA"; manufactured by Mitsui Chemicals, Inc.) and 5 g of
hydrosulfite were dissolved into 8 L of 8% (w/w %) aqueous solution
of sodium hydroxide. Then, 3.6 L of methylenechloride was added to
the aqueous solution and 500 g of phosgene was blown into the
solution over a period of 60 minutes, while stirring and keeping
the temperature of the solution at 15.degree. C. After completion
of blowing phosgene,
##STR00015##
("a" is 40 on average) 608 g of polysiloxane monovalent phenol
(hereinafter, "S1"; manufactured by Shin-Etsu Chemical Co., Ltd.)
having the above-shown structure was added thereto and then stirred
intensely to emulsify the reaction solution. After emulsification,
5 ml of triethylamine was added and the emulsion was stirred for
about 1 hour for polymerization.
[0149] The polymerization reaction solution was separated into an
aqueous phase and an organic phase. The organic phase was
neutralized by phosphoric acid and was washed repeatedly with water
until pH of the wash liquid became neutral. Subsequently, the
organic phase was dropped into warm water of 60.degree. C. to
precipitate a polymer substance. After filtering, the precipitate
was dried to obtain a powdery polymer product.
[0150] The intrinsic viscosity [.eta.] of the solution of the
polymer in the solvent of methylenechloride with a concentration of
0.5 g/dl at 20.degree. C. was 0.42 [dl/g].
[0151] The polymer thus obtained was analyzed by means of infrared
absorption spectrometry, and as a result, absorption due to a
carbonyl group was observed at a position of 1770 cm.sup.-1 and
absorption due to an ether bond was observed at a position of 1240
cm.sup.-1, whereby it was confirmed that the polymer had a
carbonate bond. In addition, absorption due to a hydroxy group was
scarcely observed at a position of 3650 to 3200 cm.sup.-1.
Furthermore, a peak due to a siloxane group was observed at a
position of 1100 to 1020 cm.sup.-1. By means of fluorescent X-ray
analysis using a Cr tube bulb, it was confirmed that the polymer
comprises silicon (Si) elements. Consequently, the polymer was
determined to be a polycarbonate polymer having the following
structure. In addition, on the analysis, the ratio of the terminal
Si elements in the polymer was 13.4% by weight based upon the total
amount of the polymer.
##STR00016##
("n" is 44 on average)
Examples of Synthesis 2
[0152] Synthesis was carried out in the same manner as Example of
Synthesis 1 except for using 608 g of polysiloxane monovalent
phenol having the following structure:
##STR00017##
("a" is 20 on average) (hereinafter, "S2"; manufactured by
Shin-Etsu Chemical Co., Ltd.) in place of the polysiloxane
monovalent phenol in Example of Synthesis 1. The intrinsic
viscosity [.eta.] of the polymer thus obtained was 0.22 [dl/g].
According to infrared absorption spectrometry analysis and
fluorescent X-ray analysis, the polymer was determined to be a
polycarbonate polymer having the following structure. In addition,
the ratio of the terminal Si elements in the polymer was 13.0% by
weight based upon the total amount of the polymer.
##STR00018##
("n" is 22 on average)
Examples of Synthesis 3
[0153] Synthesis was carried out in the same manner as Example of
Synthesis 2 except for using 912 g of BPA and 152 g of
.alpha.,.omega.-bis[3-(o-hydroxyphenyl)propyl]polydimethylsiloxane
having the following structure:
##STR00019##
("c" is 20 on average) (manufactured by Shin-Etsu Chemical Co.,
Ltd.) in place of 912 g of BPA and changing the amount of S2 to 456
g. The intrinsic viscosity [.eta.] of the polymer thus obtained was
0.33 [dl/g]. According to infrared absorption spectrometry analysis
and fluorescent X-ray analysis, the polymer was determined to be a
polycarbonate polymer having the following structure. In addition,
the ratio of the Si elements in the polymer was 12.9% by weight
based upon the total amount of the polymer.
##STR00020##
n: m=approximately 48:1 (molar ratio) n+m .about.30 on average
Examples of Synthesis 4
[0154] Synthesis was carried out in the same manner as Example of
Synthesis 3 except for changing the amount of S2 to 304 g and
adding 152 g of dimethyl silicone oil having the following
structure:
##STR00021##
("e" is 40 on average) (manufactured by Shin-Etsu Chemical Co.,
Ltd.) concurrently with S2. The intrinsic viscosity [.eta.] of the
polymer mixture thus obtained was 0.33 [dl/g]. According to
infrared absorption spectrometry analysis and fluorescent X-ray
analysis, the polymer was determined to be a polycarbonate polymer
mixture having the similar structure as the one in Example of
Synthesis 3. In addition, the ratio of the Si elements in the
polymer was 13.1% by weight based upon the total amount of the
polymer.
Examples of Synthesis 5
[0155] Synthesis was carried out in the same manner as Example of
Synthesis 1 except for using 1,1-bis(4-hydroxyphenyl)cyclohexane,
manufactured by Honshu Chemical Industry Co., Ltd., in place of
BPA. The intrinsic viscosity [.eta.] of the polymer thus obtained
was 0.40 [dl/g]. According to infrared absorption spectrometry
analysis and fluorescent X-ray analysis, the polymer was determined
to be a polycarbonate polymer having the following structure. In
addition, the ratio of the terminal Si elements in the polymer was
13.5% by weight based upon the total amount of the polymer.
##STR00022##
("n" is 36 on average)
Examples of Synthesis 6
[0156] Synthesis was carried out in the same manner as Example of
Synthesis 1 except for using
2,2-bis(4-hydroxy-3-methylphenyl)propane, manufactured by API
Corporation, in place of BPA. The intrinsic viscosity [.eta.] of
the polymer thus obtained was 0.43 [dl/g]. According to infrared
absorption spectrometry analysis and fluorescent X-ray analysis,
the polymer was determined to be a polycarbonate polymer having the
following structure. In addition, the ratio of the terminal Si
elements in the polymer was 13.5% by weight based upon the total
amount of the polymer.
##STR00023##
("n" is 38 on average)
Examples of Synthesis 7
[0157] Synthesis was carried out in the same manner as Example of
Synthesis 1 except for using 775 g of BPA and 137 g of
4,4'-biphenyldiol, manufactured by Honshu Chemical Industry Co.,
Ltd., in place of 912 g of BPA. The intrinsic viscosity [.eta.] of
the polymer thus obtained was 0.42 [dl/g]. According to infrared
absorption spectrometry analysis and fluorescent X-ray analysis,
the polymer was determined to be a polycarbonate polymer having the
following structure. In addition, the ratio of the terminal Si
elements in the polymer was 13.3% by weight based upon the total
amount of the polymer.
##STR00024##
n: m=approximately 5:1 (molar ratio) n+m .about.44 on average
Examples of Synthesis 8
[0158] Synthesis was carried out in the same manner as Example of
Synthesis 1 except for using 638 g of BPA and 274 g of
bis(4-hydroxyphenyl)methane, manufactured by SANKO CO., LTD., in
place of 912 g of BPA. The intrinsic viscosity [.eta.] of the
polymer thus obtained was 0.42 [dl/g]. According to infrared
absorption spectrometry analysis and fluorescent X-ray analysis,
the polymer was determined to be a polycarbonate polymer having the
following structure. In addition, the ratio of the terminal Si
elements in the polymer was 13.3% by weight based upon the total
amount of the polymer.
##STR00025##
n: m=approximately 2:1 n+m=44 on average
Examples of Synthesis 9
[0159] Synthesis was carried out in the same manner as Example of
Synthesis 1 except for using 608 g of polysiloxane-containing
monovalent phenol having the following structure:
##STR00026##
("a" is 10 on average) (hereinafter, "S3"; manufactured by
Shin-Etsu Chemical Co., Ltd.) in place of the polysiloxane
monovalent phenol in Example of Synthesis 1. The intrinsic
viscosity [.eta.] of the polymer thus obtained was 0.17 [dl/g].
According to infrared absorption spectrometry analysis and
fluorescent X-ray analysis, the polymer was determined to be a
polycarbonate polymer having the following structure. In addition,
the ratio of the terminal Si elements in the polymer was 11.6% by
weight based upon the total amount of the polymer.
##STR00027##
("n" is 13 on average)
Examples of Synthesis 10
[0160] Synthesis was carried out in the same manner as Example of
Synthesis 3 except for using 608 g of
.alpha.,.omega.-bis[3-(o-hydroxyphenyl)propyl]polydimethylsiloxane
and using 28 g of p-t-butylphenol, manufactured by DIC Co., Ltd.,
in place of S1. The intrinsic viscosity [.eta.] of the polymer thus
obtained was 0.43 [dl/g]. According to infrared absorption
spectrometry analysis and fluorescent X-ray analysis, the polymer
was determined to be a polycarbonate polymer having the following
structure. In addition, the ratio of the Si elements in the polymer
was 11.9% by weight based upon the total amount of the polymer.
##STR00028##
n: m=approximately 12:1 n+m=46 on average
[0161] Evaluating methods and test methods carried out in the
Examples using the terminally-modified polycarbonate resins
obtained by the above Examples of synthesis were shown below:
1) Evaluation of Roll Staining:
[0162] Degree of accumulation of lubricants on the first roll was
evaluated by eye observation.
.largecircle.: Deterioration of a sheet appearance by roll staining
in the process of producing a multilayer sheet for 8 hours did not
occur. .DELTA.: Deterioration of a sheet appearance by roll
staining in the process of producing a multilayer sheet for 1 hour
did not occur, and deterioration of a sheet appearance by roll
staining in the process of producing a multilayer sheet for 8 hours
occurred. X: Deterioration of a sheet appearance by roll staining
in the process of producing a multilayer sheet for 1 hour
occurred.
2) High-Temperature and High-Humidity Test
[0163] The sheets obtained by Examples and Comparative Examples
were maintained under the conditions of 80.degree. C. and 85% RH
for 200 hours, and then the degree of whitening of the acrylic
resin composition layers thereof were determined by visual
observation from the thickness direction.
.largecircle.: Whitening was not observed. .DELTA.: Whitening was
slightly observed. X: Whitening was clearly confirmed.
3) Evaluation of Releasability
[0164] After a continuous molding for 8 hours, stability of release
position on the third polishing roll was evaluated.
.largecircle.: Highly stable and there was not varied in the
release position even after a continuous molding for 8 hours.
.DELTA.: After a continuous molding for 8 hours, the release
position was lowered to be unstable, and therefore deterioration of
appearance (or a release mark) caused by variance of release
position emerged. X: The release position was lowered in the
process of a continuous molding for 8 hours and the sheet was wound
around the third polishing roll to stop.
4) Evaluation of Surface Slidability
[0165] After wiping the surface of the acrylic resin composition
layer of the multilayer sheet lightly with a cotton bud containing
methanol, the coefficient of static friction thereof was measured
and evaluated by a measuring device, tradename; "Muse 94iII",
manufactured by Shinto Scientific Co., Ltd.,
5) Evaluation of Water Repellency:
[0166] After wiping the surface of the acrylic resin composition
layer of the multilayer sheet lightly with a cotton bud containing
methanol, the sheet was dried in air, and then a contact angle was
measured by purified water and evaluated.
[0167] Lubricants, polycarbonate resins and acrylic resins used in
Examples and Comparative Examples were shown below.
1) Lubricants
[0168] SPC1: Terminally silicone-modified polycarbonate resin
obtained by Example of synthesis 1 SPC2: Terminally
silicone-modified polycarbonate resin obtained by Example of
synthesis 2 SPC3: Terminally silicone-modified polycarbonate resin
obtained by Example of synthesis 3 SPC4: Terminally
silicone-modified polycarbonate resin obtained by Example of
synthesis 4 SPC5: Terminally silicone-modified polycarbonate resin
obtained by Example of synthesis 5 SPC6: Terminally
silicone-modified polycarbonate resin obtained by Example of
synthesis 6 SPC7: Terminally silicone-modified polycarbonate resin
obtained by Example of synthesis 7 SPC8: Terminally
silicone-modified polycarbonate resin obtained by Example of
synthesis 8 SPC9: Terminally silicone-modified polycarbonate resin
obtained by Example of synthesis 9 SPC10: Main chain
silicone-modified polycarbonate resin obtained by Example of
synthesis 10 Lubricant A: Ethylene bis stearic acid amide,
tradename "LIGHT-AMIDE WEF", manufactured by KYOEISHA CHEMICALS Co,
LTD. Lubricant B: Stearic acid monoglyceride, manufactured by
Kishida Chemical Co., Ltd. Lubricant C: Silicone oil, tradename
"KF-96-30cs", manufactured by Shin-Etsu Chemical Co., Ltd.
Lubricant D: Stearyl alcohol, manufactured by Wako Pure Chemical
Industries, Ltd.
2) Polycarbonate Resin
[0169] A polycarbonate resin derived from bisphenol A as
bisphenols, tradename; "Iupilon E-2000", manufactured by Mitsubishi
Gas Chemical Company, Inc., wherein "Iupilon" is a registered
trademark, having a viscosity average molecular weight of 27,000
was used.
3) Acrylic Resin:
[0170] Polymethylmethacrylate, tradename "Altuglas V020",
manufactured by ARKEMA, having a weight average molecular weight of
100,000, was used as an acrylic resin. The acrylic resin was
blended with lubricants before extrusion.
Examples 1 to 11 and Comparative Examples 1 to 7
[0171] The extruder for the polycarbonate resin layer was set up as
follows: barrel diameter=65 mm, screw L/D=35, cylinder
temperature=270.degree. C.
[0172] The extruder for the acrylic resin composition layer to form
coating layers on the both sides of the polycarbonate resin layer
was set up as follows: barrel diameter=32 mm, screw L/D=32,
cylinder temperature=250.degree. C.
[0173] The two resins are melt-extruded at the same time and a feed
block was used to laminate to form a coating layer formed of the
acrylic resin composition on both sides of the polycarbonate resin
layer.
[0174] The inside temperature of the die head was set to
260.degree. C. The resins laminated and combined with each other in
the die were introduced to three mirror-finished polishing rolls
placed horizontally. Of the three polishing rolls, the temperature
of the first roll was set to 110.degree. C., the temperature of the
second roll was set to 140.degree. C. and the temperature of the
third roll was set to 180.degree. C. The bank was formed at the
interval of the roll which the resins were firstly flowed in, and
then the resins were passed through the second and third rolls. The
withdrawing rate of the first roll and the second roll was 2.5
m/min, the withdrawing rate of the third roll was 2.6 m/min and the
speed of the pinch roll for withdrawing was 2.7 m/min.
[0175] The multilayer sheets thus obtained had the thickness of 0.5
mm. The thicknesses of both of the coating layers formed of the
acrylic resin composition were respectively 20 .mu.m. The results
of the evaluations for the multilayer sheets were shown in Table
1.
[0176] The contents of the lubricants comprised in the acrylic
resin composition of Examples 1 to 11 and Comparative Examples 1 to
7 were shown in Table 1.
[0177] According to Table 1, it is apparent that the acrylic resin
composition/polycarbonate resin multilayer sheet of the present
invention is excellent in releasability, high-temperature
high-humidity resistance and surface slidability.
Examples 12 and 13, Comparative Examples 8 and 9
[0178] 99 parts by weight of methyl methacrylate manufactured by
Mitsubishi Gas Chemical Company, Inc., 0.5 parts by weight of
pentaerythritol tetraacrylate manufactured by DAICEL-CYTEC COMPANY,
LTD. and 0.5 parts by weight of
2-methyl-1-[4-(methylthio)phenyl]-2-morphorinopropane-1-one,
tradename "IRGACURE 907", manufactured by Ciba Specialty Chemicals
Inc., were mixed with each other to obtain a mixed solution, and
then the lubricant of the present invention was added thereto.
Then, the mixed solution was coated on the surface of a
polycarbonate resin sheet having the thickness of 0.5 mm with 30 cm
wide and 30 cm long, manufactured by Mitsubishi Gas Chemical
Company, Inc., by a bar coater to form a coating layer having the
thickness of about 20 um with 20 cm wide and 20 cm long. After
coating, the coated surface was subjected to an UV irradiation for
30 seconds by a metal halide lamp, trade name "MAL-250NL",
manufactured by Nippondenchi, having irradiation energy of 80 W/cm
to carry out curing.
[0179] The contents of the lubricants mixed with the
methylmethacrylate mixed solution in Examples 12 and 13 and
Comparative Examples 8 and 9 were shown in Table 2. According to
Table 2, it is apparent that the acrylic resin
composition/polycarbonate resin multilayer sheet of the present
invention is excellent in surface slidability and water
repellency.
TABLE-US-00001 TABLE 1 The content High-temperature Coefficient of
Contact of lubricant Roll High-humidity Static Friction Angle
Lubricant (wt %) *1 Staining Releasability Resistance (.mu.)
(.degree.) Example 1 SPC1 1.0 .largecircle. .largecircle.
.largecircle. 0.20 89 2 SPC2 0.5 .largecircle. .largecircle.
.largecircle. 0.22 92 3 SPC3 1.0 .largecircle. .largecircle.
.largecircle. 0.21 95 4 SPC4 0.5 .largecircle. .largecircle.
.largecircle. 0.23 89 5 SPC5 1.0 .largecircle. .largecircle.
.largecircle. 0.19 94 6 SPC6 1.0 .largecircle. .largecircle.
.largecircle. 0.21 92 7 SPC7 1.0 .largecircle. .largecircle.
.largecircle. 0.20 95 8 SPC8 1.0 .largecircle. .largecircle.
.largecircle. 0.21 93 9 SPC9 3.0 .largecircle. .largecircle.
.largecircle. 0.15 96 10 SPC1 + A 0.8 + 0.2(A) .largecircle.
.largecircle. .largecircle. 0.20 91 11 SPC1 + D 0.6 + 0.4(D)
.largecircle. .largecircle. .largecircle. 0.23 90 Comparative
Example 1 -- -- *2 X .largecircle. 0.45 70 2 A 1.0 X .largecircle.
X 0.41 79 3 B 1.0 X .largecircle. .DELTA. 0.42 78 4 C 1.0 X .DELTA.
.DELTA. 0.38 82 5 D 1.0 X X .DELTA. 0.43 71 6 SPC10 1.0
.largecircle. X .largecircle. 0.34 84 7 SPC10 3.0 .largecircle.
.largecircle. *3 0.25 88 *1 The content based upon the acrylic
resin *2 Since roll winding occurred often, the extrusion process
ceased in 30 minutes. *3 Whitening was slightly observed before
tests.
TABLE-US-00002 TABLE 2 The content of Coefficient of Contact
lubricant Static Friction Angle Lubricant (wt %) *4 (.mu.)
(.degree.) Example 12 SPC5 1.0 0.18 96 13 SPC6 1.0 0.20 94
Comparative Example 8 -- -- 0.46 69 9 A 1.0 0.42 80 *4: The content
based upon the methyl methacrylate mixed solution
INDUSTRIAL APPLICABILITY
[0180] The molded product formed of the acrylic resin composition
of the present invention is hardly whitened and can maintain
excellent slidability even under the conditions of high temperature
and high humidity. Especially, in the case when the acrylic resin
composition is laminated with a polycarbonate resin by co-extrusion
molding, a multilayer laminate having excellent productivity and
environmental stability which is hardly whitened and can maintain
excellent appearance and slidability even under the conditions of
high temperature and high humidity can be obtained, since roll
releasability of the acrylic resin composition layer is improved
and roll fouling is significantly reduced.
[0181] Therefore, the multilayer laminate thus obtained is suitable
for usages wherein high scratch resistance and high impact
resistance are required such as various materials for windowpanes,
optical materials and protection sheets for a LCD and an EL
display.
* * * * *