US 20040082706A1

( 12) Patent Application Publication ( 10) Pub. N 0. : US 2004/ 0082706 A1

( 19 ) United States
T s ai et al. ( 43 ) Pub. D ate: Apr. 29 , 2004
( 5 4) WAT ER RESIST AN T POLYVIN YL ACET AT E ( 3 0) F oreig n Application Priority D ata
AQUEOUS EMULSION F OR APPLYIN G T O
WOOD MAT ERIAL Oct. 24, 2002 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 09 1124724
( 75 ) Inv entors : J ing - J in T s ai, Miaoli ( T W) ; Li- Sh ing
Lin, Miaoli ( T W) ; Gan- D ar F an,
Miaoli ( J P)
Corres pondence Addres s :
BACON & T HOMAS, PLLC
625 SLAT ERS LAN E
F OURT H F LOOR
ALEXAN D RIA, VA 223 14
( 73 ) As s ig nee: CHAN G CHUN PET ROCHEMICAL
CO. , LT D . , T aipei ( 21) Appl. N o. : 10/ 606, 9 02
( 22) F iled: J un. 27, 2003
Publication Clas s i? cation
( 5 1) Int. Cl? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . C08J 3 / 00
( 5 2) US. Cl. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 24/ 5 03
( 5 7) ABST RACT
T h e pres ent inv ention relates to a Water res is tant poly v iny l
acetate aqueous emuls ion, Wh ich is us ef ul as an adh es iv e f or
apply ing to Wood material. T h e pres ent poly v iny l acetate
aqueous emuls ion is f ree of f ormalin and ex h ibits ex cellent
Water res is tance.
T h e poly v iny l acetate aqueous emuls ion of th e pres ent
inv ention can be eith er us ed alone or combined With addi
tional cros s - link ing ag ent to f urth er improv e th e Water
res is tance. Als o, Wh en th e poly v iny l acetate aqueous emul
s ion of th e pres ent inv ention is us ed to mak e ply w ood, th e
later can s atis f y s econd ty pe ply w ood s tandard reg ulated in
CN S13 49 .
US 2004/ 0082706 A1
WAT ER RESIST AN T POLYVIN YL ACET AT E
AQUEOUS EMULSION F OR APPLYIN G T O WOOD
MAT ERIAL
F IELD OF T HE IN VEN T ION
[ 0001] T h e pres ent inv ention relates to a Water res is tant
poly v iny l acetate aqueous emuls ion, Wh ich is us ef ul as an
adh es iv e f or apply ing to Wood material. T h e pres ent poly
v iny l acetate aqueous emuls ion is f ree of f ormalin and
ex h ibits ex cellent Water res is tance.
BACKGROUN D OF T HE IN VEN T ION
[ 0002] In manuf acture of ply Wood and f urniture, Wood
g luing ag ent is g enerally bas ed on urea res in. HoWev er, it is
potentially dang erous to us e th e urea res in as Wood g luing
ag ent, as it Will releas e f ormalin during proces s ing . T h e urea
res in us ed as ply Wood g luing ag ent Will g radually be
af f ected by acid material and Water contained in Wood and
af f ected by mois ture atmos ph ere, Wh ich is in turn ag ed and
deg raded to f orm and releas e f ree f ormalin. Such f ree
f ormalin is h armf ul to h uman being ( Wood Adh es iv e In
19 85 : Status and N eeds ) . T h eref ore, h oW to decreas e f ree
f ormalin in urea res in becomes important. Unf ortunately , no
res olution is s ucces s f ully propos ed till noW.
[ 0003 ] Alth oug h poly v iny l acetate res in h as been Widely
us ed f or bonding Wood and its proces s ing , a Water res is tance
and a h eat res is tance of th e poly v iny l acetate are ins uf ? cient
s o th at it is not s uitable f or ply Wood and th e circums tance
Wh ere a Water res is tance is required. T h eref ore, it is impor
tant to improv e th e Water and h eat res is tance of poly v iny l
acetate. Armour et al. , in US. Pat. N o. 3 , 5 63 , 85 1 dis clos ed
a meth od f or increas ing Water res is tance by co- poly meriZ ing
v iny l acetate and acry lates th en h eating and curing in th e
pres ence of acidic metal s alt as a curing ag ent.
[ 0004] T h e curing mech anis m of poly v iny l acetate is
dif f erent f rom th e curing mech anis m of condens ing ty pe
res in. Poly v iny l acetate emuls ion h as relativ ely h ig h poly
meriZ ation deg ree s o th at in curing proces s its molecule
ch ain Would not continue to poly meriZ e but only ev aporate
aqueous s olv ent to f orm a ? lm. Af ter apply ing poly v iny l
acetate emuls ion, th e dis tance betWeen emuls ion particle
become clos er due to ev aporation of Water contained th erein.
Wh en Water is ev aporated completely , th e particles are f us ed
each oth er to become a trans parent ? lm. Such a curing
mech anis m alloWs th e adh es iv e attaining its max imum adh e
s iv e s treng th . Its curing rate is f as ter th an condens ation rate
at ambient temperature ( s ee, eg Ok iZ u, T 19 5 6) .
[ 0005 ] T h e f ree f ormalin as s ociated With urea res in ty pe
adh es iv e is problematic at pres ent. Wh ile alth oug h th e f ree
f ormalin problem is ov ercome by us ing is ocy anate res in
ty pe adh es iv e, it h as not Widely us ed in th e ? eld due to h ig h
cos t of th e is ocy anate res in ty pe adh es iv e.
[ 0006] Bas ed on th e abov e dis adv antag es , th e pres ent
inv entors h av e conducted an inv es tig ation on th e property of
poly v iny l acetate emuls ion and th eref ore completed th e
pres ent inv ention.
OBJ ECT S OF T HE IN VEN T ION
[ 0007] One obj ect of th e pres ent inv ention is to prov ide a
Water res is tant poly v iny l aqueous acetate emuls ion, Wh ich is
us ef ul as an adh es iv e f or apply ing to Wood material. T h e
Apr. 29 , 2004
poly v iny l acetate aqueous emuls ion is f ree of f ormalin and
ex h ibits ex cellent Water res is tance.
[ 0008] T h e poly v iny l acetate aqueous emuls ion of th e
pres ent inv ention can be eith er us ed alone or combined With
additional cros s - link ing ag ent to f urth er improv e th e Water
res is tance. Als o, Wh en th e poly v iny l acetate aqueous emul
s ion of th e pres ent inv ention is us ed to mak e ply Wood, th e
res ultant ply Wood can s atis f y s econd ty pe ply Wood s tandard
reg ulated in CN S13 49 .
D ET AILED D ESCRIPT ION OF T HE
IN VEN T ION
[ 0009 ] T h e Water res is tant poly v iny l acetate emuls ion
us ed as a Wood adh es iv e according to th e pres ent inv ention
compris es th e poly v iny l acetate copoly mer of th e f olloWing
f ormula ( I) as main ing redient:
( I)
OH
OCOCH3
[ 0010] Wh erein:
[ 0011] n repres ents an integ er of f rom 0 to 5 ;
[ 0012] a ratio of x / y is f rom 4 to 1000, pref erably
f rom 4 to 19 0, mos t pref erably 15 to 19 0;
[ 0013 ] a molecular Weig h t of th e poly v iny l acetate
copoly mer is f rom 1, 000 to 800, 000, pref erably f rom
5 0, 000 to 600, 000, mos t pref erably f rom 10, 000 to
5 00, 000.
[ 0014] T h e x repeating units of ( CH2CH( OC
OCH3 ) ) and y repeating units of ( CH2CH) in th e
f ormula ( I) are eith er random poly meriZ ed or block poly
meriZ ed or a combination th ereof .
[ 0015 ] T h e Water res is tant poly v iny l acetate aqueous
emuls ion us ed as a Wood adh es iv e according to th e pres ent
inv ention ( h ereinaf ter s ometimes s imply ref er to poly v iny l
acetate) is f ree of f ormalin With out a problem of releas e of
f ormaldeh y de and pos s es s es an ex cellent adh es ion f or bond
ing Wood. T h eref ore it is adv antag e to us e as g luing ag ent f or
ply Wood and Wooden Ware. T h e Water res is tant poly v iny l
acetate emuls ion us ed as a Wood adh es iv e according to th e
pres ent inv ention can be eith er us ed alone or combined With
additional cros s - link ing ag ent or cros s - link ing ty pe adh es iv e
to f urth er improv e th e bonding s treng th .
[ 0016] T h e pres ent inv ention als o prov ides a meth od f or
producing th e poly v iny l acetate ( I) contained in th e pres ent
poly v iny l acetate aqueous emuls ion, Wh ich compris es react
ing v iny l acetate With s ilicon monomer containing eth y leni
cally uns aturated f unctional g roup repres ented by th e f ol
loWing f ormula ( II) in th e pres ence of cataly s t in aqueous
medium at an atmos ph ere pres s ure:
US 2004/ 0082706 A1
[ 0017] w h erein
[ 0018] R1= C1_ 6 alk y l g roup;
[ 0019 ] R2= C1_ 4O alk ox y g roup, pref erably CL12
alk ox y g roup;
[ 0020] n= 0 to 5 ;
[ 0021] m= 0 to 3 .
[ 0022] In th e abov e meth od, th e s ilicon monomer contain
ing eth y lenically uns aturated f unctional g roup is 0. 01 to
15 %, pref erably 0. 5 to 3 % bas ed on th e total Weig h t of v iny l
acetate and th e s ilicon monomer. T h e reaction is conducted
at a temperature of f rom 5 5 to 9 0 C. , pref erably f rom 60 to
80 C. , at an atmos ph ere pres s ure f or 4 to 8 h ours . Af ter th e
reaction is completed, th e res ultant mix ture is cured at a
temperature of f rom 65 to 9 5 C. , pref erably f rom 70 to 9 0
C. , f or 2 to 3 h ours .
[ 0023 ] T h e terms C1_ 6 alk y l g roup and CL4O alk ox y
g roup us ed h erein include a s traig h t and branch ed one.
[ 0024] T h e cataly s t us ed in th e pres ent meth od can be
perox ide, f or ex ample, pers ulf ate s uch as ammonium per
s ulf ate, s odium pers ulf ate, potas s ium pers ulate, h y drog en
perox ide, benZ oy l perox ide, permang anate, and th e lik e.
[ 0025 ] T h e aqueous medium us ed in th e pres ent meth od
can be any aqueous medium, as long as it does not interf ere
With th e proceeding of th e reaction.
[ 0026] Ex amples of th e s ilicon monomer containing eth
y lenically uns aturated f unctional g roup include, f or
ex ample, but not limited to, v iny ltrimeth ox y s ilane, v iny ltri
eth ox y s ilane, v iny ltriis opropox y s ilane, v iny lmeth
y ldimeth ox y s ilane, v iny ltributox y s ilane, v iny leth y ldipro
pox y s ilane, v iny ltripentox y s ilane, v iny ltrih ex y lox y s ilane,
and th e lik e.
[ 0027] T h e f olloWing s ch emes A and B f urth er illus trate
reaction of th e Water res is tant poly v iny l acetate aqueous
emuls ion:
( II)
Rlm
OCOCH3
( III)
3 H2O Hy droly s is
>
Apr. 29 , 2004
- continued
OH
ococH3
( W)
m RIOH + 3 - m RZ OH
OH
ococH3
OH
ococH3
[ 0028] According to th e abov e Sch emes , it is k noWn th at
v iny l acetate is copoly meriZ ed With s ilicon monomer con
taining eth y lenically uns aturated f unctional g roup to f orm a
s ilicon- containing poly v iny l acetate copoly mer of f ormula
( III) . T h e copoly mer ( III) is th en h y droly Z ed in th e pres ence
of Water to f orm a s ilicon- and h y drox y - containing poly v iny l
acetate copoly mer of f ormula ( IV) . T h e s ilicon- and
h y drox y - containing poly v iny l acetate copoly mer of f ormula
( IV) is th en s elf cros s - link ed af ter ev aporation of Water to
f orm th e pres ent poly v iny l acetate of f ormula ( I) Wh ich is
Water res is tant. In oth er Words , th e emuls ion of th e pres ent
inv ention is th e emuls ion of th e s ilicon- and h y drox y
containing poly v iny l acetate copoly mer of f ormula ( IV) in
aqueous medium, Wh ich is Water res is tant Wh en it is applied
on Wooden s ubs trates as g luing ag ent and dried.
[ 0029 ] F urth er, f rom th e Sch eme B it is k noWn th at
alth oug h th e copoly mer ( III) is h y droly Z ed to f orm copoly
mer ( IV) in th e pres ence of Water, th e copoly mer Would not
be s elf cros s - link ed due to th e pres ence of Water. T h eref ore,
th e poly v iny l acetate aqueous emuls ion of th e pres ent inv en
tion h as long operation time and s h elf time. T h e poly v iny l
acetate aqueous emuls ion of th e pres ent inv ention Will be
s elf cros s - link ed af ter ev aporation of Water With out adding
of oth er metal cataly s t nor h eating . Moreov er, a bonding Will
be f ormed betWeen th e h y drox y g roup contained in th e
copoly mer ( IV) and a h y droph ilic portion of s ubs trate to be
bonded s uch as Wooden s ubs trate to f urth er improv e th e
adh es iv e s treng th betWeen th em. If th e poly v iny l acetate
aqueous emuls ion of th e pres ent inv ention is us ed as a
US 2004/ 0082706 A1
compos ition combined With oth er cros s - link ing ty pe adh e
s iv e ( s uch as urea res in, is ocy anate res in etc. , ) to bonding
ply w ood, a Water res is tance Will be f urth er improv ed. Wh en
th e poly v iny l acetate aqueous emuls ion of th e pres ent inv en
tion is us ed as a compos ition combined With oth er cros s
link ing ty pe adh es iv e, th e poly v iny l acetate aqueous emul
s ion of th e pres ent inv ention is us ed in an amount of f rom
5 to 9 5 . 5 % by Weig h t of th e compos ition.
[ 003 0] T h e poly v iny l acetate aqueous emuls ion of th e
pres ent inv ention h as a long operation time. It Would not be
cured due to its long s h elf time of 8 h ours or more. T h us ,
th ere is no curing problem in s h ort time Wh en operation.
[ 003 1] T h e pres ent inv ention Will f urth er be ex plained
th roug h th e f olloWing Ex amples . HoWev er, it s h ould be
unders tood by th os e s k illed in th e art th at th e Ex amples are
only us ed to illus trate th e pres ent inv ention With out limiting
th e s cope of th e pres ent inv ention.
EXAMPLE 1
[ 003 2] In emuls ion poly meriZ ation reactor an aqueous
s olution of 10% poly v iny l alcoh ol ( 9 80 g rams ) h av ing a
deg ree of poly meriZ ation ( D P) of 1700 Was prepared at
atmos ph ere pres s ure. In a s eparate reactor an aqueous s olu
tion of 8- 10% ammonium pers ulf ate ( 5 0 g rams ) Was pre
pared. Als o, a monomer mix ture of 9 00 g rams of v iny l
acetate monomer and 60 g rams of v iny ltrimeth ox y s ilane
Was prepared. T h e aqueous s olution of 10% poly v iny l
alcoh ol ( 9 80 g rams ) Was h eated to 80 C. in th e emuls ion
poly meriZ ation reactor and th en 20 g rams of th e ammonium
pers ulf ate s olution Was added into th ereto. T h e res ultant
mix ture Was s tirred to f orm a unif orm mix ture. T h e abov e
monomer mix ture and 20 g rams of th e ammonium pers ulf ate
s olution Were added dropWis e to th e unif orm mix ture in
rates of 3 ml/ min and 0. 07 g / min, res pectiv ely . T h e reaction
Was carried out at a temperature of 80 C. f or 5 h ours . Af ter
th e reaction is completed, th e temperature of th e reaction
mix ture Was rais ed to 9 0 C. , th e remaining ammonium
pers ulf ate s olution Was th en added to th e reaction mix ture
and cured f or 1. 5 h ours . Af ter ag ing , th e res ultant mix ture
Was alloWed to room temperature to obtain th e emuls ion of
th e s ilicon- and h y drox y - containing poly v iny l acetate
copoly mer of f ormula ( IV) in aqueous medium of th e
pres ent inv ention.
[ 003 3 ] T h e emuls ion of th e s ilicon- and h y drox y - contain
ing poly v iny l acetate copoly mer of f ormula ( IV) in aqueous
medium of th e pres ent inv ention Was tes ted its v is cos ity ,
s olid content, and pH v alue according to th e meth ods of
J IS- K6828. Moreov er, a rig id ? lm produced by dry ing and
cros s - link ing th e emuls ion Was tes ted its Water res is tance
according to EN 204. T h e data Was compared With a com
mercial product B ( a poly v iny l acetate emuls ion s old by
Ch ang Ch un Petroch emical Co. , Ltd. under catalog number
AE- 15 0) and th e res ult is s h oWn in th e f olloWing T able 1.
EXAMPLE 2
[ 003 4] An emuls ion of th e s ilicon- and h y drox y - contain
ing poly v iny l acetate copoly mer of f ormula ( IV) in aqueous
Apr. 29 , 2004
medium of th e pres ent inv ention Was produced according to
th e meth od of Ex ample 1, ex cept s ubs tituting v iny ltriis o
propox y s ilane f or v iny ltrimeth ox y s ilane. T h e res ultant
emuls ion Was tes ted its v arious properties according th e
meth ods mentioned in Ex ample 1 and its res ult Was als o
s h oWn in T able 1.
T ABLE 1
Order of Water
Vis cos ity Solid content pH v alue res is tance
Ex ample 1 15 , 000 cps 5 2% 5 . 1 >D 3
Ex ample 2 13 , 000 cps 5 2. 2% 4. 9 >D 3
Commercial 11, 400 cps 5 0. 2% 5 . 0 >D 2
product B
EXAMPLE 3 - 6
[ 003 5 ] Emuls ions of th e s ilicon- and h y drox y - containing
poly v iny l acetate copoly mer of f ormula ( IV) in aqueous
medium of th e pres ent inv ention Was produced according to
th e meth od of Ex ample 1, ex cept s ubs tituting v iny ltriis o
propox y s ilane f or v iny ltrimeth ox y s ilane and th e Weig h t
ratio of v iny l acetate monomer/ v iny ltriis opropox y s ilane
monomer Was ch ang ed to 9 24/ 40, 884/ 80, 864/ 110, and
824/ 140 res pectiv ely in Ex amples 3 to 6. T h e res ultant
emuls ions Were tes ted th eir v arious properties according th e
meth ods mentioned in Ex ample 1 and its res ult Was als o
s h oWn in T able 2.
T ABLE 2
Order of Water
Vis cos ity Solid content pH v alue res is tance
Ex ample 3 11, 000 cps 5 2. 2% 4. 9 >D 3
Ex ample 4 12, 400 cps 5 1. 2% 5 . 0 >D 3
Ex ample 5 15 , 000 cps 5 1. 6% 4. 8 >D 3
Ex ample 6 14, 000 cps 5 1. 8% 4. 8 >D 3
Ex periment Ex ample 1
[ 003 6] T h e emuls ion produced f rom Ex ample 1, a com
mercial product A ( a poly v iny l acetate emuls ion s old by
Ch ang Ch un Petroch emical Co. , Ltd. under catalog number
AE- 9 5 0) , and a commercial product B ( a poly v iny l acetate
emuls ion s old by Ch ang Ch un Petroch emical Co. , Ltd.
under catalog number AE- 15 0) Were each applied on ply
Woods at an amount of 10 g rams / m2. T h e ply Woods applied
With th e s ame emuls ion Were pres s ed tog eth er at a pres s ure
of 1 k g / cm2 and a temperature of 110 C. f or 15 to 48 h ours ,
and th en back to ambient temperature, according to th e
meth od of CN S 13 49 . T h e ply Woods Were th en tes ted its
peeling leng th and g luing s h ear f orce af ter impreg nating in
Water, according to th e meth od of CN S 13 49 concerning th e
s econd ty pe ply Wood. T h e res ults are s h oWn in T able 3 .
US 2004/ 0082706 A1
T ABLE 3
Commercial Commercial
product product
Adh es iv e Ex ample 1 A B
Peeling s treng th 0 15 26
af ter impreg nating in
Water ( mm) *
Gluing s h ear f orce 7. 2 1. 5 0. 5
( k g f / cm2) **
As s es s ment Pas s F ail F ail
N ote:
*Peeling s treng th af ter impreg nating in Water: T h e ply w ood s h eet s ample
Was impreg nated in Water at 70 C. f or 2 h ours , th en dried at 60 C. f or 3
h ours , and th en tes ted its peeling s treng th according to th e meth od of CN S
13 49 . It is pas s ed if peeling leng th is 25 mm or les s .
**Gluing s h ear f orce: T h e ply Wood s h eet s ample Was impreg nated in
Water at 60 C. f or 3 h ours th en back to ambient temperature. T h e ply
Wood s h eet s ample Was tes ted its pulling s treng th in Wet s tate according to
th e meth od of CN S 13 49 . It is pas s ed if th e s treng th is 6 k g f / cm2 or more.
Ex periment Ex ample 2
[ 003 7] T h e emuls ion produced f rom Ex ample 1 Was
mix ed With is ocy anate res in ty pe adh es iv e in a Weig h t ratio
of 85 : 15 to g iv e a compos ition A. Separately , th e emuls ion
produced f rom Ex ample 1 Was mix ed With urea res in ty pe
adh es iv e in a Weig h t ratio of 85 : 15 to g iv e a compos ition B.
T h e emuls ion produced f rom Ex ample 1 alone, compos ition
A, compos ition B, and th e urea res in ty pe adh es iv e alone
Were each tes ted its peeling leng th and g luing s h ear f orce
af ter impreg nating in Water according to th e meth od of
Ex periment Ex ample 2. T h e res ults are s h oWn in T able 4.
T ABLE 4
Compos ition Compos ition Urea res in
Adh es iv e Ex ample 1 A B ty pe adh es iv e
Peeling 0 0 0 0
s treng th af ter
impreg nating in
Water ( mm) *
Gluing s h ear 7. 2 7. 6 9 . 5 8. 5
f orce
( k g f / cm2) **
As s es s ment Pas s F ail F ail F ail
N ote:
*and **are de? ned as th e s ame as T able 3 .
[ 003 8] F rom th e abov e res ults , it is k noWn th at th e Water
res is tant poly v iny l acetate aqueous emuls ion ex h ibits ex cel
Apr. 29 , 2004
lent bonding s treng th and ex cellent Water res is tance Wh en
us ed as an adh es iv e f or Wood material.
Wh at is claimed is :
1. Apoly v iny l acetate aqueous emuls ion us ed as adh es iv e
f or Wood material, Wh erein th e poly v iny l acetate is a copoly
mer of th e f olloWing f ormula ( I) :
( I)
OH
ococH3
Wh erein:
n repres ents an integ er of f rom 0 to 5 ;
a ratio of x / y is f rom 4 to 1000;
a molecular Weig h t of th e poly v iny l acetate copoly mer is
f rom 1, 000 to 800, 000.
2. T h e poly v iny l acetate aqueous emuls ion according to
claim 1, Wh erein th e ratio of x / y is f rom 4 to 19 0.
3 . T h e poly v iny l acetate aqueous emuls ion according to
claim 1, Wh erein th e ratio of x / y is f rom 15 to 19 0.
4. T h e poly v iny l acetate aqueous emuls ion according to
claim 1, Wh ich is f urth er us ef ul f or combining With is ocy
anate res in ty pe adh es iv e.
5 . T h e poly v iny l acetate aqueous emuls ion according to
claim 1, Wh ich is f urth er us ef ul f or combining With is ocy
anate res in ty pe adh es iv e.
6. T h e poly v iny l acetate aqueous emuls ion according to
claim 1, Wh ich is produced by reacting v iny l acetate With
s ilicon monomer containing eth y lenically uns aturated f unc
tional g roup repres ented by th e f olloWing f ormula ( II) :
CH2: CH( CH2) nSi( R1) m( R2) 3 _ rn ( II) Wh erein
R1= C1_ 6 alk y l g roup;
R2= C1_ 4O alk ox y g roup, pref erably CM2 alk ox y g roup;
n= 0 to 5 ;
m= 0 to 3 .