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Патент USA US2123155

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Patented July 5, ‘193a
comrosrrn MATERIAL I
Charleston, W.“ Va., assignor, by
‘Frazier Grofl,
‘ mesne assignments,
to Union Carbide and‘ Car- ‘
hon Corporation; a corporation of‘ New York “ ‘l ‘
‘Nb Drawing. ‘Application July 15. 1931,
, a
Serial No. 551,061,
6 ‘Claims. (cl. 154-43)
and ‘time required to cause, the theme-setting
The‘invention relates‘to the production of ar- - resins
to be converted to the final‘ iniusible‘
ticles, or stock‘ from which‘ to make ,?nished arti state differ widely ‘from a the optimum condi
cles, by combining a plurality of types of resinous
‘materials, whereby one ‘ofthe resinous materials
can be ‘caused to supply qualitiesin which .an
" tions for molding vinyl resins.‘
U'l‘he, present, invention avoids or minimizes
these di?lculties and has. for its principal object
the‘ provision of a process for forminglcornposlte
afterdescribed. ‘j
materials including thermo-setting resins and ‘
, ad , Thermo-setting resins, ‘for example phenol-l
. other, is de?cient, all as‘ moreparticularly herein
‘ ‘methylene, phenol-aldehyde, ‘phenol-iurfural,‘
urea-formaldehyde and glyptal‘resins, can be
vinyl resins.
,I havefound by‘ experimentationthat an ob
jectmcompaosed of infusible and non-absorbing
‘formed ,at moderatetemperatures, but higher, ‘ thermo-setting resin can be provided with inte
temperatures render‘ them permanently immobile gral absorbent surface, portion to which a vinyl
, and 'infusible. f?Such‘resins are extensively used‘ resin will adhere‘ when it is molded thereagainst.
3 ‘ ‘ 1‘ as molding plasticsland possess desirable‘ prop
This discovery has'enabled me to attain the ob
‘ 15 erties,,such as insolubility, resistance, to ‘heat,
ject‘of the ‘inventionand to prepare composite
mechanical strength and rigidity;
but‘tliese res
articles by molding each resin under conditions
best suited to its properties. The resultant com
from ‘ their ,usefulness.‘ For example, some, of > posite combines the desirable properties of both
these , resins are. "diiiicult to prepare in light
‘qualities ‘which detract
q ins ., also possess certain
colors or their colors tend to be unstable toward
The following examples are ‘illustrative of the
light; others are characterized by a low degree
of electrical arc/resistance; and those‘ prepared
,I. A plurality of ‘sheets of paper were impreg
,irom‘phenols _ usually retain a phenolic odor.‘ ‘ nated with potentially‘ reactive phenolic plastic
Still other ,thermo-settingnresins are di?icult to and placed together between unimpregnated
mold and the quality oi the shaped article varies
with ‘the molding conditions.
Vinyl ‘resins, that‘ is, resins _, made by ‘ poly
merizingucertain ,vinyl‘ compounds are tough,
permanently , thermoplastic,
moldable'and chemically inert.‘ They are readi
ly ‘prepared in. stable ‘colors of anyshade, and
possessa high degree of electrical arc resistance,
‘ but the heatresistance of ‘the vinyl resins is
usually ‘inferior ‘to, that oi‘ the thermo-‘setting
‘ Thus, it is, immediately apparent that if the
sheets so that‘the latter formed the top and
bottom layers of the assembly. The ‘ assembly
was ‘then molded ata temperature of about 150°
C. to 170° C. until the thermo-setting resin was
entirely converted to the infusible state. The re:
sulting p‘rodu‘ct‘was a‘ laminated ‘press board hav
ing an infusible interior, integrally joined ‘to ab
sorbing‘su‘rfaces of untreated paper. This press
board‘ was then dipped in a 20% solution of
vinyl‘resin‘ in acetone, the solvent was evaporated,
and the board was molded at about 130° to 140°
to form‘ a composite material having an infusi
desirable qualities .of each type of resin could ble thermo-setting resin. interior with asurface
.be combined in va composite material, the latter of vinyl resin. The vinyl resin solution may be
would be superior for many purposes to any prod ‘colored with lakes, dyes or pigments.
uct which would be made from either type of
If a thicker surface of vinyl resin is desired, the
resin alone. ‘But on attempting to mold the two resin may be applied in the form‘of preformed
types of resins together ‘to form a composite, sheet, or as powder. This can be done with or
combining a surface of vinyl resin with a core
, or base of an lnfuslble ,thermo-setting resin, the
unexpected fact was discovered that vinyl resins
is ‘ molded against cured or iniusible thermo-setting .
resins do not adhere thereto. In fact this lack
of adhesion is so ‘marked that vinyl resins may
be molded in matrices ‘formed from thermo-set
ting'resins, which have been converted‘ to the
infusible state, in lieu of ‘metal molds. Also,
difficulties ,are “ encountered ‘in molding vinyl
, resins against thermo-setting resins which are
not cured but which are in the potentially reac
tive state, for the reason that the temperature
without the application of a solution of vinyl res
in to the original press board. Instead of using
sheets of paper which are impregnated with the ‘
thermosetting resin, untreated‘. paper may be used
and the thermosetting resin may be distributed
between the layers of paper.
II. A piece of a fibrous material, such as pulp 50
board, was treated with a solution of a poten
tially reactive‘ phenolic resin.
The solvent ‘was
evaporated and the‘board ,wasbaked ‘until the
thermo-setting resin was‘ partially converted to
the infusible state. Sheets of paper treated‘ on 55
2 ‘
one surface with a potentially reactive phenolic
resin were molded against the outer surfaces of
the impregnated board and the resin was convert
ed to the infusible state. The product was a lam
inated article having an infusible interior, in
tegrally joined to absorbing surfaces. This lami~
nated paper and pulp boardbase was then sur
?ve minutes on heated differential rolls to thor
oughly incorporate the ingredients. The prod
uct after being rolled was ground and used as a
general molding composition.
Many types of vinyl resins may be used to form 5
A preferred vinyl resin is a
product resulting from the polymerization of a
my new material.
faced with a‘vinyl resin. by the application of a
of 70% to 95%v of vinyl, chloride and
vinyl resin‘solution“ orl‘fmolding composition, or, mixture
5%_ to;30% of‘ vinyl'acetate, and which is less than
10 ‘both, as described in Example I.
30% soluble in cold (20° to 30° C.) toluene. I 10
The pulp board which is impregnated with ‘a, diprefer to insure complete stability of the vinyl
partially cured phenolic resin may be molded di- " resin by incorporating therewith a basic stabiliz
rectly against a vinyl resin composition without’ >iingisubstance which does not include any acid
the inclusion of the absorbing layers of paper. _. forming or oxidizinggroups in its composition,
This is possible because the. uncured phenolic reuse} 1 ‘such asalkelineveartii metal salts of the fatty l5
in is at least partially soluble‘ in’th'ecvinylresin,
vnatural 'orQarti?cial acid resins, such
and because the temperature at whichthe vinyl‘ acidsior
stabilizers preferably being colloidal in nature
resin is molded, viz., about 130°C;
is sufficient
resin to ' {and ‘insoluble 'in' water. The use of a ?uxing
complete the ‘conversion of the
‘agent; such as carnauba wax, in conjunction with
the infusible final state.
t .
wthe stabilizer is also advantageous.
a, I» A- mixture ,_ of
Phenolic resin , welding
vMany modifications of my process and material
cbninositmn ‘andiafvi‘riyi resin molding eoniposif
and are‘ included within thejinvern
tiqeicontainmig so; parts‘fbf ithé. phenolic. resin are'possible"
tion “as defined by‘th‘e appended claims.‘ " "
composition} and" so parts‘o‘r‘ the vinyl resin‘ com?
position was dusted oy'e‘rkpape'r impregnated" with
a potentially reactive phenolic‘resini‘ This assem:
1 5"”
'1‘. 1i‘ compositematerial comprising an infusibl'e‘ 25
thermo-settihg resin ?rmly united to a'vinyl res-"
bly wasyin turn ‘coveredvz‘with vlnyluresin sheet: in through an intermediate bonding ‘surface com”—'
stock or molding‘ ‘composition‘and molded‘ at 150?
C. to form a’ phenolic‘resin composite surfaced
with a vinyl resimcomposltlon.
} -
Y iii... A piece of felt was‘impreg'nated with a solu-v
prising a thermo-setting resin modi?ed by the in
corporation‘ therewith of another resinous mate
rial to-which‘ said vinyl resin is'adherent.
2. ‘A‘com'pos'ite material comprising an’infusible
‘ phenolicrefsiniandfrqilnacontainingabout“ thermo7s'etting' resin ‘?rmly united to a vinyl resin:
through’ an intermediate bonding surface‘ com
The‘ impregnated .rnaterialbwas‘jdried "and baked prising
a“ "thermo-setting' resin modified by the
to‘ cur‘efthe phenolic resin ‘,Thistreatment pro! , incorporationtherewith of rosin? ' '7
du'ced an‘'impregna‘ted= basejuwhich was soft and.
13:34 composite material‘ comprising an ‘infusible '
which; remained. ?brous‘, ‘but 7' which was } siti?e‘r thermo-setting resin ?rmly unitedto "a vinyl resin
and stronger “ than‘; thejo'riginal ,"materiall; The through‘ an intermediate'bonding‘ ‘surface com;
tion of
phenolic resin‘ was'dilutedwith the ‘rosin. hence,
a thermo-setting resin modified by the
49 it "was‘possible to ‘create a bond between the; imf-f. prising
incorporation" therewith‘ of a vinyl resin. '
‘ ‘ pregnated; base‘ and a Vinyl resin. ‘ A vinyl resin
molding composition" was‘then molded against
J 4'.ffA‘coinpos'ite material comprisingan infusible'
phenolic resin portion‘?rmly united vto'a. surface
the upper and lower surfaces of the impregnated portioiijfcfjviriyl
resin " through an intermediate
This typejorprocess
be advantageously ap- bondinggflayerj comprising. about equal parts of;
plied to the formation‘of ‘articles having'a; softer
interior with a hard Iexterlor'of a; vinyl'resin' come
V. A molding composition including both then-V
mo-séttingand e‘vinyl' resins‘ was prepared as fol‘
lows; aquantity of wood flour was treated with a‘
solution containing,‘ the reaction. product of '2
phenolic resin‘a'nd ‘another resinous material ‘to 45
which said‘ vinyl resin is adherent.’ "
~ ' "
5;. A composite material comprising ‘an infusible
phenolic resin'portion ?rmlyuunlted to a surface
portion of’ vinyl resin through an"intermediatev
bonding layer‘jco‘mprising about ‘equal parts of‘ 50
phenolic resin and ‘rosin.v
6. A compositematerial comprising an infusible
molsv of formaldehyde and l mol. of urea.v ‘This phenolic resin portion ?rmlyvu'nited toa surface
mixturef'was driedand baked: in‘a‘n. oven at 90"v portion of‘vinyl resin through an intermediate
to ‘100°C. ‘to cure theresi'n. Three hundred parts bonding layer ‘comprising about e'cjual parts‘of 55
of thisfproductl was mixed with 250 parts of vinyl
resin,.l part of. carnauba wax and. 1. part of cale
phenolic resin and a vinyl resin.
clum stearate. The mixture wa’srolled for about
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