DE2215632A1 - adhesive - Google Patents

Description

The invention relates to adhesive® a «f basis vea slastomer« ■ like iJat'jrgiiaiffiii SeopranlfifeGSE *

sue eat polychloroprene * S
of he improves the binding depth and especially the production of high quality laminates from any material, such as, in particular, wood-like material, such as SpawItaiZs of improved strength, (ti © using this? Elast © = merlatioes.

In most of the known bonding agents in the adhesive® quality, organic solutions are used which are used as a component. Some vob them SLAs entzUndlioh and even tnanolie explosive "Change ^ © niFsaetea Afc mungsßchwierlgkeiten, dermatitis, irritation dee Äwges WIA The binders of the invention include water dagegen- wml WEI

209850/1023

therefore do not dissolve any of these Naohteile. They make bonds high strength and only small amounts of them are required, so that their use is very economical. In addition, the adhesives can burn out according to the invention can be produced with conventional adhesives in a relatively simple manner, and there is no release of harmful solvents into the environment.

However, the adhesives according to the invention have many more Advantages. They can be easily removed from skin or tools with soap and water. They adhere better to a wider variety of materials than usual Adhesives.

In addition, the adhesives according to the invention have good freeze / thaw stability, which means that during transport and Storage in cold weather no «difficulties arise. she can be filled into relatively thin plastic containers instead of those made of metal or glass, because they do not contain organic solvents and consequently do not contain solvents can penetrate the container or enforce it. The new adhesives are usually milky white when used, but go into clear films when they connect two Carriers are used together. They can also be applied to relatively moist surfaces and nevertheless develop excellent adhesion because of the chemical bonds they have entered into. In the end These water-containing adhesives can be used on cellulose plastics, where adhesives based on solvents last for a long time Tent can cause cavities and sohließlloh disintegrate, can be used. With the new adhesives, in Bonds of high mechanical strength are obtained for a short time and are burned out to achieve maximum adhesive strength with solvent-based adhesives, only a small amount of time is required.

209850/1023

The quality of a laminate is determined by a number of factors, one of the most important of which is the bond strength, like Absohälfesfcig & iit, tensile strength and lap shear strength.

The present invention relates to ingredients of very good strength obtained using a mixture of an elastomer latex and an aory modifier.

As mentioned, the elastomer latex can be, for example, a neoprene latex, a rubber latex or a styrene / butadiene latex * These Latices can vary in their composition. Xm following some examples of latices which can be used according to the invention are given.

Latex 1

Firestone S-4 natural latex containing ammonia. This is an ammonia Containing high quality centrifuged latex with the following typical properties:

Total solids, % 62.7

Trooke gum content, % 61.3

Dry solids content minus dry rubber content IA

Total alkalinity, % NH-,

based on the water in the latex 1 * 93

based on wet weight 0.78

PH 10.5

Viscosity @ 6o £ total solids

salary (T.S.) # Cp 55

Sludge content, %, based on the «

Wet weight 0.009

Coagulum content, based on the

Solids 0.007

209850/1023

KOH number 0.62

Mechanical stability, eek. 900 Copper content, Jf, based on Oeaamtfeetoff content 0.0001 Color «vlauell white Oeruoh - after neutralization «it Boric acid not a putrid oeruoh Manganese content, % » based on Total Solids β O, 0003

Latex 2

Firestone 3-5, same as 8-4, apart from a higher velvet solids content t

Oeß amt fest et off salary, % 68, 8

Ammonia content, % 0.8?

KOH number 0.45

Mechanical stability, sec. 1110.00

Latex 3

Firestone S-239, an aromatic butadiene / styrene latex

Total solids, % 50.0 ° 51.5

Residual tyrene, % 0.05 max.

pH 8.0-9.0

Coagulum 80 meoh, % 0.05 λ * χ

Mooney, ML ₄ 110-150

Bound styrene, % 48.5 - 51 # 5

Viscosity, Cp HVP # 2§20 400 max.

209850/1023

Latex 4

Pirestone 8-242 A, carboxylated of medium pipe at off content, produced to a » merization system with an etouling agent:

Oesanite solids content, %

PH ■■ 9.2

Remainder styrene, % 0.05

Moonoy, ML ^ @ lOCffi (2I2 ° P) Bound styrene, '%

Latex 5

Firestone 8-245, an oarbojsfiiodiflsisrtei?

Total solids. % Reet styrene, %

pH

Kottgulvun, 80 mech, % Mooney, VSL · ^

Formed styrene, % viscosity, Cp RW # a «S0

Allaweoklatioes such as DwPorat ΙΙ © ορρβΒβ can also be used tterd © ». These lAtiees elai have, according to their Herntellimg β la dB lter IS en fixed «« Alk & li v <m least » '3S hydroxy- Je 100 g L« t®ic eateppiel *. © Ιββββ Iltali wii

through very little Itongpa aa Slilawiiiiierefeefff # dl © meet meoprene polymer in freedom gpeeifeafe weräea _ö ÄeiÄPClioios ^ o Eae in these Alleweöklatiöe © ssstiaiteiie fol ^ [2 * F isü säcai & ste kos. The Iteoney viscosity ttbeF £ 00 (WB 1/3 taänie All «Polymers ßind

2QS8S0 / 1023

Typical properties are as follows

label e I Utax 7 (750) Latex 6 (400) 50 Fuel content, % 50 12.5 Beginning pH 1S, 5 Specifically low weight 1.10 latex 1.15 1.35 polymer 1.4δ 13th Brookfield Viscosity, cp 15th 40 Surface tension, dyn / om Medium QeI polymer Medium OeI salary salary

Other natural-based latioes containing ammonia « rubber, carboxylated butadiene / styrene and polychloroprene bind:

Latex 8

Ammoniacal natural gummilatioes. I am a typical representative of Elnea such latex is a centrifuged one with ammonia added High quality latex with the following properties

Total solids,% Trookengummigehalt,%

Qeaamt solids content minus trocar gum content OssamtalkalinltKt, % NH ₅ based on the water in the latex sucked on NaSgewloht pH

Viscosity up to 690 content content, cp

62.7 61.3

1.4

1.93 0.72 10.5 55

209850/1023

Lamb salary, $, based on Nae weight 0.009 Coagulum content, based on

Solids 0.007 KOH number 0.62 Meohanieche stability, eek. 900 Copper content, % based on
Total solids 0.001 Odor ° after neutralization with
Boric acid no putrid Gsruoh Color, visual know Manganese content, £, based on
Total solids 0.0005 Latex 9

Carboxylated butadiene / styrene latex. A typical representative this latloes has the following characteristics:

Total solids content, % 50.0 - 51.5 . Residual styrene, # 0.5 max.

pH 8.0 - 9.0

Koaguluffluf, 80 meoh, % 0.05 Biax

Nooney, ML ^ 110-130

Bound styrene, % 48.5 - 51 »5

Viscosity, Cp RVF # 2 at 20 400 max.

Latex 10

Polychloroprene. A typical representative of such a latex has the following properties,

Solids content, % 50 (same poly

(roughly) nier, another festival "

substance content)

Physical Properties Initial pH (minimum) 12.5

specific oewioht 1.10

209850/102 3

latex

polymer

Brookfield Viscosity, cp Surface tension, dyn / on

(Middle) bollard

Emulsifier

Naöge le igen Tensile strength elongation hardening rate

Flame adhesive

Module of the hardened Qumrai Tensile strength of the cured rubber 1.83 - 15

medium oil content

KaliuroaalE by dia-

proportioned a

rosin

very hooh Ho Oh

middle

low middle very low

A suitable aoryl modifying agent for the elastomer 1atices is RHOPLEX AC-34 (Rohm and Haas):

Appearance

Solids content

pH (as delivered)

Awarded »pounds per gallon Specific weight of the solids

milky white liquid

46 = 475 * 9 * 5 to 10.0 8.9 1.15

Further suitable aoryl modification agents are (Rohm and Haas)?

209850/1023

T abe 1 1 e II

O CD CO

Not networking:
Medium designation «Peststoff =
salary, % Rhoplex
AC-22 46.5 Pounds
by
gallon pH (like
ab
fills) Emulsifier <=
system approximate·'
Viscose
ity, Cp
(as from =
filled) minimum
Film image
manure.
Temp ,, K Ti, ⁴ 1 Rhoplex
AC-33 46.5 8.9 9.8 N 500 + 8 + 16 2 Rhoplex
B-6OA 46.5 8.9 9.7 N 6000 + 8 + 16 3 Rhoplex
AC-34 46.5 8.9 9.7 N 1500 + 8 + 16 4th Rhoplex
AC-35 46.5 8.9 9.8 N 1200 +12 * 7 5 Rhoplex
AC-61 45 8.8 9.5 N 850 + 9 + 12 6th Rhoplex
C-72 46.5 8.9 9.8 A. 60 +18 + 16 7th Rhoplex
AC-73 38 8.9 9.5 N —— +3? + 32 8th Rhoplex
B-85 8.9 9.5 -N ■ 250 · + 52 9 8.8 9.8 A. 10 > 90 +103

ok

The alkyl acrylic agent preferably has the following properties aohaften:

Si

0)

ο · β « SxI

GO +

OJ

«Η

CO

«Λ

OJ

χ>

Xi O

ΟΛ

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00

00

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Φ XJ N © XJ C9

αοαιι α ο η ρ

β) Ή

tjH Φ XS W

a » OjQ

4 C3

HHdrl S ePJ4

«Λ

• »τ

209850/1023

The proportions of elastomer latex and aoryl modifier can vary within wide limits. Preferably Is each of the two ingredients in an amount of about 30 to 7Q $, for example about 5Q #, based on the total weight of these materials in the mass.

In the adhesives according to the invention, other polymers or resins, for example polyvinyl acetate, shellac, Casein, flaxseed oil *! Emulsified in water Alkyd resins, etc., be present.

The recipe of a typical polychloroprene / aorylate binder according to the invention is given in Table 3V:

Table IV

Oew. Divider Specific percent Polychloroprene latex 60 - 120 (I) 50 42.7 for antioxidants 1 - 2 1 0.9 Zinc oxide 8th 5 4.3 Pheriol resin emulslon O - 100 10 8.5 Alkyl acrylate latex 60 - 120 (2) 50 42.7

Polyacrylate inlay »

medium 0 ° 3 _! 0.9

117 100.0 £ Same as "Santo-white" crystals, DuPont Heozone D special

(1) latex 10

(2) Rohm ft Haas

This mass is made byr

209850/1023

Stage 1: Emulsification of the phenolic resin, zinc oxide and antioxidant

Stage 2: Sinmisohen of the polychloroprene latex, alkyl aylate latex Into the emulsion from stage 1

Stage 3t addition of the poly aorylate dioding agent

The recipe of a typical aorylate modified centrifuge Natural rubber latex with ammonium leaf addition is given in Table Y:

Tab hurry

Composed of tongue
range, weight · » 30th »45 Special To »
composition Natural gun milatex 40.0 (D 1 - 4th Aqueous dispersion 1.5 (2) 0 - 0.25 Sodium iliac 0.2 (3) 0 - 5th Terpene resin emulsion 2.0 <*) 0 - 0.3 activated dithlooarbamate 0.3 (5) 25, .0 »40 Alkyl acrylate emulsion latex 40.0 (6) 0. . - 5th 70 # dispersion of
amorphous silica 2.0 (7) i - 2.5 Freeze / thaw stabilizer 1.0 (8th) 0 - 4th Polyacrylate thickener 2.0 (9) * 0 - 5th Alkali-soluble acrylic resin
solution 3.0 (OK) 0 > 12 water 8.0 ' (H)

100.0

* An acidic acrylic emulsion copolymer can also be used as Thickeners can be used.

209850/1023

An aqueous dispersion consists of;

10 ° 20Ji Sehwef el

Antioxidants - 2 _i 2 ^l -Methylene-bis- (4 ° ethyl =

6-tert-butylphenol)

Zinc oxide

Zinc dibutyl dithiocarbamate Alcoholic shellac solution, plasticized with Diethanolamine

5 $ aromatic petroleum resin emulsion 5 # casein 5 # sodium salts of polymerized aikylnaphfchalln-

sulfonic acid as a dispersant

o-Pheny! phenol

Phenolic modified coumarin / Xnden ^ Hapz 2% anti-foaming agent :; (12) 45 - "'

(2) * 15 - O) 2.5- (4) 0 - (5) 0 - (6) (6) 0 => (7) 2 - (8th) 2 - (95 0 « (10) 0 - (11) 0 -

s The antioxidant can also be used 2.,? ¹ -4eethylene- = biB »> (4-methyl '4« terto »butylphenol) be o

Manufacture of the adhesive;

The additives are added to the natural rubber latex with slow stirring added in the following order:

(a) aqueous dispersion

(b) sodium silicate

(o) Tarpen resin emulsion

(d) activated dithiooarbaaate

(e) allcylaorylate latex

(f) Dispersion of amorphous silicon dioxide

(g) Freeze / Thaw Stabilizer (h) alkali-soluble aoryl resin solution

209850/1023

Stir for 30 minutes - adjust the pH to 10 alt 28 £ ° igem NH ^, thereafter

Mixing the polyacrylate thickener with the Water and slow addition,

Mix for 50 to 60 minutes and if necessary adjust the pH to 9.5 to 10 with 28% NH ₄ OH.

The following examples illustrate the invention. The bond strength is called peel strength, tensile strength and Lap shear strength specified. Thieves" These values are tuned as follows:

Acc the Abac hälfest igke it measured ASTH D "9O3- ^J l9 * is the resistance of a flexible binding strip to peeling or down at an angle of l8o ° against the carrier and is expressed in kg / cm or pounds per linear inch width . The tensile strength is the resistance to a force exerted perpendicular to the plane of the bond and is given in kg / am or lbs./sq.in. The envelope / sole strength is the resistance of a bond against pulling apart when a tension is applied in a plane parallel to the bond and is given in pel or kg / cm ² , ie it is the resistance against forces perpendicular to the plane of the bonded area can be applied.

209850/1023

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OO mo

gg , SS

loo cu

8 S ft S a R.

a? «

in m ία

OO CU

ft ft

O

ft OO O O

ft ft «k ft

CU CO O O O O

β «

O h- CO O ΙΛ ΪΟ

oo ο σ \ cu in co ο co in ο

ft

OOOQOOOOQOQ

"-I W ft if in VO I" OD ChO

8 & 8 '£ SS Π2

it:

Φ

O A

Pd " H

209850/1023

It can be seen from the values in this table that the peel strength is a maximum when each of the components is in one Amount of about 40 to 60 pounds is present. The maximum of the envelope Shear strength is about 10 to 50 $ aory modifier. According to this, the optimal properties are to be » Settlement of $ 40 to $ 60 on each ingredient.

Example 2

Further tests were carried out as in Example 1, Jedooh the latex used was Firestone S-239. The results were (butadiene / styrene);

Table VIX

adhesive volume
latex Aoryl modification =
middle Envelope / Shear strength =
speed ρ
psi kg / om 8.09 A. 100 0 115 7.64 B. 90 10 109 7 * 38 C. 80 20th 105 7.38 D. 70 30th 105 7.56 E. 60 40 108 8.09 P. 50 50 115 12.5 0 40 60 178 14.1 H 30th 70 200 I4, i I. 20th 80 200 12.7 J 10 90 180 ti, ε K 0 J. 00 160

? Over 9 8 5 over / 1 0 ? 3

From the values in this table it can be seen that if the Latex a butadiene / styrene »latex is» the optimal adhesive Has properties when the acrylic modifier in a Quantity of about 60 to 90 volume ^ present 1st.

Example 3

Further test pieces made using different adhesives were tested. The results are shown in the table VX2X put together:

20 9 8 5.0 / 1.02.3

Table VIII

O CO co cn

O IO to

Weight-56 dee Mixture Peel strength »
speed
pounds kg / cm
by
linear
inch 0.68 Einhttll / Seer "
strength ₂
pounds kg / cm
by
square
inch 3.23 Tensile strength
ability ο
pounds kg / cm
by
square
inch 2.11 Recipe Haturguomi
latex (62.7 *
Solids /
37.3 * water
u. Stabilisie
funds) Alkyl acrylate
latex (46.5 *
Pests /
53.5 * water
and emulsifiers
middle 3.8 0.74 46 4.22 30th 2.25 A. 100 0 4.2 1.07 60 5.13 32 3.30 3 90 10 6.0 1.36 73 5.55 47 3.09 C. 80 20th 7.8 1.80 79 5.55 44 2.53 D. 70 30th 10.3 2.45 79 5.13 36 2.11 E. 60 40 13.5 2.92 73 2.46 30th 1.69 F. 50 50 16.7 1.97 35 1.76 24 1.34 Q 40 60 11.0 0.68 25th 1.34 19th 0.98 E. 30th 70 3.8 0.46 19th 1.12 14th 0.70 I. 20th 80 2.6 0.36 16 1.05 10 0.42 J 10 90 2.0 15th 6th K 0 100

IbJ-

NJ CTI NJ

IQ

The values in this table show that when the The peel strength, the wrapping / shear strength and the tensile strength that adhesives D or E are optimal. But it can other recipes have also been chosen to achieve specific required values of these properties.

Example 4

The results of further tests are summarized in Table IX:

λ 0 9 8 b 0/1 Ο; 3

Table IX

* Recipe Weight ~ # des
Polyohloro
prenlatex
($ 50 fixed
fabrics /
$ 50 water
u · emulsifier
middle Mixture
Alkyl acrylate »
latex (46.5 #
Pests /
55 * $ 5 water
and emulsifiers
middle Peel resistant ig-
speed
pounds kg / cm
by
linear
inch 0 * 56 Envelope / Shear ™
strength ₂
pounds kg / cm
by
square
inch 0.42 tensile strenght
pounds kg / cm
by
square
inch
i. 0.55 ta A. 100 0 2.0 0.81 6.0 2.11 5.0 2.59 O ISi B. 90 10 4.6 1.55 50.0 5.09 34.0 5.50 O
co C. 80 20th 7.6 1.51 44.0 3.45 47.0 3.73 GO
cn
ο D. 70 50 8.6 1.26 49.0 5.52 55.0 5.45 E. 60 40 7.2 0.96
0.77 50.0 3.50
2.81 49.0 2.81
1.76 O
NJ
CO P.
α 50
40 50
60 5.5
4.4 0.63 47.0
40.0 1.97 40.0
25.0 1.20 H 50 70 3.6 0.53 28.0 1.69 17.0 0.77 2215632 I. 20th 80 5.0 0.42 24.0 1.48 11.0 0.56 j 10 90 2.4 0.56 21 _r 0 1.41 8th 0.42 K 0 100 2.0 20.0 6.0

From the four benches of this table it can be seen that when the three properties measured are taken into account, adhesives D or E have optimal properties . However, other recipes can also be selected in order to achieve the values required for a particular case *

Example ^

Further test pieces were produced and tested. «The results are compiled in table X!

T_a_b_g_l le X

Weight of the room

Formulation carboxylated alkyl ethylate peel strength Butadiene / styrene (46.5 $ Pest ° pounds kg / om (5O # pests / fabrics / 43.5 # per linear 50 $ water & water & inoh emulsifier emulsifier

A. £ 00 0 2.5 0.44 B. 90 10 3.0 0.53 C. 80 20th 3.7 0.65 D. 70 30th 4.4 0.77 is 60 40 4.8 0.84 P. 50 50 5.0 0.88 σ 40 60 4.8 0.84 H 30th 70 4.3 0.75 I. SO 80 3.5 0.61 j 10 90 2.2 0.39 κ 0 100 0.8 0.14

209850/1023

From the advertisements in this table it can be seen that each of the two components is expediently in an amount of 30 paw 70 Wt. "# Is present"

Thus, according to the invention, there are generally alkyl aylate resins used »to improve the adhesive properties of elastomer resins to improve significantly.

Annotation;

Firestone, DuPonfc, Rohm & Haas »Rhoplex AC-, Neozone D and Santo-white are trade names.

209850/1023

Claims (1)

1. Adhesive or binding agent with good binding properties, characterized in that he has a Contains elastomer latex and an Aory! Modifier. 2. Adhesive or binding agent according to claim 1 _9, characterized in that it contains about 30 to 70 wt .- # of elastomer latex, based on the total amount of elastomer latex and acrylic modifier. 3. adhesive or binder according to claim 2, d a d u r ο h It is well worth the fact that the elastomer latex is a neo ~ prenlatex, rubber latex or styrene / butadiene latex. 4. adhesive or binder according to claim 3 »thereby characterized in that the acrylic modifier an alkyl aylate with a pesticide content of about $ 46.5 pH of about 9 »8 and a viscosity of about 85Ο Cp. 5 · Fiberboard of excellent peel strength and Ein = lap shear strength consisting of several Wooden boots * which are made from <$ 40 to 60 Qew. ~ £ a neoprene latex and about 60 to 4θίί of an acrylic modifier is glued together. 6. Plate according to claim 5, characterized in that g e k e η η ° draws that the glue is about 30 volumes a carboxylated butadiene / 3tyrene »latex and about $ 70 of an acrylic» contains modifier. 209850/1023 7 «Plate according to claim 6, characterized by the fact that the aoryl modifying agent Solids content of about 46.5 #, a specific gravity of about 8 * 9 pounds / oallons, a pH of about 9.8 and a Vlekoeltät (Brookfield) of about 1200. 8. Plywood board of excellent Absohaifestigkeit, a "hüll / äoherfestigkelt and tensile strength wedge:, consisting of a number of fiber layers, which are glued together by means of an adhesive of about 40 to βθ wt." £ natural rubber latex and 60 to 40 # of an alkyl aylate "whereby the guauai latex about 62.7 $ solids and about 37 * 3 # water and the alkyl aylate contains about 46.5 # solids and about 53.5 # water and emulsifiers. 9 »Plate according to claim 8, characterized ze is worthwhile. that the adhesive is about the same Kengen on the Rubber latex and the alkyl aylate by weight. 10. Process for the preparation of an adhesive, daduroh characterized in that an aqueous emulsion of a phenolic resin, zinc oxide and an antioxidant and in this emulsion a Polyohloroprenlatex and a Alkylaorylate latex mixed in » 11. The method according to claim 10, daduroh characterized da8 about 60 to 40 £ on the Polyohloroprene latex and about 40 to 60 0ew.- £ on the alkyl aylate, based on the Total amount of polychloroprene latex and alkyl aylate latex, used " 12. Plate according to claim 8, characterized in that the natural gun latex has a Trockengumnlgehait of about $ 61.3, an OeeamtalkallnltKt, based on the 2098 50/102 3 Water in the latex, of about 1.93, a pH of about 10 * 5 a viscosity of about 55 cp with total strength owns. 13 · _s adhesive according to claim l characterized in that the latex Ls.te ain ^ em au® carboxylated butadiene / styrene is "the @inen Oesanrfcfeetet off gebalt of about $ 50, a pH in the range of about 8.0 to 9 * O ₉ ice Mooney = viscosity in the range from @ttra 110 to 130 » a® flonge of bound styrene in the» Bereloh of about 48 _# 5 htm-5t _s 5t and a maximum viscosity of about 400 cp HVF # 3 tei SO asked. ' 14. Plate according to claim 13, characterized in that the alkyl acrylate is a pl ¥ oa ®tä 8 a non-ionic system and a © ¥ isk © @ i% lt ' ^: Jm 1200 Cp at 25 «C (Brookfield) hat. 15 · Adhesive according to claim 13 * thereby g β It β η η draws «. that the acrylic modification ^ itt ©! substance content of about 46 * 5 $, an anionic Syetsai is »a has a pH of about 9.8 and a viscosity of about 60 (Brookfield). 209 8 507 102 3