DE2005244A1 - - Google Patents

Description

i-'Iina-sota i-linin! / ¹ and r-'ianuf ao door in; Co-. 'Inany, Jaint Paul, Minnesota ^>t> 101, V.Jt.A.

fi; adlicri'jr adhesive strips with polyvinyl chloride underlay, the -alt .'ooxydiertom Fet säuroest ^ r w-jich ^ einacnt was.

Di ^r i ' ¹ Jr Tina un, ·; oo meets a bio ^ sarr.'eri, s or'ockf ähigen and zurüokzi-nu-jr-jn aruoice: nr) i'indlioh "n adhesive tape, the base of which is a polymer made of mainly polyvinyl chloride and etv / a j50 - ¹ JZ - G "Wio ^ ts heile an niohtfliiohtl-j / jni 'i ^ icnmachermatorial je ΙΟϋ T ^ il ¹ ". · 7inyJ polymerisat contains. At least 20 parts of Welchmacnerma teriaIr ha t

a) "inen Ox. Iran value over 4 J ^,

b) an iodine value below <-j,

c) a hydroxyl number below j> 0, and

d) a according to the Dam η f 'Hr unkme Ui ode best L rim te s through-

so unit ti i.chf'ij ilolecular weight of about;> 00 - j ^ OOO.

'.-'. ipf'Jndllohf: Adhesive tape with a well-made polyvinyl chlorid pads are included. further the predominant electrical I3olierstreiff.-n and are also used for a multitude of familiar

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Application areas applied. I.vjr groundbreaking stripes of this class are suggested in U.S. Patent Newspaper 2J5 d4 ^, which issued June 29, 19 ^; ;> ^ Was published. Because of their huge market, strips of this type are manufactured by a large number of companies that have for many years sought competitive advantages in improved quality and reduced cost.

Many years ago it was recognized that eooxidized fatty acid esters such as enoxidized soybean oil had a ·! Polyvinyl chloride film should be effective in plasticizing; see Greenspan et al. in "Epoxy Fatty Acid Lister Piasticizers", Industrial and Engineering Chemistry , 195 ^ * page 2722-6. Such e ^ oxidized ^ n lister warm because of their low cost, compared to the other, interesting, but failed because of economic efforts Excessive exudation of the epoxidized list on the vinyl film.

As one might expect from such results with vinyl film itself, apparently no one has tried to create a fiber plasticized with an enoxidized ester in a pressure-sensitive adhesive to exploit economically where the restrictions regarding of the plasticizer are particularly acute. Instead it is Use of enoxidized ester as a plasticizer in vinyl strips has been limited to fairly small proportions, usually because of it their stabilizing effect in combination with much larger ones Amounts of conventional plasticizers. For example, the teaches Australian patent 231 029 in BeisnioL 1 vinyl strelfen pads, those made from 100 parts of polyvinyl chloride, 11 parts of one epoxidized scw ^ abohnenöIs ("Pa rap lex G-ι2") and 40 parts consist of five different plasticizer compounds. The USA patent ^ 22 ^) 661 suggests Viny] filtno for use for pressure sensitive Adhesive strips made from 100 parts Vinylchlorld-Polymorisfi t, 40 parts of a common polyoster plasticizer and LO parts one of either deoxidized soybean oil or a Pheaol-inodified DerLvat of the same compound Stabilizer before.

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There is little evidence that in the previous technology an enoxidized fatty acid ester was the main Weiclimacner (e.g. in quantities of 20 or more parts per 100 parts of vinyl) in the vinyl underlay of a druoker.mindlicnen vinyl adhesive strip was used. Furthermore, there is no reference to a significant? In the bisaerigea technique; Reduction of the Rohrna cost of materials compared to the streak of the new US patent without quality degradation.

Despite the prejudice in the previous Tecuiiik, certain result epoxidized fatty acid esters, if they are used as the main softener used, a pressure sensitive vinyl adhesive tape of at least as good quality as those proposed in the new US patent 2] p 343 and essential reduced cost. Indeed, the preferred strips of the present invention are the strips of the Neuapa tents deutlica superior, especially with regard to the improved flexibility at low temperatures and the electrical insulation values.

The τ * pressure sensitive adhesive tape of the present invention has a polyvinyl chloride base with an epoxidized Fatty acid ester is softened, whichever

a) an oxirane value above 4 -; ₀ , preferably at least 6% -,

b) an iodine under 5, preferably not less than 2,

c) a hydroxyl number below 30, preferably not: than 20, and

d) a according to the Daniofdruck.nethode. a certain average of 1, borrowed a molecular weight of about 600 - j ^ nat.

With "oxirane value" are cii- weight percent oxirane oxygen in the enoxydi ^ rth Kst'-T ^1. -Iem

Urn both <; in ' \ y. (\ R -. ^ X. "i \ at: fl'-rabs«. ■ bzun ■ ^r )'. R costs as auci a -. ;; <\ '*. V w tr ^ ¹ Ίί _ii'.i::; to achieve 'jnscija I't-jn, Vi is to

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epoxidized fatty acid esters are used in amounts that are equivalent to flour than 15 parts and generally at least 20 parts per 100 parts by weight of the vinyl polymer.

The epoxidized fatty acid ester can be the sole softener for the vinyl film base or it can be used in combination with one of the weic, imacner proposed in the United States new patent 23 ' ^: Aj and the USA patent 3 129 dlo, if non-polymeric low molecular weight Liquids such as Dioc tylputhala τ are not present in amounts that exceed about 20 parts per 100 parts of the vinyl polymer. In order for the strip to be sufficiently pliable, stretchable, and retractable, the total plasticizer should provide at least 30 parts, and preferably about 35-55 parts per 100 parts by weight of the vinyl polymer for common uses. If good low temperature flexibility for cold weather use is desired, a total softness content of about 45-50 parts is preferred.

Where the Oxiranwerte are close to the minimum of 4 / o, it may be desirable to increase the amount of epoxidized fatty acid ester under 4C parts to halt3n to problems of compatibility with the Wicht Viny! Polymer to avoid. Slightly larger amounts of epoxidized jester with a leathery oxirane value can be used if the iodine value is below 2 % . Epoxidized monotallates, which when fully epoxidized typically have an oxirane value of about 4-6 % , are preferably used in amounts not exceeding 40 parts per 100 parts of vinyl and in combination with other plasticizers when a more pliable strip is desired. Epoxidized Multitaila te generally have higher oxirane values and can therefore be used in larger quantities.

Linseed oil can quickly reach an oxirane value of 7-10 # are epoxidized and yields epoxidized esters, which in hibhen Proportions, e.g. 75 parts per 100 parts vinyl, can be used

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kSiinori. Furthermore, epoxidized fatty acid esters allow such high Qxiran value, relatively large amounts of liquid v / eicn.-iacharn such as dioctyl phtaalate, whereas the latter in smaller quantities in connection with enoxidized Esters with a relatively low oxirane value were used should be.

With over 75 parts of total plasticizer, you can see compatibility ^ Face problems, and the film base is inclined in addition, in their respect, z.3. Strength and stability honing temperatures, resistance to attack by solvents, to get worse.

Apart from the use of the epoxidized fatty acid esters as defined above, the vinyl strips of the present invention are composed in the same manner as those of the prior art. Vinyl polymers and adhesives and primers which are taught in the above-mentioned United States patent specification and in United States patents 3,129,885 and 3,228,275 can be used in accordance with the invention. For example, it is known in the art that the vinyl polymer of the film base is preferably the homopolymer of vinyl chloride or a copolymer of vinyl chloride with up to about 12 % vinyl acetate. Higher levels of vinyl acetate or other monomers copolymerizable with vinyl chloride provide useful strips, although in some cases with somewhat lower strength, stability at high temperatures, and lower resistance to solvents.

Additives such as fillers, stabilizers and lubricants are used normally in a non-vinyl film backing of the novel strips used for the same purposes as in the previous technology. Clays such as aluminum silicate and carbon black are particularly useful since everyone can increase the adhesiveness, both at the beginning and after aging. Because aluminum silicate clay is cheap, or contributes to it at, the raw material costs overall to a minimum nalten.

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Preferred adhesive wets for strips of the present invention are those of the examples of U.S. Patent 3,129 Bio. Strips of the present invention coated with the solid pressure sensitive adhesives of those examples provide good adhesiveness over a wide temperature range and are particularly preferred in applications such as very high or very low temperatures. A primer coat should be used to ensure that the adhesive is properly anchored to the vinyl backing. The primers of US Pat. No. 3 232 J'ot> are preferred, especially where the strips are intended for use at low temperatures, because the tendency for the adhesive to separate or overflow becomes more pronounced at low temperatures.

example 1 Viny! Underlay weight parts

Polyvinyl chloride homopolymer ■ 100

Epoxidized soybean oil with a
Oxirane value of 7.3 %, an iodine value
of 2.6 and a hydroxy number of 13 30

Di-2-äthylhexylphthalat ^15-7 J

Aluminum silicate clay Ii; Dibasic lead phthalate stabilizer 3

White Oil Sealing Agent 1

Soot 1

The above materials were placed in an orbital mixer for 30 minutes mixed. The mixture was then blended in a Banbury mixer, held there until a temperature of ΐ5θ ° C is reached was processed on a 2-roll mill at 1HS ° C for 3 minutes and then placed in a 4-roll calender of upside-down L fitted with rolls kept at 1 ^ 0 ° C to close it a film of 0.15 mm thick.

This film was made with a mixture of butadiene-aorylnitrile copolymer latex and raw chews latex, as it is in the USA-Pa-

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tentschrif t "5 2 ^ 2 785 is described, primed, whereupon with a knife, the following adhesive mass was drawn, which to a thickness of about 0.025 mm, the strip wonaca cut to 1.8 cm widths and wrapped around itself in Roll shape was wound.

Adhesive composition - distorted by weight

Raw Smoked Leaf 50

Rubber-like butadiene styrene

Copolymer (SBR-1004) 50

polymerized terpene resin

("Hercules" S-1010) 45

polymerized terpene resin

("Piccolite" S-85) 45

Phenol-Aldehyde Resin ("Bakelite" CKR-1634) 12

Aluminum triangle 10

Di-tert-amyl-hydroquinone 2

Soot 10

Calcium carbonate 50

Heptane 640

Ethanol 10

The "Bakelite" CKR-1654, which is used in the adhesive, is to be understood as a p-tert-butylphsnol-formaldehyde resin which is produced with an alkali catalyst and with more than one mole, ie between 1.5 and 2 , 0 moles of formaldehyde per mole of substituted phenol has been produced. One of the polymerized terpene resins ("Hercules" S-1010 \ was a polymerized homogeneous mixture of CC and β-pinene with a ball and ring scrim point of 115 ° C, and the other was essentially a polymer of the β- Pinens with a melting point of 85 ° C. and an acid number of 0. The rubber-like copolymer was a copolymer of 75 parts of butadiene and 25 parts of styrene.

The adhesive was made by preparing the rubbers and any powdered materials in a cold 2-roll rubber mill. The terpene resins were added to the batch in proportions

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in a stiff Baker-Perkin internal mixer (or Mughal mixer ) given while heat was being applied, and that Phenol-aldehyde resin is added after the temperature is 130 ° C had achieved. When the Mogulmiscner's power requirements are high increased, the adhesive was cooled and mixed with the solvents mixed to a spreadable consistency »

Example 2

A pressure-sensitive adhesive strip was used as in Example 1 produced, with the exception that in the vinyl film Uaterlage the amount of epoxidized soybean oil increased to 50 parts that Amount of di-2-äthylhexylnhthalat decreased to ^ parts and the Clay and the carbon black were omitted.

The pressure-sensitive adhesive strips of Examples 5-5 are identical to those from Example 1, with the following exceptions: (1) polyethylene was used as a lubricant instead of white oil, (2) the amount of aluminum silicate clay was reduced to 10 parts, (3 ) the di-2-ethylhexylnhthalate has been omitted, and (4) the epoxidized fatty acid ester and its amounts have been changed as follows:

Example 3 Parts by weight

Epoxidized soy with one
Oxirane value of 7.0 %, an iodine value
of 1.6 and a hydroxyl number of Ij5 4 ^

Example 4 Parts by weight

Epoxidized linseed oil with an oxirane value of 9.5 %, an iodine value of 3.2 and a hydroxyl number of 14.5 k'j>

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Example 5 Parts by weight

Epoxidized Dita Hat with an oxirane value of 6.0 Y> _t an iodine value of 1.9

and a Hydroxylzaal of j50 ^ 5

Examples 6-8 deal with pressure-sensitive vinyl adhesive strips which are identical to those of Example 4, with the exception that the only plasticizer is a mixture of the specified epoxidized F-at'o acid ester plus a conventional polyester plasticizer, ie the one in the USA tents car if t 3 129 3lö as "Polyester B" designated wfeicnmacher (eg "Adrnex" J ¹ Ol ) was replaced.

Example 6

Spoxidized linseed oil from Example 4 "Polyester B"

Parts by weight 2.5

Example J

Epoxidized linseed oil with an Oxiranvjort of 1.2 %, a Joa value of 2.2 and -iiner Hydroxy Iz ^ nI / on 1.5

"Poly-is ^ r ß"

Gewic.ri.ts parts

J50

Be is piol B

Epoxidized liquid from example ^l j "Polyester B"

Parts by weight

23 2 3

Example 9

became a Druckemnfindlicht-r adhesive tape, which comes with the fj-.ie L 1 idontiscn was made, with a ^ r Ausna.'irne that

; '; my Untorlago how fol ^ t was:

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Vinyl underlay weight parts

Polyvinyl chloride homopolymer 100

Epoxidized soybean oil from Example 1 23

"Polyester Λ" 20.5 "Polyester B" 6, p

Di-2-ethylhexylPhthala t 5

Antimony trioxide 5

Dibasic lead phthalate stabilizer 3

Polyethylene lubricant 1

Black coal 1

"Polyester A" and "Polyester B" were conventional polyester plasticizers, ie the plasticizers described in US Pat. No. 3,129 oil 6 (for example "Admex" 562 and "Admex" / oil).

Example 10

A strip was produced which was identical to that of Example 3 was identical except that a decrease in the amount of the epoxidized fatty acid ester and the addition of the low molecular weight liquid plasticizer has been made to provide the following plasticizer mixture:

Weight parts

Epoxidized Soybean Oil 30

Di-2-ethylhexyl phthalate 15

The pressure-sensitive adhesive vinyl ^<3 3treifen the Bois ^ pgLele Il and are identical to dom strip of Example 10, except that different adhesives with them as reasonable ^ were used ben:

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Example 11

Adhesive composition ?

Copolymers of 97 parts of Mettiyl- -isoamyl acrylate and J parts of acrylic acid

Polyalkyleneimine curing agent

Solvent (mixture of ethyl acetate and heptane) to provide a spreadable mass?

to have

Weight parts

100
0.05

Example 12

Adhesive composition

Parts by weight

1,4-polybutadiene ("Ameripol" CB 220) 100

Hydrocarbon resin ("Nevpene" 1 ^ 0) 85.5

Ptlenol Formaldehyde Resin ("Bakelite" CKR-1634) 15

Aluminum trihydrate 10

4,4-thio-bis (5-tert-butyl-m-cresol) 1

RusskOiile 5

Heptane 645

Ethanol 10

The 1,4-polybutadiene had about 98 fo cis configuration and a MLA Mooney viscosity of about 41. In the hydrocarbon resin is a copolymer of jCrFinen and a petroleum hydrocarbon! Nitsinem ball and ring melting point of 1 ^ 1 ° C and an acid number zero .

BATH

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Adhesive 3.4 not available on 31 Table Λ Adhesive an aar Unterla l, ( ; ahl ge kg / cm ■ Ursnii. 2.3 still 95,; Urs no. after y6 / gene At- ■ 1 3.2 relative humidity To rel. hum .-, - Op s pit: 1.3 ke £ t bi
ου C • C- 56 ⁰ C activity 2.9 3.5 i "i furnace at 55 ° C in the oven 3.1 2.4 3.1 2.4 2.1 1 2.3 3.1 2.1 ¹ , · 1.9 'T / ι 11
¹ V J- 2 1.9 4/2 N / T .-',O 1.9 3 2.4 2.0 2.3 3.9 2.9 4th 1.3 2.3 1.4 2.1 1.1 5 2.2 3, 2 1.4 2.3 3.3 3.2 Ö 2.3 2.9 2, ^ 3, - 2.9 '(' 2.3 2.7 1.9 2, -I 2.0 2, Y 2.0 1.5 1.9 N / T 9 1.7 N / T 1.9 2.2 1.0 10 2.1 1 '' 1.9 1.6 0.9 11 0.9 1.4 1.9 1.2 12th 1.4

N / T means "not checked".

Because the strips of Examples 1-12 were produced in the laboratory and a certain 8c;: wank; ung in the values when transferred to commercial production can be expected, the strips of Table A with adhesion values of about 1.5 kg / crn or -v.ehv are preferred for commercial exploitation in order to ensure adequate liability.

The dielectric strength tests reported in Table B. were carried out according to United States Federal Specification HH-I-395A; first as received and then after 24 hours Dip in water at room temperature.

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Table B. Did? Ctrical strength in volts / micron example

1
2

5
• 5

7th
8th

10
11
12th

Urs Prünglion

53 5 -'5

oil 55 49

57 52

59 51 57

After 24 hours of immersion

61 55 50

51 43 49 50 43 49

51 51

The electrical insulation values reported in Table B for each strip of Examples 1-12 are at least as good as the values for preferred examples of the United States Newspaper rather than 2 ~ j> 343 and generally far superior.

The tensile strength test values shown in Table C were carried out in accordance with AoTM D 1000-66, initially as received and then in a cold room at the specified temperatures, after the specimen had been brought to a coolant temperature for 30 minutes.

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Table C. at
-12 ⁰ C at
-18 ° C strain at
-12 ° C at
-18 ° C Tensile strength (kg / cm ² ) 350 475 at room
tempera door 80 10 Stripes
the end
example With space
temperature 438 453 320 210 190 1 231 375 385 330 115 50 2 297 257 IT / T 370 10 N / T 3 242 367 369 ^ O 190 45 4th 247 275 N / T 365 10 'N / T 5 2 ^ 3 344 N / T 325 10 N / T 6th 243 453 M / T 360 10 N / T ( 264 393 401 335 195 1Ϊ5 3 253 35 ^ 412 330 70 10 9 224 343 424 360 105 10 10 244 368 4lj> 315 100 10 11 221 3/5 12th 245

All pressure-sensitive adhesive marks in examples 1-12 are better suited for cold weather use than any of the strips discussed in U3A New Patent Curift 23,343, and the Values in Table C confirm this superiority, as would one skilled in the art will understand. The strips of Examples 2 and 9 are in particularly good in this regard.

That one ton such excellent self sheep in carrying out the present invention as they are given in Tables A, B ₁ and G achieved is very surprising lkosten particularly in view of the great savings in Rohmateri? When dt2sc epoxidized fatty acid ester used instead of the much more expensive plasticizers of the previous Teohnik .

- patent claims -

0 0 9 8 3 2/1 7 3 A

BATH ORIGINAL

Claims (7)

20052U - 15 - M 2766 patent claims 1. Pressure-sensitive adhesive strip, the backing of which consists of a stable homogeneous mixture of 100 parts of a film-forming Polymer of monomers, of which at least a major proportion belongs to vinyl chloride, and consists of about 30-75 parts of a non-volatile Weicrimacher material, characterized in that at least 20 parts of the whitening material an epoxidized fatty acid ester with a) an oxirane value above 4 % _t b) an iodine value below 5 * c) a hydroxyl number below 30, and d) eirlem average determined by the vapor pressure method Molecular weight of about 600-3000 are. 2. Pressure-sensitive adhesive strip according to claim 1, characterized in that the epoxidized ester is the epoxidized Is an ester of a natural fatty acid. 3. Pressure-sensitive adhesive strip according to claim 1 or 2, characterized in that the onoxidized ester is an epoxidized natural triglyceride. 009832/1734 BAD - 16 - M 2766 4. Pressure-sensitive adhesive strip according to claim 3, characterized characterized in that the epoxidized natural triglyceride is an epoxidized soybean oil. 5. Pressure-sensitive adhesive strip according to claim 3, characterized in that the epoxidized natural triglyceride is an epoxidized linseed oil. 6. Pressure-sensitive adhesive strip according to claim 2, characterized characterized that the natural fatty acid is tall oil. 7. Pressure-sensitive adhesive strip according to claim 3, 4 or 5, characterized in that the epoxidized natural triglyceride a) an oxirane value of at least 6 % _t b) an iodine value of not more than 2, and c) a hydroxyl number of not more than 20 Has. BAD ORiGINAL Dr.Pa./Dr. 009832/1734