GB2386374A - Slip agent comprising fatty acid amides - Google Patents

Abstract

A composition comprises gadoleic amide represented by the following formula 1: <EMI ID=1.1 HE=32 WI=62 LX=894 LY=826 TI=CF> <PC>and erucic amide represented by the following formula 2: <EMI ID=1.2 HE=29 WI=65 LX=884 LY=1212 TI=CF> <PC>characterized in that the weight ratio of gadoleic amide and erucic amide is 1:15 to 1:2. The composition imparts initial slip property and blocking resistance to a resin. The resin is preperably a polyolefin such as polyethylene.

Description

BLIPPING AGENT

Background of the Invention

The present invention relates to slipping agents for 5 imparting an excellent initi1 Blip property and a bloc king resistance when added to a resin, and relates to films acntainlog them.

Fatty acid amides are commonly used an a sllpplag agent for resin. For example, slip characteristics and blocking 10 resistance are required for polyolefn resins ( polypropylene, low-density polyethylene(LDPE), linear low-densltypolyethylene(LLDPE),ethylene copolymer end the like) that are widely used for wrapping film when they are fabricated and secondarily elaborated. If clip 15 characteristics and blocking resistance are inadequate, Film cannot be rolled up properly in fabricating or fail to be unstuck because of blocking. Also the secondary elaboration line and the line for infllling contents would not proceed smoothly. Therefore fatty aai a amides are 20 usually added an a slipping agent to provide slip characteristics and blocking resistance.

It is supposed that fatty acid Tildes kneaded into a resin move from its inside to the surface simultaneously with molding of B film, and form bimolecular layer of the fatty 25 acid amide on the surface of the film and its neighbor, anti the bimolecular layer impart a good slip property to the reed n. After the formation of the bimolecular layer, the coefficient of friction (COP) converges to a certain value - 1 -

and 1e not lowered thereafter. Therefore, in order to obtain the excellent lnltlal slip property, it is necessary to form the bimolecular layer in the surface early.

It is also required that the fatty acid amides have a 5 function of impartlug B blocking resistanae for preventing bloaklng between films, simultaneously with the slip property. Among the fatty BCi amides, unsaturated fatty Said amides having 18-22 carbon atoms, such as Olivia amide and 10 eruclc amide, impart a yood slip property, as compared with saturated fatty said amides. Fatty aalds used as the raw materials for these fatty acid amides &an be obtained from fats and oils of animal or plant sources. Industrially, the fatty acid amldesobtalnable from olaic said end eruclc acid, 15 which have abundant sources in the nature, and ammonia are generally utillsed as the slipping agents. Many studies have lre-dy been made or. the slipping agents using oleic amide end those uslag eruaic amide. While oleic amide 1e better than erucic amide in the initial slip property, it is zo remarkably inferior to eruaio amide in the bloating resistance. On the other hand, while eruclc amide is inferior to olelc amide in the initial slip property, it is by far better than oleic amide in the blocking resistance.

Many other studies have been made on the improvement 25 in the initial slip property and brooking resistance. For example, in JP-A-61-281143 and JP-A-6-1894, it is proposed that an unsaturated Eatty acid amide (oleic amide or eructa anile) is mixed with a saturated fatty acid amide (stsalc - 2 A, A MA... ^ A A

amid-8 or bfahenlc amide) for improving the block) ng relstance. In these methods, however, while the blocking resistance is certainly improved, the initial slip property G not improved but is rather deteriorated. At the present 5 time, a slipping agent containing fatty acid amide having both of an excellent initial slip property and a brooking resistance has not been obtained.

The present invention provides novel slipping agents for imparting both of an excellentinitial Blip property and 10 a blocking resistance when added to resin, and relates to films containing them.

As the result of extensive studies, the inventors have found that a composition aamprislng gsOoleic am' do and erucic amide in a specific ratio and content allows 15 improvement in the initial Blip property and the block' ng resistance, thus allowing attainment of the above-dencribed problem. The present invention has been Completed on the basin of the finding.

20 Summary of the Invention

That is, the present invention provides a Composition usable as slipping agent comprising gadoleic amide represented by the f ollouing formula 1: H$.CH29CH3

(CH2.17CONH:

,...

and erucia am' de represented by the following formula 2s H 'fCW2)7 CiHe Pi (21 1C NH2

charactarlzed in that the weight ratio of gadoleic amide and erucc amide is 1:15 to 1:2. Amount of the erupts amide is preferably 50t by weight or more based on the total amides.

l O mbodimcat of the Invention The weight rati o of gado, eia amide and erucic amide in the slipping agents composition according to the invention B;:15;G 1. 2, preferably 1:12 to 1:. and more prefershly 1:8 to 1:3. When the content of the gadoi ale amide is smaller 15 than 115, the initial slip property is not improved.

Altcrnatlvely, when the Content of the gadolela amide is greater than 1.2, the blocking resistance is inf erlos.

The erect a acid used as the raw material fatty acid in the pzesent invention is usually obtained from rapeseeO oil ZO by subjecting it to hydrolysis and distillation. It is also possible to use erucic acid obtained from white mustard oil, high eruclc acid rapeseed oil, crambe oil or cod liver oil in place of the eruclc acid obtained from rapeseed oil.

The gadoleic acid is contained in rapeseed oil an a 4 - ..,

minor component and obtained, similar to eruaia acid, by subjecting it to hydrolysis and distillation. It is also possible to use gadoeia said obtained from white mustard oil, high erucic acid rapeseed oil, crambe oil or cod liver 5 oil in place of gadoleic acid obtained from rapeseed oil.

Eruala amide or gadolelc amide can be obtest ned by reactlag erucic acid ox gadoleic acid obtained in the above process with ammonia. product obtained by amldatlon of previously mixed gadoleic acid and erucic acid can be used 10 es the composition of the present invention. Alternatively, amiGatlon of erucic acid and amidatlon of gadoleia acid are carried out independently, and a mixture of the produato can also be used as the composition of the present invention.

In addition, when erupts Said and gdoleic acid are obtained 15 from oils, a suitable mixture of eruclc acid and gadoleic acid can be obtained by selecting conditions for distillation such that the ratio of aruclc amide and gadoleic amide is within the content range defined in the invention.

Amldation can be carried out by using a generally 20 accepted grocers, For example, the acid chloride process, the direct process, the ester process or the like.

For example, in the direct process, the amidation can be oaried1 out by nixing erucic acid andlor gadoleic acid With an acid catalyst such as silica or phosphorlo BCi and 25 bubbling ammonia gas in the mixture at about 180 C under pressure. After the amidatlon, the catalyst is removed by passing through a filter such as filter press and then the filtrate in powdered by an appropriate method such as spray - 5 -

cooling, crushing and the like.

Thereafter, a purification step such as distillation, recyatallzation and the like can be carried out, if necensaryr as far as the ratio is not deviated from the 5 content range defined in the invention.

The slipping agent of the invention may contain Known additives such as other lubricants, antloxidants, light stabilizers, anti-blocking agents, antistatic agents, anti-fogging agents and the like, if necessary, an far as 10 the purpose of the invention is not deteriorated. Examples of the lubricants include saturated fatty acid amides such a palmitic amlds, stearic amlde,behenicamlde end the like: unsaturated fatty acid amides such as oleic amide, lnolelo amide and the like: bisamldes such as IS stearylethyleneblsamide end the like: secondary amides such as Nsteaylerualc amide, N-oleylpalmitlc amide and the ilke; and 80 on.

Examples of the antioxidants include phenol antioxidants such as octadecy} 20 3-3,5-di-t-butyl--hydroxylphenyl)propionate,BHT and the like phosphor antioxidant such so triphenyl phosphate, diphenyl phosphite and the like; sulfur antioxidants such as dltearylthio dipropionate and the like; and SO 0.

Examples of the light stabillzereluolude benzophenone 25 ultraviolet absorbers such as 2-hydroxy-4-methoxyUsuzophenone ana the like; salicylate ultraviolet absorbers such as 2,4-di-t-butylphenyl-3,5-di-tbutyl-4-hydroxybenzoate and - 6 -..

the like; benzotriazole ultraviolet absorbers such as 2(2'-hyOroxy-3'-tbutyl-5'-methylphenyl)-S-chlorobenzot riazole and the like; HALSe such as bis-(2,2,6,6-tetramethyl-4-iperldyl)sebacate and the 5 like; and so on.

Examples of the anti-blocklag agents include slllea, talc, clay, diatomaceous earth, feldspar and the like as the natural minerals: synthetic silica, synthetic zeolite as the synthetic products: and others as well as inorganic 10 anti-blocking agents such as lnorgania powders surface-treated with stearla acid. a divans coupling agent, a titanium coupling agent or the like: organic anti-bloaking agents such as crosslinked aaryl resin powders, cross-linkeC polystyrene resin powders, crosslinked 15 polyethylene resin powders and the like; and SO on.

Examples of antistatic agents end antl-fogging agents include anion surfaotants such as alkyl phosphate ester malts and the like; cation surfactants such as acyloylamidspropyl trimethylammonlum methoulfate and the 20 like; nonion surEaotants such as di-(-hydroxyethyl)alkylamine and the like; and so on.

The resins to which the slipping agent of the invention is applied include polyolefin resins, polyamide xeslns, polyester resins, polyaaryl resins, polyvinyl chloride 25 resins, polylacticacid resins and the like. Among them, the polyolein resins are particularly preferred. Examples of the polyolefin resins include polyethylene resin", polypropylene resins, ethylene-propylene copolymer resins, - 7 -

ethylene-vlnylacetate copolymers and the like. Among them, more preferably applied substances include low-density polyethylene, linear low-density polyethylene resin and the like. S It is preferred that the slipping agent of the invention is added to a resin in an amount of about 0.03 to 0.5 part by weight per 100 part by weight of the resin. When the amount is less than O.03 part by weight, the desired effect cannot be obtained. When the amount is more than O.S 10 part by weight, a progresslv8 improvement in the effect is not expected and rather a so- called whitening phenomenon is caused on the film surface, the haze of a film is worsened as a result. In adaltion, there is a possibility that the heat-seal property and the like are deteriorated.

15 A Film Containing the slopping agent can be produced, for example, by a method in which the slipping agent is mixed with resin together with the above=dasarlbed other Positives, it necsesaxy, melt-kneaded in an extsuder, pallets zed and molded, or by method in which a master batch 20 of erucic amide, a master batch of gadoleic amide, both an the main components of the slipping agent, and a master batch of other additives are individually prepared, and they are combined at a stage of molding To an to form the composition of the invention. Anyway, the slipping agent mater be combined 25 by any method insofar as the fatty acid amide components contained in the fit na, film product meet the composition defined in the lnventlon.

As the processes used for producing a file, the T-die - 8

process and the tubular process for molding a flat film can be exemplified, The obtained film Can be widely used for generally purpose packaging material, laminate base, building material, agricultural material and the like.

The invention will be desarlbed below in detail with reference to Examples but the invention is never limited by these Examples. Resins and anti-blocklug agents used therein were those decrlbad below' 10 (1) Resin: Linear low-density polyethylene (APE): Novatee UF230. manuf sutures by Japan Polychem Corp.; Melttlow rate: 1.1 g/10 min.; Density: 0. 926 g/cm3; slipplog agents and anti-bloaklag agent are not aontalned. Hereinafter, it is 15 referred to as LL.

Low-density polyethylene (LOPE): Novatec LE425, manufactured by Japan Polychem Corp.; MeltElow rate: 2.0 g/10 min. Density: 0.923 glam3 elipplng agent and anti-blocking agent are not aontai ned. Hereinafter, it is 20 referred to as LD.

(2) Anti-blocking agent: Synthatlc zeolite anti-blocking agent Sllton JC30, manufactured by lzusawa Industrial Chemicals. Ltd.; Average particle diameter: 2.9 m; Hereinafter, it is 25 referred to as AB Agent.

Characteristic values in Examples were measured aacor6ing to the following methods: 9 _

(1) Slip Property: This was measured according to AsTM D 1894-95. A film sample to be measured was stored in a thermostatic chamber at 20C after molding. The coefficient of Friction (COF) after 1 hour from molding was used for evaluation of the initial slip property, and the coefficient after 1 day cap used for evaluation of the converged slip property. In Examples 1 to 5, and Comparative Example 2 and3,the initial slip property of 0.29 or below, which is 0.8 times or lower 10 of the initial slip property of commercially available erucic amide composition (Neutron-S, manufactured by Nippon Fine Chemical Co.' Ltd.: Comparative Example 1, which was taken as the standard), was Considered as a good Blip property (in Table 2, indicated as O), and the initial slip t5 property of o. as or below was considered as en excellent slip property (in Table 2, indicated as I).

The $11m to be measured was prepared by the followlug process: Using a 20 mm twin-screw extruder manufactured by 20 Toyo Seiki Seisaku-Sho, Ltd., LL, o., or 0.15 part by weight of a llpplug agent based on 10Q ports by weight of LL, and 0.3 part by weight of AB Agent based on 100 parts by weight of LL were melt-kneaded at 1806C and 80 rpm. and they were molded with a small T-die molding machine at an extrusion 25 temperature of 180 C, cooling roll temperature of 30 C,nd a roll speed of 3 m/min to give a film having a thickness of 20 Am and a width of 100 mm.

(2) Blocking Assistance: - 10

This was measured according to ASTM 3 3 5 4 - 9 6. An inflation film sample to be measured was used after storing in thermostatic chamber at 20 . In Examples 1 to S. and Comparatire Example and 3, the blocking resistance of 48 S g/lOOcm2or below, whlah is 1.2 times or lower of the blooklng reslstanoe of commercially available eruclc amide composition tNeutron-s: Comparative Example 1, which was talcen as the standard), was coned dered as a good blocking resistance in Table 3, lndioated as O), and a bloating 10 resistance of 44 g/lOOcm2 or below was considered as an excellent blocking resistance(in Table 3, indicated as I).

The lnlation film to be measured was prepared by the following process: Using a 20 mmtwin-sasew extruded manufactured by Tayo 15 Seiki SaisakuSho, Ltd., a LL mixture Containing 103 by weight of LO for stabilization of molding property in film-blow molding, 0.1 or 0.15 part by weight of a slipping agent based on 100 parts by weight of the LL mixture, and 0.3 part by weight of AB Agent based on 100 parts by weight 20 of the LL mixture were melt-knoAded at 180 C and so rpm, and they were molded w' th a 50.mm "inflation film molding machine manufactured by Placo Co., Ltd. at an extrusion temperature of 180 C and 80 rpm to give a film having a thickness of 20 Am and a lay flat width of 150 mm.

25 (3) Percentages by weight of fatty acid am, deB: Percentages by weight of eruaia amide and gdoleic amide were obtained by a ga-chromatography apparatus uslag the internal standard method. The used gas-Chromatography - 11

apparatus was GC-17A, manufactured by Shimadzu Corp., with a column or DB1 (inside diameter: 0.2S mm, length: 30 m, film thickness: 0.25 m), manufactured by JEW Scientific.

Conditions for analysis were: injector temperature: 300 G, 5 detector temperature: 300C, initial column temperature: 180aC, f] nal column temperature: 280 C, and programming rate: 5 /mn.

Examples 1 - 5 and Comparative examples 1 - 3 10 Commercially available eruclc acid (ERUCIC ACID, manufactured by Henkel: the main component iB eruclc Bald, but other acids such as gadoleic acid and oldie acid are also acntained) and gadolsic acid (EICOSENOIC ACID, manufactured by Sichuan SIPO Co., Ltd.: the main component in gadoleia Is acid, but other acids such as srucic acid and oleic acid are also contained) were mixed and reacted (direct method) With ammonia at a temperature of '80 C to give fatty acid amide (bald value of unreacted fatty acid: less than 2) having the ratio of oruclc amide and gadolele amide shown in Table 1.

20 The product was purified by distillation to give a slipping agent used lnExampleslto 5, The slip property and blocking resistance of films using the slipping agent in an amount of O.1 part by weight based on 100 parts by weight of LL (or LL mixture) are shown in Tables 2 and 3.

2S Comparatlve example 1 commercially available eruc:ic amide composition (Neutron-5, manufactured by Nippon Fine Chemi Cal Co., Lt6.: - 12

the main componentis erupts amide,but amides of other acids, such as gadoleic acid and oleic aaid, are also contained) was used as the elipplng agent. The slip property and blocking resistance of films using the Blipping agent in an S amount of 0.1 part by weight based on 100 parts by weight of LL (or LL mixture) are shown in Tables 2 and 3.

Comparative examples 2 and 3 According to the same manner an that in Examples 1-5, 10 except that the ratio of erucic acid and gsdoleic sold to be mixed was changed, a Catty acid amide having the ratio of sruaia amide and gadoleic amide shown in Table 1 was obtained. The product was purified by distillation to give a slipping agent used in Comparative examples 2 and 3. The 15 slip property and blocking resistance of films using the alipplng agent in an amount of 0.1 part by weight based on loo parts by weight of LL (or LL mixture) are shown in Tables 2 and 3.

20 Example 6

According to the same manner as in Example 3 except that the amount of slipping agent was changed from O.1 part by weight to 0.15 part by weight based on 100 parts by weight of LL (or LL mixture), the Blip property and blocking 25 resistance of films were measured end the results are shown in Tables 2 and 3.

Comparative example 4 - 13

According to the Same manner aB in comparative example 1 except that the amount of slipping agent was changed from o.1 part by wed ght to 0.15 part by wed ght based on 100 parts by weight of LL t or LL mixture), the slip property and 5 blocking resistance of films were measured and the results are shown in Tables 2 and 3.

C:omparatlre example 5 A commercially available oleic amide compost tion 10 (Neutron, menufaotured by Nippon Fine Chemical Co., Itd.: contai nine Cl8-1; 70 I, C18: 71) was used as the slipping agent. The slip property and blocking resistance of films using the slipping agent in an amount of o.1 part by weight ballad on 100 parts by weight of LL for LL mixture) are shown IS in Tables 2 and 3.

- 14 -

[Table 1]

Resln Amount of Ratlo o Coposition slipping Gadololc (t by weight) agent. t amide and Bruaia umldo LL Exmple l LL mixture 0.1 1; 12.57 88 7 LL Example 2 LL mixture 0.1 l: 8.5 85 10 LL Bxamplo 3 LL mixtuxe 0.1 1; 4. 53 77 17 1L _

Example 4 LL mixture 01 1: 2.72 68 2S LL. _ Example 5. 0.1 1: 2.07 62 30 LL mixture LL Examplo LL mixture 0.15 1 4.53 77 17 Compartlve LL 1 93 3 example 1 LL mixture 0.1 31 Comparative LL 1 2 91 5 examplo 2 r mixture 0, 1 18.

Comparat$ve LL 0.1 1, 1.27 51 40 example 3 LL mixture Comperetivo LL mixture 0.15 1 31 93 3 Comparative O 1 _ _ _ oxample 5 LL mixture _. *1. Paxt by weight based on 100 1?arts by weight of LL ( or LL mixture) -

[Table 2]

Slip property _ Initial stage Evaluation Convergence Realn (after 1 hour) of niti^1 (after 1 day) stage *: Example 1 LO 0.26 O 0.08 Example 2 LL 0. 22 0.08 _ Example LL 0.17 0,08 Example 4 LL 0.16 0.08 Example 5 LL 0.15 0. 09 Example 6 LL 0.11 0.08 _. _. Compar tlvo LL 0.36 0,09 example 2 LL 0. 34 X 0.10 Campar tlve 0.14 0.09.

example 4 LL 0.22 0.09 Comparatl o L example 5 0.07 0.07 *2. In the evaluation of the initial blip property, At) indicates 0,25 or below, 0 indicates 0.29 or below, and X 5 indicates more than 0.29.

[Table 3]

. Blockinq Evaluation of resistanoe bloa31nst Resin (g/loO cm3) resiatance 3 Example 1 LL mixture 4 0 example 2 LI mixture 42 __ Example 3 LL mixture 42 Q) zxAmplo i LL mixture -I- O ExmP1e 5 LL mixture 4 6 - O Example 6 rib mixture t4 Comparative LL mixture 40 At) example 1. .... -..DTD: Comparelt are LL mixture 4 0 Get example 2 _ _ __

Comparative Lr. mixture 52 X examp1o 3.

CompBrat 4 ve bra mixture $ example 4

Comparat ve LL mixture O X example 5 _

*3. In the evaluation of the blocking resistance, 5 indicates 44 g/100 cm2 or below, O indicates 48 g/100 cm2 or below, and X indlcates.more than 48 g/100 cm2.

*4. No blocking was observed.

Examples 1 to 5 show that products retalulng a good 10 blocking resistance and imparting a good initial slip property Could be obtained when the ratio of gsdoleic amide and erucla amide He within the range of the present invention; 1:15 to ls2. (Gadoleic amide was contained in a range of 7 to 301 by weight.) In addition, it was shown 15 that more preferred products could be obtained when the ratio i. within the range of 112 to 1:2.S. (Gadoleic amide wan contained in a range of 1Q to 25% by weight.)

Al go in cases in which 0.15 part by weight of the slipping agent based on 100 parts by weight of AL (or LL mixture) was used, the slipping agent of the present invention (Example 6) gave a better initial slip property 5 than Neutron-S (Comparative example 4). In addition, as it own be clearly seen from comparison of Examples 1 to 5 and Comparatlve Example 4, the slipplug agent of the present invention gave an almost same initial slip property at 0.1 part by weight based on 100 parts by weight of LL (or LL 10 mixture) as compared with 0.15 part by weight of Neutron-S (Comparative example 1).

Comparative example 5 shows that, when an oleic amide is used as the slipping agent, the blocking rsslstanoe was very bad although good slip property can be obtained.

As desorlbed above in detail, the Slipping agents of the present invention impart an excellent Initial slip pro perty and a blocking resistance when added to a resin, and effective in the initial slip property in a smaller 20 amount as compared with the conventional erucic amide aompositi on. Thore f ore, the invention has s high economic performance. _ 18

Claims (12)

-19 CLAIMS

1. A composition comprising gadoleic amide of formula 1: T rc/(CH2)9CH3 HC\ (1)

(CH2)7COHN2

and erucic amide of formula 2: (CH')7CH

H ICl HC\ (2),

(CH2)llCOHN2 5 the weight ratio of gadoleic amide to erucic amide being 1:15 to 1:2.

2. A composition according to claim 1 wherein amount of the erucic amide is 50% by weight or more based on the total amides.

l O

3. A composition according to claim 1 or 2 wherein the weight ratio of gadoleic amide toerucicamideis 1:12and 1:2.5.

4. A composition according to claim 1 and substantially as hereinbefore described with reference to the Examples.

5. A resin composition comprising a resin and the compositio according to any one of claims 1 to 4.

-20

6. A resin composition according to claim 5, wherein the resin is a polyolefin resin.

7. A resin composition according to claim 6, wherein the polyolefin 5 resin is a low-density polyethylene resin or linear low-density polyethylene resin.

8. A resin composition according to claim 5 and substantially as hereinbefore described with reference to the Examples.

10

9. A film made from the resin composition according to any one of claims 5 to 8.

10. A film according to claim 9 and substantially as hereinbefore described with reference to the Examples.

11. Use of a composition according to any one of claims 1 to 4 as a slipping and antiblocking agent.

12. Use according to claim 11 and substantially as hereinbefore described 20 with reference to the Examples.

12. Use according to claim 11 and substantially as hereinbefore described 20 with reference to the Examples.

Amendments to the claims have been filed as follows 1. A composition comprising gadoleic amide of formula l: HC'(CH2)9CH3

HC\ (1)

(CH2)7CoNH2 and erucic amide of formula 2: HC'(CH2)7CH3

HC. (2),

(CH2t1CONH2 5 the weight ratio of gadoleic amide to erucic amide being 1:15 to 1:2.

2. A composition according to claim 1 wherein amount of the erucic amide is 50% by weight or more based on the total amides.

10 3. A composition according to claim 1 or 2 wherein the weight ratio of gadoleic amide to erucic amide is 1:12 and 1:2.5.

4. A composition according to claim 1 and substantially as hereinbefore described with reference to the Examples.

5. A resin composition comprising a resin and the composition according to any one of claims 1 to 4.

-2a 6. A resin composition according to claim 5, wherein the resin is a polyolefin resin.

7. A resin composition according to claim 6, wherein the polyolefin 5 resin is a low-density polyethylene resin or linear low-density polyethylene resin.

8. A resin composition according to claim S and substantially as hereinbefore described with reference to the Examples.

10 - 9. A film made from the resin composition according to any one of claims 5 to 8.

10. A film according to claim 9 and substantially as hereinbefore described with reference to the Examples.

11. Use of a composition according to any one of claims 1 to 4 as a slipping and antiblocking agent.